JP3939287B2 - Acrylic sol composition - Google Patents

Description

  The present invention relates to an acrylic sol composition. Specifically, it does not generate hydrogen chloride gas or dioxin at the time of incineration, has excellent storage stability, can be cured at a relatively low temperature, and has a coating film base. The present invention relates to an acrylic sol composition having excellent adhesion to materials, cold resistance of 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. The plastisol is applied to a substrate, and a tough coating film is formed by applying 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 a polyvinyl chloride plastisol has good long-term storage stability at room temperature, and the coating film is flexible and excellent in durability. For example, such as steel sheet coating, clothing, building materials, daily necessities, miscellaneous goods, automobile parts, etc. Widely used in the field.

  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 replacing the polyvinyl chloride plastisol, Patent Document 1 discloses a plastisol comprising an acrylate polymer and an organic plasticizer. However, the plastisol has a drawback in that the storage stability and film formability are not sufficient. have.

  Patent Document 2 discloses a plastisol containing no methyl chloride polymer or copolymer, plasticizer, filler, blocked polyisocyanate, and polyvinylamine containing polyamine. When the processing temperature of the coating film is relatively low, since the curing reaction of the urethane resin does not proceed, the plastisol is not sufficient in the performance of the coating film obtained. Not practical because it gels in 2 days.

  Patent Document 3 proposes an acrylic sol containing fine acrylic polymer particles, block type urethane resin, solid hydrazine-based curing agent, plasticizer, and filler. Patent Document 4 discloses an acrylic polymer. Acrylic sol for soundproof undercoat containing fine particles, plasticizer, filler, block type urethane resin, curing agent and foaming agent has been proposed. However, these acrylic sols also have drawbacks such as insufficient adhesion to the base material and insufficient flexibility at low temperatures.

  Further, Patent Document 5 discloses a thermosetting composition comprising a plastisol obtained by dispersing core-shell type acrylic resin particles and a filler in a plasticizer, and a blocked urethane or blocked isocyanate and a latent curing agent. In Patent Document 6, a plastisol obtained by dispersing acrylic resin particles and a filler with a plasticizer, a blocked urethane or a blocked isocyanate, and a melting point of room temperature solid particles of 60 ° C. or higher and 40 ° C. or lower. Proposes a thermosetting composition comprising a latent curing agent that does not dissolve in a plasticizer. However, these thermosetting compositions are still not satisfactory in terms of viscosity stability, adhesiveness 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 No. 01 / 88009A1 Pamphlet International Publication No. 01 / 88011A1 Pamphlet

  The present invention has been made in view of the current situation as described above, does not generate hydrogen chloride gas or dioxin during incineration, has excellent storage stability, and can be cured even 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, adhesion to a top coating, coloration of a coating film, cold resistance of a coating film, and coating film strength.

  As a result of intensive studies, the present inventors have incorporated the above-mentioned modified product of a polyether polyamine compound and a polyaminoamide compound into an acrylic sol composition containing acrylic polymer fine particles, block polyurethane and the like. The present inventors have found that an acrylic sol composition having an improved problem can be provided.

  That is, the present invention includes (a) acrylic polymer fine particles, (b) block polyurethane, (c) a modified product of a polyether polyamine compound represented by the following general formula (I), (d) a polyaminoamide compound, (e The present invention provides an acrylic sol composition comprising a plasticizer and (f) a filler.

  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 a coating film to a substrate. It has excellent properties, adhesion to top coating, colorability of coating film, cold resistance of coating film, and coating film strength, and is useful in a wide range of fields such as sealing materials, coating materials, and daily necessities.

  Hereinafter, the acrylic sol composition of the present invention will be described in detail.

First, (a) acrylic polymer fine particles will be described below.
As the (a) acrylic polymer fine particles used in the present invention, a polymer usually used in an acrylic sol composition can be used, and for example, selected from acrylic acid alkyl ester, methacrylic acid alkyl ester, and the like. Monomers and copolymers of monomers can be used. Specific examples of the monomer 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.
Moreover, styrene, (alpha) -methylstyrene, methacrylic acid, acrylic acid, itaconic acid, crotonic acid etc. can also be used as a copolymerization component.

