JP2007238934A - Crosslinkable aqueous dispersion composition and method for producing the same, and adhesive and coating agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a crosslinkable aqueous dispersion composition excelletn in water resistance, especially boiling water resistance, and shelf viscosity stability(long in pot-life), to provide a method for producing the same, and to provide an adhesive and a coating agent. <P>SOLUTION: The crosslinkable aqueous dispersion composition contains (A) polymer microparticles composed mainly of at least one kind of monomer units selected from ethylenically unsaturated monomer and diene unsaturated monomer units and containing 0.1-10 wt.% of at least one kind of crosslinkable unsaturated monomer units selected from carboxy group-containing unsaturated monomer, N-methylol (meth)acrylamide, N-butoxymethyl (meth)acrylamide, diacetoneacrylamide and acetoacetoxyethyl (meth)acrylate units, (B) a vinyl alcohol-based copolymer having 1-10 mol% of ethylene units and 0.1-10 mol% of carboxy group-containing monomer units and (C) a crosslinking agent. The method for producing the crosslinkable aqueous dispersion composition is also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a crosslinkable aqueous dispersion composition, a method for producing the same, and an adhesive and a coating agent. More specifically, a crosslinkable aqueous dispersion composition comprising fine polymer particles containing a specific crosslinkable unsaturated monomer unit, a vinyl alcohol copolymer having an ethylene unit and a carboxyl group-containing monomer unit, and a crosslinking agent. And a manufacturing method thereof, and an adhesive and a coating agent. More specifically, the present invention relates to a crosslinkable aqueous dispersion composition excellent in water resistance, particularly boiling water resistance and viscosity standing stability (long pot life), a method for producing the same, and the crosslinkable aqueous dispersion composition. It relates to an adhesive and a coating agent comprising

  Polyvinyl alcohol (hereinafter sometimes abbreviated as PVA) is widely used as a protective colloid for emulsion polymerization of ethylenically unsaturated monomers, particularly vinyl ester monomers represented by vinyl acetate. Vinyl ester aqueous emulsions obtained by emulsion polymerization using as a protective colloid are various adhesives for paper, woodwork and plastics, various binders for impregnated paper and non-woven products, admixtures, joints Widely used in fields such as materials, paint, paper processing and fiber processing.

  Such an aqueous emulsion is effective in various applications by forming a film having strong mechanical strength under dry conditions, but forms a continuous phase in the film under high humidity or water wet conditions. Since PVA is water-soluble, there is a problem that elution and water absorption of PVA are large, and mechanical strength is remarkably lowered.

  For this reason, various means have been tried so far in order to increase the water resistance and hot water resistance of a film obtained from an emulsion containing PVA as a dispersant. As a typical example, a method of blending a polyvalent isocyanate compound into an emulsion using PVA as a dispersant is known. In this method, since the isocyanate strongly reacts with the hydroxyl group of PVA and the like, remarkable water resistance is exhibited. On the other hand, since the isocyanate reacts with water, the pot life of the composition is very short, and the workability is improved. There's a problem.

In addition, various adhesives using an aqueous emulsion having a PVA polymer as a dispersant have been proposed. For example, (1) an aqueous emulsion using PVA as a dispersant, and an adhesive comprising an aliphatic aldehyde such as glyoxal (Patent Document 1), (2) an amino compound such as PVA, an aqueous emulsion, a crosslinking agent, and chitosan Adhesives (Patent Document 2), (3) Crosslinking agents such as PVA, aqueous emulsion, aluminum chloride, and adhesives composed of polyvalent isocyanate compounds (Patent Document 3), (4) α-olefin units having 4 or less carbon atoms An adhesive mainly composed of an emulsion containing PVA as a dispersant (Patent Document 4), (5) an emulsion obtained by emulsion polymerization in the presence of a carboxyl group-modified PVA, a reaction product of a polyamide and an epoxy group-containing compound Composition (Patent Document 5), (6) PVA polymer having an α-olefin unit in the molecule and carbo Known is an aqueous emulsion having a PVA polymer having a xyl group as a dispersant, an epoxy compound, an amino group-containing aqueous resin, a composition comprising a water-resistant agent selected from an aluminum compound and a titanium compound (Patent Document 6). Yes.
JP 55-94937 A JP-A-3-45678 Japanese Patent Publication No.57-16150 Japanese Patent No. 3466316 Japanese Patent No. 3311086 JP 2001-40231 A

  However, in the adhesives of the above (1), (2), (4), (5) and (6), although water resistance is improved, boiling water resistance is not always sufficient. In addition, the adhesive (3) has poor viscosity storage stability (short pot life) and a problem in workability. Therefore, it is no exaggeration to say that there are no aqueous dispersions, compositions, adhesives and coating agents that have both high water resistance, particularly boiling water resistance and viscosity storage stability, at the current technical level. There is room for improvement.

