JP4462421B2 - UV-absorbing group-containing organosilicon compound, method for producing the same, coating composition, and coated article - Google Patents

Description

  The present invention relates to a novel ultraviolet-absorbing group-containing organosilicon compound, a method for producing the same, a coating composition using the organosilicon compound, and a coated article using the composition.

  Conventionally, organic ultraviolet absorbers have been blended in various binders such as acrylic resins and used as ultraviolet cut paints or weather resistant paints. However, when used for a long period of time, there has been a problem that the performance deteriorates due to bleeding out of the ultraviolet absorber or photodegradation of the organic polymer as a binder. In order to overcome these problems, the binder component has been improved or an antioxidant has been used in combination (Japanese Patent Laid-Open No. 63-43972: Patent Document 1). In addition, attempts have been made to eliminate bleed out by copolymerization using an organic ultraviolet absorber having a methacryloyl group (for example, JP-A-6-88064: Patent Document 2). However, since these resins themselves have a number of ester bonds in the main chain, the weather resistance is not sufficient, causing a Norrish type reaction, or having a drawback that they cannot be used in a high temperature environment exceeding 200 ° C. .

  In addition, in order to improve the weather resistance, a silicone resin is also used as a binder. In this case, however, simply adding an ultraviolet absorber causes deterioration in performance due to the bleeding out of the ultraviolet absorber. . Thus, many attempts have been made so far to introduce a group capable of reacting with a silicone resin into an ultraviolet absorber (for example, JP-A-2-243695: Patent Document 3). However, these reactive silylated UV absorbers still have some problems, such as the need for multi-step synthesis and troublesome processes such as removal of the hydrosilylation catalyst.

JP-A-63-43972 JP-A-6-88064 JP-A-2-243695

  The present invention has been made in view of the above circumstances, and provides a novel ultraviolet absorbing group-containing organosilicon compound having an excellent ultraviolet absorption and having an alkoxysilyl group, and a method for producing the same. Also, by using this ultraviolet absorbing group-containing organosilicon compound, a coating composition that is excellent in heat resistance and water resistance and can be stably held in the coating film without causing bleedout, and the like, and It aims at providing the coated article formed by coat | covering with the cured film of this composition.

  As a result of intensive studies to achieve the above object, the present inventor has found a novel ultraviolet absorbing group that has not been known so far and is represented by the following general formula (1) or the following average composition formula (2). Since the organosilicon compound contains only a few production steps and the reaction catalyst used can be removed by a general neutralization reaction, the target product can be easily produced, and the above compound can be reacted with a reactive silylate. Coating composition having excellent UV protection, heat resistance, water resistance, bleed-out resistance, and storage stability by combining with various binders such as organic resins such as acrylic resins and silicone resins as a UV absorber As a result, the present invention has been made.

  Accordingly, the present invention provides an ultraviolet absorbing group-containing alkoxysilane represented by the following general formula (1) and an ultraviolet absorbing group-containing polyorganosiloxane represented by the following average composition formula (2).

{Wherein R ¹ is the same or different alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, R ² is the same or different alkyl group having 1 to 8 carbon atoms; ³¹ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms or an acyloxy group having 1 to 8 carbon atoms, and R ³² , R ³³ and R ³⁴ are each independently And a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and R ³⁵ is represented by the following formula (7) or (8):

In a divalent organic group represented, R ³⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms, a is an integer of 0 to 2. }

[Wherein Z represents the following general formula (3)
{In the formula, R ³¹ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an acyloxy group having 1 to 8 carbon atoms, and R ³² , R ³³ , R ³⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and R ³⁵ represents the following formula (7) Or (8)

In a divalent organic group represented, R ³⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms. }
R is the same or different hydrogen atom or unsubstituted or halogen having 1 to 18 carbon atoms , γ-methacryloxypropyl group, γ-acryloxypropyl group, γ-glycidoxypropyl group 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group or γ-aminopropyl group- substituted monovalent hydrocarbon group, R ² is the same or different alkyl group having 1 to 8 carbon atoms, m , N, p, q are numbers satisfying 0 <m ≦ 1, 0 ≦ n ≦ 2, 0 ≦ p <3, 0 ≦ q ≦ 3, and 0 <m + n + p + q <4, respectively. ]

  Moreover, this invention provides the following manufacturing method as a manufacturing method of these novel ultraviolet absorptive group containing organosilicon compounds.

[Production Method (I)]
By reacting a (meth) acryl group-containing hydroxybenzotriazole represented by the following general formula (4) with a mercapto group-containing alkoxysilane represented by the following general formula (5) in the presence of a base, A method for producing an alkoxysilane of formula (1).
{Wherein R ¹ is the same or different alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, R ² is the same or different alkyl group having 1 to 8 carbon atoms; ³¹ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms or an acyloxy group having 1 to 8 carbon atoms, and R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group or an alkoxy group having 1 to 8 carbon atoms having 6 to 12 carbon atoms, R ^{35 'carbon} atoms 3-20 of CH ₂ = A monovalent organic group represented by CR′—COO—R ″ — (R ′ is a hydrogen atom or a methyl group, and R ″ is a divalent hydrocarbon group having 0 to 17 carbon atoms); R ³⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms, a is an integer of 0 to 2. }

[Production Method (II)]
The polyorganosiloxane of the formula (2) is obtained by (co) hydrolytic condensation of the alkoxysilane of the formula (1) or at least one other hydrolyzable silane and / or hydrolyzable siloxane. How to manufacture.

[Production Method (III)]
A process for producing a polyorganosiloxane of the formula (2) by equilibrating the alkoxysilane of the formula (1) and at least one other silane and / or siloxane in the presence of an acid or a base. .

[Production Method (IV)]
By reacting the (meth) acrylic group-containing hydroxybenzotriazole of the formula (4) with the mercapto group-containing polyorganosiloxane represented by the following average composition formula (6) in the presence of a base, the formula (4) 2) A process for producing the polyorganosiloxane.

{In the formula, Y is HS-R ³⁶ - mercapto group-containing group represented by, R ³⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms, R represents a hydrogen atom or a carbon atoms of the same or different 1-18 unsubstituted or halogen, γ-methacryloxypropyl group, γ-acryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group or γ-aminopropyl A group- substituted monovalent hydrocarbon group, R ² is the same or different alkyl group having 1 to 8 carbon atoms, and m, n, p, and q are 0 <m ≦ 1, 0 ≦ n ≦ 2, respectively. , 0 ≦ p <3, 0 ≦ q ≦ 3, and 0 <m + n + p + q <4. }

  Furthermore, the present invention provides a coating composition containing these novel UV-absorbing group-containing organosilicon compounds and a cured coating of this composition directly or via at least one other layer on a substrate. A coated article is provided.

  According to the present invention, a novel organosilicon compound having excellent ultraviolet absorption and having an alkoxysilyl group can be easily obtained. In addition, the coating composition using the ultraviolet-absorbing organosilicon compound of the present invention is excellent in heat resistance and water resistance, and can be stably held in the coating film without bleeding out the ultraviolet absorber. Become.

  The first ultraviolet absorbing group-containing organosilicon compound of the present invention is an alkoxysilane represented by the following general formula (1).

{Wherein R ¹ is the same or different alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, R ² is the same or different alkyl group having 1 to 8 carbon atoms; ³¹ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms or an acyloxy group having 1 to 8 carbon atoms, and R ³² , R ³³ and R ³⁴ are each independently And a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and R ³⁵ is an ester bond containing 2 to 20 carbon atoms. R ³⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and a is an integer of 0 to 2. }

In the above formula (1), as the alkyl group having 1 to 8 carbon atoms or the aryl group having 6 to 12 carbon atoms of R ¹ , for example, in the case of an alkyl group, a methyl group, an ethyl group, an n-propyl group, i- Propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, etc. In the case of an aryl group, a phenyl group, a tolyl group, a xylyl group and the like can be exemplified, and a methyl group is particularly preferable from the viewpoint of weather resistance and availability.

Specific examples of the alkyl group having 1 to 8 carbon atoms of R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, and t-butyl group. , N-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, etc., but availability and control of hydrolysis In view of ease of treatment, a methyl group or an ethyl group is preferable.

R ³¹ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an acyloxy group having 1 to 8 carbon atoms, specifically, a hydrogen atom or a chlorine atom , Bromine atom, hydroxyl group, methyl group, ethyl group, n-propyl group, t-butyl group, phenyl group, tolyl group, xylyl group, acetoxy group, propoxy group, etc. From the viewpoint, a hydrogen atom is preferable.

R ³² , R ³³ , and R ³⁴ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. Examples include atoms, chlorine atoms, bromine atoms, methyl groups, ethyl groups, n-propyl groups, t-butyl groups, phenyl groups, tolyl groups, xylyl groups, methoxy groups, ethoxy groups, and propoxy groups. From the viewpoint of availability, a hydrogen atom is preferable.

