JPH04108863A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having a specific substituted silicon group in a mixed resin containing a reactive silane group, epoxy group and hydroxyl group as essential functional group components, and capable of producing a cured coating film having excellent physical properties such as weather resistance, acid resistance and stain resistance. CONSTITUTION:The objective composition comprising a mixed resin containing, as the essential functional groups, an epoxy group, hydroxy group and silane group hydrolyzable due to the direct bonding of hydroxysilane radical, 1-5C alkoxyl radical, etc., to silicon atom and having a group expressed by formula I or formula II [R is 1-8C alkyl, aryl, aralkyl or OSI(R')3 (R' is 1-8C alkyl, aryl or aralkyl); (a) is <=2] in one or more kinds of resins among said mixed resin. Furthermore, the composition is preferably blended with a curable catalyst.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a curable resin composition.

(Prior art and its problems) As a method for curing a resin having a hydroxyl group as a functional group,
Conventionally, a method using diisocyanate, melamine resin, etc. as a curing agent 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 the diisocyanate.

On the other hand, when using a melamine resin, baking is required at a high temperature of about 140° C. or higher, and the resulting film has insufficient acid resistance and water resistance.

The present applicant has published Japanese Patent Application Laid-Open No. 63-108049 as a one-component resin composition that is non-toxic and has excellent low-temperature curability.
JP-A No. 63-221123 discloses a curable product prepared by blending a metal chelate compound with a copolymer containing an alkoxysilane group-containing vinyl monomer and an oxirane group-containing vinyl monomer as monomer components. proposed a composition.

However, although this one-component composition has excellent low-temperature curability, it has been found that the weather resistance, acid resistance, and stain resistance of the cured film are insufficient.

An object of the present invention is to provide a curable resin composition that provides a cured film with excellent physical properties such as weather resistance, acid resistance, and stain resistance.

(Means for Solving the Problems) As a result of extensive research in order to obtain a curable resin composition that overcomes the above problems, the present inventors have found that, in particular, resins having organic silane groups in their molecular side chains The present inventors have discovered that a film with excellent physical properties such as weather resistance, acid resistance, and stain resistance can be formed by using this method, and have completed the present invention.

That is, the present invention provides at least one silane group selected from a hydroxysilane group and a hydrolyzable group directly bonded to a silicon atom (hereinafter referred to as a "reactive silane group"), an epoxy group, and a hydroxyl group as essential functional groups. A mixed resin contained as a base component, and at least one selected from the mixed resins.
The seed resin is RRR (wherein R is the same or different and represents a C3-8 alkyl group, an aryl group, an aralkyl group, an -O3i (R-)s group, and a represents an integer of 2 or more.

Here, R' is the same or consists of 01-8 alkyl group, aryl group, or aralkyl group. ) group (hereinafter abbreviated as "organosilane group"), and a curable resin composition obtained by blending this composition with a curing catalyst.

In this specification, a hydrolyzable group directly bonded to a silicon atom is a residue that generates a hydroxysilane group by hydrolysis in the presence of water, such as a C7-5 alkoxy group: phenoxy group, tolyloxy aryloxy groups such as acetoxy, propionyloxy, bukunoyloxy, benzoyloxy, phenylacetoxy, formyloxy, and -N ( R112, ON (R512,0N=
C(R,)2. -NR2CORII, each R8
are the same or different and represent a C1 to B alkyl group, aryl group, or aralkyl group, and R2 represents an H, C, to 8 alkyl group. ), etc. Among the above, 01-5 because of its excellent curability and film physical properties.
An alkoxy group and an acyloxy group are preferred.

The resin used in the composition of the present invention is, for example, a resin composition containing three components: (1) a hydroxyl group-containing compound (A), an epoxy group-containing compound (B), and a reactive silane group-containing compound (C); , and at least one compound selected from the compound (A), the compound (B), and the compound (C) is a resin composition containing an organic silane group (hereinafter abbreviated as "resin composition (1)"). ), (2) a hydroxyl group-containing compound (A), and a compound (D) containing a reactive silane group and an epoxy group; ) is a resin containing an organic silane group (hereinafter referred to as "resin composition (2)").
It is abbreviated as ), (2) A resin composition containing two components: a compound (E) containing a hydroxyl group and a reactive silane group, and an epoxy group-containing compound (B), and the compound (E) and the compound (
Resin composition c, in which at least one compound selected from B) is a resin containing an organic silane group, will be abbreviated as "resin composition (3)" hereinafter. ), (2) A resin composition containing two components: a compound (F) containing a hydroxyl group and an epoxy group, and a compound (C) containing a reactive silane group, and the compound (F) and the compound (C). Examples include a resin composition (hereinafter abbreviated as "resin composition (4)") in which at least one compound selected from the following is a resin containing an organic silane group.

The hydroxyl group-containing compound (A) used in the resin composition (1) is
It has an average of two or more hydroxyl groups in one molecule, and preferably has a number average molecular weight of i,ooo to 200,000, preferably 3,000 to 80,000. If the number of hydroxyl groups is less than 2 on average, the curability (gel fraction) will be poor, which is not preferable. The number of hydroxyl groups is preferably 400 or less on average from the viewpoint of weather resistance, water resistance, etc. If the number average molecular weight is less than 1.000, the physical properties (impact resistance), weather resistance, etc. will be poor, while if it exceeds 200.000, the compatibility with other components will decrease, resulting in uneven curing. This is not preferable because the weather resistance of the coating film becomes inferior.

As the hydroxyl group-containing compound (A), a hydroxyl group-containing compound (A-1) that does not contain an organic silane group and a hydroxyl group-containing compound (A2) that contains an organic silane group will be described below.

