Water-soluble melt adhesive, use thereof, method of producing multilayer material, method of producing paper, which is adhesive when wet and method of producing multilayer textile material
FIELD: textiles; paper.
SUBSTANCE: invention relates to producing water-soluble melt adhesive, which can be widely used in cardboard and paper industry for gluing and laminating cardboard, as well as for making joints of not less than two layers of paper, used for making toilet paper. The water-soluble melt adhesive contains 40-70 wt.% of not less than one homopolymer or copolymer with free carboxylate groups based on monomers with unsaturated ethylene bonds (component A), 15-45 wt % of not less than one water-soluble or polyurethane dispersed in water (component B), 12-35 wt % of not less than one alkanolamine (component C) and 0-20 wt % target additives.
EFFECT: obtained melt adhesives have high viscosity, elasticity and high strength of adhesive bonds on packages at low temperatures during storage of products, and at high temperatures the adhesive does not soften and does not flow.
11 cl, 1 tbl, 3 ex
The invention relates to adhesives, and more particularly to water-soluble glue to melt application method for producing a multilayer material, method for producing securities, the acquiring stickiness when wet, and to a method for producing a multilayer textile material.
Key melts are adhesives, which at room temperature are solid and almost completely free of water or solvents, that is, the amount of water or solvent does not exceed 5 wt.%. Hot melt adhesives applied on the joined substrates in the molten state, the connection is formed during cooling as a result of hardening.
The underlying polymer (base polymer) largely determine such important adhesive properties as adhesion, strength and thermal characteristics.
As base polymers in hot melt adhesives (HMAS use is usually presented in the following polymers:
such thermoplastic polymers such as block copolymers, for example styrene-butadiene, styrene-best choice, styrene-isoprenaline, styrene-ethylene-butylenediamine, styrene-ethylene-Propylenediamine;
ethylenevinylacetate polymers, other ethyleneimine polymers and copolymers, for example ethylene with acrylate, ethylene n-butyl acrylate and copolymers of the ethyl is and acrylic acid;
such polyolefins as polyethylene and polypropylene, for example amorphous propylene-α-olefin copolymers;
the polyvinyl acetate and polyvinyl acetate copolymers, polyacrylates, polyamides, polyesters, polyvinyl alcohols and copolymers of polyvinyl alcohol, polyurethanes, polystyrenes, polyepoxide, copolymers of vinyl monomers and polyalkylbenzene polymers, such containing aldehyde resin, as phenolaldehyde, urea-aldehyde, melamine-aldehyde, and the like.
In commercially available adhesive systems with a sticky surface, and solid, granulated.
Adhesives find wide industrial application in cardboard and paper industry for sizing and laminating cardboard, as activated by moistening the adhesive on postage stamps and postal envelopes or to obtain a multilayer material of not less than two layers of paper that is used to obtain tissue paper. Requirements that must be met for hot melt adhesives in this field productions, multi-faceted.
Thus, the hot melt adhesives must be of average or long open shutter (this definition refers to the time interval between applying the adhesive and fixing the connected parts), but after fixing the welded parts should happens is ü fast enough setting for to ensure the adhesive connection of the appropriate quality, in particular on high-speed packaging machines, machines for processing paper and machines for labeling. Along with the speed setting another important criterion for selection of hot melt glue is the viscosity. For machine processing, in particular for the uniform deposition of a layer of hot melt glue viscosity, with appropriate treatment temperature should be sufficiently low. For formation of adhesive joints on packages in the region of low temperatures, when the packaged product is stored at temperatures down to -35°C, requires an appropriate elasticity in a cooled state. This means that on cold should exhibit high strength adhesive bonding, and adhesive must not crack or break. On the other hand, often are Packed food or beverages prepared in the warm or hot, resulting adhesive should be stable. Under sufficiently high stability should be understood that the adhesive under the action of elevated temperatures is not soft and does not leak and that the glue joint is not at variance and/or glued parts do not move relative to each other. In addition, in particular, in the manufacture of food products t is buesa, to develop the hot melt adhesives according to the possibilities were deprived of odor or smell. The components that are used in the respective hot melts, should be approved for use on food products. In addition, it should be considered that the bonding subject to such diverse substrates as paper, cardboard, cardboard with a polyolefin coating, and much more. The hot-melt should be sufficient adhesion to these different substrates.
Another requirement for hot melts, which, in particular, are used for gluing tissue paper, is that the adhesive should be water soluble. This requirement is based on the high percentage of recycling in the production of tissue paper, this means that waste should be implemented the possibility of direct use to produce new layers of paper. However, this requires that the adhesive connection between the individual layers of paper completely removed from the pulp fibers recycling. Water-insoluble or poorly water-soluble components of adhesives that come in a strip of paper during the manufacture of new paper layer received on recycling of fibrous material, can lead to serious consequences to the stop of the production is DSTV. In the normal case, these residues of adhesive obtained in the course of recycling the paper strips form the so-called "glue", that is, the adhesive areas which are firmly glued a strip of paper to the rollers or other conveying elements for the paper strip. The consequence is usually breaks in paper strips and a long downtime. It is therefore not enough to adhesive bonding dispersed again in water, and that this was accompanied by the formation of a dispersion adhesive substance in water, it is necessary that the adhesive substance itself were completely dissolved in water. This will prevent the formation of sticky agglomerates (adhesions) from the separated fine glue substance.
Dispersible in water hot melt adhesives are known. Thus, U.S. patent No. 4129539 relates to dispersible in cold water glue to melt on the basis of a copolymer of vinyl acetate and cretonne easy acid, esters of rosin acids and dipentaerythritol and aliphatic amerosport Lack declared adhesive system is that it does not form a transparent aqueous solution. Moreover, the adhesion force is made by bonding layers of paper is often insufficient.
According to the materials of the application for international patent No. 99/59808 a method of obtaining a multilayer material of not less than two layers of paper and the materials, acquiring stickiness when wet, in accordance with these presents water-soluble glue melt on the basis of polyalkyleneglycol with a molecular mass (Mnin the range from 1000 to 100000, or on the basis of the nonionic polyurethane with a molecular mass (Mn) not less than 2000, or on the basis of polyester with a molecular mass (Mn) not less than 3000. However, in such compositions the adhesive strength is often insufficient.
In accordance with the above there was the task of the creation of hot melt glue for cardboard and paper industry, which is applied in the form of a melt, which is already at the minimum damage amount (less than 0.3 g/m2) provides a long-lasting and quick bonding after connection of the securities and, in addition, completely soluble in water, that is miscible with water in any quantity It should also be suitable for high speed processing of packaging machines and machines for labelling, as well as for more hygienic paper and processing.
To obtain a multilayer textile material stitched together laid out on the plane elements of textiles, leather or artificial leather. Ordinary methods of crosslinking include the firmware, probasco hooks or knitting needles.
The problem with this is the precise fit of rastrac from the Kani for their connection. Depending on the material type and size, as well as from selected processing conditions laid one on another pattern may shift, resulting in defective products. Here the production is finding cost-effective solutions that allow for accurate recording of textile patterns before joining, do not adversely affect the properties of materials stitched textiles. Proceeding from this prior art, was also noteworthy for the development of hot melt glue to obtain a multilayer textile materials.
The problem is solved proposed-melt adhesive containing
from 40 to 70 wt.% not less than one homopolymer or copolymer with free carboxylate groups on the basis of the monomers ethylene with unsaturated bonds (component a),
from 15 to 45 wt.% at least one water-soluble or dispersible in water polyurethane (component B) and
from 12 to 35 wt.% not less than one alkanolamine (component b), and
from 0 to 20 wt.% special additives, where the sum of the components is 100 wt.%.
Corresponding to the invention glue melt soluble in water, this means that the number of hot melt glue, equal to 3 g, dissolved in 600 g of water at a pH value of from 5 to 8 and at a temperature of 40°C. the Term "complete dissolution" t understand what to, that water is not the formation of sticky dispersed particles, in the preferred case a solution with a molecular dispersion.
