JPH10279879A - Water-based matting agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-base matting agent composition which can give highly transparent matte effect to a substrate without detriment to the color or pattern of the substrate and is reduced in reversion of luster otherwise occurring in heat processing by mixing an emulsion of a (meth)acrylic or vinyl chloride copolymer having a specified glass transition temperature with a water-soluble polymer, a matting agent and an aqueous medium. SOLUTION: This composition comprises an emulsion (A) of a (meth)acrylic or vinyl chloride copolymer having a glass transition temperature(Tg) in the range: -30 deg.C<=Tg<=25 deg.C or an emulsion (A) being a blend of a (meth)acrylic emulsion with a vinyl chloride emulsion in which the Tg of the blend resin is in the range: -30 deg.C<=Tg<=25 deg.C, a water-soluble polymer (B), a malting agent (C) and an aqueous medium. The mixing ratio is such that 15-80 wt.% (in terms of the solid matter) component A, 5-50 wt.% component B and 10-70 wt.% component C are present, provided that the total of the solid matter of component A, component B and component C is 100 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous matting agent composition, and more particularly to a water-based matting agent composition used as a surface coating agent for synthetic resin wallpaper, synthetic resin flooring, synthetic resin ceiling sheet, and synthetic leather. The present invention relates to an aqueous matting agent composition which exhibits a transparent matting property without impairing the pattern and color of a substrate and has an excellent matting prevention effect during heat processing.

[0002]

2. Description of the Related Art Conventionally, organic solvents have been used for surface finishing of wallpaper materials, floor materials, ceiling sheets, etc. made of synthetic resin.
So-called solvent-based paints have been widely used because of their excellent finished appearance. However, in recent years, solvent-based paints use organic solvents, so air pollution problems, work environment problems, fire and price problems, etc.
The transition to water-based paints using water as a medium is increasing. Currently, synthetic resin emulsions that are blended in aqueous matting agents include polyvinyl chloride and acrylic polymers alone or in combination, or vinyl chloride monomers and acrylic monomers. Copolymer emulsion, vinyl chloride-vinyl acetate copolymer emulsion, ethylene-vinyl acetate copolymer emulsion, etc. may be used. Compared with solvent-based paints, the appearance and performance of coatings (anti-adhesion, flexibility, cold resistance) Properties and heat resistance) are being obtained. However, when a matting agent is coated on a dark-colored base material or a base material on which a pattern is printed, it is difficult to obtain a matting effect with a sense of transparency, and the matting agent impairs the color and pattern of the base material. There was a disadvantage. In addition, when heating is performed after matting, a phenomenon in which gloss is generated by heating, that is, a so-called matte phenomenon, occurs, and it is difficult to sufficiently maintain matting properties.

For example, in Examples 1 to 3 described in JP-A-50-113536, a vinyl chloride resin emulsion was used, and in Comparative Example 2, an acrylic emulsion was used to improve appearance, blocking resistance, and softness. It is stated that using such an emulsion to obtain a matte composition having a desired matte effect having a transparent feeling and an effect of preventing a matte finish during heat processing. Did not. Further, the method disclosed in Japanese Patent Application Laid-Open No. 50-112427 employs a blend system of a vinyl chloride emulsion and an acrylic resin emulsion, and is free from tackiness,
It is intended to improve cold resistance and surface gloss. Even with this method, it has been difficult to obtain a matting composition having the performance intended for the present application.

The method disclosed in Japanese Patent Application Laid-Open No. 50-34626 is
An emulsion of an organic solvent is blended, abrasion resistance, anti-adhesion, a composition for the purpose of obtaining aging resistance, because it contains an organic solvent, it is difficult to apply to recent environmental problems,
A vinyl chloride resin emulsion, a vinyl chloride-vinyl acetate copolymer resin emulsion described on page 156,
In the method of blending a methyl methacrylate resin emulsion, a methyl methacrylate-butyl methacrylate copolymer resin emulsion, or a methyl methacrylate-ethyl methacrylate copolymer resin emulsion, it is difficult to obtain the desired performance of the present invention. Further, Japanese Unexamined Patent Publication No.
The composition disclosed in -70061 contains a film-forming aid and was carried out for the purpose of improving coating unevenness, and there is no description of the intended performance of the present invention, and the described acrylic resin It was difficult to obtain the resin of the present invention by the emulsion polymerization method.

