WO2011089970A1

WO2011089970A1 - Coating composition and silicon resin composition

Info

Publication number: WO2011089970A1
Application number: PCT/JP2011/050489
Authority: WO
Inventors: 一路尼崎; 木村　桂三; 和史古川; ゆきえ渡邊
Original assignee: 富士フイルム株式会社
Priority date: 2010-01-19
Filing date: 2011-01-13
Publication date: 2011-07-28

Abstract

Disclosed is a coating composition which is capable of forming a coating film that exhibits a shielding effect up until the UV-A region, has an unprecedented light resistance, and does not deteriorate over time. The coating composition is characterized by containing a binder component and and a compound represented by general formula (1). [In the formula, R^1a, R^1b, R^1c, R^1d and R^1e independently represent hydrogen atoms, or monovalent substituents excluding hydroxy groups, and at least one of the substituents represents a substituent having a Hammett σp value which is positive. The substituents may bond to one another to form rings. R^1g, R^1h,R¹ⁱ,R^1j,R^1k,R^1m,R¹ⁿ, and R^1pindependently represent hydrogen atoms or monovalent substituents. The substituents may bond to one another to form rings.]

Description

Coating composition and silicone resin composition

The present invention relates to a coating composition. More specifically, the present invention relates to a coating composition having long-term light resistance.

The present invention also relates to a silicone resin composition containing a triazine compound and a silicone resin, and a molded article using the same.

In recent years, in the paint field, the required performance for paint has become high. In order to improve the light resistance of the paint film, it is common practice to add a light resistance improver such as a hindered amine type light stabilizer (HALS) or an ultraviolet absorber (UVA) to the paint (Patent Literature). 1). However, many commercially available HALS and UVA have a relatively low molecular weight and bleed out from the coating film, so that high light resistance cannot be maintained over a long period of time.

Conventionally, ultraviolet absorbers have been imparted by sharing ultraviolet absorbers with various resins. As ultraviolet absorbers, there are inorganic ultraviolet absorbers and organic ultraviolet absorbers. Inorganic ultraviolet absorbers (see, for example, Patent Documents 2 to 4) have excellent durability such as weather resistance and heat resistance, but are free to be selected because the absorption wavelength is determined by the band gap of the compound. There is no such thing that can absorb up to 400 nm in the long wave ultraviolet (UV-A) region, and those that absorb the long wave ultraviolet ray have absorption up to the visible region and are colored.
Compared to inorganic ultraviolet absorbers, organic ultraviolet absorbers have a high degree of freedom in the structural design of the absorbent, and therefore, various absorption wavelengths can be obtained by devising the structure of the absorbent.

A system using various organic ultraviolet absorbers has been studied so far, and Patent Document 5 discloses a triazole-based ultraviolet absorber. Patent Document 6 describes a trisaryl-s-triazine having an alkoxy group and a hydroxy group at specific positions. However, those having a maximum absorption wavelength in the long wave ultraviolet region have poor light resistance, and the ultraviolet shielding effect decreases with time.

Furthermore, high transparency and refractive index are required for optical materials applied to sealing materials such as lenses, solar cells, and LEDs that have been developed in recent years, and silicone resin has attracted attention (see Patent Document 7). . In addition, they may be exposed to sunlight outdoors for a long time, and it has been unavoidable that the properties of the material, such as changes in hue over time, are deteriorated by exposure to ultraviolet rays over time. Therefore, there is a need for a compound that can be used as an ultraviolet absorber that exhibits a shielding effect up to the UV-A region and has an excellent light resistance.

On the other hand, benzophenone-based and benzotriazole-based UV absorbers have relatively good light resistance, and can be cut relatively clearly up to a long wavelength region by increasing the concentration and film thickness (see, for example, Patent Documents 8 and 9). . However, when these ultraviolet absorbers are added to the silicone resin, there is a problem that the refractive index of the resin is lowered or coloring is caused by the treatment at a high temperature at the time of molding and the light transmittance is lowered.

Japanese Patent Publication No. 3-46506 Japanese Unexamined Patent Publication No. 5-339033 Japanese Laid-Open Patent Publication No. 5-345639 Japanese Unexamined Patent Publication No. 6-56466 Japan Special Table 2002-524442 Japanese Patent No. 3965631 Japanese Unexamined Patent Publication No. 2009-148670 Japanese Unexamined Patent Publication No. 6-145387 Japanese Unexamined Patent Publication No. 2003-177235

This invention is made | formed in view of the said situation, and it aims at providing the composition for coating materials which can form the film which has the light resistance excellent in the long term which fully satisfies the light resistance performance which improves.
Another object of the present invention is to provide a silicone resin composition that can maintain a long wave ultraviolet ray shielding effect for a long time, has excellent transparency, exhibits high hardness, and can form a molded article having excellent light resistance. . Another object of the present invention is to provide a molded article such as a lens or a sealing material that has excellent transparency, high hardness, excellent light resistance, and has a long-wave ultraviolet shielding effect without hue change. .

As a result of detailed studies on the above problems, the present inventors have found a coating composition that can provide a coating film that exhibits a shielding effect up to the UV-A region and that has no change over time and has excellent light resistance. The present invention has been completed based on this finding.
Further, as a result of examining the above-mentioned problems in detail, the present inventors have shown a shielding effect up to the UV-A region, do not decrease the hardness even when added to the silicone resin composition, and have an unprecedented light resistance. The inventors have found a novel triazine-based compound having the above and have completed the present invention by including it in a silicone resin composition.

The object of the present invention has been achieved by the following means.
(1)
A coating composition comprising a compound represented by the following general formula (1) and a binder component.

[R ^1a , R ^1b , R ^1c , R ^1d and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or a hydroxy group (OH), and at least one of the substituents is Hammett. It represents a substituent having a positive σp value. Moreover, you may combine with substituents and may form a ring. R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p each independently represent a hydrogen atom or a monovalent substituent. Moreover, you may combine with substituents and may form a ring. ]
(2)
The monovalent substituent is a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, substituted or Unsubstituted alkylcarbonyl group, nitro group, substituted or unsubstituted amino group, hydroxy group, alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group, substituted or unsubstituted sulfamoyl group, thiocyanate group, Or a substituted or unsubstituted alkylsulfonyl group, where the substituent is a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylcarbonyl group, Nitro group, amino group, hydroxy group, alkoxy group having 1 to 20 carbon atoms, aryloxy group A sulfamoyl group, characterized in that it is a thiocyanate group, or an alkylsulfonyl group, A composition according to (1).
(3)
The composition according to (1) or (2), wherein R ^1c is a substituent having a positive Hammett's σp value.
(4)
R ^1a , R ^1c and R ^1e represent a hydrogen atom, R ^1b and R ^1d each independently represent a hydrogen atom or a substituent having a positive Hammett's σp value, and at least one of R ^1b and R ^1d One is a substituent having a positive Hammett's σp value. The coating composition according to (1) or (2),
(5)
The composition according to any one of (1) to (4), wherein the Hammett's rule σp value is in the range of 0.1 to 1.2.
(6)
The substituent having a positive σp value according to the Hammett rule is a group selected from COOR ^r , CONR ^s ₂ , a cyano group, a trifluoromethyl group, a halogen atom, a nitro group, and SO ₃ M. , (1) to (5) The composition according to any one of (1) to (5).
[R ^r and R ^{s each} represent a hydrogen atom or a monovalent substituent. M represents a hydrogen atom or an alkali metal. ].
(7)
The composition according to any one of (1) to (4) or (6), wherein the substituent having a positive Hammett's σp value is COOR ^r .
[R ^r represents a hydrogen atom or a monovalent substituent. ].
(8)
The composition according to any one of (1) to (3), (5) and (6), wherein R ^1c is a cyano group.
(9)
The composition according to any one of (1) to (8), wherein R ^1h or R ¹ⁿ is a hydrogen atom.
(10)
Any one of (1) to (9), wherein R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p are hydrogen atoms. Composition.
(11)
The composition according to any one of (1) to (10), wherein the pKa of the compound represented by the general formula (1) is in the range of −5.0 to −7.0.
(12)
In any one of (1) to (11), the compound represented by the general formula (1) is contained in an amount of 0.1 to 30% by mass based on the total mass of the coating composition. The composition as described.
(13)
Binder component is chlorinated rubber resin, phenol resin, alkyd resin, amino alkyd resin, urea resin, vinyl resin, acrylic resin, polyester resin, epoxy resin, polyurethane resin, silicone resin, The composition according to any one of (1) to (12), which is a component containing at least one of a silicon resin, a fluororesin, a silazane resin, and a melamine resin.
(14)
The composition according to any one of (1) to (12), wherein the binder component is a silicone resin.
(15)
The composition according to (14), wherein the silicone resin has an aromatic group in the molecule.
(16)
The composition according to (14) or (15), further comprising at least one selected from a light stabilizer or an antioxidant as an additive.
(17)
The composition according to any one of (14) to (16), wherein the Shore D hardness of a cured product obtained by curing the composition is 30 or more and 100 or less.
(18)
The composition according to any one of (1) to (13), further comprising a curing agent.
(19)
Any one of (1) to (13) and (18), wherein the binder component is a hydroxyl group-containing resin having a hydroxyl value of 30 to 600 mgKOH / g and an acid value of 0 to 100 mgKOH / g. The composition according to one.
(20)
(1) to (13), a film obtained by the composition according to any one of (18) and (19).
(21)
The coating according to (20), wherein the thickness of the coating is 0.1 to 10,000 μm.
(22)
(20) A member having the coating according to (21).
(23)
The composition according to any one of (1) to (15), (18) and (19), wherein the composition is for paint.
(24)
The composition according to (23), wherein the composition is for a vehicle.
(25)
(1) A lens obtained by molding the composition according to any one of (17).
(26)
(1) A sealing material obtained by molding the composition according to any one of (17).

The composition of the present invention contains a compound represented by the general formula (1) and a binder component. By containing the compound represented by the general formula (1), it has excellent light resistance (ultraviolet light fastness) even in the long wave ultraviolet region, and the light stability of the member coated with the composition is improved. Can be increased.
The composition of the present invention is preferably for paint (hereinafter may be referred to as paint composition).
In addition, the present invention is highly soluble in an organic solvent, exhibits an ultraviolet shielding effect even in a long wavelength region, has light resistance, and contains a compound represented by the general formula (1) and a silicone resin, thereby providing transparency. It is possible to provide a composition (hereinafter sometimes referred to as a silicone resin composition) capable of forming a molded article having excellent hardness, high hardness, and excellent light resistance.
By molding the silicone resin composition of the present invention, a molded article having excellent transparency, high hardness, and excellent light resistance can be obtained.

Hereinafter, the present invention will be described in detail.
The composition of this invention can be prepared by adding the compound represented by General formula (1) to the common coating material containing a binder component and an additive as needed.
Hereinafter, the component which the composition of this invention contains is demonstrated.
The binder component is preferably a silicone resin, and the silicone resin composition of the present invention contains a compound represented by the following general formula (1) and a silicone resin.
The compound represented by the general formula (1) is highly soluble in an organic solvent, exhibits an ultraviolet shielding effect even in a long wavelength region, and has light resistance. Therefore, when added to a silicone resin as an ultraviolet absorber, a molded product having excellent transparency, high hardness, and excellent light resistance can be formed. In addition, long-wave ultraviolet absorption ability can be maintained for a long period of time, and the change in the hue of the resin can be suppressed.
<Compound represented by the general formula (1)>

[R ^1a , R ^1b , R ^1c , R ^1d and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or a hydroxy group, and at least one of the substituents is a Hammett's σp Represents a substituent whose value is positive. Moreover, you may combine with substituents and may form a ring. R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p each independently represent a hydrogen atom or a monovalent substituent. Moreover, you may combine with substituents and may form a ring. ]

R ^1a , R ^1b , R ^1c , R ^1d , and R ^1e each independently represent a monovalent substituent other than a hydrogen atom or a hydroxy group, and at least one of the substituents has a Hammett's σp value Represents a substituent which is positive.
Of the substituents represented by R ^1a , R ^1b , R ^1c , R ^1d , and R ^1e, one to three preferably represent a substituent having a positive Hammett's σp value, and one or two represent a Hammett rule. More preferably, it represents a substituent having a positive σp value.

Examples of the monovalent substituent (hereinafter referred to as A) in the general formula (1) include, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group having 1 to 20 carbon atoms (for example, Methyl, ethyl), aryl groups having 6 to 20 carbon atoms (for example, phenyl, naphthyl), cyano groups, carboxyl groups, alkoxycarbonyl groups (for example, methoxycarbonyl), aryloxycarbonyl groups (for example, phenoxycarbonyl), substituted or unsubstituted Carbamoyl groups (eg carbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl), alkylcarbonyl groups (eg acetyl), arylcarbonyl groups (eg benzoyl), nitro groups, substituted or unsubstituted amino groups (eg amino, dimethyl) Amino, anilino, substituted sulfoamino) An acylamino group (for example, acetamide, ethoxycarbonylamino), a sulfonamide group (for example, methanesulfonamide), an imide group (for example, succinimide, phthalimide), an imino group (for example, benzylideneamino), a hydroxy group, an alkoxy group having 1 to 20 carbon atoms ( Methoxy), aryloxy group (eg phenoxy), acyloxy group (eg acetoxy), alkylsulfonyloxy group (eg methanesulfonyloxy), arylsulfonyloxy group (eg benzenesulfonyloxy), sulfo group, substituted or unsubstituted sulfamoyl Groups (eg sulfamoyl, N-phenylsulfamoyl), alkylthio groups (eg methylthio), arylthio groups (eg phenylthio), thiocyanate groups, alkylsulfonyl groups For example methanesulfonyl), an arylsulfonyl group (e.g., benzenesulfonyl), and the like Hajime Tamaki having 6 to 20 carbon atoms (for example, pyridyl, morpholino).
Further, the substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. In that case, the above-mentioned monovalent substituent A can be mentioned as an example of a substituent.
Moreover, you may combine with substituents and may form a ring.

Rings formed by bonding between substituents include benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, oxadiazole And a ring, a thiazole ring, a thiadiazole ring, a furan ring, a thiophene ring, a selenophene ring, a silole ring, a gelmol ring, and a phosphole ring.

Examples of the monovalent substituent in the general formula (1) include a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted group. Substituted carbamoyl group, substituted or unsubstituted alkylcarbonyl group, nitro group, substituted or unsubstituted amino group, hydroxy group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group , A substituted or unsubstituted sulfamoyl group, a thiocyanate group, or a substituted or unsubstituted alkylsulfonyl group is preferable, and OR ^U (R ^u represents a hydrogen atom or a monovalent substituent), an alkyl group, or an amide group. More preferably, OR ^u and an alkyl group are still more preferable.
R ^u represents a hydrogen atom or a monovalent substituent, and examples of the monovalent substituent include the substituent A. Among them, it is preferable to represent a linear or branched alkyl group having 1 to 20 carbon atoms. A linear or branched alkyl group having 1 to 6 carbon atoms is more preferable. Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i- Mention may be made of pentyl, t-pentyl, n-hexyl, i-hexyl, t-hexyl, n-octyl, t-octyl and i-octyl, preferably methyl or ethyl, particularly preferably methyl.
When these have a substituent, examples of the substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylcarbonyl group, a nitro group, an amino group, and a hydroxy group. And an alkoxy group having 1 to 20 carbon atoms, an aryloxy group, a sulfamoyl group, a thiocyanate group, or an alkylsulfonyl group.

As a preferred first embodiment of the present invention, an embodiment in which at least one of R ^1a , R ^1c and R ^1e represents a substituent having a positive Hammett's σp value can be mentioned.
More preferably, R ^1c represents a substituent having a positive Hammett's σp value.
More preferably, R ^1c is a substituent having a positive Hammett's σp value, and R ^1a , R ^1b , R ^1d , and R ^1e represent a hydrogen atom.
When R ^1c represents a substituent having a positive Hammett's σp value, LUMO is stabilized by the electron-attracting group, which is preferable because the excitation lifetime is shortened and the light resistance is improved. Thereby, the compound represented by the general formula (1) is particularly excellent in light resistance, and the coating composition containing the compound has an effect of being excellent in improving light resistance.
As a preferred second embodiment, R ^1a , R ^1c and R ^1e each represents a hydrogen atom, and R ^1b and R ^1d are each independently a hydrogen atom or a substituent having a positive Hammett σp value. Wherein at least one of the substituents has a positive Hammett σp value.
Thereby, the compound represented by the general formula (1) is particularly excellent in solvent solubility, and has an effect of being excellent in preventing precipitation from a coating film to which a coating composition containing the compound is applied.
Solvent solubility means solubility in organic solvents such as ethyl acetate, methyl ethyl ketone, and toluene, and is 10% by mass with respect to the solvent used in terms of preventing precipitation from the coating film to which the coating composition is applied. It is preferable to dissolve the above, and it is more preferable to dissolve 30% by mass or more.
Furthermore, the compound represented by the general formula (1) is particularly excellent in solvent solubility because of excellent solvent solubility, and the silicone resin composition containing the compound has excellent transparency and high hardness, In addition, it has the effect of forming a molded product having excellent light resistance.
Solvent solubility means solubility in organic solvents such as ethyl acetate, methyl ethyl ketone, and toluene, and is preferably 10% by mass or more based on the solvent used in terms of compatibility with the silicone resin. It is more preferable to dissolve 30% by mass or more.

