JPH09296123A - New curable composition containing non-aqueous liquid dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new curable composition containing a specific nonaqueous liquid dispersion as an essential film-forming component and giving a coating film having good appearance, smoothness and mechanical properties and excellent durability, acid resistance, scratch resistance, etc. SOLUTION: This curable composition contains, as an essential film-forming component, a non-aqueous liquid dispersion produced by hydrolyzing (A) a silicon compound having at least two hydrolyzable groups bonded to Si atom (preferably a tetraalkoxysilane, etc.) in the presence of (B) a dispersion- stabilizing polymer (preferably an acrylic polymer, etc.), optionally condensing the hydrolysis product to obtain a modified resin and subjecting the modified resin to non-aqueous dispersion polymerization together with (C) a vinyl monomer in the presence of (D) an organic solvent dissolving the vinyl monomer and unable to dissolve its polymer (preferably hexane, etc.). A (meth)acrylic acid ester monomer having a <=3C alkyl group is preferably used as an essential component of the component D.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition containing, as an essential film-forming component, a novel and useful specific non-aqueous dispersion liquid. More specifically, the present invention provides at least two hydrolyzable groups bonded to a silicon atom in one molecule in the presence of a dispersion stabilizing polymer that functions as a dispersion stabilizer for a non-aqueous dispersion. A hydrolyzate of the silicon compound obtained by hydrolyzing the silicon compound having, and if necessary, a condensation reaction, or a modified resin in the form of a complex of the hydrolytic condensate,

A non-aqueous solution obtained by subjecting the vinyl-based monomer to non-aqueous dispersion polymerization in the presence of a specific organic solvent in which the vinyl-based monomer dissolves but the polymer does not dissolve. The present invention relates to a curable composition comprising a dispersion as an essential film-forming component, and particularly useful as a coating composition capable of forming a coating film having excellent durability such as weather resistance.

And, such a novel curable composition containing a non-aqueous dispersion according to the present invention,
For automobile top coating, building exterior, heat resistant paint, adhesive,
It is also used in a wide range of applications such as inks, impregnating agents for fibers and papers, and surface treatment agents.

[0004]

2. Description of the Related Art As a non-aqueous dispersion containing a silicon compound, a non-aqueous dispersion containing an alkoxypolysiloxane as a polymer for stabilizing dispersion has been disclosed in JP-A-62-11.
It is disclosed in Japanese Patent No. 6605. However, such a non-aqueous dispersion liquid has a drawback that the appearance and smoothness are inferior especially when it is formed into a coating film, and in addition, there is a problem that it is also inferior in mechanical properties. .

[0005]

As described above, the non-aqueous dispersion containing a silicon compound, which is obtained according to the conventional technique, is inevitably poor in appearance, smoothness and mechanical properties. Therefore, a non-aqueous dispersion having good performances such as these is strongly desired, and such a non-aqueous dispersion containing a silicon compound is particularly excellent in so-called durability such as weather resistance. It is intended to provide a curable composition which can form a coating film which is excellent and which is useful as a coating composition.

[0006] Therefore, the problem to be solved by the present invention is to solve the above problems by providing a non-aqueous dispersion liquid which is excellent in appearance, smoothness and mechanical properties, and which is novel and useful. The present invention is to provide a curable composition used, and more specifically, and finally, it has good appearance and mechanical properties, among others, and in particular, weatherability and the like. An object of the present invention is to provide a coating composition having extremely high practicality, which is also excellent in so-called durability.

[0007]

SUMMARY OF THE INVENTION However, the present inventors have found problems in such conventional non-aqueous dispersions, among others,
In view of the existence of problems such as appearance and mechanical properties of conventional non-aqueous dispersions, at the same time, focusing on the problems to be solved by the invention as described above, the research was earnestly started. .

That is, as a result of intensive studies to solve the above-mentioned problems of the present invention, as a result, in the presence of a dispersion stabilizing polymer which functions as a dispersion stabilizer for a non-aqueous dispersion, Hydrolyzing a silicon compound having at least two hydrolyzable groups bonded to a silicon atom in the molecule,
Further, if necessary, a specific resin hydrolyzate obtained by performing a condensation reaction, or a modified resin in the form of a complex hydrolyzed condensate,

A non-aqueous dispersion polymerization of the vinyl monomer is carried out in the presence of a specific organic solvent such that the vinyl monomer dissolves but the polymer does not dissolve. A curable composition containing an aqueous dispersion, whether it can be fulfilled, the appearance and mechanical properties of the problem is good, yet found that it is possible to form a cured coating film having excellent durability, The present invention has now been completed by convincing that the above-mentioned problems can be solved satisfactorily.

That is, the present invention basically comprises a silicon compound having at least two hydrolyzable groups bonded to a silicon atom in one molecule in the presence of the dispersion stabilizing polymer (a). An organic solvent (d) in which the modified resin obtained by hydrolyzing (b) and, if necessary, a condensation reaction and the vinyl-based monomer (c) are dissolved but the polymer is not dissolved In the coexistence with, the non-aqueous dispersion (A) obtained by non-aqueous dispersion polymerization of the vinyl-based monomer (c) is essential,

To be precise, this non-aqueous dispersion (A) is
A curable composition in various forms in which, as an essential film-forming component, a curing catalyst (B) or a compound (C) that reacts with a functional group contained in the non-aqueous dispersion (A) is used as the case may be. It is an attempt to provide something.

[0012]

As described above, according to the present invention, in the presence of the dispersion stabilizing polymer (a),
A modified resin obtained by hydrolyzing at least two silicon compounds (b) having a hydrolyzable group bonded to a silicon atom in one molecule, and further subjecting the compound to a condensation reaction, and a vinyl-based resin. A non-aqueous dispersion obtained by subjecting the vinyl-based monomer (c) to non-aqueous dispersion polymerization in the presence of an organic solvent (d) in which the monomer (c) is soluble but the polymer is insoluble. And claiming a curable composition comprising A) as an essential film-forming component,

Second, in the presence of the dispersion stabilizing polymer (a), hydrolysis of at least two silicon compounds (b) having a hydrolyzable group bonded to a silicon atom in one molecule. In the coexistence of a modified resin obtained by carrying out a condensation reaction and an organic solvent (d) in which the vinyl monomer (c) is dissolved but the polymer is not dissolved, if necessary, A curable composition comprising a non-aqueous dispersion (A) obtained by non-aqueous dispersion polymerization of a vinyl-based monomer (c) and a curing catalyst (B) as essential components. I'm billing,

Thirdly, in the presence of the dispersion stabilizing polymer (a), hydrolysis of at least two silicon compounds (b) having a hydrolyzable group bonded to a silicon atom in one molecule. In the coexistence of a modified resin obtained by carrying out a condensation reaction and an organic solvent (d) in which the vinyl monomer (c) is dissolved but the polymer is not dissolved, if necessary, The non-aqueous dispersion liquid (A) obtained by non-aqueous dispersion polymerization of the vinyl monomer (c) and the compound (C) which reacts with the functional group contained in the non-aqueous dispersion liquid (A) are essential. It is said that a curable composition consisting of containing as a component is also claimed,

Fourthly, in the presence of the dispersion-stabilizing polymer (a), hydrolysis of at least two silicon compounds (b) having a hydrolyzable group bonded to a silicon atom in one molecule. In the coexistence of a modified resin obtained by carrying out a condensation reaction and an organic solvent (d) in which the vinyl monomer (c) is dissolved but the polymer is not dissolved, if necessary, A non-aqueous dispersion liquid (A) obtained by non-aqueous dispersion polymerization of a vinyl-based monomer (c), a compound (C) that reacts with a functional group contained in the non-aqueous dispersion liquid (A), and a curing catalyst ( B) is also claimed as a curable composition comprising as an essential component,

It is also claimed that the above-mentioned dispersion stabilizing polymer (a) is a polymer having a hydrolyzable silyl group and / or a hydroxyl group, in particular. Is something

The above-mentioned dispersion-stabilizing polymer (a) also claims a specific curable composition, particularly in the form of a vinyl-based polymer,

It is also claimed that the specific curable composition is in the form of the above-mentioned vinyl polymer being an acrylic polymer.

It is also claimed that a specific curable composition in the form of the above vinyl polymer being a fluoroolefin polymer is claimed.

The above-mentioned at least two molecules in one molecule,
The silicon compound (b) having a hydrolyzable group bonded to a silicon atom is a tetraalkoxysilane, an organotrialkoxysilane, a diorganodialkoxysilane, a partially hydrolyzed condensate thereof, and a partially cohydrolyzed condensation thereof. Claiming a particular curable composition in the form of at least one alkoxysilane selected from the group consisting of

A specific curable composition is also claimed, in which the vinyl monomer (c) has an alkoxysilyl group as the hydrolyzable silyl group. And

A specific curable composition in the form of the above-mentioned vinyl monomer (c) obtained by using a hydrolyzable silyl group-containing vinyl monomer as an essential monomer component. It is said that they are also charging for things,

The above vinyl-based monomer (c) is particularly preferably
As the above-mentioned hydrolyzable group, a specific curable composition in the form of having an alkoxy group is also claimed,

Also claimed is a specific curable composition in which the above-mentioned vinyl-based monomer (c) uses, as at least a part thereof, a monomer having a reactive functional group. It is said that

The above-mentioned monomer having a reactive functional group is
In particular, a monomer having a hydroxyl group, a monomer having a blocked hydroxyl group, a monomer having a carboxyl group, a monomer having a blocked carboxyl group, a monomer having a cyclocarbonate group, a primary amide A monomer having a bond, a monomer having a secondary amide bond, a monomer having an amino group, a monomer having a cabamate group, a monomer having an epoxy group, a monomer having a carboxylic acid anhydride group And the following structural formula (I)

[0026]

Embedded image —NH—C (O) —NC (O) — (I)

It also claims a specific curable composition in the form of at least one selected from the group consisting of monomers having a functional group represented by:

The present invention will be described in more detail below.

Here, the "hydrolysis" referred to in the present invention.
Is meant to include not only hydrolysis, but also to include not only such hydrolysis but also the condensation reaction that occurs as it is.
"Condensation reaction" is the hydrolysis (reaction) thus obtained.
It means a reaction for further condensing a product or a hydrolyzed condensate.

First, in the presence of the dispersion stabilizing polymer (a), a silicon compound (b) having at least two hydrolyzable groups bonded to a silicon atom in one molecule.
The hydrolysis reaction and the condensation reaction, if necessary, are carried out in the presence of an organic solvent or without a solvent. At that time, it can be said that a catalyst that accelerates the hydrolysis and condensation reactions is added.

Then, in the presence of a so-called modified resin obtained by the hydrolysis or the hydrolysis-condensation reaction, the vinyl-based monomer (c) is dissolved but the polymer is not dissolved. The organic solvent (d) is added first, and then the vinyl monomer (c) is subjected to non-aqueous dispersion polymerization,

Alternatively, a specific organic solvent (d) which dissolves the vinyl monomer (c) but does not dissolve the polymer and the vinyl monomer (c) are simultaneously added. Thus, the point of the present invention is to obtain the desired non-aqueous dispersion polymer by subjecting the vinyl-based monomer (c) to non-aqueous dispersion polymerization.

