JPWO2011099505A1 - Outdoor installation device and antireflection layer for outdoor installation device - Google Patents

Abstract

The present invention provides an outdoor installation device and an antireflection layer for an outdoor installation device having an antireflection layer having an antireflection ability that is excellent in light resistance and can be formed by a simple method. Layer (I) containing polyorganosiloxane (A) and metal oxide particles (B), hollow or porous particles mainly composed of polyorganosiloxane (C) and silica having a number average particle diameter of 1 to 100 nm An antireflection layer composed of a laminate with the layer (II) containing (D) is formed on the base material using the surface member of the outdoor installation device as a base material.

Description

  The present invention relates to an outdoor installation device having an antireflection layer and an antireflection layer for an outdoor installation device. More specifically, the present invention relates to an outdoor installation device having an antireflection layer that can be formed by a simple method and exhibits excellent weather resistance in outdoor use, and the antireflection layer.

Conventionally, as a means for improving the visibility of an article, an antireflection film composed of a low refractive index material on the surface of the article, or an antireflection film composed of a multilayer structure of a low refractive index layer and a high refractive index layer Has been made to form. Moreover, in a solar cell, conversion efficiency can be improved by performing the antireflection process on the surface. In particular, in recent years, there has been a demand for a technique that can form an antireflection film on a large-sized substrate by a low-cost and simple method.
As a method of forming these antireflection films, for example, a method using an organic ultraviolet / radiation curable material or a method of forming an inorganic material by vapor deposition or the like is known (Patent Documents 1 to 3). ).

JP 2003-311911 A JP 2007-25078 A Patent 2989923

However, when using organic materials, for example, those having a polyfunctional (meth) acrylate structure are used as the hard coat layer, especially when used for outdoor installations where weather resistance is required Had a major problem with long-term reliability. In addition, when an inorganic material is used, the layer is formed by a vacuum process such as vapor deposition, which is excellent in long-term reliability. However, since a vacuum facility is required, the production cost is high and a large area base is required. There is a problem that it is difficult to form a uniform antireflection film with high efficiency on the material. As a non-vacuum process type inorganic material laminate used outdoors, a so-called photocatalyst laminate proposed in the structure of base material / intermediate layer / top layer is known. However, since the top layer contains a large amount of high-refractive-index metal oxides such as titanium oxide and zinc oxide, the difference in refractive index from air becomes large, and instead of preventing surface reflection, the reflectance is reversed. Is incompatible with anti-reflective applications.
In addition, although polydimethylsiloxane (silicone) may be used as a highly durable polymer material, it is necessary to use an expensive platinum compound as a curing catalyst, and the coating film has low hardness. It has been difficult to use as an antireflection layer due to problems such as inferior adhesiveness, difficulty in increasing the refractive index, and difficulty in designing a laminate.

Accordingly, an object of the present invention is to provide an outdoor installation device having an antireflection layer that exhibits excellent weather resistance in outdoor use and that can be formed on a substrate by a simple method.
Another object of the present invention is to provide an antireflection layer for a device for outdoor installation, which exhibits excellent weather resistance in outdoor use and can be formed on a substrate by a simple method.

  As a result of intensive studies, the present inventors have found that the above-described problems can be solved by the antireflection layer described below, and have completed the present invention.

  The outdoor installation device of the present invention mainly comprises a layer (I) containing polyorganosiloxane (A) and metal oxide particles (B), polyorganosiloxane (C) and silica having a number average particle diameter of 1 to 100 nm. It has an antireflection layer comprising a laminate with a layer (II) containing hollow or porous particles (D) as a component.

The layer (I) has the following formula (1)
R ¹ _n Si (OR ² ) _4-n (1)
(Wherein, R ¹ represents a non-hydrolyzable organic group having 1 to 12 carbon atoms, optionally .R ² be different be the same as each other if there are two or more are each independently Represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 3.)
At least one silane compound (a1) and metal oxide particles (B) selected from the group consisting of at least one organosilane represented by the formula: hydrolyzate of the organosilane and condensate of the organosilane Obtained from a cured product of the composition (I) containing,
The layer (II) is represented by the following formula (2)
R ³ _m Si (OR ⁴ ) _4-m (2)
(In the formula, R ³ represents a non-hydrolyzable organic group having 1 to 12 carbon atoms, and when two or more exist, they may be the same as or different from each other. R ⁴ is independently selected. Represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and m is an integer of 0 to 3.)
At least one silane compound (c1) selected from the group consisting of at least one organosilane represented by the formula: a hydrolyzate of the organosilane and a condensate of the organosilane, and a number average particle size of 1 to 100 nm It is preferably obtained from a cured product of the composition (II) containing hollow or porous particles (D) mainly composed of silica.

The silane compound (a1) of the composition (I) preferably contains a silane compound in which at least one of R ¹ in the formula (1) is a phenyl group.
Moreover, it is preferable that 5-80 mol% of all R < ¹ > in the said Formula (1) is a phenyl group as for the silane compound (a1) of the said composition (I).

  Typical examples of the outdoor installation device on which the antireflection layer is formed include an outdoor installation display and a solar cell.

  The antireflection layer for a device for outdoor installation of the present invention comprises a layer (I) containing a polyorganosiloxane (A) and metal oxide particles (B), a polyorganosiloxane (C) and a number average particle diameter of 1 to 100 nm. It consists of a laminated body with the layer (II) containing the hollow or porous particle | grains (D) which have silica as a main component.

  ADVANTAGE OF THE INVENTION According to this invention, it can form simply by means, such as application | coating, and the device for outdoor installation which has the anti-reflective layer which shows the outstanding weather resistance in outdoor use can be obtained.

Hereinafter, embodiments of the present invention will be specifically described.
The device for outdoor installation of the present invention comprises a layer (I) containing polyorganosiloxane (A) and metal oxide particles (B) on the surface of the surface member of the device for outdoor installation as a base material, and polyorganosiloxane. It has an antireflection layer comprising a laminate of (C) and a layer (II) containing hollow or porous particles (D) mainly composed of silica having a number average particle diameter of 1 to 100 nm. .
In the present invention, “polyorganosiloxane” refers to a polymer having a Si—O bond as a skeleton.

(1) Device for outdoor installation The device for outdoor installation of the present invention is not particularly limited as long as antireflection properties are required on the surface thereof, for example, a display for outdoor installation, a solar cell, and the like. Can be mentioned. A surface forming member that forms such a surface in a device for outdoor installation is used as a base material, and an antireflection layer is formed thereon. The material of this base material is not particularly limited, and examples thereof include metals, ceramics, glass, resin, wood, slate and the like.
Examples of the resin include polycarbonate, polymethyl methacrylate, polystyrene / polymethyl methacrylate copolymer, polystyrene, polyester, polyolefin, triacetyl cellulose resin (TAC), diallyl carbonate of diethylene glycol (CR-39), ABS resin, and AS resin. , Polyamide, epoxy resin, melamine resin, cyclized polyolefin resin (for example, norbornene resin), and the like. By forming an antireflection layer on the surface of these substrates, an excellent antireflection effect can be obtained.

(2) Layer (I)
Layer (I) contains polyorganosiloxane (A) and metal oxide particles (B).
The layer (I) has a refractive index of 1.50 or more and less than 1.85, and a film thickness of 0.01 μm to 10 μm, although it depends on the type of outdoor installation device.

(2-1) Composition (I)
Such a layer (I) has, for example, the following formula (1):
R ¹ _n Si (OR ² ) _4-n (1)
(Wherein, R ¹ represents a non-hydrolyzable organic group having 1 to 12 carbon atoms, optionally .R ² be different be the same as each other if there are two or more are each independently Represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 3.)
Selected from the group consisting of at least one organosilane (hereinafter also referred to as “organosilane (1)”), hydrolyzate of organosilane (1), and condensate of organosilane (1). It can be obtained from a cured product of a composition comprising at least one silane compound (a1) and metal oxide particles (B) (hereinafter also referred to as “composition (I)”).

(Silane compound (a1))
The silane compound (a1) used in the present invention is selected from the group consisting of organosilane (1) represented by the above formula (1), hydrolyzate of organosilane (1) and condensate of organosilane (1). At least one silane compound, and among these three silane compounds, only one silane compound may be used, or any two silane compounds may be used in combination, or You may mix and use all three types of silane compounds. Moreover, when using organosilane (1) as a silane compound (a1), organosilane (1) may be used individually by 1 type, or may use 2 or more types together. The hydrolyzate and condensate of the organosilane (1) may be formed from one kind of organosilane (1) or may be formed by using two or more kinds of organosilane (1) in combination. Good.
The hydrolyzate of the organosilane (1) is sufficient if at least one of the OR ² groups contained in 1 to 4 of the organosilane (1) is hydrolyzed, for example, one OR ² group. In which two or more OR ² groups are hydrolyzed, or a mixture thereof.

  The condensate of the organosilane (1) is formed by condensation of silanol groups in the hydrolyzate produced by hydrolysis of the organosilane (1) to form Si—O—Si bonds. In the present invention, it is not necessary that all of the silanol groups are condensed, and the condensate is a product obtained by condensing a small part of silanol groups, a product obtained by condensing most (including all) silanol groups, Includes a mixture thereof.

In the above formula (1), R ¹ is a non-hydrolyzable organic group having 1 to 12 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group. Alkyl groups such as heptyl group, octyl group, decyl group, 2-ethylhexyl group;
Acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, caproyl group;
Vinyl group, allyl group, cyclohexyl group, phenyl group, epoxycycloalkyl group, 3,4-epoxycyclohexylethyl group, glycidyl group, 3-glycidyloxypropyl group, (meth) acryloxy group, 3- (meth) acryloxy A propyl group, a ureido group, an amide group, a fluoroacetamide group, an isocyanate group, etc. are mentioned.
Furthermore, examples of R ¹ include substituted derivatives of the above organic groups. Examples of the substituent of the substituted derivative of R ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth) acryloxy group, A ureido group, an ammonium base, etc. are mentioned. When a plurality of R ¹ are present in the formula (1), they may be the same or different.

Examples of R ² that is an alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and R is an acyl group having 1 to 6 carbon atoms. Examples of ² include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group. When a plurality of R ² are present in the formula (1), they may be the same or different.

As a specific example of the hydrolyzable silane compound represented by the above formula (1),
Examples of the silane compound substituted with four hydrolyzable groups include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, etc. ;
As a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxy Silane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, n-butyl Trimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, n-decyltri Ethoxy Run, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloro Propyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxy Ethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethyl Xysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acrylic Oxypropyltrimethoxysilane, 3- (meth) atacryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, methyltriacetyloxysilane Trialkoxysilane, etc .;

As a silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane , Di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxy Silane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyl Dimethoxysilane, di-n-octyldiethoxysilane, di-n-decyldi Tokishishiran, di -n- decyl diethoxy silane, di -n- cyclohexyl dimethoxysilane, di -n- cyclohexyl diethoxysilane, diphenyl dimethoxysilane, di-alkoxysilanes such as diphenyl diethoxy silane, dimethyl acetyloxy silane;
As a silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group, tributylmethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, tributylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane Etc., respectively.

Among these, in formula (1), at least one of R ¹ contains a silane compound which is a phenyl group, and in formula (1), the phenyl group is 5 to 80 mol% with respect to all R ¹ . What is contained is preferable.
This organosilane having a phenyl group is a mole of the organosilane having a phenyl group in the formula (1) from the viewpoint of storage stability of the composition (I) according to the present invention and crack resistance of the layer (I) to be formed. The concentration is preferably 5 to 80% with respect to all R ¹ , more preferably 5 to 60%. When the content of the organosilane having a phenyl group is more than the above range, the composition (I) When the content of the organosilane having a phenyl group is too less than the above range, the storage stability of the composition (I) and the crack resistance of the layer (I) to be formed may be inferior. is there.

