Coating composition for thermoforming, laminate, and method for manufacturing the same

Abstract

To provide a coating composition for thermoforming which is excellent in storage stability, scratch resistance, formability, and weather resistance in a protective layer of a film for thermoforming or the like, a laminate, and a method for manufacturing the same.SOLUTION: A coating composition for thermoforming contains a resin composition containing a resin (A) containing an alkoxysilyl group and a hydroxyl group, and alkoxysilane or its condensate (B), or a specific compound, and a resin (E) containing no alkoxysilyl group and a hydroxyl group, wherein each weight average molecular weight of the resin (A) and the resin (E) is 10,000 to 200,000, and a weight average molecular weight (MwE) of the resin (E) and a weight average molecular weight (MwA) of the resin (A) satisfy a relation of (MwE) / (MwA)>1.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermoforming coating composition, a laminate, and a method for producing the same, which are excellent in storage stability, scratch resistance, formability, and weather resistance when used as protective layers for thermoforming films for use in automobile parts and building materials. [Background technology]

[0002] Conventionally, coating agents are applied to the outermost layer of various materials such as plastic films, laminated sheets, printed materials, and metal plates, and are used as a surface protective layer to protect the coating from various external factors.

[0003] To protect and decorate automobile bodies and parts, painting and drying processes have traditionally been repeated, but due to the energy costs involved, there is a need to replace conventional painting with decorative films. The surface protective layer of automotive decorative films must be weather-resistant enough to withstand outdoor use, and moldable and scratch-resistant for processing, but achieving all of these properties has been difficult.

[0004] To provide weather resistance while maintaining the processability of the film, organic materials, especially acrylic resin-based coatings, have traditionally been used as surface protection layers. However, while these coatings ensure formability, they are prone to oxidation due to ultraviolet rays and have low scratch resistance, making them unsuitable for use in automotive components.

[0005] It is generally known that coating films containing Si-O bonds, such as silica particles, are preferred because of their high bond energy, which reduces degradation due to UV rays, and their hardness and scratch resistance. For this reason, coating compositions that combine acrylic resin with alkoxysilane or its condensate and silica particles are known. However, due to reduced flexibility, they are unsuitable for applications requiring moldability, and storage stability is an issue due to the hydrolysis and condensation reaction of alkoxysilyl groups in the coating solution caused by moisture in the air.

[0006] For example, Patent Document 1 discloses a coating resin composition for thermoforming applications that contains a silane-containing oligomer, an alkoxysilyl group-containing resin, metal oxide particles, and a condensation catalyst. The composition controls the degree of hydrolysis and condensation to achieve both scratch resistance and moldability. However, the document only describes the presence or absence of cracks when molded into a three-dimensional object with the desired final shape, and does not specifically state the elongation rate. Furthermore, there is no mention of storage stability.

[0007] Furthermore, Patent Document 2 discloses a coating composition containing a resin containing an alkoxysilyl group, a hydroxyl-containing resin that does not contain an alkoxysilyl group, silica particles, and a catalyst, and describes that the coating composition has good storage stability, but does not describe its moldability. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Patent No. 5671549 [Patent Document 2] Patent No. 7467794 Summary of the Invention [Problem to be solved by the invention]

[0009] The problem to be solved by the present invention is to provide a thermoforming coating composition, a laminate, and a method for producing the same, which are excellent in storage stability, scratch resistance, formability, and weather resistance when used in protective layers for thermoforming films, etc. [Means for solving the problem]

[0010] As a result of extensive research, the present inventors have discovered a polymerizable composition comprising a resin (A) containing an alkoxysilyl group and a hydroxyl group and a resin (E) containing no alkoxysilyl group but containing a hydroxyl group, and the weight average molecular weight (MW The weight average molecular weight (M W E) satisfies the relationship of the following formula (1), the present inventors have found that both storage stability and moldability can be achieved, and high levels of weather resistance and scratch resistance can also be achieved, and have arrived at the present invention. Equation (1) (M W E) / (M W A)>1

[0011] That is, the present invention provides a thermoforming coating composition containing at least one selected from the group consisting of a resin composition of the following (1), a compound (D-1) of the following (2), a composite particle (D-2) of the following (3), and a composite particle composition of the following (4), and a resin (E) that does not contain an alkoxysilyl group but contains a hydroxyl group, The thermoforming coating composition is characterized in that the weight-average molecular weights of resin (A) and resin (E) are each 10,000 to 200,000, and the weight-average molecular weight (MwE) of resin (E) and the weight-average molecular weight (MwA) of resin (A) satisfy the relationship (MwE) / (MwA)>1. (1) A resin composition containing (A) a resin containing an alkoxysilyl group and a hydroxyl group, and (B) an alkoxysilane or a condensate thereof. (2) Compound (D-1) obtained by partial hydrolysis and condensation reaction of resin (A) containing alkoxysilyl groups and hydroxyl groups with alkoxysilane or its condensate (B). (3) Composite particles (D-2) obtained by partial hydrolysis and condensation reaction of a resin (A) containing an alkoxysilyl group and a hydroxyl group, an alkoxysilane or its condensate (B), and silica particles (C). (4) A composite particle composition containing composite particles (D-3) obtained by a partial hydrolysis condensation reaction of a resin (A) containing an alkoxysilyl group and a hydroxyl group with silica particles (C), and an alkoxysilane or a condensate thereof (B).

[0012] The present invention also relates to the above-mentioned coating composition for thermoforming, which further contains silica particles (C).

[0013] The present invention also relates to the above-mentioned thermoforming coating composition, which further comprises a curing agent (F).

[0014] The present invention also relates to the above-mentioned coating composition for thermoforming, further comprising at least one member selected from the group consisting of an ultraviolet absorber (H) and a hindered amine light stabilizer (I).

[0015] The present invention also relates to the above-mentioned thermoforming coating composition, wherein the resin (A) containing an alkoxysilyl group and a hydroxyl group, and the resin (E) containing no alkoxysilyl group but containing a hydroxyl group, are acrylic resins.

[0016] The present invention also relates to the above-mentioned coating composition for thermoforming, wherein the weight-average molecular weight of the resin (A) is 10,000 to 100,000, and the weight-average molecular weight of the resin (E) is 30,000 to 200,000.

[0017] The present invention also relates to the above-mentioned coating composition for thermoforming, which further contains a condensation catalyst (J).

[0018] The present invention also relates to a laminate having at least a substrate and a coating layer formed using the coating composition.

[0019] The present invention also relates to a method for producing a laminate having at least a substrate and a coating layer formed using the coating composition, the method comprising the following step (1) and at least one step selected from the group consisting of the following step (2) and step (3): Step (1) applying the coating composition onto a substrate Step (2): Moisture-curing the applied coating composition in an environment with a humidity of 50% to 100%. Step (3) A step of heat-curing the applied coating composition in an environment at a temperature of 40°C to 100°C.

[0020] The present invention also relates to a method for producing a thermoforming coating composition containing compound (D-1) obtained in the following step (4), resin (E) that contains hydroxyl groups but does not contain alkoxysilyl groups, and solvent (G), wherein the weight-average molecular weights of resin (A) and resin (E) are each 10,000 to 200,000, and the weight-average molecular weight (MwE) of resin (E) and the weight-average molecular weight (MwA) of resin (A) satisfy the relationship (MwE) / (MwA)>1. Step (4) A step of subjecting a mixture of the resin (A) containing an alkoxysilyl group and a hydroxyl group and the alkoxysilane or its condensate (B) to a partial hydrolysis condensation reaction in a solvent (G) to obtain a compound (D-1).

[0021] The present invention also provides a method for producing a thermoforming coating composition comprising composite particles (D-2) obtained by a production method including the following step (5), a resin (E) that does not contain alkoxysilyl groups but does contain hydroxyl groups, and a solvent (G), wherein the weight-average molecular weights of the resins (A) and (E) are each 10,000 to 200,000, and the weight-average molecular weight (MwE) of the resin (E) and the weight-average molecular weight (MwA) of the resin (A) satisfy the relationship (MwE) / (MwA)>1: Step (5): A step of subjecting a mixture of an alkoxysilyl group- and hydroxyl group-containing resin (A), an alkoxysilane or its condensate (B), and silica particles (C) to a partial hydrolysis and condensation reaction in a solvent (G) to obtain composite particles (D-2).

[0022] A method for producing a thermoforming coating composition comprising composite particles (D-3) obtained by a production method including the following step (6), an alkoxysilane or a condensate thereof (B), a resin (E) that does not contain an alkoxysilyl group but does contain a hydroxyl group, and a solvent (G), wherein the weight-average molecular weights of the resins (A) and (E) are each 10,000 to 200,000, and the weight-average molecular weight (MwE) of the resin (E) and the weight-average molecular weight (MwA) of the resin (A) satisfy the relationship (MwE) / (MwA)>1. Step (6): A step of subjecting a mixture of the resin (A) containing an alkoxysilyl group and a hydroxyl group and the silica particles (C) to a partial hydrolysis and condensation reaction in a solvent (G) to obtain composite particles (D-3). [Effects of the Invention]

[0023] The present invention can provide a thermoforming coating composition and laminate that, when used as a protective layer for a thermoforming film, are excellent in storage stability, scratch resistance, formability, and weather resistance, and a method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0024] Hereinafter, embodiments of the present invention will be described in detail. In this application, unless otherwise specified, the terms "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" refer to "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively.

