JP6304121B2 - UV-absorbing organosilicon compound, paint, and laminate - Google Patents

Description

  The present invention relates to an ultraviolet-absorbing organosilicon compound, a paint containing the same, and a laminate including the coating film. More specifically, the present invention relates to an ultraviolet absorbing organic silicon compound having an ultraviolet absorbing group and a siloxane (meth) acrylate moiety. The ultraviolet-absorbing organosilicon compound of the present invention is excellent in blending into an active energy ray-curable coating and does not deteriorate the scratch resistance even when blended at a high concentration. The ultraviolet-absorbing organosilicon compound of the present invention is suitable for an active energy ray-curable coating. When the layer (i) obtained by applying and curing the coating is used as a primer layer of the inorganic vapor deposition layer (ii), a laminate having excellent durability can be provided.

  In order to impart ultraviolet absorptivity to an active energy ray-curable coating, a technique using an organic ultraviolet absorber having a vinyl polymerizable group such as a (meth) acryl group has been proposed (Patent Document 1: US Patent No. 1). No. 5,990,188). However, when a large amount of an organic ultraviolet absorber having a vinyl polymerizable group such as a (meth) acrylic group is blended in the paint, the scratch resistance is deteriorated, so that the blending amount is limited. It is considered that the deterioration of scratch resistance can be alleviated by increasing the number of functional groups of vinyl polymerizable groups such as (meth) acrylic groups, and reactive UV absorption having such polyfunctional (meth) acrylic groups. An agent has also been proposed (Patent Document 2: US Pat. No. 3,159,646, Patent Document 3: Japanese Patent No. 2180909).

US Pat. No. 5,990,188 US Pat. No. 3,159,646 Japanese Patent No. 2180909

  However, increasing the number of functional groups of vinyl polymerizable groups such as (meth) acrylic groups contained in the molecule of the reactive UV absorber results in a highly viscous liquid or a crystalline solid that dissolves in the paint. Since another problem such as deterioration of the properties occurs, there is a limit to the blending into the paint. In addition, the synthesis of molecules having easily polymerized units such as polyfunctional (meth) acrylates is greatly restricted in terms of functional group conversion and purification, and the introduction of UV-absorbing groups is complicated in terms of synthetic chemistry. It was.

It is an object of the present invention to provide an organosilicon compound having a chemical structure that solves compounding properties in paint and complexity of synthesis. Furthermore, the problem of the present invention is not limited only to the difficulty of blending into paint and the complexity of synthesis. In the case where the inorganic vapor deposition layer (ii) is formed on the layer (i) formed by applying and curing the paint, generally, a large amount of the ultraviolet absorber inhibits the adhesion between the layer (i) and the layer (ii). However, it became clear by examination of this inventor.
Therefore, the present invention is an organic ultraviolet absorber having a polyfunctional (meth) acrylic group in the molecule, excellent in blendability into a paint, and applied and cured to the organic resin substrate. When the inorganic vapor deposition layer (ii) is formed with respect to the layer (i) to be formed, the object is to provide an ultraviolet-absorbing organosilicon compound that has excellent adhesion and is easy to synthesize. . Moreover, it aims at providing the laminated body containing the coating material containing this ultraviolet-absorbing organosilicon compound, and its coating film.

［一般式（Ｉ）中において、Ｒ¹は紫外線吸収性の有機基、Ｒ²は下記一般式（ＩＩ）

（一般式（ＩＩ）中において、Ｙは炭素数１〜１２のアルキレン基、Ｒ⁴は水素原子又はメチル基である。）
で表される有機基、Ｒ³は炭素数１〜６のアルキル基、ｎは０又は１である。］ Conventionally, it is an organic ultraviolet absorber that can be used in an active energy ray-curable coating, and the problem of compatibility between the high blendability in the coating and the formation of an inorganic vapor deposition layer has not been focused so far. No means for solving the problem was known. In particular, the specific structure of the ultraviolet absorbing group and the specific structure of the linking group for connecting the ultraviolet absorbing group and the reactive group have not been known.
On the other hand, as a result of intensive studies by the inventor, the ultraviolet-absorbing organosilicon compound represented by the following general formula (I) is excellent in the compounding property to the paint, and the paint is applied to the organic resin substrate. It has been found that when the inorganic vapor deposition layer (ii) is formed on the cured layer (i), the adhesion is excellent. The ultraviolet-absorbing organosilicon compound represented by the following general formula (I) can be easily produced by a chemical reaction process including a simple unit operation.

[In the general formula (I), R ¹ is an ultraviolet-absorbing organic group, R ² is the following general formula (II)

(In general formula (II), Y is an alkylene group having 1 to 12 carbon atoms, and R ⁴ is a hydrogen atom or a methyl group.)
R ³ is an alkyl group having 1 to 6 carbon atoms, and n is 0 or 1. ]

［一般式（Ｉ）中において、Ｒ¹は下記一般式（ＩＩＩ）

｛一般式（ＩＩＩ）中において、Ａ¹〜Ａ¹⁰は、それぞれ独立に、水素原子、水酸基、炭素数１〜５のアルキル基、又は、下記式（ＩＶ）

（一般式（ＩＶ）中において、Ｙ’は炭素数１〜１２のアルキレン基であり、酸素側で一般式（ＩＩＩ）に含まれるベンゼン環と直結し、Ｙ’側で一般式（Ｉ）に含まれるケイ素原子と直結する。）
で表される基で、式（ＩＩＩ）は少なくとも一つの水酸基と少なくとも一つの式（ＩＶ）で表される基を有する。｝
で表される紫外線吸収性の有機基、Ｒ²は下記一般式（ＩＩ）

（一般式（ＩＩ）中において、Ｙは炭素数１〜１２のアルキレン基、Ｒ⁴は水素原子又はメチル基である。）
で表される有機基、Ｒ³は炭素数１〜６のアルキル基、ｎは０又は１である。］
〔２〕
〔１〕に記載の紫外線吸収性有機ケイ素化合物を含有する活性エネルギー線硬化性塗料。
〔３〕
多官能（メタ）アクリレート、アクリル系ポリマー、及び無機酸化物微粒子を含む〔２〕に記載の活性エネルギー線硬化性塗料。
〔４〕
紫外線吸収性有機ケイ素化合物を除く塗料固形分１００質量部に対して紫外線吸収性有機ケイ素化合物を１〜４０質量％含有する〔２〕又は〔３〕に記載の活性エネルギー線硬化性塗料。
〔５〕
有機樹脂基材の少なくとも一方の面に〔２〕〜〔４〕のいずれかに記載の活性エネルギー線硬化性塗料を塗布・硬化してなる被覆物品。
〔６〕
有機樹脂基材がポリカーボネートである〔５〕に記載の被覆物品。
〔７〕
〔５〕又は〔６〕に記載の被覆物品に無機蒸着層を積層してなる積層体。
Accordingly, the present invention provides the following ultraviolet-absorbing organosilicon compound, paint, and laminate.
[1]
An ultraviolet-absorbing organosilicon compound represented by the following general formula (I).

[In the general formula (I), R ¹ represents the following general formula (III)

{In General Formula (III), A ^{1 to} A ¹⁰ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or the following formula (IV):

(In general formula (IV), Y ′ is an alkylene group having 1 to 12 carbon atoms, directly connected to the benzene ring contained in general formula (III) on the oxygen side, and in general formula (I) on Y ′ side. (Directly connected to the silicon atoms contained.)
In which the formula (III) has at least one hydroxyl group and at least one group represented by the formula (IV). }
R ² is an ultraviolet-absorbing organic group represented by the following general formula (II)

(In general formula (II), Y is an alkylene group having 1 to 12 carbon atoms, and R ⁴ is a hydrogen atom or a methyl group.)
R ³ is an alkyl group having 1 to 6 carbon atoms, and n is 0 or 1. ]
[2]
An active energy ray-curable coating material containing the ultraviolet absorbing organosilicon compound according to [1].
[3]
The active energy ray-curable coating according to [2], comprising a polyfunctional (meth) acrylate, an acrylic polymer, and inorganic oxide fine particles.
[4]
The active energy ray-curable coating material according to [2] or [3], which contains 1 to 40% by mass of the ultraviolet absorbing organic silicon compound with respect to 100 parts by mass of the coating solid content excluding the ultraviolet absorbing organic silicon compound.
[5]
A coated article obtained by applying and curing the active energy ray-curable coating material according to any one of [2] to [4] to at least one surface of an organic resin substrate.
[6]
The coated article according to [5], wherein the organic resin base material is polycarbonate.
[7]
The laminated body formed by laminating | stacking an inorganic vapor deposition layer on the coated article as described in [5] or [6].

  The ultraviolet-absorbing organosilicon compound of the present invention exhibits useful properties as an ultraviolet absorber for active energy ray-curable coatings, while having a chemical structure that can be easily synthesized. Specifically, it is excellent in compounding with the paint, and the ultraviolet absorber does not crystallize and precipitate in the paint and / or during film formation of the coating film. Even when blended with the paint in a high concentration, the scratch resistance of the coating formed by applying and curing the paint does not deteriorate. When the coating film formed by applying and curing the coating material is the layer (i) and the inorganic vapor deposition layer (ii) is formed on the layer (i), it is effective for the adhesion between the layer (i) and the layer (ii). Works.

2 is a ¹ H nuclear magnetic resonance spectrum of the substance produced in Synthesis Example 1. FIG. 2 is a ¹ H nuclear magnetic resonance spectrum of the substance produced in Synthesis Example 2. FIG. 2 is a ¹ H nuclear magnetic resonance spectrum of the material produced in Example 1. FIG. 3 is a ¹³ C nuclear magnetic resonance spectrum of the material produced in Example 1. FIG.