  (A) As the acrylic polymer fine particles, it is preferable to use core-shell type acrylic polymer fine particles composed of a core part and a shell part. When an acrylic sol composition is prepared using core-shell type acrylic polymer fine particles, the storage stability of the acrylic sol composition is further improved, the viscosity rises when applied, and bleed occurs after heat curing. There is an advantage that can be suppressed more.

  Furthermore, when (a) 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 part that is poorly compatible with the plasticizer coats the core part that is compatible with the plasticizer, so that the increase in viscosity of the acrylic sol composition during storage can be further suppressed. More improved. Moreover, since the polymer of such a shell part becomes compatible with a plasticizer by heating to an appropriate temperature, bleeding does not occur after heat curing.

  It is preferable that the component of the said core part contains 50 mass% or more of at least 1 type chosen from the single polymer and copolymer of methacrylate, such as n-butyl methacrylate, isobutyl methacrylate, and ethyl methacrylate. Thus, by making the component of a core part highly compatible with a plasticizer, generation | occurrence | production of the bleeding after heat-hardening 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 50 masses of at least one selected from homopolymers and copolymers of methacrylates such as methyl methacrylate and benzyl methacrylate, and copolymers of these methacrylates and copolymerization components such as styrene. % Or more is preferable. Thus, by making the component of a shell part low compatibility with a plasticizer, the viscosity rise of the acrylic sol composition in storage can be suppressed, and storage stability improves more. In particular, from the viewpoint of further improving storage stability, it is preferable that the component of the shell portion is mainly composed of a polymer of methyl methacrylate.

  Furthermore, the polymer ratio (the former / the latter) of the core part and the shell part is preferably selected from the range of 25/75 to 70/30 by mass ratio. When the core part is less than 25 parts by mass with respect to 75 parts by mass of the shell part, there is a higher possibility that bleed occurs after heat curing than in the case of the above desired range. Further, when the shell part is less than 30 parts by mass with respect to 70 parts by mass of the core part, the core part may not be sufficiently covered with the shell part as compared with the case of the above desirable range, and storage May affect stability.

  Examples of the core-shell type acrylic polymer fine particles that can be used in the acrylic sol composition of the present invention include, for example, JP-A-6-172734, JP-A-2001-329135, and JP-A-2001-329208. And core-shell type acrylic resin fine particles described in International Publication No. 01/88009 pamphlet and the like.

  The (a) acrylic polymer fine particles preferably have a molecular weight of 100,000 to several million in terms of mass average molecular weight from the viewpoint of coating film strength, storage stability, etc., and are diffusible to plasticizers and storage stability. From the viewpoint of safety, it is preferable to use those having an average particle diameter in the range of 0.1 to 10 μm.

Next, (b) block polyurethane will be described below.
The (b) block polyurethane used in the present invention is obtained by blocking a polyurethane obtained by reacting a polyisocyanate and an α-polyol such as polyether polyol or polyester polyol with a blocking agent. .

  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 carbon atom of diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, alkyl group number 7-11 (hereinafter referred to as C ₇ -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 - in plasticizer trimellitic acid esters of 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 Base, fat Polymerized by a known method using an alkali metal of an acid, alcoholate or the like. Those subjected to the polymerization reaction in a highly volatile solvent are desirably subjected to solvent replacement treatment with a suitable high boiling point solvent such as a plasticizer.

  Among these polyisocyanates, when at least one selected from 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI) is used, among others. This is preferable because an acrylic sol composition having excellent storage stability can be obtained.

  As said polyether polyol which can be used for manufacture of (b) block polyurethane with the said polyisocyanate, the polyalkylene glycol (molecular weight about 100-5500) addition product of a polyhydric alcohol is used preferably.