  Under such circumstances, an object of the present invention is to provide a crosslinkable aqueous dispersion composition, an adhesive and a coating agent which are excellent in both water resistance, in particular boiling water resistance, and viscosity standing stability. To do.

  The present inventors have prepared polymer fine particles containing a specific crosslinkable unsaturated monomer unit, a PVA polymer having an ethylene unit, a PVA polymer having a carboxyl group as an aqueous dispersion to achieve such an object. A patent application was previously filed as Japanese Patent Application No. 2005-203788 for an aqueous dispersion containing a coalescence and a crosslinking agent and having a specific composition ratio. This aqueous dispersion has the above-mentioned preferable properties, and is a promising aqueous dispersion in the future as an adhesive or a coating agent.

  As a result of further studies on the aqueous dispersion, the present inventor has obtained polymer fine particles containing a specific crosslinkable unsaturated monomer unit, and a vinyl alcohol copolymer having an ethylene unit and a carboxyl group-containing monomer unit. The inventors have found that the above object can also be achieved by a crosslinkable aqueous dispersion composition comprising a crosslinking agent and the present invention. That is, the present invention provides (A) an unsaturated monomer having at least one monomer unit selected from ethylenically unsaturated monomers and diene unsaturated monomers as a main component and having a carboxyl group, N-methylol. Heavy weight containing 0.1 to 10% by weight of at least one crosslinkable unsaturated monomer unit selected from (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide and acetoacetoxyethyl (meth) acrylate Coalesced fine particles, (B) a vinyl alcohol copolymer having 1 to 10 mol% of ethylene units and 0.1 to 10 mol% of carboxyl group-containing monomer units, (C) consisting of a crosslinking agent, (A) / (B) = 99 / 1-80 / 20 (solid content weight ratio), [(A) + (B)] / (C) = 99.9 / 0.1-90 / 10 (solid content weight ratio) Is a crosslinkable aqueous dispersion composition is.

  Another invention of the present invention is an adhesive comprising such a crosslinkable aqueous dispersion composition. Another invention of the present invention is a coating agent comprising such a crosslinkable aqueous dispersion composition.

  Furthermore, another invention of the present invention uses a vinyl alcohol copolymer having 1 to 10 mol% of ethylene units and 0.1 to 10 mol% of carboxyl group-containing monomer units as a dispersion stabilizer, Unsaturated monomer having at least one monomer unit selected from monomers and diene unsaturated monomers as a main component and having a carboxyl group, N-methylol (meth) acrylamide, N-butoxymethyl (meth) A crosslinkable aqueous solution characterized by blending an aqueous emulsion obtained by emulsion polymerization of at least one crosslinkable unsaturated monomer selected from acrylamide, diacetone acrylamide and acetoacetoxyethyl (meth) acrylate. It is a manufacturing method of a dispersion liquid composition.

  According to the present invention, there is provided a crosslinkable aqueous dispersion composition comprising polymer fine particles containing a crosslinkable unsaturated monomer unit, a vinyl alcohol copolymer having an ethylene unit and a carboxyl group-containing monomer unit, and a crosslinker. can do. Such a crosslinkable aqueous dispersion composition has both high water resistance, particularly excellent boiling water resistance, and excellent viscosity storage stability, and is suitably used as a high-performance adhesive and coating agent. It is done.

  The polymer fine particles (A) in the crosslinkable aqueous dispersion composition of the present invention are composed mainly of at least one monomer unit selected from ethylenically unsaturated monomers and diene unsaturated monomers. Group-containing unsaturated monomer, at least one crosslinkable unsaturated monomer selected from N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide and acetoacetoxyethyl (meth) acrylate Contains units.