Used in the framework of the invention, homopolymers or copolymers with free carboxylate groups on the basis of the monomers ethylene with unsaturated bonds (component a) are obtained as a result of homopolymerization or copolymerization of monomers or oligomers ethylene with unsaturated bonds, which contain not less than one carboxyl group per molecule, for example, is used for the base polymer. In the preferred case as a component And use polymers that can be obtained by copolymerization of unsaturated ethylene monomers or oligomers, in molecules lacking the carboxyl group, with an unsaturated aliphatic ethylene copolymers that contain at least one carboxyl group in the molecule. As the unsaturated ethylene monomer in the molecule which lacks the carboxyl group, particular preference is given to vinyl acetate. Examples copolymerizate unsaturated aliphatic ethylene comonomers with at least one carboxyl group are acrylic acid, methacrylic acid, crotonic acid, Sekretareva acid, t is Pinova acid, maleic acid, fumaric acid, titanova acid, musicanova acid, taconova acid and komitova acid.
In the copolymerization reaction can be used other monomers. Examples of other comonomers are ethylene, propylene, butylene, 1-hexene, as well as anhydrides or esters mentioned unsaturated ethylene copolymers with at least one carboxyl group in the molecule.
The copolymer (component a) is in the preferred case, an acid number of from 10 to 200 mg, in particular in the preferred case from 20 to 150 mg KOH/g (determined according to ASTM D 974).
Corresponding to the invention water-soluble glue melt preferably contains from 45 to 65 wt.% component A.
In a particularly preferred variant of the invention the water-soluble glue melt contains as component a copolymer of vinyl acetate and crotonic acid with an acid number of from 10 to 200 mg KOH/g, in the preferred case from 20 to 150 mg and especially preferred from 25 to 100 mg KOH/g (determined according to ASTM D 974). The softening temperature of the copolymer of vinyl acetate and crotonic acid is in the range from 80 to 130°C., in the preferred case from 90 to 120°C (method a ball-ring, DIN 52011). The molecular mass (Mn) is in the range from 10000 to 60000, in the preferred case from 20,000 to 50,000.
Relating to polymeric compounds which contained data on the molecular masses of presents, unless otherwise stated, srednekislye values of molecular masses (Mn). All data on the molecular mass, unless otherwise specified, refer to values that can be obtained using gel permeation chromatography. Marketed copolymers of vinyl acetate and crotonic acid may be acquired, for example, the firm Synthomer under the trademark Synthomer MCT 5 or Wacker from a number of Vinnapas®.
As component B corresponding to the invention water-soluble glue melt preferably contains from 20 to 40 wt.% and more preferably from 25 to 35 wt.%, at least one water-soluble or dispersible in water polyurethane.
Polyurethanes, which in the framework of the present invention can be used as component B, get usually the result of the interaction of at least one MDI, in the preferred case of a diisocyanate, and a polyol as one component, which in the preferred case consists of diols. This polyol as one component can contain only one polyol, but as a polyol as one component can be used and a mixture of two or more different polyols. Especially well suited for polyol as one component or for at least part of the polyol as one component, for example, polyalkylene, in particular, al is lanoxin.
The concept of "ionogenic" means that the polyurethane contains ionic or at least an ionisable within the acid-base equilibrium of the group, giving it the ability to dissolve, for example carboxylate, sulphonate, phosphonate or ammonium group.
The term "nonionic" in accordance with this means that the polyurethane does not contain any ionic groups as emulsifying groups, i.e. does not contain a carboxylate, sulphonate, phosphonate or ammonium groups. Solubility in water is based primarily on such hydrophilic nonionic groups, as polyoxyethylene -(CH2-CH2O)n-. These structural units are, in particular, derived from preferably used as the polyol as one of the components of polyethylene oxide. However, the concept of polyethylene oxide refers not only to the polyaddition products of ethylene oxide to water or ethylene glycol as the original molecule, but also to the polyaddition products of ethylene oxide to other diatomic alcohols such as butanediol, hexanediol or 4,4'-dihydroxydiphenylpropane. Can also be used a mixture of two or more different oxides, which, for example, differ in mean molecular mass Mwor Mnor by both indicators. In quality the ve polyol as one component can also be used copolymers of ethylene oxide with higher acceleratedly, for example, propylene oxide, if they are sufficiently soluble in water, i.e., if more than about 3 g to about 100 g of water at 20°C remain in solution over approximately six months.
10, in the preferred case to not more than 5, in particular to less than 2 wt.%, the polyethylene oxide in the polyol as one component can be replaced by other diols which contain a hydrophobic residue with a solubility in water at best 2 g per 100 g of water. In particular, a hydrophobic residue presents aliphatic or alicyclic structures with the number of carbon atoms from two to forty-four, in particular from six to thirty-six. These residues may also contain aromatic structures. Preference is given dilam containing at least one primary hydroxyl group, in particular 1,2 - or α,ω-dilam. However, are suitable for this purpose and with vicinal diols location hydroxyl groups.
The polyethylene oxide in the polyol as one component in the preferred case has a molecular mass (Mnfrom about 200 to 20,000, in particular from about 1000 to about 15000, for example, about 1550, 3000, 6000 or 12000.
In addition, it is possible to replace up to 10%, in the preferred case from 0.5 to 5%, of polyethylene glycol on hydrophobic homopolymer polyalkylene glycols, when Allenova group includes more than two carbon atoms, site is Cetelem case, three or four carbon atoms. Their molecular masses are, in particular from 150 to 10,000 g/mol. Specific examples of hydrophobic diols with pure SN-residues and functional groups of ester represented by polypropylenglycol, poliatilenglikole, polytetrahydrofuran, polybutadiene, ethylene-butylene copolymers with terminal hydroxyl groups (for example, KRA-TON LIQUID Polymer L-2203), gidrirovanny polybutadiene and arcangioli with the number of carbon atoms from four to forty-four. Dialami, which are preferred, are polypropylenglycol, polytetrahydrofuran with molecular weight of 150 to 10,000, in particular from 200 to 4500, in a particularly preferred case from 250 to 1000, and 1,10-decanediol, 1,12-dodecanediol, 1,12-octadecanol, diol based on dimeric fatty acids, 1,2-octanediol, 1,2-dodecanediol, 1,2-hexadecanediol, 1,2-octadecanol, 1,2-tetradecanol, 4,4-isopropylidenedicyclohexanol and mixture of its isomers, 4,8-bis(hydroxymethyl)tricyclo[5,2,1,02,6]Dean and mixture of its isomers, 1,4:3,6-dianhydro-D-mannitol, 1,4:3,6-dianhydro-D-sorbitol, 1,16-hexadecanediol, bisphenol a, as well as products propoxycarbonyl or ethoxycarbonyl or their mixtures, in particular, with the number ethylenoxide structural units 30 and, finally, monoether of glycerol with fatty acids containing up to twenty-two carbon atoms, for example, mo is Hoefer glycerin with beganovi acid, oleic acid, stearic acid, myristic acid. Of course, can be used and mixtures consisting of two or more of the mentioned hydrophobic diols.
In addition, the polyethylene glycol may be replaced by alcohols higher degree of functionalization in the amount of from 0 to 5%, in particular from 0.2 to 2%, in particular trioligy, for example glycerol, trimethylolpropane, triethanolamine, or their ethoxylated or propoxycarbonyl derivatives. You can find application and pentaerythritol. It is also possible the use of ethoxylated or propoxycarbonyl derivatives of amines or aminoalcohols, for example, based on Ethylenediamine, Diethylenetriamine and their higher homologues, such as aminophenol, N-2-AMINOETHYLPIPERAZINE.
In order to obtain polyurethanes with particularly high molecular weight, should be used as clean as possible diols. For this purpose, the content of ions of alkali or alkaline earth metals must not exceed 500 ppm, in particular it should be less than 150 parts per million, and in the preferred case below 10 parts per million. In addition, the water content, as determined by Fisher, should not exceed 0.5 wt.%, in particular, it should be below 0.1 wt.%, in the preferred case is below 0.05 wt.%.