R ³⁵ is an ester bond-containing divalent organic group having 2 to 20 carbon atoms, particularly 3 to 10 carbon atoms, and has the following formula: —R ″ —OC (═O) —R ′ ″ —
(R ″ is a divalent hydrocarbon group having 0 to 17 carbon atoms, particularly 1 to 7 carbon atoms, especially an alkylene group. R ′ ″ is a divalent hydrocarbon group having 2 to 9 carbon atoms, particularly —CH ₂ -CH ₂ - or -CH (CH ₃₎ -CH ₂ - are preferred).
The group represented by these is preferable.
Specifically, —CH ₂ —OC (═O) — (CH ₂ ) ₂ —, —CH ₂ —OC (═O) —CH (CH ₃ ) CH ₂ —, —CH ₂ —OC (═O) _{-C (CH 3) 2 -,} - (CH 2) 2 -OC (= O) - (CH 2) 2 -, - (CH 2) 2 -OC (= O) -CH (CH 3) CH 2 - _{, - (CH 3) CH-} OC (= O) - (CH 2) 2 -, - (CH 3) CH-OC (= O) -CH (CH 3) CH 2 -, - (CH 2) 3 - OC (= O) - (CH 2) 2 -, - (CH 2) 3 -OC (= O) -CH (CH 3) CH 2 -, - (CH 3) CH-OC (= O) - (CH _{2) 2 -, - (CH} 3) 2 C-OC (= O) - (CH 2) 2 -, - (CH 3) CH-OC (= O) -CH (CH 3) CH 2 -, - ( _{CH 3) 2 C-OC (} = O) -CH (CH 3) CH 2 -, - (CH 2) _{4 -OC (= O) - (} CH 2) 2 -, - (CH 2) 4 -OC (= O) -CH (CH 3) CH 2 -, - (CH 2) 5 -OC (= O) - (CH ₂ ) ₂ —, — (CH ₂ ) ₅ —OC (═O) —CH (CH ₃ ) CH ₂ —, — (CH ₂ ) ₆ —OC (═O) —CH (CH ₃ ) CH ₂ — , — (CH ₂ ) ₈ —OC (═O) —CH (CH ₃ ) CH ₂ —, — (CH ₂ ) ₂ —C ₆ H ₁₀ — (CH ₂ ) ₂ —OC (═O) —CH (CH ₃ ) CH ₂ — and the like can be mentioned. From the viewpoint of easy availability and economy, — (CH ₂ ) ₂ —OC (═O) —CH (CH ₃ ) CH ₂ —, or — (CH ₂ ) ₂ —OC (═O) —CH ₂ CH ₂ — is preferred.

R ³⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms, preferably an alkylene group. Specifically, —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₃ ) ₂ C—, — (CH ₂ ) ₃ —, — (CH ₃ ) CH—, — (CH ₂ ) ₄ — , — (CH ₂ ) ₅ —, — (CH ₂ ) ₆ —, —C ₆ H ₁₀ —, — (CH ₂ ) ₈ —, — (CH ₂ ) ₂ —C ₆ H ₁₀ — and the like. . From the viewpoint of easy availability and economy, — (CH ₂ ) ₃ — is preferable.

  a is an integer of 0 to 2, preferably 0 or 1. When a is larger than 2, the number of hydrolyzable groups in one molecule of the resulting UV-absorbing group-containing alkoxysilane is reduced, and as a result, when a coating composition is formed, it is not incorporated into the binder network and easily bleeds out. Or the crosslinking density of the binder may be reduced, and it may be difficult to obtain wear resistance, or curing may be difficult to proceed sufficiently.

Some specific examples of the alkoxysilane represented by the formula (1) are shown below.

  The alkoxysilane represented by the formula (1) can be produced by the following production method (I).

Manufacturing method (I)
A method in which a (meth) acryl group-containing hydroxybenzotriazole represented by the following general formula (4) is reacted with a mercapto group-containing alkoxysilane represented by the following general formula (5) in the presence of a base.

In the formula, R ¹ , R ² , R ³¹ , R ³² , R ³³ , R ³⁴ , and R ³⁶ are the same as described above, and R ^{35 ′} represents —R ″ —OC (═O having 3 to 20 carbon atoms). ) —CR′═CH ₂ is a monovalent organic group (R ″ is as described above, R ′ is a hydrogen atom or a methyl group), specifically,
_{-CH 2 -OC (= O) -CH} = CH 2, -CH 2 -OC (= O) -C (CH 3) = CH 2, -CH 2 CH 2 -OC (= O) -CH = CH 2 , —CH ₂ CH ₂ —OC (═O) —C (CH ₃ ) ═CH ₂ , — (CH ₂ ) ₃ —OC (═O) —CH═CH ₂ , — (CH ₂ ) ₃ —OC (= _{O) -C (CH 3) =} CH 2, - (CH 2) 4 -OC (= O) such as -CH = CH ₂ can be mentioned.

  In this reaction, in the presence of a base, the (meth) acryl group-containing hydroxybenzotriazole represented by the formula (4) may be dropped into the mercapto group-containing alkoxysilane represented by the formula (5). Further, a mercapto group-containing alkoxysilane may be dropped into the (meth) acryl group-containing hydroxybenzotriazole. In this case, the alkoxysilane of the formula (5) is preferably 0.5 to 3.0 mol, particularly preferably a reaction molar ratio of 0.8 to 2.0 mol with respect to 1 mol of the benzotriazole of the formula (4). .

  Examples of the base include hydroxides of alkali metals and alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide; lithium methoxide, sodium methoxide, potassium methoxide Alkali metal and alkaline earth metal alkoxides such as potassium carbonate and calcium carbonate alkaline metal and alkaline earth metal carbonates; alkaline metal and alkaline earth metal carboxylates such as potassium formate, sodium acetate and potassium propionate Acid salts; alkali metal and alkaline earth metal siliconate such as sodium siliconate and potassium siliconate; ammonium hydroxide, tetramethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium Quaternary ammonium hydroxides such as hydroxide and trimethylbenzylammonium hydroxide; Ammonium carboxylates such as ammonium acetate, dimethylamine acetate, ethanolamine acetate, dimethylaniline formate; Triethylamine, triethylenediamine, benzyltrimethylamine, pyridine, γ An amine such as aminopropyltrimethoxysilane; an anion exchange resin in which the base is made of a styrene-divinylbenzene copolymer and the like, and a basic functional group such as ammonium salt or amine is bonded as a functional group. Although the usage-amount of a base is selected suitably, it is preferable that it is 0.0001-2.0 molar ratio with respect to 1 mol of alkoxysilanes of Formula (5), especially 0.001-0.5 molar ratio.

  In the reaction, a general solvent may be used, for example, alcohols such as methanol, ethanol, isopropanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol; diethyl ether, tetrahydrofuran, ethylene Polar solvents such as ethers such as glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are preferred.

  The reaction temperature should just be the range of 0-150 degreeC, Preferably it is the range of 10-100 degreeC. If the reaction temperature is higher than 150 ° C., the benzotriazole of formula (4) and the ester bond of formula (1) which is the target product may be cleaved, resulting in a decrease in yield. The reaction time may be in the range of 30 minutes to 24 hours, although it depends on the reaction temperature. Preferably it is the range of 1 to 6 hours.

  The second ultraviolet absorbing group-containing organosilicon compound of the present invention is a polyorganosiloxane represented by the following average composition formula (2).

[Wherein Z represents the following general formula (3)
{In the formula, R ³¹ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an acyloxy group having 1 to 8 carbon atoms, and R ³² , R ³³ , R ³⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and R ³⁵ has 2 to 20 carbon atoms. R ³⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms. }
R is the same or different hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, and R ² is the same or different carbon number 1 to 8 M, n, p, q are numbers satisfying 0 <m ≦ 1, 0 ≦ n ≦ 2, 0 ≦ p <3, 0 ≦ q ≦ 3, and 0 <m + n + p + q <4, respectively. ]

  In the above formula (2), R is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, specifically a hydrogen atom; a methyl group, an ethyl group, a propyl group, or a butyl group. Alkyl groups such as pentyl group, hexyl group, heptyl group and octyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group, tolyl group and xylyl group Halogen-substituted hydrocarbon groups such as chloromethyl group, γ-chloropropyl group, 3,3,3-trifluoropropyl group; γ-methacryloxypropyl group, γ-acryloxypropyl group, γ-glycidoxypropyl group And substituted hydrocarbon groups such as 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group, γ-aminopropyl group, etc. . In particular, when considering weather resistance, a methyl group, an ethyl group, and a trifluoropropyl group are preferable, and a methyl group is particularly preferable. In consideration of compatibility with an organic resin binder, reactivity, and the like, a phenyl group, a vinyl group, γ -Substituted hydrocarbon groups such as methacryloxypropyl group, γ-acryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group, γ-aminopropyl group and the like are preferable.

