CN1293141C

CN1293141C - Acrylic acid sol composition

Info

Publication number: CN1293141C
Application number: CN 200410097345
Authority: CN
Inventors: 鹤田直树; 浅见和代; 马场一孝
Original assignee: Asahi Rubber Ltd By Share Ltd; Honda Motor Co Ltd; Asahi Denka Kogyo KK
Current assignee: Parker Huixu Ltd By Share Ltd; Honda Motor Co Ltd; Adeka Corp
Priority date: 2003-11-28
Filing date: 2004-11-29
Publication date: 2007-01-03
Anticipated expiration: 2024-11-29
Also published as: CN1637061A; JP3939287B2; JP2005154657A

Abstract

The invention obtains an acrylic sol composition incinerable without generating hydrogen chloride gas and dioxins, having excellent storage stability, hardenable at a relatively low temperature and having excellent adhesivity of the coating film to a substrate, adhesive property to a top-coating layer, colorability of the coating film, cold-resistance of the coating film and coating film strengths. This acrylic sol composition contains (a) fine particles of an acrylic polymer, (b) a blocked polyurethane, (c) a modified product of a polyether polyamine compound expressed by formula (I) (X is a residue produced by removing (m) hydroxy groups from a 2-6 hydric polyol; A is a 2-4C alkylene; B is a 1-4C alkylene; (m) is 2-6; and (n) is 0-50; a plurality of A, B or (n) in one molecule are respectively same or different from each other), (d) a polyaminoamide compound, (e) a plasticizer and (f) a filler.

Description

Acrylic acid sol composition

Technical field

The present invention relates to acrylic acid sol composition, specifically, relate to when burning and can not produce hydrogen chloride gas with Er Evil compounds, even storage stability is good and it is solidified, and for the acrylic acid sol composition of the cementability of the base material of filming, the winter hardiness of filming and coating strength excellence.

Background technology

Now, to be the polymer particle that will have the particle diameter of special adjustment and a size-grade distribution be distributed in the softening agent and the viscous composition of the aqueous or pasty state that forms with weighting agent industrial widely used plastisol equably.In addition, this plastisol is by being applied on the base material, and suitable in addition processing temperature just forms tough filming.

As above-mentioned polymer particle, usually polyvinyl chloride materials such as multipolymer that use ryuron, vinylchlorid and vinyl acetate more.This polyvinyl chloride plastisol Long-term Storage at room temperature has good stability, and therefore film also softness and excellent in te pins of durability are used widely in fields such as for example steel plate lining, dress material, building materials, daily necessities, groceries, auto parts.

But the polyvinyl chloride plastisol produces hydrogen chloride gas owing to light and heat decompose.Here the hydrogen chloride gas of Chan Shenging has the root that becomes the destruction of ozonosphere reason, perhaps become the reason of acid rain, perhaps when burning, quicken the problems such as damage of incinerator, and might produce Er Evil compounds owing to burn the difference of condition, therefore aspect safety and sanitation and the environmental pollution aspect not preferred.Therefore, the wait in expectation appearance of the plastisol that substitutes this polyvinyl chloride plastisol.

The plastisol of polyvinyl chloride plastisol disclose the plastisol that acrylic ester polymer and organic softening agent constitute in the special public clear 55-16177 communique, but this plastisol has storage stability and the inadequate shortcoming of film-forming properties as an alternative.

In addition, the plastisol that does not contain polyvinyl chloride that contains methyl methacrylate polymer or multipolymer, softening agent, weighting agent, end-blocking polyisocyanates and polyamine formation is disclosed in the special public clear 63-66861 communique, but when this plastisol is lower temperature in the processing temperature of filming, the curing reaction of urethane resin does not carry out, therefore the performance of filming of preparation is insufficient, in addition, if about 35 ℃, place, with 1～2 day with regard to gelation, therefore impracticable.

In addition, the spy opens the acrylic acid sol that has proposed to contain acrylate copolymer particulate, block urethane resin, solid hydrazine class solidifying agent, softening agent and weighting agent in the 2001-329135 communique, and the spy opens the soundproof undercoat acrylic acid sol that has proposed to contain acrylate copolymer particulate, softening agent, weighting agent, block urethane resin, solidifying agent and whipping agent in the 2001-329208 communique.But these acrylic acid sols still have shortcoming such as flexibility deficiency under the adherence deficiency, particularly low temperature with base material.

In addition; International disclose proposed in the 01/88009A1 brochure core-shell type acrylic resin particle and filler are being distributed to the thermoset composition that cooperates end-blocking carbamate and end-blocking isocyanates and potentiality curing agent in the plastisol that forms in the plasticizer and form, and the international fusing point that has proposed in plasticizer dispersion acrylic resin particle and the formed plastisol of filler cooperation end-blocking carbamate or end-blocking isocyanates and normal temperature solid particulate in the 01/88011A1 brochure that disclose is 60 ℃～40 ℃ thermoset compositions that the potentiality curing agent that is not dissolved in plasticizer forms. But these thermoset compositions can not be satisfied the demand at aspects such as viscosity stability, cementabilities.

Summary of the invention

The present invention proposes in view of above-mentioned present situation, purpose is to provide a kind of acrylic acid sol composition, it can not produce hydrogen chloride gas with Er Evil compounds when burning, even storage stability is good and it is solidified, and for the cementability of the base material of filming, tack, the tint permanence of filming, the winter hardiness of filming and coating strength excellence for coating.

Present inventors etc. have carried out research with keen determination repeatedly, it found that by contain the modifier and the multi-amino amide compound of polyether polyamine compound in the acrylic acid sol that contains acrylate copolymer particulate, blocked polyurethane etc., the acrylic acid sol composition that the problems referred to above are improved can be provided, thereby finish the present invention.

Promptly, the invention provides a kind of acrylic acid sol composition, it is characterized in that: contain the modifier, (d) multi-amino amide compound, (e) softening agent of the polyether polyamine compound shown in (a) acrylate copolymer particulate, (b) blocked polyurethane, (c) following general formula (I) and (f) weighting agent

In the formula, X represents to remove the residue of m hydroxyl from 2～6 yuan polyvalent alcohol, A represents that carbonatoms is 2～4 alkylidene group, B represents that carbonatoms is 1～4 alkylidene group, m represents 2～6, and n represents 0～50, in addition, same molecular memory a plurality of A, B can be identical separately with n, also can be different.

Acrylic acid sol composition of the present invention can not produce hydrogen chloride gas with Er Evil compounds when burning, even storage stability is good and also can make its curing under lower temperature, and for the cementability of the base material of filming, the tack for coating, the tint permanence of filming, the winter hardiness of filming and coating strength excellence, useful in extensive fields such as sealing material, coating material, daily necessities.

