The method of sizing paper, paper with glued surface and a sizing substance

 

(57) Abstract:

The method relates to paper sizing to obtain paper with glued surface with the use of sizing agents. A sizing agent for paper is a 2-oxetanone of multimer that at 35C is not in the solid state, in particular a mixture of multimers, in which at least 25 wt.% hydrocarbon substituents contain branched alkyl radicals, linear and branched alkeneamine radicals. These multimeric obtained using the reaction mixture of fatty acid and dicarboxylic acid containing a molar excess of dicarboxylic acid. The technical result is the production in alkaline conditions, high-grade paper. 3 S. and 61 C.p. f-crystals, 2 tab.

The invention relates to 2-oxetanone sizing agents, their preparation and application for paper sizing.

The number of high-grade paper made under alkaline conditions, is growing rapidly, aided by cost savings, the ability to use precipitated calcium carbonate (COC), a growing need for improved paper, gloss and an increasing trend towards the elimination of the wet part of managemeny to the sizing before processing or target application, in particular, the paper machine development with additives and paper for inkjet printers, paper for high-speed Photocopying, envelopes, letterheads and bond paper, including paper for computer printers. Due to the growing popularity of inkjet printing devices, an increasing attention is paid to the requirements for the sizing of paper, intended for this end use.

The most common sizing agents for high-grade paper made under alkaline conditions, are alchemistry anhydride (AA) and alkylbetaine aneurysm (AAA). A sizing agent of both types contain reactive functional groups that covalently bind with cellulose fiber and a hydrophobic tail portion, which is oriented from the fiber. The nature and orientation of these hydrophobic tail parts causes the fiber to repel water.

Technical sizing agent based on AA can be obtained by reaction of maleic anhydride with14-C18the olefin.

Technical AAA containing - lactonase ring, are prepared by the reaction of alkylbetaine, policendarlehen and/or stearic acid. Industrial applications are also other ketonovye dimers, such as ketonovy dimer on alkenilovyh basis (product Aquapel421 company Hercules Incorporated, Wilmington, pieces of Delaware, USA).

As substances for sizing paper pulp in tiled applications for patents Japan 168991/89 and 168992/89, which are included in the present description as the link described ketonovye multimer containing more than one-lactoovo rings. In applications it is said that ketonovye multimer show improved sizing ability in comparison with the previously used ketonovye the dimers, when they are used as substances for gluing in the mass introduced into the fibrous raw materials. Such ketonovye multimer prepared from a mixture of mono - and dicarboxylic acids.

In the application EP-A1-0629741 described mixture alkylating dimer with MultiTerm as a sizing substances for the manufacture of paper used in high-speed converting and copying and copying machines. Alkylbetaine multimer receive as a result of interaction molar excess monocarboxylic acid, as a rule, fatty acid, dicarboxylic acid. At 25oC these multimeric compounds nakhodyatsyaya processes, which is glued in weight alkyl - or alkynylamino dimeric and/or multimeric sizing agent. Preferred 2-oxetanone multimer obtained when the ratio between the fatty acid and the dicarboxylic acid ranges from 1:1 to 3.5:1.

Although glued paper, described in applications EP-A1-0629741 and EP-A2-0666368, exhibits superior performance properties when processing at high speed precision processing and duplicating and copying equipment, there is still a need for manufactured under alkaline conditions the paper, which is suitable for printing superior quality in inkjet printing devices. Criteria of operational properties of paper for ink-jet printing device when the print quality is higher, quite different from the criteria of operational properties of paper, intended for processing in high-speed accurate processing and duplicating and copying equipment, when the main concern are the problems associated with feeding in the car.

Quality inkjet printing with black ink can be evaluated using the following criteria: increment the black line, usually measured on the scale correspond to a wide fuzzy lines, usually due to capillary absorption into the paper; front optical density, a measure of density (degree of darkness) of the test section on the front side sealed paper, which is entirely sealed with black paint, and the optical density on the reverse side, the measure of the amount of dye, which penetrates through the paper to the reverse, unsealed sides of the paper.

Criteria print black paint is also applicable for the evaluation of printing colored inks in inkjet printing devices. In addition, the quality of printing colored inks can be estimated by the leakage of one color to another in case of contact printed different colors of the image, usually measured on a scale of 1-5, in which small figures indicate weak or no leakage of one color of paint to another, or mixing (required feature), and large values correspond to the leakage of one color to another in case of contact printed in different colors images. For minimal leakage of one color of paint in a different colour inkjet printing requires high quality paper, i.e. its ability to absorb and hold the ink, which is different from balano to raise a modification of the inkjet printing device or the paint composition; modification of paper pulp or paper manufacturing process and/or using additives introduced in the manufacture of paper. Due to high demand in the market for inkjet printers in the paper industry are striving to find means of improving the paper used for inkjet printing. The increased popularity of inkjet printing devices associated with the expectation by the consumer that the print quality should be commensurate with the high performance standards for laser printing devices, which are widely used in commercially available printing devices, providing a high-quality image.

Thus, the present invention was based on the task to get produced in alkaline conditions, high grade paper, to create an alkaline sizing agent, and to develop ways of sizing, this paper not only need to possess improved performance characteristics when working with it in accurate high-speed converting and copying and copying equipment, but also to achieve excellent print quality in inkjet printing devices, in particular in jet pacatiana.

One of the objects of the invention is a sizing substance, including 2-oxetanone of multimer that when the temperature of the 35oWith is not in the solid state and which is obtained from the reaction of a mixture of fatty acids and dicarboxylic acids, characterized by a molar excess of dicarboxylic acid. Such 2 - oxetanone multimer especially useful when used as a sizing substances, the most preferred as surface sizing agents (sometimes also called external sizing agents).

Another object of the invention is a method of sizing paper by surface sizing of paper sizing agent, including 2 - oxetanone of multimer that when the temperature of the 35oC is not in the solid state.

Another object of the invention is the surface of the paper, taped such 2-oxetanone multimeric sizing substances.

Proposed in the present invention, the method of surface sizing paper made under alkaline conditions, provides a degree of sizing made under alkaline conditions high-grade paper with glued surface is truinas print but also excellent performance properties in accurate high-speed converting and copying and copying equipment.

Occurring in the present description, the term "percent" or "%" in all cases, unless otherwise specified, in respect of the components or ingredients, tools, composition or mixture used as a measure of the mass fraction of a component or ingredient in terms of the mass of the enclosing means, the composition or mixture.

According to the present invention offers, first, a sizing substance, representing a multimeric sizing substance 2-oxetanone basis (referred to in the present description 2-oxetanone multimeric sizing substance or katenevym multimeric sizing substance) that, when 35oC is not in the solid state (which is not essentially crystalline, semi-crystalline or waxy solid, i.e., when heated, flows without releasing heat of fusion); secondly, the paper, the surface of which is processed by a sizing treatment using such a sizing agent, and, thirdly, the method of manufacturing sized paper using the connection in accordance with the present invention is in a liquid state at the 35oC, preferably at 25oC, and most preferably at 20oC (references to "liquid state" applies, obviously, to a sizing substance, and not the emulsion or another combination containing a sizing agent).

In a preferred embodiment, a multimeric sizing substance 2-oxetanone basis is characterized by inhomogeneities in the chemical structure of the side chains as hydrophobic components, i.e., chemical structure contains discontinuities, such as carbon-carbon double bond or side groups in one or more hydrocarbon chains (normal alkylbetaine dimers are characterized by homogeneity in the sense that they have saturated straight hydrocarbon chain).

In the preferred embodiment, surface sizing substance of the present invention is a 2 - oxetanone of multimer formulas (1)

< / BR>
in which n denotes an integer equal to at least 1, preferably from 1 to about 20, more preferably from about 1 to about 8 [when in the formula (1) n denotes 0, such a connection is called 2-oxetanone dimer or katenevym dimer]. Surface proclivity (1). Ketonovye multimeric mixture of the present invention is prepared from a mixture of fatty acid with a dicarboxylic acid in a molar ratio between the fatty acid and the dicarboxylic acid is from about 1:1 to about 1:5.

