Sized paper manufacturing process (options)

FIELD: paper-and-pulp industry.

SUBSTANCE: process comprises manufacturing sized paper in presence of sizing substance and water-soluble amphoteric promoter resin, which is obtained via polymerization of a monomer including at least one polymerizable cationic amine monomer and at least one polymerizable organic acid and wherein molar percentage of cationic amine constitutes at least 25% of monomers in amphoteric promoter resin and molar percentage of organic acid units constitutes at least 25% of monomers in amphoteric promoter resin, while whiteness loss is below 0.5 TAPPI units as compared to whiteness of composition obtained without promoter resin.

EFFECT: improved sizing characteristics due to optical bleacher added and with excellent preservation of whiteness.

3 cl, 12 dwg, 2 tbl, 19 ex

 

The technical field to which the invention relates.

The present invention relates to compounds, promotership the sizing of paper, compositions, compounds, promoting the sizing, to methods of applying the promoting the sizing compositions to paper, manufactured using the promoting the sizing compositions.

Background of invention

In the process of making and finishing paper to achieve the desired characteristics sought in the finished paper product, often used sizing agent.

Gluing or characteristic sizing is a measure of the resistance of the manufactured paper products or cardboard penetration or wetting of the aqueous liquid. A sizing agent are internal additives used during the manufacturing of paper, or an external additive, used as coating materials during finishing paper, which increase the resistance.

The paper manufacturing process can be performed under conditions of acidic, neutral or alkaline pH, and the choice of the sizing agent is usually dependent on pH. For example, derivateservlet of rosin sizing agent, usually used in the acidic conditions of paper making. Under the conditions of alkaline pH values, which are widely used in the process is Ah the manufacture of high grade paper, typical sizing agent include alkylbetaine or alkenilovyh dimers or anhydrides of acids, such as alkenylamine anhydrides.

The speed with which manifests the characteristics of sizing in sized paper, is very important. In a preferred embodiment, after adding or applying a sizing agent feature sizing is manifested as quickly as possible. It is known that as the drying of the sized paper to remove moisture, the degree of manifestation of sizing increases. To reduce or eliminate water build-up and the additive in the size press of the paper machine speed is necessary manifestations of glue. High speed sizing is also important to determine the exact properties of the finished paper at the end of the paper machine without waiting or additional heat. In the process of making paper, in which a sizing substance added in the wet end of the papermaking machine, in order to achieve adequate manifestation of the characteristics of the sizing before reaching the paper size press the glued paper, usually dried to a moisture content of from about 0.8 to 3 wt.%; after processing in the sizing press, the paper is typically dried to a moisture content of from about 4 to 6 wt.%.

If at the end of bamidele Inoi machines feature sizing is manifested not fully, it is necessary to implement corrective actions, such as paper should be stored in sufficient time (hours or days), until the characteristics of the sizing will not appear in the extent corresponding to the intended use, or if the improved property is required before the full manifestation of the characteristics of sizing (for example, during the stages of finishing or processing of paper), to achieve adequate characteristics sizing should use the excess sizing agent.

Features sizing attached to conventional sizing agents for paper, can be improved by the use of promoters sizing, also called accelerators sizing. Numerous promoters paper sizing known (see, for example, US 4040984, US 4764365, US 4772462, US 4478682, US 4847315, US 4895621, US 5498648 and US 5853542).

Despite the improved performance of the sizing provided by these previously known promoters paper sizing, there is still a great need for further improvement. Promoter resin described in the above patents, affect the efficiency of optical brighteners, which are introduced in the paper manufacturing process for increasing the whiteness or brightness of the paper. Therefore, the disadvantage of using conventional promoters sizing is that the promoters procla and reduce the efficiency of optical brighteners, which is used for the clarification of white paper. In other words, adding an optical Brightener paper, manufactured using a sizing agents and promoters sizing, does not seem as white as unsized paper. Thus, some technological advantage, which give the promoters sizing, is achieved at the expense of reduced white paper.

In another embodiment, the interaction involving optical brighteners may hinder the manifestation of the promoter sizing performance. Thus, in order to achieve a white paper, and enhance the sizing of these agents must be added to the papermaking machine in more significant quantities.

Well known as is used for different industrial purposes cationic polymers and copolymers obtained on the basis of cyclopolymerization of dimethyldiallylammonium. Polydiallyldimethyl the homopolymers are well known cationic polymeric compounds, which find industrial application in the manufacture of paper for a wide variety of purposes, such as to facilitate the retention of the fibrous material and the retention of additives in the paper, to increase the rate of dewatering the wet paper web, to neutralize Ani is neaktivnyh materials recycled water, as well as to improve the sizing, to improve the efficiency of the paper sizing and speed of its manifestations. One such product is holding additive Reten®203 (Hercules Incorporated, Wilmington, stdelivery).

Known copolymers and ternary copolymers comprising as one of the Monomeric components in copolymerization combination diallylamine type, such as diallyldimethylammoniumchloride (DADMAC), marylandagralumni.org and diallylammonium (also called YEAH•HCl and DAH). In the Japan patent 57161197 described the use of a sizing agent for paper copolymers of sulfur dioxide and diallyldimethylammonium salts, such as DADMAC, or diallylammonium salt as a dispersant. In EP 282081 described (meth)acrylamide ternary copolymers, which also include the links of DADMAC or diallylamine, which can be used in combination with aluminum sulfate to increase the strength of paper. In the Japan patent 5247883 described copolymers of acrylamide and connections diallylamine type, which can be used in the manufacture of more durable paper. In the US 4279794 and 4295931 described the use of poly(diallylamine)epichlohydrin resins as accelerators paper sizing. In the Japan patent 6299494 describes the use of copolymers diallylammonium salts and some who ryh nonionic water-soluble monomers (e.g., acrylamide) with a sizing agent for paper to ensure the manifestation of the increased sizing ability.

Another technical trick to improve the sizing is reported in US 5853542. It talks about the improvement of the paper sizing a copolymer of DADMAC and YEAH•HCl. Because the resulting copolymers are cationic, they are believed to surely inhibit the effectiveness of optical brighteners. Adverse interactions involving cationic additives for paper well documented for William F.Scott in Principles of Wet End Chemistry, TAPPI Press, 1996, c.48.

In other literary sources described polymers of the monomers of DADMAC and YEAH•HCl, and optionally less than 20% of an alpha, beta-carboxylic acid. In the patent application of Japan No. Hei (9) 1997-3793 described polymer system based polymer diallylamine, methacrylamide critical cross-linking monomer, and optionally less than 20% anionic unsaturated carbonbearing connection, which increases the strength of paper and increases the rate of dehydration of wood-fiber carpet [measure of the ability of the fibrous mass to dehydration] without violating the molding process of the paper. The most important monomers for obtaining serve acrylamide and substituted acrylamide, which are cationic in connection with their acrilamide the second functional group.

In Japan patent No. Hei (8) 1996-49193 described polymers, derivateservlet of hydrophilic vinyl monomers with amino groups and/or Quaternary ammonium groups and a hydrophobic vinyl monomers. Hydrophilic vinyl monomers, when their quaternionic function cations. In this reference presents the polymers comprising up to 5% of units of acrylic acid. The resulting polymers used for coating paper to give excellent printing properties.

A white paper produced by the addition of optical brighteners in the form of fluorescent dyes. These dyes are very effective when used with highly chemically bleached fibrous masses. Such fluorescent dyes absorb radiation in the ultraviolet region (less than 370 nm) and back emit radiation in the visible range (typically in field of blue). This leads to the effect of fluorescence, which in daylight creates the impression of a bright white color, masking the inherent chemically bleached fibrous mass yellowing [Principles of Wet End Chemistry, William F. Scott, TAPPI Press, 1996, c.47].

In the work Principles of Wet End Chemistry, William F. Scott, TAPPI Press, 1996, p.48 Reynolds writes that it is crucial that the addition of anionic dyes did not occur near the point of introduction of cationic additives.

Fluor is santie dyes are typically anionic, and in terms of their effectiveness largely suppressed cationic promoters sizing. Representatives of manufacturers of optical brighteners, such as the company Clariant Corporation, Charlotte, North Carolina, and Bayer Corporation, Pittsburgh, Pennsylvania, it is recommended to add optical brighteners in the paper manufacturing process at points substantially removed from points of introduction of cationic chemicals, such as promoting the sizing resin.

Attempt to reduce the negative impact of the promoters padding on optical brighteners are described in the patent US 5498648. This is done by mixtures for sizing paper, which is prepared by mixing the aqueous slurry of cooked cationic starch with a water dispersion of fine polymer and emulsified in this mixture With14-C20acidication at a temperature of not lower than 70°C. In this patent it is said that the merger cooked cationic starch dispersion negative impact on the whiteness of the paper is weakened.

Despite reports about the usefulness of cationic polymers on dilloway the basis for many industrial purposes, in the literature devoted to the art, any assumptions about the usefulness of binary and ternary copolymers diallyldimethylammonium salts, n is necessarily diallylammonium salts, and unsaturated organic acids to enhance the performance of sizing sized paper at the same time without a negative impact on the whiteness of the paper, realized through optical brighteners, not detected.

Summary of the invention

One object of the present invention is a reaction product of the polymerization of one or more selected cationic unsaturated monomers capable of free radical polymerization and one or more selected anionic unsaturated monomers, is also capable of free radical polymerization.

Before the creation of the present invention, it was unknown that the composition of the present invention, in which use polymers that have significant fractions of some cationic components, can be used as successfully as they apply to the implementation of the present invention. Specifically, it was assumed that the use of the polymer with the content of the cationic component is more than 50% will prevent the use of some other additives such as optical brighteners, which, depending on the particular market, may have an economic value. It was found that when performing the present invention these resins, of which the possession is t anionic and cationic components, are effective promoter resins, even when used in relatively small quantities. In order to indicate the presence of cationic and anionic properties of their components, these resins are called amphoteric promoter resin. Unexpected was that, unlike pampoernig cationic resins, amphoteric promoter resin, when these amphoteric promoter resin is used in small quantities, not oppose such additives, and much less inhibiting their properties even at high concentrations. Especially important additives are optical brighteners, which are injected to lighten and whiten the paper.

In the broadest sense of new polymeric amphoteric promoter resins are polymers that include a) the segments based on the Quaternary amine is at least one type, which increase the speed of manifestation sizing, and b) anionic segments of at least one type that normally compensate for the influence of the cationic portion of the polymer provided on the optical brighteners (CBOs).

Option amphoteric polymer resin of the present invention, which is prepared from one or more Quaternary diallylammonium monomers, optional diallylammonium monomer and nenas the seal organic acid monomer, is a new connection, when the molar proportion of units of the unsaturated organic acid, calculated on a molar basis is at least 25% and a total molar proportion of units of Quaternary diallylammonium monomer and diallylammonium monomer, calculated on a molar basis is at least 25%.

More specifically, the composition according to the invention is a water-soluble amphoteric promoter polymer composition which consists essentially of the product with recurring units of a monomer comprising at least one capable of cationic polymerization amine of the formula (I)

where the value G is selected from alkyl, allyl, alkenyl, sterile, and the values of J, K and L are selected from hydrogen atom, alkyl, alkenyl, allyl, sterile and aryl; and at least one is able to cure the organic acid of formula (II)

where each of Rx, Ryand Rzdenotes a hydrogen atom, alkyl, alkenyl or aryl, and E denotes organic Deputy, chosen from a number of COO-, SO3-, HSO4-and H2PO4-and where the molar proportion of units of cationic amine monomer of the formula I stood at the focus of at least 25% of units of monomers in the amphoteric promoter resin and the molar proportion of units of an organic acid of formula II is at least 25% of units of monomers in the amphoteric promoter resin.

A more preferred object of the present invention is the promoter of sizing paper, which consists essentially of recurring units of at least one Quaternary diallylammonium monomer of formula (III)

optional including diallylammonium monomer of the formula (IV)

where each of R1A, R1B, R1Cand R1Ddenotes a hydrogen atom or remotemachine or branched C1-C8alkyl; each of R2and R3denote alkyl, alkenyl, aryl, interrupted by a heteroatom alkyl or alkenyl, where the heteroatoms are selected from the series N, S and O; R4denotes a hydrogen atom, alkyl, alkenyl, aryl, interrupted by a heteroatom alkyl or alkenyl, where the heteroatoms are selected from the series N, S and O,

and X-denotes a monovalent anion or polyvalent equivalent of a monovalent anion,

and organic acids of the formula (II)

where each of Rx, Ryand Rzdenotes a hydrogen atom, alkyl, alkenyl or aryl, interrupted by a heteroatom alkyl or alkenyl, where the heteroatoms are selected from the series N, S and O; and E denotes organic Deputy, chosen from a number of COO, SO3, HSO4and H2PO4.

In addition, to obtain the product polymer is saved, you can use the monomer of formula (III), the monomer of formula (IV) and the monomer of formula (II) more than one type or variety.

Yet another object of the invention is a method of manufacturing sized paper with improved performance sizing the application of the promoter sizing paper of the present invention.

And yet another object of the invention is a coated paper, comprising the promoter of sizing paper of the present invention.

Among the advantages of the present invention should be mentioned that when the promoters sizing use with sizing agents, these promoters sizing increase the speed with which manifests itself in the paper characteristic of the sizing. Glued the paper made with the sizing promoter of the present invention, showing an increased rate of manifestation of the characteristics of the sizing, so it may be necessary to use a smaller amount of a sizing agent. Other features and advantages of the present invention is apparent from the present description.

Brief description of drawings

Figure 1 presents a graph showing how industrial cationic promoter resin inhibit the action of optical brighteners.

Figure 2 presents a graph showing that the two used industrial cationic promoter resin, and(DADMAC) and poly(DADMAC/YEAH• HCl), reduce the efficiency of optical brighteners.

Figure 3 presents a graph showing the efficiency of the amphoteric promoter resin in the sizing of paper.

Figure 4 presents a graph showing the efficiency of the amphoteric promoter resin in the sizing of paper, showing the influence of different concentrations of amphoteric promoter resin.

Figure 5 presents a graph showing the efficiency of the amphoteric promoter resin in the sizing of paper, showing the influence of different ratios of the Monomeric components of the amphoteric promoter resin.

Figure 6 presents a graph showing the efficiency of the amphoteric promoter resin in the sizing of paper, showing the influence of different ratios of the Monomeric components of the amphoteric promoter resin.

Figure 7 presents a graph showing the efficiency of the amphoteric promoter resin in the sizing of paper, showing the influence of different ratios of the Monomeric components of the amphoteric promoter resin.

On Fig presents a graph showing the efficiency of the amphoteric promoter resin in the sizing of paper.

Figure 9 presents a graph showing the efficiency in the sizing of paper amphoteric promoter resin, showing the impact of alkanesulphonic Monomeric components amphoteric promotor the Yu resin.

Figure 10 presents a graph showing the efficiency of the amphoteric promoter resin in the sizing of paper, showing the impact of alkanesulphonic Monomeric components in the amphoteric promoter resin.

Figure 11 presents a graph showing the efficiency of the amphoteric promoter resin in the sizing of paper, showing the influence of the other Monomeric components in the amphoteric promoter resin.

On Fig presents a graph showing the efficiency of the amphoteric promoter resin in the sizing of paper and optical whiteness of the final products.

Detailed description of the invention

In the present description the terms "paper" and "paper making" should be considered as encompassing not only the paper (and its production), but also cardboard, paper handmade character and other similar materials based on cellulose fabric (and their production), which, as a rule, are made using equipment and methods of making paper that requires the use of additives such as sizing agent, to modify the characteristics of the sizing of the resulting product.

Before further discussion is given the meaning of the following terms, which contributes to the understanding of the essence of the present invention.

The SIZING of the PAPER: the paper handling for the purpose of stability against penet the emission of liquid or using supplements for the wet part, any surface treatment.

ADHESIVE: any material used for sizing in the mass or surface sizing, for example rosin with alum, starch, animal glue, gelatin, latex, alkylcatechols dimer, alilandry anhydride, etc.

PROMOTER RESIN: chemicals added in the process of making paper, which accelerates the action of the adhesive for paper sizing.