In the present invention, one type of organosilane (1) may be used alone as the silane compound (a1), but two or more types of organosilane (1) may be used in combination. When two or more organosilanes (1) used as the silane compound (a1) are averaged and expressed by the above formula (1), the averaged n (hereinafter also referred to as “average value of n”) is. Preferably it is 0.5-2.0, More preferably, it is 0.6-1.8, Most preferably, it is 0.7-1.6. When the average value of n is less than the lower limit, the storage stability of the composition (I) and the crack resistance of the layer (I) may be inferior, and when the upper limit is exceeded, the curability of the composition (I) is inferior. There is.
The average value of n can be adjusted to the above range by appropriately using a monofunctional to tetrafunctional organosilane (1) and appropriately adjusting the blending ratio.

The above situation is the same when the hydrolyzate or condensate of organosilane (1) is used as the silane compound (a1).
In the present invention, organosilane (1) may be used as it is as silane compound (a1), but hydrolyzate and / or condensate of organosilane (1) can be used. When the organosilane (1) is used as a hydrolyzate and / or a condensate, a product prepared by previously hydrolyzing and condensing the organosilane (1) may be used, but the composition (I) is prepared. In this case, the hydrolyzate and / or condensate of organosilane (1) can also be prepared by hydrolyzing and condensing organosilane (1).

(Method for producing silane compound (a1))
The conditions for hydrolyzing and condensing the silane compound (a1) represented by the above formula (1) are hydrolyzable by hydrolyzing at least a part of the organosilane (1) represented by the above formula (1). Although it does not specifically limit as long as it converts a group into a silanol group or causes a condensation reaction, it can be carried out as follows as an example.

(water)
The water used for hydrolysis of the organosilane (1) represented by the above formula (1) is preferably water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment or distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. The amount of water used is preferably 0.1 to 3 mol, more preferably 1 mol with respect to 1 mol of the total amount of hydrolyzable groups (—OR ² ) of the organosilane (1) represented by the above formula (1). Is an amount of 0.3-2 mol, more preferably 0.5-1.5 mol. By using such an amount of water, the reaction rate of hydrolysis can be optimized.

(Organic solvent)
Although it does not specifically limit as a solvent which can be used for hydrolysis and condensation of the organosilane (1) represented by the said Formula (1), Usually, for manufacture of the polymer (A1) mentioned later. The thing similar to the solvent used can be used. Preferable examples of such a solvent include propyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid esters. . Among these solvents, propyl alcohol, methyl isobutyl ketone, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate or methyl 3-methoxypropionate is preferable.

(catalyst)
Although it does not specifically limit as a catalyst which can be used for the hydrolysis and condensation reaction of organosilane (1) represented by the said Formula (1), Usually, manufacture of the polymer (A1) mentioned later The same catalyst as used in the above can be used. Preferred examples of such catalysts include acid catalysts (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resins, various Lewis acids), Basic catalysts (for example, ammonia, primary amines, secondary amines, tertiary amines, nitrogen-containing compounds such as pyridine; basic ion exchange resins; hydroxides such as sodium hydroxide; carbonates such as potassium carbonate Carboxylates such as sodium acetate; various Lewis bases] or alkoxides (for example, zirconium alkoxide, titanium alkoxide, aluminum alkoxide) and the like. For example, tetra-i-propoxyaluminum can be used as the aluminum alkoxide. The amount of the catalyst used is preferably 0.2 mol or less, more preferably 0.00001 to 0.1 mol with respect to 1 mol of the hydrolyzable silane compound monomer from the viewpoint of promoting the hydrolysis reaction. It is.

The reaction temperature and reaction time in hydrolysis / condensation of the organosilane (1) represented by the above formula (1) are appropriately set. For example, the following conditions can be adopted. The reaction temperature is preferably 40 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours. By setting such reaction temperature and reaction time, the hydrolysis reaction can be most efficiently performed. In this hydrolysis / condensation, the reaction may be carried out in one step by adding a hydrolyzable silane compound, water and a catalyst to the reaction system at one time. Alternatively, the hydrolyzable silane compound, water and the catalyst may be The hydrolysis and condensation reaction may be performed in multiple stages by adding them into the reaction system in several times. After the hydrolysis / condensation reaction, water and the produced alcohol can be removed from the reaction system by adding a dehydrating agent and then subjecting it to evaporation.
The condensate of the organosilane (1) preferably has a polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) measured by a gel permeation chromatography method (GPC method), preferably 300 to 100,000. More preferably, it is 500-50,000.

  When the condensate of organosilane (1) is used as the silane compound (a1) in the present invention, it may be prepared from the organosilane (1) or a commercially available condensate of organosilane. Commercially available organosilane condensates include MKC silicate manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, silicone resin and silicone oligomers manufactured by Toray Dow Corning Silicone Co., Momentive Performance Examples include silicone resins and silicone oligomers manufactured by Materials Co., Ltd., silicone resins and silicone oligomers manufactured by Shin-Etsu Chemical Co., Ltd., and hydroxyl group-containing polydimethylsiloxane manufactured by Dow Corning Asia Co., Ltd. These condensates of commercially available organosilanes may be used as they are or may be further condensed.

(Polymer A1)
In the present invention, as the composition (I), the above silane compound (a1) and the vinyl polymer (a2) containing a specific silyl group are hydrolyzed / condensed for the purpose of improving the adhesion to the substrate. You may use what contains the polymer (A1) and metal oxide particle (B) which were prepared by making it react. More specifically, the polymer (A1) comprises a catalyst containing water and a catalyst that promotes hydrolysis / condensation reaction to a mixture containing the silane compound (a1) and a vinyl polymer (a2) containing a silyl group. And added.

(Silyl group-containing vinyl polymer (a2))
The vinyl polymer (a2) containing a specific silyl group used in the present invention (hereinafter also referred to as “specific silyl group-containing vinyl polymer (a2)”) is composed of a hydrolyzable group and / or a hydroxyl group. It contains a silyl group having a bonded silicon atom (hereinafter referred to as “specific silyl group”).
The specific silyl group-containing vinyl polymer (a2) preferably has a specific silyl group at the terminal and / or side chain of the polymer molecular chain.
The hydrolyzable group and / or hydroxyl group in the specific silyl group co-condenses with the silane compound (a1) to form the polymer (A1). By coating the composition containing this polymer (A1) and metal oxide particles (B) on the surface of the substrate, it acts as a high refractive index layer, and further layer (II) described later is further coated. An antireflection layer can be formed.

(Specific silyl group)
The specific silyl group has the following formula (3):
(In the formula, X represents a hydrolyzable group such as a halogen atom, an alkoxyl group, an acetoxy group, a phenoxy group, a thioalkoxyl group, an amino group or a hydroxyl group, and R ⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or An aralkyl group having 1 to 10 carbon atoms; i is an integer of 1 to 3)
It is preferable that it is group represented by these.

(Method for producing specific silyl group-containing vinyl polymer (a2))
Such a specific silyl group-containing vinyl polymer (a2) can be produced, for example, by the following methods (I) and (II).

(I) A hydrosilane compound having a specific silyl group represented by the above formula (3) (hereinafter also simply referred to as “hydrosilane compound (I)”) is converted into a vinyl polymer having a carbon-carbon double bond (hereinafter referred to as “hydrosilane compound (I)”). , "Unsaturated vinyl polymer") in which the carbon-carbon double bond is subjected to an addition reaction.

(II) The following formula (4)
(In the formula, X, R ⁵ and i are respectively synonymous with X, R ⁵ and i in the above formula (3), and R ⁶ represents an organic group having a polymerizable double bond.)
A silane compound represented by the formula (hereinafter referred to as "unsaturated silane compound (II)") and a vinyl monomer.

Examples of the hydrosilane compound (I) used in the above method (I) include halogenated silanes such as methyldichlorosilane, trichlorosilane, and phenyldichlorosilane; methyldimethoxysilane, methyldiethoxysilane, and phenyldimethoxy. Alkoxysilanes such as silane, trimethoxysilane and triethoxysilane; Acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane and triacetoxysilane; Methyldiaminoxysilane, triaminoxysilane and dimethylaminoxysilane And aminoxysilanes. These hydrosilane compounds (I) can be used alone or in admixture of two or more.
The unsaturated vinyl polymer used in the method (I) is not particularly limited as long as it is not a polymer having a hydroxyl group. For example, the following methods (I-1) and (I-2) Or it can manufacture by these combinations.

(I-1) After (co) polymerizing a vinyl monomer having a functional group (hereinafter referred to as “functional group (α)”), the functional group (α) in the (co) polymer By reacting a functional group that can react with the functional group (α) (hereinafter referred to as “functional group (β)”) and an unsaturated compound having a carbon / carbon double bond, the side chain of the polymer molecular chain is reacted. Of producing an unsaturated vinyl polymer having a carbon-carbon double bond in (1-2) radical polymerization initiator having a functional group (α) (for example, 4,4′-azobis-4-cyanovaleric acid Or a compound having a functional group (α) in both radical polymerization initiator and chain transfer agent (for example, 4,4′-azobis-4-cyanovaleric acid and dithioglycolic acid). (Co) polymerization of the vinyl monomer, and one end of the polymer molecular chain or After synthesizing a (co) polymer having a functional group (α) derived from a radical polymerization initiator or a chain transfer agent at the terminal, a functional group (β) is added to the functional group (α) in the (co) polymer. For producing an unsaturated vinyl polymer having a carbon-carbon double bond at one or both ends of a polymer molecular chain by reacting the unsaturated compound having a carbon / carbon double bond

  Examples of the reaction between the functional group (α) and the functional group (β) in the methods (I-1) and (I-2) include an esterification reaction between a carboxyl group and a hydroxyl group, and a carboxylic anhydride group and a hydroxyl group. Ring-opening esterification reaction, carboxyl group and epoxy group ring-opening esterification reaction, carboxyl group and amino group amidation reaction, carboxylic acid anhydride group and amino group ring-opening amidation reaction, epoxy group Ring-opening addition reaction between a hydroxyl group and an amino group, urethanization reaction between a hydroxyl group and an isocyanate group, a combination of these reactions, and the like.

(Vinyl monomer)
(I) Vinyl monomer having a functional group (α) Examples of the vinyl monomer having a functional group (α) include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and the like. Of unsaturated carboxylic acids;
Unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride;
Hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, 2-hydroxyethyl vinyl ether;
Amino group-containing vinyl monomers such as 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-aminoethyl vinyl ether;
1,1,1-trimethylamine (meth) acrylimide, 1-methyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2-hydroxypropyl) amine (meth) acrylimide, 1,1 -Dimethyl-1- (2'-phenyl-2'-hydroxyethyl) amine (meth) acrylimide, 1,1-dimethyl-1- (2'-hydroxy-2'-phenoxypropyl) amine (meth) acrylimide Amine-imide group-containing vinyl monomers such as
Examples thereof include epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate and allyl glycidyl ether. These vinyl monomers having a functional group (α) can be used alone or in admixture of two or more.

(Ii) Other vinyl monomers Other vinyl monomers copolymerizable with the vinyl monomer having a functional group (α) include, for example, styrene, α-methylstyrene, 4-methylstyrene. 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 3,4-diethylstyrene, 2-chlorostyrene Aromatic vinyl monomers such as 3-chlorostyrene, 4-chloro-3-methylstyrene, 4-t-butylstyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, 1-vinylnaphthalene;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl Alkyl such as (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2.6 ] decan-8-yl methacrylate (Meth) acrylate compounds;
Divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) ) Acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra ( Polyfunctional monomers such as (meth) acrylates;

(Meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N′-methylenebisacrylamide, diacetone acrylamide, maleic acid amide, maleimide, Acid amide compounds such as phenylmaleimide and cyclohexylmaleimide;
Vinyl compounds such as vinyl chloride, vinylidene chloride and fatty acid vinyl esters;
1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2- Aliphatic conjugated dienes such as substituted linear conjugated pentadienes substituted with substituents such as cyano-1,3-butadiene, isoprene, alkyl groups, halogen atoms, cyano groups, linear and side chain conjugated hexadienes;
Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;
Fluorine atom-containing monomers such as trifluoroethyl (meth) acrylate and pentadecafluorooctyl (meth) acrylate;
4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1, Piperidine monomers such as 2,2,6,6-pentamethylpiperidine;

2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methacryloxyethylphenyl) -2H-benzotriazole UV-absorbing monomers such as 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone and 2-hydroxy-4- (acryloyloxyethoxy) benzophenone;
Examples include dicaprolactone and allyl (meth) acrylate. These can be used alone or in combination of two or more.
As an unsaturated compound having a functional group (β) and a carbon / carbon double bond, for example, a vinyl monomer similar to the vinyl monomer having a functional group (α), or the above hydroxyl group-containing vinyl type An isocyanate group-containing unsaturated compound obtained by reacting a monomer and a diisocyanate compound in an equimolar amount can be exemplified.

