JP2007217593A - Acrylic sol composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an acrylic sol composition that does not generate a hydrogen chloride gas and dioxins in incineration, has excellent storage stability, is cured at a relatively low temperature and has excellent adhesiveness of a coating film to a substrate, cold resistance of coating film and coating film strength. <P>SOLUTION: The acrylic sol composition comprises (a) an acrylic polymer fine particle, (b) a block polyurethane, (c) a polyamine compound, (d) a diphenyl compound represented by general formula (I) (R<SB>1</SB>and R<SB>2</SB>are each a hydrogen atom or an alkyl group; R<SB>3</SB>and R<SB>4</SB>are each an alkyl group), (e) a plasticizer and (f) a filler. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an acrylic sol composition, and in particular, it does not generate hydrogen chloride gas or dioxin during incineration, has excellent storage stability, can be cured at a relatively low temperature, and is applied to a coating film substrate. The present invention relates to an acrylic sol composition excellent in adhesiveness, cold resistance of a coating film, and coating film strength.

  At present, plastisol, which is widely used industrially, is a liquid or paste-like viscosity obtained by uniformly dispersing polymer particles having a specially adjusted particle size and particle size distribution in a plasticizer together with a filler. It is a thick composition. And a tough coating film is formed by apply | coating to a base material and adding an appropriate processing temperature.

  As the polymer particles, polyvinyl chloride based polymers such as vinyl chloride homopolymers and copolymers of vinyl chloride and vinyl acetate are often used. Such polyvinyl chloride-based plastisol has good long-term storage stability at room temperature, and the coating film is flexible and excellent in durability. For example, the fields of steel sheet coating, clothing, building materials, daily necessities, miscellaneous goods, automobile parts, etc. Widely used.

  However, polyvinyl chloride plastisol is decomposed by heat or light to generate hydrogen chloride gas. The hydrogen chloride gas generated here causes problems such as causing ozone layer depletion, causing acid rain, and accelerating damage to the incinerator during incineration. Dioxins may be generated depending on the conditions, which is not preferable in terms of health and safety and environmental pollution. For this reason, the appearance of plastisol, which replaces the polyvinyl chloride plastisol, is awaited.

  As a plastisol that replaces the polyvinyl chloride plastisol, Japanese Patent Publication No. 55-16177 discloses a plastisol composed of an acrylate polymer and an organic plasticizer, but has a drawback of insufficient storage stability and film formability. have.

  Japanese Examined Patent Publication No. 63-68661 discloses a plastisol containing no methyl methacrylate polymer or copolymer, plasticizer, filler, blocked polyurethane, and polyvinylamine containing polyamine. However, when the processing temperature of the coating film is relatively low, since the curing reaction of the urethane resin does not proceed, the performance of the resulting coating film is not sufficient, and if it is left at about 35 ° C., it will gel in 1-2 days. It is not practical because

  Further, JP 2001-329135 A proposes an acrylic sol containing acrylic polymer fine particles, a block-type urethane resin, a solid hydrazine-based curing agent, a plasticizer, and a filler, and JP 2001-329208 A. The publication proposes an acrylic sol for soundproof undercoat containing acrylic polymer fine particles, plasticizer, filler, block type urethane resin, curing agent and foaming agent, but has insufficient adhesion to the substrate. And has disadvantages such as insufficient flexibility at low temperatures.

  Furthermore, International Publication WO01 / 88009A1 is formed by blending a blocked urethane or a blocked isocyanate and a latent curing agent in a plastisol obtained by dispersing core-shell type acrylic resin particles and a filler in a plasticizer. A thermosetting composition has been proposed, and International Publication WO01 / 88011A1 discloses a plastisol in which acrylic resin particles and a filler are dispersed in a plasticizer, a blocked urethane or a blocked isocyanate, and a melting point of room temperature solid particles. A thermosetting composition has been proposed in which a latent curing agent that is not dissolved in a plasticizer at a temperature of 60 ° C. or higher and 40 ° C. or lower has been proposed, but is still not satisfactory in terms of viscosity stability, adhesiveness, etc. Absent.

  JP 2004-51948 A proposes an acrylic sol composition containing acrylic polymer fine particles, block polyurethane, polyamine compound, phenol resin, plasticizer and filler, and International Publication WO 03/102077 discloses An acrylic sol composition containing a block polyurethane obtained from an acrylic polymer fine particle, a polyol and a diisocyanurate, a plasticizer and a filler has been proposed, but has not yet been satisfactory in terms of viscosity stability and the like. .

Japanese Patent Publication No.55-16177 Japanese Patent Publication No. 63-66861 JP 2001-329135 A JP 2001-329208 A International Publication WO01 / 88009A1 International Publication WO01 / 88011A1 JP 2004-51948 A International Publication WO 03/102077

  The present invention has been made in view of the present situation as described above, does not generate hydrogen chloride gas or dioxin during incineration, has excellent storage stability, and can be cured at a relatively low temperature. An object of the present invention is to provide an acrylic sol composition excellent in adhesion of a coating film to a substrate, cold resistance of the coating film, and coating film strength.

