JP2024005577A - Resin composition, coating composition and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of forming a coating film having excellent storage stability, coating film appearance, adhesiveness, weather resistance, solvent resistance and contamination resistance.

SOLUTION: There is provided a resin composition comprising a polysiloxane composite resin and a hydrocarbon-based organic solvent, wherein the polysiloxane composite resin is a composite resin in which a vinyl polymer (A) and a polysiloxane (B) are bonded, the vinyl polymer (A) includes a vinyl polymer (a1) having a hydrolyzable silyl group and/or a silanol group and a vinyl polymer (a2) other than the vinyl polymer (a1) and the difference (SP difference) between the solubility parameter (SP1) of the vinyl polymer (a1) and the solubility parameter (SP2) of the vinyl polymer (a2) is 0.1 to 1.5 (cal/cm³)^1/2.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

TECHNICAL FIELD The present invention relates to resin compositions, coatings, and articles.

Hydrocarbon solvent-based paints have excellent film-forming properties and quick-drying properties, and have been used in various paint applications, mainly in cold regions and on roofs. As a paint with a low-staining function added to such a paint, a top coat composition containing a polyol resin dispersion, a curing agent, and a condensate of a silane compound has been proposed (see, for example, Patent Document 1).

However, against the backdrop of the demand for repainting structures and high-rise housing, ultra-high weather resistance is required to extend the lifespan of paint films, and there is a problem in that the paint films obtained from the above paint compositions lack weather resistance. Ta.

Patent No. 3877040

The problem to be solved by the present invention is to provide a resin composition that has excellent storage stability and can form a coating film that has excellent coating appearance, adhesion, weather resistance, solvent resistance, and stain resistance. be.

As a result of intensive research to solve the above problems, the present inventors found that a resin composition in which a specific polysiloxane composite resin is dissolved or dispersed in a hydrocarbon organic solvent has excellent storage stability. The present invention was completed based on the discovery that the resulting cured coating film has excellent appearance, adhesion, weather resistance, solvent resistance, and stain resistance.

That is, the present invention provides a polysiloxane segment (B) of a composite resin (AB) formed by bonding a vinyl polymer segment (A) and a polysiloxane segment (B), and a condensate (c) of trialkoxysilane. A resin composition in which a composite resin (ABC) in which polysiloxane segments (C) are bonded via silicon-oxygen bonds is dissolved or dispersed in a hydrocarbon organic solvent, A vinyl polymer (a) in which the combined segment (A) contains a vinyl polymer (a1) having a hydrolyzable silyl group and/or a silanol group and a vinyl polymer (a2) other than the vinyl polymer (a1). The difference (SP difference) between the solubility parameter (SP1) of the vinyl polymer (a1) and the solubility parameter (SP2) of the vinyl polymer (a2) is 0.1 to 1.5. (cal/cm ³ ) ^1/2 .

The resin composition of the present invention has excellent storage stability and the resulting coating film has excellent appearance, adhesion, weather resistance, solvent resistance, and stain resistance. Interior and exterior materials for buildings; civil engineering components such as repair applications for concrete structures, soundproof walls, and drainage ditches; housings for home appliances such as televisions, refrigerators, washing machines, and air conditioners; personal computers, smartphones, mobile phones, digital cameras, It can be suitably used for various coating applications such as housings of electronic devices such as game machines; housings of office automation equipment such as printers and facsimiles; interior and exterior materials of various vehicles such as automobiles and railway vehicles; and various coating applications such as industrial machinery.

The resin composition of the present invention comprises a polysiloxane segment (B) of a composite resin (AB) formed by bonding a vinyl polymer segment (A) and a polysiloxane segment (B), and a condensate of trialkoxysilane (c A resin composition in which a composite resin (ABC) in which polysiloxane segments (C) derived from ) are bonded via silicon-oxygen bonds is dissolved or dispersed in a hydrocarbon organic solvent, A vinyl polymer (A) in which the vinyl polymer segment (A) contains a vinyl polymer (a1) having a hydrolyzable silyl group and/or a silanol group, and a vinyl polymer (a2) other than the vinyl polymer (a1). a), and the difference (SP difference) between the solubility parameter (SP1) of the vinyl polymer (a1) and the solubility parameter (SP2) of the vinyl polymer (a2) is 0.1 to 1. .5 (cal/cm ³ ) ^1/2 .

First, composite resin (ABC) will be explained. The composite resin (ABC) is composed of a polysiloxane segment (B) of a composite resin (AB) formed by bonding a vinyl polymer segment (A) and a polysiloxane segment (B), and a condensate of trialkoxysilane (c ) is bonded to the polysiloxane segment (C) derived from ) through a silicon-oxygen bond.

Examples of the composite resin (ABC) include a composite resin having a graft structure in which the polysiloxane segment (B) is chemically bonded to the side chain of the vinyl polymer segment (A), and a composite resin having a graft structure in which the polysiloxane segment (B) is chemically bonded to the side chain of the vinyl polymer segment (A); A polysiloxane segment (B) of a composite resin having a block structure in which the polysiloxane segment (B) is chemically bonded to the terminal of A), and a polysiloxane segment (C) derived from a condensate of trialkoxysilane (c). Examples include composite resins having a structure in which and are chemically bonded via silicon-oxygen bonds.

The chemical bond between the vinyl polymer segment (A) and the polysiloxane segment (B) that the composite resin (ABC) has includes, for example, the bonding mode of the following general formula (3) or (4). Among them, it is preferable to use a composite resin having the bonding mode of general formula (3) because it can form a coating film with excellent weather resistance.

（一般式（３）中の炭素原子は前記ビニル重合体セグメント（Ａ）の一部分を構成し、珪素原子と酸素原子は前記ポリシロキサンセグメント（Ｂ）の一部分を構成するものである。）

(The carbon atom in general formula (3) constitutes a portion of the vinyl polymer segment (A), and the silicon atom and oxygen atom constitute a portion of the polysiloxane segment (B).)

（一般式（４）中の炭素原子は前記ビニル重合体セグメント（Ａ）の一部分を構成し、珪素原子と酸素原子は前記ポリシロキサンセグメント（Ｂ）の一部分を構成するものである。）

(The carbon atom in general formula (4) constitutes a portion of the vinyl polymer segment (A), and the silicon atom and oxygen atom constitute a portion of the polysiloxane segment (B).)

The composite resin (ABC) may be a combination of the vinyl polymer segment (A) and the polyester resin, since the storage stability, appearance, adhesion, weather resistance, solvent resistance, and stain resistance of the resulting coating film are further improved. The bond with the polysiloxane segment (B) is the hydrolyzable silyl group and/or silanol group possessed by the vinyl polymer segment (A) and the hydrolyzable silyl group and/or silanol group possessed by the polysiloxane segment (B). Preferably, it is a condensed bond with a group.

The vinyl polymer segment (A) has a hydrolyzable silyl group, while the polysiloxane composite resin (ABC) is stably dispersed in the hydrocarbon solvent and has excellent storage stability and coating appearance. and/or derived from a vinyl polymer (a) containing a vinyl polymer (a1) having a silanol group and a vinyl polymer (a2) other than the vinyl polymer (a1); The difference (SP difference) between the solubility parameter (SP1) of a1) and the solubility parameter (SP2) of the vinyl polymer (a2) is 0.1 to 1.5 (cal/cm ³ ) ^1/2 . is important.

Since the vinyl polymer (a) contains the vinyl polymer (a1) having a hydrolyzable silyl group and/or silanol group, the hydrolyzable silyl group contained in the polysiloxane segment (B) or its synthetic raw material is and/or can be easily hydrolyzed and condensed with a silanol group to form a chemical bond in the bonding mode of general formula (3). Note that the vinyl polymer (a2) may or may not have a hydrolyzable silyl group and/or a silanol group.

