JPH0748538A - Composition for water-based coating material and ink - Google Patents

Abstract

PURPOSE:To obtain the composition which can form a tough coating film by neutralizing a vinyl polymer made from methyl methacrylate, an acid-group- containing compound, etc., dissolving the neutralized polymer in water and mixing the obtained aqueous solution with a specified aqueous urethane polymer dispersion. CONSTITUTION:A mixture comprising 30-90wt.% methyl methacrylate, 0-30wt.% aromatic vinyl compound especially styrene, 4-20wt.% acid-group-containing vinyl compound especially (meth)acrylic acid and 0-66wt.% other vinyl monomers such as alkyl methacrylate is suspension-polymerized to obtain a vinyl polymer having a Tg of 10-150 deg.C, a specified molecular weight and an acid value of 35-200mgKOH/g, this polymer is neutralized, and the neutralized polymer is dissolved in water to obtain an aqueous solution (A). This solution A is combined with an aqueous urethane polymer dispersion obtained by neutralizing a urethane prepolymer made from an aliphatic or alicyclic diisocyanate, a polyether or an ester diol of a specified molecular weight and an acid-group- containing diol with a tert. amine, and dispersing the neutralized polymer in water in an A/B weight ratio of 5/95 to 95/5 (in terms of the solid content) to obtain the composition for use on an plastic film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has good pigment dispersibility,
The present invention relates to a composition for water-based paints and inks which forms a coating film which is tough with less generation of insoluble aggregates during coating and has good adhesion to a plastic film.

[0002]

2. Description of the Related Art A coating composition containing an aqueous solution of a vinyl polymer has the advantages of good pigment dispersibility and less generation of dust, and many varieties have been developed. However, one that forms a sufficiently tough coating film and one that has good adhesion to a plastic film have not been developed.

On the other hand, a coating composition comprising an aqueous dispersion of a urethane polymer has the advantages of forming a tough coating film and adhering well to a plastic film. It has been. However, the urethane polymer aqueous dispersions that have been developed so far cannot achieve the conditions that the pigment dispersibility is sufficiently good and that the insoluble aggregates during coating are sufficiently low.

Good pigment dispersibility of vinyl polymer water-dissolved product and low generation of insoluble aggregates, and ability to form a tough coating film of urethane polymer aqueous dispersion and good property for plastic film. Although various studies have been made to achieve compatibility with the adhesiveness, since vinyl polymers and urethane polymers have low compatibility, few have been obtained that are compatible with each other in a wide range of blend ratios. In order to improve this point, a method has been developed in which a urethane polymer is allowed to be present in the polymerization process of vinyl monomers to obtain an aqueous composition having good compatibility. For example, Japanese Examined Patent Publication No. 4-81447 and Japanese Patent Laid-Open No. 4-415.
No. 17, U.S. Pat. No. 4,1983,330 and the like.

However, these methods require a large-scale apparatus such as a polymerization apparatus, which is disadvantageous in developing a wide variety of products in a wide variety of products. A simple blend of a urethane-based polymer and a vinyl-based polymer is used for the urethane-based polymerization. It has been desired to develop an aqueous composition capable of satisfying both the characteristics of the polymer and the vinyl polymer.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a composition for aqueous paints and inks comprising a mixed solution of an aqueous vinyl polymer solution and an aqueous urethane polymer dispersion, which has a pigment dispersibility. Good, less insoluble aggregates are generated during coating, tough, can form a coating film with good adhesion to plastic films, and a wide variety of aqueous dispersions of urethane polymers can be used It is to provide an aqueous composition.