As the dispersion stabilizing polymer (a) used in the present invention, any polymer can be used as long as it functions as a dispersion stabilizer in a non-aqueous dispersion liquid. However, among them, only typical ones are exemplified by vinyl-based polymers, polyether-based polymers, polyester-based polymers, polyamide-based polymers, polyurethane-based polymers, alkyl etherified aminos. A resin or an alkyd resin, or a vinyl-based polymer and another polymer,
Block or graft polymers and the like.

Among these polymers, particularly preferred are acrylic polymers, fluoroolefin polymers, carboxylic acid vinyl ester polymers, aromatic vinyl polymers or polyolefin polymers; or vinyl polymers. Various vinyl polymers such as graft polymers or block copolymers of the same polymer may be mentioned. Among them, acrylic polymers and fluoroolefin polymers are particularly preferable from the viewpoint of durability.

The dispersion stabilizing polymer (a) may be, for example, dispersion polymer particles obtained by polymerizing the vinyl monomer (c) described above; A hydrolyzate of at least two silicon compounds (b) having a hydrolyzable group bonded to a silicon atom; or a compound having no functional group capable of reacting with a hydrolyzed condensate may be used. In order to obtain a non-aqueous dispersion liquid having higher dispersion stability, various functional groups such as a hydrolyzable silyl group, a hydroxyl group, a polymerizable unsaturated double bond, a carboxyl group, an epoxy group or an amino group are used. The use of such as having a group is particularly desirable.

The dispersion stabilizing polymer (a) for preparing the curable composition containing the non-aqueous dispersion according to the present invention includes a hydrolyzable silyl group, a hydroxyl group and a carboxyl group. It is desirable to use those having various functional groups represented by epoxy group, amino group and the like.

As such a dispersion-stabilizing polymer (a), vinyl-based monomers used in the preparation of an acrylic polymer or a fluoroolefin-based polymer, and a non-aqueous dispersion-polymerized polymer are used. If only typical examples of the vinyl-based monomer (c) are given,

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or lauryl (meth) acrylate. Like,
Various esters of primary or secondary alkyl alcohol having ₁ to ₂₂ carbon atoms and (meth) acrylic acid;

Benzyl (meth) acrylate or 2
-Various aralkyl (meth) acrylates, such as phenylethyl (meth) acrylate; various cycloalkyl (meth) acrylates, such as cyclohexyl (meth) acrylate or isobornyl (meth) acrylate; 2-methoxyethyl (meth) Various ω-alkoxyalkyl (meth) acrylates, such as acrylate or 4-methoxybutyl (meth) acrylate;

Various aromatic vinyl monomers such as styrene, p-tert-butylstyrene, α-methylstyrene or vinyltoluene; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate or benzoate. Various carboxylic acid vinyl esters such as vinyl acrylate;

Various alkyl esters of crotonic acid such as methyl crotonic acid or ethyl crotonic acid; dimethyl maleate, di-n-butyl maleate, dimethyl fumarate, di-n-butyl fumarate, dimethyl itaconate or di-. various dialkyl esters of unsaturated dibasic acids such as n-butyl itaconate;

Various cyano group-containing monomers, such as (meth) acrylonitrile or crotononitrile; various kinds of vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene or hexafluoropropylene. Fluoroolefins;
Various chlorinated olefins, such as vinyl chloride or vinylidene chloride; various α, such as ethylene, propylene, isobutylene, 1-butene or 1-hexene
-Olefins;

Various alkyl vinyl ethers such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether or n-hexyl vinyl ether; various cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or 4-methylcyclohexyl vinyl ether. Then

Further, such as methoxy polyethylene glycol or methoxy polypropylene glycol,
Polyethers having one hydroxyl group in one molecule,
Examples include various polyether-containing monomers such as esters with (meth) acrylic acid.

As the monomer having a functional group,
Among them, only typical ones are exemplified by a vinyl monomer having a hydroxyl group, a vinyl monomer having a blocked hydroxyl group, a vinyl monomer having a carboxyl group, and a block. Vinyl monomer having a carboxyl group, vinyl monomer having a carboxylic acid anhydride group, vinyl monomer having an amino group, vinyl monomer having a cyclocarbonate group, vinyl having an epoxy group System monomer,

A vinyl-based monomer having a primary amide bond,
Group consisting of vinyl-based monomer having secondary amide bond, vinyl-based monomer having carbamate group and vinyl-based monomer having functional group represented by structural formula (I) as described above. At least one kind of monomer selected from

These are obtained by copolymerizing a monomer having two or more of the above-mentioned functional groups together with a vinyl-based monomer having a hydrolyzable silyl group, or as described above. It can be used by copolymerizing a monomer having a functional group, a monomer having a hydrolyzable silyl group, and another vinyl-based monomer copolymerizable therewith. it can.

If only typical examples of the vinyl monomer having a hydroxyl group (hydroxyl group-containing vinyl monomer) are mentioned above,

Various hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate; 2-hydroxyethyl vinyl ether or 4-
Various hydroxyl-containing vinyl ethers such as hydroxybutyl vinyl ether;

Various hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether; various polyether polyols such as polyethylene glycol, and (meth) acrylic acid. Monoesters of polyoxyalkylene glycols obtained from various unsaturated carboxylic acids, such as:

As represented by various kinds of hydroxyl group-containing monomers described above and ε-caprolactone,
Adducts with various lactones; or various epoxy group-containing unsaturated monomers represented by glycidyl (meth) acrylate and the like; and various adducts represented by acetic acid and the like. Adducts with acids;

Furthermore, it is represented by various unsaturated carboxylic acids represented by (meth) acrylic acid and the like, "Cardura E" (trade name of Shell company in the Netherlands) and the like. In addition to epoxides of α-olefins, various hydroxyl group-containing monomers such as adducts with various monoepoxy compounds and the like.

As the vinyl type monomer having a blocked hydroxyl group (block hydroxyl group-containing vinyl type monomer), only typical ones will be exemplified.
-Trimethylsiloxyethyl (meth) acrylate, 2
-Trimethylsiloxypropyl (meth) acrylate,
Various silyl ether group-containing vinyl-based monomers such as those disclosed in JP-A-62-283163, such as 4-trimethylsiloxybutyl (meth) acrylate or 2-trimethylsiloxyethyl vinyl ether or 4-trimethylsiloxybutyl vinyl ether. Quantities;

2- (1-ethoxy) ethoxyethyl (meth) acrylate, 2- (1-n-butoxy) ethoxyethyl (meth) acrylate, 2- [2- (meth) acryloyloxy] ethoxytetrahydrofuran or 2,2 Various vinyl monomers containing an acetal group or a ketal group as disclosed in JP-A-4-41515, such as dimethyl-4- (meth) acryloyloxymethyldioxolane;

Alternatively, 3- [2- (meth) acryloyloxy] ethyloxazolidine, 2,2-dimethyl-3
-[2- (meth) acryloyloxy] ethyloxazolidine or 2-isobutyl-2-methyl-3- [2-
(Meth) acryloyloxy] ethyl oxazolidine, and various oxazolidine group-containing vinyl monomers.

As typical examples of the vinyl monomer containing a carboxyl group, only (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, maleic acid or Various unsaturated carboxylic acids such as fumaric acid;

Monomethyl itaconate, mono-itaconate
n-butyl, monomethyl maleate, mono-maleic acid
n-butyl, monomethyl fumarate, mono-n-fumarate
Monoesters (half esters) of unsaturated dicarboxylic acids such as butyl and saturated monohydric alcohols; such as monovinyl adipate or monovinyl succinate,
Various monovinyl esters of saturated dicarboxylic acids;

Alternatively, succinic anhydride, glutaric anhydride,
Addition reaction products of various saturated polycarboxylic acid anhydrides such as phthalic anhydride or trimellitic anhydride with various hydroxyl group-containing vinyl-based monomers as described above; Such various monomers containing carboxyl group-containing monomers and lactones can be obtained by addition reaction.

To exemplify only particularly representative examples of the other acid group-containing monomer, various phosphoric acids such as "light ester PM or PA" [product of Kyoeisha Oil and Fat Chemical Industry Co., Ltd.] are listed. Ester group-containing monomers; or various sulfonic acid group-containing monomers such as styrene sulfonic acid or vinyl sulfonic acid, and monomers in such a form can also be used.

As only specific examples of monomers having a blocked carboxyl group, specific examples such as trimethylsilyl (meth) acrylate or dimethyl-tert-butylsilyl (meth) acrylate trimethylsilyl crotonate are given. Kaisho 62-25
Vinyl monomers containing a silyl ester group as disclosed in Japanese Patent No. 4876;

1-Ethoxyethyl (meth) acrylate, 1-n-butoxyethyl (meth) acrylate or 2-methoxy-2- (meth) acryloyloxypropane 2- (meth) acryloyloxytetrahydrofuran, such as JP-A-5- Various monomers having a hemiacetal ester group or a hemiketal ester group as disclosed in JP-A-222134; or t
tert-butyl (meth) acrylate or tert-
Various tert-butyl ester group-containing monomers such as butyl crotonate.

As only specific examples of the monomer having a carboxylic acid anhydride group, anhydrides of various unsaturated polycarboxylic acids such as maleic anhydride and itaconic anhydride; or Anhydrides of various unsaturated monocarboxylic acids such as acrylic acid anhydride or methacrylic acid anhydride; or various unsaturated carboxylic acids such as acrylic acid or methacrylic acid, and acetic acid, propionic acid or benzoic acid And mixed acid anhydrides with various saturated carboxylic acids.

As only vinyl monomers having an amino group, only typical ones are exemplified, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate and 2-di- Various tertiary such as n-propylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 4-dimethylaminobutyl (meth) acrylate or N- [2- (meth) acryloyloxy] ethylmorpholine. Amino group-containing (meth) acrylic acid esters;

A variety of tertiary amino group-containing aromatic vinyl monomers such as vinyl pyridine and N-vinylcarbazole N-vinylquinoline; N- (2-dimethylamino) ethyl (meth) acrylamide, N- ( 2-diethylamino) ethyl (meth) acrylamide, N- (2-di-n
-Propylamino) ethyl (meth) acrylamide, N
-(3-Dimethylamino) propyl (meth) acrylamide, N- (4-dimethylamino) butyl (meth) acrylamide or N- [2- (meth) acrylamide]
Various tertiary amino group-containing (meth) acrylamides such as ethylmorpholine;

N- (2-Dimethylamino) ethyl crotonic acid amide, N- (2-diethylamino) ethyl crotonic acid amide, N- (2-di-n-propylamino) ethyl crotonic acid amide, N- (3- Various tertiary amino group-containing crotonic acid amides such as dimethylamino) propyl crotonic acid amide or N- (4-dimethylamino) butyl crotonic acid amide;

Alternatively, 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether,
3-dimethylaminopropyl vinyl ether or 4-
Various types of 3 such as dimethylaminobutyl vinyl ether
Examples thereof include vinyl ethers containing a primary amino group.