<Preferred first embodiment>
In the first embodiment, the substituent having a positive Hammett's σp value in the general formula (1) is preferably an electron withdrawing group having a σp value of 0.1 to 1.2. Specific examples of the electron withdrawing group having a σp value of 0.1 or more include COOR ^r (R ^r represents a hydrogen atom or a monovalent substituent, and includes a hydrogen atom and an alkyl group, preferably a hydrogen atom. CONR ^s ₂ (R ^s represents a hydrogen atom or a monovalent substituent), a cyano group (CN), a halogen atom, a nitro group (NO ₂ ), SO ₃ M (M is a hydrogen atom) Represents an atom or an alkali metal.), Acyl group, formyl group, acyloxy group, acylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, dialkylphosphono group, diarylphosphono group, dialkylphosphinyl group, diarylphosphini Group, phosphoryl group, alkylsulfinyl group, arylsulfinyl group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, An imino group, an imino group substituted with an N atom, a carboxy group (or a salt thereof), an alkyl group substituted with at least two or more halogen atoms (for example, a trifluoromethyl group), substituted with at least two or more halogen atoms Alkoxy groups, aryloxy groups substituted with at least two or more halogen atoms, acylamino groups, alkylamino groups substituted with at least two or more halogen atoms, alkylthio groups substituted with at least two or more halogen atoms And aryl groups substituted with other electron-withdrawing groups having a σ _p value of 0.2 or more, heterocyclic groups, halogen atoms, azo groups, selenocyanate groups, and the like. For Hammett σp values, see Hansch, C .; Leo, A .; Taft, R .; W. Chem. Rev. 1991, 91, 165-195.

More preferably, the substituent having a positive Hammett's σp value in the general formula (1) is COOR ^r , CONR ^s ₂ , cyano group, trifluoromethyl group (CF ₃ ), halogen atom, nitro group, SO ₃ M [R ^r and R ^s each independently represent a hydrogen atom or a monovalent substituent. M represents a hydrogen atom or an alkali metal]. Among these, COOR ^r or a cyano group is more preferable, and COOR ^r is more preferable. This is because it has excellent light resistance and solubility.

R ^r and R ^s represent a hydrogen atom or a monovalent substituent, and examples of the monovalent substituent include the substituent A. Of these, a linear or branched alkyl group having 1 to 20 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable. Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i- Mention may be made of pentyl, t-pentyl, n-hexyl, i-hexyl, t-hexyl, n-octyl, t-octyl and i-octyl, preferably methyl or ethyl, particularly preferably methyl.

In the compound represented by the general formula (1), R ^1c is preferably any one of COOR ^r , CONR ^s ₂ , a cyano group, a trifluoromethyl group, a halogen atom, a nitro group, and SO ₃ M, and COOR ^r or a cyano group is preferable, and a cyano group is more preferable.

In the present invention, when R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p represent a monovalent substituent, R ^1g , R ^1h , R ¹ⁱ , R More preferably, at least one of ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p represents a substituent having a positive Hammett's σp value, and R ^1g , R ^1h , R ¹ⁱ and R ^1j More preferably, at least one of the substituents has a positive (preferably 0.1 to 1.2) σp value in the Hammett rule, and R ^1h is a substituent in which the σp value in the Hammett rule is positive. Is more preferable. It is particularly preferred that R ^1c and R ^1h represent a substituent having a positive Hammett σp value (preferably 0.1 to 1.2). This is because it has excellent light resistance.
In the present invention, R ^1h or R ¹ⁿ is preferably each independently a hydrogen atom, COOR ^r , CONR ^s ₂ , a cyano group, a trifluoromethyl group, a halogen atom, a nitro group, or SO ₃ M, More preferably, ^1h or R ¹ⁿ is a hydrogen atom, R ^1h and R ¹ⁿ are more preferably a hydrogen atom, R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and It is particularly preferred that R ^1p represents a hydrogen atom. It is for showing the outstanding light resistance.

In the compound represented by the general formula (1), R ^1c is a substituent whose Hammett's σp value is positive (preferably 0.1 to 1.2), and R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p preferably represent a hydrogen atom, and R ^1c is COOR ^r , CONR ^s ₂ , a cyano group, a trifluoromethyl group, a halogen atom, a nitro group, SO ₃ More preferably, R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p are hydrogen atoms. It is for showing the outstanding light resistance.

<Preferred second embodiment>
In a preferred second embodiment, R ^1a , R ^1c and R ^1e each represents a hydrogen atom, and R ^1b and R ^1d each independently represent a hydrogen atom or a substituent having a positive Hammett's σp value. , At least one of the embodiments may be a substituent having a positive Hammett's σp value.
R ^1a , R ^1c and R ^1e represent a hydrogen atom, R ^1b and R ^1d each independently represent a hydrogen atom or a substituent having a positive Hammett's σp value, and at least one is a Hammett In the second embodiment in which the σp value of the rule is positive, the substituent having a positive Hammett's σp value in the general formula (1) is more preferably COOR ^r , CONR ^s ₂ , A cyano group, a trifluoromethyl group, a halogen atom, a nitro group, or SO ₃ M [R ^r and R ^s each independently represent a hydrogen atom or a monovalent substituent. M represents a hydrogen atom or an alkali metal]. ^{Examples of} the monovalent substituent for R ^r and R ^s include the substituent A as described above.
The substituent having a positive Hammett's σp value in the general formula (1) is more preferably a COOR ^r or cyano group, and further preferably COOR ^r . This is because when the substituent having a positive Hammett's σp value is a cyano group, excellent light resistance is exhibited. Further, when the substituent having a positive Hammett's σp value is COOR ^r , excellent solubility is exhibited.
R ^r preferably represents a hydrogen atom or an alkyl group, more preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and still more preferably a linear or branched alkyl group having 1 to 15 carbon atoms.

R ^r is more preferably a branched alkyl group having 5 to 15 carbon atoms from the viewpoint of solubility in a solvent.
The branched alkyl group has a secondary carbon atom or a tertiary carbon atom, preferably contains 1 to 5 secondary carbon atoms or tertiary carbon atoms, preferably contains 1 to 3, preferably 1 or 2 It is preferable to contain it, and it is more preferable to contain 1 or 2 secondary carbon atoms and tertiary carbon atoms. Further, it preferably contains 1 to 3 asymmetric carbons.
R ^r is a branched alkyl group having 5 to 15 carbon atoms containing 1 or 2 secondary carbon atoms and tertiary carbon atoms and 1 or 2 asymmetric carbons from the viewpoint of solubility in a solvent. It is particularly preferred.
This is because the symmetry of the compound structure is broken and the solubility is improved.

On the other hand, a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable from the viewpoint of ultraviolet absorbing ability.
Examples of the straight or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i- Mention may be made of pentyl, t-pentyl, n-hexyl, i-hexyl, t-hexyl, n-octyl, t-octyl and i-octyl, preferably methyl or ethyl, particularly preferably methyl.

In the present invention, when R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p represent a monovalent substituent, R ^1g , R ^1h , R ¹ⁱ , R More preferably, at least one of ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p represents a substituent having a positive Hammett's σp value, and R ^1g , R ^1h , R ¹ⁱ and R ^1j More preferably, at least one of the substituents has a positive (preferably 0.1 to 1.2) σp value in the Hammett rule, and R ^1h is a substituent in which the σp value in the Hammett rule is positive. Is more preferable. It is particularly preferable that R ^1b or R ^1d and R ^1h represent a substituent having a positive (preferably 0.1 to 1.2) σp value according to the Hammett rule. This is because it has excellent light resistance.
In the present invention, R ^1h or R ¹ⁿ is preferably each independently a hydrogen atom, COOR ^r , CONR ^s ₂ , a cyano group, a trifluoromethyl group, a halogen atom, a nitro group, or SO ₃ M, More preferably, ^1h or R ¹ⁿ is a hydrogen atom, R ^1h and R ¹ⁿ are more preferably a hydrogen atom, R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and It is particularly preferred that R ^1p represents a hydrogen atom. It is for showing the outstanding light resistance.

In the compound represented by the general formula (1), R ^1b or R ^1d is a substituent having a positive Hammett's σp value (preferably 0.1 to 1.2), and R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p preferably represent a hydrogen atom, and R ^1b or R ^1d is COOR ^r , CONR ^s ₂ , a cyano group, a trifluoromethyl group, Any one of a halogen atom, a nitro group and SO ₃ M, and R ^1g , R ^1h , R ¹ⁱ , R ^1j , R ^1k , R ^1m , R ¹ⁿ and R ^1p are more preferably hydrogen atoms. It is for showing the outstanding light resistance.

In the first and second aspects, the compound represented by the general formula (1) preferably has a pKa in the range of −5.0 to −7.0. Further, it is more preferably in the range of -5.2 to -6.5, particularly preferably in the range of -5.4 to -6.0.

Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.
In the following specific examples, Me represents a methyl group, Ph represents a phenyl group, and —C ₆ H ₁₃ represents n-hexyl. Ph represents a phenyl group, and —C ₆ H ₁₃ represents n-hexyl.

The compound represented by the general formula (1) can take a tautomer depending on the structure and the environment in which the compound is placed. Although the present invention is described in one of the representative forms, tautomers different from those described in the present invention are also included in the compounds of the present invention.

The compound represented by the general formula (1) may contain an isotope (for example, ² H, ³ H, ¹³ C, ¹⁵ N, ¹⁷ O, ¹⁸ O, etc.).

The compound represented by the general formula (1) can be synthesized by any method.
For example, known patent documents and non-patent documents, for example, Japanese Patent Laid-Open No. 7-188190, Japanese Patent Laid-Open No. 11-315072, Japanese Patent Laid-Open No. 2001-220385, “Dye and Drug”, Vol. 40 No. 12 (1995), 325 Can be synthesized with reference to pp. 339. Specifically, exemplary compound (16) can be synthesized by reacting salicylamide, 3,5-bis (trifluoromethyl) benzoyl chloride and 2-hydroxybenzamidine hydrochloride. Alternatively, it can be synthesized by reacting salicylamide, salicylic acid and 3,5-bis (trifluoromethyl) benzamidine hydrochloride.

The compound in the present invention is particularly suitable for stabilizing organic materials against damage by light, oxygen or heat. Among them, the compound represented by the general formula (1) can be suitably used as a light stabilizer, particularly an ultraviolet absorber.

Since the compound represented by the general formula (1) has a substituent having a positive Hammett's σp value at a specific position, LUMO is stabilized by an electron-attracting group, so that an excitation lifetime is shortened. It has the feature of having excellent light resistance. Even when it is used as an ultraviolet absorber, when a known triazine compound is used, it has an adverse effect such as decomposition and yellowing when used for a long time.
On the other hand, since the compound represented by the general formula (1) has excellent light resistance, the effect of not decomposing and yellowing even when used for a long time can be obtained.

The maximum absorption wavelength of the compound represented by the general formula (1) is not particularly limited, but is preferably 250 to 400 nm, and more preferably 280 to 380 nm. The full width at half maximum is preferably 20 to 100 nm, more preferably 40 to 80 nm.

A person skilled in the art can easily measure the maximum absorption wavelength and the full width at half maximum defined in the present invention. The measurement method is described in, for example, “The Fourth Edition Experimental Chemistry Course 7 Spectroscopy II” (Maruzen, 1992), pages 180 to 186, edited by the Chemical Society of Japan. Specifically, the sample is dissolved in a suitable solvent, and measurement is performed by a spectrophotometer using a cell made of quartz or glass and using two cells for sample and control. The solvent to be used is required to have no absorption in the measurement wavelength region, have a small interaction with the solute molecule, and have a very low volatility in addition to the solubility of the sample. Any solvent that satisfies the above conditions is selected.

Examples of the organic solvent include amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (for example, sulfolane) sulfoxide solvents (for example, dimethyl sulfoxide), ureido Solvent (eg tetramethylurea), ether solvent (eg dioxane, tetrahydrofuran, cyclopentylmethyl ether), ketone solvent (eg acetone, cyclohexanone), hydrocarbon solvent (eg toluene, xylene, n-decane), halogen type Solvent (eg, tetrachloroethane, chlorobenzene, chloronaphthalene), alcohol solvent (eg, methanol, ethanol, isopropyl alcohol, ethylene glycol, cyclohexanol, phenol), pyridine Solvent (eg, pyridine, γ-picoline, 2,6-lutidine), ester solvent (eg, ethyl acetate, butyl acetate), carboxylic acid solvent (eg, acetic acid, propionic acid), nitrile solvent (eg, acetonitrile), sulfonic acid A system solvent (for example, methanesulfonic acid), an amine system solvent (for example, triethylamine, tributylamine), or the like can be used.
As the inorganic solvent, for example, sulfuric acid, phosphoric acid and the like can be used.

From the solubility point of the compound of the general formula (1), amide solvents, sulfone solvents, sulfoxide solvents, ureido solvents, ether solvents, ketone solvents, halogen solvents, hydrocarbon solvents, ester solvents. A solvent is preferred.

The concentration of the compound of the general formula (1) for measurement is not particularly limited as long as the maximum wavelength of spectral absorption can be confirmed, and is preferably in the range of 1 × 10 ⁻⁷ to 1 × 10 ¹³ mol / L. It is.
The temperature for measurement is not particularly limited, and is preferably 0 ° C. to 80 ° C.

The spectral absorption measurement device is not particularly limited, and an ordinary spectral absorption measurement device (for example, U-4100 spectrophotometer manufactured by Hitachi High-Technologies Corporation) can be used.

In the present invention, measurement is performed using ethyl acetate (EtOAc) as a solvent.

The maximum absorption wavelength and half width of the compound in the present invention are values measured using a quartz cell having an optical path length of 10 mm by preparing a solution having a concentration of about 5 × 10 ⁻⁵ mol · dm ^{−3 using} ethyl acetate as a solvent. Is used.

The half width of the spectrum is described in, for example, “Chapter 4 of Experimental Chemistry Lecture 3, Basic Operation III” (Maruzen, 1991), page 154, edited by the Chemical Society of Japan. In the above-mentioned book, the half-value width is explained with an example in which the horizontal axis is taken on the wave number scale, but the half-value width in the present invention is the value when the axis is taken on the wavelength scale, The unit is nm. Specifically, it represents the width of the absorption band that is half the absorbance at the maximum absorption wavelength, and is used as a value that represents the shape of the absorption spectrum. A spectrum with a small half-value width is a sharp spectrum, and a spectrum with a large half-value width is a broad spectrum. The UV-absorbing compound that gives a broad spectrum has absorption in a wide region from the maximum absorption wavelength to the long wave side. Therefore, in order to effectively block the long wave UV region without yellowing, a spectrum with a small half-value width is used. The ultraviolet absorbing compound having is preferable.

As described on pages 154 to 155 of “Chemistry Seminar 9 Color Chemistry” by Sumio Tokita (Maruzen, 1982), the light absorption intensity, that is, the oscillator strength, is proportional to the integral of the molar extinction coefficient, and the absorption spectrum. When the symmetry is good, the oscillator strength is proportional to the product of the absorbance at the maximum absorption wavelength and the full width at half maximum (however, the full width at half maximum is a value obtained by taking an axis on the wavelength scale). This means that when the transition moment values are the same, a compound having a spectrum with a small half width has a large absorbance at the maximum absorption wavelength. Such UV-absorbing compounds have the advantage of being able to effectively shield the area around the maximum absorption wavelength with a small amount of use, but since the absorbance decreases sharply when the wavelength is slightly away from the maximum absorption wavelength, a wide range of areas can be used. It cannot be shielded.

The compound represented by the general formula (1) preferably has a molar extinction coefficient at the maximum absorption wavelength of 20000 or more, more preferably 30000 or more, and particularly preferably 50000 or more. If it is 20000 or more, the absorption efficiency per mass of the compound represented by the general formula (1) can be sufficiently obtained, so that the compound represented by the general formula (1) for completely absorbing the ultraviolet region can be obtained. The amount used can be reduced. This is preferable from the viewpoint of preventing skin irritation and accumulation in a living body and from the point that bleeding out hardly occurs. Moreover, in the silicone resin composition, this is preferable from the viewpoint of preventing skin irritation and accumulation in the living body, and from the viewpoint of being able to form a molded article having excellent transparency, high hardness, and excellent light resistance. . The molar extinction coefficient uses the definition described in, for example, “New Edition Experimental Chemistry Lecture 9 Analytical Chemistry [II]” (Maruzen, 1977), page 244, edited by the Chemical Society of Japan. It can be determined together with the absorption wavelength and the half width.

The composition of this invention can contain the compound represented by the said General formula (1) in arbitrary quantity required in order to provide desired performance. These vary depending on the compound used, the binder component, and the like, but the content can be appropriately determined.
The compound represented by the general formula (1) is 0.1 to 30% by mass, preferably 0.1 to 20% by mass, more preferably 0.5 to 20% by mass, based on the total mass of the coating composition. More preferably, the content is 1 to 10% by mass.
The compound represented by the general formula (1) is generally 0.1 to 50% by mass, preferably 0.1 to 30% by mass, more preferably 0.5%, based on the total amount of the binder component. -30% by mass, more preferably 1-20% by mass.
The content in the silicone resin composition is preferably 0.1 to 30% by mass of the compound represented by the general formula (1) with respect to the total mass of the silicone resin composition, More preferably, it is contained in an amount of ˜15.0 mass%, more preferably 0.3-5.0 mass%. If the content is within the above range, an ultraviolet shielding effect can be obtained, a molded article having excellent transparency, high hardness, and excellent light resistance can be formed.

The composition of the present invention may contain two or more compounds represented by the general formula (1) having different structures as the ultraviolet absorber as described above. Moreover, you may use together the compound represented with the said General formula (1), and 1 or more types of ultraviolet absorbers which have another structure. When two types (preferably three types) of ultraviolet absorbers having different basic skeleton structures are used in combination, ultraviolet rays in a wide wavelength region can be absorbed. Further, when two or more kinds of ultraviolet absorbers are used in combination, the dispersion state of the ultraviolet absorber is also stabilized.