[0007]

That is, the present invention is
(A) Methyl methacrylate 30 to 90% by weight, (b)
It comprises 0 to 30% by weight of an aromatic vinyl compound, (c) 4 to 20% by weight of an acid group-containing vinyl compound, and (d) 0 to 66% by weight of another copolymerizable vinyl monomer, and has a second-order transition temperature. Is 30 to 110 ° C. and the weight average molecular weight is 6,000 to 3
A vinyl polymer aqueous solution obtained by neutralizing a vinyl polymer (I) having an acid value of 35 to 130 mgKOH / g with a base and dissolving it in water, and a second-order transition temperature of 30 to
120 ° C, weight average molecular weight of 200,000 to 2,000
And an aqueous dispersion of the polymer (II) of which the polymer solid content ratio is polymer (I) / polymer (II) = 5/95.
It is an aqueous coating composition obtained by mixing so as to be about 60/40.

[0008]

The vinyl polymer (I) used in the present invention is
(A) Methyl methacrylate 30 to 90% by weight, (b)
It is composed of 0 to 30% by weight of an aromatic vinyl compound, 4 to 20% by weight of (c) an acid group-containing vinyl compound, and (d) 0 to 66% by weight of another copolymerizable vinyl monomer.

Methyl methacrylate (a) is an essential component for imparting hardness to the vinyl polymer, and is 30 to 30%.
Used in a proportion of 90% by weight. If it is less than 30% by weight, the hardness is lowered, while if it exceeds 90% by weight, the water solubility is lowered. Further, if it is out of the above range, compatibility with the aqueous dispersion of the polymer (II) is lacking.

The aromatic vinyl compound (b) has the effect of imparting water resistance to the coating film, is copolymerized in the range of up to 30% by weight, and is preferably used in the range of 0 to 25% by weight. However, if it exceeds 30% by weight, the water solubility is lowered and the compatibility with the aqueous dispersion of the polymer (II) is lacking, which is not suitable. Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, benzyl (meth) acrylate, and the like, of which styrene is particularly preferable.

The acid group-containing vinyl compound (c) imparts an acid group to the vinyl polymer and is a vinyl compound having an acidic group such as carboxylic acid or sulfonic acid.
The acid group-containing vinyl compound has an acid value of 35 to 200 mgK of the vinyl polymer (I) obtained in the range of 4 to 20% by weight.
Used to be OH / g. Specific examples of the acid group-containing vinyl compound include monobasic acids such as acrylic acid, methacrylic acid and crotonic acid; dibasic acids such as fumaric acid, maleic acid and itaconic acid; and partial esters thereof. It is also possible to use a mixture of two or more of these. In particular, when a vinyl compound having a carboxylic acid is copolymerized, a compound having good water solubility and compatibility with the aqueous dispersion of the polymer (II) can be obtained. Also,
Particularly, when it is copolymerized with methacrylic acid or acrylic acid, it has a very good water solubility and compatibility.

The other vinyl-based monomer (d) copolymerizable with the above-mentioned monomers (a) to (c) is used in the range of 0 to 66% by weight, and at least one polymerizable monomer is used. It can be arbitrarily selected from those having various vinyl groups according to the purpose. Specific examples of the vinyl-based monomer (d) include ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) having an alkyl group having 1 to 18 carbon atoms such as 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate
Acrylic acid alkyl ester; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and other hydroxyalkyl (meth) acrylates; ethylene glycol di (meth) acrylate, butylene glycol (meth) acrylate and other glycol di ( (Meth) acrylate; alkylamino (meth) acrylates such as dimethylaminoethyl (meth) acrylate; and dimethylaminoethyl (meth) acrylate methyl chloride salt, cyclohexyl (meth) acrylate, allyl (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, glycidyl (meth) acrylate, vinyl acetate, vinyl propionate, (meth) acrylonitrile and the like.