[0025] The coating composition of the present invention is a thermoforming coating composition containing at least one selected from the group consisting of a resin composition of (1) below, a compound (D-1) of (2) below, a composite particle (D-2) of (3) below, and a composite particle composition of (4) below, and a resin (E) that does not contain an alkoxysilyl group but does contain a hydroxyl group, wherein the weight-average molecular weights of the resins (A) and (E) are each 10,000 to 200,000, and the weight-average molecular weight (MwE) of the resin (E) and the weight-average molecular weight (MwA) of the resin (A) satisfy the relationship (MwE) / (MwA)>1. (1) A resin composition containing (A) a resin containing an alkoxysilyl group and a hydroxyl group, and (B) an alkoxysilane or a condensate thereof. (2) Compound (D-1) obtained by partial hydrolysis and condensation reaction of resin (A) containing alkoxysilyl groups and hydroxyl groups with alkoxysilane or its condensate (B). (3) Composite particles (D-2) obtained by partial hydrolysis and condensation reaction of a resin (A) containing an alkoxysilyl group and a hydroxyl group, an alkoxysilane or its condensate (B), and silica particles (C). (4) A composite particle composition containing composite particles (D-3) obtained by a partial hydrolysis condensation reaction between a resin (A) containing an alkoxysilyl group and a hydroxyl group and silica particles (C), and an alkoxysilane or a condensate thereof (B).

[0026] <Resin (A) containing an alkoxysilyl group and a hydroxyl group> The resin (A) containing an alkoxysilyl group and a hydroxyl group is a resin having at least one alkoxysilyl group and at least one hydroxyl group in one molecule. As the resin skeleton of the resin (A) containing an alkoxysilyl group and a hydroxyl group, a wide range of known resins can be used, including, for example, the resin skeletons of vinyl resins, acrylic resins, polyester resins, polyurethane resins, polyether resins, polycarbonate resins, and epoxy resins.

[0027] Among these, vinyl resins and acrylic resins are preferred as the resin skeleton of the resin (A) containing an alkoxysilyl group and a hydroxyl group from the viewpoint of weather resistance, and acrylic resins are more preferred.

[0028] <Acrylic resin containing alkoxysilyl groups and hydroxyl groups> The (meth)acrylic monomers constituting the acrylic resin containing an alkoxysilyl group and a hydroxyl group are characterized by including a (meth)acrylic monomer containing an alkoxysilyl group, a (meth)acrylic monomer containing a hydroxyl group, and other (meth)acrylic monomers.

[0029] [(Meth)acrylic monomers containing alkoxysilyl groups] The (meth)acrylic monomer containing an alkoxysilyl group may be any monomer containing one (meth)acryloyl group and one or more alkoxysilyl groups in one molecule. The (meth)acrylic monomer containing an alkoxysilyl group may be a synthesized product or a commercially available product. Methods for synthesizing a (meth)acrylic monomer containing an alkoxysilyl group include conventionally known methods, such as a urethane reaction between a compound having an isocyanate group and an alkoxysilyl group and a (meth)acrylic monomer compound having a hydroxyl group, and an epoxy ring-opening reaction between a compound having an epoxy group and an alkoxysilyl group and a (meth)acrylic monomer compound having a hydroxyl group or a carboxyl group. On the other hand, specific examples of (meth)acrylic monomers containing an alkoxysilyl group include γ-(meth)acryloylpropyltrimethoxysilane, γ-(meth)acryloylpropyltriethoxysilane, γ-(meth)acryloylpropylmethyldimethoxysilane, and γ-(meth)acryloylpropylmethyldiethoxysilane, and commercially available products thereof include KBM-503, KBE-503, KBM-502, and KBE-502 manufactured by Shin-Etsu Chemical Co., Ltd. The (meth)acrylic monomer containing an alkoxysilyl group is contained in the acrylic resin in an amount of preferably 0.5 to 50% by mass, more preferably 1 to 30% by mass.

[0030] By using a (meth)acrylic monomer containing an alkoxysilyl group, an acrylic resin containing an alkoxysilyl group is formed, and this can be reacted with an alkoxysilane or its condensate (B) or the alkoxysilyl group or silanol group in the silica particles (C) to form a uniform and hard coating film.

[0031] [Hydroxyl group-containing (meth)acrylic monomer] The hydroxyl group-containing (meth)acrylic monomer may be a monomer containing one (meth)acryloyl group and one or more hydroxyl groups in one molecule. Examples of the hydroxyl group-containing (meth)acrylic monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate (product name: 4HBA, Mitsubishi Chemical), α-hydroxymethylethyl (meth)acrylate, α-hydroxymethyl (meth)acrylate, caprolactone-modified hydroxy(meth)acrylate (product name: Placcel F series, manufactured by Daicel Chemical Industries, Ltd.), and 2,3-dihydroxypropyl (meth)acrylate. The hydroxyl group-containing (meth)acrylic monomer is contained in the acrylic resin in an amount of preferably 0.1 to 40% by mass, more preferably 0.5 to 20% by mass.

[0032] By using a hydroxyl group-containing (meth)acrylic monomer, an acrylic resin containing hydroxyl groups is formed, and after coating, the hydroxyl groups contained in the hydroxyl group-containing acrylic resin are reacted with a curing agent to form a hard coating film that adheres closely to the substrate.

[0033] [Other (meth)acrylic monomers] Other (meth)acrylic monomers that do not contain an alkoxysilyl group or a hydroxyl group include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl ( Examples of the acrylate include methyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-lauryl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, n-stearyl (meth)acrylate, isostearyl (meth)acrylate, isobornyl (meth)acrylate, 2-(acetoacetoxy)ethyl (meth)acrylate, phenoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, and cyclododecyl (meth)acrylate. Furthermore, carboxyl group-containing monomers such as (meth)acrylic acid, maleic acid, maleic anhydride, or their anhydrides, as well as non-acrylic vinyl monomers such as styrene, vinyl acetate, etc. Of these, it is preferable to use cyclohexyl (meth)acrylate from the viewpoint of weather resistance.

[0034] An organic solvent may be used during synthesis of the resin (A) containing alkoxysilyl groups and hydroxyl groups. Examples of organic solvents include alcohol-based solvents such as methanol, ethanol, and isopropyl alcohol; ester-based solvents such as ethyl acetate and propyl acetate; glycol ether-based solvents such as propylene glycol monomethyl ether; ketone-based solvents such as acetone and methyl ethyl ketone; aromatic solvents such as toluene and xylene; and mixtures thereof. When the resin (A) containing alkoxysilyl groups and hydroxyl groups and the resin (E) containing hydroxyl groups but not alkoxysilyl groups contain an organic solvent, the solids content is preferably 10% to 70% by mass, and more preferably 20% to 60% by mass.

[0035] The content ratio of the resin (A) containing alkoxysilyl groups and hydroxyl groups is not particularly limited, but in order to provide compatibility and exhibit weather resistance, it is preferably 1% by mass or more and 80% by mass or less, more preferably 2% by mass or more and 60% by mass or less, based on the total amount of solids in the coating composition. Note that when the compound (D-1) or composite particles (D-2), (D-3) are contained in the coating composition, the content of the resin (A) containing alkoxysilyl groups and hydroxyl groups is calculated by including the resin (A) containing alkoxysilyl groups and hydroxyl groups used in the reaction of the compound (D-1) or composite particles (D-2), (D-3).

[0036] <Method for synthesizing acrylic resin containing alkoxysilyl groups and hydroxyl groups> As a method for synthesizing an acrylic resin containing an alkoxysilyl group and a hydroxyl group, known methods such as anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, radical polymerization, and living radical polymerization in the presence of the organic solvent can be used.

[0037] In the case of radical polymerization, it is preferable to use a polymerization initiator. Examples of the polymerization initiator include azo compounds and organic peroxides. Examples of the azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Examples of organic peroxides include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150°C, more preferably 50 to 120°C, and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

[0038] As a method for incorporating alkoxysilyl groups into an acrylic resin containing an alkoxysilyl group and a hydroxyl group, in addition to the method of copolymerizing the above-mentioned (meth)acrylic monomer containing an alkoxysilyl group, the (meth)acrylic monomer containing a hydroxyl group, and further with other (meth)acrylic monomers, it is also possible to obtain by adding a compound containing an alkoxysilyl group to a resin obtained by copolymerizing a (meth)acrylic monomer containing a hydroxyl group with other (meth)acrylic monomers using a conventionally known method. For example, there is a method of subjecting a resin containing a hydroxyl group to a urethane reaction with a compound having an isocyanate group and an alkoxysilyl group, and a method of subjecting a resin having a hydroxyl group or a carboxyl group to an epoxy ring-opening reaction with a compound having an epoxy group and an alkoxysilyl group.