Embodiment

Below acrylic acid sol composition of the present invention is described in detail.

At first, below (a) acrylate copolymer particulate is described.

(a) acrylate copolymer particulate as using among the present invention can use the polymkeric substance that is generally used for acrylic acid sol composition, for example, can use monomeric homopolymer and multipolymers such as being selected from alkyl acrylate, alkyl methacrylate.As this monomer, specifically, can enumerate methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, benzyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the secondary butyl ester of methacrylic acid, methacrylic tert-butyl acrylate, cyclohexyl methacrylate, benzyl methacrylate etc.

In addition, as copolymer composition, also can use vinylbenzene, alpha-methyl styrene, methacrylic acid, vinylformic acid, methylene-succinic acid, butenoic acid etc.

As (a) acrylate copolymer particulate, the preferred acrylate copolymer particulate that uses the core-shell type that partly constitutes by nuclear part and shell.When using the acrylate copolymer particulate modulation acrylic acid sol composition of core-shell type, the storage stability of acrylic acid sol composition improves, have viscosity in the time of can further suppressing to be coated with rise and be heating and curing after the advantage of separating out generation.

In addition, when making (a) acrylate copolymer particulate be core-shell type, preferably constitute the nuclear part, constitute the shell part with the non-affinity polymkeric substance of softening agent with softening agent affinity polymkeric substance.With the polymkeric substance of the shell part of the consistency difference of softening agent by coating the nuclear part that has consistency with softening agent, the viscosity of acrylic acid sol composition rises in can further suppressing to preserve, storage stability further improves.In addition, the polymkeric substance of this shell part is by being heated to proper temperature, has the consistency with softening agent, can not produce after therefore being heating and curing and separate out.

The composition of above-mentioned nuclear part preferably contains at least a among 50 quality % or above homopolymer that is selected from methacrylic esters such as n-BMA, Propenoic acid, 2-methyl, isobutyl ester, Jia Jibingxisuanyizhi and the multipolymer.Make the one-tenth of nuclear part be divided into the part high, the generation of separating out after can suppressing to be heating and curing like this with the consistency of softening agent.From giving the viewpoint of soft film coating, the composition of preferred especially nuclear part is based on the multipolymer of butyl methacrylate and Propenoic acid, 2-methyl, isobutyl ester.

In addition, the composition of above-mentioned shell part preferably contains 50 quality % or above homopolymer and the multipolymer that is selected from methacrylic esters such as methyl methacrylate, benzyl methacrylate, and at least a among the multipolymer of the copolymer composition of these methacrylic esters and vinylbenzene etc.Make the composition of shell part be the part low with the consistency of softening agent like this, the viscosity of acrylic acid sol composition rises in can suppressing to preserve, and storage stability further improves.From the viewpoint that storage stability is improved, the composition of preferred especially shell part is based on the Polymerization of Methyl thing.

In addition, the polymkeric substance of above-mentioned nuclear part and above-mentioned shell part is represented with mass ratio than (the former/latter), is preferably selected in 25/75～70/30 scope.With respect to shell part 75 mass parts, when examining part after a little while, to compare with above-mentioned preferred range than 25 mass parts, the back that is heating and curing produces the possibility of separating out and improves.In addition, with respect to nuclear part 70 mass parts, when shell partly after a little while than 30 mass parts, compare during with above-mentioned preferred range, the shell part is insufficient to the coating of nuclear part sometimes, sometimes storage stability is exerted an influence.

As the acrylate copolymer particulate of the core-shell type that can in acrylic acid sol composition of the present invention, use, for example can enumerate the special flat 6-172734 communique, spy opened and open 2001-329135 communique, spy and open 2001-329208 communique, the international acrylic resin particulate that disclose core-shell type that No. 01/88009 brochure etc. put down in writing etc.

From viewpoints such as coating strength, storage stabilitys, represent with the matter average molecular weight, (a) molecular weight of acrylate copolymer particulate be preferably 100,000～several 1,000,000, from the viewpoint of diffustivity softening agent and storage stability, preferably using median size is the scope of 0.1～10 μ m.

Then, below (b) blocked polyurethane is described.

(b) blocked polyurethane that uses among the present invention is by making polyisocyanates and α-polyol reactions such as polyether glycol or polyester polyol, and the use end-capping reagent makes the urethane end-blocking of preparation and prepares.

As above-mentioned polyisocyanates, can enumerate propane-1, the 2-vulcabond, 2,3-dimethylbutane-2, the 3-vulcabond, 2-methylpentane-2, the 4-vulcabond, octane-3, the 6-vulcabond, 3,3-dinitrobenzene pentane-1, the 5-vulcabond, octane-1, the 6-vulcabond, 1,6-hexamethylene diisocyanate (HDI), trimethyl hexamethylene diisocyanate, lysinediisocyanate, tolylene diisocyanate (TDI), Xylene Diisocyanate, between tetramethylxylene diisocyanate, isophorone diisocyanate (3-isocyanic ester methyl-3,5,5-3-methyl cyclohexanol based isocyanate), 1,3-or 1,4-two (isocyanic ester methyl) hexanaphthene, ditan-4,4 '-vulcabond (MDI), dicyclohexyl methyl hydride-4,4 '-vulcabond (hydrogenation MDI), hydrogenated tolylene diisocyanate etc., and their mixture.The isocyanuric acid ester body that these polyisocyanates can form for trimerizing.

Here, the isocyanuric acid ester body of polyisocyanates is in inert solvents such as ritalin, vinyl acetic monomer, N-BUTYL ACETATE, methyl ethyl ketone, diox for example, or diethyl phthalate, dibutyl phthalate, phthalic acid two (2-ethylhexyl) ester, (following note is made C to carbonatoms 7～11 _7～11) phthalic ester such as mixed alkyl phthalic ester, butyl benzyl phthalic ester, hexanol benzyl phthalic ester of alkyl, phosphoric acid ester such as Tritolyl Phosphate, triphenylphosphate, adipic acid ester or C such as two-2-ethylhexyl adipic acid ester _7～11Softening agent such as trimellitic acid ester such as mixed alkyl trimellitate in, use known catalyzer, for example basic metal of tertiary amine, quaternary ammonium compound, Mannich base, lipid acid, alkoxide etc. adopt known method polymerization preparation.Carry out polyreaction under high-volatile solvent, preferred finally with suitable high boiling solvent, for example softening agent carries out the solvent exchange processing.

