WO2006001354A1

WO2006001354A1 - Layered product

Info

Publication number: WO2006001354A1
Application number: PCT/JP2005/011575
Authority: WO
Inventors: Katsuhiro Mori; Noriaki Tahara
Original assignee: Tokuyama Corporation
Priority date: 2004-06-25
Filing date: 2005-06-17
Publication date: 2006-01-05
Also published as: JP2006008869A

Abstract

A layered product comprising a resin base and formed on the surface thereof a cured layer obtained from a coating composition, characterized in that the coating composition comprises (A) an antimony pentaoxide sol, (B) a silicon compound represented by the following general formula (1): R1R2aSi(OR3)3-a (1) (wherein R1 is C6-30 alkyl or C6-30 alkenyl; R2 is C1-5 alkyl, C1-5 cycloalkyl, C1-5 alkenyl, or aryl; R3 is hydrogen or C1-4 alkyl; and a is an integer of 0-2), (C) an epoxidized silicon compound, (D) an organic solvent, and (E) an acetylacetonato complex and that the resin base is selected among ones made of (meth)acrylic resins, allyl resins, and epoxy resins. This layered product is extremely useful as a plastic lens. The coating composition is less affected by water. Even when the coating composition is applied in a high-humidity atmosphere or after having absorbed water, it gives a coating film (cured layer) which suffers no blushing and has excellent thermal shock resistance. The layered product can retain the satisfactory cured layer.

Description

Specification Laminate Technical Field>

The present invention relates to a laminate in which a cured product layer of a coating composition is formed on the surface of a resin substrate made of a specific synthetic resin, and the cured product layer has adhesion, scratch resistance, and chemical resistance. The present invention relates to a laminate having excellent durability such as heat resistance, hot water resistance, heat resistance, and weather resistance, and in which interference fringes are hardly generated between a resin substrate and a cured product layer.

Synthetic resin lenses have characteristics that are not found in glass lenses, such as lightness, safety, ease of processing, and fashionability, and have been rapidly spreading in recent years. As such synthetic resin lenses, those made of diethylene glycol bisvalyl carbonate resin have been widely used. However, the refractive index is 1.50 or more, which is lower than that of glass, and the outer periphery of the lens is thick. There are drawbacks. For this reason, recently, the thickness of the lens has been reduced by increasing the refractive index of the synthetic resin lens.

-On the other hand, since synthetic resin lenses have the disadvantage of being easily scratched, generally, a silicone-based coating film is applied to the surface of the synthetic resin lens. This silicone-based coating film is obtained by, for example, applying a coating composition mainly composed of silica fine particles, a polymerizable organic silane compound, a polymerization catalyst, an acid aqueous solution, and a solvent to the surface of a synthetic resin lens and heating. Thus, the composition is cured and the solvent is volatilized (see Japanese Patent Publication No. SHO 5-7-27 35).

However, when a high refractive index synthetic resin lens having a refractive index of 1.54 or more is used, when the coating film is formed using the coating composition as described above, the refractive index between the synthetic resin lens and the coating film is reduced. There is a problem that interference fringes are generated due to the difference in the rate, resulting in poor appearance, and improvements are required.

In order to solve this problem, various coating compositions for forming a hard coat layer having a high refractive index have been proposed. For example, silica fine particles blended in the coating composition described above are used as a refractive index. Coated with various complex metal oxides In particular, the following coating compositions have been proposed.

(1) Coating composition in which fine particles of metal oxide or composite oxide containing at least one metal selected from Al, Sn, Sb, Ta or Ce are used in place of silli force fine particles (Japanese Patent Laid-Open No. 8-31 1 408)

(2) Coating composition using fine particles of complex oxide containing Sb, Si or AI instead of silica fine particles (Japanese Patent Publication No. 8-22997)

(3) A metal oxide or composite metal oxide fine particle containing at least one metal selected from Ti, Sb, Ce, Sn, W or Fe is used instead of silica fine particles. Iting composition (Patent No. 28821 8 1)

(4) Coating composition in which fine particles of composite metal oxide containing Ti and Sb are used instead of silica fine particles (Japanese Patent Laid-Open No. 2002-363442) However, the oxide fine particles of (1) are used The coating composition must be used in combination with an epoxy compound. Therefore, although the sensitivity to moisture is low, the film (cured product of the coating composition) has a reduced scratch property (especially with time). There is a problem that In addition, the coating compositions (2) to (4) have a problem that although the scratch resistance is high, the film is hard and the heat shock resistance of the film is low. Further, in the coating compositions of (1), (2) and (4), when Sb oxide or Ti oxide is contained, the film is whitened (white turbid) due to high sensitivity to moisture. When the film is held for a long time under light irradiation and the adhesion between the film and the synthetic resin lens is lowered, the problem arises. Hereinafter, a coating composition using a metal oxide having a refractive index higher than that of silica fine particles alone is referred to as a high refractive index coating composition.

Therefore, the present invention is a laminate in which a cured product layer of a coating composition is formed on the surface of a resin base material such as a synthetic resin lens, and the cured product layer (coat film) is whitened by the influence of moisture. Is effectively suppressed, and even when heat shock is applied, the cured product layer does not crack, and furthermore, it has excellent weather resistance, and even when kept under light irradiation for a long time, the cured product layer And the resin substrate are maintained at a high level as in the initial stage. An object of the present invention is to provide a laminated body. The present inventors have intensively studied to solve the above problems. As a result, an antimony pentoxide sol, a silicon compound having a specific structure or a hydrolyzate thereof, an epoxy group-containing silicon compound or a hydrolyzate thereof, an organic solvent and a coating composition containing an acetylylacetonate complex are used. When the cured product layer of the coating composition is formed on the surface of the substrate made of a specific synthetic resin, whitening of the cured product layer due to the influence of moisture is effectively suppressed (sensitivity to moisture) is transparent. To obtain a laminate excellent in heat resistance, adhesion, scratch resistance, weather resistance, and heat shock resistance (especially with respect to moisture sensitivity and heat shock resistance, it is greatly improved compared to conventional technologies) This has been found and the present invention has been completed.