Along with dialami polyol as one important component structures of the diversified elements used as component B of the polyurethane are the diisocyanates. It concerns the compounds of General formula O=C=N-X-N=C=O, and X is aliphatic, alicyclic or aromatic residue, in the preferred case of aliphatic or alicyclic residue with the number of carbon atoms from four to eighteen.
As examples of such suitable isocyanates, such as 1.5-naphthylenediisocyanate, 4,4'-diphenylmethanediisocyanate, hydrogenated 4,4'-diphenylmethanediisocyanate, xylylenediisocyanate, tetramethylcyclopentadienyl, 4,4'-diphenylmethanediisocyanate, di - and tetraamminepalladium, 4,4'-dibenzoylresorcinol, 1,3-delete the entry, 1,4-delete the entry, isomeric toluylenediisocyanate, 1-methyl-2,4-diisocyanatohexane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane, chlorinated and brominated diisocyanates, phosphorus-containing diisocyanates, 4,4'diisocyanatobutane, tetramethoxysilane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane-1,6-diisocyanate, dicyclohexylmethane, cyclohexane-1,4-diisocyanate, atlantaatlanta, bis-isocyanatomethyl ester of phthalic acid, in addition, such diisocyanates with reactive halogen atoms such as 1-CHLOROTHALONIL-2,4-diisocyanate, 1-bromomethylphenyl-2,6-diisocyanate or 3,3-bis-chloromethylating 44'-diphenyldiisocyanate. The sulfur-containing polyisocyanates receive, for example, by the interaction of two moles of hexamethylenediisocyanate with one mol of thiodiglycol or dihydroxydiphenylsulfone. Can also be used in other diisocyanates, for example trimethylhexamethylenediamine, 1,4-diisocyanatobutane, 1,12-diisocyanatobutane and diisocyanate based on dimeric fatty acids.
More suited tetramethylene, hexamethylene-, undecane, dodecamethyl-, 2,2,4-trimethylhexane-, 1,3-cyclohexane-, 1,4-cyclohexane-, 1,3 - or 1,4-tetramethylol-, isophorone-, 4,4-dicyclohexylmethane-diisocyanate and the diisocyanate ester-based lysine.
Particular preference is given tetramethylethylenediamine, in particular m-TMXDI production Fa. Cyanamid.
For even higher molecular weight, for example, by known methods to increase the length of the chain. To do this, first with an excess of diisocyanate get the prepolymers, the length of which then increase the short-chain aminoalcohols, dialami, diamines or water with increasing molecular weight.
To do this, first with an excess of diisocyanate get the prepolymers, the length of which after that increase short-chain dialami or diamines or water. Specific examples of the means for increasing chain length are:
such saturated and nanasawa the data glycols, as ethylene glycol, or condensation products of ethylene glycol, butanediol-1,3, butanediol-1,4, 2-butene-1,4-diol, 2-butyn-1,4-diol, propandiol-1,2, propandiol-1,3, neopentylglycol, hexanediol, bis-(hydroxymethyl)cyclohexane, diacetoxyscirpenol, bis-glycol ester of terephthalic acid, di-2-hydroxyethylamide succinic acid, di-N-methyl(2-hydroxyethyl)amide of succinic acid, 1,4-di(2-hydroxymethylamino)-2,3,5,6-tetrachlorobenzene, 2-medienproduktion-1,3, 2-methylpropanol-1,3, 3-pyrrolidino-1,2-propandiol, 2-methylindenyl-2,4, 3-alkoxy-1,2-propandiol, 2-ethylhexane-1,3-diol, 2,2-DIMETHYLPROPANE-1,3, 1,5-pentanediol, 2,5-dimethyl-2,5-hexanediol, 3-phenoxy-1,2-propandiol, 3-benzyloxy-1,2-propandiol, 2,3-dimethyl-2,3-butanediol, 3-(4-methoxyphenoxy)-1,2-propandiol and hydroxymethylbenzene alcohol;
such aliphatic, cycloaliphatic and aromatic diamines, as Ethylenediamine, hexamethylenediamine were, 1,4-cyclohexanediamine, piperazine, N-methylpropylamine, diaminodiphenylsulfone, diaminodiphenyl ether, diaminodiphenylmethane, 2,4-diamino-6-phenyltriazine, isophorondiamine, a diamine based on dimer fatty acids, diaminodiphenylmethane or isomers of phenylenediamine;
- in addition, also carbohydrazide or hydrazides of dicarboxylic acids;
- aminoalcohols such as ethanolamine, propanolamine, butanamine, N-methylethanolamine, N-methylisourea is alamin, diethanolamine, triethanolamine, and higher di - or trialkanolamines;
such aliphatic, cycloaliphatic, aromatic and heterocyclic mono - and diaminocarbenes acids, like glycine, 1 - and 2-alanine, 6-aminocaproic acid, 4-aminobutyric acid, the isomeric mono - and diaminobenzoic acid, and isomeric mono - and diaminonaphthalene acid.
However, in the preferred case, the polyurethane receive the one-stage method. Thus, for example, first mix all of the original substance in the presence of an organic solvent with a water content of less than 0.5 wt.%. The mixture in the course of time from about 1 to 30 hours, heated at a temperature of from 60 to 200°C., in particular from 80 to 180°C and in the preferred case from 100 to 150°C.
The reaction time can be reduced due to the presence of a catalyst.
In particular, suitable tertiary amines such as triethylamine, 1,4-diazabicyclo[2,2,2]octane, dimethylbenzylamine, bis-(dimethylaminoethyl) ether and bis(methylaminomethyl)phenol. More suited 1-Mei, 2-methyl-1-vinylimidazole, 1-allylimidazole, 1-phenylimidazole, 1,2,4,5-tetramethyldisilazane, 1-(3-aminopropyl)imizol, pyrimidal, 4-dimethylaminopyridine, 4-pyrrolidinone, 4-morpholinopropan, 4-methylpyridin.
As catalysts may be used as ORGANOTIN compounds. To them from Osada connection which contain both tin and an organic residue, in particular compounds which contain one or more relationships tin with carbon. In a broad sense to ORGANOTIN compounds include, for example, such salts as octoate tin and tin stearate. In a more narrow sense to compounds of tin are primarily compounds of tetravalent tin General formula Rn+1SnX3-nand n denotes a number from 0 to 2, R is alkyl or aryl group, or both, and, finally, X is a compound of oxygen, sulfur or nitrogen or a mixture of two or more such compounds. In the appropriate case R contains at least four carbon atoms, in particular at least eight. The upper bound is, as a rule, the twelve carbon atoms. In the preferred case X means an oxygen atom, i.e. forms an ORGANOTIN oxide, hydroxide, carboxylate, or ester of an inorganic acid. However, X can also mean the sulfur compound, that is, to form an ORGANOTIN sulfide, tiolet or ether timeslot. In the case of Sn-S compounds primarily suitable esters of thioglycolic, for example compounds with residues of
Such compounds correspond to the selection rule, which reads as follows: molecular weight ORGANOTIN compounds in the preferred case of the invention must be more than 250, in particular more than 600.
Another class of compounds, which are preferred, presents the dialkyl tin(IV)carboxylates (X means O-CO-R1). Carboxylic acids contain two, in the preferred case, at least ten, in particular from fourteen to thirty-two carbon atoms. Can be used and dicarboxylic acid. In the role of acids include, for example, adipic acid, maleic acid, fumaric acid, terephthalic acid, phenylacetic acid, benzoic acid, acetic acid, propionic acid, and, in particular, Caprylic, capric, lauric, myristic, palmitic and stearic acid. More suited, for example, the diacetate dibutylamine and dilaurate dibutylamine, as well as the diacetate dactylology and dilaurate dactylology.