  As a result of intensive studies, the present inventors have incorporated the polyamine compound and the specific diphenyl compound into the acrylic sol composition containing acrylic polymer fine particles, block urethane, etc. We have found that an improved acrylic sol composition is provided and have arrived at the present invention.

  That is, the present invention comprises (a) acrylic polymer fine particles, (b) block polyurethane, (c) polyamine compound, (d) diphenyl compound represented by the following general formula (I), (e) plasticizer, and ( f) An acrylic sol composition comprising a filler is provided.

（式中、Ｒ１及びＲ２は、それぞれ独立して水素原子又は炭素原子数１〜５のアルキル基を表し、Ｒ３及びＲ４は、それぞれ独立して炭素原子数１〜５のアルキル基を表し、ｐ及びｑはそれぞれ独立して０〜５の数を表す。また、ｐ２以上の場合には、それぞれのＲ３が異なる炭素原子数のアルキル基でもよく、ｑが２以上である場合には、それぞれのＲ４が異なる炭素原子数のアルキル基でもよい。）

(Wherein R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R3 and R4 each independently represent an alkyl group having 1 to 5 carbon atoms, p And q each independently represents a number from 0 to 5. When p2 or more, each R3 may be an alkyl group having a different number of carbon atoms, and when q is 2 or more, R4 may be an alkyl group having a different number of carbon atoms.)

  The acrylic sol composition of the present invention does not generate hydrogen chloride gas or dioxin at the time of incineration, has excellent storage stability, can be cured even at a relatively low temperature, and further adheres to the substrate of the coating film Moreover, it is excellent in the cold resistance of the coating film and the coating film strength, and becomes an acrylic sol composition useful in a wide range of fields such as sealing materials, coating materials, and daily necessities.

Hereinafter, preferred embodiments of the acrylic sol composition of the present invention will be described in detail.
The acrylic sol composition of the present invention comprises (a) acrylic polymer fine particles, (b) block polyurethane, (c) a polyamine compound, (d) a diphenyl compound represented by the above general formula (I), and (e) a plasticizer. And (f) containing a filler.

  Specifically, the acrylic sol composition of the present invention has (b) a block polyurethane content of 11 to 567 parts by mass and (c) a polyamine compound content of (a) 100 mass parts of the acrylic polymer fine particles. 0.01 to 10 parts by mass, (e) the plasticizer content is 50 to 500 parts by mass, and (f) the filler content is 50 to 800 parts by mass, and per 100 parts by mass of the (c) polyamine compound. (D) Content of the diphenyl compound represented by general formula (I) is 0.1-10 mass parts.

As the acrylic polymer fine particles as the component (a) used in the present invention, a polymer usually used as an acrylic sol composition can be used. For example, a monomer single polymer or copolymer selected from acrylic acid alkyl ester, methacrylic acid alkyl ester, and the like can be used. Specific examples of these monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, ter-butyl acrylate, cyclohexyl acrylate, benzyl acrylate, and methyl methacrylate. Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, ter-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate and the like.
Further, styrene, α-methylstyrene, or the like can be used as a copolymerization component.

  As the acrylic polymer fine particles, those having a core-shell type composed of a core portion and a shell portion are preferably used. When an acrylic sol is prepared using core-shell type acrylic polymer fine particles, the storage stability of the acrylic sol is further improved, and the increase in viscosity when applied and the occurrence of bleeding after heat curing are further suppressed. There is an advantage of doing.

  Further, when the acrylic polymer fine particles are of a core-shell type, it is preferable that the core portion is composed of a plasticizer affinity polymer and the shell portion is composed of a plasticizer non-affinity polymer. The polymer in the shell portion that is poorly compatible with the plasticizer coats the compatible core portion, thereby suppressing an increase in the viscosity of the acrylic sol during storage and further improving the storage stability. Further, since the polymer of the shell portion is compatible with the plasticizer by heating to an appropriate temperature, no bleeding occurs after the heat curing.

  The component of the core part is preferably composed of a polymer containing 50% by mass or more of at least one methacrylate selected from n-butyl methacrylate, isobutyl methacrylate, ethyl methacrylate and the like. Thus, by making the core component highly compatible with the plasticizer, the occurrence of bleeding after heat curing can be suppressed. In particular, from the viewpoint of imparting flexibility to the coating film, the core component is preferably mainly composed of a copolymer of butyl methacrylate and isobutyl methacrylate.

  The component of the shell part is preferably composed of a polymer containing 50% by mass or more of at least one methacrylate selected from methyl methacrylate, benzyl methacrylate, styrene and the like, or a copolymer thereof. Thus, by making a shell component low compatibility with a plasticizer, the viscosity increase of the acrylic sol during storage is suppressed and storage stability improves more. In particular, from the viewpoint of further improving the storage stability, it is preferable that the component of the shell portion is mainly composed of methyl methacrylate.

