Coating composition and laminate

Abstract

To provide a coating composition that comprises an organic-inorganic composite resin containing a hydrolyzable silyl group, which is capable of preventing lifting during overcoating.SOLUTION: A coating composition comprises: an organic-inorganic composite resin (A) having a hydrolyzable silyl group and including a vinyl-based polymer component and a polysiloxane component; a curing catalyst (B); an amino group-containing silane condensate (C); and an organic solvent (D). It is preferable that the condensate (C) be a condensate of an amino group-containing alkoxysilane and an alkylalkoxysilane. It is preferable that the content of the condensate (C) be 2 pts.wt. or more based on 100 pts.wt. of the resin (A).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a coating composition containing a resin having a hydrolyzable silyl group, and a laminate using the composition. [Background technology]

[0002] Various resins have been considered as curable resin components that can be used as paint components. Among them, polysiloxane-based paints are known as paints that aim to extend the life of coating films, especially to achieve high weather resistance and high heat resistance. Polysiloxane is a curable resin formed by the hydrolysis and dehydration condensation reaction of organoalkoxysilane. The siloxane bonds that form this resin are energetically strong, so polysiloxane has the property of being difficult to decompose due to heat or ultraviolet light.

[0003] On the other hand, acrylic silicone paints, which are mainly composed of acrylic resins having hydrolyzable silyl groups, are also known. The coating films obtained from acrylic silicone paints have the advantage of being flexible and less prone to cracking.

[0004] As a paint having both advantages of the polysiloxane paint and the acrylic silicone paint, a combination of both paints is known (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2020-196750 [Patent Document 2] JP 2006-182995 A Summary of the Invention [Problem to be solved by the invention]

[0006] When applying paint, in order to improve the appearance and durability of the paint film, it is customary to apply a second coat after one coat has been applied, leaving a gap of about 6 hours to 3 days between coats. However, paints containing composite resins that have hydrolyzable silyl groups and that contain both organic and inorganic components are prone to a phenomenon known as lifting, in which the first coating layer softens, swells, and lifts off the base when recoated.

[0007] In view of the above-mentioned current situation, an object of the present invention is to provide a coating composition containing a hydrolyzable silyl group-containing organic-inorganic composite resin, which is capable of suppressing lifting when recoating. [Means for solving the problem]

[0008] As a result of intensive research by the present inventors to solve the above problems, they discovered that by blending a specific silane condensate with a coating composition containing an organic-inorganic composite resin having a hydrolyzable silyl group, lifting during recoating can be suppressed, and thus arrived at the present invention.

[0009] That is, the present invention relates to an organic-inorganic composite resin (A) having a hydrolyzable silyl group and containing a vinyl polymer component and a polysiloxane component; Curing catalyst (B), An amino group-containing silane condensate (C), and The coating composition further comprises an organic solvent (D). The present invention also relates to a laminate comprising a substrate and at least two coating layers formed from the coating composition. Effect of the Invention

[0010] According to the present invention, it is possible to provide a coating composition containing a hydrolyzable silyl group-containing organic-inorganic composite resin, which is capable of suppressing lifting when the coating is applied in multiple layers. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, an embodiment of the present invention will be described in detail. The present embodiment relates to a coating composition for forming a coating film by applying it to the surface of a substrate, which contains at least an organic-inorganic composite resin (A), a curing catalyst (B), an amino group-containing silane condensate (C), and an organic solvent (D).

[0012] [Organic-inorganic composite resin (A)] The organic-inorganic composite resin (A) has a hydrolyzable silyl group and contains a vinyl polymer component, which is an organic component, and a polysiloxane component, which is an inorganic component. The polysiloxane component refers to a polysiloxane obtained by hydrolysis and dehydration condensation reaction of a silane compound having a hydrolyzable silyl group. In the polysiloxane component, each constituent unit is bonded by a siloxane bond (Si-O-Si bond).

[0013] [Organic-inorganic composite resin (A) according to the first aspect] In the organic-inorganic composite resin (A) according to the first embodiment (hereinafter also referred to as organic-inorganic composite resin (A1)), the polysiloxane component and the vinyl polymer component are preferably graft-bonded.

[0014] (Polysiloxane Component in the First Aspect) The polysiloxane component in the first embodiment preferably contains at least a hydrolysis condensation product of the following silane compound (a) and silane compound (b). (a) a silane compound having a radical reactive group and a hydrolyzable silyl group (b) a silane compound having a hydrocarbon group and a hydrolyzable silyl group

[0015] The silane compound (a) has a radical reactive group, which allows graft bonding between the polysiloxane component and the vinyl polymer component to be realized. The radical reactive group is preferably one that exhibits lower radical reactivity than the methacryloyl group. By using such a radical reactive group, gelation during the production of the organic-inorganic composite resin can be suppressed, and the storage stability of the organic-inorganic composite resin can be improved.

[0016] Examples of radical reactive groups that exhibit lower radical reactivity than the methacryloyl group include vinyl groups, allyl groups, p-styryl groups, and mercapto groups. Only one of these may be used, or two or more of them may be used in combination.

[0017] It is preferable to use a vinyl group as the radical reactive group. The vinyl group referred to here refers to a vinyl group directly bonded to a silicon atom, and does not refer to a vinyl group contained in an allyl group or a p-styryl group. The radical reactive group may be only a vinyl group, or may be a combination of a vinyl group and at least one group selected from the group consisting of an allyl group, a p-styryl group, and a mercapto group.

[0018] The radical reactive group is preferably directly bonded to the silicon atom of the silane compound (a). By using such a radical reactive group, graft bonding between the polysiloxane component and the vinyl polymer component via only the hydrocarbon group is possible, gelation during production is suppressed, and the storage stability of the organic-inorganic composite resin can be improved. In order to realize the graft bonding between the polysiloxane component and the vinyl polymer component via only the hydrocarbon group, it is preferable not to use an alkoxysilane having an ester-containing group such as an acryloyl group or a methacryloyl group, or an ether bond-containing group such as vinyloxy.

[0019] The silane compound (a) is a compound having a hydrolyzable silyl group. Specifically, it is preferable that the silane compound (a) is a compound having 1 to 3 alkoxy groups on a silicon atom. That is, it is preferable that the silane compound (a) is at least one selected from the group consisting of monoorganotrialkoxysilane, diorganodialkoxysilane, and triorganomonoalkoxysilane. Among them, it is preferable to include monoorganotrialkoxysilane. Here, the monoorganotrialkoxysilane refers to a silane compound having one organic group and three alkoxy groups as substituents on a silicon atom. The diorganodialkoxysilane refers to a silane compound having two organic groups and two alkoxy groups as substituents on a silicon atom. The triorganomonoalkoxysilane refers to a silane compound having three organic groups and one alkoxy group as substituents on a silicon atom.

[0020] The organic group of the silane compound (a) refers to an organic group other than an alkoxy group, and specific examples thereof are not particularly limited, but include, for example, an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms, such as a phenyl group, in addition to the above-mentioned radical reactive groups. The alkyl group and the aryl group may be unsubstituted or may have a non-radical reactive substituent, such as a glycidyloxy group or an epoxycyclohexyl group. The alkyl group having 1 to 6 carbon atoms is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group. The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 1 to 2. The organic group may be of only one type, or may be of two or more types mixed together.

[0021] The alkoxy group of the silane compound (a) is not particularly limited, and examples thereof include alkoxy groups having 1 to 3 carbon atoms. Specifically, the alkoxy groups are methoxy, ethoxy, and propoxy groups, with methoxy and ethoxy groups being preferred, and methoxy being more preferred. The alkoxy groups may be of one type only, or may be of two or more types mixed together.

[0022] Specific examples of the silane compound (a) include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane; allyltrimethoxysilane, allyltriethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane; p-styryltrimethoxysilane, p-styryltriethoxysilane, p-styrylmethyldimethoxysilane, p-styryldimethylmethoxysilane, p-styrylmethyldiethoxysilane, p-styryldimethylethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, and the like. Of these, silane compounds having a vinyl group are preferred, with vinyltrialkoxysilane being particularly preferred.

[0023] The smaller the amount of silane compound (a) used, the more effective it is to suppress gelation during production, while the larger the amount used is to increase the graft ratio between the polysiloxane component and the vinyl polymer component, thereby improving the physical properties of the coating film. From these viewpoints, the proportion of the structural units derived from the silane compound (a) relative to the total structural units contained in the polysiloxane component is preferably 0.1% by weight or more and 30% by weight or less, more preferably 1% by weight or more and 20% by weight or less, and even more preferably 3% by weight or more and 10% by weight or less.

[0024] The silane compound (b) is a silane compound having a hydrocarbon group and a hydrolyzable silyl group, and is a silane compound having no radical reactive group.

[0025] The silane compound (b) is preferably at least one selected from the group consisting of monoorganotrialkoxysilanes, diorganodialkoxysilanes, and triorganomonoalkoxysilanes, and among these, it is preferable to include monoorganotrialkoxysilanes.

[0026] The hydrocarbon group that the silane compound (b) has as a substituent on the silicon atom does not contain the radical reactive group and is a hydrocarbon group other than an alkoxy group, specifically, an alkyl group, an aryl group, etc. As the silane compound (b), it is preferable to use a silane compound (b1) having an alkyl group and / or a silane compound (b2) having an aryl group.

[0027] In particular, it is preferable to use the silane compound (b1) having an alkyl group and the silane compound (b2) having an aryl group in combination, which makes it easier to suppress gelation during production and improves the storage stability of the organic-inorganic composite resin.