The preferred mixture of 2-oxetanone of multimers include regioisomers such multimeric compounds and the preferred average value of n ranges from about 1 to about 8, more preferably from more than about 1 to about 8, even more preferably from about 2 to about 6, with an average value from about 2 to about 4 are most preferred. As a consequence of the implementation of the method described below, upon receipt of multimeric a mixture of 2-oxetanone of multimers may also include some amount of 2 - oxetanone dimer, i.e., the component in the formula (I), n denotes 0.

By nature of the groups R and R" are essentially hydrophobic, they are acyclic, preferably a hydrocarbon group containing at least about 4 consecutive carbon atoms, and they may be the same or different. More preferred groups R and R" represent about 10-With

R' can refer to a branched, remotemachine, i.e., linear or alicyclic, i.e. containing ring, saturated or unsaturated hydrocarbon group, and in the preferred embodiment is a hydrocarbon group containing from about 1 to about 40 carbon atoms. More preferred values of R' is Rupp; in such cases, the preferred value of R' is remotemachine alkyl. In another embodiment, the preferred value of R', you can choose among about20-C40groups, and the most preferred among the approximately C28-C32groups; the preferred value of R' is branched or alicyclic group, more preferably FROM about20- C40group, and most preferably FROM about28-C32group.

When ketonovy of multimer prepare for interaction monobasic acid component with a dibasic acid component, as set out below, the group R' is usually derived dicarbonate acid reagent.

Preferred 2 - oxetanone of multimer is a mixture of 2-oxetanone of multimers, in particular a mixture of 2-oxetanone of multimers, in which at least about 25 wt.%, more preferably at least about 50 wt.% and most preferably not less than about 75 wt.% accounted for multimers containing hydrocarbon substituents with inhomogeneities, which can be a branched alkali, the linear alkenyl or does is provide improved operational characteristics of the printing, in the case of the final application in a typical process, inkjet printing, contain reactive 2-oxetanone group side and a hydrophobic hydrocarbon tail part. In this respect they resemble traditional sizing agent based on AAA, but, unlike sizing substances with saturated straight chains, residues of fatty acids used to obtain a sizing substances on the basis of conventional solid alkylating dimer or multimer, hydrocarbon chain one or both of the acid chlorides of fatty acids used to prepare the sizing substances of this class contains inhomogeneities in the chemical structure of the hydrocarbon side chains, such as carbon-carbon double bond and branch circuits. Due to such heterogeneity in the hydrocarbon side chains of these sizing agent at room or near the temperature, i.e. approximately 25oC are not in the solid state, and in the preferred embodiment, is a liquid.

2-oxetanone multimeric surface sizing agent of the present invention can be prepared from mixtures of fatty acids with dicarboxylic acid. Preferred examples of fatty acids include oleic (octadeca acid, and mixtures of these and/or other fatty acids. Preferred technically available fatty acids are liquid fatty acid Pamak-1, Pamak-131 and Pamolyn380 (a mixture of fatty acids supplied by Hercules Incorporated, Wilmington, pieces of Delaware, USA), which comprise mainly of oleic acid and linoleic acid. Other examples of fatty acids that can be used include unsaturated fatty acids: dolezelova, tetradecanoate (Mirandolina), octadecadienoate (linolelaidic), Aksenova (gadolinia), eicosatetraenoic (arachidonic acid), CIS-13-docosanoate (erucic), TRANS-13-docosanoate (brassicicola) and docosapentaenoic (kopandanova) acid, and mixtures of such fatty acids.

In a more preferred embodiment, the share of 2-oxetanone multimeric sizing agent obtained by the use of fatty acids of the above type containing discontinuities, such as unsaturated or side groups, have at least 25 wt.% a sizing agent, more preferably at least about 50 wt.% and most preferably not less than about 70 wt.%.

Dicarboxylic acids which can be used DGU acid and dodecadienol acid, and all of them are preferred; you can also use a mixture of dicarboxylic acids. In addition, it is possible to use dicarboxylic acids obtained by dimerization of unsaturated (monocarboxylic fatty acids, when in the preferred embodiment, the resulting dicarboxylic acid is a dicarboxylic24-C44acid, more preferably dicarboxylic32-C36the acid. In those cases, when the dicarboxylic acid is a dimer fatty acids, the presence of discontinuities in the resulting 2-oxetanone multimeric sizing substance contribute side groups and/or cyclic structure such dimers of fatty acids.

Ketonovye multimer of the present invention can determine the molar ratio between the fatty acid component and dicarbonate acid component used in obtaining ketonovyh of multimers. Chain length metanovogo multimeric oligomer, i.e., the value of p in the above formula depends on the molar ratio between the fatty acid and dicarboxylic acid used in obtaining multimer.

Typically, such ketonovye multimer are a mixture of ketonovyh multimer the EPA, although in accordance with the present invention necessary in the presence of such metanovogo dimer no. In a preferred embodiment, 2-oxetanone multimer of the present invention are mixtures, characterized by an average value of n is from about 1 to about 8, mostly from more than about 1 to about 8, more preferably from about 2 to about 6, and the average value of n is from about 2 to about 4 is preferred. The average value of n to a mixture of 2-oxetanone of multimers can be calculated molecular masses, a certain pressure chromatography, also called gel chromatography, i.e., using techniques well known to experts in the art, 2-oxetanone multimer characterized by a particular value of n, for example, equal to 3, it is possible to recover or select from mixtures ketonovyh of multimers with conventional separation techniques.

The preferred molar ratio between the fatty acid component and decarbonisation component in the reaction mixture of such components used for preparation of multimeric is from about 1:1 to approx the RNO 1:3. In a more preferred embodiment, the molar ratio between the fatty acid component and decarbonisation component should be such that provides the excess dibasic acid (decarbonisation connection) in comparison with the amount of monobasic acid (fatty acid) component. Preferred examples include 2-oxetanone multimer obtained from mixtures of Pamak-131 and dibasic acids selected from azelaic acid, sabatinovka acid, dodecadienol acids and their mixtures in which the molar ratio of monobasic acid dibasic acid is from about 1:1 to about 1:4.

In the case of use as surface sizing agents for the preferred manufactured under alkaline conditions high-grade paper, the preferred molar ratio between the fatty acid component (monobasic acid) and decarbonisation component (dibasic acid) is from about 1:1 to about 1:5, more preferred molar ratio is so, in which is provided a molar excess decarbonisation component, which is sustained fashion molar ratio of monobasic acid dibasic acid is from about 1:1.5 to about 1:4, most preferably approximately 1:2.

These surface sizing agent can be obtained by known methods (see , for example, EP-A2-666363, tiled application Japan 168991/89 and 168992/89, descriptions of which are included in the present description as references). In the first phase of a mixture of fatty acids with dicarboxylic acid using trichloride trivalent phosphorus or other conventional glorieuses agent receive the anhydrides of the acids. In another embodiment of this method the acid chlorides of the acids can be obtained from the fatty acid component and decarbonisation component separately or sequentially. Further, the anhydrides of the acids in the reaction mixture dehydrochlorinated in the presence of triethylamine or other suitable base to obtain 2-oxetanone multimeric mixture. Stable emulsions of these surface sizing substances can be prepared the same way as conventional emulsion AAA.

The surface sizing agent of the present invention is used in the form of their aqueous emulsions, which are usually prepared with the help of emulsifiers, such as cationic or basic derivatives of starch, carboxymethylcelluose the suspended colloids. The preferred emulsifier is cationic starch or cationic starch derivatives. The emulsifiers can be used in conjunction with surface-active substances, and the preferred surface-active agent is sodium lignosulfonate. Non-limiting examples of other surfactants which can optionally be used together with the emulsifier include surfactants on polyoxyethylene basis, such as ethoxylated sarbatorile, ethoxylated servicescreate, ethoxylated corbillard and ethoxylated sorbifolia-laurate.

