JPH02233714A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain a curable composition giving a film having excellent storing stability, low-temperature curing property, weatherability and resistance to acid without fear of toxicity, comprising polymers respectively containing specific silane compound and epoxy group-containing polymerizable unsaturated monomer, etc. CONSTITUTION:A curable composition suitable for coating material, adhesive and ink, etc., is obtained from (A) a polymer containing (i) a silane compound having at least one alkoxysilane group and/or silanol group and at least one radical-polymerizable unsaturated group expressed by formula I-VI (Ra and Rb are 1-20C hydrocarbon group) and (ii) epoxy group-containing polymerizable unsaturated monomer as essential ingredients, (B) a mixture of a polymer containing the component (i) as essential ingredient and a polymer containing the component (ii) as essential ingredient, or (C) a composition added of metal chelate compound to the component (A) and the polymer containing the component (i) as essential ingredient and/or a polymer containing the component (ii) as essential ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a curable composition. (Prior art and its problems) Conventionally, a method of curing a hydroxyl group-containing resin with a crosslinking agent such as diisocyanate melamine has been adopted. 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 are not sufficient, and when it is cured only with moisture in the air, it hardens from the surface, making it difficult to harden the inside and causing the cured product to sag. The present inventor has conducted extensive research in order to solve the above-mentioned problems, and as a result, the present inventors have discovered that a resin or A composition containing a mixture of a resin having a hydroxyl group and/or a hydrolyzable group directly bonded to a silicon atom and a resin having an epoxy group has excellent storage stability even in a one-component type, and there is no fear of toxicity. Excellent hardenability,
We have discovered that a film with excellent weather resistance and acid resistance can be formed, and have completed 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 compound of the general formula CI. =CI- CH*”CHCH*- CH*:CHO- CH!=CHO-Ra- CH.=CHCH10- CHm”CICI-0-Rゎ- In the formula, Ra and Ra are each C, ~,. Indicates a hydrocarbon group. A polymer (I) containing as essential monomer components a silane compound (A) having at least one radically polymerizable unsaturated group selected from
), 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), wherein a metal chelate compound is added to the curable composition. The copolymer (I) used in the composition of the present invention is a copolymer obtained by copolymerizing a silane compound (A) and an epoxy group-containing polymerizable unsaturated monomer (B), or a copolymer thereof. It is a copolymer obtained by copolymerization reaction with other polymerizable unsaturated monomers. 3I1 KohachiL At least one alkoxysilane group and/or in one molecule
Or, it is a compound having a silanol group and a radically polymerizable unsaturated group. The "alkoxysilane group" is preferably a C, to 4 alkoxysilane group. Examples of the alkoxysilane group include methoxy, ethoxy, n-proboxy, i
so-proboxy, n-butoxy, iso-proboxy,
Examples include sec-butoxy and tert-butoxy. Further, as the radically polymerizable unsaturated group, the following general formula CH. =CH-CH. =CHCH*- CHm"CHO- CI!=CHO-Ra- CI.=CHCH.O- CH*"CICHaO-R-- In the formula, Ra and Ra each represent a 01-20 hydrocarbon group. It is an unsaturated group selected from. ? In the general formula, the C, ~2o hydrocarbon group is,
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. lL-, -C
sH6-, -CH. -CH-CH. −, CI{, CH. CH2CH-(:2H., -CH2CH.-C-CH2
CH2CHa CH3-CHz
CHiCHz-CH-CIIzCHzCHa-, -(:
lOH2Q-, CHaC, 2+1 24-, -Cl! One example is lHi8. CH-=CHSi(OCRal- CH.=CHSi (OC.H-1 -CHs;CHS
i (OCHsl 2 CHS CH. CHa"CHSiOCHs [CH, CHz:CHSx (OHI - CHx=CHSx fOH) x CH. CHw:CHCHxSL (OCH31 sCH.=C
HCH. Si (OHI. Preferably a 01-1o alkylene group. Typical specific examples of the silane compound (A) include the following. (:H=:CHOSx (OC
Hs) -CL=CHOSt[OHlz CH2=CHOSl (OCH31 aCH. CH2=CHOC, HaSi(OCL) 3CH.=(
I, HOC2H. Si (QC}13+.CHs CI+2=CHC}120Si(OCH31.?H2・
CHCH2QC2H-Sl(OCJs)! CH. CI■”CHCH20C3HaSl fOcHsl −
Epoxy group, polymeric, saturated monomer B A compound that has an epoxy group and a radically polymerizable unsaturated group in each molecule. Examples of the radically polymerizable unsaturated group include λ, CH. =CRaCOD- CIIt=CRaCG- CH. =CRaC-N ■ CH2=CHCH2-0- CHa=CHO- CH. =CH- In the formula, Ra represents a hydrogen atom or a methyl group. etc. can be mentioned. The radical/polymerizable unsaturated group is CH2/CR, COO
- As the epoxy group-containing polymerizable unsaturated monomer, examples λ
Examples include compounds represented by the following general formulas (I) to (I3). In each formula, R1 has the same meaning as above, and R2 is Cl~.
