JP2007039659A - Adhesiveness imparting agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesiveness imparting agent to an acrylic plastisol excellent in coating workability, chipping resistance, hot water resistance, storage stability, and adhesiveness to a metal coated surface, because a conventional acrylic plastisol is unsatisfactory respecting to storage stability and adhesiveness to a metal coated surface, although the coating workability on an electrocoated film, chipping resistance, and hot water resistance are excellent. <P>SOLUTION: The adhesiveness imparting agent for an acrylic plastisol comprises a blocked polyurethane and a ketimine formed from a 6-10C polyethylene-polyamine and a ketone, and the acrylic plastisol comprises the adhesiveness imparting agent, an acrylic polymer, and a plasticizer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an adhesiveness imparting agent. More specifically, the present invention relates to an adhesion imparting agent for acrylic plastisol, which is coated on an outer plate of an automobile and prevents corrosion of a car body steel plate, and an acrylic plastisol using the same.

  Conventionally, a plastisol having adhesion to a metal painted surface (hereinafter abbreviated as a metal painted surface) by cationic electrodeposition has been vinyl chloride plastisol. However, in recent years, replacement from vinyl chloride plastisol to acrylic plastisol has been progressing in consideration of the environment. Further, as an adhesiveness imparting agent for plastisol, one made of blocked polyurethane and ketimine (for example, see Patent Document 1) is known.

JP-A-2-14271

  However, when the adhesion-imparting agent described in Patent Document 1 is used, the coating property (coating appearance), chipping resistance and hot water resistance to the metal painted surface are excellent, but the storage stability of acrylic plastisol and adhesion to the metal painted surface. The sex was not fully satisfactory. An object of the present invention is to provide an adhesion-imparting agent for acrylic plastisol that is excellent in storage stability and adhesion to a metal-coated surface.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention provides an adhesive for acrylic plastisol characterized by comprising a blocked polyurethane (A) and a ketimine (B) formed from a polyethylene polyamine (b1) having 6 to 10 carbon atoms and a ketone (b2). Agent (C): An acrylic plastisol comprising the adhesion-imparting agent (C), the acrylic polymer (D) and the plasticizer (E).

The acrylic plastisol containing the adhesiveness imparting agent of the present invention has the following effects. (1) Excellent storage stability.
(2) Excellent adhesion to the metal coating surface.
(3) It has sufficient curability by heat treatment at a low temperature or in a short time.
(4) The acrylic plastisol coating on the metal painted surface has excellent chipping resistance.

The adhesiveness imparting agent (C) of the present invention comprises a blocked polyurethane (A) and a ketimine (B) formed from a polyethylene polyamine (b1) having 6 to 10 carbon atoms and a ketone (b2).
The carbon number (hereinafter abbreviated as C) of (b1) is 6 to 10, and when C is less than 6, the storage stability of the acrylic plastisol is deteriorated, and when it exceeds 10, the adhesion to the metal coating surface is deteriorated.
(B1) includes triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine. Of these, tetraethylenepentamine is preferred, and triethylenetetramine is more preferred.

(B2) includes C3-9 aliphatic ketones such as acetone, and methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone , Abbreviated as MEK, MPK, MIPK, MIBK, DEK, DPK, DIPK, DBK and DIBK, respectively). Among these, MIPK, MIBK, DEK, DPK, and DIPK, DBK and DIBK are more preferable from the viewpoint of storage stability of the acrylic plastisol described later, and DIBK is particularly preferable.

  (B) can be produced by subjecting (b1) and (b2) to a dehydration condensation reaction. The condensation reaction is usually carried out while distilling off water in the presence of a dehydrating agent (benzenesulfonic acid, zinc chloride, boron trifluoride, etc.). Specifically, an excess of ketone equivalent to the chemical equivalent to (b1) is added, and if necessary, a solvent (toluene, xylene, etc.) is added, and then dehydration condensation reaction is performed while distilling off water under heating and reflux. If necessary, excess ketone and solvent can be distilled off.

  In (A), the terminal isocyanate group of the urethane prepolymer obtained by the reaction of organic poly (divalent to tetravalent or higher) isocyanate (a1) and polyol (a2) is blocked with a blocking agent (a3). Compounds are included.

Examples of (a1) include the following, and a mixture of two or more thereof. (1) C (excluding C in the NCO group, the same shall apply hereinafter) 6 to 20 aromatic polyisocyanate (polyisocyanate is hereinafter abbreviated as PI)
Diisocyanates (hereinafter abbreviated as DI), such as 1,3- and / or 1,4-phenylene DI, 2,4- and / or 2,6-tolylene DI (hereinafter abbreviated as TDI),
4, 4′- and / or 2,4′-diphenylmethane DI (hereinafter abbreviated as MDI),
m- and p-isocyanatophenylsulfonyl isocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3
'-Dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene DI, and m- and p-isocyanatophenylsulfonyl isocyanate; and tri- or higher functional PI (such as triisocyanate), such as crude TDI, crude MDI (polymethylene polyphenylene polyisocyanate) and 4,4 ', 4 "-triphenylmethane triisocyanate

(2) C2-18 aliphatic polyisocyanates DI, such as ethylene DI, tetramethylene DI, hexamethylene DI (HDI), heptamethylene DI, octamethylene DI, decamethylene DI, dodecamethylene DI, 2,2,4- and / Or 2,4,4-trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethylcaproate, 2,6-diisocyanatoethylcaproate, bis (2-isocyanatoethyl) fumarate, bis ( 2-isocyanatoethyl) carbonate and trimethylhexamethylene diisocyanate (TMDI); and tri- or higher functional polyisocyanates (such as triisocyanate) such as 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl Octane, 1,3,6-hexamethylene triisocyanate and lysine ester triisocyanate (phosgenates of the reaction product of lysine and alkanolamine, such as 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2 -And / or 3-isocyanatopropyl-2,6-diisocyanatohexanoate, etc.)