[0028] The silane compound (b1) has an alkyl group as a substituent on a silicon atom. The alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 3. The alkyl group may be an unsubstituted group, or may have a non-radical reactive substituent such as a glycidyloxy group or an epoxycyclohexyl group. The alkyl group is particularly preferably a methyl group and / or an ethyl group, and most preferably a methyl group. The alkyl group may be one type only, or two or more types may be mixed.

[0029] The silane compound (b2) has an aryl group as a substituent on a silicon atom. The aryl group is not particularly limited, and examples thereof include a phenyl group and a naphthyl group. The aryl group may be an unsubstituted group or may have a non-radical reactive substituent such as a glycidyloxy group or an epoxycyclohexyl group. The number of carbon atoms in the aryl group is preferably 6 to 10. The aryl group may be of one type or may be of two or more types.

[0030] Among them, it is preferred that the silane compound (b1) contains a methyl group and / or an ethyl group as the alkyl group, and the silane compound (b2) contains a phenyl group as the aryl group.Moreover, it is particularly preferred that the silane compound (b1) contains a methyl group as the alkyl group, and the silane compound (b2) contains a phenyl group as the aryl group.

[0031] The alkoxy group that the silane compound (b1) and the silane compound (b2) have as a substituent on the silicon atom is not particularly limited, and examples thereof include alkoxy groups having 1 to 3 carbon atoms. Specifically, the alkoxy group is a methoxy group, an ethoxy group, and a propoxy group, with a methoxy group and an ethoxy group being preferred, and a methoxy group being more preferred. The alkoxy group may be of one type only, or may be of two or more types mixed together.

[0032] Specific examples of the silane compound (b1) are not particularly limited, but examples of monoorganotrialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltriisopropoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltriisopropoxysilane, octyltrimethoxysilane, and decyltrimethoxysilane. Examples of diorganodialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, etc. Examples of triorganomonoalkoxysilanes include trimethylmonomethoxysilane, etc.

[0033] Specific examples of the silane compound (b2) include, but are not limited to, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, tolyltrippropoxysilane, xylyltrimethoxysilane, xylyltriethoxysilane, xylyltrippropoxysilane, naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltrippropoxysilane, diphenyldimethoxysilane, triphenylmonomethoxysilane, and the like.

[0034] It is preferable to use methyltrialkoxysilane and / or ethyltrialkoxysilane as the silane compound (b1), and phenyltrialkoxysilane as the silane compound (b2).Moreover, it is particularly preferable to use methyltrialkoxysilane as the silane compound (b1), and phenyltrialkoxysilane as the silane compound (b2).

[0035] In the polysiloxane component, the ratio of the alkyl group of the silane compound (b1) to the aryl group of the silane compound (b2) is not particularly limited, but from the viewpoint of the stability of the organic-inorganic composite resin, the molar ratio of the alkyl group to the aryl group is preferably 1:99 to 80:20, more preferably 10:90 to 75:25, more preferably 20:80 to 70:30, particularly preferably 30:70 to 70:30, and most preferably 40:60 to 70:30.

[0036] In the polysiloxane component, it is preferable to set the amount of each silane compound used so that the ratio of the radical reactive group of the silane compound (a) to the total number of moles of the radical reactive group of the silane compound (a) and the hydrocarbon group of the silane compound (b) is 20 mol % or less. Within this range, gelation during production of the organic-inorganic composite resin is unlikely to occur, and the storage stability of the organic-inorganic composite resin tends to be good.

[0037] (Vinyl Polymer Component in the First Aspect) The vinyl polymer component constituting the organic component in the organic-inorganic composite resin (A1) according to the first embodiment is formed by polymerization of a radically polymerizable monomer component. In the vinyl polymer component, each structural unit is bonded by a polymerization reaction between radically reactive groups, that is, by a carbon-carbon bond. The vinyl polymer component may be a graft chain to the polysiloxane component.

[0038] The vinyl polymer component in the first embodiment preferably contains at least a structural unit derived from a monomer (c) having a radical reactive group and no hydrolyzable silyl group. The radical reactive group refers to a group capable of forming a vinyl polymer component by addition polymerization, and generally refers to a carbon-carbon double bond. The hydrolyzable silyl group refers to a group capable of forming a siloxane bond by hydrolysis-dehydration condensation reaction, and a representative example is an alkoxysilyl group.

[0039] As the monomer (c), it is preferable to use a (meth)acrylic acid ester monomer having no hydrolyzable silyl group and / or a radical polymerizable monomer having no hydrolyzable silyl group other than the (meth)acrylic acid ester monomer. As the monomer (c), only the (meth)acrylic acid ester monomer may be used, or the (meth)acrylic acid ester monomer may be used in combination with a radical polymerizable monomer other than the (meth)acrylic acid ester monomer.

[0040] The (meth)acrylic acid ester monomer is not particularly limited, and examples thereof include alkyl (meth)acrylates having an alkyl group having 1 to 22 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; aralkyl (meth)acrylates, such as benzyl (meth)acrylate and 2-phenylethyl (meth)acrylate; acrylates; cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; ω-alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate and 4-methoxybutyl (meth)acrylate; hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerol mono(meth)acrylate. These may be used alone or in combination of two or more.

[0041] The radical polymerizable monomer other than the (meth)acrylic acid ester monomer is not particularly limited, and examples thereof include unsaturated carboxylic acids such as (meth)acrylic acid; acrylamides such as (meth)acrylamide, α-ethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methyl(meth)acrylamide, and N-methylol(meth)acrylamide; aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene, and vinyltoluene; acid anhydrides of unsaturated carboxylic acids such as maleic anhydride; and mixtures of these acid anhydrides with linear or branched alcohols or amines having 1 to 20 carbon atoms. Examples of the vinyl ester include esters of unsaturated carboxylic acids such as diesters or half esters of vinyl acetate, vinyl propionate, diallyl phthalate, and other vinyl esters and aryl compounds, amino group-containing vinyl compounds such as vinylpyridine and aminoethyl vinyl ether, amide group-containing vinyl compounds such as itaconic acid diamide, crotonic acid amide, maleic acid diamide, fumaric acid diamide, and N-vinylpyrrolidone, (meth)acrylonitrile, 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin maleimide, N-vinylimidazole, and vinyl sulfonic acid. These may be used alone or in combination of two or more.

[0042] The ratio of the (meth)acrylic acid ester monomer to the entire radical polymerizable monomer components forming the vinyl polymer component can be appropriately set, but from the viewpoint of adhesion of the produced organic-inorganic composite resin to a substrate, the (meth)acrylic acid ester monomer preferably accounts for 60% by weight or more of the total amount of the radical polymerizable monomer components, more preferably 65% ​​by weight or more, and even more preferably 70% by weight or more.

[0043] The vinyl polymer component may be composed of only a constituent unit derived from a monomer (c) having no hydrolyzable silyl group, but it is preferable that the vinyl polymer component further contains a constituent unit derived from a monomer (d) having a radical reactive group having a (meth)acryloyl group and a hydrolyzable silyl group in addition to the constituent unit derived from the monomer (c). By forming the vinyl polymer component using the monomer (d), a hydrolyzable silyl group can be introduced into the vinyl polymer component, and the compatibility between the vinyl polymer component and the polysiloxane component can be improved, and the stability of the organic-inorganic composite resin can be improved.

[0044] The monomer (d) is not particularly limited, and examples thereof include hydrolyzable silyl group-containing (meth)acrylates such as 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, (meth)acryloyloxyoctyltrimethoxysilane, and (meth)acryloyloxyoctyltriethoxysilane.

[0045] The hydrolyzable silyl group of the monomer (d) refers to a group formed by bonding an alkoxy group to a silicon atom. The alkoxy group is not particularly limited, and examples thereof include alkoxy groups having 1 to 3 carbon atoms. The hydrolyzable silyl group of the monomer (d) is preferably a silyl group having an ethoxy group on the silicon atom, and particularly preferably a triethoxysilyl group. The silyl group having an ethoxy group is less hydrolyzable than the silyl group having a methoxy group, and therefore has the advantage of improving the storage stability of the organic-inorganic composite resin and easily increasing the uniformity of the coating film formed.

[0046] The amount of the monomer (d) used can be appropriately set, but from the viewpoint of the effect of using the monomer (d), it is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and particularly preferably 1 to 10% by weight, of the total amount of the radical polymerizable monomer components forming the vinyl polymer component.

[0047] The number of carbon atoms contained in the monomer unit constituting the vinyl polymer component is not particularly limited, but for example, when dissolving an organic-inorganic composite resin in a weak solvent to prepare a paint, the carbon number of the side chain of the monomer unit is preferably in the range of 3 to 7 on average, more preferably in the range of 3.3 to 6.7, and even more preferably in the range of 3.5 to 6.2. The carbon number of the side chain is, for example, the carbon number of the ester portion in the case of a (meth)acrylic acid ester monomer, and in the case of other monomers, the carbon number of the portion excluding the carbon-carbon unsaturated bond forming the main chain of the polymer. Specifically, the carbon number of the side chain of methyl methacrylate is 1, the carbon number of the side chain of butyl methacrylate is 4, the carbon number of cyclohexyl methacrylate is 6, the carbon number of the side chain of 2-hydroxyethyl methacrylate is 2, the carbon number of the side chain of 3-methacryloyloxypropyltrimethoxysilane is 6, and the carbon number of the side chain of styrene is 6. When a large amount of monomers with large steric hindrance around the main chain, such as butyl methacrylate or cyclohexyl methacrylate, are used, the compatibility with the polysiloxane component decreases, generally making it difficult to form a composite. However, according to the production method disclosed in the present application, even when a large amount of such monomers with a large carbon number are used, it is possible to produce an organic-inorganic composite resin in which a polysiloxane component and a vinyl polymer component are composited.