Examples of the hydroxyl group-containing compound (A-1) include the following
~■ can be mentioned.

(2) Hydroxyl group-containing vinyl resin A polymer containing the following hydroxyl group-containing polymerizable unsaturated monomer (a) and, if necessary, other polymerizable unsaturated monomers (b) as monomer components.

Hydroxyl group-containing polymerizable unsaturated monomer (a) Examples include compounds represented by the following general formulas (1) to (4).

[In the formula, R3 represents a hydrogen atom or a hydroxyalkyl group. [In the formula, R3 is the same as above. ] (:H2=(:Z O COGmH21,lo(CG,H,pOh-H(3)[
In the formula, Z represents a hydrogen atom or a methyl group, m represents an integer of 2 to 8, p represents an integer of 2 to 18, and q represents an integer of 0 to 7.

] CH2=CZ to 0 (T+-o)r-+T2-7H(4) [wherein Z is the same as above. T and T2 are the same or different and represent a divalent hydrocarbon group having 1 to 20 carbon atoms. S and ■ each represent an integer of 0 to 10. However, the sum of S and ■ is 1 to 10. ] In the general formulas (1) and (2), the hydroxyalkyl group is a hydroxyalkyl group in which the alkyl moiety has 1 to 6 carbon atoms. Specifically, C2H4OH, -C3H6
Examples include 0H1-C4H, OH, and the like.

The divalent hydrocarbon group having 4 to 20 carbon atoms in general formula (4) is, for example, -CH, -(CH212-1-(
CH2)3-, -CR2CH2H2-1CH.

CH.

-(CH2)iCH((:R2)-1-CH2CH2C
CH2CH2-CH,CH.

Ru.

As the monomer component of general formula (1), for example, CH,=
Examples include CH0H CHz=CI(0(CH2)40H).

As the monomer component of general formula (2), for example, CH2=(:H(:R20H CH2=CHCH20CHzCHiO)lCH2=CH
CH20(CH2CH20)yHCH2=CHCH20
iCH2CH20)T), etc.

As the monomer component of general formula (3), for example, CH2=C(CH3)C00C2H40HCH2=CH
COOC,H,OH CH2=C(CH31C00CsH6-0(C-CH2
Examples include CH2-CH2CH and CH20h-TH.

As the monomer component of general formula (4), for example, CH2・CfcH3) Coo-fcH2cHcH30
hmadCH2・C)Iooo((1:I(2G)120
←−τHCM2=C(CH3)COOiCH2CH20
)y=rHCH2・CHCOO(CH2CH2CH20
H = HCH2 = C(CH, l Coo(CH2Cl,
Oh=τ(CH2CHCH30h-TH, etc. can be mentioned.

Furthermore, in addition to the above, hydroxyl group-containing unsaturated monomers represented by the general formulas (1) to (4), ε-brolactone, γ
-Adducts with lactones such as valerolactone can be used.

Other polymerizable unsaturated monomers (b) The following (b-1) to (b-6) can be mentioned.

(b-1) Olefin compounds 0 such as ethylene, propylene, butylene, isoprene, chloroprene, etc.

(b-2) Vinyl ethers and allyl ethers, such as ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, te
alkyl vinyl ethers such as rt-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl 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, 0-m- and p-trivinyl ethers, aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether, and the like.

(b-3) Vinyl esters and propenyl esters, such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate, vinyl esters such as vinyl parsitate, vinyl caprate, and isopropenyl acetate. Propenyl esters such as isopropenyl propionate, etc.

(b-4) ester of nialic acid or methacrylic acid,
For example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, Alkyl esters of acrylic acid or methacrylic acid having 1 to 18 carbon atoms such as butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate: methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxy methacrylate Alkoxyalkyl esters of acrylic acid or methacrylic acid having 2 to 18 carbon atoms, such as ethyl, ethoxybutyl acrylate, and ethoxybutyl methacrylate.

(b-5) Vinyl aromatic compound: for example, styrene, α
-Methylstyrene, vinyltoluene, p-chlorostyrene, etc.

(b-6) Others, such as acrylonitrile and methacrylonitrile.

■Polyester resin containing hydroxyl groups Polybasic acids (e.g. (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, (anhydrous) maleic acid, (anhydrous) pyromellitic acid, (anhydrous) trimellitic acid, (anhydrous) succinic acid, cepacic acid , azelaic acid, dodecanedicarboxylic acid, dimethyl isophthalate, dimethyl terephthalate, and other compounds having 2 to 4 carboxyl groups or carboxylic acid methyl ester groups in one molecule), and polyhydric alcohols (e.g., engineered tisine glycol, Alcohols having 2 to 6 hydroxyl groups in one molecule such as polyethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, glycerin, tricyclodecane dimethanol)
It can be obtained by subjecting them to an ester reaction or transesterification reaction. In addition to the above, monobasic acids (for example, fatty acids such as castor oil fatty acid, soybean oil fatty acid, tall oil fatty acid, linseed oil fatty acid, etc., benzoic acid, etc.) can be used as necessary.

■Hydroxyl group-containing polyurethane resin Free from isocyanate groups obtained by modifying hydroxyl group-containing vinyl resins, hydroxyl group-containing polyester resins, etc. with polyisocyanate compounds (e.g., tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc.) resin.

monomer (C) having a group and a radically polymerizable unsaturated group, the hydroxyl group-containing radically polymerizable unsaturated monomer (a), and optionally the other radically polymerizable unsaturated monomer (
A copolymer obtained by radical polymerization of b) can be used.