  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. Of these, divalent to tetravalent alcohols are preferable, and propylene glycol, glycerin, and the like are particularly preferable.

  The polyether polyol 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 that can be used in the production of (b) block polyurethane together with the polyisocyanate include conventionally known polyesters produced from polycarboxylic acids and polyhydric alcohols, and polyesters obtained from lactams. Can be mentioned.

  Examples of the polycarboxylic acid 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, thiol Dipropionic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid or any suitable carboxylic acid similar thereto can be used.

  Examples of the polyhydric alcohol 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.

  Among the α-polyols described above, polyether polyols, particularly tri- or higher functional polyether polyols are preferable. Particularly, when glycerin tris (polypropylene glycol) is used, an acrylic sol composition having excellent adhesion to the substrate can be obtained. Therefore, it is most preferable.

(B) The polyurethane constituting the block polyurethane is, for example, a polyhydroxy compound such as the above-described polyether polyol and / or polyester polyol, or a mixture thereof with OH group-containing glycerides such as castor oil, and the above-mentioned poly It can be obtained by reacting with isocyanate.
In obtaining the polyurethane, the molar ratio of the polyisocyanate to the polyhydroxy compound such as α-polyol (the former / the latter) is usually 1.5 to 3.5 / 1, preferably 2.0 to 3.5. / 1. The NCO% of the prepolymer (polyurethane) is usually 1 to 20%, preferably 1 to 10%.

  The polyurethane can be obtained by a usual method. The reaction temperature is usually 40 to 140 ° C, preferably 60 to 130 ° C. A known urethane polymerization catalyst for promoting the reaction when the urethane prepolymer formation reaction is performed, such as dibutyltin dilaurate, stannous octoate, stannous octoate, lead octylate, lead naphthenate, zinc octylate, etc. It is also possible to use tertiary amine compounds such as organic metal compounds, triethylenediamine and triethylamine.

  (B) Block polyurethane is obtained by blocking the above-mentioned polyurethane with a blocking agent. Examples of the blocking agent include active methylene compounds such as malonic acid diester (such as diethyl malonate), acetylacetone and acetoacetic acid ester (such as ethyl acetoacetate); acetoxime, 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; Black amine compounds such as hexylamine and the like. Among these, oxime compounds are preferable.

  (B) The blocking reaction for obtaining the block polyurethane can be carried out by a known reaction method. The addition amount of the blocking agent is usually 1 to 2 equivalents, preferably 1.00 to 1.5 equivalents, relative to the free isocyanate group.

  The polyurethane blocking reaction is usually a method in which the blocking agent is added in the final reaction of the polymerization of the polyurethane. However, even if the blocking agent is added and reacted at any stage, (b) blocked polyurethane Can be obtained.

  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. Preferably, it is added at the end of the polymerization. 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 at the time of adding the blocking agent is usually 50 to 150 ° C, preferably 60 to 120 ° C. The reaction time is usually 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 mentioned later used for this invention in reaction.

  In the acrylic sol composition of the present invention, the blending amount of (b) block polyurethane is such that (a) acrylic polymer fine particles and (b) block polyurethane have a mass ratio (the former / the latter) of 90/10 to 15/85. In particular, it is desirable to select from a range of 90/10 to 50/50. When (b) the block polyurethane is less than 10 parts by mass with respect to 90 parts by mass of the acrylic polymer fine particles (b), the adhesiveness of the coating film to the substrate and the coating are compared with those in the above desired range. There is a risk that the cold resistance and coating strength of the film will be insufficient. In addition, when (b) the block polyurethane is more than 85 parts by mass with respect to 15 parts by mass of the (a) acrylic polymer fine particles, the viscosity of the prepared acrylic sol composition is higher than that of the above desired range. There is a risk that the workability during application may be affected.