Because you have a uniform dispersion of a sizing substances throughout the aquatic environment, which allows to achieve good results sizing, surface sizing substance use in the form of aqueous emulsions. Surface sizing agent in water emulsion is generally in the form of tiny particles surface sizing agent, each of which is surrounded by a stabilizing coating or layer of emulsifier, for example, casinoaction derived starch. Aqueous emulsion containing surface prochiral emulsifier, optional together with surface - active agent, and then with vigorous stirring enter surface sizing agent. In the presence of emulsifier for the preparation of a stable aqueous emulsion of a high-speed stirring or mechanical homogenizers typically becomes optional.

The amount of surface sizing agent used in the aqueous emulsion can be varied in a wide range, in particular from about 0.1 to about 50 wt.%, the most preferred content is about 5 wt.%. Typically, the emulsifier in the aqueous emulsion used in mass ratio with a sizing substance from about 1:40 to about 4:1, preferably from about 1:8 to about 1:1.

According to the invention serves as paper made in acidic or alkaline conditions the production of paper, preferably the latter, and the surface of which is coated multimeric sizing substance 2 - oxetanone basis, i.e. katenevym multimeric sizing substance containing 2-oxetanone functional group.

In a preferred embodiment, the invention further includes manufactured the ove, proposed in accordance with the invention and containing a water-soluble inorganic salt of an alkali metal, preferably Sodium chloride, and alum and precipitated calcium carbonate (COC). However, the paper of the present invention are often made without NaCI.

Paper with glued surface according to the present invention often can serve as a paper high grade, which usually requires sizing. This paper refers countless types of paper for printing of documents for various purposes, copy paper, paper envelopes, paper for offset printing, inkjet paper, and also production of precise processing, such as envelopes and paper machine development with additives.

Proposed by the present invention a surface sizing agent and method can also be applied to paper any other types, including paper, manufactured in acidic or alkaline conditions, paper production, and including, for example, without limitation, newsprint, cardboard, such as cardboard for packaging liquids, backing cardboard from recycled paper and, in addition, the paper for those areas of technology where necessary paper ruchnoj the glue, inkjet printing and offset printing.

Further according to the invention proposes a method of sizing paper by gluing the paper surface 2-oxetanone multimeric sizing agents according to the invention.

The surface sizing agent of the present invention is applied by known methods gluing surface (also called an external sizing) by applying on the outer surface of pre-cast paper. Surface sizing typically involves applying a sizing agent in the size press of the paper machine, which is a sizing substance is applied or served in a dosed quantity on the surface of the paper. In another embodiment, the gluing surface can be carried out by applying a sizing agent to the battery calender rolls by spraying or using other equipment coating. The paper on the glued surface, usually dried at elevated temperatures using known techniques of drying.

In the preferred embodiment, surface sizing substance of the present invention is applied to the surface of the paper, which is treated with a surface sizing, the number on membernet, taped 2-oxetanone multimeric sizing substance according to the present invention includes from about 0,0025 to about 0.5. %, more preferably from roughly 0.005 to about 0.2 wt.% and most preferably from about 0.01 to about 0.1 wt.% sizing substances on dry glued paper, in recalculation on weight of dry paper glued surface.

In combination with a sizing substance of the present invention, when it is served in the size press, you can use water or any aqueous solution of the additive introduced into the size press. The amount of starch applied in the size press may be from 0 to about 100 kg/t dry sized paper. Enter in the size press starch derivatives, which are suitable for use in conjunction with a sizing substance of the present invention include ethyl starch, oxidized starch, starch modified with persulfate ammonium starch, modified enzymes, cationic starch, etc.

Application of 2 - oxetanone multimeric sizing agent of the present invention in a sizing press or other means of surface is to alsowhat adhesive for gluing in the mass. However, if necessary you can apply adhesive for gluing in the mass. In the case of using adhesive for gluing in the mass of the preferred amount of such a substance for paper sizing in the mass according to the present invention is at least about 0.05 kg/t (0.005 wt%), more preferably at least about 0.25 kg/t of 0.025 wt.%), and most preferably not less than about 0.5 kg/t (0,05 wt.%), all quantities are expressed in terms of dry weight sized paper. As adhesives for gluing in the weight you can use any normal substance for paper sizing, and the preferred adhesive for gluing in the mass include alkylbetaine dimer, alkylcatechols of multimer, alkenylamine dimer, alkenylamine of multimer, alilandry anhydride, alchemistry anhydride, rosin, and mixtures thereof. In addition, adhesive for gluing in mass can be used in combination with paper, prepared at neutral pH or acidic conditions, and it may be produced in the acid conditions of the paper which is coated with rosin.

Although in the preferred embodiment, 2-oxetanone multimer on nastojashemu adhesives for paper sizing in mass.

Below the invention is explained in more detail with specific examples, not limiting its scope.

Experimental methods

2-oxetanone sizing agent, including multimer, were prepared by methods which are usually used for technical alkylating dimers (AKD), i.e., the anhydrides of the acids prepared from a mixture of fatty acids with dicarboxylic acid using conventional glorieuses agent and the acid chlorides were dehydrochlorinated in the presence of reasonable grounds.

A common method of obtaining 2-oxetanone product in laboratory scale using monocarboxylic fatty acid and dicarboxylic acid such as azelaic acid or dimer fatty acid, is the following. The molar ratio of monocarboxylic fatty acid component and dicarboxylic acid component is selected depending on the necessity of domination or metanovogo dimer or metanovogo multimer. If ketonovyh of multimers with an average value of n is from about 1 to 6, the preferred molar ratio of monocarboxylic fatty acid and the dicarboxylic acid ranges from about 1:1 to 1:4.

Girocollo the 70oC. Decarbonisation component, if it is in a liquid state, is added to the reactor together with the fatty acid or, if it is in the solid state, it is added gradually with stirring, resulting in a mixture of both components. Then the mixture of both components glorious at a temperature of approximately 65-70oC trichloride phosphorus by a gradual introduction of PCl3as glorieuses agent for 15-30 minutes or longer. After entering PCl3chlorinated reaction product is stirred for another 15 min and then let it settle. From the bottom of the reactor is drained of phosphorous acid, which are formed as a by-product of the chlorination reaction, and then from the reaction product by evaporation in a vacuum to remove the excess reagent PCl3.

Proof that in the reaction product obtained according to this method, contains the resulting acid chlorides of the acids can be easily obtained infrared (IR) spectral analysis for the presence in the spectrum characteristic of the acid chlorides of the acids absorption band at 1800 cm-1. The technique of IR spectral analysis and their equipment is well known and technically available iwago product is carried out in the reactor, which creates a nitrogen atmosphere. In the reactor with stirring 2-7 wt.h. 1,2-dichloropropane as solvent injected approximately 1 wt.h. triethylamine grounds that, as a rule, amounts to 5% molar excess of triethylamine, and both components are heated to a temperature of about 30-40oC. In a reactor with stirring slowly for about 40 minutes add about 1-3 hours of carboxylic acid as the reaction product in about half of the amount of 1,2-dichloropropane while maintaining a temperature of about 40-45oC. for Approximately two hours after the start of addition of the carboxylic acid as the reaction product of the completion of the reaction dehydrochlorinating confirmed by infrared spectrogram, and if at 1800 cm-1detected characteristic of the acid chlorides of the acids absorption band, you can enter the additional amount of triethylamine, which is required to complete the reaction dehydrocorydaline.