According to the present invention, in the laminate in which the cured product layer of the coating composition is formed on the surface of the resin substrate,

The coating composition contains the following components (A) to (E):

(A) antimony pentoxide sol;

(B) The following general formula (1) or the following general formula (2):

R ¹ R ² _a S i (OR ³ ) 3-a… (1)

In the formula, R ¹ is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms,

R ² is an alkyl group having 5 or less carbon atoms, a cycloalkyl group having 5 or less carbon atoms, an alkenyl group having 5 or less carbon atoms, or an aryl group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A is an integer from 0 to 2,

X [S i R ⁵ _b (OR ⁶ ) ₃ — _b ] 2… (2)

In the formula, R ⁵ is an alkyl group having 5 or less carbon atoms, a cycloalkyl group having 5 or less carbon atoms, an alkenyl group having 5 or less carbon atoms, or an aryl group, R ⁶ is a hydrogen atom or an alkyl having 1 to 4 carbon atoms. Group,

X is a divalent organic residue or oxygen atom,

b is an integer from 0 to 2,

And at least selected from the group consisting of these hydrolysates One kind of gay compound;

(C) an epoxy group-containing silicon compound or hydrolyzate;

(D) an organic solvent; and

(E) Acetylasetonate complex;

There is provided a laminate in which the resin base material is made of (meth) acrylic resin, aryl resin or epoxy resin.

The laminate of the present invention is a substrate in which the hardened layer of the coating composition containing the above components (A) to (E) is made of a specific resin (that is, (meth) acrylic resin, aryl resin or epoxy resin). Since it is formed on the surface, it has the characteristics of low sensitivity to moisture and excellent weather resistance. For example, even when the coating composition is applied under high humidity or when the coating composition is applied to the surface of the resin substrate in a water-absorbed state, a transparent cured product layer without cloudiness can be obtained. In addition, as shown in the examples described later, even after a long time (20 hours) deterioration promotion test, the adhesion between the cured product layer and the resin base material does not decrease, and is high. Adhesion is maintained. Thus, the laminate of the present invention is extremely excellent in terms of both moisture sensitivity and weather resistance.

For example, even if a specific resin substrate as described above is used, when a cured product layer is formed using a coating composition of another composition, the sensitivity to moisture is low, and curing due to the influence of moisture Although the self-turbidity of the physical layer does not occur, the weather resistance is poor, and the adhesion between the cured product layer and the resin base material is greatly reduced after the deterioration acceleration test. Further, even when a coating composition containing the components (A) to (E) is used, when a resin base material other than the specific resin described above, for example, a polycarbonate resin base material is used, the resin base material itself is used. It will cause cloudiness. (Probably, this is because the surface of the polycarbonate resin substrate is dissolved by the contact between the epoxy group-containing silicon compound (C) component or its hydrolyzate and the polycarbonate resin substrate.) In addition, solvent resistance, scratch resistance, and adhesion are insufficient, making it unsuitable for use as a plastic lens.

In the present invention, the presence or absence of cloudiness (or whitening) of the laminate is visually observed by irradiating the laminate with light along the layer direction of the cured product layer. When light is irradiated in a direction perpendicular to the layer direction of the cured product layer, the cloudy layer is very thin. This is because the light path of the light passing through the cloudy layer is extremely short, and the cloudiness is hardly observable with the sun.

Thus, the laminate of the present invention is excellent in both moisture sensitivity and weather resistance, and excellent properties such as transparency, adhesion, and scratch resistance are maintained over a long period of time. As a lens, its industrial value is high.

[Coating composition]

The coating composition used for producing the laminate of the present invention contains the following components (A) to (E).

(A) component

The component (A) in the coating composition used in the present invention is an antimony pentoxide sol. This component is usually used in a colloidal dispersion with water, alcohol or other organic solvent as a dispersion medium.

As the dispersion medium of the antimony pentoxide sol, alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, t-butyl alcohol, and n-butyl alcohol are preferable, and methanol and 2-propanol are particularly preferable.

In addition, the ratio of the antimony pentoxide sol in the dispersion medium at this time increases the refractive index of the cured layer (coat film) of the coating composition, so that the antimony pentoxide sol is not contained in the dispersion medium. In order to prevent stabilization, 10 to 50% by mass is preferable.

Further, in order to increase the dispersion stability of the antimony pentoxide sol in the dispersion medium of the antimony pentoxide sol, and further in the coating composition, the surface of the antimony pentoxide sol is made of an amine compound and a phosphonic acid or carboxylic acid. It is also possible to use the processed one. Examples of such amine compounds include ethylamine, 卜 ethylamine, isopropylamine, n-propylamine, dimethylamine, jetylamine, dipropylamine, alkylpropylamine such as dipropylamine, and alkylammonium; aralkylamine such as benzylamine; morpholine, piperidine Alicyclic amines such as monoethanolamine, diethanolamine, trietanoh Alkanolamines such as luamine and isopropanolamine; Examples of the carboxylic acid include acetic acid, oxalic acid, lactic acid, malic acid, citrate, tartaric acid, salicylic acid, glycolic acid, benzoic acid, phthalic acid, malonic acid, and mandelic acid. These amine compounds and carboxylic acids can be added in an amount of about 0.01 to 5% by mass relative to the antimony pentoxide sol.