In these polyisocyanates, owing to can prepare the acrylic acid sol composition of excellent storage stability, therefore preferred especially the use is selected from 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and dicyclohexyl methyl hydride-4, at least a among 4 '-vulcabond (hydrogenation MDI).

As being used from the above-mentioned polyether glycol that (b) blocked polyurethane is made, preferably use polyalkylene glycol (about molecular weight 100～5500) affixture of polyvalent alcohol with above-mentioned polyisocyanates one.

As above-mentioned polyvalent alcohol, can enumerate for example ethylene glycol, propylene glycol, 1, aliphatic dihydroxy alcohols such as 4-butyleneglycol, neopentyl glycol; Glycerine, trihydroxy-Trimethylmethane, 1,2,3-trihydroxybutane, 1,2,3-penta triol, 2-methyl isophthalic acid, 2,3-glycerol, 2-methyl-2,3,4-trihydroxybutane, 2-ethyl-1,2,3-trihydroxybutane, 2,3,4-penta triol, 2,3,4-hexanetriol, 4-propyl group-3,4,5-triol in heptan, 2,4-dimethyl-2,3,4-penta triol, pentamethyl-glycerine, new penta triol, 1,2,4-trihydroxybutane, 1,2, trivalent alcohols such as 4-penta triol, TriMethylolPropane(TMP); Butantetraol, tetramethylolmethane, 1,2,3,4-penta tetrol, 2,3,4, the own tetrol of 5-, 1,2,3,5-penta tetrol, 1,3,4, tetravalent alcohols such as the own tetrol of 5-; Pentavalent alcohols such as ribitol, arabitol, Xylitol; Hexavalent alcohol such as Sorbitol Powder, mannitol, iditol etc.Wherein, preferred 2～4 yuan of alcohol, preferred especially propylene glycol, glycerine etc.

By making C with well-established law _2～4Epoxide and this polyvalent alcohol addition to reach required molecular weight, can make above-mentioned polyether glycol.As C _2～4Epoxide, can enumerate for example oxyethane, propylene oxide, butylene oxide ring, especially preferably use propylene oxide.

In addition, as the above-mentioned polyester polyol that can be used from manufacturing (b) blocked polyurethane, for example can enumerate the known in the past polyester made from polycarboxylic acid and polyvalent alcohol or from the polyester of lactams preparation etc. with above-mentioned polyisocyanates one.

As above-mentioned polycarboxylic acid, can use for example benzene tricarboxylic acid, hexanodioic acid, succsinic acid, suberic acid, sebacic acid, oxalic acid, methyl hexanodioic acid, pentanedioic acid, pimelic acid, nonane diacid, phthalic acid, terephthalic acid, m-phthalic acid, thio-2 acid, toxilic acid, fumaric acid, citraconic acid, methylene-succinic acid or the arbitrarily suitable carboxylic acid similar with them.

As above-mentioned polyvalent alcohol, can use for example ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1,3-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, two (methylol chloro-hexane), glycol ether, 2,2-dimethyl propylene glycol, 1,3,6-hexanetriol, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder, glycerine or any suitable polyvalent alcohol similar with them.In addition, as polyol, also can use poly-(1, the 4-butyleneglycol), polycaprolactone glycol etc.

In above-mentioned α-polyvalent alcohol, the preferred, polyethers polyvalent alcohol, preferred especially trifunctional or above polyether glycol, if particularly use glycerine three (polypropylene glycol) (グリセリ Application トリス (Port リプロピレ Application グリコ one Le)), can obtain the acrylic acid sol composition with the adherence excellence of base material, therefore most preferably.

Constitute the urethane of (b) blocked polyurethane, can make for example above-mentioned polyether glycol and/or polyester polyol or they and castor-oil plant wet goods contain the polyol such as mixture of glyceride type of OH base and above-mentioned polyisocyanates and react and obtain.

When the above-mentioned urethane of preparation, and the mol ratio of polyols such as above-mentioned polyisocyanates and α-polyvalent alcohol (the former/latter) be generally 1.5～3.5/1, preferred 2.0～3.5/1.In addition, the NCO% of prepolymer (urethane) is generally 1～20%, is preferably 1～10%.

Above-mentioned urethane can adopt the usual method preparation.Temperature of reaction is generally 40～140 ℃, preferred 60～130 ℃.When carrying out the carbamate prepolymer formation reaction, in order to promote reaction, can use known carbamate catalyst for polymerization, organometallic compounds such as dibutyl tin laurate, stannous octoate (a スズオ Network トエ one ト), stannous octoate (sannous octate), lead octoate 36, lead naphthenate, zinc octoate for example, tertiary amine compounds such as triethylenediamine, triethylamine.

(b) blocked polyurethane is for using the material of end-capping reagent with above-mentioned urethane end-blocking preparation.As this end-capping reagent, can enumerate for example diester malonate (diethyl malonate etc.), methyl ethyl diketone, acetylacetic ester (methyl aceto acetate etc.) isoreactivity methylene compound; Acetyl oxime, methyl ethyl ketone oxime (MEK oxime), methyl isobutyl ketoxime oxime compounds such as (MIBK oximes); Monohydroxy-alcohol or their isomer such as methyl alcohol, ethanol, propyl alcohol, butanols, enanthol, hexanol, octanol, 2-Ethylhexyl Alcohol, isononyl alcohol, stearyl alcohol; Glycol derivatives such as methyl glycol, glycol monoethyl ether, ethyl carbitol, triglycol one ether, ethylene glycol monobutyl ether, butylcarbitol; Amine compound such as dicyclohexyl amine etc.Wherein, preferred oxime compound.

The end capping that is used for preparing (b) blocked polyurethane can adopt known reaction method to carry out.The addition of above-mentioned end-capping reagent is generally 1～2 equivalent with respect to the free isocyanate group, is preferably 1.00～1.5 equivalents.

The end capping of above-mentioned urethane adopts the method for adding above-mentioned end-capping reagent in the end reaction of urethane polymerization usually, also can add above-mentioned end-capping reagent in any stage and react, preparation (b) blocked polyurethane.

As the addition means of above-mentioned end-capping reagent, can be when the polymerization that sets finishes, to add, or add, or add a part at the polymerization initial stage at the polymerization initial stage, when finishing, polymerization adds the remainder method of grading, preferably interpolation when polymerization finishes.In this case, the standard when finishing as the polymerization that sets can be a benchmark with isocyanic ester % (for example can adopt the method for " urethane " Omaki bookstore, clear and distribution in 35 years, the 21st page of record to measure).Temperature of reaction when adding above-mentioned end-capping reagent is generally 50～150 ℃, preferred 60～120 ℃.Reaction times was generally about 1～7 hour.During reaction, also can add above-mentioned known carbamate catalyst for polymerization and promote reaction.In addition, can add the aftermentioned softening agent that uses among the present invention of any amount during reaction.