[0005]

SUMMARY OF THE INVENTION Under such circumstances,
The present invention has been made in order to provide a highly matte effect having high transparency without impairing the color and pattern of the base material, and to provide an aqueous matting agent composition having a low glossiness during heat processing. is there.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have adjusted the Tg of an acrylic polymer or a vinyl chloride polymer, and adjusted the Tg of the polymer particles. By adjusting the composition of the particle surface layer and the amounts of the matting agent and the water-soluble polymer to be added, it was found that there was a possibility of solving the problem, and the present invention was completed.

That is, the present invention relates to (A) a glass transition temperature (T
g) is an emulsion of a (meth) acrylic or vinyl chloride copolymer in the range of −30 ° C. ≦ Tg ≦ 25 ° C. or a blend resin in a blend of a (meth) acrylic emulsion and a vinyl chloride polymer emulsion An emulsion having a Tg of -30 ° C ≦ Tg ≦ 25 ° C,
An aqueous matting agent composition comprising (B) a water-soluble polymer, (C) a matting agent, and an aqueous medium, wherein the emulsion (A) has a solid content of 15 to 80% by weight, B)
5 to 50% by weight of water-soluble polymer, (C) 10 matting agents
70% by weight [However, the total of the solid content of the component (A) and the components (B) and (C) is 100% by weight. (A) (A), wherein the emulsion (A) has a different particle composition between the inside of the particle and the surface layer of the particle in the particle structure of the emulsion (A).
Wherein the functional group is localized in the particle surface layer of the emulsion of (A).
And 2. The aqueous matting agent composition according to any one of claims 1 and 2, which is used as a coating agent for a synthetic resin wallpaper material, a synthetic resin floor material, a synthetic resin ceiling sheet, and a synthetic leather material. 3. The aqueous matting resin composition according to any one of (3) to (4).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The synthetic resin emulsion to be blended in the present invention can be obtained by emulsion polymerization. When the monomer is emulsion-polymerized, the range of Tg of the polymer is -30 ° C ≦ Tg ≦
25 ° C., more preferably −10 ° C. ≦ Tg
≦ 20 ° C. is preferred. Even when the resin emulsion is blended, the range of the Tg of the total resin is preferably the above range.

When the temperature exceeds 25 ° C., it is difficult to obtain a desired matte effect having a desired transparent feeling, and thus there is a problem in that the color and pattern of the base material are kept clear. If the Tg is lower than -30 ° C, the surface coated with the matting agent is increased in tackiness, which is not preferable since there are problems in terms of tactile sensation, stain resistance, and anti-glare effect. Further, while maintaining a transparent matting effect, in order to further improve the matte prevention effect at the time of heat processing, in the particle structure of the emulsion to be blended, in the particle structure described above, that is, with the inside of the particle. It is preferable to use an acrylic resin emulsion or a vinyl chloride resin emulsion having different compositions in the surface layer, alone or as a mixture of these resin systems.
As described above, these synthetic resin emulsions can be obtained by emulsion polymerization, and the polymer composition of the inside of the particle of the synthetic resin emulsion and the polymer composition of the particle surface layer are different. (A) In order to obtain an emulsion, a normal emulsion polymerization method may be adopted, but in order to make the composition different between the inside of the particle and the particle surface layer, it is preferable to adopt the following two-stage polymerization method. First, polymerization in the first step: Polymerization is performed by continuously or collectively supplying each component of one or more monomers in an aqueous medium to obtain polymer particles serving as seeds. Next, the second stage polymerization: the desired synthetic resin is obtained by continuously or collectively supplying each component of one or more monomers to the dispersion containing the seed particles obtained in Emulsion (A) can be obtained. In particular, in the step (ii), when a monomer forming the particle surface layer is polymerized, it is preferable to localize a functional group on the surface layer, and one or more monomers containing the functional group are preferably used. It is more preferable to continuously supply or collectively supply the respective components to the dispersion liquid containing the seed particles obtained in the above to carry out emulsion polymerization. The matting agent containing the emulsion (A) thus obtained has a superior matte preventing effect at the time of heating, as compared with a matting agent containing a synthetic resin emulsion having a uniform composition throughout the particles.