The particle diameter of the antimony pentoxide sol to be used is not particularly limited, but the average particle diameter is preferably 1 to 300 nm in order not to impair the transparency of the resulting cured product layer.

Also, when antimony pentoxide sol is used dispersed in a dispersion medium, it is possible to prevent a decrease in the transmittance of the dispersion due to a decrease in the dispersibility of the antimony pentoxide sol, In order to prevent a decrease in storage stability, the pH of the dispersion is preferably 4.0 to 9.5.

The blending amount of the antimony pentoxide sol in the coating composition used in the present invention may be appropriately determined according to the desired physical properties depending on the purpose of the finally obtained cured product layer (coat film), which will be described later (B). The total amount of the component and the (C) component is preferably 25 to 2500 parts by mass, more preferably 40 to 200 parts by mass, with respect to 100 parts by mass. When the blending amount of the antimony pentoxide sol based on the above standard is less than 25 parts by mass, the cured product layer is scratch-resistant, or adheres to the inorganic vapor deposition film formed on the cured product layer as necessary, and is cured. The refractive index of the physical layer becomes insufficient, and if it exceeds 250 parts by mass, the cured product layer tends to crack.

(B) component

As the component (B) in the coating composition, the following general formula (1):

R ¹ R ² _a S i (OR ³ ). - _a ... (1)

R ² is an alkyl group having 5 or less carbon atoms, a cycloalkyl group having 5 or less carbon atoms, an alkenyl group having 5 or less carbon atoms, or an aryl group,

R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a is an integer from 0 to 2,

The Ge compound represented by the following general formula (2):

X [S i R ⁵ _b (OR ⁶ ) ₃ 1 _b ] 2… (2)

In the formula, R ⁵ is an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, or an aryl group,

R ⁶ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

X is a divalent organic residue or oxygen atom,

b is an integer from 0 to 2,

And at least one kind of silicon compound selected from the group consisting of hydrolysates thereof and the following compounds:

The group R ¹ in the general formula (′ 1) is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms. Specifically, as the alkyl group, a hexyl group, heptyl Group, octyl group, decyl group, dodecyl group, octadecyl group and the like, and examples of the alkenyl group include octenyl group, docosenyl group and the like. These alkyl groups and alkenyl groups may have a substituent. Examples of such substituent include halogen atoms such as chlorine, bromine and fluorine; acryloyloxy group, methacryloyloxy group , Aryl group, aryloxy group, aldehyde group, amino group and the like. In addition, when these alkenyl groups and alkenyl groups have a substituent, the number of carbon atoms must be within the range (6 to 30) including the substituent (illustrated below). The same applies to the groups that do).

The group R ² in the general formula (1) is an alkyl group having 5 or less carbon atoms, a cycloalkyl group having 5 or less carbon atoms, an alkenyl group having 5 or less carbon atoms, or an aryl group. Specifically, alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a heptyl group; a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group; a propenyl group, 1 An alkenyl group such as a butenyl group; an aryl group such as a benzyl group or a naphthyl group; In addition, these groups may have a substituent, and examples thereof include halogenated alkyl groups such as chloromethyl group, bromoethyl group, and dichloropropyl group.

The group R ³ in the general formula (1) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isop A mouth pill group, a butyl group, etc. can be mentioned, These alkyl groups may also have the substituent mentioned above.

Furthermore, a in the general formula (1) is an integer of 0 to 2, and is preferably 0 or 1 from the viewpoint of obtaining a highly hard film (cured product layer).

Specific examples of the silicon compound represented by the above general formula (1) include n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexylmethyl dimethoxysilane, n-octyltrimethoxysilane, n-octyl. Trieoxysilane, n-octylmethyldimethoxysilane, n-octyldimethylmethoxysilane, n-octylmethyljetoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, n-hexadecyltrimethoxysilane, n-hexadecyltriethoxysilane, n-year-old decadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecylmethyldimethoxysilane, n-year-old Decylmethyldi卜 xysilane, n-year-old decadecyldimethylmethoxysilane, isooctyltrimethoxysilane, 7-octenyltrimethoxysilane, 10-undecenyltrimethoxysilane, aralkyloxydecyltrimethoxysilane, dococenyltriethoxysilane And triethoxysilylundecanal. Further, b in the general formula (2) is an integer of 0 to 2, and is preferably 0 or 1 from the viewpoint of obtaining a high-hardness film (cured product layer).

The group R ⁵ in the general formula (2) is an alkyl group, a cycloalkyl group, an alkenyl group (all having 5 or less carbon atoms), or an aryl group, and the group R ² in the general formula (1) It is synonymous.

The group R ⁶ in the general formula (2) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and has the same meaning as the group R ³ in the general formula (1).

X in the general formula (2) is a divalent organic residue or an oxygen atom. The structure of the organic residue is not particularly limited as long as it is a group capable of bonding two Ge atoms having one or more alkoxy groups. For example, the structure includes an ether bond, Steal bond, amide bond, amino bond, urethane bond, thioether bond, It may have a bond other than a carbon-carbon bond such as a phonyl bond, and may further contain an oxa group (ketone carbon). Specific examples of such a divalent organic residue X include an alkylene group having 1 to 15 carbon atoms such as a methylene group, an ethylene group, a propylene group, a trimethylene group, a butylene group; or a group represented by the following formula: And a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; an alkyl group such as a methyl group or an ethyl group; an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group; a hydroxyl group And groups in which an amino group, a mercapto group or the like is bonded as a substituent. (In addition, m, n and I in the following formula are each an integer of 0 to 10)

2

2 NHC? HC Specific examples of the silicon compound represented by the general formula ( ₂₎ include those represented by the following formula.