(Unsaturated silane compound)
Moreover, as unsaturated silane compound (II) used for the method of said (II),
_{CH 2 = CHSi (CH 3)} (OCH 3) 2,
CH ₂ = CHSi (OCH ₃ ) ₃ ,
CH ₂ = CHSi (CH ₃ ) Cl ₂ ,
CH ₂ = CHSiCl ₃ ,
_{CH 2 = CHCOO (CH 2)} 2 Si (CH 3) (OCH 3) 2,
_{CH 2 = CHCOO (CH 2)} 2 Si (OCH 3) 3,
_{CH 2 = CHCOO (CH 2)} 3 Si (CH 3) (OCH 3) 2,
CH ₂ = CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,
_{CH 2 = CHCOO (CH 2)} 2 Si (CH 3) Cl 2,
CH ₂ = CHCOO (CH ₂ ) ₂ SiCl ₃ ,
CH ₂ = CHCOO (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ ,
CH ₂ = CHCOO (CH ₂ ) ₃ SiCl ₃ ,
_{CH 2 = C (CH 3)} COO (CH 2) 2 Si (CH 3) (OCH 3) 2,
_{CH 2 = C (CH 3)} COO (CH 2) 2 Si (OCH 3) 3,
_{CH 2 = C (CH 3)} COO (CH 2) 3 Si (CH 3) (OCH 3) 2,
_{CH 2 = C (CH 3)} COO (CH 2) 3 Si (OCH 3) 3,
_{CH 2 = C (CH 3)} COO (CH 2) 2 Si (CH 3) Cl 2,
CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ SiCl ₃ ,
_{CH 2 = C (CH 3)} COO (CH 2) 3 Si (CH 3) Cl 2,
_{CH 2 = C (CH 3)} COO (CH 2) 3 SiCl 3,

Can be mentioned. These can be used alone or in combination of two or more.

  Examples of other vinyl monomers copolymerized with the unsaturated silane compound include, for example, vinyl monomers having the functional group (α) exemplified in the method (I-1) and other vinyl monomers. A monomer etc. can be mentioned.

Examples of the method for producing the specific silyl group-containing vinyl polymer (a2) include, for example, a method in which each monomer is added at once and polymerized, and a part of the monomer is polymerized and then the remainder is continuously formed. For example, a method in which polymerization is carried out by adding them intermittently or a method in which a monomer is continuously added from the start of polymerization. These polymerization methods may be combined.
A preferred polymerization method includes solution polymerization. The solvent used in the solution polymerization is not particularly limited as long as it can produce the specific silyl group-containing vinyl polymer (a2). For example, alcohols, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene Examples thereof include glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ethers, ketones and esters.

  Examples of the alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-octyl alcohol, and ethylene glycol. , Diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, diacetone alcohol, and the like. Examples of diethylene glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether. Ethylene glycol alkyl Examples of ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate. Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether and propylene glycol monoethyl ether. Propylene glycol monopropyl ether, propylene glycol monobutyl ether, and the like. As propylene glycol monoalkyl ether acetates, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol And propylene glycol monoalkyl ether propionates such as propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol mono Examples include butyl ether propionate.

Examples of aromatic hydrocarbons include benzene, toluene, xylene, etc., examples of ethers include tetrahydrofuran, dioxane and the like, and examples of ketones include acetone, cyclohexanone, 2-heptanone, 4-hydroxy- 4-methyl-2-pentanone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and the like. Examples of esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, Methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, normal propyl lactate, isopropyl lactate Butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, Propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butylpropoxyacetate, methylbutoxyacetate, ethylbutoxyacetate, butoxyacetic acid Propyl, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2- Methyl Tokishipuropion acid, 2-ethoxy ethyl propionate, propylene carbonate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate and the like. These organic solvents may be used individually by 1 type, or 2 or more types may be mixed and used for them.
Moreover, in the said superposition | polymerization, a well-known thing can be used for a polymerization initiator, a molecular weight modifier, a chelating agent, and an inorganic electrolyte.

In the present invention, as the specific silyl group-containing vinyl polymer (a2), in addition to the specific silyl group-containing vinyl polymer polymerized as described above, the specific silyl group-containing epoxy resin and the specific silyl group-containing polyester resin are used. Other specific silyl group-containing vinyl polymers can also be used. Examples of the specific silyl group-containing epoxy resin include epoxy groups in epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, aliphatic polyglycidyl ether, and aliphatic polyglycidyl ester. And aminosilanes having a specific silyl group, vinylsilanes, carboxysilanes, glycidylsilanes, and the like. The specific silyl group-containing polyester resin is produced, for example, by reacting a carboxyl group or a hydroxyl group contained in the polyester resin with aminosilanes, carboxysilanes, glycidylsilanes or the like having a specific silyl group. Can do.
The Mw in terms of polystyrene measured by the GPC method of the specific silyl group-containing vinyl polymer (a2) is preferably 2,000 to 100,000, more preferably 3,000 to 50,000. In the present invention, the specific silyl group-containing vinyl polymer (a2) can be used alone or in admixture of two or more.

  In the present invention, the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2) may be co-condensed. Preferably, it can be prepared by adding a hydrolysis / condensation reaction catalyst and water to a mixture of the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2) and co-condensing it.

In this reaction, the weight ratio (Wa1 / Wa2) between the content (Wa1) of the silane compound (a1) and the content (Wa2) of the specific silyl group-containing vinyl polymer (a2) is set to Wa1 + Wa2 = 100. / 95 to 95/5, preferably 15/85 to 85/15. In addition, Wa1 is a complete hydrolysis condensate conversion value of the silane compound (a1), and Wa2 is a solid content conversion value of the specific silyl group-containing vinyl polymer (a2). When the weight ratio (Wa1 / Wa2) is in the above range, the layer (I) excellent in transparency and weather resistance can be obtained.
In the present specification, the completely hydrolyzed condensate means a product in which the —OR group of the silane compound is hydrolyzed to 100% to form an Si—OH group, and further completely condensed to a siloxane structure.

Specifically, the polymer (A1) is preferably prepared by the following methods (1) to (2).
(1) Water is added to a mixed solution of the silane compound (a1), the specific silyl group-containing vinyl polymer (a2), and the hydrolysis / condensation reaction catalyst, and the temperature is 40 to 80 ° C., the reaction time is 0.5. The polymer (A1) is prepared by co-condensing the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2) in ˜12 hours. Thereafter, if necessary, other additives such as a stability improver may be added.

(2) Water is added to the silane compound (a1), and the hydrolysis / condensation reaction of the silane compound (a1) is performed at a temperature of 40 to 80 ° C. for 0.5 to 12 hours. Subsequently, the specific silyl group-containing vinyl polymer (a2) and the catalyst for hydrolysis / condensation reaction are added and mixed, and further subjected to a condensation reaction at a temperature of 40 to 80 ° C. and a reaction time of 0.5 to 12 hours to obtain a polymer. Prepare (A1). Thereafter, if necessary, other additives such as a stability improver may be added. When an organometallic compound is used as the hydrolysis condensation catalyst, it is preferable to add the stability improver after the reaction.
The weight average molecular weight of the polymer (A1) obtained by the above method is usually 2500 to 200,000, preferably 3,000 to 150,000, more preferably in terms of polystyrene measured by gel permeation chromatography. 3,500 to 100,000.

(catalyst)
In the present invention, when the polymer (A1) is prepared, the silane compound (a1) or the specific silyl group-containing vinyl polymer (a2) is promoted by hydrolysis / condensation reaction. And a specific silyl group-containing vinyl polymer (a2). By adding a catalyst, the degree of crosslinking of the resulting polymer (A1) can be increased, and the molecular weight of the polysiloxane produced by the polycondensation reaction of the organosilane (1) is increased, resulting in strength, long-term A layer (I) excellent in durability and the like can be obtained. Furthermore, the addition of the catalyst promotes the reaction between the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2), and sufficient reaction sites (alkoxy groups) are formed in the polymer (A1). . Examples of the catalyst used for promoting such hydrolysis / condensation reaction include basic compounds, acidic compounds, salt compounds, and organometallic compounds.

(Basic compound)
Examples of the basic compound include ammonia (including ammonia aqueous solution), organic amine compounds, alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals, alkalis such as sodium methoxide and sodium ethoxide. Examples thereof include metal alkoxides. Of these, ammonia and organic amine compounds are preferred.

Examples of the organic amine include alkylamine, alkoxyamine, alkanolamine, and arylamine.
Alkylamines include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine , Alkylamines having an alkyl group having 1 to 4 carbon atoms, such as triethylamine, tripropylamine, and tributylamine.

  Alkoxyamines include methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxybutylamine, butoxymethylamine , Alkoxyamines having 1 to 4 carbon atoms such as butoxyethylamine, butoxypropylamine, and butoxybutylamine.

Alkanolamines include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, min, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N -Methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N -Dimethylmethanolamine, N, N-diethylmethanolamine, N, N-dipropylmethanolamine, N, N-dibutylmethanolamine, N, N-dimethylethanolamine, N, N- Ethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanolamine, N, N-dimethylpropanolamine, N, N-diethylpropanolamine, N, N-dipropylpropanolamine, N, N- Dibutylpropanolamine, N, N-dimethylbutanolamine, N, N-diethylbutanolamine, N, N-dipropylbutanolamine, N, N-dibutylbutanolamine, N-methyldimethanolamine, N-ethyldimethanolamine N-propyldimethanolamine, N-butyldimethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-methyldipropanolamine, N-ethyl Propanolamine, N-propyldipropanolamine, N-butyldipropanolamine, N-methyldibutanolamine, N-ethyldibutanolamine, N-propyldibutanolamine, N-butyldibutanolamine, N- (aminomethyl) ) Methanolamine, N- (aminomethyl) ethanolamine, N- (aminomethyl) propanolamine, N- (aminomethyl) butanolamine, N- (aminoethyl) methanolamine, N- (aminoethyl) ethanolamine, N -(Aminoethyl) propanolamine, N- (aminoethyl) butanolamine, N- (aminopropyl) methanolamine, N- (aminopropyl) ethanolamine, N- (aminopropyl) propanolamine, N- (aminopropyl) Butano Alkanols having an alkyl group having 1 to 4 carbon atoms such as allamine, N- (aminobutyl) methanolamine, N- (aminobutyl) ethanolamine, N- (aminobutyl) propanolamine and N- (aminobutyl) butanolamine Examples include amines.
Examples of the arylamine include aniline and N-methylaniline.

  Further, as organic amines other than the above, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide; tetramethylethylenediamine, tetraethylethylenediamine Tetraalkylethylenediamine such as tetrapropylethylenediamine and tetrabutylethylenediamine; methylaminomethylamine, methylaminoethylamine, methylaminopropylamine, methylaminobutylamine, ethylaminomethylamine, ethylaminoethylamine, ethylaminopropylamine, ethylaminobutylamine, Propylaminomethylamine, propylamino Alkylaminoalkylamines such as tilamine, propylaminopropylamine, propylaminobutylamine, butylaminomethylamine, butylaminoethylamine, butylaminopropylamine, butylaminobutylamine; ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepenta Polyamines such as amine, m-phenylenediamine, and p-phenylenediamine; pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, morpholine, methylmorpholine, diazabicycloocrane, diazabicyclononane, diazabicycloundecene, etc. Can be mentioned.

  Such basic compounds may be used alone or in combination of two or more. Of these, triethylamine, tetramethylammonium hydroxide, and pyridine are preferable.

(Acidic compounds)
Examples of the acidic compound include organic acids and inorganic acids. Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, maleic anhydride, methylmalonic acid, adipic acid, Sebacic acid, gallic acid, butyric acid, meritic acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfone Examples include acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, methanesulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

  Such acidic compounds may be used alone or in combination of two or more. Of these, maleic acid, maleic anhydride, methanesulfonic acid, and acetic acid are particularly preferred.