［一般式（Ｉ）中において、Ｒ¹は紫外線吸収性の有機基、Ｒ²は下記一般式（ＩＩ）

（一般式（ＩＩ）中において、Ｙは炭素数１〜１２のアルキレン基、Ｒ⁴は水素原子又はメチル基である。）
で表される有機基、Ｒ³は炭素数１〜６のアルキル基、ｎは０又は１である。］ Hereinafter, the ultraviolet-absorbing organosilicon compound, paint and laminate of the present invention will be described in detail.
UV-absorbing organosilicon compound The UV-absorbing organosilicon compound in the present invention is an UV-absorbing organosilicon compound represented by the following general formula (I).

[In the general formula (I), R ¹ is an ultraviolet-absorbing organic group, R ² is the following general formula (II)

(In general formula (II), Y is an alkylene group having 1 to 12 carbon atoms, and R ⁴ is a hydrogen atom or a methyl group.)
R ³ is an alkyl group having 1 to 6 carbon atoms, and n is 0 or 1. ]

  The ultraviolet ray in the present invention means light in the region of 200 to 400 nm. The light may be a single wavelength or may include a plurality of wavelengths. In the case of light including a plurality of wavelengths, if it includes a region of 200 to 400 nm, it is regarded as light including ultraviolet rays, and is preferably a target of light to be absorbed in the present invention. Specific examples of light including a plurality of wavelengths include sunlight and ultraviolet lamps. The ultraviolet-absorbing organosilicon compound of the present invention can absorb wavelengths in the region of 200 to 400 nm contained in these sunlight and ultraviolet lamps, and can reduce harmful effects of ultraviolet rays. The ultraviolet-absorbing organosilicon compound of the present invention may be used as an isolated single substance, or used as a mixture containing one or more selected from the group of compounds included in the above formula. May be provided.

In the general formula (I), R ¹ is an ultraviolet-absorbing organic group, preferably monovalent. The UV-absorbing organic group can include one or more structures selected from the group consisting of benzophenone, triazine, benzotriazole, resorcinol, and distyryl ketone, and includes benzophenone, triazine, and benzotriazole. Preferably, it is a benzophenone type. The UV-absorbing organic group preferably has an absorption maximum at 200 to 400 nm, more preferably 230 to 390 nm, and still more preferably 250 to 380 nm.

［一般式（ＩＩＩ）中において、Ａ¹〜Ａ¹⁰はそれぞれ独立に、水素原子、水酸基、炭素数１〜５のアルキル基、又は、下記式（ＩＶ）

（一般式（ＩＶ）中において、Ｙ’は炭素数１〜１２のアルキレン基であり、酸素側で一般式（ＩＩＩ）に含まれるベンゼン環と直結し、Ｙ’側で一般式（Ｉ）に含まれるケイ素原子と直結する。）
で表される基で、式（ＩＩＩ）は少なくとも一つの水酸基と少なくとも一つの式（ＩＶ）で表される基を有する。］ When R ¹ is a benzophenone-based organic group, it can be preferably selected from the group of organic groups represented by the following general formula (III).

[In General Formula (III), A ^{1 to} A ¹⁰ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or the following formula (IV):

(In General Formula (IV), Y ′ is an alkylene group having 1 to 12 carbon atoms, directly connected to the benzene ring contained in General Formula (III) on the oxygen side, and represented by General Formula (I) on the Y ′ side. (Directly connected to the silicon atoms contained.)
In which the formula (III) has at least one hydroxyl group and at least one group represented by the formula (IV). ]

A ¹ , A ⁵ , A ⁶ and A ¹⁰ can be selected independently, but at least one is particularly preferably a hydroxyl group. When at least one of A ¹ , A ⁵ , A ⁶ , and A ¹⁰ is a hydroxyl group, it interacts with the carbonyl group in the general formula (III) and easily absorbs ultraviolet rays. A ² , A ³ , A ⁴ , A ⁷ , A ⁸ , and A ⁹ can be independently selected, but at least one of them is more preferably a group represented by the general formula (IV), and less steric hindrance. From the viewpoint of absence, A ³ and / or A ⁸ is particularly preferably a group represented by the general formula (IV). A ^{1 to} A ¹⁰ may each independently introduce an alkyl group having 1 to 5 carbon atoms for the purpose of increasing solubility. If there is no particular molecular design purpose, a hydrogen atom is selected. Also good.

  In general formula (IV), Y 'is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms. Such alkylene groups include methylene, ethylene, propylene, tri (methylene), tetra (methylene), isobutylene, penta (methylene), hexa (methylene), hexylene, cyclohexylene, heptylene, octylene, ethylhexylene and the like. A chain type, branched type or cyclic alkylene group can be mentioned, and a tri (methylene) group is more preferable in terms of synthetic chemistry.

（構造式（Ｖ）中において、右末端のＣＨ₂は置換基の結合位置であり、ＣＨ₂から一般式（Ｉ）中のケイ素原子に結合する。） Specific examples of R ¹ represented by the general formula (III) and the general formula (IV) include organic groups represented by the following structural formula (V).

(In Structural Formula (V), CH _{2 at} the right end is the bonding position of the substituent, and bonds from CH ₂ to the silicon atom in General Formula (I).)

［一般式（ＶＩ）中において、Ｂ¹〜Ｂ¹⁵はそれぞれ独立に、水素原子、水酸基、炭素数１〜５のアルキル基、又は、下記式（ＩＶ）

（一般式（ＩＶ）中において、Ｙ’は炭素数１〜１２のアルキレン基であり、酸素側で一般式（ＶＩ）に含まれるベンゼン環と直結し、Ｙ’側で一般式（Ｉ）に含まれるケイ素原子と直結する。）
で表される基で、式（ＶＩ）は少なくとも一つの水酸基と少なくとも一つの式（ＩＶ）で表される基を有する。］ When R ¹ is a triazine-based organic group, it can be preferably selected from the group of organic groups represented by the following general formula (VI).

[In General Formula (VI), B ^{1 to} B ¹⁵ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or the following formula (IV):

(In the general formula (IV), Y ′ is an alkylene group having 1 to 12 carbon atoms, directly connected to the benzene ring contained in the general formula (VI) on the oxygen side, and represented by the general formula (I) on the Y ′ side. (Directly connected to the silicon atoms contained.)
In which the formula (VI) has at least one hydroxyl group and at least one group represented by the formula (IV). ]

B ³ , B ⁴ , B ⁸ , B ⁹ , B ¹³ and B ¹⁴ can be selected independently, but it is particularly preferred that at least one is a hydroxyl group. When at least one of B ³ , B ⁴ , B ⁸ , B ⁹ , B ¹³ and B ¹⁴ is a hydroxyl group, it interacts with the aromatic nitrogen atom in the general formula (IV) and easily absorbs ultraviolet rays. B ¹ , B ² , B ⁵ , B ⁶ , B ⁷ , B ¹⁰ , B ¹¹ , B ¹² , and B ¹⁵ can be independently selected, but at least one is a group represented by the general formula (IV) It is more preferable. B ^{1 to} B ¹⁵ may each independently introduce an alkyl group having 1 to 5 carbon atoms for the purpose of increasing solubility, etc. If there is no particular molecular design purpose, a hydrogen atom is selected. Also good.

  In general formula (IV), Y 'is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms. Such alkylene groups include methylene, ethylene, propylene, tri (methylene), tetra (methylene), isobutylene, penta (methylene), hexa (methylene), hexylene, cyclohexylene, heptylene, octylene, ethylhexylene and the like. A chain type, branched type or cyclic alkylene group can be mentioned, and a tri (methylene) group is more preferable in terms of synthetic chemistry.

［一般式（ＶＩＩ）中において、Ｃ¹〜Ｃ⁹はそれぞれ独立に、水素原子、水酸基、炭素数１〜５のアルキル基、又は、下記式（ＩＶ）

（一般式（ＩＶ）中において、Ｙ’は炭素数１〜１２のアルキレン基であり、酸素側で一般式（ＶＩＩ）に含まれるベンゼン環と直結し、Ｙ’側で一般式（Ｉ）に含まれるケイ素原子と直結する。）
で表される基で、式（ＶＩＩ）は少なくとも一つの水酸基と少なくとも一つの式（ＩＶ）で表される基を有する。］ When R ¹ is a benzotriazole-based organic group, it can be preferably selected from the group of organic groups represented by the following general formula (VII).

[In General Formula (VII), C ^{1 to} C ⁹ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or the following formula (IV):

(In General Formula (IV), Y ′ is an alkylene group having 1 to 12 carbon atoms, directly connected to the benzene ring contained in General Formula (VII) on the oxygen side, and represented by General Formula (I) on the Y ′ side. (Directly connected to the silicon atoms contained.)
In which the formula (VII) has at least one hydroxyl group and at least one group represented by the formula (IV). ]

  In general formula (IV), Y 'is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms. Such alkylene groups include methylene, ethylene, propylene, tri (methylene), tetra (methylene), isobutylene, penta (methylene), hexa (methylene), hexylene, cyclohexylene, heptylene, octylene, ethylhexylene and the like. A chain type, branched type or cyclic alkylene group can be mentioned, and a tri (methylene) group is more preferable in terms of synthetic chemistry.

C ¹ and / or C ⁵ can be independently selected, but at least one is particularly preferably a hydroxyl group. When C ¹ and / or C ⁵ is a hydroxyl group, it interacts with the triazole nitrogen atom in the general formula (VII) and easily absorbs ultraviolet rays. C ² , C ³ , C ⁴ , C ⁶ , C ⁷ , C ⁸ , and C ⁹ can be independently selected, but at least one is more preferably a group represented by the general formula (IV). C ^{1 to} C ⁹ may each independently introduce an alkyl group having 1 to 5 carbon atoms for the purpose of increasing solubility. If there is no particular molecular design purpose, a hydrogen atom is selected. Also good.