  Here, various types of ethylenically unsaturated monomer units and diene monomer units that mainly constitute polymer fine particles can be used, but olefins such as ethylene, propylene, and isobutylene, vinyl chloride, vinyl fluoride, Halogenated olefins such as vinylidene chloride and vinylidene fluoride, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl versatic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid Dodecyl, acrylic esters such as 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, etc. Kuryl ester, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and quaternized products thereof, acrylamide, methacrylamide, N, N-dimethylacrylamide, acrylamido-2-methylpropanesulfonic acid and its sodium salt, etc. Acrylamide monomers, styrene, α-methylstyrene, p-styrenesulfonic acid and styrene monomers such as sodium and potassium salts, other N-vinylpyrrolidone, and diene series such as butadiene, isoprene and chloroprene Monomer.

  Also, crosslinkable unsaturated monomers having an alkoxysilane group such as vinyltrimethoxysilane and methacryloxypropyltrimethoxysilane, crosslinkable unsaturated monomers having an epoxy group such as glycidyl methacrylate and allyl glycidyl ether, vinyl oxazoline Crosslinkable unsaturated monomers having an oxazoline group such as 2-propenyl-2-oxazoline can also be used as long as the performance of the present invention is not impaired.

  Among the above unsaturated monomers, vinyl ester monomers, ethylene and vinyl ester monomers and vinyl esters and (meth) acrylic acid ester monomers are preferred, from an industrial viewpoint. As the vinyl ester monomer unit, vinyl acetate is particularly preferable.

  Further, in the present invention, (A) the unsaturated monomer having a carboxyl group constituting the polymer fine particles includes acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, (anhydrous) maleic acid, (anhydrous) Examples include phthalic acid and cinnamic acid. These can also be used in the form of neutralized products such as sodium salts and half esters.

  In the present invention, (A) the polymer fine particle is an unsaturated monomer having a carboxyl group mainly comprising at least one monomer unit selected from an ethylenically unsaturated monomer and a diene unsaturated monomer, At least one crosslinkable unsaturated monomer unit selected from N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide and acetoacetoxyethyl (meth) acrylate is included in all monomer units. It is necessary to contain 0.1 to 10 weight%, Preferably it is 0.2 to 8 weight%, More preferably, it is 0.3 to 6 weight%.

  When the content of the crosslinkable unsaturated monomer unit is less than 0.1% by weight, when the resulting crosslinkable aqueous dispersion composition is formed into a film, the crosslink density is low. In addition, when this content exceeds 10% by weight, there is a problem that the viscosity standing stability of the resulting crosslinkable aqueous dispersion composition is lowered. Of these crosslinkable unsaturated monomers, unsaturated monomers having a carboxyl group are preferred, and among unsaturated monomers having a carboxyl group, acrylic acid and methacrylic acid are preferred. (A) The particle size of the polymer fine particles is preferably about 0.05 to 10 μm, more preferably 0.1 to 7 μm, more preferably 0.1 to 0.1 μm, as measured by a dynamic light scattering method. ~ 5 μm.

  In the present invention, (B) a vinyl alcohol copolymer having 1 to 10 mol% of ethylene units and 0.1 to 10 mol% of carboxyl group-containing monomer units is a vinyl ester, a monomer having ethylene and a carboxyl group. It can be obtained by saponifying a copolymer with a monomer. Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate and the like, and vinyl acetate is preferable from an economical viewpoint.

  In the present invention, the content of the ethylene unit in the vinyl alcohol polymer (B) having an ethylene unit and a carboxyl group-containing monomer unit needs to be 1 to 10 mol%, preferably 2 to 8 mol%. When the ethylene unit content is less than 1 mol%, the water resistance when the resulting aqueous dispersion is formed into a film is not sufficient, and when it exceeds 10 mol%, the vinyl alcohol polymer is dissolved in water. As a result, the stable aqueous dispersion may not be obtained.

  In addition, the content of the carboxyl group-containing monomer unit of the vinyl alcohol polymer needs to be 0.1 to 10 mol%, preferably 0.2 to 8 mol%, more preferably 0. .25-7 mol%. When the monomer unit having a carboxyl group is less than 0.1 mol%, the crosslinking point is reduced, and sufficient performance such as boiling resistance is not exhibited, and when it exceeds 10 mol%, a crosslinking agent is added. There are problems such as a decrease in viscosity stability. Examples of the unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, itaconic acid, crotonic acid, and fumaric acid. Acids and their half esters or anhydrides are preferred.