In acrylic acid sol composition of the present invention, (b) use level of blocked polyurethane is 90/10～15/85 from (a) acrylate copolymer particulate and (b) mass ratio of blocked polyurethane (the former/latter) preferably, and preferred especially 90/10～50/50 scope is selected.With respect to (a) acrylate copolymer particulate 90 mass parts, when (b) blocked polyurethane than 10 mass parts after a little while, compare with above-mentioned preferred range, the film cementability on base material and the winter hardiness of filming and coating strength might be insufficient.In addition, with respect to (a) acrylate copolymer particulate 15 mass parts, when (b) blocked polyurethane than 85 mass parts for a long time, compare with above-mentioned preferable range, the viscosity increased of synthetic acrylic acid sol composition might exert an influence to the operability in when coating.

Then, the modifier to the polyether polyamine compound shown in (c) above-mentioned general formula (I) below describes.

In above-mentioned general formula (I), X represents to remove from 2～6 yuan polyvalent alcohol the residue of m hydroxyl, as 2～6 yuan the polyvalent alcohol that X can be provided, can enumerate for example ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, xylyl alcohol, cyclohexanedimethanol, glycerine, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, two glycerine, two (trishydroxymethyl) propane, Sorbitol Powder, mannitol, Dipentaerythritol etc., wherein, preferred 2～3 yuan polyvalent alcohol.As the represented carbon atom of A is 2～4 alkylidene group, can enumerate for example ethylidene, propylene, trimethylene, 1,2-butylidene, 1, and groups such as 3-butylidene, tetramethylene, wherein, preferred ethylidene, propylidene.As the represented carbon atom of B is 1～4 alkylidene group, can enumerate methylene radical, ethylidene, propylene, trimethylene, 1,2-butylidene, 1, and groups such as 3-butylidene, tetramethylene, wherein, preferred ethylidene, propylidene.In addition, m is preferred 2～3, and n preferred 0～10.

Polyether polyamine compound shown in the above-mentioned general formula (I) is known for oneself, can be by after for example making epoxide such as oxyethane, epoxy two alkane and giving the polyvalent alcohol addition of residue shown in the X, make the method for terminal hydroxyl aminoization, or reduce after making vinyl cyanide add to terminal hydroxyl, itrile group is transformed to amino method etc. makes.

As the typical example of the polyether polyamine compound shown in the above-mentioned general formula (I), can enumerate following compound N o.1～8.

(in the following formula, n1 represents 3～100 number, and n2 and n3 represent 1～50 number, and n4, n5 and n6 represent 0～50 number.)

As their commercially available product, can enumerate ジエ Off ア one ミ Application D series (D-230, D-400, D-2000, D-4000), ジエ Off ア one ミ Application ED series (ED-600, ED-2003), ジエ Off ア one ミ Application T series (T-403, T-3000, T-5000) of Ha イ Application Star company for example etc.

The modifier of the polyether polyamine compound shown in (c) the above-mentioned general formula (I) that uses among the present invention is the part of the N-H base of above-mentioned polyether polyamine compound is destroyed and to be made reactive the reduction, can enumerate epoxy addition modification thing, vinylformic acid addition modification thing, polyamide modified thing, Mannich modifier etc.In the present invention, use and to be selected from least a among these modifiers.

In these modifiers, be selected from the epoxy addition modification thing of the polyether polyamine compound shown in the above-mentioned general formula (I) and among the vinylformic acid addition modification thing one or more if use, the acrylic acid sol composition that then can prepare excellent storage stability, therefore preferred.

Above-mentioned epoxy addition modification thing can provide by using epoxide such as multi-shrinking glyceryl compound, as this epoxy compounds, can enumerate for example polyglycidyl ether compound of monokaryon polyphenol compounds such as quinhydrones, Resorcinol, pyrocatechol, Phloroglucinol; Dihydroxy naphthlene, bis-phenol, methylene radical bis-phenol (Bisphenol F), methylene-bis (ortho-cresol), the ethylidene bis-phenol, isopropylidene bis-phenol (dihydroxyphenyl propane), isopropylidene two (ortho-cresol), tetrabromo-bisphenol, 1,3-two (4-hydroxyl cumenyl benzene), 1,4-two (4-hydroxyl cumenyl benzene), 1,1,3-three (4-hydroxyphenyl) butane, 1,1,2,2-four (4-hydroxyphenyl) ethane, thiobisphenol, the sulfo group bis-phenol, the oxo bis-phenol, phenol resol, the o-Hydroxytoluene urea formaldehyde, the ethyl phenol urea formaldehyde, the butylphenol urea formaldehyde, the octyl phenol urea formaldehyde, resorcin phenolic resin, bisphenol A phenolic resin, bisphenol F phenolic resin, the polyglycidyl ether compound of multinuclear polyphenol compounds such as terpenes diphenol; The oxyethane of above-mentioned monokaryon polyphenol compound or multinuclear polyphenol compound and/or the polyglycidyl ether compound of propylene oxide adduct; The polyglycidyl ether compound of the hydrogenation thing of above-mentioned monokaryon polyphenol compound; The polyglycidyl ether of polyalcohols such as ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, polyoxyethylene glycol, sulfo-glycol ether, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder, dihydroxyphenyl propane-ethylene oxide adduct, Dicyclopentadiene (DCPD) dimethanol; The glycidyl ester class of aliphatics, aromatic series or alicyclic polyprotonic acids such as toxilic acid, fumaric acid, methylene-succinic acid, succsinic acid, pentanedioic acid, suberic acid, hexanodioic acid, nonane diacid, sebacic acid, dimeracid, trimer acid, phthalic acid, m-phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, Pyromellitic Acid, tetrahydrophthalic acid, hexahydrophthalic acid, first bridge tetrahydrophthalic acid and the homopolymer or the multipolymer of glycidyl methacrylate; N, N-diglycidylaniline, two (4-(N-methyl-N-Racemic glycidol amino) phenyl) methane etc. has the epoxy compounds of Racemic glycidol amino; Vinyl cyclohexene diepoxide, Dicyclopentadiene (DCPD) diepoxide, 3,4-epoxycyclohexyl methyl-3,4-epoxycyclohexane carboxylate, 3, the epoxide of cyclic olefin compounds such as 4-epoxy-6-methyl cyclohexane ylmethyl-6-methylcyclohexanecarboxylic acid ester, two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipic acid ester; Heterogeneous ring compounds such as epoxidation such as epoxidized polybutadiene, epoxidation vinyl benzene-butadienecopolymer conjugated diolefin polymer, triglycidyl group isocyanuric acid ester.In addition, these epoxy compoundss can carry out internal crosslinking with the prepolymer of terminal isocyanate.Wherein, preferred bisphenol A-type or bisphenol f type epoxy resin.

