Composition, cured product, laminate, and method for producing cured product

Abstract

To provide a composition that exhibits excellent curability and enables formation of a cured product with superior appearance, water repellency, and durability.SOLUTION: A composition comprising a copolymer (A) containing a polyalkylsiloxane unit, a component (B) comprising at least one silane compound represented by the formula R44-nSi(OR5)n (where R4 represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group; R5 represents an alkyl group or a phenyl group; n represents an integer of 2 to 4; the n OR5 groups may be different from each other; and when n is 2, the (4-n) R4 groups may be different from each other) or a partial hydrolytic condensate thereof, and a component (C) comprising a compound having a refractive index of 1.45 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition, a cured product, a laminate, and a method for producing the cured product. [Background technology]

[0002] Polyurethane is used in various automotive lamp lenses, glazing, exteriors, instrument covers, etc. Methyl methacrylate resin, polymethacrylimide resin, polycarbonate resin, poly The materials used are polyethylene resin, acrylonitrile styrene resin, etc. The resulting resin molded products are lightweight, have excellent impact resistance, and are also highly transparent. In recent years, with the miniaturization of various parts, transparent glass, which has excellent durability, has become the cover material. It has also become increasingly used in

[0003] In recent years, in order to ensure the safety of drivers, pedestrians, and oncoming vehicles, Equipping vehicles with advanced driver assistance systems (ADAS), including a vehicle distance control system For example, an example of a vehicle distance control system is a frequency of about 30 to 300 GHz. Sensor devices that use radio waves in the millimeter wave band (sometimes called millimeter wave radar) and radar A sensor device that uses laser irradiation to measure the characteristics and distance of an object (called LiDAR) (There are some examples.) The sensor device is designed to be mounted on the front emblem or front grille of the vehicle, while also being aesthetically pleasing. However, electromagnetic waves are easily attenuated and scattered by raindrops and snow. If raindrops or snow adhere to the top surface of the emblem or front grille through which electromagnetic waves pass, This can cause problems when measuring the distance to an object. Surface materials are required to have a water-repellent function that allows water droplets to slide off easily.

[0004] As a method for imparting water slippage to the surface of a substrate, a resin containing a polydimethylsiloxane structure is used.

[0003] Methods for coating substrate surfaces with coating compositions containing hydroxybenzoates are known. Patent Document 1 describes a water-repellent composition containing a copolymer of silicone macromer and silicate. A composition with good properties has been proposed. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2022 / 05912 Summary of the Invention [Problem to be solved by the invention]

[0006] However, according to the investigations of the present inventors, the composition described in Patent Document 1 is a thin film of a low refractive index material. For painting, use a substrate or primer with a high refractive index, such as a substrate and / or primer. When the external light source was used, interference patterns occurred, resulting in an unsatisfactory appearance.

[0007] The present invention is characterized in that a high refractive index material is blended to reduce the difference in refractive index between the substrate and / or the primer layer. By reducing the amount of acrylic resin, it is possible to form a cured product with a good appearance that suppresses interference fringes, and excellent water slip and durability. a cured product having excellent appearance with suppressed interference fringes, excellent water slippage and durability, and a method for manufacturing the same; Manufacturing method, good appearance with suppressed interference fringes, laminated film having a cured material layer with excellent water slippage and durability The purpose is to provide the body. [Means for solving the problem]

[0008] The present invention has the following aspects. [1] A copolymer (A) containing a polyalkylsiloxane unit and at least one of the following: Component (B) consisting of a silane compound represented by formula (b) or a partial hydrolysis condensate thereof; A copolymer (A) and a component (C) made of a compound having a refractive index of 1.45 or more, different from the component (B). ) and a composition comprising: R 4 4-n Si(OR 5 ) n (b) However, R 4 represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group; R 5 Haa represents an alkyl group or a phenyl group, n represents an integer of 2 to 4, and n OR 5 are different from each other If n is 2, then (4-n) R 4 may be different from each other. [2] The copolymer (A) is a silicone containing the polyalkylsiloxane unit. The composition according to [1], which contains a structural unit based on a macromonomer (X). [3] The copolymer (A) is based on a monomer (Y) having a group represented by the following formula (1): The composition according to [1] or [2], which contains a structural unit. -R 1 -M(R 2 ) r (OR 3 ) m-r ···(1) where M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta. and R 1 represents a hydrocarbon group having 1 to 5 carbon atoms, and R 2 is an alkyl group having 1 to 5 carbon atoms, represents an alkenyl group having 2 to 5 carbon atoms or an aryl group; R 3 is an alkyl group having 1 to 5 carbon atoms, represents an alkenyl group, an aryl group, or an acyl group having a number of 2 to 5, and m is an integer of 3 to 4 depending on M; represents a number, and r represents an integer from 0 to 3. If r is 2 or more, r R 2 are different from each other If mr is 2 or more, (mr) OR 3 may be different from each other. [4] The ratio of the silicone monomer to the total mass of all structural units constituting the copolymer (A) is Ratio of structural units based on the chromomonomer (X) and ratio of structural units based on the monomer (Y) The composition according to any one of [1] to [3], wherein the total of [5] The component (C) contains Al, Fe, In, Ge, Hf, Si, Ti, Sn in the molecule. Any of [1] to [4] containing at least one selected from the group consisting of Zr, Zr, and Ta. The composition according to any one of claims 1 to 4. [6] The ratio of the silicone monomer to the total mass of all structural units constituting the copolymer (A) is The proportion of the structural units based on the chromomonomer (X) is 10 to 70 mass %, and the monomer (Y) The composition according to any one of [1] to [5], wherein the proportion of the structural unit based on thing. [7] The component (B) is a partial hydrolysis condensate of a tetraalkoxysilane. [1 The composition according to any one of [1] to [6]. [8] The component (B) is a partial hydrolysis condensate of at least one of the silane compounds. and a weight average molecular weight of 300 to 3000, in the presence of a catalyst. The composition according to any one of [1] to [7] above, which is obtained by a hydrolysis and condensation reaction. [9] The composition according to any one of [1] to [8], which contains an initiator (D).

[10] The initiator (D) is a small compound selected from the group consisting of a photoacid generator and a photobase generator. The composition according to any one of [1] to [9] above, which contains at least one kind.

[11] A cured product of the composition according to any one of [1] to

[10] .

[12] A laminate having a substrate and a layer made of the cured product.

[13] A copolymer (A) containing a polydimethylsiloxane unit and at least one a component (B) consisting of a silane compound represented by the following formula (b) or a partial hydrolysis condensate thereof; and a component (C) consisting of a compound having a refractive index of 1.50 or more, and curing the composition by irradiating the composition with light. R 4 4-n Si(OR 5 ) n (b) However, R 4 represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group; R 5 Haa represents an alkyl group or a phenyl group, n represents an integer of 2 to 4, and n OR 5 are different from each other If n is 2, then (4-n) R 4 may be different from each other. [Effects of the Invention]

[0009] According to the present invention, a cured product having a good appearance with suppressed interference fringes, excellent water slippage and durability can be formed. a composition that can be produced by the method, a cured product that has a good appearance with suppressed interference fringes and is excellent in water slippage and durability, and The manufacturing method of the present invention provides a cured product layer having a good appearance with suppressed interference fringes, and excellent water slip properties and durability. A laminate can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0010] The embodiments of the present invention will be described in detail below. The following description is merely an example, and the present invention is not limited to the following description unless it goes beyond the gist of the invention. stomach. In this specification, when the expression "~" is used, the numerical values ​​or physical properties before and after it are The numerical ranges disclosed in this specification are intended to include the lower and upper limits. Any combination of values ​​can be used to create new ranges. In addition, in the present invention, when the expression "(meth)acrylic" is used, "acrylic" "(Meth)acrylate", " The same applies to "(meth)acryloyl" and the like.

[0011] [Composition] The composition according to one embodiment of the present invention (hereinafter also referred to as "the composition") is a polydimethylsiloxane. a copolymer (A) containing a silane unit and at least one specific silane compound or its Component (B) consisting of a partial hydrolysis condensate and a component consisting of a compound with a refractive index of 1.50 or more (C) and The composition may further contain an initiator and a diluent, if necessary. The present composition may further contain other components in addition to those described above, if necessary.

[0012] <Copolymer (A)> The copolymer (A) contains a polyalkylsiloxane unit. By including the copolymer (A) containing the unit, the cured product of the composition exhibits water-repellent properties. The polyalkylsiloxane unit contains two or more alkylsiloxane units. The alkylsiloxane unit may be, for example, a linear type, a branched type, or a dendrimer type. Among them, -(Si(R 18 )2O) n - A linear polyalkylsiloxane unipolymer represented by It is preferable that R 18 represents a hydrocarbon group having 1 to 10 carbon atoms, and The hydrocarbon group is preferably a methyl group, and n is a polyalkylsiloxane unit. The average degree of polymerization of the compound is shown. The average degree of polymerization of the polyalkylsiloxane unit is preferably 5 to 1000, more preferably 10 to 5 00 is more preferable, 30 to 300 is further more preferable, and 50 to 200 is particularly preferable. When the homogeneous degree of polymerization is equal to or greater than the above lower limit, the cured product of the composition has better water slippage properties, and when the homogeneous degree of polymerization is equal to or greater than the above upper limit, If the monomer has a polyalkylsiloxane unit (a silicone monomer as described below), The chromomonomer (X) is highly compatible with other monomers, making it easy to produce copolymer (A). There is.

[0013] The copolymer (A) may contain polyalkylsiloxane units in the main chain and in the side chain. The water-repellent and copolymer (A) may be contained in the main chain or in both the main chain and the side chain. In terms of ease of production, the polydimethylsiloxane unit at least in the side chain is preferred. It is preferable.

[0014] The copolymer (A) containing a polyalkylsiloxane unit at least in the side chain is The ease of introducing the trialkylsiloxane unit and the control of performance such as slippage are also important. Considering ease of use, silicone macromonomers containing polyalkylsiloxane units are preferred. A structural unit based on (X) (hereinafter also referred to as “macromonomer (X)”) (hereinafter also referred to as “structural unit”) Copolymers containing units (X) are preferred. The copolymer (A) is a copolymer represented by a specific formula (1) from the viewpoint of improving performance such as water slippage. A structural unit based on a monomer (Y) having a group corresponding to the structural unit (hereinafter also referred to as "structural unit (Y)"). ) is preferably further included. The copolymer (A) may contain, as necessary, a macromonomer (X) and a copolymer (B) within a range that does not impair the performance. and a structural unit based on a monomer (Z) other than the monomer (Y) (hereinafter also referred to as "structural unit (Z)"). ) may be further included.

[0015] (Macromonomer (X)) The macromonomer (X) is a compound having a polyalkylsiloxane unit and a polymerizable functional group. Examples of compounds include compounds containing: The polymerizable functional group is a group containing a polymerizable unsaturated bond such as a polymerizable carbon-carbon double bond. For example, a (meth)acryloyl group, a vinyl group, a (meth)acrylamide group, etc. Among these, (meth)acrylates are preferred from the viewpoint of ease of copolymerization with other monomers. The acryloyl group is preferred. The polyalkylsiloxane unit and the polymerizable functional group may be bonded via a linking group. Examples of the linking group include hydrocarbon groups such as alkylene groups having 1 to 6 carbon atoms. do.

[0016] Examples of the macromonomer (X) having a (meth)acryloyl group include those represented by the following formula (2): Examples of the compound include compounds represented by the following formula: CH2=CR 19 -CO-OR 20 -(Si(R 18 )2O) n -R 21 ···( 2) However, R 18 represents a hydrocarbon group having 1 to 10 carbon atoms, n represents the average degree of polymerization, and R 19 represents a hydrogen atom or a methyl group, and R 20 represents a hydrocarbon group having 1 to 10 carbon atoms, and R 21 teeth It represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an aryl group. The preferred range of n is the preferred average degree of polymerization of the polyalkylsiloxane units described above. The range is similar to that of Among these, R 18 represents a hydrocarbon group having 1 to 10 carbon atoms, and represents a hydrocarbon group having 1 to 5 carbon atoms. A hydride group is preferred, a methyl group is more preferred, and R 19 is preferably a methyl group, and R 20 teeth A hydrocarbon group having 1 to 6 carbon atoms is preferred, a hydrocarbon group having 2 to 4 carbon atoms is more preferred, and R 2 1 is preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 4 carbon atoms.

[0017] The weight average molecular weight (hereinafter also referred to as "Mw") of the macromonomer (X) is 500 to 4 0000 is preferable, 700 to 30000 is more preferable, and 800 to 20000 is even more preferable. is preferable, 1,000 to 18,000 is particularly preferable, and 2,000 to 15,000 is most preferable. When the Mw of the macromonomer (X) is equal to or greater than the lower limit, the cured product of the composition has good water slipping properties. It is more preferable that the macromonomer (X) is not more than the upper limit of the above range, and the monomer (Y) and the monomer (Z) ), which tends to facilitate the production of copolymer (A). The Mw of macromonomer (X) was determined by gel permeation chromatography (GPC). This is a value calculated as standard polystyrene measured by

[0018] As the macromonomer (X), commercially available products can be used. Linear macromonomer (X) As a commercially available product, for example, Silaplane (registered trademark) FM-0711 (manufactured by JNC) Average molecular weight listed in the catalog: 1000), Silaplane FM-0721 (number average molecular weight (Number average molecular weight catalog value: 5000), Silaplane FM-0725 (Number average molecular weight catalog value: Published value: 10000); X-22-174ASX (number average molecular weight cat.) manufactured by Shin-Etsu Chemical Co., Ltd. Log published value: 900), X-22-174BX (number average molecular weight catalog published value: 230 0), KF-2012 (number average molecular weight listed in the catalog: 4600), X-22-24 26 (number average molecular weight listed in the catalog: 12,000). An example of the chromomonomer (X) is HGO-3002 manufactured by Silicon Material Development Co., Ltd. do. The macromonomer (X) may be used alone or in combination of two or more kinds.