  In the present invention, (B) the vinyl alcohol polymer having an ethylene unit and a carboxyl group-containing monomer unit is a copolymer of an ethylenically unsaturated monomer that can be copolymerized within a range that does not impair the effects of the present invention. It may be polymerized. Examples of such ethylenically unsaturated monomers include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, trimethyl- (3-acrylamide-3-dimethylpropyl) -ammonium chloride, acrylamide-2-methylpropanesulfonic acid. And its sodium salt, ethyl vinyl ether, butyl vinyl ether, N-vinyl pyrrolidone, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, sodium vinyl sulfonate, sodium allyl sulfonate, etc. It is done. Also obtained by copolymerizing vinyl ester monomers such as vinyl acetate with monomers having ethylene and carboxyl groups in the presence of thiol compounds such as thiol acetic acid and mercaptopropionic acid, and saponifying it. It is also possible to use a terminal modified product.

  The saponification degree of the vinyl alcohol polymer having an ethylene unit and a carboxyl group-containing monomer unit of the present invention is preferably 80 to 99.5 mol%, more preferably 85 mol% to 99.99. It is 5 mol%, More preferably, it is 86-99.5 mol%. When the saponification degree is within this range, the water resistance of the aqueous dispersion of the present invention, particularly the boiling water resistance and the viscosity standing stability are well maintained.

  Moreover, the range of 100-4000 is preferable and, as for the polymerization degree of this polymer, 200-3000 are more preferable. When the degree of polymerization is within this range, the dispersion stability of the aqueous dispersion of the present invention and the water resistance of the film are well maintained.

  In the present invention, (C) the crosslinking agent can be selected from those which undergo a crosslinking reaction with a carboxyl group and a hydroxyl group. From the viewpoints of crosslinking reactivity in crosslinking with the functional group in the aqueous dispersion and pot life, methylol. Group-containing compounds (resins), epoxy compounds (resins), aziridine group-containing compounds (resins), oxazoline group-containing compounds (resins), carbodiimide compounds, aldehyde compounds (resins), various water-soluble or colloidal metal salts, etc. . Specifically, water-soluble epoxy compounds, polyamidoamine epichlorohydrin adducts, urea-glyoxal resins, aluminum salts, zirconium salts, and titanium salts are preferably used.

  More specifically, from the viewpoints of crosslinkability and pot life, polyamidoamine epichlorohydrin adducts, water-soluble aluminum salts such as aluminum chloride and aluminum nitrate, and glyoxal resins such as urea-glyoxal resins can be mentioned. Alternatively, two or more are more preferable, and in particular, the combined use of a water-soluble aluminum salt and a polyamidoamine epichlorohydrin adduct or a glyoxal resin exhibits a high effect.

  The crosslinkable aqueous dispersion composition of the present invention can be obtained by various methods. (B) Vinyl alcohol having 1 to 10 mol% of ethylene units and 0.1 to 10 mol% of carboxyl group-containing monomer units. An unsaturated monomer having a carboxyl group, the main component of which is a main component of at least one monomer unit selected from (A) an ethylenically unsaturated monomer and a diene unsaturated monomer. And at least one cross-linkable unsaturated monomer selected from N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide and acetoacetoxyethyl (meth) acrylate. It can manufacture preferably by mix | blending (C) crosslinking agent with an aqueous emulsion.

  The emulsion polymerization method using the above (A) and (B) is not particularly limited, and conventionally known emulsion polymerization conditions (temperature, pressure, stirring speed, etc.), monomer addition method {initial batch addition, Continuous addition, addition of a monomer pre-emulsion solution (continuous addition of a monomer emulsified in a dispersion stabilizer aqueous solution, etc.)} can be performed using a conventionally known initiator. In the emulsion polymerization, any of the vinyl alcohol polymers (B) is used as a dispersion stabilizer, and the emulsion polymerization of the monomer constituting the polymer fine particles (A) is started, and the polymerization is completed or completed. A method of post-adding the remaining aqueous solution (B) later can also be employed.

  The quantitative relationship of each of the crosslinkable aqueous dispersion compositions containing (A), (B) and (C) of the present invention is a solid content weight ratio, and (A) / (B) is 99/1 to 80/20, preferably 98.5 / 1.5 to 87/13, more preferably 98/2 to 85/15. In this case, when (A) is too much, there is a problem that the viscosity standing stability and mechanical stability of the crosslinkable aqueous dispersion composition are lowered. When (A) is too small, the crosslinkable aqueous dispersion composition The water resistance, particularly boiling water resistance, when a product is formed into a film is lowered, and at the same time, the viscosity standing stability is deteriorated.