(H ₃ CH ₂ CC)) ₃ Si CH ₂ CH-CH ₂ OCH ₂

, 'Hg

, .C

fH ₃ CH ₂ CO) ₃ Si CH ₂ CH ₂ CH ₂ OCH ₂ 'CH ₂ OH

(H ₃ CH ₂ CO) ₃ Si— ~ CH ₂ CH ₂ CH ₂ — SS CH ₂ CH ₂ CH ₂ — Si (OCH ₂ CH ₃ ) ₃

(H ₃ CO) ₃ Si CH ₂ CH ₂ CH ₂ NHCH ₂ t: H ₂ N CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ — Si (OCH ₃ ) ₃ In the present invention, the compound represented by the above general formula (1) or (2) is used as the component (B) in the form of a hydrolyzate or a combination of two or more, respectively. Among the compounds exemplified above, particularly from the viewpoint of heat shock resistance and scratch resistance, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, n-year-old octylmethyldimethoxysilane, n-decyltrimethoxysilane, n- Octadecyltrimethoxysilane, n-octadecyltrioxysilane, 10-undecenyltrimethoxysilane, aralkyloxydecyltrimethoxysilane, triethoxysilylundecanal, represented by the following formula Compounds and their hydrolysates are preferred.

(n ₃ CH ₂ CO) ₃ Si ~ ~ C ~ ~ Si (OCH ₂ CH

(H ₃ CH ₂ CO) ₃ Si CH ₂ CH ₂ CH ₂ — SS CH ₂ CH ₂ CH ₂ — Si (OCH ₂ CH ₃ ) ₃

(H ₃ CO) ₃ Si CH ₂ CH ₂ CH ₂

NH

(H ₃ CO) ₃ Si H ₂ CH ₂ CH ₂

(H ₃ CO) ₃ S; CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ — Si (OCH ₃ ) _{3 The} hydrolyzate is partially hydrolyzed, or The whole may be hydrolyzed, or may have progressed from hydrolysis to partial condensation. The blending amount of the component (B) in the coating composition used in the present invention may be appropriately determined according to the desired physical properties depending on the purpose of the finally obtained cured product layer (coat film), and finally formed. Cured product layer (coat film) 1 to 30 parts by mass, preferably 5 to 20 parts by mass, relative to 100 parts by mass. When the blending amount of the component (B) is less than 1 part by mass, the coating film tends to crack when the heat shock test is conducted, and when it exceeds 30 parts by mass, the scratch resistance tends to be insufficient. There is. The mass of the cured product layer (coat film) to be finally formed is (A) component, (B) component, (C) component described later, and further blended as necessary (A),

(B) and a solid component other than (C) (for example, a polymer and a condensate of an organic silicon compound or an epoxy compound other than (B) and (C)), and a coating Organic solvent such as methanol added to the composition (described later)

(D) component) is volatilized during the formation of the cured product layer, and is not left in the finally obtained cured product layer, so it is not included in the mass of the cured product layer (coat film).

(C) component

The component (C) in the present invention in the coating composition is an epoxy group-containing silicon compound, and any known silicon compound or hydrolyzate thereof may be used without any limitation as long as it contains an epoxy group. be able to. Specific examples thereof include: r-glycidoxypropyl trimethoxysilane, r-glycidoxypropylmethyldimethoxysilane, r-glycidoxypropylmethyljetoxysilane, r-glycidoxypropyl triethoxysilane, (3,4-epoxycyclohexyl) etyltrimethoxysilane and hydrolysates thereof. The hydrolyzate may be partially hydrolyzed or fully hydrolyzed, or may be one that has progressed from hydrolysis to partial condensation. In the present invention, from the viewpoint of crosslinkability and adhesion to a resin base material, r-glycidoxypropyl trimethoxysilane,: -glycidoxypropylmethyldimethoxysilane, and a hydrolyzate thereof are preferable. The epoxy group-containing silicon compound may be used alone or in combination of two or more.

In the present invention, the blending amount of the component (C) in the coating composition is appropriately determined according to the desired physical properties depending on the purpose of the finally obtained cured product layer (coat film). For example, as with the component (B), it is preferably 29 to 79 parts by mass, more preferably 30 to 65 parts by mass with respect to 100 parts by mass of the finally formed cured product layer. .

When the blending amount of the component (C) is less than 29 parts by mass, cracks tend to occur in the cured product layer (coat film) when the heat shock test is carried out, and when it exceeds 79 parts by mass, scratch resistance and curing are achieved. There is a tendency that the adhesion between the physical layer and, if necessary, the inorganic vapor-deposited film formed on the cured product layer, the refractive index of the cured product layer, and the like are insufficient.

Further, in the present invention, in order to reduce the sensitivity to moisture and to form a laminate excellent in various properties such as transparency, weather resistance, and adhesion, the component (B) described above is used.

It is most preferable to use the component (C) in such an amount that the mass ratio (B Z C) is in the range of 0.01 to 1, particularly 0.02 to 0.5.

(D) component

In the coating composition used in the present invention, the component (D) is an organic solvent, and the organic components other than the components (B) and (C) and the components (B) and (C) which are blended as necessary A solvent that dissolves the key compound and the epoxy compound and can disperse the antimony pentoxide sol (component (A)) satisfactorily, and uses any known organic solvent as long as it is volatile. can do.

Examples of such organic solvents are alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, and n-pentanol; methyl acetate, ethyl acetate, propyl acetate, propionate Esters such as ethylene, methyl acetoacetate, ethyl acetoacetate, and ethyl acetate; ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether , Ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n Ethers such as butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and dioxane; ketones such as acetone, acetylacetone and diacetone alcohol; halogenated hydrocarbons such as methylene chloride; Hexane, heptane, siku And hydrocarbons such as oral hexane, benzene, toluene, and xylene. These organic solvents may be used alone, but it is preferable to use a mixture of two or more kinds for the purpose of controlling the physical properties of the coating composition.