Next, (c) a modified product of the polyether polyamine compound represented by the general formula (I) will be described below.
In the general formula (I), X represents a residue obtained by removing m hydroxyl groups from a divalent to hexavalent polyol, and examples of the divalent to hexavalent polyol that can provide X include, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, benzenedimethanol, cyclohexanedimethanol, glycerin, tri Examples thereof include methylol ethane, trimethylol propane, pentaerythritol, diglycerin, ditrimethylol propane, sorbitol, mannitol, dipentaerythritol, and among these, a divalent to trivalent polyol is preferable. Examples of the alkylene group having 2 to 4 carbon atoms represented by A include ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, and 1,4-butylene. Among these, ethylene and propylene are preferable. Examples of the alkylene group having 1 to 4 carbon atoms represented by B include methylene, ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4. -Groups such as butylene are mentioned, and among these, ethylene and propylene are preferable. M is preferably 2 to 3, and n is preferably 0 to 10.

  The polyether polyamine compound represented by the above general formula (I) is known. For example, after adding an alkylene oxide such as ethylene oxide or propylene oxide to a polyol giving a residue represented by X, the terminal hydroxyl group is converted to an amino group. Or a method in which acrylonitrile is added to a terminal hydroxyl group and then reduced to convert the nitrile group into an amino group.

  As typical examples of the polyether polyamine compound represented by the general formula (I), the following compound No. 1-8 are mentioned.

  Examples of such commercially available products include the Heinz Jeffermin D series (D-230, D-400, D-2000, D-4000), the Jeffermin ED series (ED-600, ED-2003), and Jeffermin. T series (T-403, T-3000, T-5000) etc. are mentioned.

  (C) The modified product of the polyether polyamine compound represented by the general formula (I) used in the present invention has reduced reactivity by crushing a part of the N—H group of the polyether polyamine compound. Examples thereof include epoxy addition-modified products, acrylic addition-modified products, polyamide-modified products, and Mannich-modified products. In the present invention, at least one selected from the group consisting of these modified products is used.

  Among these modified products, when one or more selected from the group consisting of an epoxy addition modified product and an acrylic addition modified product of the polyether polyamine compound represented by the general formula (I) is used, the storage stability is excellent. Since an acrylic sol composition is obtained, it is preferable.

  The epoxy addition-modified product can be provided using an epoxy compound such as a polyglycidyl compound. Examples of the epoxy compound include mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol. Polyglycidyl ether 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) butane, 1,1, , 2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, bisphenol A novolak, bisphenol F novolak, terpene Polyglycidyl ether compound of polynuclear polyphenol compound such as diphenol; Polyglycidyl ether compound of ethylene oxide and / or propylene oxide adduct of mononuclear polyphenol compound or polynuclear polyphenol compound; Mononuclear polyphenol Polyglycidyl ether compound of hydrogenated compound; ethylene glycol, propylene glycol, butylene Polyglycidyl ether of polyhydric alcohols such as recall, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct, dicyclopentadiene dimethanol; maleic acid, fumarate 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 acid, tetrahydro Homopolymers or copolymers of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as phthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, and glycidyl methacrylate; N, N- Epoxy compounds having a glycidylamino group such as diglycidylaniline and bis (4- (N-methyl-N-glycidylamino) phenyl) methane; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl Of cyclic olefin compounds such as -3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate Epoxidized products: Epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer, and heterocyclic compounds such as triglycidyl isocyanurate. These epoxy compounds may be internally crosslinked by a prepolymer of terminal isocyanate. Among these, bisphenol A type or F type epoxy resin is preferable.

  A method for producing an epoxy-modified product, which is a modified polyamine, from the polyether polyamine compound represented by the general formula (I) and the epoxy compound is not particularly limited, but 1 mol of the polyether polyamine compound is used. On the other hand, it can be easily produced by using 0.3 to 1.2 equivalents of the epoxy compound, using a solvent as necessary, and reacting at 100 to 200 ° C. for several minutes to several hours.

  Examples of the acrylic compound that can provide the above-mentioned acrylic addition-modified product include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and methacrylic acid. Examples thereof include butyl and acrylonitrile, but alkyl acrylate is particularly preferable.