As only typical vinyl monomers having a cyclocarbonate group, 2,3-carbonate propyl (meth) acrylate, 2-methyl-2,3-carbonate propyl ( (Meth) acrylate, 3,4-carbonate butyl (meth) acrylate, 3-methyl-3,4-carbonate butyl (meth) acrylate, 4-methyl-3,4-carbonate butyl (meth) acrylate, 4,5-carbonate Pentyl (meth) acrylate, 6,7-carbonate hexyl (meth) acrylate, 5-ethyl-
5,6-carbonate hexyl (meth) acrylate 7,8-carbonate octyl (meth) acrylate,
2,3-carbonate propyl vinyl ether or di (2,3-carbonate propyl) malate di (2,3)
-Carbonate propyl) itaconate, 5-membered cyclocarbonate group-containing vinyl monomers, etc.,

Furthermore, [5-N- (meth) acryloylcarbamoyloxy] methyl-5-ethyl-1,3-
Dioxan-2-one, 5- [N- {2- (meth) acryloyloxy} ethylcarbamoyloxy] methyl-
5-ethyl-1,3-dioxan-2-one, 5-ethyl-5- (meth) acryloyloxymethyl-1,3-
6-membered cyclocarbonate group-containing vinyl monomers such as dioxan-2-one or 4- (5-ethyl-2-oxo-1,3-dioxan-5-yl) methoxymethylstyrene.

As only vinyl monomers having an epoxy group, only typical ones are exemplified, glycidyl (meth) acrylate and methylglycidyl (meth).
Various monomers such as acrylates, 3,4-epoxycyclohexylmethyl (meth) acrylate, vinylcyclohexene oxide, glycidyl vinyl ether, methyl glycidyl vinyl ether or allyl glycidyl ether.

As only vinyl monomers having a primary amide bond or a secondary amide bond, only typical ones are exemplified, (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methyl. (Meth) acrylamide, N-vinylformamide, methyl (meth) acrylamide glycolate, methyl (meth) acrylamide glycolate methyl ether, N-
In addition to methylol (meth) acrylamide or Nn-butoxymethyl (meth) acrylamide, etc., various kinds of addition products such as 2-isocyanatoethyl (meth) acrylate and acetylacetone acetoacetic acid esters are added. It is a compound.

Further, the above-mentioned secondary amide bond includes N-hydroxymethyl amide bond and N-hydroxymethyl amide bond, respectively.
Alkoxymethylamide bond or the following structural formula (II)

[0072]

Embedded image —C (O) —NH—CH (OR ₁ ) —COOR ₂ (II)

(However, R ₁ and R ₂ in the formula may be the same or different and each is a hydrogen atom,
It represents an alkyl group or an aryl group having 1 to 8 carbon atoms. )

Another example is:

Of course, N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine,
Various tertiary amide bond-containing monomers can also be used, such as N- (meth) acryloylpyrrolidine or N-vinylpyrrolidone.

If only typical examples of vinyl monomers having a carbamate group are given, N is
-Methyl (meth) acryloylcarbamate, ethyl N- (meth) acryloylcarbamate, N- [2-
((Meth) acryloyloxy] ethyl carbamate ethyl, 2-carbamoyloxyethyl (meth) acrylate, 2- (N-methylcarbamoyloxy) ethyl (meth) acrylate, 2- (N-ethylcarbamoyloxy) ethyl (meth) Including acrylates,

Furthermore, 3-isopropenyl-α, α-
Addition reaction product of dimethylbenzyl isocyanate and 2-hydroxypropyl carbamate, addition reaction product of 2-isocyanatoethyl (meth) acrylate and phenol, addition reaction of 2-isocyanatoethyl (meth) acrylate and ethanol , 2-isocyanatoethyl (meth) acrylate, and various compounds such as an addition reaction product of methylethylketoxime.

As the vinyl type monomer having a functional group represented by the structural formula (I) as described above, only representative examples are given, 2-isocyanatoethyl (meth) acrylate and Compounds such as an addition reaction product of ε-caprolactam, an addition reaction product of 2-isocyanatoethyl (meth) acrylate and γ-butyrolactam, and the like.

The vinyl-based monomer having two or more functional groups of the above-mentioned functional groups will be exemplified only by the representative ones. Mono- (hydroxyethyl) itaconate or mono- (2,2) 3-carbonate propyl)
Itaconate etc.

Further, the hydrolyzable silyl group-containing monomer has the general formula (III)

[0081]

Embedded image

[0082] (wherein, R ¹ in the formula is an alkyl group, a monovalent organic group comprising an aryl group or aralkyl group, R ²
Is a hydrogen atom, a halogen atom or an alkoxy group,
It represents an acyloxy group, a phenoxy group, a mercapto group, an amino group, an amide bond, an aminooxy group, an iminooxy group or an alkenyloxy group, and a represents an integer of 0, 1 or 2. )

The vinyl type monomers having a so-called hydrolyzable silyl group, which forms a silanol group by being hydrolyzed as shown in the above item, are referred to.

As only typical examples of such a type of hydrolyzable silyl group-containing vinyl monomer, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-butoxysilane are given. , Vinylmethyldimethoxysilane, vinyltris (β-methoxyethoxy) silane, allyltrimethoxysilane, 2-
Starting with trimethoxysilylethyl vinyl ether, 2-triethoxysilylethyl vinyl ether, 2- (methyldimethoxysilyl) ethyl vinyl ether, 3-trimethoxysilylpropyl vinyl ether or 3-triethoxysilylpropyl vinyl ether,

Furthermore, 3- (methyldimethoxysilyl) propyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3-
Examples thereof include (meth) acryloyloxypropylmethyldimethoxysilane and 3- (meth) acryloyloxypropylmethyldichlorosilane.

The various functional group monomers as described above are 1
Only the seed may be contained in the dispersion stabilizing polymer (a) as well as in the non-aqueous dispersion liquid (A), for example, a combination of a cyclocarbonate group and a carboxyl group. Of course, two or more kinds may be contained in the polymer (a) and in the non-aqueous dispersion liquid (A) as described above.

To prepare an acrylic polymer as the dispersion-stabilizing polymer (a) from the various vinyl-based monomers listed above, the carbon of these monomers is used. The (meth) acrylic acid ester-based monomer having an alkyl group of 4 or more and / or the (meth) acrylic acid ester-based monomer having a cycloalkyl group is used as an essential raw material component, and if necessary, other monomer From the viewpoint of dispersion stability, it is desirable to copolymerize the monomer.

The amount of the (meth) acrylic acid ester-based monomer having an alkyl group having 4 or more carbon atoms and / or the (meth) acrylic acid ester-based monomer having a cycloalkyl group is used. Generally, it is suitable to be in the range of about 20 to 100% by weight based on the total amount of monomers.

Further, from the viewpoint of dispersion stability as described above, a vinyl-based monomer having a specific functional group such as a hydrolyzable silyl group, a hydroxyl group, a carboxyl group, an epoxy group or an amino group is used. It is desirable to use them together as a copolymerization monomer (comonomer).

In order to introduce the polymerizable unsaturated double bond into the dispersion-stabilizing polymer (a), various known and conventional methods can be applied. The monomer copolymer may be reacted with the carboxyl group-containing monomer, or the carboxyl group-containing monomer copolymer may be reacted with the epoxy group-containing monomer.

As described above, in the present invention,
When the non-aqueous dispersion obtained by using the dispersion stabilizing polymer (a) is used for a curable composition, a hydrolyzable silyl group, a hydroxyl group, a carboxyl group, an epoxy group or an amino group is used. It is desirable that a vinyl-based monomer having such a specific functional group such as a group is used as a comonomer in combination.

The amount of such monomers having various functional groups such as hydrolyzable silyl group, hydroxyl group, carboxyl group, epoxy group or amino group constitutes the dispersion stabilizing polymer (a). In the range of about 0.1 to about 50% by weight, based on the total amount of the monomers, preferably 0.
5 to 30% by weight, more preferably 0.5
The range of up to 15% by weight is suitable.

On the other hand, in order to prepare a fluoroolefin polymer as the dispersion-stabilizing polymer (a), the above-mentioned fluoroolefins can be copolymerized with these other fluoroolefins. It may be possible to copolymerize with monomers.

[0100] To exemplify only particularly representative examples of such copolymerizable monomers used in this case, carboxylic acid vinyl esters, alkyl vinyl ethers or cycloalkyl vinyl ethers. And so on.

Further, as specific examples of such fluoroolefin polymers, only representative ones will be exemplified. JP-A-62-25103 and JP-A-62-81409. Publication or Japanese Patent Laid-Open No. 2-6
Various fluoroolefin-based polymers as disclosed in Japanese Patent Publication No. 9507 are available.

From the viewpoint of dispersion stability as described above, the fluoroolefin polymer can be treated in the same manner as in the case of the acrylic polymer as described above.
It is desirable to introduce various specific functional groups such as a hydrolyzable silyl group, a hydroxyl group, a carboxyl group, an epoxy group, an amino group or a polymerizable unsaturated double bond.

As described above, in the present invention,
When the non-aqueous dispersion obtained by using the dispersion-stabilizing polymer (a) is used for a curable composition, this fluoroolefin-based polymer also contains
By the same method as in the case of the acrylic polymer as described above, respectively, such as hydrolyzable silyl group, hydroxyl group, carboxyl group, epoxy group or amino group,
It is desirable to introduce various specific functional groups.

Such a hydrolyzable silyl group, a hydroxyl group,
The amount of the vinyl monomer containing a specific functional group, which is used when introducing a specific functional group such as a carboxyl group, an epoxy group or an amino group, is a dispersion stabilizing polymer ( Based on the total monomers constituting a), the amount is about 0.1 to about 50% by weight, preferably 0.5 to 30% by weight, more preferably 0.5 to 30% by weight. A range of 15% by weight is suitable.

To prepare an acrylic polymer or a fluoroolefin polymer as the dispersion-stabilizing polymer (a), respectively, from vinyl monomers as described above, various known and conventional methods are used. Although the method can be applied, it is particularly convenient to carry out radical polymerization in an organic solvent using a polymerization initiator described later.

The molecular weight of the acrylic polymer or fluoroolefin polymer as the dispersion-stabilizing polymer (a) thus obtained is from about 500 to about 100 as the number average molecular weight. The range of 100,000 is suitable, and preferably 1,000 to 50,000.
A range of 00 is suitable.

In the case where the molecular weight is less than about 500, the stability of the polymer particles is inadequate, and by extension, aggregation and precipitation are likely to occur, while about 100, If it exceeds 000 and becomes too high, the viscosity of the dispersion liquid will inevitably become extremely high, which is not preferable in any case.

The acrylic polymer or fluoroolefin polymer as the dispersion stabilizing polymer (a) as described above may be used alone or in combination of two or more kinds. In addition, these specific polymers may further include, in addition to the acrylic or fluoroolefin-based polymer, a vinyl-based polymer as described above, or a vinyl-based polymer other than the vinyl-based polymer, or a polyether-based polymer. It can be said that various polymers such as polymers and polyester-based polymers can also be used in combination.