(3) C4-45 alicyclic polyisocyanate DI, such as isophorone DI (hereinafter abbreviated as IPDI), 2,4- and / or 2,6-methylcyclohexane DI (hydrogenated TDI), dicyclohexylmethane-4, 4'-D
I (hydrogenated MDI), cyclohexylene DI, methylcyclohexylene DI, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate and 2,5- and / or 2,6-norbornane DI, dimer acid DI (DDI); and trifunctional or higher functional PI (such as triisocyanate), such as bicycloheptane triisocyanate (4) C8-15 aromatic aliphatic polyisocyanate m- and / or p-xylylene DI (XDI) , Diethylbenzene DI and α, α, α ′, α′-tetramethylxylylene DI (TMXDI)

  Of these, aromatic polyisocyanates are preferable from the viewpoint of adhesion of acrylic plastisol, and TDI and MDI are more preferable.

The polyol (a2) has a hydroxyl group equivalent (molecular weight per hydroxyl group) of 3,000 to 3,000 molecular weight [hereinafter abbreviated as Mn, measured by gel permeation chromatography (GPC) method] of 3,000, Divalent to hexavalent or higher polyols, for example, low molecular polyols having a hydroxyl equivalent of 31 to less than 250, high molecular polyols having a hydroxyl equivalent of 250 to 3,000 (polyether polyols, polyester polyols, polymer polyols, polycarbonate polyols, etc.) and A mixture of two or more of these may be mentioned.
Among these, from the viewpoint of the viscosity of acrylic plastisol and physical properties of the coating film, a polymer polyol is preferable, a polyester polyol is more preferable, and a polyether polyol is particularly preferable.

Low molecular polyols include polyhydric alcohols and low molecular OH-terminated polymers (polyether polyols and polyester polyols). The polyhydric alcohol includes the following.
Dihydric alcohols (C2-20 or higher), for example C2-12 aliphatic dihydric alcohols [(di) alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-, 2,3 -, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 3-methylpentanediol (hereinafter referred to as EG, DEG, PG, DPG, BD, HD, NPG and MPD, respectively) Abbreviation), dodecanediol etc.]; C6-10 alicyclic dihydric alcohol [1,4-cyclohexanediol, cyclohexanedimethanol etc.]; C8-20 araliphatic dihydric alcohol [xylylene glycol, bis (hydroxy Ethyl) benzene, etc.];

Trihydric to octahydric or higher polyhydric alcohols such as (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [glycerin, trimethylolpropane, pentaerythritol, sorbitol and dipentaerythritol (hereinafter referred to as GR, TMP respectively) , PE, SO and DPE), 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin and other polyglycerins, etc.], sugars and their derivatives [eg sucrose, glucose, Fructose, mannose, lactose, and glucoside (such as methyl glucoside)];

Nitrogen-containing polyols (tertiary amino group-containing polyols and quaternary ammonium group-containing polyols): nitrogen-containing diols such as C1-12 aliphatic, alicyclic and aromatic primary monoamines [methylamine, ethylamine, 1- and 2 -Propylamine, (iso) amylamine, hexylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 1-, 2- and 3-aminoheptane, nonylamine, decylamine, undecylamine, dodecylamine, cyclopropyl Amine, cyclopentylamine, cyclohexylamine, aniline, benzylamine, etc.] bishydroxyalkyl (C2-4) compounds [bis (2
-Hydroxyethyl) compounds, bis (hydroxypropyl) compounds, etc., for example, tertiary nitrogen atom-containing polyols described in US Pat. No. 4,271,217], and quaternized products thereof [in the above US patent specifications] The quaternizing agent or the quaternized product with a dialkyl carbonate described above], for example, a quaternary nitrogen atom-containing polyol described in the above-mentioned U.S. Patent Specification; and a trivalent to octavalent or higher nitrogen-containing polyol such as trialkanol (C2 -4) polyhydroxyalkyl (C2-4) compounds of amines (such as triethanolamine) and C2-12 aliphatic, cycloaliphatic, aromatic and heterocyclic polyamines [eg ethylenediamine, tolylenediamine, aminoethylpiperazine] [Poly (2-hydroxyethyl) compound, bis (hydroxypropyl) compound and the like: Tetrakis (2-hydroxypropyl) ethylenediamine and pentakis (2-hydroxypropyl) diethylenetriamine, and similar quaternary compound with these above;

Sulfo group-containing polyols: those obtained by introducing a sulfo group into the above divalent and trivalent to octavalent or higher polyhydric alcohols, such as sulfoglycerin, sulfoerythritol, sulfodi (hydroxymethyl) benzene, sulfodi (hydroxyethyl) Benzene, sulfodi (hydroxypropyl) benzene, sulfohydroxymethylhydroxyethylbenzene, and salts thereof [metal salts [alkali metal (lithium, sodium, potassium, etc.) salts, alkaline earth metals (calcium, magnesium, etc.) salts, IIB metals] (Such as zinc) salt, ammonium salt, amine (C1-20) salt and quaternary ammonium salt].

Low molecular OH-terminated polymers include polyether polyols, polyester polyols and polyurethane polyols having an OH equivalent weight of less than 250, as described below. For example, low-polymerization alkylene oxide (hereinafter abbreviated as AO. AO includes those described below) ring-opening polymerization products and low-mol AO adducts of active hydrogen atom-containing polyfunctional compounds [for example, polyethylene glycol, polypropylene glycol , Polytetramethylene glycol, bis (hydroxyethoxy) benzene and bisphenol A EO 2-4 mol adduct], low condensation polycondensation polyester polyol and polyol low mol lactone adduct [polycarboxylic acid and excess (per carboxyl group) 1 mol) of a polyhydric alcohol condensate (for example, dihydroxyethyl adipate) and EG caprolactone 1 mol adduct], and a low degree of polyurethane polyol [excess (1 mol per isocyanate group) of polyhydric alcohol The reaction product of TDI 1 reaction product of moles and EG2 mol)] and the like.

  Among the polymer polyols, examples of the polyether polyol include AO adducts of low molecular polyols (above and their mixtures), polyoxytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran, and the like. Of these, low molecular polyol AO adducts and polyoxytetramethylene glycol are preferred.