<Other UV absorbers>
Any ultraviolet absorber having a structure other than the general formula (1) can be used. Triazine, benzotriazole, benzophenone, merocyanine, cyanine, dibenzoylmethane, cinnamic acid, cyano Examples include acrylate-based and benzoate-based compounds. For example, Fine Chemical, May 2004, pages 28-38, published by Toray Research Center, Research Division, “New Development of Functional Additives for Polymers” (Toray Research Center, 1999), pages 96-140, Junichi Okachi UV absorbers described in the supervision of “Development of Polymer Additives and Environmental Countermeasures” (CMC Publishing Co., Ltd., 2003), pages 54 to 64, and the like.

The ultraviolet absorber having a structure other than the general formula (1) is preferably a benzotriazole compound, a benzophenone compound, a salicylic acid compound, a benzoxazinone compound, a cyanoacrylate compound, a benzoxazole compound, or a merocyanine compound. , A triazine compound. More preferred are benzoxazinone compounds, benzotriazole compounds, benzophenone compounds, and triazine compounds. Particularly preferred are benzoxazinone compounds. Ultraviolet absorbers having a structure other than the above general formula (1) are described in detail in paragraph numbers [0117] to [0121] of JP-A-2008-273950, and the materials described in the publication are disclosed in the present invention. It can also be applied.

As described above, the composition of the present invention and the silicone resin composition preferably contain a combination of the compound represented by the general formula (1) and the benzoxazinone compound. Since the compound represented by the general formula (1) has excellent light resistance even in the long wavelength region, it has the effect of preventing deterioration of the benzoxazinone that can be shielded to a longer wavelength region, together with the benzoxazinone compound. The use is preferable because the shielding effect can be maintained for a long time up to a longer wavelength region.
When used in combination, the mass ratio of the addition amount of the ultraviolet absorber having a structure other than the general formula (1) and the addition amount of the compound represented by the general formula (1) is 10/1 to 1/10. It is preferably 5/1 to 1/5, more preferably 1/1 to 1/5.

<Binder component>
The binder component generally contained in the composition of the present invention and the silicone resin composition may be any one of thermoplasticity, thermosetting property, photocuring property, for example, chlorinated rubber resin type, phenol resin type, Alkyd resin, amino alkyd resin, urea resin, vinyl resin, acrylic resin, polyester resin, epoxy resin, polyurethane resin, silicone resin, silicon resin, fluororesin, silazane resin, melamine Examples include a component containing at least one of resin systems.

The binder component is preferably a composite resin or an organic-inorganic hybrid resin.
Preferred examples of the composite resin include resins in which an acrylic resin and another resin are combined, such as an acrylic urethane resin and a silicone acrylic resin.

Examples of the acrylic urethane resin include acrylic urethane resins obtained by reacting a methacrylic acid ester (for example, methyl methacrylate), a hydroxyethyl methacrylate copolymer, and a polyisocyanate. Examples of the polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and the like.

Examples of the silicone acrylic resin include those obtained by combining acrylic resin and silicone resin by block copolymerization, those obtained by crosslinking the other component with either acrylic resin or silicone resin, and silicone partially acrylic. Examples thereof include those modified and those obtained by crosslinking the above two components with other crosslinking agents.

Such a silicon acrylic resin can be manufactured, for example, as follows. That is, in the polymerization of the acrylic resin, allyl (meth) acrylate and the like are radically copolymerized to obtain an acrylic copolymer into which a carbon-carbon double bond has been introduced. Using a metal complex catalyst such as platinum for the heavy bond, HSi (OR ¹⁰ ) _3-n R ²⁰ _n (n represents 0 or 1 and R ¹⁰ and R ²⁰ each independently represents an alkyl group as a silane component) Hydrosilane compounds such as.) Can be reacted to obtain a target silyl group-containing acrylic resin having a molecular weight of, for example, 1,000 to 100,000. In addition, a commercially available product can be used as the silicon acrylic resin, and examples thereof include a trade name “KP-543” (manufactured by Shin-Etsu Silicone).

Preferred examples of the organic-inorganic hybrid resin include a composition in which silica fine particles are hybridized with an acrylic resin. Commercially available products may be used as the composition in which silica fine particles are hybridized with an acrylic resin, such as Comporacene AC (manufactured by Arakawa Chemical Industries).

The content of the binder component in the coating composition of the present invention can be appropriately adjusted according to the coating method, coating thickness, etc., but can be 3 to 70% by mass, preferably 5 to 60% by mass. More preferably, it is 5 to 50% by mass. Further, when it is used as a high solid paint or a powder paint, it preferably contains 70 to 99.9% by mass of a binder component.
Moreover, you may contain the monomer and oligomer which form the said resin as a binder component in a coating composition, for example, In that case, it is preferable to contain polymerization initiators, such as a photoinitiator.
Examples of the monomer and oligomer include (meth) acrylic, maleimide, epoxy, oxetane, vinyl ether, propenyl ether, melamine, siloxane, and unsaturated polyester compounds, and a mixture of polyene and thiol. (Meth) acrylic, epoxy, oxetane and melamine compounds are preferred.
The content of the monomer or oligomer in the coating composition of the present invention can be 0.1 to 99% by mass, preferably 0.1 to 70% by mass.
Various compounds can be used as the polymerization initiator. For example, peroxide-based, azo-based, alkylphenone-based, acylphosphine-based, titanocene-based, oxime ester-based, oxyphenylacetate-based And iodonium salt compounds, and alkylphenone compounds are preferred. The content of the polymerization initiator in the coating composition of the present invention can be 0.01 to 30% by mass, preferably 0.1 to 10% by mass.
Other examples of the binder component (transparent resin component) include polymethyl methacrylate, polymethyl methacrylate styrene copolymer, polyvinyl chloride, and polyvinyl acetate.

It is preferable to add a curing agent as appropriate to the composition and the silicone resin composition of the present invention. By using a hardening | curing agent, the light resistance of the coating film obtained from a coating composition can further be improved. The curing agent preferably has a function of curing the binder component. Moreover, it is thought that the compound represented by General formula (1) may also be fixed to resin with a hardening | curing agent.
For example, when an acrylic resin is used as the binder component, a melamine resin, polyisocyanate, alkoxysilane compound, or the like can be preferably used as a curing agent.
As a binder component, for example, when a polyurethane resin system is used, an amine compound can be used as a curing agent.
For example, when an epoxy resin system is used as the binder component, a polyamine compound, a polyamide compound, or a polyol compound can be used as a curing agent.
For example, when a polyester resin system is used as the binder component, a polyisocyanate compound can be used as a curing agent.
In addition, as a suitable combination of the binder component and the curing agent, a combination described in “Crosslinking agent handbook (Yamashita Junzo et al., Taiseisha, 1981, first edition)” can be used.
Commercially available products can also be used as the curing agent, for example, polyisocyanate curing agents Sumijour N-75 (manufactured by Sumika Bayer Urethane Co., Ltd.), Bayhijoule 3100 (manufactured by Sumika Bayer Urethane Co., Ltd.), epoxy curing agent A specific example is Denacol EX-614B (manufactured by Nagase ChemteX Corporation).

In the composition and silicone resin composition of the present invention, the compound represented by the general formula (1) and the binder component have a hydroxyl value of 30 to 600 mgKOH / g and an acid value of 0 to 100 mgKOH / g. A composition containing a certain hydroxyl group-containing resin and a curing agent is particularly preferred. The composition can form a film excellent in weather resistance and crack resistance when used as a coating material. As the curing agent, it is preferable to use a compound selected from a polyisocyanate compound, a melamine resin compound, an epoxy compound, and a silanol compound.
The content of the curing agent may be appropriately determined according to the type of the curing agent, the functional group content, and the type of the binder. For example, the content is in the range of about 0.1 to 200 parts by mass with respect to 100 parts by mass of the binder resin. Is preferred.
Moreover, it is preferable to determine suitably content of a hardening | curing agent with the equivalent ratio of the functional group which a binder component and a hardening | curing agent component react. When there is too much content of a hardening | curing agent, unreacted hardening | curing agents remain | survive and it may have bad influences, such as a coating film softening. When there is too little content of a hardening | curing agent, hardening may become inadequate and adverse effects, such as deterioration of water resistance, may appear.
For example, when the hydroxyl group-containing resin is used as the binder component and the polyisocyanate compound is used as the curing agent, the equivalent ratio (NCO / OH) of the hydroxyl group of the hydroxyl group-containing resin to the isocyanate group of the polyisocyanate compound is 0. It is preferably within the range of 7 to 2.

<Other additives>
The composition of the present invention and the silicone resin composition may contain any additive generally used in paints. Examples of the additive include pigments, curing agents, diluents, acrylic resins, Leveling agents such as silicone resins, anti-foaming agents such as silicone and acrylic, anti-skinning agents, thixotropic agents, antifoaming agents, anti-color separation agents, smoothing agents, wetting agents, dispersing agents, thickeners, sedimentation Inhibitors, polymerization inhibitors, structural viscosity imparting agents, electrostatic paintability improvers, anti-sagging agents, curing accelerators, antioxidants, light stabilizers, antifouling agents, flame retardants, coating aids, etc. it can. Preferable examples of the light stabilizer and the antioxidant include compounds represented by JP-A No. 2004-117997. Specifically, compounds described in JP-A No. 2004-117997, p29 middle stage, paragraph numbers [0071] to [0111] are preferable. The compounds represented by general formula (TS-I), general formula (TS-II), general formula (TS-IV) and general formula (TS-V) described in paragraph [0072] are particularly preferred. In addition, when a binder component is a curable type, a curing catalyst can be added.

The coating composition of the present invention can provide a sufficient UV shielding effect practically only with the UV absorber represented by the general formula (1), but has a strong hiding power when more strictness is required. A white pigment such as titanium oxide may be used in combination. Further, when the appearance and color tone become problems, or a small amount (generally 0.05% by mass or less) of a colorant can be used in combination depending on the preference. Further, a fluorescent brightening agent may be used in combination for applications where transparency or white color is important. Examples of the optical brightener include those commercially available, general formula [1] described in JP-A-2002-53824, and specific compound examples 1 to 35.
The total amount of these additives is generally 0.1 to 30% by mass, preferably 0.1 to 20% by mass, based on the total amount of the binder component.
In the coating composition of the present invention, the total solid content concentration including the compound represented by the general formula (1), the binder component, additives and the like is generally 5 to 80% by mass, preferably 10 to 70%. % By mass. In the case of a high solid paint, the content is preferably 70 to 99.9% by mass, and in the case of a powder paint, the total amount is also preferably a solid content.

The coating composition of the present invention can be performed by a general coating preparation method. For example, a compound represented by the general formula (1), a binder, and, if necessary, an additive are dissolved in an arbitrary solvent. Alternatively, it can be prepared by dispersing. Moreover, when it is a powder coating material, it can prepare by mixing each component in a solid state.
As the solvent, an organic or inorganic solvent or water can be used alone or as a mixture thereof depending on the application of the paint.
Examples of the organic solvent include amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (for example, sulfolane) sulfoxide solvents (for example, dimethyl sulfoxide), ureido Solvent (eg tetramethylurea), ether solvent (eg dioxane, tetrahydrofuran, cyclopentylmethyl ether), ketone solvent (eg acetone, cyclohexanone), hydrocarbon solvent (eg toluene, xylene, n-decane), halogen type Solvents (eg tetrachloroethane, chlorobenzene, chloronaphthalene), alcoholic solvents (eg methanol, ethanol, isopropyl alcohol, butyl alcohol, ethylene glycol, cyclohexanol, phenol ), Pyridine solvents (eg pyridine, γ-picoline, 2,6-lutidine), ester solvents (eg ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate), carboxylic acid solvents (eg acetic acid, propionic acid) ), Nitrile solvents (eg acetonitrile), sulfonic acid solvents (eg methanesulfonic acid), amine solvents (eg triethylamine, tributylamine) and the like.
As the inorganic solvent, for example, sulfuric acid, phosphoric acid and the like can be used. Preferably, water, alcohol solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ketone solvents, ester solvents, ether solvents, and halogen solvents are used.
The boiling point is generally 20 to 250 ° C., preferably 40 to 235 ° C.
In addition, from the viewpoint of the solubility of the compound represented by the general formula (1), a solvent such as an aromatic hydrocarbon solvent, a ketone solvent, or an ester solvent is preferable.
The viscosity of the prepared coating composition can be arbitrarily adjusted depending on the application, but is generally 10 to 150 seconds (Ford Cup No. 4, 20 ° C.).
The prepared coating composition is generally preferably stored at a low temperature in terms of pot life.

The coating composition of the present invention is applied to any base material such as steel, non-ferrous metal, light metal, wood, glass, concrete, resin, rubber, leather, paper, skin, etc., depending on the application, to form a film. And it can be set as a desired member. In addition, the performance of the coating composition of the present invention can be effectively utilized by coating on a substrate sensitive to a wavelength of 380 nm or more.
The coating can be applied in any thickness depending on the application, but the final coating thickness is preferably 0.1 to 10,000 μm, more preferably 0.1 to 2000 μm, and still more preferably. The thickness is 1 to 1000 μm, more preferably 5 to 1000 μm, and further preferably 5 to 200 μm. The method of applying these paints is arbitrary, but includes spraying, dipping, roller coating, flow coater, flow coating, electrodeposition coating, powder flow coating, brush application, and the like.
Drying after coating varies depending on the paint components, and natural drying or heat drying (approximately from room temperature to 180 ° C. for about 10 to 90 minutes) can be performed.
In addition, when the binder component is a thermosetting type, by heating (generally 100 ° C. or more and 10 minutes), when the binder component is a photocurable type such as ultraviolet ray or electron beam curing, desired light or electron A coating film is hardened by irradiating a line.
The surface hardness of the coating varies depending on the application, but it is preferably 2B to 6H, and more preferably B to 4H, according to the pencil hardness specified in JIS K5400. The film by the coating composition of the present invention may be applied in any form, and the film may be formed as a so-called undercoat or intermediate coat. Preferably, it is coated as an overcoat to protect the object to be coated from the adverse effects of ultraviolet rays.

Examples of the form of the coating composition of the present invention include a powder coating, a water-soluble coating, an emulsion coating, a non-aqueous dispersion coating, a sol coating, a multi-component coating, and a blended coating.

Further, for example, UV shielding paints described in JP-A-7-26177, JP-A-9-169950, JP-A-9-221163, JP-A-2002-80788, JP-A-10-88039 UV- and near-infrared shielding coatings described in JP-A-2001-55541, electromagnetic wave shielding coatings described in JP-A-8-81643, clear coatings described in JP-A-2000-186234, metallic coatings described in JP-A-2000-186234 Composition, cationic electrodeposition paint described in JP-A-7-166112, antibacterial and lead-free cationic electrodeposition paint described in JP-A-2002-294165, JP-A-2000-273362, JP-A-2001-2001 No. 279189, Japanese Patent Application Laid-Open No. 2002-271227, and Japanese Patent Application Laid-Open No. 2001-9357 Water-based intermediate coating, water-based metallic coating, water-based clear coating, top coating used in automobiles, buildings and civil engineering products described in JP-A-2001-316630, and curable properties described in JP-A-2002-356655 Paint, coating film forming composition used for plastic material such as automobile bumper described in JP-A-2004-937, metal plate coating described in JP-A-2004-2700, JP-A-2004-169182 Cured coating film described in JP-A-2004-107700, coating material for electric wires described in JP-A-2004-107700, automotive repair coating described in JP-A-6-49368, JP-A-2002-38084, JP-A-2005-307161 Anionic electrodeposition paints described in JP-A-5-78606, JP-A-5-185031, JP-A-10-140 No. 89, JP-T 2000-509082, JP-T 2004-520284, WO 2006/097201, pamphlet for coated steel sheet, JP-A-6-1945, JP-A-6-1945 -131148, stainless steel paint described in JP-A-7-3189, lamp insect-proof paint described in JP-A-7-3189, UV-curable paint described in JP-A-7-82454, JP-A-7-118576 Antibacterial paints described in JP 2004-217727 A, anti-eye strain described in JP-A 2004-217727, anti-fog paint described in JP-A 2005-314495, and super-weather resistant paint described in JP-A 10-298493 Gradient paints described in JP-A-9-241534, photocatalyst paints described in JP-A No. 2002-235028, JP-A 2000 -345109, a stripping paint for concrete described in JP-A-6-346022, an anticorrosion paint described in JP-A-2002-167545, and a protection described in JP-A-8-324576 Paints, water-repellent protective paints described in JP-A-9-12924, sheet glass scattering prevention paints described in JP-A-9-157581, alkali-soluble protective paints described in JP-A-9-59539, Aqueous temporary protective coating composition described in JP-A No. 2001-181558, a floor coating described in JP-A No. 10-183057, an emulsion coating described in JP-A No. 2001-115080, and JP-A No. 2001-262056 Two-component water-based paint described in Japanese Laid-Open Patent Publication, one-component paint described in Japanese Patent Laid-Open No. 9-263729, Japanese Patent Laid-Open No. 2001-288410 UV curable coatings described in JP-A-2002-69331, electron beam-curable coating compositions described in JP-A-2002-80731, thermosetting coating compositions described in JP-A-2002-80781, JP-T-2003-525325 Aqueous coating for baking lacquers described in JP-A-2004-162021, powder coatings and slurry coatings described in JP-A No. 2004-162021, repair coatings described in JP-A-2006-233301, and JP-A No. 11-51489 Various known paints such as aqueous dispersions of powder paints, paints for plastics described in JP-A Nos. 2001-59068 and 2006-160847, and electron beam curable paints described in JP-A No. 2002-69331 A coating composition of the present invention can be obtained by adding a compound represented by the general formula (I).
The coating composition of the present invention can be used as a coating suitable particularly for the field of vehicles.