Make the method for the epoxy addition modification thing of modified polyamine by polyether polyamine compound shown in the above-mentioned general formula (I) and above-mentioned epoxy compounds, there is no particular restriction, but with respect to 1 mole of above-mentioned polyether polyamine compound, use above-mentioned epoxy compounds 0.3～1.2 equivalent, use solvent as required, under 100～200 ℃, make its stoichiometric number branch～a few hours, can easily make.

In addition,, can enumerate for example methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, methyl propionitrile etc., preferred especially alkyl acrylate as the acrylic compound that aforesaid propylene acid addition modification thing can be provided.

The method of the vinylformic acid addition modification thing of the modified multicomponent amine of making by the polyether polyamine compound shown in the above-mentioned general formula (I) and aforesaid propylene acid compound, there is no particular restriction, but with respect to 1 mole of above-mentioned polyether polyamine compound, use 0.3～1.2 mole of aforesaid propylene acid compound, under catalyzer such as tosic acid, use solvent as required, under 100～300 ℃, make its stoichiometric number branch～a few hours (dealcoholysis), can easily make.

In acrylic acid sol composition of the present invention, (c) modifier of the polyether polyamine compound shown in the above-mentioned general formula (I), per 100 mass parts (a) acrylate copolymer particulate, preferably with 0.01～10 mass parts, especially preferably the ratio with 0.05～5 mass parts cooperates.

Then, below (d) multi-amino amide compound is described.

(d) multi-amino amide compound in the present invention, uses a kind of multi-amino amide compound at least by making polyamine compound and carboxylic acid cpd prepared in reaction.

As above-mentioned polyamine compound, can enumerate for example aliphatic polyamines such as quadrol, diethylenetriamine, Triethylenetetramine (TETA), tetren; Isophorone diamine,  alkene diamines (menthen dimine), two (4-amino-3-methyl bicyclic hexyl) methane, diamino-dicyclohexyl methane, two (aminomethyl) hexanaphthene, N-aminoethyl piperazine, 3,9-two (3-aminopropyl)-2,4,8, ester ring type polyamines such as 10-four oxaspiros (5,5) undecane; Mphenylenediamine, Ursol D, Toluene-2,4-diisocyanate, 4-diamines, Toluene-2,4-diisocyanate, 6-diamines, sym-trimethylbenzene-2,4-diamines, sym-trimethylbenzene-2,6-diamines, 3,5-diethyl Toluene-2,4-diisocyanate, 4-diamines, 3,5-diethyl Toluene-2,4-diisocyanate, monokaryon polyamines such as 6-diamines; Benzidine, 4,4-diaminodiphenyl-methane, 2,5-naphthylene diamine, 2, aromatic polyamines such as 6-naphthylene diamine etc., wherein preferred polyethylene polyamine.

As above-mentioned carboxylic acid cpd, can enumerate monocarboxylic acids such as for example sad, capric acid, tetradecanoic acid, hexadecanoic acid, stearic acid, oleic acid, linolic acid, ricinoleate acid, docosoic acid, phenylformic acid, toluylic acid, cyclohexylenedinitrilotetraacetic acid, blubber lipid acid, coco-nut oil fatty acid, tung oil lipid acid, soya fatty acid, cottonseed oil fatty acid; Di-carboxylic acid such as succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid, m-phthalic acid, terephthalic acid, dihydro phthalic acid, tetrahydrochysene m-phthalic acid, six hydrogen m-phthalic acids, dimeracid; Trimer acid, tricarballylic acid, citric acid, 1,2,3-fourth three acid, 1,2,3-butylene three acid, 1,2,3,4-fourth tetracid, trimellitic acid, trimesic acid, pyromellitic acid, 3,3 ', 4,4 '-biphenyl tetracid, 3,3 ', 4, polycarboxylic acids such as 4 '-benzophenone tetracarboxylic acid etc., wherein preferred dimeracid.

By above-mentioned polyamine compound and above-mentioned carboxylic acid cpd manufacturing method as the multi-amino amide compound of modified multicomponent amine, there is no particular restriction, but with respect to 1 mole of above-mentioned polyamine compound, use 0.3～1.2 mole of above-mentioned carboxylic acid cpd, use solvent as required, under 100～300 ℃, under several branches～a few hours normal pressure and decompression, carry out dehydration reaction, can easily make.

In acrylic acid sol composition of the present invention, per 100 mass parts (a) acrylate copolymer particulate, preferably with 0.01～10 mass parts, especially preferably the ratio with 0.05～5 mass parts cooperates (d) multi-amino amide compound.

In addition, in acrylic acid sol composition of the present invention also can and with other polyamine compound.

As other polyamine compound, can enumerate for example aliphatic polyamines such as quadrol, diethylenetriamine, Triethylenetetramine (TETA), tetren; Isophorone diamine,  alkene diamines, two (4-amino-3-methylcyclohexyl) methane, diamino-dicyclohexyl methane, two (aminomethyl) hexanaphthene, N-aminoethyl piperazine, 3,9-two (3-aminopropyl)-2,4,8, ester ring type polyamines such as 10-four oxaspiros (5,5) undecane; Mphenylenediamine, Ursol D, Toluene-2,4-diisocyanate, 4-diamines, Toluene-2,4-diisocyanate, 6-diamines, sym-trimethylbenzene-2,4-diamines, sym-trimethylbenzene-2,6-diamines, 3,5-diethyl Toluene-2,4-diisocyanate, 4-diamines, 3,5-diethyl Toluene-2,4-diisocyanate, monokaryon polyamines such as 6-diamines; Benzidine, 4,4-diaminodiphenyl-methane, 2,5-naphthylene diamine, 2, aromatic polyamines such as 6-naphthylene diamine; Or the graft modification polyamine that their addition modifications is formed with glycidyl ether, carry out modified multicomponent amine such as Mannich modified multicomponent amine that modification forms etc. with phenols and aldehydes.

In acrylic acid sol composition of the present invention, other polyamine compound can use 10 mass parts or following any amount with per 100 mass parts (a) acrylate copolymer particulate.

Below, to (e) softening agent and (f) weighting agent describe.