  Examples of the core-shell type acrylic polymer fine particles used in the present invention include, for example, JP-A-6-172734, JP-A-2001-329135, JP-A-2001-329208, and International Publication WO01 / 88009. Core-shell type acrylic polymer fine particles described in the above.

  Furthermore, the polymer ratio (the former / the latter) of the core part and the shell part is preferably 25/75 to 70/30 by mass ratio. When the core component is less than 25/75 as the mass ratio, the possibility that bleed occurs after heat curing is higher than that in the above desired range. Further, when the shell component is less than 70/30 as the mass ratio, the coating of the core component of the shell component may be insufficient as compared with the desirable range, which affects the storage stability. Because.

  The molecular weight of the acrylic polymer fine particles is preferably from 100,000 to several million in terms of mass average molecular weight from the viewpoint of coating film strength, storage stability, and the like, and the average particle diameter is diffusibility to plasticizers and storage stability. From the viewpoint of properties, it is preferable to use a material in the range of 0.1 to 10 μm.

The (b) block polyurethane used in the present invention is obtained by blocking an isocyanate group of a polyurethane having an isocyanate group obtained from an α-polyol and a polyisocyanate using a blocking agent.

  Examples of the α-polyol include polyether polyol and polyester polyol. As the polyether polyol, a polyalkylene glycol (molecular weight of about 100 to 5500) adduct of polyhydric alcohol is preferably used.

Examples of the polyhydric alcohol include aliphatic dihydric alcohols such as ethylene glycol, propylene glycol, 1,4-butylene glycol, and neopentane glycol; glycerin, trioxyisobutane, 1,2,3-butanetriol, 1, 2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3 4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerin, pentaglycerin, 1 , 2,4-butanetriol, 1,2,4-pentanetriol, trimethylolpropane, etc. Trihydric alcohol; erythritol, pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,3,5-pentanetetrol, 1,3 Examples include tetrahydric alcohols such as 4,5-hexanetetrol; pentavalent alcohols such as adnit, arabit, and xylit; hexavalent alcohols such as sorbit, mannit, and exit.
Preferred as the polyhydric alcohol is a divalent to tetravalent alcohol, and propylene glycol, glycerin and the like are particularly preferable.

  These polyether polyols can be produced by adding an alkylene oxide having 2 to 4 carbon atoms to such a polyhydric alcohol so as to have a desired molecular weight. Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and butylene oxide, and it is particularly preferable to use propylene oxide.

  Examples of the polyester polyol include conventionally known polyesters produced from polycarboxylic acids and polyhydric alcohols, and polyesters obtained from lactams. Examples of such polycarboxylic acids include benzenetricarboxylic acid, adipic acid, succinic acid, suberic acid, sebacic acid, succinic acid, methyl adipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, thiodiacid. Propionic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid or any suitable carboxylic acid similar thereto can be used.

  Examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, and bis (hydroxymethylchlorohexane). , Diethylene glycol, 2,2-dimethylpropylene glycol, 1,3,6-hexanetriol, trimethylolpropane, pentaerythritol, sorbitol, glycerin, or any suitable polyhydric alcohols similar to these can be used. In addition, polytetramethylene glycol, polycaprolactone glycol, and the like can be used as the polyhydroxy compound.

Examples of the polyisocyanate include propane-1,2-diisocyanate, 2,3-dimethylbutane-2,3-diisocyanate, 2-methylpentane-2,4-diisocyanate, octane-3,6-diisocyanate, 3,3- Dinitropentane-1,5-diisocyanate, octane-1,6-diisocyanate, 1,6-hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate, lysine diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate, metatetramethyl Xylylene diisocyanate, isophorone diisocyanate (3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate), 1,3- or 1,4-bis (isocyanate methyl) Cyclohexane, diphenylmethane-4,4'-diisocyanate (MDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), hydrogenated tolylene diisocyanate or the like, and mixtures thereof.
These polyisocyanates may be isocyanurates obtained by trimerization.

Here, the isocyanurate of polyisocyanate is, for example, in an inert solvent such as methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, dioxane or the like, or 7 carbon atoms of diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, alkyl group. 11 (hereinafter C ₇ referred as in -C ₁₁₎ mixed alkyl phthalate, butyl benzyl phthalate, phthalic acid esters such as hexanol benzyl phthalate, tris cresyl phosphate, phosphoric acid esters such as tris phenyl phosphate, di-2 in plasticizer such as trimellitate mixtures such as alkyl trimellitate adipate ester or C ₇ -C _11, such as 2-ethylhexyl adipate, known catalysts such as tertiary amines, quaternary ammonium compounds, Mannich bases, fatty acids No al Use Li metal, alcoholates and the like obtained by polymerizing in a known manner. It is desirable to subject the polymerized reaction in a highly volatile solvent to a solvent replacement treatment with a suitable high boiling point solvent such as a plasticizer.