R ² is the same as described above. M, n, p, and q are numbers satisfying 0 <m ≦ 1, 0 ≦ n ≦ 2, 0 ≦ p <3, 0 ≦ q ≦ 3, and 0 <m + n + p + q <4, preferably 0 .001 ≦ m ≦ 1, 0.01 ≦ n ≦ 1.99, 0 ≦ p <2.99, 0 ≦ q ≦ 2.99, 0.001 ≦ m + n + p + q <3. This is because when m is 0, the ultraviolet absorbing ability is not exhibited, and when it is larger than 1, the solubility in other siloxane resins and organic resins is lowered and whitening is likely to occur. Further, when n is larger than 2, the molecular weight is difficult to increase, and bleeding and scattering are likely to occur, and when p is 3 or more, the storage stability is likely to be lowered.

Z is an organic group represented by the general formula (3), in which R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ are the same as described above.

  The polyorganosiloxane represented by the formula (2) of the present invention can be produced by the following production methods (II) to (IV).

Manufacturing method (II)
The method of (co) hydrolytic condensation reaction of the alkoxysilane of the said Formula (1) of this invention, or this and at least 1 type of other hydrolysable silane and / or hydrolysable siloxane.

Manufacturing method (III)
The method of carrying out the equilibration reaction of the alkoxysilane of the said Formula (1) of this invention, and an at least 1 sort (s) of other silane and / or siloxane in presence of an acid or a base.

Manufacturing method (IV)
A method in which the (meth) acrylic group-containing hydroxybenzotriazole of the formula (4) is reacted with a mercapto group-containing polyorganosiloxane represented by the following average composition formula (6) in the presence of a base.

{Wherein Y is a mercapto group-containing group represented by HS-R ^36- (R ³⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms), and R is the same or different hydrogen atom or carbon. An unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, R ² is the same or different alkyl group having 1 to 8 carbon atoms, and m, n, p, and q are each 0 <m ≦ 1, 0 ≦ n ≦ 2, 0 ≦ p <3, 0 ≦ q ≦ 3, and 0 <m + n + p + q <4. }

  The (co) hydrolytic condensation reaction of the production method (II) and the equilibration reaction of the production methods (III) and (IV) are known reaction forms and can be performed under general conditions and procedures.

Here, as other hydrolyzable silane and hydrolyzable siloxane in the (co) hydrolysis condensation of the production method (II), the following general formula:
(R ⁴¹ ) _x Si (A) _4-x
{In the formula, R ⁴¹ is the same as R, and A is the same or different halogen atom, an alkoxy group having 1 to 3 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, an alkenoxy group having 1 to 6 carbon atoms, or Isocyanate group. x is an integer of 0-3. }
And a partially hydrolyzed condensate thereof.

  As an example of the compound of the above general formula, when x = 0, tetrahydrosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetraacetoxysilane, tetraisocyanatesilane, and a partial hydrolysis condensate of tetramethoxysilane ( Trade name “M silicate 51” manufactured by Tama Chemicals, trade name “MSI 51” manufactured by Colcoat, trade names “MS 51” and “MS 56” manufactured by Mitsubishi Chemical), partial hydrolysis condensate of tetoethoxysilane (trade name “silicate 35”, "Silicate 45" manufactured by Tama Chemicals, trade names "ESI40", "ESI48" manufactured by Colcoat), partial co-hydrolysis condensate of tetramethoxysilane and tetraethoxysilane (trade name "FR-3" manufactured by Tama Chemicals, trade name “EMSi48” manufactured by Colcoat).

  Specific examples in the case of x = 1 include hydrogentrichlorosilane, hydrogentrimethoxysilane, hydrogentriethoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltriisopropenoxysilane, Methyltriisocyanate silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxy Silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyl Limethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropyltrimethoxysilane, 3,3 , 3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-amino Partial hydrolysis-condensation product of propyltriethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, and methyltrimethoxysilane (trade names “KC-89S” and “X-40-9220” manufactured by Shin-Etsu Chemical Co., Ltd.) Methyltrimethoxysilane and and a partial cohydrolysis condensate with γ-glycidoxypropyltrimethoxysilane (trade name “X-41-1056” manufactured by Shin-Etsu Chemical Co., Ltd.).

  In the case of x = 2, methyl hydrogen dichlorosilane, methyl hydrogen dimethoxy silane, methyl hydrogen diethoxy silane, dimethyl dichloro silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, dimethyl diacetoxy silane, dimethyl diisocyanate silane, methyl Ethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, diisopropyldimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ- Glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) aminopropylmethyldimethoxysilane, etc. As an example.

  Examples of x = 3 include hydrogen dimethyl methoxy silane, trimethyl chloro silane, trimethyl methoxy silane, trimethyl acetoxy silane, trimethyl isocyanate silane, vinyl dimethyl methoxy silane, phenyl dimethyl methoxy silane, γ-glycidoxy propyl dimethyl methoxy silane , Γ-glycidoxypropyldimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyldimethylmethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-mercaptopropyldimethylmethoxy Examples include silane, γ-aminopropyldimethylethoxysilane, N- (2-aminoethyl) aminopropyldimethylmethoxysilane, and the like. .

Among them, particularly when used for applications requiring scratch resistance and weather resistance, those in which R ⁴¹ is an alkyl group such as a methyl group are preferred, and when toughness and dyeability are required, phenyl Group, an epoxy group or a (meth) acryloxy-substituted hydrocarbon group is preferable.

Other examples of hydrolyzable silane and hydrolyzable siloxane include the following general formula:
(A) _y ( ^R42 ) _3-y Si-B-Si ( ^R43 ) _3-z (A) _z
{Wherein R ⁴² and R ⁴³ are the same as R, A is the same as above, B is a divalent organic group having 1 or more carbon atoms, and y and z are each independently an integer of 0 to 3. It is. }
The hydrolyzable silane represented by these, and its partial hydrolysis-condensation product can also be mentioned.

In the above formula, B can be any divalent organic group having 1 or more carbon atoms, particularly 1 to 30, especially 1 to 20, but an alkylene group, an alkylene group and an arylene group or a cycloalkylene group can be used. , Those in which some or all of these hydrogen atoms are substituted with fluorine atoms, those in which —O— is interposed in an alkylene group or a fluorinated alkylene group, and the like are preferred.
- (CH _{2) d} - (where, d = 1~20),
—CH ₂ CH ₂ — (CF ₂ ) _e —CH ₂ CH ₂ — (where e = 2 to 20),
_{-CH 2 CH 2 -CF (CF 3} ) - (CF 2) e -CF (CF 3) -CH 2 CH 2 -,
_{-CH 2 CH 2 -CF (C 2} F 5) - (CF 2) e -CF (C 2 F 5) -CH 2 CH 2 -,
_{-CH 2 CH 2 -CF (CF 3} ) CF 2 -O- (CF 2) e -O-CF 2 CF (CF 3) -CH 2 CH 2 -,
_{-CH 2 CH 2 -C 6 H 4} -CH 2 CH 2 -,
_{-CH 2 CH 2 -C 6 F 4} -CH 2 CH 2 -,
_{-CH 2 CH 2 -C 6 H 10} -CH 2 CH 2 -,
—CH ₂ CH ₂ —C ₆ F ₁₀ —CH ₂ CH ₂ —

In particular, for the purpose of coating film hardness and weather resistance, — (CH ₂ ) _d — and —CH ₂ CH ₂ — (CF ₂ ) _e —CH ₂ CH ₂ — are preferable, and flexibility and crack resistance are preferred. -CH ₂ CH ₂ -C ₆ H ₄ -CH ₂ CH ₂ -is preferable when importance is placed on the property, and when the purpose is chemical resistance, antifouling property or antireflection property, -CH ₂ CH _{2 - (CF 2) e -CH} 2 CH 2 - is preferred.

R ⁴² and R ⁴³ are the same as R, A is the same as above, and y and z are each independently an integer of 0 to 3, particularly 2 or 3.