As described above, in the present invention, by adding the compound represented by the general formula (I) as a stabilizer to the coating composition, light, oxygen, and It also provides a method for stabilizing organic materials against damage by heat.

Next, resin components such as a silicone resin contained in the silicone resin composition of the present invention will be described.
<Silicone resin>
The silicone-based material usually refers to an organic polymer having a siloxane bond as a main chain, and examples thereof include a compound represented by the following general composition formula (S-1) and / or a mixture thereof.

(R ¹ R ² R ³ SiO _1/2 ) _M (R ⁴ R ⁵ SiO _2/2 ) _D (R ⁶ SiO _3/2 ) _T (SiO _4/2 ) _Q Formula (1)

(In the general composition formula (S-1), R ¹ to R ⁶ are selected from the group consisting of a substituent, a hydroxyl group and a hydrogen atom. Note that R ¹ to R ⁶ may be the same. In addition, in the general composition formula (S-1), M, D, T, and Q represent a number of 0 or more and less than 1, provided that M + D + T + Q = 1.

Examples of the substituent represented by R ¹ to R ⁶ include the following substituent group B.
In addition, when using a silicone type material as a curable material, what is necessary is just to harden | cure by a heat | fever or light, after apply | coating or immersing a liquid silicone type material in a base material.

The silicone resin is not particularly limited and may be appropriately selected depending on the intended purpose, but a curable silicone resin is preferable. The curable silicone resin may be a type mainly composed of this, or a modified silicone type obtained by graft polymerization with an organic resin such as a urethane resin, an epoxy resin, or an alkyd resin. As the kind of the curable silicone resin, any of the curing reaction types such as an addition type, a condensation type, an ultraviolet curable type, an electron beam curable type, a solventless type, a heat curable type, and a room temperature curable type can be used.

In the present invention, the silicone resin preferably has an aromatic group in the molecule, and the aromatic group means an aryl group and a substituted aryl group. These aromatic groups may be condensed with an aliphatic ring, another aromatic ring or a heterocyclic ring. The number of carbon atoms in the aromatic group is preferably 6 to 40, more preferably 6 to 30, and still more preferably 6 to 20. Among them, the aryl group is preferably phenyl or naphthyl, particularly preferably phenyl. This is because the aromatic group increases the hardness of the silicone resin and the durability of the material is improved.

The aryl part of the substituted aryl group is the same as the above aryl group. Examples of the substituent of the substituted aryl group include the following substituent group B.
(Substituent group B)
Halogen atom (for example, chlorine atom, bromine atom, iodine atom), alkyl group [represents a linear, branched, cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), and tricyclo structures with more ring structures Is shall. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ],

Alkenyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or unsubstituted 3 to 30 carbon atoms, or An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2, ] Is intended to encompass oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 or 6 A monovalent group obtained by removing one hydrogen atom from a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably a 5- or 6-membered aromatic having 3 to 30 carbon atoms For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably having 1 to 30 carbon atoms) Substituted or unsubstituted alkoxy groups such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2- Toxiethoxy), aryloxy groups (preferably, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetra Decanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituent having 2 to 30 carbon atoms or Unsubstituted heterocyclic oxy group, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy),

Acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy , Stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy, N, N -Diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted group having 2 to 30 carbon atoms) Substituted alkoxycarbonyloxy groups such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy groups (preferably substituted or unsubstituted aryloxy having 7 to 30 carbon atoms) A carbonyloxy group such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), an amino group (preferably an amino group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms) An amino group, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino),

An acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, Pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, Carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably substituted or unsubstituted alkoxycarbonylamino having 2 to 30 carbon atoms) Groups such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino groups (preferably substituted with 7 to 30 carbon atoms) Or an unsubstituted aryloxycarbonylamino group such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino),

Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino ), Alkyl or arylsulfonylamino group (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino) , Phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, Echi Thio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably having a carbon number) 2-30 substituted or unsubstituted heterocyclic thio groups such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), sulfamoyl groups (preferably substituted or unsubstituted sulfamoyl having 0 to 30 carbon atoms) Groups such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N ′ -Phenylcarbamoyl) sulfamoyl),

A sulfo group, an alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl; , P-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl, Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms) , 4 to 4 carbon atoms Heterocyclic carbonyl groups bonded to carbonyl groups with zero substituted or unsubstituted carbon atoms, eg acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p- t-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecy Oxycarbonyl), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl),

An aryl or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5- Ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, For example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphini ), A phosphinyloxy group (preferably having 2 carbon atoms) 30 substituted or unsubstituted phosphinyloxy groups, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino groups (preferably substituted or unsubstituted having 2 to 30 carbon atoms) Phosphinylamino group such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms such as trimethylsilyl, t-butyldimethyl Silyl, phenyldimethylsilyl).

Among the above substituents, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

As the silicone resin having an aromatic group, the organopolysiloxane more preferably contains a structural unit represented by the formula (II).

It is preferable to include a structural unit represented by the formula (II) because a lens having a high refractive index can be obtained from the silicone resin composition of the present invention. Use of a material having a high refractive index is preferable because the degree of freedom in designing the lens is increased, for example, the thickness of the optical lens can be reduced.

10 to 95 mol% of silicon atoms contained in the organopolysiloxane are preferably silicon atoms contained in the structural unit represented by the formula (II), more preferably 20 to 90 mol%, Most preferably, it is 85 mol%. It is preferable that the refractive index is within the above range because a sufficient refractive index can be obtained and a lens having excellent transparency and physical strength can be obtained.

In the present invention, the organopolysiloxane may have a structural unit other than the structural unit represented by the formula (II). Specific examples of the structural unit other than the structural unit represented by the formula (II) include siloxane, monomethylsiloxane, monoethylsiloxane, divinylsiloxane, phenylvinylsiloxane, methylphenylsiloxane, diphenylsiloxane, dimethylsiloxane, trivinylsiloxane, and divinylmethyl. One or more hydrogen atoms of organic groups of siloxane, divinylphenylsiloxane, vinyldimethylsiloxane, vinylphenylmethylsiloxane, trimethylsiloxane, dimethylphenylsiloxane, methyldiphenylsiloxane, triphenylsiloxane, methylvinylsiloxane, and these siloxane constituent units Preferred examples include siloxane substituted with a halogen atom or the like.

In the present invention, the silicone resin preferably contains an organopolysiloxane containing a structural unit represented by the formula (I).

The silicone resin composition of the present invention preferably contains an organopolysiloxane having a structural unit represented by the formula (I), and 3 mol% or more of silicon atoms contained in the organopolysiloxane is represented by the formula (I). It is more preferable that it is a silicon atom contained in the structural unit represented by these. Further, the silicon atom contained in the structural unit is more preferably 3 to 50 mol%, further preferably 5 to 40 mol%, more preferably 7 to 30 mol% of the silicon atom contained in the organopolysiloxane. Most preferably, it is mol%. If it is in the range of said numerical value, the curability of a silicone resin composition, the hardness of the lens obtained by hardening | curing a silicone resin composition, and heat resistance can be reconciled.
Hereinafter, unless otherwise specified, “3 to 50 mol%” or the like in the numerical range represents “3 mol% or more and 50 mol% or less” or the like, and the same applies to other numerical ranges. And

In the present invention, among the vinyl groups contained in the organopolysiloxane, 30 mol% or more is preferably a vinyl group contained in the structural unit represented by the formula (I), and more preferably 50 mol% or more. Preferably, it is 70 mol% or more, and it is most preferable that all vinyl groups contained in the organopolysiloxane are vinyl groups contained in the structural unit represented by the formula (I).

The organopolysiloxane contained in the silicone resin composition of the present invention preferably has a three-dimensional network structure.

The weight average molecular weight in terms of polystyrene in the gel permeation chromatography of the organopolysiloxane contained in the silicone resin composition of the present invention is preferably 3,500 to 200,000, and preferably 4,000 to 100,000. Is more preferable, and 4,500 to 50,000 is most preferable.
The number average molecular weight in terms of polystyrene in the gel permeation chromatography of the silicone resin composition of the present invention is preferably 1,500 to 15,000, more preferably 2,000 to 10,000, Most preferred is 500 to 8,000.
If the weight average molecular weight and the number average molecular weight are within the above ranges, the silicone resin composition of the present invention has a viscosity, phase transition temperature and heat resistance suitable for thermoforming.

The organopolysiloxane can be obtained by a method of cohydrolyzing and condensing a mixture of two or more organohalosilanes and / or organoalkoxysilanes corresponding to each siloxane constituent unit.
In the present invention, it is preferable to perform cohydrolytic condensation using organohalosilane, and it is more preferable to use organochlorosilane. That is, the organopolysiloxane preferably does not have a silicon functional group such as a hydroxy group or an alkoxy group directly bonded to a silicon atom. A lens produced using an organopolysiloxane having no silicon functional group is preferable because it is chemically stable and excellent in heat resistance.
Organopolysiloxanes that do not have a silicon functional group are polyorganosiloxanes obtained by cohydrolyzing and condensing organochlorosilanes corresponding to individual siloxane unit structures. It can be produced by treating with a substance and further treating with a silylating agent if necessary.

As the silylating agent, a known silylating agent can be used, and it is not limited. Specifically, hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMCS), trimethylchlorosilane (TMCS), N— Trimethylsilylacetamide (TMSA), N, O-bis (trimethylsilyl) acetamide (TMSA), N-methyl-N-trimethylsilylacetamide (BSA), N-methyl-N-trimethylsilylacetamide (MTMSA), N-methyl-N-trimethylsilyl -Trifluoroacetamide (MSTFA), N-trimethylsilyldimethylamine (TMSDMA), N-trimethylsilyldiethylamine (TMSDEA), N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA), -Trimethylsilylimidazole (TMSI), tetramethyldisilazane (TMDS), tert-butyldimethylchlorosilane (tert-BDMCS), N-methyl-N- (tert-butyldimethylsilyl) -trifluoroacetamide (MTBSTFA), dichloromethyltetra Methyldisilazane (CMTMDS), chloromethyldimethyldichlorosilane (CMDMCS), bromomethyldimethylchlorosilane (BMDMCS), furofemesylamine, furofemesyl chloride, furofemesyl diethylamine, 1,1-divinyl-1,1,3 , 3-tetramethyldisilazane, 1,1-divinyl-1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, hexavinyldisiloxane, dimethylvinylchlorosilane Emissions, and, trivinyl chlorosilane, and among them hexamethyldisilazane, hexamethyldisiloxane, dimethylvinylchlorosilane is preferably trimethylchlorosilane.

The organopolysiloxane contained in the silicone resin composition of the present invention can also be produced by mixing two or more types of organopolysiloxanes obtained by different hydrolysis condensations.

Specific examples of the curable silicone resin include KS-774, KS-775, KS-778, KS-779H, KS-856, X-62-2422, and X-62-2461 manufactured by Shin-Etsu Chemical Co., Ltd. DKQ3-202, DKQ3-203, DKQ3-204, DKQ3-205, DKQ3-210 manufactured by Dow Corning Asia Co., Ltd., YSR-3022, TPR-6700, TPR-6720 manufactured by Toshiba Silicone Co., Ltd. And TPR-6721, SD7220, SD7226, SD7229 manufactured by Toray Dow Corning Co., Ltd., and the like. The curable silicone resin may be used in combination with a release agent in order to adjust peelability and the like.

As the release agent, known ones can be used, but are not limited, but the release agent of fatty acid compound, fatty acid ester of erythritol derivative is compatible with silicone resin, transparency after curing, Furthermore, it is excellent in discoloration resistance after being left at high temperature.
Specifically, pentaerythritol tetrastearate, dipentaerythritol adipate stearate, glycerin tri-18-hydroxystearate, pentaerythritol full stearate, polyethylene oxide, highly esterified carnauba, liquemar TG-12 (glycerin tri-18 -Hydroxystearate), Riquemata EW-440A (pentaerythritol tetrastearate), LICOWAX PED136 (polyethylene oxide), Electol D-121-41 (polypropylene / maleic anhydride copolymer), Riquemata EW-200 (pentaerythritol adipate stearin) Acid ester) and Riquemata EW-400 (pentaerythritol full stearate), among which pentaerythritol Tetrastearate can be preferably used.
The release agent is preferably contained in an amount of 0.05 to 5% by mass, more preferably 0.1 to 2% by mass, based on the total amount of the silicone resin composition. Within the above numerical range, a lens molded by injection molding or the like can be easily taken out from the mold.

As described above, the silicone resin composition of the present invention includes an ultraviolet absorber having a structure other than the compound represented by the general formula (1), a light stabilizer, an antioxidant, a heat stabilizer, and a fluorescent thickening agent. An optional additive such as a flame retardant may be appropriately contained, and preferably contains at least one selected from a light stabilizer or an antioxidant.

As the antioxidant, it is preferable that the silicone resin composition of the present invention further contains a phosphorus stabilizer from the viewpoint that the thermal stability can be improved. Phosphorous stabilizers include phosphorous acid, phosphoric acid, phosphite esters, phosphate esters, etc. Among them, phosphites, phosphonites and the like are included because they contain trivalent phosphorus and easily exhibit a discoloration suppressing effect. Phosphites are preferred.

Examples of the phosphite include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tris (tridecyl) phosphite. Phyto, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, water Bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-tert- Tilphenyldi (tridecyl) phosphite), tetra (tridecyl) 4,4′-isopropylidene diphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilaurylpentaerythritol diphosphite Phosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite , 2,2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like.

Examples of phosphonites include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphospho Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6 Di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, and tetrakis (2,6-diphenyl) -Tert-butylphenyl) -3,3'-biphenylenediphosphonite and the like.

Examples of the acid phosphate include methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, and lauryl phosphate. Phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonyl phenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid Phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid Acid phosphate, bisnonylphenyl acid phosphate, etc. are mentioned.

The phosphorus stabilizer used in the present invention can be mixed and contained in two or more types. The total content of the phosphorus stabilizer is 0.0005 to 0 with respect to 100 parts by mass of the silicone resin composition. The amount is preferably 3 parts by mass, more preferably 0.001 to 0.1 parts by mass. If it is said range, the effect as a stabilizer is enough, and the fall of the molecular weight at the time of shaping | molding and a hue deterioration do not occur easily.
In particular, in the present invention, the amount of the compound represented by the general formula (1) is 0.05 to 3 parts by mass and the phosphorus stabilizer is 0.0005 to 0.3 parts by mass with respect to 100 parts by mass of the silicone resin composition. Is preferred.

As an antioxidant, the silicone resin composition of the present invention further contains a hindered phenol stabilizer, which stabilizes the compound represented by the general formula (1), thereby stabilizing the light stability of the silicone resin composition. It is preferable in that it can be improved.
Examples of the hindered phenol stabilizer include, for example, a substituent other than at least one hydrogen atom at the ortho position of the phenolic hydroxyl group (for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, And compounds having an aryloxy group, a substituted amino group, etc.).
The hindered phenol stabilizer is a compound known as an antioxidant and may be a commercially available one. For example, 2,6-dit-butyl-4-methylphenol, Ciba Specialty An antioxidant manufactured by Chemicals Co., Ltd. can be mentioned.
The hindered phenol stabilizer used in the present invention can be mixed and contained in two or more types, but the total content of the hindered phenol stabilizer is 0 with respect to 100 parts by mass of the silicone resin composition. The amount is preferably 0.0001 to 1 part by mass, and more preferably 0.001 to 0.1 part by mass.

Preferred examples of the light stabilizer used in the present invention include compounds represented by JP2009-242641A. Specifically, compounds described in [0081] to [0128] of JP-A-2009-242641 are preferable. A compound represented by the general formula (TS-II) described in paragraph [0082] is particularly preferable.
The addition amount of the light stabilizer is preferably 0.0001 to 10 parts by weight, more preferably 0.001 to 10 parts by weight, with respect to 100 parts by weight of the cellulose ester resin composition. The amount is more preferably 0.01 to 10 parts by mass, and further preferably 0.1 to 5 parts by mass.

There is no particular limitation on the method of preparing the silicone resin composition of the present invention by mixing the compound represented by the general formula (1) and a resin component such as a silicone resin.
When the compound represented by the general formula (1) is compatible with a resin component such as a silicone resin, the compound represented by the general formula (1) may be directly added to the resin component such as a silicone resin. it can. Further, there can be mentioned a method of melt kneading with a melt kneader typified by a vent type twin screw extruder and pelletizing with a device such as a pelletizer.
The compound represented by the general formula (1) may be dissolved in an auxiliary solvent having compatibility with a resin component such as a silicone resin, and the solution may be added to the resin component such as a silicone resin. The compound represented by the general formula (1) may be dispersed in a high-boiling organic solvent or polymer, and the dispersion may be added to a resin component such as a silicone resin.
The timing of addition and mixing may be before the resin component such as a silicone resin is formed by polymerization or after it is formed by polymerization.
The silicone resin composition of the present invention may be formed by dissolving a silicone resin in an arbitrary solvent.

Examples of the high boiling point organic solvent include phosphate ester, phosphonate ester, benzoate ester, phthalate ester, fatty acid ester, carbonate ester, amide, ether, halogenated hydrocarbon, alcohol and paraffin. Phosphate esters, phosphonate esters, phthalate esters, benzoate esters and fatty acid esters are preferred.