  The method for producing the acrylic addition-modified product, which is a modified polyamine, from the polyether polyamine compound represented by the general formula (I) and the acrylic compound is not particularly limited, but 1 mol of the polyether polyamine compound is used. On the other hand, using 0.3 to 1.2 mol of the above acrylic compound, using a solvent as necessary under a catalyst such as p-toluenesulfonic acid, the reaction (desorption) at 100 to 300 ° C. for several minutes to several hours. Alcohol) can be easily produced.

  In the acrylic sol composition of the present invention, (c) the modified product of the polyether polyamine compound represented by the general formula (I) is 0.01 to 10 parts by mass per 100 parts by mass of the (a) acrylic polymer fine particles. In particular, it is preferably blended at a ratio of 0.05 to 5 parts by mass.

Next, (d) the polyaminoamide compound will be described below.
(D) The polyaminoamide compound is obtained by reacting a polyamine compound and a carboxylic acid compound. In the present invention, at least one polyaminoamide compound is used.

  Examples of the polyamine compound include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; isophoronediamine, mensendiamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, Alicyclic polyamines such as bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5.5) undecane; m -Phenylenediamine, p-phenylenediamine, tolylene-2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine, mesitylene-2,6-diamine, 3,5-diethyltolylene-2 , 4-diamine, 3,5- Mononuclear polyamines such as ethyltolylene-2,6-diamine; aromatic polyamines such as biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, 2,6-naphthylenediamine, and the like. Among these, polyethylene polyamine is preferable.

  Examples of the carboxylic acid compound include octylic acid, decanoic acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, ricinoleic acid, behenic acid, benzoic acid, toluic acid, cyclohexanecarboxylic acid, tallow fatty acid, palm Monovalent carboxylic acids such as oil fatty acid, tung oil fatty acid, soybean oil fatty acid, cottonseed oil fatty acid; succinic acid, adipic acid, azelaic acid, sebacic acid, dodecadic acid, isophthalic acid, terephthalic acid, dihydrophthalic acid, tetrahydroisophthalic acid, hexa Divalent carboxylic acids such as hydroisophthalic acid and dimer acid; trimer acid, tricarballylic acid, citric acid, 1,2,3-butanetricarboxylic acid, 1,2,3-butenetricarboxylic acid, 1,2,3,4 -Butanetetracarboxylic acid, trimellitic acid, trimesic acid, pyromellitic acid 3,3 ', 4,4'-biphenyltetracarboxylic acid, 3,3', listed such polycarboxylic acids such as 4,4'-benzophenone tetracarboxylic acid, among these, dimer acid is preferred.

  A method for producing the polyaminoamide compound, which is a modified polyamine, from the polyamine compound and the carboxylic acid compound is not particularly limited, but the carboxylic acid compound is 0.3 to 1 per 1 mol of the polyamine compound. It can be easily produced by performing a dehydration reaction at 100 to 300 ° C. for several minutes to several hours at normal pressure and reduced pressure using 2 moles, using a solvent as necessary.

  In the acrylic sol composition of the present invention, (d) the polyaminoamide 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.

  In addition, other polyamine compounds can be used in combination with the acrylic sol composition of the present invention.

  Examples of other polyamine compounds include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; isophoronediamine, mensendiamine, bis (4-amino-3-methyldicyclohexyl) methane, and diaminodicyclohexylmethane. Alicyclic polyamines such as bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5.5) undecane; m-phenylenediamine, p-phenylenediamine, tolylene-2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine, mesitylene-2,6-diamine, 3,5-diethyltolylene- 2,4-diamine, 3, -Mononuclear polyamines such as diethyltolylene-2,6-diamine; aromatic polyamines such as biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, 2,6-naphthylenediamine; or these Examples include graft-modified polyamines obtained by addition modification with glycidyl ether, and modified polyamines such as Mannich-modified polyamines modified by phenols and aldehydes.