The second-order transition temperature of the vinyl polymer (I) is
It is necessary to be 10 to 150 ° C., preferably 20 to 110 ° C. as measured by the DSC method. If it is lower than 10 ° C, the stain resistance becomes insufficient or the blocking resistance decreases. On the other hand, when the temperature exceeds 150 ° C, the coating film becomes too hard and the adhesiveness deteriorates. The molecular weight of the vinyl polymer is such that the weight average molecular weight measured by the GPC method is 6,000 to 40,0.
00, preferably 8,000 to 25,
It is 000. If it is less than 6,000, various defects such as a brittle coating film tend to occur. Further, if it exceeds 40,000, the compatibility with the urethane polymer (II) is insufficient.
The acid value is based on the color change point of phenolphthalein, and KO dissolved in ethanol in an aqueous vinyl polymer solution.
When H is added dropwise and titrated to show the mg of KOH required to neutralize 1 g of the vinyl polymer, 35 to 200 mg
Must be KOH / g, preferably 40-150
It is mgKOH / g. If it is less than 35 mgKOH / g, the water solubility will decrease, and if it exceeds 200 mgKOH / g, the compatibility with the aqueous dispersion of the polymer (II) will decrease and the water resistance will be insufficient.

As a polymerization method for producing the vinyl polymer (I), a suspension polymerization method, a solution polymerization method, a bulk polymerization method or the like can be applied, but a suspension polymerization method is particularly preferable. Is. In particular, rather than a monomer produced by a method of dividing the monomer into several parts while advancing the polymerization and adding the monomer into the system while advancing the polymerization, the monomer is added to the system over several hours while the polymerization is advancing. What is produced by the batch charging method of monomers in which polymerization is started after being charged all at once into the system is excellent in water resistance and at the same time excellent in compatibility with the aqueous dispersion of the urethane polymer (II).
It is considered that these are mainly the effect of copolymerizability.

As the dispersant in the suspension polymerization, 70-
Known water-soluble polymers such as polyvinyl alcohol and polymethacrylic acid soda salt having a saponification degree of 100% can be used. The solvent in the solution polymerization is not particularly limited as long as it dissolves the monomers and polymers used in the present invention, but alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol; ethyl cellosolve, cellosolve. acetate,
Butyl carbitol; glycols such as propylene glycol methyl ether; acetic acid esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone;

As the polymerization catalyst, conventionally known initiators such as azo-based initiators such as azobisisobutyronitrile and peroxide-based initiators such as benzoyl peroxide may be optionally used according to the purpose. You can

Further, for controlling the molecular weight of the vinyl polymer (I), a chain transfer agent such as n-dodecyl mercaptan or α-methylstyrene dimer is added to the vinyl monomer mixture, if necessary. be able to.

The vinyl polymer (I) thus obtained imparts water solubility by neutralizing the acid groups in the vinyl polymer (I) with a base to form a salt. Then
Dissolved in water. It is not necessary that all the acid groups of the vinyl polymer (I) be neutralized, and normally 30% or more of the acid groups are neutralized.

Examples of the base used for neutralization include ammonia, triethylamine, propylamine, diethylamine, tripropylamine, dibutylamine, amylamine, 1-aminooctane, 2-dimethylaminoethanol, ethylaminoethanol, 2-diethylaminoethanol. , 1-amino-2-propanol, 2-amino-
1-propanol, 3-amino-1-propanol, 1
Volatile substances such as dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 2-propylaminoethanol, ethoxypropylamine, aminobenzyl alcohol, and morpholine are mentioned.

On the other hand, the aqueous dispersion of the urethane polymer (II) used in the present invention comprises (e) an aliphatic or alicyclic diisocyanate and (f) a number average molecular weight of 500 to 500.
0 polyether diol or polyester diol and (g) dimethylolalkanoic acid, and N
Self-emulsification obtained by water-extending or di- or triamine-extending a urethane prepolymer having a CO / OH equivalent ratio of 1.1 to 1.9 after neutralization with or while neutralizing with a tertiary amine and dispersing in water. It is of a type.