(Salt compound)
Examples of the salt compound include naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and alkali metal salts such as carbonic acid.

(Organic metal compound)
Examples of the organometallic compound include organometallic compounds and / or partial hydrolysates thereof (hereinafter, organometallic compounds and / or partial hydrolysates thereof are collectively referred to as “organometallic compounds”).
Examples of the organometallic compounds include the following formula (b):
M (OR ⁷ ) _r (R ⁸ COCHCOR ⁹ ) _s (b)
(Wherein M represents at least one metal atom selected from the group consisting of zirconium, titanium and aluminum, and R ⁷ and ⁸ are each independently a methyl group, an ethyl group, an n-propyl group, C1-C6 monovalent hydrocarbon group such as i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group R ⁹ represents the monovalent hydrocarbon group having 1 to 6 carbon atoms, or a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a sec-butoxy group, represents an alkoxy group having 1 to 16 carbon atoms such as t-butoxy group, lauryloxy group, stearyloxy group, and r and s are each independently an integer of 0 to 4, and (r + s) = (M Valence) A compound satisfying the relationship (hereinafter referred to as “organometallic compound (b)”), an organic tetravalent tin in which one or two alkyl groups having 1 to 10 carbon atoms are bonded to one tin atom. Examples thereof include metal compounds (hereinafter referred to as “organotin compounds”) or partial hydrolysates thereof.

  In addition, as organometallic compounds, tetraalkoxy titanium such as tetramethoxy titanium, tetraethoxy titanium, tetra-i-propoxy titanium, tetra-n-butoxy titanium; methyl trimethoxy titanium, ethyl triethoxy titanium, n-propyl tri Methoxytitanium, i-propyltriethoxytitanium, n-hexyltrimethoxytitanium, cyclohexyltriethoxytitanium, phenyltrimethoxytitanium, 3-chloropropyltriethoxytitanium, 3-aminopropyltrimethoxytitanium, 3-aminopropyltriethoxytitanium 3- (2-aminoethyl) -aminopropyltrimethoxytitanium, 3- (2-aminoethyl) -aminopropyltriethoxytitanium, 3- (2-aminoethyl) -aminopropylmethyldimethoxytita Trialkoxytitanium such as 3-anilinopropyltrimethoxytitanium, 3-mercaptopropyltriethoxytitanium, 3-isocyanatopropyltrimethoxytitanium, 3-glycidoxypropyltriethoxytitanium, 3-ureidopropyltrimethoxytitanium; Dimethyldiethoxytitanium, diethyldiethoxytitanium, di-n-propyldimethoxytitanium, di-i-propyldiethoxytitanium, di-n-pentyldimethoxytitanium, di-n-octyldiethoxytitanium, di-n-cyclohexyldimethoxy Titanium alcoholates such as dialkoxytitanium such as titanium and diphenyldimethoxytitanium and condensates thereof can be used.

Examples of the organometallic compound (b) include tetra-n-butoxyzirconium, tri-n-butoxyethylacetoacetatezirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetate). Organic zirconium compounds such as acetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, di-n-butoxybis (acetylacetonato) zirconium;
Organic titanium compounds such as tetra-i-propoxy titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (acetylacetate) titanium, di-i-propoxy bis (acetylacetone) titanium ;
Tri-i-propoxyaluminum, di-i-propoxyethyl acetoacetate aluminum, di-i-propoxy acetylacetonate aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy bis (acetylacetonate) And organoaluminum compounds such as aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonatobis (ethylacetoacetate) aluminum.

As an organic tin compound, for example,
Carboxylic acid type organotin compounds such as;

Mercaptide-type organotin compounds such as

Sulfide-type organotin compounds such as;

Chloride-type organotin compounds such as;
Reaction of organotin oxides such as (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, and ester compounds such as silicates, dimethyl maleate, diethyl maleate and dioctyl phthalate Products; and the like.

Such organometallic compounds may be used singly or in combination of two or more. Among these, di-n-butoxy bis (acetylacetonato) zirconium, dioctyltin dioctyl maleate, di-i-propoxy bis (acetylacetonato) titanium, di-i-propoxyethylacetoacetate aluminum, Tris (ethyl acetoacetate) aluminum or a partial hydrolyzate thereof is preferred.
Moreover, the said catalyst can also be used in mixture with another reaction retarder.

  The amount of the catalyst used is usually 0.001 with respect to 100 parts by weight of the silane compound (a1) (in terms of a completely hydrolyzed condensate of organosilane (1)) when the catalyst is other than organometallic compounds. -100 parts by weight, preferably 0.01-80 parts by weight, more preferably 0.1-50 parts by weight. When the catalyst is an organometallic compound, it is usually 100 parts by weight or less, preferably 0.1 to 100 parts by weight (in terms of complete hydrolysis condensate of organosilane (1)) of silane compound (a1). 80 parts by weight, more preferably 0.5 to 50 parts by weight. When the usage-amount of the said catalyst exceeds the said upper limit, it gelatinizes by the fall of the storage stability of a polymer (A1), or the crosslinking degree of a layer (1) becomes high too much, and a crack may generate | occur | produce.

(Stability improver)
In the present invention, in order to improve the storage stability of the polymer (A1), it is preferable to add a stability improver as necessary after preparing the polymer (A1). The stability improver used in the present invention is represented by the following formula (5).
R ¹⁰ COCH ₂ COR ¹¹ (5)
(In the formula, R ¹⁰ represents methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group) R 1 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms such as a phenyl group, and R ¹¹ is a monovalent hydrocarbon group having 1 to 6 carbon atoms similar to R ¹⁰ , or a methoxy group, This represents an alkoxyl group having 1 to 16 carbon atoms such as ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, lauryloxy group and stearyloxy group. At least one compound selected from the group consisting of β-diketones, β-ketoesters, carboxylic acid compounds, dihydroxy compounds, amine compounds, and oxyaldehyde compounds.
When organometallic compounds are used as the catalyst, it is preferable to add a stability improver represented by the above formula (5). By using the stability improver, the stability improver is coordinated to the metal atom of the organometallic compound, and this coordination is obtained between the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2). It is considered that excessive cocondensation reaction can be suppressed and the storage stability of the resulting polymer (A1) can be further improved.

Examples of such stability improvers include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate-sec-butyl, Acetoacetate-t-butyl, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, nonane-2,4-dione, 5-methyl Hexane-2,4-dione, malonic acid, oxalic acid, phthalic acid, glycolic acid, salicylic acid, aminoacetic acid, iminoacetic acid, ethylenediaminetetraacetic acid, glycol, catechol, ethylenediamine, 2,2-bipyridine, 1,10-phenanthroline, Diethylenetriamine, 2-ethanolamine, dimethylglyoxime, dithizone, methioni , Such as salicylic aldehyde, and the like. Of these, acetylacetone and ethyl acetoacetate are preferred.
Moreover, a stability improver may be used individually by 1 type, or 2 or more types may be mixed and used for it.

  The amount of the stability improver used in the present invention is usually 2 moles or more, preferably 3 to 20 moles per mole of the organometallic compound of the organometallic compounds. If the amount of the stability improver is less than the above lower limit, the effect of improving the storage stability of the resulting composition may be insufficient.

(water)
In the present invention, water is added to a mixture of the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2), and the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2) Can be co-condensed to prepare the polymer (A1).
The amount of water added at this time is usually 0.1 to 1.0 mol, preferably 0.2 to 0.8 mol, based on 1 mol of all OR ² groups in the silane compound (a1). More preferably, it is 0.25-0.6 mol. When the amount of water added is in the above range, gelation hardly occurs, and the composition exhibits good storage stability. Further, when the amount of water added is in the above range, a sufficiently crosslinked polymer (A1) is obtained, and by using such a composition containing the polymer (A1) and metal oxide particles (B), Layer (I) can be obtained.

(Organic solvent)
In the present invention, the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2) may be hydrolyzed and condensed in an organic solvent. At this time, the organic solvent used at the time of preparation of the silyl group-containing vinyl polymer (a2) can be used as it is. Moreover, in order to adjust the solid content density | concentration at the time of polymer (A1) preparation, an organic solvent can also be added as needed. Further, the organic solvent used in the preparation of the silyl group-containing vinyl polymer (a2) may be removed and a new organic solvent may be added.

The organic solvent is added in such an amount that the solid content concentration at the time of preparing the polymer (A1) is preferably in the range of 10 to 80% by weight, more preferably 15 to 60% by weight, and particularly preferably 20 to 50% by weight. can do. In addition, when the organic solvent used at the time of preparation of the silyl group-containing vinyl polymer (a2) is used as it is and the solid content concentration at the time of preparation of the polymer (A1) is in the above range, an organic solvent is added. However, it may not be added.
The reactivity of the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2) can be controlled by adjusting the solid content concentration during the preparation of the polymer (A1).
When the solid content concentration at the time of preparing the polymer (A1) is less than the above lower limit, the reactivity between the silane compound (a1) and the specific silyl group-containing vinyl polymer (a2) may be lowered. If the solid content concentration during the preparation of the polymer (A1) exceeds the upper limit, gelation may occur. In addition, the amount of solid content in solid content concentration said here is the usage-amount (Wa1) of the complete hydrolysis-condensation product conversion of a silane compound (a1), and the usage-amount of solid content conversion of a specific silyl group containing vinyl polymer (a2). This is the total amount of (Wa2).

  The organic solvent is not particularly limited as long as the above components can be mixed uniformly. Alcohols and diethylene glycol alkyl exemplified as the organic solvent used in the production of the specific silyl group-containing vinyl polymer (a2). Ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ethers, ketones, esters, etc. Can be mentioned. Moreover, these organic solvents may be used individually by 1 type, or may mix and use 2 or more types.

(Metal oxide particles (B))
The composition (I) of the present invention further contains metal oxide particles (B).
The metal oxide particles are not particularly limited as long as they are metal element oxide particles. For example, antimony oxide, zirconium oxide, anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, zinc oxide. , Tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, aluminum oxide, cerium oxide, scandium oxide, yttrium oxide, lanthanum oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, oxide Dysprosium, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, calcium oxide, gallium oxide, lithium oxide, strontium oxide, tungsten oxide, barium oxide, magnesium oxide Neshiumu, and these complexes, as well as indium - metal oxides such as oxides of the metal 2 or more complex such as tin composite oxides. As the metal oxide particles (B), composite oxide particles of silicon oxide and metal oxide or oxide particles obtained by coating the surface of the metal oxide with silicon oxide can also be used.

In this invention, you may use a metal oxide particle (B) individually by 1 type or in mixture of 2 or more types. The metal oxide particles (B) can be appropriately selected according to the function to be imparted. In the present invention, anatase type titanium oxide, rutile type titanium oxide, zirconium oxide, aluminum oxide, and zinc oxide can be preferably used. .
When the metal oxide particles (B) are blended, a powder or a solvent-based sol or colloid dispersed in a polar solvent such as isopropyl alcohol, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, or a nonpolar solvent such as toluene. It can also be used in the form. The metal oxide particles (B) before addition may be aggregated to form secondary particles. Moreover, in order to improve the dispersibility of a metal oxide particle (B), you may surface-treat and use.

  The primary particle diameter of these metal oxide particles (B) is usually 0.0001 to 1 μm, more preferably 0.001 to 0.5 μm, and particularly preferably 0.002 to 0.2 μm. When the metal oxide is in the form of a solvent-based sol or colloid, its solid content concentration is usually more than 0% by weight and 50% by weight or less, preferably 0.01% by weight or more and 40% by weight or less. When the metal oxide particles (B) are used in the form of sol or colloid, they can be dispersed in the solution by a stirring blade or the like. On the other hand, dispersion in the case of using powder in the metal oxide particles (B) is ball mill, sand mill (bead mill, high shear bead mill), homogenizer, ultrasonic homogenizer, nanomizer, propeller mixer, high shear mixer, paint shaker, planetary Known dispersing machines such as a mixer, a two-roll, a three-roll, a kneader roll and the like can be used. Particularly, a highly dispersed fine particle dispersion ball mill, a sand mill (bead mill, a high shear bead mill), and a paint shaker are preferably used. .

