JPH09143404A - Coating material for cutting ultraviolet ray and article having ultraviolet light absorbing layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating material capable of providing a coating film hardly deteriorating ultraviolet light absorbing ability even by irradiation with ultraviolet light for a long period of time, by introducing an ultraviolet light absorber into a silicone-based coating agent. SOLUTION: This coating material for cutting ultraviolet ray preferably comprises (A) a silicon compound of the formula, R<2> n Si (OR<1> )4-n ' (B) an organic ultraviolet light absorber having a side chain containing an ester cross-linking of the general formula,-R<3> COOR<4> (R<1> , R<2> and R<4> are each a monofunctional hydrocarbon; R<3> is a bifunctional hydrocarbon chain; (n) is 0-3), (C) an acidic catalyst and water. The component C contains acidic colloidal silica, the silica content of the silica is 5-95wt.% based on the solid content of the sum of the component A and the component C, water content is 0.001-1.0mol based on the component A of 1 equivalent OR<1> group. Further the component A preferably contains (i) R<2> Si (OR<1> )3 and (ii) a silicon compound of the formula, R<2> 2 Si (OR<1> )2 in the ratio of 0.1-60 pts.wt. of the component (ii) based on 100 pts.wt. of the component (i).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet cut coating material obtained by introducing an ultraviolet absorber into a silicone-based coating material, and more particularly to an ultraviolet cut coating material capable of obtaining a coating film whose ultraviolet absorbing ability is not easily deteriorated.

[0002]

2. Description of the Related Art Conventionally, in an ultraviolet cut coating material in which an ultraviolet absorbent is introduced into a silicone-based coating material, when it is irradiated with ultraviolet rays for a long period of time, its ultraviolet absorbing ability deteriorates due to deterioration or migration of the ultraviolet absorbent itself, There is a problem of lacking long-term durability, and its improvement is required. As an example of improving long-term durability,
As disclosed in JP-A-58-213075,
The general formula -Si (O
R ⁷ ) ₃ A UV absorber having a functional group (wherein R ⁷ represents the same or different substituted or unsubstituted monovalent hydrocarbon group) is synthesized, and the UV absorber and silicone are synthesized. A method has been proposed in which an ultraviolet absorber is immobilized on silicone by reacting it with a system coating material. However, there is a problem that it is difficult to obtain the ultraviolet absorber having this specific terminal functional group, and there is a demand for another means for improving long-term durability, which is different from this method.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is an ultraviolet cut coating material obtained by introducing an ultraviolet absorber into a silicone coating material. And to provide an ultraviolet cut coating material capable of obtaining a coating film whose ultraviolet absorption ability is less likely to deteriorate even when irradiated with ultraviolet rays for a long time, and an article having the coating film obtained by applying the ultraviolet cut coating material. To provide.

[0004]

The ultraviolet cut coating material of the invention according to claim 1 is the following (1A), (1)
It is an ultraviolet cut coating material containing B), (1C) and water. (1A) Silicon compound represented by the general formula R ² _n Si (OR ¹ ) _4-n (1B) Organic UV absorber having a side chain containing an ester bridge represented by the general formula —R ³ COOR ⁴ (1C ) Acid catalyst Here, R ¹ , R ² and R ⁴ represent a monovalent hydrocarbon group, R ³ represents a divalent hydrocarbon chain, and n represents an integer of 0 to 3.

The ultraviolet cut coating material of the invention according to claim 2 is the ultraviolet cut coating material according to claim 1, which comprises acidic colloidal silica as (1C).

In the ultraviolet blocking coating material of the invention according to claim 3, the silica content of the acidic colloidal silica is 5 to 95% by weight in the solid content of the total of (1A) and (1C). According to another aspect of the present invention, there is provided an ultraviolet cut coating material.

In the ultraviolet protection coating material of the invention according to claim 4, the content of water is 0.001 to 1.0 mol of water per (1A) of 1 equivalent of OR ¹ group. The ultraviolet cut coating material according to any one of 1.

In the ultraviolet protection coating material of the invention according to claim 5, (1A) is a silicon compound represented by R ² Si (OR ¹ ) ₃ and a silicon compound represented by R ² ₂ Si (OR ¹ ) ₂ . R ² ₂ Si based on 100 parts by weight of a silicon compound represented by R ² Si (OR ¹ ) _3.
The ratio of the silicon compound represented by (OR ¹ ) ₂ is 0.1 to 0.1.
The ultraviolet cut coating material according to any one of claims 1 to 4, which is 60 parts by weight.

[0009] The ultraviolet cut coat of the invention according to claim 6
The wing materials are (2A), (2B), (2C) and
Ultraviolet ray blocking coating material containing the above (1B)
It is. (2A) General formula R^Five _nSix_4-nIs represented by (where R is^Five
Is the same or different substituted or unsubstituted C1-8
Represents a monovalent hydrocarbon group, n is an integer of 0 to 3, and X is hydrolyzed
Represents a degradable group. ), 50 mol% or more of which n = 1
Of the hydrolyzable organosilane is dissolved in an organic solvent or water.
In acidic colloidal silica dispersed, 1 equivalent of X group
Water 0.001 to 0.5 per hydrolyzable organosilane
Organosila partially hydrolyzed under conditions using moles
Silica dispersion oligomer solution (2B)⁶ _aSi (OH)_bO
_{(4-ab) / 2}Is represented by (where R is ⁶Are the same or different
Represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms.
Where a and b are 0.2 ≦ a ≦ 2 and 0.0001, respectively.
It represents a number that satisfies the relationship of ≦ b ≦ 3 and a + b <4. )molecule
A polyorganosiloxane (2C) curing catalyst having a silanol group therein, wherein the article having the ultraviolet absorbing layer of the invention according to claim 7 is a
The ultraviolet cup according to any one of claims 1 to 6.
It has an ultraviolet absorption layer obtained by applying a coating material
It is an article that does.