, Ra represents a C1-20 hydrocarbon group. R1, R2 and Ra in each formula may be the same or different. W is O and an integer from 1 to 10. Specific examples of -fi represented by formulas (I) to (l3) include, for example. Examples of the radically polymerizable unsaturated monomer containing CH, ・CRIC-N- and the epoxy-containing polymerizable unsaturated monomer include those represented by the following general formulas (I4) to (I6). ．． can be mentioned. In each formula, R1 and R2 have the same meanings as above, and R1 and Ra may be the same or different. Specific examples of compounds represented by BQ formulas (I4) to (16) include, for example, in each formula, R+ and R2 have the same meanings as above, and Ra and R2 may be the same or different. Specific examples of the xy-containing polymerizable unsaturated monomers represented by general formulas (17) to (I9) include the following -1
Examples include compounds represented by 1Q formulas (I7) to (19). Examples of the ebony-containing polymerizable unsaturated monomer in which the radically polymerizable unsaturated group is CH2/CRaC-N- include compounds represented by the following formulas (20) to (25). ．． In each formula, Ra, R2, Ra and W have the same meanings as above, and R4 means a C, ~20 alkyl group. Ra
．． ．． Ra. Ra and R4 may be the same or different. Specific examples of the compounds represented by RB formulas (20) to (25) include the following. The radically polymerizable unsaturated group is CI. =CHCH. Examples of the O- epoxy group-containing polymerizable unsaturated monomer include compounds represented by the following general formulas (26) to (29). In each formula, Ra and Ra have the same meanings as above, and R2
may be the same or different. General formula (20) ~
Specific examples of the compound represented by (29) include: As the epoxy group-containing unsaturated monomer in which the radically polymerizable unsaturated group is CH2=CHO-, for example, the following general formula (30
) to (32) can be mentioned. can be mentioned. Examples of the epoxy group-containing unsaturated monomer in which the radically polymerizable unsaturated group is CH2/CH1 include the following general formula (33):
Compounds represented by ~(35) can be mentioned. In each formula, R1 and R2 have the same meanings as above, and R2
may be the same or different. General formula (30) ~
Specific examples of the compound represented by (32) include, for example, in each formula, Ra and R2 have the same meanings as above, and R2
may be the same or different. General formula (33) ~
Specific examples of the compound represented by (35) include: As the epoxy group-containing unsaturated monomer whose radically polymerizable unsaturated group is CHz"CR++, for example, the following general formula (36
) to (40) can be mentioned. In each formula, R+. Ra and Ra have the same meanings as in the preceding sentence, and R1 and R2 may be the same or different. Specific examples of compounds represented by general formulas (36) to (40) have the effect of further improving physical properties, for example. 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 (4l) to (44). ORa In the formula, Ra represents a hydrogen atom or a hydroxyalkyl group. Among the above-mentioned monomers, it is particularly preferable to use monomers containing an alicyclic epoxy group from the viewpoint of curability and the like. That is, when using an unsaturated monomer containing a type 11 epoxy)' group, the reactivity of the open polymerization reaction of the epoxy group is high;
CHa-0-Ri which cures quickly and forms a cured coating film. In the formula, Ra has the same meaning as above.