[0039] <Resin (E) containing no alkoxysilyl groups but containing hydroxyl groups> The resin (E) containing no alkoxysilyl groups but containing hydroxyl groups is a resin containing no alkoxysilyl groups but at least one hydroxyl group per molecule. As the resin skeleton of the resin (E) containing no alkoxysilyl groups but containing hydroxyl groups, a wide range of known resins can be used, including, for example, resin skeletons of vinyl resins, acrylic resins, polyester resins, polyurethane resins, polyether resins, polycarbonate resins, epoxy resins, etc.

[0040] Among these, vinyl resins and acrylic resins are preferred as the resin skeleton of the resin (E) that does not contain alkoxysilyl groups but does contain hydroxyl groups, from the viewpoint of weather resistance, and acrylic resins are more preferred.

[0041] <Acrylic resin containing hydroxyl groups but not alkoxysilyl groups> The (meth)acrylic monomer constituting the acrylic resin containing hydroxyl groups but not alkoxysilyl groups is characterized by including a (meth)acrylic monomer containing a hydroxyl group and other (meth)acrylic monomers. Examples are as described above. Except for not containing an alkoxysilyl group, the resin can be produced in the same manner as the acrylic resin containing alkoxysilyl groups and hydroxyl groups described above. The hydroxyl group-containing (meth)acrylic monomer is contained in the acrylic resin in an amount of preferably 0.5 to 50% by mass, more preferably 1 to 30% by mass.

[0042] The content of the resin (E) that does not contain alkoxysilyl groups but does contain hydroxyl groups is not particularly limited, but in order to exhibit moldability, it is preferably from 10% by mass to 90% by mass, and more preferably from 20% by mass to 90% by mass, based on the total amount of solids in the coating composition.

[0043] The weight-average molecular weights of the resin (A) containing alkoxysilyl groups and hydroxyl groups and the resin (E) containing no alkoxysilyl groups but hydroxyl groups are each 10,000 to 200,000, from the viewpoint of achieving both storage stability and moldability of the coating liquid. It is preferable that the weight-average molecular weight (MwE) of the resin (E) and the weight-average molecular weight (MwA) of the resin (A) satisfy the relationship (MwE) / (MwA) > 1, and more preferably (MwE) / (MwA) is 2 or greater and less than 20. The weight-average molecular weight of the resin (A) is preferably 10,000 to 100,000, and more preferably 10,000 to 70,000. The weight-average molecular weight of the resin (E) is preferably 30,000 to 200,000, and more preferably 70,000 to 200,000.

[0044] <Alkoxysilane or condensate thereof (B)> The alkoxysilane or its condensate (B) used in the present invention refers to an alkoxysilane compound itself, or an alkoxysilane compound partially hydrolyzed and condensed by a conventionally known method. The alkoxysilane or its condensate (B) may be a synthesized product or a commercially available product. Methods for synthesizing the alkoxysilane or its condensate (B) include conventionally known methods, such as a method in which an acid or a base and water are added dropwise as catalysts for the hydrolysis reaction.

[0045] Examples of alkoxysilane compounds include, but are not limited to, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane. As the alkoxysilane or its condensate (B) used in the present invention, these alkoxysilanes may be used alone or in combination of two or more. Of these, it is preferable to use alkoxysilanes containing a phenyl group from the viewpoint of compatibility with resins.

[0046] Specific examples of commercially available alkoxysilanes or condensates thereof (B) include KC-89S, KR500, KR515, X-40-9225, X-40-9246, X-40-9250, X-88-1004, X-88-1007, X-48-1500, X-48-1600, X-48-1800, KR401N, X-40-9227, KR510, KR213, KR9218, KR242A, KR251, KR112, KR211, KR212, KR255, KR271, KR282, KR300, KR311, and X-48 Examples of suitable alkoxysilanes include, but are not limited to, alkoxysilanes such as methyl silicate MS51 and methyl silicate MS56 (Mitsubishi Chemical Corporation), methyl silicate MS56, methyl silicate MS51, methyl silicate MS56 (Dow Corning Toray Co., Ltd.), methyl silicate MS56, methyl silicate MS50, methyl silicate MS51, and methyl silicate MS56 (Dow Corning Toray Co., Ltd.), and methyl silicate MS50 (Dow Corning Toray Co., Ltd.). The alkoxysilane or condensate (B) used in the present invention may be a single alkoxysilane or a mixture of two or more alkoxysilanes. Of these, from the viewpoint of compatibility with resins, it is preferable to use alkoxysilanes containing a phenyl group or condensates thereof, specifically KR401N, X-40-9227, KR510, KR213, KR9218, KR112, KR211, KR212, KR255, KR271, KR282, KR300, KR311, X-48-1030, X-40-2756, RSN-804 RESIN, RSN-805 RESIN, RSN-806 RESIN, RSN-840 RESIN, etc.

[0047] The content ratio of alkoxysilane or its condensate (B) is not particularly limited, but in order to exhibit weather resistance and scratch resistance, it is preferably 1 mass% or more and 50 mass% or less, more preferably 3 mass% or more and 30 mass% or less, based on the total amount of solid content of the coating composition. Note that, when compound (D-1) or composite particle (D-2) is contained in the coating composition, the content of alkoxysilane or its condensate (B) shall also include the alkoxysilane or its condensate (B) used during the reaction production of compound (D-1) or composite particle (D-2).

[0048] <Silica particles (C)> The coating composition of the present invention preferably contains silica particles (C). As the silica particles (C) used in the present invention, hydrophobic silica particles dispersible in an organic solvent are preferably used, and organosilica sol pre-dispersed in an organic solvent is more preferably used. Furthermore, from the viewpoint of obtaining a transparent coating film, the average particle size of the silica particles is preferably 1 nm to 100 nm.

[0049] Examples of hydrophobic silica particles include, but are not limited to, HSP-2S, HSP-3C, HSP-6A, HSP-7SHSP-10A (manufactured by Fuso Chemical Co., Ltd.), Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R805, Aerosil R812, and Aerosil RX200 (manufactured by Nippon Aerosil Co., Ltd.).

[0050] Examples of commercially available organosilica sols include, but are not limited to, MA-ST-S, MT-ST-L, IPA-ST, IPA-ST-UP, IPA-ST-L, IPA-ST-ZL, NPC-ST-30, PGM-ST, PGM-ST-ZL, PGM-ST-UP, DMAC-ST, DMAC-ST-ZL, MEK-ST-40, MEK-ST-UP, MEK-ST-L, MEK-ST-ZL, MIBK-ST, MIBK-ST-L, PMA-ST, EAC-ST, EAC-ST-ZL (manufactured by Nissan Chemical Industries, Ltd.), PL-1-IPA, PL-1-TOL, PL-2L-PGME, and PL-2L-MEK (manufactured by Fuso Chemical Co., Ltd.). These organosilica sols may be used alone or in combination.

[0051] The content ratio of silica particles (C) is not particularly limited, but in order to exhibit weather resistance and scratch resistance, it is preferably 0.5 mass% or more and 50 mass% or less, more preferably 1 mass% or more and 40 mass% or less, based on the total amount of solid content of the coating composition. Note that, when composite particles (D-2) and (D-3) are contained in the coating composition, the content of silica particles (C) is calculated by including the silica particles (C) used in the reaction production of composite particles (D-2) and (D-3).

[0052] <Hardening agent (F)> The coating composition of the present invention preferably contains a curing agent (F). The curing agent (F) that can be used in the present invention is not particularly limited as long as it undergoes a crosslinking reaction with the crosslinkable functional groups in the resin (A) containing alkoxysilyl groups and hydroxyl groups and the resin (E) containing no alkoxysilyl groups but containing hydroxyl groups. However, isocyanate curing agents are preferred because of their excellent adhesion to substrates. While there are no particular restrictions on the structure, at least one isocyanate compound selected from isocyanurate, adduct, and biuret compounds is preferred. These isocyanate compounds can be used alone or in combination. An isocyanurate-based isocyanate compound refers to a form in which a diisocyanate having two or more isocyanate groups in the molecule is trimerized to form an isocyanurate ring structure, a biuret-based isocyanate compound refers to an isocyanate compound having a biuret structure, and an adduct-based isocyanate compound refers to an isocyanate compound formed by reacting a trifunctional alcohol compound such as trimethylolpropane with a diisocyanate to form an adduct. These isocyanate compounds can be synthesized from aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, etc. listed below.

[0053] Examples of aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.

[0054] Examples of the aliphatic diisocyanate include methylene diisocyanate, ethylene diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.

[0055] Examples of alicyclic diisocyanates include cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and dimer diisocyanate in which the carboxyl group of a dimer acid is converted into an isocyanate group.

[0056] Among these, from the viewpoint of weather resistance, isocyanate compounds derived from aliphatic diisocyanates are preferred. Things are preferred.

[0057] The content ratio of the curing agent (F) is not particularly limited, but in order to achieve both moldability and scratch resistance, it is preferably from 0.5% by mass to 40% by mass, and more preferably from 1% by mass to 30% by mass, based on the total amount of solids in the coating composition.