The article having an ultraviolet absorbing layer of the invention according to claim 8 is the article having an ultraviolet absorbing layer according to claim 7, which is glass or film.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION (1A) in the present invention is a silicon compound represented by the general formula R ² _n Si (OR ¹ ) _4-n . Here, R ¹ and R ² represent a monovalent hydrocarbon group,
They may be the same or different. And n represents the integer of 0-3.

The R ² is not particularly limited as long as it is a monovalent hydrocarbon group, but a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms is preferable, for example, a methyl group. Alkyl groups such as ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group;
Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aralkyl groups such as 2-phenylethyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; chloro Halogen-substituted hydrocarbon groups such as methyl group, γ-chloropropyl group, 3,3,3-trifluoropropyl group and γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group , Γ−
A substituted hydrocarbon group such as a mercaptopropyl group can be exemplified. Among these, an alkyl group having 1 to 4 carbon atoms and a phenyl group are preferable because of their ease of synthesis or availability.

If R ¹ is a monovalent hydrocarbon group,
Although not particularly limited, an alkyl group having 1 to 4 carbon atoms is preferable. Specific examples of the tetraalkoxysilane having n = 0 include tetramethoxysilane and tetraethoxysilane, and examples of the organotrialkoxysilane having n = 1 include methyltrimethoxysilane, methyltriethoxysilane, and methyltriisopropoxy. Examples thereof include silane, phenyltrimethoxysilane, phenyltriethoxysilane, and 3,3,3-trifluoropropyltrimethoxysilane. Examples of the diorganodialkoxysilane with n = 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane, and examples of the triorganoalkoxysilane with n = 3 include Examples include trimethylmethoxysilane, triethylmethoxysilane, trimethylisopropoxysilane, and dimethylisobutylmethoxysilane.

(1B) in the present invention is represented by the general formula --R ³ C
It is an organic ultraviolet absorber having a side chain containing an ester bridge represented by OOR ⁴ . The main skeleton of the organic ultraviolet absorber is not particularly limited, and examples thereof include benzophenone-based, benzotriazole-based, salicylate-based, oxalic acid anilide-based, diphenylcyanoacrylate-based, and triazine-based.

R ⁴ represents a monovalent hydrocarbon group and is not particularly limited, but a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms is preferable, for example, a methyl group. Alkyl groups such as ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group;
Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aralkyl groups such as 2-phenylethyl group and 3-phenylpropyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; chloro Halogen-substituted hydrocarbon groups such as methyl group, γ-chloropropyl group, 3,3,3-trifluoropropyl group and γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group , Γ−
A substituted hydrocarbon group such as a mercaptopropyl group can be exemplified. Among these, an alkyl group having 1 to 12 carbon atoms is preferable from the viewpoint of ease of synthesis or availability.

R ³ is a divalent hydrocarbon chain, and is not particularly limited, and examples thereof include linear or non-linear methyl chains, ethyl chains, propyl chains, butyl chains, pentyl chains, Examples include alkyl chains such as hexyl chain, heptyl chain and octyl chain; aryl chains such as phenyl chain and tolyl chain, and aralkyl chains such as 2-phenylethyl chain and 3-phenylpropyl chain. Of these, easy synthesis is possible. Or, an alkyl chain having 1 to 12 carbon atoms is preferable from the viewpoint of easy availability.

Further, (1B) may be an organic ultraviolet absorber having a side chain containing an ester bridge dimerized with an alkyl chain. And, the preferable content of the organic ultraviolet absorber which is (1B) varies depending on the absorption wavelength and the absorption intensity specific to the organic ultraviolet absorber, but is 0.1 to 50% by weight with respect to the total weight of the ultraviolet cut coating material.
Is preferably within the range.

In the present invention, (1C) is an acidic catalyst, and this acidic catalyst acts to accelerate the curing reaction of (1A) and is not particularly limited. For example, hydrochloric acid,
Water-soluble acids such as nitric acid and acidic colloidal silica can be exemplified, and it is preferable to use acidic colloidal silica because a film having excellent film-forming properties can be obtained. When the basic colloidal silica is used, the curing reaction of (1A) is promoted, but the organic ultraviolet absorber of (1B) turns yellow, so that it is desirable to use acidic colloidal silica in the present invention.

As the acidic colloidal silica, those dispersed in water or those dispersed in a non-aqueous organic solvent such as alcohol can be used. Generally, such acidic colloidal silica contains 20 to 50% by weight of silica as a solid content. When water-dispersed colloidal silica is used, water present as a component other than the solid content can be used as a curing agent necessary for the curing reaction of the component (1A), as will be shown later. Water-dispersed acidic colloidal silica can usually be made from water glass, but commercial products are easily available. The acidic colloidal silica dispersed in an organic solvent can be easily prepared by substituting the organic solvent for water in the aqueous dispersion, but a commercially available product can be easily obtained. Examples of the organic solvent in which colloidal silica is dispersed include lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, acetic acid ethylene glycol monoethyl ether and the like. Examples thereof include ethylene glycol derivatives; diethylene glycol, diethylene glycol derivatives such as diethylene glycol monobutyl ether, and diacetone alcohol. One or more selected from the group consisting of these can be used. Further, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketone oxime, etc. can be used in combination with these hydrophilic organic solvents.