In the present invention, among the organic solvents described above, the component (B), the component (C), and the acid used for the purpose of hydrolyzing the organic silicon compound other than the component (B) and the component (C) Methanol, isopropanol, t-butanol, acetylacetone, diacetone from the viewpoints of solubility in aqueous solution, easy volatility when forming a cured product layer (coat film), and smoothness when forming a cured product layer It is preferable to use alcohol, ethylene glycol monoisopropyl ether, or the like.

The amount of such an organic solvent used is not particularly limited, but is usually 100-2500 parts by mass, particularly 140-1500 parts by mass with respect to 100 parts by mass of the total amount of the component (B) and the component (C). A range of parts is preferably used. When alcohol or the like is used as a dispersion medium for the antimony pentoxide sol as the component (A) described above, the amount of such a dispersion medium is also included in the amount of the organic solvent.

(E) Component

The component (E) in the coating composition is an acetylylacetonate complex and is used as a curing catalyst for the coating composition. Such an acetylenic toner complex is known if it is appropriately selected in consideration of physical properties such as solubility in other components, storage stability of the coating composition, and hardness of the resulting cured product layer (coat film). The compound can be used without any limitation. Specific examples include Li (I), Cu (II), Zn (II), Co (II), Ni (II), Be (II), Ce (III), Ta (III) , T i (III), Mr. (Ill), L a (III), C r (III),

V (III), Co (III), F e (III), A I (III), Ce (IV), Z r (IV),

An acetylethylacetonate complex having V (IV) or the like as a central metal atom can be mentioned. Particularly preferable examples include acetyl acetyltonate complexes having A I (III), Fe (III), and Li (I) as a central metal. Also, these acetyl acetyltonate complexes have no problem whether used alone or in combination of two or more.

The addition amount of the above acetyl acetyltonate complex is not particularly limited. The total amount of the component and the component (C) is preferably 0.1 to 15 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass.

Other ingredients

In the coating composition used in the present invention, other components than the components (A) to (E) described above may be blended as necessary.

For example, in order to improve the properties such as scratch resistance of the cured product layer (coat film), an organic silicon compound not corresponding to any of the component (B) and the component (C) can be added. Examples of such other organic silicon compounds include tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, Phenyltrimethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethyloxysilane, n-propyl trimethoxysilane, n-propyltrimethoxysilane, isoptyltrimethoxysilane, isoptyltrioxysilane,

1,6-bistrimethoxysilane, 3-ureidopropyltriethoxysilane, trifluoroprovir trimethoxysilane, perfluorooctyltritrioxysilane, T-chloropropyl trimethoxysilane, vinyltri (-methoxyethoxy) silane, valyltrime Toxisilane, acryloxypropyltrimethoxysilane, T-acryloxypropyltriethoxysilane, —methacryloxypropyltrimethoxysilane, r-methacryloxypropyltrimethoxysilane, “τ-methacryloxypropyl dimethoxymethylsilane, r-mer Captopropyltrialkoxysilane, τ-aminopropyl-trimethoxysilane, r-aminopropyl-triethoxysilane, N-phenyl-l-aminopropyl built-up Lan, 3-triethoxysilyl mono-N- (1,3-dimethyl-propylidene) propylamine, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopro Biltrimethoxysilane, N 1-2 (aminoethyl) 3-aminopropylmethyldimethyloxysilane, p-styryltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc., can be added alone. It is possible to add two or more kinds, and these other organosilicon compounds generally undergo hydrolysis. It is more effective to add it to the coating composition after the operation.

In the present invention, more preferable examples of such other organic silicon compounds include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and the like from the viewpoint of improving the scratch resistance of the resulting cured layer. be able to. The blending amount of such other organic silicon compound is preferably 100 parts by mass or less with respect to 100 parts by mass of the total amount of the component (B) and the component (C).

In addition, the coating composition used in the present invention contains an aqueous acid solution for the purpose of hydrolyzing the above-mentioned (B) component and (C) component, and the above-mentioned other organic silicon compounds. Is done. As such an acid aqueous solution, a known acid aqueous solution can be used without any limitation as long as it is an acid aqueous solution having a function of hydrolyzing and condensing an alkoxysilyl group in the above compound. Examples of such acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids such as acetic acid and propionic acid. Among these, hydrochloric acid is preferably used from the viewpoints of hydrolyzability and storage stability of the coating composition. The concentration of the acid aqueous solution is preferably from 0.01 N to 5 N.

Such an acid aqueous solution has a coating composition so that the amount of water is 0.1 to 3 times the total number of moles corresponding to the alkoxy group to be hydrolyzed contained in the polymerizable silicon compound. It is suitable to mix in the product.

Furthermore, an epoxy compound that does not correspond to the component (C) described above may be added to the coating composition in order to adjust the physical properties of the cured layer of the coating composition. Such an epoxy compound (hereinafter referred to as another epoxy compound) has an epoxy group, but unlike the component (C), it does not have a silyl group. 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, Propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, neopentyl glycol hydroxyhybalate diglycidyl ether, trimethyl Roll propane diglycidyl ether, trimethylol propane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol diglycidyl ether, diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythri! -L-diglycidyl ether, pentaerythriyl (^ ltriglycidyl ether, pentaerythritol I ^ ltetraglycidyl ether, dipentaerythryl I ^ ltetraglycidyl ether, sorb! Diglycidyl ether, tris-glycidyl ether of tris (2-hydroxyethyl) isocyanurate, etc .; isophoronediol diglycidyl ether, bis-1,2-hydroxycyclohexoxypropane diglycidyl ether, etc. Alicyclic epoxy compounds; resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, ol Phthalic acid diglycidyl ester, phenol novolak polyglycidyl ether, aromatic epoxy compounds such as cresol Pollack polyglycidyl ether; and the like.