AO added to the low molecular polyol includes C2-12 or more (preferably C2-4) AO such as ethylene oxide, propylene oxide, 1,2-, 1,3- and 2,3-butylene oxide, tetrahydrofuran. And 3-methyl-tetrahydrofuran (hereinafter abbreviated as EO, PO, BO, THF and MTHF, respectively), 1,3-propylene oxide, isoBO, C5-12 α-olefin oxide, substituted AO such as styrene oxide and epihalohydrin ( Epichlorohydrin and the like), and combinations of two or more of these (random addition and / or block addition).
Of these, preferred are EO, PO, BO, and more preferred are mixtures of two or more thereof.

The polyester polyol includes a condensed polyester polyol, a polylactone polyol, and a castor oil-based polyol.
The condensed polyester polyol includes a polyol (a diol and, if necessary, a trivalent or higher polyol), a polycarboxylic acid (a dicarboxylic acid and, if necessary, a trivalent or higher polycarboxylic acid) or an ester-forming derivative thereof, or a polycarboxylic acid anhydride and It can be produced by reacting with AO.

As the polyol, a low molecular polyol and / or a polyether polyol can be used. The low molecular polyol includes those described above, and the polyether polyol includes those having a hydroxyl equivalent of 500 or less.
As the polycarboxylic acid, a dicarboxylic acid and a dicarboxylic acid and a small proportion (for example, 10 equivalent% or less) of a trivalent to tetravalent or higher polycarboxylic acid can be used. Examples thereof include C2-12 aliphatic polycarboxylic acids [dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, itaconic acid, etc.), tricarboxylic acid (hexane Tricarboxylic acid etc.], C8-15 aromatic polycarboxylic acid [dicarboxylic acid (terephthalic acid, isophthalic acid, phthalic acid etc.), tri- and tetra-carboxylic acid (trimellitic acid, pyromellitic acid etc.)] , And C6-40 alicyclic polycarboxylic acids (such as dimer acid).
The ester-forming derivatives include acid anhydrides, lower alkyl (C1-4) esters, acid halides (such as acid chlorides), and the like.
Of the polycarboxylic acids, dicarboxylic acids are preferred from the viewpoint of the viscosity of the acrylic plastisol, aliphatic dicarboxylic acids are more preferred, and adipic acid is particularly preferred.

The polylactone polyol can be produced by ring-opening polymerization of a lactone (C4-15, for example, ε-caprolactone, γ-butyrolactone, γ-valerolactone) using a polyol as an initiator.
As the polyol, a low molecular polyol and / or a polyether polyol can be used. Examples thereof include the diol and / or a trihydric or higher polyol, and a polyether polyol having a hydroxyl equivalent weight of 500 or less.
The castor oil-based polyol includes castor oil (ricinoleic acid triglyceride) and transesterification products thereof. The transesterified product is obtained by transesterification of castor oil and a polyol, and examples of the polyol include the low molecular polyol and / or the polyether polyol.

  The polymer polyol is a vinyl monomer [acrylic monomer such as (meth) acrylonitrile, alkyl (C1-20) in a polyol [such as the above-described high molecular polyol (polyether polyol, polyester polyol, etc.) and a mixture of these and the above low molecular polyol]]. ) (Meth) acrylate (such as methyl methacrylate), aromatic hydrocarbon monomer (C8-20, such as styrene), aliphatic hydrocarbon monomer (C2-20, such as α-olefin, butadiene) and the like, and two or more of these Combinations (for example, combined use of acrylonitrile and styrene)] (polymer content, for example, 5 to 70%), for example, those described in JP-A No. 55-118948 can be used.

Polycarbonate polyols can be produced by ring-opening addition / polycondensation of alkylene carbonate using polyol as an initiator, polycondensation (transesterification) of polyol and diphenyl or dialkyl carbonate, or phosgenation of polyol or dihydric phenol (such as bisphenol A). What is obtained is included.
The polyol includes the low-molecular polyol (such as a divalent or trivalent alcohol).
Alkylene carbonates include those having a C2-6 alkylene group, such as ethylene and propylene carbonate. Dialkyl carbonates include those having a C1-4 alkyl group, such as dimethyl, diethyl and di-i-propyl carbonate.

  Among these polyols, from the viewpoint of the viscosity of the acrylic plastisol, preferred are high-molecular polyols, more preferred are low molecular weight polyol AO adducts and polyoxytetramethylene glycol, and particularly preferred is PG PO adduct (hydroxyl equivalent). 250-3,000), TMP PO adducts (hydroxyl equivalents 250-2,500) and / or GR PO adducts (hydroxyl equivalents 250-2,500).

  In the production of the urethane prepolymer having an isocyanate group in the present invention, the equivalent ratio (NCO / OH) in the reaction between the isocyanate group (NCO) of (a1) and the hydroxyl group (OH) of (a2) is the viscosity of the adhesion-imparting agent. From this viewpoint, it is preferably 1.3 / 1 to 3.0 / 1, more preferably 1.5 / 1 to 2.2 / 1. The end groups of the urethane prepolymer are NCO groups at both ends, or one end is an NCO group and the other end is an OH group. From the viewpoint of acrylic plastisol adhesion, both ends are preferably NCO groups. is there.

In order to accelerate the reaction, a known urethanization catalyst may be used. Examples of the urethanization catalyst include metal catalysts (tin-based (trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, dibutyltin maleate, etc.), lead-based ( Lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.), cobalt-based (cobalt naphthenate, etc.), mercury-based (phenylmercuric propionate, etc.)], amine catalyst [triethylenediamine, tetra Methylethylenediamine, tetramethylhexylenediamine, diazabicycloalkene, dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminoethylamine, dimethylaminooctylamine, dipropylaminopropyl Pyramine, 2- (1-aziridinyl) ethylamine, 4- (1-piperidinyl) -2-hexylamine, N-methylmorpholine, N-ethylmorpholine, triethylamine, diethylethanolamine, dimethylethanolamine and their organic acids (formic acid) , Phenol, etc.) salts, etc., and combinations of two or more of these.
The amount of the urethanization catalyst used is usually 1% or less, preferably 0.001 to 0.1%, based on the weight of the urethane prepolymer obtained.