Specific examples of silane compounds that satisfy these conditions include:
_{(CH 3 O) 3 Si-} CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 2 CH 3} Si-CH 2 CH 2 -SiCH 3 (OCH 3) 2,
_{(CH 3 O) 3 Si-} CH 2 CH 2 CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} CH 2 CH 2 -C 6 H 4 -CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} CH 2 CH 2 -C 6 H 10 -CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} CH 2 CH 2 - (CF 2) 4 -CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} CH 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} CH 2 CH 2 - (CF 2) 10 -CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} CH 2 CH 2 - (CF 2) 16 -CH 2 CH 2 -Si (OCH 3) 3,
_{(C 2 H 5 O) 3} Si-CH 2 CH 2 - (CF 2) 4 -CH 2 CH 2 -Si (OC 2 H 5) 3,
_{(C 2 H 5 O) 3} Si-CH 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -Si (OC 2 H 5) 3,
_{(CH 3 O) 2 CH 3} Si-CH 2 CH 2 - (CF 2) 4 -CH 2 CH 2 -SiCH 3 (OCH 3) 2,
_{(CH 3 O) 2 CH 3} Si-CH 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -SiCH 3 (OCH 3) 2,
_{(CH 3 O) (CH 3} ) 2 Si-CH 2 CH 2 - (CF 2) 4 -CH 2 CH 2 -Si (CH 3) 2 (OCH 3),
_{(CH 3 O) (CH 3} ) 2 Si-CH 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -Si (CH 3) 2 (OCH 3),
_{(CH 3 O) 3 Si-} CH 2 CH 2 -CF (CF 3) (CF 2) 4 CF (CF 3) -CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} CH 2 CH 2 -CF (CF 3) (CF 2) 6 CF (CF 3) -CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} CH 2 CH 2 -CF (CF 3) (CF 2) 12 CF (CF 3) -CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} CH 2 CH 2 -C 6 F 10 -CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} CH 2 CH 2 -C 6 F 4 -CH 2 CH 2 -Si (OCH 3) 3
Among these, preferably,
_{(CH 3 O) 3 Si-} CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 2 CH 3} Si-CH 2 CH 2 -SiCH 3 (OCH 3) 2,
_{(CH 3 O) 3 Si-} CH 2 CH 2 CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} CH 2 CH 2 -C 6 H 4 -CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} CH 2 CH 2 -C 6 H 10 -CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} CH 2 CH 2 - (CF 2) 4 -CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} CH 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} CH 2 CH 2 - (CF 2) 8 -CH 2 CH 2 -Si (OCH 3) 3,
_{(C 2 H 5 O) 3} Si-CH 2 CH 2 - (CF 2) 4 -CH 2 CH 2 -Si (OC 2 H 5) 3,
_{(C 2 H 5 O) 3} Si-CH 2 CH 2 - (CF 2) 6 -CH 2 CH 2 -Si (OC 2 H 5) 3
A silane compound such as

Furthermore, other examples of hydrolyzable silanes and hydrolyzable siloxanes include the following general formula:
{Wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same as R, and D and E each independently represent a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or an acyloxy group having 1 to 6 carbon atoms. A group, an alkenoxy group having 1 to 6 carbon atoms, or an isocyanate group, G is an oxygen atom or an alkylene group having 2 to 10 carbon atoms, b and c are each independently an integer of 0 to 3, and d is It is an integer of 1-30. }
The hydrolyzable siloxane represented by these, and its partial hydrolysis-condensation product can also be mentioned.

  D and E are each independently a halogen atom, an alkoxy group having 1 to 3 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, an alkenoxy group having 1 to 6 carbon atoms, or an isocyanate group. Alkenoxy such as halogen atoms such as atoms and bromine atoms, alkoxy groups such as methoxy group, ethoxy group, propoxy group and isopropoxy group, acyloxy groups such as acetoxy group, octanoyloxy group and benzoyloxy group, vinyloxy group and isopropenoxy group A group, an isocyanate group, etc. can be illustrated.

  G is an oxygen atom or an alkylene group having 2 to 10 carbon atoms, specifically, an oxygen atom, ethylene group, propylene group, n-butylene group, i-butylene group, hexylene group, decylene group, phenylene group, methyl group. Examples thereof include a phenylethylene group.

  b and c are each independently an integer of 0 to 3, particularly 2 or 3, and d is an integer of 1 to 30, particularly 1 to 20.

Specific examples of the siloxane represented by the above general formula include those shown below.
_{(CH 3 O) 3 Si-} CH 2 CH 2 - (CH 3) 2 SiO-Si (CH 3) 2 -CH 2 CH 2 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} O- (CH 3) 2 SiO-Si (CH 3) 2 -O-Si (OCH 3) 3,
_{(CH 3 CH 2 O) 3} Si-CH 2 CH 2 - [(CH _{3) 2} SiO] _{4 -Si (CH 3) 2 -CH} 2 CH 2 -Si (OCH 2 CH 3) 3,
_{(CH 3 O) 2 (CH} 3) SiO - [(CH _{3) 2} SiO] _{9 -Si (CH 3) 2 -O} -Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 3 Si-} CH 2 CH 2 - [(CH _{3) 2} SiO] _{20 -Si (CH 3) 2 -CH} 2 CH 2 -Si (OCH 3) 3

In addition, the reaction of the production method (II) is performed using 0 to 1,000 mol, particularly 0.1 to 100 mol of another silane or siloxane with respect to 1 mol of the alkoxysilane of the formula (1). preferable. Moreover, the usage-amount of water is 0.01-100 molar ratio with respect to the total 1 mol of all the hydrolysable groups, Especially 0.1-10 molar ratio is preferable. In this case, alcohols such as methanol, ethanol and isopropanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diacetone alcohol; diethyl ether, tetrahydrofuran, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl An organic solvent such as a polar solvent such as ethers such as ether acetate can be used in such an amount that the concentration of the active ingredient, which is the sum of various silanes or siloxanes, becomes 10 to 100%. In the reaction, an acid catalyst or an alkali catalyst, for example, an inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid or methanesulfonic acid; an organic acid such as acetic acid, oxalic acid or citric acid; an organic alkali such as quaternary ammonium hydroxide or amine; An inorganic alkali such as sodium hydroxide, potassium hydroxide or sodium methoxide can be used in a conventional manner using a catalytic amount, particularly hydrochloric acid, nitric acid, acetic acid, oxalic acid or citric acid.

  The reaction temperature should just be the range of 0-150 degreeC, Preferably it is the range of 10-100 degreeC. When the reaction temperature is higher than 150 ° C., it is difficult to control the reaction, and gelation may occur. The reaction time depends on the reaction temperature, but may be in the range of 30 minutes to 24 hours. Preferably it is the range of 1 to 6 hours.

  In the production method (III), the alkoxysilane of the formula (1) of the present invention may be used as it is or after (partially) hydrolytic condensation.

  In the production method (III), other silanes and siloxanes include those exemplified in the production method (II), hexamethyldisiloxane, α, ω-dihydrotetramethyldisiloxane, α, ω-divinyltetramethyldisiloxane. Linear siloxanes such as siloxane, α, ω-diphenyltetramethyldisiloxane, polydimethylsiloxane, polymethylphenylsiloxane, α, ω-dihydroxypolydimethylsiloxane; hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 1,3 , 5-tris (3,3,3-fluoropropyl) trimethylcyclotrisiloxane, 1,3,5,7-tetrahydrotetramethylcyclotetrasiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, 1,3,5,7-te Examples include cyclic siloxanes such as traphenyltetramethylcyclotetrasiloxane and decamethylcyclopentasiloxane; branched siloxanes such as 3- (trimethylsiloxy) heptamethyltrisiloxane and tetrakis (trimethylsiloxy) silane. Among these, alkyl substituents are preferred for applications requiring weather resistance, and phenyl, epoxy, or (meth) acryloxy-substituted hydrocarbon groups are preferred when resin compatibility, toughness, dyeability, and the like are required. .

  In the reaction of the production method (III), 0.001 to 1,000 mol, particularly 0.1 to 100 mol of another silane or siloxane is preferably used with respect to 1 mol of the alkoxysilane of the formula (1). In the presence of an acid or a base, at least one other silane and / or siloxane may be added dropwise to the alkoxysilane of the formula (1), and the at least one other silane and / or siloxane may be added. The alkoxysilane of the formula (1) may be dropped.

The acid or base is as described above. The amount of the base or acid used is a catalytic amount, and is particularly preferably 0.001 to 10% by mass based on the total amount of the alkoxysilane of formula (1) and other silanes and / or siloxanes.
Moreover, a general solvent may be used at the time of reaction, and the polar solvent shown above is especially preferable.

  The reaction temperature should just be the range of 0-150 degreeC, Preferably it is the range of 10-100 degreeC. If the reaction temperature is higher than 150 ° C., the yield of the desired product may decrease due to side reactions such as disproportionation. The reaction time depends on the reaction temperature, but may be in the range of 30 minutes to 24 hours. Preferably it is the range of 1 to 10 hours.

  In the production method (IV), the (meth) acryl group-containing hydroxybenzotriazole of the formula (4) and the mercapto group-containing polyorganosiloxane represented by the following average composition formula (6) are added in the presence of a base. It is what makes it react.

{Wherein Y is a mercapto group-containing group represented by HS-R ^36- (R ³⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms), and R is the same or different hydrogen atom or carbon. An unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, R ² is the same or different alkyl group having 1 to 8 carbon atoms, and m, n, p, and q are each 0 <m ≦ 1, 0 ≦ n ≦ 2, 0 ≦ p <3, 0 ≦ q ≦ 3, and 0 <m + n + p + q <4. }

In the above formula (6), Y is a mercapto group-containing group represented by HS—R ³⁶ —. R ³⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms, specifically, an alkylene group such as a methylene group, an ethylene group, a propylene group, a methylethylene group, a butylene group or a hexamethylene group, or a cyclohexylene group. Selected from arylene groups such as cycloalkylene groups such as phenylene groups, tolylene groups, and xylylene groups, groups in which some of the hydrogen atoms of these groups are substituted with halogen atoms, and groups in which the above alkylene groups and arylene groups are combined. And divalent hydrocarbon groups.
R, R ² , m, n, p, and q are the same as described above.