The silica content of the acidic colloidal silica is preferably 5 to 95% by weight in the solid content of the sum of (1A) and (1C). The solid content in this case refers to a component produced when (1A) and (1C) are hardened and solidified, and (1
It is a value calculated by calculation from the structural formulas of the raw materials used as A) and (1C), and is composed of a solid component such as a solid component produced by hydrolysis and a silica component contained in the acidic colloidal silica. When the proportion of silica contained in the acidic colloidal silica is less than 5% by weight, the coating hardness of the resulting coating film is insufficient, and when it exceeds 95% by weight, uniform dispersion of the colloidal silica becomes difficult and the coating material is gel. This may lead to inconvenience such as deterioration.

The ultraviolet cut coating material of the invention according to claim 1 contains water as a curing agent together with the above (1A), (1B) and (1C). Water content is OR
Water is preferably 0.001 to 1.0 mol per 1 equivalent of ¹ group (more preferably 0.5 to 1.0 mol).
Is a mole. The reason for this is (1
The curing reaction of A) is unlikely to occur, and when it is more than 1.0 mol, the curing reaction of (1A) is prioritized, the crosslinking between the alkoxide part of (1A) and the ester part of (1B) is inhibited, and the ultraviolet absorption. This is because the effect of preventing deterioration of performance may be insufficient. Further, when adjusting the ultraviolet cut coating material, pH adjustment may be performed as necessary.

The ultraviolet blocking coating material of the invention according to claim 5 is the coating material according to claim 1,
(1A) contains a silicon compound represented by R ² Si (OR ¹ ) ₃ and a silicon compound represented by R ² ₂ Si (OR ¹ ) ₂ and is represented by R ² Si (OR ¹ ) ₃ . The ratio of the silicon compound represented by R ² ₂ Si (OR ¹ ) ₂ to 100 parts by weight of the silicon compound is 0.1 to 60 parts by weight. As (1A), R ² Si (O
By mainly containing the silicon compound represented by R ¹ ) ₃ , the coating film hardness is increased. Then, the above R ² ₂ Si
If the proportion of the silicon compound represented by (OR ¹ ) ₂ is less than 0.1 parts by weight, cracks may occur in the coating film, and if it exceeds 60 parts by weight, the hardness of the coating film may decrease. In some cases, the above range is preferable.

An ultraviolet cut coating material according to a sixth aspect of the present invention is an ultraviolet cut coating material containing the above (2A), (2B), (2C) and (1B).

The silica-dispersed oligomer (2A) is the main component of the base polymer having a hydrolyzable group as a functional group that is involved in the curing reaction when forming a film. This is obtained by adding one or more hydrolyzable organosilanes represented by the general formula R ⁵ _n SiX _4-n to colloidal silica dispersed in an organic solvent or water, and adding water in the colloidal silica or water added separately. Then, it is obtained by partially hydrolyzing the hydrolyzable organosilane. Specific examples of R ⁵ are the same as those of the substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms exemplified in the above R ² .

Examples of the hydrolyzable group X in the general formula R ⁵ _n SiX _4-n include an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group and an amide group. An alkoxy group is preferable because it is easily available and the silica dispersion oligomer solution is easily prepared. The hydrolyzable organosilane represented by the general formula R ⁵ _n SiX _4-n is determined by n, which is an integer of 0 to 3, but mono-, di-, tri-, and tetra-functional alkoxysilanes and acetoxy. Silanes, oxime silanes,
Examples include enoxysilanes, aminosilanes, aminoxysilanes, amidosilanes and the like. Specific examples of alkoxysilanes include tetramethoxysilane and tetraethoxysilane as the tetraalkoxysilane with n = 0, and methyltrimethoxysilane and methyltriethoxysilane as the organotrialkoxysilane with n = 1. Examples thereof include methyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and 3,3,3-trifluoropropyltrimethoxysilane. Examples of the diorganodialkoxysilane with n = 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane, and examples of the triorganoalkoxysilane with n = 3 include Examples include trimethylmethoxysilane, triethylmethoxysilane, trimethylisopropoxysilane, and dimethylisobutylmethoxysilane.

In the hydrolyzable organosilane represented by the general formula R ⁵ _n SiX _4-n , 50 mol% or more is n =
It is necessary to have a trifunctionality of 1, more preferably 60 mol% or more, and most preferably 70 mol%.
That is all. If n = 1 is less than 50 mol%, sufficient coating film hardness cannot be obtained, and the dry curability tends to be poor.

The colloidal silica in (2A) is essential for increasing the hardness of the cured coating film of the coating material. The colloidal silica is preferably contained in the solid content of (2A) in the range of 5 to 95% by weight as the silica content. The solid content of (2A) refers to a component produced when (2A) is cured and solidified. For example, the solid content obtained by allowing (2A) to stand at room temperature for 48 hours is (2A). ) Is the solid content. If the silica content of the colloidal silica is less than 5% by weight, the desired coating hardness cannot be obtained, and if it exceeds 95% by weight, it is difficult to uniformly disperse the colloidal silica (2A). May be invited.