WHITE: reflective white or almost white paper products; this indicator is primarily a measure of the lack of yellow fibrous mass that is associated with the presence of lignin and other impurities remaining after incomplete chemical bleaching.

OPTICAL BRIGHTENERS FOR PAPER: fluorescent dyes, which absorb radiation in the ultraviolet region of the spectrum (less than 370 nm) and back emit radiation in the visible region (blue) (formation of sharp peaks at a wavelength of 435 nm, which causes the effect of fluorescence, which in daylight creates the impression of a bright white color, masking the inherent chemically bleached fibrous mass yellowness).

New polymeric amphoteric promoter resins are polymers that include a) the segments of the cationic basis of at least one type, which increase the speed of manifestation sizing, and b) any aktivnye segments of at least one type to compensate for the influence of the cationic portion of the polymer optical brighteners. When the polymerization mixture include diallyldimethyl (YEAH•HCl), is joining segment of the third type, consisting of formed from his links. The preferred option is the use of DADMAC in the form of a cationic segment basis, acrylic acid as the anionic segment and YEAH•HCl as an optional third monomer. It was found that the polymerization mixture, ADMAH, YEAH•HCl and acrylic acid allows to achieve a significant improvement in performance properties. In the polymer, which may contain any of the repeating units may also include links to other monomers, provided that they do not absorb UV radiation so as to suppress the influence of the optical Brightener (CBOs)that they will not tell the polymer insolubility in water and do not add in a concentration that displays a polymer composition for prescribed parameters.

Interest segments on a share basis in such a polymer are those that cause accelerated sizing. In other words, interest segments on cationic basis are the ones that usually promotirovat the sizing without adding the Oia anionic segments of the present invention. From the list of useful segments or monomers excluded those which formed polymer with a relatively intense absorption of radiation in the ultraviolet region of the spectrum, which uses optical bleach (CBOs) with the achievement of white. Some examples of suitable monomer or segments are DADMAC, methyldiethylamine, YEAH•HCl, dylandailynews.mycyberway.com and ethylenimine, as well as many derivatives of these materials.

As in the case of cationic monomers, for performing the present invention any undesirable anionic monomer, which causes the formation of a polymer with a relatively intense absorption of radiation in the ultraviolet region of the spectrum, which is used by CBOs to achieve whiteness. Anionic monomers may be compounds containing or carboxyl groups or sulphonate group, or other anionic groups, which usually reduces the interaction of the polymer with CBOs. Anionic nature can also be caused by the reaction of the other monomer segment of the polymer, in particular the reaction of acrylamide. Important it is partially anionic and partially cationic nature of the final polymer, but not the means to achieve it. Preferred anionic m is the rooms with carboxyl groups.

The promoter of the paper sizing in the present invention is a reaction product of polymerization obtained from at least one Quaternary diallylammonium monomer, at least one optional diallylammonium monomer and at least one alpha,beta-unsaturated carboxylic acid. In a preferred embodiment, the reaction product of polymerization is obtained from the following monomers:

(I) Quaternary diallylammonium monomer of formula (III)

(II) diallylammonium monomer of the formula (IV)

and (III) unsaturated organic acid of formula (II)

Alternatively unsaturated organic acid may be an unsaturated carboxylic acid of the formula (V)

In formulas (III) and (IV) among the radicals R1each of R1A, R1B, R1Cand R1Ddenotes either a hydrogen atom or methyl. The preferred value of the radicals R1is a hydrogen atom.

In the formula (III) R2denotes alkyl, alkenyl or aryl, preferably1-C22alkyl, C1-C22alkenyl or aryl. Similarly, in the formula (IV) R3denotes alkyl, alkenyl or aryl, preferably1 -C22alkyl, C1-C22alkenyl or aryl.

In the formula (IV) R4stands With1-C22alkyl, C1-C22alkenyl, aryl or hydrogen atom, preferably a structure with a hydrogen atom.

In formulas (III) and (IV) patterns of R2, R3and R4(other than hydrogen atom) can be unsubstituted or substituted, such as alkyl may be a hydroxy-, carboxy-, alkoxy-, mercapto - or thioalkyl. Similarly, in the formulas (III) and (IV) R2, R3and R4alkyl structure-alkeline patterns and aryl structures may comprise ester groups and can be interrupted by heteroatoms such as N or S, or heterogroup, for example-NH-CO - or-CO-NH-.

In formulas (III) and (IV) alkyl patterns and alkeneamine patterns R2, R3and R4can be remotemachine or branched. In a preferred embodiment, the radicals R2, R3and R4are uninterrupted alkyl radicals containing from 1 to 18 carbon atoms, more preferably from 1 to 4 carbon atoms.

Examples of acceptable alkyl structures for R2, R3and/or R4are n-docosyl, n-pentadecyl, n-decyl, isooctyl, isoheptyl, n-hexyl, isopentyl, and preferably n-butyl, isobutyl, sec-butyl, isopropyl, ethyl and methyl. In predpochtitelno embodiment, the radicals R 2, R3and R4identical, and in the preferred embodiment, each represents methyl.

Preferred alkeneamine group for structures R2, R3and R4in formulas (III) and (IV) include octadecenyl, hexadecanyl, undecenyl, octadecadienyl, hexadecanol and mixtures thereof. Preferred aryl groups for the radicals R2, R3and R4in formulas (III) and (IV) include benzyl and phenyl.

In the monomers of formula (III) patterns of R2and R3in the preferred embodiment, is chosen from (in order of decreasing preference) methyl, benzyl,2-C22of alkyl, phenyl, octadecadienyl and hexadecanyl, octadecenyl, hexadecanyl, undecenyl and other Akilov and arrow.

In the monomers of formula (IV) are preferred structure R4is a hydrogen atom.

The monomers of formulas (II) and (V) each of Rx, Ryand Rzdenotes a hydrogen atom, alkyl, alkenyl, aryl, alkynylaryl or interrupted by a heteroatom alkyl, aryl or alkenyl, where the heteroatoms are selected from the series N, S and O.

In formulas (III) and (IV) X-means compatible with sizing anion. You can use salts of mineral acids and organic acids. In a preferred embodiment, the values of X-selected from halide, nitrate, acetate, benzoate, sulfate and phosphate groups. Prefer the elegance halides are chloride, fluoride and bromide. The preferred value of X-is chloride or fluoride. The most preferred value of X-is chloride.

The preferred monomers of the formulas (III) and (IV) are those in which each of R1A, R1B, R1C, R1Dand R4denotes a hydrogen atom, a R2and R3denote methyl. For cases such preferred monomers in which X-denotes chloride, the monomer of formula (III) represents diallyldimethylammoniumchloride, sometimes in this description referred to as ADMAH, and the monomer of formula (IV) represents diallylammonium, sometimes in this description referred to as YEAH•HCl.

Values of R1, R2, R3and R4is limited by the fact that the final polymer should be water-soluble. The nature of this limitation is that it depends on the chemical properties of the radicals R1, R2, R3and R4and the quantity in which they are contained.

The preferred alpha,beta-unsaturated carboxylic acids of the formula (V) are cinnamic acid, crotonic acid, sorbic acid, acrylic acid, methacrylic acid, taconova acid, pravilova acid, maleic acid and fumaric acid. Preferred acrylic and methacrylic acid.

The AOC is e, it is possible to use compounds such as maleic anhydride and succinic anhydride. During the polymerization, they will probably remain in the form of anhydrides, but in terms of use in paper machine they apparently hydrolyzed with conversion to the desired acid form.

In a preferred embodiment, the polymeric reaction products of the polymerization of a monomer of the formula (III), a monomer of the formula (IV) and monomer of the formula (II) contain in the polymer only these Monomeric components and minor amounts of other monomer components, in addition to the polymerized monomer of the formula (III), the monomer of formula (IV) and the monomer of formula (II).

Part of the polymer, which derivateservlet from monomers of the formula III and formula IV, is in its cationic state when all the conditions provided for use in performing the present invention. Thus, the monomers of formulas III and IV is described as cationic Quaternary amines. Groups that are 4 groups, substituted on the nitrogen atom may be hydrogen atom, alkyl, alkenyl, aryl, allyl, etc. In accordance with this definition as (CH3)4N+Cl, and (CH3)3N+HCl is considered as cationic Quaternary amine.

Part of the polymer, which derivateservlet of the monomer of the formula V, in conditions that beings who have during the alkaline paper manufacturing process, is anionic. Thus, from a combination of cationic components [formula (III) and formula (IV)] and anionic component [formula (II)] is formed polymerization product of the manufacture of paper Importeren.

In the conditions used for polymers, presented in the description of the present invention, unsaturated carboxylic acid [formula V]

is in its acid form and, thus, during the synthesis of the polymer remains unchanged.

The ratio between Monomeric units or segments with cationic and aminovymi anionic groups in the polymer determines how well the polymer promotiom the sizing and how little of its impact on the effectiveness of CBOs. The final polymer, calculated on a molar basis should consist of at least 25% of the total number of cationic Monomeric units on amine-based, including the number of links YEAH•HCl, if they are contained. A more preferred amount is at least 30%. The most preferred amount is at least 40%. The specific number of cationic groups and anionic groups are best expressed in percentage, calculated on the molar basis of the total number of cationic Monomeric units. With regard to tinactive segments, in the preferred embodiment, up to 65%, and most preferably from 10 to 50%, of the total percentage of cationic segments accounted for the YEAH•HCl. The number of anionic groups should be at least 33% of the number of cationic groups. A more preferred range is 50% or more. The most preferred interval is 65% or more. For example, the polymer included in the preferred interval is, apparently, the polymer, which in terms of molar basis consists of 40% DADMAC, 20% YEAH•HCl and 40% of units of acrylic acid. In the case of such a polymer molar content of anionic units in percent in terms of cationic components is, apparently, 67%.

Before the creation of the present invention, it was unknown that the composition of the present invention, in which use polymers that have significant fractions of cationic components, can be used as successfully as they apply to the implementation of the present invention. Specifically, it was assumed that the use of the polymer with the content of the cationic component is more than 50% will prevent the use of some other additives such as optical brighteners, which, depending on exactly what about the market, may have economic value. It was found that when performing the present invention amphoteric promoter resins are effective promoter resins, even when used in relatively small quantities and that was unexpected, unlike pampoernig cationic resins amphoteric promoter resin, when these amphoteric promoter resin is used in small quantities, not oppose such additives, and significantly less counteract them even at high concentrations.

Although the use of sizing and amphoteric promoter resins may be appropriate for paper manufacturing many types, preferred paper products is paper products, which are used in printing, where the importance of the contrast between the paper and printing. Another preferred paper products is also such products, where the target is a high degree of whiteness. The most preferable paper products is that, which is usually classified as a "high-grade paper products, and such uncoated paper products used for electrocardiographically or inkjet printing. A very common application in which the effectiveness of the present invention is, of veroia is but particularly evident is the production of cut copy paper of high whiteness.

The key to the essence of the present invention is understanding how to use optical brighteners, in order to make the impression that the paper is lighter or more white. Optical brighteners (CBOs) are discussed, for example, in Encyclopedia of Chemical Thechnology, Ed. by Kirk &Othmer, edition 3rd (1978), John Wiley and Sons, new York. As stated in this work, using optical brighteners, also called fluorescent optical brighteners (OSF) or fluorescent brighteners, can be achieved optical compensation yellow tint (chemically bleached paper or textile material has a yellowish tint). The yellow tinge is caused by the absorption of shortwave radiation (from violet to blue). In the presence of optical brighteners is shortwave radiation partially recovered, due to which, without loss of radiation is achieved finished white. This additional radiation is generated by the optical bleach using fluorescence. Optical brighteners absorb the invisible part of the spectrum of natural light and convert the received energy at longer wavelengths, the visible part of the spectrum, i.e. radiation from blue to purple-g is any. Therefore, optical whitening is based on the addition of radiation. To the optical Brightener must meet two requirements: it must be optically colorless on the substrate and it must not absorb radiation in the visible part of the spectrum. CBOs paper are substances almost exclusively on stellanova basis, i.e. on the basis of one or two stilinovich residues. Most are derivatives of 4,4'-diaminostilbene-2,2'-disulfonic acid, and in particular bestrashnaya derivatives (4,4'-bis(triazine-2-ylamino)stilbene-2,2 disulfonic acid). When the composition of the paper they are in anionic form or at least partially anionic. Other examples of CBOs serve as the disodium salt distearyldimethylammonium acid, 4,4'-decreasingly-2,2'-desulfobulbus.

As can be seen from the above chemistry CBOs, these last have a negative charge. Therefore, they are electrostatically attracted cationic polymers. This interaction prevents fluorescence CBOs, often so much that it extinguishes the fluorescence, and the effect of CBOs is lost. For this reason, the paper manufacturers are careful not only with the addition of cationic polymers which promotirovat the sizing in their system of making paper, n is also the site adding this cationic promoter resin relative to the point of adding CBOs. Some cationic polymers are worse than others, and promoters sizing possess strong fluorescence quenching effect. Bond paper, in particular printing and writing paper usually contains CBOs.

Among the specific spectral and geometric characteristics of white is a common industry term, expressed by the numerical value of the coefficient of reflectivity of the sample in relation to blue radiation (test method TAPPI 452 VM-92).

Unit white is a relative term. Installed white expressed as the ratio between the coefficient of reflectivity of the sample (at an effective wavelength of 457 nm) and the coefficient of reflectivity of the sample with the ideal reflectivity multiplied by 100%. When using CBOs, white can exceed 100% (in this wavelength they fluoresce, i.e. emit radiation). For more information about the definition of whiteness can be found in the work of the "Pulp and Paper Chemistry and Chemical Technology, edition 3, volume V, edited by James P.Casey, John Wiley & Sons, new York (1981): 1828-1833.

For high-grade paper loss white 0.5% by TAPPI would be significant. Composition for sizing, which reduces the whiteness of more than this value would be, depending on the application area, a significant whatsinaname, composition for rapid sizing, which is characterized by loss of whiteness less than 0.5, for many purposes, would be considered a significant progressive step. In comparative example 11, which was mentioned in example 17, the paper, which did not include CBOs, had a white 89,6. In the case referred to as comparative example 12, example 17, adding CBOs white was 95.5.

However, in addition to the monomer of formula (III), the monomer of formula (IV) and the monomer of formula (V) without negative impact on the ability of the reaction product of polymerization promote the sizing can be used other Monomeric components. The content of these other monomer components is limited to less than 50% of the total amount of monomer mixture, and they should not inhibit the solubility. You can apply a crosslinking monomers, such as triethyleneglycoldinitrate (TEGDMA). If you use too much cross-linking monomer, produced, apparently, the product, which is probably insoluble in water. Thus, the amount of crosslinking monomer is limited by the insolubility in water of the final polymerization product.

Amphoteric promoter polymers of the present invention are water-soluble polymers having a relatively high average molecular masseuses molecular mass (M wthese polymers (not including residual monomer) is at least about 10,000, and more preferably at least about 30000. Not based on any theory, I believe that the polymer, obtained by free radical polymerization of these monomers is usually a statistical polymer or a polymer with alternating links. To facilitate the statistical distribution of the Monomeric units of the reaction conditions, polymerization regulate. Experimental methods of control of polymerization conditions shown in the examples.

The most preferred polymerization is a free radical chain polymerization, which leads to the presence of less than 4% of residual monomers and the formation of less than 5% of the product (including monomers) with srednekamennogo molecular weight less than 500 g/mol.

Monomeric components used to obtain products of the polymerization reaction of the present invention, are either known and technically available (for example, ADMAH firm CPS Chemical Company, Inc. (Old bridge, new Jersey) and company Pearl River Polymers (pearl river, stiuation); DADMAC and YEAH•HCl company Sigma Chemical Company (St. Louis, stricture)), or can be obtained by conventional methods, typically used to obtain the compounds of dialiawah type. Acrylic acid is the one available from many industrial sources, including company Rohm & Haas, Philadelphia, pieces Pennsylvania.

In a preferred embodiment, the process of obtaining a polymeric reaction product is conducted by a chain polymerization of monomers of the formulas (I) and (II). Alternatively, the monomers of formula (III), (IV) and (V) can be polymerized chain polymerization in the presence of an initiator of free radical polymerization.