  The reaction temperature for producing the urethane prepolymer is preferably 20 to 120 ° C., more preferably 60 to 110 ° C., from the viewpoint of suppressing side reactions. The reaction time is preferably 3 to 10 hours, more preferably 5 to 8 hours, from the viewpoint of suppressing side reactions.

The preferable lower limit of Mn of the urethane prepolymer is 500, more preferably 700, and the preferable upper limit is 8,000, more preferably 5,000. If the Mn is 500 or more, the resin is soft and has a favorable effect on the chipping resistance. If it is 8,000 or less, the atomization (atomization) of the acrylic plastisol paint becomes better and the appearance of the coating film (especially smoothness). Is better.
Further, the free isocyanate group content [NCO% (weight% in terms of solid content)] of the prepolymer is preferably 1 to 20%, more preferably 2 to 15%, from the viewpoint of adhesiveness of the acrylic plastisol. NCO% can be measured or confirmed by titration or infrared absorption spectrum.

Examples of the blocking agent (a3) include lactams (C4-10, such as ε-caprolactam, δ-valerolactam, and γ-butyrolactam), oximes [C3-10, such as acetoxime, methyl ethyl ketoxime (MEK oxime), and methyl isobutyl ketoxime. (MIBK oxime)], amine [secondary amine of C2-20, such as aliphatic amine (dimethylamine, diisopropylamine, etc.), alicyclic amine (methylcyclohexylamine, dicyclohexylamine, etc.) and aromatic amine (diphenylamine, etc.) ], Alkylphenols [C7-20, such as cresol, nonylphenol, xylenol and di-t-butylphenol], and mixtures of two or more thereof. Of these, oxime and amine are preferable from the viewpoint of adhesion and storage stability of acrylic plastisol, and lactam is more preferable, and ε-caprolactam is particularly preferable.

The blocked polyurethane (A) can be obtained by adding and reacting the blocking agent (a3) at any stage of the urethane prepolymer formation reaction.
The addition method includes (1) a method of adding the total amount to the polyol (a1) in advance, (2) a method of adding the total amount in the initial stage of the urethane prepolymer formation reaction, and (3) adding a part in the initial stage of the reaction or in the middle of the reaction. , A method of adding the remainder at the end of the reaction and (4) a method of adding after the end of the reaction. Among these, the method (4) is preferable from the viewpoint of the reproducibility of the reaction.
In the case of the methods (1) to (3), the amount of (a3) added is the hydroxyl group of the polyol (a2) from the number of NCO equivalents of the raw polyisocyanate (a1) from the viewpoint of the storage stability of the acrylic plastisol. It is preferable to use approximately the same equivalent as that obtained by subtracting the number of equivalents. In the case of the method (4), preferably 1 to 2 equivalents, more preferably, from the viewpoint of storage stability with respect to the NCO group of the urethane prepolymer. 1.05 to 1.5 equivalents.
In the methods (2) to (4), the system temperature when (a3) is added is preferably 50 to 110 ° C. from the viewpoint of preventing side reactions. In the above reaction, the urethanization catalyst may be added to accelerate the reaction. The use amount of the urethanization catalyst is usually 10% or less, preferably 5% or less, from the viewpoint of storage stability, based on the weight of the urethane prepolymer.
In the case of (A), a plasticizer described later may be added to adjust the viscosity.

  The adhesion-imparting agent (C) of the present invention comprises a blocked polyurethane (A) and a ketimine (B), and an equivalent ratio of the blocked NCO group in (A) to the active hydrogen in (b1). Is preferably 90/10 to 25/75, more preferably 80/20 to 40/60, from the viewpoint of adhesion of the acrylic plastisol to the metal-coated surface.

The acrylic plastisol of the present invention comprises an adhesiveness imparting agent (C), an acrylic polymer (D) and a plasticizer (E).
(D) is a single polymer or two or more copolymers of alkyl (meth) acrylate (C1-20) ester, or a copolymer of these monomers with other polymerizable unsaturated group-containing monomers. A polymer is included.
The copolymerization ratio (weight ratio) in the copolymer of (meth) acrylic acid alkyl ester and other polymerizable unsaturated group-containing monomer is preferably 50/50 to 99/1, more preferably from the viewpoint of physical properties of the resin. Is 70/30 to 95/5.

  Examples of (meth) acrylic acid alkyl esters include C4-30, such as methyl (meth) acrylate, -ethyl, -butyl, and -hexyl.

Examples of other polymerizable unsaturated group-containing monomers include the following.
(1) Aromatic unsaturated hydrocarbon (unsaturated hydrocarbon is abbreviated as HC hereinafter)
C8-20, such as styrene, methyl styrene, vinyl toluene, trimethyl styrene, halogenated styrene, t-butyl styrene, amino styrene, p-benzyl styrene, p-phenoxy styrene, oxystyrene (2) aliphatic HC
C2-18 or more, such as alkenes [ethylene, propylene, (iso) butene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other α-olefins, etc.] and dienes [butadiene, isoprene, 1,4- Pentadiene, 1,
6-hexadiene, 1,7-octadiene, etc.]
(3) Alicyclic HC
C4-18 or more, for example (di) cycloalkene [cyclohexene, (di) cyclopentadiene, pinene, limonene, indene, vinylcyclohexene, ethylidenebicycloheptene, etc.]
(4) Amino group-containing (meth) acrylic acid ester C4-30, such as 2-aminoethyl (meth) acrylate, N, N-diethylamino (meth) acrylate (5) 1-4 or more hydroxyl groups in the molecule And compounds having 1 to 4 or more polymerizable unsaturated groups C5 to 600, such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) ) Acrylate, polyethylene glycol (polymerization degree 3-100) mono (meth) acrylate, polypropylene glycol (polymerization degree 3-100) mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate 6) α, β-unsaturated dicarboxylic acids or their anhydrides C4-12 dicarboxylic acids such as (anhydrous) maleic acid, fumaric acid, crotonic acid, (anhydrous) itaconic acid (7) α, β-unsaturated Esters of dicarboxylic acids C6-30, such as fumaric esters (diethyl fumarate, dioctyl fumarate, etc.)