（一般式（ＩＩ）中において、Ｙは炭素数１〜１２のアルキレン基、Ｒ⁴は水素原子又はメチル基である。） In general formula (I), R ² is an organic group represented by the following general formula (II).

(In general formula (II), Y is an alkylene group having 1 to 12 carbon atoms, and R ⁴ is a hydrogen atom or a methyl group.)

  In general formula (II), Y is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms. Such alkylene groups include methylene, ethylene, propylene, tri (methylene), tetra (methylene), isobutylene, penta (methylene), hexa (methylene), hexylene, cyclohexylene, heptylene, octylene, ethylhexylene and the like. A chain type, a branched type or a cyclic alkylene group can be mentioned, and an ethylene group is more preferable in terms of synthetic chemistry.

In the general formula (II), R ⁴ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

In the general formula (I), R ³ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. Specific examples of R ³ include linear, branched or cyclic such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, propyl, hexyl and cyclohexyl groups. And a methyl group is preferable. For the purpose of adjusting reactivity, it is also preferable to use an ethyl group, an isopropyl group, or the like.

  In general formula (I), n is preferably 0 or 1. Since the normal silicon compound has a silicon valence of 4, n can be selected from an integer of 0 to 3. However, when n is 2 or 3, it has a high resistance to blending into an active energy ray-curable coating. This is not preferable because scratch resistance cannot be expected. When n is 0, it is particularly preferable since high scratch resistance can be expected when blended into an active energy ray-curable coating. When n is 1, high scratch resistance and flexibility can be expected when blended in an active energy ray-curable coating, and is particularly preferable. In consideration of the balance between scratch resistance and flexibility, a mixture in which n is 0 and 1 may be used.

Method for synthesizing UV-absorbing organosilicon compound The UV-absorbing organosilicon compound of the present invention may be synthesized by a known method, but the synthesis method shown below is easily produced by a chemical reaction process including simple unit operations. It is more preferable because it is possible.

The precursor of the substituent R ¹ is preferably a compound having two or more phenolic hydroxyl groups. These compounds are readily available. Examples of R ¹ include benzophenone-based compounds such as 2,4-dihydroxybenzophenone and 4,8-dihydroxybenzophenone. When R ¹ is a triazine group, 4- (4,6-diphenyl-1,3,5-triazin-2-yl) -1,3-benzenediol, 4- (4,6-diphenyl-1, 3,5-triazin-2-yl) -6-methyl-1,3-benzenediol, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3 , 5-triazine and the like. When R ¹ is a triazole group, 2- (2H-benzotriazol-2-yl) -1,4-benzenediol, 2- (5-methyl-2H-benzotriazol-2-yl) -1,4 -A benzenediol etc. can be illustrated.

For the compound having preferably two or more phenolic hydroxyl groups as a precursor, 1 equivalent of ω-haloalkene is reacted with the hydroxyl group in the presence of a base. The ω-haloalkene is a group of compounds such as vinyl bromide, vinyl chloride, allyl bromide, allyl chloride, 4-bromo-1-butene. Examples of the base include inorganic bases such as sodium hydroxide, sodium carbonate, sodium hydrogencarbonate and potassium carbonate, and organic bases such as triethylamine, diisopropylamine, imidazole, DABCO, DBU and DBN.
The reaction can be carried out in a solvent as necessary. As the solvent, one or more selected from the group consisting of hydrocarbon nonpolar solvents, aprotic polar solvents, protic polar solvents and the like can be used, and aprotic polar solvents are more preferable. The reaction can be carried out using a catalyst as necessary. Examples of the catalyst include inorganic catalysts such as transition metal complexes and organic catalysts such as nucleophilic catalysts, and nucleophilic catalysts are particularly suitable. Examples of such nucleophilic catalysts include iodine salts such as sodium iodide and potassium iodide, organophosphorus compounds such as triphenylphosphine and triphenylphosphite, N-heterocyclic carbenes such as dimethylimidazol-2-ylidene, and the like. Can be illustrated. These nucleophilic catalysts perform nucleophilic attack kinetically predominantly on the halogen moiety of ω-haloalkene and form a leaving group, thereby accelerating the subsequent nucleophilic substitution reaction of the phenolic hydroxyl group. There is. These reactions are quantitative, and by-product salts can be easily removed by washing with water to obtain a precursor having an alkenyl ether moiety.

The precursor having an alkenyl ether moiety is reacted with a monohydrogen trialkoxysilane in the presence of a transition metal catalyst using a solvent as necessary. Examples of monohydrogenialalkoxysilanes include trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM-03”), triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBE-03”) and the like. It can be illustrated.
As the transition metal catalyst, a transition metal complex containing platinum, palladium, nickel, rhodium, ruthenium, iron or the like can be used, and a platinum group element is particularly preferable. Examples of such a catalyst include a Speier catalyst, a Karsted catalyst, and chloroplatinic (IV) acid. These reactions are quantitative, and even if unreacted monohydrogenalkoxysilane is present in the system, a high-purity trialkoxysilyl can be easily obtained by distilling off the solvent simultaneously with the solvent.

The trialkoxysilyl product is reacted with ω-hydroxyalkenyl (meth) acrylates. Specific examples of ω-hydroxyalkenyl (meth) acrylates include hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, Examples thereof include hydroxybutyl methacrylate, hydroxyoctyl acrylate and hydroxyoctyl methacrylate, and hydroxyethyl acrylate (abbreviation HEA) is particularly preferable.
The reaction is preferably performed in the presence of a catalyst. Examples of the catalyst include titanium, aluminum, zinc, amine and phosphorus. An amine-based nucleophilic catalyst such as dimethylaminopyridine (abbreviation DMAP) is preferable because of its reactivity and easy removal. You may perform reaction under reduced pressure as needed. If the catalyst is amine based, the removal of the catalyst can be performed with an acidic solid. Such acidic solids can include one or more selected from the group consisting of activated clay, aluminum silicate, silica, alumina, montmorillonite, kaolin, diatomaceous earth, ion exchange resin and the like.
The reaction can be used in combination with a polymerization inhibitor. Examples of the polymerization inhibitor include di-tert-butylhydroxytoluene (abbreviation BHT). Acidic solids can be easily removed by filtration.

The ω-hydroxyalkenyl (meth) acrylate is preferably used in an amount of about 2 to 3 equivalents with respect to the silyl group contained in the trialkoxysilyl body. When about 2 equivalents are used, a derivative in which n in the general formula (I) is 1 is obtained as the main component. When about 3 equivalents are used, a derivative in which n in general formula (I) is 0 is obtained as the main component. Here, the “degree” of about 2 to 3 equivalents may mean “small excess”. In general, even in the case of a stoichiometric reaction, a component that does not cause a problem even when it is excessive may be used in a small excess in anticipation of completion and early termination of the reaction.
In this reaction, ω-hydroxyalkenyl (meth) acrylates may be used in a small excess as required. The meaning of a small excess varies depending on the reaction, but in the case of this reaction, there may be an excess of preferably 5 to 50%, more preferably 10 to 20%. The ω-hydroxyalkenyl (meth) acrylates remaining in the system after the reaction with the alcohol having 1 to 6 carbon atoms generated as the reaction proceeds can be easily removed by heating under reduced pressure. Can do.

  Although the ultraviolet-absorbing organosilicon compound of the present invention can be easily produced from commercially available general materials as described above, it exhibits excellent properties. In particular, the unit operations performed after the reaction are only washing with water, filtration and distillation under reduced pressure, but they are compounds that can withstand practical use without performing complicated purification such as distillation or column chromatography, and are industrially useful.

Active energy ray-curable coating material The ultraviolet-absorbing organosilicon compound of the present invention can be suitably used as an ultraviolet absorber for an active energy ray-curable coating material. The active energy ray-curable coating material may contain (α) polyfunctional (meth) acrylate, (β) acrylic polymer, (γ) inorganic oxide fine particles, (δ) light stabilizer, and the like.