As (e) softening agent that uses among the present invention, can use the softening agent that in the past was used for the polyvinyl chloride plastisol, can use for example diisononyl phthalate, phthalic acid two (2-ethylhexyl) ester, Di Iso Decyl Phthalate, adjacent (2-ethylhexyl) ester such as butyl benzyl phthalate, Di Iso Decyl Phthalate, O-phthalic acids softening agent such as butyl benzyl phthalate, hexanodioic acid two (2-ethylhexyl) ester, di n decyl adipate, two (2-ethylhexyl) azelate, Uniflex DBS, fatty acid ester plasticisers such as sebacic acid two (2-ethylhexyl) ester, tributyl phosphate, tri-2-ethylhexyl phosphate, phosphate plasticizer such as 2-ethylhexyl diphenyl phosphate, epoxy soybean wet goods epoxy plasticiser, other polyester softening agent, benzoic acids softening agent etc.These softening agent can use any separately, also can be with two kinds or above being used in combination.From at a low price and the viewpoint that obtains easily, especially preferably use diisononyl phthalate.In addition, from viewpoints such as coating strength, construction operations, preferably cooperate (e) softening agent of the ratio of 50～500 mass parts, preferred especially 80～300 mass parts with per 100 mass parts (a) acrylate copolymer particulate.

As the weighting agent (f) that constitutes acrylic acid sol composition of the present invention, can use the weighting agent that is generally used for plastisol, for example lime carbonate, mica, talcum, kaolin, silicon-dioxide, barium sulfate can be used, fibrous fillers such as glass fibre, wollastonite, sapphire whisker, ceramic fiber, various whiskers can be used in addition.From the preferred especially lime carbonate of reason at a low price.From viewpoints such as coating strength, costs, preferably cooperate (f) weighting agent of the ratio of 50～500 mass parts, preferred especially 80～300 mass parts with per 100 mass parts (a) acrylate copolymer particulate.

Except above-mentioned (a)～(f) component, in acrylic acid sol composition of the present invention, can also cooperate known in the past other additive, for example tinting material, oxidation inhibitor, whipping agent, thinner, UV light absorber etc.As this tinting material, can use for example mineral dye such as titanium dioxide, carbon black, pigment dyestuffs such as azo class, phthalocyanines etc.As this oxidation inhibitor, can use for example oxidation inhibitor such as phenols or amine.As this whipping agent, can use by adding the whipping agent of thermogenesis gas type, can use for example azo foaming agent such as azodicarboamide, Cellmic C 121.As this thinner, can use for example dimethylbenzene, mineral turpentine equal solvent etc.As this UV light absorber, can use benzotriazole category UV light absorber etc.The usage quantity of these additives is preferred 200 mass parts of per 100 mass parts (a) acrylate copolymer particulate or following.

In addition, there is no particular restriction for the modulator approach of acrylic acid sol composition of the present invention, can use customary way in the modulation of plastisol in the past.For example, can use known mixing machine that (a)～(f) combination and other additive are as required mixed stirring fully, modulate acrylic acid sol composition of the present invention.As this mixing machine, can use planetary-type mixer, kneader, grain grinding machine, roller etc.

Acrylic acid sol composition of the present invention can pass through known coating process in the past, i.e. hairbrush coating, roller coat cloth, aerial spraying, hydraulic spraying etc. are coated with.In addition, behind coating acrylic acid sol composition of the present invention, film by heating to form.Heating means can for example can use heat-wind circulate drying stove etc. to carry out according to usual method.

Acrylic acid sol composition of the present invention also can be applied to moulding product such as groceries, toy, industrial part, electric parts except can being applied to coating, printing ink, caking agent, tackiness agent, sealing agent etc.In addition, for example,, can be used as imitation leather, coverture, wallpaper, dress material, flashing etc.,, can be used as the non-corrosibility metal sheet if be applicable to metal sheet if be applicable to paper cloth etc.

Embodiment

Below, by embodiment etc. acrylic acid sol composition of the present invention is specifically described.The manufacturing of [Production Example 1] blocked polyurethane (BU-1)

The diisononyl phthalate of packing into 400g, glycerine three (polypropylene glycol) (molecular weight 4000) 472g and two fourth tin, two lauryl 0.025g carry out 1 hour decompression dehydration under 100～110 ℃, 30mmHg.It is cooled to 60 ℃, adds dicyclohexyl methyl hydride-4,4 '-vulcabond (hydrogenation MDI) 95g is under nitrogen atmosphere, 60～70 ℃ of reactions 3 hours down.It is cooled to 60 ℃, splashes into methyl ethyl ketone oxime 33g, under 80～90 ℃, carry out 1 hour slaking reaction, under 100～110 ℃, 30mmHg, carry out degassing reaction in 1 hour again.

Confirm the absorption 2660cm of NCO by infrared absorption spectrum ^-1Completely dissolve obtains blocked polyurethane (BU-1).

The manufacturing of [Production Example 2] blocked polyurethane (BU-2)

The diisononyl phthalate of packing into 400g, glycerine three (polypropylene glycol) (molecular weight 4000) 499g and two fourth tin, two lauryl 0.025g carry out 1 hour decompression dehydration under 100～110 ℃, 30mmHg.It is cooled to 60 ℃, adds 1,6-hexamethylene diisocyanate 65g is under nitrogen atmosphere, 60～70 ℃ of reactions 3 hours down.It is cooled to 60 ℃, splashes into methyl ethyl ketone oxime 33g, under 80～90 ℃, carry out 1 hour slaking reaction, under 100～110 ℃, 30mmHg, carry out degassing reaction in 1 hour again.

Confirm the absorption 2660cm of NCO by infrared absorption spectrum ^-1Completely dissolve obtains blocked polyurethane (BU-2).

The manufacturing of [Production Example 3] blocked polyurethane (BU-3)

The diisononyl phthalate of packing into 400g, glycerine three (polypropylene glycol) (molecular weight 4000) 482g and two fourth tin, two lauryl 0.025g carry out 1 hour decompression dehydration under 100～110 ℃, 30mmHg.It is cooled to 60 ℃, adds isophorone diisocyanate 84g, under nitrogen atmosphere, 60～70 ℃ of reactions 3 hours down.It is cooled to 60 ℃, splashes into methyl ethyl ketone oxime 33g, under 80～90 ℃, carry out 1 hour slaking reaction, under 100～110 ℃, 30mmHg, carry out degassing reaction in 1 hour again.

Confirm the absorption 2660cm of NCO by infrared absorption spectrum ^-1Completely dissolve obtains blocked polyurethane (BU-3).