The silicone resin composition of the present invention can contain other resin components in addition to the silicone resin. The resin component that can be used in combination may be either a natural or synthetic polymer. For example, polyolefins (eg, polyethylene, polypropylene, polyisobutylene, poly (1-butene), poly-4-methylpentene, polyvinylcyclohexane, polystyrene, poly (p-methylstyrene), poly (α-methylstyrene), polyisoprene, Polybutadiene, polycyclopentene, polynorbornene, etc.), copolymers of vinyl monomers (eg, ethylene / propylene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / vinylcyclohexane copolymer, ethylene / cycloolefin copolymer (eg, ethylene / propylene copolymer) Cycloolefin copolymers (COC: Cyclo-Olefin Copolymer) such as norbornene, propylene / butadiene copolymers Isobutylene / isoprene copolymer, ethylene / vinyl cyclohexene copolymer, ethylene / alkyl acrylate copolymer, ethylene / alkyl methacrylate copolymer, etc.), acrylic polymer (eg, polymethacrylate, polyacrylate, polyacrylamide, polyacrylonitrile, etc.), polyvinyl chloride, poly Vinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, vinyl chloride / vinyl acetate copolymer, polyether (eg, polyalkylene glycol, polyethylene oxide, polypropylene oxide, etc.), polyacetal (eg, polyoxymethylene), polyamide, polyimide, polyurethane, Polyurea, polycarbonate, polyketone, polysulfone polyetherketone, phenol resin, Melamine resin, cellulose ester (for example, diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polysiloxane, natural polymer (for example, cellulose, rubber, gelatin, etc.), etc. Is mentioned.

The resin component that can be used in combination is preferably a synthetic polymer, more preferably a polyolefin, an acrylic polymer, or a cellulose ester. Among these, polyethylene, polypropylene, poly (4-methylpentene), polymethyl methacrylate, polycarbonate, and triacetyl cellulose are particularly preferable. The resin component that can be used in combination is preferably a thermoplastic resin.

It is preferable that the Shore D hardness of the cured product obtained by curing the silicone resin composition is 30 or more and 100 or less. More preferably, it is 40 or more and 90 or less, More preferably, it is 50 or more and 80 or less. If the Shore D hardness is in the above range, it is preferable in that it has sufficient strength as a lens and has long-term durability. Here, the Shore D hardness represents the hardness of a resin or the like, and can be measured according to a measurement method defined in JIS K7215.

The silicone resin composition of the present invention can be used for all applications in which a synthetic resin is used, but can be particularly suitably used for applications that may be exposed to sunlight or light including ultraviolet rays. Specific examples include, for example, glass substitutes and surface coating materials thereof, housing, facilities, window glass for transportation equipment, coating materials for daylighting glass and light source protection glass, housing, facilities, window films for transportation equipment, housing, Inner and outer packaging materials for facilities, transportation equipment, etc., and coating films formed by the coating, alkyd resin lacquer coating and coating formed by the coating, acrylic lacquer coating and coating formed by the coating, fluorescence Light source components that emit ultraviolet rays, such as lamps and mercury lamps, precision machinery, components for electronic and electrical equipment, materials for blocking electromagnetic waves generated from various displays, containers or packaging materials for food, chemicals, chemicals, bottles, boxes, blisters , Cup, special packaging, compact disc coat, agricultural or industrial sheet or film material, printed matter, dyed matter, dyed face Anti-fading agents, protective films for polymer supports (eg for plastic parts such as machinery and automotive parts), printed overcoats, inkjet media coatings, laminated matte, optical light films, safety glass / windshields Intermediate layers, electrochromic / photochromic applications, overlaminate films, solar thermal control films, sunscreen creams, shampoos, rinses, hairdressing cosmetics, sportswear, stockings, hats and other clothing textiles and fibers, curtains, carpets, Home interior items such as wallpaper, plastic lenses, contact lenses, medical devices such as artificial eyes, optical filters, backlight display films, prisms, mirrors, optical materials such as photographic materials, mold films, transfer stickers, graffiti prevention Film, tape, ink, etc. Bogu, sign plate, and a marking device such as a surface coating material or the like.

Next, the molded product of the present invention will be described.
The molded article of the present invention can be molded from the silicone resin composition of the present invention.
As the shape of the molded product of the present invention formed from the silicone resin composition, a flat membrane shape, a powder shape, a spherical particle, a crushed particle, a massive continuous body, a fibrous shape, a tubular shape, a hollow fiber shape, a granular shape, a plate shape, and a porous shape However, in view of the balance with transparency, hardness, and long-wave ultraviolet shielding effect, for example, a flat film or plate having a thickness of 0.1 μm to 25 mm is preferable.

Since the silicone resin composition of the present invention contains a silicone resin, it can be made transparent. In that case, it can be molded as a lens, a sealing material, an ultraviolet absorption filter, or an ultraviolet absorption film.
In this case, the silicone resin composition of the present invention can contain other transparent resins. Examples of other transparent resins include polycarbonate, cellulose ester (eg, diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose), polyamide, polystyrene (eg, syndiotactic) Polystyrene), polyolefin (eg, polyethylene, polypropylene, polymethylpentene), polymethyl methacrylate, syndiotactic polystyrene, polysulfone, polyethersulfone, polyetherketone, polyetherimide, and polyoxyethylene.
The molded article of the present invention obtained from the silicone resin composition can be used as a transparent support, and the transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more.

The molded product of the present invention is molded from the silicone resin composition and has an excellent long-wave ultraviolet absorption capability, so that it can be used as an ultraviolet absorption filter or a container, and can protect compounds that are weak against ultraviolet rays. . For example, the molded article of the present invention can be obtained as a container or the like by molding the silicone resin composition by any method such as extrusion molding or injection molding. Moreover, it can also be set as the molded article by which the ultraviolet absorption film which consists of the said silicone resin composition was coated by apply | coating and drying the solution of the silicone resin composition of this invention to the molded article produced separately.

In order to effectively utilize the long-wave ultraviolet shielding effect and transparency of the silicone resin composition of the present invention, the silicone resin composition of the present invention is particularly useful for lenses, sealing materials, and solar cell backsheets. , Window pasting film, food / medical packaging film, agricultural film, optical film, and fiber.

〔lens〕
The silicone resin composition of the present invention can be molded by various molding methods. Since the cured product is optically transparent, it is particularly useful as an optical lens.

As the molding method, the molding method described in the book “Technology and Application of Plastic Lenses” (CMC Publishing Co., Ltd.) can be used. Specific examples include injection molding, compression molding, casting, transfer molding, and coating.

The lens of the present invention is preferably produced by curing the silicone resin composition of the present invention by heating in a mold at a temperature of 100 to 250 ° C.
The heating temperature is preferably from 100 ° C. to 400 ° C., more preferably from 150 ° C. to 350 ° C.
The heating time is generally 10 seconds to 10 hours, preferably 1 minute to 5 hours, more preferably 3 minutes to 3 hours, and most preferably 10 minutes to 1 hour.

It is preferable that the manufacturing method of the lens of this invention includes the process (post-cure process) which heats the obtained lens further. The temperature of the post-cure process is preferably 200 to 450 ° C., and the heating time is preferably about 10 minutes to 2 hours. It is preferable for it to be within the above numerical values for the reason that a volatile component can be removed by a post-cure process and a molded body having high hardness can be obtained.
The molding is preferably performed under the condition that the ratio of the molding shrinkage after molding and the molding shrinkage after post-cure is 0.9 to 1.1.

Since the lens of the present invention is optically transparent, it is particularly useful as an optical lens. Here, “optically transparent” specifically means that the light transmittance is 80% or more, preferably 90% or more, and more preferably 95% or more. This “light transmittance” is the transmittance of visible light having a wavelength of 555 nm that has passed through a cured product molded to a thickness of 1 mm. The wavelength of 555 nm is an almost intermediate value of visible light, and is a value known as the wavelength having the highest sensitivity with human eyes.

The cured product of the silicone resin composition of the present invention is a shaped product such as an optical lens, a prism, a light guide plate, a deflector plate, a light guide, a sheet and a film, a molding agent, a sealing material, a casting agent, a coating agent, It can be suitably used for an amorphous material such as an adhesive or a protective agent for a semiconductor element in an optical semiconductor device, and among them, it is preferably used as an optical lens or a sealing material.
The lens of the present invention is in direct contact with or near an optical lens exposed to a temperature higher than room temperature, for example, 50 ° C. to 300 ° C., or a light source that emits high-luminance light, particularly in the manufacturing process or usage environment. The arranged optical lens is preferred. Specifically, the lens of the present invention is particularly useful as an optical lens for a camera with a built-in mobile phone and an optical lens for an LED.

In the present invention, the matters described in paragraph numbers [0192] to [0230] of JP-A-2009-209343 can be applied.

The packaging material containing the silicone resin composition of the present invention will be described. The packaging material containing the silicone resin composition of the present invention may be a packaging material made of any kind of polymer as long as it contains the silicone resin composition. For example, thermoplastic resin, polyvinyl alcohol, polyvinyl chloride, styrene resin, polyolefin, ROMP and the like can be mentioned. For example, a resin having an inorganic vapor-deposited thin film layer may be used. For example, the paper which apply | coated resin containing a silicone resin composition may be sufficient.
The packaging material containing the silicone resin composition of the present invention may be used for packaging foods, beverages, drugs, cosmetics, personal care products and the like. For example, food packaging, colored liquid packaging, packaging for the described liquid preparations, pharmaceutical container packaging, sterilization packaging for medical products, photographic photosensitive material packaging, photographic film packaging, ultraviolet curable ink packaging, shrink labels, and the like.

The packaging material containing the silicone resin composition of the present invention may be, for example, a transparent package or a light-shielding package.

The packaging material containing the silicone resin composition of the present invention may have not only ultraviolet shielding properties but also other performances. Examples thereof include those having a gas barrier property, those containing an oxygen indicator, and combinations of a silicone resin composition and a fluorescent brightening agent.

The packaging material containing the silicone resin composition of the present invention may be produced using any method. Examples thereof include a method of forming an ink layer, a method of melt-extruding and laminating a resin containing a silicone resin composition, a method of coating on a base film, and a method of dispersing the silicone resin composition in an adhesive.

The container containing the silicone resin composition of the present invention will be described. The container containing the silicone resin composition of the present invention may be a container made of any kind of polymer as long as it contains the silicone resin composition. For example, a thermoplastic resin container, a silicone resin container, etc. are mentioned. For example, it may be a paper container containing a silicone resin. It may be a glass container having a silicone resin layer.

The use of the container containing the silicone resin composition of the present invention may contain foods, beverages, drugs, cosmetics, personal care products, shampoos and the like. Liquid fuel storage container, golf ball container, food container, liquor container, drug filling container, beverage container, oil-based food container, analytical reagent solution container, instant noodle container, light-resistant cosmetic container, pharmaceutical container, high purity Examples thereof include chemical liquid containers, liquid agent containers, ultraviolet curable ink containers, and W plastic ampules.

The container containing the silicone resin composition of the present invention may have not only ultraviolet blocking properties but also other performance. For example, an antibacterial container, a flexible container, a dispenser container, a biodegradable container, etc. are mentioned.

The container containing the silicone resin composition of the present invention may be produced using any method. For example, a method using two-layer stretch blow molding, a multilayer coextrusion blow molding method, a method of forming an ultraviolet absorbing layer on the outside of a container, a method using a shrinkable film, a method using a supercritical fluid, and the like can be mentioned.

The paint and coating film containing the silicone resin composition of the present invention will be described. The paint comprising the silicone resin composition of the present invention may be a paint comprising any component as long as it contains the compound represented by the general formula (1). For example, an acrylic resin system, a urethane resin system, an amino alkyd resin system, an epoxy resin system, a silicone resin system, a fluororesin system, etc. are mentioned. These resins can be arbitrarily mixed with a main agent, a curing agent, a diluent, a leveling agent, a repellant and the like.

For example, when acrylic urethane resin or silicon acrylic resin is selected as the transparent resin component, polyisocyanate is used as the curing agent, hydrocarbon solvents such as toluene and xylene are used as the diluent, isobutyl acetate, butyl acetate, amyl acetate, etc. Alcohol solvents such as ester solvents, isopropyl alcohol, and butyl alcohol can be used. Here, the acrylic urethane resin refers to an acrylic urethane resin obtained by reacting a methacrylic ester (typically methyl), a hydroxyethyl methacrylate copolymer and a polyisocyanate. The polyisocyanate in this case includes tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and the like. Other examples of the transparent resin component include polymethyl methacrylate, polymethyl methacrylate styrene copolymer, polyvinyl chloride, and polyvinyl acetate. Further, in addition to these components, a leveling agent such as an acrylic resin, an anti-fogging agent such as a silicone type and an acrylic type, and the like can be blended as necessary.

The use purpose of the paint containing the silicone resin composition of the present invention may be any application. For example, ultraviolet shielding paint, ultraviolet / near infrared shielding paint, electromagnetic shielding paint, clear paint, metallic paint composition, cationic electrodeposition paint, antibacterial and lead-free cationic electrodeposition paint, powder paint, aqueous intermediate paint, aqueous Metallic paints, water-based clear paints, top coat paints used in automobiles, buildings, civil engineering products, curable paints, coating film forming compositions used for plastic materials such as automobile bumpers, metal plate paints, cured gradient paints Films, wire coating materials, automotive repair coatings, anion electrodeposition coatings, automotive coatings, painted steel sheet coatings, stainless steel coatings, lamp insecticide coatings, UV curable coatings, special antibacterial coatings, and eye strain prevention coatings , Antifogging paint, super weather resistant paint, gradient paint, photocatalyst paint, peelable paint, concrete peeling paint, anticorrosion paint, protective paint, water repellent protective paint, prevention of glass sheet scattering Paint, alkali-soluble protective paint, aqueous temporary protective paint composition, floor paint, emulsion paint, two-part aqueous paint, one-part paint, UV curable paint, electron beam curable paint composition, thermosetting Examples thereof include coating compositions, aqueous coatings for baking lacquers, powder coatings and slurry coatings, repair coatings, powder coating water dispersions, plastic coatings, and electron beam curable coatings.

The paint containing the silicone resin composition of the present invention is generally composed of a paint (including a transparent resin component as a main component) and a silicone resin composition, preferably a composition of 0 to 20% by mass of the silicone resin composition. The thickness at the time of application is preferably 2 to 1000 μm, more preferably 5 to 200 μm. The method of applying these paints is arbitrary, but there are a spray method, a dipping method, a roller coat method, a flow coater method, a flow coating method and the like. Drying after application varies depending on the paint components, but it is preferably performed at room temperature to 120 ° C for about 10 to 90 minutes.

The coating film containing the silicone resin composition of the present invention is a coating film containing a silicone resin composition comprising the compound represented by the general formula (1), and a coating material containing the above-described silicone resin composition of the present invention is used. It is the coating film formed in this way.

The ink containing the silicone resin composition of the present invention will be described. The ink containing the silicone resin composition of the present invention may be any form of ink as long as it contains the silicone resin composition. Examples thereof include dye ink, pigment ink, water-based ink, and oil-based ink. Moreover, you may use for any use. For example, screen printing ink, flexographic printing ink, gravure printing ink, lithographic offset printing ink, letterpress printing ink, UV ink, EB ink and the like can be mentioned. Further examples include inkjet ink photochromic ink, thermal transfer ink, masking ink, security ink, DNA ink, and the like.

Any form obtained by using an ink containing the silicone resin composition of the present invention is also included in the present invention. Examples thereof include a printed material, a laminate obtained by laminating the printed material, a packaging material and container using the laminate, and an ink receiving layer.

The fiber containing the silicone resin composition of the present invention will be described. The fiber containing the silicone resin composition of the present invention may be a fiber containing any kind of polymer as long as it contains the silicone resin composition. Examples thereof include polyester fiber, polyphenylene sulfide fiber, polyamide fiber, aramid fiber, polyurethane fiber, and cellulose fiber.

The fiber containing the silicone resin composition of the present invention may be produced by any method. For example, a polymer preliminarily containing the compound represented by the general formula (1) may be processed into a fiber shape. For example, a compound represented by the general formula (1) is included with respect to a resin processed into a fiber shape. Processing may be performed using a solution or the like. You may process using a supercritical fluid.

The fiber containing the silicone resin composition of the present invention can be used for various applications. For example, clothing, lining, underwear, blankets, socks, artificial leather, insect-proof mesh sheets, construction mesh sheets, carpets, special moisture / water-proof sheets, non-woven fabrics, ultrafine fibers, sheet materials made of fibers, breathable cool clothing Waterproof sheet, flame retardant artificial suede-like structure, resin tarpaulin, film agent, exterior wall material, agricultural house, net for building materials, mesh, filter substrate, antifouling film agent, mesh fabric, land net, underwater Examples include nets, ultrafine fibers, woven fabrics, airbag fabrics, and UV-absorbing fiber products.

The building material containing the silicone resin composition of the present invention will be described. The building material containing the silicone resin composition of the present invention may be a building material containing any type of polymer as long as it contains the silicone resin composition. For example, vinyl chloride type, olefin type, polyester type, polyphenylene ether type, polycarbonate type and the like can be mentioned.

The building material containing the silicone resin composition of the present invention may be produced by any method. For example, it may be formed into a desired shape using a material containing the silicone resin composition, or may be formed by laminating a material containing the silicone resin composition, and is represented by the general formula (1). A coating layer using a compound may be formed, or a coating containing the silicone resin composition may be applied.

The building material containing the silicone resin composition of the present invention can be used for various applications. For example, exterior building materials, wooden structures for building materials, roofing materials for building materials, antibacterial building materials, base materials for building materials, antifouling building materials, flame retardant materials, ceramic building materials, decorative building materials, painted articles for building materials, makeup Materials, nets for building materials, moisture permeable waterproof sheets for building materials, mesh sheets for building work, film for covering materials for building materials, coating materials for building materials, adhesive compositions for building materials, civil engineering and building structures, pedestrian coating materials, Examples thereof include a sheet-like photocurable resin, wood protective coating, a cover for a push button switch, a bonding sheet agent, a base material for building material, wallpaper, a silicone resin film for covering, a silicone resin film for covering a molded member, and a flooring material.