The polyurethane constituting the (b) block polyurethane used in the present invention is, for example, a polyether polyol, a polyester polyol or a mixture thereof as described above, or a mixture of these with OH group-containing glycerides such as castor oil. Can be obtained by reacting the above polyisocyanate with the aforementioned polyisocyanate.
In obtaining the polyurethane, the molar ratio of the polydiisocyanate to the polyhydroxy compound is usually diisocyanate compound / polyhydroxy compound = 1.5 to 3.5 / 1, preferably 2.0 to 3.0 / 1. It is. The NCO% of the prepolymer is usually 1 to 20%, preferably 2 to 15%.

  The polyurethane can be obtained by a usual method. The reaction temperature is usually 40 to 140 ° C, preferably 60 to 130 ° C. In performing the urethane prepolymer formation reaction, known urethane polymerization catalysts such as dibutyltin dilaurate, stannous octoate, stannous octoate, lead octylate, lead naphthenate, zinc octylate and the like are used to accelerate the reaction. Tertiary amine compounds such as organometallic compounds, triethylenediamine, and triethylamine can also be used.

  Among these polyurethanes, a polyurethane obtained by reacting glycerin tris (polyethylene glycol) and hexamethylene diisocyanate is preferable because it has excellent adhesion to the substrate.

  Examples of the blocking agent include active methylene compounds such as malonic acid diester (such as diethyl malonate), acetylacetone, and acetoacetate (such as ethyl acetoacetate); acetooxime, methylethylketoxime (MEK oxime), methylisobutylketoxime Oxime compounds such as (MIBK oxime); monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, heptyl alcohol, hexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, isononyl alcohol, stearyl alcohol or the isomers thereof Body: Glycol derivatives such as methyl glycol, ethyl glycol, ethyl diglycol, ethyl triglycol, butyl glycol, butyl diglycol Amine compounds such as dicyclohexylamine; phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, butylphenol, tert-butylphenol, octylphenol, nonylphenol, dodecylphenol, cyclohexylphenol, chlorophenol, bromophenol, resorcin, catechol, hydroquinone , Phenols such as bisphenol A, bisphenol S, bisphenol F, and naphthol; and ε-caprolactone.

  The blocking reaction for obtaining the block polyurethane is performed by a known reaction method. The addition amount of the blocking agent is usually 1 equivalent to 2 equivalents, preferably 1.05 to 1.5 equivalents, relative to the free isocyanate group.

  Normally, the above-mentioned polyurethane blocking reaction takes a method of adding a blocking agent in the final reaction. Further, when the polyurethane is subjected to a blocking reaction, the blocking agent can be added and reacted at any stage to obtain a blocked polyurethane.

  The blocking agent may be added at the end of a predetermined polymerization, added at the beginning of the polymerization, or partially added at the beginning of the polymerization and the remainder added at the end of the polymerization. A method of adding at the end of the polymerization is preferred. In this case, the standard at the end of the predetermined polymerization may be based on isocyanate% (for example, it can be measured by the method described in “Polyurethane” Sakai Shoten, 1960, page 21). The reaction temperature when adding the blocking agent is usually from 50 to 150 ° C, preferably from 60 to 120 ° C. The reaction time is about 1 to 7 hours. In the reaction, the known urethane polymerization catalyst described above can be added to accelerate the reaction. Moreover, you may add arbitrary quantity of the plasticizer of this invention.

  In the acrylic sol composition of the present invention, the blending amount of (b) block polyurethane is 90/10 to 15/85 [(the former / latter) in the mass ratio of (a) acrylic polymer fine particles to (b) block polyurethane. a) The content of (b) the block polyurethane is 11 to 567 parts by mass per 100 parts by mass of the acrylic polymer fine particles], and particularly preferably 90/10 to 50/50. When the blending amount of (b) block polyurethane is 90/10 or less in the mass ratio of (a) acrylic polymer fine particles and (b) block polyurethane, the base material of the coating film is compared with that in the above desirable range. Adhesion to the film, cold resistance of the coating film, and coating film strength are insufficient. Further, when the blending amount is 15/85 or more, the viscosity of the prepared acrylic sol composition is higher than that in the above desired range, which affects the workability during coating.

  Examples of the (c) polyamine compound used in the present invention include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, and polyoxypropylenetriamine; isophoronediamine and mensendiamine. Bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10 -Alicyclic polyamines such as tetraoxaspiro (5.5) undecane; m-phenylenediamine, p-phenylenediamine, tolylene-2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine , Mononuclear polyamines such as Citylene-2,6-diamine, 3,5-diethyltolylene-2,4-diamine, 3,5-diethyltolylene-2,6-diamine; biphenylenediamine, 4,4-diaminodiphenylmethane Aromatic polyamines such as 2,5-naphthylenediamine and 2,6-naphthylenediamine; or modified polyamines obtained from these polyamines can be used.

  Examples of the modified polyamine include an epoxy addition modified product, an amidation modified product, an acrylate modified product, an isocyanate modified product, and a Mannich modified product.