The silica-dispersed oligomer (2A) can be obtained by partially hydrolyzing a hydrolyzable organosilane in water-dispersed colloidal silica or organic solvent-dispersed colloidal silica. The amount of water used is 0.001 to 1 part of water per 1 equivalent of hydrolyzable organosilane.
It is within the range of 0.5 mol. If it is less than 0.001 mol, a sufficient partial hydrolyzate cannot be obtained, resulting in insufficient coating strength, and if it exceeds 0.5 mol, the stability of the partial hydrolyzate becomes poor. The method of partial hydrolysis is not particularly limited, and it suffices to mix the hydrolyzable organosilane and colloidal silica and add and mix the required amount of water. At this time, the partial hydrolysis reaction proceeds at room temperature.
Further, in order to accelerate the partial hydrolysis reaction, 60 to 100
You may heat to ℃. Further, for the purpose of promoting partial hydrolysis reaction, hydrochloric acid, acetic acid, silane halide, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid,
Organic and inorganic acids such as malonic acid, toluenesulfonic acid and oxalic acid may be used as catalysts.

In order for (2A) to have stable performance for a long period of time, the pH of the liquid is 2.0 to 7.0, preferably 2.5.
-6.5, more preferably 3.0-6.0. When the pH is out of the range of 2.0 to 7.0, particularly when the amount of water used is 0.3 mol or more of water with respect to 1 equivalent of the X group, (2
Long-term performance deterioration of A) is likely to occur. PH of (2A)
If the pH is more than 2.0, it may be adjusted by adding a basic reagent such as ammonia or ethylenediamine. If the pH is more than 7.0, an acidic reagent such as hydrochloric acid, nitric acid, acetic acid, etc. It suffices to make the adjustment using, and the adjusting method is not particularly limited.

(2B) Silanol group-containing polyorgano
The average composition formula of siloxane is R⁶ _aSi (OH)_bO
_{(4-ab) / 2}It is represented by R in the formula⁶As a specific example of
R above ^FiveSimilarly to the above R^TwoExamples of carbon
The same as the substituted or unsubstituted monovalent hydrocarbon group of number 1 to 8
Although it is possible to exemplify, an alkyl group having 1 to 4 carbon atoms is preferable.
Group, phenyl group, vinyl group or γ-glycidoxy pro
Pill group, γ-methacryloxypropyl group, γ-aminop
Substituted carbon such as ropyl group and 3,3,3-trifluoropropyl group
A hydrogenated group, more preferably a methyl group or a phenyl group.
It is a nyl group. Further, a and b in the above formula are each 0.
Relationship of 2 ≦ a ≦ 2, 0.0001 ≦ b ≦ 3, a + b <4
Is a number that satisfies. a is less than 0.2 or b is more than 3
May cause inconvenience such as cracks in the cured coating film.
When a exceeds 2 and is 4 or less, or b is 0.0001.
If it is less than 1, there will be a problem that curing will not proceed well.
You. (2B) Silanol group-containing polyorganosiloxa
For example, methyltrichlorosilane, dimethyldichlorosilane
Losilane, phenyltrichlorosilane, diphenyldichlorosilane
Lolosilane, or alkoxysila corresponding to these
Water with a large amount of water.
It can be obtained by solving. In addition, containing silanol group
To obtain polyorganosiloxane containing
Alcohols that are not hydrolyzed when
We have obtained polyorganosiloxanes in which xy groups coexist.
In some cases, such polyorganosiloxane
Can be used.

The curing catalyst of (2C) is (2A) and (2C).
It has the function of promoting the condensation reaction with B) and hardening the coating film. As the curing catalyst, a metal salt of a carboxylic acid such as alkyl titanate, tin octylate dilaurate, dibutyltin dilaurate, dioctyltin dimaleate; dibutylamine-2-hexoate, dimethylamine acetate,
Amine salts such as ethanolamine acetate; carboxylic acid quaternary ammonium salts such as tetramethylammonium acetate; amines such as tetraethylpentamine; N-β
-Amine-based silane coupling agents such as aminoethyl-γ-aminopropyltrimethoxysilane and N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane;
Acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; alkali catalysts such as potassium hydroxide; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate and titanium tetraacetylacetonate, There are halogenated silanes such as methyltrichlorosilane, dimethyldichlorosilane, and trimethylmonochlorosilane, but in addition to these, (2A) and (2
There is no particular limitation as long as it is effective for promoting the condensation reaction with B).

The mixing ratio of (2A) and (2B) is (2
When the total of (A) and (2B) is 100 parts by weight, (2
A) 1 to 99 parts by weight, (2B) is preferably 99 to 1 parts by weight, and more preferably (2A) 5 to 95 parts.
95 to 5 parts by weight to (2B), most preferably (2B) 90 to 1 to 10 to 90 parts by weight.
0 parts by weight. If the content of (2A) is less than 1 part by weight, the room temperature curability is poor, and sufficient coating film hardness cannot be obtained. On the other hand, if the amount of (2A) exceeds 99 parts by weight, the curability may be unstable and a good coating film may not be obtained. Also, (2C)
The addition amount of the curing catalyst of (2A) and (2B) is 10
When it is 0 parts by weight, it is preferably 0.0001 to 10 parts by weight, more preferably 0.0005 to 8 parts by weight, and most preferably 0.0007 to 5 parts by weight. If it is less than 0.0001 parts by weight, the room temperature curing property is poor, and if it exceeds 10 parts by weight, heat resistance and weather resistance are impaired.

The hydrolyzable group contained in the silica-dispersed oligomer (2A) and the silanol group (2B) are (2)
By heating at room temperature or low temperature in the presence of the curing catalyst of C), a condensation reaction is caused to form a cured film. Therefore, unlike a moisture-curing type coating material, it is hardly affected by humidity even when cured at room temperature. Further, the heat treatment can accelerate the condensation reaction to form a cured film.