The recording medium containing the silicone resin composition of the present invention will be described. The recording medium containing the silicone resin composition of the present invention may be any as long as it contains the compound represented by the general formula (1). Examples thereof include an ink jet recording medium, an image receiving sheet for sublimation transfer, an image recording medium, a thermal recording medium, a reversible thermal recording medium, and an optical information recording medium.

An image display device containing the silicone resin composition of the present invention will be described. The image display device containing the silicone resin composition of the present invention may be any one as long as it contains the compound represented by the general formula (1). For example, an image display device using the described electrochromic element, an image display device called so-called electronic paper, a plasma display, an image display device using an organic EL element, and the like can be given. The silicone resin composition of the present invention may be, for example, an ultraviolet absorbing layer formed in a laminated structure, or a material containing the silicone resin composition in a necessary member such as a circularly polarizing plate.

The solar cell cover including the silicone resin composition of the present invention will be described. The solar cell applied in the present invention may be a solar cell comprising any type of element such as a crystalline silicon solar cell, an amorphous silicon solar cell, and a dye-sensitized solar cell. In crystalline silicon solar cells and amorphous silicon solar cells, a cover material is used as a protective member that imparts antifouling, impact resistance, and durability. In addition, since a metal oxide semiconductor that is activated by light (especially ultraviolet rays) in a dye-sensitized solar cell is used as an electrode material, the dye adsorbed as a photosensitizer deteriorates, and the photovoltaic power generation efficiency gradually increases. There is a problem of lowering, and it has been proposed to provide an ultraviolet absorbing layer.

The solar cell cover containing the silicone resin composition of the present invention may contain any kind of polymer. Examples include polyester, thermosetting transparent resin, α-olefin polymer, polypropylene, polyethersulfone, acrylic resin, and transparent fluororesin.

The solar cell cover containing the silicone resin composition of the present invention may be produced by any method. For example, an ultraviolet absorbing layer may be formed, a layer containing a silicone resin composition may be laminated, or a polymer containing a silicone resin composition may be contained in a resin of a filler layer. A film may be formed.

The solar cell cover including the silicone resin composition of the present invention may have any shape. Examples thereof include a film, a sheet, a laminated film, and a cover glass structure. The sealing material may contain a silicone resin composition.

The glass and glass coating containing the silicone resin composition of the present invention will be described. As long as the glass and glass film containing the silicone resin composition of this invention contain the compound represented by the said General formula (1), any form may be sufficient as it. Moreover, you may use for any use. For example, heat-shielding glass window glass, colored glass, UV sharp-cut glass for high-intensity light sources such as mercury lamps and metal halide lamps, frit glass, UV-shielding glass for vehicles, colored heat-ray absorbing glass, fluorescent whitening agent UV absorption Insulating glass, automotive UV heat shield glass, exterior stained glass, water repellent UV infrared absorbing glass, glass for vehicle head-up display devices, light control and heat insulation multi-layer window, UV infrared cut glass, UV cut glass, for windows UV-infrared absorbing glass, UV-blocking antifouling film for windows, translucent panel for cultivation room, UV-infrared absorbing and low-transmitting glass, low reflectance and low-transmitting glass, edgelight device, rough surface forming plate glass, laminated glass for display, conductive Glass with light-sensitive film, anti-glare glass, ultraviolet infrared absorption medium transmission glass, Window glass for privacy protection, glass for anti-fogging vehicles, glass for paving materials, glass plate with water droplet adhesion prevention and heat ray blocking properties, ultraviolet and infrared absorption bronze glass, laminated glass, glass with ID identification function, for PDP Examples include an optical filter and a skylight. The glass containing the silicone resin composition of the present invention may be made by any method.

Other examples of use include light source covers for lighting devices, artificial leather, sports goggles, deflection lenses, hard coats for various plastic products, hard coats for attaching to the outside of windows, window covering films, high-definition anti-glare hard coat films, Antistatic hard coat film, transparent hard coat film, anti-counterfeit book described in JP-A-2002-113937, turf purpura inhibitor, resin film sheet bonding sealant, light guide, rubber coating agent , Agricultural coating materials, dyed candles, fabric rinse agent compositions, prism sheets, special protective layer transfer sheets, photo-curing resin products, floor sheets, light-shielding printing labels, oiling cups, hard coating coated articles, intermediate Transfer recording media, artificial hair, low-temperature heat-shrinkable film for labels, fishing equipment, microbeads, pre-coated metal plates, Meat film, heat shrinkable film, label for in-mold molding, projection screen, decorative sheet, hot melt adhesive, adhesive, electrodeposition coat, base coat, wood surface protection, light control material, light control film, light control glass, Examples thereof include a flashlight, a touch panel, a sealing agent for bonding a resin film sheet, a polycarbonate film coating, an optical fiber tape, and a solid wax.

Next, a method for evaluating the light resistance of the polymer material will be described. As a method for evaluating the light resistance of polymer materials, “Polymer Light Stabilization Technology” (CMC Co., Ltd., 2000), pages 85 to 107, “Basic and Physical Properties of High-Functional Paints” (CMC Co., Ltd.) , 2003) pages 314 to 359, "Durability of polymer materials and composite products" (CMC Corporation, 2005), "Extension of polymer material life and environmental measures" (CMC Corporation, 2000), H.C. Zweifel's “Plastics Additives Handbook 5th Edition” (Hanser Publishers) 238-244, Katsura Tadahiko “Science of Plastic Packaging Containers” (Japan Packaging Society, 2003) Chapter 8 it can.
The evaluation for each application can be achieved by the following known evaluation method. The deterioration of the polymer material due to light is described in JIS-K7105: 1981, JIS-K7101: 1981, JIS-K7102: 1981, JIS-K7219: 1998, JIS-K7350-1: 1995, JIS-K7350-2: 1995, JIS. It can be evaluated by the method of K7350-3: 1996, JIS-K7350-4: 1996 and a method referring to this.

The light resistance when used as a packaging / container application can be evaluated by the method of JIS-K7105 and a method referring to this. Specific examples include light transmittance of bottle body, transparency evaluation, sensory test evaluation of bottle contents after UV exposure using xenon light source, haze value evaluation after xenon lamp irradiation, haze value evaluation as halogen lamp light source , Yellowing evaluation using a blue wool scale after exposure to mercury lamp, haze value evaluation using a sunshine weather meter, visual evaluation of coloring, UV transmittance evaluation, UV blocking rate evaluation, light transmittance evaluation, ink in ink container Viscosity evaluation, light transmittance evaluation, sample in container after sun exposure, color difference ΔE evaluation, ultraviolet transmittance evaluation after white fluorescent light irradiation, light transmittance evaluation, color difference evaluation, light transmittance evaluation, haze value evaluation, Color tone evaluation, yellowness evaluation, light-shielding evaluation, L ^* a ^* b ^* whiteness evaluation using the color system color difference formula, post-exposure support for each wavelength after spectral separation of xenon light Color difference ΔEa ^* b ^* in samples, after UV exposure, UV absorption rate evaluation, film tensile elongation after exposure using a sunshine weather meter, antibacterial evaluation after xenon weather meter exposure, after fluorescent light irradiation Evaluation of discoloration of packaging contents, peroxide value evaluation of oil after exposure to fluorescent lamps for bottles filled with salad oil, color evaluation, evaluation of absorbance difference after chemical lamp irradiation, surface gloss retention after exposure using sunshine weather meter Appearance evaluation, color difference after exposure using a sunshine weatherometer, bending strength evaluation, light shielding ratio evaluation, peroxide production amount evaluation in kerosene, and the like.

The long-term durability when used for paints and coatings is JIS-K5400, JIS-K5600-7-5: 1999, JIS-K5600-7-6: 2002, JIS-K5600-7-7: 1999, JIS. It can be evaluated by the method of K5600-7-8: 1999, JIS-K8741 and a method referring to this. Color difference ΔEa ^{^*} b ^* in the color density and CIE ^L * ^a * ^{b *} color coordinates after exposure by a xenon light resistance test machine and UVCON device and specific examples thereof include evaluation using residual gloss, xenon arc light for quartz slides on the film Absorbance evaluation after exposure using a tester, evaluation using a fluorescent lamp in wax, color density after exposure to UV lamp and color difference ΔEa ^* b ^* in CIE L ^* a ^* b ^* color coordinates, metal weather weathering tester Hue evaluation after exposure using a glass, gloss retention evaluation after an exposure test using a metal hydride lamp, evaluation using a color difference ΔEa ^* b ^* , evaluation of glossiness after exposure using a sunshine carbon arc light source, metal weather evaluation using the color difference after exposure using a weatherometer ΔEa ^{^*} b ^*, gloss retention, appearance evaluation, sunshine weatherometer Gloss retention evaluation after exposure using Ta, evaluation using color difference after exposure using a QUV weathering tester ΔEa ^{^*} b ^*, gloss retention evaluation, post exposure gloss retention using a sunshine weatherometer Evaluation, Appearance evaluation after exposure using sunshine weatherometer on coated plate Gloss retention after exposure using sunshine weatherometer, Evaluation of change in lightness value, Evaluation of coating deterioration after exposure to Ducycle WOM for coating Appearance evaluation, evaluation of UV transmittance of coating film, evaluation of UV blocking rate of coating film, evaluation of time comparison to achieve gloss retention of 80% using sunshine weatherometer, exposure using dew panel light control weather meter color difference after after rust evaluation the strength of the concrete evaluation of painted formwork after weathering, outdoor weathering ΔEa ^{^*} b ^* Evaluation Using crosscut adhesion evaluation, the surface appearance evaluation, gloss retention evaluation after weathering, yellowing after exposure using a carbon arc light source (.DELTA.YI) Evaluation, and the like.

The light resistance when used as an ink application can be evaluated by the method of JIS-K5701-1: 2000, JIS-K7360-2, ISO105-B02 and a method referring to this. Specifically, evaluation by measurement of color density and CIE L ^* a ^* b ^* color coordinates after exposure using an office fluorescent lamp, a fading tester, evaluation of electrophoresis after exposure to ultraviolet rays using a xenon arc light source, Density evaluation of printed matter using a xenon fade meter, evaluation of ink removal using a 100 W chemical lamp, evaluation of dye remaining rate of an image forming site using a weather meter, evaluation of choking of printed matter using an eye super UV tester, and discoloration evaluation, xenon fade For the printed matter after exposure to the meter, evaluation using the color difference ΔEa ^* b ^* in the CIE L ^* a ^* b ^* color coordinates, evaluation of the reflectance after exposure using a carbon arc light source, and the like can be given.

The light resistance of the solar cell module can be evaluated by the method of JIS-C8917: 1998, JIS-C8938: 1995 and a method referring to this. Specifically, IV measurement after light exposure using a light source with a solar simulation correction filter mounted on a xenon lamp, evaluation of photovoltaic power generation efficiency after exposure using a sunshine weather meter, fade meter, Examples include color and appearance adhesion evaluation.

The light resistance of fibers and fiber products is JIS-L1096: 1999, JIS-A5905: 2003, JIS-L0842, JIS-K6730, JIS-K7107, DIN75.202, SAEJ1885, SN-ISO-105-B02, AS / NZS4399. This method can be evaluated by the above method and a method referring to this method. Evaluation of UV transmittance, evaluation of discoloration of blue scale after exposure using xenon light source, carbon arc light source, evaluation of UV cut rate described, evaluation of UV blocking property, change of blue scale after exposure using carbon arc light source after dry cleaning Fading evaluation, lightness index after exposure using a fadeometer, color difference ΔE ^* evaluation based on chromaticness index, tensile strength evaluation after exposure using a UV tester, sunshine weather meter, total transmittance evaluation, strength retention evaluation , UVF (UPF) evaluation, discoloration gray scale evaluation after exposure using a high-temperature fade meter, appearance evaluation after outdoor exposure, yellowness (YI) after yellow exposure, yellowness (ΔYI) evaluation, regulations For example, reflectivity evaluation.

The light resistance of building materials can be evaluated by the method of JIS-A1415: 1999 and a method referring to this. Specifically, surface color evaluation after exposure using a sunshine weatherometer, appearance evaluation after exposure using a carbon arc light source, appearance evaluation after exposure using an eye super UV tester, absorbance evaluation after exposure, Chromaticity after exposure, color difference evaluation, evaluation using CIE L ^* a ^* b ^* color difference after exposure using a metal hydride light source, evaluation using color difference ΔEa ^* b ^* in color coordinates, evaluation of gloss retention, JP-A-10-44352 Gazette, Japanese Patent Application Laid-Open No. 2003-111538, evaluation of haze value change after exposure using a sunshine weather meter, evaluation of elongation retention using a tensile tester after exposure, evaluation of UV transmittance after solvent immersion, eye super Appearance visual evaluation after exposure using UV tester, gloss rate change evaluation after QUV test, gloss retention after exposure using sunshine weatherometer Value, evaluation using black light blue fluorescent color difference after ultraviolet exposure using a lamp ΔEa ^{^*} b ^*, adhesion retention evaluation after exposure using Kobukon accelerated tester, ultraviolet screening assessment, especially outdoor exposure (JIS- A1410) Appearance evaluation, total light transmittance evaluation, haze change evaluation, tensile shear bond strength evaluation, total light transmittance evaluation after exposure using a xenon weather meter, haze evaluation, yellowing degree evaluation, sunshine weathering The yellowing degree (ΔYI) after exposure using a meter, the evaluation of the residual ratio of the ultraviolet absorber, and the like can be mentioned.

The light resistance when used as a recording medium can be evaluated by the method of JIS-K7350 and a method referring to this. Specifically, the background color difference change evaluation in the printed part after the fluorescent lamp irradiation, the image density residual rate evaluation by the exposure using the xenon weather meter, the optical reflection density change evaluation by the exposure using the xenon weather meter, the Suntest CPS light L ^* a ^* b ^* post-exposure yellowing evaluation using an amber tester, fading evaluation after exposure using a fade meter, visual discoloration evaluation after exposure using a xenon fade meter, indoor sunlight Evaluation of color density retention after exposure, evaluation of color density retention after exposure using a xenon weather meter, evaluation of C / N after exposure using a fade meter, evaluation of fog density after exposure to fluorescent light, use fluorescent light There optical reflection density evaluation after exposure, erasability evaluation, color difference Delta] E ^* evaluation after exposure using Atlas fade meter, a carbon arc fade menu Fading visually after exposure using a coater evaluation, the organic EL element color conversion characteristic retention evaluation, the organic EL display luminance measurement evaluation after exposure by a xenon discoloration tester and the like.

As other evaluation methods, evaluation can be performed by the method of JIS-K7103 and ISO / DIS9050 and a method based on this method. Specifically, the appearance of the polycarbonate-coated film after exposure with a UV tester, the blue scale evaluation after exposure to ultraviolet rays on artificial hair, the evaluation of the treated water contact angle for evaluation after exposure using an accelerated weathering tester, Visual evaluation of projected images projected on the projection screen after exposure using the weathering tester described in Kaikai 2005-55615, surface deterioration of the specimen after exposure using a sunshine weather meter and metal weather meter, visual inspection of changes in design Evaluation, visual visual evaluation after exposure to lighting using a metal lamp reflector Evaluation of light transmittance of bottle labels, evaluation of deterioration of polypropylene after exposure using a xenon weather meter, hard coat using a sunshine weatherometer Film degradation assessment, substrate degradation assessment, hydrophilicity assessment, scratch resistance assessment Evaluation of grayscale color difference of artificial leather after exposure using xenon lamp light source, evaluation of liquid crystal device characteristics after exposure using mercury lamp, evaluation of adhesion after exposure using sunshine weatherometer, evaluation of turquoise purple spot, xenon UV exposure evaluation after exposure using an arc light source, tensile strength evaluation, concrete adhesion rate evaluation, post-exposure appearance evaluation using a sunshine weatherometer, coating adhesion evaluation, yellow after exposure using a carbon arc light source Degree of change, adhesion evaluation, adhesion performance evaluation using an ultraviolet fade meter, insect flying suppression evaluation during lighting, yellowing degree (ΔYI) evaluation of laminated glass using an eye super UV tester, QUV irradiation, moisture resistance test Surface appearance evaluation, gloss retention evaluation, dew panel light control weather meter Color difference evaluation over time, glossiness (DI), yellowness index (YI) evaluation in the coated state of a wood substrate after exposure using a xenon weatherometer, ultraviolet ray irradiation, ultraviolet absorption evaluation after repeated darkness, ultraviolet light And dye fading color difference ΔE evaluation after exposure.

The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
1. Synthesis Example 1 (Preparation of Exemplified Compound (1))
To 160.0 g of salicylamide, 600 mL of acetonitrile and 356.2 g of DBU (diazabicycloundecene (1,8-diazabiccyclo [5.4.0] undec-7-ene)) were added and dissolved. To this solution, 231.7 g of methyl 4- (chloroformyl) benzoate was added and stirred at room temperature for 24 hours. 1800 mL of water and 170 mL of 35% hydrochloric acid were added to the reaction solution, and the resulting solid was filtered and washed with water to obtain 343.0 g of synthetic intermediate A (yield 98%).
The following materials were used.
Reagent DBU ... Tokyo Chemical Industry Co., Ltd. Reagent 4- (Chloroformyl) methyl benzoate ... Tokyo Chemical Industry Co., Ltd. Reagent

To 2000.0 g of synthetic intermediate A, 1200 mL of acetonitrile and 98.1 g of sulfuric acid were added and stirred at 90 ° C. for 4 hours. To this reaction solution, 600 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 182.3 g of synthetic intermediate B (yield 97%).