As the aliphatic or alicyclic diisocyanate (e), hexamethylene diisocyanate,
Aliphatic diisocyanates such as 2,2,4-trimethylhexane diisocyanate; isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 4,
Examples thereof include alicyclic diisocyanates having 4 to 18 carbon atoms such as 4'-dicyclohexylmethane diisocyanate; and modified products of these diisocyanates (carbodiimide, uretdione, uretoimine-containing modified products, etc.). Particularly preferred are hexamethylene diisocyanate and isophorone diisocyanate. These may be used in combination of two or more. Aromatic diisocyanates cannot be used because they have too high a reactivity with water during water extension or amine extension.

The polyether diol or polyester diol (f) is a compound having a number average molecular weight of 500 to 5,000 and usually having a hydroxy group at the terminal. If the number average molecular weight is less than 500, the coating film becomes brittle, and if it exceeds 5,000, the coating film lacks flexibility.
Specific examples thereof include those obtained by (co) polymerizing alkylene oxides such as ethylene oxide and propylene oxide and heterocyclic ethers such as tetrahydrofuran.
For example, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol; polyethylene adipate, polybutylene adipate, polyneopentyl adipate, poly-3-methylpentyl adipate, polyethylene / butylene adipate, polyneopentyl / hexyl adipate A polylactone diol, for example, a polycaprolactone diol; a polycarbonate diol. Also, an aqueous polyester diol obtained by copolymerizing sodium 5-sulfoisophthalic acid and diethylene glycol or polyethylene glycol can be used. These may be used in combination of two or more.

The acid group-containing diol (g) is a diol compound having an acidic group such as a carboxylic acid group or a sulfonic acid group, and specific examples thereof include dimethylol acetic acid and
Examples thereof include dimethylolpropionic acid and dimethylolbutyric acid, and these may be used in combination of two or more kinds. Of these, particularly preferred is dimethylolpropionic acid.

The urethane prepolymer synthesized from these compounds must have an NCO / OH equivalent ratio of 1.1 to 1.9. If the NCO equivalent ratio is less than 1.1, the viscosity of the urethane prepolymer is Is too high to disperse water smoothly, and if it exceeds 1.9, gelation tends to occur during water extension or amine extension.

In synthesizing the urethane prepolymer,
A low molecular weight polyhydroxy compound may be additionally used. As the low molecular weight polyhydroxy compound, glycols and alkylene oxide low-molar adducts mentioned as the raw materials for the above polyester diols; trihydric alcohols such as glycerin, trimethylolethane, trimethylolpropane and alkylene oxide low-molar adducts thereof can be used. Can be mentioned. The appropriate amount of the low molecular weight polyhydroxy compound used is 20% by weight or less based on the polyether diol or polyester diol (f), and if it is used in excess of this amount, the coating film becomes brittle.

The urethane prepolymer thus obtained is dispersed in water after neutralization of the acid group derived from dimethylolalkanoic acid with a tertiary amine or water extension or di- or triamine extension while neutralizing. Turn into.

The amine used for neutralization must be tertiary. If it is of primary or secondary type, it reacts with the residual isocyanate and is not suitable. Specific examples of the tertiary amine include trialkylamines such as trimethylamine and triethylamine; N such as N-methylmorpholine.
-Alkylmorpholine; N-alkylalkanolamines such as N-dimethylethanolamine.
These may be used in combination of two or more. In addition, these are usually 0.5 to 1 per 1 equivalent of the acid group in the urethane prepolymer.
1 equivalent is used.

As the polyamine used for amine extension, diamine or triamine is usually used. Further, specific examples thereof include hexamethylenediamine, isophoronediamine, hydrazine, piperazine and the like, and these may be used in combination of two or more kinds.