  The mercapto group-containing polyorganosiloxane represented by the general formula (6) can be obtained by a known reaction. For example, (a) various hydrolyzable silanes and / or their (partial) hydrolysis condensates and mercapto group-containing hydrolyzable silanes and / or their (partial) hydrolysis condensates, (B) An equilibration reaction in the presence of an acid catalyst between various polyorganosiloxanes and an organosilane containing a mercapto group and / or a hydrolysis condensate thereof can be mentioned. The raw material used for the reaction is the same as the example shown above.

  Moreover, the said manufacturing method (IV) uses 0.01-3.0 mol, especially 0.1-1.0 mol of polyorganosiloxane of Formula (6) with respect to 1 mol of benzotriazole of Formula (4). In the presence of a base, the (meth) acrylic group-containing hydroxybenzotriazole of the above formula (4) may be dropped into the mercapto group-containing polyorganosiloxane of the above formula (6). A mercapto group-containing polyorganosiloxane may be dropped into the group-containing hydroxybenzotriazole.

  The base is as described above, and the amount used is appropriately selected, but a molar ratio of 0.001 to 0.5 is preferable with respect to 1 mol of the polyorganosiloxane of formula (6). Common solvents may be used, and the polar solvents shown above are particularly preferable.

  The reaction temperature should just be the range of 0-150 degreeC, Preferably it is the range of 10-100 degreeC. When the reaction temperature is higher than 150 ° C., the ester bond of the benzotriazole of the formula (4) or the polyorganosiloxane of the formula (2) which is the target product may be cleaved and the yield may be lowered. The reaction time depends on the reaction temperature, but may be in the range of 30 minutes to 24 hours, preferably in the range of 1 to 6 hours.

  The coating composition of the present invention comprises an alkoxysilane represented by the above general formula (1) and / or a polyorganosiloxane represented by the above average composition formula (2), preferably the above organic It contains a silicon compound, a curing catalyst, and other synthetic resins such as polyorganosiloxane and acrylic resin.

  Here, the curing catalyst is a known catalyst that hydrolyzes and condenses alkoxysilane or silanol. For example, quaternary onium hydroxides such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, tetrabutylphosphonium hydroxide; salts of these hydroxides with halogen acids, and carbon number 1 to 4 salt with carboxylic acid; alkali metal salt of carboxylic acid such as potassium formate, sodium acetate, potassium propionate; amine carboxylate such as ammonium acetate, dimethylamine acetate, ethanolamine acetate, dimethylaniline formate; Amines such as ethylenediamine, benzyltrimethylamine, pyridine, and γ-aminopropyltrimethoxysilane; alkali metal hydroxides such as sodium hydroxide and sodium methoxide Is an alkoxide; a modified (latent) amine such as dicyandiamide, 2-methylimidazole, 2-phenylimidazole; an organic acid such as acetic acid, citric acid, maleic acid, phthalic acid, terephthalic acid, pyromellitic acid, or an acid anhydride thereof , Hydrochloric acid, nitric acid, sulfuric acid, methanesulfonic acid, toluenesulfonic acid, phosphotungstic acid, phosphomolybdic acid, etc .; aluminum triisopropoxide, titanium tetrabutoxide, triacetylacetone aluminum, dioctyltin dilaurate, zinc octylate And metal compounds such as

  The blending amount of the curing catalyst is not particularly limited as long as it is an amount effective for curing all silane and / or siloxane components in the coating composition of the present invention. It is preferable that it is 0.0001-30 mass% with respect to solid content of a resin, More preferably, it is 0.001-10 mass%. If it is less than 0.0001% by mass, curing may be insufficient and the hardness may be reduced, and if it is more than 30% by mass, cracks may easily occur in the coating film, and water resistance may be reduced.

  The coating composition of the present invention includes a solvent, a pH adjuster, a leveling agent, a thickener, a pigment, a dye, a metal oxide fine particle, a metal powder, an antioxidant, an ultraviolet absorber, and an ultraviolet stabilizer as necessary. Further, a heat ray reflection / absorption imparting agent, a flexibility imparting agent, an antistatic agent, an antifouling property imparting agent, a water repellency imparting agent and the like can be added within a range that does not adversely affect the effects of the present invention.

  A solvent may be added to the coating composition of the present invention for the purpose of improving coatability and storage stability. The solvent is not particularly limited as long as it dissolves the solid content in the silicone coating composition of the present invention, but water and a relatively polar organic solvent are preferred. Specific examples of the organic solvent include alcohols such as isopropyl alcohol, n-butanol, isobutanol, t-butanol and diacetone alcohol; ketones such as methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; Ethers such as butyl ether, anisole, tetrahydrofuran, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether; propyl acetate, acetic acid Esters such as butyl, cyclohexyl acetate and γ-butyrolactone; dimethyl Amides such as formamide, dimethylacetamide and N-methylpyrrolidone; β-diketones such as acetylacetone and ethyl acetoacetate; β-ketoesters and the like can be mentioned, and one or more selected from the group consisting of these Mixtures can be used.

  The coating composition of the present invention is preferably adjusted to a solid content concentration of 1 to 30% by mass, particularly 5 to 25% by mass with a solvent. Outside this range, defects may occur in the coating film coated and cured with the composition. For example, when the amount is less than the above range, sagging, twisting, and spotting are likely to occur in the coating film, and desired hardness and scratch resistance may not be obtained. On the other hand, when the above range is exceeded, brushing, whitening and cracking of the coating film may easily occur.

  In order to obtain further storage stability of the coating composition of the present invention, the pH of the solution is preferably 2 to 7, more preferably 3 to 6. If the pH is outside this range, the storage stability may be lowered. Therefore, a pH adjuster may be added to adjust the pH to the above range. When the pH of the coating composition is outside the above range, the pH may be adjusted by adding a basic compound such as ammonia or ethylenediamine if it is more acidic than this range. PH may be adjusted using an acidic compound such as nitric acid, acetic acid and citric acid. However, the adjustment method is not particularly limited.

  The coating composition of the present invention has improved hardness and scratch resistance of a cured coating film obtained by coating, lower refractive index, higher refractive index, ultraviolet cut property, antistatic property, heat ray reflection / absorption For the purpose of further providing functions such as metal oxide fine particles, hollow fine particles thereof, metal chelate compounds such as titanium, zinc and zirconium, and (partial) hydrolysates and condensates thereof may be added as appropriate. . As the metal oxide fine particles, the particle shape and the particle size of the particles are not particularly limited, but in order to increase the transparency when formed into a coating film, it is preferable that the particle size is small.

Specific examples of the metal oxide fine particles include silica, alumina, titanium oxide, cerium oxide, tin oxide, zirconium oxide, antimony oxide, indium oxide, iron oxide, iron oxide and / or titanium oxide doped with zirconium oxide, rare earth oxidation. There may be mentioned, but not limited to, fine particles of a product, a mixture thereof, or a composite oxide fine particle thereof. These metal oxide fine particles may be used in the form of a colloidal dispersion, or may be dispersed in the form of a powder in a coating composition, and further, these may be silane-based, titanium-based, aluminum-based, Or you may use what surface-treated with organometallic compounds, such as a zirconium type coupling agent, a carboxylic acid containing organic compound, a nitrogen-containing organic compound.
The addition amount of these metal oxide fine particles is preferably 0.1 to 300% by mass, particularly 1 to 100% by mass, based on all resin components of the coating composition.

In addition, the coating composition of the present invention may contain a vinyl polymer having a functional group capable of reacting with the composition for the purpose of improving adhesion and imparting further flexibility. Examples of functional groups capable of reacting with the composition include hydrolyzable silyl groups such as trimethoxysilyl group, triethoxysilyl group, dimethoxymethylsilyl group, methoxydimethylsilyl group, and (partially) hydrolyzed hydroxysilyl groups thereof. In addition, if an epoxy group is contained in the active ingredient of the composition, an organic group containing an amino group, a carboxylic acid group, etc., or an amino group is contained in the active ingredient of the composition Examples of the organic group include an epoxy group, a carboxylic acid group, and a (meth) acryl group. Of these, hydrolyzable silyl groups, and (partially) hydrolyzed hydroxysilyl groups are preferred from the standpoint of storage stability. In particular, methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic amide, (meth) Various (meth) acrylic acids such as acrylic acid, UV-absorbing (meth) acrylic acid ester monomer having benzotriazole group or hydroxybenzophenone group, and UV-stable (meth) acrylic acid ester monomer having hindered amine group, and derivatives thereof Alternatively, a copolymer obtained by copolymerizing various vinyl polymerizable monomers such as vinyl acetate and an alkoxysilane having a (meth) acryloxy group or a vinyl group and / or a styryl group-containing alkoxysilane is preferable.
The amount of addition is preferably 0.1 to 100% by mass, particularly 1 to 50% by mass, based on the total resin components of the coating composition.