Upon completion of the reaction dehydrochlorinating the reaction mixture is filtered to remove as a by-product cleaners containing hydrochloride salt of triethylamine, formed during the reaction dehydrocorydaline. Then vacuum evaporated 1,2-di is mine removed by filtration. The isolated product is a mixture, which, depending on the specific molar ratio between the fatty acid and dicarboxylic acid used as starting reagents, contains mainly 2-oxetanone of multimer or dimer. For use as a sizing agent is prepared emulsion 2 - oxetanone product.

Emulsion 2-oxetanone sizing agent, including multimeric emulsion, prepared in accordance with U.S. patent 4317756, which is included in the present description by reference, in particular with specific reference to the example 5 of the description to this patent.

As a sizing agent emulsion metanovogo multimer (or dimer) can be prepared by mixing 880 including water, 60 hours of cationic corn-derived starch and 10 o'clock ligninsulfonate sodium. The addition of sulfuric acid the pH of the mixture adjusted to about 3.5. The mixture is maintained at 90-95oC for about one hour. Then the mixture was added water in an amount which is sufficient for the formation of mixtures of a total weight of 1750 hours In this mixture is mixed with about 240 hours metanovogo multimer (or dimer) together with 2.4 hours thiadiazine concernsfor under pressure of 3000 pounds/inch2. Homogenized product is diluted with water and bring the contents dry metanovogo multimer (or dimer) to range from about 6 to about 30%, receiving emulsion sizing agent. It should be borne in mind that the specific content of dry matter in the emulsion sizing agent not decisive.

Methods of making paper, carried out in the manufacture of paper for evaluation of surface sizing, adhesion electrophotographic developer and quality of inkjet printing, consisted in the following. The paper produced in the pilot paper machine at Western Michigan University. The paper weight was equal to 20 lb/1300 ft2(9.1 kg/121 m2).

For making up paper pulp, reaching for the manufacture of paper for printing of documents for various purposes, wood pulp (three parts of Kraft pulp from hardwood and one piece of Kraft pulp from coniferous wood) was grinded using a double disk refiner to 425 ml of degree of milling on the canadian standard instrument (PSC). Before adding in wood pulp filler (12% precipitated calcium carbonate of average particle size) using match /million) and hardness (100 h/m) paper pulp.

The wet part is characterized by the following conditions: pH subgrid pit of 7.6 to 8.0, the temperature of the 49oC and total alkalinity 180 hours/million

In the wet part was added the following materials: 12% precipitated calcium carbonate in the first metal pool, 0.50% is derived cationic starch, substituted Quaternary ammonium at the output of the first metal pool, 0.25% of alum in place a discharge valve of the second metal pool and adhesive for gluing in the mass of the valve seat of the second metal bar.

As adhesives for gluing in the mass introduced into the wet parts, used technically available alkenylamine dimer sizing agent for paper, derived from fatty acid feedstocks, including mainly oleic and linoleic acid, and it was used in three different quantities: the 0.1, 0.125 and 0.15 per cent, and all quantities listed in mass% calculated on the dry weight of the paper composition. The temperature of the mass in the pan for subgrid water and pressure drawer supported on the 49oC (120oF).

Gauge pressure in the drying machine was set at 40 pounds/inch2(207 cm RT.article winding [77 ft/min (23 m/min)]. Before glueing the pressure in the sample of paper torn from an edge of the sheet, test method company Hercules (IPG) determined the degree of sizing. Test method the company Hercules (IPG) is a standard industry test for determining the degree of sizing. In this method, using an aqueous solution of the dye as a penetrating agent, which allows the optical path to determine the front of the liquid as it advances through the sheet. The instrument measures the time required for the fall of the reflectivity of the surface of the sheet not in contact with the penetrating agent to the specified level as a percentage of its original level. In all cases, unless otherwise stated, all data definitions IPG presents how the results of the measurement of time in seconds to reach 80% reflectivity when using 1% paints based on formic acid in a mixture with Naftowy green dye (test paint N 2 company Hercules). Use this paint on the basis of formic acid creates more stringent test conditions than in the case of neutral colors, and tends to reduce the time of testing. Higher values of IPG better lower. Treb is achene "IPG for aging in vivo was determined seven days after the paper sizing.

In the size press (66oC/150oF, pH 8) was administered approximately 50 kg/t of oxidized corn starch and 2.5 kg/t of NaCI. In the size press was also added surfactant in the amounts indicated in the following examples. The pressure of the calender and humidity at the wound regulated so that when the winding of the smoothness index in Sheffield was 150 units of flow (flow units) (column N 2, felt side up).

Example 1

This example describes the preparation of a mixture of 2-oxetanone multimeric compounds from a mixture of fatty acids with dicarboxylic acid in a molar ratio between fatty acids and dicarboxylic acid 1:2. In example 1A dicarboxylic acid served WITH dicarboxylic36acid, as in example 1B as the dicarboxylic acid used azelaic acid.

Chlorination of the mixture of fatty acids and dicarboxylic acids were carried out in 500-ml glass reactor with jacket, equipped with a refrigerator, drip funnel and devices for applying current of nitrogen, which was purged with gaseous nitrogen (prior to Assembly of the device each glass element was dried in a drying Cabinet at 105oC). Stream razoobrazny and cooled at a constant current of nitrogen.

The dehydrochlorination chloranhydride reaction product were carried out in 1-liter glass reactor with jacket, equipped with a refrigerator, drip funnel and devices for applying current of nitrogen, which was purged with gaseous nitrogen (prior to Assembly of the device each glass element was dried in a drying Cabinet at 105oC). Initially, the reactor was heated to 105oC jet air dryer and cooled at a constant current of nitrogen.

Example 1A: Chlorination of fatty acids and dicarboxylic36acid was carried out as follows. After cooling, 500 ml reactor to room temperature in the reactor was introduced to 87.8 g (0,31 mole) of a mixture of fatty acids Pamak-131 (Hercules Incorporated, Wilmington, pieces of Delaware, USA) and 353,1 g (of 0.62 mol) of dicarboxylic36acid Unidyme- 14 (company Union Camp Corp. , Wayan, PCs, new Jersey, USA). At this stage mode purge of the reactor current of nitrogen gas was replaced by the regime of static nitrogen atmosphere, i.e., the supply current of nitrogen gas was stopped. Next, the reactor containing two liquid components, was heated with a bath with circulating mineral oil, which maintained the temperature of the 70oC. achievement of the B>3(1,574 g/ml, with tKip76oC, the firm Aldrich Chemical Co. , Inc. , Milwaukee, PCs Visconti, USA). 've seen tremendous selection HCl, especially in the beginning add PCl3but noted a weak increase of temperature or lack of it. After 15 min after the addition of the PCl3the stirring was stopped. After 10-minute settling from the bottom of the reactor was poured and 29.9 g of phosphorous acid, a by-product of the chlorination reaction. Over the next four hours every hour remove small amounts of phosphorous acid, and the total number of remote phosphor acid was 35,4, At the end of the roton evaporator (under the residual pressure of the vacuum pump, 60oC) for 2 hours to remove excess arereasonable PCl3. As the reaction product was isolated 453,7 g of the acid chlorides of the acids with the release of 97,9%. IR spectral analysis of isolated reaction product showed the presence of characteristic acid chlorides acid absorption band at 1800 cm-1.