  The epoxy addition-modified product is obtained by a conventional method from the polyamine compound and the epoxy compound as exemplified above. Examples of the epoxy compound include mononuclear polyvalent compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol. Polyglycidyl ether compounds of phenol compounds; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) Tan, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, bisphenol A Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as novolak, bisphenol F novolac, and terpene diphenol; polyglycidyl ether compounds of the above mononuclear polyhydric phenol compounds or polynuclear polyhydric phenol compounds with ethylene oxide and / or propylene oxide adducts A hydrogenated polyglycidyl ether compound of the above mononuclear polyphenol compound; ethylene glycol, propylene Polyglycidyl ethers of polyhydric alcohols such as glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct, dicyclopentadiene dimethanol; Acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, and glycidyl methacrylate alone Polymer or copolymer; N, N-diglycidylaniline, epoxy compound having glycidylamino group such as bis (4- (N-methyl-N-glycidylamino) phenyl) methane; vinylcyclohexene diepoxide, dicyclopentane Diene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6- Epoxidized products of cyclic olefin compounds such as methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer, and heterocyclic compounds such as triglycidyl isocyanurate That. These epoxy resins may be internally crosslinked by a prepolymer of a terminal isocyanate.

  The amidation-modified product is obtained from a polyamine compound and a carboxylic acid compound as exemplified above by a conventional method. Examples of the carboxylic acid compound include phthalic acid, isophthalic acid, and dimer acid.

  The modified acrylate ester is obtained from a polyamine compound as exemplified above and a (meth) acrylate ester compound by a conventional method. Examples of the (meth) acrylate ester compound include methyl acrylate and acrylic acid. Examples include ethyl, propyl acrylate, butyl acrylate, and methyl methacrylate.

  The isocyanate-modified product is obtained from a polyamine compound and an isocyanate compound as exemplified above by a conventional method. Examples of the isocyanate compound include propane-1,2-diisocyanate, tetramethylene diisocyanate, and 2,3-dimethyl. Butane-2,3-diisocyanate, 2-methylpentane-2,4-diisocyanate, octane-3,6-diisocyanate, 3,3-dinitropentane-1,5-diisocyanate, octane-1,6-diisocyanate, 1, 6-hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), xylylene diisocyanate, tetramethylxylylene diene Socynate, isophorone diisocyanate (3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate), 1,3- or 1,4-bis (isocyanate methyl) cyclohexane, diphenylmethane-4,4′-diisocyanate (MDI), dicyclohexyl Methane-4,4′-diisocyanate (hydrogenated MDI), hydrogenated tolylene diisocyanate, phenylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydro Naphthalene diisocyanate and the like, and mixtures thereof. These polyisocyanates may be isocyanurates obtained by trimerization.

  The Mannich modified product is obtained by a conventional method from the polyamine compounds, aldehydes and phenols as exemplified above. Examples of the aldehydes include formaldehyde, and the phenols include For example, phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, butylphenol, tert-butylphenol, octylphenol, nonylphenol, dodecylphenol, cyclohexylphenol, chlorophenol, bromophenol, resorcin, catechol, hydroquinone, bisphenol A, bisphenol S Bisphenol F, naphthol and the like.

  Among these polyamine compounds, 1,3-bisaminomethylcyclohexane or modified polyamines obtained from 1,3-bisaminomethylcyclohexane, especially epoxy addition modified products of 1,3-bisaminomethylcyclohexane, acrylic acid ester modified By using a modified polyamine consisting of at least one selected from a product and an isocyanate-modified product, an acrylic sol composition having particularly excellent storage stability can be obtained.

  In the acrylic sol composition of the present invention, the (c) polyamine compound is blended at a ratio of 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass, per 100 parts by mass of (a) acrylic polymer fine particles. It is preferable.

  The diphenyl compound (d) used in the present invention is a diphenyl compound represented by the above general formula (I), and specific examples thereof include the following compounds.

  Among these diphenyl compounds, the use of phenylxylylethane is preferable because the viscosity can be adjusted without impairing the viscosity stability and adhesiveness.

  In the acrylic sol composition of the present invention, the (d) diphenyl compound functions also as a diluent for the (c) polyamine compound, and (c) 0.1 to 10 parts by mass per 100 parts by mass of the polyamine compound, It is preferable to mix | blend in the ratio of 0.2-5 mass parts especially.