The aqueous coating composition of the present invention comprises a polymer (I) in a polymer solid content ratio of the aqueous solution of the vinyl polymer (I) and the aqueous dispersion of the urethane polymer (II). / Polymer (II) = 5/95 to 95/5 are mixed and prepared. Blend ratio of vinyl polymer is 5
% Or less, the dispersibility of pigment or the amount of dust, which is a characteristic of the vinyl polymer water-dissolved product, becomes insufficient. If the blend ratio of the vinyl polymer exceeds 95%, the urethane polymer is dispersed in water. The ability to form a tough coating film or the adhesiveness to a plastic film, which is a characteristic of the product, becomes insufficient.
Aqueous solution of vinyl polymer (I) and urethane polymer (I
The mixing method with the aqueous dispersion of I) is not particularly limited, and both liquids may be mixed at room temperature, or both liquids may be mixed after heating. The aqueous solution of the vinyl polymer (I) is usually 20-
A concentration of 35% by weight is used. As the aqueous dispersion of the urethane polymer (II), one having a concentration of the urethane polymer (II) of 25 to 45% by weight is usually used. The aqueous coating composition of the present invention thus obtained is used by adding additives such as a defoaming agent, a pigment dispersant, and an antiseptic agent in order to express high performance as a coating material and an ink. Is also possible.

The coating method for forming a coating film on the surface of various materials using the aqueous coating composition of the present invention includes spray coating method, roller coating method, bar coating method, air knife coating method and casting. Examples of the method include, but are not limited to, a method, a brush coating method, and a dipping method.

When the aqueous coating composition of the present invention is used as a paint or an ink, it is usually dried in the temperature range of room temperature to 60 ° C. for 10 seconds to 10 hours to form a coating film.

[0032]

EXAMPLES The present invention will be described in detail below with reference to examples. In addition, "part" and "%" in an Example show "weight part" and "weight%", respectively. (1) Production of vinyl-based polymer I-1 A polymerization apparatus equipped with a stirrer, a thermometer, and a reflux condenser, capable of both heating and cooling, was added with 200 parts of deionized water and polyvinyl alcohol (saponification degree). 80%, degree of polymerization 1,50
0) After adding 0.6 parts and stirring to completely dissolve polyvinyl alcohol, the stirring was stopped once, and 70 parts of methyl methacrylate (hereinafter abbreviated as MMA), 10 parts of styrene (hereinafter abbreviated as St), 10 parts of n-butyl acrylate (hereinafter abbreviated as n-BA), methacrylic acid (hereinafter, MA)
Add 10 parts of A and agitate again, add 0.5 parts of azobisisobutyronitrile (hereinafter abbreviated as AIBN) and 4 parts of n-dodecyl mercaptan (hereinafter abbreviated as n-DM), and add 75 The temperature was raised to 0 ° C., and the reaction was carried out for 3 hours so that the reaction temperature was maintained at 75 to 80 ° C. Then, the temperature was raised to 95 ° C. and maintained for 1 hour to complete the reaction. The obtained polymer had a molecular weight of 12,000, an acid value of 65 mgKOH / g, and a second-order transition temperature of 87 ° C. (2) Production of vinyl-based polymers I-2 to I-8 By the same operation as the production method of vinyl-based polymer I-1, Table 1
The vinyl-based monomer composition shown in Table 1 was polymerized using the radical initiator and the chain transfer agent shown in Table 1, and the characteristic values of the obtained polymer are shown in Table 2.

[0033]

[Table 1] Explanation of symbols BPO: Benzoyl peroxide n-BMA: n-Butyl methacrylate EHA: Ethylhexyl acrylate MeSt: α-Methylstyrene dimer AA: Acrylic acid

[0034]