At the time of emulsion polymerization, emulsifiers and polymerization initiators can be added by a method of supplying them all at once to a polymerization system.
The so-called batch addition method, the split addition method that supplies intermittently,
Further, there is a continuous addition method of continuously supplying, etc., and an addition method according to the purpose can be adopted. Further, when the emulsifier or initiator is added by the above-mentioned addition method, a method of dissolving and adding the monomer, a method of adding by emulsifying a mixed solution of the monomer and water, and a method of mixing with the monomer A method in which each of the emulsifier and the initiator is added independently without using it can be adopted.

In the present invention, the monomers listed below can be polymerized by one kind or a combination of two or more kinds. Acrylic acid ester with an alcohol having an alkyl group having 1 to 18 carbon atoms, methacrylic acid ester with an alcohol having an alkyl group having 1 to 18 carbon atoms, styrene, vinyltoluene, α-methylstyrene, β-methylstyrene,
Examples include vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, and acrylonitrile. Examples of the carboxyl group-containing monomer include (meth) acrylic acid,
Examples include itaconic acid, (anhydrous) maleic acid, crotonic acid, fumaric acid, aconitic acid, and citraconic acid. In addition, allyl alcohol, 2-hydroxyethyl (meth)
Hydroxyl group-containing monomers such as acrylate and 2-hydroxypropyl (meth) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, N-
Amide group-containing monomers such as methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, and maleamide; aminos such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate Group-containing monomers, alkoxyl group-containing monomers such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate, and pyridine structure-containing monomers such as vinylpyridine.

When a functional group is localized on the particle surface layer,
In the polymerization step, among the above monomers, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, an alkoxyl group-containing monomer, and pyridine It is preferable to use one or more of the containing monomers, or to use these functional group-containing monomers by copolymerizing them with other monomers, and more preferably,
One or more of a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an amide group-containing monomer, and an amino group-containing monomer, or these functional group-containing monomers and other monomers Is used after being copolymerized. In particular, it is preferable that the carboxyl group-containing monomer be copolymerized alone or with another monomer to be localized in the particle surface layer. The more the functional group is localized in the particle surface layer, the better the effect of preventing gloss return.

In the present invention, in order to obtain a matting agent having a transparent matting effect and a good matte preventing effect, the composition distribution in the particle structure is adjusted, and the Tg of the polymer emulsion is adjusted. By combining these adjustments, it is possible to obtain a matting agent composition excellent in both properties. still,
The glass transition temperature of the copolymer or resin emulsion blend system is determined by the following equation.

1 / Tg = Σ (Wi / Tgi) Tg: Glass transition temperature of copolymer or resin blend system (absolute temperature) Tgi: Glass transition temperature of homopolymer of monomer i component (absolute temperature display) ) Wi: weight fraction of the i component in the copolymer or the resin blend system (by the method of TG Fox, Bull. Am. Phys. Soc., Vol. 1, p. 123, published in 1956)
The following values were used for Tg of each monomer.