[0048] In the organic-inorganic composite resin (A1) related to the first aspect, the weight ratio of the polysiloxane component to the vinyl polymer component can be appropriately set, but from the viewpoint of the stability of the organic-inorganic composite resin, it is preferably 20:80 to 99:1, more preferably 30:70 to 90:10, even more preferably 40:60 to 80:20, particularly preferably 40:60 to 70:30, and most preferably 40:60 to 60:40.

[0049] The weight average molecular weight (Mw) of the organic / inorganic composite resin (A1) according to the first embodiment can be appropriately determined according to the desired physical properties, and may be, for example, in the range of 2,000 to 500,000. In this range, gelation during production can be avoided while improving the storage stability of the organic / inorganic composite resin. Among them, the weight average molecular weight of the organic / inorganic composite resin (A1) is preferably 50,000 or more, more preferably 60,000 or more, and particularly preferably 80,000 or more, since there is an advantage that the viscosity of the coating composition is increased, it is difficult to drip during application, and the thickness of the coating film can be easily ensured. The weight average molecular weight of the organic / inorganic composite resin can be determined by the method described in the Examples section.

[0050] (Method for producing organic-inorganic composite resin according to the first embodiment) Next, a method for producing the organic-inorganic composite resin (A1) according to the first embodiment will be described. The organic-inorganic composite resin (A1) according to the first embodiment can be produced by obtaining a polysiloxane component by hydrolysis and dehydration condensation reaction of a silane compound, and then performing radical polymerization of a radically polymerizable monomer component in the presence of the polysiloxane component to form a vinyl polymer component. Each step will be described below.

[0051] (Hydrolysis and dehydration condensation reaction) First, a silane component including a silane compound (a) and a silane compound (b) is subjected to hydrolysis and dehydration condensation reaction in the presence of water and a condensation catalyst to form a polysiloxane component. The produced polysiloxane component has a radical reactive group derived from the silane compound (a).

[0052] In a preferred embodiment, some of the alkoxy groups contained in each silane compound remain unreacted, or after the silane compound undergoes hydrolysis, the dehydration condensation reaction does not proceed and the alkoxy groups remain as silanol groups, so that the produced polysiloxane component can further have a hydrolyzable silyl group. Here, the hydrolyzable silyl group is a concept including both an alkoxysilyl group and a silanol group.

[0053] In the hydrolysis and dehydration condensation reactions, it is preferable to add water to allow the reactions to proceed. At this time, by controlling the amount of water used, it is possible to suppress gelation during radical polymerization and improve the storage stability of the organic-inorganic composite resin. From this viewpoint, the amount of water used is preferably 20 mol% or more and 60 mol% or less, with the total number of moles of alkoxy groups directly bonded to silicon atoms contained in the silane compound being 100%. The upper limit is more preferably 55 mol% or less. The lower limit is more preferably 25 mol% or more, even more preferably 30 mol% or more, and particularly preferably 35 mol% or more.

[0054] In the hydrolysis and dehydration condensation process, an organic solvent other than water may be used in addition to water. As such an organic solvent, a water-soluble organic solvent is preferable because it is used in combination with water. In addition, in order to ensure the solubility of the silane compound, an organic solvent having 4 or more carbon atoms is preferable. From the above viewpoint, preferable organic solvents include, for example, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, etc., but are not limited thereto.

[0055] Since the organic solvent is volatilized after production of the organic-inorganic composite resin or during formation of the coating film, an organic solvent having a boiling point of 150° C. or less under atmospheric pressure is preferred, and specifically, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monoethyl ether, and propylene glycol dimethyl ether are particularly preferred.

[0056] The hydrolysis and dehydration condensation reactions are preferably carried out in the presence of a condensation catalyst in order to promote the reactions. As the condensation catalyst, an acid catalyst, a basic catalyst, or a neutral salt can be used.

[0057] As the acid catalyst, from the viewpoint of compatibility with the silane compound and the organic solvent, an organic acid is preferable, and a phosphoric acid ester or a carboxylic acid is more preferable. Specific examples of the organic acid include ethyl acid phosphate, butyl acid phosphate, butyl pyrophosphate (or dibutyl pyrophosphate), butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, isotridecyl acid phosphate, dibutyl phosphate, bis(2-ethylhexyl)phosphate, formic acid, acetic acid, butyric acid, isobutyric acid, etc.

[0058] Examples of the basic catalyst include amine compounds such as N-ethylmorpholine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, Nt-butyldiethanolamine, triethylamine, n-butylamine, hexylamine, triethanolamine, diazabicycloundecene, and ammonia; and metal hydroxides such as sodium hydroxide and potassium hydroxide.

[0059] A neutral salt is a positive salt consisting of a strong acid and a strong base, and is, for example, a salt consisting of a combination of a cation selected from the group consisting of a Group 1 element ion, a Group 2 element ion, a tetraalkylammonium ion, and a guanidinium ion, and an anion selected from the group consisting of a Group 17 element ion excluding fluoride ion, a sulfate ion, a nitrate ion, and a perchlorate ion. In particular, as an anion, a Group 17 element ion is preferred because of its high nucleophilicity, and as a cation, a Group 1 element ion or a Group 2 element ion is preferred because it is not bulky so as not to inhibit the nucleophilic action.

[0060] Specific compounds of the neutral salt are not particularly limited, but preferred neutral salts include, for example, lithium chloride, sodium chloride, potassium chloride, rabidium chloride, cesium chloride, magnesium chloride, calcium chloride, strontium chloride, lithium bromide, sodium bromide, potassium bromide, rabidium bromide, cesium bromide, magnesium bromide, calcium bromide, strontium bromide, lithium iodide, sodium iodide, potassium iodide, rabidium iodide, cesium iodide, magnesium iodide, calcium iodide, and strontium iodide.

[0061] The amount of the condensation catalyst added can be appropriately adjusted, but may be, for example, about 10 ppm to 3% by weight based on the silane compound.

[0062] The reaction temperature when carrying out the hydrolysis and dehydration condensation steps can be appropriately set by those skilled in the art, but for example, the reaction liquid is preferably heated to a range of 50 to 150° C. The reaction time can also be appropriately set by those skilled in the art, but may be, for example, about 10 minutes to 12 hours.

[0063] After carrying out the hydrolysis and dehydration condensation steps, it is preferable to carry out a step of removing the alcohol generated in the hydrolysis step from the reaction solution. By removing the alcohol, the hydrolysis reaction that produces alcohol as a by-product can be further promoted. The alcohol removal step can be carried out by subjecting the reaction solution after the hydrolysis and dehydration condensation steps to reduced pressure distillation to distill off the alcohol. The conditions for reduced pressure distillation can be appropriately set by those skilled in the art.

[0064] In the hydrolysis and dehydration condensation reactions, the radical reactive groups of the silane compound (a) are not substantially affected, and therefore the polysiloxane component produced by these reactions has radical reactive groups derived from the silane compound (a), as described above.

[0065] (Radical Polymerization) Next, the polysiloxane component obtained by the hydrolysis and dehydration condensation reaction is mixed with a radically polymerizable monomer component containing a monomer (c) to carry out radical polymerization. This allows the production of an organic-inorganic composite resin (A1) containing a polysiloxane component and a vinyl polymer component. In this radical polymerization, first, the polymerization of the radically polymerizable monomer component containing a monomer (c) proceeds to preferentially form a vinyl polymer component, and then the radically reactive group of the polysiloxane component reacts with the main chain end of the vinyl polymer component, thereby realizing graft bonding between the polysiloxane component and the vinyl polymer component. However, there may be cases where a part of the radically reactive group of the polysiloxane component is copolymerized with a portion other than the main chain end of the vinyl polymer component.

[0066] The radical polymerization can be carried out by a conventional method, and known polymerization methods such as bulk radical polymerization, solution radical polymerization, and non-aqueous dispersion radical polymerization can be used.

[0067] Radical polymerization can be carried out in the presence of a radical polymerization initiator. The radical polymerization initiator is not particularly limited, but examples thereof include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide, and diisopropyl peroxycarbonate. These may be used alone or in combination of two or more.

[0068] The amount of the radical polymerization initiator used may be, for example, 0.1 to 10 parts by weight, and preferably 0.5 to 7 parts by weight, based on 100 parts by weight of the radically polymerizable monomer component.

[0069] The radical polymerization may be carried out in the presence of a β-dicarbonyl compound. The β-dicarbonyl compound refers to a compound having a structure in which two carbonyl groups are bonded with one carbon atom between them. By allowing the β-dicarbonyl compound to exist in the polymerization system, the dehydration condensation reaction of the silanol group of the polysiloxane component during radical polymerization can be suppressed. The β-dicarbonyl compound is not particularly limited, and examples thereof include acetylacetone, dimedone, cyclohexane-1,3-dione, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate, diethyl malonate, and Meldrum's acid. The amount of the β-dicarbonyl compound used may be, for example, 0.01 to 10 parts by weight, or about 0.1 to 5 parts by weight, relative to 100 parts by weight of the polysiloxane component.

[0070] The polymerization temperature during the radical polymerization can be selected according to a conventional method. The hydrolysis and dehydration condensation reactions, and the radical polymerization are preferably carried out in an atmosphere substantially free of oxygen molecules.

