JPH02233717A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain a curable composition consisting of a polymer composed of a specific silane compound and specific epoxy group-containing polymerizable unsaturated monomer, having excellent storage stability and low-temperature curing properties and capable of providing a coating film having excellent weather resistance and acid resistance without fear of toxicity. CONSTITUTION:The curing composition obtained by adding a metal chelate to a nonaqueous dispersing liquid of polymer granules insoluble in an organic solvent and obtained by polymerizing a radical polymerizable unsaturated monomer using a mixture of (A) a polymer consisting essentially of (i) a silane compound having one or more alkoxysilane groups and/or silanol group and one or more radical polymerizable unsaturated groups expressed by formula I- formula VI (Ra and Rb are 1-20C hydrocarbon groups) and (ii) an epoxy group- containing polymerizable unsaturated monomer, (B) mixture of a polymer consisting essentially of the component i and polymer consisting essentially of the component ii or (C) a polymer consisting essentially of the component A and component i and/or polymer consisting essentially of the component ii, as a dispersing stabilizer in the above-mentioned organic solvent and suitable for coating, adhesive, ink, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a curable composition. (Prior art and its problems) Conventionally, as a method for curing resin, a method has been adopted in which a hydroxyl group-containing resin is cured with a crosslinking agent such as diisocyanate or melamine. However, when diisocyanates are used, the resulting film has insufficient weather resistance and is susceptible to yellowing. Additionally, the pot life of the resin composition is short, and there are also problems with the toxicity of diisocyanates. On the other hand, when using melamine resin, baking is required at a high temperature of about 140° C. or higher, and the resulting film has insufficient acid resistance. As a one-component, non-toxic, low-temperature curable composition, for example, JP-A-60-67553 discloses a method in which an aluminum chelate compound is blended with a vinyl polymer containing an alkoxysilane such as methacrylate trimethoxysilane. A composition is disclosed. However, in the above-mentioned conventional composition, the only crosslinking functional group is the silanol group produced by hydrolysis of the alkoxysilane, so a large amount of water is required for curing, and a large amount of by-products such as alcohol produced during this hydrolysis. Therefore, the physical properties of the cured product cannot be said to be sufficient, and is it possible to cure it with only moisture in the air? Since it hardens from the surface, it has the disadvantage that it is difficult to harden the inside and the cured product tends to sag. h
Steps to Solve the Problems The inventors of the present invention have conducted extensive research to solve the above problems, and as a result, the present inventor has developed a resin containing an alkoxysilane group and/or a silanol group and an epoxy group in the same resin. A composition containing a metal chelate compound in a non-aqueous dispersion containing a resin or a mixture of a resin having an alkoxysilane group and/or a silanol group and a resin having an epoxy group has excellent storage stability even in a one-component type. They also discovered that a film with excellent curability, weather resistance, and surface acidity can be formed without worrying about toxicity, leading to the completion of the present invention. That is, the present invention provides at least one alkoxysilane group and/or silanol group (hereinafter referred to as "silane group") in one molecule, and a -fi formula CIl=CH- CHz:(:H(H,- (;lb=CHO- ?H.=CHO-R.- (:H,=CHCH.O- CH.=CHCH■0-RI,- In the formula, R. and R. are each a 01-2o hydrocarbon group A polymer (processed polymer) containing as essential monomer components a silane compound (A) having at least one radically polymerizable unsaturated group selected from the following and an epoxy group-containing polymerizable unsaturated monomer (B). ), or a polymer (TI) containing the silane compound (A) as an essential monomer and a polymer (II1) containing the epoxy group-containing polymerizable unsaturated monomer CB) as an essential monomer. A mixture or a mixture of polymer (1) and polymer (II) and/or polymer (III) is used as a dispersion stabilizer resin, and a radically polymerizable unsaturated monomer is used in an organic solvent in the presence of the resin. It relates to a curable composition characterized in that a metal chelate compound is contained in a non-aqueous dispersion of polymer particles insoluble in the organic solvent obtained by polymerizing the copolymer ( 1) is a copolymer obtained by copolymerizing a silane compound (A) and an epoxy group-containing polymerizable unsaturated monomer (B), or a copolymer obtained by copolymerizing these and other polymerizable unsaturated monomers. It is a copolymer obtained by a copolymerization reaction. At least one alkoxysilane group and/or
Or, it is a compound having a silanol group and a radically polymerizable unsaturated group. Examples of the "alkoxysilane group" include C, ~4 aproboxy, iso-broboxy, n-ptoxy, iso-
Examples include butoxy, sec-butoxy, tert-butoxy, and the like. Further, as the radically polymerizable unsaturated group, the following general formula CHt=CH-CHs=CHCHx- CI. =CHO- CH2=CHO-RII- CH2; CHCH2Q- CH. =CHCH. O-R. , - where R. and Rb are C1-2, respectively. Indicates a hydrocarbon group. It is an unsaturated group selected from.

In the above general formula, Cl~2. As a hydrocarbon group,
Examples include alkylene groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The aliphatic ring or aromatic ring may be substituted or unsubstituted. Examples of the "alkylene group" include -CH. - , -C. H. −
, -C-H6-, -CH2-CH-CH2-, CH. Preferably CI~1. It is an alkylene group. Typical specific examples of the silane compound (A) include the following. CH2=C}ISi (OCH
sl 3CILa=C}ISi fOc. H5+ 3C
H. =CHSi (OCH-1 - CH. CI{. CHz=CHSiOCH- CH. ?CH2(:H2CH2-CH-C11.CH2Cl+
■-, -CIoHzo-, CM. ? 1■H24-t-CIaH36 can be mentioned. ? H. =CHSi fOHl. CH2=CHSi fOHl 2 CH. CI ■=CHCHzS i(0(:H-) sCH2
”CHCH2Sl (OH) sCH2=CHCH2S
i (OCH2l 2CH3 ?H*=CHOSi (0(:H31 sCH2”CH
OS1 (OH) z CHi”CHOSl (OCHsl 2CH. CI■=C:HOC.H8Si (OCI13+ 30
Hz”CHOCzH4SL (OCH31 xCH, CHx・CHCHxOSl(OCH31 sCH2=C
H(:HzOCJ4Si (OC2H8) 2CH3 CH-=CHCHaOC-H-Sl (OCH31 s
Eboxy group A Saturated B A compound that has an epoxy group and a radically polymerizable unsaturated group in one molecule. Examples of the radically polymerizable unsaturated group include CH2=CR. COO-CH. =C:R,CC-CH. =CR. C-N-n CH. =CH(:H.-0 CHa=CI{O- CH.=CH- In the formula, R1 represents a hydrogen atom or a methyl group. For example, the radically polymerizable unsaturated group is cL・CR.Coo Examples of the first epoxy group-containing polymerizable unsaturated monomer include compounds represented by the following general formulas (1) to (13).