  In the acrylic sol composition of the present invention, other polyamine compounds can be used in any amount of 10 parts by mass or less per 100 parts by mass of the (a) acrylic polymer fine particles.

  Next, (e) the plasticizer and (f) the filler will be described below.

  As the (e) plasticizer used in the present invention, a plasticizer used in a conventional polyvinyl chloride plastisol can be used, for example, diisononyl phthalate, di- (2-ethylhexyl) phthalate, Phthalic acid plasticizers such as diisodecyl phthalate and butyl benzyl phthalate, di- (2-ethylhexyl) adipate, di-n-decyl adipate, di- (2-ethylhexyl) azelate, dibutyl sebacate, di- (2-ethylhexyl) Fatty acid ester plasticizers such as sebacate, phosphate plasticizers such as tributyl phosphate, tri- (2-ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, epoxy plasticizers such as epoxidized soybean oil, and other polyester plastics Agent, benzoic acid plasticizer, etc. It 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. Moreover, (e) plasticizer is mix | blended in the ratio of 50-500 mass parts with respect to 100 mass parts of (a) acrylic polymer microparticles, especially 80-300 mass parts from viewpoints, such as coating film strength and construction workability | operativity. It is preferable.

  As the (f) filler constituting the acrylic sol composition of the present invention, those usually used for plastisol can be used, such as calcium carbonate, mica, talc, kaolin clay, silica, barium sulfate, etc. In addition, fibrous 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. (F) The filler is preferably blended at a ratio of 50 to 800 parts by mass, particularly 80 to 500 parts by mass per 100 parts by mass of the acrylic polymer fine particles, from the viewpoints of coating film strength, cost, and the like. .

  In the acrylic sol composition of the present invention, in addition to the components (a) to (f) described above, other conventionally known additives such as a colorant, an antioxidant, a foaming agent, a diluent, and an ultraviolet absorber. Etc. can be blended. 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, a phenol-based or amine-based antioxidant can be used. As the foaming agent, a type of foaming agent that generates gas by heating can be used. For example, azo foaming agents such as azodicarbonamide and azobisformamide can be used. As the diluent, for example, a solvent such as xylene or mineral terpene can be used. As the ultraviolet absorber, a benzotriazole-based ultraviolet absorber or the like can be used. The amount of these additives used is preferably 200 parts by mass or less per 100 parts by mass of (a) acrylic polymer fine particles.

  The method for preparing the acrylic sol composition of the present invention is not particularly limited, and a method conventionally used for preparing plastisol can be used. For example, the acrylic sol composition of the present invention can be prepared by sufficiently mixing and stirring the components (a) to (f) and other additives as necessary using a known mixer. . As the mixer, a planetary mixer, a kneader, a glen mill, a roll or the like 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 the acrylic sol composition of this invention, a coating film is formed by heating. 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, sealing agents, and the like, as well as molded products such as sundries, toys, industrial parts, and electrical parts. Also, for example, if applied to paper cloth, it can be an artificial leather, rug, wallpaper, clothing, waterproof sheet, etc., and if applied to a metal plate, it can be a corrosion-resistant metal plate.

  Hereinafter, the acrylic sol composition of the present invention will be described more specifically with reference to examples and the like.

[Production Example 1] Production 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 dilaurate were charged and dehydrated under reduced pressure at 100 to 110 ° C. and 30 mmHg for 1 hour. Was done. 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. This was cooled to 60 ° C., 33 g of methyl ethyl ketone oxime was added dropwise, a aging reaction was performed at 80 to 90 ° C. for 1 hour, and a deaeration reaction was further performed at 100 to 110 ° C. 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 polyurethane (BU-1) was obtained.