(Α) Polyfunctional (meth) acrylate The polyfunctional (meth) acrylate that can be used in the active energy ray-curable coating using the ultraviolet absorbing organic silicon compound of the present invention is not particularly limited. The following can be used. Methyl methacrylate (abbreviation MMA), methyl acrylate (abbreviation MA), ethyl methacrylate, ethyl acrylate, hydroxyethyl acrylate (abbreviation HEA), hydroxyethyl methacrylate (abbreviation HEMA), hydroxypropyl acrylate, acrylic acid 4 -Hydroxylbutyl, isobutyl acrylate, tert-butyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, lauryl acrylate, stearyl acrylate, isostearyl acrylate, isonorbornyl acrylate, tetrahydrofurfuryl acrylate , Acrylic acid (methoxyethyl), methoxypolyethylene glycol acrylate, acrylic acid (2-methyl-2-ethyl-1,3-dioxolan-4-yl), acrylic acid [{cyclo Monoesters such as xanthspiro-2- (1,3-dioxolan-4-yl)} methyl] and acrylic acid {(3-ethyloxetane-3-yl) methyl}; ethylene glycol diacrylate, propylene glycol diacrylate, butane Diol diacrylate, pentanediol diacrylate, hexanediol diacrylate, heptanediol diacrylate, octanediol diacrylate, nonanediol diacrylate, decanediol diacrylate, glycerin-1,2-diacrylate, glycerin-1,3-di Acrylate, pentaerythritol diacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, tricyclodecane dimethanol diacrylate, dipropylene glycol diacrylate Diesters such as rate and tripropylene glycol diacrylate; glycerin triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol triacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated glycerin triacrylate, ethoxylated trimethylol Polyvalent esters such as propane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, trimethylolpropane trimethacrylate, trispentaerythritol octaacrylate; acryloyloxymethyltri Methoxysilane, Acryloyloxymethyldimethoxymethylsilane, acryloyloxymethylmethoxydimethylsilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyldimethoxymethylsilane, methacryloyloxymethylmethoxydimethylsilane, 2-acryloyloxyethyltrimethoxysilane, 2-acryloyl Oxyethyldimethoxymethylsilane, 2-acryloyloxyethylmethoxydimethylsilane, 2-methacryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyldimethoxymethylsilane, 2-methacryloyloxyethylmethoxydimethylsilane, 3-acryloyloxypropyl Trimethoxysilane, 3-acryloyloxypropyldimethoxymethylsilane 3-acryloyloxypropylmethoxydimethylsilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyloxypropylmethoxydimethylsilane, 8-acryloyloxyoctyltrimethoxysilane, 8 -Methacryloyloxyoctyltrimethoxysilane, acryloyloxymethyltriethoxysilane, acryloyloxymethyldiethoxymethylsilane, acryloyloxymethylethoxydimethylsilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyldiethoxymethylsilane, methacryloyl Oxymethylethoxydimethylsilane, 2-acryloyloxyethyltriethoxysila 2-acryloyloxyethyldiethoxymethylsilane, 2-acryloyloxyethylethoxydimethylsilane, 2-methacryloyloxyethyltriethoxysilane, 2-methacryloyloxyethyldiethoxymethylsilane, 2-methacryloyloxyethylethoxydimethylsilane , 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyldiethoxymethylsilane, 3-acryloyloxypropylethoxydimethylsilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyldiethoxymethylsilane 3-methacryloyloxypropylethoxydimethylsilane, 8-acryloyloxyoctyltriethoxysilane, 8-methacryloyl And polyvalent esters such as basic hydrolysis condensates of (meth) acryloyloxyalkylenealkoxysilanes such as ruoxyoctyltriethoxysilane.

  Monoesters can be used in an amount of 0 to 70% by mass, more preferably 0 to 60% by mass, and still more preferably 0 to 50% by mass with respect to the total amount of component (α). . The diester can be used in an amount of 1% by mass to 30% by mass, more preferably 2% by mass to 25% by mass, and still more preferably 5% by mass to 20% by mass with respect to the total amount of the esters. The polyvalent esters can be used in an amount of 50% by mass to 99% by mass, more preferably 50% by mass to 90% by mass, and still more preferably 50% by mass to 80% by mass with respect to the total amount of esters. Although monoesters are optional components, they are important components from the viewpoint of solvent-free (lower solvent) coating and can be used in place of solvents. In addition, when mix | blending monoesters, it can be 3 mass% or more. When the ratio of monoesters is more than 70% by mass, the film may be fragile. When the proportion of the diester is less than 1% by mass, the flexibility of the film may be insufficient, and when it is more than 30% by mass, the scratch resistance may not be sufficient. The polyvalent ester is an essential component, but if it is less than 50% by mass, the hardness of the film may not be sufficient.

(Β) Acrylic polymer The acrylic polymer that can be used in the active energy ray-curable coating material using the ultraviolet-absorbing organosilicon compound of the present invention is not particularly limited. For example, the following general formula (VIII) The vinyl polymer represented by these can be used.
poly-[(D) _d- co- (E) _e- co- (F) _f ] (VIII)
(In the formula, D, E and F each independently represent a vinyl monomer unit, square brackets and -co- represent a random copolymer, and d, e and f represent molar fractions. D is a vinyl monomer having an alkoxysilyl group, d is a mole fraction such that the monomer D is 1 to 50% by mass with respect to the total amount of the polymer, and E is an ultraviolet absorbing vinyl type Wherein e is a molar fraction such that the monomer E is 5 to 40% by mass with respect to the total amount of the polymer, and F is another monomer copolymerizable with these vinyl monomers. Wherein f is a mole fraction such that monomer F is [100- (content of monomer D)-(content of monomer E)] mass% with respect to the total amount of polymer. .)

  The vinyl monomer unit D is preferably formed by addition polymerization of a vinyl monomer having an alkoxysilyl group. Examples of vinyl monomers having an alkoxysilyl group include acryloyloxymethyltrimethoxysilane, acryloyloxymethyldimethoxymethylsilane, acryloyloxymethylmethoxydimethylsilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyldimethoxymethylsilane, Acryloyloxymethylmethoxydimethylsilane, 2-acryloyloxyethyltrimethoxysilane, 2-acryloyloxyethyldimethoxymethylsilane, 2-acryloyloxyethylmethoxydimethylsilane, 2-methacryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyl Dimethoxymethylsilane, 2-methacryloyloxyethylmethoxydimethylsilane, 3-acrylic Yloxypropyltrimethoxysilane, 3-acryloyloxypropyldimethoxymethylsilane, 3-acryloyloxypropylmethoxydimethylsilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyl Oxypropylmethoxydimethylsilane, 8-acryloyloxyoctyltrimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, acryloyloxymethyltriethoxysilane, acryloyloxymethyldiethoxymethylsilane, acryloyloxymethylethoxydimethylsilane, methacryloyloxy Methyltriethoxysilane, methacryloyloxymethyldiethoxymethylsilane, meta Acryloyloxymethylethoxydimethylsilane, 2-acryloyloxyethyltriethoxysilane, 2-acryloyloxyethyldiethoxymethylsilane, 2-acryloyloxyethylethoxydimethylsilane, 2-methacryloyloxyethyltriethoxysilane, 2-methacryloyl Oxyethyldiethoxymethylsilane, 2-methacryloyloxyethylethoxydimethylsilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyldiethoxymethylsilane, 3-acryloyloxypropylethoxydimethylsilane, 3-methacryloyloxy Pripyrutriethoxysilane, 3-methacryloyloxypropyldiethoxymethylsilane, 3-methacryloyloxypropyl (Meth) acryloyloxyalkylenealkoxysilanes such as ethoxydimethylsilane, 8-acryloyloxyoctyltriethoxysilane, 8-methacryloyloxyoctyltriethoxysilane; vinyltrimethoxysilane, vinyldimethoxymethylsilane, vinylmethoxydimethylsilane, allyl Trimethoxysilane, allyldimethoxymethylsilane, allylmethoxydimethylsilane, methallyltrimethoxysilane, methallyldimethoxymethylsilane, methallylmethoxydimethylsilane, 4-trimethoxysilyl-1-butene, 5-trimethoxysilyl-1-pentene , 6-trimethoxysilyl-1-hexene, 7-trimethoxysilyl-1-heptene, 8-trimethoxysilyl-1-octene, etc. N-alkoxysilanes; aromatic unsaturated alkoxysilanes such as p-trimethoxysilylstyrene, 1,4-divinyl-2-trimethoxysilylbenzene, p-trimethoxysilyl-α-methylstyrene; One or more selected from the group can be mentioned, and 3-methacryloyloxypropyltrimethoxysilane (for example, product name “KBM-503” manufactured by Shin-Etsu Chemical Co., Ltd.) is available from the viewpoint of availability and reactivity. preferable.

  The vinyl monomer unit D can be copolymerized with other monomer units E and F at a molar fraction d of 1 to 50% by mass relative to the total amount of the polymer (VIII), preferably 2 to 40 It is 5 mass%, More preferably, it is 5-35 mass%. When the vinyl monomer unit D is less than 1% by mass with respect to the total amount of the polymer, it may be difficult to form a network with the inorganic fine particle component, and when it exceeds 50% by mass, the storage stability and weather resistance may be reduced. There is.

  The vinyl monomer unit E is preferably formed by addition polymerization of a vinyl monomer having an ultraviolet absorbing group. Any vinyl monomer having an ultraviolet absorbing group can be used as long as it has an ultraviolet absorbing group and a vinyl polymerizable group. The ultraviolet ray in the present invention refers to light having a wavelength of about 200 to 400 nm. Examples of the ultraviolet absorbing group include organic groups having benzotriazoles, benzophenones, resorcinols, triazines and the like. Examples of the vinyl polymerizable group include organic groups having a vinyl group, an allyl group, a styryl group, an acrylic group, a methacryl group, and the like.

  Specific examples of such a vinyl monomer having an organic ultraviolet absorbing group include a (meth) acrylic monomer having an ultraviolet absorbing group in the molecule, represented by the following general formula (IX): The benzotriazole type compound represented, and the benzophenone type compound represented by the following general formula (X) can be mentioned.

（式中、Ｘは水素原子又は塩素原子を示す。Ｒ⁵は水素原子、メチル基、又は炭素数４〜８の第３級アルキル基を示す。Ｒ⁶は直鎖状又は分岐鎖状の炭素数２〜１０のアルキレン基を示す。Ｒ⁷は水素原子又はメチル基を示す。ｑは０又は１を示す。）

(In the formula, X represents a hydrogen atom or a chlorine atom. R ⁵ represents a hydrogen atom, a methyl group, or a tertiary alkyl group having 4 to 8 carbon atoms. R ⁶ represents a linear or branched carbon. And represents an alkylene group having a number of 2 to 10. R ⁷ represents a hydrogen atom or a methyl group, and q represents 0 or 1.)

（式中、Ｒ⁷は上記と同じ意味を示す。Ｒ⁸は置換又は非置換の直鎖状もしくは分岐鎖状の炭素数２〜１０のアルキレン基を示す。Ｒ⁹は水素原子又は水酸基を示す。Ｒ¹⁰は水素原子、水酸基、又は炭素数１〜６のアルコキシ基を示す。）

(Wherein R ⁷ has the same meaning as described above. R ⁸ represents a substituted or unsubstituted linear or branched alkylene group having 2 to 10 carbon atoms. R ⁹ represents a hydrogen atom or a hydroxyl group. R ¹⁰ represents a hydrogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.)