[0019] (Monomer (Y)) The monomer (Y) has a group represented by the following formula (1) (hereinafter also referred to as "group (1)"). When the group (1) is introduced into the copolymer (A) by the monomer (Y), The group (1) reacts with component (B), and the polydimethylsiloxane unit forms a polymer that is hardened by the curing of the composition. This can prevent bleeding out onto the surface of the object, improving durability. -R 1 -M(R 2 ) r (OR 3 ) m-r ···(1) where M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta. and R 1 represents a hydrocarbon group having 1 to 5 carbon atoms, and R 2 is an alkyl group having 1 to 5 carbon atoms, R represents an alkenyl group or an aryl group having a number of 1 to 5; 3 is an alkyl group having 1 to 5 carbon atoms, represents 2 to 5 alkenyl groups, aryl groups, or acyl groups, and m is an integer of 3 to 4 depending on M; where r represents an integer of 0 to 3, and when r is 2 or more, r R 2 are different from each other If mr is 2 or more, then (mr) R 3 may be different from each other.

[0020] In formula (1), M is Al (aluminum), Fe (iron), In (indium), Ge (germanium), Hf (hafnium), Si (silicon), Ti (titanium), Sn ( Although it may be any of tin (tin), zirconium (Zr), and tantalum (Ta), it is preferable to use Al, Si, Ti, or Zr is preferred because of its availability, low cost, and ease of use. Among these, Si is particularly preferred.

[0021] R 2 and R 3 Examples of the aryl group include a phenyl group, a toluyl group, and a naphthyl group. Examples include: R 2 and R 3 The alkyl group, alkenyl group, and aryl group each have a substituent. The substituent may be, for example, a halogen atom such as a chlorine atom, a methoxy group, or an ethoxy group. Examples thereof include an alkoxy group. R 3 Examples of the acyl group include a (meth)acrylic group, an acetyl group, and an acetimidoyl group. group, aldehyde group, thioacetyl group, propionyl group, benzenesulfonyl group, benzoyl group Examples thereof include a methyl group.

[0022] OR 3 represents an alkoxy group, an alkenyloxy group, an aryloxy group, an acyloxy group, Among these, alkoxy groups are the most reactive. The preferred groups are alkyloxy, alkenyloxy, and acyloxy groups, which are easy to control hydrolysis and handle. Alkoxy groups such as methoxy and ethoxy are particularly preferred because they are easily substituted.

[0023] When M in formula (1) is Si, the group (1) (also called a hydrolyzable silyl group) is , for example, a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group , dimethoxymethylsilyl group, diethoxymethylsilyl group, diisopropoxymethylsilyl group tris(2-propenyloxy)silyl group, (chloromethyl)dimethoxysilyl group , (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, ( ethoxymethyl)dimethoxysilyl group. Of the above, trimethoxysilyl is the most popular because it is versatile, highly active, and provides good curing properties. group, triethoxysilyl group, and dimethoxymethylsilyl group are preferred, and dimethoxymethylsilyl group is From the viewpoint of storage stability, dimethoxymethylsilyl group and triethoxysilyl group are preferred. A silyl group is preferred. In particular, (chloromethyl)dimethoxysilyl is preferred in terms of exhibiting high curability. The silyl group and (methoxymethyl)dimethoxysilyl group are preferred. These groups improve the recovery of the cured product. In terms of the tendency, trifunctional silyl groups such as trimethoxysilyl groups and triethoxysilyl groups is preferred.

[0024] The monomer (Y) may be the above-mentioned group (1) or a polymerizable functional group or a group which is added to a polymer (high Examples of such compounds include compounds having a reactive group capable of molecular reaction. Examples of the polymerizable functional group include the same as those described above, and preferred embodiments are also the same. Examples of the reactive group include a vinyl group, a (meth)acryloyl group, a (meth)acrylic group, and the like. Amido group, epoxy group, cyclic epoxy group, mercapto group, amino group, diamino group, acid anhydride groups, isocyanate groups, etc. The group (1) and the polymerizable functional group or reactive group may be bonded via a linking group. Examples of the group include hydrocarbon groups such as alkylene groups having 1 to 6 carbon atoms.

[0025] Examples of the monomer (Y) include vinyltrimethoxysilane and vinyltriethoxysilane. , vinyl tris(β-methoxyethoxy)silane, (meth)acrylic acid (3-trimethacrylate (3-dimethoxymethylsilyl)propyl (meth)acrylate, (3-dimethoxymethylsilyl)propyl (meth)acrylate, (2-trimethoxysilyl)ethyl (meth)acrylate, (2-dimethylsilyl)ethyl (meth)acrylate (meth)acrylate trimethoxysilylmethyl, (meth)acrylate trimethoxysilylmethyl, (meth)acrylate Vinyl silane compounds such as (dimethoxymethylsilyl)methyl acrylate, γ-aminopropanol N-β-(aminoethyl)γ-aminopropyltrimethoxysilane Lanthanum, N-β-(aminoethyl)γ-aminopropylmethyldimethoxysilane, γ-urea Aminosilane compounds such as hydroxypropyltriethoxysilane, γ-glycidoxypropyl Trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane , γ-glycidoxypropylmethyldiethoxysilane and other epoxy-based silane compounds, γ- Mercaptosilane compounds such as mercaptopropyltrimethoxysilane, N-phenyl- Silane compounds such as phenylamino silane compounds such as γ-aminopropyltrimethoxysilane These silane coupling agents are commercially available. This is preferable from the standpoint of price and ease of handling. However, the monomer (Y) is not limited to these. For example, it may be copolymerized with other monomers. Titanium having a reactive group other than the polymerizable functional group that can be bonded to a polymer or the group that can be added to a polymer (1) Alternatively, a carboxylate-, aluminate- or zirconate-based coupling agent may be used. The monomer (Y) may be used alone or in combination of two or more kinds.

[0026] When macromonomer (X) and monomer (Y) are copolymerized, The better the copolymerization with the monomer (Y), the more the amount of unreacted monomer can be reduced. The durability of the cured product tends to be improved. When the synthetic functional group is a (meth)acryloyl group, the monomer (Y) is a (meth)acryloyl Vinyl silane compounds having a vinyl group are particularly preferred.

[0027] (Monomer (Z)) The monomer (Z) may be any monomer as long as it is copolymerizable with the macromonomer (X). Compounds having the above polymerizable functional groups (wherein macromonomer (X) and monomer (Y) are (Excluding.)

[0028] Specific examples of the monomer (Z) include the following: Methyl (meth)acrylate, Ethyl (meth)acrylate, n-Propylene (meth)acrylate (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate Isobutyl acrylate, tert-butyl (meth)acrylate, n-pentane (meth)acrylate (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth) n-Heptyl acrylate, n-Octyl (meth)acrylate, 2-Ethyl (meth)acrylate Cylhexyl, (meth)acrylate nonyl, (meth)acrylate decyl, (meth)acrylate Dodecyl (meth)acrylate, Phenyl (meth)acrylate, Toluyl (meth)acrylate, (meth)acrylate Benzyl acrylate, 2-methoxyethyl (meth)acrylate, 3-methyl (meth)acrylate 2-Hydroxyethyl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate Acryloyloxypropyl, (meth)acrylate stearyl, (meth)acrylate glycidyl, (meth)acrylate 2-aminoethyl acrylate, (meth)acrylic acid ethylene oxide adduct, ( Trifluoromethylmethyl (meth)acrylate, 2-trifluoromethyl (meth)acrylate 2-Perfluoroethylethyl (meth)acrylate, 2-Perfluoroethylethyl (meth)acrylate Perfluoroethyl-2-perfluorobutylethyl, (meth)acrylic acid perfluoro Ethyl (meth)acrylate, trifluoromethyl (meth)acrylate, bis(trifluoromethyl) (meth)acrylate (Meth)acrylic acid 2-trifluoromethyl-2-perfluoroethyl ester 2-Perfluorohexylethyl (meth)acrylate, 2-Perfluorohexylethyl (meth)acrylate -Perfluorodecylethyl, (meth)acrylic acid 2-perfluorohexadecylethyl (Meth)acrylic acid monomers such as: (Meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide Acrylamide, Nn-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide Acrylamide, N-dimethylaminoethyl (meth)acrylamide, N-dimethylamino Propyl (meth)acrylamide, diacetone (meth)acrylamide, N-(meth)acrylamide (Meth)acrylamide monoesters such as acroylpiperidine and (meth)acryloylmorpholine Monomer.

[0029] Styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfone Styrenic monomers such as acids and their salts. Maleic anhydride, maleic acid, mono- and di-alkyl esters of maleic acid fumaric acid, mono- and dialkyl esters of fumaric acid. Maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide Imide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide maleimide monomers such as phenylmaleimide, cyclohexylmaleimide, etc. Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile. Amide group-containing vinyl monomers such as acrylamide and methacrylamide. Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate Vinyl esters such as: Alkenes such as ethylene and propylene. Conjugated dienes such as butadiene and isoprene. Vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, etc. The monomer (Z) may be used alone or in combination of two or more kinds.

[0030] When macromonomer (X) and monomer (Z) are copolymerized, The better the copolymerization with the monomer (Z), the more the amount of unreacted monomer can be reduced. The durability of the cured product tends to be improved. When the synthetic functional group is a (meth)acryloyl group, the monomer (Z) is a styrene-based monomer and and (meth)acrylic acid-based monomers are preferred, and (meth)acrylic acid The base monomers are particularly preferred.

[0031] (Proportion of each structural unit in copolymer (A)) The ratio of the structural unit (X) to the total mass of all structural units constituting the copolymer (A) is 1 5 to 70 mass% is preferable, 20 to 60 mass% is more preferable, and 30 to 60 mass% is even more preferable. When the proportion of the structural unit (X) is at least the above lower limit, the water slippage of the cured product is improved. If the amount is equal to or less than the upper limit, the amount of unpolymerized macromonomer (X) can be reduced. Therefore, the transparency of the cured product tends to be good.

[0032] The ratio of the structural unit (Y) to the total mass of all structural units constituting the copolymer (A) is 4 The content is preferably 0 to 85% by mass, more preferably 40 to 80% by mass, and even more preferably 40 to 75% by mass. When the proportion of the structural unit (Y) is at least the above lower limit, the durability of the cured product is improved. If the ratio of the structural unit (X) is not more than the upper limit, the hardness can be increased sufficiently. The water sliding properties of the compound tend to be improved.

[0033] The silicone macromonomer ( The total of the proportion of structural units based on monomer (X) and the proportion of structural units based on monomer (Y) is 55 mass % or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, It is particularly preferably 90% by mass or more, and most preferably 100% by mass. When the total proportion of the unit (Y) is equal to or greater than the above lower limit, the durability and water slippage of the cured product are improved. It tends to be better.

[0034] The ratio of the structural unit (Z) to the total mass of all structural units constituting the copolymer (A) is 0 Preferably, the content is from 0 to 45% by mass, more preferably from 0 to 40% by mass, and even more preferably from 0 to 30% by mass. The content of the structural unit (Z) is preferably 0 to 20 mass %, more preferably 0 to 10 mass %. The lower the proportion of the structural unit (Z), the better the water slipping property of the cured product tends to be. The higher the ratio, the better the copolymerizability when producing the copolymer (A) tends to be. The proportion of each structural unit can be determined using analytical methods such as nuclear magnetic resonance and infrared spectroscopy using total reflectance measurement. It is more in demand.

[0035] (Mw of copolymer (A)) The Mw of the copolymer (A) is preferably 3,000 to 400,000, and more preferably 5,000 to 10,000. 00 is more preferable, and 7000 to 80000 is particularly preferable. When the Mw of the copolymer (A) is equal to or greater than the above lower limit, the copolymer (A) is Since the resin is firmly fixed in the cured product, water slippage and durability tend to improve. If the content is less than 100%, the compatibility with other components in the composition is improved, and the appearance of the cured product is improved. There is a tendency to The Mw of copolymer (A) was determined by gel permeation chromatography (GPC). The measured value is converted into standard polystyrene.

[0036] (Production of Copolymer (A)) The method for producing the copolymer (A) is not particularly limited, and any known method can be appropriately adopted. For example, the copolymer having the structural unit (X) and the structural unit (Y) may be the following (i) or (ii): It can be produced by the method ii). (i) Macromonomer (X), monomer (Y) containing a polymerizable functional group, and optionally a monomer A method for polymerizing a monomer mixture containing the compound (Z). (ii) Polymerizing a monomer mixture containing macromonomer (X) and, if necessary, monomer (Z). and mixing the resulting polymer with a monomer (Y) containing a reactive group capable of being added to the polymer. How to react.

[0037] In the methods (i) and (ii), the macromonomer (X), the monomer (Y), and the monomer (Z) The proportion of the macromonomer (X) to the total mass of the above is preferably 15 to 60 mass%, and The content is more preferably 5 to 50% by mass, and even more preferably 15 to 50% by mass. If the ratio of X) is equal to or greater than the above lower limit, the cured product will have better water slippage, and if it is equal to or greater than the above upper limit, If the amount of unpolymerized macromonomer (X) is less than 100%, the transparency of the cured product will be improved. The clarity tends to be good.

[0038] The ratio of the weight of the monomer (Y) to the total weight of the macromonomer (X), the monomer (Y), and the monomer (Z) The proportion of ) is preferably 40 to 85 mass%, more preferably 40 to 80 mass%, and more preferably 40 to 7 When the proportion of the monomer (Y) is equal to or greater than the above lower limit, the durability of the cured product is improved. If the proportion of macromonomer (X) is sufficient, the durability will be improved and the proportion will be below the upper limit. Since the viscosity can be increased, the cured product tends to have good water sliding properties.