[Table 2] (3) Production of vinyl-based polymer I-9 Isopropyl alcohol (hereinafter abbreviated as i-PA) 100 in a polymerization apparatus equipped with a stirrer, a thermometer, and a reflux condenser and capable of both heating and cooling. Part, MMA65 part, St
10 parts, 12 parts of n-BA, 13 parts of MAA, 2 parts of AIBN and 3 parts of n-DM were added and stirring was started, the temperature was raised to 80 ° C. to start polymerization, and 0.2 parts of AIBN was added at intervals of 1 hour. Polymerization was completed by maintaining temperature for 51 hours, solid content 51%,
An i-PA solution of a vinyl polymer having a viscosity of 10,000 cps was obtained. Then, this solution was put in a vat, and i-PA was evaporated in a dryer heated to 50 ° C. to obtain a solid content of 99.5.
% Vinyl polymer solids were obtained. The obtained polymer had a molecular weight of 13,000, an acid value of 85.5 mgKOH / g, and a second-order transition temperature of 84 ° C. (4) Production of vinyl-based polymer I-10 100 parts of i-PA was added to a polymerization apparatus equipped with a stirrer, a thermometer, and a reflux condenser, and both heating and cooling were possible, and stirring was started. The temperature was raised to ℃, MMA 65 parts, St10
Part, n-BA 12 parts, MAA 13 parts and AIBN 3 parts were added dropwise over a period of 4 hours, and then A was added every 1 hour.
Polymerization was terminated by adding 0.1 part of IBN while maintaining the temperature for 4 hours to obtain a vinyl polymer i-PA solution having a solid content of 50% and a viscosity of 2,000 cps. After that, this solution was put in a vat, and i-PA was placed in a dryer heated to 50 ° C.
Was evaporated to obtain a vinyl polymer solid having a solid content of 99.5%. The obtained polymer has a molecular weight of 11,000 and an acid value of 8.
It was 5.5 mgKOH / g and the second-order transition temperature was 84 ° C. (5) Dissolution of vinyl-based polymer in water 50 g of vinyl-based polymer I-1 and deionized in a 300 ml flask equipped with a stirrer, thermometer, reflux condenser and capable of both heating and cooling. Water (148 g) was added and stirring was started, 28% ammonia water (3.5 g) was gradually added, the temperature was then raised to 50 ° C., the temperature was maintained for 2 hours to complete the dissolution, and the vinyl-based polymer I-1 aqueous solution was added. A lysate was obtained. The obtained aqueous solution had a solid content of 25% and a viscosity of 500 cps.

For the vinyl polymers I-2 to I-8, the addition amount of 28% ammonia water and deionized water was calculated according to the following calculation method, and the dissolution operation was performed in the same manner. However, the vinyl polymer I-5 could not be dissolved. Required ammonia water (g) = A / 56.1 / 1000 × 5
0 × 17 ÷ 0.28 (In the formula, A represents the acid value (mgKOH / g) of the polymer.) Necessary deionized water (g) = 150−Necessary ammonia water (g) × 0.72 (6) Production of Urethane Polymer Aqueous Dispersion II-1 13 parts of dimethylolpropionic acid, 80 parts of N-methyl-2-pyrrolidone, polytetramethylene glycol (number average) in a 1000 ml reaction vessel equipped with a thermometer, a stirrer and a condenser. Molecular weight 1900) was added and heated to 90 ° C. Then add 48 parts of isophorone diisocyanate and add 1
After stirring for 0 minutes, 0.1 part of dibutyltin dilaurate was added,
The temperature was raised to 95 ° C. and the reaction was carried out for 1 hour.

The hydrophilic group-containing urethane prepolymer thus obtained was neutralized with 10 parts of triethylamine, 300 parts of deionized water was added, and the mixture was stirred for 1 hour to extend the water. The resulting composition is a stable aqueous dispersion with a solids content of 29.2.
%, The viscosity was 5,000 cps. (7) Production of Urethane Polymer Aqueous Dispersion II-2 In the reaction vessel used in (6) above, 6 parts of dimethylolpropionic acid, 40 parts of N-methyl-2-pyrrolidone, polypropylene glycol (number average molecular weight of 1850 ) Added 9
Heated to 0 ° C. Then isophorone diisocyanate 48
After adding 10 parts by weight and stirring for 10 minutes, 35 parts of hexamethylene diisocyanate was added and after stirring for 10 minutes, 0.1 part of dibutyltin dilaurate was added and the temperature was raised to 95 ° C. and the reaction was carried out for 1 hour.