Methyl methacrylate 105 degrees 2-ethylhexyl acrylate -68 degrees butyl acrylate -55 degrees acrylic acid 87 degrees methacrylic acid 144 degrees vinyl chloride 80 degrees As emulsifiers used in the emulsion polymerization of the present invention, those used in ordinary emulsion polymerization are used. There is no particular limitation so long as it is, for example, an ionic or nonionic surfactant. Examples of the anionic surfactant include fatty acid salts such as sodium oleate, sulfate salts of higher alcohols such as sodium lauryl sulfate, dodecylbenzene sulfonate, and alkylallyl sulfonate such as isooctylbenzene sulfonate; Formalin condensed naphthalene sulfonate, sodium dioctyl sulfosuccinate and the like. As the cationic surfactant,
Representative examples include imidazoline laurate, ammonium hydroxide, laurylamine acetate, stearylamine acetate, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and the like. Examples of the nonionic surfactant include polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl ether, Representative examples include polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether. Surfynol 1 is a nonionic acetylene emulsifier.
04, 420, 440, 465, 485 (Air Pro
ducts and Chemicals Inc.).

Further, in the present invention, as an emulsifier, 1
A reactive surfactant having a polymerizable double bond in the molecule can be used, and thereby the particle surface can be modified with a functional group. Specific examples of the reactive emulsifier include RM
A-506, MA-30, MA-50, MA-100,
MA-150, MPG-130MA (all manufactured by Nippon Emulsifier Co., Ltd.), Aqualon RN-20, RN-30, RN
-50, AQUALON HS-10, HS-20, HS-1
025 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adecaria Soap NE-10, NE-20, NE-30, NE-4
0, SE-10N (all manufactured by Asahi Denka Kogyo KK) and the like.

These emulsifiers can be used alone or in combination of two or more. The amount of emulsifier used is
The amount is preferably in the range of 1 to 10 parts by weight based on 100 parts by weight of the total amount of the monomers. Generally, the role of the emulsifier is to provide a place for polymerization, to stabilize the resulting polymer emulsion, and to improve the mechanical and chemical stability of the emulsion. For this purpose, a sufficient amount of an emulsifier must be present, but when an emulsion obtained by polymerization in an amount exceeding 10 parts by weight is mixed with a matting agent, the water resistance of the coating film is poor, and the coating surface is poor. Is not preferred because it is easily contaminated. When the amount of the emulsifier is reduced to improve physical properties such as water resistance, if the amount is less than 1 part by weight, the polymerization stability is poor, the obtained emulsion becomes unstable and aggregates are generated. For this reason, it is preferable that the amount of the emulsifier be used within the above-mentioned range according to the purpose.

Examples of the polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisisobutyronitrile, aqueous hydrogen peroxide, t-butyl hydroperoxide, dibutyl peroxide, azobisamidinopropane hydrochloride. Benzoyl peroxide, diisopropyl peroxy carbonate, cumyl peroxy octoate, cumyl peroxy neodecanoate, cumene hydroperoxide and the like.

Further, if necessary, a reducing agent such as sodium acid sulfite, Rongalit, L-ascorbic acid, saccharide, amine or the like, and a transition metal ion such as copper ion, iron ion, cobalt ion, nickel ion or the like; A redox initiator using a chelate compound of a transition metal ion and a chelating agent such as disodium ethylenediaminetetraacetate together can also be used.

The amount of the polymerization initiator to be used is as follows.
The amount may be about 0.01 to 10 parts by weight with respect to 00 parts by weight. If the amount is less than 0.01 part by weight, the polymerization does not proceed. It is not preferable because physical properties such as water resistance at the time of coating film formation and the protective power of the matting agent are reduced. The polymerization temperature of the emulsion polymerization in the present invention may be about 30 ° C. to 90 ° C., and the reaction time is usually about 2 to 20 hours.