  As the plasticizer (e) used in the present invention, a plasticizer conventionally used in a polyvinyl chloride plastisol can be used. For example, phthalic acid plasticizers such as diisononyl phthalate, di- (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate; di- (2-ethylhexyl) adipate, di-n-decyl adipate, di- (2-ethylhexyl) ) Fatty acid ester plasticizers such as azelate, dibutyl sebacate, di- (2-ethylhexyl) sebacate; Phosphate ester plasticizers such as tributyl phosphate, tri- (2-ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate; Epoxy Epoxy plasticizers such as modified soybean oil; trimellitate plasticizers, pyromellitate plasticizers, benzoic acid plasticizers, polyester plasticizers, sulfonate ester plasticizers, and the like can be used. Any one of these plasticizers may be used alone, or two or more thereof may be used in combination. In particular, diisononyl phthalate is preferably used from the viewpoint of being inexpensive and easily available. In addition, (e) the plasticizer is blended at a ratio of (e) 50 to 500 parts by weight, particularly 80 to 300 parts by weight of the plasticizer per 100 parts by weight of the acrylic polymer fine particles from the viewpoints of coating film strength, construction workability, etc. It is preferred that

As the above-mentioned filler (f) constituting the acrylic sol composition of the present invention, those usually used can be used, for example, calcium carbonate, mica, talc, kaolin clay, silica, barium sulfate, etc. Fiber fillers such as glass fiber, wollastonite, alumina fiber, ceramic fiber, and various whiskers can be used. In particular, it is preferable to use calcium carbonate because it is inexpensive. In addition, (f) a filler is mix | blended in the ratio of (f) 50-800 mass parts of fillers, especially 80-500 mass parts per 100 mass parts of acrylic polymer microparticles from viewpoints of coating-film strength, cost, etc. It is preferable.
In the acrylic sol composition of the present invention, the total amount of the essential components [components (a) to (f)] is not particularly limited, but it is preferably blended in at least 90% by mass or more in the acrylic sol composition. .

The acrylic sol composition of the present invention may contain other conventionally known additives such as colorants, antioxidants, foaming agents, diluents, ultraviolet absorbers and the like as optional components. . As the colorant, for example, inorganic pigments such as titanium dioxide and carbon black, azo-based and phthalocyanine-based organic pigments, and the like can be used. As the antioxidant, for example, phenol-based, phosphorus-based, sulfur-based, amine-based antioxidants can be used. As the foaming agent, a type of foaming agent that generates gas by heating can be used, and for example, azo foaming agents such as azodicarbonamide and azobisformamide can be used. As diluents, for example, solvents such as xylene and mineral terpenes can be used, and as ultraviolet absorbers, benzotriazole, benzophenone, triazine, and the like can be used.
In the acrylic sol composition of the present invention, the optional component is contained in the acrylic sol composition.
It is preferable to use 0-10 mass%.

  There is no restriction | limiting in particular about the preparation method of the acrylic sol composition of this invention, The method conventionally used for preparation of the plastisol can be used. For example, the acrylic sol composition of the present invention can be obtained by sufficiently mixing and stirring the acrylic polymer fine particles, block polyurethane, polyamine, plasticizer, filler, and other additives using a known mixer. Can be prepared. As a mixer, a planetary mixer, a kneader, a Glen mill, a roll, etc. can be used.

  The acrylic sol composition of the present invention can be applied by a conventionally known coating method, that is, brush coating, roller coating, air spray coating, airless spray coating or the like. And after apply | coating acrylic sol, it heats and forms a coating film. The heating method may follow a normal method, for example, using a hot air circulating drying furnace.

  The acrylic sol composition of the present invention can be applied to paints, inks, adhesives, pressure-sensitive adhesives, sealants, and the like, and can also be applied to molded products such as sundries, toys, industrial parts, and electrical parts. If applied to paper cloth, it becomes artificial leather, rug, wallpaper, clothing, tarpaulin, etc., and if applied to metal plate, it can be made a corrosion-resistant metal plate.

Hereinafter, the acrylic sol composition of the present invention will be specifically described with reference to Examples.
In addition, Production Example-1 to Production Example-3 show production examples of block polyurethane, and Production Example-4 to
Production Example-6 shows a production example of a modified polyamine diluted with a diphenyl compound.
Comparative Production Example-1 shows a production example of a comparatively modified polyamine diluted with a comparative compound.
Examples 1-5 show preparation examples of acrylic sol compositions, and Comparative Examples 1-3 show preparations of comparative acrylic sol compositions.
Moreover, about the acrylic sol composition obtained in Examples 1-5 and the comparative acrylic sol composition obtained in Comparative Examples 1-3, evaluation of viscosity stability, adhesiveness, and coating film strength was performed by the following method [ Table 1].

[Production Example 1] Production Example of Block Polyurethane (BU-1) 400 g of diisononyl phthalate, 472 g of glycerin tris (polypropylene glycol) (molecular weight 4000) and 0.025 g of dibutyltin laurate were charged at 100 to 110 ° C. and 30 mmHg for 1 hour. Vacuum dehydration was performed. This was cooled to 60 ° C., 95 g of dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI) was added, and reacted at 60 to 70 ° C. for 3 hours in a nitrogen atmosphere. Moreover, it cooled to 60 degreeC, methyl ethyl ketone oxime 33g was dripped, aging reaction was performed at 80-90 degreeC for 1 hour, and also deaeration reaction was performed at 100-110 degreeC and 30 mmHg for 1 hour.
In the infrared absorption spectrum, it was confirmed that the absorption 2660 cm ^{−1 of} NCO completely disappeared, and block urethane (BU-1) was obtained.