[0071] By the above radical polymerization, a vinyl polymer component is formed, and at the same time, the radical reactive group of the polysiloxane component reacts with the main chain terminal of the vinyl polymer component to bond the polysiloxane component, thereby producing an organic-inorganic composite resin (A1) in which the polysiloxane component and the vinyl polymer component are graft-bonded.

[0072] According to a preferred embodiment, the polysiloxane component contained in the organic-inorganic composite resin (A1) can have a hydrolyzable silyl group (alkoxysilyl group and / or silanol group). The hydrolyzable silyl group allows the organic-inorganic composite resin to exhibit curability by utilizing the hydrolysis and dehydration reaction of the hydrolyzable silyl group.

[0073] In this case, in order to ensure the stability of the hydrolyzable silyl group, a dehydrating agent may be mixed into the produced organic-inorganic composite resin. This can improve the storage stability of the organic-inorganic composite resin having a hydrolyzable silyl group in the polysiloxane component. As the dehydrating agent, a known agent can be used, and is not particularly limited. For example, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, or ethyl orthoacetate is preferred. Only one of these may be used, or multiple types may be used.

[0074] The amount of the dehydrating agent used is not particularly limited, and can be appropriately determined by a person skilled in the art, taking into consideration the amount of water contained in the organic-inorganic composite resin before dehydration and the target water content after dehydration. For example, the amount is about 0.01 to 20 parts by weight, and may be about 0.1 to 10 parts by weight, relative to 100 parts by weight of the organic-inorganic composite resin.

[0075] [Organic-inorganic composite resin (A) according to the second aspect] In the organic-inorganic composite resin (A) according to the second embodiment (hereinafter also referred to as organic-inorganic composite resin (A2)), the polysiloxane component and the vinyl polymer component are in a mixed state, but may be independent components that are not bonded to each other.

[0076] (Vinyl Polymer Component in the Second Aspect) The vinyl polymer component in the second embodiment is preferably a vinyl polymer component having a hydrolyzable silyl group, and particularly preferably a (meth)acrylic acid ester polymer having a hydrolyzable silyl group.

[0077] <Hydrolyzable silyl group> The hydrolyzable silyl group contained in the vinyl polymer component can be represented by the following formula (1). -Si(R 1 ) 3-a X a (1) (In formula (1), R 1 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a hetero-containing group; each X independently represents a hydroxyl group or a hydrolyzable group; and a is 1, 2, or 3.

[0078] R 1 R is a hydrocarbon group having 1 to 20 carbon atoms. 1 The number of carbon atoms in the hydrocarbon group as the substituent is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 4. The hydrocarbon group may be an unsubstituted hydrocarbon group, or a hydrocarbon group having a substituent.

[0079] R 1 The hetero-containing group which the hydrocarbon group may have as a substituent is a group containing a hetero atom, where an atom other than carbon and hydrogen atoms is defined as a hetero atom.

[0080] Suitable examples of the heteroatom include N, O, S, P, Si, and halogen atoms. In the hetero-containing group, the total number of carbon atoms and heteroatoms is preferably 1 to 10, more preferably 1 to 6, and further preferably 1 to 4.

[0081] Suitable examples of the hetero-containing group include a hydroxyl group; a mercapto group; halogen atoms such as Cl, Br, I, and F; a nitro group; a cyano group; alkoxy groups such as a methoxy group, an ethoxy group, an n-propyloxy group, and an isopropyloxy group; alkylthio groups such as a methylthio group, an ethylthio group, an n-propylthio group, and an isopropylthio group; acyl groups such as an acetyl group, a propionyl group, and a butanoyl group; acyloxy groups such as an acetyloxy group, a propionyloxy group, and a butanoyloxy group; substituted or unsubstituted amino groups such as an amino group, a methylamino group, an ethylamino group, a dimethylamino group, and a diethylamino group; substituted or unsubstituted aminocarbonyl groups such as an aminocarbonyl group, a methylaminocarbonyl group, an ethylaminocarbonyl group, a dimethylaminocarbonyl group, and a diethylaminocarbonyl group; and a cyano group.

[0082] R 1 When R is a hydrocarbon group substituted with a hetero-containing group, 1 The total number of carbon atoms and heteroatoms in is preferably 2 to 30, more preferably 2 to 18, further preferably 2 to 10, and particularly preferably 2 to 6.

[0083] R 1Specific examples of the hydrocarbon group having 1 to 20 carbon atoms as the substituent include alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a 2-ethyl-n-hexyl group, a n-nonyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group, a n-tridecyl group, a n-tetradecyl group, a n-pentadecyl group, a n-hexadecyl group, a n-octadecyl group, a n-nonadecyl group, and a n-icosyl group; alkenyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; aryl groups such as phenyl, naphthalene-1-yl, naphthalene-2-yl, o-phenylphenyl, m-phenylphenyl, and p-phenylphenyl; and aralkyl groups such as benzyl, phenethyl, naphthalene-1-ylmethyl, and naphthalene-2-ylmethyl.

[0084] These hydrocarbon groups may also be substituted with the hetero-containing groups described above. 1 As preferred.

[0085] R 1 Suitable examples of R include alkyl groups such as methyl and ethyl groups; alkyl groups having a hetero-containing group such as chloromethyl and methoxymethyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl groups; and aralkyl groups such as benzyl groups. 1 As the alkyl group, a methyl group, a methoxymethyl group, and a chloromethyl group are preferable, a methyl group and a methoxymethyl group are more preferable, and a methyl group is further preferable.

[0086] a is 1, 2, or 3. a is preferably 2 or 3, and more preferably 3 from the viewpoints of the curability of the curable composition and the productivity of the polymer.

[0087] Examples of X include hydroxyl, halogen, alkoxy, acyloxy, ketoximate, amino, amide, acid amide, aminooxy, mercapto, and alkenyloxy groups. Among these, alkoxy is more preferred because it is mildly hydrolyzable and easy to handle. In general, the smaller the carbon number of an alkoxy group, the higher its reactivity. That is, the lower the reactivity is in the order of methoxy, ethoxy, and propoxy. By utilizing this property, the specific structure of the hydrolyzable silyl group can be appropriately determined according to the method for producing the polymer and the application.

[0088] Specific examples of the hydrolyzable silyl group represented by formula (1) include a dimethoxysilyl group, a trimethoxysilyl group, a diethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxymethylsilyl group. From the viewpoint of the curability of the curable composition, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a trimethoxysilyl group, a triethoxysilyl group, and the like are preferred, and a dimethoxymethylsilyl group is particularly preferred.

[0089] The average number of hydrolyzable silyl groups contained in one polymer molecule is preferably in the range of 0.05 to 10, more preferably in the range of 0.5 to 9, and particularly preferably in the range of 1 to 8, from the viewpoint of performance such as adhesiveness and tensile properties of the cured product.

[0090] The position of the hydrolyzable silyl group contained in the polymer is not particularly limited, and may be any of the side chain, the main chain terminal, and / or the region near the terminal of the polymer. When designing a rubber material excellent in flexibility and elongation, it is preferable to have the hydrolyzable silyl group at least at the main chain terminal of the polymer.

[0091] The hydrolyzable silyl group-containing (meth)acrylic acid ester polymer is a polymer having a structural unit derived from a (meth)acrylic acid ester monomer and a hydrolyzable silyl group. The polymer can be obtained, for example, by polymerizing a monomer mixture containing a (meth)acrylic monomer and a vinyl monomer having a hydrolyzable silyl group. In this specification, "(meth)acrylic" means acrylic and / or methacrylic.

[0092] The (meth)acrylic monomer is a monomer having a (meth)acryloyl group in the molecule, and a representative example is a (meth)acrylic acid alkyl ester, etc. The (meth)acrylic monomer may include the above-mentioned vinyl monomer having a hydrolyzable silyl group.

[0093] The amount of the (meth)acrylic monomer used is preferably in the range of 10 to 100% by weight, more preferably in the range of 30 to 100% by weight, and even more preferably in the range of 50 to 100% by weight, based on the total constituent monomers of the hydrolyzable silyl group-containing (meth)acrylic acid ester polymer.

[0094] Specific examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. xyl, n-nonyl (meth)acrylate and isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, behenyl (meth)acrylate, tetracosyl (meth)acrylate, (meth)acrylate )Hexacosyl acrylate, octacosyl (meth)acrylate, triacontyl (meth)acrylate, dotriacontyl (meth)acrylate, tetratriacontyl (meth)acrylate, hexatriacontyl (meth)acrylate, octatriacontyl (meth)acrylate, tetracontyl (meth)acrylate, isodecyl (meth)acrylate, isoundecyl (meth)acrylate, isolauryl (meth)acrylate, isotridecyl (meth)acrylate, isotetradecyl (meth)acrylate, isopentadecyl (meth)acrylate, (meth)acrylic isohexadecyl (meth)acrylate, isoheptadecyl (meth)acrylate, isostearyl (meth)acrylate, isononadecyl (meth)acrylate, isoeicosyl (meth)acrylate, isoheneicosyl (meth)acrylate, isobehenyl (meth)acrylate, isotetracosyl (meth)acrylate, isohexacosyl (meth)acrylate, isooctacosyl (meth)acrylate, isotriacontyl (meth)acrylate, isodotriacontyl (meth)acrylate, isotetratriacontyl (meth)acrylate, isohexatriacontyl (meth)acrylate,Examples include (meth)acrylic acid alkyl esters having a linear or branched aliphatic alkyl group or an alicyclic alkyl group, such as isooctatriacontyl (meth)acrylate and isotetracontyl (meth)acrylate. One or more of these can be used. Among these, from the viewpoint of the mechanical properties of the cured product, (meth)acrylic acid alkyl esters having a linear or branched aliphatic alkyl group having 1 to 8 carbon atoms are preferred.