Specifically, the monomer (C) is an ethylenically unsaturated carboxylic acid compound such as (meth)acrylic acid or 2-carboxyethyl (meth)acrylate, and one or more organic silane groups in one molecule. A monomer obtained by reacting an equimolar amount of a silane compound (2) with one or more functional groups (e.g., hydroxyl group, silanol group, alkoxysilane group, epoxy group, etc.) in one molecule that reacts with the carboxyl group in the carboxylic acid compound. the monomer (a), one or more organosilane groups in one molecule, and the monomer (a)
A functional group (e.g. isocyanate group, carboxyl group, mercapto group, amine group, etc.) that reacts with the hydroxyl group in
A monomer obtained by equimolar reaction with a silane compound (1) having one or more silane compounds in the molecule, an isocyanate group-containing monomer (
For example, α,α-dimethylisopropenyl benzyl isocyanate, incyanatoethyl (meth)acrylate, (meth)acryloyl isocyanate, etc.) or by adding equimolar amounts of monomer (a) and a diisocyanate compound (such as isophorone diisocyanate). Examples include isocyanate group-containing monomers, and monomers obtained by reacting one or more organic silane groups and a silane compound @ having a hydroxyl group in one molecule.

The above-mentioned silane compounds (■ to ■) include, for example, 1,000 H
2) It can be used by appropriately selecting from linear silane compounds represented by -r-YR and cyclic silane compounds represented by .

In each of the above formulas, X is a hydroxyl group, an alkoxyl group, OR
"U group, -R" C0OH group, -R'NH-R"-NH2
group, -R=SH group or R'NGO group, Y represents a carboxyl group, hydroxyl group, epoxy group or -R'NGO group, n represents an integer from 0 to 300, and r represents an integer from 1 to 10. , t represents an integer of 0 to 300, k represents an integer of 0 to 6, h represents an integer of O or 1, and 1 represents an integer of 0 to 6. Here, R'' represents a C3-12 divalent hydrocarbon group substituted or unsubstituted with oxygen or nitrogen, and U represents an alicyclic epoxy group. R, R' and a have the same meanings as above. show.

Preferred specific examples of the above-mentioned silane compounds 1 to 2 include 0H3i fcH-13, H, C03i (CH313
,HOCJ6S1 fcHxl 3,HOC3H,Si
(OSi (CH-) -1s, HOCJgSi [
CLl zO3i (CHil 2IOC3H6S1
[CH-1foSi(CHs) 21x, HOC3Ha
Si (CH3) 2(OSi (CH312) 1゜OSi fcH3)3, Si (CH31J (Si
(CH3] 20) xsi (CH3) (CJJH
CJ4NH2)OSi (CHxl −, Si (CH3) 3 (OSi (CHil 216
5cJsOcJ40)1,Si(CHils[O
Si (CLI 2113 xcJ60cJJH, Si
(CH,) , 0 (Si (CH3) 20) 2
Si (CH,,) (C3HaOHI OSi (C
H313, Si (CH31g, Si (CH, l , 0 (Si fcH, l 20)
sSi fcH31[C3H6COOH)O-3l
fcHx) 3, Sl[CHil 3o (Si(C)1312013
SL (CH31 [CJ6SHI OSi (CH31
3, OSi fcH3)3, and the like.

Further, as a preferable specific example of the monomer (C), for example, CI (2=ccH-COOC3HsSl fcH-)
s, CH2 to CHCOOCJsSi [CHil m,
CH2”CCHiCOOCJaSl (OSi (CH
al 3) s, CH2”CHCOOCJaSl (O
Si [CH3) -1s, CH2”CCH3CO0C
3) 163ICH3FO3I (CH31-12, CH
2・CCHxCOOCsHsSx (CH312(OS
i (CH31il +.OSi [CH31z, C,
Hz=CHCOOC-H6Si (CH312(OSi
(CJI-1211゜OSi (C)l-)-1CH
2・CCH3CO0CsHaS1 (CHi) (O8
1(CHil fC-Htl) 50O5i fcH
315 CH2”CCHxCOOCJaSl(OSi (CH-
) 2] 20Si fcHslg, CH3 CH2=CCH3COOC2H-OC3H6[Sl f
cH, l 2o) +, ssx (CHsl s , C
H.

OSi (CH-15 CH2・CCH3CO0CH2CHCH20CJsSi
fO3x fcH31it -OHCH.

OSi fcH,l 8, CH2・CCH3C0NHCOOCsH6SiCH3(
OSi (CHs) il t, CH2=CHC0NH
Examples include COOC3H, kidney A stroke, and yυ force.

Moreover, as the hydroxyl group-containing compound (A-2), in addition to those mentioned above, the hydroxyl group-containing compound (A1) and the compound (
The above-mentioned silane compounds ① to O having a group (for example, a silanol group, an alkoxysilane group, a carboxyl group, an incyanate group, etc.) that reacts with the hydroxyl group in A-1) are reacted, and the reaction results in the formation of a compound (A-1). A compound obtained by reacting with a portion of the hydroxyl groups in compound (A-1) such that hydroxyl groups remain in the compound (A-1) can also be used.

The epoxy group-containing compound (B) has an average of 2 to 1 molecule
It has 300 epoxy groups and preferably has a number average molecular weight of 120 to 200,000, preferably 240 to 80.
000. If the number of epoxy groups is less than 2 on average, the curability and impact resistance will be poor, which is not preferable. It is difficult to obtain a compound with a number average molecular weight of less than 120; - If the number average molecular weight exceeds 200,000, the compatibility with other components will be poor, resulting in a decrease in the weather resistance of the resulting coating film. So I don't like it.

Epoxy group-containing compound (B-
Specific examples of 1) include compounds represented by the following general formula.

NO2C [In the formula, R4 is a hydrogen atom or a methyl group, R is a carbon number of 1 to
8 represents a divalent hydrocarbon group. R4 and R6 may be the same or different.