(12) In each formula, R+ has the same meaning as above, and R2 is C, ~.
The hydrocarbon group, R, is C+-t. represents a hydrocarbon group. R in each formula. ．． R* and R may be the same or different. W is 0 and an integer from 1 to 10. Specific examples represented by general formulas (1) to (13) include:
For example, etc. The radically polymerizable unsaturated group is CH2・CR, C-N-
Examples of the epoxy-containing polymerizable unsaturated monomer include those represented by the following general formulas (14) to (16). The radically polymerizable unsaturated group is CH.・CR. Examples of C-C-1 epoxy-containing polymerizable unsaturated monomers include compounds represented by the following general formulas (17) to (19). In each formula, R1 and R2 have the same meanings as above, and R1 and R2 may be the same or different. Specific examples of compounds represented by formulas (14) to (16) include, for example, in each formula, R and R2 have the same meanings as above, and R1 and R2 may be the same or different. Specific examples of general formulas (17) to (19) include the following. The radically polymerizable unsaturated group is CH2/CR. Examples of the C-N- Evo II xy-containing polymerizable unsaturated monomer include compounds represented by the following general formulas (20) to (25).

In each formula, R,, R2, R, and W have the same meanings as above, and R4 is C, ~2. means an alkyl group. R,
, R2, R, and R may be the same or different. Specific examples of the compounds represented by formulas (20) to (25) include the following. The radically polymerizable unsaturated group is CH . = CHCI{ .
Examples of the 0-epoxy group-containing polymerizable unsaturated monomer include compounds represented by the following general formulas (26) to (29). In each formula, R and R2 have the same meanings as above, R.
may be the same or different. General formula (26) ~
Specific examples of the compound represented by (29) include: The radically polymerizable unsaturated group is CH. - Examples of CHO- epoxy group-containing unsaturated monomers include the following general formula (30
) to (32) can be mentioned. can be mentioned. The radically polymerizable unsaturated group is CI. - As the unsaturated monomer containing a CH-1 epoxy group, for example, the following general formula (33)
Compounds represented by ~(35) can be mentioned. In each formula, R and R2 have the same meanings as above, and R2
may be the same or different. flfl expression (30
) to (32) In each formula, R, and R2
has the same meaning as above, and R2 may be the same or different. Specific examples of the compounds represented by AH formulas (33) to (35) include the following. For example, as the epoxy group-containing unsaturated monomer in which the radically polymerizable unsaturated group is CH2'' (:Rlu), the following BB formula (3
Compounds represented by 6) to (40) can be mentioned. In each formula, R, . R. and R have the same meanings as above, and R and R2 may be the same or different. As specific examples of the compounds represented by general formulas (36) to (40), it is preferable to use monomers containing groups, for example, from the viewpoint of curability and the like. That is, when an alicyclic epoxy group-containing unsaturated monomer j21 is used, the reactivity of the ring-opening polymerization reaction of the epoxy group is high, so that the effects of rapid curing and further improvement of the physical properties of the cured coating film can be obtained. Other polymerizable unsaturated monomers are compounds having a radically polymerizable unsaturated group in one molecule, and can be selected from a wide range depending on the desired performance. Representative examples of such unsaturated monomers are as follows. Hydroxyl group-containing polymerizable unsaturated monomer (a) Examples include compounds represented by the following general formulas (41) to (44). OR. In the formula, R represents a hydrogen atom or a hydroxyalkyl group. C.I. -0-R. Among the monomers mentioned above, in particular, in the alicyclic epoxy formula, R
, has the same meaning as above.

CHa=CRI O C-0=C:. H2. -0i C-C, Hi. -0}vl
+ (4 3) In the formula, R has the same meaning as above, m is an integer of 2 to 8, p is an integer of 2 to 18, q
indicates an integer from 0 to 7. CH2=CR. τH of C-0{T, -Oh-+T2- (44
) in the formula, R. l has the same meaning as above, T, and T
2 is the same or different and is 01-2. represents a divalent hydrocarbon group, S and U are each an integer of 0 to 10, provided that the sum of S and U is 1 to 10. General formulas (41) and (4
The "hydroxyalkyl group" in 2) is 01 to 6. Specifically, for example, 1C. H40H.
-C. l{. OH. -fl:4H. Examples include OH. Examples of the C1-2o divalent hydrocarbon group in general formula (44) include -CH. −． -CHffi-CH.