The reaction of polymerization of the Monomeric components of dialiawah type and organic acids is carried out in a suitable solvent, preferably polar solvents. Especially preferred solvent for carrying out the polymerization reaction is water. You can also use other polar solvents that do not adversely affect the course of the polymerization reaction. When the selection of an appropriate solvent is necessary to take into account one factor, which is the potential for interaction between the initiator and solvent, which leads to the attenuation of the polymerization reaction.

Suitable solvents include water, mixed with a miscible with water, solvent or solvents, and does not have a negative influence on the course of the polymerization reaction.

In order to ensure a high concentration of monomers in the reaction medium, the amount of water or organic dissolve the El, used in the environment of the polymerization reaction, should be kept to a minimum. The lower limit for the amount of the reaction medium is generally determined by the need to achieve adequate mixing of the reaction medium throughout the polymerization reactions and the need to ensure adequate heat transfer to ensure that during the process to avoid polymerization of ectothermy and overheating. Because as the formation of the Monomeric components of high molecular weight polymers, the viscosity of the reaction medium tends to regulate the viscosity of the reaction medium may be advisable to add during the course of the polymerization reaction an additional quantity of solvent.

In a preferred embodiment, the concentration of Monomeric reactants in the polymerization solvent is from about 5 to about 60 wt.%, and more preferably from about 10 to about 50 wt.%, in terms of the weight of the reaction medium.

Before polymerization, it is advisable to adjust the pH of the reaction medium by bringing the pH to between about 1.5 to about 6. For such regulation of pH, as a rule, use acid, preferably a mineral acid, such as galoidvodorodnykh acid like HCl.

The temperature at which carry out the reaction of polim the polarization, usually due to the operating characteristics of the initiator used, it also is determined by the target rate of polymerization and degree of polymerization (molecular weight). The polymerization generally takes place at temperatures from about 40 to about 100°C, preferably from about 50 to about 95°s, and more preferably at a temperature of from about 60 to about 90°Since, under normal pressure (one atmosphere). In the early stages of the polymerization reaction is usually characterized as vysokoekonomichnyj. To guarantee the relative completeness of the reaction of monomer components for carrying out the polymerization may take many hours.

The reaction of polymerization of the Monomeric components start in the usual way, as a rule, the addition of suitable initiator, preferably the initiator, which is water.

In the preferred embodiment, as an initiator using ammonium persulfate, tert-butyl hydroperoxide, 2,2'-azobis(2-amidinopropane)dihydrochloride, 2,2'-azobis(2-imidazol-2-improper)dihydrochloride, dihydrate 2,2'-azobis(2-carbamoylbiphenyl) or 2,2'-azobis(2-methoxycarbonylamino).

Other useful initiators, i.e. substances which form free radicals include hydrogen peroxide, benzoyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide is, peroxide of Laurila, perbenzoic tert-butyl, perftect di-tert-butyl, azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2-cyano-2-propylacetamide, azodiisobutyronitrile, atomicmolecular of dimethyl, diethyl and di-n-butyl, peretekaet tert-butyl peroxide of diisononyl, perpivalate tert-amyl, di-2-ethylhexylcarbonate, peroxide of Dilauroyl, distributedparameter, percarbonate tert-butylperoxyisopropyl. Can also be used in combination or mixture of initiators.

Use from about 0.01 to about 10 wt.%, preferably from about 0.1 to about 5 wt.%, the initiator in terms of quantity (weight) of monomer components. For information to the minimum amount of initiator used and the maximum molecular weight of the polymer, the polymerization should be carried out in the absence of oxygen. This can be done in the usual way, for example by purging or degassing using an inert gas, such as nitrogen and argon. The initiator can be added at the beginning of the reaction or, alternatively, can be added continuously or aliquot during the polymerization reaction until until used the main part of the Monomeric components. The use of Monomeric components, including the speed of the x-flow, during the polymerization can be monitored by NMR-analysis by carbon 13 or liquid and ion exchange chromatography.

In this system, the polymerization reaction of acrylic acid and similar unsaturated carboxylic acid represented by the formula (V)are more reactive than the components of the formula (III) and formula (IV). For this reason, in order to minimize the formation of homopolymer components of the formula (V) component or components of the formula (V) is introduced into the reaction mixture slowly. To the component of the formula (V) can add features or formula (III), or formula (IV) and this mixture to enter into the reaction mixture.

Three of the monomer corresponding to the formula (III), formula (IV) and formula (V), used in such relative quantities in which the product of the polymerization reaction contains the target molar ratio, in the above preferred ranges, the monomer component of formula (III), the monomer component of formula (IV) and the monomer component of formula (V).

The molecular weight of the polymer product was determined by gel permeation chromatography using a Waters of the device 717 Wisp with pump for HPLC Waters 515, a module for regulating the temperature of the Waters and the heating module column. Mobile phase served aqueous 1%sodium nitrate, 0,1%triperoxonane acid/acetonitrile in the ratio 50:50. what the objects of study were the following columns: sequentially placed Eichrom column CATSEC 4000 (particle size 10 μm) + 1000 (with a particle size of 7 μm) + 300 (with a particle size of 5 μm) + 100A (particle size 5 μm). Material-served basis silica gel with a fixed polyominoes surface. The temperature in the column was 35°and the injected volume of 100 ál. The detector consisted of a differential detector refractive index Hewlett Packard A. The flow rate was 1.0 ml/min Calibration standards: American Polymer Standards - poly(2-vinylpyridine) from 2,900 to 1250000 Yes, 1-propylpyrimidine. The concentration of the sample was 5 mg/ml, and the internal standard served as dimethylformamide, the total time of the experiment 60 minutes

The residual monomer was determined using a spectrometer, nuclear magnetic resonance. The samples were dissolved in D2O as a solvent that can capture, and as an internal standard was used with acetonitrile setting signals at chemical shift 119 hours/million Analysis13C-NMR was carried out at 100 or 125 MHz. The relative mass percentage was determined by integration of the peaks due to residual monomers, relative to the whole, the total area of peaks of the polymer and monomer.

The reaction product of the polymerization of the present invention is a water-soluble polymer, and therefore it can be used in aqueous solution. Such aqueous solutions of the reaction product of polymerization can be used as a promoter in the paper sizing in the manufacture of PR is glued paper, moreover, in the aqueous medium may contain, optionally, a sizing agent.

The products of the polymerization reaction of the present invention serve as highly efficient promoters paper sizing in combination with conventional for the manufacture of paper under alkaline conditions sizing agents. The preferred sizing agent based on alkyl(remotemachine or branched)or alkenylboronic dimers or multimers and a sizing agent based on alkenylamine anhydride. Can also be used by combining them with other sizing agents for paper.

These and other hydrophobic sizing agent in the art is well-known, and in combination with the promoter in the paper sizing according to the present invention can use a variety of these sizing agents. A sizing agent for paper usually used in the form of aqueous emulsions, aqueous dispersions or aqueous solutions. The term "emulsion" used in the present description, the same conventional in the art sense, to denote the variance of any type of fluid in the fluid, or the type of solids in a liquid.

Under stable AAA emulsion imply emulsion, which can be cooked, then leave at 22°C for 24 h, during which skolik is significant heterogeneity are not formed. Significant heterogeneity is such that when the emulsion becomes unsuitable for use in papermaking machine provided for this purpose.

The application of these emulsions for paper sizing is often limited by their stability, because when the emulsion layers, the material in the form of layered emulsion is unfit for use. An additional unexpected advantage of the amphoteric promoter resin of the present invention is that when it is added to the emulsion sizing agent, the stability of the resulting emulsion is acceptable.

Ketonovye dimers used as a sizing agent for paper, are well known. Alkylbetaine dimers containing one β-lactonase ring, usually prepared by the reaction of alkylating obtained from the two anhydrides of fatty acids. Industrial alkylenediamine sizing agent is often prepared from palmitic and/or stearic fatty acids, for example, a sizing agent Hercon®(Hercules Incorporated, Wilmington, stdelivery). Similar alkylbetaine dimer sizing agent can be obtained from branched alkylating dimers. Example source for alkyl branched metanovogo dimer is ezoterikova group idotea inovas acid.

Alkenylamine dimer sizing agent is also technically available, such as a sizing agent Aquapel®(Hercules Incorporated, Wilmington, stdelivery) and a sizing agent Precis®(Hercules Incorporated, Wilmington, stdelivery). As sizing agents for paper, you can also use ketonovye multimer containing more than one β-lactoovo rings, they can serve as alkyl - or alkenylamine dimers.

Ketonovye dimers used as sizing agents for paper, are typically dimers corresponding to the formula

where R5denotes a hydrocarbon radical, such as alkyl containing at least 8 carbon atoms, cycloalkyl containing at least 6 carbon atoms, aryl, aralkyl and alkaryl. In the name ketonovyh dimers name of the radical "R5" is preceded by the words "ketonovy dimer". Examples ketonovyh dimers include octyl-, decyl-, dodecyl-, tetradecyl-, hexadecyl, octadecyl-, eicosyl-, decoil-, tetracosyl-, phenyl-, benzyl-, beta-naphthyl - and cyclohexylmethanol dimers, as well as ketonovye dimers derived from montenovo acid, naphthenic acid, Δ9,10-dellenbaugh acid, Δ9,10-dodecylamino acid, palmitoleic acid, oleic acid, ricinoleic to the slots, linoleic acid, linolenic acid and oleostearin acid, as well as ketonovye dimers derived from naturally occurring mixtures of fatty acids, such as mixtures thereof in coconut oil, oil of Brazilian babassu nut, palm kernel oil, palm oil, olive oil, peanut oil, rapeseed oil, melted beef fat, pork fat and top whale fat. You can also use any mix of the above fatty acids with each other.

As sizing agents for paper, you can use a hydrophobic acid anhydrides, such as

(I) the anhydrides of the acids of rosin (see, for example, US patent No. 3582464, the content of which is incorporated into this description by reference);

(II) anhydrides having the structure

where R6denotes a saturated or unsaturated hydrocarbon radical, a hydrocarbon radical is remotemachine or branched alkyl radical, a substituted aromatic group, alkyl radical or alkyl substituted aromatic radical, the length of which is determined by the content in the hydrocarbon radical is in General from about 14 to about 36 carbon atoms, and

(III) cyclic anhydrides of dicarboxylic acids having the structure

the de R 7means dimethylpropyl or trimethylenebis radical and where R8is a hydrocarbon radical containing more than 7 carbon atoms, which are selected from the series comprising alkyl, alkenyl, aralkyl and aralkyl. Preferred substituted cyclic anhydrides of dicarboxylic acids covered by the above formula (VIII), represent a substituted succinic and glutaric anhydrides. In the above formula (VII) all R6may be the same hydrocarbon radicals or all R6can be different hydrocarbon radicals.

Specific examples of anhydrides of formula (VII) are myristoleic anhydride, politology anhydride, oleography anhydride and stearilovy anhydride.

Specific examples of anhydrides of formula (VIII) are the anhydrides ISO - and n-octadecylamino acids, anhydrides ISO - and n-hexadecylamine acids, anhydrides ISO - and n-tetradecanoate acid anhydride dodecylamino acid anhydride detailentry acid anhydride acteylanthranilic acid anhydride and heptylphenol acid.

Hydrophobic organic isocyanates, such as alkylated isocyanates, constitute another class of compounds that are used as sizing agents for paper, which in the art is well known. In preferred in which the Rianta hydrocarbon chain isocyanates are alkali, which contain at least 12 carbon atoms, preferably from 14 to 18 carbon atoms. Such isocyanates include diisocyanates components of rosin, dodecylsulfonate, octadecylsilane, tetradecylbenzene, hexadecanesulfonate, akazimiselanga, dokotilisya, 6-ethylcellosolve, 6-phenyltetrazole and polyisocyanates, such as 1,18-octadecylsilane and 1,12-dodecylbenzene, having one long chain alkyl group is two isocyanate radicals and gives the molecule as a whole hydrophobic properties.

Other conventional sizing agent for paper, acceptable for use in performing the present invention include alkylcarboxylic, alkylated melamine, such as sterilizovannye the melamine.

The reaction product of polymerization in the invention can be used as the amphoteric promoter resin for paper sizing in accordance with the present invention by a method of adding mass or through the superficial (external) processing, or through a combination of these methods. Satisfactory performance properties of the product of the polymerization reaction in the form of the amphoteric promoter resin typically achieve regardless of the specific method of processing.

In the method of adding in the weight of the promoter prachaniwat in the pulp during the paper manufacturing process. The sizing promoter is administered in combination with a sizing substance (or substances) for paper or in the form of a separately added raw material streams, either in the form of an aqueous environment containing both components. Preferably the addition of pre-mixed promoter sizing and sizing agent (or agents) of the paper. With the sizing promoter and/or a sizing substance can also use other conventional for the manufacture of paper compounds or additives. In accordance with the General guidelines for the art optical brighteners should not be added simultaneously with the addition of cationic promoter resin. However, the amphoteric promoter resin can be added simultaneously with optical Brightener, thus minimizing the number of points added to the paper machine. Seems reasonable, also adding amphoteric promoter resin on the area other than the point of introduction of optical Brightener. Taking into account the complexity of the manufacturing process of paper (sources fibrous mass, other chemical additives), the optimal insertion point for amphoteric resin on a particular paper mill should be determined, apparently, by the method of trial and error. In examples 11 to 19 sizing substance, amphoteric promoter resin and optical is the second bleach was added to the base sheet simultaneously as part of a starch solution with a pH of 8.

In the method of surface treatment on preformed paper promoter sizing is usually applied during processing in the sizing press or in the form of a coating by the conventional methods of coating or spraying, and then the paper or the product processing or coating is dried. Next, the paper is processed with the proper sizing substance (or substances) to paper and dried again. Alternatively a sizing agent for paper and a sizing promoter can be applied in the method of surface processing in a single phase application using aquatic environment for processing/coating containing a sizing agent for paper, the sizing promoter and optionally other conventional components. In accordance with the General guidelines for the art optical brighteners should not be added simultaneously with the addition of cationic promoter resin. However, the amphoteric promoter resin can be added simultaneously with optical Brightener, thus minimizing the number of points added to the paper machine. Seems reasonable, also adding amphoteric promoter resin on the area other than the point of introduction of optical Brightener. Taking into account the complexity of the manufacturing process of paper (sources fibrous mass is, other chemical additives), the optimal insertion point for amphoteric resin on a particular paper mill should be determined, apparently, by the method of trial and error.

Preferred paper products is paper products, which are used in printing, where the importance of the contrast between the paper and printing. Another preferred paper products is also such products, where the target is a high degree of whiteness. The most preferable paper products is that, which is usually classified as a "high-grade paper products, and such uncoated paper products used for electrocardiographically or inkjet printing. A very common application in which the effectiveness of the present invention is likely to be especially obvious, is making the cut copy paper of high whiteness.

Other optional components for use in the method of adding mass and/or method, the surface treatment may include a variety of additives commonly used in the paper manufacturing process, such as starch, fillers, fibrous mass, retention additives, reinforcing additives, substances to facilitate drainage, dyes, optical brighteners, pinoges the teli, etc.

Regardless of the method amphoteric promoter resin as a reaction product of polymerization ("polymer") and a sizing agent for paper (glue) should be used in the respective weight ratio of polymer/adhesive from approximately 0.05:1 to about 4:1, preferably in the ratio of polymer/adhesive is from about 0.1:1 to about 1:1, and most preferably from 0.10:1 to 0.5:1.

Sizing substance (or substances) for paper usually used in an amount to provide the achievement of the good characteristics of sizing in the paper. Glued paper, typically contains from about 0.005-about 1.5 wt.%, preferably from about 0.025 to about 0.5 wt.%, and more preferably from about 0.05 to about 0.25 wt.%, a sizing agent for paper, calculated on the weight of the dried sized paper.

When the reaction product of the polymerization of the present invention is used in the form amphoteric promoter resin in combination with a conventional sizing agent for paper, the amount of a sizing agent for paper taped the paper can be reduced without compromising the characteristics of the paper sizing. The sizing promoter of the present invention can also be used in combination with other conventional promoters sizing or supplements for sizing.