In the general formula (IX), examples of the tertiary alkyl group having 4 to 8 carbon atoms represented by R ⁵ include a tert-butyl group, a tert-pentyl group, a tert-hexyl group, a tert-heptyl group, and a tert-butyl group. An octyl group, a di tert-octyl group, etc. can be mentioned.
Examples of the linear or branched alkylene group having 2 to 10 carbon atoms represented by R ⁶ include an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a 1,1-dimethyltetramethylene group, and a butylene group. Octylene group, decylene group and the like.

In the general formula (X), the linear or branched alkylene group having 2 to 10 carbon atoms represented by R ⁸ is the same as those exemplified for R ⁶ above, or hydrogen thereof. The group etc. which substituted a part of atom with the halogen atom can be mentioned. Examples of the alkoxy group represented by R ¹⁰ include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

Specific examples of the benzotriazole-based compound represented by the general formula (IX) include, for example, 2- (2′-hydroxy-5 ′-(meth) acryloxyphenyl) -2H-benzotriazole,
2- (2′-hydroxy-3′-tert-butyl-5 ′-(meth) acryloxymethylphenyl) -2H-benzotriazole,
2- [2′-hydroxy-5 ′-(2- (meth) acryloxyethyl) phenyl] -2H-benzotriazole,
2- [2′-hydroxy-3′-tert-butyl-5 ′-(2- (meth) acryloxyethyl) phenyl] -5-chloro-2H-benzotriazole,
2- [2′-hydroxy-3′-methyl-5 ′-(8- (meth) acryloxyoctyl) phenyl] -2H-benzotriazole and the like can be mentioned.

Specific examples of the benzophenone compound represented by the general formula (X) include, for example,
2-hydroxy-4- (2- (meth) acryloxyethoxy) benzophenone,
2-hydroxy-4- (4- (meth) acryloxybutoxy) benzophenone,
2,2′-dihydroxy-4- (2- (meth) acryloxyethoxy) benzophenone,
2,4-dihydroxy-4 ′-(2- (meth) acryloxyethoxy) benzophenone,
2,2 ′, 4-trihydroxy-4 ′-(2- (meth) acryloxyethoxy) benzophenone,
2-hydroxy-4- (3- (meth) acryloxy-2-hydroxypropoxy) benzophenone,
And 2-hydroxy-4- (3- (meth) acryloxy-1-hydroxypropoxy) benzophenone.

As the UV-absorbing vinyl monomer, a benzotriazole compound represented by the formula (IX) is preferable, and 2- [2′-hydroxy-5 ′-(2- (meth) acryloxyethyl) is particularly preferable. Phenyl] -2H-benzotriazole is preferably used.
Furthermore, you may use the said ultraviolet absorptive vinyl-type monomer individually by 1 type or in mixture of 2 or more types.

  The vinyl monomer unit E can be copolymerized with other monomer units D and F at a molar fraction e of 5 to 40% by mass relative to the total amount of the polymer (VIII), preferably 5 to 30. It is 8 mass%, More preferably, it is 8-25 mass%. If the vinyl monomer unit E is less than 5% by mass relative to the total amount of the polymer, the weather resistance may be insufficient, and if it exceeds 40% by mass, the adhesion to the substrate may be reduced.

  Next, the other vinyl monomer unit F copolymerizable with the vinyl monomer units D and E is not particularly limited as long as it is a copolymerizable monomer, but has a (meth) acrylic structure having a cyclic hindered amine structure. Examples include monomers, (meth) acrylic acid esters, (meth) acrylonitrile, (meth) acrylamides, alkyl vinyl ethers, alkyl vinyl esters, styrene, and derivatives thereof.

  Specific examples of the (meth) acrylic monomer having a cyclic hindered amine structure include 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 1,2,2,6,6-pentamethyl-4. -Piperidinyl methacrylate and the like.

Specific examples of (meth) acrylic acid esters and derivatives thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid. n-butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, (meth) acrylic acid n-hexyl, isohexyl (meth) acrylate, n-heptyl (meth) acrylate, isoheptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylic acid Isooctyl, n-nonyl (meth) acrylate, isononyl (meth) acrylate, (meth) N-decyl crylate, isodecyl (meth) acrylate, n-undecyl (meth) acrylate, n-dodecyl (meth) acrylate, lauryl (meth) acrylate, palmityl (meth) acrylate, (meth) acrylic acid Stearyl, cyclohexyl (meth) acrylate, 4-methylcyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth ) (Meth) acrylic acid esters of monohydric alcohols such as dicyclopentenyloxyethyl acrylate and benzyl (meth) acrylate;
2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-methoxybutyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-methoxybutyl ( Of alkoxy (poly) alkylene glycols such as meth) acrylate, methoxypolyethylene glycol (meth) acrylate (the number of ethylene glycol units is, for example, 2 to 20), and methoxypolypropylene glycol (meth) acrylate (the number of propylene glycol units is, for example, 2 to 20). (Meth) acrylic acid esters;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( (Meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate (the number of ethylene glycol units is, for example, 2 to 20), polypropylene glycol mono (meth) acrylate (the number of propylene glycol units) Are mono (meth) acrylic acid esters of polyhydric alcohols such as 2-20);
Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate (the number of ethylene glycol units is, for example, 2 to 20), polypropylene glycol di (meth) acrylate (the number of propylene glycol units is, for example, 2 To 20) poly (meth) acrylic acid esters of polyhydric alcohols;
Succinic acid mono [2- (meth) acryloyloxyethyl], succinic acid di [2- (meth) acryloyloxyethyl], adipic acid mono [2- (meth) acryloyloxyethyl], adipic acid di [2- (meta ) Acryloyloxyethyl], mono [2- (meth) acryloyloxyethyl] phthalate, di [2- (meth) acryloyloxyethyl] phthalate, and other nonpolymerizable polybasic acids and hydroxyalkyl (meth) acrylates (Poly) esters of
(Meth) acrylic acid 2-aminoethyl, (meth) acrylic acid 2- (N-methylamino) ethyl, (meth) acrylic acid 2- (N, N-dimethylamino) ethyl, (meth) acrylic acid 2- ( N-ethylamino) ethyl, (meth) acrylic acid 2- (N, N-diethylamino) ethyl, (meth) acrylic acid 3- (N, N-dimethylamino) propyl, (meth) acrylic acid 4- (N, Amino group-containing (meth) acrylic acid esters such as N-dimethylamino) butyl;
Mention may be made of epoxy group-containing (meth) acrylic acid esters such as glycidyl (meth) acrylate.

Specific examples of the derivative of (meth) acrylonitrile include α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-trifluoromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, vinylidene cyanide, and the like. it can.
Specific examples of (meth) acrylamide derivatives include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N- Methoxy (meth) acrylamide, N, N-dimethoxy (meth) acrylamide, N-ethoxy (meth) acrylamide, N, N-diethoxy (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-dimethylaminomethyl (meth) acrylamide, N- (2-dimethylamino) ethyl (meth) acrylamide, N, N′-methylenebis (meth) acrylamide, N, N'-ethylenebis (meth) acrylic Mention may be made of the bromide and the like.

Specific examples of the alkyl vinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, hexyl vinyl ether and the like.
Specific examples of the alkyl vinyl ester include vinyl formate, vinyl acetate, vinyl acrylate, vinyl butyrate, vinyl caproate, and vinyl stearate.
Specific examples of styrene and its derivatives include styrene, α-methylstyrene, vinyltoluene and the like.

Among these monomers, (meth) acrylic acid esters are preferable, and in particular, (meth) methyl acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( Isobutyl acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid 4-methylcyclohexyl, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and the like are preferable.
The vinyl-type monomer unit F can use the said monomer individually or in mixture of 2 or more types.

  The vinyl monomer unit F is [100- (content of monomer D)-(content of monomer E)]% by mass, that is, 10 to 94% by mass, based on the total amount of polymer (VIII). It can be copolymerized with other monomer units D and E at such a molar fraction f, preferably 20 to 94% by mass, more preferably 35 to 90% by mass. When the vinyl monomer unit F is less than 10% by mass relative to the total amount of the polymer, a coating appearance defect may occur. When it exceeds 94% by mass, crosslinking with inorganic fine particles is insufficient and durability is reduced. There is.

  The component (β) is preferably obtained by copolymerizing vinyl-based monomer units D, E, and F. In the copolymerization reaction, a radical polymerization initiator selected from peroxides such as dicumyl peroxide and benzoyl peroxide or azo compounds such as azobisisobutyronitrile is added to a solution containing these monomers, It can be easily obtained by reacting under heating (50 to 150 ° C., particularly 70 to 120 ° C. for 1 to 10 hours, particularly 3 to 8 hours).

  The weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) of the component (β) is preferably 1,000 to 300,000, particularly 5,000 to 250,000. If the molecular weight is too large, the viscosity becomes too high and it may be difficult to synthesize, or it may be difficult to handle, and if it is too small, it may cause poor appearance such as whitening of the coating film and weathering cracks, sufficient adhesion, durability, Weather resistance may not be obtained.

  As the component (β), those produced using the components described above may be used, or similar commercially available products may be used. As such commercial products, New Coat UVA-101, 102, 103, 104, Vanaresin UVA-5080, 55T, 55MHB, 7075, 73T (all manufactured by Shin-Nakamura Chemical Co., Ltd.) Product name).

