JP5599155B2 - Water-dispersed resin composition for flocking - Google Patents

Description

  The present invention relates to a water-dispersed resin composition for flocking. More specifically, for example, it is used for flocking polyolefin base materials used for interior parts of automobiles such as pillars, glove boxes, console boxes, coin boxes and spectacle boxes, and other automobile parts such as glass channels. The present invention relates to a water-dispersed resin composition for flocking.

  Molded parts made of ABS resin (acrylonitrile-butadiene-styrene resin) in which piles (short fibers) are planted with acrylic emulsion adhesive have been used for the interior of automobiles. Therefore, in recent years, polyolefin, not ABS resin, has been used as a base material for molded articles. Although the weight of the vehicle body has been reduced by the polyolefin base material, the acrylic emulsion adhesive is difficult to adhere to the polyolefin, so a primer is applied to the molded product made of the polyolefin base material in advance (that is, after the primer treatment), the acrylic emulsion System adhesive is applied.

  As described above, flocking to a molded article made of a polyolefin base material requires a primer treatment and is very time-consuming. Therefore, compared with flocking to a molded article made of ABS resin, the cost increases. As a means for reducing costs, it is desired to develop a flocking composition that can be directly applied to a polyolefin substrate without applying a primer treatment.

  As an example of a flocking composition that does not require primer treatment, Patent Document 1 describes a reaction-curable coating mainly composed of a urethane / acryl-modified chlorinated polyolefin resin, and Patent Document 2 polymerizes cyclohexyl methacrylate. There is a disclosure of a water-dispersed resin composition for flocking comprising a water-dispersed resin obtained as described above.

  However, it cannot be said that these water-dispersed resin compositions for flocking sufficiently satisfy pile retention at high temperatures. In the summer, the temperature inside the automobile becomes abnormally high, so high temperature adhesion between the pile and the polyolefin substrate is required. Furthermore, since the appearance of an automobile interior is important, it is necessary to maintain a high-class feeling of the automobile interior by applying a water-dispersed resin composition for flocking excellent in abrasion resistance to a base material of a molded product. Considering the productivity and cost of automobiles, the water-dispersed resin composition for flocking is naturally required to be further excellent in overall performance such as coating property and storage stability.

JP 2003-088802 A JP 2003-313387 A

  The present invention has been made to solve the above-mentioned problems, and is excellent in high-temperature adhesion, and also has excellent overall performance such as wear resistance, coating property, storage stability, and the like. An object of the present invention is to provide a water-dispersed resin composition for flocking that is suitable for producing a resin composition, particularly an automobile interior part.

As a result of extensive studies, the present inventor has found that component (A): a specific monomer represented by chemical formula (1) (hereinafter also referred to as “monomer (a)”)
^{_{CH 2 = C (R 1)}} -COO-R 2 (1)
[In the chemical formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is a monocyclic alkyl group. And a water-dispersed resin composition containing a copolymer obtained by polymerizing a monomer mixture containing other unsaturated monomers, and (B) component: a water-dispersed resin composition of chlorinated polyolefin. The water-dispersed resin composition for flocking can be used as a water-dispersed resin composition for flocking which can plant a pile on a polyolefin substrate that has not been primed by adding a specific silane coupling agent. Furthermore, the resin composition was found to be excellent in high-temperature adhesion and excellent in overall performance such as wear resistance, coating property, and storage stability, and thus completed the present invention.

That is, the present invention
A water-dispersed resin composition for flocking comprising the following component (A), component (B) and component (C) is provided.
(A) component: monomer (a) represented by chemical formula (1)
^{_{CH 2 = C (R 1)}} -COO-R 2 (1)
[In the chemical formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is a monocyclic alkyl group. And a copolymer obtained by polymerizing a monomer mixture containing other unsaturated monomers, a water-dispersed resin composition,
(B) Component: Water-dispersed resin composition of chlorinated polyolefin (C) Component: Epoxy silane coupling agent.

In one aspect, the present invention provides a water-dispersed resin composition for flocking for producing automobile interior parts.
Furthermore, this invention provides the water-dispersed resin composition for flocking whose monomer (a) is a cyclohexyl (meth) acrylate in another aspect.
Moreover, this invention is a preferable aspect. Water dispersion for flocking whose solid content of (C) component is 0.1-1.0 weight part with respect to 100 weight part of solid content of (A) component and (B) component. A mold resin composition is provided.
Furthermore, the water-dispersed resin composition for flocking according to the present invention can contain a film-forming aid.

  In the present specification, the “water-dispersed resin composition” refers to a composition in which the resin is dispersed (or suspended) in an aqueous medium, but at least a part of the resin is dissolved in the aqueous medium. May be. “Aqueous medium” refers to general water such as distilled water, ion-exchanged water, pure water, etc., as long as it does not adversely affect the properties of the water-dispersed resin composition for flocking according to the present invention. May be included.

  The water-dispersed resin composition for flocking according to the present invention includes (A) component, (B) component, and (C) component, and thus has excellent high-temperature adhesion, wear resistance, coating property, storage stability, etc. The overall performance is excellent.

  By manufacturing an automotive interior part using the water-dispersed resin composition for flocking of the present invention, the pile planted on the polyolefin base material of the automotive interior part is retained even if the interior of the automobile becomes hot in summer. Also, since the wear resistance is excellent, it is possible to maintain a high-class feeling of the automobile interior.

  In this invention, the adhesiveness of the water dispersion type resin composition for flocking can be improved more by making a monomer (a) into cyclohexyl (meth) acrylate.

  In the water-dispersed resin composition for flocking according to the present invention, the solid content of the component (C) is 0.1 to 1.0 part by weight with respect to 100 parts by weight of the solid content of the component (A) and the component (B). In some cases, the balance of high temperature adhesion, wear resistance, coatability, and storage stability is better.

  In order to further increase the high temperature adhesion of the water-dispersed resin composition for flocking of the present invention, it is also conceivable to increase the glass transition temperature of the resin composition. However, when the glass transition temperature of the resin composition is increased, the adhesion may be lowered due to poor film formation. Therefore, when the water-dispersed resin composition for flocking of the present invention contains an appropriate amount of a film-forming aid, the film-forming property is further improved, and due to the balance of high-temperature adhesion, wear resistance, coating property, and storage stability. Excellent.

The water-dispersed resin composition as the component (A) in the present invention is a specific monomer (a) represented by the chemical formula (1).
^{_{CH 2 = C (R 1)}} -COO-R 2 (1)
[In the chemical formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is a monocyclic alkyl group. And a copolymer obtained by polymerizing a monomer mixture containing other unsaturated monomers.

The monomer (a) is not particularly limited as long as it is represented by the chemical formula (1). In the chemical formula (1), the “monocyclic alkyl group” refers to an alkyl group having one ring among the cyclic alkyl groups, and may have a substituent. The number of carbon atoms in R ² are calculated including the number of carbon atoms of the substituent. Examples of R ² include a cyclohexyl group and a methylcyclopentyl group, and a cyclohexyl group is preferable. As the monomer (a), cyclohexyl (meth) acrylate is particularly preferable.