In the formula, Ra has the same meaning as above, m is an integer of 2 to 8, p is an integer of 2 to 18, and q is an integer of 0 to 7. C.I. =CRa C-OiTl-0to1-1,000T. -Oh-H
(44)n In the formula, R, if has the same meaning as above, T1 and T, are the same or different and represent a divalent hydrocarbon group of 01 to 2o, and S and U each represent O-10 is an integer, where the sum of S and U is l-10. General formula (4l) and (
The "hydroxyalkyl group" in 42) is 01 to 6. Specifically, for example -(:.H40H
．． -C. H. OH. -C. H. Examples include OH. The divalent hydrocarbon group of C I-ffo in general formula (44) is, for example, one CH. −． -CI. -CH.
1CH. -CH. -CH. −． -CH2CI. -C
H. -, CH. ? H■-CH2-CI. C-CI. CH. - CI. -CH. -CH. -CH. -CH-CI. -CH. -C
H. −． -C,. Examples include H20-, CH, -CHbeyuCH*-, etc. -19 As the monomer component of formula (42), for example, CI. =CICI. OH CHi”CHCHtOCH*CHJH CH!=CHCH.O{CH.CH, ($dlCHi”
Examples include CHCHJ{CHaCH20}TH. Examples of the monomer component of general formula (43) include CHx”CCHmCOOCJ-OH CH*:CHCOOCsHaOH CI.=CCH.COO-CJ.-0{C-CH.-C
Hffi-CH,. -CI. -CI! -0tor=yH etc. Examples of the monomer component of general formula (44) include CH. =CCH. COO{CH! CHCH. OhτdC
L=c}IcooICH-CI-Oh=rHCH. =C
CH. COOi CHxCHtO h-TICH-・CH
COO {CH*CHzCH-CHJtrTHCI. =
CCH. COO{CH. CH. Oh-. τ{CH2CH
CH. One example is Ohτ Pass. Furthermore, in addition to the above, hydroxyl group-containing unsaturated monomers represented by the general formulas (41) to (44) and εcabrolactone,
Adducts with lactones such as γ-valerolactone can be used. Other 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, chlorobrene, etc. (b-2) Vinyl ether and allyl ether: for example, ethyl vinyl ether, probyl vinyl ether, isobrobyl vinyl ether, butyl vinyl ether, te
rt-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl. Ether, linear alkyl vinyl ethers such as isohexyl vinyl ether, cyclotyl vinyl ether, 4-methyl-1-pentyl vinyl ether, cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether, phenyl vinyl ether, 0-m-, p-trivinyl ether aryl vinyl ethers such as, aralkyl vinyl ethers such as penzyl vinyl ether, phenethyl vinyl ether, etc. (b-3) Vinyl esters and propenyl esters: for example, vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutate, vinyl caproate, vinyl isocabroate, vinyl barrate, vinyl caproate, and isobropenyl acetate. Brobenyl esters such as imbrobenyl penylbrobenate, etc. (b-4) Esters of acrylic acid or methacrylic acid: for example, methyl acrylate, ethyl acrylate, probyl acrylate, isobrobyl acrylate, butyl acrylate, hexyl acrylate, butyl acrylate, lauryl acrylate, methacrylic acid C1-18 alkyl esters of acrylic acid or meccrylic acid such as methyl, ethyl methacrylate, probyl methacrylate, isoprobyl methacrylate, butyl meccrylate, hexyl meccrylate, methyl meccrylate, lauryl methacrylate: acrylic acid C2-18 alkoxyalkyl esters of acrylic acid or meccrylic acid, such as methoxybutyl, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate. (b-5) Vinyl aromatic compound: for example, styrene, α
-Methylstyrene, vinyltoluene, p-chlorostyrene, etc. (b-6) Others - acrylonitrile, mekurikunitrile, 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 0.1 to 80% by weight of monomer (A), preferably 1 to 60% by weight, and monomer (B) of 0.1 to 80% by weight. is preferably 1 to 90% by weight, preferably 3 to 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 upper range, the physical properties of the cured product tend to deteriorate, which is preferable. do not have. The mixture used in the composition of the present invention contains the silane compound (
A) homopolymer or copolymer of the silane compound (A) and the other polymerizable unsaturated monomer (hereinafter collectively referred to as [polymer (II) J), and the epoxy group-containing polymerizable A homopolymer of the unsaturated monomer (B) or a copolymer of the monomer (B) and the other polymerizable unsaturated monomers (hereinafter collectively referred to as polymer (IIIN)) Other polymerizable unsaturated monomers used for copolymerizing with the silane compound (A) and/or monomer (B) include hydroxyl group-containing polymerizable unsaturated monomers. It is preferable to use this compound because it forms a film with excellent curability.The amount of silane compound (A) used in polymer (II) is about 3 to 100% by weight of the monomers used. %, preferably about 20~
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 (II+) 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 polymers (II) and polymers (III), 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. In addition, the blending ratio of polymer (n) and polymer (II+) is 5% of polymer (II) based on the total amount of both.