Examples of such other epoxy compounds include 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether Particularly preferred is glycerol triglycidyl ether. These other epoxy compounds may be used in combination of two or more.

The blending amount of the other epoxy compound in the coating composition used in the present invention is 100 parts by mass or less with respect to 100 parts by mass of the total amount of the component (B) and the component (C) (B). Is preferred.

Further, a curing catalyst other than the aforementioned acetylylacetonate complex (hereinafter referred to as other curing catalyst) can be used in combination. Examples of such other curing catalysts include perchloric acids such as perchloric acid, magnesium perchlorate, aluminum perchlorate, zinc perchlorate, and ammonium perchlorate: sodium acetate, zinc naphthenate, and naphthenic acid. Organic metal salts such as balt and zinc octylate; stannic chloride, aluminum chloride, chloride Lewis acids such as ferric iron, titanium chloride, zinc chloride, and antimony chloride; These other curing catalysts can be generally used in an amount of 100 parts by mass or less per 100 parts by mass of the acetylyl senanate complex ((E) component).

Furthermore, in order to improve the coating property of the coating composition and the film performance after curing, various additives can be blended as necessary. Examples of such additives include surfactants, antistatic agents, ultraviolet absorbers, antioxidants, disperse dyes, oil-soluble dyes, fluorescent dyes, materials, photochromic compounds, hindered amines, hindered phenols, and the like. These additives can be used alone or in admixture of two or more.

[Resin substrate]

In the present invention, it is extremely important to select and use a (meth) acrylic resin, aryl resin or epoxy resin as the resin base material. That is, a resin base material composed of these resins is selectively used, and a cured product layer is formed on the surface of the resin base material using the coating composition containing the components (A) to (E) described above. Thus, as shown in Examples described later, it is possible to obtain a laminate having low transparency, effectively suppressing white turbidity due to the influence of moisture, and having excellent transparency, and the laminate. Has excellent solvent resistance, scratch resistance, heat shock resistance, adhesion between the resin substrate and the cured product layer, and excellent adhesion even when subjected to a deterioration acceleration test (weather resistance test) by light irradiation. It retains sex. When other resin base materials such as polycarbonate resin base materials are used, even if the above-described coating composition is used, the obtained laminate becomes cloudy due to the influence of moisture and becomes low in transparency. In addition, the solvent resistance is poor, the adhesion between the resin substrate and the cured product layer is extremely low, and the scratch resistance of the cured product layer is insufficient (see Comparative Example 3 described later).

In the present invention, the reason why the laminate having the excellent characteristics as described above can be obtained by selecting the above-mentioned specific resin base material has not been clearly elucidated, but is probably the coating composition described above. However, it forms a chemical or physical cross-linking bond with the surface of the (meth) acrylic resin base material, the aryl resin base material or the epoxy resin base material, and thus the adhesion between the cured product layer and the resin base material surface. In addition, the cross-linking bond and the composite metal oxide in the coating composition are improved by light and water. This is probably because the cross-linking bond is stably formed even when kept in a poor environment for a long time.

In addition, these resin substrates used in the present invention preferably have a refractive index of 1.55 or more in order to prevent generation of interference fringes due to a difference in refractive index from the coating composition.

In the present invention, the (meth) acrylic resin used as a resin base material is a polymer obtained by polymerization of a monomer having a (meth) acrylic group such as (meth) acrylic acid or (meth) acrylic acid ester, The aryl resin is a polymer obtained by polymerization of a monomer containing an aryl group such as aryl diglycol power, ponate, diaryl isophthalate and its oligomer, diaryl terephthalate and its oligomer. The epoxy resin is a polymer obtained by polymerization of a monomer containing an epoxy group such as 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether or the like. In addition, the above resin base material is a blend or co-polymer of the above-mentioned various resins and other resins (for example, vinyl resins) as long as the excellent characteristics due to the formation of the cured product layer of the coating composition described above are not impaired. It may be made of a polymer. For example, in the range of 30% by mass or less, other resin components or polymerized units that become other resin components can be contained.

[Manufacture of laminates]

The laminate of the present invention is produced by applying the coating composition to the surface of the resin substrate described above and curing the composition to form a cured product layer.

When applying the coating composition, in order to improve the adhesion between the substrate and the cured product layer, the substrate surface is treated beforehand with alkali treatment, acid treatment, surfactant treatment, UV ozone treatment, inorganic or organic fine particles. It is effective to perform polishing or plasma or corona discharge treatment. The coating composition can be applied by a dipping method, a spin coating method, a spray method, a flow method, or the like. Particularly for eyeglass lens applications, the dating method is preferably used in order to efficiently coat both surfaces of many substrates.

Curing after application is usually performed by heat treatment after drying in dry air or air. Is done by doing. The heating temperature is generally 80 ° C. or higher, particularly 100 ° C. or higher, and a temperature at which the resin base material does not deform, generally 150 ° C. or lower is preferable. The curing time is about 2 hours at 1300C and about 2 to 5 hours at 100 to 120 ° C. The cured product layer formed by curing can have a thickness of about 0.1 to 50 / m. However, when this laminate is used for an eyeglass lens, the thickness of the cured product layer is 1 A range of ˜10 m is particularly suitable.