Amphoteric promoter resin n is required to use the number, sufficient for the manufacture of sized paper containing the sizing promoter in a concentration of from about 0.002 to about 0.6 wt.%, preferably from 0,007 to about 0.3 wt.%, and more preferably from about 0,012 to approximately 0.15 wt.%, in terms of the mass of the dried sized paper.

One advantage of the sizing promoter of the present invention is that to achieve a satisfactory immediate characteristics sizing glued paper needs only drying to a residual moisture level of from about 8 to about 12 wt.% in terms of the weight of the paper. Without accelerator sizing to achieve the equivalent direct sizing characteristics such coated paper, as a rule, needs to be dried to a residual moisture level of from about 4 to 6 wt.%. The term "direct" refers to the properties of paper at the end of the process of paper making and finishing without aging, which is often necessary in the case of intentional sizing AAA. After drying to normal levels of humidity glued paper, which used the sizing promoter of the present invention becomes superior characteristic of sizing if in the process deliberately introduced a sizing substance is not completely reavley their characteristics sizing.

The second advantage is that when using optical brighteners, compared with when the conventional cationic promoter resins known to create the present invention, coated paper, manufactured using amphoteric promoter resin, has increased the whiteness or lightness.

Here are a few common methods that are applicable to the products of the polymerization reaction of the present invention and their use.

Test sizing method company Hercules (IPG)

The operational properties of sizing in sized paper can be characterized by testing the sizing method of the company Hercules, well-established yourself test method for determining performance characteristics of sizing. Test sizing method company Hercules described in Pulp and Paper Chemistry and. Chemical Technology, edited by J.P.Casey, volume 3, s-1554 (1981). In the test sizing method company Hercules degree water sizing that is reached in the paper, set by determining the change in the reflectivity of the surface of the paper as a result of penetration of an aqueous solution of the dye with the opposite surface side. In the examples described below, the ring on the top side of the paper contains an aqueous solution of the dye, such as naphthol is the new green, in 1%formic acid; the change of the reflectivity determined by photovoltaic.

In the examples described below, the test length limit by choosing an appropriate endpoint, in particular, by reducing the reflectivity of 20%, which corresponds to 80%reflectivity. Sensor time shows the time (in seconds) reaching the end point of the test. Over long periods of time correspond to a higher performance sizing, i.e. increased resistance to the penetration of water. For unsized paper "breakthrough", as a rule, is observed at 0, lightly sized paper usually record the time from about 1 to about 20, in the case of moderately sized paper time is from about 21 to about 150 C, and for a well-sized paper, it is from about 151 to about 2000 C.

White fibrous pulp, paper and paperboard is determined by the directional reflectance at 457 nm. This method is described in TAPPI method T 452 VM-92.

A General method of obtaining the product of the polymerization reaction

Water-soluble polymer of diallyldimethylammoniumchloride (DADMAC), diallylammonium (YEAH•HCl) and acrylic acid can be obtained according to the following General method.

An aqueous mixture of three Monomeric components is cooked add the group of the respective monomer components in the water acceptable in a molar ratio, sought in the product of the polymerization reaction. Water the reaction mixture Tegaserod using an inert gas, such as nitrogen and argon. In the reaction vessel at 80°slowly and continuously added as the monomer mixture and an aqueous solution of a water-soluble initiator of free radical polymerization, such as 2,2'-azobis(2-amidinopropane)dihydrochloride, until in the polymerization reaction is not spent the main part of the Monomeric components. In order to prevent excessive increase in the viscosity of the aqueous reaction mixture during the polymerization reaction in the reaction mixture usually add water. The concentration of the monomer component in the aqueous reaction mixture should not be lower dilution, since a high concentration of monomers provides improved results of polymerization.

Another option in a vessel together with a certain amount of water injected entire HMMM•HCl with approximately 90% of DADMAC and approximately 20% of AK. Prepare a solution of the initiator and the mixture remaining DADMAC and AK. All solutions Tegaserod. The reaction vessel is heated to 60°With slowly for some time (12 h) to introduce the initiator solution and the solution of monomers. The solution of monomers added with a declining rate and the temperature slowly over a period of 10 hours, increase to 95°C.

Specialists in the data is the second region of the techniques you need to take into account, in the above options, you can make changes without going beyond the broad concept of the invention. Thus, it is obvious that the present invention is not limited to the described specific cases, on the contrary, we must assume that it covers modifications within the essence and scope of the present invention, which is defined by the attached claims.

The following examples 1 through 8 are illustrations of this General method of obtaining products of the polymerization reaction of the present invention.

In all the following examples the characteristics of the paper sizing was determined using the test method of sizing the company Hercules (as presented above) immediately after the manufacture of paper, as well as (a few examples) after aging paper at 50%relative humidity and at a temperature of 22°With within seven days or longer (as noted in the examples).

In the examples, all references to "parts" refer to mass parts, except in those cases where the specified pounds/so This is the last expression is common in the paper industry.

The invention is further illustrated by the following specific non-limiting examples.

An example of the synthesis of polymer 1

Water-soluble copolymer diallyldimethylammoniumchloride (DADMAC), diallylammonium (YEAH#x02022; HCl) and acrylic acid (AA) was prepared as follows. The molar ratio between the monomers (DADMAC/AK/YEAH•HCl)used for producing the product of the polymerization reaction, was approximately 45:45:10.

The three parts were prepared and introduced into a glass reaction flask thus, to form the final composition.

Part I: YEAH•HCl was obtained by introducing into the reaction vessel to 6.75 hours YEAH. Under stirring YEAH added 25,35 including 10%aqueous HCl solution (2,54 including HCl, 22,81 frequent. of water). The final pH value was equal to 3.5.

Part II: in a separate vessel with stirrer was preparing a mixture of DADMAC and AK. To this vessel was added 106,1 including water, 19,4 including AK, and then to 8.2 hours 65%aqueous solution of DADMAC. The solution was stirred. The final pH value was ˜2. For some time the mixture was added into the reaction vessel, which contained YEAH•HCl.

Part III was prepared in the reaction vessel by the addition to part I 74,07 including 65%-aqueous solution of DADMAC and 4,87 including AK.

Part IV. The second vessel with a stirrer were introduced 30,71 including water 2,78 including initiator V50. The mixture was stirred to dissolve the V50 in the water.

To eliminate dissolved oxygen in each of these three mixtures were purged with nitrogen and during the polymerization reaction in vessels with agitators supported not containing oxygen atmosphere.

The reaction mixture of part III was heated up to 6° With and added to 3.35 PM part IV. A Monomeric mixture of part II and the initiator solution of part IV was added to the reaction vessel slowly and constantly with a prescribed speed. Profile add shown in table 1.

Table 1
TimeThe pace. reactionAdding monomer in timeAdding initiator
from 0 to 60 min60°Within 1 h were added 1/2 part 2Within 1 h was added to 8.2% solution part 4
(the reaction is exothermic, so if you do not perform the cooling, the temperature rises; the most noticeable temperature increase occurs in the first hour, during the first 2 h temperature should be maintained below 75S)
from 60 to 240 min70Within 3 h was added 1/4 of a solution part 2Within 3 h was added a 25% solution of part 3
from 240 to 600 rpm85°Within 6 h was added 1/4 of a solution part 2 Within 6 h was added a 50% solution of part 3
480 min85AbsentAdded a 15% solution of part 3
from 480 to 600 rpm
600 rpm85AbsentThe remaining solution part 3 (14,4%). After 600 min was added to the residue of the initiator
from 600 to 720 min95AbsentAbsent
At 85°before dilution viscosity, according to the definition, was 1125 SP, and dry matter content, according to the definition 31%
At the end of the hot mixture was added water to dilute (149,7 including water)
Was cooled to room temperature

Note: points added to the reaction vessel initiator and monomers, you must take precautions in order to ensure their immediate and uniform mixture with the reaction solution.

The resulting aqueous solution of the amphoteric promoter resin included 20 wt.% polymer and 80 wt.% water. The residual content of monomers in a molar % of the initial number of monomers was determined13C-NMR analysis, which found that it was approximately as follows: acrylic acid is less than 0.1%; YEAH•HCl - less than 0.4%, and DADMAC - less than 1%. Other properties include viscosity according to Brookfield at 22°With less than 300 SP, pH 2 to 4, not quite a white color and a specific gravity of 1.05 g/scooter

Example of synthesis of polymer 2

The following solutions were prepared, mixed to homogeneity, and immediately before use by purging with nitrogen for 30 min was desoxyribose (freed from oxygen) (for preparation of all solutions used deionized water). The target composition was included DADMAC/AK/YEAH•HCl in a ratio of 40:40:20.

R is the target: and 26.8 g of a 50%aqueous solution HMMM• HCl in water (prepared by mixing YEAH and HCl (see example 1)) + 48,3 g of a 60%aqueous solution of DADMAC + 55,0 g of water (in our experiments we used deionized water).

Solution B: 14,4 g AK+5,4 g of a 60%aqueous solution of DADMAC + 100.0 g of water.

Solution: 1.8 g of 2,2'-azobis(2-amidinopropane)dihydrochloride + 50 ml of water.

The solution was introduced into a closed reaction vessel equipped with installed at the top of the agitator and a means of purging with nitrogen.

Solution B was introduced into the addition funnel, mounted with the possibility of feed drops into the reaction vessel. The funnel is oriented to supply drops directly into the liquid in the vessel, and not on the walls of the flask.

For slow feed solution In the reaction vessel was fitted pump.

During the polymerization in the reaction vessel is maintained constant uniform stirring at about 60 rpm throughout the reaction maintained a stream of nitrogen. To one of the outlet openings in the upper part of the reaction vessel was attached to the condenser. The purging with nitrogen during the reaction was carried out through the upper end of the condenser through a liquid trap.

The reaction vessel was heated to 75°C.

Upon reaching 75°quickly added 1/6 solution of the initiator.

Via a pump was added 2/3 of the initiator, since the addition, when the temperature reached 75°and continued with essentially the second speed for 6 hours After 6 hours (when the temperature was increased to 95° (C) added the last 1/6 of the initiator.

The monomers of the dropping funnel were added at a constant rate, starting adding, when the temperature reached 75°and was continued for 7 hours

The reaction temperature was maintained at 75°C for 4 h, and then increased to 85°C for 3 h, and then increased to 95°C for 1 h

After one hour of heating at 95°the reaction mixture was let to cool down slowly to room temperature. The sample was diluted with water to a dry matter content of approximately 20%. Next, the flask was opened and the polymer solution were analyzed.

The dry matter content in the polymer solution was 22.5%. According to the13C-NMR analysis, the solution contained polymer with 43 PM (in terms of molar basis) parts of acrylic acid, 38 including links of DADMAC and 7 o'clock links YEAH•HCl. Calculated on the same basis it contained 1 h residual AK, 8 hours remaining DADMAC and 3 o'clock residual YEAH•HCl.

Example of synthesis of polymer 3

The following solutions were prepared, mixed to homogeneity, and immediately before use by purging with nitrogen for 30 min was desoxyribose (freed from oxygen) (for preparation of all solutions used deionized water). The target composition was included DADMAC/AK/YEAH•HCl in sootnoshenie the 45:45:10.

Solution: 9,9 g of 68%aqueous solution HMMM•HCl in water (see above) + 60,4 g of a 60%aqueous solution of DADMAC + 30.0 g of water (in the experiments we used deionized water).

Solution B: 16.2 g AK + 50.0 g of water.

Solution: 1,77 g of 2,2'-azobis(2-amidinopropane)dihydrochloride + 50 g water.

The solution was introduced into a closed reaction vessel equipped with installed at the top of the agitator and a means of purging with nitrogen.

Solution B was introduced into the addition funnel, mounted with the possibility of feed drops into the reaction vessel. The funnel is oriented to supply drops directly into the liquid in the vessel, and not on the walls of the flask.

For slow feed solution In the reaction vessel was fitted pump.

During the polymerization in the reaction vessel is maintained constant uniform stirring at about 60 rpm throughout the reaction maintained a stream of nitrogen. To one of the outlet openings in the upper part of the reaction vessel was attached to the condenser. The purging with nitrogen during the reaction was carried out through the upper end of the condenser through a liquid trap.

The reaction vessel was heated to 75°C.

Upon reaching 75°quickly added a 1/10 solution of the initiator.

Via a pump was added 2/3 of the initiator, since the addition, when the temperature reached 75°and continued at a constant speed in those who begins 7 PM After 7 hours (when the temperature was increased to 95° (C) was added to the remainder of the initiator.

AK monomer of the dropping funnel were added at a constant rate, starting adding, when the temperature reached 75°and was continued for 7 hours

The reaction temperature was maintained at 75°C for 4 h, and then increased to 85°C for 3 h, and then increased to 95°C for 1 h

After one hour of heating at 95°the reaction mixture was let to cool down slowly to room temperature. The sample was diluted with water to a dry matter content of approximately 20%. Next, the flask was opened and the polymer solution were analyzed.

The dry matter content in the polymer solution was 24.7%. According to the13C-NMR analysis, the solution contained polymer with 48 hours (calculated on a molar basis) parts of acrylic acid, 45 p.m. links of DADMAC and 5 o'clock links YEAH•HCl. Calculated on the same basis it contained less than 1 h residual AK, 1 h residual DADMAC and 1 h residual YEAH•HCl.

Example of synthesis of polymer 4

The following solutions were prepared, mixed to homogeneity, and immediately before use by purging with nitrogen for 30 min was desoxyribose (freed from oxygen) (for preparation of all solutions used deionized water). The target composition was included DADMAC/AK/YEAH•HC in the ratio of 45:45:10.

Solution: 44,6 g of a 50%aqueous solution HMMM•HCl in water (see above) + 201,3 g of a 60%aqueous solution of DADMAC+100 g water were used in the experiments deionized water).

Solution B: 54,0 g AK + of 200.0 g of water.

Solution: 5,9 g 2,2'-azobis(2-amidinopropane)dihydrochloride + 50 ml of water.

The solution was introduced into a closed reaction vessel equipped with installed at the top of the agitator and a means of purging with nitrogen.

Solution B was introduced into the addition funnel, mounted with the possibility of feed drops into the reaction vessel. The funnel is oriented to supply drops directly into the liquid in the vessel, and not on the walls of the flask.

For slow feed solution In the reaction vessel was fitted pump.

During the polymerization in the reaction vessel is maintained constant uniform stirring at about 60 rpm throughout the reaction maintained a stream of nitrogen. To one of the outlet openings in the upper part of the reaction vessel was attached to the condenser. The purging with nitrogen during the reaction was carried out through the upper end of the condenser through a liquid trap.

The reaction vessel was heated to 75°C.

Upon reaching the 70°quickly added a 10% solution of the initiator.

Via a pump was added 70% initiator, starting adding, when the temperature reached 70°and continued at a constant speed in those who tell 6 o'clock After 7 hours (when the temperature is already within 1 h was 95° (C) was added for the last 20% of the initiator.

AK monomer of the dropping funnel were added at a constant rate, starting adding, when the temperature reached 70°and was continued for 7 hours

The reaction temperature was maintained at 75°C for 4 h, and then increased to 85°C for 2 h, and then increased to 95°C for 2 hours

After exposure for 2 h at 95°the reaction mixture was let to cool down slowly to room temperature. The sample was diluted with water to a dry matter content of approximately 20%. Next, the flask was opened and the polymer solution were analyzed.

The dry matter content in the polymer solution was 23,0%. According to the13C-NMR analysis, the solution contained polymer with 49 PM (in terms of molar basis) parts of acrylic acid 47 am links of DADMAC and 2 o'clock links YEAH•HCl. Calculated on the same basis it contained less than 1 h residual AK, 1 h residual DADMAC and 0.4 hours residual YEAH•HCl.

Example of synthesis of polymer 5

The following solutions were prepared, mixed to homogeneity, and immediately before use by purging with nitrogen for 30 min was desoxyribose (freed from oxygen) (for preparation of all solutions used deionized water). The target composition was included ON THE DMAH/AK/YEAH• HCl in the ratio of 45:45:10.