[0039] The ratio of the weight of the monomer (Z) to the total weight of the macromonomer (X), the monomer (Y), and the monomer (Z) The proportion of ) is preferably 0 to 45 mass%, more preferably 0 to 40 mass%, and more preferably 0 to 30 mass%. %, more preferably 0 to 20 mass %, particularly preferably 0 to 10 mass %. The lower the proportion of the monomer (Z), the better the water slipping property of the cured product tends to be. The higher the proportion of (Z), the better the copolymerizability of the monomer mixture tends to be. In particular, in applications where water sliding is important, the content of compounds containing silicon atoms should be as high as possible. It is preferable to make the viscosity as high as possible, and therefore it is preferable that the structural unit (Z) is not contained.

[0040] In the methods (i) and (ii), the polymerization method of the monomer mixture is not particularly limited. Known polymerization methods such as liquid polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization can be used. The polymerization conditions are not particularly limited, but may be, for example, at 30 to 180°C for 0.5 to 24 hours. This can be done.

[0041] The monomer mixture is preferably polymerized in the presence of a polymerization initiator. As the polymerization initiator, various known polymerization initiators can be used. For example, 2,2 -Azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70, Fujifilm (Wako Pure Chemical Industries, Ltd.), 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65, 2,2'-Azobisisobutyronitrile (V-60, Fujifilm Wako Pure Chemical Industries, Ltd.) lum (Wako Pure Chemical Industries, Ltd.), 2,2'-azobis(2-methylbutyronitrile) (V-59, Fuji Azonitrile compounds such as film (manufactured by Wako Pure Chemical Industries); octanoyl peroxide (peroxide) (registered trademark) O, manufactured by NOF Corp.), lauroyl peroxide (Perloyl L, manufactured by NOF Corp.), stearic acid Peroyl peroxide (Peroyl S, NOF Corp.), succinic acid peroxide (Peroyl S, NOF Corp.), Benzoyl peroxide (Niper (registered trademark) BW, manufactured by NOF Corp.) (manufactured by NOF Corp.), isobutyryl peroxide (Perloyl IB, manufactured by NOF Corp.), 2,4-dichlorobenzene Zoyl peroxide (Niper CS, NOF Corp.), 3,5,5-trimethylhexanoyl peroxide diacyl peroxides such as di-n-propyl peroxide (Peroyl 355, manufactured by NOF Corp.); Diisopropyl peroxydicarbonate (Perloyl NPP-50M, NOF Corp.), diisopropyl percarbonate -oxydicarbonate (Peroyl IPP-50, NOF Corp.), bis(4-t-butylsilyl) Cyclohexyl) peroxydicarbonate (Peroyl TCP, manufactured by NOF Corp.), Di-2-ethoxy Diethoxyethyl peroxydicarbonate (Peroyl EEP, manufactured by NOF Corp.), Di-2-ethoxy Hexyl peroxydicarbonate (Peroyl OPP, manufactured by NOF Corp.), di-2-methoxybutane Chiller peroxydicarbonate (Peroyl MBP, NOF Corp.), di(3-methyl-3-methyl) Peroxybutyl) peroxydicarbonate (Peroyl SOP, NOF Corp.) dicarbonate; t-butyl hydroperoxide (Perbutyl® H-69, NOF Corp.), 1,1,3,3-tetramethylbutyl hydroperoxide (Perocta (Registered) Hydroperoxides such as di-t-butyl peroxide (Pan), etc. -butyl D, NOF Corp.), 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyl Dialkyl peroxides such as Sun (Perhexa (registered trademark) 25B, manufactured by NOF Corp.); α,α '-Bis(neodecanoylperoxy)diisopropylbenzene (Diaper®) ND, NOF Corp.), cumyl peroxy neodecanoate (Percumyl (registered trademark) ND, NOF Corp.) oil), 1,1,3,3-tetramethylbutyl peroxyneodecanoate (peroctadecanoate ND, NOF Corp.), 1-cyclohexyl-1-methylethyl peroxyneodecanoate ( Percyclo (registered trademark) ND, NOF Corp.), t-hexyl peroxyneodecanoate (Percyclo (registered trademark) ND, NOF Corp.), -Hexyl (registered trademark) ND, manufactured by NOF Corp.), t-butyl peroxyneodecanoate (Per Butyl ND (NOF Corp.), t-Hexyl peroxypivalate (Perhexyl PV (NOF Corp.) ), t-butyl peroxypivalate (Perbutyl PV, NOF Corp.), 1,1,3,3-tetramethyl- Tetramethylbutylperoxy-2-ethylhexanoate (Perocta O, NOF Corp.) 2, 5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane (perhexane 250, NOF Corp.), 1-cyclohexyl-1-methylethylperoxy-2-ethylhexyl Xanoate (Percyclo O, NOF Corp.), t-Hexylperoxy 2-ethylhexanoate Perhexyl O, NOF Corp.), t-butylperoxy 2-ethylhexanoate (Per -butyl O, manufactured by NOF), t-butyl peroxyisobutyrate (Perbutyl IB, manufactured by NOF) ), t-hexylperoxyisopropyl monocarbonate (Perhexyl I, NOF Corp.) peroxyl such as t-butyl peroxymaleic acid (Perbutyl MA, manufactured by NOF Corp.) However, the polymerization initiator is not particularly limited to these. It's not something like that. The polymerization initiator may be used alone or in combination of two or more kinds. The amount of the polymerization initiator used is, for example, 0.01 to 10 parts by mass per 100 parts by mass of the monomer mixture. It is a department.

[0042] In the method (ii), examples of the method for reacting the polymer with the monomer (Y) include: After copolymerizing macromonomer (X) with hydroxyl group-containing monomer (Z), isocyanate Examples of such a method include, but are not limited to, a method in which a group is subjected to an addition reaction with a compound containing the group (1).

[0043] <Ingredient (B)> Component (B) is at least one silane compound represented by the following formula (b) (hereinafter referred to as "silane"). (b)) or a partial hydrolysis condensate thereof. R 4 4-n Si(OR 5 ) n (b) However, R 4 represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group; R 5 Haa represents an alkyl group or a phenyl group, n represents an integer of 2 to 4, and n OR 5 are different from each other If n is 2, then (4-n) R 4 may be different from each other.

[0044] In formula (b), R 4 The alkyl group may be linear or branched. , 1 to 20 is preferred, and 1 to 4 is more preferred. Examples of the aryl group include a phenyl group, a toluyl group, and a naphthyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0045] R 5 The alkyl group may be linear or branched, and from the viewpoint of the hydrolysis rate, it is preferable to use a linear alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 5 from the viewpoint of the hydrolysis rate. 1 or 2 is more preferred, and 1 is even more preferred.

[0046] A silane compound in which n in formula (b) is 4 (hereinafter also referred to as "silane compound (b1)") ) is expressed by the following formula (b1). Si(OR 6 ) a (OR 7 ) b (OR 8 ) c (OR 9 ) d (b1) However, R 6, R 7 , R 8 and R 9 each independently represents an alkyl group or a phenyl group. a, b, c, and d are 0≦a≦4, 0≦b≦4, 0≦c≦4, and 0≦d≦4. It is also an integer that satisfies the condition a+b+c+d=4. R 6 , R 7 , R 8 and R 9 is the above R 5 is the same as:

[0047] A silane compound in which n in formula (b) is 3 (hereinafter also referred to as "silane compound (b2)") ) is expressed by the following formula (b2). R 10 Si(OR 11 ) e (OR 12 ) f (OR 13 ) g (b2) However, R 10 represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. 11 , R 12 and R 13 each independently represents an alkyl group or a phenyl group. g satisfies the conditions 0≦e≦3, 0≦f≦3, 0≦g≦3, and e+f+g=3. is an integer. R 10 is the above R 4 Similar to R 11 , R 12 and R 13 is the above R 5 is the same as:

[0048] A silane compound in which n is 2 in formula (b) (hereinafter also referred to as "silane compound (b3)") ) is expressed by the following formula (b3). R 14 R 15 Si(OR 16) h (OR 17 ) i (b3) However, R 14 and R 15 are each independently a hydrogen atom, an alkyl group, an aryl group, or an Represents a ralkyl group. 16 and R 17 each independently represents an alkyl group or a phenyl group h and i are integers that satisfy the conditions 0≦h≦2, 0≦i≦2, and h+i=2. be. R 14 and R 15 is the above R 4 Similar to R 16 and R 17 is the above R 5 is the same as .

[0049] Specific examples of the silane compound (b1) include tetramethoxysilane and tetraethoxysilane. silane, tetrapropoxysilane, tetrabutoxysilane, tetrapentyloxysilane, tetra Triphenyloxysilane, trimethoxymonoethoxysilane, dimethoxydiethoxysilane Silane, triethoxymonomethoxysilane, trimethoxymonopropoxysilane, monomethacrylate Tributoxysilane, Monomethoxytripentyloxysilane, Monomethoxytrif Phenyloxysilane, dimethoxydipropoxysilane, tripropoxymonomethoxysilane silane, trimethoxymonobutoxysilane, dimethoxydibutoxysilane, triethoxymono Propoxysilane, diethoxydipropoxysilane, tributoxymonopropoxysilane , dimethoxymonoethoxymonobutoxysilane, diethoxymonomethoxymonobutoxysilane Lan, diethoxymonopropoxymonobutoxysilane, dipropoxymonomethoxymonoe Dipropoxymonomethoxymonobutoxysilane, Dipropoxymonoethoxy Dibutoxymonobutoxysilane, Dibutoxymonomethoxymonoethoxysilane, Dibutoxymonoethoxysilane Monomethoxymonoethoxymonopropoxysilane, Monomethoxymonoethoxymonopropoxymonobutoxysilane Among these, tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane are mentioned. Xysilane is preferred.

[0050] Specific examples of the silane compound (b2) include trimethoxysilane, triethoxysilane, Tripropoxysilane, tripentyloxysilane, triphenyloxysilane, dimethicone Diethoxymonoethoxysilane, diethoxymonomethoxysilane, dipropoxymonomethoxysilane Silane, dipropoxymonoethoxysilane, dipentyloxylmonomethoxysilane, dipentyloxyl Dipentyloxymonoethoxysilane, Dipentyloxymonopropoxysilane, Diphenyl Oxylmonomethoxysilane, diphenyloxymonoethoxysilane, diphenyloxy Monopropoxysilane, methoxyethoxypropoxysilane, monopropoxydimethoxy Silane, Monopropoxydiethoxysilane, Monobutoxydimethoxysilane, Monoplier hydrosilanes such as monophenyloxydiethoxysilane and monophenyloxydiethoxysilane compound; Methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane , methyltripentyloxysilane, methyltriphenyloxysilane, methylmonometh Diethoxysilane, Methylmonomethoxydipropoxysilane, Methylmonomethoxydipropoxysilane Pentyloxysilane, methyl monomethoxydiphenyloxysilane, methyl methoxy ethoxysilane methylmonomethoxymonoethoxymonobutoxysilane, and methylmonomethoxymonoethoxymonobutoxysilane Methylsilane compounds; Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane , ethyltripentyloxysilane, ethyltriphenyloxysilane, ethylmonomethoxysilane Diethoxysilane, Ethylmonomethoxydipropoxysilane, Ethylmonomethoxydipropoxysilane Pentyloxysilane, ethyl monomethoxydiphenyloxysilane, ethyl methoxy ethoxysilane ethoxypropoxysilane, and ethylmonomethoxymonoethoxymonobutoxysilane Ethylsilane compounds; Propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxy silane, propyltripentyloxysilane, and propyltriphenyloxysilane; Propyl monomethoxydiethoxysilane, propyl monomethoxydipropoxysilane, Propylmonomethoxydipentyloxysilane, Propylmonomethoxydiphenyloxysilane Silane, propyl methoxyethoxypropoxysilane, and propyl monomethoxymonoethoxysilane Propylsilane compounds such as monobutoxysilane and the like; Butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane , butyltripentyloxysilane, butyltriphenyloxysilane, butylmonomethoxysilane Diethoxysilane, Butylmonomethoxydipropyloxysilane, Butylmonomethoxydipropyloxysilane Pentyloxysilane, butyl monomethoxydiphenyloxysilane, butyl methoxyethylene butylmonomethoxymonoethoxymonobutoxysilane, and butylmonomethoxymonoethoxymonobutoxysilane Butylsilane compounds; Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxy Silane, phenyltripentyloxysilane, phenyltriphenyloxysilane, phenyl Phenylmonomethoxydiethoxysilane, phenylmonomethoxydipropoxysilane, phenyl Monomethoxydipentyloxysilane, Phenylmonomethoxydiphenyloxysilane , phenyl methoxyethoxy propoxy silane, and phenyl monomethoxy monoethoxy phenylsilane compounds such as monobutoxysilane; Hydroxyphenyltrimethoxysilane, hydroxyphenyltriethoxysilane, Hydroxyphenyltrippropoxysilane, Hydroxyphenyltripentyloxysilane , hydroxyphenyltriphenyloxysilane, hydroxyphenylmonomethoxydiene Hydroxyphenyl monomethoxydipropoxysilane, Hydroxyphenyl monomethoxydipropoxysilane, Hydroxyphenyl Monomethoxydipentyloxysilane, Hydroxyphenylmonomethoxydiphenyloxysilane hydroxyphenyl methoxyethoxypropoxysilane, and hydroxyphenyl Hydroxyphenylsilane compounds such as phenylmonomethoxymonoethoxymonobutoxysilane thing; Naphthyltrimethoxysilane, naphthyltriethoxysilane, naphthyltripropoxy Silane, naphthyltripentyloxysilane, naphthyltriphenyloxysilane, naphthyltriphenyloxysilane Naphthyl monomethoxydiethoxysilane, Naphthyl monomethoxydipropoxysilane, Naphthyl Monomethoxydipentyloxysilane, Naphthylmonomethoxydiphenyloxysilane , naphthyl methoxyethoxy propoxy silane, and naphthyl monomethoxy monoethoxy naphthylsilane compounds such as monobutoxysilane; Benzyltrimethoxysilane, benzyltriethoxysilane, benzyltripropoxy Silane, benzyltripentyloxysilane, benzyltriphenyloxysilane, benzyl Benzyl monomethoxydiethoxysilane, benzyl monomethoxydipropoxysilane, benzyl Benzyl monomethoxydipentyloxysilane, Benzyl monomethoxydiphenyloxysilane , benzyl methoxyethoxy propoxy silane, and benzyl monomethoxy monoethoxy benzylsilane compounds such as monobutoxysilane; Hydroxybenzyltrimethoxysilane, Hydroxybenzyltriethoxysilane, Hydroxybenzyltriethoxysilane Hydroxybenzyl tripentyloxysilane, Hydroxybenzyl tripentyloxysilane , hydroxybenzyltriphenyloxysilane, hydroxybenzylmonomethoxydiene Hydroxybenzyl monomethoxydipropoxysilane, Hydroxybenzyl Monomethoxydipentyloxysilane, Hydroxybenzylmonomethoxydiphenyloxysilane hydroxybenzyl methoxyethoxypropoxysilane, and hydroxybenzyl methoxyethoxypropoxysilane. Hydroxybenzylsilane compounds such as benzylmonomethoxymonoethoxymonobutoxysilane Things include:

[0051] Specific examples of the silane compound (b3) include dimethoxysilane, diethoxysilane, dipropylsilane, propyloxysilane, dipentyloxysilane, diphenyloxysilane, methoxyethoxy Silane, methoxypropoxysilane, methoxypentyloxysilane, methoxyphenyl Oxysilane, ethoxypropoxysilane, ethoxypentyloxysilane, and ethoxy hydrosilane compounds such as diphenyloxysilane; Methyldimethoxysilane, methylmethoxyethoxysilane, methyldiethoxysilane, Methyl methoxypropoxysilane, methyl methoxypentyloxysilane, methyl ethoxy Dipropoxysilane, Methyldipropoxysilane, Methyldipentyloxysilane, Methyl methylhydrosilanes such as methyldiphenyloxysilane and methylmethoxyphenyloxysilane compounds; Ethyldimethoxysilane, ethylmethoxyethoxysilane, ethyldiethoxysilane, Ethyl methoxypropoxysilane, ethyl methoxypentyloxysilane, ethyl ethoxy Dipropoxysilane, Ethyldipropoxysilane, Ethyldipentyloxysilane, Ethyl Ethylhydrosilanes such as ethyldiphenyloxysilane and ethylmethoxyphenyloxysilane compounds; Propyldimethoxysilane, propylmethoxyethoxysilane, propyldiethoxysilane Silane, propyl methoxypropoxysilane, propyl methoxypentyloxysilane, Propylethoxypropoxysilane, Propyldipropoxysilane, Propyldipentyloxysilane Oxysilane, propyldiphenyloxysilane, propylmethoxyphenyloxysilane Propylhydrosilane compounds such as; Butyldimethoxysilane, butylmethoxyethoxysilane, butyldiethoxysilane, Butyl methoxypropoxysilane, butyl methoxypentyloxysilane, butyl ethoxy Dipropoxysilane, butyldipropoxysilane, butyldipentyloxysilane, butyl butylhydrosilanes such as butyldiphenyloxysilane and butylmethoxyphenyloxysilane compounds; Phenyldimethoxysilane, phenylmethoxyethoxysilane, phenyldiethoxysilane Silane, phenyl methoxypropoxysilane, phenyl methoxypentyloxysilane, Phenylethoxypropoxysilane, phenyldipropoxysilane, phenyldipentyloxysilane Oxysilane, phenyldiphenyloxysilane, phenylmethoxyphenyloxysilane Phenylhydrosilane compounds such as; Hydroxyphenyldimethoxysilane, Hydroxyphenylmethoxyethoxysilane, Hydroxyphenyldiethoxysilane, Hydroxyphenylmethoxypropoxysilane, Hydroxyphenyl methoxypentyloxysilane, Hydroxyphenyl ethoxypropion Hydroxyphenyldipropoxysilane, Hydroxyphenyldipentyloxysilane Xysilane, hydroxyphenyldiphenyloxysilane, hydroxyphenylmethoxy Hydroxyphenylhydrosilane compounds such as phenyloxysilane; Naphthyldimethoxysilane, naphthylmethoxyethoxysilane, naphthyldiethoxysilane Silane, naphthyl methoxypropoxysilane, naphthyl methoxypentyloxysilane, Naphthyl ethoxypropoxysilane, naphthyl dipropoxysilane, naphthyl dipentyl silane Oxysilane, naphthyldiphenyloxysilane, naphthylmethoxyphenyloxysilane Naphthylhydrosilane compounds such as; Benzyldimethoxysilane, benzylmethoxyethoxysilane, benzyldiethoxysilane Benzyl methoxypropoxysilane, benzyl methoxypentyloxysilane, Benzylethoxypropoxysilane, Benzyldipropoxysilane, Benzyldipentyloxysilane Oxysilane, benzyldiphenyloxysilane, benzylmethoxyphenyloxysilane benzylhydrosilane compounds such as; Hydroxybenzyldimethoxysilane, Hydroxybenzylmethoxyethoxysilane, Hydroxybenzyldiethoxysilane, Hydroxybenzylmethoxypropoxysilane, Hydroxybenzyl methoxypentyloxysilane, Hydroxybenzyl ethoxypropion Hydroxybenzyldipropoxysilane, Hydroxybenzyldipentyloxysilane Oxysilane, Hydroxybenzyldiphenyloxysilane, Hydroxybenzylmethoxy Hydroxybenzylhydrosilane compounds such as phenyloxysilane; Dimethyldimethoxysilane, Dimethylmethoxyethoxysilane, Dimethylmethoxypropyl Dimethyloxysilane, Dimethyldiethoxysilane, Dimethyldipentyloxysilane, Dimethyl Diphenyloxysilane, dimethylethoxypropoxysilane, dimethyldipropoxysilane Dimethylsilane compounds such as oran; Diethyldimethoxysilane, Diethylmethoxyethoxysilane, Diethylmethoxypropion Diethyldiethoxysilane, Diethyldipentyloxysilane, Diethyl Diphenyloxysilane, diethylethoxypropoxysilane, diethyldipropoxysilane Diethylsilane compounds such as oran; Dipropyldimethoxysilane, Dipropylmethoxyethoxysilane, Dipropylmethoxy Dipropoxysilane, Dipropyldiethoxysilane, Dipropyldipentyloxysilane , dipropyldiphenyloxysilane, dipropylethoxypropoxysilane, dipropyl dipropoxysilane compounds such as dipropoxysilane; Dibutyldimethoxysilane, Dibutylmethoxyethoxysilane, Dibutylmethoxypropion Dibutyldiethoxysilane, Dibutyldipentyloxysilane, Dibutyl Diphenyloxysilane, dibutylethoxypropoxysilane, dibutyldipropoxysilane dibutylsilane compounds such as oran; Diphenyldimethoxysilane, diphenylmethoxyethoxysilane, diphenylmethoxy Dipropoxysilane, diphenyldiethoxysilane, diphenyldipentyloxysilane , diphenyldiphenyloxysilane, diphenylethoxypropoxysilane, diphenyl diphenylsilane compounds such as dipropoxysilane; Di(hydroxyphenyl)dimethoxysilane, di(hydroxyphenyl)methoxyethoxy Di(hydroxyphenyl)methoxypropoxysilane, di(hydroxyphenyl)methoxypropoxysilane di(hydroxyphenyl)dipentyloxysilane, di(hydroxyphenyl)dipentyloxysilane, di(hydroxyphenyl)dipentyloxysilane Di(hydroxyphenyl)ethoxypropoxy Di(hydroxyphenyl)silane, di(hydroxyphenyl)dipropoxysilane, etc. Silane compounds; Dinaphthyldimethoxysilane, Dinaphthylmethoxyethoxysilane, Dinaphthylmethoxy Dipropoxysilane, Dinaphthyldiethoxysilane, Dinaphthyldipentyloxysilane , Dinaphthyldiphenyloxysilane, Dinaphthylethoxypropoxysilane, Dinaphthyl dinaphthylsilane compounds such as dipropoxysilane; Dibenzyldimethoxysilane, Dibenzylmethoxyethoxysilane, Dibenzylmethoxy Dipropoxysilane, Dibenzyldiethoxysilane, Dibenzyldipentyloxysilane , dibenzyldiphenyloxysilane, dibenzylethoxypropoxysilane, dibenzyl dibenzylsilane compounds such as dipropoxysilane; Di(hydroxybenzyl)dimethoxysilane, Di(hydroxybenzyl)methoxyethoxy Di(hydroxybenzyl)methoxypropoxysilane, di(hydroxybenzyl)methoxypropoxysilane Di(hydroxybenzyl)diethoxysilane, di(hydroxybenzyl)dipentyloxysilane, di(hydroxy Di(hydroxybenzyl)diphenyloxysilane, Di(hydroxybenzyl)ethoxypropoxy Di(hydroxybenzyl)silane, di(hydroxybenzyl)dipropoxysilane, etc. Silane compounds; Methylethyldimethoxysilane, Methylethylmethoxyethoxysilane, Methylethyl Methoxypropoxysilane, methylethyldiethoxysilane, methylethyldipentyloxysilane Oxysilane, methylethyldiphenyloxysilane, methylethylethoxypropoxysilane methylethylsilane compounds such as methylethyldipropoxysilane; Methylpropyldimethoxysilane, Methylpropylmethoxyethoxysilane, Methylpropyl Propylmethoxypropoxysilane, Methylpropyldiethoxysilane, Methylpropyldi Pentyloxysilane, methylpropyldiphenyloxysilane, methylpropylethoxy Methylpropylsilane compounds such as dipropoxysilane and methylpropyldipropoxysilane thing; Methylbutyldimethoxysilane, Methylbutylmethoxyethoxysilane, Methylbutyl Methoxypropoxysilane, methylbutyldiethoxysilane, methylbutyldipentyl silane Oxysilane, Methylbutyldiphenyloxysilane, Methylbutylethoxypropoxysilane methylbutylsilane compounds such as methylbutyldipropoxysilane; Methyl(phenyl)dimethoxysilane, methyl(phenyl)methoxyethoxysilane, Methyl(phenyl)methoxypropoxysilane, Methyl(phenyl)diethoxysilane, Methyl(phenyl)dipentyloxysilane, Methyl(phenyl)diphenyloxysilane methyl(phenyl)ethoxypropoxysilane, methyl(phenyl)dipropoxysilane Methyl(phenyl)silane compounds such as oran; Methyl(hydroxyphenyl)dimethoxysilane, Methyl(hydroxyphenyl)meth methoxyethoxysilane, methyl(hydroxyphenyl)methoxypropoxysilane, methyl (Hydroxyphenyl)diethoxysilane, Methyl(hydroxyphenyl)dipentyl Oxysilane, Methyl (hydroxyphenyl) diphenyloxysilane, Methyl (hydroxy Diphenyl)ethoxypropoxysilane, Methyl(hydroxyphenyl)dipropoxysilane Methyl(hydroxyphenyl)silane compounds such as oran; Methyl(naphthyl)dimethoxysilane, Methyl(naphthyl)methoxyethoxysilane, Methyl(naphthyl)methoxypropoxysilane, Methyl(naphthyl)diethoxysilane, Methyl(naphthyl)dipentyloxysilane, Methyl(naphthyl)diphenyloxysilane silane, methyl(naphthyl)ethoxypropoxysilane, methyl(naphthyl)dipropoxysilane Methyl(naphthyl)silane compounds such as oran; Methyl(benzyl)dimethoxysilane, Methyl(benzyl)methoxyethoxysilane, Methyl(benzyl)methoxypropoxysilane, Methyl(benzyl)diethoxysilane, Methyl(benzyl)dipentyloxysilane, Methyl(benzyl)diphenyloxysilane methyl(benzyl)ethoxypropoxysilane, methyl(benzyl)dipropoxysilane Methyl(benzyl)silane compounds such as oran; Methyl(hydroxybenzyl)dimethoxysilane, Methyl(hydroxybenzyl)meth hydroxyethoxysilane, methyl(hydroxybenzyl)methoxypropoxysilane, methyl (Hydroxybenzyl)diethoxysilane, Methyl(hydroxybenzyl)dipentyl Oxysilane, Methyl (hydroxybenzyl) diphenyloxysilane, Methyl (hydroxy Dibenzyl)ethoxypropoxysilane, Methyl(hydroxybenzyl)dipropoxysilane Methyl(hydroxybenzyl)silane compounds such as oran; Ethylpropyldimethoxysilane, Ethylpropylmethoxyethoxysilane, Ethylpropyl Propylmethoxypropoxysilane, Ethylpropyldiethoxysilane, Ethylpropyldiethoxysilane Pentyloxysilane, ethylpropyldiphenyloxysilane, ethylpropylethoxy Ethylpropylsilane compounds such as dipropoxysilane and ethylpropyldipropoxysilane thing; Ethylbutyldimethoxysilane, Ethylbutylmethoxyethoxysilane, Ethylbutyl Methoxypropoxysilane, ethylbutyldiethoxysilane, ethylbutyldipentyl silane Oxysilane, ethyl butyl diphenyl oxysilane, ethyl butyl ethoxy propoxysilane silane, ethylbutylsilane compounds such as ethylbutyldipropoxysilane; Ethyl(phenyl)dimethoxysilane, Ethyl(phenyl)methoxyethoxysilane, Ethyl(phenyl)methoxypropoxysilane, Ethyl(phenyl)diethoxysilane, Ethyl(phenyl)dipentyloxysilane, Ethyl(phenyl)diphenyloxysilane silane, ethyl(phenyl)ethoxypropoxysilane, ethyl(phenyl)dipropoxysilane Ethyl(phenyl)silane compounds such as oran; Ethyl(hydroxyphenyl)dimethoxysilane, Ethyl(hydroxyphenyl)meth Ethoxyethoxysilane, Ethyl (hydroxyphenyl) methoxypropoxysilane, Ethyl (Hydroxyphenyl)diethoxysilane, Ethyl(hydroxyphenyl)dipentyl Diphenyloxysilane, Ethyl (hydroxyphenyl) diphenyloxysilane, Ethyl (hydroxy Di(hydroxyphenyl)ethoxypropoxysilane, Ethyl(hydroxyphenyl)dipropoxysilane Ethyl(hydroxyphenyl)silane compounds such as oran; Ethyl(naphthyl)dimethoxysilane, Ethyl(naphthyl)methoxyethoxysilane, Ethyl(naphthyl)methoxypropoxysilane, Ethyl(naphthyl)diethoxysilane, Ethyl(naphthyl)dipentyloxysilane, Ethyl(naphthyl)diphenyloxysilane silane, ethyl (naphthyl) ethoxypropoxysilane, ethyl (naphthyl) dipropoxysilane Ethyl(naphthyl)silane compounds such as oran; Ethyl(benzyl)dimethoxysilane, Ethyl(benzyl)methoxyethoxysilane, Ethyl(benzyl)methoxypropoxysilane, Ethyl(benzyl)diethoxysilane, Ethyl(benzyl)dipentyloxysilane, Ethyl(benzyl)diphenyloxysilane silane, ethyl (benzyl) ethoxypropoxysilane, ethyl (benzyl) dipropoxysilane Ethyl(benzyl)silane compounds such as oran; Ethyl(hydroxybenzyl)dimethoxysilane, Ethyl(hydroxybenzyl)meth Ethoxyethoxysilane, Ethyl (hydroxybenzyl) methoxypropoxysilane, Ethyl (Hydroxybenzyl)diethoxysilane, Ethyl (hydroxybenzyl) dipentyl silane Diphenyloxysilane, Ethyl (hydroxybenzyl) diphenyloxysilane, Ethyl (hydroxy Dibenzyl)ethoxypropoxysilane, Ethyl (hydroxybenzyl)dipropoxysilane Ethyl(hydroxybenzyl)silane compounds such as oran; Propyl butyl dimethoxy silane, propyl butyl methoxy ethoxy silane, propyl Butyl methoxypropoxy silane, propyl butyl diethoxy silane, propyl butyl di Pentyloxysilane, propyl butyl diphenyloxysilane, propyl butyl ethoxy Propylbutylsilane compounds such as dipropoxysilane and propylbutyldipropoxysilane thing; Propyl(phenyl)dimethoxysilane, Propyl(phenyl)methoxyethoxysilane Silane, propyl(phenyl)methoxypropoxysilane, propyl(phenyl)diethoxy Silane, Propyl(phenyl)dipentyloxysilane, Propyl(phenyl)diphenyl Propoxysilane, Propyl(phenyl)ethoxypropoxysilane, Propyl(phenyl)ethoxypropoxysilane ) Propyl(phenyl)silane compounds such as dipropoxysilane; Propyl(hydroxyphenyl)dimethoxysilane, Propyl(hydroxyphenyl) Methoxyethoxysilane, propyl(hydroxyphenyl)methoxypropoxysilane, Propyl(hydroxyphenyl)diethoxysilane, Propyl(hydroxyphenyl)di Pentyloxysilane, propyl(hydroxyphenyl)diphenyloxysilane, pro Pyl(hydroxyphenyl)ethoxypropoxysilane, Propyl(hydroxyphenyl)ethoxypropoxysilane ) Propyl(hydroxyphenyl)silane compounds such as dipropoxysilane; Propyl(naphthyl)dimethoxysilane, Propyl(naphthyl)methoxyethoxysilane silane, propyl(naphthyl)methoxypropoxysilane, propyl(naphthyl)diethoxy Silane, Propyl(naphthyl)dipentyloxysilane, Propyl(naphthyl)diphenyl Propoxysilane, Propyl(naphthyl)ethoxypropoxysilane, Propyl(naphthyl)ethoxypropoxysilane ) Propyl(naphthyl)silane compounds such as dipropoxysilane; Propyl(benzyl)dimethoxysilane, Propyl(benzyl)methoxyethoxysilane Silane, propyl (benzyl) methoxypropoxysilane, propyl (benzyl) diethoxy Silane, Propyl(benzyl)dipentyloxysilane, Propyl(benzyl)diphenyl Propoxysilane, Propyl(benzyl)ethoxypropoxysilane, Propyl(benzyl)ethoxypropoxysilane ) Propyl(benzyl)silane compounds such as dipropoxysilane; Propyl(hydroxybenzyl)dimethoxysilane, Propyl(hydroxybenzyl) Methoxyethoxysilane, propyl(hydroxybenzyl)methoxypropoxysilane, Propyl(hydroxybenzyl)diethoxysilane, Propyl(hydroxybenzyl)di Pentyloxysilane, propyl(hydroxybenzyl)diphenyloxysilane, pro Pyl(hydroxybenzyl)ethoxypropoxysilane, Propyl(hydroxybenzyl)ethoxypropoxysilane propyl(hydroxybenzyl)silane compounds such as propyl(hydroxybenzyl)dipropoxysilane. The silane compound (b) may be used alone or in combination of two or more kinds.