  The amount of the metal oxide particles (B) used is generally more than 10% by weight and 90% by weight or less, preferably 20% by weight or more and 80% by weight based on the total solid weight in the composition (I). % Or less. When the amount of the metal oxide particles (B) used is larger than the above weight, the storage stability of the composition (I) may be inferior. When the amount used is smaller than the above weight, the layer (II) is formed on the layer (I). ) May not be sufficiently reduced, and the crack resistance of the layer (I) may be inferior.

(Curing catalyst)
A curing catalyst can also be added to the composition (I) used in the present invention. Examples of such a curing catalyst include the basic compound, acidic compound, salt compound, and organometallic compound used in preparing the polymer (A1). A basic compound may be used individually by 1 type, or may be used in mixture of 2 or more types, and triethylamine, tetramethylammonium hydroxide, and pyridine are particularly preferable. An acidic compound may be used individually by 1 type, or may be used in mixture of 2 or more types, Maleic acid, maleic anhydride, methanesulfonic acid, and acetic acid are especially preferable. The organometallic compound may be used singly or as a mixture of two or more thereof. Di-n-butoxy bis (acetylacetonato) zirconium, dioctyltin dioctyl maleate, di-i- Propoxy bis (acetylacetonate) titanium, di-i-propoxy ethyl acetoacetate aluminum, tris (ethyl acetoacetate) aluminum, or partial hydrolysates thereof are preferred.

(Organic solvent, water)
An organic solvent or water may be further added to the composition (I) used in the present invention to adjust the solid content concentration. As an organic solvent, what was illustrated by the term of the said polymer (A1) preparation can be used.

(Optional additive)
In the composition (I) used in the present invention, a leveling agent, a wettability improver, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, ( Inorganic fillers other than the component B) can be added.

(2-2) Preparation Method of Composition (I) The composition (I) used in the present invention is a powder of metal oxide particles (B) on the silane compound (a1) and / or the polymer (A1). It is obtained by adding a body and performing a dispersion | distribution process or mixing the dispersion | distribution sol of the metal oxide particle (B) produced previously.
In the dispersion step, (i) a solvent-based sol or colloid is used as the metal oxide particles (B), and a stirring blade or the like is used. (Ii) a ball mill, a bead mill, or a paint shaker is used when powder particles are used. Etc. can be used. The composition (I) may contain the above-mentioned organic solvent, water, stability improver, curing catalyst, and optional additive components as necessary, and these may be added before the dispersion step. It may be added after the dispersion step.
In addition, about the said curing catalyst, since the metal oxide particle (B) works also as a curing catalyst of composition (I), you may reduce the addition amount of the said curing catalyst as needed.

(2-3) Film-forming method of composition (I) The composition (I) used in the present invention is applied to a base material that is a surface member of a device for outdoor installation, and is heated and dried.
The application method is not particularly limited, but brush coating, brush coating, bar coater, knife coater, doctor blade, screen printing, spray coating, spin coater, applicator, roll coater, flow coater, centrifugal coater, ultrasonic coater , (Micro) gravure coater, dip coating, flexographic printing, potting, and the like can be used, and they may be transferred onto another substrate (transfer substrate) and transferred.

The heat drying is preferably performed at a temperature in the range of 50 to 250 ° C. for 0.5 to 180 minutes. A normal oven is used for heat drying, but a hot air type, a convection type, an infrared type, or the like can be used. While removing the solvent by heating, the condensation reaction proceeds in the layer, and a stronger layer can be obtained.
It is desirable that the heating temperature is high, the heating time is long, the residual solvent is small, and the condensation reaction further proceeds. The heating process may be performed through a plurality of stages, or may be performed in one stage. Depending on the content and boiling point of the solvent to be used and the heating conditions, the surface of the obtained layer may be rough. Therefore, it is desirable to examine an appropriate heating step in advance.

(3) Layer (II)
The layer (II) contains hollow or porous particles (D) mainly composed of polyorganosiloxane (C) and silica having a number average particle diameter of 1 to 100 nm.
The layer (II) has a refractive index of 1.25 or more and less than 1.50, and a film thickness of 0.01 μm to 10 μm, depending on the type of outdoor installation device.

(3-1) Composition (II)
Such a layer (II) has, for example, the following formula (2):
R ³ _m Si (OR ⁴ ) _4-m (2)
(Wherein, R ³ represents a monovalent organic group having 1 to 12 carbon atoms, optionally .R ⁴ be different be the same as each other if there are two or more are each independently, A C1-C5 alkyl group or a C1-C6 acyl group is shown, m is an integer of 0-3.)
At least one organosilane (hereinafter also referred to as “organosilane (2)”), a hydrolyzate of organosilane (2), and a condensate of organosilane (2). It can be obtained from a cured product of a composition containing at least one silane compound (c1) (hereinafter referred to as “composition (II)”).

(Silane compound (c1))
The silane compound (c1) used in the present invention is at least one silane compound selected from the group consisting of the organosilane (2), the hydrolyzate of organosilane (2), and the condensate of organosilane (2). Of these three silane compounds, only one silane compound may be used, any two silane compounds may be mixed, or all three silane compounds may be mixed. May be used. Moreover, when using organosilane (2) as a silane compound (c1), organosilane (2) may be used individually by 1 type, or may use 2 or more types together. Further, the hydrolyzate and condensate of the organosilane (2) may be formed from one kind of organosilane (2) or may be formed by using two or more kinds of organosilane (2) in combination. Good.

The hydrolyzate of the organosilane (2) is sufficient if at least one of the OR ² groups contained in 1 to 4 of the organosilane (2) is hydrolyzed, for example, one OR ² group. In which two or more OR ² groups are hydrolyzed, or a mixture thereof.

  The condensate of the organosilane (2) is a product in which a silanol group in a hydrolyzate generated by hydrolysis of the organosilane (2) is condensed to form a Si—O—Si bond. In the present invention, it is not necessary that all of the silanol groups are condensed, and the condensate may be one obtained by condensing a small part of silanol groups, one containing most (including all) silanol groups, These mixtures are also included.

In the above formula (2), R ³ is a non-hydrolyzable organic group having 1 to 12 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group. Alkyl groups such as heptyl group, octyl group, decyl group, 2-ethylhexyl group;
Acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, caproyl group;
Examples thereof include a vinyl group, an allyl group, a cyclohexyl group, a phenyl group, an epoxycycloalkyl group, a glycidyl group, a (meth) acryloxy group, a ureido group, an amide group, a fluoroacetamide group, and an isocyanate group.

Furthermore, examples of R ³ include substituted derivatives of the above organic groups. Examples of the substituent of the substituted derivative of R ³ include a substituted or unsubstituted amino group, hydroxyl group, mercapto group, isocyanate group, glycidoxy group, 3-glycidyloxypropyl group, 3,4-epoxycyclohexyl group, 3,4 -Epoxy cyclohexyl ethyl group, (meth) acryloxy group, 3- (meth) acryloyloxypropyl group, ureido group, ammonium base, etc. are mentioned. When a plurality of R ³ are present in the formula (2), they may be the same or different.

Examples of R ⁴ which is an alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and R is an acyl group having 1 to 6 carbon atoms. Examples of ² include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group. When a plurality of R ⁴ are present in the formula (2), they may be the same or different.

As a specific example of the hydrolyzable silane compound represented by the above formula (2),
Examples of the silane compound substituted with four hydrolyzable groups include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, etc. ;

  As a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxy Silane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, n-butyl Trimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, n-decyltri Ethoxy Run, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltri Ethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 , 4-Epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Trialkoxysilanes such as silane and methyltriacetyloxysilane;

  As a silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane , Di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxy Silane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyl Dimethoxysilane, di-n-octyldiethoxysilane, di-n-decyldi Tokishishiran, di -n- decyl diethoxy silane, di -n- cyclohexyl dimethoxysilane, di -n- cyclohexyl diethoxysilane, diphenyl dimethoxysilane, di-alkoxysilanes such as diphenyl diethoxy silane, dimethyl acetyloxy silane;

  As a silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group, tributylmethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, tributylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane Etc., respectively.

Among these, in formula (2), R ³ is preferably an organic group that does not contain fluorine. For the purpose of the present invention for reducing the reflectance as a laminate, it is advantageous to introduce fluorine into the layer (II) to lower the refractive index and increase the refractive index difference from the layer (I). However, in general, a functional group containing fluorine acts in the direction of reducing the interaction between molecules. Accordingly, when fluorine is introduced into the polymer, there is a problem that the coating film becomes soft and the hardness decreases.

In the present invention, one type of organosilane (2) may be used alone as the silane compound (c1), but two or more types of organosilane (2) may be used in combination. When two or more kinds of organosilanes (2) used as the silane compound (c1) are averaged and expressed by the above formula (2), the averaged n (hereinafter also referred to as “average value of n”) is. Preferably it is 0.5-2.0, More preferably, it is 0.6-1.8, Most preferably, it is 0.7-1.6. When the average value of n is less than the above lower limit, the storage stability of the composition (II) may be inferior, and when it exceeds the above upper limit, the curability of the layer (II) may be inferior.
The average value of n can be adjusted to the above range by appropriately using a monofunctional to tetrafunctional organosilane (2) and appropriately adjusting the blending ratio.

The above situation is the same when the hydrolyzate or condensate of organosilane (2) is used as the silane compound (c1).
In the present invention, organosilane (2) may be used as it is as silane compound (c1), but hydrolyzate and / or condensate of organosilane (2) can be used. When the organosilane (2) is used as a hydrolyzate and / or condensate, a product prepared by previously hydrolyzing and condensing the organosilane (2) may be used, but the composition (II) is prepared. In this case, the hydrolyzate and / or condensate of organosilane (2) can also be prepared by hydrolyzing and condensing organosilane (2).

(Method for producing silane compound (c1))
The conditions for hydrolyzing and condensing the silane compound (c1) represented by the above formula (2) are hydrolyzable by hydrolyzing at least a part of the organosilane (2) represented by the above formula (2). Although it does not specifically limit as long as it converts a group into a silanol group or causes a condensation reaction, it can be carried out as follows as an example.

(water)
The water used for hydrolysis of the organosilane (2) represented by the above formula (2) is preferably water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment or distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. The amount of water used is preferably from 0.1 to 3 mol, more preferably from 1 mol of the total amount of hydrolyzable groups (—OR ² ) of the organosilane (2) represented by the above formula (2). Is an amount of 0.3-2 mol, more preferably 0.5-1.5 mol. By using such an amount of water, the reaction rate of hydrolysis can be optimized.

(Organic solvent)
Although it does not specifically limit as a solvent which can be used for hydrolysis and condensation of the organosilane (2) represented by the said Formula (2), Usually, in manufacture of the polymer (A1) mentioned above. The thing similar to the solvent used can be used. Preferable examples of such a solvent include propyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid esters. . Among these solvents, propyl alcohol, methyl isobutyl ketone, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate or methyl 3-methoxypropionate is preferable.

(catalyst)
Although it does not specifically limit as a catalyst which can be used for the hydrolysis and condensation reaction of organosilane (2) represented by the said Formula (2), Usually, manufacture of the polymer (A1) mentioned above The same catalyst as used in the above can be used. Preferred examples of such catalysts include acid catalysts (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resins, various Lewis acids), Basic catalysts (for example, ammonia, primary amines, secondary amines, tertiary amines, nitrogen-containing compounds such as pyridine; basic ion exchange resins; hydroxides such as sodium hydroxide; carbonates such as potassium carbonate Carboxylates such as sodium acetate; various Lewis bases] or alkoxides (for example, zirconium alkoxide, titanium alkoxide, aluminum alkoxide) and the like. For example, tetra-i-propoxyaluminum can be used as the aluminum alkoxide. The amount of the catalyst used is preferably 0.2 mol or less, more preferably 0.00001 to 0.1 mol with respect to 1 mol of the hydrolyzable silane compound monomer from the viewpoint of promoting the hydrolysis reaction. It is.