In the framework of the present invention are also suited olowookere, sulfides and thiolate. Specific compounds are bis-(tributylamine)oxide, dibutyltindilaurate, dioctylsulfosuccinate, dibutylamino-bis-(2-ethylhexylacrylate), octisalate-Tris-(2-ethylhexyladipate is), dictyosome-bis-(diethyleneglycol-2-ethylhexoic), dibutylamino-bis-(diethylenglycol), dibutylbarbituric, dioctylfluorenyl, bis-(tributylamine)sulfide, dibutylamino-bis-(2-ethylhexylacrylate), dictyosome-bis-(diethyleneglycol-2-ethylhexoic), trichloroacetimidate-2-ethylhexoic and dictyosome-bis-(2-ethylhexylcarbonate), bis-(S,S-methoxycarbonylethyl)tin bis(2-ethylhexylcarbonate), bis-(S,S-acetylethyl)tin-bis-(2-ethylhexylcarbonate), occultist tin (II) and diethylenglycol-2-ethylhexoic tin (II).
In addition, they should still be called dibutylaminoethanol, vexillological, dibutyltindilaurate, dibutyltindilaurate, bis-(butyldichlorosilane)oxide, bis(dibutylamino)sulfide, phenolate tin (II)acetylacetonate, tin (II), and derivatives of such other α-dicarbonyl compounds such as acetylacetone, dibenzoylmethane, benzoylacetone, ethyl ester of acetoacetic acid n-propyl ester of acetoacetic acid, ethyl ester of α,α'-diphenylsiloxane acid and dehydroacetate acid.
In the preferred case, the catalyst is added to the polyol. Its amount is determined by its activity and reaction conditions. Preferably, when it is in the range from 0.001 to 0.5 wt.% based on the polyol.
But the PR is doctitle case work without catalyst. It is also advisable to do without solvent. Under this text, the term "solvent" refers to an inert organic liquid substances with a boiling point below 200°C. at normal pressure (1 bar).
In the preferred case, the interaction is conducted so that the ratio of hydroxyl groups in the polyol as one component to isocyanate groups in the polyisocyanate ranged from about 1.0 to about a 2.0, in particular from about of 1.05 to 1.8, for example from about 1.1 to 1.7, or from about 1.3 to 1.6.
The possibility of introducing ionic structural elements represented by the reaction of the polyurethane oligomers having terminal hydroxyl groups with anhydrides of dicarboxylic acids. They can contain from two to forty-four, in the preferred case from two to twelve carbon atoms between the bis-acyl groups, for example, it alkylene, alkenylamine or allenbyi groups. Suitable, for example, succinic acid anhydride, glutaric acid anhydride, the anhydride 1,2,3,6-tetrahydrophthalic acid and its isomers, phthalic anhydride, the anhydride trimellitic acid anhydride 7-oxabicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid and its isomers, anhydride diglycolic acid, maleic acid anhydride, the anhydride of dimethylmaleic the th acid, anhydride tarakanovas acid anhydride basis of itaconic acid, anhydrides alchemistry acids, in the preferred case, such that alkeneamine groups have more than two carbon atoms, in particular more than five, in a particularly preferred case more than seven carbon atoms. Specific examples include the anhydride of n-oktaviantrie acid anhydride n-dodecalactone acid anhydride tetrapropylene acid anhydride n-hexadecylamine acid anhydride and n-octadecylamino acid. Alkanniny residue may be linear or branched structure. In addition, there may be present a mixture alkenyl groups with different numbers of carbon atoms. Possible mixture of several anhydrides, however, preference is given to cyclic anhydrides.
It is also possible to use a molar excess of isocyanate, resulting in the formation of the oligomer with isocyanate terminal groups.
However, in the General case isocyanate groups in the final product is undesirable. And yet they can be used to enter, for example, hydrophobic or ionic structural elements.
Hydrophobic structural elements can be obtained by the reaction of oligomers containing terminal isocyanate groups, with Manorama or monofunctional amines is the number of carbon atoms, greater than or equal to two, in particular containing ≥ 6, ≥ 10 or ≥ 16 carbon atoms. Specific examples include ethylene-butylene copolymer with one hydroxyl group, for example, with hydroxyl equivalent weight equal to 3600 (Kraton L-1203), and 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 10-undecen-1-ol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 9-CIS-octadecene-1-ol, 9-TRANS-octadecene-1-ol, 9-CIS-octadecane-1,12-diol, CIS-CIS-9,12-octadecadiene-1-ol, 9,12,15-octadecatrienoic-1-ol with colodny structure of all double bonds, 1-nonadienal, 1-eicosanol, 9-CIS-eicosan-1-ol, 5,8,11,14-eicosatetraenoic-1-ol, 1-heneicosanol, 1-docosanol, 13-CIS-dokusen-1-ol, 13-TRANS-dokusen-1-ol. In the role of the hydrophobic structural elements may also be appropriate fatty amines.
And finally, another possibility is the introduction of ionic structures represented by reaction of oligomers containing terminal isocyanate groups, with hydroxycarbonate acids or aminocarbonyl acids, including alkylene, alkenylamine or allenbyi grouping, as in the case of anhydrides of dicarboxylic acids. As examples are glycolic acid, lactic acid, hexanoic acid and mandelic acid, and aminocaproic acid, aminododecanoic to the slot, glycine, alanine and phenylalanine.
In a preferred embodiment of the invention as component B, the use of nonionic polyurethane with a molecular mass (Mn) not less than about 2000, in particular nonionic polyurethane, which can be obtained by the interaction of not less than one MDI with not less than one polyalkyleneglycol with a molecular weight of at least 1000. Used as component B nonionic polyurethane has a viscosity at 150°C from 500 to 80000 MPa·s, in the preferred case from 1000 to 60,000 MPa·s, more preferred scenario, from 2000 to 40000 MPa·s (determined by Brookfield, spindle 27, ASTM D 3236-88).
The use of nonionic polyurethane leads to improved stability of the product and the homogeneity of the adhesive when it is received, and practical application. In particular, this improves the rheological properties of the adhesive composition. This is manifested, for example, when used on high-speed machines (about 600 m/min). Matching the invention the glue melts when applying spasatelami work uniform filament of adhesive and do not form "blobs".
In the preferred case, component a is in the form of a salt. In accordance with invention of water-soluble glue-melt used as a component in alkanolamine service is t, to ensure the solubility of the component And for mixing the adhesive composition with water. As alkanolamine prefer trialkanolamines with the number of carbon atoms in alkanones residue from two to six, and alcoholnye remains one molecule may be the same or different lengths of carbon chains. When using triethanolamine get a clear solution of hot melt glue in the water.
The quantity of the component In the invention is water-soluble glue-melt is preferably from 15 to 25 wt.%.
As the target additives glue melt may contain, for example, the base polymers, plasticizers, additives to improve the rheological characteristics, antioxidant defenses to protect against UV radiation, dyes, or increase the adhesiveness of the resin, and water and/or organic solvents up to 3 wt.%, if these additives do not impair the solubility of the composition of hot melt glue in the water.
As a means of improving the adhesiveness, using, for example, hydrocarbon resin, in particular C5 or C9-resins or C9-resin, modified C5-resins. In addition, for use as a means of enhancing adhesion, suitable resins based on pure hydrocarbon monomers, such as resin, which can be obtained by polymerization of mixtures of styrene, α-meth is lesterol and vinyltoluene. Named hydrocarbon resin can be partially gidrirovanie or fully gidrirovanie.
For use as a means to improve the adhesiveness suitable as such a natural resin, as obtained from trees balsamina resin or tall oil resin obtained in the production of paper. Natural resins can be used as a means to increase the stickiness in the above form, but you can also use the above resin after esterification with the corresponding polyfunctional alcohols in the form of their esters with pentaerythritol, esters with glycerol, esters with diethylene glycol, triethylene glycol or methyl esters.
As a means to improve the adhesiveness is also suitable polyterpene resin. Terpenes are formed by separation of the resin acids from their natural solvents and can be polimerizuet to polyterpene resins. For use as a means for increasing the viscosity suitable also serpentinely resin obtained from polyterpenes of phenolic resins by modification. The preferred water-soluble means to improve adhesiveness.