The SP difference is the absolute value of the difference between SP1 and SP2. In addition, the value of the solubility parameter ((cal/cm ³ ) ^1/2 ) of the vinyl polymer is calculated by adding the value obtained by multiplying the SP value of the homopolymer by the mass ratio, and specifically, It can be calculated using the following formula. Incidentally, the SP value of the homopolymer is described in Journal of Paint Technology, Vol. 42, No. 541, p. 76 (1970) by K. L. The numerical values described in the literature described by Hoy are adopted.
SP1=ΣSP(m)*X(m)
SP (m): SP value of the homopolymer of each monomer constituting the vinyl polymer (a1) X (m): Composition mass ratio of each monomer ΣX (m) = 1
SP2=ΣSP(n)*X(n)
SP (n): SP value of the homopolymer of each monomer constituting the vinyl polymer (a2) X (n): Composition mass ratio of each monomer ΣX (n) = 1

The hydrolyzable silyl group may be any functional group that can generate a hydroxyl group (silanol group) bonded to a silicon atom by being hydrolyzed, such as a halogen atom bonded to a silicon atom, a silicon atom, etc. Alkoxy group bonded to an atom, acyloxy group bonded to a silicon atom, phenoxy group bonded to a silicon atom, mercapto group bonded to a silicon atom, amino group bonded to a silicon atom, amide group bonded to a silicon atom, Examples include a bonded aminooxy group, an iminooxy group bonded to a silicon atom, an alkenyloxy group bonded to a silicon atom, etc. Among these, hydrolysis reactions can easily proceed, and by-products after the reaction can be easily removed. Therefore, an alkoxy group bonded to a silicon atom is preferred.

The hydrolyzable silyl group and/or silanol group in the vinyl polymer (a1) is preferably 0.012 to 1.2 mol/kg, more preferably 0.012 to 0.6 mol/kg.

The vinyl polymer segment (A) may have a functional group other than a hydrolyzable silyl group or a silanol group, as long as the effects of the present invention are not impaired. Examples of the other functional groups include carboxyl groups, blocked carboxyl groups, carboxylic anhydride groups, hydroxyl groups, blocked hydroxyl groups, cyclocarbonate groups, epoxy groups, carbonyl groups, primary amide groups, and secondary amide groups. , a carbamate group, a polyethylene glycol group, a polypropylene glycol group, and a group represented by the following general formula (5).

Examples of the polysiloxane segment (B) constituting the composite resin (ABC) include segments derived from polysiloxane having a silicon atom-bonded hydroxyl group and/or a hydrolyzable group. In addition, examples of the hydrolyzable group bonded to the silicon atom include those similar to the hydrolyzable group bonded to the silicon atom described in the vinyl polymer segment (A), and preferred ones are also the same.

Among the polysiloxane segments (B), those having structures represented by the following general formulas (1) and (2) are particularly preferred. Since the polysiloxane segment having the structure represented by the following general formula (1) or (2) has a three-dimensional network polysiloxane structure, the resulting coating film has excellent solvent resistance, weather resistance, etc. It is something that

（一般式（１）及び（２）中、Ｒ^１は珪素原子に結合した炭素原子数が４～１２の有機基であり、Ｒ^２及びＲ^３は、それぞれ独立して珪素原子に結合したメチル基又は珪素原子に結合したエチル基である。なお、Ｒ^１としては、珪素原子に結合した炭素原子数が４～１２の炭化水素基であることが好ましく、フェニル基又は炭素原子数４のアルキル基であることがより好ましい。Ｒ^２及びＲ^３は、いずれも珪素原子に結合したメチル基又は珪素原子に結合したエチル基であることが好ましく、いずれも珪素原子に結合したメチル基であることがより好ましい。）

(In general formulas (1) and (2), R ¹ is an organic group having 4 to 12 carbon atoms bonded to a silicon atom, and R ² and R ³ are each independently a methyl bonded to a silicon atom. or an ethyl group bonded to a silicon atom. Note that R ¹ is preferably a hydrocarbon group bonded to a silicon atom and having 4 to 12 carbon atoms, such as a phenyl group or an alkyl group having 4 carbon atoms. R ² and R ³ are both preferably a methyl group bonded to a silicon atom or an ethyl group bonded to a silicon atom, and both are methyl groups bonded to a silicon atom. is more preferable.)

The polysiloxane segment having the structure represented by the general formula (1) or (2) may be an organoalkoxysilane, preferably an organic group having 4 to 12 carbon atoms bonded to a silicon atom (hereinafter referred to as a "silicon atom bond"). monoorganotrialkoxysilane having a methyl group bonded to a silicon atom and/or an ethyl group bonded to a silicon atom (hereinafter abbreviated as a ``organic group having 4 to 12 carbon atoms''). Examples include segments derived from polysiloxanes obtained by hydrolyzing and condensing diorganodialkoxysilanes having two atomically bonded methyl groups and/or ethyl groups. These polysiloxane segments include a silicon-bonded organic group having 4 to 12 carbon atoms, a silicon-bonded hydroxyl group and/or a hydrolyzable group, and/or a silicon-bonded methyl group and/or an ethyl group. It has a hydroxyl group and/or a hydrolyzable group bonded to individual silicon atoms, and may have any structure among linear, branched, and cyclic structures.

Examples of the organic group having 4 to 12 carbon atoms bonded to a silicon atom include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like, all of which have 4 to 12 carbon atoms bonded to a silicon atom. It will be done. Note that these organic groups may have a substituent.

Such a silicon-bonded organic group having 4 to 12 carbon atoms is preferably a hydrocarbon group bonded to a silicon atom, such as an n-butyl group, an iso-butyl group, or an n-butyl group, all of which are bonded to a silicon atom. Alkyl groups such as hexyl group, n-octyl group, n-dodecyl group, cyclohexylmethyl group; cycloalkyl group such as cyclohexyl group, 4-methylcyclohexyl group; aryl group such as phenyl group, 4-methylphenyl group; benzyl group Among them, a phenyl group bonded to a silicon atom or an alkyl group having 4 carbon atoms bonded to a silicon atom is more preferable.

The polysiloxane segment (C) constituting the composite resin (ABC) is a segment derived from a trialkoxysilane condensate (c), and the trialkoxysilane condensate (c) used here has silicon atoms. It has a hydroxyl group bonded to and/or an alkoxy group bonded to a silicon atom.

The trialkoxysilane condensate (c) is preferably an alkyltrialkoxysilane condensate in which the alkyl group has 1 to 3 carbon atoms. When using an alkyltrialkoxysilane whose alkyl group has 1 to 3 carbon atoms together with another silane raw material, a condensation product containing 60% by mass or more of an alkyltrialkoxysilane whose alkyl group has 1 to 3 carbon atoms is used. A condensate containing 70% by mass or more is more preferred. Since the polysiloxane segment derived from the condensate of trialkoxysilane has a three-dimensional network polysiloxane structure, the resulting coating film has excellent solvent resistance, weather resistance, etc.

The polysiloxane segment content in the composite resin (ABC) is preferably 5 to 80% by mass, more preferably 10 to 75% by mass from the viewpoint of weather resistance, stain resistance, etc. In addition, the said polysiloxane segment content is the content which combined the said polysiloxane segment (B) and the said polysiloxane segment (C).

Further, the content of the polysiloxane segment (C) in the composite resin (ABC) is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, from the viewpoint of weather resistance, stain resistance, etc.

The mass proportion of the polysiloxane segment is based on the charged mass of the raw materials used for manufacturing the composite resin (ABC), based on the amount of methanol, ethanol, etc. that can be produced by the hydrolytic condensation reaction of raw materials having hydrolyzable silyl groups, etc. This value excludes the mass of by-products.