The reaction temperature and reaction time in the hydrolysis / condensation of the organosilane (2) represented by the above formula (2) are appropriately set. For example, the following conditions can be adopted. The reaction temperature is preferably 40 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours. By setting such reaction temperature and reaction time, the hydrolysis reaction can be most efficiently performed. In this hydrolysis / condensation, the reaction may be carried out in one step by adding a hydrolyzable silane compound, water and a catalyst to the reaction system at one time. Alternatively, the hydrolyzable silane compound, water and the catalyst may be The hydrolysis and condensation reaction may be performed in multiple stages by adding them into the reaction system in several times. After the hydrolysis / condensation reaction, water and the produced alcohol can be removed from the reaction system by adding a dehydrating agent and then subjecting it to evaporation.
The condensate of the organosilane (2) has a polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) measured by a gel permeation chromatography method (GPC method), preferably 300 to 100,000. More preferably, it is 500-50,000.

  When using the condensate of organosilane (2) as a silane compound (c1) in this invention, you may prepare from the said organosilane (2) and may use the condensate of the organosilane marketed. Commercially available organosilane condensates include MKC silicate manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, silicone resin and silicone oligomers manufactured by Toray Dow Corning Silicone Co., Momentive Performance Examples include silicone resins and silicone oligomers manufactured by Materials Co., Ltd., silicone resins and silicone oligomers manufactured by Shin-Etsu Chemical Co., Ltd., and hydroxyl group-containing polydimethylsiloxane manufactured by Dow Corning Asia Co., Ltd. These condensates of commercially available organosilanes may be used as they are or may be further condensed.

(Hollow or porous particles (D) mainly composed of silica having a number average particle diameter of 1 to 100 nm)

The composition (II) of the present invention contains hollow or porous particles (D) mainly composed of silica having a number average particle diameter of 1 to 100 nm. The particle size is measured with a transmission electron microscope. By blending the particles (D), a cured product obtained by curing the composition of the present invention can exhibit a low refractive index and scratch resistance. (D) As a particle, a well-known thing can be used, Moreover, the shape is not restricted spherical and may be indefinite. Colloidal silica having a solid content of 5 to 40% by weight is preferred.

  The dispersion medium is preferably water or an organic solvent. Examples of organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethyl Examples include amides such as acetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; and organic solvents such as ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in combination of two or more as a dispersion medium. (D) As a commercial item of particle | grains, the product name: JX1008SIV, JX1009SIV, JX1010SIV, JX1012SIV etc. made from a catalyst chemical industry Co., Ltd. can be mentioned, for example.

  (D) The compounding quantity of component is normally 10-80 weight% with respect to composition whole quantity except an organic solvent, 20-80 weight% is preferable and 30-80 weight% is further more preferable. The amount of particles means solid content, and when the particles are used in the form of a solvent-dispersed sol, the amount of the solvent does not include the amount of solvent. When the amount of the metal oxide particles (D) used is less than the above weight, the reflectance, luminous reflectance, and scratch resistance of the resulting antireflection layer may be inferior.

Further, the particles (D) containing silica as a main component can be obtained by subjecting the particle surface to a surface treatment such as chemical modification. For example, a hydrolyzable silicon compound having one or more alkyl groups in the molecule. Or what contains the hydrolyzate etc. can be made to react. Such hydrolyzable silicon compounds include trimethylmethoxysilane, tributylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, 1,1. , 1-trimethoxy-2,2,2-trimethyl-disilane, hexamethyl-1,3-disiloxane, 1,1,1-trimethoxy-3,3,3-trimethyl-1,3-disiloxane, α-trimethylsilyl -Ω-dimethylmethoxysilyl-polydimethylsiloxane, α-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxane, hexamethyl-1,3-disilazane, and the like. A hydrolyzable silicon compound having one or more reactive groups in the molecule can also be used. Hydrolyzable silicon compounds having one or more reactive groups in the molecule include, for example, urea propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethylsilane having NH ₂ groups as reactive groups. Methoxysilane, etc., having OH group, bis (2-hydroxyethyl) -3-aminotripropylmethoxysilane, etc., having isocyanate group, 3-isocyanatopropyltrimethoxysilane, etc., having thiocyanate group, 3- 3-mercapto as a compound having a thiol group such as (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as a compound having an epoxy group such as thiocyanate propyltrimethoxysilane Propyltrimethoxy Mention may be made of the emissions and the like. A preferred compound is 3-mercaptopropyltrimethoxysilane.
The surface treatment of the particles (D) containing silica as a main component can be performed with an organic compound containing a polymerizable unsaturated group such as an acryloyl group.

  The composition (II) is laminated on the previously formed layer (I) and cured to form a layer (II), whereby a low refractive index layer is formed, and this laminate forms an antireflection layer. The

(Compound (E) having a polydimethylsiloxane skeleton)
In the composition (II) of the present invention, a compound (E) having a polydimethylsiloxane skeleton can be blended as necessary. The compound (E) having a polydimethylsiloxane skeleton can improve surface slipperiness, improve the scratch resistance of the cured coating film, and can impart antifouling properties. The compound (E) having these polydimethylsiloxanes preferably has a high molecular weight, and further preferably has a reactive group such as a (meth) acryloyl group, a hydroxyl group, an epoxy group, a carboxyl group, or an amino group. Specific examples of these include Silaplane FM-4411, FM-4421, FM-4425, FM-7711, FM-7721, FM-7725, FM-0411, FM-0421, FM-0425, FM-DA11, FM -DA21, FM-DA26, FM0711, FM0721, FM-0725, TM-0701, TM-0701T (manufactured by Chisso Corporation), UV3500, UV3510, UV3530 (manufactured by Big Chemie Japan Corporation), YF3800, XF3905, YF3057 YF3807, YF3802, YF3897, XC96-723 (made by Momentive Performance Materials Japan), BY16-004, SF8428 (made by Toray Dow Corning Silicone Co., Ltd.), VPS-1001 (made by Wako Pure Chemical Industries, Ltd.) Rad 2500, 2600 (manufactured by TEGO), KF-101, X-22-2046, X-22-163C, X-22-164B, X-22-162C, X-22-9002 (manufactured by Shin-Etsu Silicone), etc. It is done. Silaplane FM-7711, FM-7721, FM-7725, FM-0411, FM-0421, FM-0425, FM0711, FM0721, FM-0725, XF3905, YF3807, VPS-1001, and Rad2600 are particularly preferable.

  (E) The addition amount of a component is 0.01 to 20 weight% normally with respect to the composition whole quantity except an organic solvent. The reason for this is that when the addition amount is less than 0.01% by weight, the effect of improving the slipperiness cannot be sufficiently obtained. On the other hand, when the addition amount exceeds 20% by weight, the coating strength decreases due to an excessive amount of components. This is because the coatability deteriorates. For this reason, the amount of component (E) added is more preferably 0.1 to 15% by weight, and even more preferably 0.5 to 10% by weight.

(Curing catalyst)
A curing catalyst can be further added to the composition (II) used in the present invention. Examples of such a curing catalyst include the basic compound, acidic compound, salt compound, and organometallic compound used in preparing the polymer (A1). A basic compound may be used individually by 1 type, or may be used in mixture of 2 or more types, and triethylamine, tetramethylammonium hydroxide, and pyridine are particularly preferable. An acidic compound may be used individually by 1 type, or may be used in mixture of 2 or more types, Maleic acid, maleic anhydride, methanesulfonic acid, and acetic acid are especially preferable. The organometallic compound may be used singly or as a mixture of two or more thereof. Di-n-butoxy bis (acetylacetonato) zirconium, dioctyltin dioctyl maleate, di-i- Propoxy bis (acetylacetonate) titanium, di-i-propoxy ethyl acetoacetate aluminum, tris (ethyl acetoacetate) aluminum, or partial hydrolysates thereof are preferred.

(Organic solvent, water)
An organic solvent or water may be further added to the composition (II) used in the present invention to adjust the solid content concentration. The organic solvent is not particularly limited. For example, alcohols, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionate. , Aromatic hydrocarbons, ethers, ketones, esters and the like.

  Examples of the alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-octyl alcohol, and ethylene glycol. , Diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, diacetone alcohol, and the like. Examples of diethylene glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether. Ethylene glycol alkyl Examples of ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate. Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether and propylene glycol monoethyl ether. Propylene glycol monopropyl ether, propylene glycol monobutyl ether, and the like. As propylene glycol monoalkyl ether acetates, for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol And propylene glycol monoalkyl ether propionates such as propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol mono Examples include butyl ether propionate.

  Examples of aromatic hydrocarbons include benzene, toluene, xylene, etc., examples of ethers include tetrahydrofuran, dioxane and the like, and examples of ketones include acetone, cyclohexanone, 2-heptanone, 4-hydroxy- 4-methyl-2-pentanone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and the like. Examples of esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, Methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, normal propyl lactate, isopropyl lactate Butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, Propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butylpropoxyacetate, methylbutoxyacetate, ethylbutoxyacetate, butoxyacetic acid Propyl, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2- Methyl Tokishipuropion acid, 2-ethoxy ethyl propionate, propylene carbonate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate and the like. These organic solvents may be used individually by 1 type, or 2 or more types may be mixed and used for them.

(Optional additive)
In the composition (II) used in the present invention, a leveling agent, a wettability improver, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, an inorganic, if necessary Fillers can be added.

(3-2) Preparation Method of Composition (II) The composition (II) used in the present invention is a silane compound (c1) that is hollow or mainly composed of silica having a silica number average particle diameter of 1 to 100 nm. It is obtained by adding porous particles (D) and performing a mixing and / or dispersion step.
When the dispersion step is performed, a method such as a stirring blade is used when (i) a solvent-based sol or colloid is used as the hollow or porous particle (D) mainly composed of silica having a number average particle diameter of 1 to 100 nm. (Ii) When powder particles are used, a technique such as a ball mill, a bead mill, or a paint shaker can be used. If necessary, the composition (II) may contain the organic solvent, water, stability improver, curing catalyst, and optional additive components, which are added before the dispersion step. It may be added after the dispersion step.

(3-3) Method for Forming Composition (II) The composition (II) used in the present invention is applied onto the layer (I) formed on the substrate, and is heated and dried. The layer (II) has a lower refractive index than the layer (I), and antireflection ability can be imparted by forming such a laminate. The coating method of the composition (II) is not particularly limited, but brush coating, brush coating, bar coater, knife coater, doctor blade, screen printing, spray coating, spin coater, applicator, roll coater, flow coater, Methods such as a centrifugal coater, ultrasonic coater, (micro) gravure coater, dip coating, flexographic printing, and potting can be used, and they may be used after being applied on another substrate (transfer substrate). .
The heat drying is preferably performed at a temperature in the range of 50 to 250 ° C. for 0.5 to 180 minutes.

  A normal oven is used for heat drying, but a hot air type, a convection type, an infrared type, or the like can be used. While removing the solvent by heating, the condensation reaction proceeds in the layer, and a stronger layer can be obtained. It is desirable that the heating temperature is high, the heating time is long, the residual solvent is small, and the condensation reaction further proceeds. The heating process may be performed through a plurality of stages, or may be performed in one stage. Depending on the content and boiling point of the solvent to be used and the heating conditions, the surface of the obtained layer may be rough. Therefore, it is desirable to examine an appropriate heating step in advance.

(4) Use of antireflection layer The antireflection layer formed by the present invention has a siloxane structure as a main skeleton, and is excellent in heat resistance, light resistance, and weather resistance as compared with a normal organic polymer. Moreover, since it can manufacture by application | coating, it is excellent in the cost side and the process side compared with methods, such as a vacuum evaporation.

The antireflection layer obtained in the present invention is useful as an antireflection film, and can be used indoors, but is used particularly for large screen display devices used outdoors, car navigation systems, mobile phones, video monitors, Various displays such as cathode ray tube display, liquid crystal display, plasma display, organic EL display, rear projection display, crystalline silicon type, amorphous silicon type, organic thin film type, dye sensitized type, compound semiconductor type, polymer type, quantum dot type It can be suitably used as an antireflection film for the glue of various solar cells.
In particular, it is useful for devices for outdoor installation, especially for devices for outdoor installation such as digital signage.