[0058] <Solvent (G)> The coating composition of the present invention preferably contains a solvent (G). The solvent (G) that can be used in the present invention is not particularly limited as long as it can dissolve the resin (A) containing an alkoxysilyl group and a hydroxyl group, the resin (E) containing no alkoxysilyl group but containing a hydroxyl group, and the alkoxysilane or its condensate (B), and can disperse the silica particles (C).

[0059] Examples of such solvents include ketone-based organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester-based organic solvents such as ethyl acetate, propyl acetate, and butyl acetate, alcohol-based organic solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and isobutyl alcohol, water, glycol ether-based solvents such as propylene glycol 1-monomethyl ether and propylene glycol monomethyl ether acetate, aromatic organic solvents such as toluene and xylene, hydrocarbon-based solvents such as methylcyclohexane, and known solvents such as tetrahydrofuran, and it is preferable to contain these as a mixed solvent. Furthermore, it is preferable to contain water in order to improve storage stability.

[0060] The thermoforming coating composition of the present invention is characterized by containing at least one selected from the group consisting of the resin composition of (1) below, the compound (D-1) of (2) below, the composite particle (D-2) of (3) below, and the composite particle composition of (4) below, and a resin (E) that does not contain an alkoxysilyl group but does contain a hydroxyl group. (1) A resin composition containing (A) a resin containing an alkoxysilyl group and a hydroxyl group, and (B) an alkoxysilane or a condensate thereof. (2) Compound (D-1) obtained by partial hydrolysis and condensation reaction of resin (A) containing alkoxysilyl groups and hydroxyl groups with alkoxysilane or its condensate (B). (3) Composite particles (D-2) obtained by partial hydrolysis and condensation reaction of a resin (A) containing an alkoxysilyl group and a hydroxyl group, an alkoxysilane or its condensate (B), and silica particles (C). (4) Composite particles (D-3) obtained by partial hydrolysis and condensation reaction of a resin (A) containing an alkoxysilyl group and a hydroxyl group with silica particles (C), and a composite particle composition containing an alkoxysilane or a condensate thereof (B).

[0061] <Compound (D-1)> The coating composition of the present invention may contain a compound (D-1) obtained by a partial hydrolysis condensation reaction between a resin (A) containing an alkoxysilyl group and a hydroxyl group and an alkoxysilane or a condensate thereof (B).

[0062] <Method for synthesizing compound (D-1)> The compound (D-1) may be synthesized by any known method, and can be synthesized by the method of the following step (4), although there are no particular limitations. Step (4) A step of subjecting a mixture of the resin (A) containing an alkoxysilyl group and a hydroxyl group and the alkoxysilane or its condensate (B) to a partial hydrolysis condensation reaction in a solvent (G) to obtain a compound (D-1).

[0063] A more detailed synthesis method for compound (D-1) involves mixing a resin (A) containing alkoxysilyl groups and hydroxyl groups with an alkoxysilane or its condensate (B) in the presence of a solvent (G) while stirring. The alkoxysilyl groups in (A) and (B) undergo partial hydrolysis and polycondensation, forming a bond between (A) and (B). During the reaction and stirring / mixing, the mixture may be heated to 40°C to 100°C, or a condensation catalyst (J) may be added. The solid content is preferably 5% to 30% by mass, and more preferably 7% to 20% by mass.

[0064] The progress of the reaction of the alkoxysilyl groups can be confirmed by tracking the decrease in the peaks derived from the alkoxysilyl groups in the IR spectrum, which allows the conversion rate to be calculated.

[0065] In the compound (D-1), the content of the resin (A) containing an alkoxysilyl group and a hydroxyl group is 20% by mass to 95% by mass, more preferably 30% by mass to 95% by mass, and the content of the alkoxysilane or its condensate (B) is 5% by mass to 80% by mass, more preferably 5% by mass to 70% by mass. The content of the compound (D-1) is not particularly limited, but is preferably 5% by mass to 80% by mass, more preferably 5% by mass to 70% by mass, based on the total amount of solids in the coating composition.

[0066] <Composite particles (D-2)> The coating composition of the present invention may contain composite particles (D-2) obtained by a partial hydrolysis and condensation reaction of a resin (A) containing an alkoxysilyl group and a hydroxyl group, an alkoxysilane or a condensate thereof (B), and silica particles (C).

[0067] <Method for synthesizing composite particles (D-2)> The synthesis method for the composite particles (D-2) is the same as the synthesis method for the compound (D-1) except for mixing silica particles, and is not particularly limited, but can be synthesized by the method of step (5) below. Step (5): A step of subjecting a mixture of an alkoxysilyl group- and hydroxyl group-containing resin (A), an alkoxysilane or its condensate (B), and silica particles (C) to a partial hydrolysis and condensation reaction in a solvent (G) to obtain composite particles (D-2).

[0068] In the composite particles (D-2), the content of the resin (A) containing alkoxysilyl groups and hydroxyl groups is 10% by mass to 85% by mass, more preferably 20% by mass to 80% by mass, the content of the alkoxysilane or its condensate (B) is 5% by mass to 80% by mass, more preferably 10% by mass to 75% by mass, and the content of the silica particles (C) is 5% by mass to 60% by mass, more preferably 5% by mass to 50% by mass. The content ratio of the composite particles (D-2) is not particularly limited, but is preferably 5% by mass to 80% by mass, more preferably 5% by mass to 70% by mass, based on the total amount of solids in the coating composition.

[0069] <Composite particles (D-3)> The coating composition of the present invention may contain composite particles (D-3) obtained by a partial hydrolysis condensation reaction between a resin (A) containing an alkoxysilyl group and a hydroxyl group and silica particles (C).

[0070] <Method for synthesizing composite particles (D-3)> The synthesis method for composite particles (D-3) is the same as that for compound (D-1), except that silica particles are mixed without mixing alkoxysilane or its condensate, and is not particularly limited, but can be synthesized by the method of step (6) below. Step (6): A step of subjecting a mixture of the resin (A) containing an alkoxysilyl group and a hydroxyl group and the silica particles (C) to a partial hydrolysis and condensation reaction in a solvent (G) to obtain composite particles (D-3).

[0071] In the composite particles (D-3), the content of the resin (A) containing an alkoxysilyl group and a hydroxyl group is 1% by mass to 90% by mass, more preferably 5% by mass to 80% by mass, and the content of the silica particles (C) is 10% by mass to 99% by mass, more preferably 20% by mass to 95% by mass. The content of the composite particles (D-3) is not particularly limited, but is preferably 5% by mass to 80% by mass, more preferably 5% by mass to 70% by mass, based on the total amount of solids in the coating composition.

[0072] <Condensation catalyst (J)> As the condensation catalyst of the present invention, any known condensation catalyst used to promote the hydrolysis reaction and dehydration condensation reaction of an alkoxysilyl group can be used as appropriate. Specific examples include acidic catalysts, basic catalysts, and metal-based catalysts. Among these, metal-based catalysts are preferred.

[0073] The acidic catalyst is preferably an organic acid because of its compatibility with the alkoxysilane component and the organic solvent. 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, and isobutyric acid.

[0074] Examples of basic catalysts include amine compounds such as N-ethylmorpholine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, Nt-butyldiethanolamine, triethylamine, n-butylamine, hexylamine, triethanolamine, diazabicycloundecene, and ammonia.

[0075] Examples of metal catalysts include organotin catalysts such as dioctyltin bis(2-ethylhexyl maleate), condensates of dioctyltin oxide or dibutyltin oxide with silicate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin distearate, dibutyltin diacetylacetonate, dibutyltin bis(ethyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(2-ethylhexyl maleate), dibutyltin bis(oleyl maleate), stannous octoate, tin stearate, and di-n-butyltin laurate oxide. Other examples include titanium chelate catalysts such as titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetoacetate, titanium phosphate compounds, titanium octylene glycolate, and titanium ethylacetoacetate. Further examples include aluminum chelate compounds such as ethyl acetoacetate aluminum diisopropylate, ethyl acetoacetate aluminum di-n-butyrate, aluminum tris(acetylacetate), aluminum tris(ethyl acetoacetate), aluminum monoacetylacetonate bis(ethyl acetoacetate), alkyl acetylacetate aluminum diisopropylate, and aluminum mono-n-butoxydiethyl acetoacetate. Of these, aluminum chelate compounds are preferred.

[0076] The amount of the condensation catalyst (J) added is not particularly limited, but from the viewpoint of achieving both storage stability and curing speed, it is preferably from 0.01% by mass to 10% by mass, and more preferably from 0.05% by mass to 5% by mass, based on the total amount of solids of the compound (D-1), the composite particles (D-2), and (D-3) or the total amount of solids of the coating composition.