[0095] Examples of monomers other than (meth)acrylic acid alkyl esters include functional group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, and ethylene oxide adducts of (meth)acrylic acid; aromatic (meth)acrylic esters such as phenyl (meth)acrylate, toluyl (meth)acrylate, and benzyl (meth)acrylate; 2-methoxyethyl (meth)acrylate, 2-(meth)acrylic acid, Alkoxyalkyl (meth)acrylates such as ethoxyethyl and 3-methoxypropyl (meth)acrylate; trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, and 2-perfluoromethyl-2-perfluoroethyl (meth)acrylate. Fluorine-containing (meth)acrylic acid esters such as methyl, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, perfluoroethylene, perfluoropropylene, and vinylidene fluoride; aromatic monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and its salts; maleic anhydride; unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and their monoalkyl esters and dialkyl esters; maleic Maleimide compounds such as imide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, phenylmaleimide, and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene;Examples of the vinyl chloride include, but are not limited to, vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, etc. One or more of these may be used.

[0096] The number average molecular weight (Mn) of the hydrolyzable silyl group-containing (meth)acrylic acid ester polymer is preferably in the range of 2,000 to 100,000, and more preferably 8,000 to 80,000, in terms of polystyrene equivalent molecular weight determined by gel permeation chromatography (hereinafter also referred to as "GPC").

[0097] <Method of producing hydrolyzable silyl group-containing (meth)acrylic acid ester polymer> Next, a method for producing a hydrolyzable silyl group-containing (meth)acrylic acid ester polymer will be described. The hydrolyzable silyl group-containing (meth)acrylic acid ester polymer can be produced by normal radical polymerization. For example, any of solution polymerization, bulk polymerization, dispersion polymerization, high-temperature continuous polymerization, etc. may be adopted, or the living radical polymerization method developed in recent years may be used. The reaction process may be any of batch, semi-batch, and continuous polymerization. Among these, the living radical polymerization method is preferred.

[0098] The high-temperature continuous polymerization method may be performed according to known methods disclosed in JP-A-57-502171, JP-A-59-6207, JP-A-60-215007, etc. For example, a pressurizable reactor is filled with a solvent, and a predetermined temperature is set under pressure, and then a monomer mixture consisting of each monomer and, if necessary, a polymerization solvent is fed to the reactor at a constant feed rate, and an amount of polymerization liquid corresponding to the amount of the monomer mixture fed is extracted. In addition, a polymerization initiator may be blended into the monomer mixture as necessary. When a polymerization initiator is blended, the blending amount is preferably 0.001 to 2 parts by weight per 100 parts by weight of the monomer mixture. The pressure depends on the reaction temperature and the boiling points of the monomer mixture and the solvent used, and does not affect the reaction, but may be a pressure that can maintain the reaction temperature. The residence time of the monomer mixture is preferably 1 to 60 minutes.

[0099] In general, when hydrolyzable silyl groups are uniformly introduced into a polymer, the curability of a curable composition containing the polymer and the physical properties such as weather resistance of the obtained cured product are good. In this respect, when the living radical polymerization method is used, a (meth)acrylic acid ester-based polymer having a relatively narrow molecular weight distribution can be obtained, and the number of hydrolyzable silyl groups in one molecular chain of the polymer and the position of the hydrolyzable silyl group (side chain, terminal or near terminal) can be freely controlled.

[0100] When using a living radical polymerization method, there is no particular limitation on the type, and various polymerization methods such as reversible addition-fragmentation chain transfer polymerization (RAFT method), nitroxy radical method (NMP method), atom transfer radical polymerization (ATRP method), polymerization method using an organotellurium compound (TERP method), polymerization method using an organoantimony compound (SBRP method), polymerization method using an organobismuth compound (BIRP method), iodine transfer polymerization method, and reversible transfer catalysis polymerization method (RTCP method) using an organic catalyst, reversible coordination mediated polymerization method (RCMP method), etc. can be adopted. Among these, the RAFT method, the NMP method, and the ATRP method are preferable from the viewpoint of polymerization controllability and ease of implementation.

[0101] Among the living radical polymerization methods, the "atom transfer radical polymerization method" (so-called ATRP method), which polymerizes (meth)acrylic acid ester monomers using organic halides or sulfonyl halide compounds as initiators and transition metal complexes as catalysts, is more preferable as a method for producing (meth)acrylic acid ester polymers having specific functional groups, since it has halogens at the terminals, which are relatively advantageous for functional group conversion reactions, and has a large degree of freedom in the design of initiators and catalysts, in addition to the characteristics of the living radical polymerization method described above. This ATRP method is described, for example, in Matyjaszewski et al., Journal of the American Chemical Society (J.Am.Chem.Soc.), 1995, Vol. 117, p. 5614, etc.

[0102] In the ATRP method, a polymerization reaction is generally carried out using an organic halide as an initiator and a transition metal complex as a catalyst. The organic halide used as the initiator may be monofunctional or bifunctional or higher. In addition, the type of halogen is preferably bromide or chloride. For example, JP-A-9-272714 discloses a production method using an atom transfer radical polymerization method, but the present invention is not limited thereto.

[0103] A known method may be used to introduce a hydrolyzable silyl group into the main chain of the (meth)acrylic acid ester polymer. For example, a (meth)acrylic acid ester polymer having a hydrolyzable silyl group in a side chain can be easily obtained by copolymerizing a (meth)acrylic monomer with a vinyl monomer having a hydrolyzable silyl group. As the vinyl monomer having a hydrolyzable silyl group, a compound having a hydrolyzable silyl group and a polymerizable unsaturated group in the molecule can be used.

[0104] Examples of vinyl monomers having a hydrolyzable silyl group include hydrolyzable silyl group-containing vinyl silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinyldimethylmethoxysilane; hydrolyzable silyl group-containing (meth)acrylic acid esters such as trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, dimethylmethoxysilylpropyl (meth)acrylate, and methyldimethoxysilylpropyl (meth)acrylate; hydrolyzable silyl group-containing vinyl ethers such as trimethoxysilylpropyl vinyl ether; and hydrolyzable silyl group-containing vinyl esters such as vinyl trimethoxysilylundecanoate. One or more of these can be used.

[0105] The (meth)acrylic acid ester polymer containing a hydrolyzable silyl group may be produced by copolymerizing, in addition to the above-mentioned monomers, other monomers copolymerizable therewith.

[0106] When a halogen compound having a hydrolyzable silyl group (or a functional group that can be converted into a hydrolyzable silyl group) is used as an initiator for the ATRP method, a polymer having a hydrolyzable silyl group (or a functional group that can be converted into a hydrolyzable silyl group) at the polymer end on the polymerization initiation side can be obtained.

[0107] In the ATRP method, a halogen group is generally present at the polymer growth terminal, and this halogen group can be converted to a functional group having a hydrolyzable silyl group by a conventionally known method.

[0108] In this way, by making full use of the method of introducing a hydrolyzable silyl group to the terminal or the method of copolymerizing a vinyl monomer having a hydrolyzable silyl group, the position of the hydrolyzable silyl group can be freely controlled according to the purpose, such as the terminal of the main chain, near the terminal, or in the side chain of the polymer.

[0109] (Polysiloxane Component in the Second Aspect) In a second embodiment, the polysiloxane component has the formula (2): (R 3O) 4-b -Si-R 4 b (2) (In the formula, R 3 and R 4 are the same or different and represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, and b represents 0 or 1).

[0110] In the formula (2), R 3 R represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. Preferred is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, or an i-butyl group. A methyl group or an ethyl group is particularly preferred. 3 When multiple are present, they may be the same or different.

[0111] R 4 represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. Preferred are alkyl groups having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, or an i-butyl group, aryl groups having 6 to 9 carbon atoms, such as a phenyl group, and aralkyl groups having 7 to 9 carbon atoms, such as a benzyl group. In addition, in the formula (2), b represents 0 or 1, but from the viewpoint of improving the curability of the coating composition according to the present disclosure, b is preferably 0.

[0112] Specific examples of the silicon compound represented by formula (2) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, and tetra-i-butoxysilane; and trialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and octadecyltriethoxysilane.

[0113] The hydrolysis condensate of the silicon compound represented by formula (2) is obtained by hydrolyzing the silicon compound represented by formula (2) to form a silanol group, and then condensing the silanol group. In particular, a partial hydrolysis condensate is preferable. Specific examples thereof include partial hydrolysis condensates of tetraalkoxysilanes such as MSI51, ESI40, ESI48, EMSi48 (30 / 70), ESi48 (50 / 50) ESi48 (75 / 25) (all manufactured by Colcoat Co., Ltd.), MS51, MS56, MS56S (all manufactured by Mitsubishi Chemical Co., Ltd.), FR-3, silicate 40, silicate 45, silicate 48, ES-48 (all manufactured by Colcoat Co., Ltd.), and partial hydrolysis condensates of trialkoxysilanes such as AFP-1 (manufactured by Shin-Etsu Chemical Co., Ltd.). The hydrolysis condensation product of the silicon compound represented by formula (2) may be used alone or in combination of two or more kinds.

[0114] In the organic-inorganic composite resin (A2), the amount of the hydrolysis condensate of the silicon compound represented by formula (2) may be about 1 to 100 parts by weight, preferably 2 to 50 parts by weight, and more preferably 3 to 30 parts by weight, per 100 parts by weight of the vinyl polymer component.