--CHz-CHg-Cl{*-? 011■CH. -CI. -, CH, CH. -CHx-CHiC-CHaClb- CH. -CHI-CI. -CI! -CH-CH. -CH. -C
H. -, -CNoH26-, CH, etc. As the monomer component of general formula (42), for example, CH. =CICI. OH CH! =CHCH! OCH. CH. OHCH*=CHC
HJ{CH*CHzO}-rHCHt=(:HCH*O
Examples include {CH*CH20}-rH. As the monomer component of general formula (43), for example, CH. =CCH. COOC. H40H CI. =CHCOOC. H. OH GHz"CCHaCOO-CsHa-0{(:-CH*
Examples include -CHa-(:HaicH.-co.-o)-, :τH, and the like. -J9 The monomer component of formula (44) is, for example, CH2=CCH. COO{CH. CHCll. Oh se τ
HCHt:CHCOO{CI-CI-Ohfutoge CH2:
CCH,C00{CH2CH20'h-TI1CHz=
CHC00{CH-CH2CH*CH20}T=l'T
H(:H2=CCH,Coo{CH.CH20hfur{
Examples include CHaCHCHsOhr=τH. Furthermore, in addition to the above, hydroxyl group-containing unsaturated monomers represented by the general formulas (4l) to (44) and εcabrolactone,
Adducts with lactones such as γ-parerolactone can be used. Polymerizable unsaturated monomers (b) other than those listed above include the following (b-1) to (b-6). (b-1) Olefin compounds: for example, ethylene, brobylene, butylene, isobrene, chloroprene, etc. (b-2) Vinyl ethers and allyl ethers: e.g. ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, te
Chain alkyl vinyl ethers such as rt-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, rt-butyl vinyl ether, 4-methyl-1-pentyl vinyl ether,
Cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether, aryl vinyl ethers such as phenyl vinyl ether and 0-m+,p-}-rivinyl ether, aralkyl vinyl ethers such as penzyl vinyl ether and phenethyl vinyl ether, etc. (b-3) Vinyl esters and brobenyl esters: for example, vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl cabroate, vinyl isocabroate, vinyl bivaricate, vinyl cabrate, and imbrobenyl acetate. Brobenyl esters such as isobropenyl rubrobinate, etc. (b-4) Esters of acrylic acid or meccrylic acid: for example, methyl acrylate, ethyl acrylate, probyl acrylate, isoprobyl acrylate, butyl acrylate, hexyl acrylate, lactyl acrylate, lauryl acrylate, meccrylate Alkyl esters of acrylic acid or methacrylic acid having 1 to 18 carbon atoms such as methyl methacrylate, ethyl methacrylate, probyl meccrylate, isoprobyl methacrylate, butyl meccrylate, hexyl methacrylate, methyl methacrylate, and lauryl meccrylate; acrylic C2-18 alkoxyalkyl esters of acrylic acid or meccrylic acid, such as methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate. (b-5) Vinyl aromatic compounds such as styrene, α
-Methylstyrene, vinyltoluene, p-chlorostyrene, etc. (b-6) Others: Acrylic nitrile, Mekuri nitrile, etc. Among the other polymerizable unsaturated monomers mentioned above, it is preferable to use the hydroxyl group-containing polymerizable unsaturated monomer (a) because it forms a film with excellent curability. The amount of each monomer used in the copolymer (I) used in the composition of the present invention is such that monomer (A) is O 1 to 80% by weight, preferably 1 to 60% by weight, and monomer CB) is 1 to 80% by weight. -90% by weight, preferably 3-60% by weight. If the amount of monomer (A) and monomer (B) used is less than the above range, the curability tends to be poor, while if it is more than the above range, the physical properties of the cured product tend to deteriorate, which is not preferable. The mixture used in the composition of the present invention contains the silane compound (
The homopolymer of A) or the copolymer of the silane compound (A) and the other polymerizable unsaturated monomer (hereinafter referred to as "Polymer (II) J"), and the epoxy group-containing polymerizable monomer. A homopolymer of the saturated monomer (B) or the monomer (B)
) and the other polymerizable unsaturated monomers (hereinafter referred to as [Polymer (III) J]). When a hydroxyl group-containing polymerizable unsaturated monomer is used as the other polymerizable unsaturated monomer to be copolymerized with the above-mentioned silane compound (A) and/or monomer (B), it has excellent curability. It is preferable to use this material because it forms a thin film. The amount of the silane compound (A) used in the polymer (II) is about 3 to 100% by weight, preferably about 20 to 100% by weight based on the monomers used.
It is in the range of 90% by weight. In addition, when using the hydroxyl group-containing polymerizable unsaturated monomer (a), about 0.1 to
50% by weight, preferably 1 to 30% by weight. The amount of monomer (B) used in the polymer (III) is about 3 to 100% by weight, preferably about 20% by weight based on the monomers used.
~90% by weight. In addition, when using the hydroxyl group-containing polymerizable unsaturated monomer (a), about 0.1 to
50% by weight, preferably 1 to 30% by weight. In the above polymer (TI) and polymer (II+), if the silane compound (A) or monomer (B) is less than the above range, the curability tends to decrease, whereas if it is more than the above range, the cured product This is undesirable because the physical properties of the material tend to deteriorate. Furthermore, the blending ratio of polymer (II) and polymer (III) is 5 to 95% by weight, preferably 10 to 80% by weight, and polymer (II+), based on the total amount of both. ) in 95-5% by weight, preferably 90-2
It is in the range of 0% by weight. If the polymer (II) is less than 5% by weight or the polymer (II+) is more than 95% by weight, the curability decreases, while the polymer (II) is less than 9% by weight.
If the amount of the polymer (II+) is more than 1% by weight or less than 5% by weight, the physical properties of the cured product will deteriorate and sagging will easily occur, which is not preferable.The above polymers (I) to (III) can be obtained in the same manner and under the same conditions as ordinary synthetic reactions for acrylic resins, vinyl resins, etc. As an example of such a synthetic reaction, each monomer component is dissolved or dispersed in an organic solvent, and a radical A method of heating with stirring at a temperature of about 60 to 180°C in the presence of a polymerization initiator can be shown.The reaction time is usually about 1 to 10 hours.In addition, as the organic solvent, the above-mentioned The same alcohol-based solvents, ether-based solvents, ester-based solvents, hydrocarbon-based solvents, etc. can be used.When using a hydrocarbon-based bay medium, other solvents may be used in combination from the viewpoint of solubility. Preferably, as the radical initiator, any commonly used radical initiator can be used, examples of which include peroxides such as benzoyl peroxide and t-butylperoxy-2-ethylhexanoate; Examples include azo compounds such as azoisobutylnitrile and azobisdimethylvaleronitrile.The above polymers (1) to (II+) have a number average molecular weight of 2.0
00 to 200,000 is preferable, and 4.00
0 to so, ooo is more preferable. Polymer (II) or polymer (II) and polymer (I)
I+ ) or a mixture of polymer (I) and polymer (II)
and/or a mixture with polymer (III) as a dispersion stabilizer, and in the presence of the dispersion stabilizer, one or more radically polymerizable monomers and a polymerization initiator are combined with the monomer and the dispersion stabilizer. All of the above monomers can be used as additives in an organic solvent in which the monomer is dissolved, but the polymer particles obtained from the monomer are not dissolved. Since the polymer serving as the particle component must not be dissolved in the organic solvent used, it is preferably a copolymer containing a large amount of highly polar monomer.