In the laminate thus obtained, if necessary, an antireflection film made of an inorganic material can be formed on the surface of the cured product layer. Examples of such film forming means include vacuum vapor deposition, ion Examples thereof include a plating method and a sputtering method. In the vacuum deposition method, an ion beam assisted method of simultaneously irradiating an ion beam during deposition may be used. Such an antireflection film may be either a single layer or a multilayer structure. Examples of the inorganic material forming the antireflection film include S i O, S i O, Z r 0 ₂ , T i 0 ₂ , T i O, and T i. 0. , T i. 0 ₅ ,

AI 2 ° 3 · T a. 0 ₅ , C e 0 ₂ , MgO, Y ₂ O ₃ , Sn O ₂ , Mg F ₂ ,

Oxides such as W0 ₃ and the like. These inorganic oxides may be used alone or in combination of two or more.

EXAMPLES Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these examples.

The abbreviations and names of the compounds used in the examples and comparative examples are shown below.

[Each component for forming coating composition]

(A) Ingredient

S b sol:

Methanol-dispersed antimony pentoxide sol

Nissan Chemical Industries, Ltd. AMT-330S

Solid content concentration 3 1.0 mass%

p H = 6.0

T i — Z r — S i sol (comparative example): Methanol-dispersed titanium oxide Zirconium monoxide Ge monoxide composite metal oxide sol

Made by Catalytic Chemical Industry Co., Ltd.

Solid content concentration 30.0% by mass

p H = 4.8

(B) Component

Gay compound represented by the general formula (1)

HTS: n-Hexyltrimethoxysilane

OTS: n-octyltrimethoxysilane

ODS: n-year-old octylmethyldimethoxysilane

DTS: n-decyltrimethoxysilane

ODTS: n-octadecyltrimethoxysilane

ODT ES: n-year-old kutadecyltriethoxysilane

UDTS: 1 0—Undecenyl trimethoxysilane

AUDTS: allylooxydecyltrimethoxysilane

TESU: Triethoxysilylundecanal

Gay compound represented by the general formula (2)

Gay Elemental Compound (B 1):

Gay Element Compound (B2)

Gay Element Compound (B3):

(H ₃ CH ₂ CO) ₃ Si——CH ₂ CH ₂ CH ₂ OCH ₂

—H2

, C

(H ₃ CH ₂ CO) ₃ Si——CH ₂ CH ₂ CH ₂ OCH ₂ / _C H ₂ .OH Ge compound (B4):

(H ₃ CH ₂ C0) ₃ Si i (CH ₂ ) 8— Si (0CH ₂ CH ₃ ) ₃ Ge elemental compound (B5):

(H ₃ G0) ₃ Si— (GH ₂ ) 6—Si (0CH ₃ ) ₃ Key compound (B6):

(H ₃ GH ₂ G0) ₃ Si— CH ₂ CH ₂ GH ₂ — S— S— CH ₂ GH ₂ CH ₂ — Si (0CH ₂ CH ₃ ) ₃ Ge elemental compound (B7):

Gay Elemental Compound (B 8):

Gay Elemental Compound (B 9):

(H ₃ G0) ₃ Si—GH GH ₂ GH ₂ NHCH GH ₂ NHCH ₂ CH ₂ NHGH ₂ CH ₂ GH ₂ — Si (0CH ₃ ) ₃

(C) Component

GTS: T-Glycidoxyprovir trimethoxysilane

GDS: r-Glycidoxypropylmethyldimethoxysilane ETS:

β— (3,4-epoxycyclohexyl) ether trimethylsilane

(D) Component

Me ：: Methanol

E t O H: Ethanol

I P A: Isopropanol

N P A: n-propanol

NBA: n-butanol

T B A: t-butanol

A c P r: Propyl acetate

EG P E: Ethylene glycol monoisopropyl ether

EGEE: Ethylene glycol monoethyl ether

EGBE: Ethylene glycol mono-t-butyl ether

P G P E: Propylene glycol mono-n-propyl ether

M I B K: Methyl isobutyl ketone

A c A c: Acetylaseton

DAA: Diaceton alcohol

(E) Component

E 1: squirrel (2,4 one pentagona) aluminum (m)

E2 ： Squirrel (2, 4 one pentaneath) Iron (）)

E3: 2, 4 One pentanezona lithium Other ingredients

(1) Gay compounds other than the components (B) and (C)

T ES: Tetraethoxysilane

M T E S: Methyltrioxysilane

MTMS: Methyltrimethoxysilane

BTMS: n-butyltrimethoxysilane AP TES :: T-acryloxyprovir triethoxysilane

(2) Epoxy compounds

P ETGE ： Pentaerythri I ^ Litriglycidyl ether

[Plastic lens substrate (resin substrate)]

TKA: Aryl resin plastic lens (refractive index = 1. 60)

TKB: Aril resin plastic lens (refractive index = 1. 55)

S E: Methacrylic resin + vinyl resin plastic lens (refractive index = 1. 60) K R: epoxy resin (refractive index = 1. 59)

P C: Polycarbonate (refractive index 1.59) The characteristics of the lenses (laminates) obtained in the examples and comparative examples were evaluated by the following methods.

(1) Appearance

The transparency of the coat film (cured product layer) was observed by visual inspection. That is, the sample lens is arranged in the light beam so that the optical axis of the sample lens is perpendicular to the direction of the light beam from the light source (Cabin Industry Co., Ltd. colorCABIN 111), and is visually observed from the optical axis direction of the lens. By observing, the transparency of the cured product layer was evaluated based on the degree of cloudiness. The evaluation criteria are as follows.

©: Lens with coated film is almost transparent

O: Slightly cloudy

△: The cloudiness is worse than 〇

X: completely cloudy

(2) Solvent resistance

Each sample lens (laminated body) was impregnated with methanol, isopropyl alcohol, toluene, acetone, or 0.4 mass% aqueous NaOH solution for 24 hours, and the surface state change was examined. The evaluation criteria are as follows.