In order to improve the polymerization stability, freezing stability, mechanical stability, chemical stability, etc. of the emulsion,
It is preferable to add a basic substance at the start or end of the emulsion polymerization to adjust the pH to 5 or more. In particular, in the case of an emulsion copolymerized to localize a neutralizable functional group-containing monomer in the particle surface layer, polymerization stability, freezing stability, mechanical stability, It is more preferable because chemical stability and the like can be remarkably improved. Examples of the basic substance used for neutralization include caustic soda, caustic potash, ammonia, ethanolamine, triethanolamine, dimethylethanolamine, ethylamine, diethylamine, and triethylamine.

The amount of the emulsion (A) having a different polymer composition between the inside of the particle and the surface layer of the particle in the matting agent composition is as follows: the solid content of the component (A), the component (B) and the component (B). When the total amount of the component (C) is 100% by weight, the content is preferably 15 to 80% by weight in terms of solid content. If the amount is less than 15% by weight, the component serving as a binder is reduced, and in the intended use of the present invention, the adhesion of the matting agent composition, which is a basic physical property, to the substrate is deteriorated, which is not preferable. %, The amount of the binder component increases and the adhesion becomes good, but the mixing ratio of the water-soluble polymer and the matting agent decreases, so that appropriate fluidity during coating and the manifestation of the matting effect are exhibited. It is not preferable in respect of the point.

The water-soluble polymer of the component (B) adjusts the flowability of the matting agent composition, and can impart an appropriate viscosity behavior at the time of coating. As the water-soluble polymer that can be used in the present invention, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose,
Polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyacrylamide, sodium polyacrylate, polyvinylpyrrolidone, polyvinyl ether, polyethyleneimine, casein, gelatin and the like. Further, as a polyacrylamide-based ionic polymer, Hiset P-710 , 713, 720, 73
0, 790, 3210, 3213, 3220, Hiset CA (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), cellogens 5A, 6A, 7A, BS, and BSH-12 having various degrees of etherification of sodium carboxymethylcellulose. , Manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
415, TL-425, TL-706, LS-20, G
L-186 (all manufactured by Nippon Shokubai Co., Ltd.) and the like. These water-soluble polymers can be used alone or in combination of two or more.

The compounding amount of the water-soluble polymer of the component (B) in the matting agent composition is assuming that the solid content of the component (A) and the total of the components (B) and (C) are 100% by weight. , 5-5
It is preferably 0% by weight. When the amount is less than 5% by weight, the fluidity during coating is not appropriate, and the viscosity of the composition is lowered, so that uniform coating cannot be performed. If the content is more than 50% by weight, the coating film has poor water resistance and the viscosity of the composition is too high. For the purpose of facilitating the blending, the water-soluble polymer is more preferably dissolved in water before blending.

The matting agent of the component (C) is used to express the matting effect of the coating film of the matting agent composition, and includes silicic acids such as silicic anhydride and hydrous silicic acid, aluminum silicate, magnesium silicate and the like. Silicate compounds, calcium carbonate, barium carbonate, titanium oxide, gypsum, clay, talc, aluminum white, and crosslinked polymer fine particles such as poly (meth) acrylate, polystyrene, polyamide, and polyvinyl chloride.

The compounding amount of the matting agent is 100% by weight of the total of the solid content of the component (A) and the components (B) and (C).
In this case, the content is preferably set to 10 to 70% by weight. If the amount is less than 10% by weight, a sufficient matting effect of the coating film cannot be obtained, which is not preferable. If it exceeds 70% by weight, the proportion of the emulsion (A) which functions as a binder is reduced, and as a result, the retention of the matting agent is deteriorated, and the practical strength of the coating film cannot be obtained. Further, the object of the present invention is not preferable because it is impossible to obtain a transparent matting effect that does not impair the color or pattern of the substrate. The matting agent may be used by dispersing it in water in advance, or may be used by directly dispersing it in the composition. Generally, when a matting agent is dispersed, it is dispersed using a high-speed disper, a homogenizer, a sand mill, a paint shaker, or the like.