The above-mentioned silicon compound (b) having at least two hydrolyzable groups bonded to a silicon atom in one molecule, which is used in the present invention, means a hydrogen atom bonded to a silicon atom, respectively. Alternatively, a halogen atom or an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, a mercapto group, an amino group, an amide bond, an aminooxy group, an iminooxy group or an alkenyloxy group, which is hydrolyzed and has at least 2 in one molecule. It refers to a specific compound having a group that forms a hydroxyl group bonded to a silicon atom.

If only typical examples of the silicon compound (b) are exemplified, various known and commonly used compounds can be used, but among them, only typical ones can be used. To give an example,
The following general formula (IV)

[0105]

Embedded image R ¹ _a SiR ² _4-a (IV)

(Wherein R ¹ in the formula may be an alkyl group which may or may not have a substituent,
A monovalent organic group consisting of an aryl group, an aralkyl group or an alkenyl group, R ² is a hydrogen atom or a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, a phenoxy group, a mercapto group, an amino group, an amide bond, an aminooxy group. , An iminooxy group or an alkenyloxy group, and a is an integer of 0, 1 or 2. )

Silicon compounds of the form represented by the following; including their partial (co) hydrolyzed condensates, and further,

(CH ₃ CH ₂ O) ₃ SiOCH ₂ CH ₂
OSi (OCH ₂ CH ₃ ) ₃ or (CH ₃ CH ₂ O)
₃ SiOCH ₂ CH ₂ CH ₂ OSi (OCH ₂ CH ₃ )
Silicon compounds such as ₃ and the like having two or more hydrolyzable silyl groups in one molecule.

As only the silicon compounds represented by the general formula (IV), which have been described above, are specifically exemplified, various tetra compounds such as tetraethoxysilane, tetramethoxysilane or tetrabutoxysilane can be used. Alkoxysilanes;

Methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane or butyltrimethoxysilane. Ethoxysilane,

Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-butoxysilane, vinyltris (β-methoxyethoxy) silane or allyltrimethoxysilane,

Alternatively, trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylpropyl vinyl ether, γ- (meth) acryloyloxypropyltrimethoxysilane or γ-
Various organotrialkoxysilanes such as (meth) acryloyloxypropyltriethoxysilane;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane or dibutyldiethoxysilane,

Diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, vinylmethyldimethoxysilane, methyldimethoxysilylethylvinylether, methyldimethoxysilylpropylvinylether or γ- (meth). Various diorganodialkoxysilanes such as acryloyloxypropylmethyldimethoxysilane;

Tetrachlorosilane, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltotichlorosilane, vinyltrichlorosilane, γ- (meth) acryloyloxypropyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, methyl Various chlorosilanes such as phenyldichlorosilane, vinylmethyldichlorosilane or γ- (meth) acryloyloxypropylmethyldichlorosilane;

Or tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane,
Acetoxysilanes such as dimethyldiacetoxysilane or diphenyldiacetoxysilane.

Further, as the silicon compound (b), a commercially available polysiloxane can be used, and if only typical examples of commercially available products of such a polysiloxane are exemplified, the silicon atom can be "TSR-165" [trade name of Toshiba Silicone Co., Ltd.] or "DC3037 or DC", which is commercially available as a polysiloxane having a bound methoxy group, respectively.
3074 "[Toray Dow Corning Silicone Co., Ltd.
And a partially hydrolyzed condensate having a linear or branched (branched) structure.

Of these, only the particularly representative ones of the silicon compounds (b) having at least two hydrolyzable groups bonded to a silicon atom in one molecule are listed below. Alkoxysilane, organotrialkoxysilane or diorganodialkoxysilane, or their partial hydrolysates or partial cohydrolysates, and further, their partial hydrolytic condensates or partial cohydrolytic condensations. Such as things.

Further, the silicon compound (b) used in the present invention contains one hydrolyzable group per silicon atom such as trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane or triphenylethoxysilane. It can be said that various silicon compounds in the form of being bonded are also used together.

The ratio of the dispersion-stabilizing polymer (a) to the silicon compound (b) used is such that the former polymer (a) and the latter compound (b) are hydrolyzed or hydrolyzed and condensed. The weight ratio to the product, in other words, the weight% ratio is preferably set to about 10:90 to about 95: 5, and more preferably about 20:80 to 85:15. It is better to set

When the weight ratio of the dispersion-stabilizing polymer (a) is set to be less than about 10%, the non-aqueous dispersion stable by the subsequent polymerization reaction of the non-aqueous dispersion is inevitable. It is not preferable because the liquid is less likely to be generated. On the other hand, when it exceeds about 95% and becomes too large, the hydrolyzate or hydrolyzate of the silicon compound (b) contained in the obtained non-aqueous dispersion is inevitable. In this case, too, the amount of decomposition condensate tends to be low, which is not preferable.

In the presence of the dispersion stabilizing polymer (a),
It is particularly representative as a catalyst used in the hydrolysis of the silicon compound (b) having at least two hydrolyzable groups bonded to a silicon atom in one molecule and, if necessary, in the condensation reaction. To give only examples, various inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid; p
Various organic acids such as toluene sulfonic acid or acetic acid;

Various inorganic bases such as sodium hydroxide or potassium hydroxide; various titanic acid esters such as tetraisopropyl titanate or tetrabutyl titanate; various phosphoric acid esters such as monoisopropyl phosphate; dibutyltin Various tin carboxylates such as dilaurate or tin octylate;

Naphthenates of various metals such as iron, cobalt, manganese or zinc; various metal carboxylates such as octylates; various aluminum compounds such as aluminum trisacetylacetate;

Various amine compounds such as butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine or N-methyl-imidazole; or various quaternary ammonium salts such as tetrabutylammonium hydroxide. is there.

The amount of the catalyst used is the above-mentioned dispersion-stabilizing polymer (a) and this silicon compound having at least two silicon-bonded hydrolyzable groups in one molecule ( In the range of about 0.0001 to about 10% by weight, preferably 0.0005 to 5% by weight based on the total amount of b).
A range of 5% by weight is suitable.

The amount of water used is about 0.05 mol or more, preferably 0.1 mol or more, relative to 1 mol of the hydrolyzable group bonded to the silicon atom. However, 0.2 mol or more is more preferable.

When the amount is less than about 0.05 mol, the rate of hydrolysis is inevitably slowed down, which is not preferable in practice, but the amount of water is
There is no problem in using 5 mol, more preferably 10 mol, in excess with respect to 1 mol of the hydrolyzable group bonded to the silicon atom.

The addition of these catalysts and water is
Needless to say, they may be added all at once, or may be added in a divided manner, or may be added in the form of a mixture of the catalyst and water, or may be added separately.

The reaction temperature of such a hydrolysis reaction or condensation reaction is appropriately about 0 ° C to about 150 ° C, preferably about 20 ° C to 100 ° C. On the other hand, these reactions It can be said that the above-mentioned pressure is applied under any conditions of normal pressure, increased pressure or reduced pressure.

If the by-products of these various reactions, such as alcohol and water, cause problems in the polymerization process of the subsequent non-aqueous dispersion polymerization and the stability of the resulting non-aqueous dispersion. It can be removed from the reaction system by means such as distillation, and if there is no problem, it can be left as it is in the reaction system and there is no problem.

Hydrolysis or condensation of at least two silicon compounds (b) having a hydrolyzable group bonded to a silicon atom in one molecule, carried out in the presence of the dispersion stabilizing polymer (a). In the reaction, an organic solvent may or may not be used, but it is desirable to use an organic solvent so that stirring can be easily performed.

When an organic solvent is used, any of various known and commonly used organic solvents can be used, and they may be used alone or in combination of two or more kinds. Of course.

To exemplify only particularly representative ones among them, a mixture of various hydrocarbons such as white spirit or mineral spirit, hexane, heptane, octane,
Various aliphatic hydrocarbons such as cyclohexane, cyclopentane or cyclooctane;

Various aromatic hydrocarbons such as toluene, xylene or ethylbenzene; various kinds such as ethyl acetate, butyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or ethylene glycol monobutyl ether acetate Esters of

Methanol, ethanol, propanol,
Butanol, ethylene glycol monomethyl ether,
Various alcohols such as ethylene glycol monoethyl ether or ethylene glycol monobutyl ether; various ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone or cyclohexanone;

Dimethoxyethane, tetrahydrofuran,
Various ethers such as dioxane, diisopropyl ether or di-n-butyl ether; various chlorinated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, trichloroethane or tetrachloroethane; or N-methylpyrrolidone, dimethylform Examples include amide, dimethylacetamide, and ethylene carbonate.

Further, each of the dispersion stabilizing polymer (a) and the silicon compound (b) having at least two hydrolyzable groups bonded to a silicon atom in one molecule in the above organic solvent. It is desirable that the concentration in the above is about 5% by weight or more as the total amount of both components (a) and (b).

A typical polymer used for preparing the curable composition according to the present invention is a polymer forming dispersed polymer particles obtained by dispersion polymerization of the above-mentioned vinyl monomer (c). Examples of acrylic polymers, fluoroolefin polymers, carboxylic acid vinyl ester polymers, aromatic vinyl polymers, and the like include, among others, easiness of preparation, among others. From the viewpoint of the above, use of an acrylic polymer is particularly desirable.

First, of course, as the vinyl-based monomer (c) forming the acrylic polymer, which is the polymer-dispersed particles, any of various known and commonly used monomers can be used. Of these, only typical ones are exemplified, and the above-mentioned ones when the dispersion stabilizing polymer (a) is prepared are exemplified as they are. .

That is, particularly typical vinyl monomers for the preparation of so-called acrylic polymer dispersed particles are particularly representative in preparing the above-mentioned dispersion stabilizing polymer (a). The various monomers as exemplified above can be used as they are.

Among these monomers, a (meth) acrylic acid ester-based monomer having an alkyl group having a carbon number of 3 or less is used as an essential raw material component and, if necessary, other monomers are copolymerized. Is desirable.

The amount of such a (meth) acrylic acid ester-based monomer having an alkyl group having 3 or less carbon atoms is about 20 to 100% by weight based on the total amount of all monomers. Good.

Further, in order to make the polymer dispersed particles into crosslinked particles, a so-called polyfunctional vinyl monomer having two or more functional groups, represented by hexamethylene dimethacrylate or glycerin trimethacrylate, is used. It can also be used together.

The polymer-dispersed particles obtained by polymerizing the vinyl-based monomer (c) are the dispersion-stabilizing polymer (a) forming a dispersion medium,
Alternatively, it does not have a functional group capable of reacting with at least two hydrolyzates or hydrolyzed condensates of the silicon compound (b) having a hydrolyzable group bonded to a silicon atom in one molecule. But you can

In order to obtain a non-aqueous dispersion having even higher dispersion stability, it is necessary to use a form having various functional groups such as a hydrolyzable silyl group, a hydroxyl group, a carboxyl group, an epoxy group or an amino group. It is particularly desirable to use.