  The acrylic polymer of component (β) may be a polycarbonate-based and / or polyester-based urethane-modified vinyl polymer. The polycarbonate-based and / or polyester-based urethane-modified vinyl polymer acts as an adhesion improver, and is a polycarbonate-based and / or polyester-based urethane-modified vinyl polymer. Polycarbonate-based and / or polyester-based urethane-modified vinyl polymers are separated from other components in the cured coating, and the concentration gradient in the thickness direction of the coating makes it possible to reduce the scratch resistance. It is considered that the affinity to the resin base material is increased and the adhesiveness is developed. The polycarbonate-based and / or polyester-based urethane-modified vinyl-based polymer is obtained by grafting a polycarbonate-based or polyester-based polyurethane to a vinyl-based polymer, and specifically, an aliphatic polycarbonate diol or an aliphatic polyester diol. A vinyl polymer having a polycarbonate-based or polyester-based polyurethane obtained from the reaction of styrene with an aromatic diisocyanate in the side chain is preferred. More preferably, it is a vinyl polymer having a polycarbonate urethane obtained from the reaction of an aliphatic polycarbonate diol and an aromatic diisocyanate in the side chain.

  Specific examples of the aliphatic polycarbonate diol include 1,4-tetramethylene type, 1,5-pentamethylene type, 1,6-hexamethylene type, 1,12-dodecane type, 1,4-cyclohexane type, A mixed type etc. can be mentioned. Examples of the aromatic diisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-xylene diisocyanate, naphthalene diisocyanate, and mixtures thereof. By reacting these in accordance with a conventional method, a polycarbonate-based polyurethane can be obtained.

As the monomer constituting the vinyl polymer, any monomer can be used as long as it contains a vinyl polymerizable group. Specific examples include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and (meth) acrylic. Acid, styrene, vinyl acetate and the like can be mentioned.
A vinyl polymer is obtained by polymerizing these monomers by a known method.

  A urethane-modified vinyl polymer that is dissolved in an organic solvent is preferable in terms of ease of synthesis and ease of handling. As the organic solvent, an organic solvent that dissolves a polycarbonate-based and / or polyester-based urethane-modified vinyl polymer component well and has a relatively high polarity is preferable. Specific examples of such organic solvents include alcohols such as isopropyl alcohol, n-butanol, isobutanol, tert-butanol and diacetone alcohol; ketones such as methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone and diacetone alcohol Ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate; ethyl acetate, propyl acetate, butyl acetate, cyclohexyl acetate Ester etc. can be mentioned.

  The molecular weight of the polycarbonate-based and / or polyester-based urethane-modified vinyl polymer is preferably 5,000 to 50,000 in terms of weight average molecular weight by GPC analysis based on polystyrene. Furthermore, it is more preferable that it is 7,000-40,000. If the weight average molecular weight is less than 5,000, sufficient adhesion to the organic resin substrate may not be exhibited, and if it exceeds 50,000, the transparency when formed into a cured film may be impaired, There is a possibility that the solubility in the composition is lowered or separated.

  The hydroxyl value of the polycarbonate-based and / or polyester-based urethane-modified vinyl polymer is preferably 10 or more in terms of the solid content of this component. More preferably, the solid content of this component is in the range of 20 to 100. When the hydroxyl value of this component is less than 10 in terms of solid content, the solubility in the composition is lowered, and this component may be separated.

  As the polycarbonate-based and / or polyester-based urethane-modified vinyl polymer component, commercially available products can be used. For example, Acryt 8UA-347, 357, 366 (polycarbonate-based) manufactured by Taisei Fine Chemical Co., Ltd. ), 140, 146, 301, 318 (polyester), etc. can be used.

(Γ) Inorganic oxide fine particles The inorganic oxide fine particles that can be used in the active energy ray-curable coating using the ultraviolet-absorbing organosilicon compound of the present invention are not particularly limited, and examples thereof include the following. Can be suitably used. One or more selected from the group of inorganic oxide fine particles such as silicon oxide, zinc oxide, titanium oxide, cerium oxide, and aluminum oxide are preferred.

(Δ) Light stabilizer The light stabilizer that can be used in the active energy ray-curable coating using the ultraviolet-absorbing organosilicon compound of the present invention is not particularly limited. For example, those listed below are suitable. Can be used. (Meth) acrylic monomers having a cyclic hindered amine structure, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, alkyl vinyl ether, alkyl vinyl ester, styrene, and derivatives thereof are preferable.

  Specific examples of the (meth) acrylic monomer having a cyclic hindered amine structure include 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 1,2,2,6,6-pentamethyl-4. -Piperidinyl methacrylate and the like.

(Ξ) Other components Other components that can be used in the active energy ray-curable coating using the ultraviolet-absorbing organosilicon compound of the present invention include those such as curing catalysts, photoinitiators, solvents, and leveling agents. Ingredients known as technical common sense can be added.

Mixing ratio of active energy ray-curable coating material The active energy ray-curable coating material using the ultraviolet-absorbing organosilicon compound of the present invention is a solid component of a base paint in which the above components (α) to (δ) and (ξ) are mixed. On the other hand, the ultraviolet-absorbing organosilicon compound of the present invention can be added preferably in an amount of 1 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 20% by mass. If it is less than 1% by mass, the ability to shield ultraviolet rays may not be sufficient. When it exceeds 40 mass%, adhesiveness with an organic resin base material may not be enough. However, according to the contrivance of the base paint, the possibility of blending 40% by mass or more is not disturbed. The compounding ratio of the components (α) to (δ) in the base paint is preferably 20 to 100 parts by mass, more preferably 20 to 100 parts by mass in 100 parts by mass, when the solid content of the base paint is 100 parts by mass. Is 30 to 89.9 parts by mass, particularly preferably 30 to 80 parts by mass. If it is less than 20 parts by mass, the strength of the film may be insufficient. The component (β) is preferably 5 to 30 parts by mass, more preferably 10 to 20 parts by mass in 100 parts by mass. If it is less than 5 parts by mass, the flexibility of the film may be insufficient. If it exceeds 30 parts by mass, the scratch resistance of the film may be insufficient. The component (γ) is preferably 5 to 30 parts by mass, more preferably 10 to 20 parts by mass in 100 parts by mass. An inorganic vapor deposition layer may be difficult to be formed as it is less than 5 mass parts. If it exceeds 30 parts by mass, the flexibility of the film may be insufficient. The component (δ) is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass in 100 parts by mass. If the amount is less than 0.1 parts by mass, the film may easily turn yellow. If it exceeds 10 parts by mass, the chemical stability of the film may be insufficient.

Coated article The active energy ray-curable coating material using the UV-absorbing organosilicon compound of the present invention forms a coated article having a cured coating layer (i) formed by applying and curing on at least one surface of an organic resin substrate. can do. The coated article has not only weather resistance and scratch resistance, but also has adhesion to an organic resin substrate and lamination of a cured film composed of an inorganic vapor-deposited layer. Organic resin base materials that can be used in the present invention are polycarbonate resin, polyethylene terephthalate resin, polyethylene resin, polypropylene resin, polyoxymethylene resin, polyacrylic resin, polyepoxy resin, polyphenol resin, polyetheretherketone resin, silicone resin. A single resin or one or more composites (including a multilayer body and / or a polymer alloy) selected from the group consisting of, and the like can be exemplified, and a polycarbonate resin is particularly preferable. The thickness of the organic resin substrate is preferably 0.1 to 100 mm, more preferably 1 to 10 mm, and still more preferably 4 to 8 mm. In special applications such as for bulletproof purposes, a substrate of about 100 mm may be preferred. In applications where lightness is also required, such as for automobiles, a substrate of about 1 to 10 mm may be preferred. If it is thinner than 0.1 mm, the weather resistance deterioration of the resin base material itself becomes significant, or the warpage at the time of curing becomes remarkable, or the organic resin base material may be deteriorated at the time of laminating a cured film composed of an inorganic vapor deposition layer. is there. In the present invention, the upper limit of the thickness of the organic resin base material is not particularly provided, but it is generally about 100 mm.
The film formed by applying and curing the active energy ray-curable coating material containing the ultraviolet absorbing organic silicon compound of the present invention to an organic resin substrate is preferably 0.1 to 50 μm, more preferably 1 to 30 μm, More preferably, it is 5-20 micrometers. If it is thinner than 0.1 μm, the weather resistance may not be sufficient. If it is thicker than 50 μm, a phenomenon that the film physical properties such as cracks deteriorate may occur.

Laminate A laminate obtained by laminating an inorganic vapor-deposited layer (ii) on a layer (i) obtained by applying and curing an active energy ray-curable paint containing the ultraviolet-absorbing organosilicon compound of the present invention to an organic resin. Shows extremely high scratch resistance and excellent weather resistance. The inorganic vapor deposition layer (ii) is not particularly limited as long as it is formed by a dry film forming method. For example, Si, Ti, Zn, Al, Ga, In, Ce, Bi, Sb, B And a layer mainly composed of at least one or more kinds of metals or metal oxides, nitrides, sulfides and the like having elements such as Zr, Sn, and Ta. In addition, for example, a diamond-like carbon film layer having high hardness and excellent insulating properties can be used. The method for laminating the inorganic vapor deposition layer is not particularly limited as long as it is a dry film formation method, for example, physical vapor phase such as resistance heating vapor deposition, electron beam vapor deposition, molecular beam epitaxy, ion beam deposition, ion plating, sputtering, etc. Examples thereof include dry deposition methods such as growth methods and chemical vapor deposition methods such as thermal CVD, plasma CVD, photo CVD, epitaxial CVD, atomic layer CVD, and catCVD. In this case, it is preferable that the thickness of an inorganic vapor deposition layer is 0.1-10 micrometers.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the examples, unless otherwise specified, compounds were identified using a Bruker (400M) nuclear magnetic resonance spectrometer. In the description of the resonance magnetic field, tetramethylsilane was used as an external standard, and resonance lines on the lower magnetic field side than the standard were shown as positive values in parts per million.