The composite resin (ABC) can be manufactured by various methods, but it is particularly preferable to manufacture it by the process consisting of the following manufacturing steps (I) and (II).

As the manufacturing step (I), the vinyl polymer (a) is hydrolyzed and condensed with the organoalkoxysilane (b) and/or its hydrolyzed condensate (b1) to obtain a vinyl polymer derived from the vinyl polymer (a). A step of obtaining a composite resin (AB) in which the combined segment (A) and the polysiloxane segment (B) derived from the organoalkoxysilane (b) are chemically bonded.

As the manufacturing step (II), the obtained composite resin (AB) and the trialkoxysilane condensate (c) are hydrolyzed and condensed to form the polysiloxane segment (B) of the composite resin (AB) and the trialkoxysilane. A step of obtaining a composite resin (ABC) in which polysiloxane segments (C) derived from condensate (c) are bonded via silicon-oxygen bonds.

The hydrolytic condensation reaction in the production process can be carried out by various methods, but a method in which the reaction is carried out by supplying water and a catalyst during the production process is simple and preferred.

Note that the hydrolytic condensation reaction refers to a condensation reaction in which a portion of the hydrolyzable group is hydrolyzed under the influence of water to form a hydroxyl group, and then proceeds between the hydroxyl group and the hydrolyzable group.

The vinyl polymer (a1) and the vinyl polymer (a2) are prepared by, for example, treating a hydrolyzable group-containing vinyl monomer bonded to a silicon atom and other vinyl monomers with the hydrocarbon organic solvent. It can be produced by radical polymerization in a medium. The hydrolyzable group-containing vinyl monomer bonded to the silicon atom in the vinyl polymer (a2) is an optional raw material.

In the radical polymerization, for example, the vinyl monomer is sequentially fed, divided into portions, or all at once into a hydrocarbon organic solvent containing a polymerization initiator, and then the vinyl monomer is fed under stirring at a temperature of 20 to 150°C. It is preferable to carry out the treatment for about 5 to 24 hours.

As the vinyl monomer containing a hydrolyzable group bonded to the silicon atom, for example, a vinyl monomer having a hydrolyzable group represented by the following general formula (6) can be used.

（一般式（７）中のＲ^５はアルキル基、アリール基、アラルキル基等の１価の有機基であり、Ｒ^６はハロゲン原子、アルコキシ基、アシロキシ基、フェノキシ基、アリールオキシ基、メルカプト基、アミノ基、アミド基、アミノオキシ基、イミノオキシ基又はアルケニルオキシ基であり、ｎは０～２の整数である。）

(R ⁵ in general formula (7) is a monovalent organic group such as an alkyl group, aryl group, or aralkyl group, and R ⁶ is a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, or a mercapto group. , an amino group, an amide group, an aminooxy group, an iminooxy group, or an alkenyloxy group, and n is an integer of 0 to 2.)

Examples of the vinyl monomer having a hydrolyzable group represented by the general formula (7) include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltri(2-methoxyethoxy)silane, and vinyltriacetoxy. Silane, vinyltrichlorosilane, 2-trimethoxysilylethyl vinyl ether, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, Examples include 3-(meth)acryloyloxypropyltrichlorosilane, among others, vinyltrimethoxysilane, because the hydrolysis reaction can proceed easily and by-products after the reaction can be easily removed. 3-(meth)acryloyloxypropyltrimethoxysilane is preferred.

Further, the other vinyl monomers are not particularly limited, and the type and amount thereof may be selected as appropriate within the range where the SP difference is 0.1 to 1.5 (cal/cm ³ ) ^1/2 . You can choose.

Examples of the other vinyl monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)a, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate. Alkyl (meth)acrylates having an alkyl group having 1 to 22 carbon atoms such as meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate; cyclohexyl (meth)acrylate; Cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate; ω-alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate and 4-methoxybutyl (meth)acrylate; styrene, p-tert-butylstyrene Aromatic vinyl monomers such as , α-methylstyrene, and vinyltoluene; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, and vinyl benzoate; Crotonic acid such as methyl crotonate and ethyl crotonate alkyl esters of unsaturated dibasic acids such as dimethyl maleate, di-n-butyl maleate, dimethyl fumarate, and dimethyl itaconate; α-olefins such as ethylene and propylene; vinylidene fluoride, tetrafluoroethylene, hexa Fluoroolefins such as fluoropropylene and chlorotrifluoroethylene; Alkyl vinyl ethers such as ethyl vinyl ether and n-butyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether; N,N-dimethyl(meth)acrylamide, N-(meth) Tertiary amide group-containing monomers such as acryloylmorpholine, N-(meth)acryloylpyrrolidine, and N-vinylpyrrolidone;

Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; containing hydroxyl groups such as 2-hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether Vinyl ethers; hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether and 2-hydroxybutyl allyl ether; addition reaction products of vinyl monomers containing hydroxyl groups bonded to these carbon atoms and lactones such as ε-caprolactone;

2-dimethylaminoethyl (meth)acrylate, 2-diethylaminoethyl (meth)acrylate, 2-di-n-propylaminoethyl (meth)acrylate, 3-dimethylaminopropyl (meth)acrylate, 4-dimethylaminobutyl (meth)acrylate ) Acrylate, tertiary amino group-containing (meth)acrylic acid esters such as N-[2-(meth)acryloyloxy]ethylmorpholine; Tertiary amino group-containing aromatics such as vinylpyridine, N-vinylcarbazole, and N-vinylquinoline Group vinyl monomer; N-(2-dimethylamino)ethyl (meth)acrylamide, N-(2-diethylamino)ethyl (meth)acrylamide, N-(2-di-n-propylamino)ethyl (meth) Tertiary amino group-containing (meth)acrylamide such as acrylamide; tertiary amino group-containing crotonic acid amide such as N-(2-dimethylamino)ethylcrotonic acid amide, N-(4-dimethylamino)butylcrotonic acid amide; 2 -Dimethylaminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 4-dimethylaminobutyl vinyl ether, and other tertiary amino group-containing vinyl ethers.

Examples of polymerization initiators that can be used in producing the vinyl polymers (a1) and (a2) include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4 -dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile); tert-butylperoxypivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexa Examples include peroxides such as noate, di-tert-butyl peroxide, cumene hydroperoxide, and diisopropyl peroxycarbonate.

Examples of the hydrocarbon organic solvents include "Marcazol R" (manufactured by Maruzen Sekiyu Co., Ltd.), "Swazol 310" (manufactured by Maruzen Sekiyu Co., Ltd.), "LAWS" (manufactured by Shell Japan Co., Ltd.), and "HAWS" (manufactured by Shell Japan Co., Ltd.). Shell Japan Co., Ltd.), "Merveille 30 or 40" (Idemitsu Kosan Co., Ltd.), "IP Solvent 1016 or 16 20" (Idemitsu Kosan Co., Ltd.), "A Solvent" (ENEOS Co., Ltd.), "AF Solvent" (manufactured by ENEOS Corporation), "Exor D40, D60 or D80" (manufactured by ExxonMobil Corporation), "Isopar E, G or H" (manufactured by ExxonMobil Corporation), as well as n-hexane or n-heptane, etc. Aliphatic hydrocarbon solvents such as Note that these hydrocarbon solvents may be used alone or in combination of two or more. Other organic solvents such as aromatic hydrocarbon solvents such as "Swazol 1500" (manufactured by Maruzen Sekiyu Co., Ltd.) and "T-SOL 100 or 150" (manufactured by TonenGeneral Sekiyu Co., Ltd.) can also be used in combination.