  Furthermore, the content ratio of the (C) crosslinking agent is [(A) + (B)] / (C) = 99.9 / 0.1 to 90/10, preferably 99.8 / 0.2 to 91/9, more preferably 99.7 / 0.3 to 92/8. When the amount of (C) is too small, the water resistance when the crosslinkable aqueous dispersion composition is formed into a film due to a decrease in the crosslinking density, in particular, the boiling water resistance is not sufficiently exhibited. The viscosity storage stability of the water-based aqueous dispersion composition deteriorates.

  Various adhesiveness, water resistance, boiling water resistance, etc. can be improved by mix | blending a filler (filler) with the crosslinkable aqueous dispersion composition of this invention. Examples of the filler include organic or inorganic fillers. Examples of the organic filler include wood flour, wheat flour, and starch, and examples of the inorganic filler include clay, kaolin, talc, calcium carbonate, and titanium oxide. In particular, when an inorganic filler is blended, the effect of improving water resistance, particularly boiling water resistance, is remarkably preferable. There is no restriction | limiting in particular in the mixture ratio of the aqueous dispersion liquid of this invention, and a filler (filler), Although it can set suitably according to a use and the objective, The compounding quantity of a filler is [(A) + (B )] 5 to 200 parts by weight, more preferably 10 to 150 parts by weight per 100 parts by weight.

  The crosslinkable aqueous dispersion composition of the present invention has various organic solvents such as toluene, perylene, dichlorobenzene, and trichlorobenzene, dibutyl phthalate, etc. in order to adjust the drying property, setting property, viscosity, film forming property, etc. Various plasticizers, various film-forming aids such as glycol ethers, ester starch, modified starch, oxidized starch, sodium alginate, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, maleic anhydride / isobutene copolymer, maleic anhydride / styrene copolymer Polymers, maleic anhydride / methyl vinyl ether copolymers, water-soluble polymers such as various polyvinyl alcohols other than the above (B), nonionic, anionic and cationic surfactants, antifoaming agents, dispersants, antifreezes Various additives such as preservatives, preservatives, and rust inhibitors are required It may be added in response.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these. In Examples and Comparative Examples, “parts” and “%” mean weight basis unless otherwise specified. Table 1 summarizes the compositions and dispersion stability of the crosslinkable aqueous dispersion compositions of Examples and Comparative Examples. The symbols in Table 1 are as follows.

  * 1)% by weight in parentheses * 2) in parentheses (A) parts by weight per 100 parts by weight, * 3) in parentheses (A) + (B) parts by weight per 100 parts by weight, VAC: acetic acid Vinyl, Et: ethylene, BA: butyl acrylate, St: styrene, Bd: butadiene, AA: acrylic acid, MAA: methacrylic acid, NMA: N-methylolacrylamide, BMA: N-butoxymethylmethacrylamide, AAEM: acetoacetoxyethyl Methacrylate, DAA: diacetone acrylamide, PAEpi: polyamidoamine epichlorohydrin resin, GOX: glyoxal resin

Example 1
In a 1 liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, and a nitrogen blowing port, ion-exchanged water 350 g, PVA-1 (ethylene unit content 4.5 mol%, itaconic acid unit content 1. 29.6 g of 0 mol%, saponification degree 98.1 mol%, polymerization degree 1300) were charged and completely dissolved at 95 ° C. Next, this PVA aqueous solution was cooled, purged with nitrogen, charged with 36.6 g vinyl acetate and 0.4 g acrylic acid while stirring at 200 rpm, heated to 60 ° C., and then a hydrogen peroxide / tartaric acid redox initiator. To initiate the polymerization.

  15 minutes after the start of polymerization, a mixture of 329.7 g of vinyl acetate and 3.3 g of acrylic acid was continuously added over 3 hours to complete the polymerization, so that the solid concentration was 50.0% and the particle size was 0.9 μm. A polyvinyl acetate emulsion was obtained. 5 parts of dibutyl phthalate as a plasticizer is added to and mixed with 100 parts of the solid content of the emulsion, and further 2.7 parts of a polyamidoamine epichlorohydrin adduct (WS-4020, 25% aqueous solution, manufactured by Hokko PMC) and aluminum nitrate 2 0.0 part was added and the crosslinkable aqueous dispersion liquid composition was obtained. The obtained composition was free from aggregation and gelation and had high dispersion stability. Table 2 shows the results of evaluating the film water resistance, water-resistant adhesive strength, and viscosity storage stability (pot life) in the following manner.