  In this specification, acrylic acid and methacrylic acid are collectively referred to as “(meth) acrylic acid”, and acrylic acid ester and methacrylic acid ester are collectively referred to as “(meth) acrylic acid ester” or “(meta ) Acrylate ".

  Further, the “other unsaturated monomer” is an unsaturated monomer copolymerizable with the monomer (a) and can obtain the desired component (A). There is no particular limitation. Other unsaturated monomers include, for example, (meth) acrylic acid, maleic acid, maleic anhydride, acrylamide, methacrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl Examples include (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, styrene, methylstyrene, acrylonitrile and methacrylonitrile. The

  The polymerizable silane monomer is also included in the “other unsaturated monomer”. The polymerizable silane monomer is a compound having silicon and a polymerizable functional group at the same time, and is an ethylenic silane compound represented by the chemical formula (I).

（Ｒは−Ｈ又は−ＣＨ₃、Ｘは−（ＣＨ₂）_n−又は−ＣＯＯ−（ＣＨ₂）_n−ただしｎは０から３の整数、Ｙは−ＯＣＨ₃もしくは−ＯＣ₂Ｈ₅又は−Ｏ（ＣＨ₂）_m−Ｏ（ＣＨ₂）_p−Ｈただしｍ、ｐは１から３の整数、Ｚは−（ＣＨ２）_q−Ｈただしｑは０から３の整数、ａは０から２の整数を示す。）

(R is —H or —CH ₃ , X is — (CH ₂ ) _n — or —COO— (CH ₂ ) _n —, where n is an integer from 0 to 3, Y is —OCH ₃ or —OC ₂ H ₅ or —O (CH ₂ ) _m —O (CH ₂ ) _p —H where m and p are integers from 1 to 3, Z is — (CH 2) _q —H where q is an integer from 0 to 3, and a is from 0 to 2 Indicates an integer.)

  Specifically, (meth) acryloxyalkyltrialkoxy such as 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 4- (meth) acryloxyethyltrimethoxysilane, etc. Silanes, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropylethyldiethoxysilane, 3- (meth) acryloxyethylmethyl (Meth) acryloxyalkylalkylalkoxysilanes such as dimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxyethoxysilane, vinyltri (methoxyethoxy) silane, vinyltri (ethoxymethoxy) silane and other vinyl Trialkoxysilane, vinyl methyl dimethoxy silane, Biniruechiruji (methoxyethoxy) silane, vinyl dimethyl methoxysilane, vinyl alkyl alkoxy silane such as vinyl diethyl (methoxyethoxy) silane and the like are preferable.

  The weight ratio of “monomer (a)” to “other unsaturated monomer” contained in the monomer mixture (monomer (a) / other unsaturated monomer) is 30/70. It is preferably ˜90 / 10, more preferably 40/60 to 80/20, and particularly preferably 50/50 to 70/30. When the monomer (a) / other unsaturated monomer is less than 30, the adhesion between the olefin substrate and the coating film to be formed may be insufficient. In order to obtain a water-dispersed resin composition for flocking having good characteristics, the monomer (a) / other unsaturated monomer is 30/70 to 90/10. Preferably there is.

The component (A) is a monomer mixture containing the monomer (a) and other unsaturated monomers in an aqueous medium using a stirrer capable of applying a shearing force in the presence of a catalyst and an emulsifier. It can be produced by copolymerization.
Here, the types of “catalyst” and “emulsifier”, and their concentrations, as well as the polymerization reaction conditions such as reaction temperature, reaction time, and stirring speed, are appropriately selected depending on the characteristics of the intended aqueous resin composition for flocking of the present invention. Can be done.

  The “catalyst” is a compound that can cause the polymerization reaction of the monomer mixture by addition of a small amount, and preferably usable in an aqueous medium. For example, ammonium persulfate, sodium persulfate, potassium persulfate, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethyl) valeronitrile and the like can be exemplified, and ammonium persulfate, sodium persulfate and potassium persulfate are particularly preferable. In addition, a compound having a reducing action that promotes the action of the catalyst may be used in combination as a co-catalyst. Examples of such compounds include sodium thiosulfate and ferrous chloride.

  “Emulsifier” refers to a surfactant used to form an emulsion of an aqueous medium and a monomer mixture and does not adversely affect the polymerization reaction. The emulsifier is preferably a compound having a sulfonic acid group, a compound having a sulfonate group, a compound having a sulfate ester group, and a mixture thereof, but a normal surfactant can also be used. Examples of such emulsifiers include the following compounds: anionic surfactants such as soaps, alkyl sulfonates, and polyoxyethylene alkyl sulfates; and polyoxyalkyl aryl ethers and oxyethylene oxypropylene block copolymers Nonionic surfactants such as

In addition, it is more preferable to use a polymerizable emulsifier as the emulsifier. The use of a polymerizable emulsifier is preferable because the water resistance of a coating film formed from the resin composition for flocking is improved.
Here, the “polymerizable emulsifier” refers to a compound having a polymerizable functional group and capable of functioning as an emulsifier capable of forming an emulsion of an aqueous medium and a monomer mixture. Examples of such a compound include compounds having a double bond between ethylenic carbon atoms having a sulfonic acid group, a sulfonate group, a sulfate ester group or an ethylene oxide group, and mixtures thereof. Furthermore, ammonium ions, potassium ions and sodium ions are preferred as the counter cation of the sulfonic acid group or sulfonate group of the polymerizable emulsifier.

  The glass transition temperature of the copolymer obtained by polymerizing the monomer mixture containing the monomer (a) and other unsaturated monomers (hereinafter also referred to as “copolymer Tg”) is 10 to 60. ° C is preferable, 20 to 40 ° C is preferable, and 25 to 35 ° C is particularly preferable. When the Tg of the copolymer is less than 10 ° C., the pile holding strength may be insufficient because the coating film formed from the obtained water-dispersed resin composition for flocking is insufficient. In addition, when the Tg of the copolymer exceeds 60 ° C., the coating film formed from the finally obtained water-dispersed resin composition for flocking becomes brittle, and is formed by flocking to the coated composition layer. The wear resistance of the coating film may be reduced.

  Since the copolymer contained in the component (A) is obtained by polymerizing a monomer mixture containing the monomer (a) and “other unsaturated monomer”, the monomer (a) and “ The Tg of the copolymer is determined by the type of “other unsaturated monomer” and the mixing ratio (parts by weight) of monomer (a) and “other unsaturated monomer”. In order to design a copolymer having a desired Tg, a homopolymer obtained when each of the monomer (a) and other unsaturated monomers in the monomer mixture is homopolymerized. The mixing ratio (parts by weight) of the monomer (a) and “other unsaturated monomer” is determined in consideration of the glass transition temperature (hereinafter also referred to as “homopolymer Tg”). Specifically, the “copolymer Tg” can be obtained by calculating using the calculation formula (1) of the theoretical Tg of the copolymer.