As the use of antioxidants known specialist antioxidants. They are antioxidants on the basis of simple thioethers, sterically obstructed and/or multifunc the optional phenols, hydroxylamine or organic phosphorus compounds, for example organic diphosphite. The antioxidants used in the form of a single substance or in a mixture. Preference is given to using water-soluble antioxidants. Typical antioxidants produced by commercial, come Fa Ciba under the trademark Irganox 1010 and Irganox 1076. The amount of antioxidants in the final composition is from 0.05 to 2.5 wt.%, in the preferred case from 0.1 to 2 wt.%, in a particularly preferred case from 0.25 to 1.5 wt.%.
Target additives may be present in the adhesive is melt in the form of a single substance or a mixture of two or more of these compounds. The amount of additives should not exceed about 20 wt.% (based on the entire adhesive-melt). Suitable, for example, amounts from about 0.1 to about 15 wt.% or from about 1 to about 10 wt.%, for example, in a preferred implementation of the invention use about 2, 3, 4, 5, 7 or 9 wt.% additives.
The proposed water-soluble glue melt can be obtained due to the fact that the mix before formation of a homogeneous melt at a temperature of from 70 to 150°C, in the preferred case from 90 to 120°C
from 40 to 70 wt.% at least one homopolymer or copolymer with free carboxylate groups on the basis of the unsaturated ethylene monomers (component a), in which lastnosti, in the preferred case of a copolymer of vinyl acetate and crotonic acid with an acid number of from 10 to 200 mg KOH/g (determined according to ASTM D 974), and from 15 to 40 wt.% at least one water-soluble or dispersible in water polyurethane (component B), in particular nonionic polyurethane having a viscosity of 500 to 80000 MPa·s at 150°C (determined by Brookfield, spindle 27, ASTM D 3236-88),
and also, if necessary, targeted supplements, such as antioxidants, then at a temperature of not more than 100°C, in the preferred case from 80 to 100°C. and in a particularly preferred case from 85 to 95°C, add 12 to 35 wt.% at least one alkanolamine, in the preferred case of trialkanolamines, in a particularly preferred case, triethanolamine, and, if necessary, additional additives target, and the total number of target components is up to 20 wt.%, and the sum of the components is 100%, and stirred until the formation of homogeneous mixture.
Corresponding to the invention water-soluble glue melt has a viscosity that allows the use of glue melt in the normal method of application. In the preferred case, the glue melt has a viscosity at 120°C (Brookfield Thermosell, spindle 27, ASTM D 3236-88)lying in the range from 1000 MPa·s to 20,000 MPa·s, in the preferred case from 1500 MPa·s to 15,000 MPa·s and in a particularly preferred case is from 2000 to 8000 MPa·S.
In the preferred case, corresponding to the invention water-soluble glue melt used as adhesives in the textile, cardboard and paper industry for gluing paper or textile material on the plane. Corresponding to the invention water-soluble glue melt suitable for producing a multilayer material of the at least two paper sheets, in particular to obtain not less than a two-layer tissue paper, and/or laminated textile materials.
In addition, the invention includes a method of obtaining a laminate of at least two paper layers and multi-layer textile material using the appropriate invention of hot melt glue.
Multilayer textile materials to be used, in particular, in the manufacture of clothing. The concept of multi-layer textile materials refers to not less than two-layer flat textile materials, for example, from knitted, woven or knitted materials. Flat textile materials composed of synthetic and/or synthetic fibers, for example polyester, polyamide, polypropylene, cotton, viscose and mixtures thereof.
Flat textile materials can be laminated with a plastic film. In particular, they can be laminated plastic the films, which provide a waterproof and windproof, but allow water vapor. Such textile laminates are described, for example, in European patent No. 0238014. Corresponding to the invention glue melt is applied to at least one surface of the first planar textile material, which may already be part of a multilayer textile materials, and carry out the laminating surface of the second planar textile material. After laminating the multilayer textile materials cut out with getting the desired shape and sew where it is needed. Since in the preferred case, corresponding to the invention glue melt is used for temporary fixation during the fusion process, its out of stitched laminated textile materials. It makes unnecessary such commonly used mechanical auxiliary means for fixing stitched textile materials, such as pins, clips, and more, and better performance.
The concept of "tissue paper" refers in the context of the present invention to be used in households, public institutions and for personal hygiene varieties of papers, for example, this kitchen towels (kitchen crepe), paper handkerchiefs, paper hankies, napkins, toilet paper, detsk the e diaper and the like. Corresponding to the invention water-soluble glue melt is suitable, in particular, to obtain a multi-layer paper products from lignin.
The term "lignin" refers to a very thin, soft, mostly free from wood material, which may be slightly krepelova (in dry state). This material has a very high water-absorbing capacity in the form of a monolayer he has, as a rule, the density of more than 25 g/m2(before keperawanan). Such layers of lignin obtained by the relevant invention method, do first of all toilet paper, paper hankies or cosmetic wipes.
Obtaining not less than two-layer materials of paper or textile material, typically includes at least one processing operation, during which corresponds to the invention glue melt is applied to the first layer of paper or respectively at least one surface of the first textile flat material, and after a certain interval in space and in time of laminating the second layer of paper or, respectively, the second planar textile material on the adhesive side of the first layer of paper or, respectively, at least one of the upper surface of the first planar textile material. For about the adowanie sufficient adhesion between the first and second layer of the substrate glue melt should be enough adhesive at the time of laminating the second layer of the substrate, that is, it must not harden physically. Time after the application of adhesive replave, during which the adhesive substance has sufficient adhesiveness for laminating the second layer of the substrate will be referred to as "open time".
When it says "sufficient stickiness", it means stickiness, which provides the connection between the layers of paper with a force of separation more than 0 N/a see
Machine speed during lamination to obtain a connection between the textile material is in the maximum of 100 m/min
At normal engine speeds when receiving multi-layer materials of not less than two-ply paper sheets, for example, up to 600 m/min, in the General case it is enough to glue melt had an open excerpts from about 0.1 to about 1 second, for example from about 0.2 to about 0.5 seconds. If glue melt should be used in conditions, when there is a full native speed, then the time of the open shutter of the above mentioned order of values is usually sufficient. If glue melt should provide a multilayer material of not less than two layers of paper in the starting mode of the machine, then the time of the open shutter should cover a wider time interval than specified above. In this case, preference should be given, for example, lying is neither open shutter from about 1 to about 10 seconds, for example, from about 2 to about 8, or from about 4 to about 6 seconds.
The advantage of corresponding to the invention the water-soluble hot melt adhesives is that they simplify the return on recycling already glued layers of paper to produce new paper layers. Generally, for this to already glued the layers of paper add water, solvent glue melt, and in the process receive the pulp from fibres that are suitable for further processing. Typically, this water has a higher temperature than ambient temperature, for example, it ranges from about 25 to about 80°C. When the solubility in water of not less than 3 g of hot melt glue in 600 g of water with pH value of from 5 to 8 adhesive during processing in the course of recycling is guaranteed to remain in solution and are thus excluded production disruptions caused by adhesions".
In a preferred variant implementation of the method of producing a multilayer material of not less than two layers of paper or mnogoslojnych textile materials used correspond to the invention the hot melt adhesives, which are virtually unlimited mixed with water, i.e. at a concentration not less than about 10 wt.% or, for example, more than 20 wt.% or about 50 wt.% or even more, they have no failures in solubility.
Processing sootvetstvuyuschego the invention the water-soluble hot-melt occurs as a rule, the result of applying adhesive in the molten state to layers of paper or on at least one surface of a flat textile material using conventional methods of application. Suitable methods of application are, for example, coating with rollers, slot nozzles or spray nozzles, and for multilayer textile materials is primarily the application using templates.
If the application is carried out with the help of rollers, as a rule, this leads to relatively high costs of adhesive per unit area. Therefore, the application of using rollers are used usually for strong connection of the individual layers of paper. For coating with rollers are suitable, for example, hot melt adhesives, which are in the molten state at a temperature of from about 120 to about 150°C, have a viscosity (Brookfield Thermosell, spindle 27, ASTM D 3236-88) from about 1000 MPa·s to about 6000 MPa·s, in particular from about 2000 MPa·s to about 3000 MPa·S. When applied using rollers can be obtained, for example, paper, acquiring stickiness when wet.