-95% by weight preferably 10-80% by weight, and 95-5% by weight of the polymer (If), preferably 90-20% by weight
The range is . When the polymer (II) is less than 5% by weight or the polymer (II+) is more than 95% by weight,
On the other hand, if the polymer (II) is more than 95% by weight or if the polymer (Il+) is less than 5% by weight, the physical properties of the cured product will deteriorate and sagging will easily occur, so it is preferable. do not have. The above-mentioned polymers (I) to (Il1) can be obtained by the same method and conditions as those for general synthesis reactions of acrylic resins, vinyl resins, and the like. As an example of such a synthetic reaction, we will show a method in which each monomer component is dissolved or dispersed in an organic solvent and heated with stirring at a temperature of about 60 to 180°C in the presence of a radical polymerization initiator. Can be done. The reaction time is usually about 1 to 10 hours. Further, as the organic solvent, the same alcohol solvents, ether solvents, ester solvents, hydrocarbon solvents, etc. as mentioned above can be used. When using a hydrocarbon solvent, it is preferable to use another sanding medium in view of solubility. In addition, as the radical initiator, any commonly used radical initiator can be used, and examples include peroxides such as benzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, and azoisoisopropylene. This can include azo compounds such as butyronitrile and azobisdimethylpareguchinitrile. The above polymers (I) to (Il!) have a number average molecular weight of 2
．． 000~2. O of about 0.000 is preferable, and 4
．． 000~so. A grade of ooo is more preferable. 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-diketones (acetylacetone, etc.), acetoacetic esters (methyl acetoacetate, etc.), malonic acid esters (ethyl malonate, etc.), and Ketones having a hydroxyl group (such as guaacetone alcohol), 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, acetoacetic acid esters, β
- Favorable results are obtained using diketones. The aluminum chelate compound has, for example, the general formula RaO-Af-ORs [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 10 alkyl groups, examples include undecyl, dodecyl, tridecyl, tetradecyl, occudecyl, etc., and examples of alkenyl groups include vinyl, allyl, etc. Q9 Aluminum alcoholates represented by formula (45) include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisoptoxide, aluminum Examples include tri-sec-butoxide, aluminum tri-tert-butoxide, etc., and it is particularly preferable to use aluminum triisoproboxide, aluminum tri-SeC monobutoxide, aluminum tri-sec-butoxide, and the like. The titanium chelate compound has, for example, the general formula [wherein, W
and R6 have the same meaning as above. ] For 1 mole of Ti in titanates,
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. - Titanates represented by formula (46) include W
In those with 1, tetramethyl titanate, tetraethyltichnate, tetra n-probyl titanate, tetraisobutyl titanate, tetra n-butyl titanate, tetraisobutyl titanate, tetra tert
-butyl titanate, tetra-n-pentyl titanate, tetra-n-hexyl titanate, tetra-isoctyl titanate, tetra-n-lauryl titanate, etc., especially tetraisobutyl titanate, tetra-n-
Suitable results are obtained using butyl titanate, tetraisobutyltichnate, tetratert-butyltichnate, and the like. In addition, for those where W is 1 or more, tetraisobutyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, ettra-tert
-butyl titanate dimers to llffi forms (w=1 to 10 in general formula (46)) give preferable results. The zirconium chelate compound is, for example, a general [formula, W
and R6 have the same meaning as above. ] A compound capable of forming the above-mentioned keto enol tautomer is mixed with 1 mole of Zr in the zirconates represented by the formula at a molar ratio of usually about 4 moles or less, and is preferably heated if necessary. It can be prepared. Examples of the titanates represented by formula (47) include tetraethyl zirconate, tetra n-probyl diconate, tetraisobuvir zirconate, and tetra n-provir zirconate.