[0115] The organic-inorganic composite resin (A2) can be produced by preparing a vinyl polymer component having a hydrolyzable silyl group and a silicon-containing hydrolysis condensate represented by formula (2) and then mixing the two components by a conventional method.

[0116] [Curing catalyst (B)] The curing reaction of the organic-inorganic composite resin (A) is accelerated in the presence of the curing catalyst (B), and the working time for forming the coating film can be shortened. Therefore, the coating composition according to the present embodiment is preferably a two-liquid composition that contains the curing catalyst (B) in a state mixed with the organic-inorganic composite resin (A) or contains the curing catalyst (B) in a separate package.

[0117] As the curing catalyst (B), a substance known as a curing catalyst used for a curable resin composition utilizing the hydrolysis reaction and dehydration condensation reaction of a hydrolyzable silyl group can be appropriately used. Specifically, as the curing catalyst (B), the above-mentioned condensation catalyst can be used, and also, an organic tin compound, a titanium chelate compound, an aluminum chelate compound, an organic amine compound, etc. can be used.

[0118] Specific examples of organotin compounds include dioctyltin bis(2-ethylhexyl malate), condensates of dioctyltin oxide or dibutyltin oxide with silicate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin distearate, dibutyltin diacetylacetonate, dibutyltin bis(ethyl malate), dibutyltin bis(butyl malate), dibutyltin bis(2-ethylhexyl malate), dibutyltin bis(oleyl malate), stannous octoate, tin stearate, and di-n-butyltin laurate oxide. Specific examples of organotin compounds having an S atom in the molecule include dibutyltin bisisononyl-3-mercaptopropionate, dioctyltin bisisononyl-3-mercaptopropionate, octylbutyltin bisisononyl-3-mercaptopropionate, dibutyltin bisisooctylthioglucarate, dioctyltin bisisooctylthioglucarate, octylbutyltin bisisooctylthioglucarate, and the like.

[0119] Specific examples of titanium chelate compounds include titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetoacetate, titanium phosphate compounds, titanium octylene glycolate, and titanium ethylacetoacetate.

[0120] Specific examples of aluminum chelate compounds include ethyl acetoacetate aluminum diisopropylate, aluminum tris(acetylacetate), aluminum tris(ethylacetoacetate), aluminum monoacetylacetonate bis(ethylacetoacetate), and alkyl acetylacetate aluminum diisopropylate.

[0121] Specific examples of the organic amine compound include triethylamine, triethylenediamine, trimethylamine, tetramethylenediamine, N-methylmorpholine, N-ethylmorpholine, N,N'-diethyl-2-methylpiperazine, laurylamine, and dimethyllaurylamine.

[0122] The amount of the curing catalyst (B) used can be appropriately adjusted depending on the curing temperature and curing time, but is preferably about 0.01 to 20 parts by weight, more preferably about 0.1 to 10 parts by weight, per 100 parts by weight of the organic-inorganic composite resin (A).

[0123] [Amino group-containing silane condensate (C)] The coating composition according to the present disclosure contains an amino group-containing silane condensate (C). By blending the amino group-containing silane condensate (C), lifting can be suppressed when the coating composition containing the organic-inorganic composite resin (A) is applied in multiple coats.

[0124] The amino group-containing silane condensate (C) is a silane oligomer that is a hydrolysis condensation product of an alkoxysilane, and refers to a silane oligomer having an amino group. The condensate can be obtained by hydrolyzing the alkoxy group of an alkoxysilane to form a silanol group (Si-OH), and then condensing these silanol groups together. All or a part of the alkoxysilane as the raw material may have an amino group.

[0125] Examples of the amino group-containing silane condensate (C) include a condensate of an amino group-containing alkoxysilane, or a condensate of an amino group-containing alkoxysilane and an alkylalkoxysilane, with the latter condensate being preferred.

[0126] Alkylalkoxysilane refers to a compound in which at least one alkyl group and at least two alkoxy groups are directly bonded to a silicon atom.Alkylalkoxysilane is preferably a monoalkyltrialkoxysilane in which one alkyl group and three alkoxy groups are directly bonded to a silicon atom.Specific examples of alkylalkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and hexyltrimethoxysilane, and ethyltriethoxysilane is preferred.

[0127] The amino group-containing alkoxysilane refers to a compound having at least one amino group-containing functional group and at least two alkoxy groups directly bonded to a silicon atom in one molecule. The amino group-containing functional group is preferably directly bonded to a silicon atom. The amino group-containing alkoxysilane is preferably a compound having one amino group-containing functional group and three alkoxy groups directly bonded to a silicon atom in one molecule.

[0128] From the viewpoint of suppressing lifting, the amino group-containing functional group is preferably an aminopropyl functional group. Examples of the aminopropyl functional group include -(CH2)3-NH2 and -(CH2)3-NHR 2 , -(CH2)3-NH(CH2)2-NH2 (3-[N-(2-aminoethyl)amino]propyl group), and -(CH2)3-NH(CH2)2-NH(CH2)2-NH2 (3-[[2-(2-aminoethylamino)ethyl]amino]propyl group). Among these, -(CH2)3-NH(CH2)2-NH2 is preferred.

[0129] The aforementioned -(CH2)3-NHR 2 In R 2represents an alkyl group having 1 to 18 carbon atoms, a monovalent saturated alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0130] Examples of the alkyl group having 1 to 18 carbon atoms include linear alkyl groups and branched alkyl groups. Examples of the linear alkyl group include methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, and n-octadecyl groups. Examples of the linear alkyl group include methyl, ethyl, and n-butyl groups. Examples of the branched alkyl group include isopropyl, isobutyl, sec-butyl, and tert-butyl groups.

[0131] Examples of the monovalent saturated alicyclic hydrocarbon group having 3 to 18 carbon atoms include a cyclopentyl group, a cycloheptyl group, a cyclohexyl group, a 4-methylcyclohexyl group, and a cyclooctyl group, with a cyclohexyl group being preferred.

[0132] An example of the aryl group having 6 to 12 carbon atoms is a phenyl group.

[0133] Specific examples of amino group-containing alkoxysilanes include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methylaminopropyltrimethoxysilane, N-methylaminopropyltriethoxysilane, Nn-butylaminopropyltrimethoxysilane, Nn-butylaminopropyltriethoxysilane, N-cyclohexylaminopropyltrimethoxysilane, N-cyclohexylaminopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, and N-phenylaminopropyltriethoxysilane. Propyltriethoxysilane, 3-[N-(2-aminoethyl)amino]propyltrimethoxysilane, 3-[N-(2-aminoethyl)amino]propyltriethoxysilane, [3-[2-(2-aminoethylamino)ethylamino]propyl]trimethoxysilane, [3-[2-(2-aminoethylamino)ethylamino]propyl]triethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-methyl-aminopropylmethyldimethoxysilane, N-methyl-aminopropyl N-butyl-aminopropyl methyldimethoxysilane, N-butyl-aminopropyl methyldiethoxysilane, N-cyclohexylaminopropyl methyldimethoxysilane, N-cyclohexylaminopropyl methyldiethoxysilane, N-phenyl-aminopropyl methyldimethoxysilane, N-phenyl-aminopropyl methyldiethoxysilane, 3-[N-(2-aminoethyl)amino]propyl methyldimethoxysilane, 3-[N-(2-aminoethyl)amino]propyl methyldiethoxysilane silane, [3-[2-(2-aminoethylamino)ethylamino]propyl]methyldimethoxysilane, [3-[2-(2-aminoethylamino)ethylamino]propyl]methyldiethoxysilane, N,N'-bis-[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(triethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(methyldimethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(trimethoxysilyl)propyl]hexamethylenediamine, and N,N'-bis-[3-(triethoxysilyl)propyl]hexamethylenediamine and the like are included. Among these, 3-[N-(2-aminoethyl)amino]propyltrimethoxysilane and 3-[N-(2-aminoethyl)amino]propyltriethoxysilane are preferred, and 3-[N-(2-aminoethyl)amino]propyltriethoxysilane is more preferred.

[0134] The amino group-containing silane condensate (C) is preferably a hydrolysis condensate of a monoalkyltrialkoxysilane and an amino group-containing alkoxysilane in which one aminopropyl functional group and three alkoxy groups are directly bonded to a silicon atom, and more preferably a hydrolysis condensate of a monoalkyltrialkoxysilane and a 3-[N-(2-aminoethyl)amino]propyltrialkoxysilane. The monoalkyltrialkoxysilane is preferably a monoalkyltriethoxysilane, and particularly preferably an ethyltriethoxysilane. The 3-[N-(2-aminoethyl)amino]propyltrialkoxysilane is preferably a 3-[N-(2-aminoethyl)amino]propyltriethoxysilane. The amino group-containing silane condensate (C) is particularly preferably a hydrolysis condensate of an ethyltriethoxysilane and a 3-[N-(2-aminoethyl)amino]propyltriethoxysilane.

[0135] The amino group-containing silane condensate (C) preferably has an aminopropyl functional group. The aminopropyl functional group of the amino group-containing silane condensate (C) is preferably -(CH2)3-NH2, -(CH2)3-NHR 2 , -(CH2)3-NH(CH2)2-NH2 (3-[N-(2-aminoethyl)amino]propyl group), and -(CH2)3-NH(CH2)2-NH(CH2)2-NH2 (3-[[2-(2-aminoethylamino)ethyl]amino]propyl group). Among these, -(CH2)3-NH(CH2)2-NH2 is particularly preferred. Note that R 2 is the same as R described in the amino group-containing alkoxysilane. 2 Since it is the same as the above, the explanation will be omitted.