Further, R2 has the same meaning as above.

R6 is the same or different and has a hydrogen atom or a carbon number of 1 to 4
represents an alkyl group. W represents O and an integer of 1 to 10.] Here, the divalent hydrocarbon group having 1 to 8 carbon atoms can be selected from the above-mentioned divalent hydrocarbon groups having 1 to 20 carbon atoms.

Specific examples of the compounds represented by flQ formulas (5) to (12) include, for example.

In addition to the above, for example, the following can be used.

etc.

In addition, as the epoxy group-containing compound (B-1), an epoxy group-containing polymerizable unsaturated monomer (d) and, if necessary, other polymerizable unsaturated monomers (b) are used as monomer components. Polymers can also be used.

As the epoxy group-containing polymerizable unsaturated monomer (d), 1
It is a compound that has an epoxy group and a radically polymerizable unsaturated group in its molecule. Radical polymerizability [In each general formula, R2 is a hydrogen atom or a methyl group, R8 is a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R8 is a divalent hydrocarbon having 1 to 10 carbon atoms. Indicates the group. J represents an integer from 0 to 10. ] Monomers represented by (for example, those described in JP-A-2-73825) can be suitably used.

Epoxy group-containing compound containing an organic silane group (B-2
), for example, the above epoxy group-containing compound (B-1
) and the silane compounds ① to ＠ having a group (for example, a carboxyl group, a mercapto group, an amine group, etc.) that reacts with the epoxy group in the compound (B-1), and this reaction 1) Those obtained by reacting with a part of the epoxy group in compound (B-1) so that the epoxy group remains in the monomer (a), monomer (d)
and, if necessary, a copolymer containing a hydroxyl group and an epoxy group obtained by subjecting the monomer (b) to a radical polymerization reaction, and the above-mentioned compound having a group (for example, incyanate group, etc.) that reacts with the hydroxyl group in the copolymer. Those obtained by reacting silane compounds 1 to 0 can be used.

The reactive silane compound (C) has an average of one or more reactive silane groups in one molecule, and if the average number of reactive silane groups is less than one, the curability (gel fraction) will be poor. Become. In addition, when the number of reactive silane groups increases, the reaction between the reactive silane groups and epoxy groups occurs preferentially, and the number of epoxy groups required for reaction with hydroxyl groups decreases, resulting in poor curing properties, impact resistance, etc. The number of reactive silane groups in one molecule is preferably 2.500 or less on average.

The reactive silane compound (C) has a number average molecular weight of 104 to 2.
00.000 is used. It is difficult to obtain those having a number average molecular weight of less than 104, and if it exceeds 200,000, the compatibility with other components is poor and a coating film with excellent weather resistance etc. cannot be obtained.

A reactive silane compound containing no organic silane group (C-1
) Specific examples include the following (1) and (2).

(2) Reactive silane compounds Compounds represented by the following general formulas (29) to (31) can be mentioned.

Y'Y'-3i-Y' (29
) Y'Y'-3i-Y' (30) Y'R+-3t-Y' (31) Y' [In each formula, Y' is the same or different and represents a hydrogen atom, a hydroxyl group, or a hydrolyzable group. R, is the same as above,
R1 may be the same or different. ] Specific examples of the compounds represented by general formulas (29) to (31) include dimethyldimethoxysilane, dibutyldimethoxysilane, di-1so-propyldipropoxysilane, diphenyldibutoxysilane, diphenyljethoxysilane, and diethyldisilanol. , dihexyldisilanol methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, phenyltriethoxysilane, phenyltributyloxysilane, hexyltriacetoxysilane, methyltrisilanol, phenyltrisilanol,
Tetramethoxysilane, tetraethoxysilane, tetrapropioxysilane, tetraacetoxysilane, G1
Examples include so-probioxydivaleroxysilane, tetrasilanol, and the like.

In addition to those mentioned above, condensates of the above-mentioned polysilane compounds can also be used.

■Polymer-reactive silane group-containing radically polymerizable unsaturated monomer (e)
A polymer containing as a monomer component, and if necessary, another polymerizable unsaturated monomer (b) can be used.

As the monomer (e), RIOR+2 CH2:C-A-R+ +I5l-OFK-R14 (3
2) ○ is a hydrogen atom or a methyl group, R1□ is a C1-6 divalent aliphatic saturated hydrocarbon group, R12 and RR3 are the same or different and are a C7-6 alkyl group, aryl group, aralkyl group, R14 represents a hydrolyzable group or a hydroxy group, and R14 represents a C3-6 alkyl group or a hydrogen atom. y is 1~l
O is an integer. ) can be used, specifically, for example, γ-
(meth)acryloxypropyltrimethoxysilane, γ
-(meth)acryloxyethyltriethoxysilane, γ
-(meth)acryloxypropyltriethoxysilane,
γ-(meth)acryloxypropyltripropoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylphenyldimethoxysilane, γ-(meth)acryloxybutylphenyldimethoxysilane, Preferred examples include γ-(meth)acryloxypropyltrisilanol and 2-styrylethyltrimethoxysilane.

In addition to the above monomer (e), the general formula (where RI5 is an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a phenyl group, and R36, R1□ and R+a are alkoxyls having 1 to 4 carbon atoms) or hydroxyl group) 70 to 99.999 mol% of compound (A) represented by the general formula % formula %) (wherein, R19 is a hydrogen atom or a methyl group, and R2°, R21 and R2 , represents an alkoxyl group having 1 to 4 carbon atoms or an aliphatic hydrocarbon group having 1 to 8 carbon atoms.However, R2ov, R21 and R2゜ are not all aliphatic hydrocarbon groups having 1 to 8 carbon atoms. .X is 1~
Indicates an integer of 6. ) is reacted with 30 to o, ooi mol% of the compound (B) represented by the formula (B), and an average of two or more free functional groups selected from hydroxyl groups and alkoxyl groups are present per molecule of the reactant, and The average molecular weight of the reactant is 400-100.00
A polysiloxane macromonomer having a molecular weight of 0 (for example, those described in JP-A-62-27513) can be suitably used.