[0052] The partial hydrolysis condensate of at least one silane compound (b) is a silane compound (b) or can be obtained by subjecting a mixture of two or more of these to a hydrolysis condensation reaction by a known method. do. For example, a predetermined amount of water and, if necessary, an organic solvent are added to a tetramethoxysilane monomer. In the presence of a catalyst, the reaction is usually carried out at room temperature to 100°C while distilling off the by-produced alcohol. This causes the hydrolysis and condensation of tetramethoxysilane to proceed, resulting in the formation of a liquid tetramethoxysilane. Trimethoxysilane partial hydrolysis condensate (average polymerization degree is usually 2-8, mostly 3-7) The liquid tetramethoxysilane partial hydrolysis condensate is, for example, CH3O- (Si(OCH3)2-O) s -CH3, where s is a number between 2 and 8 that represents the average degree of polymerization. The degree of hydrolysis can be adjusted appropriately by the amount of water used. The liquid tetramethoxysilane partial hydrolysis condensate obtained as described above was further added. The liquid tetramethoxysilane partial hydrolysis condensate may be further subjected to a hydrolysis condensation reaction. The method for carrying out the hydrolysis condensation reaction is the same as the method for converting the primary reactant into the secondary reactant, which will be described later. do. In the case of silane compounds (b) other than tetramethoxysilane, partial hydrolysis condensation is also carried out in the same manner. A mixture of two or more silane compounds (b) can be used as a partial hydrolysis condensation product. You may do so.

[0053] Examples of the catalyst include inorganic acids such as hydrochloric acid, acetic acid, nitric acid, formic acid, sulfuric acid, and phosphoric acid; Acetic acid, propionic acid, oxalic acid, paratoluenesulfonic acid, benzoic acid, phthalic acid, maleic acid Organic acids such as phosphate, potassium hydroxide, sodium hydroxide, calcium hydroxide, ammonia Alkali catalysts such as organometallics, metal alkoxides, for example, dibutyltin dilaurate, Organotin compounds such as dibutyltin dioctiate and dibutyltin diacetate, aluminum Umtris(acetylacetonate), Titanium tetrakis(acetylacetonate) , titanium bis(butoxy)bis(acetylacetonate), titanium bis(isopropyl) hydroxy)bis(acetylacetonate), zirconium tetrakis(acetylacetonate) ate), zirconium bis(butoxy)bis(acetylacetonate) and zirconium Metal chelate compounds such as bis(isopropoxy)bis(acetylacetonate), boric acid butoxide, boron compounds such as boric acid, etc. Among these, the production of secondary reaction products is particularly For the above, organic acids or metal chelate compounds are preferred, and maleic acid or metal acetylacetonates are preferred. Particularly preferred is methyl methyl acrylate. The amount of the acid catalyst used is not particularly limited as long as it is an amount that can exhibit catalytic function. However, it is usually about 0.001 to 10 parts by mass per 100 parts by mass of the silane compound (b). The content is selected from the range, preferably 0.003 to 5 parts by mass.

[0054] From the viewpoint of reactivity, component (B) is R 6 , R 7 , R 8 and R 9 GaAruki Silane compound (b1) is a silane group, i.e., tetraalkoxysilane or its partial hydrolyzate. It is preferably a decondensation product, and more preferably a partial hydrolysis condensation product of tetraalkoxysilane. More preferably, the partial hydrolysis and condensation of tetramethoxysilane or tetraethoxysilane is carried out. A mixture is particularly preferred.

[0055] From the viewpoint of the appearance of the cured product, the Mw of component (B) is preferably 500 or more, and more preferably 600 or more. The upper limit of Mw of component (B) is, for example, 10,000. The Mw of component (B) was measured by gel permeation chromatography (GPC). This is a value converted into standard polystyrene.

[0056] From the viewpoint of reactivity, component (B) is a compound capable of partially hydrolyzing at least one silane compound (b). A partial hydrolysis condensate having a Mw of 300 to 3000 (hereinafter referred to as "primary reaction") The product is subjected to a hydrolysis and condensation reaction in the presence of a catalyst (hereinafter referred to as the "secondary reaction product"). "). The use of a secondary reaction product as component (B) enhances the curability of the composition and the appearance of the cured product. The reason for this is unclear, but the following is thought to be the cause: In this case, hydrolysis is promoted, and the silanol groups (Si-O H) is present in large amounts. Silanol groups are Si-OR 5 It has higher reactivity than In addition, the condensation reaction is promoted, which increases the molecular weight and suppresses cracks. This can improve the appearance.

[0057] If the Mw of the primary reaction product is 300 or more, the appearance of the cured product will be good. If there is a high molecular weight, the reactivity tends to be good. The Mw of the primary reactant is preferably 400 to 2,000. It is preferable that the number of carbon atoms is 500 to 1,000. As the silane compound (b) forming the primary reaction product, from the viewpoint of hardness of the cured product, silane Compound (b1) is preferred, and tetraalkoxysilane is more preferred, and tetra More preferably, it is a methoxysilane. As described above, the primary reactant is a silane compound (b) or a mixture of two or more thereof. It is obtained by decomposition and condensation reaction. Commercially available primary reactants can also be used, for example, MS51 manufactured by Mitsubishi Chemical. , MS53, MS57, MS56S, Colcoat's Ethyl Silicate 40, Ethyl Silica Methyl silicate 48, Methyl silicate 51, Methyl silicate 53A, EMS-485, etc. can be done. As a method for subjecting the primary reactant to a hydrolysis condensation reaction in the presence of a catalyst, a method for subjecting the primary reactant to a hydrolysis condensation reaction in the presence of a catalyst is to add water, A method in which a catalyst and a solvent are added and stirred at 25°C for at least one day is also included. Heating the reaction can accelerate the reaction, for example, at 30°C to 100°C. Alternatively, the mixture may be stirred for more than 1 hour. The Mw of the secondary reaction product was 40% from the experimental temperature and reaction time in the inventors' investigations. Preferably, it is 0 to 50,000, more preferably 600 to 30,000, and more preferably 800 to 10,000. 00 is more preferable, 900 to 9,000 is particularly preferable, and 1,000 to 8,000 is Most preferred.

[0058] In addition, since the reaction of the secondary reaction product progresses over time, its structure and properties (e.g., It is difficult to identify the size (e.g. radius, hydroxyl value, etc.) using general analytical methods. Mw can be measured, but the difference is between the case where the primary reactant is used as component (B) and the case where the secondary reactant is used. The reactivity of this composition and the appearance of the cured product are different when the secondary reaction product is It is impossible or impractical to directly identify it by its structure or characteristics. Therefore, there are circumstances where the secondary reactant is "at least one A partial hydrolysis condensate of the silane compound (b) having an Mw of 300 to 3000. It would be more appropriate to define it as "the hydrolysis condensation product was subjected to a hydrolysis condensation reaction in the presence of a catalyst." It is said that. Commercially available secondary reactants can also be used, for example, HAS-1, H Examples include AS-6 and HAS-10.

[0059] <Component (C)> Component (C) is a compound having a refractive index of 1.45 or greater. More specifically, the lower limit of the refractive index of component (C) is preferably 1.45 or more, and more preferably 1.50 or more. It is more preferable that the β-saturation coefficient is 1.55 or more, and even more preferable that the β-saturation coefficient is 1.60 or more. The upper limit of the refractive index of ) is preferably 3.0 or less, more preferably 2.75 or less, and more preferably 2.5 or less. The refractive index of component (C) is more preferably 2.25 or less, and particularly preferably 2.25 or less. If the upper limit is less than the above, the control range of the refractive index becomes wider, and interference fringes tend to be more suppressed. If the refractive index is less than this value, the difference in refractive index between copolymer (A) and component (C) will be reduced, resulting in a transparent coating film. Sexuality tends to improve. Component (C) is selected from Al, Fe, and Metal alkoxides containing In, Ge, Hf, Ti, Sn, Zr, Si, Ta, etc. It is preferable.

[0060] Component (C) consists of metal fine particles (c1), a metal compound (c2), and a compound having an aromatic ring (c3). It is composed of at least one selected from the group.