i.e. methyl (meth)acrylate, ethyl (mec)
Acrylate, (meth)acrylonitrile, 2-hydroxy(meth)acrylate, hydroxyptyrovir(meth)acrylate, (meth)acrylamide, acrylic acid, methacrylic acid, itaconic acid, styrene, vinyltoluene, alpha-methylstyrene, N- It is preferable that it contains a large amount of monomers such as methylol(mek)acunolamide. Furthermore, the particles of the non-aqueous dispersion can be crosslinked if necessary. Methods for crosslinking the inside of particles include copolymerizing two or more types of monomers having functional groups that react in a complementary manner into particles, and copolymerizing polyfunctional monomers such as divinylbenzene and ethylene glycol dimecrylate. There is a method of polymerization. Complementary functional groups include epoxy groups and carboxylic combinations. Monomers that can be used include glycidyl meccrylate, (mec)acrylic acid, isocyanoethyl methacrylate, m-isobropenyl α.
α-Dimethylpenzyl isocyanate, 2-hydroxyethyl (mek)acrylate, 1,4-butanediol mono(mek)acrylate, etc. can be used. Examples of organic solvents used in the non-aqueous dispersion include those that do not substantially dissolve the dispersed polymer particles produced by the polymerization but are good solvents for the dispersion stabilizer and radically polymerizable monomer. It will be done. Organic liquids that can be used include:
For example, aliphatic hydrocarbons such as pentane, hexane, hebukun, octane, mineral spirits, and naphtha; aromatic hydrocarbons such as benzene, toluene, and xylene; alcohol-based, ether-based, ester-based, and ketone-based solvents, such as isobrobyl alcohol , n-butyl alcohol, isobutyl alcohol, lactyl alcohol, cellosolve, butyl cellosolve, diethylene glycol monobutyl ether, methyl isobutyl ketone, diisobutyl ketone, ethyl acyl ketone, methylhexyl ketone, ethyl butyl ketone, ethyl acetate, isobutyl acetate, Examples include acyl acetate, 2-ethylhexyl acetate, etc., and these may be used alone or in combination of two or more types, but -fi mainly contains aliphatic hydrocarbons, A suitable combination of this with an aromatic hydrocarbon or the above-mentioned alcohol, ether, ester or ketone solvents is preferably used. Furthermore, trichlorotrifluoride ethane, metaxylene hexafluoride, tetrachlorotrifluoride butane, and the like can also be used if necessary.

Polymerization of the above monomers is carried out using a radical polymerization initiator. Usable radical polymerization initiators include, for example, azo initiators such as 2,2-azoisobutyronitrile, 2,2'-azobis(2,4-dimethylbaret nitrile), benzoyl peroxide, lauryl, etc. peroxide,
Examples include peroxide-based initiators such as tert-butyl peroctoate, and these polymerization initiators are generally used in an amount of 0.2 to 10 parts by weight per 100 parts by weight of monomers to be subjected to polymerization. Can be done. The formulation of the dispersion stabilizer to be present during the above polymerization can be selected from a wide range depending on the type of resin, but in general, 3 parts by weight of the radically polymerizable unsaturated monomer are added to 100 parts by weight of the dispersion stabilizer. It is appropriate that the amount is about 240 parts by weight, preferably 5 to 82 parts by weight. In the present invention, by combining a dispersion stabilizer resin and polymer particles, the storage stability of a non-aqueous dispersion is improved, and a cured film with excellent transparency, smoothness, and mechanical properties is formed. be able to. The dispersion stabilizer and the polymer particles can be bonded by polymerizing a radically polymerizable unsaturated monomer in the presence of the dispersion stabilizer having a polymerizable double bond.

A method for introducing a polymerizable double bond is to add α. The most convenient method is to add a β-ethylenically unsaturated monocarboxylic acid, but it is also possible to add an isocyanate group-containing monomer such as isocyanoethyl methacrylate to a hydroxyl group that has been previously incorporated into the copolymer. There are methods. Furthermore, as a method for bonding the dispersion stabilizer and the polymer particles, in addition to the above-mentioned method, as a monomer component forming the polymer particles, for example, γ-methacrylate silane, γ-methacrylate triethoxysilane, γ-acryloxib trimethoxysilane,
Bonding can also be achieved by using reactive monomers such as γ-meccryloxybutyltriethoxysilane and γ-acryloxybutyltrisilanol. The composition of the present invention is a mixture of the above copolymer and a metal chelate compound. The metal chelate compound is preferably an aluminum chelate compound, a titanium chelate compound, or a zirconium chelate compound. Among these chelate compounds, chelate compounds containing a compound capable of forming a keto-enol tautomer as a ligand forming a stable chelate ring are preferred. Compounds that can constitute keto-enol tautomers include β-ditons (acetinoleacetone, etc.)