(8) Other vinyl monomers Nitrile group-containing vinyl monomers [C3-15, such as (meth) acrylonitrile, cyanostyrene, cyanoalkyl (C1-4) acrylate];
Vinyl esters [aliphatic vinyl esters (C4-15, such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl adipate, isopropenyl acetate, vinyl methoxyacetate), aromatic vinyl esters (C9-20, such as diallyl Phthalate, methyl-4-vinylbenzoate, acetoxystyrene) and the like];
Halogen-containing vinyl monomers (C2-4, such as vinyl chloride, vinylidene chloride);
Vinyl ether {aliphatic vinyl ether [C3-15 vinyl alkyl (C1-10) ether [vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl-2-chloroethyl ether, etc.] , Vinyl alkoxy (C1-6) alkyl (C1-4) ether [vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxyethyl ether, 3,4-dihydro-1,2-pyran, 2-butoxy -2'-vinyloxydiethyl ether, vinyl-2-ethylmercaptoethyl ether, etc.], poly (2-4) (meth) allyloxyalkane (C2-6) (dialyloxyethane, triaryloxyethane, tetra-allyl Roxyethane, tetraallyloxy Propane, tetraallyloxybutane, tetrametaallyloxyethane, etc.)], aromatic vinyl ethers (C8-20, such as vinylphenyl ether and phenoxystyrene), etc.};

Heterocycle-containing vinyl monomers [pyridine compounds (C7-14, such as 4-vinylpyridine and 2-vinylpyridine), imidazole compounds (C5-12, such as N-vinylimidazole), pyrrole compounds (C6-13, such as N-vinyl) Pyrrole), pyrrolidone compounds (C6-13, such as N-vinyl-2-pyrrolidone), carbazole compounds (C14-20, such as N-vinylcarbazole) and the like];
Sulfo group-containing vinyl monomers [C4-25, such as vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide, vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfosuccinate, styrene sulfonic acid, α-methyl styrene sulfonic acid , Sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, alkyl (C3-18) Allylsulfo Haq acid, and alkali metal (sodium, potassium, etc.) salts thereof];
Vinyl ketone [aliphatic vinyl ketone (C4-25, such as vinyl methyl ketone and vinyl ethyl ketone), aromatic vinyl ketone (C9-21, such as vinyl phenyl ketone), etc.];
Sulfide group-containing monomers (C4-20, such as divinyl sulfide, p-vinyl diphenyl sulfide, and vinyl ethyl sulfide);
Vinylene carbonate, 2-vinyl furan, vinyl phenyl disiloxane, vinyl urethane and the like.

Among these, from the viewpoint of resin physical properties, a homopolymer of methyl (meth) acrylate, a copolymer of methyl (meth) acrylate and the above-mentioned other monomers, more preferably methyl (meth) acrylate Homopolymer of (meth) acrylic acid methyl and (meth) acrylic acid butyl copolymer.
The monomer can be polymerized by a known method (solution polymerization, emulsion polymerization, suspension polymerization, etc.).

The Mn in (D) is not particularly limited, but is preferably 100,000 to 5,000,000, more preferably 300,000 to 3,000,000 from the viewpoint of resin physical properties.
The form (D) is usually a fine powder, and the volume average particle size of the fine particles is preferably 0.1 to 50 μm, more preferably 0.2 to 10 μm. (D) can use 2 or more types together.

As the plasticizer (E), aromatic carboxylic acid ester [phthalic acid ester (diethyl phthalate (DEP), dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), dilauryl phthalate, distearyl phthalate, diisononyl phthalate] (Hereinafter abbreviated as DINP), triethylene glycol dibenzoate, etc.], aliphatic carboxylic acid ester [methyl acetyl ricinolate, di-2-ethylhexyl adipate (DOA), di-2-ethylhexyl sebacate (DOS), adipic acid -Propylene glycol polyester, 2,2,4-trimethyl 1,3-pentanediol diisobutyrate, etc.]
, Phosphate esters [triphenyl phosphate, tricresyl phosphate, etc.], and mixtures of two or more of these.
Of these, aromatic carboxylic acid esters are preferred from the viewpoint of solubility in the blocked polyurethane (A), and di-2-ethylhexyl phthalate (DOP) and diisononyl phthalate (DINP) are more preferred.

  Based on the total weight of (C), (D) and (E), the content of (C) is preferably 1 to 40%, more preferably 2 to 2, from the viewpoint of adhesion of acrylic plastisol to the metal-coated surface. The content of 30% and (D) is preferably 10 to 50%, more preferably 15 to 40% from the viewpoint of the viscosity of the acrylic plastisol, and the content of (E) is preferably from the viewpoint of the viscosity of the acrylic plastisol. It is 10 to 50%, more preferably 20 to 45%.

In addition to the above (C), (D) and (E), the acrylic plastisol contains other additives (fillers, foaming agents, colorants, stabilizers) as long as the effects of the present invention are not inhibited as necessary. And / or diluent). The total amount of the other additives is usually 50% or less, preferably 1 to 40%, based on the total weight of the acrylic plastisol.

  As fillers, inorganic fillers (calcium carbonate, talc, clay, diatomaceous earth, silicic acid, silicate, kaolin, asbestos, mica, glass fiber, glass balloon, carbon fiber, metal fiber, ceramic whisker, titanium whisker) And organic fillers [cellulose powder, powder rubber, organic crosslinked fine particles (epoxy, urethane, etc.), urea, etc.]. The amount of the filler used is usually 40% or less, preferably 1 to 35% from the viewpoint of the viscosity of the acrylic plastisol based on the total weight of the acrylic plastisol.