[0061] Specific examples of the metal fine particles (c1) include Al, Fe, In, Ge, Hf, Ti, Sn, and Zr. From the viewpoint of transparency of the coating film, fine particles of smaller particle diameter are used. Particularly preferred are Al, Ti, and Zr, which can be easily prepared. good. The particle diameter of the metal fine particles (c1) is preferably 1 to 200 nm, more preferably 1 to 100 nm. The metal fine particles (c) are preferably 1 to 75 nm, more preferably 1 to 50 nm. If the particle size of 1) is equal to or less than the upper limit, the transparency of the coating film tends to be good. If the value is equal to or greater than the lower limit, interference fringes tend to be easily suppressed. The metal fine particles (c1) may be used alone or in combination of two or more kinds.

[0062] Specific examples of the metal compound (c2) include Al, Fe, In, Ge, Hf, Ti, Sn, and Zr. Examples of suitable compounds include alkoxides, chelates, and acylates of Ta, etc. From this viewpoint, Al, Ti and Zr are particularly preferred. The metal compound (c2) may be used alone or in combination of two or more kinds.

[0063] Specific examples of the compound (c3) having an aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and Examples of the ring include a phenanthrene ring, a fluorene ring, and the like. The compound (c3) having an aromatic ring may be used alone or in combination of two or more. As for the compound having an aromatic ring, from the viewpoint of compatibility and reactivity with component (A) and component (B), Metallic alloys including Al, Fe, In, Ge, Hf, Ti, Sn, Zr, Si, or Ta It is preferable that the compound contains alkoxide, and more preferably Ti, Zr, or Si. It is particularly preferred that:

[0064] <Initiator (D)> The inclusion of the initiator (D) in the composition allows the hydrolysis and condensation reaction of the component (B) and the group (1) to proceed. This facilitates the curing of the composition, improving its curability. Examples of the initiator (D) include a photopolymerization initiator, a thermal polymerization initiator, a metal catalyst, and an acid catalyst. Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photoacid generator, and a photobase generator. Examples of the thermal polymerization initiator include a thermal radical polymerization initiator, a thermal acid generator, and a thermal base. The metal catalyst or acid catalyst is a catalyst for partially hydrolyzing the silane compound (b). The catalysts used in obtaining the condensation product are the same as those used in the present invention. They may be used alone or in combination of two or more.

[0065] Among the above, the photopolymerization initiator (D) is preferred. When the composition contains an initiator, it can be cured by irradiating it with active energy rays such as ultraviolet rays. When the composition is applied to a resin substrate and then cured by heat, the resin substrate is However, if it is cured with active energy rays, the resin substrate will not be affected by the heat. Since deformation due to heat can be suppressed, it can also be applied to resin substrates with low heat resistance. Curing by energy rays takes less time than other curing methods such as heat curing or moisture curing. Productivity is expected to improve. The photopolymerization initiator is capable of initiating the hydrolysis and condensation reaction of component (B) and group (1). Since the present composition can be cured efficiently, a photo-acid generator and a photo-base generator are preferably used. At least one selected from the group is preferred, and a photoacid generator is more preferred.

[0066] Representative examples of photoradical polymerization initiators (hereinafter also simply referred to as "photoinitiators") include: Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1- Benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxyethoxy)phenyl hydroxy-2-propyl) ketone, 1-[4-(2-hydroxyethoxy)-phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4- [4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2- Methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl 2-benzyl-2-morpholino(4-thiomethylphenyl)propan-1-one -Dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl Acetophenone such as ethyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer Non-benzoins, benzoin, benzoin methyl ether, benzoin ethyl ether, benzo benzoins such as benzoin isopropyl ether and benzoin isobutyl ether; phenone, o-benzoylbenzoic acid methyl ester, 4-phenylbenzophenone, 4-benzoyl -4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t-butylphenyl) (oxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzyl N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl benzoyl] ]Benzenemethanaminium bromide, (4-benzoylbenzyl)trimethylammonium Benzophenones such as benzophenone chloride; 2-isopropylthioxanthone, 4-isopropyl Thioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy Thioxanes such as 3,4-dimethyl-9H-thioxanthone-9-one mesochloride Tonnes; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-Dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide However, the photo-radical polymerization initiator is The photoradical polymerization initiator is not limited to the exemplified compounds. Alternatively, two or more types may be used in combination.

[0067] A typical example of a photoacid generator is triarylsulfonium hexafluorophosphate. phosphates (e.g., p-phenylthiophenyldiphenylsulfonium hexafluorophosphine sulfonium compounds such as triarylsulfonium hexafluoroantimonate, etc. Salts (especially triarylsulfonium salts): diaryliodonium hexafluorophosphate Phosphate, diaryliodonium hexafluoroantimonate, bis(dodecyl phenoxy) iodonium tetrakis(pentafluorophenyl)borate, iodonium [4 -(4-methylphenyl-2-methylpropyl)phenyl]hexafluorophosphate However, the photoacid generator is not limited to the compounds exemplified above. The photoacid generators may be used singly or in combination of two or more.

[0068] A typical example of a photobase generator is N-cyclohexylcarbamate 1-(anthracene). Quinone-2-yl)ethyl, N,N-diethylcarbamate 9-anthrylmethyl, pipet Lysine-1-carboxylic acid 9-anthrylmethyl, N,N-dicyclohexylcarbamic acid 9-Anthrylmethyl, N,N-dicyclohexylcarbamate 1-(anthraquinone- 2-yl)ethyl, imidazole-1-carboxylic acid 1-(anthraquinone-2-yl) ester ethyl, cyclohexylammonium 2-(3-benzoylphenyl)propionate, ( E)-N-Cyclohexyl-3-(2-hydroxyphenyl)acrylamide, dicyclo Hexylammonium 2-(3-benzoylphenyl)propionate, 1,2-dicyclohexyl 4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate 1,2-Diisopropyl 3-[bis(dimethylamino)methylene]guanidinium 2-(3-benzoylphenyl)propionate, 4-hydroxypiperidine-1-carboxylate (2-Nitrophenyl)methyl carboxylate, 4-(methacryloyloxy)piperidine-1 -(2-nitrophenyl)methyl carboxylate, guanidinium 2-(3-benzoylphenyl) (E)-1-piperidino-3-(2-hydroxyphenyl)-2-propionate However, the photobase generator is not limited to the exemplified compounds. The photobase generators may be used alone or in combination of two or more.

[0069] <Diluent> When the present composition contains a diluent, the coating workability when applying the present composition to a substrate and the quality of the coating formed are deteriorated. The smoothness and uniformity of the film and its cured film, as well as the adhesion of the cured film to the substrate, are improved. Examples of the diluent include water and organic solvents, with organic solvents being preferred. When component (B) is a hydrolysis condensate of silane compound (b), the diluent is It may contain water blended to cause the hydrolysis condensation reaction of the substance (b).

[0070] Organic solvents include alcohol-based solvents, glycol-based solvents, hydrocarbon-based solvents, and esters. Examples of the alcohol-based solvent include methyl alcohol, ... Alcohol, ethanol, isopropyl alcohol, n-butanol, isobutanol, octyl alcohol ethanol, n-propyl alcohol, acetylacetone alcohol, etc. Coal-based solvents include ethylene glycol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether , ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether Diethylene glycol monoethyl ether, propylene glycol monomethyl ether propylene glycol monoethyl ether, propylene glycol monobutyl ether Ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene Examples of hydrocarbon solvents include glycol monomethyl ether acetate. Examples of ester solvents include benzene, kerosene, toluene, and xylene. Examples include methyl, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate. Ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, Examples of ether solvents include ethyl ether, butyl ether, and the like. Tetramethylcellulose, methylcellosolve, ethylcellosolve, dioxane, furan, tetrahydrofuran The organic solvents may be used alone or in combination of two or more. As a diluent, it is easy to handle, has good storage stability in liquid form, and has a high viscosity. Alcohol-based solvents are preferred due to their excellent properties, and methanol, ethanol, and ethanol are preferred. Among these, isopropanol and butanol are more preferred, as they can easily produce a cured product with high hardness. Methanol or ethanol is preferred because it can

[0071] <Other ingredients> Examples of other components include polymers other than the copolymer (A), ultraviolet absorbers, light stabilizers, Silane coupling agents, inorganic fine particles, antioxidants, anti-yellowing agents, bluing agents, pigments, Examples of the additives include leveling agents, antifoaming agents, thickening agents, antisettling agents, antistatic agents, and antifogging agents.

[0072] <Content of each ingredient> The content of the copolymer (A) is 1 to 9% by mass relative to 100% by mass of the total nonvolatile components in the composition. 5% by mass is preferable, 10 to 90% by mass is more preferable, and 20 to 85% by mass is even more preferable. The content is preferably 25 to 85 mass %, more preferably 30 to 65 mass %. When the content of A) is equal to or greater than the above lower limit, the cured product has better water slip properties and appearance, and when the content of A) is equal to or greater than the above upper limit, the cured product has better water slip properties and appearance. If it is less than this, the appearance and strength of the cured product will be better. The non-volatile components refer to the components excluding the organic solvent.

[0073] The content of component (B) is 1 to 90 mass % relative to 100 mass % of the total nonvolatile components in the composition. % by mass is preferable, 5 to 80% by mass is more preferable, and 10 to 75% by mass is even more preferable, The content of component (B) is particularly preferably 18 to 70 mass %, and most preferably 30 to 65 mass %. If the amount is equal to or greater than the lower limit, the strength of the cured product will be superior, and if the amount is equal to or less than the upper limit, the strength of the cured product will be superior. The appearance of the item is better.

[0074] The content of component (C) is 1 to 90 mass % relative to 100 mass % of the total nonvolatile components in the composition. % by mass is preferable, 5 to 80% by mass is more preferable, 5 to 50% by mass is even more preferable, and 1 The content of component (C) is particularly preferably 0 to 50% by mass. When the thickness is equal to or less than the upper limit, the appearance is better, and the curability and transparency are better.

[0075] The content of the initiator (D) is 0.01% by mass relative to 100% by mass of the total nonvolatile components in the composition. Preferably, the content is 0.05 to 10% by mass, more preferably 0.05 to 9% by mass, and even more preferably 0.1 to 8% by mass. It is preferably 0.2 to 5 mass %, particularly preferably 0.2 to 3 mass %. When the content of the agent (D) is equal to or greater than the lower limit, the curability (reactivity) of the composition and the yield of the cured product are improved. When the content is equal to or less than the upper limit, the cured product has better water slippage.

[0076] When the composition contains a diluent, the concentration of non-volatile components in the composition is adjusted to suit the application method. The lower the concentration of the non-volatile components, the easier it is to form a coating film. The smoothness and uniformity of the cured film (cured product layer) and the adhesion between the substrate and the cured film tend to be good. The higher the concentration of non-volatile components, the more effective it is in suppressing sagging when applying the composition to a substrate. It tends to be good.

[0077] The concentration of non-volatile components in the entire composition is not particularly limited, but is preferably 80% by mass or less. , more preferably 0.1 to 60 mass%, further preferably 1 to 40 mass%, particularly preferably The content is preferably in the range of 1 to 30% by mass, and most preferably in the range of 1 to 20% by mass. This makes it possible to obtain a composition with excellent coatability.

[0078] The composition is sprayed onto a substrate and cured to form a cured film (initial cured film). The sliding angle of 20 μL of water at 23° C. on the surface of the Preferably, the angle is 40° or less, more preferably 30° or less, and most preferably 20° or less. There is no particular restriction on the lower limit of the water sliding angle, and it is, for example, 1° or more. If the water sliding angle of the film is equal to or less than the upper limit, raindrops and snow adhering to the surface will slide off easily. . The sliding angle is measured by changing the inclination angle step by step. As described in the examples. Conventionally, the sliding angle has been measured by continuously changing the inclination angle. The sliding angle is measured by changing the slope angle by 1°. It tends to be larger than the sliding angle measured while continuously changing the inclination angle. The sliding angle can be adjusted by the content and type of polyalkylsiloxane unit in the composition. Specifically, the content of copolymer (A) is increased, or copolymerized in copolymer (A) Increasing the proportion of macromonomer (X) or using longer chain polymers as macromonomer (X) By selecting a material containing alkylsiloxane units, the water sliding angle of the initial cured film becomes tends to be smaller.

[0079] In addition, the sliding angle after durability testing is particularly important in a wide range of applications, and the lower the angle, the better. It is preferable that the change from the initial stage is small. A cured film was formed as described above, and the film was then left to withstand 96 hours of durability at 50°C and 99% RH or higher. After the durability test, 20 μL of the cured film was applied to the surface of the cured film (cured film after the durability test) at 23°C. The sliding angle of water is preferably 60° or less, more preferably 50° or less, and even more preferably 40° or less. The lower limit of the sliding angle of water is preferably 30° or less, particularly preferably 20° or less. There is no particular limitation on the angle, and it is, for example, 1° or more. The change in the water sliding angle of the cured film after the durability test from the initial water sliding angle (after the durability test) The water sliding angle of the cured film (water sliding angle of the initial cured film) is preferably 40° or less, and 3 It is more preferably 0° or less, even more preferably 20° or less, and most preferably 15° or less. Although there is no particular limit, it is preferably 0°. By setting it in this range, it is possible to maintain the initial state over a long period of time. This makes it possible to achieve the same level of performance, making product design easier.

[0080] <Method of producing the composition> The composition comprises a copolymer (A), a component (B), a component (C), an initiator (D), and optionally It can be prepared by mixing a diluent and other ingredients. When the diluent contains water, the water is added during the preparation of the hydrolysis condensation product of the silane compound (b). The silane compound (b) may be added to the composition or may be added during the production of the composition. They may be blended both during preparation of the product and during manufacture of the composition.

[0081] The composition described above comprises copolymer (A), component (B), component (C), and initiator. Since it contains (D), it is possible to form a cured product that is excellent in productivity, appearance, water slippage, and durability.