[0077] <Ultraviolet absorber (H)> The coating composition of the present invention preferably contains an ultraviolet absorber and a light stabilizer for the purpose of imparting weather resistance. An ultraviolet absorber is generally a compound that absorbs ultraviolet light with a wavelength of approximately 200 to 400 nm, converts it into energy such as heat or infrared light, and then emits the converted energy. Examples of inorganic ultraviolet absorbers that can be used include metal oxide fine particles such as titanium dioxide, zinc oxide, iron oxide, cerium oxide, thallium oxide, lead oxide, and zirconium oxide. Examples of organic ultraviolet absorbers that can be used include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzoxazine-based ultraviolet absorbers, salicylic acid ester-based ultraviolet absorbers, diphenylmethanone-based ultraviolet absorbers, 2-cyanopropenoic acid ester-based ultraviolet absorbers, anthranilate-based ultraviolet absorbers, cinnamic acid derivative-based ultraviolet absorbers, camphor derivative-based ultraviolet absorbers, benzalmalonate derivative-based ultraviolet absorbers, resorcinol-based ultraviolet absorbers, oxalinide-based ultraviolet absorbers, and coumarin derivative-based ultraviolet absorbers. Of these, triazine-based ultraviolet absorbers are preferred.

[0078] Examples of triazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris-(diisobutyl 4'-amino-benzalmalonate)-s-triazine, 4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy 2-(2,4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, etc. Among these, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol is preferred.

[0079] Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-5'-t-octylphenyl)-benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6[(2H-benzotriazol-2-yl)phenol]], 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, and 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol.

[0080] Examples of diphenylmethanone-based ultraviolet absorbers include diphenylmethanone, methyldiphenylmethanone, 4-hydroxydiphenylmethanone, 4-methoxydiphenylmethanone, 4-octoxydiphenylmethanone, 4-decyloxydiphenylmethanone, 4-dodecyloxydiphenylmethanone, 4-benzyloxydiphenylmethanone, 4,2′,4′-trihydroxydiphenylmethanone, 2′-hydroxy-4,4′-dimethoxydiphenylmethanone, 4-(2-ethylhexyloxy)-2-hydroxy-diphenylmethanone, methyl o-benzoylbenzoate, and benzoin ethyl ether.

[0081] Examples of 2-cyanopropenoate ultraviolet absorbers include ethyl α-cyano-β,β-diphenylpropenoate and isooctyl α-cyano-β,β-diphenylpropenoate.

[0082] Examples of salicylate-based ultraviolet absorbers include isocetyl salicylate, octyl salicylate, glycol salicylate, and phenyl salicylate.

[0083] Examples of anthranilate-based ultraviolet absorbers include menthyl anthranilate.

[0084] Examples of cinnamic acid derivative-based ultraviolet absorbers include ethylhexyl methoxycinnamate, isopropyl methoxycinnamate, isoamyl methoxycinnamate, diisopropyl methyl cinnamate, glyceryl-ethylhexanoate dimethoxycinnamate, methyl-α-carbomethoxycinnamate, and methyl-α-cyano-β-methyl-p-methoxycinnamate.

[0085] Examples of camphor derivative ultraviolet absorbers include benzylidene camphor, benzylidene camphorsulfonic acid, camphor benzalkonium methosulfate, terephthalylidene dicamphorsulfonic acid, and polyacrylamidomethyl benzylidene camphor.

[0086] Examples of the resorcinol-based ultraviolet absorbers include dibenzoylresorcinol and bis(4-tert-butylbenzoylresorcinol).

[0087] Examples of oxalinide ultraviolet absorbers include 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxanilide, and 2-ethoxy-5-tert-butyl-2'-ethoxyoxanilide.

[0088] Examples of coumarin derivative ultraviolet absorbers include 7-hydroxycoumarin.

[0089] The content ratio of the ultraviolet absorber (H) is not particularly limited, but is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 20% by mass or less, relative to 100% by mass of the solid content of the coating composition.

[0090] <Light stabilizer> The light stabilizer is a compound that captures radicals generated by photodegradation, and can be, for example, a radical scavenger such as a thiol-based, thioether-based, or hindered amine-based compound, which can be used alone or in combination of two or more. Among them, it is preferable to use a hindered amine-based light stabilizer (I) from the viewpoint of further improving compatibility and light resistance stability.

[0091] Examples of the hindered amine light stabilizer (I) include aminoesters such as a reaction product of cyclohexane with N-butyl 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-triazine peroxide and 2-aminoethanol (trade name: Tinuvin 152 (BASF Ltd.)), decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester (trade name: Tinuvin 123 (BASF Ltd.)), and a reaction product of 1,1-dimethylethyl hydroperoxide and octane. hindered amine compounds having an ether group, N-acetyl-3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione (trade name: Hostavin 3058, manufactured by Clariant Japan Co., Ltd.)) and other N-acetyl-based hindered amine compounds, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (trade name: Sanol LS765, manufactured by BASF Japan Co., Ltd.), bis(1,2,2,6,6-pentamethyl-4-piperidyl){[3,5-bis(1,1-dimethylethyl)-4-hydroxybenzoyl]benzoate (trade name: benzoylbenzoyl]benzoate (trade name: benzoylbenzoyl]benzoate (trade name: benzoylbenzoyl) ... [{4-methoxyphenyl}methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidyl) ester (trade name: Hostavin® PR-31 (Clariant Japan Co., Ltd.)), propanedioic acid [{4-methoxyphenyl}methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidyl) ester (trade name: Hostavin® PR-31 (Clariant Japan Co., Ltd.)), N-Alkyl hindered amine compounds bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], 2,2'-thiobis(4-t-octylphenolate) alkylamine nickel, dibutylamine·1,3,Examples include polycondensates of 5-triazine·N,N-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine·N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine. Of these, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester is preferred.

[0092] The content ratio of the hindered amine light stabilizer (I) is not particularly limited, but is preferably 0.05% by mass or more and 20% by mass or less, and more preferably 0.5% by mass or more and 15% by mass or less, relative to 100% by mass of the solid content of the coating composition.

[0093] The ultraviolet absorber or hindered amine light stabilizer may be added to the coating composition as an additive, or an ultraviolet absorber or hindered amine light stabilizer having a reactive functional group may be used by reacting with a (meth)acrylic copolymer or with another resin. As a method for reacting with a (meth)acrylic copolymer, for example, a method of copolymerizing an ultraviolet absorbing group-containing (meth)acrylic monomer or a hindered amine light-stabilizing group-containing (meth)acrylic monomer with another (meth)acrylic monomer may be mentioned.

[0094] (Other additives) The coating composition of the present invention may contain various commonly used additives, such as plasticizers, leveling agents, dispersants, antifoaming agents, antistatic agents, antioxidants, chelating agents, trapping agents, antiblocking agents, wax components, matting agents, etc. Furthermore, it is also possible to blend in oils, flame retardants, fillers, stabilizers, reinforcing agents, matting agents, abrasives, organic fine particles, inorganic fine particles, polymeric compounds (acrylic resins, polyester resins, urethane (urea) resins, etc.), etc.

[0095] (Production of resin composition, composite particle composition, and coating composition) The resin composition, composite particle composition, and coating composition of the present invention can be produced by stirring the necessary raw materials for about 30 minutes to 3 hours using a disperser, etc. If mixing is difficult and the viscosity is likely to become non-uniform, a roller mill, ball mill, pebble mill, attritor, sand mill, etc. may also be used.

[0096] <Laminate> The laminate of the present invention has at least a substrate and a coating layer formed using the above-described coating composition.

[0097] <Base material> Substrates that can be used in the present invention can be appropriately selected depending on the purpose and application, and include, for example, polyolefin substrates such as polyethylene and polypropylene; alicyclic polyolefin substrates such as polynorbornene, hydrogenated polynorbornene, polydicyclopentadiene, and hydrogenated polydicyclopentadiene; polyester substrates such as polyethylene terephthalate and polylactic acid; polycarbonate substrates; acrylic substrates such as polymethyl methacrylate; polyamide substrates such as 6-nylon and 6,6-nylon; cellulose substrates such as cellulose acetate, cellulose propionate, and nitrocellulose; chlorine-based substrates such as polyvinyl chloride and polyvinylidene chloride; fluorine-based resins such as polytetrafluoroethylene and polyvinylidene fluoride; polystyrene substrates; AS resins; and polystyrene-based substrates such as ABS resins. Film or sheet-like substrates are preferred. The substrate layer can be obtained using one or a mixture of two or more of these thermoplastic resins. The substrate layer may be a laminate such as a decorative sheet. Furthermore, the substrate layer may be subjected to a surface treatment such as a corona treatment. Alternatively, a colored base material may be used in which a colorant is kneaded into the thermoplastic resin. The colorant is not particularly limited, and the above-mentioned organic pigments, inorganic pigments, etc. may be used as appropriate.

[0098] In addition to the substrate and coating layer, the laminate of the present invention may be provided with an anchor coat layer, a primer layer, a printing layer, and an adhesive layer as needed.

[0099] The laminate of the present invention can be used as a decorative film for thermoforming, for example, for automobile interior and exterior components such as the body, window moldings, pillars, front grilles, and rooftops, and as a decorative material for various building materials, furniture, home appliances, etc.