The method of compounding the matting agent composition is not particularly limited, and the components (A), (B),
A predetermined amount of each component of the composition comprising the component (C) and the aqueous medium is measured and dispersed using a high-speed disper, a homogenizer, a sand mill, a paint shaker, or the like until the component (C) has a required particle size, The desired aqueous matting agent composition is obtained. The solid content of the matting agent composition is from 10 to 20.
It is preferable that the weight% and viscosity are 50 to 5000 cps.

Further, the matting agent composition of the present invention may contain, if necessary, an antifoaming agent, a wetting agent, a flame retardant, a fungicide, a film-forming aid, and the like. In order to improve the properties, an organic solvent such as alcohol can be blended.

[0029]

The present invention will be described below in more detail with reference to examples. Note that the present invention is not limited to this embodiment. Parts and% in the examples are parts by weight and% by weight, respectively.
Is shown. Synthesis Example 1 (Synthesis of emulsion-1) 1000 ml with a stirrer, a reflux condenser, and a dropping funnel
Dissolve 320 parts of distilled water, 0.00192 parts of ferrous sulfate (ll) heptahydrate, 0.00256 parts of disodium ethylenediaminetetraacetate, and 0.448 parts of Rongalite in a separable flask, and stir in a nitrogen stream under stirring. It was kept at 50 ° C. To this solution were added 171.8 parts of methyl methacrylate (MMA),
138.6 parts of ethylhexyl acrylate (EHA),
9.6 parts of acrylic acid (AA), 4.8 parts of n-dodecyl mercaptan (DM), cumene hydroperoxide (C
An emulsion obtained by emulsifying 0.96 parts of HP (80% product), 160 parts of distilled water and 4.8 parts of Emal 2F (emulsifier manufactured by Kao Corporation) was continuously added dropwise over 3 hours, and then further added. 2
After stirring for an hour, the polymerization was completed, and the emulsion was neutralized with aqueous ammonia. The solid content of the obtained polymer emulsion was about 40%.

Synthesis Examples 2 to 5 (Synthesis of emulsions 2 to 5) In the same manner as in Synthesis Example 1, the types of monomers shown in Table 1
Polymerization was carried out at a quantitative ratio (%) to obtain emulsions 2 to 5. The vinyl chloride used in the emulsion 6 was obtained by emulsion polymerization of a vinyl chloride monomer in water at 60 ° C. using a redox initiator system using dodecylbenzenesulfonate as an emulsifier. This is a synthetic resin emulsion having a solid content concentration of 250 nm and a solid content of 45%.

[0031]

[Table 1]

Synthesis Example 6 (Synthesis of Emulsion-7) 1000 ml with a stirrer, reflux condenser and dropping funnel
Dissolve 320 parts of distilled water, 0.00192 parts of ferrous sulfate (ll) heptahydrate, 0.00256 parts of disodium ethylenediaminetetraacetate, and 0.448 parts of Rongalite in a separable flask, and stir in a nitrogen stream under stirring. It was kept at 50 ° C. To this aqueous solution, an emulsion of 171.8 parts of MMA, 0.52 parts of CHP, 2.6 parts of Emal 2F and 85.9 parts of water was added dropwise over 1 hour, polymerized, and further stirred for 1 hour to carry out the first-stage polymerization. Was completed. In the seed particles obtained in this way,
138.6 parts of EHA, 9.6 parts of AA, 0.44 parts of CHP,
An emulsion prepared from 2.2 parts of Emal 2F and 74.1 parts of water was added dropwise over 1 hour, polymerized, and further stirred for 2 hours to complete the second-stage polymerization. After completion of the polymerization, the mixture was neutralized with aqueous ammonia to obtain an emulsion having a solid content of about 40%.