(Evaluation of aqueous dispersion and composition)
(1) Water resistance of the film The obtained crosslinkable aqueous dispersion composition was cast on a PET film at 20 ° C. and 65% RH and dried for 7 days to obtain a dry film of 500 μm. Water absorption% [{(weight after immersion−weight before immersion) / weight before immersion} when the film was punched into a diameter of 2.5 cm and immersed in water at 20 ° C. for 24 hours as a sample. × 100].
(2) Water-resistant adhesive strength (boil-resistant adhesive strength)
The obtained crosslinkable aqueous dispersion composition was applied to a hookwood (mesh) at 150 g / m ² , and bonded to each other for 16 hours under a load of 7 kg / m ² . After decompression, curing at 20 ° C. and 65% RH for 5 days, immersing in boiling water for 4 hours, drying at 60 ° C. for 20 hours, further immersing in boiling water for 4 hours and then compressing in a wet state Shear strength was measured.
(3) Viscosity storage stability (pot life)
When the obtained crosslinkable aqueous dispersion composition was allowed to stand at 30 ° C., the viscosity change after 30 days was observed.

Example 2
In Example 1, a crosslinkable aqueous dispersion composition was obtained in the same manner as in Example 1 except that the polyamidoamine epichlorohydrin adduct was not added. The results are shown in Table 2.

Example 3
In Example 1, a crosslinkable aqueous dispersion composition was obtained in the same manner as in Example 1 except that aluminum nitrate was not added. The results are shown in Table 2.

Example 4
In Example 1, instead of polyamidoamine epichlorohydrin adduct and aluminum nitrate, glyoxal resin (Clariant Co., Ltd., Carterbond TSI, 42% aqueous solution) was added in the same manner as in Example 1 except that 2.4 parts were added. An aqueous dispersion composition was obtained. The results are shown in Table 2.

Comparative Example 1
In Example 1, a crosslinkable aqueous dispersion composition was obtained in the same manner as in Example 1 except that the polyamidoamine epichlorohydrin adduct and aluminum nitrate were not added. The results are shown in Table 2.

Example 5
In Example 1, 351.5 g of vinyl acetate (initial 35.2 g, sequential addition 316.3 g) and 18.5 g of acrylic acid (initial 1.9 g, sequential addition 16.6 g) were used in the same manner as in Example 1 to perform crosslinking. An aqueous dispersion composition was obtained. The results are shown in Table 2.

Comparative Example 2
In Example 1, 329.3 g of vinyl acetate (initial 32.9 g, sequential addition 296.4 g) and 40.7 g of acrylic acid (initial 4.1 g, sequential addition 36.6 g) were used in the same manner as in Example 1. A crosslinkable aqueous dispersion composition was obtained. The dispersion stability was poor and aggregates were formed.

Example 6
A crosslinkable aqueous dispersion composition was obtained in the same manner as in Example 1 except that the same weight of N-methylolacrylamide was used instead of acrylic acid. The results are shown in Table 2.

Example 7
A crosslinkable aqueous dispersion was obtained in the same manner as in Example 1 except that the same weight of N-butoxymethylmethacrylamide was used instead of acrylic acid. The results are shown in Table 2.

Example 8
In Example 1, a crosslinkable aqueous dispersion composition was obtained in the same manner as in Example 1 except that the same weight of acetoacetoxyethyl methacrylate was used instead of acrylic acid. The results are shown in Table 2.

Example 9
In Example 1, a crosslinkable aqueous dispersion composition was obtained in the same manner as in Example 1 except that the same weight of diacetone acrylamide was used instead of acrylic acid. The results are shown in Table 2.

Comparative Example 3
In Example 1, a crosslinkable aqueous dispersion composition was obtained in the same manner as in Example 1 except that acrylic acid was not used. The results are shown in Table 2.