butyl zirconate, tetra sec-butyl zirconate, tetra tert-butyl zirconate, tetra n-bentyl zirconate, tetra tert-bentyl zirconate, tetra tert-hexyl zirconate, tetra n-heptyl zirconate, Tetler n-butyl zirconate, Tetler n-stearyl zirconate, etc., especially Tetler n-butyl zirconate, Tetler n-probyl zirconate, Tetler isobutyl zirconate, Tetler n-butyl zirconate, Tetler see-butyl zirconate. Nate, Tetler T
Favorable results are obtained when ert-butyl zirconate and the like are used. In addition, for wIJ51 or higher, tetraisobutyl zirconate, tetra n-probyl zirconate, tetra n-butyl zirconate, tetra isobutyl zirconate, tetra sec-butyl zirconate, tetra tert-butyl zirconate, etc.
mer to 11-mer (w=1 to 1 in general formula (47)
0) gives suitable results. It may also contain a constituent unit in which these zirconates are associated. Particularly preferred chelate compounds in the present invention include tris(ethylacetoacetate)aluminum, tris(n-pro-and-ruacetoacetate)aluminum, tris(isobrobylacetoacetate)aluminum, tris(n-butylacetoacetate)aluminum, and tris(n-butylacetoacetate)aluminum. ) Aluminum, Isoproboxybis(ethylacetoacetate)aluminum, Diisoproboxylacetoacetatealuminum, Tris(acetylacetonato)aluminum, Tris(Probioxynylacetonato)aluminum, Diisoproboxybrobinylacetonatoaluminum, Acetylacetonato・Aluminum chelate compounds such as bis(probionylacetonato)aluminum, monoethylacetoacetate bis(acetylacetonato)aluminum, tris(acetylacetonato)aluminum; diisobroboxy bis(ethylacetoacetate) thicnate, diisoproboxy bis(acetyl acetonate) titanate, diisobroboxy bis(
Titanium chelate compounds such as acetylacetonato) titanate; zirconium chelate compounds such as tetrakis(acetylacetonato)zirconium, tetrakis(n-propylacetoacetate)zirconium, tetrakis(acetylacetonato)zirconium, tetrakis(ethylacetoacetate)zirconium, etc. can be mentioned. 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 blending amount of the crosslinking reaction curing agent is 10% of the solid content of the polymer (A).
It is appropriate to set the amount to about 0.01 to 30 parts by weight relative to 0 parts by weight. If the amount is less than this range, crosslinking curability 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 0.1-10 parts by weight, and the more preferred amount is 1-5 parts by weight. The composition of the present invention may contain, for example, Epicoat 1, if necessary.
Epoxy group-containing resins such as 00l (manufactured by Shell Chemical); hydroxyl group-containing resins such as styrene allyl alcohol copolymers; monofunctional or polyfunctional epoxy compounds; It is also possible to add other resins such as molecular weight silane compounds and general silicone resins having alkoxysilane groups. Among these, it is advantageous to add a compound containing two or more alicyclic group xylan groups in one molecule, since it is possible to achieve a high solid content of the curable composition without reducing the curability. Such compounds include, for example, compounds represented by the following chemical formulas, adducts of CH20H and the following polyisocyanate compounds (useful polyisocyanate compounds include, for example, hexamethylene diisocyanate or trimethylhexamethylene diisocyanate). aliphatic diisocyanates such as xylylene diisocyanate or isophorone diisocyanate; tolylene diisocyanate; organic diisocyanates themselves such as aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate; or each of these Additives of organic diisocyanates and polyhydric alcohols, low molecular weight polyester resins, water, etc., or polymers of each of the organic diisocyanates listed above, and even incyanates.