[0082] This composition is used in parts through which electromagnetic waves pass in sensing components (millimeter wave radar, LiDAR, etc.). Sensing material applications such as surface materials for materials; various lamp lenses (vehicle lighting fixtures) for automobiles and resin glass Hard coating agents for lasing, road signs, traffic lights, camera lenses, 5G-related materials, It can be used for antennas, solar panels, window glass, resin glass, automotive glass, etc. do. Among the uses of the present composition, its use as a sensing element is preferred. For example, Emblems and front grilles located on the front side of vehicles equipped with millimeter wave radars and LiDAR If the surface material of an emblem is made of the cured product of this composition, raindrops or snow will adhere to the outermost surface of the emblem, etc. Even if the vehicle is installed, it will easily slide off, and the electromagnetic waves of millimeter-wave radar and LiDAR will be attenuated and scattered by raindrops and snow. This can reduce the risk of being affected.

[0083] [Cured product] The cured product according to one embodiment of the present invention (hereinafter also referred to as the "present cured product") is a cured product of the present composition. is.

[0084] The present cured product can be obtained by curing the present composition. The curing method may be a method of irradiating the composition with active energy rays or a method of curing the composition by heating. The method of curing using moisture in the air is one of them. From this viewpoint, a method of irradiating the present composition with active energy rays is preferred.

[0085] Examples of active energy rays include ultraviolet rays and electron beams. Ultraviolet light is preferred because it has excellent compatibility. When the present composition is cured by ultraviolet irradiation, the light source may be a high-pressure mercury lamp or an ultra-high-pressure Mercury lamp, metal halide lamp, UV-LED, low-pressure mercury lamp, xenon excimarlan From the viewpoint of productivity, the maximum irradiation intensity is set at wavelengths of 150 to 420 nm. It is preferable to use a light source that exhibits the following. The cumulative irradiation amount of ultraviolet light is 50 to 3000 mJ. / cm 2 is preferred, and 100 to 2000 mJ / cm 2 is more preferred. The active energy rays may be irradiated in an air atmosphere or in an inert gas atmosphere such as nitrogen or argon. Irradiation may be carried out in a gas atmosphere. The time for irradiating the active energy rays is preferably set to 100° C. in relation to the appearance and strength of the cured product. The time is preferably in the range of 1 minute or less, more preferably 30 seconds or less, and even more preferably 15 seconds or less. There is no particular lower limit, but it is, for example, 0.1 seconds. This method allows for faster curing than the thermal curing method, which improves productivity and cost. This is a preferable form considering the cost.

[0086] When the present composition contains a diluent, the diluent is removed before the present composition is irradiated with actinic rays. To remove the fluorine-containing compound, the composition may be subjected to a heat treatment. This heat treatment may be performed using a near-infrared lamp. This can be done by irradiation with light or by circulating hot air. Furthermore, a heat treatment may be carried out after the irradiation of the active energy rays. This can be done by irradiating with a near-infrared lamp, circulating hot air, etc. The cured product obtained by heat treatment after curing by irradiation has a condensation reaction rate that is higher than that of the product obtained by heat treatment. Since the hardness is higher than that of conventional steel sheets, they tend to have better hardness and durability.

[0087] The surface appearance of the cured product (initial cured product) formed as described above is low Hz (%). Preferably, it is about 5% or less, more preferably 3% or less, and even more preferably 2% or less. The haze value is preferably 1% or less, more preferably 0.5% or less, and most preferably 1% or less. If so, good light transmittance is exhibited.

[0088] The hardness of the cured product (initial cured product) formed as described above was measured using commercially available steel wool. (Nippon Steel Wool Co., Ltd., product name: Bonstar #0000) at 125 g / cm 2 of The increase in haze value before and after the scratch resistance test in which a load is applied and the cured film surface of the laminate is rubbed back and forth 11 times The lower the better, 15% or less is preferable, 10% or less is more preferable, and 5% or less is even more preferable. The haze value is preferably 4% or less, particularly preferably 3% or less. If it is less than this, the hardness is good.

[0089] The surface of the hardened material (initial hardened material) formed as described above was exposed to 1 μL of water at 23°C. The higher the antennae, the better. 80° or more is preferable, 85° or more is more preferable, and 90° or more is preferable. 3° or more is more preferred, 95° or more is particularly preferred, and 100° or more is most preferred. There is no particular limit to the lower limit of the contact angle, and it is 0° or more. If so, raindrops and snow that adhere to the surface will easily slide off.

[0090] The surface of the cured product (initial cured product) formed as described above was treated with 20 μL of water at 23°C. The lower the sliding angle, the better. 60° or less is preferable, 50° or less is more preferable, and 4 It is more preferably 0° or less, particularly preferably 30° or less, and most preferably 20° or less. There is no particular limit to the lower limit of the sliding angle of the water, and it is 0° or more. If so, raindrops and snow that adhere to the surface will easily slide off.

[0091] In addition, the water sliding angle after durability testing is particularly important for a wide range of applications, and the lower the better. It is preferable that the change from the initial stage is small. A cured product was formed as described above, and the product was then left to withstand 96 hours of durability at 50°C and 99% RH or higher. After the durability test, 20 μL of the cured product was applied to the surface of the cured product (cured product after the durability test) at 23°C. The sliding angle of water is preferably 60° or less, more preferably 50° or less, and even more preferably 40° or less. The lower limit of the sliding angle of water is preferably 30° or less, particularly preferably 20° or less. There is no particular limitation on the angle, and it is, for example, 1° or more. The change in the water sliding angle of the hardened material after the durability test from the initial water sliding angle (after the durability test) The sliding angle of water on the hardened product minus the sliding angle of water on the initial hardened product is preferably 40° or less, and 3 It is more preferably 0° or less, even more preferably 20° or less, and most preferably 15° or less. Although there is no particular limit, the angle is preferably −40°. This allows the product to achieve performance on par with that of the previous model, making product design easier.

[0092] The cured product described above comprises copolymer (A), component (B), component (C), and initiator Since it is a cured product of a composition containing (D), it has excellent productivity, appearance, water slippage and durability.

[0093] This cured product is used in areas where electromagnetic waves from sensing components (millimeter wave radar, LiDAR, etc.) pass through. Sensing material applications such as surface materials for materials; various lamp lenses (vehicle lighting fixtures) for automobiles and resin glass Hard coating for lasing, road signs, traffic lights, camera lenses, 5G related materials, Can be used for antennas, solar panels, window glass, resin glass, automotive glass, etc. Among the above applications, the present cured product is preferably used as a sensing element.

[0094] [Laminate] The laminate according to one embodiment of the present invention (hereinafter also referred to as "the present laminate") comprises a substrate and the above-described and a layer made of a cured product (hereinafter also referred to as "cured product layer"). The cured product layer is preferably located as the outermost layer of the present laminate. A primer layer may be provided between the substrate and the cured product layer.

[0095] The substrates include glass substrates, zinc-plated steel sheets, zinc alloy-plated steel sheets, stainless steel sheets, Metal substrates such as tin-plated steel sheets; polymethyl methacrylate resin, polycarbonate resin, poly Ester resin, polystyrene resin, ABS resin, AS resin, polyamide resin, polyaryl Polyurethane resins such as thermoplastic polyurethane elastomer (TPU), polyvinyl alcohol Nyl resin, triacetyl cellulose, polymethacrylimide resin and polyallyl diglycol Examples of the resin substrate include resin substrates and resin films made of olefin carbonate resins. As for the fat, considering that the laminate will be used for various components, it is necessary to consider transparency and mechanical strength. Glass, polycarbonate resin, polyester resin, triacetyl cellulose, poly Urethane resin or polyvinyl resin is preferred, polycarbonate resin, polyurethane resin The resin substrate may contain, in addition to the resin, an ultraviolet absorber, a light stabilizer, Plasticizers, antistatic agents, flame retardants, reinforcing materials, fillers, colorants, lubricants, foaming agents, lubricants, hardening catalysts The solvent may contain additives such as a solvent. If necessary, a primer layer may be present on the substrate to improve adhesion, etc. It is also possible to have a functional layer such as an adhesive layer on the side opposite to the side where the cured material layer of the substrate is present. . The refractive index of the substrate and / or primer layer is preferably 1.40 or more and 1.75 or less. It is preferable that the ratio is 1.40 or more and 1.73 or less, and more preferable that the ratio is 1.40 or more and 1.70 or less. It is more preferable that the substrate and / or primer have a single layer structure or a two-layer structure. The above multi-layer structure may also be used.

[0096] The thickness of the cured product layer is preferably 10 nm to 5 μm, more preferably 50 nm to 5 μm. 100 nm to 5 μm is more preferable, 500 nm to 5 μm is particularly preferable, and 1 μm to When the thickness of the cured material layer is equal to or greater than the above lower limit, the interference pattern of the cured material layer is If the cured product has a viscosity of 1000 ppm or less, cracks are unlikely to occur in the cured product layer. There is a tendency for

[0097] <Method of manufacturing laminate> The present laminate can be produced, for example, by applying the present composition to a substrate and curing it. Before applying the composition, the substrate may be coated with a primer.

[0098] Coating methods include brush coating, gravure coating, die coating, and bar coating. , spray coating method, flow coating method, dip coating method, spin coating method and curtain Known methods such as coating methods can be used. The curing method may be the same as that described above, and may be a method of irradiating the composition with active energy rays. The method is preferred.

[0099] When the composition contains a diluent, after applying the composition to a substrate, the composition is heated to a temperature of 1000°C. Before the irradiation with γ-rays, a heat treatment for drying may be carried out to remove the diluent. Heat treatment for drying is carried out by irradiating with a near-infrared lamp or circulating hot air. The cured layer obtained by irradiating the active energy ray after the heat treatment can be cured. Since the diluent is less likely to remain inside the material layer, it can be stored outdoors for a long period of time compared to products that have not been heat-treated. The drying conditions are determined based on the appearance and adhesion of the cured layer. The temperature is preferably 40 to 90°C, more preferably 50 to 70°C, and the drying time is The time is preferably 60 to 180 seconds, and more preferably 90 to 150 seconds.

[0100] After the composition is irradiated with active energy rays, it may be subjected to a heat treatment. The activation energy can be applied by irradiation with a near-infrared lamp, by circulating hot air, or the like. The cured layer obtained by heat treatment after curing by irradiation with radiation has a condensation reaction rate that is proportional to the rate of the heat treatment. Since the hardness is higher than that of untreated materials, they tend to have better hardness and durability.

[0101] The surface of the cured layer (initial cured layer) formed as described above was treated with 20 μL of The lower the water sliding angle, the better, preferably 60° or less, and more preferably 50° or less. , 40° or less is more preferable, 30° or less is particularly preferable, and 20° or less is most preferable. There is no particular limit to the lower limit of the water sliding angle, and it is 0° or more. If it is below this level, raindrops and snow adhering to the surface will easily slide off.

[0102] In addition, the water sliding angle after durability testing is particularly important for a wide range of applications, and the lower the better. It is preferable that the change from the initial stage is small. A cured layer was formed as described above, and the layer was then subjected to 96-hour resistance testing at 50°C and 99% RH or higher. After the durability test, the surface of the cured material layer (cured material layer after the durability test) was The sliding angle of μL of water is preferably 60° or less, more preferably 50° or less, and most preferably 40° or less. The sliding angle of water is more preferably 30° or less, particularly preferably 20° or less. There is no particular restriction on the lower limit, and it is, for example, 1° or more. The change in the water sliding angle of the hardened layer after the durability test from the initial water sliding angle of the hardened layer (durability The sliding angle of water on the hardened layer after the durability test - the initial sliding angle of water on the hardened layer) is 40° or less. Preferably, the angle is 30° or less, more preferably 20° or less, and even more preferably 15° or less. Most preferred. There is no particular lower limit, but it is preferably 0°. By setting the range within this value, the performance equivalent to the initial state can be exhibited over a long period of time, and it becomes easy to design products. .

[0103] In the laminate described above, since the cured product layer is composed of a cured product of a composition containing copolymer (A), component (B), component ( C), and initiator (D), it is excellent in productivity, appearance, water repellency, and durability.

[0104] This laminate can be used for sensing member applications such as electromagnetic wave passing parts of sensing members (millimeter wave radar, LiDAR, etc.); various lamp lenses (vehicle lamps) of automobiles, resin glazing, road signs, traffic signal lights, camera lenses, 5G related members, antennas, solar panels, window glass, resin glass, automotive glass, etc. Among the applications of this laminate, sensing member applications are particularly suitable.

Examples

[0105] Examples and comparative examples are given below to explain the present invention in more detail, but the present invention is not limited to these. "Parts" in the description represents "parts by mass". The measurements and evaluations were performed by the following methods.

[0106] [Measurement and evaluation methods] <Measurement of Mw> The Mw of the copolymer and the partially hydrolyzed condensate of the silane compound produced in this example was measured by gel permeation chromatography (GPC) under the following conditions. Equipment: "e2695" manufactured by Waters, Column: "TSKgel Super H3000 + H4000 + H6000" manufactured by Tosoh ",​ Detector: Differential refractive index detector (RI detector / built-in), Solvent: tetrahydrofuran, Temperature: 40℃, Flow rate: 0.5mL / min, Injection volume: 10μL, Concentration: 0.2% by mass, Calibration sample: monodisperse polystyrene, Calibration method: Polystyrene equivalent.

[0107] <Appearance> The appearance of the evaluation sample was evaluated visually, and the criteria for evaluation were as follows: (Judgment criteria) A: No abnormalities such as whitening, cracks, or blisters are observed, and a transparent, smooth coating film has been formed. B: Slight bleaching is observed. C: Abnormalities such as whitening, cracks, and swelling are observed.

[0108] <Interference fringe pattern> The interference fringe patterns of the evaluation samples were visually evaluated under fluorescent lighting. The evaluation criteria were as follows: is. (Judgment criteria) A: No interference pattern is observed B: A slight interference pattern is visible C: Interference patterns are visible D: Interference patterns can be seen even under LED lamps

[0109] <hz> The cured film surface of the evaluation sample was subjected to JIS K713 in an atmosphere of 23°C and 55% RH. The haze value was measured in accordance with ISO 6:2000.