The concept of "paper purchasing stickiness when wet" refers to securities that can be converted into self-adhesive system as the result of wetting. For this paper or, respectively, the first paper layer has on the end is th least one side of the layer, which when moistened with water becomes sticky and can be, for example, are used for connection with the second paper layer. After evaporation of the water layers of paper are held to each other by adhesion. Examples of such materials are postage stamps, envelopes, labels and the like.
The method of producing securities, the acquiring stickiness when wet, is a further object of the invention.
If glue melt is applied using a slit die, for this use, as a rule, glue melt, which in the molten state at a temperature of from about 120 to about 150°C. has a viscosity (Brookfield Thermosell, spindle 27, ASTM D 3236-88) from about 400 to about 20,000 MPa·s, in particular from about 600 to about 5000 MPa·S.
During the bonding of lignin preference is given to application of hot melt glue with spray nozzles, resulting in no formation of a continuous coating. Bonding of lignin can be as spraying and not spraying the spray nozzles in the latter case we can talk about spinning filero.
Spray the spray nozzles require, as a rule, of hot melt glue, which is in the molten state at a temperature of from about 120 to about 150°C. has a viscosity (Brookfield Thermosell, spindle 27, ASTM D 3236-88) from about to about 10,000 MPa·s, in particular, from about 600 to about 5000 MPa·S. No spray spray nozzles require adhesives with a somewhat higher viscosity in order to provide the desired cohesion of the fibers. For this approach, for example, hot melt adhesives with a viscosity in the molten state (Brookfield Thermosell, spindle 27) from about 3000 to about 10,000 MPa·s at a temperature of from about 120 to about 150°C.
Further, the invention is illustrated in more detail by examples.
Getting hot melt adhesives
At a temperature of 120°C. homogenize 34 wt.% nonionic polyurethane (Technomelt 337VP, Henkel KGaA) with a solubility of 3 g 600 g of water at 40°C. and with a viscosity of 4000 MPa·s at 150°C (Brookfield Thermosell, spindle 27, ASTM D 3236-88) together with a 50.5 wt.% Synthomer MCT 5 (a copolymer of vinyl acetate with cretonne easy acid production Fa. Synthomer, an acid number of 35 to 45 mg KOH/g). The mixture is then cooled to 90°C and add 15 wt.% triethanolamine and 0.5 wt.% antioxidant (Irganox 1010, Fa. Ciba). Mix before formation of a homogeneous melt.
At a temperature of 120°C. homogenize 28 wt.% nonionic polyurethane (Technomelt 337VP, Henkel KGaA) with a solubility of 3 g 600 g of water at 40°C. and with a viscosity of 4000 MPa·s at 150°C (Brookfield Thermosell, spindle 27, ASTM D 3236-88) with 54 wt.% Synthomer MCT 5 (a copolymer of vinyl acetate with crotonic acid production Fa. Synthomer, kislon the e number of 35-45 mg KOH/g). The mixture is then cooled to 90°With a gain of 17.5 wt.% triethanolamine and 0.5 wt.% antioxidant (Irganox 1010, Fa. Ciba). Mix before formation of a homogeneous melt.
At a temperature of 120°C. homogenize 16 wt.% nonionic polyurethane (Tech-nomelt 337VP, Henkel KGaA) with a solubility of 3 g 600 g of water at 40°C. and with a viscosity of 4000 MPa·s at 150°C (Brookfield Thermosell, spindle 27, ASTM D 3236-88) along with 63 wt.% Synthomer MCT 5 (a copolymer of vinyl acetate with crotonic acid production Fa. Synthomer, an acid number of 35 to 45 mg KOH/g). The mixture is then cooled to 90°With a gain of 20.5 wt.% triethanolamine and 0.5 wt.% antioxidant (Irganox 1010, Fa. Ciba). Mix before formation of a homogeneous melt.
Results and analytical methods
Properties relevant to the invention compositions according to examples 1 to 3 and comparison examples 4 and 5 (corresponding to the examples 3 and 5 of U.S. patent No. 4129539) in the table. The viscosity is determined by Brookfield (Thermosell, spindle 27, ASTM D 3236-88).
The parameter "color" is determined visually; and he refers to the solid product, b) to the melt.
Compatible understand how the homogeneity of the mixture in the form of melt and solid.
In the case of comparison examples during the cooling process of hot melt glue was observed allocation of another phase in the form of droplets in the melt and the melt surface. Heat V. the mobility is determined in accordance with the methodology Unichim Nr. 665.
In an aluminum container is weighed 200 g of hot melt glue and kept in an oil bath at 120°C. After the adhesive substance forms a homogeneous melt, select a sample of 1.5 g and pour it into a round shape with a diameter of 1.3 see the Color of the cooled hot-melt is considered the "standard color" at time t=0. In a period of 16 hours, every hour visually assess the color, selecting in each case, by analogy with the above method of test for determining the "standard color" and evaluating it after cooling. If the color is only slightly different from the standard color to light yellow hue, thermal stability is good. Change the color to intense yellow hues is acceptable.
Solubility in water (in accordance with European standard EN 1720)
Two chemical glass with a volume of 800 ml is poured in 600 g of water. In the first glass is water pH is brought to 5 (±0,1) adding a solution of phosphoric acid (1 part phosphoric acid to 100 parts water). In the second glass is water pH adjusted to 8 (±0,1) the addition of an aqueous sodium hydroxide solution (1 part of sodium hydroxide in 100 parts of water).
In both chemical glasses maintain the temperature of 40°C. Prepare two samples of 3 g of adhesive, cutting pieces of size 1 cm inuyahsa film adhesive with a density of about 200 g/m 2. 3 g samples of the cut film adhesive under stirring loaded into the first and second chemical beaker and stirred for 90 minutes at 40°C.
After that, immediately before filtering conduct a visual assessment, determining what the solution obtained by dispersing: turbid, translucent or transparent. Visual evaluation is conducted by comparing with the water quality standard. The standard corresponds to the contents of the first and second cups without residue film of adhesive. Corresponding to the invention of adhesive a visual assessment did not show differences from the standard, i.e. they dissolve with the formation of a transparent solution) filtered all the contents of the first and second glasses through a filter with pore size of 100 micrometers, and the mass filter was defined before being filtered. The filters are dried in a drying Cabinet at 60°C for 2 hours to constant weight and then weighed. Number from 0 to 0.5 wt.% the residue on the filter is based on an arbitrary number of adhesives suggests that the adhesive is well dispersed and suitable for use in the process of recycling.
|Example 1||Example 3||Example 4 comparison||Example compare 5|
|Viscosity (120°C)||7000-8000 MPa·s||5500-6500 MPa·s||8.000 to 9.000 MPa·s||2500-3000 MPa·s||5000-6000 MPa·s|
|Solubility in water (3 g glue in 600 g of water, pH 5 and pH 8 at 40°C)||Transparent and stable solution||Transparent and stable solution||Transparent and stable solution||Dispersed, muddy and unstable||Dispersed, muddy and unstable|
|Solid||a) Light yellow||a) Light yellow||a) Light yellow||a) Whitish||a) Whitish|
|Melt||b) Transparent||b) PR is transparent||b) Transparent||b) Opaque||b) Opaque|
|Compatibility||Very good||Very good||Very good||Tends to incompatibility||Tends to incompatibility|
|Dried film of glue||Very soft||Very soft||Very soft||Solid||Solid|
1. Water-soluble glue melt containing
from 40 to 70 wt.% not less than one homopolymer or copolymer with free carboxylate groups on the basis of monomers ninasimone ethylene bonds (component A),
from 15 to 45 wt.% at least one water-soluble or dispersible in water polyurethane (component B) and
from 12 to 35 wt.% not less than one alkanolamine (component In),
from 0 to 20 wt.% target additives
moreover, the sum of the components is 100 wt.%.