  When the substrate on which the coating composition of the present invention is applied is an organic resin or wood product, other ultraviolet absorbers and / or ultraviolet stabilizers are added for the purpose of preventing yellowing of the substrate and surface deterioration. In this case, it is preferable to use an ultraviolet absorber and / or an ultraviolet stabilizer having good compatibility with the coating composition of the present invention and low volatility.

  Examples of ultraviolet absorbers include the above-described oxide fine particles such as titanium oxide, cerium oxide, and zirconium oxide, and metal chelate compounds such as titanium, zinc, and zirconium, and (partial) hydrolysates and condensate inorganic systems. And organic ones can be used. As organic examples, compound derivatives whose main skeleton is hydroxybenzophenone, benzotriazole, cyanoacrylate, or triazine are preferable. Further, polymers such as vinyl polymers containing these UV absorbers in the side chain, copolymers with other vinyl monomers, or silylated and modified UV absorbers other than the alkoxysilane and / or polyorganosiloxane of the present invention. It may be an agent or its (partial) hydrolysis condensate.

  Specifically, 2,4-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2 -Hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-benzyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 2,2′-dihydroxy-4,4′-diethoxybenzophenone, 2,2′-dihydroxy-4,4′-dipropoxybenzophenone, 2,2′-dihydroxy-4,4′-dibutoxybenzophenone, 2, , 2'-Dihydroxy-4-methoxy-4'-propoxybenzopheno 2,2′-dihydroxy-4-methoxy-4′-butoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy- 5-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano- (Co) polymer of 3,3-diphenyl acrylate, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyltriazine, 2-hydroxy-4- (2-acryloxyethoxy) benzophenone, 2 -(2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzoto (Co) polymer of azole, reaction product of 2,4-dihydroxybenzophenone and γ-glycidoxypropyltrimethoxysilane, 2,2 ′, 4,4′-tetrahydroxybenzophenone and γ-glycidoxypropyltri A reaction product with methoxysilane, a (partial) hydrolyzate thereof, and the like. Two or more of these organic ultraviolet absorbers may be used in combination.

  As the UV stabilizer, one having at least one cyclic hindered amine structure in the molecule, good compatibility with the coating composition of the present invention, and low volatility is preferable. Specific examples of the ultraviolet light stabilizer include 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, N-methyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) Pyrrolidine-2,5-dione, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1 , 2,3,4-bu Tetracarboxylate, condensate of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-piperidinol and tridecanol, 8-acetyl-3-dodecyl-7,7,9 , 9-Tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl A condensate of -4-piperidinol and β, β, β, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol, 1,2, 3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β, β′-tetramethyl-3,9- (2,4,8,10- Tetraoxaspiro [5,5] undecane) di For the purpose of immobilizing a condensate with tanol or a light stabilizer, a silylated modified light stabilizer such as disclosed in JP-B-61-56187, for example, 2,2,6,6-tetramethylpi Peridino-4-propyltrimethoxysilane, 2,2,6,6-tetramethylpiperidino-4-propylmethyldimethoxysilane, 2,2,6,6-tetramethylpiperidino-4-propyltriethoxy Silane, 2,2,6,6-tetramethylpiperidino-4-propylmethyldiethoxysilane, (partial) hydrolyzate thereof, and the like. These light stabilizers are used in combination of two or more. Also good.

  The coating composition of the present invention can be coated on a substrate by a usual application method, for example, selecting various application methods such as brush coating, spraying, dipping, flow, roll, curtain, spin, knife coating, etc. Can do.

  Although there is no restriction | limiting in particular in the thickness of the coating film of a coating composition, it is preferable that it is 0.1-50 micrometers, and the hardness of a coating film, scratch resistance, long-term stable adhesiveness, and a crack are hard to generate | occur | produce. In order to satisfy | fill, it is more preferable that it is 1-20 micrometers. If the thickness is less than 0.1 μm, the coating film may be easily damaged or may not be provided with sufficient ultraviolet absorbing ability, and if it exceeds 50 μm, the coating film may be easily cracked.

  Curing after applying the coating composition of the present invention may be left in the air and air-dried, or may be heated. Although the curing temperature and the curing time are not limited, it is preferable to heat at a temperature lower than the heat resistant temperature of the substrate for 2 minutes to 2 hours. Specifically, heating at 80 to 150 ° C. for 5 minutes to 2 hours is more preferable. If the heat curing time is less than 2 minutes, curing is insufficient, and satisfactory coating film hardness may be difficult to obtain, and if it exceeds 2 hours, it is not practical.

  Here, examples of the substrate to be used include organic resins such as plastic moldings, wood products, fibers, ceramics, glass, metals, and composites thereof. Suitable for use in materials, especially polycarbonate resin, polystyrene resin, acrylic resin, modified acrylic resin, urethane resin, thiourethane resin, polycondensate of halogenated bisphenol A and ethylene glycol, acrylic urethane resin, halogenated aryl group-containing acrylic Resins, sulfur-containing resins, polyalkylene terephthalate resins, cellulose resins, amorphous polyolefin resins, and the like, and composite resins thereof are preferable. Further, the surface of these resin base materials is treated, specifically, chemical conversion treatment, corona discharge treatment, plasma treatment, treatment with acid or alkaline liquid, and the base material body and the surface layer are formed of different types of resins. The laminated body currently used can also be used. Examples of laminates include laminates in which an acrylic resin layer or urethane resin layer is present on the surface layer of a polycarbonate resin substrate manufactured by a coextrusion method or a laminate method, or an acrylic resin layer is present in the surface layer of a polyester resin substrate. And the like.

  In addition, it can also be formed on the surface of the substrate directly or as necessary via a primer layer, an ultraviolet absorbing layer, a printing layer, a recording layer, a heat ray shielding layer, an adhesive layer, an inorganic vapor deposition film layer, etc. during coating. .

  Further, if necessary, on the surface of the cured coating film of the coating composition of the present invention, an ultraviolet absorbing layer, a printing layer, a recording layer, a heat ray shielding layer, an adhesive layer, an inorganic vapor-deposited film layer, a water- and oil-repellent layer, and a hydrophilic layer. Other coating layers such as a dirty layer may be applied.

  The coated article coated with the cured product of the coating composition of the present invention thus obtained can be excellent in ultraviolet cut property, heat resistance, water resistance and bleed out resistance.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, “part” and “%” mean “part by mass” and “% by mass”, respectively, unless otherwise specified. Moreover, a weight average molecular weight is a weight average molecular weight of polystyrene conversion by GPC.

<Preparation of organosilicon compound>
[Example 1]
Into a 2 L flask, 196 g (1.0 mol) of KBM-803 (manufactured by Shin-Etsu Chemical; 3-mercaptopropyltrimethoxysilane) was charged, and under stirring, SM-28 (manufactured by Kawaken Fine Chemicals; 28% of sodium methoxide) 25 g of methanol solution was added dropwise. Next, a solution in which 323 g of RUVA-93 {manufactured by Otsuka Chemical; 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole} is dissolved in 969 g of tetrahydrofuran in advance has an internal temperature exceeding 40 ° C. The solution was added dropwise while cooling. After completion of dropping, the reaction was carried out at 60 ° C. for 4 hours. Next, 12.5 g of methanesulfonic acid was added and stirred at room temperature to neutralize the system. After further concentration under reduced pressure, the solution was passed through a column filled with silica gel to obtain a yellowish brown transparent solution. When the solvent of this solution was removed under reduced pressure, a tan viscous liquid was obtained. From the results of proton nuclear magnetic resonance spectrum (1H-NMR; FIG. 1) and infrared absorption spectrum (IR; FIG. 2), this liquid was a compound represented by the following formula (purity 89%) (compound A). .

[Example 2]
In a 2 L flask, compound A 22 g (0.04 mol), methyltrimethoxysilane 338 g (2.24 mol), silicate 35 (manufactured by Tama Chemical Industry; partial hydrolysis condensate of tetraethoxysilane, average dimer) 56 g (0.16 mol, 0.33 Si mol) and 40 g of tetrahydrofuran were charged and mixed well. Then, 308 g of a 0.25N acetic acid aqueous solution was dropped, and hydrolysis was performed while cooling so that the internal temperature did not exceed 40 ° C. After completion of dropping, the mixture was stirred at 40 ° C. or lower for 1 hour and then at 60 ° C. for 3 hours to complete the hydrolysis.

  Thereafter, 300 g of cyclohexanone was added, and the methanol and ethanol produced by hydrolysis were condensed while distilling off at normal pressure until the liquid temperature reached 95 ° C., and then with isopropanol so that the nonvolatile content concentration became 20%. Dilution and filtration with filter paper were performed to obtain a pale yellow transparent polyorganosiloxane B solution.

This is a polyorganosiloxane represented by the following average composition formula from the result of silicon nuclear magnetic resonance spectrum ( ²⁹ Si-NMR), and the weight average molecular weight Mw by gel permeation chromatography (GPC) is 7, 800.