In addition, when a non-aqueous dispersion obtained by subjecting the vinyl-based monomer (c) to non-aqueous dispersion polymerization is used for a curable composition, the vinyl-based monomer The polymer-dispersed particle portion of the non-aqueous dispersion liquid (A) obtained by polymerizing the body (c) is also a hydrolyzable silyl group, hydroxyl group, blocked hydroxyl group, carboxyl group, blocked carboxyl group, cyclocarbonate. Group, primary or secondary amide bond, epoxy group, carbamate group, amino group carboxylic acid anhydride group or structural formula (I)

[0148]

Embedded image —NH—C (O) —NC (O) — (I)

It is particularly desirable that it is in the form of having various functional groups as shown in.

In order to introduce such a functional group, a monomer having the functional group among the various monomers described above may be used together as a copolymerization component.

Each of these functional group-containing vinyl monomers used for introducing a specific functional group such as a hydrolyzable silyl group, a hydroxyl group, a carboxyl group, an epoxy group or an amino group. The usage of
Within the range of about 0.1 to about 50% by weight, and preferably within the range of 0.5 to 30% by weight, of the polymer dispersed particles of the resulting non-aqueous dispersion (A). However, more preferably, the range is 0.5 to 15% by weight.

In the present invention, as the above-mentioned organic solvent (d) used in the non-aqueous dispersion polymerization, the vinyl monomer (c) is dissolved, but the polymer is not dissolved. In addition, various known and commonly used compounds can be used as long as they can dissolve the dispersion stabilizing polymer (a).

Of these, only typical ones will be exemplified. At least two silicon atoms in one molecule, which are prepared in the presence of the above-mentioned dispersion stabilizing polymer (a), are used. Organic solvents that can be used in the hydrolysis or condensation reaction of the silyl group-containing silicon compound (b) having a bonded hydrolyzable group can be mentioned as they are, or they can be used alone or Of course, more than one kind may be used in combination.

At that time, as described above, the vinyl monomer (c) is also dissolved, and the dispersion stabilizing polymer (a) is obtained.
, But the polymer does not dissolve,
It is necessary to select the organic solvent (d) in such a form, paying particular attention to so-called solubility balancing.

As the organic solvent, only typical ones are exemplified, and various aliphatic or alicyclic compounds represented by white spirit, mineral spirit, hexane or octane are used. Formula type hydrocarbon is the main component, but if necessary,
Of course, other organic solvents can be used together.

Next, when the vinyl monomer (c) is subjected to non-aqueous dispersion polymerization in the presence of the reaction mixture obtained by the above-mentioned hydrolysis or condensation reaction,
Usually, it is appropriate to use a radical polymerization initiator.

As the polymerization initiator that can be used here, of course, various known and commonly used compounds can be used, but of these, only typical ones will be mentioned. 2,2'- Various azo compounds such as azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) or 2,2′-azobis (2-methylbutyronitrile);

Or tert-butyl peroxypivalate, tert-butyl peroxybenzoate, te
rt-butylperoxy-2-ethylhexanoate,
Benzoyl peroxide, lauroyl peroxide, acetyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide or diisopropyl peroxycarbonate. Peroxides and the like.

The amount of these polymerization initiators used is preferably in the range of about 0.05 to about 15 parts by weight per 100 parts by weight of the vinyl monomer (c) used for polymerization, A range of 0.1 to 10 parts by weight is suitable.

The above-mentioned dispersion-stabilizing polymers (a) obtained by a hydrolysis or hydrolysis-condensation reaction, which should coexist in the above-mentioned non-aqueous dispersion polymerization, and at least 2 per molecule. The ratio of the composite resin amount of the silicon compound (b) having a hydrolyzable group bonded to a silicon atom to the vinyl monomer (c) is the same as the former [(a)
+ (B)] component to 100 parts by weight, the latter component (c) is appropriately in the range of about 1 to about 300 parts by weight, preferably about 5 to 200 parts by weight. is there.

Further, as described above, the dispersion stabilizing polymer (a) in the organic solvent in the dispersion polymerization reaction and at least two hydrolyzable groups bonded to silicon atoms in one molecule are contained. The total concentration of the vinyl-based monomer (c) and the composite resin composed of the hydrolyzed or hydrolyzed condensate of the silicon compound (b) is preferably about 20 to about 80% by weight, and preferably About 30 to 70% by weight is suitable.

The suitable polymerization temperature for the non-aqueous dispersion polymerization reaction is about 0.degree. C. to about 160.degree. C., preferably about 50 to 120.degree. It can be performed under any pressure, such as reduced pressure.

The polymerization reaction at that time is about 1 to
About 20 hours is suitable, and usually the reaction is completed within such a range.

Further, the above-mentioned catalyst for hydrolysis or condensation reaction is added to the thus obtained non-aqueous dispersion liquid (A) to prepare at least two hydrolyzed compounds bonded to silicon atoms in one molecule. It can also be said that a further condensation reaction of the hydrolyzate or the hydrolyzed condensate of the silicon compound (b) having a decomposable group is advanced.

The compound (C) used in the present invention which reacts with the functional group contained in the non-aqueous dispersion liquid (A) is contained in the polymer dispersed particles of the non-aqueous dispersion liquid (A) described above. It has various functional groups capable of reacting with various functional groups as described above and has at least one kind in one molecule, and various known and commonly used compounds are referred to. To exemplify only typical ones as the functional group, an isocyanate group, a blocked isocyanate group, a hydroxyl group, a blocked hydroxyl group, a carboxyl group, a blocked carboxyl group, a carboxylic acid anhydride group, an amino group, Cyclocarbonate group, chain carbonate group, epoxy group, primary amide bond, secondary amide bond, carbamate group, oxazoline group, N-hydroxymethyl group It is an amino group, an N-alkoxymethylamino group, a carbonyl group, an acetoacetyl group, a phosphoric acid group, a sulfonic acid group, a silanol group or a hydrolyzable group bonded to a silicon atom, or the following structural formula (II )

[0166]

Embedded image —NH—CH (OR ₁ ) —COOR ₂ (V)

(Wherein R ₁ and R ₂ in the formula may be the same or different, a hydrogen atom,
It represents an alkyl group or an aryl group having 1 to 8 carbon atoms. )

And functional groups such as those shown in.

The functional group (f- in the compound (C) which reacts with the functional group (f-1) in the non-aqueous dispersion (A) referred to herein.
It can be said that 2) is appropriately selected, but such representative combinations of the functional group (f-1) and the functional group (f-2), particularly only typical ones, will be exemplified. If you stay,

Functional group (f-1) Functional group (f-2)

Hydroxyl group, isocyanate group, hydroxyl group, carboxylic anhydride group, isocyanate group, hydroxyl group, isocyanate group, amino group, carboxyl group, epoxy group, epoxy group, carboxyl group, epoxy group, amino group

And the like.

In particular, a combination of a hydroxyl group, an amino group and / or a carboxyl group as the functional group (f-1) and an isocyanate group as the functional group (f-2), or a functional group (f-1 ), A combination of an amino group and / or a carboxyl group with an epoxy group as the functional group (f-2), and the like. It is desirable from the viewpoint that the control of the crosslinked structure is easy.

The compound (C) has two or more of the various functional groups described above, depending on the functional groups contained in the non-aqueous dispersion liquid (A). Good. Further, as the compound (C),
It can be said that various resins are used in addition to the compound having a relatively low molecular weight.

[0175] As such resins, only typical ones are exemplified, and various vinyl-based polymers such as acrylic resin or fluororesin, polyester resin, alkyd resin, polyurethane resin or epoxy resin. And so on. When using a compound having two or more kinds of functional groups as described above as the compound (C), it is convenient to use a vinyl polymer as the compound (C). Is.

Specific examples of the compound (C) are as follows: polyisocyanate compounds; blocked polyisocyanate compounds; polyepoxy compounds; polycyclocarbonate compounds; amino resins; primary or secondary amides. Bond-containing compound; polycarboxy compound; polyhydroxy compound; compound having blocked hydroxyl group; polyamine compound;

With an epoxy group or an amino group in one molecule,
A compound having both a hydrolyzable group bonded to a silicon atom;
A compound having at least two carboxylic acid anhydride groups; a polyoxazoline compound; a polysiloxane having a silanol group and / or a hydrolyzable group bonded to a silicon atom, etc., and these various compounds can be used alone. As a matter of course, it may be present or two or more types may be used in combination.

Of these, particularly preferable are polyisocyanate compounds, blocked polyisocyanate compounds, polyepoxy compounds, polycyclocarbonate compounds, amino resins, primary or secondary amide bond-containing compounds, polycarboxy compounds, polyhydroxy compounds. A compound or a compound having both an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule.

As the above-mentioned polyisocyanate compounds, only typical ones will be exemplified. Tolylene diisocyanate or diphenylmethane-4,
Various aromatic diisocyanates such as 4'-diisocyanate; meta-xylylene diisocyanate, α,
various aralkyl diisocyanates such as α, α ′, α′-tetramethyl-meta-xylylene diisocyanate;

Hexamethylene diisocyanate, lysine diisocyanate, 1,3-bisisocyanatomethylcyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane or isophorone diisocyanate. , Various aliphatic or cycloaliphatic diisocyanates;

Alternatively, prepolymers having an isocyanate group, which can be obtained by addition reaction of various polyisocyanates such as those mentioned above with polyhydric alcohols; cyclization of various polyisocyanates such as those mentioned above Various types of prepolymers having an isocyanurate ring, which can be obtained by quantification.

Various polyisocyanates having a biuret structure, which can be obtained by reacting various polyisocyanates as described above with water, and further, 2-isocyanatoethyl ( Homopolymers of various vinyl monomers having an isocyanate group such as (meth) acrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate or (meth) acryloyl isocyanate; or these isocyanate group-containing vinyl monomers The quantity

(Meth) acryl-based, vinyl ester-based, vinyl ether-based, aromatic vinyl-based or fluoroolefin-based vinyl monomer as the other vinyl-based monomer copolymerizable with the monomer, respectively. As obtained by copolymerizing with a body, such as an isocyanate group-containing acrylic copolymer, a vinyl ester copolymer or a fluoroolefin copolymer,
Examples include various vinyl-based copolymers.

Among such polyisocyanates, particularly from the viewpoint of weather resistance and the like, those derived from aliphatic or alicyclic diisocyanate compounds and the like, and further derived from the respective diisocyanate compounds It is particularly preferable to use various prepolymers or isocyanate group-containing vinyl polymers.

As the above-mentioned blocked polyisocyanate compounds, only representative ones will be exemplified, and various polyisocyanate compounds as mentioned above will be blocked with various blocking agents as mentioned later. Various block polyisocyanate compounds in the form obtained by squeezing,

The compounds of the class in which the isocyanate group is regenerated by heat, such as the compounds having various uretdione structures obtained by cyclizing and dimerizing the isocyanate group, are included.

[0187] Then, only the typical blocking agents mentioned above which are used in the preparation of the block (poly) isocyanate (compound) are exemplified by methanol, ethanol and benzyl alcohol. Or various carbinol group-containing compounds such as lactate ester;

Various phenolic hydroxyl group-containing compounds such as phenol, salicylic acid ester or cresol; or various amides such as ε-caprolactam, 2-pyrrolidone or acetanilide;

Also, various oximes such as acetone oxime or methyl ethyl ketoxime, and various active methylene compounds such as methyl acetoacetate, ethyl acetoacetate or acetylacetone.