The coating material according to claim 6 can be diluted with various organic solvents before use. The type of organic solvent is (2
It can be appropriately selected depending on the type or molecular weight of the monovalent hydrocarbon group of A) or (2B). For specific examples of this organic solvent, see (1C) above.
As the organic solvent in which the colloidal silica is dispersed when the acidic colloidal silica is used as the organic solvent, the same organic solvents as those exemplified can be exemplified.

An article having an ultraviolet absorbing layer of the invention according to claim 7 has an ultraviolet absorbing layer obtained by applying the ultraviolet cut coating material according to any one of claims 1 to 6. . The application method of the ultraviolet cut coating material is not particularly limited, and various application methods such as brush application, spraying, dipping, flow, roll, curtain, knife coating and the like can be selected. After applying the coating material, drying (baking if necessary) is performed to obtain the ultraviolet absorbing layer. When applying the coating material, a primer layer may be formed in advance on the surface of the article depending on the material and surface condition of the article. The thickness of the ultraviolet absorbing layer is not particularly limited, but is 0.1 to 50 μm.
It is preferably about 1 to 10 μm, because the coating film is stably adhered and held for a long period of time and cracks and peeling do not occur. The article is not particularly limited, but glass or film is preferable because it can be used for windows and the like.

[0036]

The present invention will be described below based on examples and comparative examples. In the examples and comparative examples, all "parts" represent "parts by weight" and all "%" represent "% by weight". Further, the molecular weight is measured by GPC (gel permeation chromatography), and HLC8 manufactured by Tosoh Corp. is used as a measuring model.
Using 020, create a calibration curve with standard polystyrene,
Measured. In addition, this invention is not limited to a following example.

Example 1 100 parts of methyltrimethoxysilane [(1A) component] and 100 parts of acidic colloidal silica [(1C) component] IPA organosilica sol [trade name "OSCAL1432", manufactured by Catalyst Chemical Industry Co., Ltd.] ,
Solid content 30%] 60 parts, dimethyldimethoxysilane [(1A) component] 30 parts and the following organic UV absorber [(1B) component] 5 parts are mixed, and then 100 parts of isopropyl alcohol (hereinafter abbreviated as IPA). Dilute, add 39 parts of water, and stir. The obtained liquid was heated in a constant temperature bath at 60 ° C. to adjust the molecular weight to M _w = 1200 to obtain an ultraviolet cut coating material.

As the above-mentioned organic ultraviolet absorber, -R ^{8 of the} benzotriazole derivative represented by the following general formula 1 is used.
A There _{-C (CH 3) 3, -R} 9 is -C ₂ H ₄ COO
C ₈ H ₁₇ benzotriazole-based UV absorber (trade name “TINUVIN 384”, CIBA-GEIGY
Was used. In addition, R ⁸ and R ⁹ in the general formula 1 represent a monovalent organic group.

[0039]

Embedded image

The UV-cut coating material obtained above was applied onto a glass plate (made of Pyrex glass) washed with acetone by spray coating so that the coating film thickness was 5 μm and cured at 150 ° C. for 30 minutes. A glass plate having an ultraviolet absorbing layer was obtained. With respect to the glass plate having this ultraviolet absorbing layer, the deterioration rate of the ultraviolet absorbing ability was evaluated by the test method described below, and the results are shown in Table 1.

(Example 2) 100 parts of methyltrimethoxysilane [(1A) component] and 100 parts of acidic colloidal silica [(1C) component] IPA organosilica sol [trade name "OSCAL1432", manufactured by Catalyst Chemical Industry Co., Ltd.] ,
Solid content 30%] 90 parts and the above-mentioned benzotriazole-based ultraviolet absorber (trade name "TINUVIN384", CI
BA-GEIGY) 5 parts, and then IPA1
Dilute with 00 parts, add 37.7 parts of water, and stir. The obtained liquid was heated in a constant temperature bath at 60 ° C. to adjust the molecular weight to M _w = 1500 to obtain an ultraviolet cut coating material.

The UV-cut coating material obtained above was applied onto a glass plate (made of Pyrex glass) washed with acetone by spray coating so as to have a coating film thickness of 5 μm and cured at 150 ° C. for 30 minutes. A glass plate having an ultraviolet absorbing layer was obtained. With respect to the glass plate having this ultraviolet absorbing layer, the deterioration rate of the ultraviolet absorbing ability was evaluated by the test method described below, and the results are shown in Table 1.

(Example 3) 100 parts of methyltrimethoxysilane [(1A) component] and 100 parts of acidic colloidal silica [(1C) component] IPA organosilica sol [trade name "OSCAL1432", manufactured by Catalyst Chemical Industry Co., Ltd.] ,
Solid content 30%] 60 parts and the above-mentioned benzotriazole-based ultraviolet absorber (trade name "TINUVIN384", CI
(Manufactured by BA-GEIGY) 10 parts, and then IPA
Dilute with 100 parts, add 37.7 parts of water, and stir. The obtained liquid was heated in a constant temperature bath at 60 ° C. to adjust the molecular weight to M _w = 1300 to obtain an ultraviolet cut coating material.

The UV-cut coating material obtained above was applied onto a glass plate (made of Pyrex glass) washed with acetone by spray coating so that the coating film thickness was 5 μm and cured at 150 ° C. for 30 minutes. A glass plate having an ultraviolet absorbing layer was obtained. With respect to the glass plate having this ultraviolet absorbing layer, the deterioration rate of the ultraviolet absorbing ability was evaluated by the test method described below, and the results are shown in Table 1.