[Synthesis Example 1]
Synthesis of 4-allyl-2-hydroxybenzophenone A 5-L flask equipped with a mechanical stirring blade, a thermometer, a reflux tube, and a dropping funnel was charged with 2,4-dihydroxybenzophenone (428 g, 2 mol), and dimethylformamide (2 kg) was added. In addition, dissolved, potassium carbonate (276 g, 2 mol) and potassium iodide (2 g) were added. The mixture was heated to 60 ° C. and allyl bromide (242 g, 2 mol) was added dropwise. The reaction mixture was reacted at 60 ° C. for 6 hours. After the reaction, it was washed with water and distilled under reduced pressure to obtain 4-allyl-2-hydroxybenzophenone (500 g, 98%).
¹ H NMR (400 MHz, CDCl ₃ ) δ 12.66 (s, 1H), 7.75-7.35 (m, 6H), 6.53 (d, J = 2.4 Hz, 1H), 6.43 ( dd, J = 8.8, 2.4 Hz, 1H), 6.04 (m, 1H), 5.44 (dd, J = 17.2, 1.2 Hz, 1H), 5.33 (dd, J = 10.8, 1.2 Hz, 1H), 4.61 (d, J = 5.2 Hz, 2H). FIG. 1 shows a ¹ H nuclear magnetic resonance spectrum.

[Synthesis Example 2]
Synthesis of 4- (3′-trimethoxysilylpropoxy) -2-hydroxybenzophenone In a 2 L flask equipped with a mechanical stirring blade, a thermometer, a reflux tube, and a dropping funnel, 4-allyl-2-yl obtained in Synthesis Example 1 was used. Hydroxybenzophenone (300 g, 1.2 mol) and toluene (500 g) were added. To this was added a tetrahydrofuran (3 g) solution of chloroplatinic (IV) acid (0.3 g), and the mixture was stirred. Trimethoxysilane (145 g, 1.2 mol, “KBM-03” manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise from the dropping funnel. Along with the dropwise addition, heat generation to the extent of reflux was confirmed. After the reaction, silica gel (10 g, “silica gel N60” manufactured by Kanto Chemical Co., Inc.) was added and stirred. After filtration, the volatile component was distilled off to give 4- (3′-trimethoxysilylpropoxy) -2-hydroxybenzophenone. (400 g, 90%) was obtained.
¹ H NMR (400 MHz, CDCl ₃ ) δ 12.67 (s, 1H), 7.66-7.45 (m, 8H), 4.01 (t, J = 6.8 Hz, 2H), 3.59 ( s, 9H), 1.97-1.88 (m, 2H), 0.79 (t, J = 8 Hz, 1H). FIG. 2 shows the ¹ H nuclear magnetic resonance spectrum.

[Synthesis Example 3]
Synthesis of basic condensate of 3-acryloyloxypropyltrimethoxysilane A basic condensate of 3-acryloyloxypropyltrimethoxysilane was synthesized as one of the paint components (α). To a 2 L flask equipped with a mechanical stirring blade, thermometer, reflux tube, and dropping funnel, 3-acryloyloxypropyltrimethoxysilane (100 g, manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM-5103”) and isopropyl alcohol (200 g) was added. Tetramethylammonium hydroxide (7 g) and water (50 g) were added thereto and reacted at room temperature for 2 hours. Toluene (400 g) was added thereto and washed with water (200 g). In the organic layer after washing, a volatile component was distilled off under reduced pressure to obtain a condensate. The viscosity of the condensate was 5 Pa · s.

[Synthesis Example 4]
An acrylic polymer was synthesized as one of the synthetic coating components (β) of the acrylic polymer. A 2 L flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer was charged with 33.7 g of diacetone alcohol and heated to 80 ° C. under a nitrogen stream. Monomer mixed solution prepared in advance here:
γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBM-503”) 20 g (corresponding to the monomer unit D, the proportion of the monomer unit D in the polymer is 20% by mass),
2- [2′-hydroxy-5 ′-(2-methacryloxyethyl) phenyl] -2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd., product name “RUVA-93”) 15 g (corresponding to monomer unit E, heavy The proportion of the monomer unit E in the coalescence is 15% by mass),
60 g of methyl methacrylate (MMA), 5 g of glycidyl methacrylate (GMA) (corresponding to the monomer unit F, the proportion of the monomer unit F in the polymer is 65% by mass),
A mixture of 140 g of diacetone alcohol,
And initiator solution:
2,2′-azobis (2-methylbutyronitrile) 0.5 g,
A mixture of 40 g of diacetone alcohol,
A part of both was sequentially added and reacted at 80 ° C. for 30 minutes, and then both solutions were added dropwise at 80 to 90 ° C. over 20 minutes. Furthermore, it stirred at 80-90 degreeC for 5 hours, and obtained the acrylic polymer ((beta)) containing material.
The content is a diacetone alcohol solution containing 40% by mass of the polymer component (β). The polymer solution had a viscosity of 5 Pa · s, and the polymer component (β) had a weight average molecular weight of 6 × 10 ⁴ by GPC analysis in terms of polystyrene.

（式中、Ｍｅはメチル基を示す。）
で表される化合物１ａ（ｎ＝０）及び化合物１ｂ（ｎ＝１）の合成を行った。
機械攪拌羽根、温度計、ディーンスタークトラップを有する還流管を備えた２Ｌの４つ口褐色フラスコに、合成例２で得た４−（３’−トリメトキシシリルプロポキシ）−２−ヒドロキシベンゾフェノン（１８８ｇ、０．５ｍｏｌ）、アクリル酸ヒドロキシエチル（１７４ｇ、１．５ｍｏｌ）、４−ジメチルアミノピリジン（０．６ｇ）、ジ−ｔｅｒｔ−ブチルヒドロキシトルエン（０．３ｇ）を順次加えて、攪拌しながら内温が１００℃に達するまで加熱した。１００℃で２時間加熱したところ、メタノール（４５ｇ）がディーンスタークトラップに凝縮した。室温まで冷却した後、ケイ酸アルミニウム（１２ｇ、協和化学工業（株）製、製品名「キョーワード７００」）を加えて３０分攪拌した。反応後、固形分を加圧ろ過で除去し、ジ−ｔｅｒｔ−ブチルヒドロキシトルエン（０．１ｇ）を更に加えて、加熱（１００℃）減圧（１０ｍｍＨｇ）下で１時間攪拌した。橙色の液体（２５８ｇ、８２％収率）を得た。¹Ｈ ＮＭＲより、生成物は１ａと１ｂの物質量比約３：１の混合物であることが明らかとなった。
１ａの¹Ｈ ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ₃）δ１２．６６（ｓ、１Ｈ、Ａｒ−ＯＨ）、７．６５−７．４０（ｍ、５Ｈ、Ａｒ−Ｈ）、６．５４−６．３０（ｍ、６Ｈ、ＣＨ＝ＣＨ ₂）、６．２０−６．０８（ｍ、３Ｈ、Ａｒ−Ｈ）、５．９９−５．７６（ｍ、３Ｈ、ＣＨ＝ＣＨ₂）、４．３６−４．２１（ｍ、６Ｈ、ＳｉＯＣＨ₂ＣＨ ₂Ｃ（＝Ｏ））、４．０７−３．９４（ｍ、６Ｈ、ＳｉＯＣＨ ₂ＣＨ₂Ｃ（＝Ｏ））、１．９５−１．８５（ｍ、２Ｈ、ＡｒＯＣＨ ₂ＣＨ₂Ｓｉ）、０．８５−０．７６（ｍ、２Ｈ、ＡｒＯＣＨ₂ＣＨ ₂Ｓｉ）。図３に¹Ｈ核磁気共鳴スペクトルを示した。
１ａの¹³Ｃ ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ₃）δ１９９．９、１６６．３、１６５．９、１６５．２、１３５．２、１３１．３、１２８．８、１２８．２、１２８．１、１１３．０、１０７．５、１０１．６、６５．１、６１．０、２２．３、６．２。図４に¹³Ｃ核磁気共鳴スペクトルを示した。
１ｂの¹Ｈ ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ₃）（抜粋）δ２．１６（ｓ、３Ｈ、Ｓｉ（ＯＣＨ ₃））。
１ｂの¹³Ｃ ＮＭＲ（１００ＭＨｚ、ＣＤＣｌ₃）（抜粋）δ１９９．９、６９．９、６６．１、６１．８、５０．５、５．９。 [Example 1]
Synthesis of UV-absorbing organosilicon compound As the UV-absorbing organosilicon compound, the following general formula (XI)