Reactive silane compound containing an organic silane group (C-2)
For example, the monomer (e), the monomer (c)
and, if necessary, a copolymer containing monomer (b) as a monomer component: monomer (a), monomer (c), and, if necessary, monomer (b), subjected to a radical polymerization reaction. A product obtained by reacting a copolymer containing a hydroxyl group and a reactive silane group with the silane compounds (1) to (O) having a group (for example, an isocyanate group) that reacts with the hydroxyl group in the copolymer. can be used.

The compound (D) containing an epoxy group and a reactive silane group used in the resin composition (2) has an average of 2 to 30 in one molecule.
It has 0 epoxy groups and an average of 1 or more reactive silane groups per molecule, and if the number of epoxy groups and reactive silane groups is below the above range, curability, impact resistance, etc. will be poor. I don't like it because it becomes a thing. On the other hand, as mentioned above, when the number of reactive silane groups increases, the epoxy groups are consumed and fewer epoxy groups are required for the curing reaction of hydroxyl groups, resulting in poor curing properties of the resin composition. The number of silane groups in one molecule is preferably 2.500 or less on average. Further, the number average molecular weight of compound (D) is 1.000 to 200.000, preferably 3.000.
~80.000, and less than 1.000, hardenability,
If it exceeds 200,000, the compatibility with other components decreases, which is not preferable.

As the compound (D-1) that does not contain an organic silane group,
For example, there may be mentioned a copolymer containing the monomer (e), the monomer (d), and, if necessary, another monomer (b) as monomer components.

The compound (D-2) containing an organic silane group includes monomer (C), monomer (d), monomer (e) and, if necessary, monomer (b) as monomer components. Examples include copolymers.

The hydroxyl group- and reactive silane group-containing compound (E) used in the resin composition (3) has an average of two or more hydroxyl groups in one molecule and an average of one or more reactive silane groups in one molecule. If the hydroxyl group and reactive silane group are below the above range, the curability, impact resistance, etc. will be poor, which is not preferable. From the viewpoint of weather resistance, water resistance, etc., the hydroxyl group is 1
It is preferable that the number of reactive silane groups is 400 or less in a molecule, and from the viewpoint of curability (gel fraction), it is preferable that the number of reactive silane groups is 2.500 or less in one molecule. Compound (E
) has a number average molecular weight of 1.000 to 200.000, preferably 3.000 to 80.000, l,000
If it is less than 200, the weather resistance etc. will be poor.
If it exceeds 000, the compatibility with other components will decrease, which is not preferable.

As the compound (E-1) that does not contain an organic silane group,
Monomer (a), monomer (e) and, if necessary, monomer (
Examples include copolymers containing b) as a monomer component.

As the compound (E-2) containing an organic silane group, monomer (a), monomer (C), monomer (e) and, if necessary, monomer (b) are used as monomer components. Examples include copolymers.

The hydroxyl group- and epoxy group-containing compound (F) used in the resin composition (4) has an average of two or more hydroxyl groups in one molecule, and one
It has an average of two or more epoxy groups in the molecule, and if the hydroxyl group and epoxy group are below the above range, the curability, impact resistance, etc. will be poor, which is not preferable. The number of hydroxyl groups in one molecule is 2.5 from the viewpoint of weather resistance, water resistance, etc.
It is preferable that the number is 00 or less. The number average molecular weight of compound (F) is 1.000 to 200.000, preferably 3.000 to 80,000; less than 1.000 results in poor weather resistance, while more than 200.000 results in poor weather resistance. This is not preferable because it reduces compatibility with other components.

As the compound (F-1) that does not contain an organic silane group,
Monomer (a), monomer (d) and, if necessary, monomer (
Examples include copolymers containing b) as a monomer component.

The compound (F-2) containing an organic silane group includes monomer (a), monomer (C), monomer (d), and if necessary, monomer (b). Examples include copolymers used as body components.

Each of the above-mentioned ingredients can be obtained by conventionally known methods. That is, reactions between hydroxyl groups and incyanate groups, condensation reactions between silane groups, copolymerization reactions, etc. can be carried out based on conventionally known methods. For example, the reaction between a hydroxyl group and an isocyanate group is sufficient for about 30 to 360 minutes at room temperature to about 130°C. The condensation reaction of silane groups is carried out in the presence of an acid catalyst (e.g. hydrochloric acid, sulfuric acid, formic acid, acetic acid, etc.) with a
Heating at about 0°C for about 1 to 24 hours is sufficient. In addition, the copolymerization reaction can be carried out using the same method and conditions as those used for general synthesis reactions of acrylic resins, vinyl resins, and the like. An example of such a synthesis reaction is a method in which each monomer component is dissolved or dispersed in an organic solvent and heated while stirring at a temperature of about 40 to 180°C in the presence of a radical polymerization initiator. can. The reaction time may normally be about 1 to 24 hours. Further, as the organic solvent, one that is inert to the monomer or compound used, such as an ether solvent, an ester solvent, a hydrocarbon solvent, etc., can be used. When using a hydrocarbon solvent, it is preferable to use other solvents in view of solubility. Further, as the radical polymerization initiator, any commonly used initiator can be used, and examples thereof include benzoyl peroxide, t-
Examples include peroxides such as butyl peroxy-2-ethylhexanoate, and azo compounds such as azoisobutyronitrile and azobisdimethylvaleronitrile.