Solution: 9,9 g of 68%aqueous solution HMMM•HCl in water (see above) + 60,4 g of a 60%aqueous solution of DADMAC + 30.0 g of water (in the experiments we used deionized water).

Solution B: 16.2 g AK + 44,0 g of water.

Solution: 1,77 g of 2,2'-azobis(2-amidinopropane)dihydrochloride + 50 g water.

The solution was introduced into a closed reaction vessel equipped with installed at the top of the agitator and a means of purging with nitrogen.

Solution B was introduced into the addition funnel, mounted with the possibility of feed drops into the reaction vessel. The funnel is oriented to supply drops directly into the liquid in the vessel, and not on the walls of the flask.

For slow feed solution In the reaction vessel was fitted pump.

During the polymerization in the reaction vessel is maintained constant uniform stirring at about 60 rpm throughout the reaction maintained a stream of nitrogen. To one of the outlet openings in the upper part of the reaction vessel was attached to the condenser. The purging with nitrogen during the reaction was carried out through the upper end of the condenser through a liquid trap.

The reaction vessel was heated to 65°C.

Upon reaching 65°quickly added a 1/10 solution of the initiator.

Via a pump was added 2/3 initiator, starting adding, when the temperature reached 65°and continued with Tannoy speed for 8 hours After 8,5 hours (when the temperature is already within 30 min was 95° (C) was added to the residue of the initiator.

AK monomer of the dropping funnel were added at a constant rate, starting adding, when the temperature reached 65°and continued for 8 hours

The reaction temperature was maintained at 65°C for 6 h, and then increased to 85°C for 2 h, and then increased to 85°C for 2 hours

After exposure for 2 h at 95°the reaction mixture was let to cool down slowly to room temperature. The sample was diluted with water to a dry matter content of approximately 20%. Next, the flask was opened and the polymer solution were analyzed.

The dry matter content in the polymer solution was 24.7%. According to the13C-NMR analysis, the solution contained polymer with 47 PM (in terms of molar basis) parts of acrylic acid, 44 including links of DADMAC and 5 o'clock links YEAH•HCl. Calculated on the same basis it contained less than 1 h residual AK, 3 hours remaining DADMAC and 0.6 hours residual YEAH•HCl.

Example of synthesis of polymer 6

The following solutions were prepared, mixed to homogeneity, and immediately before use by purging with nitrogen for 30 min was desoxyribose (freed from oxygen) (for preparation of all solutions used deionized water). The target composition was included YES THE MAX/AK in the ratio of 50:50. In this example, YEAH•HCl is not used.

Solution: to 66.7 g of a 60%aqueous solution of DADMAC + 33,3 g of water (in our experiments we used deionized water).

Solution B: 18.0 g AK + 122,0 g of water.

Solution: 1,74 g of 2,2'-azobis(2-amidinopropane)dihydrochloride + 50 g water.

The solution was introduced into a closed reaction vessel equipped with installed at the top of the agitator and a means of purging with nitrogen.

Solution B was introduced into the addition funnel, mounted with the possibility of feed drops into the reaction vessel. The funnel is oriented to supply drops directly into the liquid in the vessel, and not on the walls of the flask.

For slow feed solution In the reaction vessel was fitted pump.

During the polymerization in the reaction vessel is maintained constant uniform stirring at about 60 rpm throughout the reaction maintained a stream of nitrogen. To one of the outlet openings in the upper part of the reaction vessel was attached to the condenser. The purging with nitrogen during the reaction was carried out through the upper end of the condenser through a liquid trap.

The reaction vessel was heated to 75°C.

Upon reaching 75°quickly added a 15% solution of the initiator.

Via a pump added 1/2 initiator, starting adding, when the temperature reached 75°and continued at a constant speed for which the 6 o'clock After 6 hours (when the temperature was increased to 95°) just added 17% initiator, and after 7 h fast was added to the residue.

AK monomer of the dropping funnel were added at a constant rate, starting adding, when the temperature reached 75°and was continued for 7 hours

The reaction temperature was maintained at 75°C for 4 h, and then increased to 85°C for 2 h, and then increased to 95°C for 2 hours

After soaking for one hour at 95°the reaction mixture was let to cool down slowly to room temperature. The sample was diluted with water to a dry matter content of approximately 25%. Next, the flask was opened and the polymer solution were analyzed.

The dry matter content in the polymer solution was 25.5%. According to the13C-NMR analysis, the solution contained polymer with 51 PM (in terms of molar basis) parts of acrylic acid and 44 am links of DADMAC. Calculated on the same basis it contained less than 1 h residual AK and 4 o'clock residual DADMAC.

Example of synthesis of polymer 7

The following solutions were prepared, mixed to homogeneity, and immediately before use by purging with nitrogen for 30 min was desoxyribose (freed from oxygen) (for preparation of all solutions used deionized water). The target composition was included DADMAC/AK/YEAH•HCl is a rate of 40:40:20.

Solution: to 26.8 g of a 50%aqueous solution HMMM•HCl in water (see above) + 48,3 g of a 60%aqueous solution of DADMAC + 55,0 g of water (in our experiments we used deionized water).

Solution B: 14,4 g AK + 5,4 g of a 60%aqueous solution of DADMAC + 100.0 g of water.

Solution: 1.8 g of 2,2'-azobis(2-amidinopropane)dihydrochloride + 50 ml of water.

The solution was introduced into a closed reaction vessel equipped with installed at the top of the agitator and a means of purging with nitrogen.

Solution B was introduced into the addition funnel, mounted with the possibility of feed drops into the reaction vessel. The funnel is oriented to supply drops directly into the liquid in the vessel, and not on the walls of the flask.

For slow feed solution In the reaction vessel was fitted pump.

During the polymerization in the reaction vessel is maintained constant uniform stirring at about 60 rpm throughout the reaction maintained a stream of nitrogen. To one of the outlet openings in the upper part of the reaction vessel was attached to the condenser. The purging with nitrogen during the reaction was carried out through the upper end of the condenser through a liquid trap.

The reaction vessel was heated to 75°C.

Upon reaching 75°quickly added 1/6 solution of the initiator.

Via a pump added 1/2 initiator, starting adding, when the temperature reached 75°and continued and constant speed for 6 hours After 6 hours (when the temperature was increased to 95° (C) was rapidly added 1/6 initiator, and after 7 h fast was added to the residue.

AK, ADMAH monomers of the dropping funnel were added at a constant rate, starting adding, when the temperature reached 75°and was continued for 7 hours

The reaction temperature was maintained at 75°C for 4 h, and then increased to 85°C for 2 h, and then increased to 95°C for 2 hours

After one hour of heating at 95°the reaction mixture was let to cool down slowly to room temperature. The sample was diluted with water to a dry matter content of approximately 20%. Next, the flask was opened and the polymer solution were analyzed.

The dry matter content in the polymer solution was 22.5%. According to the13C-NMR analysis, the solution contained polymer with 43 PM (in terms of molar basis) parts of acrylic acid, 38 including links of DADMAC and 7 o'clock links YEAH•HCl. Calculated on the same basis it contained less than 1 h residual AK, 8 hours remaining DADMAC and 3 o'clock residual YEAH•HCl.

Example of synthesis of polymer 8

The following solutions were prepared, mixed to homogeneity, and immediately before use by purging with nitrogen for 30 min was desoxyribose (freed from oxygen) (for preparation of all solutions used deionized water). C left composition included DADMAC/AK/YEAH• HCl in the ratio of 33:33:35.

Solution A: of 53.6 g of a 50%aqueous solution HMMM•HCl in water (see above) + 53,7 g of a 60%aqueous solution of DADMAC+50.0 g of water (in the experiments we used deionized water).

Solution B: 14,4 g AK + 100.0 g of water.

Solution: 2.2 g of 2,2'-azobis(2-amidinopropane)dihydrochloride + 50 ml of water.

The solution was introduced into a closed reaction vessel equipped with installed at the top of the agitator and a means of purging with nitrogen.

Solution B was introduced into the addition funnel, mounted with the possibility of feed drops into the reaction vessel. The funnel is oriented to supply drops directly into the liquid in the vessel, and not on the walls of the flask.

For slow feed solution In the reaction vessel was fitted pump.

During the polymerization in the reaction vessel is maintained constant uniform stirring at about 60 rpm throughout the reaction maintained a stream of nitrogen. To one of the outlet openings in the upper part of the reaction vessel was attached to the condenser. The purging with nitrogen during the reaction was carried out through the upper end of the condenser through a liquid trap.

The reaction vessel was heated to 75°C.

Upon reaching 75°quickly added a 1/10 solution of the initiator.

Via a pump was added 2/3 of the initiator, since the addition, when the temperature reached 75°and continued with p the constant rate over 6 hours After 7 hours (when the temperature within 1 h was 95° (C) was rapidly added to the residue of the initiator.

AK monomer of the dropping funnel were added at a constant rate, starting adding, when the temperature reached 75°and was continued for 7 hours

The reaction temperature was maintained at 75°C for 4 h, and then increased to 85°C for 2 h, and then increased to 95°C for 2 hours

After one hour of heating at 95°the reaction mixture was let to cool down slowly to room temperature. The sample was diluted with water to a dry matter content of approximately 20%. Next, the flask was opened and the polymer solution were analyzed.

The dry matter content in the polymer solution was 22,2%. According to the13C-NMR analysis, the solution contained polymer with 35 PM (in terms of molar basis) parts of acrylic acid, 32 including links of DADMAC 24 hours links YEAH•HCl. Calculated on the same basis it contained less than 1 h residual AK, 4 hours remaining DADMAC and 5 o'clock residual YEAH•HCl.

General methods for the manufacture of paper

In the following examples 9 through 19 described the manufacture of paper using the following General methods.

For promotion sizing substances used amphoteric promoter resin. A sizing agent was prepared in accordance with the following descriptions or is Uchali of commercially available sources.

Hercon®195 - reactive adhesive, which is a highly effective emulsion alkylating dimer (AKD), specially designed to enhance drainage and optimize the efficiency of sizing in most systems the manufacture of paper. Although reactive adhesive Hercon 195 firms Hercules is a cation is stable and self-perpetuating emulsion, to maximize the retention of the adhesive and performance recommend adding either cationic starch or cationic resin (Hercules Incorporated, Wilmington, stdelivery).

Hercon®79 - interacting with cellulose sizing emulsion, designed to perform functions in the alkaline range of pH at low alkalinity. Product Hercon 79 is slightly cationic and has an affinity to the fibre. For retention may require additional promoter resin or cationic starch.

Hercon 79 - glue, which quickly manifested in the paper machine, inhibiting the accumulation of solutions for size press or calender. Full sizing typically is achieved outside peramuna-cutting machine. Product Hercon 79 has a minimal negative effect on the optical brighteners in the wet end in comparison with products Hercon more cationic varieties (Hercules Incorporate, Wilmington, stdelivery).

Hercon®70 - reactive adhesive, representing a highly reactive sizing emulsion for use against a variety of wetting agents. Its action does not depend on alum, it interacts directly with the pulp, providing sizing. Execution of the process at close to neutral pH values creates an opportunity to use calcium carbonate as a low-cost, high white filler and for making a more robust, durable, vysokoplotnoy paper (Hercules Incorporated, Wilmington, stdelivery).

AQUAPEL®364 represents alkylcatechols dimer, derivationally of long-chain fatty acids. It chemically reacts under mild conditions with many substances, having in its structure active hydrogen atoms. The resulting products can have a new and necessary properties. For example, the product Aquapel 364 characterized by particularly outstanding ability to make cellulosic materials of various forms of water-repellent properties.

Chemical structure

R denotes alkyl group, derivatisation of fatty acids (Hercules Incorporated, Wilmington, STDEVA is).

RETEN®201 - cationic resin and retention additive, representing an effective source of cations developed for coagulation trivia and other anionic contaminants, usually contained in a chemically bleached and unbleached paper products. He is a low molecular weight polyamine-epichlorhydrin polymer with high charge density (Hercules Incorporated, Wilmington, stdelivery).

Hercon®70 - sizing emulsion.

Sizing substance Hercon®70 paper (Hercules Incorporated, Wilmington, stdelivery) is an aqueous sizing dispersion alkylating dimer (AKD). A sizing agent (AKD) was evaluated at a concentration of 0.09 wt.%, and a sizing substance Hercon®70 was evaluated at two different concentrations of 0.06 and 0.07 wt.%. All the concentration of the sizing agent, given in this example and subsequent examples, calculated on the dry weight of the fibrous composition.

Polyethylenimine can be purchased from a commercial source, such as a company Sigma-Aldrich, Milwaukee, steveascension. The sample possessed the claimed molecular weight of 10000.

Polyacrylamide can be purchased from a commercial source, such as a company Sigma-Aldrich, Milwaukee, steveascension.

The following examples demonstrate the possibility of PR is, the changes in the amphoteric promoter resin. Examples of two types: examples of work in the pilot paper machine and examples of laboratory experiments with processing in the sizing press. Similarly conducted experiments of comparative examples with cationic promoter resins or without promoter resins.

The performance properties of products of polymerization obtained in examples 1-8 were evaluated in sized paper when it is used in several different concentrations and with different industrial sizing agents. System included also technically available promoters sizing in order to have a benchmark to evaluate the performance properties of the reaction product of polymerization as a promoter sizing of the present invention. These experiments are called comparative examples. Conducted several experiments in which the accelerator sizing was absent. These experiments are called comparative examples.

As an industrial sizing substances used sizing agent for paper Precis®2000 (Hercules Incorporated, Wilmington, stdelivery), water stable starch reactive alkaline sizing dispersion.

For comparative purposes used three proven in the field of industrial accelerator PR the tapes.

The experiments that were conducted in the pilot paper machine, resembled in many ways the processes in the real world with the use of the invention for most of the envisaged objectives. In the pilot car AAA, amphoteric promoter resin and CBOs were entered into a mixed fibrous mass on her way to the formation of her paper. As in the case of a real paper machine, before winding on a bobbin paper was molded, extruded and dried. Speed manifestations sizing was determined IPG indicator, which was shown in the paper as it is drying and at the end of the paper machine. Samples for IPG cut from the paper web after the drying cylinders in the course of its movement along the dryer section of paper machines. Metric sizing was determined immediately, without any additional processing. It is crucial to determine the metric sizing from sample to sample within the same time because the measure sizing in paper pattern cut out from the paper web, usually continues to grow. Metric sizing was determined after several weeks of aging (sizing after natural aging)when sizing has reached the constant condition. The result after aging served as a guide to show what is equal to the number of AAA contained in each of the samples (which is equivalent to holding AAA). In the experiments presented in the present description, the retention of AAA in the samples remained essentially constant, as a result of differences in the IPG, which was observed during drying and at the end of the paper machine, were associated with differences in speed manifestations sizing.

As for the experiments with a laboratory size press, AAA, amphoteric promoter resin and CBOs was added to the starch solution, which is then applied to the base paper web, which before this specially made. The experiments of comparative examples with cationic promoter resins or without promoter resins was performed in the same way. The base fabric after its formation did not contain starch or sizing agent. The additive was applied by passing the paper from top to bottom through the rollers over which kept the mass of the chemical solution. Once on the base paper web inflicted AAA promoter resin, CBOs and starch, the base cloth was dried on drying cylinders. Experiments with laboratory size press was allowed to create a model that was closer to what would occur if the additive was applied in the sizing press. However, it served a good relative measure of the effectiveness of the new promoter resins truly izopet the tion against the background of more traditional promoter resins. In addition, experiments with laboratory size press is not very far from modeling in the wet part in determining the operation properties of the additives with the aim to show how the sizing is manifested in the first dryer section of the papermaking machine. Paper received in the drying part of paper machine for the manufacture of high grade paper, contains about 50% water. After processing in the laboratory sizing press, the weight of the base paper web due to water increased and, thus, the water content before drying was also about 50%.

In each of the examples of making paper amphoteric promoter resin with the ratio between the monomers, in which they were introduced in the polymerization process. These amphoteric promoter resin synthesized by the methods described in the examples of synthesis 1-8 or by similar methods of polymerization.