[Production Example 2] Production 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 dilaurate were charged and dehydrated under reduced pressure at 100 to 110 ° C. and 30 mmHg for 1 hour. Was done. This was cooled to 60 ° C., 65 g of 1,6-hexamethylene diisocyanate was added, and the mixture was reacted at 60 to 70 ° C. for 3 hours in a nitrogen atmosphere. This was cooled to 60 ° C., 33 g of methyl ethyl ketone oxime was added dropwise, a aging reaction was performed at 80 to 90 ° C. for 1 hour, and a deaeration reaction was further performed at 100 to 110 ° C. 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 polyurethane (BU-2) was obtained.

[Production Example 3] Production 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 dilaurate were charged and dehydrated under reduced pressure at 100 to 110 ° C. and 30 mmHg for 1 hour. Was done. 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 in a nitrogen atmosphere. This was cooled to 60 ° C., 33 g of methyl ethyl ketone oxime was added dropwise, a aging reaction was performed at 80 to 90 ° C. for 1 hour, and a deaeration reaction was further performed at 100 to 110 ° C. 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 polyurethane (BU-3) was obtained.

[Production Example 4] Production of modified polyamine (PA-1) 183 g of isophoronediamine and 200 g of toluene were charged and heated to 80 ° C., and Adekaresin EP-4100E (Asahi Denka Kogyo Co., Ltd .; bisphenol A type epoxy resin, epoxy) Equivalent 190) 218 g was added in portions and further aged at 90-100 ° C. for 2 hours.
600 g of Jeffamine T-403 (manufactured by Heinz; polyether polyamine) was added thereto, heated to 120 ° C., and nitrogen was blown to remove toluene. Furthermore, the pressure reduction reaction was performed at 120-130 degreeC and 30 mmHg or less for 2 hours, and modified polyamine (PA-1) was obtained.

[Production Example 5] Production of modified polyamine (PA-2) 300 g of diisononyl phthalate and 526 g of Jeffamine T-403 were charged and heated to 80 ° C., and Adeka Resin EP-4100E (Asahi Denka Kogyo Co., Ltd .; Bisphenol A) Type epoxy resin, epoxy equivalent 190) 174 g was added in portions, and further aged at 80 to 90 ° C. for 2 hours to obtain a modified polyamine (PA-2).

[Production Example 6] Production of modified polyamine (PA-3) 895 g of Jeffamine D-230 and 1 g of p-toluenesulfonic acid were charged and heated to 80 ° C., and 167 g of methyl acrylate was added dropwise thereto, and further 80 to 90 The mixture was aged at 1 ° C for 1 hour. Thereafter, methanol removal was performed at 180 to 190 ° C. for 2 hours. Furthermore, the pressure reduction reaction was performed at 180-190 degreeC and 30 mmHg or less for 1 hour, and modified polyamine (PA-3) was obtained.

[Production Example 7] Production of modified polyamine (PA-4) 146 g of triethylenetetramine and 295 g of dimer acid were charged and subjected to a dehydration reaction at 180 to 190 ° C. for 2 hours at normal pressure, and further at 180 to 190 ° C. and 30 mmHg or less. The reaction was performed under reduced pressure for 2 hours to obtain a modified polyamine (PA-4).

[Examples 1 to 7 and Comparative Examples 1 to 3 ]
Examples 1 to 7 and Comparative Examples 1 to 3 were prepared by blending acrylic polymer fine particles, block polyurethane obtained in the following production examples, modified polyamines, and the like in the ratios shown in Tables 1 and 2 and mixing and dispersing them with a kneader. Each of the acrylic sol compositions was obtained.

About the obtained acrylic sol composition of Examples 1-7 and Comparative Examples 1-3 , viscosity stability, adhesiveness, coloring property, coating-film intensity | strength, and topcoat adhesiveness were evaluated with the following method, respectively. These results are shown in Tables 1 and 2.