The reaction dihydrochloride was carried out as follows. After cooling, 1-liter reactor to room temperature in the reactor was injected 440 ml of 1,2-dichloropropane solvent (1,156 g/ml, the, with tKip88,8oC, the firm Aldrich Chemical Co., Inc., Milwaukee, PCs Wisconsin, USA), included a stirrer (150 rpm) and using baths with curculioninae water contents of the reactor were heated to 30oC. At this point, the mode of feed to the reactor current of nitrogen gas was replaced by the regime of maintaining a nitrogen atmosphere. Further, in the addition funnel with 110 ml of 1,2-dichloropropane as aliquots of the reaction product was introduced 235,4 g of the acid chlorides of the acids. The contents of the dropping funnel slowly over 40 min was added to the reactor. The rotation speed of the stirrer, the temperature of the bath with circulating water and the speed of adding chlorohydric acid as the reaction product was regulated in such a way as to suppress the exothermic effect and maintain the temperature of the reaction mixture in the range of 40-45oC. During the operation of adding the mixer rotation speed is gradually increased from 150 to 400 rpm Over two hours after the start of the addition the reaction mixture was checked for the presence of acid anhydrides IR spectral analysis. On completion of the reaction dehydrochlorinating pointed out the lack of observed absorption band at 1800 cm-1characteristic of the acid chlorides of the acids. If you need to Sovershenstvovanie the reaction mixture was cooled to room temperature (approximately 25oC) and filtered using a Buchner funnel to remove cleaners containing hydrochloride salt of triethylamine, which was formed as a side product of the reaction. Then using a rotary evaporator (vacuum pump, 60oC) was deleted about half contained in the filtrate 1,2-dichloropropane solvent. The reaction product was filtered a second time to remove the additional number of cleaners containing hydrochloride salt of triethylamine, which precipitated during the evaporation of 1,2-dichloropropane. Then in a rotary evaporator (vacuum pump, 60oC, three hours) was removed, the residue of 1,2 - dichloropropane. After the reaction product was filtered a third time, removing any remaining cleaners containing hydrochloride salt of triethylamine. The total product yield was 137 g (2 - oxetanone multimeric material, 65%). At 25oC the product was a liquid, and analysis gel chromatography showed that the average value of n mixture ketonovyh of multimers was about 4.

Example 1B: Chlorination fatty acid and azelaic dicarboxylic acid was carried out as follows. After cooling, 500 ml reactor to room temperature in the reactor was introduced 140.0 g (of 0.50 mole) smery 70oC. At this point, the mode of feed to the reactor current of nitrogen gas was replaced by the regime of maintaining a nitrogen atmosphere. Next to the reactor with vigorous stirring (250 rpm) for 3 min was administered to 181 g (1.0 mol) of a mixture of 85% azelaic acid, comprising 15% of other dicarboxylic acids with chains of different lengths (product E-1110, Department Emery Group company Henkel Corporation, Gulf mills, PCs PA, USA). In the reactor the solid decarbonisation component formed with a liquid fatty acid component of the dense dispersion during the addition the temperature dropped about 10oC. After the reactants temperature of 70oC in the addition funnel was loaded and within 30 min the mixture was added 108 ml PCIg (1,574 g/ml, with tKip76oC, the firm Aldrich Chemical Co., Inc., Milwaukee, PCs Wisconsin, USA). 've seen tremendous selection HCl, especially in the beginning add PCl3but noted a weak increase of temperature or lack of it. While adding PCI3dispersion decarbonisation component was dissolved. After 15 min after the addition of the PCl3the stirring was stopped. After 10-minute settling from the bottom of the reactor was poured and 70.8 g of phosphorous acid, a by-product of Realit, the total number of remote phosphor acids amounted to 71.9 g (104% of theoretically possible amount). At the end in a rotary evaporator (under the residual pressure of the vacuum pump, 60oC) for 2 h, removed the excess unreacted PCl3. As the reaction product was isolated 349,6 g of the acid chlorides of the acids with the release of 93%. IR spectral analysis of isolated reaction product showed the presence of characteristic acid chlorides acid absorption band at 1800 cm-1weak side strip, which is observed at 1710 cm-1.

The reaction dihydrochloride was carried out as follows. After cooling, 1-liter reactor to room temperature in the reactor were introduced 500 ml of 1,2 - dichloropropane solvent (1,156 g/ml, with tKip95-96oC, the firm Fluca Chemical Corp. , Ronkonkoma, PCs, new York, USA) and 286 ml (2,05 mole) of triethylamine (0,726 g/ml, with tKip88,8oC, the firm Aldrich Chemical Co., Inc., Milwaukee, PCs Wisconsin, USA), included a stirrer (150 rpm) and using bath with circulating water contents of the reactor were heated to 40oC. At this point, the mode of feed to the reactor current of nitrogen gas was replaced by the regime of maintaining a nitrogen atmosphere. Later in drip voranc is from. The contents of the dropping funnel slowly over 40 min was added to the reactor. The rotation speed of the stirrer, the temperature of the bath with circulating water and the speed of addition of the acid chlorides of the acids as the reaction product was regulated in such a way as to suppress the exothermic effect and maintain the temperature of the reaction mixture in the range of 40-45oC. During the operation of adding the mixer rotation speed is gradually increased from 150 to 400 rpm After 2 h after the start of the addition the reaction mixture was checked for the presence of acid anhydrides IR spectral analysis. On completion of the reaction dehydrochlorinating pointed out the lack of observed absorption band at 1800 cm-1characteristic of the acid chlorides of the acids, although the results of these observations can be supplemented by the presence of absorption bands at 1815 cm-1characteristic of the acid chlorides of the acids. If necessary to complete this reaction, you can add an additional amount of triethylamine.

Upon completion of the reaction dehydrochlorinating the reaction mixture was cooled to room temperature (approximately 25oC) and filtered using a Buchner funnel to remove cleaners containing hydrochloride salt of triethyl is Ino 25oC, re-suspended in 150 ml of 1,2-dichloropropane order to extract all dihydrochloride the reaction product is captured by these salts, and filtered a second time. The filtrates were combined and using a rotary evaporator (vacuum pump, 60oC) was deleted about half contained in the filtrate 1,2-dichloropropane solvent. The reaction product was again filtered to remove additional number of cleaners containing hydrochloride salt of triethylamine, which precipitated during the evaporation of 1,2 - dichloropropane. Then in a rotary evaporator (vacuum pump, 60oC, three hours) was removed, the residue of 1,2-dichloropropane. The overall yield of the reaction product was 175 g (2-oxetanone multimeric material, 82%). At 25oC the product was a liquid, and analysis

gel chromatography showed that the average value of n mixture ketonovyh of multimers was about 4.

Example 2

This example describes the use of three ketonovyh of multimers of the present invention as surface sizing agents.

Using mixtures of fatty acids, product Pamak-131 with azelaic acid under the following solaryjnych ketonovyh multimer was prepared using a molar excess of dibasic acid (decarbonisation component) relative amounts of monobasic acids (fatty acid component). The method used in obtaining ketonovyh multimeric mixtures was similar to that described in example 1. For sizing these ketonovye multimeric mixture used in the form of aqueous emulsions prepared as described in the Methods section of experiment."

For comparison as a control for three different values of the content listed in table. 1, used two surface sizing agent: alkenylamine dimer obtained from a mixture of linoleic and oleic acids (as described in the Methods section of experiment), and a copolymer of styrene and maleic anhydride.

Four ketonovyh multimer was introduced in the size press in the following quantities: 0,005, of 0.015 and 0.025 wt.% in terms of the dry weight of the sized paper.

In addition to surface sizing agents used in the sizing press, were also used adhesive for gluing in weight: alkenylamine dimer (as described above) was added to the wet end of the papermaking machine at a flow rate of 0.1-0.15 wt.% in terms of the dry weight of the sized paper.

The results of the evaluation of such surface sizing are given in table.1. The effectiveness of the sizing bretado company Hercules, conducted in three stages: before size press, when the winding after the size press and after exposure in vivo for about seven days.

In all four tested ketonovyh of multimeric received substantial improvement in the quality of sizing if the wound after treatment of the surface sizing in sizing press with all the estimated values of the content.