  As foaming agents, azo foaming agents (azodicarbonamide, azobisisobutyronitrile, etc.), nitroso foaming agents (dinitrosopentamethylenetetramine, etc.) and hydrazide foaming agents [toluenesulfonylhydrazide, oxybis (benzenesulfonylhydrazide) And the like]. The amount of foaming agent used is usually 5% or less, preferably 0.1 to 2%, based on the total weight of the acrylic plastisol.

Examples of the colorant include inorganic pigments, organic pigments, and dyes.
Inorganic pigments include white pigments (titanium oxide, lithopone, lead white, zinc white, etc.), cobalt compounds (aureolin, cobalt green, cerulean blue, cobalt blue, cobalt violet, etc.), iron compounds (iron oxide, bitumen, etc.), Examples thereof include chromium compounds (chromium oxide, lead chromate, barium chromate, etc.), sulfides (cadmium sulfide, cadmium yellow, ultramarine, etc.), and mixtures thereof.

Organic pigments include azo pigments (azo lake, monoazo, disazo, chelate azo), polycyclic pigments (benzimidazolone, phthalocyanine, quinacridone, dioxazine, isoindolinone, thioindigo, and perylene. Quinophthalone, anthraquinone, etc.), and mixtures thereof.
As dyes, azo, anthraquinone, indigoid, sulfide, triphenylmethane, pyrazolone, stilbene, diphenylmethane, xanthene, alizarin, acridine, quinoneimine, thiazole, methine, nitro Nitroso, aniline, and mixtures thereof. The amount of the colorant used is usually 5% or less, preferably 0.1 to 2%, based on the total weight of the acrylic plastisol.

  Stabilizers include metal soap (calcium stearate, aluminum stearate, etc.), inorganic acid salts (dibasic phosphite, dibasic sulfate, etc.) and organometallic compounds (dibutyltin dilaurate, dibutyltin maleate) Etc.). The amount of stabilizer used is usually 10% or less, preferably 0.2-5%, based on the total weight of the acrylic plastisol.

  Diluents include xylene and mineral terpenes. The amount of diluent used is usually 20% or less, preferably 5 to 15%, based on the total weight of the acrylic plastisol.

A formulation example of acrylic plastisol is as follows (% indicates% by weight).
-Adhesiveness imparting agent (C) [Solid content conversion] 2-30%
-Acrylic polymer (D) 15-40%
・ Plasticizer (E) 20-45%
・ Other additives (fillers, foaming agents, etc.) 1-40%

The acrylic plastisol of the present invention can be produced by a usual method (for example, a method described in JP-A-2-14271). For example, the above components are charged, disperser, ball mill, steel mill, pebble mill, attritor, sand mill, sand grinder, pot mill, planetary mixer, kneader, glen mill, roll, and universal mixer [(C) dispersibility and simple manufacturing. From the viewpoint of properties, it is preferable that the dispersion is uniformly mixed and stirred with a disper] or the like. There are no particular restrictions on the order in which the components are charged, but from the viewpoint of uniform mixing of (C), (D) and (E), it is preferable to first mix (C), (D) and (E). Thereafter, other additives are added and mixed.
The mixing temperature is usually 0 to 40 ° C. (preferably 10 to 30 ° C.), and the mixing time is usually 20 minutes to 1.5 hours (preferably 30 minutes to 1 hour).

The storage stability of the acrylic plastisol of the present invention (retention rate of initial viscosity during production as measured by the method described later) is preferably 30% or less, more preferably 0 to 20% from the viewpoint of paintability.

The acrylic plastisol of the present invention can be applied to various undercoating surfaces applied to various metal (especially steel) surfaces, but can be advantageously applied to cationic electrodeposition coating surfaces from the viewpoint of adhesion of acrylic plastisols.
The coating amount of acrylic plastisol is preferably 500 to 3,000 g / m 2 from the viewpoint of chipping resistance, and the coating film thickness is preferably 0.5 to 3 mm from the viewpoint of chipping resistance. In addition, the film thickness at the time of application | coating and the film thickness after the heat processing mentioned later hardly change.
Examples of the application method include brush coating, spatula coating, roller coating, and airless spray coating, and airless spray coating is preferred from the viewpoint of coating efficiency and coating with a high viscosity paint. In addition, although heat treatment is performed after coating, the heat treatment temperature is preferably 110 to 160 ° C., more preferably 120 to 140 ° C. from the viewpoint of adhesion and curability of the acrylic plastisol, and the heat treatment time is preferably 10 from the same viewpoint. -40 minutes, more preferably 20-30 minutes.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by this. In the following, “parts” means parts by weight, and “%” means% by weight.

[Production Example of Blocked Polyurethane (A)]
Production Example 1
A reaction vessel equipped with a stirrer was charged with 1,218 parts of TDI, 2,000 parts of polytetramethylene glycol (Mn 1,000), 134 parts of TMP, 4,222 parts of carbitol acetate, and stirred and mixed under a nitrogen stream. It was made to react at -80 degreeC for 3 hours, and the urethane prepolymer solution of NCO% 3.9 (solid content conversion value 8.8) was obtained. Next, after 870 parts of ε-caprolactam was added and further reacted at 80 to 90 ° C. for 3 hours, it was confirmed by titration that the NCO group had disappeared. A blocked polyurethane solution (A1) having a solid content of 50% and a blocked apparent NCO% (hereinafter abbreviated as latent NCO%) 3.5 (solid content conversion value 7.0) was obtained.

Production Example 2
In Production Example 1, except that MDI 1,750 parts and carbitol acetate 4,554 parts were used instead of TDI 1,218 parts and carbitol acetate 4,222 parts, NCO% A urethane prepolymer solution of 4.1 (solid content conversion value 8.9) was obtained. Next, after adding 670 parts of methyl ethyl ketoxime and further reacting at 80 to 90 ° C. for 3 hours, it was confirmed by titration that the NCO group had disappeared. A blocked polyurethane solution (A2) having a solid content of 50% and a latent NCO% of 3.8 (solid content conversion value 7.6) was obtained.