(In the formula, Me represents a methyl group.)
The compound 1a (n = 0) and the compound 1b (n = 1) represented by these were synthesized.
To a 2 L four-necked brown flask equipped with a mechanical stirring blade, a thermometer, and a reflux tube having a Dean-Stark trap, 4- (3′-trimethoxysilylpropoxy) -2-hydroxybenzophenone (188 g) obtained in Synthesis Example 2 was added. , 0.5 mol), hydroxyethyl acrylate (174 g, 1.5 mol), 4-dimethylaminopyridine (0.6 g), and di-tert-butylhydroxytoluene (0.3 g) were added in that order while stirring. Heated until the temperature reached 100 ° C. When heated at 100 ° C. for 2 hours, methanol (45 g) condensed in the Dean-Stark trap. After cooling to room temperature, aluminum silicate (12 g, manufactured by Kyowa Chemical Industry Co., Ltd., product name “KYOWARD 700”) was added and stirred for 30 minutes. After the reaction, the solid content was removed by pressure filtration, di-tert-butylhydroxytoluene (0.1 g) was further added, and the mixture was stirred for 1 hour under heating (100 ° C.) and reduced pressure (10 mmHg). An orange liquid (258 g, 82% yield) was obtained. ¹ H NMR revealed that the product was a mixture of 1a and 1b in a mass ratio of about 3: 1.
1a of _{^{1 H NMR (400MHz, CDCl 3}} ) δ12.66 (s, 1H, Ar-O H), 7.65-7.40 (m, 5H, Ar- H), 6.54-6.30 ( m, 6H, CH = C H 2), 6.20-6.08 (m, 3H, Ar- H), 5.99-5.76 (m, 3H, C H = CH 2), 4.36 _{-4.21 (m, 6H, SiOCH 2} C H 2 C (= O)), 4.07-3.94 (m, 6H, SiOC H 2 CH 2 C (= O)), 1.95-1 .85 (m, 2H, ArOC H 2 CH 2 Si), 0.85-0.76 (m, 2H, ArOCH 2 C H 2 Si). FIG. 3 shows the ¹ H nuclear magnetic resonance spectrum.
¹³ C NMR of la (100 MHz, CDCl ₃ ) δ 199.9, 166.3, 165.9, 165.2, 135.2, 131.3, 128.8, 128.2, 128.1, 113.0 107.5, 101.6, 65.1, 61.0, 22.3, 6.2. FIG. 4 shows a ¹³ C nuclear magnetic resonance spectrum.
1b ¹ H NMR (400 MHz, CDCl ₃ ) (excerpt) δ 2.16 (s, 3H, Si (OC H ₃ )).
1b ¹³ C NMR (100 MHz, CDCl ₃ ) (excerpt) δ 199.9, 69.9, 66.1, 61.8, 50.5, 5.9.

[Example 2]
Production of active energy ray curable paint, coated article, laminate As a paint component (α) in a brown plastic bottle (100 mL),
The component of Synthesis Example 3 (9 g), trimethylolpropane triacrylate (abbreviation TMPT-A, 6 g), hexanediol diacrylate (abbreviation HDDA, 1 g),
As a paint component (β),
Component of Synthesis Example 4 (4 g (1.6 g as polymer solid content)), manufactured by Taisei Fine Chemical Co., Ltd., product name “Acryt 8UA-347” (1 g (0.3 g as polymer solid content)),
As paint components (γ) and (ξ),
A titanium oxide in which tin (5 mol%) and manganese (1 mol%) described in Japanese Patent No. 5704133 is dissolved is used as a nucleus, and a shell made of silicon oxide is formed at 25 mass% with respect to 75 mass% of the nucleus. The core-shell fine particles have a volume average 50% cumulative distribution diameter of the core fine particles measured by a dynamic light scattering method of the fine particles of 15 nm, and the volume average 50% cumulative distribution diameter of the core-shell fine particles is 20 nm. A dispersion obtained by dispersing certain core-shell fine particles (2 g) in colloidal ethanol (10 g) and cyclopentanol (15 g);
As a coating component (δ), 2,2,6,6-tetramethyl-4-piperidyl methacrylate (manufactured by ADEKA, product name “Adeka Stub LA-87”, 0.3 g),
As photoinitiators, 2-hydroxy-2-methyl-1-phenyl-1-propanone (abbreviation SB-PI703, 1.3 g) and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (abbreviation L-TPO, 0. 6g),
Each component (1 g) synthesized in Example 1 as an ultraviolet absorber was measured and stirred well to obtain a uniform coating composition.
The obtained paint was flow coated on one side of a polycarbonate organic resin substrate (5 mm thick), and stood vertically at about 70 ° at room temperature and allowed to stand for 5 minutes. After standing, it was placed horizontally in an oven at 80 ° C. and preheated for 5 minutes. After preheating, the resin substrate is placed in an ultraviolet irradiation device equipped with a belt conveyor (model “ECS-401XN2” manufactured by Eye Graphics Co., Ltd.), and the coating is cured by irradiating a dose of 600 mJ / cm ² An article was obtained.
With respect to the obtained coated article, a laminate was produced by the method described in the literature (Journal of the American Chemical Society, 2006, Vol. 128, page 11018). Under vacuum induced by an RF coil, oxygen, argon, and tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KBE-04”) are supplied as source gases to generate plasma to generate an inorganic vapor deposition layer. Formed. As an experimental apparatus, a Pyrex (registered trademark) tube having an inner diameter of 25 mm was maintained at a vacuum degree of 5 × 10 ⁻⁷ Torr, and a coil was formed by winding a rough drawn copper wire (JIS C 3002).

The obtained coated article was evaluated in terms of coatability, scratch resistance, and weather resistance. The evaluation results are shown in Table 1.
Coatability : “○” indicates that a uniform film was formed when the paint was applied to the organic resin base material, and “X” indicates that the appearance of components such as UV absorbers was poor, resulting in poor appearance. evaluated.
Abrasion resistance : According to ASTM D1044, the coated article was equipped with a wear wheel CS-10F in a Taber abrasion test, and the haze after 500 revolutions under a load of 500 g was measured (Nippon Denshoku Industries Co., Ltd.) The value before and after the test was defined as haze difference (ΔHz). A haze difference (ΔHz) of 10 or less was evaluated as “◯”, and a value larger than 10 was evaluated as “x”.
Weather resistance : The coated article uses an I-super UV tester W-151 manufactured by Iwasaki Electric Co., Ltd., and the test conditions are ultraviolet light with an intensity of 1 × 10 ³ W / m ² , temperature 60 ° C., humidity 50% RH. In this environment, the change in appearance was examined when 300 MJ of accumulated ultraviolet energy per 1 m ² was irradiated. The case where cracks, film peeling, whitening and yellowing were observed was evaluated as “×”, and the case where no abnormality was observed was evaluated as “◯”.

About the obtained laminated body, it evaluated by each item of inorganic vapor deposition layer formation property and a weather resistance. The evaluation results are shown in Table 1.
Inorganic vapor deposition layer formability : When the laminate is surface-analyzed by infrared spectroscopy (ATR-IR), a transparent film derived from silicon oxide is formed with good adhesion, “◯”, laminate The coating surface was rough, whitening, cracks, and other defects were evaluated as “x”.
Weather resistance : The laminate was made using I-Super UV Tester W-151 manufactured by Iwasaki Electric Co., Ltd., and the test conditions were ultraviolet light with an intensity of 1 × 10 ³ W / m ² , temperature 60 ° C., humidity 50% RH. In this environment, the change in appearance was examined when 300 MJ of accumulated ultraviolet energy per 1 m ² was irradiated. The case where cracks, film peeling, whitening and yellowing were observed was evaluated as “×”, and the case where no abnormality was observed was evaluated as “◯”.

[Examples 3 to 6]
The component synthesized in Example 1 as an ultraviolet absorber was changed to the amount shown in Table 1, or silicon oxide (manufactured by Nissan Chemical Industries, Ltd., “ A coating material, a coated article, and a laminate were produced in the same manner as in Example 2 except that “IPA-ST” and 2 g) as the solid content were used. The results are shown in Table 1.

[Comparative Examples 1-5]
Other than using 2- [3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] ethyl methacrylate (manufactured by Otsuka Chemical Co., Ltd., product name “RUVA-93”) as an ultraviolet absorber, It carried out similarly to Examples 2-6. The results are shown in Table 2. When this ultraviolet absorber was used, there was a tendency that crystals of RUVA-93 were precipitated during coating, and the coating appearance was markedly deteriorated.

[Comparative Examples 6 to 10]
It carried out similarly to Examples 2-6 except having used the component of the synthesis example 2 as a ultraviolet absorber. The results are shown in Table 3. When this ultraviolet absorber was used, there was a tendency that the scratch resistance of the coated article deteriorated.

  The ultraviolet-absorbing organosilicon compound of the present invention has wide applicability as an ultraviolet absorber for active energy ray-curable coatings. The paints, coated articles and laminates of the present invention are used for transportation of automobile headlamp covers, protective films for liquid crystal displays used outdoors, building materials such as carports and sunroofs, motorcycle windshields and bullet trains, and heavy machinery windows for construction. It has applicability to protective articles for machine articles, automotive glazing, CVD primers, solar cell collector mirrors, and the like.

Claims (7)

An ultraviolet-absorbing organosilicon compound represented by the following general formula (I).

[In the general formula (I), R ¹ represents the following general formula (III)

{In General Formula (III), A ^{1 to} A ¹⁰ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or the following formula (IV):

(In General Formula (IV), Y ′ is an alkylene group having 1 to 12 carbon atoms, directly connected to the benzene ring contained in General Formula (III) on the oxygen side, and represented by General Formula (I) on the Y ′ side. (Directly connected to the silicon atoms contained.)
In which the formula (III) has at least one hydroxyl group and at least one group represented by the formula (IV). }
R ² is an ultraviolet-absorbing organic group represented by the following general formula (II)

(In general formula (II), Y is an alkylene group having 1 to 12 carbon atoms, and R ⁴ is a hydrogen atom or a methyl group.)
R ³ is an alkyl group having 1 to 6 carbon atoms, and n is 0 or 1. ]   An active energy ray-curable coating material containing the ultraviolet-absorbing organosilicon compound according to claim 1.   The active energy ray-curable coating material according to claim 2, comprising a polyfunctional (meth) acrylate, an acrylic polymer, and inorganic oxide fine particles.   The active energy ray-curable coating material according to claim 2 or 3, comprising 1 to 40% by mass of the ultraviolet absorbing organic silicon compound with respect to 100 parts by mass of the solid content of the coating material excluding the ultraviolet absorbing organic silicon compound.   A coated article formed by applying and curing the active energy ray-curable coating material according to any one of claims 2 to 4 on at least one surface of an organic resin substrate.   The coated article according to claim 5, wherein the organic resin base material is polycarbonate.   The laminated body formed by laminating | stacking an inorganic vapor deposition layer on the coated article of Claim 5 or 6.

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