, acetoacetate esters (methyl acetoacetate, etc.), malonic acid esters (ethyl malonate, etc.), and ketones having a hydroxyl group at the β position (diaheptone alcohol, etc.), β
Aldehydes having a hydroxyl group at the β position (such as salicylaldehyde), esters having a hydroxyl group at the β position (methyl salicylate), etc. can be used. In particular, suitable results can be obtained by using acetoacetic acid esters and B-diketones. The aluminum chelate compound has, for example, the general formula R60-Af-OR6 [wherein R6 is the same or different and has 1 to 20 carbon atoms]
represents an alkyl group or an alkenyl group. ] Preferably prepared by mixing a compound capable of forming the above-mentioned keto enol tautomer at a molar ratio of usually about 3 moles or less with respect to 1 mole of the aluminum alkoxide represented by the formula, and heating as necessary. be able to. As the alkyl group having 1 to 20 carbon atoms, the above-mentioned alkyl group having 1 to 20 carbon atoms
In addition to the alkyl group of lO, undecyl, dodecyl, tridecyl, tetradecyl, octadecyl groups, etc. can be exemplified, and the alkenyl group can be exemplified by vinyl, allyl group, etc. Examples of the aluminum alcoholates represented by the general formula (45) include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-proboxide, aluminum tri-isoproboxide, aluminum tri-n-butoxide, aluminum triisoptoxide, and aluminum tri-n-proboxoxide. See-butoxide, aluminum tri-tert-butoxide, etc., and it is particularly preferable to use aluminum triisopropoxide, aluminum tri-sec-butoxide, aluminum tri-n-butoxide, etc. The titanium chelate compound is, for example, in the general formula E, W
and R6 has the same meaning as above. ] For 1 mole of Ti in the ticnates,
It can be suitably prepared by mixing the compounds that can constitute the above-mentioned keto-enol tautomer at a molar ratio of usually about 4 moles or less, and heating if necessary. As the titanates represented by the general formula (46), W
For those with 1, tetramethyl titanate, tetraethyl titanate, tetra n-probyl titanate, tetra isobyl titanate, tetra n-butyl titanate, tetra isobutyl titanate, tetra tert
-butyltitanate, tetran-pentyltichnate, tetran-hexyltichnate, tetraisocutyl titanate, tetran-lauryltichnate, etc., especially tetraisobuvirtichnate, tetran-hexyltichnate,
-Butyl titanate, tetra-isobutyl titanate, tetra-tert-butyl titanate, etc. are used to give preferable results. In addition, for those where W is 1 or more, tetraisobutyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, etora-te
Dimers to 1l-mers (w=1 to 10 in general formula (46)) of rt-butyl titanate give preferable results. The zirconium chelate compound has, for example, the general formula [where W and R6 have the same meanings as above]. ] The above-mentioned compound capable of forming the keto enol tautomer is preferably mixed in a molar ratio of about 4 mol or less per 1 mol of Zr in the zirconates represented by the formula, and heated if necessary. It can be prepared. Examples of the titanates represented by the general formula (47) include tetraethyl zirconate, tetra n-probyl zirconate, tetraisobuvir zirconate, and tetra n-probyl zirconate.
-butyl zirconate tetra sec-butyl zirconate, tetra tert -butyl zirconate, tetra n-pentyl zirconate, tetra tert-pentyl zirconate, tetra tert-hexyl zirconate, tetra n-heptyl zirconate, tetra There are n-cutyl zirconate, tetra n-stearyl zirconate, etc., especially tetraisobutyl zirconate, tetra n-propyl zirconate, tetra isobutyl zirconate, tetra n-butyl zirconate, tetra sec-butyl zirconate. , Tetler t
Favorable results are obtained when ert-butyl zirconate and the like are used. In addition, for those where W is 1 or more, tetraisobutyl zirconate, tetra n-probyl zirconate, tetra n-butyl zirconate, tetra isobutyl zirconate, tetrasee-butyl zirconate, tetra tert-butyl zirconate dimer to 1l-mer (w=1 to 10 in general formula (47))
gives suitable results. Further, it may contain a structural unit in which these zirconates are associated.

Particularly preferred chelate compounds in the present invention include tris(ethylacetoacetate)aluminum, tris(n-propylacetoacetate)aluminum, tris(isobrobylacetoacetate)aluminum, and tris(n-butylacetoacetate). Aluminum, imbroboxybis(ethylacetoacetate)aluminum, diisobutyboxylacetoacetatealuminum, tris(acetylacetonato)aluminum, tris(probionylacetonato)aluminum, diisobutoxybenzylacetonatoaluminum, Aluminum chelato compounds such as acetylacetonatobis(propylacetonate)aluminum, monoethylacetoacetatebis(acetylacetonato)aluminum, tris(acetylacetonato)aluminum; diisobroboxybis(ethylacetoacetate)titanate, diisobroboxy. Titanium chelate compounds such as bis(acetylacetonato) titanate and diisopropoxy bis(acetylacetonato)tichnate: tetrakis(acetylacetonato)zirconium, tetrakis(n-propylacetoacetate)zirconium, tetrakis(acetylacetonato)zirconium, Examples include zirconium chelate compounds such as tetrakis(ethyl acetoacetate) zirconium. Any one type of the aluminum chelate compound, zirconium chelate compound, and titanium chelate compound may be used, or two or more types may be used in combination as appropriate. The amount of the crosslinking reaction curing agent is 100% of the solid content of the non-aqueous dispersion.
It is appropriate that the amount is about 0.01 to 30 parts by weight. If it is less than this range, the crosslinking rate tends to decrease, and if it is more than this range, it tends to remain in the cured product and reduce water resistance, which is not preferable. The preferred amount is 0.1 to 10 parts by weight, and the more preferred amount is 1 to 5 parts by weight.

The composition of the present invention may contain, for example, Ebicoat 1, if necessary.