[0136] As the amino group-containing silane condensate (C), commercially available products can be used, such as those available from Evonik Japan under the product names "Dynasylan SIVO 210", "Dynasylan SIVO 214", "Dynasylan SIVO 260", "Dynasylan SIVO 280" and "Dynasylan 1146".

[0137] The amount of the amino group-containing silane condensate (C) to be blended can be appropriately set, but since it has an excellent effect in suppressing lifting, it is preferably 2 parts by weight or more per 100 parts by weight of the organic-inorganic composite resin (A). More preferably, it is 3 parts by weight or more, and even more preferably, it is 4 parts by weight or more. The upper limit is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, even more preferably 8 parts by weight or less, and particularly preferably 6 parts by weight or less.

[0138] [Organic solvent (D)] The coating composition according to the present disclosure includes an organic solvent (D). The organic solvent (D) is not particularly limited, and examples thereof include ketones such as methyl ethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbons such as butane, pentane, cyclopentane, hexane, cyclohexane, heptane, octane, nonane, decane, and dodecane; aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as dimethyl ether, diethyl ether, and diisopropyl ether; and halogenated hydrocarbons such as methylene chloride, methyl chloroform, carbon tetrachloride, dichlorodifluoromethane, and perchloroethylene.

[0139] Among these, from the viewpoint of safety during coating and of suppressing corrosion of the substrate, it is preferred that the organic solvent (D) contains a weak solvent.

[0140] Weak solvents include those classified as Class 3 organic solvents under the Industrial Safety and Health Act, and solvents equivalent to Class 3 organic solvents. Specific examples include gasoline, kerosene, coal tar naphtha (including solvent naphtha), petroleum ether, petroleum naphtha, petroleum benzine, turpentine oil, and mineral spirits (including mineral thinner, petroleum spirits, white spirits, and mineral turpentine).

[0141] More specifically, examples of such solvents include Solvesso 100 (manufactured by Exxon Mobil), which is a third-class organic solvent containing 100% aromatic hydrocarbons, and non-aqueous solvents with an aromatic content of 50% or less, such as Isopar E, Isopar G, and A Solvent (all manufactured by Nippon Oil Corporation), LAWS (manufactured by Shell Chemical), Pegasol AN45, Exxon Naphtha No. 6, Exxon Naphtha No. 5, Exxon Naphtha No. 3, Exxol D40, and Exxol D80 (all manufactured by Exxon Mobil), IP Solvent 1620, and IP Solvent 2028 (all manufactured by Idemitsu Petrochemical).

[0142] In the coating composition according to the present disclosure, the amount of the organic solvent (D) is not particularly limited and can be appropriately determined by a person skilled in the art. For example, it may be about 10 to 500 parts by weight per 100 parts by weight of the organic-inorganic composite resin (A).

[0143] (Other ingredients) The coating composition according to the present disclosure may contain components other than the organic-inorganic composite resin (A), the curing catalyst (B), the amino group-containing silane condensate (C), and the organic solvent (D). Examples of such components include known paint additives such as pigments, plasticizers, dispersants, anti-settling agents, anti-skinning agents, drying agents, anti-sagging agents, matting agents, antistatic agents, conductive agents, and flame retardants.

[0144] From the viewpoint of stability, the coating composition according to the present disclosure is preferably a two-liquid mixed type composed of an A agent containing an organic-inorganic composite resin (A) and an B agent containing a curing catalyst (B) and an amino group-containing silane condensate (C). The organic solvent (D) is preferably blended in at least one of the A agent and the B agent, and is particularly preferably blended in both the A agent and the B agent.

[0145] (Application method) The coating composition according to the present disclosure can be applied to the surface of a substrate and cured to form a coating film. The conditions for application and curing are not particularly limited, but when curing, the composition may be left at room temperature for a certain period of time, or may be heated using a heat source to promote evaporation of the solvent and the curing reaction.

[0146] The coating composition according to the present disclosure can suppress the occurrence of lifting when recoating, and therefore can be suitably recoated. Recoating refers to coating the coating composition according to the present disclosure once, and then coating the coating surface again after a predetermined time (for example, about 6 hours to 3 days) has elapsed.

[0147] (Laminate) Another aspect of the present invention relates to a laminate having a coating film formed on a surface of a substrate using the coating composition. The coating film may be composed of at least two layers.

[0148] The thickness of the coating film to be formed is not particularly limited, but may be, for example, 5 μm or more and 100 μm or less in thickness after drying.

[0149] The substrate to which the coating composition according to the present disclosure can be applied is not particularly limited, and examples of substrates that can be used include organic substrates such as polycarbonate (PC), acrylic, ABS, ABS / PC, and polyethylene terephthalate (PET), and inorganic substrates such as glass, aluminum, SUS, copper, iron, and stone.

[0150] The following items enumerate preferred aspects of the present disclosure, but the present invention is not limited to the following items. [Item 1] (A) an organic-inorganic composite resin having a hydrolyzable silyl group and containing a vinyl polymer component and a polysiloxane component; Curing catalyst (B), An amino group-containing silane condensate (C), and A coating composition comprising an organic solvent (D). [Item 2] 2. The coating composition according to item 1, wherein the amino group-containing silane condensate (C) is a condensate of an amino group-containing alkoxysilane and an alkylalkoxysilane. [Item 3] 3. The coating composition according to item 1 or 2, wherein the content of the amino group-containing silane condensate (C) is 2 parts by weight or more based on 100 parts by weight of the organic-inorganic composite resin (A). [Item 4] 4. The coating composition according to any one of items 1 to 3, wherein the vinyl polymer component is a (meth)acrylic polymer component. [Item 5] 5. The coating composition according to any one of items 1 to 4, wherein the polysiloxane component comprises a hydrolysis condensate of a silane compound (a) having a radical reactive group and a hydrolyzable silyl group, and a silane compound (b) having a hydrocarbon group and a hydrolyzable silyl group. [Item 6] 6. The coating composition according to item 5, wherein the radical reactive group is a group that exhibits lower radical reactivity than a methacryloyl group. [Item 7] The polysiloxane component has the formula (2): (R 3 O) 4-b -Si-R 4 b (2) (In the formula, R 3 and R 4and a is the same or different, and represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; and b is 0 or 1. [Item 8] 8. The coating composition according to any of items 1 to 7, wherein the organic solvent (D) comprises a weak solvent. [Item 9] 9. The coating composition according to any one of items 1 to 8, which is a two-liquid mixed type composed of an A component containing an organic-inorganic composite resin (A) and a B component containing a curing catalyst (B) and a silane condensate (C). [Item 10] A laminate comprising a substrate and at least two coating layers formed from the coating composition according to any one of items 1 to 9. EXAMPLES

[0151] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0152] 〔material〕 The following materials were used in the examples and comparative examples. <Coating layer> (Silane Monomer) Methyltrimethoxysilane (abbreviated as "M-TMS"): "Z-6366" manufactured by Dow Toray Co., Ltd. Phenyltrimethoxysilane (abbreviated as "Ph-TMS"): "Z-6124" manufactured by Dow Toray Co., Ltd. Vinyltrimethoxysilane (abbreviated as "V-TMS"): "A-171" manufactured by Momentive Performance Materials Japan, LLC

[0153] (Reaction catalyst) Dibutyl phosphate (abbreviated as "DBP"): manufactured by Johoku Chemical Industry Co., Ltd.

[0154] (solvent) S100 (Mineral oil, cumene, xylene, trimethylbenzene mixture): Sanwa Chemical Co., Ltd. LAWS (Mineral spirits, xylene, trimethylbenzene, nonane mixture): Shell Chemicals Japan Co., Ltd. Isopropyl alcohol (abbreviated as "IPA"): Fujifilm Wako Pure Chemical Corporation

[0155] (Acrylic Monomer) Cyclohexyl methacrylate (abbreviated as "CHMA"): Manufactured by Nippon Shokubai Co., Ltd. Butyl acrylate (abbreviated as "BA"): manufactured by Nippon Shokubai Co., Ltd. 3-Methacryloyloxypropyltriethoxysilane (abbreviated as "TESMA"): "Y-9936" manufactured by Momentive Performance Materials Japan, LLC Isobutyl methacrylate (abbreviated as "IBMA"): Manufactured by Mitsubishi Chemical Corporation S-lauryl methacrylate (abbreviated as "SLMA"): manufactured by Mitsubishi Gas Chemical Company, Inc. 2-Ethylhexyl acrylate (abbreviated as "2EHA"): Manufactured by Nippon Shokubai Co., Ltd. Methyl methacrylate (abbreviated as "MMA"): Manufactured by Mitsubishi Chemical Corporation N,N-Dimethylacrylamide (abbreviated as "DMAA"): Fujifilm Wako Pure Chemical Industries, Ltd. 3-Methacryloyloxypropyltrimethoxysilane (abbreviated as "TSMA"): "A-174" manufactured by Momentive Performance Materials Japan, LLC

[0156] (Reaction catalyst) 2,2'-Azobis(2-methylbutyronitrile) (abbreviated as "V-59"): Fujifilm Wako Pure Chemical Industries, Ltd.