_{1 / Tg = C 1 / Tg} 1 + C 2 / Tg 2 + ··· + C n / Tg n (1)
[In the calculation formula (1), Tg is the theoretical Tg, C _n of the copolymer, the weight ratio of n-th monomer n is included in the monomer mixture, Tg _n is the n-th monomer Tg of the homopolymer of the body n, n is the number of monomers constituting the copolymer, and is a positive integer. ]

  The value described in the literature can be used as the Tg of the monomer homopolymer. As such documents, for example, the following documents can be referred to: Mitsubishi Rayon's acrylic ester catalog (1997 edition); and Kyozo Kitaoka, “New Polymer Library 7, Introduction to Synthetic Resins for Paints”, Polymer Publications Association, 1997, pages 168-169.

  Below, an example of design of Tg of the above-mentioned copolymer is demonstrated. As the monomer (a), cyclohexyl (meth) acrylate (hereinafter also referred to as “CHMA”), which is a monomer having a homopolymer Tg of 83 ° C., is used, and the ratio contained in the monomer mixture is 40. In the case of ˜67 parts by weight, as the “other unsaturated monomer”, for example, a monomer having a Tg of homopolymer of 95 ° C. or more and a monomer having a Tg of homopolymer of −50 ° C. or less are used. In this case, the ratio contained in the monomer mixture is 20-30 parts by weight for the former and 13-30 parts by weight for the latter.

  Specifically, CHMA having a homopolymer Tg of 83 ° C. is used as 40 to 67 parts by weight of “other unsaturated monomer”, which is a monomer having a homopolymer Tg of 95 ° C. or more. 20 to 30 parts by weight of methacrylate (hereinafter also referred to as “MMA”. Tg of homopolymer is 105 ° C.) and / or styrene (hereinafter also referred to as “St”. Tg of homopolymer is 100 ° C.) 2-ethylhexyl acrylate (hereinafter also referred to as “2HEA”. Tg of homopolymer is −85 ° C.) and / or butyl acrylate (hereinafter also referred to as “BA”) whose polymer Tg is −50 ° C. or less. Is −54 ° C.), and a copolymer having a theoretical Tg of 10 to 60 ° C. is obtained by polymerizing the monomer mixture using 13 to 30 parts by weight. Can be obtained free of component (A).

  As “monomer (a)”, for example, methylcyclopentyl methacrylate can be exemplified in addition to CHMA. Examples of “monomer having a homopolymer Tg of 95 ° C. or higher” include, for example, acrylamide (Tg of homopolymer is 153 ° C.), acrylic acid (hereinafter also referred to as “AA”) in addition to MMA and St. Tg of 106 ° C.), methacrylic acid (hereinafter also referred to as “MAA”. Tg of homopolymer is 130 ° C.), acrylonitrile (Tg of homopolymer is 100 ° C.) and maleic acid (Tg of homopolymer) Is 130 ° C.). Examples of the “monomer having a Tg of homopolymer of −50 ° C. or lower” include, for example, dodecyl methacrylate (Tg of homopolymer is −65 ° C.) in addition to 2EHA and BA.

  As for the Tg value of the homopolymer of CHMA, the values in the acrylic ester catalog (1997 edition) of Mitsubishi Rayon Co., Ltd. are used as MMA, St, 2EHA, BA, AA, MAA, acrylamide, acrylonitrile, maleic acid, dodecyl. For methacrylate, the values described in Kitaoka Kyozo, “New Polymer Library 7, Introduction to Synthetic Resins for Paints”, Kobunshi Shuppankai, 1997, pages 168-169 were used.

  Component (B) according to the water-dispersed resin composition for flocking of the present invention is a water-dispersed resin composition of chlorinated polyolefin. Specifically, for example, water-dispersed resin compositions such as chlorinated polyethylene, chlorinated polypropylene, chlorinated polybutene, chlorinated isobutylene, chlorinated products of ethylene-propylene copolymer, and chlorinated products of propylene-1-butene copolymer In particular, a water-dispersed resin composition of chlorinated polypropylene is preferable. These can be used alone or in combination.

  In the present invention, the component (B) is a polyolefin such as polyethylene (including low density polyethylene and high density polyethylene), polypropylene (including crystalline polypropylene and amorphous polypropylene), polybutene, polyisobutylene, and ethylene-propylene copolymer. After chlorinating a polymer, propylene-1-butene copolymer, ethylene-propylene-diene copolymer, ethylene-vinyl acetate copolymer, etc. in an organic solvent, it is emulsified by adding water and an emulsifier. Can be obtained. The organic solvent is then preferably recovered. Here, the “emulsifier” is the same as described above.

  As the component (B), a commercially available water-dispersed resin composition of chlorinated polyolefin can be used. Examples of such component (B) include Super Clone E633 (trade name), Super Clone S-4032 (trade name), Super Clone S-4044 (trade name), and Super Clone S4397 (trade name) manufactured by Nippon Paper Industries. Moreover, Hardren EH202 (trade name) manufactured by Toyo Kasei Kogyo Co., Ltd. can be exemplified.

  (C) component used for this invention is an epoxy-type silane coupling agent. The epoxy silane coupling agent has a functional group represented by, for example, chemical formula (2) and / or chemical formula (3).

The functional group represented by the (CH ₂ OCH) CH ₂ O— group is a glycidoxy group (see chemical formula (2)), and the functional group represented by the (CH ₂ CHOCH (CH ₂ ) ₂ ) CH— group is 3, 4-epoxycyclohexyl group (see chemical formula (3)).

Epoxy silane coupling agents are roughly classified into glycidyl silane coupling agents and epoxycyclohexyl silane coupling agents.
The glycidyl-based silane coupling agent has a glycidoxy group, and specifically includes 3-glycidoxypropylmethyldiisopropenoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrisilane. Examples include ethoxysilane and 3-glycidoxypropyldiethoxysilane.

Epoxycyclohexyl-based silane coupling agents have 3,4-epoxycyclohexyl groups, specifically 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl). ) Ethyltriethoxysilane.
These epoxy silane coupling agents can be used alone or in combination. In the water-dispersed resin composition for flocking according to the present invention, the (C) epoxy silane coupling agent is preferably a glycidyl silane coupling agent, and among the glycidyl silane coupling agents, 3-glycidoxypropyltri Methoxysilane is particularly preferred.

The water-dispersed resin composition for flocking according to the present invention comprises the above-described component (A), component (B), and component (C), and is produced by mixing three components.
In the present invention, the water-dispersed resin composition for flocking can contain a film-forming aid. The film-forming aid may be added in any process of producing the resin composition for flocking according to the present invention. For example, it may be added after blending the components (A) to (C) and blending the three components. It may be contained in any of the components (A) to (C). In the case where a film-forming aid is included in the component (A) or the component (B) in advance, for example, after obtaining the (A) water-dispersed resin composition and (B) the water-dispersed resin composition by emulsion polymerization, It is preferable to add a film-forming aid to the component (A) or (B).