In the resin composition of the present invention, when a resin composition into which an alicyclic epoxy group is introduced as an epoxy group is used, the addition reaction of the epoxy group to the hydroxyl group is rapid, and the effect of improving the curability of the catalyst can be obtained.

In the resin composition of the present invention, the content of organic silane groups is about 1 to 70% by weight, preferably about 5 to 60% by weight in the mixture containing the above-mentioned silane compounds ■ to ◎ or their unsaturated monomers as constituent components. can have a range of If the content is less than the above range, the film will have poor scratch resistance, stain resistance, weather resistance, acid resistance, etc. If it exceeds the above range, the unit price of the resin composition will become high, which is not practical. Moreover, manufacturing becomes difficult.

The resin composition of the present invention can be used, for example, in 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. Used in the form of solutions, dispersed types, non-aqueous dispersion types, etc. dissolved or dispersed in solvents, alcoholic solvents such as butanol and propatool, aliphatic hydrocarbons such as pentane, hexane, heptane, etc. .

The non-aqueous curable resin composition described above uses at least one of the mixed resins of the present invention as a dispersion stabilizer, and in the presence of the dispersion stabilizer, it contains one or more radically polymerizable unsaturated monomers. A non-aqueous dispersion is obtained by adding a polymerization initiator to an organic solvent in which the monomer and dispersion stabilizer are dissolved, but the polymer particles obtained from the monomer are not dissolved, and a polymerization reaction is carried out. can be manufactured. (However, if not all of the mixed resin is used as a dispersion stabilizer, add the remaining resin to the obtained non-aqueous dispersion so that all resin components of the mixed resin are contained in the non-aqueous dispersion.) Mix as desired.

All the monomers described above can be used to form the polymer that is the particle component of the non-aqueous dispersion. Preferably, the polymer serving as the particle component is a copolymer containing a large amount of highly polar monomer, since it must not be dissolved in the organic solvent used. Namely, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxy (meth)acrylate, hydroxypropyl (meth)
It is preferable to contain a large amount of monomers such as acrylate, [methacacrylamide, acrylic acid, methacrylic acid, itaconic acid, styrene, vinyltoluene, α-methylstyrene, and N-methylol(meth)acrylamide. Further, the particles of the non-aqueous dispersion can be crosslinked if necessary. An example of a method for crosslinking the inside of the particles is to copolymerize a polyfunctional monomer such as divinylbenzene or ethylene glycol dimethacrylate.

Although the dispersed polymer particles produced by the polymerization are not substantially dissolved in the organic solvent used for the non-aqueous dispersion, it is a good solvent for the dispersion stabilizer and the radically polymerizable unsaturated monomer. things are included. In general, aliphatic hydrocarbons are preferably used in combination with aromatic hydrocarbons and alcohol, ether, ester, or ketone solvents such as those mentioned above. Furthermore, trichlorotrifluoroethane, metaxylene hexafluoride, tetrachlorohexafluorobutane, etc. 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-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, t
Examples include peroxide-based initiators such as ert-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. I can do it. The formulation of the dispersion stabilizing resin to be present during the above polymerization can be selected from a wide range depending on the type of resin, but in general, 3 to 3 to 100 parts by weight of the radically polymerizable unsaturated monomer are added to 100 parts by weight of the resin. A suitable amount is about 240 parts by weight or 5 to 82 parts by weight.

In the present invention, the dispersion stabilizer resin and the polymer particles can also be combined.

The non-aqueous dispersion resin composition described above is a non-aqueous dispersion in which a dispersion stabilizer resin is dissolved in an organic solvent, and a solid phase, which is a polymer particle formed by polymerizing a radically polymerizable unsaturated monomer, is stably dispersed in a liquid phase. It is an aqueous dispersion that can significantly increase the solid content during coating, and also increases the viscosity after coating, causing sagging and
It is possible to form a film with excellent finished appearance and no run-off. Furthermore, the formed film is a light and chemically stable film in which the continuous phase of the film has an organic silane group, and furthermore, the polymer particle components in the film are stabilized by the continuous phase, and the film is stable. Since the particles are reinforced by the particle component, a film with excellent mechanical properties such as impact resistance can be formed.

In the curable composition of the present invention, the resin composition may contain a curing catalyst. Examples of the curing catalyst include metal alkoxides in which an alkoxy group is bonded to metals such as aluminum, titanium, zirconium, calcium, and barium; and chelate compounds capable of forming a keto-enol tautomer to the metal alkoxides. metal chelate compounds; AβCρ3, A'42 (C2
Hs 12 Cj2-1TICI24, ZrCj2+,
5nCf14. FeCn4. BF3. BF3 (QC2H
Lewis acids such as J2; protonic acids such as organic protonic acids (methasulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), inorganic protonic acids (phosphoric acid, phosphorous acid, phosphinic acid, sulfuric acid, etc.); aluminum silicate; Compounds having a 5i-0-Aj2 bond such as the following can be suitably used. Among the above, metal chelate compounds are preferred, and furthermore, diisopropoxyethylacetoacetate aluminum, tris(ethylacetoacetate) aluminum, isopropoxy bis(ethylacetoacetate) aluminum, monoacetylacetonate
Bis(ethylacetoacetate)aluminum, tris(n-pro and ruacetoacetate)aluminum, tris(n-butylacetoacetate coaluminum, monoethylacetoacetate bis(acetylacetonato)aluminum, tris(acetylacetonato)aluminum Aluminum chelate compounds such as tris(propionyl acetonato)aluminum, acetylacetonato bis(propionyl acetonato)aluminum, etc. )
Titanium chelate compounds such as titanium, tetrakis(n-propylacetoacetate)zirconium, tetrakis(acetylacetonato)zirconium,
Zirconium chelate compounds such as tetrakis(ethyl acetoacetate) zirconium and the like are preferred.