The weight average molecular weight of the vinyl polymer containing the vinyl polymers (a1) and (a2) is such that storage stability, appearance of the obtained coating film, adhesion, weather resistance, solvent resistance, and stain resistance are further improved. Therefore, it is preferably 5,000 to 300,000, more preferably 5,000 to 250,000, and even more preferably 15,000 to 200,000. Here, the weight average molecular weight is a value converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement.

Next, the organoalkoxysilane (b) and/or its hydrolyzed condensate (b1) used to constitute the polysiloxane segment (B) in the manufacturing step (I) will be described.

The organoalkoxysilane (b) is not particularly limited, but it is particularly suitable because it can produce a composite resin (ABC) with excellent dispersion stability and form a coating film with excellent durability. , monoorganotrialkoxysilane having an organic group having 4 to 12 carbon atoms, and diorganodialkoxysilane having two methyl and/or ethyl groups are preferred.

The hydrolyzed condensate (b1) of the organoalkoxysilane (b) may be one obtained by hydrolyzing and condensing the organoalkoxysilane (b), and is not particularly limited. A monoorganotrialkoxysilane having 12 organic groups and/or a diorganodialkoxysilane having two silicon-bonded methyl groups and/or ethyl groups are preferably hydrolyzed and condensed.

Examples of the monoorganotrialkoxysilane having a silicon-bonded organic group having 4 to 12 carbon atoms include iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- Examples include (meth)acryloyloxypropyltrimethoxysilane and 3-(meth)acryloyloxypropyltriethoxysilane.

Examples of the diorganodialkoxysilane having two silicon-bonded methyl groups and/or ethyl groups include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, dimethyldiacetoxysilane, and diethyldimethoxysilane. Examples include silane and diethyldiacetoxysilane.

Among these organoalkoxysilanes (b), iso-butyltrimethoxysilane, phenyltrimethoxysilane, and dimethyldimethoxysilane are used because the hydrolysis reaction can easily proceed and the by-products after the reaction can be easily removed. preferable. Further, these organoalkoxysilanes (b) may be used alone or in combination of two or more types.

In addition, in the production step (I), it is fully possible to use the hydrolysis condensate (b1) of the organoalkoxysilane (b) alone, but it is also possible to produce the composite resin (A'B) by hydrolysis condensation. For ease of use, it is preferable to use organoalkoxysilane (b) alone or a combination of organoalkoxysilane (b) and its hydrolyzed condensate (b1), and use of organoalkoxysilane (b) alone is particularly preferable. Here, the use of organoalkoxysilane (b) alone means the use of only organoalkoxysilane (b), and also includes the case where two or more types of organoalkoxysilane (b) are used in combination.

The hydrolytic condensation reaction in the production step (I) can be carried out by various methods, but a method in which the reaction is carried out by supplying water and a catalyst during the production process (I) is preferable. It is convenient and preferable.

Examples of the catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate, and acetic acid; inorganic bases such as sodium hydroxide and potassium hydroxide; tetraisopropyl titanate, and tetrabutyl. Titanate esters such as titanates; 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo [2.2.2] Compounds containing basic nitrogen atoms such as octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 1-methylimidazole; tetramethylammonium salt, tetrabutyl Quaternary ammonium salts such as ammonium salts and dilauryldimethylammonium salts, which have chloride, bromide, carboxylate, hydroxide, etc. as counteranions; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin Tin carboxylates such as dilaurate, dibutyltin diacetylacetonate, tin octylate, and tin stearate can be used alone or in combination of two or more.

The catalyst is preferably used in an amount of 0.0001 to 10 parts by mass, and preferably 0.0005 to 3 parts by mass, based on 100 parts by mass of the organoalkoxysilane (b) and/or its hydrolyzed condensate (b1). It is more preferable to use it in a range of 0.001 to 1 part by weight, particularly preferably in a range of 0.001 to 1 part by weight.

Moreover, the water used when proceeding with the hydrolytic condensation reaction is based on 1 mole of the hydrolyzable group and hydroxyl group that the organoalkoxysilane (b) and/or its hydrolyzed condensate (b1) has. 0.05 mol or more is suitable, preferably 0.1 mol or more, particularly preferably 0.5 to 3.0 mol.

The catalyst and water may be supplied all at once or sequentially, or a mixture of the catalyst and water may be supplied.

The reaction temperature of the hydrolysis condensation reaction is suitably within the range of 0 to 150°C, preferably within the range of 20 to 100°C. Furthermore, the reaction can be carried out under any conditions including normal pressure, increased pressure, or reduced pressure.

Alcohol and water, which are by-products that may be produced in the hydrolytic condensation reaction, may be removed by a method such as distillation if they degrade the stability of the resulting aqueous curable coating composition.

Next, the trialkoxysilane condensate (c) used to constitute the polysiloxane segment (C) in the manufacturing step (II) will be described in detail.

The trialkoxysilane includes, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, iso-propyltrimethoxysilane, etc., depending on the number of carbon atoms in the alkyl group. Alkyltrialkoxysilanes having 1 to 3; trialkoxysilanes having a glycidoxy group such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane; among these, hydrolysis reaction Alkyltrialkoxysilanes in which the alkyl group has 1 to 3 carbon atoms are preferable, and methyltrimethoxysilane and ethyltrimethoxysilane are more preferable because they allow easy reaction and easy removal of by-products after the reaction. . Note that these trialkoxysilanes may be used alone or in combination of two or more types.

The method for obtaining the condensate (c) from the trialkoxysilane is not particularly limited, and various methods may be used, but a simple method is to proceed the hydrolysis condensation reaction by supplying water and a catalyst. preferable.

The water and catalyst used at this time can be used under the same conditions as in the hydrolysis condensation reaction in the production step (I).

Further, in the manufacturing step (II), in addition to the trialkoxysilane condensate (c), other silane compounds or hydrolyzed condensates thereof can be used in combination.

Examples of the other silane compounds include tetrafunctional alkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane or tetra-n-propoxysilane; 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, Epoxysilane compounds such as ethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, 3-(meth)acryloyloxypropyltrichlorosilane, Examples include chlorosilane compounds such as dimethyldichlorosilane, diethyldichlorosilane, and diphenyldichlorosilane; hydrolyzed condensates of these silane compounds; and the like. These can be used in combination without impairing the effects of the present invention.

When the tetrafunctional alkoxysilane compound or its hydrolyzed condensate is used in combination, the tetrafunctional alkoxysilane compound is It is preferable that the silicon atom contained in the silane compound or its hydrolyzed condensate is used in combination within a range not exceeding 20 mol%.

In the resin composition of the present invention, the composite resin (ABC) is dissolved or dispersed in an aliphatic hydrocarbon organic solvent. The solvents and the like listed as those that can be used in the production of coalesce (a1) and (a2) can be used.

The organic solvent in the resin composition of the present invention suppresses a rapid increase in viscosity during production, and from the viewpoint of improving the productivity of the resin composition, ease of coating, drying properties, etc. It is preferably 30 to 75% by weight, more preferably 35 to 70% by weight.

The resin composition of the present invention can also contain a thermosetting resin if necessary. Examples of such thermosetting resins include vinyl resins, polyester resins, polyurethane resins, epoxy resins, epoxy ester resins, acrylic resins, phenol resins, petroleum resins, ketone resins, silicone resins, and modified resins thereof.

Various inorganic particles such as clay minerals, metals, metal oxides, and glass can be used in the resin composition of the present invention, if necessary. Examples of the metal include gold, silver, copper, platinum, titanium, zinc, nickel, aluminum, iron, silicon, germanium, antimony, and metal oxides thereof.

The resin composition of the present invention may optionally contain photocatalytic compounds, inorganic pigments, organic pigments, extender pigments, waxes, surfactants, stabilizers, flow regulators, dyes, leveling agents, rheology control agents, ultraviolet absorbers, etc. Various additives such as antioxidants, plasticizers, etc. can be used.