(5) Anti-reflective layer forming composition kit A kit comprising the above composition (I) and composition (II) is constructed, and the kit is made anti-reflective on the surface using the surface member of the device for outdoor installation as a base material. Can be used to form a layer.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In the examples and comparative examples, “parts” and “%” indicate “parts by weight” and “% by weight” unless otherwise specified. In addition, various measurements in Examples and Comparative Examples were performed by the following methods.

(1) GPC measurement The weight average molecular weight Mw of the polyorganosiloxane was measured by gel permeation chromatography under the following conditions and indicated as a polystyrene equivalent value. Apparatus: HLC-8120C (manufactured by Tosoh Corp.) Column: TSK-gel Multipore H _XL- M (manufactured by Tosoh Corp.) Eluent: THF, flow rate 0.5 mL / min, load 5.0%, 100 μL, measurement temperature: 40 ° C.

(2) Storage stability of the composition The composition to be measured was put in a polyethylene container, sealed, and stored at room temperature for 1 month, and the presence or absence of gelation and particle sedimentation was visually determined. About the thing which is not gelatinized, the viscosity was measured at 25 degreeC with the BM type | mold viscosity meter by Tokyo Keiki Co., Ltd., and the following reference | standard evaluated.
A: Viscosity change rate before and after storage is 20% or less B: Viscosity change rate before and after storage exceeds 20%

(3) Refractive Index Measurement The composition to be measured was applied on a silicon wafer by spin coating so that the coating film thickness was 1 μm, and baked and dried in an oven as a sample. A prism coupler apparatus (Metricon) The refractive index at 633 nm was measured by a company manufactured 2010).

(4) Concentration of solid content About 2 g of the composition solution to be measured was measured on an aluminum dish and obtained from a change in weight after heating at 200 ° C. for 30 minutes on a hot plate.

(5) Initial luminous reflectance (Y value) measurement Assuming the use of an outdoor display, the initial luminous reflectance (Y value) is measured using a spectrophotometer (manufactured by JASCO Corporation, V-670), and 380 Analysis was performed in the wavelength range of −780 nm.
○: Y value is less than 1% Δ: Y value is 1% or more and less than 1.5% ×: Y value is 1.5% or more

(6) Initial reflectance measurement Assuming a crystalline silicon solar cell application, the initial reflectance was measured using a spectrophotometer (manufactured by JASCO Corporation, V-670) and analyzed in the wavelength range of 900 to 1200 nm.
○: Less than 2% reflectance △: More than 2% reflectance but less than 4% ×: More than 4% reflectance

(7) Accelerated weather resistance Using a sunshine carbon arc lamp type weather resistance tester for the sample to be measured in accordance with JIS A 5759 (temperature 63 ° C., humidity 50%, rainfall 18 minutes / 120 minutes irradiation conditions). An accelerated weathering test was conducted. The measurement was carried out until 2000 hours later, the appearance observation and luminous reflectance (Y value) of the cured product were measured, and the weather resistance was evaluated according to the following criteria.
(Standard for antireflection layer when used for outdoor display)
A: No change in appearance (crack, whitening, etc.) up to 2000 hours, Y value less than 1% B: No change in appearance (crack, whitening, etc.) up to 1000 hours, Y value less than 1% Δ: Appearance change (cracks) No whitening, etc.), but Y value is 1% or more and less than 1.5%. X: Appearance change (crack, whitening, etc.) is recognized, Y value is 1.5% or more (crystalline silicon type solar cell application (Anti-reflection layer standard)
◎: No change in appearance (crack, whitening, etc.) up to 2000 hours, reflectance less than 2% ○: No change in appearance (crack, whitening, etc.) up to 1000 hours, reflectance less than 2% △: Change in appearance (cracks) No whitening, etc.), but Y value is 2% or more and less than 4%.

(8) Pencil hardness (surface hardness) test Pencil hardness (surface hardness) was measured by the 8.4.1 pencil scratch test of JIS K-5400-1990 about the sample to be measured.

(9) Scratch resistance test The specimen to be measured was reciprocated 10 times on a steel wool # 0000 using a Gakushin type abrasion tester on a steel wool # 0000. The condition of scratches on the surface of the cured film was evaluated with the naked eye according to the following criteria.
◎: No damage occurs in the cured film ○: Peeling of the cured film or generation of scratches is hardly observed, or slight thin scratches are observed in the cured film △: Streaky scratches are observed throughout the cured film X: Peeling of the cured film occurs. If ◎ or ○, it can be said that the film has good scratch resistance.

(10) Effect of crack resistance The sample to be measured is allowed to stand at 23 ° C. for 24 hours, and it is confirmed by using a laser microscope (Keyence VK-8500) whether cracks are generated on the surface of the antireflection laminated film. Evaluation was made according to the following criteria.
◎: No crack at all ○: There are few (1-3) cracks only at the edge of the substrate △: There are 3-10 cracks ×: There are 10 or more cracks ◎, if ○ It can be said that the result of confirming the presence or absence of cracks is good.

<Synthesis Example 1>
In a reactor equipped with a reflux condenser and a stirrer, 72 parts of methyltrimethoxysilane, 28 parts of phenyltrimethoxysilane, 8 parts of 3-glycidoxypropyltrimethoxysilane, 71 parts of propylene glycol monomethyl ether as a solvent, 19 parts of water Then, 1 part of di-i-propoxy ethylacetoacetate aluminum 10% diluted solution of di-i-propoxy ethylacetoacetate was mixed as a catalyst and subjected to hydrolysis condensation reaction at 75 ° C. for 3 hours. After cooling to room temperature, a polymer (1) solution having a solid content concentration of 30% by weight and Mw of 3000 was obtained.

<Synthesis Example 2>
In a reactor equipped with a reflux condenser and a stirrer, 70 parts of methyl methacrylate, 10 parts of 2-ethylhexyl acrylate, 9 parts of cyclohexyl methacrylate, 20 parts of butyl acrylate, 7 parts of γ-methacryloxypropyltrimethoxysilane, 4- (meth) After adding and mixing 5 parts of acryloyloxy-2,2,6,6-tetramethylpiperidine, 75 parts of i-butyl alcohol, 50 parts of methyl ethyl ketone and 25 parts of methanol, the mixture was heated to 80 ° C. with stirring. A solution prepared by dissolving 3 parts of azobisisobutyronitrile in 8 parts of butyl acetate was added dropwise to the mixture over 30 minutes, and then reacted at 80 ° C. for 5 hours. After cooling, 40 parts of methyl ethyl ketone was added to obtain a polymer (2) solution having a solid concentration of 40% and Mw of 15000.

<Synthesis Example 3>
In a reactor equipped with a stirrer and a reflux condenser, 17 parts of methyltrimethoxysilane and 25 parts of phenyltrimethoxysilane, 43 parts of the polymer (2) solution, 50 parts of methyl isobutyl ketone as the organic solvent, and hydrolysis / As a condensation reaction catalyst, 1 part of a di-i-propoxyethylacetoacetate aluminum 10% diluted solution of i-propyl alcohol was added and mixed, and the temperature was raised to 50 ° C. with stirring. Water was added dropwise to this over 8 parts 30 minutes, and then reacted at 60 ° C. for 4 hours. Thereafter, 4 parts of acetylacetone as a stability improver was added and stirred for 1 hour, and then cooled to room temperature to obtain a polymer (3) solution having a solid content concentration of 30% by weight and Mw of 18000.

<Synthesis Example 4>
In a reactor equipped with a reflux condenser and a stirrer, 50 parts of methyltrimethoxysilane, 29 parts of phenyltrimethoxysilane, 27 parts of dimethyldimethoxysilane, 74 parts of propylene glycol monomethyl ether as a solvent, 18 parts of water, and triethylamine i as a catalyst -2 parts of 10% propyl alcohol diluted solution was mixed and subjected to hydrolysis condensation reaction at 75 ° C for 3 hours. After cooling to room temperature, a polymer (4) solution having a solid concentration of 30% by weight and Mw of 2500 was obtained.

<Synthesis Example 5>
In a reactor equipped with a stirrer and a reflux condenser, 24 parts of methyltrimethoxysilane, 14 parts of phenyltrimethoxysilane, 11 parts of trimethylmethoxysilane, 43 parts of the polymer (2) solution, and methyl isobutyl ketone 41 as an organic solvent. And 3 parts of a 10% oxalic acid diluent as a hydrolysis / condensation reaction catalyst were added and mixed, and the temperature was raised to 50 ° C. while stirring.
8 parts of water was added dropwise thereto over 30 minutes, and then reacted at 60 ° C. for 4 hours. Thereafter, 4 parts of acetylacetone as a stability improver was added and stirred for 1 hour, and then cooled to room temperature to obtain a polymer (5) solution having a solid content concentration of 30% by weight and Mw of 17000.

<Synthesis Example 6>
In a reactor equipped with a reflux condenser and a stirrer, 108 parts of methyltrimethoxysilane, 10 parts of 3-glycidoxypropyltrimethoxysilane, 58 parts of propylene glycol monomethyl ether as a solvent, 23 parts of water, i- of triethylamine as a catalyst 1 part of a 10% propyl alcohol dilution was mixed and subjected to a hydrolytic condensation reaction at 75 ° C. for 3 hours. After cooling to room temperature, a polymer (6) solution having a solid concentration of 30% by weight and Mw of 3500 was obtained.

<Synthesis Example 7>
In a reactor equipped with a reflux condenser and a stirrer, 38 parts of methyltrimethoxysilane, 22 parts of phenyltrimethoxysila, 37 parts of trifluoropropyltrimethoxysilane, 87 parts of propylene glycol monomethyl ether as solvent, 15 parts of water, as catalyst One part of a 10% diluted solution of triethylamine in i-propyl alcohol was mixed and subjected to a hydrolytic condensation reaction at 75 ° C. for 3 hours. After cooling to room temperature, a polymer (7) solution having a solid concentration of 30% by weight and Mw of 2400 was obtained.

<Synthesis Example 8>
In a reactor equipped with a reflux condenser and a stirrer, 39 parts of tetramethoxysilane, 43 parts of methyltrimethoxysilane, 25 parts of phenyltrimethoxysilane, 73 parts of propylene glycol monomethyl ether as a solvent, 19 parts of water, iethyl triethylamine as a catalyst -1 part of a 10% propyl alcohol dilution was mixed and subjected to a hydrolytic condensation reaction at 75 ° C for 3 hours. After cooling to room temperature, a polymer (8) solution having a solid content concentration of 30% by weight and Mw of 3500 was obtained.

(Preparation of composition)
<Preparation Example 1>
To 27 parts of the polymer (1) solution of the present invention, 4 parts of titanium oxide powder having a primary particle size of 10 nm, 18 parts of methyl isobutyl ketone and 0.01 part of triethylamine are added and dispersed for 4 hours with a paint shaker. A composition (X-1) having a partial concentration of 25% by weight was obtained. The storage stability was A.

<Preparation Example 2>
To 15 parts of the polymer (1) solution of the present invention, 8 parts of zirconium oxide powder having a primary particle size of 10 nm, 28 parts of methyl isobutyl ketone and 0.01 part of triethylamine are added and dispersed for 4 hours with a paint shaker. A composition (X-2) having a partial concentration of 25% by weight was obtained. The storage stability was A.

<Preparation Example 3>
To 15 parts of the polymer (1) solution of the present invention, 8 parts of zinc oxide powder having a primary particle size of 10 nm, 28 parts of methyl isobutyl ketone and 0.01 part of triethylamine are added and dispersed for 4 hours with a paint shaker. A composition (X-3) having a partial concentration of 25% by weight was obtained. The storage stability was A.

<Preparation Example 4>
To 30 parts of the polymer (3) solution of the present invention, 4 parts of titanium oxide powder having a primary particle size of 10 nm, 17 parts of methyl isobutyl ketone and 0.01 part of triethylamine are added and dispersed for 4 hours with a paint shaker. A composition (X-4) having a partial concentration of 25% by weight was obtained. The storage stability was A.

<Preparation Example 5>
To 17 parts of the polymer (3) solution of the present invention, 8 parts of zirconium oxide powder having a primary particle diameter of 10 nm, 25 parts of methyl isobutyl ketone and 0.01 part of triethylamine are added and dispersed for 4 hours with a paint shaker. A composition (X-5) having a partial concentration of 25% by weight was obtained. The storage stability was A.