[0157] (others) Kaneka XMAP SA120S (liquid acrylic resin with hydrolyzable silyl groups at both ends of the polymer main chain) (abbreviated as "SA120S"): manufactured by Kaneka Corporation Methyl orthoacetate: Fujifilm Wako Pure Chemical Industries, Ltd. Ethyl silicate 48 (hydrolysis condensation product of tetraethoxysilane): manufactured by Colcoat Co., Ltd. Dynasylan 1146 (condensation product of amino group-containing alkoxysilane and alkylalkoxysilane): manufactured by Evonik Japan Co., Ltd. Silane coupling agent Z: "A-1122" manufactured by Momentive Performance Materials Japan, LLC and "A-187" manufactured by Momentive Performance Materials Japan, LLC in a molar ratio of 1:2.2, where the amino group of "A-1122" is added to the epoxy group of "A-187." Silane coupling agent Y: "jER828" manufactured by Mitsubishi Chemical Corporation and "KBM-903" manufactured by Shin-Etsu Chemical Co., Ltd. are used in a molar ratio of 1:2, with the amino group of "KBM-903" being added to the epoxy group of "jER828" by reaction. 3-Aminopropyltrimethoxysilane: "KBM-903" manufactured by Shin-Etsu Chemical Co., Ltd. N-(2-aminoethyl)-3-aminopropylmethoxysilane: "A-1120" manufactured by Momentive Performance Materials Japan, LLC Bis(3-trimethoxysilylpropyl)amine: "A-1170" manufactured by Momentive Performance Materials Japan, LLC γ-Mercapto-propyltrimethoxysilane: "A-189" manufactured by Momentive Performance Materials Japan, LLC Dibutyltin dibutylmalate: "Neostan U-20" manufactured by Nitto Kasei Co., Ltd.

[0158] (Weight average molecular weight) The weight average molecular weight of the organic-inorganic composite resin was measured by GPC. GPC was performed using HLC-8320GPC manufactured by Tosoh Corporation as a liquid delivery system, TSK-GEL H type manufactured by Tosoh Corporation as a column, and THF as a solvent, and the weight average molecular weight was calculated in terms of polystyrene.

[0159] [Synthesis Example 1] (Preparation of polysiloxane component) A reactor equipped with a stirrer, a thermometer, and a reflux condenser was charged with 43.3 parts by weight of M-TMS, 37.2 parts by weight of Ph-TMS, 5.3 parts by weight of V-TMS, 0.0025 parts by weight of DBP as a reaction catalyst, and 11.1 parts by weight of water, and the mixture was reacted with reflux stirring at a jacket temperature of 90°C for 3 hours, after which the generated methanol was distilled off to obtain a polysiloxane component.

[0160] (Preparation of organic-inorganic composite resin (polymerization of vinyl polymer component)) A reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel was charged with 1.5 parts by weight of S100, 3.5 parts by weight of LAWS and the polysiloxane component, and the temperature was raised to 110 ° C. while introducing nitrogen gas, and then a mixed solution of 35.0 parts by weight of CHMA, 14.0 parts by weight of BA, 1.0 parts by weight of TESMA, 1.4 parts by weight of S100, 3.3 parts by weight of LAWS and 0.1 parts by weight of V-59, a polymerization initiator, was dropped at a constant speed from the dropping funnel over 2 hours. After that, the mixture was stirred at 110 ° C. for 2 hours, and then 21.1 parts by weight of S100, 49.3 parts by weight of LAWS and 8.6 parts by weight of SA120S were added to obtain an organic-inorganic composite resin (A-1) having a solid content concentration of 50% and a weight average molecular weight of 69,000.

[0161] [Synthesis Example 2] A reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube, and a dropping funnel was charged with 12.3 parts by weight of S100 and 28.7 parts by weight of LAWS, and the temperature was raised to 110°C while introducing nitrogen gas. After that, a mixed solution of 20.0 parts by weight of IBMA, 15.0 parts by weight of SLMA, 19.1 parts by weight of 2EHA, 37.0 parts by weight of MMA, 1.0 part by weight of DMAA, 7.9 parts by weight of TSMA, 4.5 parts by weight of S100, 10.5 parts by weight of LAWS, and 0.6 parts by weight of V-59 as a polymerization initiator was dropped at a constant rate from the dropping funnel over 5 hours. After the dropping was completed, a mixed solution of 3.0 parts by weight of S100, 7.0 parts by weight of LAWS, and 0.1 parts by weight of V-59, a polymerization initiator, was dropped at a constant rate from the dropping funnel over 1 hour, and then the mixture was stirred at 110°C for 2 hours and cooled, and 3.0 parts by weight of methyl orthoacetate and 15.0 parts by weight of ethyl silicate 48 were added to obtain an organic-inorganic composite resin (A-2) with a solid content of 55% and a weight average molecular weight of 50,000. Note that ethyl silicate 48 is a component corresponding to the hydrolysis condensation product of the silicon compound represented by formula (2).

[0162] (Preparation of main agent (T-1)) 21.1 parts by weight of the organic inorganic composite resin (A-1) obtained in Synthesis Example 1, 23.5 parts by weight of JR-805 (titanium oxide, manufactured by Teika Co., Ltd.), 0.4 parts by weight of BYK-142 (dispersing agent, manufactured by BYK), 0.5 parts by weight of S100, and 1.2 parts by weight of LAWS were added, and the mixture was mixed and stirred for 2 hours using glass beads in a paint shaker. Then, 49.3 parts by weight of the organic inorganic composite resin (A-1), 1.8 parts by weight of Disparlon 6820-10M (thixotropic agent, manufactured by Kusumoto Chemical Co., Ltd.), 0.7 parts by weight of S100, and 1.5 parts by weight of LAWS were added, and the mixture was further mixed and stirred for 30 minutes using a paint shaker to obtain a main agent (T-1).

[0163] (Preparation of main agent (T-2)) 21.1 parts by weight of the organic inorganic composite resin (A-2) obtained in Synthesis Example 2, 23.5 parts by weight of JR-805 (titanium oxide, manufactured by Teika Co., Ltd.), 0.4 parts by weight of BYK-142 (dispersing agent, manufactured by BYK), 0.5 parts by weight of S100, and 1.2 parts by weight of LAWS were added, and the mixture was mixed and stirred for 2 hours using glass beads in a paint shaker, and then 49.3 parts by weight of the organic inorganic composite resin (A-2), 1.8 parts by weight of Disparlon 6820-10M (thixotropic agent, manufactured by Kusumoto Chemical Co., Ltd.), 0.7 parts by weight of S100, and 1.5 parts by weight of LAWS were added, and the mixture was further mixed and stirred for 30 minutes using a paint shaker to obtain a main agent (T-2).

[0164] Example 1 41.5 parts by weight of LAWS, 31.5 parts by weight of IPA, 10 parts by weight of Dynasylan 1146, 5 parts by weight of A-189, and 12 parts by weight of Neostan U-20 were added and stirred at room temperature for 30 minutes to obtain a curing agent (K-1). 10 parts by weight of the base agent (T-1) and 0.7 parts by weight of the hardener (K-1) were mixed with a spatula, and the resulting composition was sprayed onto one side of the tinplate with an air spray at 0.1 kg / m 2 After aging at 23°C for the time shown in Table 1, the second layer of the same composition was painted 50 times with a brush, and the occurrence of lifting (shrinkage) on the coating surface was visually observed. A mark of ◯ was given for no lifting, a mark of △ for slight lifting, and a mark of × for lifting over the entire area where the second layer was painted.

[0165] [Examples 2 to 5, Comparative Examples 1 to 8] As in Example 1, each hardener was prepared by mixing each compounding agent in the weight ratio shown in Table 1, and the lifting test was carried out for the composition obtained by mixing the main agent (T-1) or (T-2) and each hardener in the same weight ratio as in Example 1. The results are shown in Table 1.

[0166] [Table 1]

[0167] From Table 1, it is clear that in Examples 1 to 5 in which component (C) was blended, lifting did not occur even when a second layer was applied after a predetermined time had elapsed, and lifting resistance was good. On the other hand, in Comparative Example 1, which does not contain component (C), and Comparative Examples 2 to 8, which contain a silane coupling agent that does not fall under component (C), lifting may occur when the second layer is applied after 6 hours, 8 hours, 24 hours, or 32 hours, indicating that the lifting resistance is insufficient.

Claims

1. an organic-inorganic composite resin (A) having a hydrolyzable silyl group and containing a vinyl polymer component and a polysiloxane component; curing catalyst (B), An amino group-containing silane condensate (C), and A coating composition comprising an organic solvent (D).

2. 2. The coating composition according to claim 1, wherein the amino group-containing silane condensate (C) is a condensate of an amino group-containing alkoxysilane and an alkylalkoxysilane.

3. 2. The coating composition according to claim 1, wherein the content of the amino group-containing silane condensate (C) is 2 parts by weight or more based on 100 parts by weight of the organic-inorganic composite resin (A).

4. The coating composition according to claim 1 , wherein the vinyl polymer component is a (meth)acrylic polymer component.

5. 2. The coating composition according to claim 1, wherein the polysiloxane component comprises a hydrolysis condensate of a silane compound (a) having a radical reactive group and a hydrolyzable silyl group, and a silane compound (b) having a hydrocarbon group and a hydrolyzable silyl group.

6. 6. The coating composition according to claim 5, wherein the radical reactive group is a group that exhibits lower radical reactivity than a methacryloyl group.

7. The polysiloxane component has the formula (2): (R) ３ O) ４－ｂ -Si-R ４ ｂ (2) (In the formula, R ３ and R ４ and each of the groups represented by the formula (I) is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; and b is 0 or 1.

8. The coating composition of claim 1 , wherein the organic solvent (D) comprises a weak solvent.

9. 2. The coating composition according to claim 1, which is a two-liquid mixed type composed of an A component containing an organic-inorganic composite resin (A) and an B component containing a curing catalyst (B) and a silane condensate (C).

10. A laminate comprising a substrate and at least two coating layers formed from the coating composition according to any one of claims 1 to 9.

Images