Further, the resin composition of the present invention can also contain a curing catalyst if necessary. Examples of the curing catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, tetraisopropyl titanate, tetra-n-butyl titanate, tin octylate, lead octylate, cobalt octylate, and zinc octylate. , calcium octylate, zinc naphthenate, cobalt naphthenate, di-n-butyltin diacetate, di-n-butyltin dioctoate, di-n-butyltin dilaurate, di-n-butyltin maleate, p-toluenesulfone Acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, monoalkyl phosphorous acid, dialkyl phosphorous acid, etc. can be used.

A curing agent can also be added to the resin composition of the present invention, if necessary. As the curing agent, a compound having a functional group that can react with the functional group of the composite resin (ABC) can be used, and for example, a compound having a silanol group and/or a hydrolyzable silyl group, Examples include polyepoxy compounds, polyoxazoline compounds, polycarbodiimide compounds, and polyisocyanate compounds.

The resin composition of the present invention has excellent storage stability and can be used in various applications such as paints and adhesives. Among these, the resin composition of the present invention is preferably used for paints because it can form a coating film with excellent coating appearance, adhesion, weather resistance, solvent resistance, and stain resistance, and is suitable for use in forming a top layer. It is more preferable to use it in a paint or a paint for forming a primer layer.

Examples of the base material on which the paint can be applied to form a coating film include inorganic base materials, metal base materials, plastic base materials, glass base materials, paper and wood base materials, and fibrous base materials.

The paint of the present invention can be applied directly to the surface of the base material, and then dried and cured to form a paint film with excellent paint film appearance, durability, weather resistance, etc. after an exposure test. be able to.

A coated article can be obtained by applying the above-mentioned paint onto the various base materials mentioned above and curing it. At that time, (1) the paint is applied directly to the base material, (2) an undercoat paint is applied on the base material in advance and then the paint is applied as a top coat, (3) an undercoat paint is applied to the base material. A coated object can be obtained by a coating method such as applying the above-mentioned paint as a first coat and then applying another top coat to form a coating film.

Examples of methods for applying the paint of the present invention include brush coating, roller coating, spray coating, dip coating, flow coater coating, roll coater coating, and electrodeposition coating.

In addition, when obtaining a coated object having a coating film made of the above-mentioned paint by the coating method (2) or (3) above, conventionally known acrylic resin paints, polyester resin paints, etc. Paints, alkyd resin paints, epoxy resin paints, fatty acid-modified epoxy resin paints, silicone resin paints, polyurethane resin paints, etc. can be used.

The method of drying and curing may be a method of curing at room temperature for about 1 to 10 days, but from the viewpoint of rapid curing, curing at a temperature of 50 to 250°C for 1 to 600 seconds. A method of heating to a certain degree is preferable. Furthermore, when using a plastic base material that easily deforms or discolors at relatively high temperatures, it is preferable to perform curing at a relatively low temperature of about 30 to 100°C.

The thickness of the coating film formed using the paint of the present invention can be 0.5 to 1,000 μm depending on the use of the base material.

Examples of articles having a coating film formed using the coating material of the present invention by the method described above include interior and exterior materials for buildings such as exterior walls, roofs, glass, and decorative boards; repair applications for concrete structures; , civil engineering components such as soundproof walls and drainage ditches; housings of home appliances such as televisions, refrigerators, washing machines, and air conditioners; housings of electronic devices such as computers, smartphones, mobile phones, digital cameras, and game consoles; printers, fax machines, etc. etc.; interior and exterior materials for various vehicles such as automobiles and railway vehicles; industrial machinery, etc.

Next, the present invention will be specifically explained using Examples and Comparative Examples. The average molecular weight of the resin was measured under the following GPC measurement conditions.

[GPC measurement conditions]
Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were used by connecting them in series.
"TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000" (7.8mm I.D. x 30cm) x 1 Book "TSKgel G2000" (7.8mm I.D. x 30cm) x 1 Detector: RI (differential refractometer)
Column temperature: 40℃
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL/min Injection volume: 100 μL (tetrahydrofuran solution with sample concentration 4 mg/mL)
Standard sample: A calibration curve was created using the following monodisperse polystyrene.

(Monodisperse polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
“TSKgel Standard Polystyrene F-1” manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation

The following values were used for the solubility parameters of the monomer homopolymers used.
Methyl methacrylate (MMA): 9.23 (cal/cm ³ ) ^1/2
Normal butyl methacrylate (n-BMA): 8.25 (cal/cm ³ ) ^1/2
2-ethylhexyl methacrylate (2EHMA): 7.85 (cal/cm ³ ) ^1/2 normal butyl methacrylate (n-BA): 8.63 (cal/cm ³ ) ^1/2 ,
2-hydroxyethyl methacrylate (β-HEMA): 9.90 (cal/cm ³ ) ^1/2
Acrylic acid (AA): 12.89 (cal/cm ³ ) ^1/2
Acrylonitrile (AN): 10.56 (cal/cm ³ ) ^1/2

(Synthesis Example 1: Synthesis of vinyl polymer (a2-1))
192 parts by mass of LAWS (manufactured by Shell Japan Co., Ltd.) was charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and a nitrogen gas inlet, and the temperature was raised to 110°C. Next, a mixture consisting of 720 parts by mass of 2-ethylhexyl methacrylate (2EHMA), 80 parts by mass of n-butyl methacrylate (n-BMA), and 16.0 parts by mass of tert-butylperoxy-2-ethylhexanoate (TBPEH), At the same temperature, the solution was added dropwise into the reaction vessel over 4 hours while stirring and passing nitrogen gas. Thereafter, the mixture was stirred at the same temperature for 4 hours to prepare 1000 parts by mass of a solution of vinyl polymer (a2-1) with a nonvolatile content of 80% by mass. The solubility parameter of this vinyl polymer (a2-1) was 7.9 (cal/cm ³ ) ^1/2 .

(Synthesis Example 2: Synthesis of vinyl polymer (a-1))
Into the same reaction vessel as in Synthesis Example 1, 377 parts by mass of the solution of the vinyl polymer (a2-1) obtained in Synthesis Example 1 was charged, and the temperature was raised to 110°C. Next, a mixture consisting of 209 parts by mass of n-BMA, 90 parts by mass of n-butyl acrylate (n-BA), 3 parts by mass of 3-methacryloyloxypropyltrimethoxysilane (MPTS), and 3.0 parts by mass of TBPEH was added at the same temperature. was added dropwise into the reaction vessel over 4 hours while stirring and under nitrogen gas flow. Thereafter, the mixture was stirred at the same temperature for 4 hours, and 314 parts by mass of LAWS was charged and further stirred for 30 minutes. 1000 parts by mass of a solution of vinyl polymer (a-1) containing 60% by mass was prepared. The solubility parameter of the vinyl polymer (a1-1) was 8.4 (cal/cm ³ ) ^1/2 , and the weight average molecular weight of the vinyl polymer (a-1) was 86,000.

(Synthesis Example 3: Synthesis of vinyl polymer (a-2))
Into the same reaction vessel as in Synthesis Example 1, 377 parts by mass of the solution of the vinyl polymer (a2-1) obtained in Synthesis Example 1 was charged, and the temperature was raised to 110°C. Next, a mixture consisting of 269 parts by mass of 2EHMA, 30 parts by mass of 2-hydroxyethyl methacrylate (β-HEMA), 3 parts by mass of MPTS, and 0.3 parts by mass of TBPEH was stirred at the same temperature under nitrogen gas ventilation. The mixture was added dropwise into the reaction vessel over 4 hours. Thereafter, the mixture was stirred at the same temperature for 4 hours, and 314 parts by mass of LAWS was charged and further stirred for 30 minutes. 1000 parts by mass of a solution of vinyl polymer (a-2) containing 60% by mass was prepared. The solubility parameter of the vinyl polymer (a1-2) was 8.1 (cal/cm ³ ) ^1/2 , and the weight average molecular weight of the vinyl polymer (a-2) was 145,000.