  Examples of film-forming aids include glycol ethers, aliphatic hydrocarbons, alcohols, esters and the like. Specific examples of glycol ethers include phenoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, tripropylene glycol n-butyl ether, dipropylene glycol methyl ether, and tripropylene glycol methyl ether. , Dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether and dipropylene glycol methyl ether The Tate like.

  Specific examples of the aliphatic hydrocarbons include toluene and xylene. Examples of alcohols include benzyl alcohol and 2,2,4-trimethyl-1,3-pentanediol monobutyrate. Examples of esters include dimethyl phthalate, diisononyl phthalate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, and the like.

  When manufacturing the water-dispersed resin composition for flocking, it is preferable to adjust a viscosity by adding a viscosity modifier as needed. “Mixing” is a method usually used for mixing a resin composition, and is not particularly limited as long as it is a method capable of obtaining a water-dispersed resin composition for flocking according to the present invention. Absent.

  Further, the “viscosity modifier” is usually used to adjust the viscosity of the resin composition, and is particularly limited as long as it can obtain the water-dispersed resin composition for flocking according to the present invention. However, it is preferable that it can be adjusted as small as possible so as not to affect the performance of the resin composition. Examples of the viscosity modifier include an alkali thickening type such as Yodosol KA10 (trade name) manufactured by Henkel Technologies Japan, and an association type such as Adecanol UH438 manufactured by Asahi Denka.

  Here, the solid content ratio ((A) / (B)) between the component (A) and the component (B) of the water-dispersed resin composition for flocking is preferably 40-80 / 60-20, and 45 More preferably, it is -70 / 55-30, and it is especially preferable that it is 50-60 / 50-40. When the component (A) is less than 40 parts by weight (the component (B) exceeds 60 parts by weight), the pile retention of the coating film formed from the water-dispersed resin composition for flocking, and the coated water dispersion for flocking applied The abrasion resistance of the coating film formed by flocking to the layer of the mold resin composition can be lowered. When the component (A) exceeds 80 parts by weight (the component (B) is less than 20 parts by weight), the adhesion between the coating film formed from the water-dispersed resin composition for flocking and the substrate can be lowered.

  Here, the “solid content” of the component (A) and the component (B) is obtained by heating each of the component (A) and the component (B), which is a water-dispersed resin composition, at 105 ° C. for 3 hours. Say the balance. The “concentration” of the component (A) and the “concentration” of the component (B) are obtained by heating the component (A) and the component (B) at 105 ° C. for 3 hours when obtaining the above-mentioned “solid content”. It refers to the percentage of the mass after heating (solid content) of the component (A) and the component (B) with respect to the previous mass.

  In the water-dispersed resin composition for flocking according to the present invention, the solid content of the component (C) is 0.1 to 1.0 part by weight with respect to 100 parts by weight of the solid content of the component (A) and the component (B). Preferably there is. When the component (C) is less than 0.1 part by weight, the high temperature adhesion of the water-dispersed resin composition for flocking may not be sufficiently satisfied. When the component (C) exceeds 1.0 part by weight, the storage stability of the water-dispersed resin composition for flocking may be lowered and the practicality may be lacking.

  The viscosity of the water-dispersed resin composition for flocking according to the present invention obtained as described above is measured at 30 ° C. using an SB type rotary viscometer (spindle N0.4), and is 100 to 5000 mPa · It is preferably s, more preferably 1000 to 4000 mPa · s, and particularly preferably 2000 to 3000 mPa · s. When the viscosity is less than 100 mPa · s, a coating film formed by applying a water-dispersed fat composition for flocking to a substrate may not have a target film thickness.

  When a viscosity exceeds 5000 mPa * s, the coating property to the base material of the water-dispersed resin composition for flocking may fall. As will be described later, examples of the coating method for coating the water-dispersed resin composition for flocking onto a polyolefin substrate include a doctor knife coater, a roll coater and a spray coater, but any coating method is used. However, the leveling property may be lowered, and it may be difficult to apply the water-dispersed resin composition for flocking to the substrate with a uniform thickness.

  In this specification, “viscosity” refers to a value measured in accordance with the “rotary viscometer method” described in JIS K5400. More specifically, as the “rotary viscometer”, an SB type rotational viscometer, which is a single cylindrical rotational viscometer defined in JIS K7117, is used. 4 is a value measured by rotating the spindle at 60 rpm in a resin composition kept at 30 ° C.

  The thixotropic index (hereinafter also referred to as “TI”) of the water-dispersed resin composition for flocking according to the present invention is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. 2.0 to 3.0 is particularly preferable. When TI is less than 1.5, there is a problem that the formed coating film does not have the target film thickness because the fluidity of the resin composition when applied is high. Moreover, when TI exceeds 6.0, the problem that a leveling property is low and cannot obtain the coating film of uniform thickness may arise from the reason that the fluidity | liquidity of the resin composition at the time of coating is low.

In the present specification, “TI” refers to the viscosity obtained in the same manner except that the spindle was rotated at 6 rpm in the above-described viscosity measurement (hereinafter also referred to as “viscosity (6 rpm)”). Is a value obtained by dividing by the viscosity obtained by rotating at 60 rpm (hereinafter also referred to as “viscosity (60 rpm)”). The calculation formula (2) of this TI is shown below.
TI = viscosity (6 rpm) / viscosity (60 rpm) (2)

  The above-described water-dispersed resin composition for flocking can be used as it is as a water-dispersed resin composition (or adhesive) for flocking, but if necessary, for example, bactericides, preservatives, antifoaming agents, plastics Additives such as an agent, a flow modifier, a thickener, a pH adjuster, a surfactant, a pigment, a rust inhibitor, a wetting agent, a silane coupling agent and a crosslinking agent are used.

  The water-dispersed resin composition for flocking according to the present invention is applied to a substrate. At that time, the composition applied is applied to the substrate and / or after being applied to the substrate. A pile is planted in the layer of the object, and the layer of the planted composition is dried to form a coating film. The water-dispersed resin composition for flocking can be applied using a method usually used for applying the resin composition to a substrate. For example, it can be coated on a polyolefin substrate using a spray coater, doctor knife coater, roll coater or wire coater.

The coating amount of flocking water-dispersible resin composition to the substrate is preferably from 10 to 200 g / ^{m 2} as a solid content, more preferably from ^{30~150g / m 2, 40~100g / m} 2 Is particularly preferred.