2. Water-soluble glue melt according to claim 1, characterized in that as component And it contains a copolymer of vinyl acetate and crotonic acid with an acid number of from 10 to 200 mg KOH/g
3. Water-soluble glue melt according to claim 1, characterized in that as component B. it contains a nonionic polyurethane having a viscosity of 500 to 80,000 mPas at 150°C.
4. Water-soluble glue melt according to claim 1, characterized in that as component In it contains alkanolamine with the number of carbon atoms in each alkanones residue from two to six, and the length of carbon chain in alkanols remains one molecule may be identical or different.
5. Water-soluble glue melt according to claim 1, characterized in that as alkanolamine contains triethanolamine.
6. Water-soluble glue melt according to one of claims 1 to 5, characterized in that it has a viscosity at 120°C in the range from 1000 to 20000 MPa∙C.
7. The use of water-soluble hot-melt according to one of claims 1 to 6 as an adhesive for gluing paper and/or flat textile materials.
8. PR is the application according to claim 7 to obtain securities, acquiring stickiness when wet, or not less than two-layer tissue paper, in particular from lignin.
9. A method of obtaining a multilayer material of not less than two layers of paper, in which the first paper layer put glue melt and the adhesive side of the first layer of paper cacheroot at least one second layer of paper, characterized in that the quality of hot melt glue to use water-soluble glue melt according to one of claims 1 to 6.
10. The method of producing securities, the acquiring stickiness when wet, in which glue melt is applied to at least one of the sides of the paper, characterized in that the quality of hot melt glue used water-soluble hot-melt according to one of claims 1 to 6.
11. A method of obtaining a multi-layer textile material in which the adhesive is a hot melt is applied to at least one surface of the first planar textile material and on the adhesive side of the first planar textile material is applied at least one second planar textile material, obtained by the connection of textile materials preferably sew and glue melt in particular removed from the cross-linked compounds of textile materials by washing with water, characterized in that the quality of hot melt glue to use water-soluble glue melt according to one of claims 1 to 6.
FIELD: technological processes, chemistry.
SUBSTANCE: invention is related to compositions used for binding of glass or plastic with the help of polyurethane adhesive. Technical task - development of composition that makes system together with polyurethane adhesive for durable connection of glass or plastic with structure. Composition is suggested, which contains a) one or several organic compounds - titanates having four ligands, where ligands represent hydrocarbyl, which may not contain one or several functional groups, having one or several heteroatoms selected from group that includes oxygen, nitrogen, phosphorous and sulfur, where two or more ligands may create cyclic structure; b) one or several mercapto silanes; c) one or several polyaminosilanes; d) one or several secondary aminosilanes and e) dissolvent that dissolves composition components. Also system is suggested for binding of glass with substrate, which includes suggested composition and adhesive comprising isocyanate functional polymer and catalyst for hardening of isocyanate functional prepolymer.
EFFECT: system may be used in automobile industry for window fixation to vehicle.
10 cl, 5 tbl, 24 ex
SUBSTANCE: hydropyle blocked polyisocyanates are produced by the method wherein: A) one or the several organic polyisocyanates interact with B) one or several organic compounds, containing, at least, one isocyanate reactive group and comprising b1) non-ionic hydropyle groups based on simple poly-alkylenoxide-polyethers containing at least 30 wt % of ethylene-oxide links, and/or b2) ionic or potentially ionic hydropyle groups a forming dissociation equilibrium depending upon pH in interaction with water, and, depending upon pH not having a charge and being charged positively or negatively, or interact with C) one or several blocking means containing, at least, one cyclic ketone with CH-acidity of the general formula (2) where X is the electron-acceptor group, R1, R2 mean independently from each other the hydrogen atom, saturated or unsaturated aliphatic residual containing up to 12 carbon atoms, n is 1, and, if necessary, interacting with one or several (cyclic)aliphatic mono- or polyamines with the amount of amino groups in a molecule of 1 to 4 and molecular weight of up to 400 note that, if necessary, it interacts with one or several multinuclear spirits with the number of hydroxyl groups in a molecule from 1 to 4 and molecular weight of up to 400, and, if necessary, with amino spirits in the presence D) of one or several catalysts or, if necessary, with auxiliary substances and additives and, if necessary E), with solvents. Polyisocyanates can be used for manufacturing varnishes, coatings, sizes, glues and molded products.
EFFECT: improved method of producing hydropyle blocked polyisocyanates.
6 cl, 6 ex
FIELD: compositions for coats.
SUBSTANCE: proposed composition includes heterocyclic silicon compound containing at least one alcohol-orthosilicate group and cross-linking agent interacting with hydroxylic groups. Proposed composition has low content of volatile organic solvents and is hardened at temperature of 5°C ; hardened composition contains no unreacted low-molecular blocking agents which are likely to evolve into surrounding atmosphere at hardening or during operation. Besides that, ratio of life to time to drying time is favorable. Proposed composition may be used for finishing and secondary finishing of automobiles and large transport facilities; it may be also used as an adhesive.
EFFECT: enhanced efficiency.
14 cl, 4 tbl
FIELD: polymerization processes.
SUBSTANCE: invention relates to two-component composition used to initiate curing of one or more polymerizable monomers that are cured when affected by free radicals, which composition consists of organoborane-amino complex and an isocyanate capable of destroying organoborane-amino complex, wherein equivalent ratio of amine nitrogen atoms to boron atoms ranges from more than 4.0:1 to 20.0:1. In another embodiment of invention, subject of invention is two-component composition for use as sealing materials, coatings, primers for modifying polymer surfaces, and as molded resins, which composition consists of component 1: organoborane-amino complex wherein ratio of amine nitrogen atoms to boron atoms ranges from more than 4.0:1 to 20.0:1; component 2: one or more monomers, oligomers, or polymers having olefinic instauration, which are able of being subjected to free-radical polymerization; and effective amount of an isocyanate, which can initiate dissociation of complex to free borane for initiation of polymerization of one or more monomers, oligomers, or polymers having olefinic instauration, provided that complex dissociation initiator is stored separately from complex until initiation of polymerization becomes desirable. Such compositions are handling safe, i.e. they are not self-inflammable, stable at or near ambient temperature and so they do not initiate polymerization at or near ambient temperature in absence of complex dissociation initiator. Polymerized composition show good cohesion and adhesion strength. Described are polymerizable composition polymerization process, method of gluing two or more substrates using polymerizable composition; method of modifying polymer surface having low surface energy using polymerizable composition, as well as coating and laminate containing polymerizable composition.
EFFECT: enlarged resource of polymerizable compositions and expanded application areas thereof.
10 cl, 2 dwg, 4 tbl
FIELD: building materials.
SUBSTANCE: invention relates to a hardening composition used in building industry. The composition comprising a polymer with two or more thiol groups per a molecule, compound with two or more isocyanate groups per a molecule, carbon black and calcium carbonate involves additionally a filling agent wherein silicic acid or silicate is the main component or organic filling agent wherein ground powdered carbon as the main component. The composition shows satisfactory stability in storing the basic compound and the hardening capacity even after storing the basic compound and, except for, it forms the hardened join with sufficient rupture strength limit, hardness and properties of barrier for gas. The composition comprises a hydrocarbon plasticizer and an organometallic compound preferably that provides highly effective hardening properties in combination with higher mechanical strength and properties of barrier for gas. Proposed hardening composition can be used as sealing material in manufacturing isolating glasses, frames, windows for transportation means, glues and covers.
EFFECT: improved and valuable technical properties of composition.
9 cl, 12 tbl, 11 ex
FIELD: polymer materials.