(Synthesis Example 4: Synthesis of vinyl polymer (a-3))
72 parts by mass of LAWS (manufactured by Shell Japan Co., Ltd.) was charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and a nitrogen gas inlet, and the temperature was raised to 110°C. Next, a mixture consisting of 269 parts by mass of 2EHMA, 30 parts by mass of n-BMA, and 6.0 parts by mass of TBPEH was added dropwise into the reaction vessel over 4 hours at the same temperature while stirring under nitrogen gas flow. . Thereafter, the mixture was stirred at the same temperature for 4 hours. The solubility parameter of this vinyl polymer (a2-1) was 7.9 (cal/cm ³ ) ^1/2 . Next, a mixture consisting of 239 parts by mass of MMA, 45 parts by mass of n-BA, 15 parts by mass of acrylic acid (AA), 3 parts by mass of MPTS, and 1.5 parts by mass of TBPEH was stirred at the same temperature under nitrogen gas ventilation. While doing so, the mixture was dropped into the reaction vessel over 4 hours. Thereafter, the mixture was stirred at the same temperature for 4 hours, and 314 parts by mass of LAWS was charged and stirred for an additional 30 minutes. 1000 parts by mass of a solution of vinyl polymer (a-3) containing 60% by mass was prepared. The solubility parameter of the vinyl polymer (a1-3) was 9.3 (cal/cm ³ ) ^1/2 , and the weight average molecular weight of the vinyl polymer (a-3) was 121,000.

(Synthesis Example 5: Synthesis of vinyl polymer (Ra-1))
Into the same reaction vessel as in Synthesis Example 1, 377 parts by mass of the solution of the vinyl polymer (a2-1) obtained in Synthesis Example 1 was charged, and the temperature was raised to 110°C. Next, a mixture consisting of 239 parts by mass of MMA, 60 parts by mass of acrylonitrile (AN), 3 parts by mass of MPTS, and 4.5 parts by mass of TBPEH was poured into the reaction vessel at the same temperature while stirring under nitrogen gas. The mixture was added dropwise over 4 hours. Thereafter, the mixture was stirred at the same temperature for 4 hours, charged with 314 parts by mass of LAWS, and further stirred for 30 minutes. 1000 parts by mass of a solution of vinyl polymer (Ra-1) having a concentration of 60% by mass was prepared. The solubility parameter of the vinyl polymer (a1-4) was 9.5 (cal/cm ³ ) ^1/2 , and the weight average molecular weight of the vinyl polymer (Ra-1) was 53,000.

(Synthesis Example 6: Synthesis of methyltrimethoxysilane condensate (c-1))
853 parts by mass of methyltrimethoxysilane (MTMS) was charged into the same reaction vessel as in Synthesis Example 1, and the temperature was raised to 60°C. Next, a mixture of 0.10 parts by mass of "A-3" (iso-propyl acid phosphate, manufactured by Sakai Chemical Co., Ltd.) and 124 parts by mass of deionized water was dropped into the reaction vessel over 5 minutes, and then The mixture was stirred at a temperature of 0.degree. C. for 4 hours to carry out a hydrolytic condensation reaction.
The condensate obtained by the above hydrolytic condensation reaction is subjected to a reduced pressure of 40 to 1.3 kPa (the reduced pressure condition at the start of methanol distillation is 40 kPa, and the pressure is reduced to a final pressure of 1.3 kPa). The same applies hereinafter), by distilling at a temperature of 40 to 60°C to remove methanol and water generated in the reaction process, a condensate of MTMS (c-1) with a number average molecular weight of 1,000 is produced. 600 parts by mass of a solution (70% by mass of active ingredients) was obtained.

(Example 1: Synthesis of resin composition (1))
700 parts by mass of the solution of vinyl polymer (a-1) obtained in Synthesis Example 2 was charged into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube, and a nitrogen gas inlet, and the temperature was raised to 80°C. did. Then, 48 parts by mass of phenyltrimethoxysilane (PTMS) and 29 parts by mass of dimethyldimethoxysilane (DMDMS) were added into the reaction vessel. Then, a mixture of 0.09 parts by mass of "A-3" (iso-propyl acid phosphate, manufactured by Sakai Chemical Co., Ltd.) and 22 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 4 hours. By carrying out a hydrolytic condensation reaction, a composite resin (AB-1) consisting of a vinyl polymer segment containing a hydrolyzable group bonded to a silicon atom and a polysiloxane segment derived from PTMS and DMDMS was obtained. Thereafter, 265 parts by mass of MTMS condensate (c-1) and 64 parts by mass of deionized water were added, and the mixture was stirred at the same temperature for 4 hours to undergo a hydrolytic condensation reaction, thereby forming the composite resin (AB-1). A composite resin (ABC-1) to which polysiloxane segments (C-1) derived from the MTMS condensate (c-1) were bonded was obtained. Further, the reaction product is distilled under reduced pressure of 40 to 1.3 kPa at 40 to 60°C for 2 hours to remove generated methanol and water, and then 120 parts by mass of LAWS is added. Thus, 1000 parts by mass of a resin composition (1) having a nonvolatile content of 60.0% was obtained. The polysiloxane segment content in the composite resin (ABC-1) was 30% by mass.

(Example 2: Synthesis of resin composition (2))
700 parts by mass of the solution of the vinyl polymer (a-2) obtained in Synthesis Example 3 was charged into the same reaction vessel as in Example 1, and the temperature was raised to 80°C. Then, 48 parts by mass of PTMS and 29 parts by mass of DMDMS were added into the reaction vessel. Then, a mixture of 0.09 parts by mass of "A-3" (iso-propyl acid phosphate, manufactured by Sakai Chemical Co., Ltd.) and 22 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 4 hours. By carrying out a hydrolytic condensation reaction, a composite resin (AB-2) consisting of a polymer segment containing a hydrolyzable group bonded to a silicon atom and a polysiloxane segment derived from PTMS and DMDMS was obtained. Thereafter, 265 parts by mass of MTMS condensate (c-1) and 64 parts by mass of deionized water were added, and the mixture was stirred at the same temperature for 4 hours to cause a hydrolytic condensation reaction. A composite resin (ABC-2) to which polysiloxane segments (C-1) derived from the MTMS condensate (c-1) were bonded was obtained. Further, the reaction product is distilled under reduced pressure of 40 to 1.3 kPa at 40 to 60°C for 2 hours to remove generated methanol and water, and then 120 parts by mass of LAWS is added. Thus, 1000 parts by mass of a resin composition (2) having a nonvolatile content of 60.0% was obtained. The polysiloxane segment content in the composite resin (ABC-2) was 30% by mass.

(Example 3: Synthesis of resin composition (3))
700 parts by mass of the solution of the vinyl polymer (a-3) obtained in Synthesis Example 4 was charged into the same reaction vessel as in Example 1, and the temperature was raised to 80°C. Next, 48 parts by mass of PTMS and 29 parts by mass of DMDMS were added into the reaction vessel. Then, a mixture of 0.09 parts by mass of "A-3" (iso-propyl acid phosphate, manufactured by Sakai Chemical Co., Ltd.) and 22 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 4 hours. By carrying out a hydrolytic condensation reaction, a composite resin (AB-3) consisting of a polymer segment containing a hydrolyzable group bonded to a silicon atom and a polysiloxane segment derived from PTMS and DMDMS was obtained. Thereafter, 265 parts by mass of MTMS condensate (c-1) and 64 parts by mass of deionized water were added, and the mixture was stirred at the same temperature for 4 hours to cause a hydrolytic condensation reaction. A composite resin (ABC-3) to which polysiloxane segments (C-1) derived from the MTMS condensate (c-1) were bonded was obtained. Further, the reaction product is distilled under a reduced pressure of 40 to 1.3 kPa at 40 to 60° C. for 2 hours to remove generated methanol and water, and then 120 parts by mass of LAWS is added. Thus, 1000 parts by mass of a resin composition (3) having a nonvolatile content of 60.0% was obtained. The polysiloxane segment content in the composite resin (ABC-3) was 30% by mass.