[Production Example-2] Production Example of Block Polyurethane (BU-2) 400 g of diisononyl phthalate, 499 g of glycerin tris (polypropylene glycol) (molecular weight 4000) and 0.025 g of dibutyltin laurate were charged at 100 to 110 ° C. and 30 mmHg for 1 hour. Vacuum dehydration was performed. This was cooled to 60 ° C., 65 g of hexamethylene diisocyanate was added, and the mixture was reacted at 60 to 70 ° C. for 3 hours in a nitrogen atmosphere. Moreover, it cooled to 60 degreeC, methyl ethyl ketone oxime 33g was dripped, aging reaction was performed at 80-90 degreeC for 1 hour, and also deaeration reaction was performed at 100-110 degreeC and 30 mmHg for 1 hour.
It was confirmed by infrared absorption spectrum that NCO absorption 2660 cm ⁻¹ had completely disappeared, and block urethane (BU-2) was obtained.

[Production Example 3] Production Example of Block Polyurethane (BU-3) 400 g of diisononyl phthalate, 482 g of glycerin tris (polypropylene glycol) (molecular weight 4000) and 0.025 g of dibutyltin laurate were charged at 100 to 110 ° C. and 30 mmHg for 1 hour. Vacuum dehydration was performed. This was cooled to 60 ° C., 84 g of isophorone diisocyanate was added, and the mixture was reacted at 60 to 70 ° C. for 3 hours under a nitrogen atmosphere. Moreover, it cooled to 60 degreeC, methyl ethyl ketone oxime 33g was dripped, aging reaction was performed at 80-90 degreeC for 1 hour, and also deaeration reaction was performed at 100-110 degreeC and 30 mmHg for 1 hour.
Infrared absorption of NCO in the absorption spectrum 2660cm ^-1 Make sure that disappeared completely, to obtain a block urethane (BU-3).

[Production Example 4] Production Example of Modified Polyamine (PA-1) Diluted with Diphenyl Compound 300 g of phenylxylylethane and 360 g of 1,3-bisaminomethylcyclohexane were charged and heated to 80 ° C., where Adeka Resin EP -4100E (Asahi Denka Kogyo Co., Ltd .; bisphenol A type epoxy resin, epoxy equivalent 190) was added in portions, and further aged at 80 to 90 ° C. for 2 hours and diluted with a diphenyl compound (PA- 1) was obtained.

[Production Example-5] Production Example of Modified Polyamine (PA-2) Diluted with Diphenyl Compound 50 g of xylene and 250 g of methylenebisphenyl isocyanate are charged, 180 g of methyl ethyl ketone oxime is added dropwise at 60 ° C, and further at 80-90 ° C. Aged for 2 hours. After charging 450 g of 1,3-bisaminomethylcyclohexane and aging at 120 to 130 ° C. for 2 hours, dexylene and demethyl ethyl ketone oxime was performed at 150 to 160 ° C. and 30 mmHg or less for 3 hours, and then at 90 ° C. 300 g of silylethane was added, mixed at 80 to 90 ° C. for 1 hour, and diluted with a diphenyl compound to obtain a modified polyamine (PA-2).

[Production Example 6] Production Example of Modified Polyamine (PA-3) Diluted with Diphenyl Compound First, 588 g of 1,3-bisaminomethylcyclohexane was charged, and 178 g of methyl acrylate was added dropwise at 60 ° C or lower, and then at 60 ° C. After aging for 1 hour, an atmospheric pressure methanol removal reaction was performed up to 150 ° C., and after performing vacuum methanol removal at 150 to 160 ° C. and 30 mmHg or less for 1 hour, 300 g of phenylxylylethane was added at 90 ° C. and 80 to 90 ° C. A modified polyamine (PA-3) obtained by mixing at 1 ° C. for 1 hour and diluting with a diphenyl compound was obtained.

[Comparative Production Example 1] Production Example of Comparative Modified Polyamine (HPA-1) Diluted with Comparative Compound 300 g of benzyl alcohol and 360 g of 1,3-bisaminomethylcyclohexane were charged and heated to 80 ° C., where Adeka Resin EP -4100E (Asahi Denka Kogyo Co., Ltd .; bisphenol A type epoxy resin, epoxy equivalent 190) was added in portions, further aged at 80-90 ° C. for 2 hours, and diluted with a comparative compound as a benzyl alcohol solution. A modified polyamine (HPA-1) was obtained.

[Examples 1 to 5 (preparation example of acrylic sol composition) and comparative examples 1 to 3 (preparation example of comparative acrylic sol composition)]
Acrylic polymer fine particles, the block polyisocyanate obtained above, etc. were blended in the proportions shown in Table 1, mixed and dispersed by a kneader, and the acrylic sol compositions of Examples 1 to 5 and comparative acrylics of Comparative Examples 1 to 3 A sol composition was prepared.

<Evaluation method and results>
For the acrylic sol compositions prepared in Examples 1 to 5 and the comparative acrylic sol compositions prepared in Comparative Examples 1 to 3, evaluations of viscosity stability, adhesiveness and coating strength were evaluated by the following methods, respectively. . The results are shown in [Table 1].