Synthesis Examples 7 to 16 (Synthesis of Emulsions 8 to 17) In the same manner as in Synthesis Example 6, polymerization was carried out using the types of monomers and the ratios (%) shown in Tables 2 to 4 to obtain emulsions 8 to 17. I got Synthesis Example 17 (Synthesis of emulsion 18) 1000 ml with a stirrer, a reflux condenser, and a dropping funnel
In a separator flask, 204 parts of distilled water and 356 of a vinyl chloride emulsion used in Emulsion 6 as seed particles were used.
Parts, 0.2 parts of Emal 2F, 0.2 parts of iron sulfate (ll) heptahydrate.
00192 parts, 0.00256 parts of disodium ethylenediaminetetraacetate, and 0.448 parts of Rongalite were dissolved, and the mixture was kept at 50 ° C. in a nitrogen stream with stirring. 43.2 parts of MMA, 113.6 parts of EHA, 3.2 parts of AA,
1.6 parts of DM, 0.48 parts of CHP, Emal 2F2.4
Part of water and 80.0 parts of water were added dropwise over 1 hour to carry out polymerization, followed by stirring for 2 hours to complete the polymerization. After polymerization is completed, neutralize with ammonia aqueous solution and solid concentration is about 40%
Emulsion was obtained. The vinyl chloride used in the emulsion 18 was obtained by emulsion polymerization of a vinyl chloride monomer in water at 60 ° C. using a redox initiator system using dodecylbenzenesulfonate as an emulsifier.
50, a synthetic resin emulsion having a particle diameter of 250 nm and a solid content of 45%.

Synthesis Example 18 (Synthesis of Emulsion 19) Emulsion 19 was obtained by carrying out polymerization in the same manner as in Synthesis Example 17 using the types of monomers and the ratios (%) shown in Table 4.

[0035]

[Table 2]

[0036]

[Table 3]

[0037]

[Table 4]

Example 1 In a stainless beaker, 3 parts of an emulsifier, 1 part of an antifoaming agent, and 2.2 parts of hydroxypropyl methylcellulose (HPMC) were used.
Part, 0.05 part of sodium polyacrylate (PANa), water 8
0.2 parts, 3.0 parts of silica having an average particle diameter of about 2 μm and 22.5 parts of Emulsion-1 (40% product) were added and dispersed at a high speed disperser of 4000 rpm for 10 minutes to prepare a matting agent composition. Obtained. This matting agent was coated on a black colored vinyl wallpaper using a gravure printing machine, dried at 40 ° C. for 5 minutes, and then heat-treated at 220 ° C. for 5 seconds. It was observed whether the color of the surface of the matte-coated vinyl wallpaper after the heat treatment was not damaged. Table 5 shows the results. Examples 2 to 5 Emulsions 2, 7, 8, and 18 were formulated with the same compounding agent and the same amount in the same manner as in Example 1 to provide a matting agent, and then applied, dried, and heat-treated on a similar vinyl wallpaper in the same manner. did. Table 5 shows the results.

[0039]

[Table 5]

Comparative Examples 1 to 5 Emulsions 3, 4, 9 and 10 were formulated in the same manner as in Example 1 with the same compounding agent and the same amount of matting agent. With regard to the emulsion 6, the solid content of the emulsion was as in Example 1.
Other than that, the same compounding agent of Example 1 was used in the same amount and the same amount of matting agent was mixed, and then applied to the same vinyl wallpaper as in Example 1, and applied, dried, and heat-treated in the same manner. did. The results are shown in Table 6.

[0041]

[Table 6]

To obtain a transparent matting effect, the T
It can be seen that the influence of g is large. Examples 6-7, Comparative Example 7 Emulsions 5, 11, and 1 in the same manner as in Example 1.
No. 2 was formulated with the same compounding agent and the same compounding amount as the matting agent, and applied and dried on the same vinyl wallpaper in the same manner.
Heat processing was performed at 20 ° C. for 20 seconds. The 60 ° gloss of the obtained matte-treated wallpaper was measured, and the results are shown in Table 7.