Eboxy group-containing resin such as 001 (manufactured by Shell Chemical):
For example, hydroxyl group-containing resins such as styrene allyl alcohol copolymer. Monofunctional or polyfunctional epoxy compounds; low molecular weight silane compounds such as triphenylmethoxysilane and diphenyldimethoxysilane, and other resins such as general silicone resins having alkoxysilane groups may also be added. can. Among these, it is advantageous to add a compound containing two or more alicyclic oxirane groups in one molecule, since it is possible to achieve a high solid content of the curable composition without reducing the curability. Examples of such compounds include compounds represented by the following chemical formula. Adducts of 9 cH 20 H with the polyisocyanate compounds listed below (Polyisocyanate compounds that can be used include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; cyclic diisocyanates such as xylylene diisocyanate or isophorone diisocyanate) Aliphatic diisocyanates; organic diisocyanates themselves such as aromatic diisocyanates such as tolylene diisocyanate or 4.4'-diphenylmethane diisocyanate, or each of these organic diisocyanates with polyhydric alcohols, low molecular weight polyester resins, water, etc. adducts, or polymers of each organic diisocyanate as listed above, and furthermore, isocyanate
Typical commercially available products include "Parnock D-750, -800,
DN-950. -970 or 15-455J [
The above are Dainippon Ink & Chemicals ■ products], [Desmodule L. NHL, IL or N3390J [West German Bayer product], "Takenate D-102, -2
02, -110N or -123NJ [Takeda Pharmaceutical Company ■ product], "Coronate L.HL.EH or 2
03” [Nippon Polyurethane Industries (Silence product)] or “Duranate 24A-90CXJ [Asahi Kasei Industries ■Product 1]
etc.) n Stellated products (for example, those obtained by oxidizing polyester obtained by esterifying tetrahydrophthalic anhydride, trimethylolpropane, 1,4-butanediyl, etc. with peracetic acid, etc.) The curable composition of the present invention may optionally contain an inorganic pigment,
Organic pigments etc. can be added. Inorganic pigments include oxide-based pigments (titanium dioxide, Pengara, chromium oxide, etc.), sulfate-based pigments (precipitated barium sulfate, etc.), carbonate-based pigments (precipitated calcium carbonate-based, etc.), sulfate-based pigments (clay, etc.), Examples include carbon-based powders (carbon plaque, etc.) and metal powders (aluminum powder, bronze powder, zinc powder, etc.). Examples of organic pigments include azo-based pigments (Lake Red, Fast Yellow, etc.) and futacyanine-based pigments (Fuclocyanine Blue, etc.). The curable composition of the present invention may contain an organic solvent if necessary. From the viewpoint of the curing speed of the composition, the Aiso solvent preferably has a boiling point of about 150° C. or lower, but is not limited thereto. Preferred organic solvents include, for example, hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, and ether solvents such as dioxane and ethylene glycol diethyl ether. Examples include alcoholic baying agents such as , Bukunol, and propanol. These solvents can be used alone or in an appropriate mixture, but when using an alcoholic solvent, it is preferable to use it in combination with another solvent from the viewpoint of solubility of the resin. The concentration of the resin solvent varies depending on the purpose of use, but it may generally be about 10 to 70% by weight. In addition to the above, the above-mentioned chelating agents can be added. The curable composition of the present invention can be suitably used in paints, adhesives, inks, etc. As for paint, it ranges from room temperature drying to 60~
100°C low temperature baking mold, 100~I E3 0”
It can be widely applied up to the high temperature baking type of C. It can be applied to all kinds of objects that are conventionally coated with paint, such as iron plates, plastic materials, and wood. Painting of automobile bodies is also an example to which the curable composition of the present invention is suitably applied. Solid color, metallic color,
It can be painted in the form of clear paint, etc., using a wet multi-coat method (so-called 2CIB painting), a monocoat method, and other methods. It can be used as an intermediate coating for automobile bodies, and as a top coat or undercoat for various plastic materials and metal parts used as automobile parts. When the curable composition of the present invention is used as a coating material, there are no particular limitations on the coating method, and conventional methods can be used as is. For example, methods such as air spray electrostatic air spray, airless spray, Bell electrostatic coating, Mini Bell electrostatic coating, roll coating, and Yatsuka coating can be applied. The curable composition of the present invention can be easily crosslinked and cured at a low temperature of 140°C or lower. For example, when it is cured at room temperature without any heating, it is usually sufficiently cured in about 8 hours to 7 days. Furthermore, when heated to about 40-100°C, it can be sufficiently cured in about 5 minutes to 3 hours. The reason why the curable composition of the present invention has excellent low-temperature curability is thought to be as follows. That is, as the first reaction,
The metal chelate compound reacts with the silane group to form the following bond. / \ Next, this bond coordinates to the silanol group (for alkoxysilane groups, etc., it becomes a silanol group due to moisture in the air), becoming \ / \ and polarizing the silanol group. This polarized silanol group reacts with the epoxy group, resulting in the following. This then reacts with a hydroxyl group to form -c-a-c-c-OH. This reaction between epoxy groups and hydroxyl groups proceeds at relatively low temperatures. The curable composition of the present invention contains a hydroxyl group-containing compound as an essential component, and furthermore, since the epoxy group, silane group, and metal chelate compound are present in the composition, the above reaction proceeds rapidly, resulting in low-temperature curability. It is estimated that it will be excellent. Furthermore, the composition of the present invention is a non-aqueous dispersion in which a solid phase, which is a polymer particle formed by polymerizing a radically polymerizable unsaturated monomer, is stably dispersed in a liquid phase in which a dispersion stabilizer resin is dissolved in an organic solvent. It contains a chelate compound. This makes it possible to significantly increase the solid content of the composition during coating.
Moreover, since the viscosity after painting is high, it is possible to form a film with an excellent finished appearance without sagging or running. Furthermore, the formed film is a photo- and chemically stable film in which the continuous phase of the film has a siloxane bond, and the polymer particle component in the film is stabilized by the continuous phase, and the film is stabilized by the particles. Because it is reinforced with ingredients, it has excellent optical and chemical properties, as well as mechanical properties such as impact resistance. The present invention will be explained in more detail with reference to the following examples. Unless otherwise specified, "parts" and "%" are based on weight. Synthesis of vinyl copolymer (I-a) The following monomers, solvent, and polymerization initiator were charged into a saichito crepe, and after replacing with nitrogen, the temperature was gradually raised to 80°C. (Part) Xylene 80CH.・CH-
Si- (OCH.l -CH2=CH-0-Cff●
, H The temperature rises to about 100°C due to self-heating, but then gradually decreases. Continue stirring for 16 hours while maintaining the temperature at 80°C. Thereafter, the reaction mixture in the autoclave was cooled and poured into Hebukun to precipitate a resin, followed by drying to obtain a vinyl copolymer (I-a). The number average molecular weight (Mn) of the vinyl copolymer (I-a) is 6
．． It was 500. Synthesis of vinyl copolymer (1-b) Using the following monomers, a vinyl copolymer (I- b) was obtained. The amount of active ingredient is 20 (parts) of n-buknol. Synthesis of vinyl copolymer (I-c) First, siloxane macromonomer M1 was synthesized as follows. (Department) H. CSi (OCH, l s
2 7 2 Of20mo1) CH2・CHSi (OCH-1 s
1 4 8 (lmof'1 deionized water 113436% hydrochloric acid
2 Hydroquinone
The mixture was reacted at 80°C for 5 hours to remove water and solvent. The number average molecular weight of the obtained polysiloxane macromonomer was 2.000, with an average molecular weight of 1 per molecule.