[Production Example 4] makes modified multicomponent amine (PA-1)

Pack into isophorone diamine 183g and toluene 200g are heated to 80 ℃, and (Asahi Chemical Industry's industry (Co., Ltd.) is made separately to add アデカレジ Application EP-4100E to it; Bisphenol A type epoxy resin, epoxy equivalent (weight) 190) 218g, again 90～100 ℃ of following slakings 2 hours.

(Ha イ Application Star company makes to add ジエ Off ア one ミ Application T-403 to it; Polyether glycol) 600g is heated to 120 ℃, is blown into nitrogen, carries out piptonychia benzene.Again 120～130 ℃, carry out decompression reaction in 2 hours below the 30mmHg, obtain modified multicomponent amine (PA-1).

[Production Example 5] makes modified multicomponent amine (PA-2)

The ジエ Off ア one ミ Application T-403 of the diisononyl phthalate of packing into 300g and 526g is heated to 80 ℃, and (Asahi Chemical Industry's industry (Co., Ltd.) is made separately to add アデカレジ Application EP-4100E to it; Bisphenol A type epoxy resin, epoxy equivalent (weight) 190) 174g, 80～90 ℃ of following slakings 2 hours, obtain modified multicomponent amine (PA-2) again.

[Production Example 6] makes modified multicomponent amine (PA-3)

Pack into the ジエ Off ア one ミ Application D-230 of 895g and the tosic acid of 1g are heated to 80 ℃, splash into methyl acrylate 167g to it, again 80～90 ℃ of following slakings 1 hour.Under 180～190 ℃, carry out 2 hours separating methanols then.At 180～190 ℃, 30mmHg or followingly carry out decompression reaction in 1 hour, obtain modified multicomponent amine (PA-3) again.

[Production Example 7] makes modified multicomponent amine (PA-4)

Pack into Triethylenetetramine (TETA) 146g and dimeracid 295g carry out 2 hours dehydration reactions under 180～190 ℃, normal pressure, again at 180～190 ℃, 30mmHg or followingly carry out decompression reaction in 2 hours, obtain modified multicomponent amine (PA-4).

[embodiment 1～7 and comparative example 1～5]

Cooperate blocked polyurethane and the modified multicomponent amine for preparing in acrylate copolymer particulate, the above-mentioned Production Example with the ratio shown in table 1 and the table 2, carry out blending dispersion, obtain the acrylic acid sol composition of embodiment 1～7 and comparative example 1～5 respectively with kneader.

With following method the embodiment 1～7 of preparation and the acrylic acid sol composition of comparative example 1～5 are carried out viscosity stability, cementability, tint permanence, coating strength and the evaluation of coating tack respectively.These the results are shown in table 1 and table 2.

(1) viscosity stability

Use the Type B rotational viscosimeter, in 20 ℃ of initial stage viscosity of measuring acrylic acid sol composition down of temperature.Then, acrylic acid sol composition is packed in the sealed vessel, after 40 ℃ of temperature keep a week down, be cooled to 20 ℃, similarly measure viscosity, calculate the viscosity velocity of variation with the initial stage, viscosity stability is estimated according to following benchmark.

Zero: the viscosity velocity of variation is in 50%

*: the viscosity velocity of variation be 50% or more than

* *: gelation

(2) cementability

Acrylic acid sol composition is applied to the end of the electrodeposition coating steel plate of 100 * 25 * 1.0mm, and it is 3mm that clamping is pressing backing plate (spacer) to make the thickness of bonding portion.Under this state, carry out sintering 30 minutes at 130 ℃, or carrying out sintering under 180 ℃ after 30 minutes, backing plate is removed, with draw speed 50mm/min, stretch along cutting off direction, observe collapse state, according to following benchmark cementability is estimated.

Zero: aggegation destroys

*: interfacial failure

(3) tint permanence

For with acrylic acid sol composition 130 ℃ of following sintering 30 minutes or at 30 minutes product of 180 ℃ of following sintering, visual observation is painted, according to following benchmark tint permanence is estimated.

Zero: almost do not find painted

△: find painted

*: find big painted

(4) coating strength

But acrylic acid sol composition is applied on the plate of the demoulding, thickness is 2mm, after 30 minutes, carries out stamping-out with No. 2 type dumbbells at 130 ℃ of following sintering.Under 23 ℃, this dumbbell is stretched with draw speed 50mm/min, intensity (MPa) and elongation (%) when measuring fracture.(5) be coated with tack on

Acrylic acid sol composition is applied on the electrodeposition coating steel plate, and at 140 ℃ of following sintering after 30 minutes, coating solvent type-solution curing type acrylic resin paint 140 ℃ of following sintering 30 minutes, is tested.

Table 1

			Embodiment
			Embodiment							1	2	3	4	5	6	7
			Cooperate (mass parts)	AR* ¹		27	27	27	27	1	2	3	4	5	6	7	27	27	27
BU-1 (Production Example 1)		9		AR* ¹		27	27	27	27	9	9	9	9				27	27	27
BU-1 (Production Example 1)		9		BU-2 (Production Example 2)						9	9	9	9				9
BU-3 (Production Example 3)				BU-2 (Production Example 2)											9		9
BU-3 (Production Example 3)				PA-1 (Production Example 4)		0.8	0.8	0.8							9		0.8	0.8
PA-2 (Production Example 5)				PA-1 (Production Example 4)		0.8	0.8	0.8				0.8					0.8	0.8
PA-2 (Production Example 5)				PA-3 (Production Example 6)								0.8				0.8
PA-4 (Production Example 7)		0.2		PA-3 (Production Example 6)						0.2	0.2	0.2	0.2	0.2	0.2	0.8
PA-4 (Production Example 7)		0.2		DINP* ²		27	38	27	27	0.2	0.2	0.2	0.2	0.2	0.2	27	27	27
Lime carbonate		13.5		DINP* ²		27	38	27	27	13.5	4.5	13.5	13.5	13.5	13.5	27	27	27
Lime carbonate		13.5		Surface treatment lime carbonate * ³		13.5	13.5	22.5	13.5	13.5	4.5	13.5	13.5	13.5	13.5	13.5	13.5	13.5
MSP* ⁴		9		Surface treatment lime carbonate * ³		13.5	13.5	22.5	13.5		9	9	9	9	9	13.5	13.5	13.5
MSP* ⁴		9		Performance test	Viscosity stability		○	○	○		9	9	9	9	9	○	○	○	○
Cementability	130 ℃ * 30 minutes	○	○		Viscosity stability		○	○	○	○	○	○	○	○		○	○	○	○
	130 ℃ * 30 minutes	○	○		180 ℃ * 30 minutes	○	○	○	○	○	○	○	○	○	○	○	○
	Tint permanence	130 ℃ * 30 minutes	○		180 ℃ * 30 minutes	○	○	○	○	○	○	○	○	○	○	○	○	○
180 ℃ * 30 minutes		130 ℃ * 30 minutes	○		○	○	○	○	○	○	○	○	○	○	○	○		○
180 ℃ * 30 minutes		Coating strength	Breaking tenacity (MPa)		○	○	○	○	○	2.66	2.29	4.13	2.29	2.56	○	○	2.26	2.30
Elongation (%)	468		Breaking tenacity (MPa)		549	263	432	495	504	2.66	2.29	4.13	2.29	2.56	477		2.26	2.30
Elongation (%)	468		On be coated with tack		549	263	432	495	504	100/100	100/100	100/100	100/100	100/100	477	100/100	100/100