An EXAMPLE of MANUFACTURING PAPER 9: COMPARISON IN the PILOT MACHINE SIZING SUBSTANCES HERCON®70 and HERCON®79 PREPARED using the AMPHOTERIC PROMOTER RESINS

This example illustrates the operational properties of two amphoteric promoter resins on the background of the industrial sizing and promoting the sizing substances.

Pilot paper machine was set up on robotua mixture of fibrous masses of wood, hardwood and softwood mass ratio of 80/20. In fibrous liquid mass is added various chemicals. The amount of added chemicals listed below. The following interest amount is specified on the basis of the assumption that they are completely kept in the paper. This assumption is a good approximation for the paper machine used in the study. Again on the assumption that full hold, the values given are reasonable mass percentage in the finished paper. If in the example given, which was added 0.5% starch, this means that the finished paper consisted of an estimated 99.5 dried fibrous mass and other additives and 0.5% starch. In this example, the chemicals were added as follows: 0.5% of a low molecular weight cationic starch, 14% of powdered calcium carbonate, 0.1% substances for retention of microparticles/facilitate drainage in combination with 0,015% retention additive on acrylamide basis. Added 0.05% of optical Brightener and introduced 0,075% AAA. AAA was added in the form of an emulsion. The type and number of promoter resin are shown below together with the results. Promoter resin used in the preparation of emulsion AAA and was introduced as part of such emulsions.

In all cases, the manufacture of paper to better simulate real-world conditions used water, the alkalinity of which is constituted 50 PM/million In each example in which the alkalinity was not equal 50 hours/million reported more its value.

SampleAmphoteric promoter resin (APS)The content of the APSIPG (C) after the 7th dryerIPG (C) after the 11th dryerWhite
9-1And0,019%9525690,9
9-2B0,019%10526490,7
Comparative example 1*NoNo8023191,2
Comparative example 2**In0,019%10428590,3
*Sizing substance Hercon®70

**Sizing substance Hercon®79

Amphoteric promoter resin

A: poly(DADMAC/AK/YEAH•HCl) 40:40:20 in terms of molar basis.

B: poly(DADMAC/AK/YEAH•HCl) 45:45:10 in terms of molar basis.

Cationic promoter resin

In: poly(DADMAC).

In contrast to the experiment of comparative example 1, which was performed without promoter resin, in the experiment compared the sustained fashion of example 2, made using pure cationic promoter resin, has achieved high-speed manifestations sizing (104 against 80 and 285 231 against with IPG two different drying cylinders in a paper machine). However, the data of comparative example 2 show that the addition of typical cationic promoter resin, poly(DADMAC), reduced white paper 91.2 up to 90.3. Both experimental promoter resin of the present invention increases the speed of manifestation sizing, as it was determined by IPG in two different drying cylinders. New amphoteric promoter resin has less impact on the white than pure cationic resin.

An EXAMPLE of MANUFACTURING PAPER 10: COMPARISON IN the PILOT PAPER MACHINE SIZING agent HERCON 195 SAMPLES AMPHOTERIC PROMOTER RESIN AND a SIZING agent HERCON 79

Pilot paper machine was configured to work with a mixture of fibrous masses of wood, hardwood and softwood mass ratio of 80/20. In fibrous liquid mass is added various chemicals. The amount of added chemicals listed below. The following interest amount is specified on the basis of the assumption that they are completely kept in the paper. This assumption is a good approximation for bumagodelatel the th machine, used in the study. Again on the assumption that full hold, the values given are reasonable mass percentage in the finished paper. If in the example given, which was added 0.5% starch, this means that the finished paper consisted of an estimated 99.5 dried fibrous mass and other additives and 0.5% starch. In this example, the chemicals were added as follows: 0.5% of a low molecular weight cationic starch, 14% of powdered calcium carbonate, 0.1% substances for retention of microparticles/facilitate drainage in combination with 0,015% retention additive on acrylamide basis. Added 0.05% of optical Brightener and introduced 0,075% AAA. AAA was added in the form of an emulsion. The type and number of promoter resin are shown below together with the results.

In example 10-1 promoter resin pre-mixed emulsion AAA and, therefore, added as part of this emulsion. In comparative example 3 promoter resin was not added. The experiment of comparative example 4 was performed with a sizing agent, which included AAA and poly(DADMAC) as a cationic promoter resin. The relationship between AOD and cationic resin was equal to 4:1.

SamplePromoter resin IPG (C) after the 7th dryerIPG (C) when the reel after the 11th dryerWhite
10-1B0,0075%20340491,2
Comparative example 3NoNo18932491,4
Comparative example 4In0,019%21833490,0

Amphoteric promoter resin

B: poly(DADMAC/AK/YEAH•HCl) 45:45:10 in terms of molar basis.

Cationic promoter resin

In: poly(DADMAC).

In contrast to the experiment of comparative example 3, which was performed without promoter resin, in the experiment of example 10-1 conducted using the amphoteric promoter resin, achieved higher speeds manifestations sizing (203 189 and 404 324 against with IPG two different parts of the paper machine). The data of example 7-2 show that the addition of the amphoteric promoter resin was lowered white paper only from 91.4 to 91,2. For comparison in the experiment of comparative example 4, which was performed using a typical emulsion of AAA, including cationic, not amphoteric promoter resin, showed a large negative effect for the e on white, which decreased from 91.4 to 90.0.

Examples 11-19: amphoteric promoter resin (test in a laboratory sizing press for paper)

In examples 11 to 19 were carried out following the General method of making paper, processing and testing.

The base paper web is pre-made in the pilot paper machine at Western Michigan University using a mixture of chemically bleached fibrous masses of wood, hardwood and softwood in the ratio of 75:25. This base paper web was identical copy paper manufactured in the United States. Its density was 75 g/sq.m and it included 15% precipitated calcium carbonate. In this case, it is made without the addition of starch or sizing agent.

The base fabric was treated in a laboratory sizing press. This is a basic canvas in the size press was passed through the mass and between the two rollers. Each processed sample was immediately dried in the drying cylinders, the temperature was 65°C. To simulate different time and extent of drying along the paper machine varied time in the dryer. Immediately for each sample was determined relative sizing, carried out at different drying times. The size press solution, used for about what abode paper, included approximately 0.5%solution of cationic starch. Capture solution paper was approximately 100%. Therefore, the number of added paper starch, calculated on the dry matter was 0.5 g of starch per 100 g of paper, which corresponded to 0.5%treatment rate, calculated on the dry matter. For each series of experiments was pre-determined accurately capturing the base cloth and a dry content of starch was made to target the degree of processing. Subjected to the test additives were introduced into the starch solution in the amount established by the capture of the base fabric, and thus achieved the target level of processing.

Samples for testing IPG cut during periods of drying (measured in seconds), and then tested by IPG. To guarantee the possibility of good matching samples, as expected, were selected and tested through approximately the same time intervals. Optical whiteness was determined on the finished paper.

An EXAMPLE of MANUFACTURING PAPER 11: comparison of the actions of the AMPHOTERIC PROMOTER RESIN WHEN ADDED IN TWO DIFFERENT CONCENTRATIONS

If you receive the following results CBOs were added to the paper at a concentration of 0.075%. The number of added amphoteric promoter resins are shown below. Figures sizing achieved through various the e periods of drying. The approximate moisture content for two periods of drying was 34%and 30%. AAA was added in the form of an emulsion. Promoter resin was mixed with emulsion AAA in starch size press solution. The concentration added to the paper AAA in each case was equal to 0,09%.

The content of the amphoteric promoter resinAmphoteric promoter resin: poly(DADMAC/AK/YEAH*model HC1) in a molar ratio of 45:45:10
11-10,009%Time in the dryer232527303336
IPG,71860101109223
11-20,01%Time in the dryer2123253032
IPG,61639129156
Comparative example 5Emulsion AAATime in the dryer222426283134
IPG,7710134842

Amphoteric promoter resin

B: poly(DADMAC/AK/YEAH•HCl) in a molar ratio of 45:45:10.

Adding promoter resin increased the speed of manifestation sizing at small impact on whiteness. The data of the experiment of example 11 are presented in figure 3, which shows that the amphoteric resin with a ratio of 45:45:10 has higher performance characteristics than prostora system with Hercon 195.

An EXAMPLE of MANUFACTURING PAPER 12: COMPARISON of the ACTIONS of the AMPHOTERIC PROMOTER RESIN WHEN ADDED TO FOUR DIFFERENT CONCENTRATIONS

If you receive the following results CBOs were added to the paper at a concentration of 0.075%. The number of added amphoteric promoter resins are shown below. Figures sizing achieved through different periods of drying. The approximate moisture content during these periods of drying was 29±5%. AAA was added in the form of amulet is. Amphoteric promoter resin was added to the emulsion AAA in starch size press solution. The concentration added to the paper AAA in each case was equal to 0,09%. Without promoter resin or CBOs white paper was 90,1.

Different concentrations of amphoteric promoter resin

AAA at a concentration of 0.18%, the content of the amphoteric promoter resin, poly(DADMAC/AK/YEAH) in the ratio of 45:45:10, shown in table 2, the content of CBOs: 0,15%.

/tr>
Table 2
Products, lb/tTime (s)IPG VM (C)IPG NA ()White
12-1-76-1327
0,009% APS3612
4030548
4867530
5620457594,9
12-2-76-13058
0.01% APS 3161
3618
3945570
45133509
5517666194,6
12-3-76-1296
0,020% APS3313
3719657
4194594
5126866694,8
12-4-76-13036
0,024% APS3320
38109601
44159562
5124462694,9
ComparativeHercon®70/CBOs1,8/1,5282
example 6323
376
413541
4816504
66281400for 95.3

The addition of the amphoteric promoter resin increased the rate of manifestation of sizing if only a weak effect on whiteness. The test at the highest concentration of the amphoteric promoter resin gave the greatest increase in the rate of manifestation sizing. Although the paper of comparative example 6, which does not contain a promoter, had good optical white, it showed a very low rate sizing (16) when the drying time of 48 C. Data ek is periment of example 12 are presented in figure 4.

An EXAMPLE of MANUFACTURING PAPER 13: COMPARISON of DIFFERENT POLYMER COMPOSITIONS WITHOUT CBOs IN the STRUCTURE

The following results were obtained for samples without adding paper CBOs. The number of added promoter resins are shown below. Figures sizing achieved through different periods of drying. The approximate moisture content during these periods of drying was 35±5%. AAA was added in the form of an emulsion sizing agent Hercon 70 company Hercules. Promoter resin was added to the emulsion AAA in starch size press solution. The concentration added to the paper AAA in each case was equal to 0,09%.

Amphoteric promoter resin DADMAC/AK/YEAH
0,015% amphoteric promoter resin, and 0.09% AAA without adding Spas

The molar ratio
13-150:50:00Time in the dryer1920232729
IPG,121441100247
13-245:45:10Time in the dryer202123252732
IPG,856581111230336
13-340:40:20Time in the dryer1921232528
IPG,1279127113238
13-433:33:35Time in the dryer192123252932
IPG,40496344140232

About attornye resin

A: poly(DADMAC/AK/YEAH•HCl) 40:40:20 in terms of molar basis.

B: poly(DADMAC/AK/YEAH•HCl) 45:45:10 in terms of molar basis.

G: poly(DADMAC/AK/YEAH•HCl) 50:50:0, calculated on a molar basis.

D: poly(DADMAC/AK/YEAH•HCl) 33:33:33, calculated on a molar basis.

Adding HMMM•HCl as one of the monomers has increased the speed of manifestation sizing. In this system of testing, when I attended CBOs, the best concentration YEAH•HCl ranged from approximately 10 to 20%. The data of the experiments of example 13 are presented in figure 5.

An EXAMPLE of MANUFACTURING PAPER 14: COMPARISON of DIFFERENT POLYMER COMPOSITIONS IN the presence of the COMPOSITION Spas

The following results were obtained for samples with the addition of CBOs in the paper at a concentration of 0.075%. The number of added amphoteric promoter resins are shown below. Figures sizing achieved through different periods of drying. The approximate moisture content at three periods of drying was 25±5%. AAA was added in the form of an emulsion. Amphoteric promoter resin was added to the emulsion AAA in starch size press solution. The concentration added to the paper AAA in each case was equal to 0,09%. The emulsion was prepared according to the following method.

The PREPARATION of EMULSIONS, FOR EXAMPLE, 14

Alkylcatechols dimer: 11 PM

Low molecular weight cationic KRA is small: 1,29 PM

Ligninsulfonate sodium: 0,24 h

Alum: 0,10 o'clock

Biocide: 0,05 PM

Water: 73,16 PM

Promoter resin: 13,92 including solution with a dry matter content of 20%.

Starch and ligninsulfonate sodium in water boiled at 95-100°C for one hour at a neutral pH value.

The starch solution was used within a few hours. It was stored and used at 75°C.

Alkylcatechols dimer was added to the starch (where it was melted and mixed). The mixture was passed through microvias system (with colliding flows)that is configured on the mode, 3000 psi, which turned the mixture into an emulsion.

The emulsion was cooled to a temperature of from 48 to 55°and then was cooled to 26°C.

After 4 h of exposure at 26°With it in the form of a 5%solution was added alum, mixed with it and then added promoter resin.

The final dry matter content was brought up to 15.5%.

SampleProductsTime (s)IPG VM (C)IPG NA ()Optical white
14-1N 70/50:50:0 DADMAC:AK:YEAH/CBOs263
296
3312563
376598
4317700
5220395,1
14-2N 70/45:45:10 DADMAC:AK:YEAH/CBOs266
291
322547
362532
434635
49894,9
14-3N 70/40:40:20 DADMAC:AK:YEAH261
291
332470
393545
433535
491095,1
14-4N 70/33:33:33 DADMAC:AK:YEAH/CBOs275
303
3210527
357534
3922612
4490for 95.3
Compare.AKD sizing281

SampleProductsTimeIPKVMUPGMAOptical white
Example 7substance301
321153
381109
433338
559479a 94.2

All amphoteric promoter resin increased the rate of sizing larger than in comparative example 7, even though the amphoteric promoter resin was added in a smaller amount than the amount of promoter resins, call the military in comparative example 7. Adding HMMM•HCl as one of the monomers under the conditions of this experiment did not increase the speed of manifestation sizing, except it is added at the highest concentration, when the polymer used 33 mol.% links YEAH•HCl. The data of the experiment of example 14 is presented on Fig.6.

An EXAMPLE of MANUFACTURING PAPER 15: COMPARISON of DIFFERENT POLYMER COMPOSITIONS

The following results were obtained for samples with the addition of CBOs in the paper at a concentration of 0.075%. The number of added promoter resins are shown below. Figures sizing achieved through different periods of drying. The approximate moisture content at three periods of drying was 25±5%. AAA was added in the form of an emulsion sizing agent Hercon 70 company Hercules. Promoter resin was added to the emulsion AAA in starch size press solution. The concentration added to the paper AAA in each case was equal to 0,09%.

Amphoteric prostora resin DADMAC/AK/YEAHDrying time and results IPGOptical white
15-150:50:00Time in the dryer3340455370 10594,5
IPG,112359505
15-245:45:10Time in the dryer33414653658794,8
Amphoteric prostora resin DADMAC/AK/YEAHDrying time and results IPGOptical white
IPG,2472825401
15-340:40:20Time in the dryer344150607110095
IPG,225421458
15-433:33:33Time in the dryer354754657910694,7
IPG,151335296381
Compare. approx. 8NTime in the dryer354756698511093,2
IPG,00121112

N denotes the reactive emulsion sizing agent Hercon 79.

When each of the different ratios of the monomer components sizing of paper manifested itself more quickly and optical white negative impact, in comparison with control cases, emulsions reactive adhesive Hercon 79 was not found. The data of example 15 is presented on Fig.7.

An EXAMPLE of MANUFACTURING PAPER 16: AMPHOTERIC PROMOTER RESIN AS COMPONENTS IN AAA EMULSION

In this example, the amphoteric promoter resin was added to the composition with the product Hercon 79 and experienced. The resulting emulsion AAA with promoter resins were stable (examples 16-1 and 16-2). Amphoteric promoter resin with ADMAH and AK without any additives HMMM showed about the same performance as the composition with the product Hercon 79. These mind the military operational properties of amphoteric promoter resin were determined by high content of CBOs and high ratio of amphoteric promoter resin and AAA. Optical white in both examples 16-1 and 16-2 was much better than in comparative example 9.