The hydrophilic group-containing urethane prepolymer thus obtained was neutralized with 5 parts of triethylamine, 300 parts of deionized water was added, and the mixture was stirred for 1 hour to extend the water. The resulting composition is a stable aqueous dispersion with a solids content of 30.2
%, The viscosity was 1,000 cps. (8) Production of Urethane Polymer Aqueous Dispersion II-3 In the reaction vessel used in (6) above, 6 parts of dimethylolpropionic acid, 40 parts of N-methyl-2-pyrrolidone, polypropylene glycol (number average molecular weight of 2200 ) Added 9
Heated to 0 ° C. Then isophorone diisocyanate 48
After adding 10 parts by weight and stirring for 10 minutes, 35 parts of hexamethylene diisocyanate was added and after stirring for 10 minutes, 0.1 part of dibutyltin dilaurate was added and the temperature was raised to 95 ° C. and the reaction was carried out for 1 hour.

The hydrophilic group-containing urethane prepolymer thus obtained was neutralized with 10 parts of triethylamine, and then 300 parts of deionized water was added and dispersed in water. To this, 8 parts of isophoronediamine was added and stirred for 1 hour to extend the diamine. The resulting composition is a stable aqueous dispersion with a solid content of 3
The viscosity was 0.2% and the viscosity was 1,000 cps.

Example 1 60 g of a 25% solid content aqueous solution of vinyl polymer I-1 and 120 g of urethane polymer aqueous dispersion II-1 were weighed in a beaker and mixed lightly with a stick to prepare blend liquid 1. Created. In this case, the polymer solid content ratio of the vinyl polymer I-1 and the urethane polymer aqueous dispersion II-1 is 30: 7.
It is 0. No precipitate was observed 24 hours after blending, confirming compatibility as a solution. Further, the blend liquid 1 is applied to a glass plate so that a solid film thickness is 80 μm,
When dried, a transparent coating film was obtained, and compatibility as a coating film was confirmed. 20 parts of Degussa carbon black # 100 was added to 100 parts of the polymer in the blend liquid 1, and the mixture was mixed for 2 hours in a FRITSCH planetary ball mill to disperse the pigment. After that, when left for 3 days at room temperature, no sedimentation of the pigment was observed. Also,
Blend liquid 1 with polyester film (Lumirror E-3
5. Toray Co., Ltd.) to a dry film thickness of 20 μm, cellophane tape (Nichiban Co., Ltd.) was pressed against the coating film, and then peeled off. The coating film was transferred to the adhesive layer of cellophane tape. I couldn't do it.

Examples 2-9 and Comparative Examples 1-8 A blended liquid was prepared and evaluated in the same manner as in Example 1, and the results are shown in Table 3. The symbols of the results of each evaluation test have the following meanings. [Compatibility] Solution S: No precipitate is observed.

IS: Precipitate is present. Coating film C: The coating film is transparent and has good compatibility.

VSH: The coating film is slightly opaque and the compatibility is slightly poor.

SH: The coating film is more opaque than in the VSH stage, and the compatibility is lower than in the VSH stage.

H: The coating film is opaque from the SH stage,
The compatibility is lower than that in the SH stage (a level that is not practical). [Pigment dispersibility] Good: No sedimentation of the pigment is observed after 3 days. Poor: pigment settling is observed after 3 days. [Adhesiveness] Good: Not transferred to the adhesive layer of cellophane tape. Bad: Transferred to the adhesive layer of cellophane tape.

[0045]

[Table 3]

[0046]

The composition for water-based paints and inks of the present invention has good pigment dispersibility, little generation of insoluble aggregates at the time of coating, is tough, and has good adhesion to a plastic film. A coating film can be formed. Further, since it can be prepared by a simple blend of a urethane polymer and a vinyl polymer, a wide variety of products can be developed.