Comparative Example 1 Methyltrimethoxysilane
[(1A) component] 100 parts with acidic colloidal silica
[(1C) component] IPA organosilica sol [quote
Product name "OSCAL1432", manufactured by Catalyst Kasei Kogyo Co., Ltd.
Solid content 30%] 90 parts and a compound represented by the general formula 1
-R of benzotriazole derivative⁸, -R⁹Together
-C (CH_Three) _TwoC_TwoH_FiveBenzotriazole UV
Absorbent (trade name "TINUVIN328", CIBA-
GEIGY) 5 parts, then IPA 100 parts
The mixture is diluted with, 37.7 parts of water is added, and the mixture is stirred. Profit
By heating the liquid obtained in a constant temperature bath at 60 ° C, the molecular weight is
To M_w= 1500 and UV cut coating
I got the material.

The UV-cut coating material obtained above was applied onto a glass plate (made of Pyrex glass) washed with acetone by spray coating so that the coating film thickness was 5 μm and cured at 150 ° C. for 30 minutes. A glass plate having an ultraviolet absorbing layer was obtained. With respect to the glass plate having this ultraviolet absorbing layer, the deterioration rate of the ultraviolet absorbing ability was evaluated by the test method described below, and the results are shown in Table 1.

Next, an example of adjusting each component used in the ultraviolet cut coating materials of Examples 4 to 6 and Comparative Example 2 will be described.

First, an example of adjusting the (2A) component will be described. (Preparation Example 2A-1) IPA-dispersed colloidal silica sol [trade name "IPA-ST", particle size 10 to 20 nm, solid content 30%, water content 0. 5] in a flask equipped with a stirrer, a heating jacket, a condenser and a thermometer. 5%, manufactured by Nissan Chemical Industries, Ltd.,] 100 parts, 68 parts of methyltrimethoxysilane, the general formalized -R ⁸ benzotriazole derivative represented by 1 is -C (CH _{3) 3,} and - A benzotriazole-based ultraviolet absorber in which R ⁹ is —C ₂ H ₄ COOC ₈ H ₁₇ (trade name “TINUVIN 384”, CI
3 parts of BA-GEIGY) and 10.8 parts of water were added and the partial hydrolysis reaction was carried out at a temperature of 65 ° C. for about 5 hours with stirring, followed by cooling to obtain the component (2A). This product had a solid content of 36% when left at room temperature for 48 hours. The component (2A) obtained here is referred to as 2A-1. Condition for adjusting 2A-1: -Number of moles of water relative to 1 equivalent of hydrolyzable group of methyltrimethoxysilane ------ 0.4 moles-Silica content in solid content of (2A) -------- -47.3% -mol% of hydrolyzable organosilane with n = 1 ---------- 100 mol%

(Adjustment Example 2A-2) Stirrer, heating jacket
In a flask equipped with a condenser, condenser and thermometer.
Xylene / n-butanol dispersion colloidal silica sol [quote
Product name "XBA-ST", particle size 10-20 nm, solid content
30%, moisture 0.2%, manufactured by Nissan Chemical Industries, Ltd.] 10
0 part, 68 parts of methyltrimethoxysilane and the above general formula
Of the benzotriazole derivative represented by Chemical formula 1⁸But-
C (CH_Three)_ThreeAnd -R⁹Is -C_TwoH _FourCOOC₈
H₁₇Benzotriazole-based UV absorber (trade name
"TINUVIN 384", CIBA-GEIGY
(Production) Add 3 parts and stir at a temperature of 65 ° C for about 5 hours
Partially hydrolyzes over a period of time, cools (2A)
Got a minute. This one is
The solid content was 36%. The component (2A) obtained here is 2
It is called A-2. Condition for adjusting 2A-2: -Number of moles of water relative to 1 equivalent of hydrolyzable group of methyltrimethoxysilane ------ 7 × 10^-3Silica content in solid content of (2A) ----- 47.2% Mol% of hydrolyzable organosilane of n = 1 --100 mol%

(Preparation Example 2A-3) IPA-dispersed colloidal silica sol [trade name "IPA-S" was placed in a flask equipped with a stirrer, a heating jacket, a condenser and a thermometer.
T ”, particle size 10 to 20 nm, solid content 30%, water content 0.
5%, manufactured by Nissan Chemical Industries, Ltd.] 100 parts, methyltrimethoxysilane 68 parts, dimethyldimethoxysilane 18
Parts, the general formalized -R ⁸ benzotriazole derivatives -C represented by 1 (CH ₃₎ a _3, -R ⁹ is -C ₂
H ₄ COOC ₈ H ₁₇ benzotriazole-based UV absorber (trade name “TINUVIN 384”, CIBA-
(Manufactured by GEIGY) 3 parts, water 2.7 parts and acetic anhydride 0.1
Part of the mixture was added and stirred to carry out a partial hydrolysis reaction at a temperature of 80 ° C. for about 3 hours and then cooled to obtain a component (2A). This product had a solid content of 36% when left at room temperature for 48 hours. The component (2A) obtained here is used as 2A-3
Called. 2A-3 adjustment conditions: -The number of moles of water for 1 equivalent of the hydrolyzable group of hydrolyzable organosilane (methyltrimethoxysilane and dimethyldimethoxysilane) -------- 0.1 mol- (2A) Silica content in solid content --- 40.2% -mol% of hydrolyzable organosilane with n = 1 --77-mol%