<Preparation Example 6>
To 17 parts of the polymer (3) solution of the present invention, 8 parts of zinc oxide powder having a primary particle size of 10 nm, 25 parts of methyl isobutyl ketone and 0.01 part of triethylamine are added and dispersed for 4 hours with a paint shaker. A composition (X-6) having a partial concentration of 25% by weight was obtained. The storage stability was A.

<Preparation Example 7>
To 15 parts of the polymer (4) solution of the present invention, 8 parts of zirconium oxide powder having a primary particle size of 10 nm, 28 parts of methyl isobutyl ketone and 0.01 part of triethylamine are added and dispersed in a paint shaker for 4 hours. A composition (X-7) having a partial concentration of 25% by weight was obtained. The storage stability was A.

<Preparation Example 8>
To 15 parts of the polymer (5) solution of the present invention, 8 parts of titanium oxide powder having a primary particle diameter of 10 nm, 28 parts of methyl isobutyl ketone and 0.01 part of triethylamine are added and dispersed for 4 hours with a paint shaker. A composition (X-8) having a partial concentration of 25% by weight was obtained. The storage stability was A.

<Preparation Example 9>
To 25 parts of the polymer (6) solution of the present invention, 5 parts of titanium oxide powder having a primary particle size of 10 nm, 20 parts of methyl isobutyl ketone and 0.01 part of triethylamine are added and dispersed for 4 hours with a paint shaker. A composition (X-9) having a partial concentration of 25% by weight was obtained. The storage stability was A.

<Preparation Example 10>
To 15 parts of the polymer (8) solution of the present invention, 8 parts of zirconium oxide powder having a primary particle diameter of 10 nm, 28 parts of methyl isobutyl ketone and 0.01 part of triethylamine are added and dispersed for 4 hours with a paint shaker. A composition (X-10) having a partial concentration of 25% by weight was obtained. The storage stability was A.

<Preparation Example 11>
To 4 parts of the polymer (6) solution of the present invention, 6 parts of JX1012SIV manufactured by Catalyst Kasei Kogyo Co., Ltd. and 42 parts of methyl isobutyl ketone were added and stirred in a web rotor for 30 minutes to obtain a composition having a solid content concentration of 5% by weight. A product (Y-1) was obtained. The storage stability was A.

<Preparation Example 12>
To 4 parts of the polymer (6) solution of the present invention, 6 parts of JX1012SIV manufactured by Catalytic Chemical Industry Co., Ltd., 0.1 part of VPS-1001 manufactured by Wako Pure Chemical Industries, and 42 parts of methyl isobutyl ketone were added to the web rotor. The mixture was stirred for 30 minutes to obtain a composition (Y-2) having a solid content concentration of 5% by weight. The storage stability was A.

<Preparation Example 13>
To 4 parts of the polymer (7) solution of the present invention, 6 parts of JX1012SIV manufactured by Catalytic Chemical Industry Co., Ltd. and 42 parts of methyl isobutyl ketone were added and stirred for 30 minutes with a web rotor. A product (Y-3) was obtained. The storage stability was A.

<Preparation Example 14>
To 4 parts of the polymer (6) solution of the present invention, 6 parts of MEK-ST manufactured by Nissan Chemical Co., Ltd., which is a solid particle, and 42 parts of methyl isobutyl ketone were added and stirred for 30 minutes with a web rotor to obtain a solid content. A composition (Y-4) having a concentration of 5% by weight was obtained. The storage stability was A.

<Preparation Example 15>
To 40 parts of the polymer (1) solution of the present invention, 8 parts of methyl isobutyl ketone was added and stirred with a web rotor for 30 minutes to obtain a composition (Z-1) having a solid content concentration of 25% by weight. The storage stability was A.

<Preparation Example 16>
To 40 parts of the polymer (2) solution of the present invention, 8 parts of methyl isobutyl ketone was added and stirred with a web rotor for 30 minutes to obtain a composition (Z-2) having a solid content concentration of 25% by weight. The storage stability was A.

<Preparation Example 17>
To 6 parts of the polymer (6) solution of the present invention, 30 parts of methyl isobutyl ketone was added and stirred for 30 minutes with a web rotor to obtain a composition (α-1) having a solid content concentration of 5% by weight. The storage stability was A.

  Examples 1 to 17 and Comparative Examples 1 to 6 were carried out as evaluation of the antireflection layer assuming an outdoor display application. The results are shown in Tables 1 and 2.

<Example 1>
The composition (X-1) was applied onto a glass substrate using a spin coater so that the film thickness after drying was 1.5 μm, and dried at 200 ° C. for 30 minutes (first stage drying). The composition (Y-1) is applied from above the obtained (X-1) layer using a spin coater so that the film thickness after drying is 100 nm, and dried at 200 ° C. for 30 minutes (second stage) The sample was prepared. A plurality of samples were prepared, and luminous reflectance, pencil hardness, scratch resistance, and crack resistance were measured as initial evaluation. One of the samples was subjected to an accelerated weathering test, and the appearance observation and luminous reflectance measurement after the test were performed. The results are shown in Table 1.

<Example 2>
A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (X-2) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
<Example 3>
A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (X-3) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
<Example 4>
A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (Y-2) was used instead of the composition (Y-1), and the same evaluation was performed. The results are shown in Table 1.
<Example 5>
A sample having an antireflection layer was prepared in the same manner as in Example 4 except that the composition (X-2) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
<Example 6>
A sample having an antireflection layer was prepared in the same manner as in Example 4 except that the composition (X-3) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.

<Example 7>
A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (X-4) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
<Example 8>
A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (X-5) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
<Example 9>
A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (X-6) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
<Example 10>
A sample having an antireflection layer was prepared in the same manner as in Example 7 except that the composition (Y-2) was used instead of the composition (Y-1), and the same evaluation was performed. The results are shown in Table 1.
<Example 11>
A sample having an antireflection layer was prepared in the same manner as in Example 10 except that the composition (X-5) was used instead of the composition (X-4), and the same evaluation was performed. The results are shown in Table 1.

<Example 12>
A sample having an antireflection layer was prepared in the same manner as in Example 10 except that the composition (X-6) was used instead of the composition (X-4), and the same evaluation was performed. The results are shown in Table 1.
<Example 13>
A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (X-7) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
<Example 14>
A sample having an antireflection layer was prepared in the same manner as in Example 13 except that the composition (Y-2) was used instead of the composition (Y-1), and the same evaluation was performed. The results are shown in Table 1.
<Example 15>
A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (X-8) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
<Example 16>
A sample having an antireflection layer was prepared in the same manner as in Example 4 except that the composition (X-9) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.
<Example 17>
A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (X-10) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 1.

<Comparative Example 1>
A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (Z-1) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 2.
<Comparative example 2>
A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (Y-3) was used instead of the composition (Y-1), and the same evaluation was performed. The results are shown in Table 2.
<Comparative Example 3>
A sample having an antireflection layer was prepared in the same manner as in Example 7 except that the composition (α-1) was used instead of the composition (Y-1), and the same evaluation was performed. The results are shown in Table 2.
<Comparative example 4>
A sample having an antireflection layer was prepared in the same manner as in Example 4 except that the composition (Z-2) was used instead of the composition (X-1), and the same evaluation was performed. The results are shown in Table 2.
<Comparative Example 5>
A sample having an antireflection layer was prepared in the same manner as in Example 1 except that the composition (Y-4) was used instead of the composition (Y-1), and the same evaluation was performed. The results are shown in Table 2.

<Comparative Example 6>
Instead of the composition (X-1), 25 parts by weight of dipentaerythritol penta / hexaacrylate (trade name: DPHA, manufactured by Nippon Kayaku Co., Ltd.), 25 parts by weight of urethane acrylate oligomer (trade name: UV-6300B) , Manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), 2 parts by weight of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba-Geigy) and 0.5 parts by weight of a sensitizer (trade name: Kayacure DETX, In addition to coating a coating solution of Nippon Kayaku Co., Ltd. dissolved in 50 parts by weight of methyl ethyl ketone, and irradiating the coating film with ultraviolet rays to form a hard coat layer (refractive index: 1.53, layer thickness: 5 μm) Produced a sample having an antireflection layer in the same manner as in Example 1, and carried out the same evaluation. The results are shown in Table 2.

  Examples 18 to 34 and Comparative Examples 7 to 12 were carried out as evaluation of the antireflection layer assuming a crystalline silicon type solar cell application. The results are shown in Tables 3 and 4.

<Example 18>
The composition (X-1) was applied onto a glass substrate using a spin coater so that the film thickness after drying was 1.0 μm, and dried at 200 ° C. for 30 minutes (first-stage drying). The composition (Y-1) is applied from above the obtained (X-1) layer using a spin coater so that the film thickness after drying becomes 200 nm, and dried at 200 ° C. for 30 minutes (second stage) The sample was prepared. A plurality of samples were prepared, and reflectance, pencil hardness, scratch resistance, and crack resistance were measured as initial evaluation. One of the samples was subjected to an accelerated weathering test, and an appearance observation and a reflectance measurement were performed after the test. The results are shown in Table 3.

<Examples 19 to 34>
An antireflection layer was prepared in the same manner using the compositions shown in Table 3 instead of the compositions (X-1) and (Y-1) in Example 18 and evaluated. The results are shown in Table 3.

<Comparative Examples 7-12>
An antireflection layer was prepared in the same manner using the compositions shown in Table 4 instead of the compositions (X-1) and (Y-1) in Example 18 and evaluated. The results are shown in Table 4.

Claims (7)

  Layer (I) containing polyorganosiloxane (A) and metal oxide particles (B), and hollow or porous particles mainly composed of polyorganosiloxane (C) and silica having a number average particle diameter of 1 to 100 nm A device for outdoor installation, comprising an antireflection layer comprising a laminate with a layer (II) containing (D). The layer (I) has the following formula (1)
R ¹ _n Si (OR ² ) _4-n (1)
(Wherein, R ¹ represents a non-hydrolyzable organic group having 1 to 12 carbon atoms, optionally .R ² be different be the same as each other if there are two or more are each independently Represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 3.)
At least one silane compound (a1) and metal oxide particles (B) selected from the group consisting of at least one organosilane represented by the formula: hydrolyzate of the organosilane and condensate of the organosilane Obtained from a cured product of the composition (I) containing,
The layer (II) is represented by the following formula (2)
R ³ _m Si (OR ⁴ ) _4-m (2)
(In the formula, R ³ represents a non-hydrolyzable organic group having 1 to 12 carbon atoms, and when two or more exist, they may be the same as or different from each other. R ⁴ is independently selected. Represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and m is an integer of 0 to 3.)
At least one silane compound (c1) selected from the group consisting of at least one organosilane represented by the formula: a hydrolyzate of the organosilane and a condensate of the organosilane, and a number average particle size of 1 to 100 nm The device for outdoor installation according to claim 1, wherein the device is obtained from a cured product of the composition (II) containing hollow or porous particles (D) mainly composed of silica. The device for outdoor installation according to claim 2, wherein the silane compound (a1) of the composition (I) contains a silane compound in which at least one of R ¹ in the formula (1) is a phenyl group. . The outdoor installation according to claim 3, wherein the silane compound (a1) of the composition (I) has 5 to 80 mol% of all R ¹ in the formula (1) as a phenyl group. Device.   Layer (I) containing polyorganosiloxane (A) and metal oxide particles (B), and hollow or porous particles mainly composed of polyorganosiloxane (C) and silica having a number average particle diameter of 1 to 100 nm A display for outdoor installation, comprising an antireflection layer comprising a laminate with a layer (II) containing (D).   Layer (I) containing polyorganosiloxane (A) and metal oxide particles (B), and hollow or porous particles mainly composed of polyorganosiloxane (C) and silica having a number average particle diameter of 1 to 100 nm A solar cell comprising an antireflection layer comprising a laminate with a layer (II) containing (D).   Layer (I) containing polyorganosiloxane (A) and metal oxide particles (B), and hollow or porous particles mainly composed of polyorganosiloxane (C) and silica having a number average particle diameter of 1 to 100 nm An antireflection layer for a device for outdoor installation, comprising a laminate with a layer (II) containing (D).