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[Procedure amendment]

[Submission date] December 3, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

[0007]

That is, the present invention is
(A) Methyl methacrylate 30 to 90% by weight, (b)
It comprises 0 to 30% by weight of an aromatic vinyl compound, (c) 4 to 20% by weight of an acid group-containing vinyl compound, and (d) 0 to 66% by weight of another copolymerizable vinyl monomer, and has a second-order transition temperature. Is 10 to 150 ° C. and the weight average molecular weight is 6,000 to 3
0,000, and vinyl polymer acid number is. 35 to 200 mg KOH / g (I) was neutralized with a base, a vinyl polymer solvent solution obtained by dissolving in water, (e) aliphatic or Alicyclic
Formula (i), (f) number average molecular weight of 500-
5,000 polyether diols or polyesters
Consisting of a diol and a (g) acid group-containing diol, and
Urethane resin having an NCO / OH equivalent ratio of 1.1 to 1.9
After or while neutralizing the repolymer with a tertiary amine
Ureta which is water-extended or amine-extended and dispersed in water
Water-based polymer (II) mixed with an aqueous dispersion
It is a composition for paints and inks .

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

The second-order transition temperature of the vinyl polymer (I) is
It is necessary to be 10 to 150 ° C., preferably 20 to 110 ° C. as measured by the DSC method. If it is lower than 10 ° C, the stain resistance becomes insufficient or the blocking resistance decreases. On the other hand, when the temperature exceeds 150 ° C, the coating film becomes too hard and the adhesiveness deteriorates. Regarding the molecular weight of the vinyl polymer, the weight average molecular weight measured by the GPC method is 6,000 to 30,0.
00 , preferably 8,000 to 25,
It is 000. If it is less than 6,000, various defects such as a brittle coating film tend to occur. Further, if it exceeds 30,000 , the compatibility with the urethane polymer (II) is insufficient.
The acid value is based on the color change point of phenolphthalein, and KO dissolved in ethanol in an aqueous vinyl polymer solution.
When H is added dropwise and titrated to show the mg of KOH required to neutralize 1 g of the vinyl polymer, 35 to 200 mg
Must be KOH / g, preferably 40-150
It is mgKOH / g. If it is less than 35 mgKOH / g, the water solubility will decrease, and if it exceeds 200 mgKOH / g, the compatibility with the aqueous dispersion of the polymer (II) will decrease and the water resistance will be insufficient.

Claims (3)

[Claims] 1. (a) Methyl methacrylate 30 to 90
% By weight, (b) 0 to 30% by weight of aromatic vinyl compound,
(C) 4 to 20 wt% of acid group-containing vinyl compound and (d) 0 to 66 wt% of other copolymerizable vinyl monomer.
The secondary transition temperature is 10 to 150 ° C., the weight average molecular weight is 6,000 to 30,000, and the acid value is 35 to 2.
A vinyl-based polymer solution obtained by neutralizing a vinyl-based polymer (I), which is 00 mgKOH / g, with a base and dissolving it in water.
(E) An aliphatic or alicyclic diisocyanate, (f) a polyether diol or polyester diol having a number average molecular weight of 500 to 5,000, and (g) an acid group-containing diol, and having an NCO / OH equivalent ratio of 1. 1 to
A urethane prepolymer of 1.9 is water-extended or amine-extended after or while being neutralized with a tertiary amine, and mixed with an aqueous dispersion of a urethane polymer (II), which is dispersed in water. A water-based coating composition and ink composition. 2. The aqueous coating composition and ink composition according to claim 1, wherein the vinyl polymer (I) is polymerized by a suspension polymerization method. 3. The polymer solid content mixing ratio of the vinyl polymer (I) and the urethane polymer (II) is 5/95 to 95 /.
The composition for aqueous paints and inks according to claim 1, which is 5.