For three ketonovyh of multimers (when the ratio between the fatty acid and dibasic acid 2,5:1, 1:1 and 1:2) noted differences in the effectiveness of sizing, namely, when the content of 0.005 wt.%, when it was comparable with the efficiency in the case of the control alkenylamine dimeric surface sizing agent (0.005 wt.%) and a copolymer of styrene with maleic anhydride as a control surface sizing agent (at 0.05 wt. %). The same three ketonovyh multimer when the content of 0.025 wt.% allow to achieve efficiency, which is comparable with the efficiency in the case of the control alkenylamine dimer sizing agent (of 0.025 wt. %) and a copolymer of styrene with maleic anhydride as a control sizing agent (with 0.15 wt.%). Ketonovy , what about nevertheless a noticeable improvement in the efficiency of sizing if the wound.

The results obtained for the first three ketonovyh of multimers [when the ratio between the fatty acid (LC) and dibasic acid (DK) of 2.5:1, 1:1 and 1: 2] , pointed to the fact that the used amounts of these ketonovye multimeric surface sizing agent in 6-10 times more efficient than conventional surface sizing agent, a copolymer of styrene and maleic anhydride, used as a control.

Example 3

In this example, the paper on the glued surface, obtained using four ketonovyh of multimers described in example 2, were evaluated for quality inkjet printing using an inkjet printer Deskjetmodel 560C Hewlett Packard. This was determined by two qualitative characteristics of inkjet printing: increment printed in black ink line and the optical density of the print when printing in black ink. The results are given in two columns under the title "Quality inkjet printing table. 1.

Increment printed in black ink line was determined by visual assessment of increment lines flowing paint or capillaroscopy, numbered from 1 to 10, where 1 corresponds to the best and 10 being the worst quality. The results are summarized in the column entitled "Increment printed in black ink lines in table 1.

At least the content metanovogo multimeric surface sizing agent all four ketonovyh multimer provided the increment printed in black ink line, on which the paper was at least comparable to the paper surface, glued known surface sizing substance at a significantly higher consumption of a copolymer of styrene and maleic anhydride as a surface sizing agent.

When the highest content metanovogo multimeric surface sizing agent was provided increment printed in black ink line, approximately equivalent achieved in the case of known surface sizing agent, but this is the last used with a significantly higher consumption than Kamenovo multimeric sizing agent.

Front optical density of the print obtained with the use of black paint, was determined by measuring optical is the real part, i.e. sealed sides of the paper. Target high values of optical density, since they indicate good quality, saturation, print in black ink. The results presented in the penultimate column of the table.1, show that the use of ketonovyh multimeric surface sizing substances usually provides satisfactory values of optical density in comparison with that obtained by using a copolymer of styrene with maleic anhydride as a surface sizing agent used with a much larger flow, especially with the increased consumption of adhesive for gluing in the mass applied simultaneously with katenevym multimeric surface sizing agent.

The results presented in table.1, show that all four ketonovyh multimeric surface sizing agent that has been evaluated in economic terms are effective substitutes known polymer surface sizing substances such as a copolymer of styrene with maleic anhydride, in the processing of paper those varieties that meet the requirements of high quality inkjet printing.

Ketonovy of multimer was prepared using a reaction mixture containing fatty acids Pamak- 131 and azelaic acid in a molar ratio of 1:2. The method carried out upon receipt of this metanovogo multimer, was identical to that described in example 1.

For comparison were evaluated by two known surface sizing agent. The first was a paper which is coated with a copolymer of styrene and maleic anhydride as a sizing agent to be added at the size press with two consumption values: 0.05 and 0.15 wt.% in terms of the dry weight of the sized paper. The use of such known polymeric sizing substances achieve good adhesion electrophotographic developer, and in this example, they were used as standards.

The second surface sizing tool, used for comparative purposes, was a paper, the surface of which was taped alkenylamine dimer sizing agent, obtained from a mixture of linoleic and oleic acids, and this sizing substances the paper. For the evaluation of used paper, not containing any surface sizing agent.

As an additive in the wet end of the paper machine during the process as a surface sizing agent at two values of flow rate, 0.1 and 0.15 wt.% in terms of the dry weight of the sized paper was also used alkylenedioxy dimer that serves as an adhesive for gluing in mass.

Adhesion electrophotographic developer glued to the paper were estimated using the method of optical density, the implementation of which was determined by the difference of optical density of the black electrophotographic developer, photocopied on the front surface of paper and the same black photocopied electrophotographic developer in the presence of cracks obtained by folding paper by folding and deployment). Poor adhesion electrophotographic developer, as a rule, leads to the formation during the folding of cracks greater width. Thus, the difference between the results of two measurements of optical density is large. Small values of the difference of optical density indicate horii electrophotographic developer is given in the last column.

As expected, in the case of paper, glued surface of the polymer (a copolymer of styrene and maleic anhydride) sizing substance, provided good adhesion electrophotographic developer, and paper, the surface of which was taped alkenylamine dimer showed a weaker adhesion electrophotographic developer. The increase in the content of adhesives for gluing in the mass in combination with the surface sizing agent was accompanied by a trend towards the weakening of the adhesion electrophotographic developer.

Use metanovogo multimer as a surface sizing agent led to disparate results, but in General satisfactory adhesion electrophotographic developer with very little difference adhesion electrophotographic developer from that which was reached in the case of untreated control material.

If based on these results, ketonovye multimer you can count on a more effective sizing agent compared to conventional polymer surface sizing agents and without any problems with adhesion of electrographic the P CLASS="ptx2">

Example 5

This example describes the use of two 2-oxetanone of multimers of the present invention as surface sizing agents. Both alkenylboronic multimer were obtained using mixtures of unsaturated fatty acids (monocarboxylic acid and dicarboxylic acid in which the molar ratio between the fatty acid component and decarbonisation component was 1:2. First ketonovy of multimer received from a mixture of fatty acids Pamak- 131 with azelaic acid at molar ratio of 1:2, and the second ketonovy of multimer received from a mixture of fatty acids Pamak- 131 with dimer fatty36acid (dicarboxylic acid) is also at a molar ratio of 1: 2. The method is carried out to obtain ketonovyh multimeric mixtures was similar to that described in example 1. These ketonovye multimeric mixture used for sizing in the form of aqueous emulsions prepared as described under "experimental Methods".

In the sizing press has been evaluated both ketonovyh multimeric sizing agent at four different values of the flow: of 0.0125, of 0.025, 0.05 and 0.10 wt.% in terms of dry weight proclaimeth, as shown in the table. 2: alkenylamine dimer obtained from a mixture of linoleic and oleic acids (as described above in the Methods section of experiment) and a copolymer of styrene and maleic anhydride.

Conducted three additional second control experiment without the use of a surface sizing agent at all (only with an adhesive for gluing in the mass, as described below).

Surface sizing agent was evaluated at four different values: alkylbetaine dimer sizing agent in quantities of 0.0125, of 0.025, 0.05 and 0.10 wt. % calculated on the dry weight of the sized paper (these amounts were identical to those in which he introduced two ketonovyh multimeric sizing agent) and a copolymer of styrene and maleic anhydride in amounts of 0.05, of 0.10, 0.15 and 0.20 wt.% in terms of the dry weight of the sized paper. In these latter cases, the content of the sizing agent was higher than when using other sizing agents, but nevertheless it is a typical number, which add well-known technical surface sizing agent.

In addition to surface ore, as adhesives for gluing in the mass were also used alkenylamine dimer (as described above), which was introduced into the wet part of a paper machine with the values of the flow rate of 0.1 to 0.15 wt.% in terms of the dry weight of the sized paper.

The results of the evaluation of surface sizing are given in table.2. The effectiveness of the sizing processed paper that is listed in this table were determined from the results of tests by method of the company Hercules in three stages: before size press, when the winding after the size press and after exposure in vivo for about seven days.