  The method for flocking a substrate coated with the water-dispersed resin composition for flocking of the present invention is not particularly limited as long as it is a method usually used as a method for flocking a substrate. Examples of such a method include a method of spray coating with a pile and an electrostatic flocking method. The method of spray coating with a pile can reduce the coating amount of the adhesive because the pile is easily stuck in the adhesive layer by spraying the pile. In addition, it is preferable to use an electrostatic flocking method because each pile is fixed to the adhesive coating film (coating layer) on the surface to be processed straight without a gap.

  Here, the “base material” is not particularly limited as long as it is a base material to which a resin composition for flocking is normally applied and a pile is flocked. Examples of the “substrate” include plastic substrates such as polyolefin substrates and ABS resin substrates, and fiber substrates, but the water-dispersed resin composition for flocking of the present invention is a primer treatment. It can also be preferably used for a polyolefin substrate which has not been damaged.

  “Polyolefin base material” refers to a base material manufactured using a resin that is usually made of polyolefin, for example, a base material made of polyolefin such as polyethylene, polypropylene, ethylene-propylene copolymer, etc. It can be illustrated. Furthermore, polyolefin base materials mixed with fillers such as glass fiber, calcium carbonate, and talc, as well as polycarbonate, polystyrene, acrylonitrile-styrene copolymer, polymethyl methacrylate, polyphenylene oxide, nylon, polyester, ABS resin, rubber It may be a polyolefin substrate modified with a polymer such as

  The “pile” is not particularly limited as long as it is normally used as a pile. Examples of piles include the following: natural fibers such as cotton, wool and hemp; wool fibers such as rayon and protein fibers; polyurethane, polyvinyl chloride, polyvinyl alcohol, polyvinylidene chloride, polyester , Polyamide-based (nylon), acrylonitrile polymer and acrylonitrile copolymer, polyolefin-based synthetic fibers; and fiber products such as knitted fabrics and non-woven fabrics of these blends.

  The water-dispersed resin composition for flocking according to the present invention has its coatability, adhesion to the substrate of the coating film to be formed (particularly high-temperature adhesion), abrasion resistance of the coating film formed by flocking, And a good balance of storage stability.

  In the present specification, “coating property” means that the composition can be applied to the substrate with a uniform thickness as a whole. More specifically, it refers to the ease of spraying when a water-dispersed resin composition for flocking is spray-coated on a polyolefin substrate. It is visually observed and evaluated whether or not coating can be performed evenly and uniformly. The water-dispersed resin composition for flocking according to the present invention can be coated uniformly on a polyolefin substrate by spray coating (in the examples, 実 施 and ◯. Coating properties). Those that are good) are preferred.

  In the present specification, “adhesiveness (or adhesiveness)” refers to the adhesiveness between a coating film and a polyolefin substrate obtained by using a cross-cut tape method according to JIS K5400. Specifically, through the coating film formed on the test piece, a cut reaching the base surface of the polyolefin is made in the shape of a base, and an adhesive tape is put on the grid-like cut and then peeled off. The state of adhesion of the coating film is visually observed and evaluated. Since the adhesion test was conducted paying attention to the adhesion between the base material and the coating film, after applying the water-dispersed resin composition for flocking to the base material, it was possible to transplant the coated composition without flocking the layer. This was performed using a coating formed by drying the composition layer (without the pile treatment). In this evaluation method based on JISK5400, the evaluation is quantified with 0 to 10 points. The better the score, the higher the score, and the highest score is 10. The water-dispersed resin composition for flocking according to the present invention preferably has an adhesion evaluation score of 8 to 10 (in the examples, ◎ and ◯. Excellent adhesion).

  As used herein, “high temperature adhesion” refers to adhesion after curing a coating film on a polyolefin substrate at a high temperature. Specifically, after the coating film formed on the test piece is cured at 80 ° C. for 16 hours, the state of the coating film after being strongly scratched with a nail or the like is visually observed and evaluated. Since the high temperature adhesion test was conducted by paying attention to the adhesion after curing at a high temperature of the base material and the coating film, after applying the water-dispersed resin composition for flocking to the base material, The coating layer was formed by drying the composition layer without flocking the layer. In this evaluation method, the evaluation is quantified from 0 to 10 points. The better the score, the higher the score, and the highest score is 10. The water-dispersed resin composition for flocking according to the present invention has an evaluation score of high-temperature adhesion of the formed coating film of 8 to 10 (in the examples, 実 施 and ○. Excellent high-temperature adhesion). preferable.

  In this specification, “abrasion resistance” refers to the abrasion resistance of a coating film formed by flocking, measured using a Taber method according to JIS L1096. Specifically, after preparing a circular test piece from polyolefin, applying the water-dispersed resin composition for flocking according to the present invention to the surface of the circular test piece, flocking the formed composition layer, The layer was dried to obtain a coating film. Thereafter, this circular test piece was attached to a Taber type abrasion tester, and rubbed at 70 rotations per minute, and when the load was applied to 500 g and was worn 1000 times, the change in the appearance of the test piece was visually observed. evaluate. The water-dispersed resin composition for flocking according to the present invention observes the appearance of the worn part of the coating film formed by flocking on the test piece, and no abnormality is observed (in Examples, A and B). Those having excellent wear properties are preferred.

  In the present invention, “storage stability” means that the composition can be stored without changing with time. Specifically, the composition is sealed in a metal container and evaluated by evaluating the appearance, coatability, and adhesion between the coating film and the substrate before and after standing at 40 ° C. for 30 days. The water-dispersed resin composition for flocking according to the present invention is preferably one in which no abnormal change is observed in the above properties before and after standing (in the examples, ◎ and ◯).

Furthermore, a base material planted using the water-dispersed resin composition for flocking according to the present invention is provided, and in particular, a base material made of polyolefin that is flocked is provided.
The water-dispersed resin composition for flocking according to the present invention is used for flocking to a substrate made of polyolefin or the like, for example, a pillar, a glove box, a console box, a coin box, a spectacle box, or the like (flocked). It can be suitably used to produce other (flocked) automobile parts such as automobile interior parts and glass channels.

The main aspects of the present invention are shown below.
1.
A water-dispersed resin composition for flocking comprising the following component (A), component (B) and component (C).
(A) Component: Monomer (a) represented by the following chemical formula (1)
^{_{CH 2 = C (R 1)}} -COO-R 2 (1)
[In the chemical formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is a monocyclic alkyl group. And a copolymer obtained by polymerizing a monomer mixture containing other unsaturated monomers, a water-dispersed resin composition,
(B) Component: Water-dispersed resin composition of chlorinated polyolefin (C) Component: Epoxy silane coupling agent.
2.
The water-dispersed resin composition for flocking according to the above 1, for producing automobile interior parts.
3.
The water-dispersed resin composition for flocking according to the above 1 or 2, wherein the monomer (a) is cyclohexyl (meth) acrylate.
4).
The water for flocking in any one of said 1-3 whose solid content of (C) component is 0.1-1.0 weight part with respect to 100 weight part of solid content of (A) component and (B) component Dispersion type resin composition.
5.
Furthermore, the water-dispersed resin composition for flocking according to any one of the above 1 to 4, comprising a film-forming aid.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely and in detail, these Examples are only one aspect | mode of this invention, and this invention is not restrict | limited at all by these examples.