In the resin composition (1), the blending amount of each component is 5 to 95% by weight of the hydroxyl group-containing compound (A), preferably 5 to 95% by weight, based on the total amount of the hydroxyl group-containing compound (A) and the epoxy group-containing compound (B). 20 to 80% by weight, epoxy group-containing compound (B
)95 to 5% by weight, preferably 80 to 20% by weight. If the ratio of both is outside this range, low temperature curability will deteriorate, which is not preferable. In addition, reactive silane compounds (C
) is 0.1 to 150 parts by weight based on 100 parts by weight of the hydroxyl group-containing compound (A) and the epoxy group-containing compound (B).
Parts by weight, preferably 1 to 20 parts by weight. If the reactive silane compound (C) is less than 0.1 part by weight, the curability will be significantly reduced, and if it exceeds 50 parts by weight, the remaining reactive silane compound (C) will reduce the solvent resistance of the coating film, so it is preferable. do not have. The curing catalyst is based on 100 parts by weight of the total amount of the hydroxyl group-containing compound (A) and the epoxy group-containing compound (B),
The amount is 0.01 to 30 parts by weight, preferably 0.1 to 5 parts by weight. If the amount of the curing catalyst is less than 0.01 parts by weight, the curability will decrease, while if it exceeds 30 parts by weight, the water resistance of the coating will decrease, which is not preferable.

In the resin composition (2), the hydroxyl group-containing compound (A) is 5 to 95% by weight, preferably 20 to 80% by weight, based on the total amount of the hydroxyl group-containing compound (A) and the epoxy group- and silane group-containing compound (D). %, epoxy group- and silane group-containing compound (D) 95-5% by weight, preferably 80-20% by weight
shall be. If the ratio of both is outside this range, the curability, especially the low temperature curability, will deteriorate, which is not preferable. Further, the curing catalyst is based on 100 parts by weight of the total amount of the hydroxyl group-containing compound (A) and the epoxy group- and silane group-containing compound (D).
The amount is 0.01 to 301 parts by weight, preferably 0.1 to 5 parts by weight. Curing catalyst is 0
．． If the amount is less than 0.1 part by weight, the curability will decrease, and if it exceeds 30 parts by weight, the water resistance of the coating will decrease, which is not preferable.

In the resin composition (3), the hydroxyl group- and silane group-containing compound (E) is 5 to 95% by weight, preferably 20% by weight, based on the total amount of the hydroxyl group- and silane group-containing compound (E) and the epoxy group-containing compound (B). ~80% by weight, 95-5% by weight of epoxy group-containing compound (B), preferably 80-20% by weight
shall be. If the ratio of both is outside this range, the curability, especially the low temperature curability, will deteriorate, which is not preferable. In addition, 001 to 30 parts by weight of the hydroxyl group- and silane group-containing compound (E) and the epoxy group-containing compound (B)
The amount is preferably 0.1 to 5 parts by weight. If the amount of the curing catalyst is less than 0.01 parts by weight, the curability will decrease, while if it exceeds 30 parts by weight, the water resistance of the coating will decrease, which is not preferred.

In the resin composition (4), based on the total amount of the hydroxyl and epoxy group-containing compound (F) and the silane compound (C), 5 to 95% by weight of the hydroxyl and epoxy group-containing compound (F),
Preferably 20 to 80% by weight, and silane compound (C)
The content is 95-5% by weight, preferably 80-20% by weight.

If the ratio of both is outside this range, the curability, especially the low temperature curability, will deteriorate, which is not preferable. The curing catalyst is a hydroxyl group- and epoxy group-containing compound (F) and a silane compound (C)
The amount is 0.01 to 30 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount. Curing catalyst is 0.
If it is less than 0.01 parts by weight, the curability will decrease, while if it exceeds 30 parts by weight, the water resistance of the coating will decrease, which is not preferable.

The resin composition of the present invention may optionally contain an ultraviolet absorber,
Antioxidants, light stabilizers, inorganic pigments, organic pigments, etc. can be added. Inorganic pigments include oxides (titanium dioxide, red iron oxide, chromium oxide, etc.), hydroxides (alumina white, etc.), sulfates (precipitated barium sulfate, etc.), and carbonates (sedimentated calcium carbonate, etc.). ), sulfate-based (clay, etc.)
, carbon-based (carbon black, etc.), metal powder (aluminum lamb powder, bronze powder, zinc powder, etc.). Organic pigments include azo pigments (Lake Red, Fast Yellow, etc.) and phthalocyanine pigments (Phthalocyanine Blue, etc.).
can be mentioned.

The resin composition of the present invention can be easily crosslinked and cured at a low temperature of 100°C or lower. For example, when cured at room temperature without any heating, it can be sufficiently cured usually 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 curable resin composition of the present invention can be suitably used in paints, adhesives, inks, and the like.

When the resin composition of the present invention is used as a coating material, there are no particular limitations on the coating method, and for example, it can be coated by a general coating method such as spray coating, roll coating, or coating. 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 resin composition of the present invention is suitably applied. For painting the automobile body, for example, the curable resin composition of the present invention can be applied as a top coat either directly or after applying an intermediate coat to the surface of the electrodeposited film. The top coat may be, for example, solid color,
There are methods such as clear/metallic base coat (2 coats, 1 bake, 2 coats, 2 bakes, 3 coats, 2 bakes, etc.).