The use of both alkenylboronic multimeric surface sizing substances provided significant improvement sizing for all values of consumption, according to its assessment, both at the wound, and after aging for seven days, when compared to the performance taped in the mass of paper which has not been processed surface sizing. The results of IPG sizing were comparable with those obtained in cases alkenylamine dimeric surface sizing agent and a copolymer of styrene with maleic anhydride (SMA) as the surface of isovale added in much larger quantities, than ketonovye multimeric and ketonovye dimeric surface sizing agent, these results indicate that alkenylamine multimeric surface sizing agent to be more effective surface sizing agents than the SMA copolymer as a sizing agent. As shown in the examples below, the use of alkenylboronic of multimers of the present invention allows to achieve quality inkjet printing with black paint, of comparable quality in cases of SMA copolymer as a sizing agent and alkenylamine dimer sizing agent, and significantly improved results adhesion electrophotographic developer in comparison with those achieved using alkanolamines surface sizing agent.

Example 6

In this example, the paper surface sizing both ketonovye multimarine described in example 5 was evaluated for quality inkjet printing with black ink using an inkjet printer Deskjetmodel S Hewlett Packard. This was determined by two qualitative characteristics of inkjet printing: the increment of otpechatan the Ali described in example 5, the paper surface, taped alkenylamine dimer and a copolymer of SMA, as well as paper not glued surface. The results are given in two columns under the title "Quality inkjet printing table. 2.

Increment printed in black ink line was determined by visual assessment of increment lines flowing paint or capillary absorption, i.e. by spreading the ink over the edges of the printed line as set forth in example 3. Qualitative results are shown in the column entitled "Increment printed in black ink lines in the table. 2.

The results presented in table. 2, show no appreciable difference between the results of the evaluation of all the paper samples with the glued surface for increment printed in black ink lines. Thus, the use of both ketonovyh of multimeric the present invention achieves the print quality, as it was assessed by the increment printed in black ink line, which is equivalent achieved using well-known surface sizing substances that are added in the quantities in which they investigated, but the need for 2-oxetanone multimeric size matter when it beleskey density of the imprint obtained using black paint, was determined as described in example 3; the target is the high values of optical density, since they indicate good quality, saturation, print in black ink. The results presented in the penultimate column of the table. 2, show that the use of ketonovyh multimeric surface sizing substances usually achieves values of optical density, at least comparable with that achievable using the SMA copolymer as a surface sizing agent, all used during the test quantities. The surface of the paper, taped alkenylamine multibeam obtained with the use of azelaic acid as a dicarboxylic acid, achieve values of optical density of the print when applying black paint, comparable with values in the case of paper with a surface which is coated with a copolymer of MCA, and comparable with the values in the case of a paper surface, glued alkenylamine dimer in the interval added the estimated quantities. As before, to achieve the same level of optical density, which is possible using iwaisako substances.

The results presented in table. 2, show that ketonovye multimeric surface sizing agent that has been evaluated in economic terms are effective substitutes known polymer surface sizing substances such as a copolymer of styrene with maleic anhydride, in the processing of paper those varieties that meet the requirements of high quality inkjet printing.

Example 7

In this example, the paper surface sizing both ketonovye multimarine described in example 5 was evaluated for adhesion electrophotographic developer. Similarly evaluated as described in example 5, the paper surface, glued alkenylamine dimer and a copolymer of SMA, as well as paper not glued surface. The methods that were used to evaluate the adhesion electrophotographic developer to the paper, were identical to those described previously in example 4. The results are summarized in the last column of the table. 2, which shows the values of adhesion electrophotographic developer. As described in example 4, low values indicate good adhesion electrophotographic developer.

The surface of the paper, taped alkenylamine d is richest, in which they investigated were significantly worse achieved on paper with a surface which is coated with a copolymer of MCA, or achieved on the paper surface, glued both alkenylamine multimarine of the present invention. Adhesion electrophotographic developer to the surface of the paper which is coated with a copolymer of MCA or both alkenylamine multimarine as surface sizing agents, was in General comparable with that achieved in the case of paper, not containing any surface sizing agent (but including an adhesive for gluing in the mass, as all the samples of paper surface sizing).

The result of applying both alkenylboronic of multimers as surface sizing agents in General was satisfactory adhesion electrophotographic developer, essentially similar to that which was achieved in the case of paper with a surface which is coated with a copolymer of MCA, or the control untreated samples. If based on these results, alkenylamine multimer of the present invention it is possible to count on a more effective sizing agent compared to conventional hollow developer, which is associated with the use of traditional ketonovyh dimer sizing agents.

In the present description, the examples should not be construed as limiting the scope of invention, as they are presented only to illustrate certain specific embodiments of the invention. In these options you can make any modifications and changes without going beyond the scope of the present invention, which is defined by the attached claims.

1. The method of sizing paper which comprises a surface sizing of paper sizing agent, representing a 2-oxetanone multimer or a mixture of 2-oxetanone of multimers, which is fluid at the 35oC and obtained using the reaction mixture of fatty acid and dicarboxylic acid containing a molar excess of dicarboxylic acid.

2. The method according to p. 1, in which at least 25 wt.% a mixture of 2-oxetanone of multimeric accounted for 2-oxetanone of multimers containing hydrocarbon substituents with inhomogeneities, and these hydrocarbon substituents with inhomogeneities is chosen from the group comprising branched alkyl, linear alkalise the formula I

< / BR>
in which n is an integer equal to at least 1;

R and R" independently from each other - acyclic carbon radicals containing at least about 4 carbon atoms;

R' is a branched, linear or alicyclic hydrocarbon radical containing from about 1 to about 40 carbon atoms.

4. The method according to p. 3, wherein in the formula (I), n denotes an integer from 1 to about 20.

5. The method according to p. 3, wherein in the formula (I), n denotes an integer from 1 to about 8.

6. The method according to p. 3, in which the sizing agent a mixture of 2-oxetanone of multimeric includes approximately at least 25 wt.% 2-oxetanone of multimers containing heterogeneity in R, R" or both radicals, where these variations are selected from the group comprising branched alkyl, linear alkeneamine and branched alkeneamine radicals.

7. The method according to p. 3, wherein in the formula (I) R and R" independently from each other represent a branched alkyl, linear alkyl, branched alkeneamine or linear alkeneamine radicals.

8. The method according to p. 7, in which in the formula (I) each of the radicals R and R" contains from about 10 to about 20 carbon whom B>12hydrocarbon and C20-C40hydrocarbon radicals.

10. The method according to p. 9, in which in the formula (I) R' is branched or alicyclic hydrocarbon radical containing from about 28 to about 32 carbon atoms.

11. The method according to p. 9, in which in the formula (I) R' is a linear alkyl containing from about 4 to about 8 carbon atoms.

12. The method according to p. 1, which includes obtaining a mixture of 2-oxetanone of multimers from a mixture of unsaturated fatty acids with dicarboxylic acid.

13. The method according to p. 12, in which the fatty acid is chosen from the group comprising oleic, linoleic, linolenic, palmitoleic acid, and mixtures thereof.

14. The method according to p. 12, in which the dicarboxylic acid is chosen from the group comprising azelaic, Sabatino, dodecadienol acid, dimer fatty acids, and mixtures thereof.

15. The method according to p. 13, in which the dicarboxylic acid is chosen from the group comprising azelaic, Sabatino, dodecadienol acid, dimer fatty acids, and mixtures thereof.

16. The method according to p. 1 which further includes the introduction of a surface sizing agent in the sizing press in the paper manufacturing process.

17. JV is the SS number, sufficient to achieve the content of the sizing agent is at least approximately 0,0025 wt.% in terms of the dry weight of the finished coated paper.

18. The method according to p. 1 which further includes the introduction of adhesive for gluing in the mass paper weight which can be made into paper.

19. The method according to p. 18, in which the adhesive for gluing in the mass is chosen from the group comprising alkylcatechols dimer, alkylcatechols of multimer, alkenylamine dimer, alkenylamine of multimer, alilandry anhydride, alchemistry anhydride, rosin, and mixtures thereof.