(1) Viscosity stability Using a B-type rotational viscometer, the initial viscosity of the acrylic sol composition was measured at a temperature of 25 ° C. Thereafter, the acrylic sol composition was put in a sealed container and held at a temperature of 40 ° C. for 10 days, then cooled to 25 ° C., the viscosity was measured in the same manner, and the viscosity change rate from the initial stage was determined in the following three stages. Stability was evaluated.
○: The viscosity change rate was 30% or less.
Δ: Viscosity change rate exceeded 30% but did not gel.
X: Gelled.

(2) Adhesiveness An acrylic sol composition was applied to the end of an electrodeposited steel sheet of 100 × 25 × 1.0 mm, and a spacer was sandwiched and pressure-bonded so that the thickness of the bonded portion was 3 mm. In this state, after baking at 130 ° C. for 20 minutes, the spacer was removed, the spacer was pulled in the shear direction at a pulling speed of 50 mm / min, the broken state was visually confirmed, and the adhesion was evaluated in the following three stages.
○: Cohesive failure △: Partial interface peeling ×: Interface fracture

(3) Coating film strength The acrylic sol composition was applied on a releasable plate to a thickness of 2 mm, baked at 130 ° C. for 20 minutes, and then punched with a dumbbell No. 2 type. This dumbbell was pulled at 23 ° C., 0 ° C. and −20 ° C. at a pulling speed of 50 mm / min, and the strength (MPa) and elongation (%) at break were measured.

As is clear from the examples, the acrylic sol composition comprising acrylic polymer fine particles, block polyurethane, plasticizer, and filler is not sufficient in the adhesion of the coating film and the coating film strength is completely insufficient. It is.
In addition to these, an acrylic sol composition containing a polyamine compound diluted with a diluent (benzyl alcohol) other than the diphenyl compound of the present invention can improve the coating strength, but the viscosity stability of the acrylic sol Is insufficient and the adhesiveness is poor.

  In contrast, an acrylic sol composition containing a polyamine compound diluted with a specific diphenyl compound in addition to acrylic polymer fine particles, block polyurethane, plasticizer, and filler is excellent in viscosity stability, It is possible to form a tough coating film with excellent adhesion of the coating film.

Claims (11)

(A) Acrylic polymer fine particles, (b) block polyurethane, (c) polyamine compound, (d) diphenyl compound represented by the following general formula (I), (e) plasticizer, and (f) filler. An acrylic sol composition characterized by the above.

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ₃ and R ₄ are each independently an alkyl group having 1 to 5 carbon atoms. P and q each independently represents a number of 0 to 5. When p is 2 or more, each R ₃ may be an alkyl group having a different number of carbon atoms, and q is 2 or more. In some cases, each R ₄ may be an alkyl group having a different number of carbon atoms.)   2. The acrylic sol composition according to claim 1, wherein the mass ratio (the former / the latter) of (a) the acrylic polymer fine particles and (b) the block polyurethane is 90/10 to 15/85.   The acrylic sol composition according to claim 1 or 2, wherein the (a) acrylic polymer fine particles are of a core-shell type comprising a core part and a shell part.   (B) The block polyurethane is obtained by blocking an isocyanate group of a polyurethane having an isocyanate group obtained from an α-polyol and a polyisocyanate using a blocking agent. The acrylic sol composition according to any one of the above.   The acrylic sol composition according to claim 4, wherein the polyurethane is obtained from polyether polyol and diisocyanate.   6. The acrylic sol composition according to claim 5, wherein the polyether polyol is a tri- or higher functional polyether polyol.   The acrylic sol composition according to claim 6, wherein the tri- or higher functional polyether polyol is glycerin tris (polypropylene glycol).   (C) The polyamine compound is a modified polyamine obtained from 1,3-bis (aminomethyl) cyclohexane or 1,3-bisaminomethylcyclohexane, according to any one of claims 1 to 7. Acrylic sol composition.   (C) The polyamine compound is a modified polyamine composed of at least one selected from an epoxy addition-modified product of 1,3-bis (aminomethyl) cyclohexane, an acrylate ester-modified product, and an isocyanate-modified product. The acrylic sol composition according to claim 8.   (D) The acrylic sol composition according to any one of claims 1 to 9, wherein the diphenyl compound represented by the general formula (I) is phenylxylylethane. (A) per 100 parts by mass of the acrylic polymer fine particles, (b) the content of the block polyurethane is 11 to 567 parts by mass, (c) the content of the polyamine compound is 0.01 to 10 parts by mass, (e) the plasticizer The content is 50 to 500 parts by mass and the content of (f) filler is 50 to 800 parts by mass, and (d) 100 parts by mass of the (c) polyamine compound (d) diphenyl represented by the general formula (I) Content of a compound is 0.1-10 mass parts, The acrylic sol composition in any one of Claims 1-10 characterized by the above-mentioned.