SampleProductsLb/tTimeIPG VMIPG NAWhite
Resin/CBOs(C)(C)(C)
16-1N (DADMAC-AK-YEAH)/CBOs1,8/1,524695,1
40:40:202614
2875
33104587
37134557
4661608
16-2N (DADMAC-AK)OOM1,8/1,524194,4
50:50:00272
313593
3923559
4642630
Compare.N (control)/CBOs1,8/1,5252293,6
example 92814
3232
3624615
4117534
5441553

When each of the different ratios of the monomer components sizing of paper manifested itself more quickly, and optical white negative impact, in comparison with control cases, emulsions reactive adhesive Hercon 79 was not found. Data presented in example 16 Fig.

An EXAMPLE of MANUFACTURING PAPER 17: AMPHOTERIC PROMOTER RESIN AS COMPONENTS IN AAA EMULSION

Amphoteric promoter resin in this example was prepared by synthesis technology, similar to those shown in example of synthesis No. 1, with a ratio of DADMAC/AK/YEAH 45:45:10. The paper produced by the method identical to those described in the previous examples, except that the number OS is in terms of calcium carbonate was 18, instead of 15%.

Optical white
N + N (600 gallons)Time in the dryer323947576371
Compare. approx. 10 N + R203IPG,3663654673093,7
Time in the dryer404654647589
IPG,547427550592

Reactive adhesive Hercon 70 (in the present description abbreviated designated as N) was promotional amphoteric promoter resin with a ratio of 45:45:10. In comparative example 10 amphoteric promoter resin is not used, and added a cationic resin and retaining additive Retene 203 (obtained from the company Hercules Incorporated, Wilmington, pieces of Delaware). The data of the experiment of example 17 presents on Fig.

An example of the synthesis of polymer 1

Getting amphoteric promoter resin-based alkanesulphonic groups as anionic component.

An example of DADMAC/AMPS 50/50

The following solutions were prepared, mixed to homogeneity, and immediately before use by purging with nitrogen for 30 min was desoxyribose (freed from oxygen) (for preparation of all solutions used deionized water). The target composition was included DADMAC/AMPS in a molar ratio of 50:50. AMPS means 2-acrylamide-2-methyl-1-propanesulfonic acid. In this experiment used deionized water.

Solution: 80,0 g of water and 0.5 g of V-50.

Solution B: 40,25 g of a 65%aqueous solution of DADMAC + 84,4 g water + 57,25 g AMPS (1%HCl solution pH was brought to 3.7).

Solution: 1.5 g of V-50 + 50 ml of water.

Solution G: 1.0 g of V-50 + 10.0 g of water.

The solution was introduced into a closed reaction vessel equipped with installed at the top of the agitator and a means of purging with nitrogen.

Solution B was introduced into the addition funnel, mounted with the possibility of feed drops into the reaction vessel. The funnel is oriented to supply drops directly into the liquid in the vessel, and not on the walls of the flask.

For slow feed solution In the reaction vessel was fitted pump.

During the polymerization in the reaction vessel is maintained constant uniform mixing when s is IMEMO 60 rpm During the entire reaction was supported by the stream of nitrogen. To one of the outlet openings in the upper part of the reaction vessel was attached to the condenser. The purging with nitrogen during the reaction was carried out through the upper end of the condenser through a liquid trap.

The reaction vessel was heated to 75°C.

Upon reaching 75°started With the addition of solutions B and C, which are fully injected with uniform speed during the 10 o'clock

After 10 h temperature for 2 h increased up to 90°C. after 10 h was added to the solution, After 2 h of exposure at elevated temperature the reaction mixture was let to cool down slowly to room temperature. The sample was diluted with water to a dry matter content of approximately 20%. Next, the flask was opened and the polymer solution were analyzed.

The dry matter content in the polymer solution was 18.3 percent. According to the13C-NMR analysis, the solution contained polymer with 48 hours (calculated on a molar basis) of the links of AMPS and 35 p.m links of DADMAC. Calculated on the same basis it contained 18 hours remaining DADMAC.

Example of synthesis of polymer 19

Getting amphoteric promoter resin, based on alkanesulphonic groups as anionic component.

Example of synthesis of the polymer DADMAC/AMPS 66/33

The following solutions were prepared, was mixed to homogeneity and directly edstone before use by purging with nitrogen for 30 min was desoxyribose (freed from oxygen) (for preparation of all solutions used deionized water). The target composition was included DADMAC/AMPS in a molar ratio of 50:50. AMPS means 2-acrylamide-2-methyl-1-propanesulfonic acid. In this experiment used deionized water.

Solution: 80,0 g of water and 0.5 g of V-50.

Solution B: 60,4 g of a 65%aqueous solution of DADMAC + a 126.7 g of water + 42,9 g AMPS (1%HCl solution pH was brought to 3.8).

Solution: 1.5 g of V-50 + 50 ml of water.

Solution G: 1.0 g of V-50 + 10.0 g of water.

The solution was introduced into a closed reaction vessel equipped with installed at the top of the agitator and a means of purging with nitrogen.

Solution B was introduced into the addition funnel, mounted with the possibility of feed drops into the reaction vessel. The funnel is oriented to supply drops directly into the liquid in the vessel, and not on the walls of the flask.

For slow feed solution In the reaction vessel was fitted pump.

During the polymerization in the reaction vessel is maintained constant uniform stirring at about 60 rpm throughout the reaction maintained a stream of nitrogen. To one of the outlet openings in the upper part of the reaction vessel was attached to the condenser. The purging with nitrogen during the reaction was carried out through the upper end of the condenser through a liquid trap.

The reaction vessel was heated to 75°C.

Upon reaching 75°started With the addition of solutions B and C, which are fully centuries the Dili with uniform speed during the 10 o'clock

After 10 hours the temperature for 4 h increased up to 90°C. after 10 h was added to the solution, After 4 h of exposure at elevated temperature the reaction mixture was let to cool down slowly to room temperature. The sample was diluted with water to a dry matter content of approximately 20%. Next, the flask was opened and the polymer solution were analyzed.

The dry matter content in the polymer solution was 18.1%. According to the13C-NMR analysis, the solution contained polymer with 27 PM (in terms of molar basis) links AMPS and 42 am links of DADMAC. Calculated on the same basis it contained 31 PM residual DADMAC.

An EXAMPLE of MANUFACTURING PAPER 20: COMPARISON of POLYMER COMPOSITIONS, DERIVATIZING USING ALKANESULPHONIC GROUPS

Monomer units, which contained alkanesulfonyl group as the anionic monomer component of the polymer was also promotionally the sizing. The following results are presented for samples with 0,075% of CBOs, added to the paper, and allow you to compare cationic promoter resin with amphoteric promoter resins with alkanesulfonyl groups. Synthesis alkanesulphonic APS shown in the examples of synthesis of polymers 18 and 19. The amount of added promoter resins are shown below. AAA was added in the form of an emulsion AKD sizing prophetic is tion of the company Hercules. Promoter resin was added to the emulsion AAA in starch solution for size press. The concentration added to the paper AAA in each case was equal to 0,09%.

SamplePromoter resinContents promoter resinOptical white
20-1E0,030%95,1
20-2W0,030%for 95.2
Comparative example 11NoNo(without CBOs) 89,6
Comparative example 12NoNo95,5
Comparative example 13In0,030%93,2
Comparative example 14And0,030%93,8

Cationic promoter resin

In: poly(DADMAC).

C: poly(DADMAC/acrylamide) 50:50 (in the absence of available comparative data on the sizing to exclude).

And: poly(DADMAC/vinyl pyrrolidone) 50:50 Amphoteric promoter resin.

G: poly(DADMAC/AK/YEAH*HCl) 50:50:0, calculated on a molar basis.

E: poly(DADMAC/2-acrylamide-2-methyl-1-propanesulfonic acid) 50:50.

W: poly(DADMAC/2-acrylamide-2-methyl-1-propanesulfonate to the slot 66:33.

The addition of sulfate of co monomer with DADMAC resulted in reducing the effect of resin on CBOs. Adding peninnah monomers (acrylamide or vinylpyrrolidone) has led to a weakening influence on the CBOs, which would be expected if the reduction in the content of links of DADMAC in the polymer. Comparative examples 11 and 12 demonstrate in the experiments of this series the impact of adding CBOs on the white paper: 89,6 against 95,5.

The data of example 20 presented on Fig.9.

An EXAMPLE of MANUFACTURING PAPER 21: COMPARISON of POLYMER COMPOSITIONS CONTAINING SULPHONATE GROUPS; CBOs in the paper is not added

Adding sulphonate monomer decreases, apparently, the efficiency units of another monomer (DADMAC) as a promoter speed sizing during the initial drying, while adding AK does not reduce. The following sample optical Brightener is not contained. Moreover, when in high concentrations was added to the polymer containing parts of 2-acrylamide-2-methyl-1-propanesulfonic acid, increasing the speed sizing became less significant. When added CBOs, polymers, including parts of 2-acrylamide-2-methyl-1-propanesulfonate monomer, speed sizing is not provided. Amphoteric promoter resin was added at a concentration of 0.015%.

SamplePromoter resin
21-1GTime in the dryer222426303337
IPG,142979135247234
21-2ETime2426293235
dryer
IPG,1281194103236
21-3WTime in the dryer2326283237
IPG,11424395290
Comparative the Rimera 14 Reactive adhesive Hercon 70Time in the dryer2325272939
IPG,8304238252

Amphoteric promoter resin

G: poly(DADMAC/AK/YEAH·HCl) 50:50:0, calculated on a molar basis.

E: poly(DADMAC/2-acrylamide-2-methyl-1-propanesulfonic acid) 50:50.

W: poly(DADMAC/2-acrylamide-2-methyl-1-propanesulfonic acid) 66:33.

Alkanesulfonyl amphoteric promoter resin improved the sizing. The data of example 21 presented on Fig.9.

An EXAMPLE of MANUFACTURING PAPER 22: COMPARISON of POLYMER COMPOSITIONS CONTAINING SULPHONATE GROUPS; CBOs in the paper is not added

Adding sulphonate monomer decreases, apparently, the efficiency units of another monomer (DADMAC) as a promoter speed sizing during the initial drying, while adding AK does not reduce. The following sample optical Brightener is not contained. Moreover, when in high concentrations was added to the polymer containing parts of 2-acrylamide-2-methyl-1-propanesulfonic acid, increasing the speed sizing became less significant. When added CBOs, polymers, including parts of 2-acrylamide--methyl-1-propanesulfonate monomer, speed gluing is not provided. Amphoteric promoter resin was added at a concentration of 0,030%.

21-1GTime in the dryer222426293437
IPG,1735116174173432
21-2ETime in the dryer2426293236
IPG,5333159138
21-3WTime in the dryer2528313338
IPG,8413073216

Amphoteric promoter resin

G: poly(DADMAC/AK/YEAH·HCl) 50:50:0, calculated on a molar basis.

E: poly(DADMAC/2-acrylamide-2-methyl-1-propanesulfonic acid) 50:50.

W: poly(DADMAC/2-acrylamide-2-methyl-1-propanesulfonic acid) 66:33.

Alkanesulfonyl amphoteric promoter resin improved the sizing. The data of example 22 are presented in figure 10.

An EXAMPLE of MANUFACTURING PAPER 23: AMPHOTERIC PROMOTER RESIN WITH OTHER MONOMERIC COMPONENTS

Amphoteric promoter resin was prepared using other monomers in the monomer mixture. The synthesis process was almost identical technology in the examples of the synthesis of 1 through 8, and in one of the monomer streams introduced into the mixture of polymerization, was added another monomer. Examples of other monomers shown in the following table. In the composition shown in the following table, indicated molar ratios:

N + DADMAC/AK 50:50Time in the dryer19223252729
0
IPG,12141111024
4807
N + DADMAC/AK/ styrene 48:48:4Time in the dryer 19222242730
0
IPG,1242558615
67
N + DADMAC/AK/YEAH·HClTime in the dryer20223252732
45:45:101
DADMAC/AK/YEAH·HClIPG,85681112333
5106
N + DADMAC/AK/YEAH/TEGDMA 37,5:37,5:25:1Time in the dryer192242730
DADMAC/AK/YEAH/TEGDMAIPG,2271371323
272

TEGDMA denotes triethyleneglycoldinitrate.

Amphoteric promoter resin can be obtained with other monomer units such as styrene and TEGDMA. Sample data 23 figure 11 presents.

Comparative synthesis example 1

In this example, a water-soluble copolymer diallyldimethylammoniumchloride (DADMAC) and diallylammonium (YEAH•HCl) was prepared as follows. The molar ratio between the monomers used in the reaction product of polymerization (DADMAC:YEAH•HCl), was approximately 8:2.

An aqueous mixture was prepared by combining 53,8 hours of diallyldimethylammoniumchloride in water concentration of 65 wt.% from 14.5 hours of diallylammonium in water concentration of 49.8 wt.%. The aqueous reaction mixture of these two Monomeric components was degirolami nitrogen for 40 min and was heated with stirring to a temperature of 55°C.

In an aqueous solution with a speed of 0.4 g/min was added water-soluble free radical initiator is olymerization, 4,23 including 2,2'-azobis(2-amidinopropane)hydrochloride in degassed water at a concentration of 9.09 wt.%. After adding the initiator to reduce the viscosity of the reaction medium was added to 16.9 hours degassed water and the mixture was stirred at a temperature of about 90°C.

Three times was carried out the next stage: quickly added to 4.23 including 2,2'-azobis(2-amidinopropane)hydrochloride in degassed water at a concentration of 9.09 wt.%, and then the reaction mixture was stirred for one hour.

At the end of the third one-hour period of stirring the water analysis of the reaction mixture by NMR-spectroscopy on carbon 13 indicated that polymeropoulos more than 95% of the Monomeric components. Data to determine the molecular weight of the reaction product of polymerization was obtained aqueous gel permeation chromatography (GPC), using a series of columns Synchrom DATSEC (sequentially placed speakers 4000+1000+300+100), using as mobile phase 0.4 M lithium acetate, and 2.0% of ethylene glycol (pH 4.5) at a flow rate of 0.25 ml/min the Results of these definitions has been showed that the reaction product of polymerization had srednekamennogo molecular weight (Mn) of about 21700 and srednevekovoi molecular weight (Mw) of about revised 364,000.

Comparative synthesis example 2

In this comparative example 11 synthesis received a homopolymer of diallyldimethylammonium is ignored (at a molar ratio of DADMAC/YEAH• HCl 100:0).

269,5 hours of diallyldimethylammoniumchloride in water at a concentration of 60 wt.% was degirolami nitrogen for about 30 minutes Degassed solution was heated while stirring to 70°C. After heating at a constant speed for about 25,7 including added 2,56 including 2,2'-azobis(2-amidinopropane)hydrochloride in 23 hours distilled degassed water. After about 1.5, 1.7 and 4.3 hours after the start of introduction of the initiator was added, respectively, 123,0, 120,6 and 59,2 including distilled degassed water. After approximately one hour after completion of addition of the initiator over the mix created a layer of air and she was allowed to cool to room temperature. The result has been showed that the product had srednevekovoi molecular weight (Mw) of about 385000 if polydispersity 12,9. Analysis of NMR-spectroscopy on carbon 13 indicated that polymeropoulos 95% (on a molar basis) of the monomer.

A COMPARATIVE EXAMPLE of MANUFACTURE of PAPER 1: LOSS of WHITE PAPER USING CATIONIC PROMOTER RESINS

For the manufacture of paper used typical cationic promoter resin and determined optical white. These typical materials served as poly(DADMAC) high molecular weight, poly(DADMAC) average molecular weight, polydimethylaminoethyl, polyethylenimine and Nate the resin material, polyacrylamide. Resin poly(DADMAC), polyethylenimine and polyacrylamide were acquired by the company Sigma Aldrich Chemical, Milwaukee, steveascension. Polydimethylaminoethyl received in the form of a cationic resin and retaining additives RETEN®201. The cationic nature of the cationic promoter resin and the amount of added cationic promoter resin caused a decrease in the efficiency of optical brighteners. To demonstrate this phenomenon on a comparative basis by titration of cationic component was determined cationic density of each of them. The charge density cationic polymer product was determined at pH 8.0. Used colloid titration. The charge density is the amount of cationic charge per unit mass in milliequivalent per gram of dry product.