20. The method according to any of paragraphs.1 to 19, which includes obtaining 2-oxetanone multimer or a mixture of 2-oxetanone of multimers from the reaction mixture of fatty acid and dicarboxylic acid, dicarboxylic acid in such molar excess, in which the molar ratio of fatty and dicarboxylic acids is about 1:5.

21. The method according to p. 20, in which the molar ratio is from about 1:1.5 to about 1:4.

22. The method according to p. 20, in which the molar ratio is about 1:2.

23. Paper with glued surface sizing is incostly 35oC and obtained using the reaction mixture of fatty acid and dicarboxylic acid containing a molar excess of dicarboxylic acid.

24. Paper with glued surface on p. 23, in which at least 25 wt. % mixture of 2-oxetanone of multimeric accounted for 2-oxetanone of multimers containing hydrocarbon substituents with inhomogeneities, and these hydrocarbon substituents with inhomogeneities is chosen from the group comprising branched alkyl, linear alkeneamine and branched alkeneamine radicals.

25. Paper with glued surface on p. 23, in which 2-oxetanone of multimer corresponds to the formula (I)

< / BR>
in which n is an integer equal to at least 1;

R and R" independently from each other - acyclic hydrocarbon radicals containing at least about 4 hydrocarbon atom;

R' is a branched, linear or alicyclic hydrocarbon radical containing from about 1 to about 40 carbon atoms.

26. Paper with glued surface on p. 25, in which in the formula (I) n is an integer from 1 to about 20.

27. Paper with glued surface on p. 25, in which in the formula (I) n is an integer UMich substances a mixture of 2-oxetanone of multimeric includes approximately at least 25 wt.% 2-oxetanone of multimers, containing heterogeneity in R, R" or both radicals, where these variations are selected from the group comprising branched alkyl, linear alkeneamine and branched alkeneamine radicals.

29. Paper with glued surface on p. 25, in which in the formula (I) R and R" independently of one another branched alkyl, linear alkyl, branched alkeneamine or linear alkeneamine radicals.

30. Paper with glued surface on p. 29, in which in the formula (I) each of the radicals R and R" contains from about 10 to about 20 carbon atoms.

31. Paper with glued surface on p. 25, in which in the formula (I) R' is chosen from the group comprising C2-C12hydrocarbon and C20-C40hydrocarbon radicals.

32. Paper with glued surface on p. 31 where in the formula (I) R' is branched or alicyclic hydrocarbon radical containing from about 28 to about 32 carbon atoms.

33. Paper with glued surface on p. 31 where in the formula (I) R' is a linear alkyl containing from about 4 to about 8 carbon atoms.

34. Paper with glued surface on p. 23, the manufacturing process Coty acid.

35. Paper with glued surface on p. 34, in which the fatty acid is chosen from the group comprising oleic, linoleic, linolenic, palmitoleic acid, and mixtures thereof.

36. Paper with glued surface on p. 34, in which the dicarboxylic acid is chosen from the group comprising azelaic, Sabatino, dodecadienol acid, dimer fatty acids, and mixtures thereof.

37. Paper with glued surface on p. 35, in which the dicarboxylic acid is chosen from the group comprising azelaic, Sabatino, dodecadienol acid, dimer fatty acids, and mixtures thereof.

38. Paper with glued surface on p. 23, which further includes an adhesive for gluing in mass.

39. Paper with glued surface on p. 38, in which the adhesive for gluing in the mass is chosen from the group comprising alkylcatechols dimer, alkylcatechols of multimer, alkenylamine dimer, alkenylamine of multimer, alilandry anhydride, alchemistry anhydride, rosin, and mixtures thereof.

40. Paper with glued surface on p. 23, where the surface sizing compound found this taped to the paper in an amount of from about 0,0025 to the example is .23, where this paper is chosen from the series, including plain paper, newsprint, cardboard and paper handmade character.

42. Paper with glued surface on p. 23, where this paper choose from a range that includes countless types of paper for printing of documents for various purposes, shredded paper, paper envelopes, paper for offset printing, inkjet paper, and paper machine development with additives.

43. Paper with glued surface according to any one of paragraphs.23 - 42, manufacturing process, which additionally includes obtaining 2-oxetanone multimer or a mixture of 2-oxetanone of multimers from the reaction mixture of fatty acid and dicarboxylic acid, dicarboxylic acid in such molar excess, in which the molar ratio of fatty and dicarboxylic acids is about 1:5.

44. Paper with glued surface on p. 43, in which this molar ratio is from about 1:1.5 to about 4:4.

45. Paper with glued surface on p. 43, which is the molar ratio is about 1:2.

46. Sizing substance, representing a 2-oxetanone the mul reaction mixture of fatty acid and dicarboxylic acid, containing a molar excess of dicarboxylic acid.

47. Sizing substance on p. 46, in which at least 25 wt.% a mixture of 2-oxetanone of multimeric accounted for multimers containing hydrocarbon substituents with inhomogeneities, and these hydrocarbon substituents with inhomogeneities is chosen from the group comprising branched alkyl, linear alkeneamine and branched alkeneamine radicals.

48. Sizing substance on p. 46, in which 2-oxetanone of multimer corresponds to the formula (I)

< / BR>
in which n is an integer equal to at least 1;

R and R" independently from each other - acyclic hydrocarbon radicals containing at least about 4 carbon atoms;

R' is a branched, linear or alicyclic hydrocarbon radical containing from about 1 to 40 carbon atoms.

49. Sizing substance on p. 48, in which in the formula (I) n is an integer from 1 to about 20.

50. Sizing substance on p. 48, in which in the formula (I) n is an integer from 1 to about 8.

51. Sizing substance on p. 48, where as a sizing agent a mixture of 2-oxetanone of multimeric includes approximately hence, the homogeneity is chosen from the group including branched alkyl, linear alkeneamine and branched alkeneamine radicals.

52. Sizing substance on p. 48, in which in the formula (I) R and R" independently of one another branched alkyl, linear alkyl, branched alkeneamine or linear alkeneamine radicals.

53. Sizing substance on p. 52, in which in the formula (I) each of the radicals R and R" contains from about 10 to about 20 carbon atoms.

54. Sizing substance on p. 48, in which in the formula (I) R' is chosen from the group comprising C2-C12hydrocarbon and C20-C40hydrocarbon radicals.

55. Sizing substance according to p. 54, in the formula (I) R' is branched or alicyclic hydrocarbon radical containing from about 28 to about 32 carbon atoms.

56. Sizing substance according to p. 54, in which in the formula (I) R' is a linear alkyl containing from about 4 to about 8 carbon atoms.

57. Sizing substance on p. 46, during which the mixture of 2-oxetanone of multimers prepared from a mixture of unsaturated fatty acids with dicarboxylic acid.

58. Sizing substance on p. 57, in which fatty K.

59. Sizing substance on p. 57, in which the dicarboxylic acid is chosen from the group comprising azelaic, Sabatino, dodecadienol acid, dimer fatty acids, and mixtures thereof.

60. Sizing substance on p. 58, in which the dicarboxylic acid is chosen from the group comprising azelaic, Sabatino, dodecadienol acid, dimer fatty acids, and mixtures thereof.

61. Sizing substance on p. 46, where it is a sizing substance is a surface sizing agent.

62. Sizing substance according to any one of paragraphs.46 - 61, in which the reaction mixture of fatty acid and dicarboxylic acid contains a dicarboxylic acid in such a molar excess, in which the molar ratio of fatty and dicarboxylic acids is about 1:5.

63. Sizing substance according to p. 62, in which the molar ratio of fatty and dicarboxylic acids is from about 1:1.5 to about 1:4.

64. Sizing substance on p. 46, in which the molar ratio of fatty and dicarboxylic acids is about 1:2.

 

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