(Example 4: Synthesis of resin composition (4))
900 parts by mass of the solution of the vinyl polymer (a-1) obtained in Synthesis Example 2 was charged into the same reaction vessel as in Example 1, and the temperature was raised to 80°C. Next, 16 parts by mass of PTMS and 10 parts by mass of DMDMS were added into the reaction vessel. Then, a mixture of 0.03 parts by mass of "A-3" (iso-propyl acid phosphate, manufactured by Sakai Chemical Co., Ltd.) and 7 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 4 hours. By carrying out a hydrolytic condensation reaction, a composite resin (AB-4) consisting of a polymer segment containing a hydrolyzable group bonded to a silicon atom and a polysiloxane segment derived from PTMS and DMDMS was obtained. Thereafter, 88 parts by mass of MTMS condensate (c-1) and 21 parts by mass of deionized water were added, and the mixture was stirred at the same temperature for 4 hours to carry out a hydrolytic condensation reaction. A composite resin (ABC-4) to which polysiloxane segments (C-1) derived from the MTMS condensate (c-1) were bonded was obtained. Further, the reaction product is distilled under reduced pressure of 40 to 1.3 kPa at 40 to 60°C for 2 hours to remove generated methanol and water, and then 40 parts by mass of LAWS is added. Thus, 1000 parts by mass of a resin composition (4) having a nonvolatile content of 60.0% was obtained. The polysiloxane segment content in the composite resin (ABC-4) was 10% by mass.

(Example 5: Synthesis of resin composition (5))
300 parts by mass of the solution of the vinyl polymer (a-1) obtained in Synthesis Example 2 was charged into the same reaction vessel as in Example 1, and the temperature was raised to 80°C. Next, 112 parts by mass of PTMS and 68 parts by mass of DMDMS were added into the reaction vessel. Then, a mixture of 0.21 parts by mass of "A-3" (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 51 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 4 hours. By carrying out a hydrolytic condensation reaction, a composite resin (AB-5) consisting of a polymer segment containing a hydrolyzable group bonded to a silicon atom and a polysiloxane segment derived from PTMS and DMDMS was obtained. Thereafter, 618 parts by mass of MTMS condensate (c-1) and 149 parts by mass of deionized water were added, and the mixture was stirred at the same temperature for 4 hours to carry out a hydrolytic condensation reaction. A composite resin (ABC-5) to which polysiloxane segments (C-1) derived from the MTMS condensate (c-1) were bonded was obtained. Further, the reaction product is distilled under reduced pressure of 40 to 1.3 kPa at 40 to 60°C for 2 hours to remove generated methanol and water, and then 280 parts by mass of LAWS is added. Thus, 1000 parts by mass of a resin composition (4) having a nonvolatile content of 60.0% was obtained. The polysiloxane segment content in the composite resin (ABC-5) was 70% by mass.

(Example 6: Synthesis of resin composition (6))
702 parts by mass of the solution of the vinyl polymer (a-1) obtained in Synthesis Example 2 was charged into the same reaction vessel as in Example 1, and the temperature was raised to 80°C. Then, 46 parts by mass of PTMS and 28 parts by mass of DMDMS were added into the reaction vessel. Then, a mixture of 0.09 parts by mass of "A-3" (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 21 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 4 hours. By carrying out a hydrolytic condensation reaction, a composite resin (AB-6) consisting of a polymer segment containing a hydrolyzable group bonded to a silicon atom and a polysiloxane segment derived from PTMS and DMDMS was obtained. Thereafter, 245 parts by mass of MTMS condensate (c-1), 17 parts by mass of 3-glycidoxypropyltrimethoxysilane, and 59 parts by mass of deionized water were added, and the mixture was stirred at the same temperature for 4 hours to undergo a hydrolytic condensation reaction. By doing so, a composite resin (ABC -6) was obtained. Further, the reaction product is distilled under reduced pressure of 40 to 1.3 kPa at 40 to 60°C for 2 hours to remove generated methanol and water, and then 120 parts by mass of LAWS is added. Thus, 1000 parts by mass of a resin composition (6) having a nonvolatile content of 60.0% was obtained. The polysiloxane segment content in the composite resin (ABC-6) was 30% by mass.

(Comparative Example 1: Synthesis of resin composition (R1))
438 parts by mass of the vinyl polymer (a2-1) solution obtained in Synthesis Example 1 and 146 parts by mass of LAWS were charged into the same reaction vessel as in Example 1, and the temperature was raised to 80°C. Next, 40 parts by mass of PTMS and 24 parts by mass of DMDMS were added into the reaction vessel. Then, a mixture of 0.07 parts by mass of "A-3" (iso-propyl acid phosphate, manufactured by Sakai Chemical Co., Ltd.) and 18 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 4 hours. By carrying out a hydrolytic condensation reaction, a composite resin (RAB-1) consisting of a polymer segment containing a hydrolyzable group bonded to a silicon atom and a polysiloxane segment derived from PTMS and DMDMS was obtained. Thereafter, 221 parts by mass of MTMS condensate (c-1) and 53 parts by mass of deionized water were added, and the mixture was stirred at the same temperature for 4 hours to cause a hydrolytic condensation reaction. A composite resin (RABC-1) to which polysiloxane segments (C-1) derived from the MTMS condensate (c-1) were bonded was obtained. Further, the reaction product is distilled under reduced pressure of 40 to 1.3 kPa at 40 to 60°C for 2 hours to remove generated methanol and water, and then 267 parts by mass of LAWS is added. Thus, 1000 parts by mass of a resin composition (R1) having a nonvolatile content of 50.0% was obtained. The polysiloxane segment content in the composite resin (RABC-1) was 30% by mass.

(Comparative Example 2: Synthesis of resin composition (R2))
583 parts by mass of the vinyl polymer (Ra-1) solution obtained in Synthesis Example 5 was charged into the same reaction vessel as in Example 1, and the temperature was raised to 80°C. Then, 40 parts by mass of PTMS and 24 parts by mass of DMDMS were added into the reaction vessel. Then, a mixture of 0.07 parts by mass of "A-3" (iso-propyl acid phosphate, manufactured by Sakai Chemical Co., Ltd.) and 18 parts by mass of deionized water was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 4 hours. By carrying out a hydrolytic condensation reaction, a composite resin (RAB-2) consisting of a polymer segment containing a hydrolyzable group bonded to a silicon atom and a polysiloxane segment derived from PTMS and DMDMS was obtained. Thereafter, 221 parts by mass of MTMS condensate (c-1) and 53 parts by mass of deionized water were added, and the mixture was stirred at the same temperature for 4 hours to cause a hydrolytic condensation reaction. A composite resin (RABC-2) to which polysiloxane segments (C-1) derived from the MTMS condensate (c-1) were bonded was obtained. Further, the reaction product is distilled under reduced pressure of 40 to 1.3 kPa at 40 to 60°C for 2 hours to remove generated methanol and water, and then 267 parts by mass of LAWS is added. Thus, 1000 parts by mass of a resin composition (R2) having a nonvolatile content of 50.0% was obtained. The polysiloxane segment content in the composite resin (RABC-2) was 30% by mass.