[0100] <Method of manufacturing laminate> The method for producing a laminate having a coating layer formed using the coating composition of the present invention is not particularly limited, but preferably includes the following step (1) and at least one step selected from the group consisting of the following step (2) and step (3): Step (1) Applying a coating composition to a substrate Step (2) A step of moisture-curing the applied coating composition in an environment of 50% to 100% humidity. Step (3) A step of heat-curing the applied coating composition in an environment at a temperature of 40°C to 100°C. The manufacturing order may be such that step (1) is performed, followed by step (2) and step (3), or step (3) and step (2). Alternatively, steps (2) and (3) may be performed simultaneously, and moisture curing and heat curing may be performed simultaneously in an environment of, for example, a temperature of 40°C and a humidity of 90%.

[0101] [Process (1)] The method for applying the coating composition of the present invention to the substrate in step (1) is not particularly limited, and examples thereof include wet coating methods such as spraying, showering, dipping, flow coating, gravure printing, flexographic printing, roll printing, spin printing, dispenser printing, inkjet printing, and screen printing. However, a gravure printing application method is more preferred.

[0102] [Process (2)] Step (2), in which the applied coating composition is moisture-cured in an environment with a humidity of 50% to 100%, promotes the hydrolysis and polycondensation reaction of the alkoxysilyl groups. The reaction is completed by leaving the laminate stationary for a period of one hour to one week. The higher the humidity, the more the hydrolysis and polycondensation reaction can be accelerated. However, if the curing agent is an isocyanate-based curing agent, the curing agent will also be deactivated. Therefore, a humidity of 50% to 90%, and more preferably 50% to 70%, is preferred. The progress of the alkoxysilyl group reaction can be confirmed by tracking the decrease in the peak derived from the alkoxysilyl group in an IR spectrum, which can be used to determine the conversion rate.

[0103] [Process (3)] The step (3) of heat-curing the applied coating composition in an environment at a temperature of 40 to 100°C is necessary for the crosslinking reaction between the curing agent and the resin. For example, when the curing agent is an isocyanate-based curing agent, the crosslinking reaction is completed in 1 to 7 days at a temperature of 40 to 100°C. Heat-curing at a temperature of 40 to 60°C for 3 days is preferred. The completion of the reaction can be confirmed by tracking the decrease in the peak derived from the isocyanate in an IR spectrum, which can determine the end point of the crosslinking reaction. The humidity in step (3) is preferably 10 to 49%.

[0104] The thickness of the coating layer after curing is usually preferably 1 to 30 μm. It is more preferable that it is up to 20 μm. [Example]

[0105] Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. Furthermore, unless otherwise specified, in the examples and comparative examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0106] Before going into the examples, the method for measuring the weight average molecular weight will be described.

[0107] (Weight average molecular weight (Mw)) The weight average molecular weight is a polystyrene-equivalent value measured using a gel permeation chromatography (GPC) (HLC-8420GPC, manufactured by Tosoh Corporation) equipped with a TSKgel column (manufactured by Tosoh Corporation) and an RI detector, using THF as a developing solvent.

[0108] The abbreviations used in this specification are as follows: MMA: methyl methacrylate BMA: butyl methacrylate BA: butyl acrylate CHMA: Cyclohexyl methacrylate LMA: Lauryl methacrylate KBE503: 3-methacryloxypropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.) KBM503: 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) KBE1003: Vinyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.) 2HEMA: 2-hydroxyethyl methacrylate AA: acrylic acid AIBN: Azobisisobutyronitrile KR510: Silicone oligomer containing methyl, phenyl, and methoxy groups (manufactured by Shin-Etsu Chemical Co., Ltd.) KR500: Silicone oligomer containing methyl and methoxy groups (manufactured by Shin-Etsu Chemical Co., Ltd.) KBM3103C: Decyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) MEK-ST-L: MEK-dispersed organosilica sol, particle size 45 nm / solids content 30% MEK solution (Nissan Chemical Industries, Ltd.) MEK-ST-40: MEK-dispersed organosilica sol, particle size 12 nm / solids content 40% MEK solution (Nissan Chemical Industries, Ltd.) MEK-ST-ZL: MEK-dispersed organosilica sol, particle size 80 nm / solids content 30% MEK solution (Nissan Chemical Industries, Ltd.) DX9740: Aluminum chelate compound (Shin-Etsu Chemical Co., Ltd.) S75P: Aluminum chelate compound / 75% solids isopropanol solution (Kawaken Fine Chemicals Co., Ltd.) D25: Organic titanium compound (Shin-Etsu Chemical Co., Ltd.) MEK: Methyl ethyl ketone 24A-100: Duranate 24A-100, a biuret of hexamethylene diisocyanate (manufactured by Asahi Kasei Corporation) HI100: BASONAT HI100, an isocyanurate of hexamethylene diisocyanate (manufactured by BASF) LA46: Adeka STAB LA-46 / Triazine-based UV absorber / 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (ADEKA Corporation) Tin.479: Tinuvin 479 / hydroxyphenyltriazine UV absorber (manufactured by BASF) Tin.123: Tinuvin 123 / hindered amine light stabilizer / bis[2,2,6,6-tetramethyl-1-(octyloxy)piperidin-4-yl] decanedioate (BASF) Tin.292: Tinuvin 292 / hindered amine light stabilizer / mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (BASF)

[0109] <Synthesis of Resins (A) and (E)> (Production Example 1) A four-neck flask equipped with a condenser, stirrer, thermometer, and nitrogen inlet tube was charged with 58 parts MMA, 10 parts BMA, 20 parts BA, 2 parts KBE503, 10 parts 2HEMA, and 80 parts MEK, and the mixture was heated with stirring under a nitrogen atmosphere. When the temperature inside the flask reached 75°C, this temperature was maintained as the synthesis temperature, and a solution of 1.7 parts AIBN initiator diluted with 42 parts MEK was added dropwise over 2 hours. Six hours after the initiator addition was completed, nonvolatile content measurements confirmed that the unreacted monomer in the solution was 5% or less. The reaction was terminated by cooling, yielding a solution of resin (A-1) containing alkoxysilyl groups and hydroxyl groups with a solids content of approximately 45%. Resin (A-1) had a Mw of 31,000.

[0110] (Production Examples 2 to 22, Comparative Production Examples 1 to 4) Resins (A-2) to (A-15), (E-1) to (E-7), (A-1'), (A-2'), (E-1'), and (E-2') were synthesized in the same manner as in Production Example 1, except that the raw materials and compounding amounts used in Production Example 1 were changed to those shown in Table 1.

[0111] [Table 1]

[0112] <Synthesis of Compound (D-1)> (Manufacturing Example 23) A four-neck flask equipped with a condenser, stirrer, and thermometer was charged with 65 parts of resin (A-1) (solids equivalent), 35 parts of alkoxysilane or its condensate (B) KR510, and 820 parts of solvent (G) MEK, and the temperature was raised while stirring. When the temperature inside the flask reached 60 ° C, this temperature was maintained as the synthesis temperature, and a solution of 0.15 parts of condensation catalyst (J) DX9740 diluted with 2.85 parts MEK was added. Five hours after the addition of the condensation catalyst, the reaction was stopped by cooling, and a compound (D-1-1) with a solids content of 10% was obtained.

[0113] (Production Examples 24 to 41, 49, 50, Comparative Production Examples 5 and 6) Compounds (D-1-2) to (D-1-19), (D-1-21′), (D-1-22′), (D-1-23), and (D-1-24) were synthesized in the same manner as in Production Example 23, except that the raw materials, amounts, and solid contents used in Production Example 23 were changed to those shown in Tables 2-1 and 2-2.

[0114] (Manufacturing Example 42) A four-neck flask equipped with a condenser, a stirrer, and a thermometer was charged with 65 parts of resin (A-1) in terms of solids, 35 parts of alkoxysilane or its condensate (B) KR510, and 823 parts of solvent (G) MEK, and the temperature was raised while stirring. When the temperature inside the flask reached 60°C, this temperature was maintained as the synthesis temperature, and after 5 hours, the reaction was terminated by cooling, yielding compound (D-1-20) with a solids content of 10%.

[0115] <Synthesis of Composite Particles (D-2)> (Manufacturing Example 43) A four-neck flask equipped with a condenser, stirrer, and thermometer was charged with 40 parts of resin (A-1) in solids, 30 parts of alkoxysilane or its condensate (B) KR510, 30 parts of silica particles (C) MEK-ST-L, and 778 parts of solvent (G) MEK, and the temperature was raised while stirring. When the temperature inside the flask reached 60 ° C, this temperature was maintained as the synthesis temperature, and a solution of 0.15 parts of condensation catalyst (J) DX9740 diluted with 2.85 parts of MEK was added. Five hours after the addition of the condensation catalyst, the reaction was stopped by cooling, and composite particles (D-2-1) with a solids content of 10% were obtained.

[0116] (Examples 44-48) Composite particles (D-2-2) to (D-2-6) were synthesized in the same manner as in Production Example 43, except that the raw materials, amounts, and solid contents used in Production Example 43 were changed to those shown in Table 2-1.