Production Example 3
In a reaction vessel similar to Production Example 1, 1,082 parts of TDI, 6,216 parts of GR PO adduct (Mn 3,000, the same shall apply hereinafter) and 8,000 parts of DINP were charged, and stirred and mixed under a nitrogen stream. It was made to react at -90 degreeC for 5 hours, and the urethane prepolymer solution of NCO% 1.7 (solid content conversion value 3.6) was obtained. Next, after adding 702 parts of ε-caprolactam and further reacting at the same temperature for 3 hours, it was confirmed by titration that the NCO group had disappeared. A blocked polyurethane solution (A3) having a solid content of 50% and a latent NCO% of 1.6 (solid content conversion value 3.2) was obtained.

Production Example 4
In a reaction vessel similar to Production Example 1, 1,357 parts of IPDI, 6,112 parts of PO addition product of GR, 8,000 parts of DINP, and 0.4 parts of dibutyltin dilaurate were stirred and mixed under a nitrogen stream. The mixture was reacted at 90 ° C. for 3 hours to obtain a urethane prepolymer solution having NCO% 1.6 (solid content conversion value 3.4). Subsequently, 532 parts of methyl ethyl ketoxime was added and reacted at 50 to 70 ° C. for 1 hour, and it was confirmed by titration that the NCO group had disappeared. A blocked polyurethane solution (A4) having a solid content of 50% and a latent NCO% of 1.5 (solid content conversion value 3.0) was obtained.

Production Example 5
In a reaction vessel similar to Production Example 1, 1,104 parts of TDI and 6,344 parts of PO addition product of GR and 8,000 parts of DINP were charged, stirred and mixed in a nitrogen stream, and reacted at 80 to 90 ° C. for 5 hours. A urethane prepolymer solution having an NCO% of 1.7 (solid content conversion value 3.6) was obtained. Subsequently, 552 parts of methyl ethyl ketoxime was added and further reacted at 50 to 70 ° C. for 1 hour, and it was confirmed by titration that the NCO group had disappeared. A blocked polyurethane solution (A5) having a solid content of 50% and a latent NCO% of 1.6 (solid content conversion value 3.2) was obtained.

Production Example 6
In a reaction vessel similar to Production Example 1, 1,082 parts of TDI and 6,216 parts of PO adduct of GR and 8,000 parts of DINP were charged, stirred and mixed in a nitrogen stream, and reacted at 80 to 90 ° C. for 5 hours. A urethane prepolymer solution having an NCO% of 1.7 (solid content conversion value 3.6) was obtained. Next, 1,124 parts of dicyclohexylamine was added and further reacted at the same temperature for 3 hours, and it was confirmed by titration that the NCO group had disappeared. A blocked polyurethane solution (A6) having a solid content of 50% and a latent NCO% of 1.6 (solid content conversion value 3.1) was obtained.

[Production Example of Ketimine (B)]
Production Example 7
A reaction vessel equipped with a stirrer and a reflux cooling device was charged with 417 parts of triethylenetetramine and 1,244 parts of excess DIBK, and reacted for 18 hours under reflux of DIBK to remove water. Thereafter, excess DIBK was removed from the reaction mixture under reduced pressure to obtain 980 parts of ketimine (B1) from the desired triethylenetetramine and DIBK.

Production Example 8
A reaction vessel equipped with a stirrer and a reflux cooling device was charged with 539 parts of tetraethylenepentamine and 1,244 parts of excess DIBK, and reacted for 20 hours under reflux of DIBK to remove water. Thereafter, excess DIBK was removed from the reaction mixture under reduced pressure to obtain 970 parts of the target tetraethylenepentamine and ketimine (B2) from DIBK.

Production Example 9
A reaction vessel equipped with a stirrer and a reflux cooling device was charged with 662 parts of pentaethylenehexamine and 1,244 parts of excess DIBK, and reacted for 25 hours under reflux of DIBK to remove water. Thereafter, excess DIBK was removed from the reaction mixture under reduced pressure to obtain 970 parts of the target pentaethylenehexamine and ketimine (B3) from DIBK.

Production Example 10
A reaction vessel equipped with a stirrer and a reflux cooling device was charged with 617 parts of diethylenetriamine and 1,796 parts of excess MIBK, and reacted for 15 hours under reflux of MIBK to distill off water. Thereafter, excess MIBK was removed from the reaction mixture under reduced pressure to obtain 970 parts of the target diethylenetriamine and ketimine (B4) from MIBK.

Example 1
“Zeon F-320” [manufactured by Nippon Zeon Co., Ltd., methyl methacrylate homopolymer (Mn 3 million powder, volume average particle size 1 μm powder) to a mixture of 100 parts of (A1) and 7 parts of (B1), same as below. 188 parts, “Shiraka Hana CC-R” [manufactured by Shiraishi Kogyo Co., Ltd., surface-treated ultrafine calcium carbonate (volume average particle size 0.08 μm), and so on. 188 parts and 150 parts of DINP were added and uniformly kneaded with a disper to prepare an acrylic plastisol, and performance evaluation was performed by the method described later.
The initial viscosity of the plastisol was 104 Pa · s / 25 ° C., and the viscosity after storage at 35 ° C. for 10 days was 122 Pa · s / 25 ° C. Also, the adhesion and water-resistant adhesion were extremely good. The results are shown in Table 1.

Example 2
In Example 1, an acrylic plastisol was prepared and evaluated for performance in the same manner as in Example 1 except that the same amount of (A2) was used instead of (A1). The results are shown in Table 1.

Example 3
In Example 1, an acrylic plastisol was prepared and evaluated for performance in the same manner as in Example 1 except that the same amount of (A3) was used instead of (A1). The results are shown in Table 1.

Example 4
In Example 1, an acrylic plastisol was prepared and evaluated for performance in the same manner as in Example 1 except that the same amount of (A4) was used instead of (A1). The results are shown in Table 1.

Example 5
In Example 1, an acrylic plastisol was prepared and evaluated for performance in the same manner as in Example 1 except that the same amount of (A5) was used instead of (A1). The results are shown in Table 1.