[Evaluation of storage stability]
The resin composition obtained above was stored for one month in an environment at a temperature of 50° C., and the viscosity increase rate (%) = [(viscosity after one month - initial viscosity)/initial viscosity] was evaluated using the following evaluation criteria. The viscosity measurement conditions were based on the Gardner foam viscosity measurement method of JIS K5600-2-2. The Stokes conversion value of the measured viscosity was used to calculate the viscosity increase rate.
○: Thickening rate is less than 100%.
×: Thickening rate is 100% or more.

Table 1 shows the evaluation results of Examples 1 to 4 above.

Table 2 shows the evaluation results of Example 5 and Comparative Examples 1 and 2 above.

(Example 7: Preparation of paint (1))
100 parts by mass of the resin composition (1) obtained above, 9.6 parts by mass of LAWS, and 0.6 parts by mass of tin octoate were blended to obtain a paint (1).

(Examples 8 to 12: Preparation of paints (2) to (6))
Paints (2) to (6) were obtained in the same manner as in Example 6, except that resin composition (1) used in Example 6 was changed to resin compositions (2) to (6).

(Example 13: Preparation of paint (7))
100 parts by mass of the resin composition (2) obtained above, 10.7 parts by mass of LAWS, and 4.4 parts by mass of a polyisocyanate curing agent ("DN-980" manufactured by DIC Corporation) were blended to form a paint (7). I got it.

(Comparative Examples 3 and 4: Preparation of paints (R1) to (R2))
Paints (R1) to (R2) were obtained in the same manner as in Example 7, except that resin composition (1) used in Example 7 was changed to resin compositions (R1) and (R2).

[Preparation of undercoat film]
A chromate-treated aluminum plate with a thickness of 0.8 mm was coated with an acrylic-urethane-based white paint (pigment: Taipei CR-97, PWC: 35%), baked, and sanded with water to obtain an undercoat film.

[Preparation of cured coating film for evaluation]
Each of the paints obtained above was applied onto the undercoat film so that the cured film had a thickness of 20 μm, and was dried at 23° C. for 7 days to obtain a cured film for evaluation.

[Evaluation of paint film appearance]
The cured coating film obtained above was visually observed, and the appearance of the coating film was evaluated according to the following criteria.
○: No cracks observed.
Δ: Occurrence of some cracks is observed.
×: Occurrence of cracks is observed.

[Evaluation of adhesion]
The cured coating film for evaluation obtained above was measured based on the JIS K-5600 grid test method. Cut 1 mm wide incisions on the cured coating film with a cutter to make 100 grids, apply cellophane tape to cover all the grids, and quickly peel it off to remove the remaining grids. The number was counted and evaluated using the following criteria.
○: No peeling.
△: The area of peeling is 1 to 64% of the total grid area.
×: The area of peeling is 65% or more of the total grid area.

[Evaluation of weather resistance (appearance)]
Regarding the cured coating film for evaluation obtained above, the UV fluorescent lamp type accelerated weathering tester QUV (manufactured by Q-lab, light irradiation: 0.71 W/m ² , 60°C, humid: 98% humidity, 50°C, After exposure for 1,000 hours under a light irradiation/wetting cycle = 4 hours/4 hours, the coating film was visually observed and the appearance of the coating film was evaluated using the following criteria.
○: No cracks observed.
Δ: Occurrence of some cracks is observed.
×: Occurrence of cracks is observed.

[Evaluation of weather resistance (gloss retention rate)]
The specular reflectance (gloss value) (%) of the cured coating film for evaluation immediately after preparation and the cured coating film were measured using an ultraviolet fluorescent lamp type accelerated weathering tester QUV (manufactured by Q-lab, light irradiation: 0.71 W/ Specular reflectance (gloss value) (%) of the coating after exposure for 1,000 hours at m ² , 60°C, wet: 98% humidity, 50°C, light irradiation/wetting cycle = 4 hours/4 hours) Retention rate (gloss retention rate: %) for the specular reflectance (gloss value) of the cured coating film before exposure [(100 x specular reflectance of the coating film after exposure)/(mirror finish of the cured coating film before exposure) Reflectance)] was evaluated. The larger the retention rate value, the better the weather resistance.

[Evaluation of solvent resistance]
Regarding the cured coating film for evaluation obtained above, the condition of the cured coating film was judged by finger touch and visual inspection after rubbing the cured coating film 50 times back and forth with a 1 kg load using a felt impregnated with methyl ethyl ketone. and evaluated using the following criteria.
○: No softening or reduction in gloss observed.
Δ: Some softening or reduction in gloss is observed.
×: Significant softening or reduction in gloss is observed.

[Evaluation of stain resistance]
The cured coating film for evaluation obtained above was exposed for 3 months at DIC Corporation's Sakai factory in Takaishi City, Osaka Prefecture. The color difference (ΔE) between the unwashed paint film after the exposure test and the paint film before the exposure test was evaluated according to the following criteria using a spectrophotometer "CM-5" manufactured by Konica Minolta, Inc.
○: ΔE is less than 2.5 △: ΔE is 2.5 or more and less than 5 ×: ΔE is 5 or more

Table 3 shows the evaluation results of Examples 7 to 10 above.

Table 4 shows the evaluation results of Examples 11 to 13 and Comparative Examples 3 to 4 above.

It was confirmed that the resin compositions of the present invention of Examples 1 to 6 had excellent storage stability, and the resulting coating films had excellent appearance, adhesion, weather resistance, solvent resistance, and stain resistance.

Although the resin composition of Comparative Example 1 does not use the vinyl polymer (a1), which is an essential component of the present invention, it was confirmed that the storage stability was poor and the appearance of the resulting coating film was insufficient. It was done.

Comparative Example 2 is an example in which the difference between the solubility parameter of the vinyl polymer (a1) and the solubility parameter of the vinyl polymer (a2) exceeds 1.5 (cal/cm ³ ) ^1/2 , which is the upper limit of the present invention. However, it was confirmed that the storage stability was poor and the appearance of the resulting coating film was insufficient.

Claims (5)

A polysiloxane segment (B) of a composite resin (AB) formed by bonding a vinyl polymer segment (A) and a polysiloxane segment (B) and a polysiloxane segment (C) derived from a condensate of trialkoxysilane (c) ) are bonded via silicon-oxygen bonds, a resin composition in which a composite resin (ABC) is dissolved or dispersed in a hydrocarbon-based organic solvent, wherein the vinyl polymer segment (A) is is derived from a vinyl polymer (a) containing a vinyl polymer (a1) having a hydrolyzable silyl group and/or silanol group and a vinyl polymer (a2) other than the vinyl polymer (a1). , the difference (SP difference) between the solubility parameter (SP1) of the vinyl polymer (a1) and the solubility parameter (SP2) of the vinyl polymer (a2) is 0.1 to 1.5 (cal/cm ³ ). A resin composition characterized in that it is ^1/2 . The bond between the vinyl polymer segment (A) and the polysiloxane segment (B) is a combination of the hydrolyzable silyl group and/or silanol group of the vinyl polymer (a) and the hydrolyzable silyl group of the polysiloxane. and/or a condensation bond with a silanol group. The resin composition according to claim 1 or 2, wherein the polysiloxane segment (B) has a structure represented by the following general formula (1) and/or (2).

(In general formulas (1) and (2), R ¹ is an organic group having 4 to 12 carbon atoms bonded to a silicon atom, and R ² and R ³ are each independently bonded to a silicon atom. It is a methyl group or an ethyl group bonded to a silicon atom.) A coating material comprising the resin composition according to claim 1 or 2. An article comprising a coating film of the paint according to claim 4.