Example 10
In Example 1, instead of PVA-1, PVA-2 (ethylene unit content 2.0 mol%, itaconic acid unit content 0.5 mol%, saponification degree 89.9 mol%, polymerization degree 2050) 29 A crosslinkable aqueous dispersion composition was obtained in the same manner as in Example 1 except that .6 g was used. The results are shown in Table 2.

Example 11
In Example 10, instead of PVA-2, PVA-3 (ethylene unit content 8.1 mol%, maleic acid unit content 5.1 mol% saponification degree 99.1 mol%, polymerization degree 500) 29.6 g A crosslinkable aqueous dispersion was obtained in the same manner as in Example 10 except that was used. The results are shown in Table 2.

Comparative Example 4
In Example 11, instead of PVA-3, PVA-4 (ethylene unit content 12.0 mol%, maleic acid unit content 5.1 mol%, saponification degree 99.2 mol%, polymerization degree 480) was 29. A crosslinkable aqueous dispersion composition was obtained in the same manner as in Example 11 except that .6 g was used. The composition was unstable and formed aggregates.

Comparative Example 5
In Example 11, PVA-5 (ethylene content 4.5 mol%, saponification degree 98.1 mol%, polymerization degree 1500) was used in the same manner as in Example 11 except that 29.6 g was used instead of PVA-3. Aqueous dispersion was obtained. The results are shown in Table 2.

Comparative Example 6
In Example 11, PVA-6 (content of itaconic acid unit: 1.2 mol%, saponification degree: 89.2 mol%, polymerization degree: 1700) was used in place of PVA-3, except that 29.6 g was used. Thus, a crosslinkable aqueous dispersion was obtained. The results are shown in Table 2.

Comparative Example 7
In Example 11, a crosslinkable aqueous dispersion was used in the same manner as in Example 11 except that 29.6 g of unmodified polyvinyl alcohol PVA-7 (saponification degree: 88.2 mol%, polymerization degree: 1750) was used instead of PVA-3. A liquid was obtained. The results are shown in Table 2.

Example 12
10.8 g of PVA-8 (ethylene unit content 1.5 mol%, itaconic acid unit content 2.2 mol%, saponification degree 92.0 mol%, polymerization degree 700) was dissolved in 290 g of ion-exchanged water by heating. It was charged into a pressure-resistant autoclave equipped with a nitrogen inlet and a thermometer. After adjusting the pH to 4.0 with dilute sulfuric acid, 288 g of vinyl acetate and 3.6 g of methacrylic acid were charged, and then the pressure of ethylene was increased to 42 kg / cm ² G (the amount of ethylene charged corresponds to 68.4 g). After raising the temperature to 60 ° C., polymerization was initiated with a hydrogen peroxide-Longalite redox initiator.

  Two hours later, when the residual vinyl acetate concentration reached 0.7%, the polymerization was terminated to obtain a vinyl acetate-ethylene copolymer emulsion having a solid content concentration of 52.3% and a particle size of 0.8 μm. 50 parts of calcium carbonate was added to and mixed with 100 parts of the solid content of the emulsion, and 5.0 parts of aluminum nitrate was further added to obtain a crosslinkable aqueous dispersion composition. Evaluation similar to Example 1 was performed using this composition. The results are shown in Table 2.

Example 13
In a 1 liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer, and a nitrogen blowing port, ion-exchanged water 350 g, PVA-1 (ethylene unit content 4.5 mol%, itaconic acid unit content 1. (0 mol%, saponification degree 98.1 mol%, polymerization degree 1300) 33.3 g was charged and completely dissolved at 95 ° C. Next, this PVA aqueous solution was cooled, purged with nitrogen, charged with 25.9 g of vinyl acetate and 10.4 g of butyl acrylate while stirring at 200 rpm, heated to 60 ° C., and then added with 10 g of 2% potassium persulfate aqueous solution. Polymerization was started.

  15 minutes after the start of the polymerization, a mixture of 233.1 g of vinyl acetate, 93.2 g of N-butyl acrylate and 7.4 g of N-isobutoxymethyl methacrylamide was continuously added over 4 hours to complete the polymerization. A vinyl acetate-butyl acrylate copolymer emulsion having a solid content concentration of 49.6% and a particle size of 0.8 μm was obtained. 50 parts by weight of flour was added to and mixed with 100 parts by weight of the solid content of the emulsion, and 5.0 parts of aluminum nitrate was added to obtain a crosslinkable aqueous dispersion composition. Evaluation similar to Example 1 was performed using this composition. The results are shown in Table 2.