[0043]

[Table 7]

Examples 8-10, Comparative Examples 8 and 9 Emulsions 11, 13 and 1 were prepared in the same manner as in Example 1.
4, 18 and 19 were formulated with the same compounding agent and in the same amount and with the same amount of matting agent, applied and dried on the same vinyl wallpaper in the same manner, and further heated at 220 ° C for 20 seconds. The 60 ° gloss of the obtained matte-treated wallpaper was measured, and the results are shown in Table 8.

[0045]

[Table 8]

Examples 11 and 12 and Comparative Example 10 In a stain beaker, 3 parts of an emulsifier, 1 part of an antifoaming agent, HPM
2.2 parts of C, 0.05 parts of PANa, 80.2 parts of water, about 2 μ
3.0 parts of silica having an average particle size of m, emulsion-1
22.5 for 5, 16, and 17 (40% each)
In addition, the mixture was dispersed at 4000 rpm for 10 minutes with a high-speed disper to obtain a matting agent composition. The matting agent was coated on a white vinyl wallpaper with a gravure printing machine, dried at 40 ° C. for 5 minutes, and then heated at 220 ° C. for 50 seconds. The 60 ° gloss of the obtained matte-treated wallpaper was measured, and the results are shown in Table 9.

[0047]

[Table 9]

From the above results, when the emulsions having different compositions between the inside and the surface layer of the particles obtained by two-stage polymerization than the uniform particles are matted, and when a large number of functional groups are distributed in the particle surface layer, It can be seen that the effect of preventing gloss return is exhibited. Furthermore, a matting agent having a transparent matting effect and having a low gloss can be obtained by combining with the adjustment of Tg. Examples 13 and 14, Comparative Examples 11 and 12 Emulsions-1, 2, 7, 9, 10, and 11 are shown in Table 10.
At the blend ratio (solid content ratio) shown in the above, a matting agent was blended with the same blending agent and blending amount as in Example 1, and applied and dried on the same vinyl wallpaper in the same manner, and further, the anti-glare property The test was performed under heating conditions of 220 ° C. for 20 seconds, and the color condition was performed under heating conditions of 220 ° C. for 5 seconds. The results are shown in Table 10. Similar effects were observed for the blend system.

[0049]

[Table 10]

[0050]

The aqueous matting agent composition of the present invention provides a highly transparent matting effect without impairing the color and pattern of the base material, and has an effect of preventing matting during heat processing. It is useful as a coating agent for synthetic resin wallpaper materials, synthetic resin floor materials, synthetic resin ceiling sheets, and synthetic leather materials.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 5/00 C09D 5/00 F 127/06 127/06 201/00 201/00

Claims (4)

[Claims] (A) a glass transition temperature (Tg) of -30 ° C.
Tg of the blend resin in an emulsion of a (meth) acrylic or vinyl chloride copolymer in the range of ≦ Tg ≦ 25 ° C. or in a blend of a (meth) acrylic emulsion and a vinyl chloride polymer emulsion is −30 ° C.
An aqueous matting agent composition obtained by mixing an emulsion in the range of ≦ Tg ≦ 25 ° C., (B) a water-soluble polymer, (C) a matting agent, and an aqueous medium, wherein the emulsion of (A) is a solid 15-80% by weight in terms of minute, (B) 5-50% by weight of water-soluble polymer, (C) 10-70% by weight of matting agent
[However, the solid content of the component (A), the component (B) and the component (C)]
The total of the components is 100% by weight. ] Aqueous matting agent composition mixed so that 2. The aqueous matting composition according to claim 1, wherein in the particle structure of the emulsion (A), a polymer composition is different between the inside of the particle and the surface layer of the particle. 3. The aqueous matting agent composition according to claim 1, wherein a functional group is localized in the particle surface layer of the emulsion (A). 4. The aqueous matting resin composition according to claim 1, which is used as a coating agent for a synthetic resin wallpaper material, a synthetic resin floor material, a synthetic resin ceiling sheet, and a synthetic leather material.