(Synthesis of X-2)
In a three-necked flask, 39.5 g (1.1 molar equivalent) of acetoxime, 600 mL of DMF (N, N-dimethylformamide), 60.6 g (1.1 molar equivalent) of potassium tert-butoxide were added at room temperature. Stir for minutes. Thereafter, the internal temperature was adjusted to 0 ° C., and 60 g (1.0 molar equivalent) of the compound (X-1) was slowly added dropwise thereto. After the dropwise addition, the internal temperature was raised to 25 ° C. and stirred at that temperature for 1 hour.
The reaction mixture was extracted and separated with an aqueous ammonium chloride solution and ethyl acetate, and the resulting organic phase was washed with saturated brine and separated. The organic phase thus obtained was concentrated by a rotary evaporator to obtain a residue obtained as a crude product of compound (X-2).
The following materials were used.
Acetoxime: Reagent made by Tokyo Chemical Industry Co., Ltd.

(Synthesis of X-3)
In a three-necked flask, put the entire amount of the crude product of the compound (X-2) obtained above, add 700 mL of ethanol and 500 mL of 1M hydrochloric acid, and heat the reaction mixture to an internal temperature of 80 ° C. Stir at temperature for 3 hours.
The reaction mixture was cooled to an internal temperature of 25 ° C., extracted and separated with a saturated aqueous sodium hydrogen carbonate solution and ethyl acetate, and saturated brine was added to the obtained organic phase to wash and separate the layers. The organic phase thus obtained was concentrated by a rotary evaporator to obtain a residue obtained as a crude product of compound (X-3).

(Synthesis of X-4)
After filling the flask with nitrogen gas, 6.5 g of 10% Pd—C (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the three-necked flask, 2,000 mL of ethanol, and the compound (X— The whole composition of 3) was added and heated and refluxed. Thereto was slowly added 55 mL (3 molar equivalents) of formic acid, and the mixture was stirred at this temperature for 5 hours. Thereafter, the reaction mixture was cooled to an internal temperature of 25 ° C., and 105 g of 1,5-naphthalenedisulfonic acid was added to the mother liquor filtered through celite and separated by furnace, the internal temperature was raised to 70 ° C. and stirred for 30 minutes. Thereafter, the mixture was gradually cooled to room temperature, and the crystals were separated by filtration to obtain 100 g of compound (X-4). The yield was 72% starting from compound (X-1). The obtained crystal was light brown. ¹ H NMR (heavy DMSO): δ 6.95-6.98 (1H), δ 7.02-7.04 (1H), δ 7.40-7.51 (3H), δ 7.90-7.95 (1H ), Δ 8.75 (1H), δ 8.85-8.88 (2H), δ 9.03 (2H), δ 10.89 (1H)
The following materials were used.
1,5-Naphthalenedisulfonic acid ... Reagent made by Tokyo Chemical Industry Co., Ltd.

To 5.5 g of compound (X-4), 50 mL of methanol and 3.8 g of 28% sodium methoxide methanol solution were added. To this solution, 5.0 g of synthetic intermediate B was added and stirred at 60 ° C. for 3 hours. After cooling the reaction solution to room temperature, 0.2 mL of hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 6.8 g of Exemplified Compound (1) (yield 95%). MS: m / z 400 (M +) ¹ H NMR (CDCl ₃ ): δ 7.04-7.12 (4H), δ 7.53-7.57 (2H), δ 8.24-8.27 (2H), δ 8.51-8.53 (4H), δ 12.91 (2H) λmax = 353 nm (EtOAc)

Synthesis Example 2 (Preparation of exemplary compound (m-1))
To 160.0 g of salicylamide, 600 mL of acetonitrile and 356.2 g of DBU were added and dissolved. To this solution, 231.7 g of methyl 3- (chloroformyl) benzoate was added and stirred at room temperature for 24 hours. 1800 mL of water and 170 mL of 35% hydrochloric acid were added to the reaction solution, and the obtained solid was filtered and washed with water to obtain 329.0 g of synthetic intermediate K (yield 94%).

Acetonitrile 1200mL and sulfuric acid 98.1g were added to the synthetic intermediate K200.0g, and it stirred at 90 degreeC for 4 hours. To this reaction solution, 600 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 178.5 g of synthetic intermediate L (yield 95%).

50 mL of methanol and 3.8 g of 28% sodium methoxide methanol solution were added to 5.5 g of compound (X-4). To this solution, 5.0 g of synthetic intermediate L was added and stirred at 60 ° C. for 3 hours. After cooling the reaction solution to room temperature, 0.2 mL of hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 6.9 g of exemplary compound (m-1) (yield 96%). MS: m / z 400 (M +)

Synthesis Example 3 (Preparation of exemplary compound (m-2))
To 160.0 g of salicylamide, 600 mL of acetonitrile and 355.2 g of DBU were added and dissolved. To this solution, 193.2 g of 3-cyanobenzoyl chloride was added and stirred at room temperature for 24 hours. 1200 mL of water and 150 mL of hydrochloric acid were added to the reaction solution, and the resulting solid was filtered and washed with water to obtain 296.0 g of synthetic intermediate M (yield 95%).
The following materials were used.
3-Cyanobenzoyl chloride: Reagent made by Aldrich

1200 mL of acetonitrile and 110.5 g of sulfuric acid were added to 200.0 g of the synthetic intermediate M, and the mixture was stirred at 90 ° C. for 4 hours. To this reaction solution, 600 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 177.3 g of synthetic intermediate N (yield 95%).

50 mL of methanol and 4.3 g of 28% sodium methoxide methanol solution were added to 6.2 g of compound (X-4). The synthetic intermediate N5.0g was added to this solution, and it stirred at 60 degreeC for 3 hours. After cooling the reaction solution to room temperature, 0.2 mL of hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 6.9 g of Exemplified Compound (m-2) (yield 93%). MS: m / z 367 (M +)

Synthesis Example 4 (Preparation of exemplary compound (m-20))
To 25 g of the exemplified compound (m-2), 200 g of 2-ethylhexanol and 13 g of sulfuric acid were added and stirred for 16 hours under reflux conditions. After cooling to room temperature, the resulting solid was washed with methanol and water to obtain 31 g of exemplary compound (m-20) (yield 92%). MS: m / z 498 (M +) [lambda] max = 354 nm (EtOAc)

Synthesis Example 5 (Preparation of Exemplified Compound (21))
To 10 g of the exemplified compound (1), 31.6 g of 2-ethylhexanol, 0.13 g of NaOMe and 100 mL of xylene were added and stirred at 90 ° C. for 6 hours under reduced pressure. Water and ethyl acetate were added to the reaction solution and stirred, and the separated organic phase was concentrated. The obtained residue was crystallized from hexane / isopropyl alcohol (volume ratio 1:10) to obtain 11.7 g of Exemplified Compound (21) (yield 95%). MS: m / z 498 (M +)

Synthesis Example 6 (Preparation of Exemplified Compound (24))
To 10 g of the exemplified compound (1), 9.8 g of fine oxocol 180N (manufactured by Nissan Chemical Industries), 0.13 g of NaOMe and 100 mL of xylene were added and stirred at 90 ° C. for 6 hours under reduced pressure. Water and ethyl acetate were added to the reaction solution and stirred, and the separated organic phase was concentrated. The obtained residue was crystallized from hexane / isopropyl alcohol (1:10 by volume) to obtain 14.5 g of Exemplified Compound (24) (yield 92%). MS: m / z 638 (M +)

Synthesis Example 6 (Preparation of Exemplified Compound (2))
To 160.0 g of salicylamide, 600 mL of acetonitrile and 355.2 g of DBU were added and dissolved. To this solution, 193.2 g of 4-cyanobenzoyl chloride was added and stirred at room temperature for 24 hours. To this reaction solution, 1200 mL of water and 150 mL of hydrochloric acid were added, and the resulting solid was filtered and washed with water to obtain 292.8 g of synthetic intermediate C (yield 94%).

1200 mL of acetonitrile and 110.5 g of sulfuric acid were added to 200.0 g of the synthetic intermediate C, and the mixture was stirred at 90 ° C. for 4 hours. To this reaction solution, 600 mL of triethylamine was added and cooled to room temperature. The obtained solid was filtered and washed with water to obtain 177.2 g of synthetic intermediate D (yield 95%).

50 mL of methanol and 4.3 g of 28% sodium methoxide methanol solution were added to 6.2 g of compound (X-4). Synthetic intermediate D5.0g was added to this solution, and it stirred at 60 degreeC for 3 hours. After cooling the reaction solution to room temperature, 0.2 mL of hydrochloric acid was added. The obtained solid was filtered and washed with water and methanol to obtain 7.1 g of Compound (2) (yield 96%). MS: m / z 367 (M +) ¹ H NMR (CDCl ₃ ): δ 7.01-7.13 (4H), δ 7.56-7.59 (2H), δ 7.91-7.93 (2H), δ 8.52-8.54 (2H), δ 8.58-8.60 (2H), δ 12.77 (2H) λmax = 355 nm (EtOAc)

<Measurement method of pKa>
Exemplified compound (1) was dissolved in acetonitrile so that the absorbance was 1, and 70% perchloric acid (acetic acid solvent) was added dropwise to this solution to change the pH. The solution absorption spectrum at that time was measured, and the ratio between the triazine free form and the proton adduct at each pH was calculated from the absorbance at λmax. The pKa value was determined from the point at which the values became equal. Here, the triazine-free form represents the exemplified compound (1) itself, and the proton adduct represents a compound in which a proton is added to the nitrogen atom of the triazine ring of the exemplified compound (1). Similarly, exemplary compounds (2), (21), (24), (120), (m-1), (m-2), (m-3), (m-4), (m-20) , (M-21), (m-25), (m-31), and comparative compounds (Example A1) and (Example A2), the pKa value was determined. The absorption spectrum was measured using a spectrophotometer UV-3600 (trade name) manufactured by Shimadzu Corporation. The pH was measured using a pH meter meter HM60G (trade name) manufactured by Toa Denpa Kogyo. The absorbance is a value measured at the maximum absorption wavelength of each compound. The results are shown in Table 1.

2. Examples Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto. In addition, the light resistance test in this invention can also be implemented based on JIS A 6909, JIS K 5600, etc.

The coating composition of the present invention was prepared as follows and evaluated for light resistance.

(Examples 1 to 4)
The compound (1), (120), (m-20), or (m-21) of the present invention is converted into a polyacrylate resin (Dianal BR-80: trade name, manufactured by Mitsubishi Rayon Co., Ltd.) (Tg 50 ° C. to 90 ° C. C.) was mixed at 1% by mass with respect to the solid content of the resin to prepare a coating composition. The prepared composition was applied onto glass with a doctor blade, and a coating film was prepared so that the absorbance at the maximum absorption wavelength at 300 nm or more was 1.
(Comparative Examples 1 to 3)
Coating films were prepared in the same manner as in Examples 1 to 4 except that the compounds of the present invention were changed to the compounds of Comparative Examples 1 to 3 shown in Table 2 which were not compounds of the present invention. The film thickness of the prepared coating film is as shown in the table below. The film thickness was measured using a micrometer MDC-25MJ manufactured by Mitutoyo Corporation.

In the above Examples 1 to 4 and Comparative Examples 1 to 3, the content of the ultraviolet absorber relative to the total mass of the coating composition was 0.22% by mass.

(Examples 5 to 8)
Compound (1), (21), (24), (m-25) of the present invention is a polyester resin (Byron 200: trade name, manufactured by Toyobo Co., Ltd.) in dichloromethane solution. % Was mixed to prepare a coating composition.
The prepared composition was applied onto glass with a doctor blade, and a coating film was prepared so that the absorbance at the maximum absorption wavelength at 300 nm or more was 1.
(Comparative Examples 4 to 6)
Coating films were prepared in the same manner except that the compounds of the present invention in Examples 5 to 8 were changed to the compounds of Comparative Examples 4 to 6 shown in Table 2 which are not compounds of the present invention. The film thickness of the prepared coating film is as shown in the table below.

The content of the compound of the present invention relative to the total mass of the coating composition in Examples 5 to 8 and Comparative Examples 4 to 6 was 0.1% by mass. *

(Examples 9 to 11)
The compounds (21), (m-20) and (m-21) of the present invention were added to a low-temperature curable perhydropolysilazane solution (Aquamica NP-110, trade name, manufactured by AZ Electromaterials Co., Ltd.) as a resin solid content. A coating composition was prepared by mixing at 1% by mass. The prepared composition is applied onto glass with a doctor blade, dried at 100 ° C. for 10 minutes, and then cured in an oven kept at 150 ° C. for 30 minutes, whereby the absorbance at the maximum absorption wavelength at 300 nm or more is 1. A coating film was prepared so as to be.
(Comparative Examples 7 to 9)
Coating films were prepared in the same manner except that the compounds of Examples 9 to 11 were changed to the compounds of Comparative Examples 7 to 9 shown in Table 2 which were not compounds of the present invention. The film thickness of the prepared coating film is as shown in the table below.

The content of the compound of the present invention relative to the total mass of the coating composition in Examples 9 to 11 and Comparative Examples 7 to 9 was 0.05% by mass.

(Examples 12 to 14)
The compound (2), (m-20), or (m-25) of the present invention is added to a curable methyl silicone resin solution (TSR127B, trade name, manufactured by Momentive Performance Materials Japan) and the solid content of the resin. A coating composition was prepared by mixing at 1% by mass with respect to the composition. The prepared composition is applied onto glass with a doctor blade, dried at 150 ° C. for 10 minutes, and then cured in an oven kept at 250 ° C. for 30 minutes, whereby the absorbance at the maximum absorption wavelength at 300 nm or more becomes 1. A coating film was prepared as follows. The film thickness of the prepared coating film is as shown in the table below.

(Comparative Examples 10 to 11)
Coating films were prepared in the same manner except that the compounds of the present invention in Examples 12 to 14 were changed to the compounds of Comparative Examples 10 to 11 shown in Table 2 which are not compounds of the present invention. The film thickness of the prepared coating film is as shown in the table below.

The content of the compound of the present invention relative to the total mass of the coating composition in Examples 12 to 14 and Comparative Examples 10 to 11 was 0.45% by mass.

(Light resistance test)
The prepared coating film was exposed in Eye Super UV Tester W151 (Iwasaki Electric Co., Ltd.) (exposure conditions: 90 mW / cm ² , 63 ° C., 50% relative humidity).
In addition, only in Examples 5 to 8 and Comparative Examples 4 to 6, an exposure test was performed with the SCHOTT color glass filter WG-320 applied on the coating film.
The proportion of the UV absorber retained in the sample after 100 hours (measured at λmax by spectral absorption measurement) was examined.

UV absorber:
Benzotriazole-based product is commercially available under the trade name Tinuvin 326 (manufactured by Ciba Specialty Chemicals).
It is commercially available under the trade name Tinuvin 109 (Ciba Specialty Chemicals).
It is commercially available under the trade name Tinuvin 928 (manufactured by Ciba Specialty Chemicals).
It is marketed as a triazine-based product name Tinuvin 405 (manufactured by Ciba Specialty Chemicals).
It is marketed under the trade name Tinuvin 1577 (manufactured by Ciba Specialty Chemicals).
It is marketed as a brand name Tinuvin 400 (made by Ciba Specialty Chemicals).
Benzophenone series The product is commercially available under the trade name Uvinul 3049 (manufactured by BASF).
It is marketed under the trade name SEESORB 100 (manufactured by Sipro Kasei Co., Ltd.).
It is commercially available under the trade name SEESORB 101 (manufactured by Sipro Kasei Co., Ltd.).

(Examples 15 to 20, Comparative Examples 12 to 15)
The compound of the present invention is applied to a thermosetting acrylic / melamine clear coat (based on Viacry® SC 303 / Viacry® SC 370 / Maprenal MF 650). A clear coat composition was obtained by mixing at a concentration of 3% by mass to 10% by mass with respect to the solid content (solid content: 50.4% by mass) of the formulation not included. The clear coat was sprayed onto a glass plate, and after curing (130 ° C./30 seconds), a clear coat having a dry film thickness of 20 μm was obtained.

Prior to specimen exposure, UV absorption spectra were measured using a UV / VIS spectrometer (Perkin Elmer, Lamda 40). Criteria: Acrylic / melamine clear coat not containing the compound of the present invention. Thereafter, the test piece was exposed in an eye super UV tester W151 (Iwasaki Electric Co., Ltd.) (exposure conditions: 90 mW / cm ² , 63 ° C., 50% relative humidity). The proportion of UV absorber retained during exposure (measured in λmax) was determined after measuring the UV absorption spectrum after regular exposure intervals, and the residual amount of the compound was 90% by mass based on the value measured before exposure. The time to become was compared. The test results are summarized in Table 3.

* 1: TINUVIN-1577 was deposited during the test due to insufficient solubility and could not be tested.

Clear coat formulation:
a) Viacryl SC 303 27.51 g
(65% by weight solution in xylene / butanol, 26: 9 wt./wt.)
b) Viacryl SC 370 23.34 g
(75% by mass in Solvesso 100)
c) Maprenal MF 650 27.29 g
(55% by mass in isobutanol)
d) 4.33 g of butyl acetate / butanol (37: 8 wt./wt.)
e) 4.87 g of isobutanol
f) Solvesso 150 2.72 g
g) Crystal oil 30 8.74 g
h) Baysilone MA (1% by weight in Solvesso 150)
1.20g
Total 100.00g

raw materials:
Viacry SC 303: Acrylic resin (Solutia)
Viacry SC 370: Acrylic resin (Solutia)
Solvesso 100: aromatic hydrocarbon, boiling point 163-180 ° C. (Exxon Corp.)
Maprenal MF 650: Melamine resin (Solutia)
Solvesso 150: aromatic hydrocarbon, boiling point 180-203 ° C. (Exxon Corp.)
Crystal oil 30: aliphatic hydrocarbon, boiling point 145-200 ° C. (Shell
Corp. )
Baysilone MA: Leveling agent (Bayer AG)

UV absorber:
TINUVIN-1577: Hydroxyphenyltriazine (HPT) UV absorber, Toyotsu Chemiplas Co., Ltd. TINUVIN-400: Hydroxyphenyltriazine (HPT) UV absorber, Toyotsu Chemiplas Co., Ltd. TINUVIN-928: Benzotriazole (BTZ) UV absorber, Toyotsu Chemiplus Co., Ltd.