Example 6
In Example 1, an acrylic plastisol was prepared and evaluated for performance in the same manner as in Example 1 except that the same amount of (A6) was used instead of (A1). The results are shown in Table 1.

Example 7
In Example 1, an acrylic plastisol was prepared and evaluated for performance in the same manner as in Example 1 except that the same amount of (B2) was used instead of (B1). The results are shown in Table 1.

Example 8
In Example 1, an acrylic plastisol was prepared and evaluated for performance in the same manner as in Example 1 except that the same amount of (B3) was used instead of (B1). The results are shown in Table 1.

Comparative Example 1
In Example 1, an acrylic plastisol was prepared and evaluated for performance in the same manner as in Example 1 except that the same amount of (B4) was used instead of (B1). The results are shown in Table 1. From this result, it can be seen that the adhesiveness is inferior to each example.

Comparative Example 2
In Example 1, an acrylic plastisol was prepared and evaluated for performance in the same manner as in Example 1 except that (A2) was used instead of (A1) and (B4) was used in the same amount instead of (B1). The results are shown in Table 1. This result shows that the storage stability is inferior to each example.

The test method in the performance evaluation is as follows.
(1) Initial viscosity Viscosity immediately after creation of acrylic plastisol [BH viscometer, manufactured by Tokyo Keiki Co., Ltd., unit is Pa · s / 25 ° C.].
(2) Viscosity after storage After preparation of acrylic plastisol, 90 g in a glass cylindrical container having an inner diameter of about 4 cm and a height of about 8 cm and stored at 35 ° C. for 10 days [measurement conditions, unit is the above (1) Same as. ] Measured.
(3) Storage stability The rate of increase in viscosity (%) after storage relative to the initial viscosity at the time of acrylic plastisol preparation is calculated from the following formula. The smaller the value, the better the storage stability.

Viscosity increase rate after storage (%) = (viscosity after storage−initial viscosity) × 100 / initial viscosity

(4) Curability Epoxy resin-based cationic electrodeposition paint [trade name: Konak / No. 3500, Japanese fat (
Co., Ltd.] The coated surface of the coated steel sheet (hereinafter abbreviated as electrodeposition coated steel sheet) has an internal volume of 50 x 20 x 1 m.
The frame was attached so that it might become m, and the acrylic plastisol was spatula-coated so that a film thickness might be set to 1 mm in it. After the heat treatment at 130 ° C. for 20 minutes, the degree of curing of the coating film was judged by the following criteria by finger touch.

◎ No tack, good curability ○ Slightly tacky but hard enough to be practical △ There is tack, insufficient curability x No cure is observed at all.

(5) Adhesive Acrylic plastisol is spatally applied to the end (area of about 2 x 2 cm ² ) of the coated surface of the electrodeposited steel sheet of 100 x 25 x 1 mm so that the film thickness after crimping is 1 mm. One sheet of the same electrodeposited steel sheet was crimped. In this state, after baking heat treatment at 130 ° C. for 20 minutes, the ends of the two electrodeposition coated steel plates are pulled in the shear direction at a tensile speed of 50 mm / min, and the adhesiveness to the painted surface of the electrodeposited steel plates is determined from the broken state. evaluated. Judgment criteria are as follows.

○ Cohesive failure △ Cohesive failure and interface peeling coexist × Interface peeling

(6) Water-resistant adhesion The same test piece as in (5) above was prepared, and after being baked at 130 ° C for 20 minutes, the adhesiveness to the painted surface of the electrodeposited steel sheet after being immersed in 40 ° C warm water for 3 days. Evaluation was performed using the same criteria as in (5).
(7) Chipping resistance Acrylic plastisol is applied to the coated surface of 100 x 100 x 0.8 mm electrodeposited steel sheet with a thickness of 400 µm, and after baking at 130 ° C for 20 minutes, a test piece is attached to the nut dropping device. Drop a 3-M-4 brass hex nut specified in B-1181 from a height of 2 m through a tube with a tube diameter of 20 mm onto each sample plate having an angle of 45 ° with respect to the drop direction of the nut, The total weight (kg) of the nut until the scratch on the coating reached the metal surface was measured.

  The acrylic plastisol containing the adhesion-imparting agent (C) of the present invention is excellent in storage stability and adhesion to a metal coating surface, firmly adheres to a metal coating surface at a relatively low temperature, and has excellent chipping resistance. In addition, it is applicable to various industrial uses such as adhesives, sealants, paints, etc., and particularly in the automobile industry, chipping having a cured product of the acrylic plastisol on at least a part of a car body steel plate surface subjected to cationic electrodeposition coating Since the steel sheet is excellent in chipping resistance, it is extremely useful as a body sealer and undercoat material.

Claims (8)

An adhesiveness-imparting agent (C) for acrylic plastisol, comprising a blocked polyurethane (A) and a ketimine (B) formed from a polyethylene polyamine (b1) having 6 to 10 carbon atoms and a ketone (b2). The adhesiveness imparting agent (C) according to claim 1, wherein (A) is a polyurethane blocked with one or more blocking agents selected from the group consisting of lactam, oxime and amine. The adhesiveness imparting agent (C) according to claim 1 or 2, wherein the equivalent ratio of the blocked NCO group in (A) to the active hydrogen in (b1) is 90/10 to 25/75. An acrylic plastisol comprising the adhesion-imparting agent (C) according to any one of claims 1 to 3, an acrylic polymer (D), and a plasticizer (E). 5. (C) is 1 to 40%, (D) is 10 to 50%, and (E) is 10 to 50% based on the total weight of (C), (D) and (E). Acrylic plastisol. The acrylic plastisol according to claim 4 or 5, further comprising at least one additive selected from the group consisting of a foaming agent, a colorant, a stabilizer, a diluent and a filler. Hardened | cured material formed by hardening | curing the acrylic plastisol in any one of Claims 4-6. An anti-chipping steel plate having the cured product according to claim 7 on at least a part of the surface of the steel plate.