The monomers used to obtain the component (A) in the examples are shown below:
As monomer (a), cyclohexyl methacrylate (hereinafter also referred to as “CHMA”);
2-ethylhexyl acrylate (hereinafter also referred to as “2EHA”) as another unsaturated monomer;
Styrene (hereinafter also referred to as “St”);
Methyl methacrylate (hereinafter also referred to as “MMA”);
Acrylonitrile (hereinafter also referred to as “AN”);
Methacrylic acid (hereinafter also referred to as “MAA”); and cross-linking agent 3-methacryloxypropylmethyldimethoxysilane (hereinafter also referred to as “KBM502”).
Was used.

Hereinafter, physical property evaluation of the water-dispersed resin composition for flocking will be described.
<Glass transition temperature (Tg)>
The “glass transition temperature (Tg) of the copolymer” contained in the component (A) was obtained by calculation using the calculation formula (1) of the theoretical Tg of the copolymer.
_{1 / Tg = C 1 / Tg} 1 + C 2 / Tg 2 + ··· + C n / Tg n (1)
[Tg is the theoretical Tg of the copolymer, C _n is the weight ratio of the n-th monomer _n contained in the monomer mixture, Tg _n is the Tg of the homopolymer of the n-th monomer n, n is It is the number of monomers constituting the copolymer and represents a positive integer. ]

  The value described in the literature was used for the Tg of the above-mentioned monomer homopolymer. For CHMA, the values in the acrylic ester catalog (1997 edition) of Mitsubishi Rayon Co., Ltd., for St, 2EHA, and MMA, Kyozo Kitaoka, “New Polymer Library 7, Introduction to Synthetic Resins for Paints”, Polymer Publications Published in 1997, pages 168-169. As the Tg values of the respective homopolymers of CHMA, St, MMA, 2EHA, AN and MAA, 83 ° C, 100 ° C, 105 ° C, -85 ° C, 94 ° C and 130 ° C were used.

The “solid content” of the component (A) and the component (B) was obtained by heating each of the components (A) and (B), which are water-dispersed resin compositions, at 105 ° C. for 3 hours.
The “concentration” of the component (A) and the “concentration” of the component (B) are the same as those obtained when the components (A) and (B) are heated at 105 ° C. for 3 hours when the above-mentioned “solid content” is obtained. It calculated | required as a percentage of the mass after (A) component and (B) component heating with respect to the mass of (solid content).

<Viscosity>
The viscosity of the water-dispersed resin composition for flocking was determined according to the “Rotational Viscometer Method” described in JIS K5400, and a rotational viscometer, a container, a thermometer, and a thermostatic water bath were used. As the “rotary viscometer”, an SB type rotational viscometer, which is a single cylindrical rotational viscometer defined in JIS K7117, was used. 4 was used. A “constant temperature bath” that can set the water temperature to around 30 ° C. was used.
In a resin composition in a container kept at 30 ° C. using a thermostatic water bath, the spindle is rotated at 60 rpm, the delay in rotation of the rotor caused by the resistance of the resin composition is indicated on the scale plate, and the viscosity is Asked. In addition, the viscosity of (A) component was performed using the method similar to the viscosity measurement of the above-mentioned resin composition.

<Thixotropic Index (TI)>
The TI of the water-dispersed resin composition for flocking is the same as the above-mentioned spindle in the viscosity measurement described above except that the spindle was rotated at 6 rpm (hereinafter also referred to as “viscosity (6 rpm)”). Was divided by the viscosity obtained by rotating at 60 rpm (hereinafter also referred to as “viscosity (60 rpm)”). The calculation formula (2) of this TI is shown below.
TI = viscosity (6 rpm) / viscosity (60 rpm) (2)
The obtained water-dispersed resin composition for flocking comprises the coating properties of the resin composition, the adhesion between the formed coating film and the substrate, the wear resistance of the coating film formed by flocking, and the resin composition. Storage stability was evaluated.

<Coating property>
The coatability of the resin composition was evaluated by testing the sprayability of spraying the resin composition on a polyolefin substrate in the form of a mist. The coating property is ◎ when the composition can be applied to the substrate with a uniform and uniform thickness overall, and the composition can be applied to the substrate with a substantially uniform thickness overall. The case where the film thickness is ◯, the film thickness is uneven and the coating film thickness is uneven, or the coating film thickness does not reach the target thickness is evaluated as x.

<Adhesion>
The adhesion between the coating film formed from the water-dispersed resin composition for flocking and the substrate was evaluated by conducting a cross-cut test based on the cross-cut tape method described in JIS K5400. That is, the coating film on the prepared test piece was penetrated, a cut reaching the base surface made of polyolefin was made in the shape of a base, and an adhesive tape was stretched on the base. The adhesion state of the coating film after peeling off the tape was visually observed. A case where no peeling was observed even at the intersection of cuts (corresponding to an evaluation score of 10), there was slight peeling (less than 5%) at the cut line and the intersection of the cuts, but overall peeling △ (corresponds to 6 and 4) when there is no mark ◯ (corresponding to an evaluation score of 8), and there is partial or total peeling along the cut line (less than 35%) ), And the case where large peeling occurred as a whole (35% or more) was evaluated as x (corresponding to evaluation scores of 2 and 0).

<High temperature adhesion>
The high-temperature adhesion between the coating film formed from the water-dispersed resin composition for flocking and the substrate is determined by curing the prepared test piece in a constant temperature room at 80 ° C. for 16 hours, while the test piece does not cool, The adhesion state of the coating film after being scratched more strongly was visually observed. The case where there was no pile omission or breakage was rated as ◎, the case where there was some omission or breakage in the pile, but there was no problem in appearance, O, and the state where the pile was peeled off and the substrate was visible was marked as x.

<Abrasion resistance>
The abrasion resistance of the coating film formed by flocking obtained from the water-dispersed resin composition for flocking was evaluated by conducting an abrasion resistance test using a Taber method in accordance with JIS L1096. That is, a circular test piece is prepared from polyolefin, a resin composition is applied to the surface of the circular test piece, and then the formed resin composition layer is flocked using an electrostatic flocking method. Dried to obtain a coating film. A circular test piece having a coating film formed by flocking is attached to a Taber-type abrasion tester, rotated at 70 revolutions per minute, visually applied to the test piece after being worn 1000 times by applying a load of 500 g. And observed. ◎ if there is no change in state, ◯ if there is wear but pile is missing, and there is almost no pile break, △ if there is noticeable pile break or break, △ wear is marked and there is almost no pile left and the ground can be seen The state was set to x.