It had 4 vinyl groups (polymerizable unsaturated groups) and 4 hydroxyl groups. The blending amounts in the following synthesis examples are macromonomer and (part) siloxane macromonomer Ml 30CH. =CH
-0-C. H, IOH 1 5CH
1=CI-0-0-CIHI l
5CI. =CH-0-C. 0.
20 Using the above monomers, a vinyl copolymer (I-c) was synthesized in the same manner as the vinyl copolymer (■a). Mn of the vinyl copolymer (1-c) was 9.200. Synthesis of vinyl copolymer (II-a) A vinyl copolymer (II-a) with R n = 13.000 was produced in the same manner as vinyl copolymer (I-a) using the following monomers. -a) was synthesized. (Part) CIla=CH-0-C-H-SifOcH31 -
4 0CI. =CH-0-C. H. O
H20CH. =CH-O
C. H. 3 0C
H*”CH-QC4}1s
10 Synthesis of vinyl copolymer (II-b) It was produced in the same manner as vinyl copolymer (Ia) using the following monomers, with Mn=12. ooo vinyl monomer (
II-b) was synthesized. Siloxane macromonomer Ml CHa"CH-QC-H-OH CHz"CH-OCJs (part) Synthesis of vinyl copolymer (III-a) Using the following monomers, vinyl copolymer (I-a) A vinyl copolymer (III-a) with Mn=8.200 was synthesized by the same method as . (Part) (:H.=CHOCOC.l(.
5 0CH. =CH-CI. -OC. H4-
OH I O vinyl copolymer (II
Synthesis of I-b) It was prepared in the same manner as the vinyl copolymer (I-a) using the following monomers to obtain Mn=ll. 000 vinyl copolymer (III 1b) was synthesized. (Part) CH yo=CH-0-C4H.
2 0CHa”CI-0-Calls
30 vinyl copolymer (II
I-b) Synthetic vinyl copolymer (I-a), (I-b), (II-a)
, (II-b), (III-a), (III-
b) was dissolved in a mixed solvent of xylene/butyl acetate = 80/20 to a solid content concentration of 50%, and vinyl copolymer solutions (1-a), (I-b), (TI-a), (II-
b), (Il[-a), and (III-b) were created. Synthesis of vinyl copolymer (I-a') Using the vinyl copolymer solution (I-a), isocyanoethyl meccrylate is added to the vinyl copolymer (I-a), and based on the number average molecular weight, , by adding 0.3 polymerizable double bonds per molecule, and converting this into vinyl copolymer (I-a')
It was. The solution of vinyl copolymer M-a') is referred to as vinyl copolymer solution (I-a'). The solid concentration of the solution is 50
%, solvent composition is xylene/butyl acetate = 8 0/2
It is 0. Synthesis of vinyl copolymer (1-c') Synthesis of vinyl copolymer (1-a') was repeated except that methacrylic acid was used instead of isocyanoethyl meccrylate. .Three polymerizable double bonds were added to form a vinyl copolymer (I-c'). Synthesis of vinyl copolymer (II-a') By adding isocyanoethyl methacrylate to vinyl copolymer (II-a), 0.4 polymerizable double bonds per molecule based on number average molecular weight was introduced, and this was made into a vinyl copolymer (II-a'). Synthesis of vinyl copolymer (llI-a') By adding meccrylic acid to vinyl copolymer (ill-a), 0.3 polymerizable double bonds are introduced per molecule based on the number average molecular weight. This was then converted into a vinyl copolymer (III-a'
). Vinyl copolymer solution (I-a'), (I-
c'), (II-a'), and (III-a') all have a solid concentration of 50% and a solvent composition of xylene/butyl acetate = 80/20. Synthesis of non-aqueous dispersion (N-1) 134 parts of vinyl copolymer solution (I-a'), 200 parts of ethylcyclohexane, and 50 parts of n-butanol were charged into a flask, and the following monomers and polymerization were carried out at 90°C. The initiator was added dropwise over a period of 4 hours, followed by 0.0% butyl percutoate.
2 parts were added, and then aged for 3 hours, and then compressed under reduced pressure to synthesize a non-water-resolved liquid (N-1). (Part) Methyl methacrylate 41 Styrene
10 acrylonitrile
202-Hydroxyethyl 15 acrylate acrylic acid 4 glycidyl meccrylate 10AIBN
1 The solid content concentration of the non-aqueous dispersion (N-1) is 55
%, Gardner viscosity was P. Synthetic non-aqueous dispersions (N-2) to (N-5)
N-1) was produced in the same manner as the non-aqueous dispersion (N-1).