As the above-mentioned polyepoxy compounds, only typical ones will be exemplified. Ethylene glycol, hexanediol, neopentyl glycol,
Polyglycidyl ethers of various aliphatic or cycloaliphatic polyols, such as trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, sorbitol or hydrogenated bisphenol A;

Hydroquinone, catechol, resorcin,
Polyglycidyl ethers of various aromatic diols such as bisphenol A, bisphenol S or bisphenol F; various aromatics such as ethylene oxide or propylene oxide adducts of aromatic diols as listed above Diglycidyl ethers of diol derivatives of the series;

Polyglycidyl ethers of various polyether polyols such as polyethylene glycol, polypropylene glycol or polytetraethylene glycol; polyglycidyl ethers of tris (2-hydroxyethyl) isocyanurate; adipic acid, butanetetracarboxylic Various polyglycidyl esters of aliphatic or aromatic polycarboxylic acids such as acids, propanetricarboxylic acids, phthalic acid, terephthalic acid or trimellitic acid;

Various bisepoxides of various hydrocarbon dienes such as butadiene, hexadiene, octadiene, dodecadiene, cyclooctadiene, α-pinene or vinylcyclohexene; bis (3,4-epoxycyclohexylmethyl) adipate or Three
Various cycloaliphatic polyepoxy compounds such as 4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate; or various epoxidized products of various diene polymers such as polybutadiene or polyisoprene;

Alternatively, various homopolymers of various epoxy group-containing vinyl monomers as described above, or other copolymers capable of copolymerizing these epoxy group-containing vinyl monomers with the above monomers. Epoxy group-containing, such as those obtained by copolymerization with (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl monomers as monomers Various vinyl-based copolymers such as an acrylic-based copolymer, a vinyl ester-based copolymer, or a fluoroolefin-based copolymer.

As only specific examples of the polycyclocarbonate compound, the various polyepoxy compounds as described above are reacted with carbon dioxide in the presence of a catalyst, for example. A polycyclocarbonate compound having a 5-membered cyclocarbonate group obtained by converting the epoxy group into a cyclocarbonate group; or various vinyl monomers having a cyclocarbonate group as described above. A homopolymer of

Alternatively, these cyclocarbonate group-containing vinyl monomers may be used as other monomers copolymerizable with the monomers, and are (meth) acrylic type, vinyl ester type and vinyl ether type, respectively. Of a cyclocarbonate group-containing acrylic copolymer, vinyl ester copolymer or fluoroolefin copolymer obtained by copolymerization with aromatic vinyl-based or fluoroolefin-based vinyl monomers and the like. And various vinyl-based copolymers.

As the amino resins, only typical ones will be exemplified. Melamine, benzoguanamine,
Such as acetoguanamine, urea or glycouril,
Various amino resins having an alkylol group, such as those obtained by reacting various amino group-containing compounds with various aldehyde compounds (or aldehyde supply substances) such as formaldehyde or acetaldehyde;

Alternatively, an amino resin having an alkoxyalkyl group in a form obtained by reacting such an alkylol group-containing amino resin with various lower alcohols such as methanol, ethanol, n-butanol or i-butanol. And so on.

Further, only the particularly representative examples of the primary or secondary amide bond-containing compound are exemplified, and the compounds having the primary or secondary amide bond, such as those already exemplified, are used. Homopolymers of various vinyl monomers having a primary or secondary amide bond,

[0200] Alternatively, these primary or secondary amide bond-containing vinyl monomers may be used as the other monomers copolymerizable with the (meth) acrylic type and vinyl ester, respectively. Various acrylic copolymers and vinyls having a primary or secondary amide bond, such as those obtained by copolymerizing with vinyl type, vinyl ether type, aromatic vinyl type or fluoroolefin type vinyl monomers Various vinyl-based copolymers such as ester-based copolymers and fluoroolefin-based copolymers.

Further, to exemplify only typical examples of polycarboxy compounds, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, terephthalic acid, So-called low molecular weight compounds such as isophthalic acid, tartronic acid, malic acid, tartaric acid or citric acid etc.,
further,

Homopolymers of various vinyl monomers having a carboxyl group; or these vinyl monomers containing a carboxyl group can be copolymerized with the monomer, respectively.
Various acrylic copolymers having a carboxyl group, such as those obtained by copolymerization with (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl monomers. Various vinyl-based copolymers such as a polymer, a vinyl ester-based copolymer or a fluoroolefin-based copolymer.

Specific examples of polyhydroxy compounds include low molecular compounds such as ethylene glycol, propylene glycol, butylene glycol and glycerin, and polyethylene glycol or polypropylene glycol. Further, as already exemplified, homopolymers of various vinyl monomers having a hydroxyl group, or vinyl compounds containing these hydroxyl groups can be copolymerized with the other monomers. As a monomer of (meth) acrylic type, vinyl ester type, vinyl ether type, aromatic vinyl type or fluoroolefin type vinyl monomers, etc. Having various acrylic copolymers, vinyl ester copolymers Or such fluoroolefin copolymer, various vinyl copolymers and the like.

If only a typical compound as a compound having both an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule is to be exemplified,

3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane or 3-glycidoxypropylmethyldiethoxysilane

Or "EGM-202" [trade name of a cyclic polysiloxane manufactured by Toray Dow Corning Silicone Co., which has both a methoxy group bonded to a silicon atom and 3-glycidoxypropyl]; or the above. Various copolymers comprising various epoxy group-containing vinyl monomers as described above and hydrolyzable silyl group-containing vinyl monomers as described above;

Alternatively, both of these monomers as another monomer copolymerizable with the both monomers,
(Meth) acryl-based, vinyl ester-based, vinyl ether-based, aromatic vinyl-based or fluoro-olefin-based vinyl monomers, etc., such as those obtained by copolymerization, having an epoxy group / hydrolyzable silyl group, These are various vinyl-based copolymers such as an acrylic-based copolymer; a vinyl ester-based copolymer; or a fluoroolefin-based copolymer.

To prepare a curable resin composition comprising the above-mentioned non-aqueous dispersion liquid (A) and a so-called reactive functional group-containing compound (C), this compound (C) is a polyisocyanate compound or In the case of a blocked polyisocyanate compound or the like, with respect to 1 equivalent of the functional group contained in the non-aqueous dispersion liquid (A), which reacts with an isocyanate group or a blocked isocyanate group,

The amount of isocyanate group contained in the compound (C) is within the range of about 0.1 to about 10 equivalents, preferably within the range of 0.3 to 5 equivalents, and more preferably 0.5.
The compound (C) may be blended so as to be within the range of 2 to 2 equivalents.

The compound (C) is a polyepoxy compound; a polycyclocarbonate compound; or a compound having both an epoxy group and a hydrolyzable group bonded to a silicon atom in one molecule. In this case, relative to 1 equivalent of the functional group contained in the non-aqueous dispersion (A), which reacts with the epoxy group or the cyclocarbonate group,

The total amount of epoxy groups and / or cyclocarbonate groups contained in the compound (C) is
Within the range of about 0.2 to about 5.0 equivalents, preferably 0.5
The compound (C) may be blended so as to be in the range of to 3.0 equivalents, and more preferably in the range of 0.7 to 2 equivalents.

When the compound (C) is an amino resin, the solid content of the compound (C) is 100 parts by weight of the solid content of the non-aqueous dispersion (A). Within the range of about 5 to about 200 parts by weight, preferably 10
To 150 parts by weight, more preferably 15 to 10 parts by weight.
The compound (C) may be blended so as to be in the range of 0 parts by weight.

When the compound (C) is a compound having a primary or secondary amide bond, a non-aqueous dispersion liquid (A) which reacts with such a primary or secondary amide bond. ) To 1 equivalent of the functional group contained in

The amount of the primary or secondary amide bond contained in the compound (C) is within the range of about 0.2 to about 5.0 equivalents, preferably 0.5 to 3.0 equivalents. Of these, the compound (C) may be added so that the amount is more preferably within the range of 0.7 to 2 equivalents.

In the case where the compound (C) is a polycarboxy compound, 1 equivalent of the functional group contained in the non-aqueous dispersion (A), which reacts with the carboxyl group, is added. The amount of the carboxyl group contained in the compound (C) is within the range of about 0.2 to about 5.0 equivalents, preferably within the range of 0.5 to 3.0 equivalents, and more preferably
The compound (C) may be added so that the amount falls within the range of 0.7 to 2 equivalents.

In the case where the compound (C) is a polyhydroxy compound, 1 equivalent of the functional group contained in the non-aqueous dispersion (A), which reacts with the hydroxy group, can be used. The amount of the hydroxyl group contained in the compound (C) is within the range of about 0.2 to about 5.0 equivalents, preferably
Within the range of 0.5 to 3.0 equivalents, more preferably 0.7
The compound (C) may be blended so as to be within the range of 2 to 2 equivalents.

The aqueous dispersion (A) obtained by various preparation methods as mentioned above is also used as a so-called self-crosslinking type, in which the curing catalyst (B) is used. However, it can also be used as a cross-linking type in the form of self-curing or as a cross-linking type in which a compound (C) that reacts with a functional group contained in the aqueous dispersion (A) is used in combination.

Further, the curable composition according to the present invention, in particular, the curable resin composition thus obtained, contains a functional group contained in the non-aqueous dispersion liquid (A) without adding a curing catalyst. By setting appropriate curing conditions depending on the combination of the functional group contained in the compound (C) that reacts with
Although it is possible to obtain a practical (practical) level of curability,

Further, the curing catalyst (B) can be blended in order to improve the curability at a low temperature or to achieve the curing in a short time.

If only representative examples of such curing catalyst (B) are exemplified, various catalysts as described above can be used, and in addition to these,
Various organic phosphines such as trimethylphosphine, triethylphosphine or triphenylphosphine;

Or a tetramethylphosphonium salt, a tetraethylphosphonium salt, a tetrapropylphosphonium salt, a tetrabutylphosphonium salt, a trimethyl (2-hydroxypropyl) phosphonium salt, a triphenylphosphonium salt or a benzylphosphonium salt, and the like,

Furthermore, as a typical counter anion,
It can be said that various ones such as various phosphonium salts each having chloride, bromide, carboxylate or hydroxide, etc. can be used.

When the curable composition according to the present invention is prepared from the curing catalyst (B) and the non-aqueous dispersion liquid (A), the catalyst amount of the (B) is the non-aqueous dispersion liquid ( A)
The solid content is about 0.0001 to about 10% by weight, preferably 0.001 to 5% by weight, and more preferably 0.002 to 3% by weight. But each is appropriate.

When the curing catalyst (B) is added to the composition comprising the non-aqueous dispersion liquid (A) and the reactive compound (C) to prepare the curable composition of the present invention. The catalyst amount of each is about 0.0 with respect to the total solid content of the non-aqueous dispersion liquid (A) and the reacting compound (C).
001 to about 10% by weight, preferably 0.00
001 to 5% by weight is more preferable, and more preferably 0.
The range of 002 to 3% by weight is suitable.