<Storage stability>
The storage stability of the water-dispersed resin composition for flocking is determined by the appearance, coatability, and adhesion between the coating film and substrate before storage after sealing the composition in a metal container and leaving it at 40 ° C for 30 days. ◎ indicates that there is no change in comparison to ◎, and although the appearance is slightly changed, it returns to the state before storage with gentle agitation, and 〇 indicates that there is no change in coating properties and adhesion, and markedly different from before storage When x was generated, it was set as x.

<Comprehensive evaluation>
It was described as a comprehensive evaluation in consideration of the evaluation results of the properties described above. If both properties are extremely excellent and the property balance is extremely excellent ◎, if both properties are excellent and the property balance is also excellent ○, only high temperature adhesion is insufficient, but other properties (adhesion) ) Is considered to be “X” and “XX” in consideration of the degree of Δ when excellent, and the degree when the overall properties are inferior.

Production of water-dispersed resin composition for flocking of Example 1 <Production of component (A)>
A reactor equipped with a stirrer, a condenser and a thermometer was charged with 160 parts by weight of water and 0.5 parts by weight of Adeka Soap SR10 (trade name), and the system was replaced with nitrogen gas. Heated to 80 ° C.
On the other hand, a monomer mixture comprising the following monomers separately prepared (theoretical Tg of the resulting copolymer is 35 ° C.), CHMA: 70 parts by weight, 2EHA: 18 parts by weight, AN: 10 parts by weight, MAA: 1.5 parts by weight and copolymerizable crosslinker KBM502: 0.5 parts by weight of a homogeneous solution is added to a homogeneous solution consisting of 40 parts by weight of water and 2.5 parts by weight of ADEKA rear soap SR10, and a stirrer Was used to prepare a pre-emulsion.
Furthermore, an aqueous solution in which 1 part by weight of sodium persulfate (hereinafter also referred to as “SPS”) was dissolved in 40 parts by weight of water was prepared as a polymerization catalyst.
Each of the above pre-emulsion and the aqueous solution of SPS, which is a polymerization catalyst, is simultaneously dropped into the reactor in which the inside of the system is replaced with nitrogen gas over 3 hours while maintaining the temperature in the reactor at 80 ° C. Stirring was continued at 80 ° C. for 3 hours to obtain a resin emulsion of component (A).
The viscosity of the resulting resin emulsion of component (A) was 40 mPa · s, and the concentration was 30% by weight.

<Composition of components (A) to (C)>
50 parts by weight of Supercron E633 (trade name) manufactured by Nippon Paper Industries Co., Ltd., which is a chlorinated polyolefin dispersion, is used as the component (B) with respect to 50 parts by weight of the solid content of the composition (A) described above. In addition, 0.5 parts by weight of SH-6040 (trade name) of Toray Dow Corning Silicone, which is 3-glycidoxypropyltrimethoxysilane, is added as component (C), and Yodosol KA10 (trade name) of Henkel Technologies Japan is used as a viscosity modifier. ) Was added to adjust the viscosity and thixotropic index (hereinafter also referred to as “TI”) to obtain a water-dispersed resin composition for flocking. Its viscosity was 3000 mPa · s and TI was 4.0. The evaluation results are shown in Table 1.

Production of water-dispersed resin composition for flocking in Example 2 Water-dispersed resin composition for flocking in the same manner as described in Example 1, except that 1.0 part by weight of component (C) SH-6040 was added. The thing was manufactured. The water-dispersed resin composition for flocking had a viscosity of 3100 mPa · s and a TI of 3.8.

Manufacture of water-dispersed resin composition for flocking of Example 3 Chemical manufactured by Nippon Paper Industries Co., Ltd., which is a chlorinated polyolefin dispersion as component (B) with respect to 70 parts by weight of the solid content of the composition as component (A) 30 parts by weight of Supercron E633 (trade name) of Toray Dow Corning Silicone, which is 3-glycidoxypropyltrimethoxysilane as component (C), 0.5 parts by weight of SH-6040 (trade name) In addition, Hedkel Technologies Japan's Yodosol KA10 (trade name) was added as a viscosity modifier to adjust the viscosity and thixotropic index (hereinafter also referred to as “TI”), and the same method as described in Example 1 was used for flocking. A dispersion type resin composition was produced. The water-dispersed resin composition for flocking had a viscosity of 3000 mPa · s and a TI of 3.8.

Production of water-dispersed resin composition for flocking of Example 4 A monomer mixture comprising the following monomers (theoretical Tg of the resulting copolymer is 35 ° C.), CHMA: 70 parts by weight, St: The resin emulsion obtained was changed to 10 parts by weight, 2EHA: 18 parts by weight, MAA: 1.5 parts by weight, and copolymerizable crosslinking agent KBM502: 0.5 parts by weight, and used as component (A). The viscosity of the resin emulsion of component (A) was 40 mPa · s, and the concentration was 30%.
(A) 50 parts by weight of the solid component is used, 50 parts by weight of Supercron E633 is added as the (B) component, SH-6040: 0.5 parts by weight as the (C) component, and iodosol as the viscosity modifier A water-dispersed resin composition for flocking was produced in the same manner as described in Example 1, except that KA10 was added to adjust the viscosity and TI to obtain a water-dispersed resin composition for flocking. The water-dispersed resin composition for flocking had a viscosity of 3100 mPa · s and a TI of 4.1.

Production of water-dispersed resin composition for flocking of Example 5 As described in Example 1, except that Nippon Paper Chemicals' Supercron S-4397, which is a solvent-free chlorinated polyolefin dispersion, was used as the component (B). A water-dispersed resin composition for flocking was produced in the same manner as described above. The viscosity of the water-dispersed resin composition for flocking was 3200 mPa · s, and TI was 4.0.

Production of water-dispersed resin composition for flocking of Example 6 A monomer mixture is a mixture comprising the following monomers (theoretical copolymer Tg is 13 ° C.), CHMA: 60 parts by weight, 2EHA: The resin emulsion obtained was changed to 28 parts by weight, AN: 10 parts by weight, MAA: 1.5 parts by weight, and copolymerizable crosslinking agent KBM502: 0.5 part by weight, and the resulting resin emulsion was used as component (A). The viscosity of the resin emulsion of component (A) was 30 mPa · s, and the concentration was 30%.
A water-dispersed resin composition for flocking was produced in the same manner as described in Example 1 except that this component (A) was used. The viscosity of the water-dispersed resin composition for flocking was 3100 mPa · s, and TI was 4.3.

Production of water-dispersed resin composition for flocking of Example 7 A monomer mixture is a mixture comprising the following monomers (theoretical copolymer Tg is 48 ° C.), CHMA: 70 parts by weight, St: 5 parts by weight, 2EHA: 13 parts by weight, AN: 10 parts by weight, MAA: 1.5 parts by weight, and copolymerizable crosslinking agent KBM502: 0.5 parts by weight. As a film auxiliary, 2.0 parts by weight of CS-12 (trade name) of Nisso, which is 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, was added to prepare component (A). The viscosity of the component (A) was 30 mPa · s, and the concentration was 30%.
A water-dispersed resin composition for flocking was produced in the same manner as described in Example 1 except that this component (A) was used. The viscosity of the water-dispersed resin composition for flocking was 3100 mPa · s, and TI was 4.1.