-2) to (N-5) were synthesized. (N-2) ~ (N-5
) and the Gardner viscosity are shown below. The solid content concentration of all non-aqueous dispersions was 55%. Non-aqueous dispersion (N-2) Fractional stabilizer/vinyl copolymer solution (I-b) 134 parts Particle-forming monomer. Same Gardner viscosity as for non-aqueous dispersion (N-1) Non-aqueous dispersion (N-3) (parts) Dispersion stabilizer. Vinyl copolymer 134(1-c')? Child-forming monomer: Methyl methacrylate 30 Acryonitrile 20 CH2=CHC00CH. Cll■CH2-Si-(O
CH31. l0 Acrylate Gardner viscosity: R Non-aqueous dispersion (N-4) (parts) Particle-forming monomer: Methyl mecrylate acrylonitrile 2-hydroxyethyl acrylate l5 Ethylene glycol diacrylate Glycidyl mecrylate Mecrylic acid Gardner viscosity: UV non-aqueous dispersion (N-5) (parts) Example 1 A composition was obtained using the following formulation. (Part) Non-aqueous dispersion (N-1) 91 Vinyl copolymer solution (I-a) 100 Particle-forming monomer: Same as non-aqueous dispersion (N-1). Gardner viscosity: W Field (parts) for non-aqueous dispersion (N-6) Particle-forming monomer: Same as for non-aqueous dispersion (N-1). Gardner viscosity: S The above composition was mixed with xylene/n-butanol = 90/10 (
25 seconds (weight ratio) in a #4 Ford cup with a mixed solvent of
The viscosity was adjusted to 5°C) and used for painting. Apply epoxy paint to a dull steel plate treated with zinc phosphate using the electric paint method to a dry thickness of 20μ and bake at 170°C for 20 minutes. Next, sand the painted surface with #400 sandpaper and wipe the painted surface with gauze soaked in petroleum benzene to degrease it. Then, apply aminopolyester automotive paint to a dry film thickness of 30 μm and bake at 140°C for 30 minutes. Then, the painted surface was sanded with #400 sandpaper, drained and dried, and the painted surface was wiped with petroleum benzene. The viscosity-adjusted composition was air-sprayed onto the material to a dry film thickness of approximately 50 μm, left at room temperature for 10 minutes, and then baked at 100° C. for 30 minutes. Table 1 shows the evaluation results of the coating film. In the following Examples and Comparative Examples, the materials, adjustments to coating viscosity, and baking conditions are the same as in Example 1 unless otherwise specified. Example 2 A composition was obtained using the following formulation. (Part) Non-aqueous dispersion (N-2) 100 Vinyl copolymer (1-b) 90 Example 3 A composition was obtained using the following formulation. Dispersion of titanium white was carried out using vinyl copolymer (III-a). Non-aqueous dispersion (N-3) Vinyl copolymer (III-a) (part) Example 4 A base coat for wet painting was prepared using the following formulation. Non-aqueous dispersion (N-4) Vinyl copolymer (n[-a) (parts) Toluene acetate isobutyl aluminum paste #4919 5 (Toyo Aluminum (Kiki products) Toluene/xylene/n-buknol = 4 0/4 0
15 in a #4 diameter cup using a mixed solvent of /20.
The viscosity was adjusted so that it was 1.2 seconds (25°C). A top coat for wet painting was created using the following formulation. (Part) Non-aqueous dispersion (N-3) 91 Vinyl copolymer solution (I-c) 100 Aluminum Tris
2 (Acetylacetone) A mixed solvent of Swasol #1000"/n-butanol = 80/20 was used as a viscosity-adjusting solvent, and the mixture was diluted for 25 seconds (at 25°C) with a #4 dry cup and used for painting. ( 9 Swazol #1000: Cosmo Oil ({Aromatic solvent made by Wolf) Air spray the above base coat onto the material to a dry film thickness of approximately 18μ, leave it at room temperature for 5 minutes, then apply the above top coat to a dry film thickness of approximately 18 μm. It was air-sprayed so that it had a thickness of 40μ, and after being left at room temperature for 10 minutes, it was baked at 100°C for 30 minutes.Example 5 A composition was obtained with the following formulation. (Part) Non-aqueous dispersion (N-5) ) 182 Example 6 A composition was obtained with the following formulation. (Part) Non-aqueous dispersion (N-6) Vinyl copolymer solution (r-b) Comparative Example 1 A composition was obtained with the following formulation. (Part) Vinyl copolymer solution (II-a) 200 Comparative Example 2 A composition was obtained with the following formulation. (Part) Vinyl copolymer solution (III-a) 200 Aluminum Tris 2 (acetylacetone) Example 1 ~6, Table 1 shows the evaluation results of the cured films of Comparative Examples 1 and 2.
It is shown in Notes in Table 1 (Note 1) Finished appearance was evaluated visually. (Note 2) Gasoline wiping resistance Nisseki Shinolever gasoline was moistened with gauze and the coated surface was rubbed vigorously 8 times back and forth over the locm length of the coated surface, and then the coated surface was observed. Items with almost no scratches or dullness on the painted surface were considered good. (Note 3) Impact resistance Test using a DuPont impact tester with a firing pin tip radius of 1/2 inch and a dropped bell weight of 500 g. Indicates the maximum height without cracks on the painted surface (in 5cm increments). (Note 4) Water resistance: Immerse the test piece in a constant temperature water bath at 40°C for 240 hours. Items with no abnormalities such as glossiness or blisters on the paint film after removal were considered good. (Note 5) 0.5 cc of acid-resistant 10% sulfuric acid was spotted on the painted surface and left at 20°C and 75% RH for 48 hours, then washed with water and the painted surface was observed.

Claims (1)

[Claims] [1] One molecule contains at least one alkoxysilane group and/or silanol group, and the general formula CH_2=CH- CH_2=CHCH_2- CH_2=CHO- CH_2=CHO-R_a- CH_2=CHCH_2O - CH_2=CHCH_2O-R_b- where R_a and R_b are C_1_~_2_0, respectively
Indicates a hydrocarbon group. A polymer containing as essential monomer components a silane compound (A) having at least one radically polymerizable unsaturated group selected from the following and an epoxy group-containing polymerizable unsaturated monomer (B) (
I), or a polymer (II) containing the silane compound (A) as an essential monomer and a polymer (III) containing the epoxy group-containing polymerizable unsaturated monomer (B) as an essential monomer. or a mixture of polymer (I) and polymer (II) and/or polymer (III) is used as a dispersion stabilizer resin, and a radically polymerizable unsaturated monomer is used in an organic solvent in the presence of the resin. 1. A curable composition comprising a metal chelate compound in a non-aqueous dispersion of polymer particles insoluble in an organic solvent obtained by polymerizing a polymer. [2] The curable composition according to claim 1, wherein at least one polymer selected from the polymers (I) to (III) has a hydroxyl group. [3] A curable composition comprising a hydroxyl group-containing resin and/or a hydroxyl group-containing compound in the composition according to claim 1 or 2.