Furthermore, in addition to the particularly representative curing catalysts as described above, various polymers having atomic groups or groups which exhibit the catalytic effect contained in the curing catalyst described above may also be used. It can be used as an effective catalyst.

The curable resin composition according to the present invention prepared as described above further includes various resins, color pigments, extender pigments or solvents, flow regulators and color separation inhibitors. , Antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, rheology control agents, plasticizers, etc. It can be used and applied to.

As only various typical resins as listed above, only typical ones such as nitrocellulose or cellulose acetate butyrate are listed.
Various fiber-based resins; or vinyl chloride / vinyl acetate copolymer resins; ketone resins; or petroleum resins; polyesters; alkyd resins; or epoxy resins.

Of the pigments, only typical ones are specifically exemplified, and specific examples thereof include titanium oxide, zinc white, carbon black, iron black, copper chrome black, copper / iron / manganese black, Yellow lead, cadmium yellow, ocher, titanium yellow, zinc chromate,
Rouge, Zinc / Iron Brown, Cadmium Red, Chrome Vermillion, Manganese Violet, Navy Blue, Ultramarine Blue, Cobalt Blue, Chrome Green, Chrome Oxide Green, Titanium / Cobalt / Nickel / Zinc Green, Biliyan, Emerald Green, Cobalt Green, Kaolin , Bentonite, silica white, aluminum white,
Various inorganic pigments such as gypsum, chalk, precipitated calcium carbonate or barite;

Β-naphthol type, β-oxynaphthoic acid type, naphthol AS type, acetoacetic acid anilide type, phthalocyanine type, anthraquinone type, isodigo type, perylene type, perinone type, dioxazine type, quinacridone type, isoindolinone type, In addition to various organic pigments such as metal complex salt type, fluorbin type, quinophthalone type, or various metal powders such as gold powder, silver powder, brass powder, aluminum powder or copper powder,
Examples include scaly sea urchin treated with titanium oxide.

Among the extender pigments, specific examples in the form of exemplifying only representative ones include barium sulfate, calcium carbonate, magnesium carbonate, silica, alumina and clay.

The thus obtained curable resin composition according to the present invention is dried at room temperature for about 3 to 10 days, or at a temperature range of about 80 to 250 ° C.
By baking for about 30 seconds to about 2 hours, a cured product of extremely high practicality can be obtained.

The cured product obtained from the curable composition according to the present invention is particularly excellent in durability, acid resistance, scratch resistance, etc. It can be used and applied in a wide range of applications such as coatings for building exteriors, heat resistant coatings, adhesives, inks, impregnating agents for fibers and paper, and surface treatment agents. is there.

When the curable resin composition according to the present invention is used for various kinds of coating materials and applied, in particular, only representative ones as the base material to be coated are only exemplified. Then, such as aluminum, stainless steel, chrome plating, galvanized iron plate or tin plate,
Various metallic materials or products; or roof tiles; glass; or various inorganic building materials,

Concretely, it includes an automobile body or automobile (for) parts, a motorcycle or a motorcycle (for) parts, and various building materials such as gates or fences; aluminum sashes. , Various building interior / exterior materials; or various materials or products of various ferrous or non-ferrous metals such as aluminum foil.

[0235]

EXAMPLES Next, the present invention will be explained more specifically with reference to Reference Examples, Examples and Comparative Examples, but the present invention is by no means limited to these Examples. Absent. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 [Preparation Example of Polymer (a) for Dispersion Stabilization] In a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen introducing tube, 15 parts of xylene and "LA" were added.
35 "(trade name of White Spirit containing low aromatic hydrocarbon, manufactured by Shell Co., Netherlands) was charged, and the temperature was raised to 80 ° C under aeration of nitrogen gas.

Then, at the same temperature, 50 parts of 2-ethylhexyl methacrylate and 4 parts of n-butyl methacrylate were used.
7 parts and 3 parts of γ-methacryloylpropyltrimethoxysilane, 12 parts of xylene and 28 parts of “LAWS”.
Part and 5 parts of tert-butylperoxy-2-ethylhexanoate were added dropwise over 4 hours.

Even after completion of dropping, the non-volatile content was 53.5% by stirring at the same temperature for 10 hours.
And a Gardner viscosity (hereinafter abbreviated as viscosity) at 25 ° C. of OP was obtained as a solution of the target polymer. Hereinafter, this is abbreviated as (a-1).

Reference Example 2 (same as above) 50 parts of xylene was charged into a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen introducing tube, and the mixture was heated to 80 ° C. under aeration of nitrogen gas. The temperature was raised, and then, at the same temperature, 2-ethylhexyl methacrylate
0 part, 47 parts of n-butyl methacrylate and 3 parts of γ-methacryloylpropyltrimethoxysilane, 40 parts of xylene, tert-butylperoxy-2-
A mixture consisting of 5 parts of ethyl hexanoate was added dropwise over 4 hours.

Even after completion of the dropping, the non-volatile content was 53.1% by stirring at the same temperature for 10 hours.
And a solution of the target polymer having a viscosity of J ² -K was obtained. Hereinafter, this is abbreviated as (a-2).

Reference Example 3 (same as above) A reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen inlet tube was charged with 35 parts of "LAWS" and 15 parts of n-butanol to prepare a nitrogen gas. The temperature was raised to 80 ° C. under aeration.

Then, at the same temperature, 50 parts of 2-ethylhexyl methacrylate and 47 parts of n-butyl acrylate were used.
Part and 3 parts of 2-hydroxyethylmethacrylate, 28 parts of "LAWS", 12 parts of n-butanol and 5 parts of tert-butylperoxy-2-ethylhexanoate. Dropped over time.

Even after the dropping, the non-volatile content was 53.0% by stirring at the same temperature for 10 hours.
A solution of the target polymer having a viscosity of I was obtained. Hereinafter, this is abbreviated as (a-3).

Reference Example 4 (Same as above) [0244] A reaction vessel having a content of 2 liters, a pressure vessel made of stainless steel, a thermometer, a reflux condenser, a stirrer, a dropping device, and a nitrogen introduction tube was used, and 66 xylene was added. .7 parts,
2 parts of azobis valeronitrile (ABNV), 22 parts of ethyl vinyl ether, "Veova-9" (trade name of vinyl ester of carboxylic acid having an alkyl group having 9 carbon atoms, manufactured by Shell Co., Netherlands) 19 parts, 3 parts of hydroxybutyl vinyl ether and 3 parts of vinyltrimethoxysilane were charged, cooled to −70 ° C. in a dry ice / methanol bath, and nitrogen gas was blown thereinto to replace the air in the pressure resistant tube. did.

Then, 53 parts of chlorotrifluoroethylene collected in a liquid state was charged, and the tube was sealed. After that, the pressure-resistant sealed tube was placed in a rotary high-temperature water tank heated to 60 ° C. to carry out the reaction for 16 hours, whereby the nonvolatile content was 59.5% and the viscosity was Z. A solution of the target polymer was obtained. Hereinafter, this (a-4)
Abbreviated.

Reference Example 5 (Preparation Example of Non-Aqueous Dispersion) A reaction vessel equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with 101.6 parts of the resin (a-1) for dispersion stabilizer.
Parts, 2.1 parts of xylene and 5 parts of “LAWS”, and 85.7 parts of phenyltriethoxysilane were charged, and the temperature was raised to 80 ° C.

Then, at the same temperature, 0.17 parts of "AP-3" (trade name of isopropyl acid phosphate manufactured by Daihachi Chemical Industry Co., Ltd.) and 19.3 parts of ion-exchanged water.
Parts were stirred for 5 minutes at the same temperature for 4 hours, then 13.7 parts of xylene and "L" were added.
By adding 31.9 parts of "AWS" and then removing the by-products such as ethanol by vacuum distillation,
A solution of a composite resin having a nonvolatile content of 57.7% was obtained.

Then, 173.3 parts of the composite resin solution thus obtained, 23 parts of xylene and 53.7 parts of "LWAS" were added to a thermometer, a reflux condenser, a stirrer, a dropping funnel and nitrogen introduction. A reaction vessel equipped with a tube was charged and heated to 80 ° C. under aeration of nitrogen gas.

After that, at the same temperature, 32.5 parts of methyl methacrylate, 16.0 parts of ethyl acrylate and 1.5 parts of γ-methacryloylpropyltrimethoxysilane, 22.5 parts of xylene and "LAWS".
52.5 parts and 1.0 part of tert-butylperoxy-2-ethylhexanoate.
Dropped over time.

Even after the completion of dropping, the non-volatile content was 40.0% by stirring at the same temperature for 10 hours.
And a cloudy non-aqueous dispersion (A-1) having a viscosity of A ₄ -A ₃ was obtained. This non-aqueous dispersion liquid (A-1) was left to stand at room temperature for 3 months,
It was confirmed that no sedimentation of particles was observed and the stability was extremely good.

Reference Example 6 (same as above) 121.8 of the dispersion stabilizer resin (a-2) was placed in a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel.
Part and 95.4 parts of methyltriethoxysilane were charged, the temperature was raised to 80 ° C., and then “AP-
0.0026 parts of "3" and 29.4 parts of ion-exchanged water were added dropwise over 5 minutes.

After completion of the dropping, after stirring at the same temperature for 4 hours, 57.1 parts of n-butanol was added, and then by distillation under reduced pressure, by-products such as ethanol were removed. A solution of a composite resin having a nonvolatile content of 75.6% was obtained.

Then, 132.3 parts of the thus obtained composite resin solution, 17.6 parts of xylene and 17.6 parts of n-butanol were added to a thermometer, a reflux condenser, a stirrer,
The reaction vessel was equipped with a dropping funnel and a nitrogen introducing tube, and the temperature was raised to 80 ° C. under aeration of nitrogen gas.

Then, at the same temperature, 32.5 parts of methyl methacrylate, 16.0 parts of ethyl acrylate and 1.5 parts of γ-methacryloylpropyltrimethoxysilane were used together with "IP Solvent-1620" [Idemitsu Petrochemical Trade name of aliphatic hydrocarbon solvent manufactured by Co., Ltd.] 1
A mixture of 57.5 parts and 1.0 part of tert-butylperoxy-2-ethylhexanoate was added dropwise over 3 hours.

Even after completion of dropping, the non-volatile content was 42.1% by stirring at the same temperature for 10 hours.
And a cloudy non-aqueous dispersion (A-2) having a viscosity of B ² -C was obtained. This non-aqueous dispersion (A-2) was left at room temperature for 3 months,
It was confirmed that no sedimentation of particles was observed and the stability was extremely good.

Reference Example 7 (same as above) 143.5 of the dispersion stabilizer resin (a-3) was placed in a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel.
And 63.6 parts of methyltriethoxysilane were charged, the temperature was raised to 80 ° C., and at the same temperature, 0.0018 parts of “AP-3” and 19.8 parts of ion-exchanged water were added. 5
Dropped in minutes.

After completion of the dropwise addition, after stirring at the same temperature for 4 hours, 47.2 parts of "LAWS" and 20.2 parts of n-butanol were added, and then by distillation under reduced pressure, a secondary distillation was conducted. By removing products such as ethanol,
A solution of a composite resin having a nonvolatile content of 68.4% was obtained.