[0110] <Hardness> The hardened film surface of the evaluation sample was subjected to a test using a commercially available steel wire under an atmosphere of 23°C and 55% RH. Steel wool (Nippon Steel Wool Co., Ltd., product name: Bonstar #0000) at 125 g / cm 2 A scratch resistance test was then carried out in which the surface of the cured film of the laminate was rubbed back and forth 11 times under a load of 1000 kJ / cm. The haze value was measured in accordance with JIS K7136:2000. The increase in haze value before and after the measurement was calculated.

[0111] <Contact angle> The cured film surface of the evaluation sample was placed on the sample holder under an environment of 23°C and 50% RH. The cured film surface of the evaluation sample was placed horizontally on the surface. A contact angle meter (DM-500, Kyowa Interface Science) was used to measure the cured film surface. A 1 μL droplet of distilled water was dropped onto the surface using a contact lens (manufactured by the manufacturer), and the contact angle was measured after 1 second.

[0112] <Sliding angle> The cured film surface of the evaluation sample was measured by the sliding method, and the substrate was tilted intermittently at 23°C. The sliding angle of 20 μL of water was measured at 23° C. and 50% RH to evaluate the water sliding property. In this environment, a contact angle meter was applied to the cured film surface of the evaluation sample placed horizontally on the sample fixing table. Using a DM-500 (Kyowa Interface Science), a 20 μL droplet of distilled water was dropped onto the sample, and then the sample was evaluated. The sample was tilted by 1° increments, and the tilt angle at which the droplet began to slide was taken as the sliding angle. The criteria for water sliding properties are as follows: (Judgment criteria) A: The sliding angle is greater than 1° and less than 40°. B: The sliding angle is greater than 41° and less than 60°. C: Water droplets do not slide down even when the inclination angle is over 60° or 90°.

[0113] <Durability> The cured film of the evaluation sample was subjected to 100 After the test, the appearance and sliding angle of the coating film were evaluated.

[0114] [Abbreviation] The abbreviations used below have the following meanings: KBM-503: Shin-Etsu Chemical Co., Ltd. "KBM-503" (3-methacryloxypropyl Trimethoxysilane, 100% non-volatile. FM-0725: JNC Corporation's "Silaplane FM-0725" (with metal on one end) Polydimethylsiloxane with acryloyl group, Mn10,000, 100% non-volatile components ). Copolymer (A-1): the copolymer (FM-0725:KBM50) obtained in Synthesis Example 1 described later 3=50:50 (mass ratio), Mw49,000). Ingredient (B-1): Colcoat's "HAS-10" (hydrolyzed solution of ethyl silicate) ) (non-volatile content 10%) Ingredient (C1-1): Titaniasol "NS408" manufactured by Teika Co., Ltd., refractive index 1.8 Ingredient (C2-1): Matsumoto Fine's "Orgatics PC-200" Refractive Index 1.81 Ingredient (C2-2): Matsumoto Fine's "Orgatics TC-100" Refractive Index 1.67 Ingredient (C3-1): "Ogusol SC-001" manufactured by Osaka Gas Chemicals Co., Ltd. Refractive index 1. 56 Component (C3-2): Shin-Etsu Chemical Co., Ltd. "KR-510" refractive index 1.51 Component (D): Shin-Etsu Chemical Co., Ltd. "KC-89S" refractive index 1.39 Photoacid generator: San-Apro "CPI-200K" (p-phenylthiophenyldiphenyl) Fluorosulfonium hexafluorophosphate, 50% non-volatiles. ·IPA: 2-propanol. · PGM: Propylene glycol monomethyl ether. MIBK: "MIBK" (methyl isobutyl ketone) manufactured by KH Neochem Co., Ltd. AMBN: "AMBN" (2,2'-azobis(2-methylbutyronitrile)) manufactured by Otsuka Chemical Co., Ltd.

[0115] [Method for preparing polymer] Preparation methods of copolymers and partial hydrolysis condensates of silane compounds used in the examples and comparative examples The copolymer (A-1) corresponds to the copolymer (A). do.

[0116] <Synthesis Example 1: Preparation of Copolymer (A-1)> 1000mL 5-neck separator equipped with a stirrer, dropping funnel, cooling condenser, and thermometer In a flask, add 13.0 g of KBM-503, 50.0 g of FM-0725, and MIBK. 93.4g of KBM-503 and FM-0 1.0 g of 725, 140.0 g of MIBK, and 0.25 g of AMBN were then added. The flask was placed in an oil bath, and stirring was started under a nitrogen atmosphere until the internal temperature reached 90°C. 30 minutes after the internal temperature reached 90°C, the monomer mixture was added from the dropping funnel. After dripping for 4 hours and holding for 30 minutes, 0.35g of AMBN was added. 0.35 g of AMBN was further added to the mixture, and the mixture was allowed to react for 2 hours and then cooled. The product was a polymer with a weight average molecular weight (Mw) of 73,800 and a non-volatile content of 30%.

[0117] [Example 1] <Preparation of Composition> 7 parts of copolymer (A-1), 12 parts of component (B-1), and 1.7 parts of compound (C1-1). 1 part of acrylic acid, 10 parts of IPA, 10 parts of PGM, and photoacid generator CPI-200K (San-Apro) A composition was prepared by mixing 0.04 parts of a cellulose acetate copolymer (manufactured by Epson Corporation).

[0118] <Preparation of evaluation samples> The obtained composition was applied to a 3 mm thick polycarbonate resin plate (PC plate) (Mitsubishi Engineering The surface of the product is made by Ring Plastics Co., Ltd., product name: "IUPILON ML-300" A layer of the coating is formed, and the compound is sprayed on top of it so that the thickness after drying is 2 μm. After that, the coating was dried (the solvent was evaporated) for 120 seconds in a hot air dryer preheated to 60°C. After drying, the coating was then irradiated with a high-pressure mercury lamp (eye graphite) in an air atmosphere. 1000mJ / cm2 2 (Wavelength 340~380nm The cumulative irradiation amount was measured using a UV actinometer UV-351 (manufactured by Oak Manufacturing Co., Ltd.). The coating was cured by irradiating it with ultraviolet light, and the cured film of the composition was laminated on the PC board to form an evaluation sample. obtained.

[0119] <Evaluation> The curability of the obtained composition was evaluated. The appearance and water slippage were evaluated before and after the durability test. are shown in Table 1.

[0120] [Examples 2 to 6, Comparative Examples 1 to 5] The composition was the same as in Example 1, except that the types and amounts (parts) of the components added to the composition were as shown in Table 1. In the same manner, compositions were prepared and evaluation samples were produced. The results are shown in Table 1. However, in Comparative Example 2, the cured film could not be formed, so the evaluation sample was No samples were prepared or evaluated. The primer layer was formed as follows. Caprolactone modified dipentaerythritol hexaacrylate (DPHA) (Japan A resin mixture of 22 parts of Nippon Kayaku's "DPCA-20" and 16 parts of urethane acrylate 0.9 parts of benzophenone as a photopolymerization initiator and Tinuvin 400 as an ultraviolet absorber (BASF) 3 parts, Tinuvin 123 (BASF) 0.15 parts as a light stabilizer After adding, the solid content was adjusted to 32% by mass with propylene glycol monomethyl ether. The resulting mixture was diluted to prepare an ultraviolet-curable primer. The obtained primer was applied to the surface of a 3 mm thick polycarbonate plate, and the thickness after drying was 1 After spray coating to a thickness of 3 μm, it was dried in a hot air dryer preheated to 70°C for 120 seconds. The coating was dried (the solvent was evaporated) by heating for a short time. In the room, a high-pressure mercury lamp (made by Eye Graphic, USX5-0902) was used to generate 2000mJ / cm 2 (The cumulative irradiation amount at wavelengths of 340 to 380 nm was measured using a UV actinometer UV-350 ( The coating is cured by irradiating it with ultraviolet light (measured using a UV lamp manufactured by WARK Manufacturing Co., Ltd.) to form a primer layer. Thus, a PC board with a primer layer was obtained.

[0121] The urethane acrylate used in the primer was prepared as follows. A flask equipped with a dripping funnel with heat retention, a reflux condenser, a stirring blade and a temperature sensor In the container, dicyclohexylmethane diisocyanate 530g (2mol), dilauric acid 300 ppm of di-n-butyltin was added and heated to 40°C. Polycarbonate diol (trade name: Kuraray Polyol C-770, manufactured by Kuraray Co., Ltd.) 650 g (1 mol) of 800 g of ethylenediaminetetraacetic acid (weight average molecular weight 800) was added dropwise over 4 hours. After stirring at 0°C for 2 hours, the temperature was raised to 70°C over 1 hour. 232 g (2 mol) of diethyl acrylate (HEA) was added dropwise over 2 hours, and then 2 The resulting product was 75% non-volatile and had a molecular weight of 1.04. It was a polymer of 1500.

[0122] [Table 1]

[0123] In Table 1, the content of each component includes the amount of volatile matter. Even when the tilt angle was changed up to 90°, the droplet did not move on the cured film surface, and the sliding angle could not be measured. "N / A" means that measurement was not possible due to the influence of the surface condition of the coating film, etc. means.

[0124] As shown in Table 1, the compositions of Examples 1 to 6 were excellent in appearance and interference fringe pattern. The cured product had excellent sliding properties and appearance both initially and after the durability test. On the other hand, the composition of Comparative Example 1 does not contain a copolymer that imparts slipperiness, and the surface of the cured film is hydrophilic. Therefore, it was impossible to judge the water sliding property. In addition, cracks occurred on the surface of the coating film. The composition of Comparative Example 2 did not contain component (B), and therefore had low curability and remained uncured. The composition of Comparative Example 3 did not contain component (C), and therefore had low interference fringes. The composition of Comparative Example 4 did not contain component (C) and therefore had low interference fringes. After long-term testing, cracks occurred. The composition of Comparative Example 5 did not contain component (C) and had a thin film thickness, so interference fringes were very low. there were.< / hz>

Claims

1. A copolymer (A) containing a polyalkylsiloxane unit and at least one copolymer represented by the following formula ( b) or a component (B) consisting of a silane compound represented by the formula (b) or a partial hydrolysis condensate thereof, A compound (A) and a component (C) which is different from the component (B) and has a refractive index of 1.45 or more. A composition comprising: R ４ ４－ｎ Si(OR ５ ) ｎ ・・・(b) However, R ４ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group; R ５ Haa represents an alkyl group or a phenyl group, n represents an integer of 2 to 4, and n OR ５ are different from each other When n is 2, (4-n) R ４ may be different from each other.

2. The copolymer (A) contains a silicone macromolecule containing the polyalkylsiloxane unit. The composition according to claim 1, comprising a structural unit based on a monomer (X).

3. The copolymer (A) is based on a monomer (Y) having a group represented by the following formula (1): The composition of claim 2 comprising a unit. -R １ -M(R ２ ) ｒ (OR ３ ) ｍ－ｒ ・・・(1) Here, M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta. S, R １ represents a hydrocarbon group having 1 to 5 carbon atoms, and R ２ represents an alkyl group having 1 to 5 carbon atoms, R represents an alkenyl group having 2 to 5 carbon atoms or an aryl group; ３ represents an alkyl group having 1 to 5 carbon atoms, represents an alkenyl group, an aryl group, or an acyl group having a number of 2 to 5, and m is an integer of 3 to 4 corresponding to M; represents a number, r represents an integer of 0 to 3, and when r is 2 or more, r R ２ are different from each other If m-r is 2 or more, (m-r) ORs may be used. ３ may be different from each other.

4. The silicone macromonomer is preferably 0.1 to 0.5 wt. % of the total weight of all structural units constituting the copolymer (A). The sum of the proportion of structural units based on the monomer (X) and the proportion of structural units based on the monomer (Y) The composition according to claim 2 or 3, wherein the amount of the hydroxybenzoates is 55% by mass or more.

5. The component (C) contains Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr in the molecule.

2. The composition according to claim 1, comprising at least one selected from the group consisting of:

6. The silicone macromonomer is preferably 0.1 to 0.5 wt. % of the total weight of all structural units constituting the copolymer (A). The proportion of structural units based on the monomer (X) is 15 to 60 mass %, and the proportion of structural units based on the monomer (Y) is 5. The composition according to claim 4, wherein the proportion of the structural unit is 40 to 85% by mass.

7. 2. The method according to claim 1, wherein the component (B) is a partial hydrolysis condensate of a tetraalkoxysilane. The composition described above.

8. The component (B) is a partial hydrolysis condensate of at least one of the silane compounds. A partial hydrolysis condensate having a weight average molecular weight of 300 to 3,000 is dehydrated in the presence of a catalyst.

2. The composition according to claim 1, which is obtained by a decondensation reaction.

9. The composition of claim 1, further comprising an initiator (D).

10. The initiator (D) is at least one selected from the group consisting of a photoacid generator and a photobase generator. The composition of claim 9 comprising one of:

11. A cured product of the composition according to any one of claims 1 to 3 and 5 to 10.

12. A laminate comprising a substrate and a layer comprising the cured product according to claim 11.

13. A copolymer (A) containing a polyalkylsiloxane unit and at least one copolymer represented by the following formula ( b) or a component (B) consisting of a silane compound represented by the formula (b) or a partial hydrolysis condensate thereof, A compound (A) and a component (C) which is different from the component (B) and has a refractive index of 1.45 or more. A method for producing a cured product, comprising irradiating a composition containing the compound with active energy rays to cure the composition. R ４ ４－ｎ Si(OR ５ ) ｎ ・・・(b) However, R ４ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group; R ５ Haa represents an alkyl group or a phenyl group, n represents an integer of 2 to 4, and n OR ５ are different from each other When n is 2, (4-n) R ４ may be different from each other.

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