Example 14
Anionic surfactant (Sandet BL manufactured by Sanyo Chemical Industries, Ltd.) 1.5 g and nonionic surfactant (Nonipol 200: manufactured by Sanyo Chemical Co., Ltd.) 3.0 g are dissolved in 290 g of ion-exchanged water by heating and dissolved in nitrogen. It charged in the pressure-resistant autoclave provided with the inlet and the thermometer. After adjusting to pH 4.0 with dilute sulfuric acid, charged with 120 g of styrene and 3.0 g of methacrylic acid, then charged with 177 g of butadiene from a pressure gauge, heated to 70 ° C., and injected with 10 g of 2% potassium persulfate aqueous solution. Polymerization was started. The internal pressure decreased from 4.8 kg / cm ² G with the progress of the polymerization, and after 15 hours, the polymerization was terminated when the internal pressure decreased to 0.4 kg / cm ² G.

  The obtained emulsion was adjusted to pH 6.0 with aqueous ammonia, and a styrene-butadiene copolymer emulsion having a solid content concentration of 48.5% and a particle size of 0.5 μm was obtained. 6 parts by weight of PVA-3 (content of ethylene unit: 8.1 mol%, content of maleic acid unit: 5.1 mol%, saponification degree: 99.1 mol%, polymerization degree: 500) per 100 parts of the solid content of the emulsion What was heated and dissolved in 34 parts by weight of ion-exchanged water was added and mixed, and further 2.7 parts of a polyamidoamine epichlorohydrin adduct (WS-4020, 25% aqueous solution made by Starlight PMC) and 2.0 parts of aluminum nitrate were added. An aqueous dispersion was obtained. The obtained crosslinkable aqueous dispersion composition had high dispersion stability without aggregation and gelation, and was evaluated in the same manner as in Example 1. The results are shown in Table 2. From the above results, it is clear that the aqueous dispersion of the present invention is excellent as an adhesive or a coating agent.

  The crosslinkable aqueous dispersion composition of the present invention is excellent in water resistance, particularly in boiling water resistance, and also has excellent viscosity standing stability (long pot life). It is extremely useful for various adhesives, coating materials, various coating agents for paper processing, fiber processing and the like.

Claims (7)

(A) an unsaturated monomer having at least one monomer unit selected from an ethylenically unsaturated monomer and a diene unsaturated monomer as a main component and a carboxyl group, N-methylol (meth) acrylamide, Polymer fine particles containing 0.1 to 10% by weight of at least one crosslinkable unsaturated monomer unit selected from N-butoxymethyl (meth) acrylamide, diacetone acrylamide and acetoacetoxyethyl (meth) acrylate, (B ) A vinyl alcohol copolymer having 1 to 10 mol% of ethylene units and 0.1 to 10 mol% of carboxyl group-containing monomer units, and comprising (C) a crosslinking agent, and (A) / (B) = 99 / 1-80 / 20 (solid content weight ratio), [(A) + (B)] / (C) = 99.9 / 0.1 to 90/10 (solid content weight ratio) Dispersion liquid composition. 2. The crosslinkable aqueous dispersion composition according to claim 1, wherein the polymer fine particles are polymer fine particles mainly composed of vinyl acetate units. The crosslinkable aqueous dispersion composition according to claim 1, wherein (C) the crosslinking agent is at least one selected from a polyamidoamine epichlorohydrin adduct, a water-soluble aluminum salt, and a glyoxal resin. Furthermore, the crosslinkable aqueous dispersion composition in any one of Claims 1-3 which mix | blended the filler. An adhesive comprising the crosslinkable aqueous dispersion composition according to claim 1. The coating agent which consists of a crosslinkable aqueous dispersion composition in any one of Claims 1-4. A vinyl alcohol copolymer having 1 to 10 mol% of ethylene units and 0.1 to 10 mol% of a carboxyl group-containing monomer unit is used as a dispersion stabilizer, and an ethylenically unsaturated monomer and a diene unsaturated monomer are used. Unsaturated monomer having at least one monomer unit selected from a monomer as a main component and having a carboxyl group, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide and acetoacetoxyethyl A method for producing a crosslinkable aqueous dispersion composition comprising blending a crosslinker with an aqueous emulsion obtained by emulsion polymerization of at least one crosslinkable unsaturated monomer selected from (meth) acrylates.