(Adjustment Example 2A-4) TINUVIN384
Instead of, as a benzotriazole-based ultraviolet absorber,
The general formalized -R ⁸ benzotriazole derivative represented by 1, both -C portions of _{^{-R 9 (CH 3) 2 C}} 2 H 5
Benzotriazole-based UV absorber (trade name "T
INUVIN 328 ", manufactured by CIBA-GEIGY) 3
Component (2A) was obtained in the same manner as in Preparation Example 2A-2, except that the parts were used. This product had a solid content of 36% when left at room temperature for 48 hours. The component (2A) obtained here is referred to as 2A-4. Condition for adjusting 2A-4: -Number of moles of water relative to 1 equivalent of methyltrimethoxysilane of the hydrolyzable group ------ 7 x 10 ^-3 moles-Silica content in solid content of (2A) --- --47.2% Mol% of hydrolyzable organosilane with n = 1 ------- 100 mol%

Next, an example of adjusting the (2B) component will be described. (Adjustment Example 2B-1) 220 parts (1 mol) of methyltriisopropoxysilane and 150 parts of toluene were weighed out in a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer, and in a mixed solution thereof. With stirring, 108 parts of a 1% hydrochloric acid aqueous solution was added dropwise over 20 minutes to hydrolyze methyltriisopropoxysilane. After 40 minutes from the end of the dropping, stirring was stopped, and the reaction solution was transferred to a separating funnel and allowed to stand still to separate into two layers. The lower layer mixture of water and isopropyl alcohol containing hydrochloric acid was removed by liquid separation, then the remaining hydrochloric acid in the resin solution of toluene was removed by washing with water, and the toluene was removed under reduced pressure. Diluted with, average molecular weight (M _w ) about 20
A silanol group-containing polyorganosiloxane of No. 00 in 40% isopropyl alcohol was obtained. Got here (2
Component B) is referred to as 2B-1.

(Preparation Example 2B-2) 1000 parts of water and 50 parts of acetone were weighed into a flask equipped with a stirrer, a heating jacket, a condenser, a dropping funnel and a thermometer, and methyltrichlorosilane 44 was added to the mixed solution. .8
Parts (0.3 mol), dimethyldichlorosilane 38.7 parts (0.3 mol) and phenyltrichlorosilane 84.6.
One part (0.4 mol) dissolved in 200 parts of toluene was hydrolyzed while being added dropwise with stirring. 40 from the end of dropping
After a minute, stirring was stopped, and the reaction solution was transferred to a separating funnel and allowed to stand to separate into two layers. The lower layer liquid containing hydrochloric acid is separated and removed,
Then, the remaining toluene solution of the upper polyorganosiloxane was subjected to vacuum stripping, and the water and hydrochloric acid remaining in this solution were distilled off together with an excess of toluene, thereby containing a silanol group having an average molecular weight (M _w ) of about 3000. A 60% toluene solution of polyorganosiloxane was obtained. The component (2B) obtained here is referred to as 2B-2.

Example 4 As shown in Table 2, (2A)
70 parts of 2A-1 which is an ingredient, 2B which is a (2B) ingredient
-1 was mixed with 30 parts and 1 part of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as a component (2C) to obtain an ultraviolet cut coating material. In addition,
The component (1B) is contained in the above 2A-1.

Next, an acrylic primer was applied onto a polyester film washed with ethanol by spray coating so that the film thickness for curing would be 1 μm, and after curing at 80 ° C. for 30 minutes, the above was obtained above. An ultraviolet cut coating material was applied so as to have a cured film thickness of about 10 μm, and cured at 80 ° C. for 30 minutes to obtain a film having an ultraviolet absorbing layer. The deterioration rate of the ultraviolet absorbing ability of the film having the ultraviolet absorbing layer was evaluated by the test method described below, and the results are shown in Table 2.

(Example 5) As shown in Table 2, (2A)
60 parts of component 2A-2, 2B of component (2B)
40 parts of -1 and 2 parts of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as the component (2C) were mixed to obtain an ultraviolet cut coating material. In addition,
The component (1B) is contained in the above 2A-2.

Next, an acrylic primer was applied onto a polyester film washed with ethanol by spray coating so that the film thickness for curing would be 1 μm, and after curing at 80 ° C. for 30 minutes, the above was obtained above. An ultraviolet cut coating material was applied so as to have a cured film thickness of about 10 μm, and cured at 80 ° C. for 30 minutes to obtain a film having an ultraviolet absorbing layer. The deterioration rate of the ultraviolet absorbing ability of the film having the ultraviolet absorbing layer was evaluated by the test method described below, and the results are shown in Table 2.

Example 6 As shown in Table 2, (2A)
50 parts of 2A-3 which is an ingredient, 2B which is a (2B) ingredient
-2 parts and 50 parts of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as a component (2C) were mixed to obtain an ultraviolet cut coating material. In addition,
The component (1B) is contained in the above 2A-3.

Next, an acrylic primer was applied onto the polyester film washed with ethanol by spray coating so that the film thickness for curing would be 1 μm, and after curing at 80 ° C. for 30 minutes, the above-obtained product was obtained thereon. An ultraviolet cut coating material was applied so as to have a cured film thickness of about 10 μm, and cured at 80 ° C. for 30 minutes to obtain a film having an ultraviolet absorbing layer. The deterioration rate of the ultraviolet absorbing ability of the film having the ultraviolet absorbing layer was evaluated by the test method described below, and the results are shown in Table 2.