[0117] (Manufacturing Example 51) A four-neck flask equipped with a condenser, a stirrer, and a thermometer was charged with 40 parts of resin (A-13) in solids, 30 parts of alkoxysilane or its condensate (B) KR510, 30 parts of silica particles (C) MEK-ST-L, and 281 parts of solvent (G) MEK, and the mixture was heated with stirring. When the temperature inside the flask reached 60 ° C, this temperature was maintained as the synthesis temperature, and after 5 hours, the mixture was cooled to terminate the reaction, yielding composite particles (D-2-7) with a solids content of 20%.

[0118] (Examples 52-60) Composite particles (D-2-8) to (D-2-16) were synthesized in the same manner as in Production Example 51, except that the raw materials, blending amounts, and solid contents used in Production Example 51 were changed to those shown in Table 2-2.

[0119] <Synthesis of Composite Particles (D-3)> (Manufacturing Example 61) A four-neck flask equipped with a condenser, a stirrer, and a thermometer was charged with 10 parts of resin (A-13) in solids, 90 parts of silica particles (C) MEK-ST-L, and 178 parts of solvent (G) MEK, and the mixture was heated with stirring. When the temperature inside the flask reached 60°C, this temperature was maintained as the synthesis temperature, and after 5 hours, the mixture was cooled to terminate the reaction, yielding compound (D-3-1) with a solids content of 20%.

[0120] (Examples 62-66) Composite particles (D-3-2) to (D-3-6) were synthesized in the same manner as in Production Example 61, except that the raw materials, blending amounts, and solid contents used in Production Example 61 were changed to those shown in Table 2-2.

[0121] [Table 2-1]

[0122] [Table 2-2]

[0123] <Preparation of Thermoforming Coating Composition> [Example 1] 26 parts in terms of solid content of the compound (D-1-1) obtained in the above Production Example, 64 parts of resin (E-1), 5 parts of curing agent (F) 24A-100, 4 parts of ultraviolet absorber (H) LA46, 1 part of light stabilizer (I) Tin.123, and 42 parts of solvent (G) MEK were charged and mixed at room temperature to obtain a coating composition (X-1) with a solid content of 22%.

[0124] [Examples 2 to 25, 34 to 39, 41 to 54, Comparative Examples 1 to 5] Coating compositions (X-2) to (X-25), (X-34) to (X-39), (X-41) to (X-54), and (CX-1) to (CX-5) were obtained in the same manner as in Example 1, except that the raw materials and blending amounts used in Example 1 were changed to those shown in Tables 3-1 to 3-3.

[0125] [Examples 26 to 27] 17 parts of the resin (A-1) obtained in the above Preparation Example (solids content), 9 parts of alkoxysilane or its condensate (B) KR510, 64 parts of resin (E-1), 5 parts of curing agent (F) 24A-100, 4 parts of ultraviolet absorber (H) LA46, 1 part of light stabilizer (I) Tin.123, and 252 parts of solvent (G) MEK were charged and mixed at room temperature. A solution of 0.15 parts of condensation catalyst (J) DX9740 diluted with 2.85 parts of MEK was added and mixed at room temperature to obtain coating compositions (X-26) and (X-27) with a solids content of 22%.

[0126] [Examples 28 to 29] Coating compositions (X-28) and (X-29) were obtained in the same manner as in Example 26, except that the raw materials and blending amounts used in Example 26 were changed to those shown in Table 3-1.

[0127] [Example 30] 26 parts in terms of solids of the compound (D-1-1) obtained in the above Production Example, 9 parts of silica particles (C) MEK-ST-L, 55 parts of resin (E-1), 5 parts of curing agent (F) 24A-100, 4 parts of ultraviolet absorber (H) LA46, 1 part of light stabilizer (I) Tin.123, and 32 parts of solvent (G) MEK were charged and mixed at room temperature to obtain a coating composition (X-30) with a solids content of 22%.

[0128] [Examples 31 to 33] Coating compositions (X-31) to (X-33) were obtained in the same manner as in Example 30, except that the raw materials and blending amounts used in Example 30 were changed to those shown in Table 3-2.

[0129] [Example 40] 12 parts in terms of solid content of the resin (A-1) obtained in the above Production Example, 9 parts of an alkoxysilane or its condensate (B) KR510, 9 parts of silica particles (C) MEK-ST-L, 60 parts of resin (E-1), 5 parts of a curing agent (F) 24A-100, 4 parts of an ultraviolet absorber (H) LA46, 1 part of a light stabilizer (I) Tin.123, and 242 parts of a solvent (G) MEK were charged, A solution prepared by diluting 0.15 parts of condensation catalyst (J) DX9740 in 2.85 parts of MEK was added thereto and mixed at room temperature to obtain a coating composition (X-40) with a solids content of 22%.

[0130] [Example 55] 30 parts in terms of solid content of the composite particles (D-2-11) obtained in the above Production Example, 60 parts of resin (E-6), 5 parts of curing agent (F) 24A-100, 4 parts of ultraviolet absorber (H) LA46, 1 part of light stabilizer (I) Tin.123, 161 parts of solvent (G) MEK, and 5 parts of water were charged and mixed at room temperature to obtain a coating composition (X-55) with a solid content of 22%.

[0131] [Example 56] 10 parts of the composite particles (D-3-1) obtained in the above Production Example, converted to solids, 9 parts of alkoxysilane or its condensate (B) KR510, 71 parts of resin (E-1), 5 parts of curing agent (F) 24A-100, 4 parts of ultraviolet absorber (H) LA46, 1 part of light stabilizer (I) Tin.123, and 228 parts of solvent (G) MEK were charged and mixed at room temperature to obtain a coating composition (X-56) with a solids content of 22%.

[0132] [Examples 57 to 62] Coating compositions (X-57) to (X-62) were obtained in the same manner as in Example 56, except that the raw materials and blending amounts used in Example 56 were changed to those shown in Table 3-3.

[0133] [Table 3-1]

[0134] [Table 3-2]

[0135] [Table 3-3]

[0136] The results of evaluation tests for storage stability, compatibility, moldability, scratch resistance, and weather resistance, which will be described later, are shown in Tables 4-1 to 4-3. The evaluations are: ◎◎, ◎, ◯, △, which indicate pass and practical use possible, and ×, which indicates fail. If a coating composition fails even one of the evaluation tests, it is deemed to have failed.

[0137] <Evaluation of Coating Composition> The resulting coating compositions were evaluated for storage stability and compatibility by the following methods, and the results are shown in Tables 4-1 to 4-3.

[0138] (Storage stability) The resulting coating compositions were left to stand at 25°C, and after one month, the coating liquid was visually observed for changes, and the change in viscosity was measured. The viscosity was measured using an EMS viscometer (Kyoto Electronics Manufacturing Co., Ltd.) and was the average of 10 measurements obtained under the following conditions: a measurement temperature of 25°C, a motor rotation speed of 1000 rpm, and a spherical probe Al2 mm. Note that the coating compositions (X-1) to (X-62) and comparative compositions (CX-1) to (CX-5) were observed without the curing agent (F) or condensation catalyst (J) mixed in, and were evaluated according to the following criteria. ◎◎: Viscosity change of 5% or less ◎: Viscosity change is greater than 5% and less than 10% ○: Viscosity change is greater than 10% and less than 20% △: Viscosity change is more than 20%, but fluidity is maintained ×: The entire coating solution solidified and lost its fluidity

[0139] (compatibility) The resulting coating composition was visually observed and evaluated according to the following criteria. ◎:Transparent ×: The occurrence of lumps, cloudiness, etc. is observed.

[0140] (Preparation of laminate) [Examples 1 to 25, 30 to 39, 41 to 62, Comparative Examples 1 to 5] Using a bar coater, coating compositions (X-1) to (X-25), (X-30) to (X-39), (X-41) to (X-62), and (CX-1) to (CX-5) were applied onto Technoloy S001G acrylic substrate film #125 (manufactured by Sumitomo Chemical Co., Ltd.) to a dry thickness of 9 μm. The coated product was kept at a temperature of 60°C and a humidity of 15% for 72 hours to obtain a laminate.

[0141] [Examples 26, 28, 29, and 40] Using a bar coater, coating compositions (X-26), (X-28), (X-29), and (X-40) were applied to Technoloy S001G acrylic substrate film #125 (manufactured by Sumitomo Chemical Co., Ltd.) to a dry thickness of 9 μm. The coated product was kept at a temperature of 40°C and a humidity of 30% for 168 hours to obtain a laminate.

[0142] [Example 27] Using a bar coater, the coating composition (X-27) was applied to a Technoloy S001G acrylic substrate film #125 (manufactured by Sumitomo Chemical Co., Ltd.) so that the thickness after drying would be 9 μm. The coated product was kept at a temperature of 40°C and a humidity of 90% for 168 hours to obtain a laminate.