SUBSTANCE: invention relates to polymer compositions including at least one polyurethane prepolymer A with isocyanate terminal groups obtained from at least one polyisocyanate with at least one polyol A1 and, if necessary, with at least one polyol A2. wherein A1 is linear polyoxyalkylenepolyol with unsaturation degree ,less than 0.04 m-equ/g; A2 is polyol, which is present in amount 0-30%, preferably 0-20%, in particular 0-10% based on total amount A1+A2; and at least one polyaldimine B. Composition is a mixture of polyurethane prepolymer A with polyaldimine B. In absence of moisture, such compositions are stable on storage. When being applied, such compositions are brought into contact with moisture, after which polyaldimines are hydrolyzed into aldehydes and polyamines, and polyamines react with polyurethane prepolymer containing isocyanate groups. Products obtained from such composition possess very wide spectrum of properties, including tensile strength varying within a range from 1 to 20 MPa and ultimate elongation above 1000%. Composition may be used as glue, hermetic, coating, or facing.
EFFECT: expanded possibilities of polyurethanes.
3 cl, 7 tbl, 34 ex
FIELD: polymer materials.
SUBSTANCE: invention relates to compositions based on polyols and high-molecular weight diisocyanates with low monomer content as well as to a method for preparation of indicated compositions as binders for reactive glues. In particular, invention provides reactive polyurethane composition based on polyols and high-molecular weight diisocyanates prepared by reaction of diols having average number molecular weight mot higher than 2000 with monomeric diisocyanates having molecular weight not higher than 500. Thus obtained high-molecular weight diisocyanates have maximum monomer content 10%. Invention also describes a method for preparation of indicated composition. Thus obtained compositions are used as glues/hermetics imparting improved adhesion characteristics and having significantly reduced contents of health-detrimental monomeric diisocyanates having molecular weight below 500. For instance, resistance to detachment of film attached to surface using claimed glue is 4.3 N/mm, heat resistance lies at a level of 148°C, and frost resistance below -30°C.
EFFECT: improved adhesive characteristics.
13 cl, 3 tbl, 20 ex
SUBSTANCE: invention relates to compositions based of synthetic high-molecular weight compounds and, in particular, to composition comprising polyurethane-based preparation DESMOCOLL, perchlorovinyl resin, epoxide resin, aliphatic-series polyamine, and polar organic solvent.
EFFECT: enabled retention of high elasticity of glue joint and considerably increased gluing strength for siloxane-coated materials, kapron fabrics, and glass cloth.
FIELD: gluing compositions.
SUBSTANCE: invention relates to a composition that comprises polypropylene glycol glycerol adipinate as a polyester, monophenyl urethane, stabilizing agent, phenolformaldehyde resin, p-dinitrobenzene as a polymerization activating agent, urotropin as a cross-linking agent, a mixture of cyclohexanone, xylene and methyl ethyl ketone as a solvent. The composition can be used in applying on cold and hot surface. Invention is used for teasing articles made of industrial rubber, in preparing monocomponent polyurethane glues for teasing rubber surfaces by electrostatic flocculation method and can be used in industrial rubber and automobile industries. Invention provides conferring thermal stability, reducing vulcanization time and enhancing adhesion strength.
EFFECT: improved and valuable properties of composition.
FIELD: rocketry; development of a composition of binding substance for manufacture of the brush type products.
SUBSTANCE: the invention is pertaining to the field of rocketry, in particular, to development of a composition of binding substance for manufacture of the brush type products. The composition contains, in mass %: hydroxyl-containing polybutadiene rubber - 31.0-33.0; zinc oxide or carbon technical - 7.4-8.0; 1.4- butyleneglycol - 0.7-0.8; trimethylolpropane - 0.08-0.1; transformer oil - 5.2-5.6; stannous dibutyldilaurate - 0.013-0.036; a hardener - oligodiene urethane prepolymer in a combination with 20 % solution of triphenylmethanetriisocyanate in dichlorethane or 27 % solution of triphenylmethanetriisocyanate in ethylacetate with the contents of isocyanate groups of 3.5-4.5% and 53.0-55.5%. The technical result of the invention - manufacture of the composition of binding substance with the high mechanical, binding and operational characteristics and with provision of serviceability of the finished products in the range of temperatures from plus 50°C to minus 50°C at action of high loadings.
EFFECT: the invention ensures production of the binding substance composition with high mechanical, binding and operational characteristics and serviceability of the finished products at the temperatures of plus 50°C - minus 50°C at action of high loadings.
SUBSTANCE: invention refers to adhesive polymer composite material, method of production thereof, product keeping its shape, and hermetic or adhesive composition containing mentioned composite material used in automotive engineering, constructional engineering, wood working, printing industry, footwear industry, as well as in sealing materials and insulation substance. The task in view is solved due to application of polymer composite including at least one hydrogenated or nonhydrogenated polymer nitrile rubber with Mooney viscosity (ML 1+4 at 100°C) less than 30 at least one cross-linking agent or vulcanizing system, and if required at least one bulking agent. Hydrogenated or nonhydrogenated polymer nitrile rubber is derived from metathesis reaction of polymer nitrile rubber with one or several compounds of general formulas I, II, III or IV. If required it is followed by hydrogenation.
EFFECT: development of composite material with long adhesive capacity, elasticity and thermal stability.
9 cl, 3 tbl, 3 ex
FIELD: adhesion materials.
SUBSTANCE: invention relates to adhesion compositions designated for their applying on synthetic fabrics, in particular, for their doubling. The composition consists of the following components, mas. p. p.: copolymer of ethylene with vinyl acetate, 100; blocked polyisocyanate, 1.5-6.0; filling agent, 1-20; stabilizing agent, 0.1-1.0, and resinous agent for enhancing stickiness. The claimed composition shows the enhanced defoliation strength from synthetic fabrics.
EFFECT: improved, enhanced and valuable properties of composition.
1 tbl, 7 ex
SUBSTANCE: invention relates to ethylene copolymers-based adhesive compositions used as adhesives when depositing polymeric protective coating on metallic surface utilizing extrusion and co-extrusion techniques and winding thermosetting multiple-layer adhesive tape. Using composition containing ethylene/vinyl acetate copolymer, silicate filler, and modifying agent (resin OSR-100) results in providing preservation of high adhesion and strength characteristics and resistance to cathode peeling when lowering metal temperature heating to 100-130°C in double-layer coating structure and also ensuring high values of adhesion strength for ground epoxide layer in triple-layer coating structure.
EFFECT: enhanced adhesive properties in multiple-layer coating applications.
FIELD: adhesive composition, in particular adhesive paste for wallpaper.
SUBSTANCE: claimed composition contains flavoring agent releasing adhesive, component comprising of at least one flavoring agent, and at least one carrier. Composition is in dry form such as powder or granules and can be mixed with water. Moreover in odor-releasing component at least one flavoring agent is bond to carrier in such a manner that said flavoring agent in released from composition only after component contact with water. As carrier preferably cyclodextrin or derivatives thereof are used.
EFFECT: composition free from displeasing odor after blending with water.
7 cl, 1 ex
FIELD: polymers, adhesives.
SUBSTANCE: invention relates to polymer dispersion useful in production of adhesive and coating agent. Claimed dispersion contains water, at least one polymer, obtained by emulsion polymerization, at least one anticoagulant, at least one water soluble metal acid salt and at least one cross-linking resin based on hydroxymethyl-substituted imidazolidinones such as 1,3-dimethylol-4,5-dihydroxyimidazolidinone (4,5-dihydroxy-N,N'-dimethylolethylenecarbamide), hydroxymethyl-substituted pyrimidinones or hydroxymethyl-substituted triazinones, or products of self-condensation thereof, or mixed condensates of two or more abovementioned compounds, or mixture of two or more abovementioned compounds. Method for production of polymer dispersion also is disclosed.
EFFECT: adhesive and coating agent containing polymer dispersion of present invention with increased moisture resistance.
18 cl, 9 ex, 1 tbl
FIELD: mechanical engineering and adhesives.
SUBSTANCE: method consists in mixing glue (of special type) with a solvent to viscosity 30-50 sec and then, at ratio 1:(0.15-0.13), with phenol-formaldehyde resin being a constituent of composite friction element and preliminarily diluted with a solvent to viscosity 30-50 sec so that glue composition is homogenous and has viscosity 30-50 sec.
EFFECT: increased joint strength.