Production of water-dispersed resin composition for flocking of Example 8 A monomer mixture is a mixture comprising the following monomers (theoretical Tg of the resulting copolymer is 36 ° C.), CHMA: 60 parts by weight, St: 10 parts by weight, 2EHA: 18 parts by weight, AN: 10 parts by weight, MAA: 1.5 parts by weight, and copolymerizable crosslinking agent KBM502: 0.5 parts by weight. ) Component. The viscosity of this (A) component was 30 mPa · s, and the concentration was 30%. Except for adjusting the viscosity and TI by changing the amount of iodosol KA10 added as a viscosity modifier using this (A) component, A water-dispersed resin composition for flocking was produced in the same manner as described in Example 1. The viscosity of the water-dispersed resin composition for flocking was 1500 mPa · s, and TI was 3.1.

Production of water-dispersed resin composition for flocking of Comparative Example 1 A water-dispersed resin composition for flocking was produced in the same manner as described in Example 1 except that the component (B) was not used. The viscosity of the water-dispersed resin composition for flocking was 3300 mPa · s, and TI was 3.8.

Production of water-dispersed resin composition for flocking in Comparative Example 2 A water-dispersed resin composition for flocking was produced in the same manner as in Example 1 except that the component (A) was not used. The viscosity of the water-dispersed resin composition for flocking was 2900 mPa · s, and TI was 3.4.

Production of water-dispersed resin composition for flocking of Comparative Example 3 A monomer mixture was made of a mixture of the following monomers (theoretical copolymer Tg was 35 ° C.), MMA: 66 parts by weight, 2EHA: The resin emulsion thus obtained was changed to 22 parts by weight, AN: 10 parts by weight, MAA: 1.5 parts by weight, and copolymerizable crosslinking agent KBM502: 0.5 part by weight as component (A). The viscosity of the component (A) was 30 mPa · s, and the concentration was 30%.
With respect to 50 parts by weight of the component (A), 50 parts by weight of Supercron E633 is added as the component (B), and Yodosol KA10 (trade name) of Henkel Technologies Japan is added as a viscosity modifier. A thixotropic index (hereinafter also referred to as “TI”) was adjusted to produce a water-dispersed resin composition for flocking. The viscosity of the water-dispersed resin composition for flocking was 3000 mPa · s, and TI was 3.7.

Production of water-dispersed resin composition for flocking in Comparative Example 4 (C′-1) As a component, 3-aminopropyltriethoxysilane SILQUEST A-1100 SILANE (trade name) of Momentive Performance Materials Japan GK A water-dispersed resin composition for flocking was produced in the same manner as described in Example 1 except that the amount was changed to 0.5 parts by weight. The viscosity of the water-dispersed resin composition for flocking was 3100 mPa · s, and TI was 3.6.

Manufacture of water-dispersed resin composition for flocking of Comparative Example 5 (C'-2) As described in Example 1, except that the component was changed to 0.5 parts by weight of vinyltrimethoxysilane KBM1003 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. A water-dispersed resin composition for flocking was produced by the same method as described above. The viscosity of the water-dispersed resin composition for flocking was 3000 mPa · s, and TI was 3.9.

  For the water-dispersed resin composition for flocking of Examples 1 to 8 and the water-dispersed resin composition for flocking of Comparative Examples 1 to 5, the coating properties, adhesion, high-temperature adhesion, wear resistance, and storage stability described above were obtained. evaluated. The results are shown in Tables 1 and 2.

a)単量体混合物に含まれる単量体及びその量（重量部）である。
b)共重合体のガラス転移温度（℃）である。
c)（A）成分と（B）成分の固形分の重量比である。
d)30℃での粘度（ｍＰａ・ｓ）である。
e)30℃でのTIである。

a) Monomers contained in the monomer mixture and their amounts (parts by weight).
b) Glass transition temperature (° C) of the copolymer.
c) Weight ratio of the solid content of the component (A) and the component (B).
d) Viscosity at 30 ° C. (mPa · s).
e) TI at 30 ° C.

a)単量体混合物に含まれる単量体及びその量（重量部）である。
b)共重合体のガラス転移温度（℃）である。
c)（A）成分と（B）成分の固形分の重量比である。
d)30℃での粘度（ｍＰａ・ｓ）である。
e)30℃でのTIである。

a) Monomers contained in the monomer mixture and their amounts (parts by weight).
b) Glass transition temperature (° C) of the copolymer.
c) Weight ratio of the solid content of the component (A) and the component (B).
d) Viscosity at 30 ° C. (mPa · s).
e) TI at 30 ° C.

As shown in Table 1, each of the water-dispersed resin compositions for flocking of Examples 1 to 8 has coating properties, adhesion, high-temperature adhesion, and storage stability, all of which are ○ or ◎, and their properties are comprehensive. The overall balance is excellent and the overall evaluation is ◎ or ○.
On the other hand, as shown in Table 2, since the water-dispersed resin compositions for flocking of Comparative Examples 1 to 5 do not contain any of the components (A) to (C), their properties are in a comprehensive balance. Inferior. In any case, the high-temperature adhesion is x, and the overall evaluation is xx for Comparative Examples 1 and 2, x for Comparative Example 3, and Δ for Comparative Examples 4 to 5. The water-dispersed resin composition for flocking with poor high-temperature adhesion is unsuitable for producing automotive interior parts that become hot in summer.
Thus, the water-dispersed resin composition for flocking containing the components (A) to (C) according to the present invention is excellent in high-temperature adhesion and can be suitably used for producing automobile interior parts, It was confirmed that the overall balance was excellent.

Claims (4)

A water-dispersed resin composition for flocking comprising the following component (A), component (B) and component (C).
(A) Component: Monomer (a) represented by the following chemical formula (1)
^{_{CH 2 = C (R 1)}} -COO-R 2 (1)
[In the chemical formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is a monocyclic alkyl group. And a copolymer obtained by polymerizing a monomer mixture containing other unsaturated monomers, and the other unsaturated monomers include an ethylenic silane compound and are selected from acrylic acid and methacrylic acid. A water-dispersed resin composition comprising at least one selected from the group consisting of:
(B) Component: Water-dispersed resin composition of chlorinated polyolefin (C) Component: Epoxy silane coupling agent.   The water for flocking of Claim 1 whose solid content of (C) component is 0.1-1.0 weight part with respect to 100 weight part of total weight of solid content of (A) component and (B) component. Dispersion type resin composition.   The water-dispersed resin composition for flocking according to claim 1 or 2, further comprising a film-forming aid.   The water-dispersed resin composition for flocking according to any one of claims 1 to 3, for producing an automobile interior part.