[0143] (Moldability) The resulting laminate was evaluated for moldability during heating using a tensile tester AGS-X (Shimadzu Corporation). Test pieces 20 mm wide and 100 mm long were cut out from the laminate. The test pieces were placed in a heating oven at 135°C with a chuck distance of 84 mm and left to stand for 3 minutes. After that, the test pieces were pulled at a pulling rate of 30 mm / min, and the elongation at which the test pieces cracked was observed. Evaluation was performed according to the following criteria. ◎: The elongation at which cracks occur is 100% or more ○: The elongation at which cracks occur is 50% or more but less than 100% △: The elongation at which cracks occur is between 30% and 50% ×: The elongation at which cracks occur is less than 30%

[0144] (Scratch resistance) The obtained laminate was subjected to a rub fastness test using a Gakushin type rub fastness tester AB-301 (manufactured by Tester Sangyo Co., Ltd.) by rubbing a No. 3 gold-stripe cloth back and forth 200 times with a load of 500 g, and evaluated according to the following criteria. ◎: No scratches at all 〇: Scratched, less than 10 pieces △: Scratched, 10 to less than 50 pieces ×: Damaged, 50 or more

[0145] (Weather resistance evaluation) The resulting laminate was subjected to a weather resistance test by being left for 500 hours under the following test conditions: The difference in haze (ΔHaze) of the laminate before and after the test was measured, and evaluation was carried out according to the following criteria. ◎◎: Less than ΔHaze3 ◎: ΔHaze 3 or more and less than 5 ○: ΔHaze 5 or more and less than 10 △: ΔHaze 10 or more and less than 20 ×: ΔHaze 20 or more

[0146] (Weather resistance test conditions) During the 500-hour test period, the following irradiation conditions, shower, condensation conditions, and shower were repeated in this order. Test equipment: Ultra-accelerated weather resistance tester (Eye-Sover UV Tester SUV-W161, manufactured by Iwasaki Electric Co., Ltd.) Illuminance meter: UVP-365-01 (manufactured by Iwasaki Electric Co., Ltd.) was used. Irradiation conditions Illuminance: 100mW / cm 2 Black panel temperature: 63℃ Humidity: 50% Duration: 20 hours Condensation conditions Illuminance: 0mW / cm 2 Humidity: 98% Duration: 4 hours Shower: 30 seconds (before and after condensation)

[0147] [Table 4-1]

[0148] [Table 4-2]

[0149] [Table 4-3]

[0150] Examples 1 to 62, which are thermoforming coating compositions of the present invention, each characterized by the weight-average molecular weights of Resin (A) and Resin (E) being 10,000 to 200,000, and the weight-average molecular weight (MwE) of Resin (E) and the weight-average molecular weight (MwA) of Resin (A) satisfying the relationship (MwE) / (MwA) > 1, all exhibited excellent storage stability, compatibility, weather resistance, moldability, and scratch resistance. On the other hand, Comparative Examples 1 to 4, in which (MwA) and (MwE) were outside the range of 10,000 to 200,000, and Comparative Example 5, in which the relationship (MwE) / (MwA) > 1 was not satisfied, failed in any of storage stability, compatibility, moldability, and weather resistance.

[0151] In particular, Examples 1 and 3, in which (MwE) / (MwA) was 2 or more and less than 20, were superior in both storage stability and moldability compared to Examples 2 and 4, in which (MwE) / (MwA) was less than 2.

[0152] In particular, Examples 30, 32 to 34, and 36 to 40, in which silica particles (C) were added in an amount of 9% or more, exhibited excellent scratch resistance.

[0153] In particular, Examples 1 to 25, 30 to 39, and 41 to 62, in which compound (D-1), composite particles (D-2), or (D-3) was added, had superior storage stability compared to Examples 26 to 29 and 40, in which compound (D-1), composite particles (D-2), or (D-3) was not added.

[0154] In particular, in Examples 41 to 45 and 47 to 62, which used resin (A) and resin (E) containing 20% ​​or more of CHMA, the weather resistance was excellent.

[0155] In particular, Examples 44 to 50, 55, and 59 to 62, which contained 15 parts or more of alkoxysilane or its condensate (B) KR510 and 8 parts or less of silica particles (C), were excellent in achieving both weather resistance, scratch resistance, and storage stability.

[0156] In particular, Example 55, in which water was added, had excellent storage stability compared to Example 48, in which water was not added.

Claims

1. A thermoforming coating composition comprising at least one selected from the group consisting of a resin composition of the following (1), a compound (D-1) of the following (2), a composite particle (D-2) of the following (3), and a composite particle composition of the following (4), and a resin (E) which does not contain an alkoxysilyl group but contains a hydroxyl group, A thermoforming coating composition characterized in that the weight average molecular weights of resin (A) and resin (E) are each 10,000 to 200,000, and the weight average molecular weight (MwE) of resin (E) and the weight average molecular weight (MwA) of resin (A) satisfy the relationship (MwE) / (MwA) > 1. (1) A resin composition containing (A) a resin containing an alkoxysilyl group and a hydroxyl group, and (B) an alkoxysilane or a condensate thereof. (2) Compound (D-1) obtained by partial hydrolysis and condensation reaction of resin (A) containing an alkoxysilyl group and a hydroxyl group with alkoxysilane or its condensate (B) (3) Composite particles (D-2) obtained by partial hydrolysis and condensation reaction of a resin (A) containing an alkoxysilyl group and a hydroxyl group, an alkoxysilane or its condensate (B), and silica particles (C). (4) A composite particle composition containing composite particles (D-3) obtained by a partial hydrolysis condensation reaction of a resin (A) containing an alkoxysilyl group and a hydroxyl group with silica particles (C), and an alkoxysilane or a condensate thereof (B).

2. 2. The coating composition for thermoforming according to claim 1, further comprising silica particles (C).

3. 2. The thermoforming coating composition according to claim 1, further comprising a curing agent (F).

4. 2. The thermoforming coating composition according to claim 1, further comprising at least one member selected from the group consisting of an ultraviolet absorber (H) and a hindered amine light stabilizer (I).

5. 2. The thermoforming coating composition according to claim 1, wherein the resin (A) containing an alkoxysilyl group and a hydroxyl group, and the resin (E) containing no alkoxysilyl group but containing a hydroxyl group are acrylic resins.

6. 2. The thermoforming coating composition according to claim 1, wherein the weight-average molecular weight of the resin (A) containing an alkoxysilyl group and a hydroxyl group is 10,000 to 100,000, and the weight-average molecular weight of the resin (E) containing no alkoxysilyl group but containing a hydroxyl group is 30,000 to 200,000.

7. 2. The thermoforming coating composition according to claim 1, further comprising a condensation catalyst (J).

8. A laminate comprising at least a substrate and a coating layer formed using the coating composition according to any one of claims 1 to 7.

9. A method for producing a laminate having at least a substrate and a coating layer formed using the coating composition according to any one of claims 1 to 7, comprising: A method for producing a laminate, comprising the following step (1) and at least one step selected from the group consisting of the following step (2) and step (3): Step (1) A step of applying the coating composition according to any one of claims 1 to 7 onto a substrate. Step (2): Moisture-curing the applied coating composition in an environment with a humidity of 50% to 100%. Step (3): Heat-curing the applied coating composition in an environment at a temperature of 40°C to 100°C.

10. A method for producing a thermoforming coating composition comprising a compound (D-1) obtained by a production method including the following step (4): a resin (E) containing no alkoxysilyl groups but containing hydroxyl groups; and a solvent (G), A method for producing a thermoforming coating composition, characterized in that the weight average molecular weights of resin (A) and resin (E) are each 10,000 to 200,000, and the weight average molecular weight (MwE) of resin (E) and the weight average molecular weight (MwA) of resin (A) satisfy the relationship (MwE) / (MwA) > 1. Step (4): A step of subjecting a mixture of the resin (A) containing an alkoxysilyl group and a hydroxyl group and the alkoxysilane or its condensate (B) to a partial hydrolysis condensation reaction in a solvent (G) to obtain a compound (D-1).

11. A method for producing a coating composition for thermoforming, comprising composite particles (D-2) obtained by a production method including the following step (5): a resin (E) containing no alkoxysilyl groups but containing hydroxyl groups; and a solvent (G), A method for producing a thermoforming coating composition, characterized in that the weight average molecular weights of resin (A) and resin (E) are each 10,000 to 200,000, and the weight average molecular weight (MwE) of resin (E) and the weight average molecular weight (MwA) of resin (A) satisfy the relationship (MwE) / (MwA) > 1. Step (5): A step of subjecting a mixture of an alkoxysilyl group- and hydroxyl group-containing resin (A), an alkoxysilane or its condensate (B), and silica particles (C) to a partial hydrolysis and condensation reaction in a solvent (G) to obtain composite particles (D-2).

12. A method for producing a coating composition for thermoforming, comprising composite particles (D-3) obtained by a production method including the following step (6): (B) an alkoxysilane or a condensate thereof; (E) a resin containing no alkoxysilyl groups but containing hydroxyl groups; and (G) a solvent, A method for producing a thermoforming coating composition, characterized in that the weight average molecular weights of resin (A) and resin (E) are each 10,000 to 200,000, and the weight average molecular weight (MwE) of resin (E) and the weight average molecular weight (MwA) of resin (A) satisfy the relationship (MwE) / (MwA) > 1. Step (6): A step of subjecting a mixture of the resin (A) containing an alkoxysilyl group and a hydroxyl group and the silica particles (C) to a partial hydrolysis condensation reaction in a solvent (G) to obtain composite particles (D-3).

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