(Example 21)
The coating compositions prepared in Examples 15, 16, 17, 20, and Comparative Examples 12, 14, and 15 were applied onto an automotive aluminum panel precoated with a polyester coating.
The test piece was exposed in an eye super UV tester W151 (Iwasaki Electric Co., Ltd.) (exposure conditions 90 mW / cm ² , 63 ° C., 50% relative humidity). Thereafter, the adhesion between the paint layer and the precoat layer was measured by a tape test. The test method was performed according to JIS A 6909 and JIS K 5600. The test results are summarized in Table 4.

It can be seen that the coating composition of the example can provide a film excellent in light resistance for a long period of time.

(Examples 22 to 24)
The compound (21), (24), or (m-21) represented by the general formula (1) in the present invention is added to a silicone acrylic resin solution (trade name “KP-543”, manufactured by Shin-Etsu Silicone Co., Ltd.). A coating composition was prepared by mixing at 1% by mass with respect to the solid content. The prepared composition was applied onto glass with a doctor blade, and dried at 150 ° C. for 2 minutes, whereby a coating film was prepared so that the absorbance at the maximum absorption wavelength at 300 nm or more was 1.

(Comparative Examples 16 to 17)
A coating film was prepared in the same manner as in Examples 22 to 24 except that the compound represented by the general formula (1) in the present invention was changed to the compounds shown in Table 5 below.

(Examples 25 to 26)
The compound (m-25) represented by the general formula (1) in the present invention is added to a dichloromethane solution of a polyester resin (trade name “Byron 200”, manufactured by Toyobo Co., Ltd.) in a dichloromethane solution at 1% by mass with respect to the solid content of the resin. Further, Sumidur N-75 (manufactured by Sumika Bayer Urethane Co., Ltd.) was added as a curing agent at 1% by mass with respect to the polyester resin to prepare a coating composition.
The prepared coating composition was applied onto glass with a doctor blade, dried at 100 ° C. for 5 minutes, and a coating film was prepared so that the absorbance at the maximum absorption wavelength at 300 nm or more was 1 (Example 25).
Similarly, a coating film was prepared in the same manner except that the curing agent of Example 25 was Denacol EX-614B (manufactured by Nagase ChemteX Corporation) and the addition amount was changed to 2% by mass with respect to the polyester resin (Examples). 26).

The film thickness of the prepared coating is as shown in the table below.

For the coating films of Examples 22 to 26 and Comparative Examples 16 to 17, light resistance tests were performed in the same manner as in Examples 1 to 14. The results are shown in Table 5 below.

(Example 27)
[Preparation of hydroxyl group-containing resin]
Into a 5 liter reactor equipped with a stirrer, a heating device, a cooling device, and a decompression device, 763.2 g of methyl ethyl ketone was introduced and heated to 60 ° C. A polymerizable monomer mixture consisting of 453.6 g of methyl methacrylate, 320 g of ethyl acrylate, 240 g of n-butyl acrylate, 444.8 g of hydroxyethyl methacrylate, 80 g of lauryl methacrylate and 61.6 g of acrylic acid, and 2,2′-azobis at the same time A mixed solution consisting of 20 g of (2,4-dimethylvaleronitrile), 224 g of solvent naphtha and 64 g of ethylene glycol monobutyl ether was charged at this temperature over 4 hours.

After further stirring for 2 hours at this temperature, 596.8 g of methyl ethyl ketone and 30 g of exemplified compound (m-21) were added. The resulting mixture was cooled to 40 ° C., 68.6 g of dimethylethanolamine was added and mixed uniformly, and dispersed in 2033.6 g of deionized water. *

Next, the obtained dispersion was decompressed while being kept at 40 ° C., and 1392 g of an organic solvent such as methyl ethyl ketone contained in the dispersion was distilled off to obtain an acrylic resin (A) having a solid content of 40% by mass. *

The obtained acrylic resin (A) had a hydroxyl value of 120 mgKOH / g, an acid value of 30 mgKOH / g, and a mass average molecular weight of 30,000.

A mixture of 60 parts by mass of acrylic resin (A) and 40 parts by mass of Bihijoule 3100 (curing agent, manufactured by Sumika Bayer Urethane Co., Ltd., trade name) is added to an ethylene glycol monobutyl ether / solvent naphtha mixed solvent (1/1 by mass ratio). A mixed liquid composed of 20% by mass and 80% by mass of water was added to obtain an aqueous and transparent coating composition (B) (solid content 52% by mass, content of compound of general formula (1) 0.43% by mass) %). An aqueous and transparent coating composition (B) was applied to a glass substrate so as to have a cured film thickness of 40 μm, and cured by heating at 140 ° C. for 30 minutes to obtain a test plate C.

(Weather resistance test)
Test plate C was tested by QUV accelerated exposure using an accelerated weathering tester manufactured by Q Panel. The test conditions were as follows: UV irradiation 16 hours and water condensation 8 hours / 50 ° C. as one cycle, and the transparent coating surface after observing 125 cycles (3,000 hours) continuously was visually observed. No deterioration was observed, and the condition was good.

(Examples 28 to 29)
In the present invention, the compound (21) or (m-20) represented by the general formula (1) is mixed with a resin solution (Comporacene AC (manufactured by Arakawa Chemical Industries)) in which silica fine particles are hybridized with an acrylic resin. A coating composition was prepared by mixing at 1% by mass with respect to the composition. The prepared composition was applied onto glass with a doctor blade, and dried at 150 ° C. for 2 minutes, whereby a coating film was prepared so that the absorbance at the maximum absorption wavelength at 300 nm or more was 1.

(Comparative Example 18)
A coating film was prepared in the same manner as in Examples 28 and 29 except that the compound represented by formula (1) in the present invention was changed to the compound described in Table 6 below.

The film thickness of the prepared coating is as shown in the table below.

The light resistance test was conducted on the coating films of Examples 28 to 29 and Comparative Example 18 in the same manner as in Examples 1 to 14. The results are shown in Table 6 below.

UVINUL-3050 used in Comparative Example 18 is represented by the following structural formula and is commercially available under the trade name Uvinul 3050 (manufactured by BASF).

Example 101
An organochlorosilane mixed solution was prepared by mixing 33.85 parts of phenyltrichlorosilane, 3.23 parts of vinyltrichlorosilane, and 3.40 parts of tetrachlorosilane, and then 20.80 parts of toluene, 9.37 parts of isopropyl alcohol, 4 -The organochlorosilane mixed solution was dropped into a mixed solution of 0.003 part of methoxyphenol and 12 parts of water over 60 minutes while keeping the liquid temperature at 30 ° C or lower and stirring vigorously. After further stirring for 60 minutes, 80 parts of toluene was added and washed with water until the washed aqueous layer became neutral. After washing with water, a toluene solution having a siloxane concentration of 10% by mass was prepared, 0.024 part of potassium hydroxide was added, and the mixture was polymerized by heating under reflux while removing water with a Dean-Stark tube for 5 hours. Subsequently, it concentrated until it became solid content concentration 75 mass%, and also it recirculate | refluxed for 3 hours.
Next, 6 parts of trimethylchlorosilane was added and stirred at room temperature for 60 minutes to neutralize the alkali and remove the remaining silanol groups. After filtration, toluene was distilled off under reduced pressure by heating, 156.2 parts of isopropyl alcohol was added, and the precipitate was isolated by decantation. The obtained precipitate was dried and pulverized to obtain a solid organopolysiloxane (resin A).
When the molecular weight in terms of polystyrene was measured by gel permeation chromatography, the weight average molecular weight was 14,800 and the number average molecular weight was 4,900. The Tg of organopolysiloxane (Resin A) was 190 ° C.
Composition formula of organopolysiloxane A: Vi _0.10 Me _0.05 Ph _0.76 SiO _1.55 (Hereinafter, Vi represents a vinyl group, Me represents a methyl group, and Ph represents a phenyl group)
From the preparation ratio, composition formula, and NMR spectrum, it is clear that the organopolysiloxane (resin A) contains the structural unit of formula (I).
100 parts by mass of the obtained powder of solid organopolysiloxane (resin A) and 1 part of compound (2) were mixed with a mixer to obtain a silicone resin composition.

(Example 102)
A mixture consisting of 698 parts of phenyltrichlorosilane, 169 parts of methylvinyldichlorosilane, 194 parts of dimethyldichlorosilane, and 530 parts of toluene was dropped into 2,500 parts of water over 60 minutes with vigorous stirring. The mixture was further stirred for 60 minutes and then washed with water until neutrality. After washing with water, a toluene solution having a siloxane concentration of 25% was added, 0.42 parts of potassium hydroxide was added, and the mixture was heated to reflux and polymerized for 5 hours. Next, 13.8 parts of trimethylchlorosilane was added and stirred at room temperature for 60 minutes to neutralize the alkali and remove the remaining silanol groups. Thereafter, filtration was performed, and toluene was distilled off under reduced pressure by heating to obtain a transparent vinyl group-containing organopolysiloxane (resin B).
To 100 parts of the resulting vinyl group-containing organopolysiloxane (resin B), 30 parts of an organohydrogenpolysiloxane represented by the following formula and 0.05 part of an octyl alcohol solution of 1% chloroplatinic acid were mixed, and further compound (2) 1.3 parts was added to obtain a silicone resin composition.

Example 103
A silicone resin composition was obtained in the same manner as in Example 101 except that 1 part of the compound (2) was changed to 1 part of the compound (24).
Example 104
A silicone resin composition was obtained in the same manner as in Example 102 except that 1.3 parts of the compound (2) was changed to 5 parts of the compound (21).
[Examples 105 to 113]
In the same manner, a silicone resin composition was prepared. The created samples are shown in the table.
[Examples 114 to 116]
A silicone resin composition was obtained in the same manner as in Example 101 except that 1 part of the compound (2) was changed to 1 part of the compound (m-21) and an additive was further added.

(Light resistance test)
The obtained silicone resin composition was molded at an injection molding pressure of 20 Mpa and a molding time of 1 hour to prepare a molded plate having a thickness of 1 mm. The molding temperature is shown in the table.
Subsequently, the obtained molded plate was exposed for 200 hours in an i-super UV tester W151 (Iwasaki Electric Co., Ltd.) (exposure conditions: 90 mW / cm ² , 63 ° C., 50% humidity). Samples after the test were confirmed, and those in which yellowing, haze, or precipitation of additives were observed were evaluated as x, and the others were evaluated as ◯.

* (Example A1) and (Example A2) represent the following compounds.

The above-mentioned compound is commercially available, Example A1 is Cinba Tinuvin 1577FF, and Example A2 is CYTEC CYASORB UV-1164.
B0 (antioxidant): IRGNOX 1010 (manufactured by Ciba Specialty Chemicals)
B1 (UV absorber): TINUVIN 928 (manufactured by Ciba Specialty Chemicals)
B2 (light stabilizer): TINUVIN 770 (manufactured by Ciba Specialty Chemicals)

From the above results, it was found that the silicone resin compositions of the present invention (Examples 101 to 116) were superior in light resistance and solubility as compared with Comparative Examples.

<Example 1; Lens>
The silicone resin composition of Example 106 was molded with an injection molding pressure of 20 Mpa and a molding time of 1 hour to mold a lens. When the hardness of the obtained lens was measured with a type D hardness meter in accordance with JIS 6253 at room temperature, it was 50.
The obtained lens was used as a lens for a bullet-type LED. As a comparison, when a lens made from the composition of Comparative Example 105 was used as a bullet-type LED lens and the state of the lens after 1000 hours of use was observed, only the lens made from the composition of Comparative Example 105 was yellowed. Occurred.

<Example 2; Use as sealant>
An electrolyte was injected between two glass electrodes, one of which was an FTO-deposited glass with a dye-adsorbed titanium oxide film and the other was an FTO-deposited glass on which platinum was deposited. Covered with a composition, cured, and sealed to produce a solar cell module.
Similarly, a module was prepared using the composition of Comparative Example 105, and was irradiated with a solar simulator (manufactured by Pexel) at 1000 (irradiation conditions AM1.5, 1SUN). When the sample after irradiation was observed, liquid leakage occurred only in the module prepared from the composition of Comparative Example 105.

The coating composition of the present invention contains the compound represented by the general formula (1), so that the coating composition has excellent light resistance (fastness to ultraviolet light) even in the long wave ultraviolet region. The light stability of the member coated with can be improved.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is a Japanese patent application filed on Jan. 19, 2010 (Japanese Patent Application No. 2010-009540), a Japanese patent application filed on Mar. 30, 2010 (Japanese Patent Application No. 2010-079930), and an application filed on Mar. 30, 2010. This is based on a Japanese patent application (Japanese Patent Application No. 2010-079931) and a Japanese patent application filed on November 19, 2010 (Japanese Patent Application No. 2010-259579), the contents of which are incorporated herein by reference.

Claims

A composition comprising a compound represented by the following general formula (1) and a binder component.

[R 1a , R 1b , R 1c , R 1d and R 1e each independently represent a monovalent substituent other than a hydrogen atom or a hydroxy group, and at least one of the substituents is a Hammett's σp Represents a substituent whose value is positive. Moreover, you may combine with substituents and may form a ring. R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n and R 1p each independently represent a hydrogen atom or a monovalent substituent. Moreover, you may combine with substituents and may form a ring. ]
The monovalent substituent is a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted carbamoyl group, substituted or Unsubstituted alkylcarbonyl group, nitro group, substituted or unsubstituted amino group, hydroxy group, alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group, substituted or unsubstituted sulfamoyl group, thiocyanate group, Or a substituted or unsubstituted alkylsulfonyl group, where the substituent is a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cyano group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylcarbonyl group, Nitro group, amino group, hydroxy group, alkoxy group having 1 to 20 carbon atoms, aryloxy , Sulfamoyl group, characterized in that it is a thiocyanate group, or an alkylsulfonyl group, the coating composition according to claim 1.
The composition according to claim 1, wherein R 1c is a substituent having a positive Hammett's σp value.
R 1a , R 1c and R 1e represent a hydrogen atom, R 1b and R 1d each independently represent a hydrogen atom or a substituent having a positive Hammett's σp value, and at least one of R 1b and R 1d The composition according to claim 1 or 2, wherein the composition is a substituent having a positive Hammett's σp value.
The composition according to any one of claims 1 to 4, wherein the Hammett's rule has a σp value in the range of 0.1 to 1.2.
The substituent having a positive σp value according to the Hammett rule is a group selected from COOR r , CONR s 2 , a cyano group, a trifluoromethyl group, a halogen atom, a nitro group, and SO 3 M. The composition according to any one of claims 1 to 5, wherein [R r and R s each represent a hydrogen atom or a monovalent substituent. M represents a hydrogen atom or an alkali metal. ]
The composition according to any one of claims 1 to 4, wherein the substituent having a positive Hammett's σp value is COOR r . [R r represents a hydrogen atom or a monovalent substituent. ].
The composition according to any one of claims 1 to 3, and 5 to 7, wherein R 1c is a cyano group.
The composition according to any one of claims 1 to 8, wherein R 1h or R 1n is a hydrogen atom.
10. The composition according to claim 1 , wherein R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n and R 1p are hydrogen atoms. object.
The composition according to any one of claims 1 to 10, wherein the compound represented by the general formula (1) has a pKa in the range of -5.0 to -7.0.
The compound represented by the general formula (1) is contained in an amount of 0.1 to 30% by mass, based on the total mass of the coating composition, according to any one of claims 1 to 11. Composition.
Binder component is chlorinated rubber resin, phenol resin, alkyd resin, amino alkyd resin, urea resin, vinyl resin, acrylic resin, polyester resin, epoxy resin, polyurethane resin, silicone resin, The composition according to any one of claims 1 to 12, which is a component containing at least one of a silicon resin, a fluororesin, a silazane resin, and a melamine resin.
The composition according to any one of claims 1 to 12, wherein the binder component is a silicone resin.
The composition according to claim 14, wherein the silicone resin has an aromatic group in the molecule.
The composition according to claim 14 or 15, further comprising at least one selected from a light stabilizer or an antioxidant as an additive.
The composition according to any one of claims 14 to 16, wherein the Shore D hardness of a cured product obtained by curing the composition is 30 or more and 100 or less.
14. The composition according to any one of 1 to 13, further comprising a curing agent.
The binder component according to any one of claims 1 to 13 and 18, wherein the binder component is a hydroxyl group-containing resin having a hydroxyl value of 30 to 600 mgKOH / g and an acid value of 0 to 100 mgKOH / g. Composition.
A film obtained from the composition according to any one of claims 1 to 13, 18 and 19.
The coating according to claim 20, wherein the thickness of the coating is 0.1 to 10,000 μm.
A member having the coating according to claim 20 or 21.
The composition according to any one of claims 1 to 15, 18 and 19, wherein the composition is a coating composition.
24. The composition according to claim 23, wherein the composition is for vehicles.
A lens obtained by molding the composition according to any one of claims 1 to 17.
A sealing material obtained by molding the composition according to any one of claims 1 to 17.