^*1) AR: the nuclear part is based on the multipolymer of butyl methacrylate and Propenoic acid, 2-methyl, isobutyl ester, and the shell part is based on the core-shell type acrylate copolymer particulate of methyl methacrylate polymer

^*2) DINP: diisononyl phthalate

^*3) surface treatment lime carbonate: stearic acid surface treatment lime carbonate

^*4) MSP: mineral turpentine

Table 2

			Comparative example
			Comparative example					1	2	3	4	5
			Cooperate (mass parts)	AR		27	27	1	2	3	4	5	27	27	27
BU-1				AR		27	27	10	9	9			27	27	27
BU-1				BU-2				10	9	9
BU-3				BU-2
BU-3				PA-1								1
PA-2				PA-1								1
PA-2				PA-3
PA-4				PA-3						1	10
PA-4				DIP		27	27			1	10	27	27	27
Lime carbonate		13.5		DIP		27	27	13.5	3.5	13.5	13.5	27	27	27
Lime carbonate		13.5		Surface treatment lime carbonate		13.5	13.5	13.5	3.5	13.5	13.5	13.5	13.5	13.5
MSP		9		Surface treatment lime carbonate		13.5	13.5	9	9	9	9	13.5	13.5	13.5
MSP		9		Performance test	Viscosity stability zero		○	9	9	9	9	○	○	×	××
Cementability	130 ℃ * 30 minutes	×	×		Viscosity stability zero		○	○	×	×		○	○	×	××
	130 ℃ * 30 minutes	×	×		180 ℃ * 30 minutes	×	×	○	×	×	○	×	×
	Tint permanence	130 ℃ * 30 minutes	○		180 ℃ * 30 minutes	×	×	○	○	○	○	×	×	×
180 ℃ * 30 minutes		130 ℃ * 30 minutes	○		○	○	○	○	○	○	△	××		×
180 ℃ * 30 minutes		Coating strength	Breaking tenacity (MPa)		○	○	○	1.4	1.23	2.42	△	××	2.52	2.97
Elongation (%)	370		Breaking tenacity (MPa)		335	520	421	1.4	1.23	2.42	323		2.52	2.97
Elongation (%)	370		On be coated with tack		335	520	421	0/100	0/100	60/100	323	0/100	0/100

Can see from above result, the cementability of the acrylic acid sol composition that constitutes by acrylate copolymer particulate, softening agent and weighting agent and on to be coated with tack inadequate, and coating strength also inadequate (comparative example 1).In addition, even only also use blocked polyurethane therein, be coated with improve (comparative example 2) of tack and coating strength on also not finding, even only also use multi-amino amide compound, though find the improvement of coating strength, but viscosity stability and tint permanence significantly reduce, do not find yet cementability and on be coated with improve (comparative example 5) of tack.In addition, when only also using multi-amino amide compound with blocked polyurethane, though find the improvement of coating strength, but viscosity stability is poor, filming, it is painted upward to produce, and does not also find improve (comparative example 4) of cementability and coating adhesion, when only also using the modifier of polyether polyamine compound with blocked polyurethane, though find the improvement of viscosity stability, cementability, tint permanence and coating strength, with the tack of coating still be inadequate (comparative example 3).

In contrast to this, by particles of acrylic polymer, blocked polyurethane, have the acrylic acid sol composition of the present invention that modifier, multi-amino amide compound, softening agent and the weighting agent of the polyether polyamine compound of ad hoc structure constitute, has excellent viscosity stability, and cementability, tint permanence and with the tack excellence of coating, and can form tough filming (embodiment 1～7).

Claims

1, a kind of acrylic acid sol composition, it is characterized in that: contain (a) acrylate copolymer particulate, (b) blocked polyurethane, (c) modifier of the polyether polyamine compound shown in the following general formula (I), (d) multi-amino amide compound, (e) softening agent and (f) weighting agent, wherein (a) acrylate copolymer particulate and (b) mass ratio of blocked polyurethane be 90/10～15/85, (c) modifier of polyether polyamine compound is 0.01～10 mass parts with respect to 100 mass parts (a) acrylate copolymer particulate, (d) multi-amino amide compound is 0.01～10 mass parts with respect to 100 mass parts (a) acrylate copolymer particulate, (e) softening agent is 50～500 mass parts with respect to 100 mass parts (a) acrylate copolymer particulate

2, acrylic acid sol composition according to claim 1 is characterized in that: (a) the acrylate copolymer particulate core-shell type that nuclear part and shell partly constitute of serving as reasons.

3, acrylic acid sol composition according to claim 1 is characterized in that: (b) blocked polyurethane is prepared from by polyether glycol and vulcabond.

4, acrylic acid sol composition according to claim 3 is characterized in that: described polyether glycol is trifunctional or above polyether glycol.

5, acrylic acid sol composition according to claim 4 is characterized in that: described polyether glycol is glycerine three (polypropylene glycol).

6, acrylic acid sol composition according to claim 3, it is characterized in that: described vulcabond is for being selected from 1,6-hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexyl methyl hydride-4, at least a among 4 '-vulcabond.

7, acrylic acid sol composition according to claim 1 is characterized in that: (c) modifier of the polyether polyamine compound shown in the described general formula (I) is to be selected from least a among epoxy addition modification thing and the acrylic acid alkyl addition modification thing.

8, acrylic acid sol composition according to claim 7 is characterized in that: the poly epihydric alcohol based compound that described epoxy addition modification thing is provided is bisphenol A-type or F type Resins, epoxy.

9, acrylic acid sol composition according to claim 1 is characterized in that: (d) multi-amino amide compound of multi-amino amide compound for being prepared from by polyethylene polyamine and carboxylic acid cpd.