{In the formula, Z 'is the following formula
OX has a UV-absorbing group-containing organic group, and most of OX (90% or more) is a hydroxyl group, and the remainder is an alkoxy group. }

[Example 3]
In a 2 L flask, the general formula (CH ₃ O) ₃ Si—CH ₂ CH ₂ — [(CH ₃ ) ₂ SiO] _{d ′} (CH ₃ ) ₂ Si—CH ₂ CH ₂ —Si (OCH ₃ ) ₃
{D ′ is 5 on average. }
30 g (0.04 mol), 33 g (0.06 mol) of Compound A, and 38 g of tetrahydrofuran were charged and mixed well. Subsequently, 50 g of 0.05N nitric acid aqueous solution was dropped, and hydrolysis was performed while cooling so that the internal temperature did not exceed 40 ° C. After completion of the dropping, the mixture was stirred at 40 ° C. or lower for 2 hours, and then a mixture of 260 g of 0.05N nitric acid aqueous solution, 330 g (2.43 mol) of methyltrimethoxysilane and 104 g (0.5 mol) of tetraethoxysilane prepared in advance. Stirring was carried out in order, and the mixture was stirred at 40 ° C. or lower for 1 hour and then at 60 ° C. for 3 hours to complete the hydrolysis.

  Thereafter, 300 g of propylene glycol monomethyl ether acetate was added, and the methanol and ethanol produced by hydrolysis were condensed while being distilled off at normal pressure until the liquid temperature reached 95 ° C., and then the nonvolatile content concentration was reduced to 20%. The solution was diluted with isopropanol and filtered through filter paper to obtain a pale yellow transparent polyorganosiloxane C solution.

This is a polyorganosiloxane represented by the following average composition formula from the results of ²⁹ Si-NMR and carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR), and the weight average molecular weight Mw by GPC is 6,400. there were.

{In the formula, Z 'is the following formula
OX has a UV-absorbing group-containing organic group, and most of OX (90% or more) is a hydroxyl group, and the remainder is an alkoxy group. }

[Example 4]
A 2 L flask is charged with 716 g (2.42 mol) of octamethylcyclotetrasiloxane, 36 g (0.22 mol) of hexamethyldisiloxane, and 118 g (0.88 Si mol) of a hydrolytic condensate of mercaptopropylmethyldichlorosilane. And mixed well. Subsequently, it stirred at 110 degreeC for 2 hours, and dehydration distillation was performed. Thereafter, the mixture was cooled to room temperature, 48 g of activated clay (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at 80 ° C. for 7 hours for polymerization. After cooling to room temperature, the activated clay was removed by filtration to obtain a colorless and transparent mercapto group-containing polyorganosiloxane (mercapto equivalent 980).

Into a 2 L flask, 700 g of the obtained mercapto group-containing polyorganosiloxane and 25 g of anion exchange resin IRA-900 (OH) -HG (manufactured by Organo) were charged and stirred well. Next, a solution in which 183 g (0.567 mol) of RUVA-93 {manufactured by Otsuka Chemical; 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole} in 800 g of tetrahydrofuran was dissolved in room temperature. It was dripped at. After completion of the dropwise addition, the mixture was reacted at 60 ° C. for 24 hours, and the solvent of the filtrate obtained by filtering off the anion exchange resin was removed under reduced pressure to obtain yellow transparent polyorganosiloxane D. This was a polyorganosiloxane represented by the following average composition formula from the results of ²⁹ Si-NMR and 1H-NMR, and the weight average molecular weight Mw by GPC was 5,500.

{In the formula, Z 'is the following formula
It is an organic group containing an ultraviolet absorbing group represented by: }

[Example 5]
In a 2 L flask, 52 g (0.10 mol) of compound A, 100 g (0.56 mol) of methyltriethoxysilane, 99 g (0.42 mol) of γ-glycidoxypropyltrimethoxysilane, and (CH ₃ O) ₃ SiCH ₂ CH ₂ —C ₄ F ₈ —CH ₂ CH ₂ Si (OCH ₃ ) ₃ 100 g (0.20 mol) was charged and mixed well. Subsequently, 508 g of 0.25N acetic acid aqueous solution was dropped, and hydrolysis was performed while cooling so that the internal temperature did not exceed 40 ° C. After completion of dropping, the mixture was stirred at 40 ° C. or lower for 12 hours, and 600 g of methanol silica sol (manufactured by Nissan Chemical Industries; methanol dispersion, solid content 30%) was added and stirred at room temperature for 1 hour. Thereafter, the solution was diluted with isobutanol so as to have a nonvolatile content concentration of 20% and filtered with a filter paper to obtain a pale yellow almost transparent polyorganosiloxane E solution.

This was a polyorganosiloxane represented by the following average composition formula from the results of ²⁹ Si-NMR and ¹³ C-NMR, and the weight average molecular weight Mw by GPC was 1,100.

{In the formula, Z 'is the following formula
An organic group containing a UV-absorbing group represented by: Gly is a γ-glycidoxypropyl group, OX is mostly (90% or more) hydroxyl groups, and the remainder is an alkoxy group. }

[Comparative Example 1]
In Example 2, a solution of polyorganosiloxane F having no ultraviolet absorptivity was obtained in the same manner except that compound A was not used.

[Comparative Example 2]
In Example 5, a solution of polyorganosiloxane G having no ultraviolet absorptivity was obtained in the same manner except that compound A was not used.

<Preparation of coating composition and evaluation of cured film>
[Example 6]
Various additives were added to the polyorganosiloxane B solution obtained in Example 2 in the amounts shown in Table 1 and mixed well, followed by filtration with filter paper to obtain a coating composition 1. This was applied to a quartz glass plate (thickness 1 mm × length 4 cm × width 1 cm) by a flow coating method and cured at 130 ° C. for 1 hour. When the transmission spectrum was measured about the obtained coating film, as shown in FIG. 3, it turned out that the ultraviolet-ray of the area | region of a wavelength of 390 nm or less is absorbed.

[Comparative Example 3]
In Example 6, the coating composition 2 was similarly obtained using the polyorganosiloxane F solution obtained in Comparative Example 1 instead of the polyorganosiloxane B solution. Further, as in Example 6, when a coating film was obtained and its transmission spectrum was measured, it was found that it hardly absorbs ultraviolet rays as shown in FIG.

[Examples 7 to 9, Comparative Examples 4 to 6]
The polyorganosiloxane solutions obtained in Examples 2, 3 and 5 and Comparative Example 2 and various additives were blended in the amounts shown in Table 1 to obtain coating compositions 3-8. These coating compositions were applied to the acrylic resin surface of a polycarbonate / acrylic resin coextruded plate (thickness 0.5 mm × length 30 cm × width 20 cm) by a flow coating method and cured at 130 ° C. for 1 hour.

  The coating films obtained in Examples 6 to 9 and Comparative Examples 3 to 6 were evaluated as follows, and the results are shown in Table 2.

<Curing catalyst>
TBAH: 0.25% aqueous solution of tetrabutylammonium hydroxide Na acetate: 10% aqueous solution of sodium acetate AlAA: aluminum acetylacetonate

<Leveling agent>
LV-I: 10% isopropanol solution of Florard FC-4430 (manufactured by Sumitomo 3M)

<Ultraviolet absorber>
UVA-I: 2- [4-[(2-hydroxy-3-dodecyl / tridecyl-oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 , 5-Triazine (Tinubin 400, manufactured by Ciba Specialty Chemicals)
UVA-II: 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole (RUVA-93, manufactured by Otsuka Chemical)
UVA-III: 2,4-dihydroxybenzophenone (SEESORB 100, manufactured by Cypro Kasei)

<Hindered amine light stabilizer>
HALS-I: N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione (Sandbar 3058Liq., Manufactured by Clariant Japan)

<Metal oxide fine particles>
Fine particle-I: 20% methanol dispersion product of titanium oxide-containing composite metal oxide sol (Optlake 1120Z, manufactured by Catalyst Chemical Industries)

Evaluation method of cured film <Appearance of coated film>
The coating film was visually observed to determine the presence or absence of abnormality.

<Abrasion resistance>
In accordance with ASTM 1044, a wear wheel CS-10F was attached with a Taber abrasion tester, and the haze after 500 rotations under a load of 500 g was measured, and the difference in haze after the test and before the test was defined as scratch resistance.

<Adhesion>
In accordance with JIS K5400, using a razor blade, cut 6 vertical and horizontal cuts at 2 mm intervals into the coating film to prepare 25 grids, and after attaching cello tape (manufactured by Nichiban) well, 90 The number of squares (X) remaining without peeling off of the coating film when peeled off rapidly in the front direction was expressed as X / 25.

<Water resistance>
The appearance change and adhesion after the evaluation sample was immersed in boiling water for 2 hours were evaluated.

<Heat resistance>
The evaluation sample was visually observed for cracks after heating for 1 hour in a hot air circulating dryer at 130 ° C.