The sample was titrated with potassium polyvinyl sulphate, UKBA, with the receipt of the colloid. After titration of the charge excess UKBA interacted with the indicator endpoint, toluidine blue, the color of which changed from blue to purple. For the implementation of the titration was used colorimeter with submersible probe tuned to the wavelength of 620 nm, and an automatic titrator (analog or digital). The results of the titration was calculated charge density on the basis of dry matter. The charge density of the criminal code is indicated in milliequivalent/gram. The total charge due to the cationic promoter resin was the charge density multiplied by the number of cationic promoter resin in pounds/ton. Using each of these promoter resins produced paper and determined optical white. White apromotional paper was 96,5. Thus defined, optical white listed for the two concentrations of cationic promoter resin. As the overall charge increased loss of whiteness. Cationic promoter resin provided on the optical white paper the harmful effects. Conditions of carrying out the process of making paper for this series of results included the lack of AAA, 1.5 lb/ton of Spas, 80 lbs/ton low viscosity anionic starch; hardness of water used was 100 hours/million, but any additional alkalinity. This information is presented in figure 1

Typical technical cationic promoter resinCertain charge densityAdd numberThe total chargeLoss of white (1.5 lb/t CBOs)
High molecular weight poly(DADMAC)6,10,251,530,85
0,5 3,051,65
Poly(DADMAC) average molecular weight60,251,50,95
0,53,051,5
Polydimethyl-epichlorohydrin6,10,251,530,6
0,53,051,15
Polyethylenimine11,20,252,81,1
0,55,62,5
Polyacrylamide (neutral resin)00,2500
0,500

A COMPARATIVE EXAMPLE of MAKING PAPER 2:

REDUCTION of WHITE, WHEN USING CATIONIC PROMOTER RESINS POLY(DADMAC) AND POLY(DADMAC/YEAH•HCl)

Poly(DADMAC) and poly(DADMAC/YEAH•HCl) was synthesized according to comparative examples of the synthesis of polymers 1 and 2, respectively. CBOs were added with a flow rate of 1 lb/T. These cationic promoter resin used for the manufacture of paper and determined optical white. With increasing amount of added cationic promoter resin is harmful impact on the whiteness of the paper was increased. These data are presented in figure 2.

White depending on the number in lbs/ton of cationic promoter.

Cationic promoter
Lb/t0,380,751,121,12
Poly(DADMAC)91,791,290,7
Poly(DADMAC/YEAH•HCl)90,6

White paper without any cationic additive was 92,2.

1. The method of manufacturing sized paper containing optical Brightener, including the manufacture of sized paper in the presence of a sizing agent and a water-soluble amphoteric promoter resin which is a reaction product of polymerization of a monomer comprising at least one capable of cationic polymerization of amine monomer of the formula (I)

where the value G is selected from alkyl, alkenyl, allyl, aryl, interrupted by a heteroatom of the alkyl or alkenyl, where the heteroatoms are selected from the series N, S and O;

a J, K and L are selected from a series of hydrogen atom, alkyl,alkenyl, allyl, styryl and aryl, interrupted by a heteroatom alkyl or alkenyl, where the heteroatoms are selected from the series N, S and O,

and X denotes compatible with sizing anion, and

at least one is able to cure the organic acid of formula (II)

where each of Rx, Ryand Rzdenotes a hydrogen atom, alkyl, alkenyl, aryl, interrupted by a heteroatom alkyl or alkenyl, where the heteroatoms are selected from the series N, S and O; and E denotes organic Deputy, selected from a number soo, SO3, HSO4and H2PO4,

and where the molar proportion of units of cationic amine of formula I is at least 25% of monomers in the amphoteric promoter resin and the molar proportion of units of an organic acid of formula II is at least 25% of monomers in the amphoteric promoter resin, and thus loss of whiteness is less than 0.5% by TAPPI compared with white compositions obtained without promoter resin.

2. The method according to claim 1, wherein E in the monomer of formula II denotes soo.

3. The method of manufacturing sized paper, which includes the manufacture of sized paper in the presence of a sizing agent optical Brightener and water-soluble amphoteric promoter resin, which is the Wallpaper of the reaction product of polymerization of a monomer, includes links, at least one cationic Quaternary diallylammonium monomer of formula (III)

not necessarily including at least one cationic diallylammonium monomer of the formula (IV)

where each of R1A, R1B, R1Cand R1Ddenotes a hydrogen atom or remotemachine or branched C1-C22alkyl; R2and R3denote alkyl, alkenyl, aryl, interrupted by a heteroatom alkyl or alkenyl, where the heteroatoms are selected from the series N, S and O;

R4denotes a hydrogen atom, alkyl, alkenyl, aryl, interrupted by a heteroatom alkyl or alkenyl, where the heteroatoms are selected from the series N, S and O, and X-means compatible with sizing anion and at least one organic acid of formula (II)

where each of Rx, Ryand Rzdenotes a hydrogen atom, alkyl, alkenyl, aryl, interrupted by a heteroatom alkyl or alkenyl, where the heteroatoms are selected from the series N, S and O, and E denotes organic Deputy, selected from a number soo, SO3, HSO4and H2PO4,

and where the sum of the molar percentages of the links cationic Quaternary diallylammonium monomers form the s (III) and the molar percentage of links diallylammonium monomers of formula (IV) is at least 25% of monomers in the amphoteric promoter resin and the molar percentage of unsaturated organic acid of the formula (II) is at least 25% of monomers in the amphoteric promoter resin.



 

Same patents:

FIELD: paper-and-pulp industry.

SUBSTANCE: : process comprises preparation of paper pulp, flocculation of pulp, shear force-involving mechanical treatment of pulp, second flocculation of pulp, drainage of pulp on the screen to form sheet, and subsequent drying of sheet. Flocculation is carried out by adding water-soluble optionally having intrinsic viscosity above 3 dl/g. Polymer is further characterized by oscillation delta tangent value at 0.005 Hz above 1.1.

EFFECT: improved drainage and retention on moving screen, and formation process.

10 cl, 1 dwg, 4 tbl, 4 ex

FIELD: paper-and-pulp industry.

SUBSTANCE: process comprises preparation of paper pulp, flocculation of pulp, drainage of pulp on the screen to form sheet, and subsequent drying of sheet. Flocculation involves flocculation system including water-soluble anionic branched polymer and silicon-containing material. Polymer is prepared using water-soluble anionic ethylenically-unsaturated monomer or monomer mixture and ramification-forming agent. Polymer is characterized by intrinsic viscosity above 1.5 dl/g and/or Brookfield viscosity in salt solution above about 2.0 mPa·s, rheological oscillation delta tangent value at 0.005 Hz above 0.7, and/or reduced viscosity in deionized water at least thrice exceeding reduced viscosity in salt solution of corresponding nonbranched polymer obtained in absence of ramification-forming agent.

EFFECT: improved drainage, retention, and formation process.

14 cl, 1 dwg, 6 tbl, 6 ex

FIELD: paper-and-pulp industry.

SUBSTANCE: process comprises preparation of paper pulp, flocculation of pulp, drainage of pulp on the screen to form sheet, and subsequent drying of sheet. Flocculation involves flocculation system including clay and water-soluble anionic branched polymer. The latter is prepared using water-soluble anionic ethylenically-unsaturated monomer or monomer mixture and ramification-forming agent. Polymer is characterized by intrinsic viscosity above 1.5 dl/g and/or Brookfield viscosity in salt solution above about 2.0 mPa·s, rheological oscillation delta tangent value at 0.005 Hz above 0.7, and/or reduced viscosity in deionized water at least thrice exceeding reduced viscosity in salt solution of corresponding nonbranched polymer obtained in absence of ramification-forming agent.

EFFECT: improved drainage, retention, and formation process.

20 cl, 10 tbl, 8 ex

FIELD: pulp-and-paper industry.

SUBSTANCE: method involves preparing cellulose suspension; providing flocculation and draining of suspension on netted surface; molding and drying of resultant sheet. Flocculation of suspension is provided by introducing of water-soluble polymer selected from the group consisted of polysaccharide and synthetic polymer with characteristic viscosity of at least 4 deciliter/g. Repeated flocculation procedure is provided by adding of system including silicon-containing material and water-soluble polymer. According to one of versions, silicon-containing material is added before or simultaneously with water-soluble polymer. According to other version, water-soluble polymer is of anionic kind of polymers, which is added before introduction of silicon-containing material.

EFFECT: improved draining and holding procedures facilitating adequate conditions for paper and cardboard molding procedure.

18 cl, 2 tbl, 4 ex

FIELD: mining industry and mechanical engineering.

SUBSTANCE: the invention is dealt with methods of production of a paper, in particular, with its smoothing. The water suspension containing cellulose fibers and optional fillers (i) add the sizing dispersion containing a sizing agent and a polymer including one or several aromatic groups and (ii) a sizing promoter containing a polymer intercalating one or several aromatic groups. Mould and dry the produced suspension. The sizing dispersion and sizing promoter are added to the water suspension separately. The invention ensures improvement of the process of sizing the cellulose fibers having a high conductivity.

EFFECT: the invention ensures improvement of the process of sizing the cellulose fibers having a high conductivity.

41 cl, 6 tbl, 6 ex

Papermaking process // 2244776

FIELD: paper industry.

SUBSTANCE: invention relates to technology of manufacturing paper from aqueous suspension containing cellulose fibers and optional fillers. Process comprises separately adding to suspension cationic processing polymer with one or several aromatic groups and anionic polymer with one or several aromatic groups. The latter is selected from polymers prepared according to stepped molecule growth mechanism, naturally occurring polysaccharides and aromatic polymers and modifications thereof, provided that, if anionic polymer is polymer prepared according to stepped molecule growth mechanism, then it cannot be anionic condensation polymer based on melaminesulfonic acid. Another condition that could be alternatively fulfilled is that anionic polymer is not anionic polystyrenesulfonate or anionic condensation polymer based on melaminesulfonic acid. Suspension is then molded into sheet and dehydrated on screen.

EFFECT: improved dehydration and/or retention during making of paper from all types of fibrous pulps, including those with high content of salts, and increased strength of dry paper.

19 cl, 10 tbl, 11 ex

The invention relates to the technology of making paper lichtovannaya

The invention relates to methods of making paper (including cardboard) and, in particular, to methods of making paper, reinforced with starch

The invention relates to methods of making paper, and particularly relates to such methods that involve the use of water-soluble polysilicate microgels, especially polyaluminosilicate microgels and aluminiumand polysilicate microgels as auxiliaries to improve uderzhivaemoi filler and enhance dewatering
The invention relates to the manufacture of paper for corrugation and/or planar layers in the manufacture of corrugated cardboard

The invention relates to methods of making paper (including cardboard) and, in particular, to methods of making paper, reinforced with starch

FIELD: food industry; packing.

SUBSTANCE: invention relates to packing material containing base paper or cardboard layer for packing container formed by bending and welding the sheet, or flat blank of packing material. Laminated packing material has base paper or cardboard layer and outer coatings from both sides of base layer made of thermoweldable polymer impermeable to liquids. Said paper or cardboard base layer is made water-repelling by sizing the mass by water dispersoid solution or emulsion of alkylketene dimer or mixture of alkylketene dimers so that content of alkylketene dimer (dimers)in base layer is from 0.25 to 0.4 by dry weight, weight %. Invention contains description of method of manufacture of laminated material and packing container to be sterilized.

EFFECT: provision of laminated packing material protected from penetration of hot steam or liquid designed for packing food products and capable of withstanding heat treatment in autoclave at high humidity and temperature without separation of packing material into layers.

6 cl, 2 dwg

FIELD: pulp-and-paper industry, in particular, manufacture of paper and cardboard.

SUBSTANCE: method involves preparing aqueous cellulose pulp; adding holding system into cellulose pulp system; draining pulp through cloth for forming of paper web; drying resultant paper web. Holding system comprises swelling clay having whiteness of at least 70.

EFFECT: increased whiteness of paper and improved filler retention capability.

16 cl, 1 tbl, 20 ex

FIELD: pulp and paper industry; methods of production of the pigment for manufacture of the cardboard and paper.

SUBSTANCE: the invention is pertaining to the method of production of the pigment for manufacture of the cardboard and paper and may be used in pulp and paper industry at production of the filled paper, the coated paper and the cardboard. Calcium carbonate is treated with aluminum sulfate in the aqueous medium. The treatment is conducted at aluminum sulfate consumption of 25-105 % to the mass of absolutely dry calcium carbonate at the temperature of 80-85°С during 90-180 minutes with production of the suspension containing 25-35 % dry substances in it. The suspension may be additionally dried and to produce the powder. The technical result of the invention is improvement of the pigment quality and expansion of the field of its application.

EFFECT: the invention ensures improvement of the pigment quality and expansion of the field of its application.

2 cl, 2 tbl

FIELD: pulp and paper industry; methods of production of the pigment for manufacture of the cardboard and paper.

SUBSTANCE: the invention is pertaining to the method of production of the pigment for manufacture of the cardboard and paper and may be used in pulp and paper industry at production of the filled paper, the coated paper and the cardboard. Calcium carbonate is treated with aluminum sulfate in the aqueous medium. The treatment is conducted at aluminum sulfate consumption of 25-105 % to the mass of absolutely dry calcium carbonate at the temperature of 80-85°С during 90-180 minutes with production of the suspension containing 25-35 % dry substances in it. The suspension may be additionally dried and to produce the powder. The technical result of the invention is improvement of the pigment quality and expansion of the field of its application.

EFFECT: the invention ensures improvement of the pigment quality and expansion of the field of its application.

2 cl, 2 tbl

FIELD: pulp and paper industry; methods of production of the pigment for manufacture of the cardboard and paper.

SUBSTANCE: the invention is pertaining to the method of production of the pigment for manufacture of the cardboard and paper and may be used in pulp and paper industry at production of the filled paper, the coated paper and the cardboard. Calcium carbonate is treated with aluminum sulfate in the aqueous medium. The treatment is conducted at aluminum sulfate consumption of 25-105 % to the mass of absolutely dry calcium carbonate at the temperature of 80-85°С during 90-180 minutes with production of the suspension containing 25-35 % dry substances in it. At that they use the aqueous medium containing the binding chosen from the group, which includes starch and polyvinyl alcohol in the amount of 0.5-3.0 mass % from the mass of the absolutely dry pigment, and-or the water soluble colorant in the amount of 0.1-0.5 mass % from the mass of the absolutely dry pigment. The suspension is additionally dried and grinded. The technical result of the invention is the improved quality of the pigment as well as expansion of its field of application.

EFFECT: the invention ensures the improved quality of the pigment as well as expansion of its field of application.

2 tbl

FIELD: pulp and paper industry; methods of production of the pigment for manufacture of the cardboard and paper.

SUBSTANCE: the invention is pertaining to the method of production of the pigment for manufacture of the cardboard and paper and may be used in pulp and paper industry at production of the filled paper, the coated paper and the cardboard. Calcium carbonate is treated with aluminum sulfate in the aqueous medium. The treatment is conducted at aluminum sulfate consumption of 25-105 % to the mass of absolutely dry calcium carbonate at the temperature of 80-85°С during 90-180 minutes with production of the suspension containing 25-35 % dry substances in it. At that they use the aqueous medium containing the binding chosen from the group, which includes starch and polyvinyl alcohol in the amount of 0.5-3.0 mass % from the mass of the absolutely dry pigment, and-or the water soluble colorant in the amount of 0.1-0.5 mass % from the mass of the absolutely dry pigment. The suspension is additionally dried and grinded. The technical result of the invention is the improved quality of the pigment as well as expansion of its field of application.

EFFECT: the invention ensures the improved quality of the pigment as well as expansion of its field of application.

2 tbl

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