Examples of typical commercially available products include "Parnock D-750, -800,
DN-950, -970 or l5-455J [
As mentioned above, Dainippon Ink Chemical Industry (Kawa products), "Desmodule L.NHL.IL or N3390J [Product of Bayer AG, West Germany], "Takenate D-102, -
202, -110N If -123NJ [Takeda Pharmaceutical {Kawa products], "Coronate L.HL.EH or 203" [Nippon Boriurekun Industries ■product] or "Duranate 24A-90CXJ [L8 Kasei Koi [m
(ll], etc.); The curable composition of the present invention may contain inorganic pigments,
Organic pigments etc. can be added. Inorganic pigments include oxide-based (titanium dioxide, red iron oxide, chromium oxide, etc.), sulfate-based (precipitated barium sulfate, etc.), carbonate-based (precipitated calcium carbonate-based, etc.), sulfate-based (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 Ero 1, etc.) and futacyanine-based pigments (Fuclocyanin Blu 1, etc.). In the curable composition of the present invention, an organic solvent may be used if necessary. From the viewpoint of curing speed of the composition, organic solvents having a boiling point of about 150° C. or lower are preferred; It is not limited to. 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, dioxane, ethylene glycol diethyl ether, etc. Examples include ether solvents and alcohol solvents such as Buknol and Probanol. 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 is generally 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~
It can be applied to a wide range of applications, from low-temperature baking types of 100°C to high-temperature baking types of 100 to 160°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 wet-on-wet layered painting methods (so-called 2CIB painting), monocoat painting methods, 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 painting, Mini Bell electrostatic painting, roll painting, and eight-layer 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 to 100°C, it can be sufficiently cured in about 5 minutes to 3 hours. The reason why the 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, 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-o-c-c-OH. This reaction between epoxy groups and hydroxyl groups proceeds at relatively low temperatures. The composition of the present invention contains a hydroxyl group-containing compound as an essential component, and further contains an epoxy group, a silane group, and a metal chelate compound, so that the above reaction proceeds quickly and has excellent low-temperature curability. It is estimated that . The present invention will be explained in more detail with reference to Examples below. 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 purging with nitrogen, the temperature was gradually raised to 80°C. (Part) Xylene 80n-butanol 20CH. =CH-Si- (O
Clhl 3 2 0CI. =CH-
0-C2 City CH. =+1,H-0-(:.The temperature rises to about 1O・0℃ due to HgOH self-heating, but then gradually decreases.Stirring is continued for 16 hours while maintaining the temperature at 80℃.After that, cool and automate. The reaction mixture in the crepe was poured into hebutane to precipitate the resin, and then dried.
A vinyl copolymer (I-a) was obtained. The number average molecular weight (Mn) of the vinyl copolymer (I-a) is 6
,500. Synthesis of vinyl copolymer (r-b) Using the following monomers, a vinyl copolymer B-b with Mn 8.200 was prepared in the same manner as in the case of vinyl copolymer (I-a). ) was obtained. (Part) CHi"CI-CH2-0-C-HaSl focn.
l s 2 0CH. =CHOCOCH3
50 vinyl copolymer (
Synthesis of I-c) First, siloxane macromonomer Ml was synthesized as follows. (Department) H. CSifOcH-1 −
2 7 2 0 (20mof1 CHz=CHSi fOcHsl s
1 4 8flmoi'1 Deionized water 113436% hydrochloric acid
2 Hydroquinone
1 These mixtures were reacted at 80°C for 5 hours to remove water and solvent. The number average molecular weight of the polysiloxane macromonomer obtained 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 amount blended in the following synthesis examples is the amount of the active ingredient as a macromonomer. (Part) Siloxane Macromo/? -M130 CH. =CH-0-C. H@OH
1 5CH. =CH-0-C. H. 3S A vinyl copolymer (■-C) was synthesized using the above monomer in the same manner as the vinyl copolymer (Ia).
The Mn of the vinyl copolymer (I-c) was 9,200. Synthesis of vinyl copolymer (n-a) Using the following monomers, the vinyl copolymer (I-a) was produced in the same manner as vinyl copolymer (I-a). (
II-a) was synthesized. (Part) CH*”CH-0-CsHaSi fOcHal sC
Hi=CH-0-C4HsOH CIyo=CH-OC. Hi CH*"CH-QC4H, Synthesis of vinyl copolymer (II-b) Produced in the same manner as vinyl copolymer (I1a) using the following monomers?iiTn=12. OOO vinyl monomer (II-b) was synthesized.(Part) Siloxane macromonomer M1 40(:H2”CH
-0(:4H60H 1 0CH2
=(:H-OC2H8 2 5C
H2=CH-OC4H. 2 5
Synthesis of vinyl copolymer (III-a) A vinyl copolymer (III-a) with Mn=8.200 was produced in the same manner as vinyl copolymer (I-a) using the following monomers. a) was synthesized. (Part) CH2=lOCOC2H.