Then, 146.2 parts of the composite resin solution thus obtained, 14.9 parts of "LAWS", and 6.4 parts of n-butanol were added to a thermometer, a reflux condenser, a stirrer, and dropwise. The reaction vessel was equipped with a funnel and a nitrogen introducing tube, and the temperature was raised to 80 ° C. under aeration of nitrogen gas.

Then, at the same temperature, 32.5 parts of methyl methacrylate, 16.0 parts of ethyl acrylate and 1.5 parts of γ-methacryloylpropyltrimethoxysilane and 157.
A mixture of 5 parts and 1.0 part of tert-butylperoxy-2-ethylhexanoate was added dropwise over 3 hours.

Even after the dropping, the non-volatile content was 40.1% by stirring at the same temperature for 10 hours.
In, and a viscosity of Z _1, milky aqueous dispersion (A-
3) was obtained. This non-aqueous dispersion (A-3) has extremely good stability, in that no sedimentation of particles was observed even after leaving it at room temperature for 3 months. It was confirmed.

Reference Example 8 (same as above) 129.3 of the dispersion stabilizer resin (a-4) was placed in a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel.
Part and 42.9 parts of phenyltriethoxysilane were charged, the temperature was raised to 80 ° C., and at the same temperature, “AP-3”
Of 0.086 parts and 9.6 parts of ion-exchanged water were added dropwise over 5 minutes.

After completion of the dropping, after stirring at the same temperature for 4 hours, 47.6 parts of xylene was added, and then by distillation under reduced pressure, by-products such as ethanol were removed. A composite resin solution having a content of 60.0% was obtained.

Then, 166.6 parts of the composite resin solution thus obtained and 0.9 part of xylene were charged into a reaction vessel equipped with a thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen introducing tube. The temperature was raised to 80 ° C. under aeration of nitrogen gas.

Then, at the same temperature, 32.5 parts of methyl methacrylate, 16.0 parts of ethyl acrylate and 1.5 parts of γ-methacryloylpropyltrimethoxysilane and 157. of “IP Solvent-1620” were used.
A mixture of 5 parts and 1.0 part of tert-butylperoxy-2-ethylhexanoate was added dropwise over 3 hours.

Even after the completion of dropping, the non-volatile content was 40.0% by stirring at the same temperature for 10 hours.
And a cloudy, non-aqueous dispersion (A
-4) was obtained. This non-aqueous dispersion (A-4)
It was confirmed that even after standing at room temperature for 3 months, no sedimentation of particles was observed and the stability was extremely good.

Example 1 The non-aqueous dispersion liquid (A-1) obtained in Reference Example 5 was used as a top coat as it was by itself and was used in advance.
It was applied onto an electrodeposited plate and onto a substrate having a commercially available intermediate coat and metallic base.

Examples 2 and 3 100 parts of each of the non-aqueous dispersions (A-1) and (A-2) obtained in Reference Examples 5 and 6 were separately used as a curing catalyst (B). A curable composition was obtained in which 0.1 part of dibutyltin dilaurate was blended.

Examples 4 and 5 100 parts of each of the non-aqueous dispersions (A-3) and (A-4) obtained in Reference Examples 7 and 8 were separately added as a reactive compound (C). Of "Super Beckamine L
-127-75B "[trade name of melamine resin manufactured by Dainippon Ink and Chemicals, Inc.] was obtained to obtain a curable composition in the form of 13 parts.

Examples 6 and 7 100 parts of each of the non-aqueous dispersions (A-3) and (A-4) obtained in Reference Examples 7 and 8 were separately added as a reactive compound (C). Of the "Burnock DN-99
0S "[trade name of polyisocyanate compound manufactured by Dainippon Ink and Chemicals, Inc.] was added, and 0.01 part of dibutyltin dilaurate as a curing catalyst (B) was also added. A curable composition in the form of was obtained.

Table 1 shows the various performances of each curable composition obtained in each of the examples as described above.

Comparative Example 1 A non-aqueous dispersion liquid (HA-1) for control was obtained in the same manner as in Reference Example 5 except that the silicon compound (b) phenyltriethoxysilane was not used at all. Subsequently, a curable composition for control was obtained in the same manner as in Example 2 except that this non-aqueous dispersion liquid (HA-1) was used.

Application Example A dry film thickness was 40 μm on an electrodeposition coated plate,
An intermediate coat was applied and heat curing was carried out at 140 ° C. for 20 minutes. Then, a commercially available acrylic melamine-based metallic base paint was applied thereon, and then cured at 140 ° C. for 20 minutes, and thereafter, obtained by each example. The curable composition and the control curable composition obtained in the comparative example were separately applied so that the dry film thickness was 30 μm, and baked under the respective conditions as shown in Table 1. Or, it was dried at room temperature to obtain various test pieces. Table 1 collectively shows the test results of the evaluation judgment for each of the test pieces.

[0273]

[Table 1]

<< Footnote in Table 1 >> Note 1) Curing condition (1): baking at 160 ° C./30 minutes (2): baking at 140 ° C./20 minutes (3): forced drying at 70 ° C./30 minutes In the case of the evaluation, the evaluation judgment was carried out after leaving it for one week after the forced drying.

Note 2) DuPont type, with 1/2 inch notch, height (cm) at the time when the coating film does not crack under a load of 500 g

Note 3) The temperature that a sulfuric acid etching method can withstand

Note 4) Gloss retention (%) at 20 ° gloss after rubbing test

Note 5) Gloss retention (%) after 3,000 hours

Note 6) Gloss retention rate (%) two years after exposure in the suburbs of Miyazaki City

[0280]

[Table 2]

As described in detail above, the non-aqueous dispersion liquid used in preparing the curable composition according to the present invention is
A hydrolyzate or a hydrolyzate obtained by hydrolyzing or condensing at least two silicon compounds having a hydrolyzable group bonded to a silicon atom in one molecule in the presence of a dispersion stabilizing polymer. Hydrolyzed condensate in a complex form, in the coexistence of so-called modified resin, obtained by polymerizing a vinyl-based monomer, from the novel,

The curable composition according to the present invention comprises, inter alia:
Appearance, smoothness and mechanical properties are good, and moreover, especially, as a coating composition capable of forming a coating film having excellent so-called durability such as weather resistance, It is extremely practical.

[0283]

EFFECTS OF THE INVENTION The curable composition of the present invention using the above-mentioned non-aqueous dispersion has particularly good appearance, smoothness, and mechanical properties and is exposed to light. It is possible to form a cured coating film having excellent durability such as gloss retention property and water repellency retention property, acid resistance, scratch resistance, etc., and particularly a so-called durable coating film such as weather resistance. As a coating composition, it is extremely highly practical.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location C09D 201/00 PDC C09D 201/00 PDC

Claims (14)

[Claims] 1. In the presence of the dispersion stabilizing polymer (a),
A modified resin obtained by hydrolyzing at least two silicon compounds (b) having a hydrolyzable group bonded to a silicon atom in one molecule, and further subjecting the compound to a condensation reaction, and a vinyl-based resin. A non-aqueous dispersion obtained by subjecting the vinyl-based monomer (c) to non-aqueous dispersion polymerization in the presence of an organic solvent (d) in which the monomer (c) is soluble but the polymer is insoluble. A curable composition containing A) as an essential film-forming component. 2. In the presence of the dispersion stabilizing polymer (a),
A modified resin obtained by hydrolyzing at least two silicon compounds (b) having a hydrolyzable group bonded to a silicon atom in one molecule, and further subjecting the compound to a condensation reaction, and a vinyl-based resin. A non-aqueous dispersion obtained by subjecting the vinyl-based monomer (c) to non-aqueous dispersion polymerization in the presence of an organic solvent (d) in which the monomer (c) is soluble but the polymer is insoluble. A curable composition comprising A) and a curing catalyst (B) as essential components. 3. In the presence of the dispersion stabilizing polymer (a),
A modified resin obtained by hydrolyzing at least two silicon compounds (b) having a hydrolyzable group bonded to a silicon atom in one molecule, and further subjecting the compound to a condensation reaction, and a vinyl-based resin. A non-aqueous dispersion obtained by subjecting the vinyl-based monomer (c) to non-aqueous dispersion polymerization in the presence of an organic solvent (d) in which the monomer (c) is soluble but the polymer is insoluble. A curable composition comprising A) and a compound (C) which reacts with a functional group contained in the non-aqueous dispersion (A) as essential components. 4. In the presence of the dispersion stabilizing polymer (a),
A modified resin obtained by hydrolyzing at least two silicon compounds (b) having a hydrolyzable group bonded to a silicon atom in one molecule, and further subjecting the compound to a condensation reaction, and a vinyl-based resin. A non-aqueous dispersion obtained by subjecting the vinyl-based monomer (c) to non-aqueous dispersion polymerization in the presence of an organic solvent (d) in which the monomer (c) is soluble but the polymer is insoluble. A curable composition comprising A), a compound (C) that reacts with a functional group contained in the non-aqueous dispersion (A), and a curing catalyst (B) as essential components. 5. The dispersion-stabilizing polymer (a),
The curable composition according to claim 1, which is a polymer having a hydrolyzable silyl group and / or a hydroxyl group. 6. The curable composition according to claim 1, wherein the dispersion stabilizing polymer (a) is a vinyl polymer. 7. The curable composition according to claim 6, wherein the vinyl polymer is an acrylic polymer. 8. The curable composition according to claim 6, wherein the vinyl-based polymer is a fluoroolefin-based polymer. 9. The above-mentioned silicon compound (b) having at least two hydrolyzable groups bonded to a silicon atom in one molecule is tetraalkoxysilane, organotrialkoxysilane, diorganodialkoxysilane, The curable composition according to any one of claims 1 to 4, which is at least one alkoxysilane selected from the group consisting of partial hydrolysis-condensation products thereof and partial co-hydrolysis-condensation products thereof. 10. The curable composition according to claim 1, wherein the vinyl-based monomer (c) has an alkoxysilyl group as the hydrolyzable silyl group. . 11. The method according to claim 1, wherein the vinyl-based monomer (c) is obtained by using a hydrolyzable silyl group-containing vinyl monomer as an essential monomer component. Curable composition in any one. 12. The vinyl-based monomer (c) according to claim 1, which has an alkoxy group as the hydrolyzable group. Curable composition. 13. The curing according to claim 1, wherein the vinyl-based monomer (c) uses a monomer having a reactive functional group as at least a part thereof. Sex composition. 14. The monomer having a reactive functional group described above has a monomer having a hydroxyl group, a monomer having a blocked hydroxyl group, a monomer having a carboxyl group, and a blocked carboxyl group. Monomer, monomer having cyclocarbonate group, monomer having primary amide bond, monomer having secondary amide bond, monomer having amino group, monomer having cabamate group, epoxy A monomer having a group, a monomer having a carboxylic acid anhydride group and a functional group represented by the following structural formula (I) -NH-C (O) -NC (O)-(I) 14. The curable composition according to claim 13, which is at least one selected from the group consisting of monomers having.