[Examples 10 to 13, Comparative Examples 7 to 9]
After applying primer PC-7A (manufactured by Shin-Etsu Chemical Co., Ltd.), an acrylic primer, to a polycarbonate resin plate (thickness 0.5 mm × length 30 cm × width 20 cm) by a flow coating method and curing at 130 ° C. for 30 minutes. The mixture was cooled at room temperature for 1 hour. Thereafter, coating compositions 1 to 6 and 8 prepared in Examples 6 to 9 and Comparative Examples 3, 4 and 6 were each applied by a flow coating method and cured at 130 ° C. for 1 hour. . Table 3 shows the results of the following weather resistance evaluation for the obtained coating film. The coating film comprising the coating composition containing the organic silicon compound containing the ultraviolet absorbing group of the present invention effectively absorbs the ultraviolet wavelength region in which the polycarbonate resin as the base material deteriorates. The degree of change was equal to or slightly increased from the initial value, and no coating film abnormality was observed. On the other hand, in the coating film of the coating composition containing no ultraviolet absorbing group-containing organosilicon compound of the present invention, the yellowing degree after the weather resistance test was increased, and the coating film was abnormal.

[Example 14]
A composition obtained by mixing 8% of the compound A of Example 1 as a solid content with respect to the solid content of PC-7A in a primer PC-7A (manufactured by Shin-Etsu Chemical Co., Ltd.) which is an acrylic primer, a polycarbonate resin plate (thickness) 0.5 mm × length 30 cm × width 20 cm) was applied by a flow coating method, cured at 130 ° C. for 30 minutes, and then cooled at room temperature for 1 hour. Thereafter, the coating composition 1 prepared in Example 6 was applied on the coating film of the composition by a flow coating method and cured at 130 ° C. for 1 hour. Table 3 shows the results of the following weather resistance evaluation for the obtained coating film.

  When the coating composition containing the UV-absorbing group-containing organosilicon compound of the present invention is used as an overcoat or undercoat, the UV-absorbing property is greatly increased, so that the deterioration of the polycarbonate resin as the substrate is greatly suppressed, and the weather resistance The yellowing after the property test was almost the same as the initial value, and no coating film abnormality was observed.

<Weather resistance evaluation>
Using I-Super UV Tester W-151 manufactured by Iwasaki Electric Co., Ltd., [Black panel temperature 63 ° C, humidity 50% RH, illuminance 50 mW / cm ² , rain 10 seconds / 1 hour 5 hours] → [Black panel temperature The test was conducted for 100 hours and 250 hours under the conditions of repeating this cycle, with 1 cycle at 30 ° C. and 95% RH as one cycle. Before and after the weather resistance test, in accordance with JIS K7103, the degree of yellowing and the state of weather coating cracking and weather coating peeling were observed visually or with a microscope (250 times magnification).

<Weather-resistant coating cracking properties>
The appearance of the coating film after the weather resistance test was evaluated according to the following criteria.
○: No abnormality △: There is a slight crack ×: There is a crack in the entire coating film

<Weather-resistant film peeling>
The state of the coating film after the weather resistance test was evaluated according to the following criteria.
○: No abnormality Δ: Partial peeling between the cured coating layer and the primer cured coating layer of the coating composition ×: Total peeling between the cured coating layer and the primer cured coating layer of the coating composition

It is the figure which showed the proton nuclear magnetic resonance spectrum of the compound obtained in Example 1 of this invention. It is the figure which showed the infrared absorption spectrum of the compound obtained in Example 1 of this invention. It is the figure which showed the transmission spectrum of the compound obtained in Example 6 of this invention. It is the figure which showed the transmission spectrum of the compound obtained by the comparative example 3 of this invention.

Claims (11)

An ultraviolet-absorbing group-containing organosilicon compound represented by the following general formula (1).
{Wherein R ¹ is the same or different alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, R ² is the same or different alkyl group having 1 to 8 carbon atoms; ³¹ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms or an acyloxy group having 1 to 8 carbon atoms, and R ³² , R ³³ and R ³⁴ are each independently And a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and R ³⁵ is represented by the following formula (7) or (8):

In a divalent organic group represented, R ³⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms, a is an integer of 0 to 2. } R ¹ is a methyl group, R ² is a methyl group or an ethyl group, R ³¹ is a hydrogen ^{atom, R 32, R 33, R} 34 are each hydrogen atom, R ³⁶ is _{-CH 2 CH 2 CH 2 -,} a is 0 Or an organosilicon compound according to claim 1, wherein An ultraviolet absorbing group-containing organosilicon compound represented by the following average composition formula (2).
[Wherein Z represents the following general formula (3)
{In the formula, R ³¹ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an acyloxy group having 1 to 8 carbon atoms, and R ³² , R ³³ , R ³⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and R ³⁵ represents the following formula (7) Or (8)

In a divalent organic group represented, R ³⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms. }
R is the same or different hydrogen atom or unsubstituted or halogen having 1 to 18 carbon atoms , γ-methacryloxypropyl group, γ-acryloxypropyl group, γ-glycidoxypropyl group 3,4-epoxycyclohexylethyl group, γ-mercaptopropyl group or γ-aminopropyl group- substituted monovalent hydrocarbon group, R ² is the same or different alkyl group having 1 to 8 carbon atoms, m , N, p, q are numbers satisfying 0 <m ≦ 1, 0 ≦ n ≦ 2, 0 ≦ p <3, 0 ≦ q ≦ 3, and 0 <m + n + p + q <4, respectively. ] R is methyl group, ethyl group, trifluoropropyl group, phenyl group, vinyl group, γ-acryloxypropyl group, γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ- mercaptopropyl group or a γ- aminopropyl group, R ² is a methyl group, an ethyl group, or propyl group, R ³¹ is a hydrogen ^{atom, R 32, R 33, R} 34 are each hydrogen atom, R ³⁶ is -CH ₂ CH ₂ CH ₂ —, m, n, p, q are 0.001 ≦ m ≦ 1, 0.01 ≦ n ≦ 1.99, 0 ≦ p <2.99, 0 ≦ q ≦ 2.99, 0 4. The organosilicon compound according to claim 3, which is a number satisfying .001 ≦ m + n + p + q <3. A (meth) acryl group-containing hydroxybenzotriazole represented by the following general formula (4) and a mercapto group-containing alkoxysilane represented by the following general formula (5) are reacted in the presence of a base, The method for producing an organosilicon compound according to claim 1.
{Wherein R ¹ is the same or different alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, R ² is the same or different alkyl group having 1 to 8 carbon atoms; ³¹ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms or an acyloxy group having 1 to 8 carbon atoms, and R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group or an alkoxy group having 1 to 8 carbon atoms having 6 to 12 carbon atoms, R ^{35 'carbon} atoms 3-20 of CH ₂ = A monovalent organic group represented by CR′—COO—R ″ — (R ′ is a hydrogen atom or a methyl group, and R ″ is a divalent hydrocarbon group having 0 to 17 carbon atoms); R ³⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms, a is an integer of 0 to 2. }   The organic silicon compound according to claim 1, wherein the organosilicon compound according to claim 1 or at least one other hydrolyzable silane and / or hydrolyzable siloxane is subjected to (co) hydrolytic condensation reaction. A method for producing a silicon compound.   4. The method for producing an organosilicon compound according to claim 3, wherein the organosilicon compound according to claim 1 and at least one other silane and / or siloxane are equilibrated in the presence of an acid or a base. . Reacting a (meth) acrylic group-containing hydroxybenzotriazole represented by the following general formula (4) with a mercapto group-containing polyorganosiloxane represented by the following average compositional formula (6) in the presence of a base: The method for producing an organosilicon compound according to claim 3.
{In the formula, R ³¹ is a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an acyloxy group having 1 to 8 carbon atoms, and R ³² , R ³³ , R ³⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and R ^{35 ′} represents 3 to 3 carbon atoms. 20 monovalent organic groups represented by CH ₂ ═CR′—COO—R ″ — (R ′ is a hydrogen atom or a methyl group, and R ″ is a divalent hydrocarbon group having 0 to 17 carbon atoms. Y) is a mercapto group-containing group represented by HS—R ³⁶ — (R ³⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms), and R is the same or different hydrogen atom or unsubstituted or halogen, .gamma.-methacryloxypropyl group having 1 to 18 carbon atoms, .gamma.-acryloxypropyl , .Gamma.-glycidoxypropyl group, 3,4-epoxycyclohexyl ethyl group, a .gamma.-mercaptopropyl group or .gamma.-aminopropyl group-substituted monovalent hydrocarbon group, R ² is 1 to the number of carbon atoms of the same or different M, n, p, q are numbers satisfying 0 <m ≦ 1, 0 ≦ n ≦ 2, 0 ≦ p <3, 0 ≦ q ≦ 3, and 0 <m + n + p + q <4, respectively. is there. }   The coating composition containing the organosilicon compound of any one of Claims 1 thru | or 4.   A coated article obtained by coating a cured film of the coating composition according to claim 9 on a substrate directly or via at least one other layer.   The coated article according to claim 10, wherein the substrate is glass, metal, ceramics, organic resin, wood, or fiber.