5 0CI12=CH-CI. -OC2H4-OH
10 vinyl copolymer (III
Synthesis of -b) Using the following monomers, a vinyl copolymer (III
-b) was synthesized. (Part) CH2=CH-0-C4H* 2o CH. =CH-0-C. H.
Synthesis of 30 vinyl copolymer (III-b) Vinyl copolymer (I-a), (I-b), (+1-a)
, (II-b), (m-a), (III-b)
was dissolved in a mixed solvent of xylene/butyl acetate = 80/20 to give a solid content concentration of 50%, and vinyl copolymer solutions (I-a), (Step-b), (II-a), (
n-b), (III-a), and (nt-b) were created. Example 1 A composition was obtained using the following formulation. Vinyl copolymer solution (I-a) 200 parts Aluminum tris 2 parts (acetylacetone) The above composition was heated in a #4 hot cup for 25 seconds (25°C) with a mixed solvent of xylene/n-bucnol 90/to. The viscosity was adjusted and used for painting. Apply cationic epoxy Densuga Coating O4 to a glue steel plate treated with zinc phosphate using the electrodeposition coating method to a dry film thickness of 20μ and bake at 170℃ 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 pre-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. Vinyl copolymer solution (I-b) (part) Zirconium Example 3 A composition was obtained using the following formulation. (Parts) Vinyl copolymer solution (I-c) 120 Vinyl copolymer solution (III-a) 80 (Dispersion of titanium white was carried out using vinyl copolymer solution (I]l-a).
) Example 4 A composition was obtained with the following formulation. (Part) Vinyl copolymer solution (II-a) 100 vinyl copolymer? Solution (III-a) 100 Example 5 A paste coat for wet-on-wet painting was prepared using the following formulation. (Part) Vinyl copolymer solution (I-c) 140 Vinyl copolymer solution (II-a) 60 Isobutyl acetate Toluene/xylene/n-butanol = 40/4 0/
The viscosity was adjusted to 15 seconds (25°C) using a #4 Ford cup using a mixed solvent of 20%. A top coat for wet painting was created using the following formulation. (Part) Vinyl copolymer solution (II-b) 50 Vinyl copolymer solution CIII-b) 5.0 Vinyl copolymer solution (I-a) 100 Aluminum tris (ethylacetoacetate) 2 Solvent for adjusting viscosity As Swazor #1000'/n-Pukunor=
Using a mixed solvent of 80/20, it was diluted for 25 seconds (at 25°C) in a #4 open cup and used for painting. (゜Swazol #1000: Aromatic solvent manufactured by Cosmo Oil Co., Ltd.) Air spray the above base coat onto the material to a dry film thickness of approximately 18μ, leave it for 5 minutes at room temperature, then apply the above Totsubu coat to a dry film thickness of approximately 40μ It was air sprayed so that Comparative Example 2 A composition was obtained with the following formulation. Vinyl copolymer solution (III-a) 200 parts The evaluation results of the cured films of Examples 1 to 5 and Comparative Examples 1 to 2 are shown in Table 1. Table 1 (Notes) (Note 1) Finished appearance was visually evaluated. (Note 2) Gasoline wiping resistance Nisseki Silver gasoline was moistened with gauze and a 10cm length of the painted surface was vigorously rubbed 8 times. The painted surface was observed. The one with almost no scratches or dullness on the painted surface was considered good. (Note 3) Impact resistance Using a DuPont impact tester, the firing pin tip radius was 1/2 inch, and the weight of the falling bell was 500 g. Test. The maximum height without cracks on the painted surface is shown (in 5 cm increments). (Note 4) Water resistance Immerse the test piece in a constant temperature water bath at 40°C for 240 hours. After taking it out, there will be no gloss or blisters on the paint film. (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 (III) and/or polymer (III). [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.