(1) Viscosity stability Using a B-type rotational viscometer, the initial viscosity of the acrylic sol composition was measured at a temperature of 20 ° C. Thereafter, the acrylic sol composition is put in a sealed container and kept at a temperature of 40 ° C. for one week, and then cooled to 20 ° C., the viscosity is measured in the same manner, and the rate of change in viscosity from the initial stage is calculated. Viscosity stability was evaluated.
○: Viscosity change rate within 50% ×: Viscosity change rate 50% or more XX: Gelation

(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 30 minutes or 180 ° C. for 30 minutes, the spacer was removed, the spacer was pulled in the shear direction at a pulling speed of 50 mm / min, and the fractured state was observed to evaluate the adhesion according to the following criteria. .
○: Cohesive failure ×: Interface failure

(3) Colorability About what baked the acrylic sol composition at 130 degreeC for 30 minutes or 180 degreeC for 30 minutes, coloring was observed visually and colorability was evaluated according to the following references | standards.
○: Coloring is hardly seen.
Δ: Coloring is observed.
X: Big coloring is seen.

(4) Coating film strength The acrylic sol composition was applied on a releasable plate to a thickness of 2 mm, baked at 130 ° C. for 30 minutes, and then punched with a dumbbell No. 2 type. The dumbbell was pulled at a pulling speed of 50 mm / min at 23 ° C., and the strength (MPa) and elongation (%) at break were measured.

(5) Top coat adhesion After applying an acrylic sol composition to an electrodeposited steel sheet and baking at 140 ° C. for 30 minutes, apply a solvent-based one-component curable acrylic resin paint and perform baking at 140 ° C. for 30 minutes. A cross-cut test was performed.

As is clear from the above results, the acrylic sol composition comprising the acrylic polymer fine particles, the plasticizer and the filler is not sufficient in adhesiveness and topcoat adhesion, and the coating strength is quite insufficient. (Comparative Example 1). Further, this, even in combination with port Riaminoamido compound alone, improved coating strength is remarkably lowered viscosity stability and coloring property of those found, improvement in adhesion and topcoat adhesion nor observed (Comparative Example 3 ). Furthermore, when used in combination only modified product of a polyether polyamine compound with block polyurethanes, viscosity stability, adhesion, although improved colorability and film strength was observed, adhesion of the top coat is still Insufficient (Comparative Example 2 ).

  On the other hand, the acrylic sol composition of the present invention comprising acrylic polymer fine particles, block polyurethane, a modified product of a polyether polyamine compound having a specific structure, a polyaminoamide compound, a plasticizer, and a filler has viscosity stability. Moreover, it is excellent in adhesiveness, coloring property, and adhesiveness with top coat, and can form a tough coating film (Examples 1-7).

Claims (10)

(A) acrylic polymer fine particles, (b) block polyurethane, (c) a modified product of a polyether polyamine compound represented by the following general formula (I), (d) a polyaminoamide compound, (e) a plasticizer, and ( f) An acrylic sol composition comprising a filler.

  2. The acrylic sol composition according to claim 1, wherein a 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.   The acrylic sol composition according to any one of claims 1 to 3, wherein (b) the block polyurethane is obtained from a polyether polyol and a diisocyanate.   The acrylic sol composition according to claim 4, wherein the polyether polyol is a tri- or higher functional polyether polyol.   The acrylic sol composition according to claim 5, wherein the tri- or higher functional polyether polyol is glycerin tris (polypropylene glycol).   7. The diisocyanate according to claim 4, wherein the diisocyanate is at least one selected from the group consisting of 1,6-hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane-4,4′-diisocyanate. Acrylic sol composition.   (C) The modified product of the polyether polyamine compound represented by the general formula (I) is at least one selected from the group consisting of an epoxy addition-modified product and an alkyl acrylate addition-modified product. The acrylic sol composition according to any one of 1 to 7.   9. The acrylic sol composition according to claim 8, wherein the polyglycidyl compound providing the epoxy addition-modified product is a bisphenol A type or F type epoxy resin. The acrylic sol composition according to any one of claims 1 to 9, wherein the polyaminoamide compound (d) is a polyaminoamide compound obtained from a polyethylene polyamine and a carboxylic acid compound.