(Comparative Example 2) As shown in Table 2, (2A)
60 parts of component 2A-4, 2B of component (2B)
40 parts of -1 and 2 parts of N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane as the component (2C) were mixed to obtain an ultraviolet cut coating material. In addition,
(1B) is a component TINUVIN384 is not included in the 2A-4, benzotriazole derivatives of -R ⁸ represented by instead general formalized 1, -C are both part of the -R ⁹ (CH ₃ ) ₂ C ₂ H ₅ benzotriazole-based UV absorber (trade name “TINUVIN 328”, CI
2A-4 contains BA-GEIGY).

Next, an acrylic primer was applied by spray coating on a polyester film washed with ethanol so that the film thickness for curing would be 1 μm, and after curing at 80 ° C. for 30 minutes, the above-obtained product was obtained. An ultraviolet cut coating material was applied so as to have a cured film thickness of about 10 μm, and cured at 80 ° C. for 30 minutes to obtain a film having an ultraviolet absorbing layer. The deterioration rate of the ultraviolet absorbing ability of the film having the ultraviolet absorbing layer was evaluated by the test method described below, and the results are shown in Table 2.

(Test Method for Deterioration Rate of Ultraviolet Absorbing Ability) For the prepared glass having an ultraviolet absorbing layer or a film having an ultraviolet absorbing layer, an accelerated weather resistance tester (manufactured by Suga Test Instruments Co., Ltd., trade name Sunshine Super Long) is used. 12 by life weather meter, model number WEL-SUN-HC type)
The accelerated test for 00 hours is performed to perform the accelerated test for deterioration of the ultraviolet absorbing ability. The ultraviolet absorption rate of the test sample before and after the acceleration test is measured using a spectral characteristic tester, and the deterioration rate of the ultraviolet absorption capacity is calculated from the following formula. The ultraviolet absorption was measured in the range of 300 to 380 nm. Deterioration rate of UV absorption capacity = (1-UV absorption rate after accelerated test / UV absorption rate before accelerated test) × 100

[0063]

[Table 1]

[0064]

[Table 2]

From the results shown in Tables 1 and 2, it was confirmed that the examples of the present invention had a lower deterioration rate of the ultraviolet absorbing ability than the comparative examples.

[0066]

UV coating material according to claims 1 to 6, according to the invention are organic ultraviolet having a side chain containing an ester bridge of the general formula -R ³ COOR ⁴ as an ultraviolet absorber in the silicone based coating material Since the absorbent is introduced, the ultraviolet cut coating materials according to claims 1 to 6 can provide a coating film in which the ultraviolet absorbing ability is not easily deteriorated even when irradiated with ultraviolet rays for a long period of time.

Further, since the article having the ultraviolet absorbing layer according to claim 7 and claim 8 has the ultraviolet absorbing layer formed by using the ultraviolet cut coating material according to claim 1 to claim 6, The article has a preferable performance that the ultraviolet absorbing ability is not easily deteriorated even when the ultraviolet ray is irradiated.

Claims (8)

[Claims] 1. An ultraviolet cut coating material containing the following (1A), (1B), (1C) and water. (1A) Silicon compound represented by the general formula R ² _n Si (OR ¹ ) _4-n (1B) Organic UV absorber having a side chain containing an ester bridge represented by the general formula —R ³ COOR ⁴ (1C ) Acid catalyst Here, R ¹ , R ² and R ⁴ represent a monovalent hydrocarbon group, R ³ represents a divalent hydrocarbon chain, and n represents an integer of 0 to 3. 2. The ultraviolet cut coating material according to claim 1, which comprises acidic colloidal silica as (1C). 3. The ultraviolet cut coating material according to claim 2, wherein the silica content of the acidic colloidal silica is 5 to 95% by weight in the solid content of the total of (1A) and (1C). 4. A water content of 1 equivalent of OR ¹ group (1A)
The ultraviolet cut coating material according to any one of claims 1 to 3, which has a water content of 0.001 to 1.0 mol. 5. (1A) contains a silicon compound represented by R ² Si (OR ¹ ) ₃ and a silicon compound represented by R ² ₂ Si (OR ¹ ) ₂ , and R ² Si (OR ¹ ) R ² ₂ Si based on 100 parts by weight of the silicon compound represented by ₃
The ratio of the silicon compound represented by (OR ¹ ) ₂ is 0.1 to 0.1.
The ultraviolet cut coating material according to any one of claims 1 to 4, which is 60 parts by weight. 6. The following (2A), (2B), (2C) and
And an ultraviolet cut coating containing the above (1B)
Wood. (2A) General formula R^Five _nSix_4-nIs represented by (where R is^Five
Is the same or different substituted or unsubstituted C1-8
Represents a monovalent hydrocarbon group, n is an integer of 0 to 3, and X is hydrolyzed
Represents a degradable group. ), 50 mol% or more of which n = 1
Of the hydrolyzable organosilane is dissolved in an organic solvent or water.
In acidic colloidal silica dispersed, 1 equivalent of X group
Water 0.001 to 0.5 per hydrolyzable organosilane
Organosila partially hydrolyzed under conditions using moles
Silica dispersion oligomer solution (2B)⁶ _aSi (OH)_bO
_{(4-ab) / 2}Is represented by (where R is ⁶Are the same or different
Represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms.
Where a and b are 0.2 ≦ a ≦ 2 and 0.0001, respectively.
It represents a number that satisfies the relationship of ≦ b ≦ 3 and a + b <4. )molecule
Polyorganosiloxane (2C) curing catalyst having silanol groups in the interior 7. An article having an ultraviolet absorbing layer obtained by applying the ultraviolet cut coating material according to any one of claims 1 to 6. 8. The article having an ultraviolet absorbing layer according to claim 7, wherein the article is glass or film.