Since the curable resin composition according to the present invention uses a resin having a specific organic silane group in the side chain, it exhibits remarkable effects in physical properties such as weather resistance, acid resistance, and stain resistance. It is something.

EXAMPLES The present invention will be explained in detail with reference to Examples below. "Part J" and "%" in the examples are based on weight.

Examples 1 to 8 Copolymers (A) to (N) (number average molecular weight 10.000) shown in Table 1 were blended in the proportions shown in Table 2 to obtain the results of Examples 1 to 8. A curable resin composition was obtained. The film performance of the composition is shown in Table 3. Silane macromonomer, 2.720 parts of methyltrimethoxysilane, 256 parts of γ-methacryloxypropyltrimethoxysilane, 1 part of deionized water
．． A mixture of 134 parts of 30% hydrochloric acid, 2 parts of hydroquinone, and 1 part of hydroquinone was reacted at 80° C. for 5 hours. The obtained polysiloxane macromonomer had an average molecular weight of 2.000, and had on average one vinyl group (polymerizable unsaturated group) and four hydroxyl groups per molecule.

Organosilane monomer〇: CH2:CCHsCOOCJaSl(OSi(CHxl
i) sOrganosilane monomer■ CH2=CCH,C0NHCOOC,H,5iCH,(
OSi (CH,] 2) 2 silane monomer ■ Hydroxyl group-containing copolymer with a number average molecular weight of 10.000 obtained by polymerizing 40 parts of 2-hydroxypropyl methacrylate, 30 parts of n-butyl methacrylate, and 30 parts of styrene. A hydroxyl group- and organic silane group-containing polymer (R) was obtained by reacting 10 parts of . A cured resin composition was obtained by blending the polymer (L) in the proportions shown in Table 2. The film performance of the composition is shown in Table 3.

Comparative Example 1 A composition was obtained with the formulation shown in Table-2. The film performance of the composition is shown in Table 3.

Organic silane monomer■ CH2・CCH3CO0CiHsSi fcH3) 2
(OSi (CH312t +.OSi fcHzl
z Example 9 Film preparation method Using a mixed solvent of xylene/n-butanol = 80/20, the viscosity was adjusted to 25 seconds using a #4 Ford Cup (
25°C) and used for spray painting.

Glass plates, mild steel plates, and aluminum plates were used as coating materials depending on the test items.

The coating was applied using an air spray gun so that the film thickness after drying was approximately 60μ, and after setting for 15 minutes at room temperature,
It was heated at 80°C for 30 minutes and cured.

Painted surface condition: Mild steel plate was used as the material. A coated surface with high gloss and no wrinkles was considered good.

Impact resistance, the material used is mild steel plate. Using a DuPont impact tester, a 500 g weight was dropped onto the painted surface, and the maximum fall distance (cm) without cracking or peeling of the paint film was determined.

Acid-resistant material: A glass plate was used. The test piece was heated to 40% H2
It was immersed in an SO4 aqueous solution (40°C) for 8 hours, and the appearance of the coating film (blurring, whitening, etc.) was observed.

Painted surface condition: Mild steel plate was used as the material. The presence or absence of any abnormalities in the painted surface condition (glossy pockets, smudges, cracks, peeling, etc.) was examined.

5 g of stain-resistant Nigest 15 types (JIS) was swept 100 times back and forth on the coated plate using a flat brush. After washing the panel with water, it was wiped with ethanol. The degree of contamination was evaluated by comparing the coated plate after the test with the original plate.

○: No contamination observed.

×: Contamination is observed.

Weather resistance: The material used is aluminum plate. Q manufactured by The Q Panel Co., Ltd.
UV weather meter (ultraviolet fluorescent lamp r No.
QFS-40, UV-B, wavelength range 320-28
0nm) at a temperature of 40-70°C (15 minutes)
The degree of deterioration of the coating film was observed after repeating this cycle for 3,000 hours.

Examples 10 to 16 Using copolymers (a) to (e), (wo) to (yo) (number average molecular weight 10.000) shown in Table 4, blending in the proportions shown in Table 5. This was carried out to obtain curable resin compositions 1O to 16 on the actual flow side. The coating performance of the composition is shown in Table 6.

Comparative example 2 A composition was obtained with the formulation shown in Table-5.

of the composition Shows coating performance 6.

Examples 17-21 Using the copolymers (Y) to (N) (number average molecular weight 10.000), (F), and (G) shown in Table-7, they were blended in the proportions shown in Table-8. The curable resin compositions of Examples 17 to 21 were obtained. The coating performance of the composition is shown in Table 9.

Comparative example 3 A composition was obtained with the formulation shown in Table-8.

of the composition Shows coating performance 9.

Examples 22 to 27 Using the copolymers (S) to (A) to (I) to (N) (number average molecular weight 10.000) shown in Table 10, they were blended in the proportions shown in Table 11. Curable resin compositions of Examples 22 to 27 were obtained. The coating performance of this composition is shown in Table-12.

Comparative example 4 A composition was obtained with the formulation shown in Table 11.

the composition Table 12 shows the coating performance.

Claims (2)

[Claims] (1) A mixed resin containing at least one reactive silane group selected from a hydroxysilane group and a hydrolyzable group directly bonded to a silicon atom, an epoxy group, and a hydroxyl group as essential functional group components; At least one resin selected from resins ▲ has a mathematical formula, chemical formula, table, etc. ▼ and/or ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼ (In the formula, R is the same or different and represents a C_1_ to_8 alkyl group, aryl group, aralkyl group, -OSi(R')_3 group, and a represents an integer of 2 or more. Here A curable resin composition characterized in that R' is the same or different and represents a C_1_-_8 alkyl group, aryl group, or aralkyl group. (2) A curable resin composition comprising the composition according to claim 1 and a curable catalyst.