○: No change from before impregnation.

X: Change is recognized compared with before impregnation.

(3) Scratch resistance Using steel wool (Bonstar # 0 0 0 0 No. 0 made by Nippon Steel Wool Co., Ltd.), the sample lens surface was rubbed 10 times with 1 kg ^ weight, and the degree of damage was visually evaluated in three stages. The evaluation criteria are as follows.

A: Almost no damage.

B: Slightly scratched.

C: The coat film (cured product layer) is peeled off.

(4) Adhesion

The adhesion between the coating film and the lens was determined by a cross-cut tape test according to JISD-02020.

That is, using a cutter knife, make a cut on the lens surface at intervals of about 1 mm to form 100 squares. A cellophane adhesive tape (manufactured by Nichiban Co., Ltd.) was affixed strongly on it, and was then pulled away from the surface in a 90 ° direction at once, and then the cells with the remaining coating film were measured.

The evaluation results are expressed as (number of remaining cells) Z 1 0 0.

(5) Weather resistance

In order to evaluate the durability of the coating film by light irradiation, the following deterioration acceleration test was conducted. That is, the lens having the obtained coating film was accelerated and deteriorated for 20 hours using a Xenon Weather Meter X 2 5 manufactured by Suga Test Instruments Co., Ltd. Thereafter, adhesion was evaluated by the same method as in (4) above.

(6) Heat shock resistance

The sample lens (laminated body) was immersed in boiling water for 1 hour, and then immersed in cold water adjusted to 5 ° C or lower for 1 minute, and the degree of occurrence of cracks in the coating film was visually evaluated in three stages. The evaluation criteria are as follows.

A: No cracks occur.

B: A slight crack is generated.

C: Innumerable cracks have occurred.

(7) Storage stability

After preparing the coating composition, after storing it at 20 ° C for 3 weeks and 5 weeks, use each coating composition to form a coating film on the surface of the plastic lens substrate by the method shown in each example and comparative example. The appearance, solvent resistance, and abrasion resistance of the resulting coating film Scratch, adhesion, weather resistance and heat shock resistance were evaluated by the methods described above. Example 1

(1) Preparation of coating composition

r-Glycidoxypropyl trimethysilane (GTS) 31 7 g, gay compound (B 1) 1 77 g, tetraethoxysilane (TES) 1 30 g were mixed. While thoroughly stirring this mixed solution, 150 g of 0.05 N hydrochloric acid aqueous solution was added, and stirring was continued for 5 hours after the addition was completed. Then, to this mixture,

Silicone surfactant (made by Nippon Tunica Co., Ltd., trade name “Shiichi 7001”)

2.0 g

A I (III) Acetylacetonate 7.3 g

t-Butyl alcohol 280 g

700 g of methanol

S b sol 1 250 g

The mixture was stirred for 5 hours and then aged overnight to obtain a coating composition (a). Further, a part of the coating composition (a) was subdivided, and distilled water was added thereto so that the content was 10% by mass, followed by stirring for about 1 hour. This coating composition to which water was added was designated as a coating composition (a ′).

(2) Formation of coat film (cured product layer)

The coating composition (a) and (a ′) obtained above were dipped on a plastic lens substrate (T KA) that had been immersed in a 10% aqueous solution of 10% NaOH at 40 ° C for 5 minutes. The coating composition was applied to the surface of the lens substrate (TKA) with a pulling speed of 30 cmZ. Datebing was performed under three conditions: relative humidity 30% RH, 50% RH, and 70% RH (all at a temperature of about 23 ° C). After coating, the film was dried at 70 ° C. for 20 minutes, and then cured by holding at 120 ° C. for 4 hours to form a coating film to obtain a laminate (sample lens).

The coating film of the obtained laminate was a colorless and transparent film having a thickness of about 2 microns and a refractive index of 1.58.

Table 1 shows the composition of the coating composition used to form the coating film and the type of plastic lens substrate (resin substrate). In addition, with respect to the coating film obtained, the coating compositions (a) and (a ′) devised under 3 Oo / oRH conditions are as described in (1) Appearance, (2) Solvent resistance, (3 ) Scratch resistance, (4) Adhesion, (5) Weather resistance, and (6) Heat resistance Shock resistance is evaluated. Are shown in Table 2.

Further, after the coating compositions (a) and (a ′) prepared above were stored for 3 weeks and 5 weeks, a coating film was formed in the same manner as described above, and (7) storage stability was evaluated. . The evaluation results are shown in Table 3 (3 weeks storage) and Table 4 (5 weeks storage). One Example 2 to 1 5

Coating compositions (b) to (o) were obtained in the same manner as in Example 1 except that the components shown in Table 1 were used. Further, a part of each coating composition was subdivided, and distilled water was added thereto so that the content became 10% by mass, followed by stirring for about 1 hour. The coating compositions to which water was added were designated as coating compositions (b ′;) to (ο ′). Using the above coating composition, a coat film was formed on the surface of the plastic lens substrate (resin substrate) shown in Table 1 in the same manner as in Example 1 to obtain a laminate (sample lens). It was.

About the obtained laminated body, various characteristic evaluation was performed similarly to Example 1, and the result was shown in Table 2-Table 4. Comparative Examples 1 and 2—

Coating compositions (Ρ), (Ρ ′), (q) and (q ′) were obtained in the same manner as in Examples 1 to 15 except that the components shown in Table 1 were used.

Using the above coating composition, a coat film was formed on the surface of the plastic lens substrate (resin substrate) shown in Table 1 in the same manner as in Example 1 to obtain a laminate (sample lens). It was.

About the obtained laminated body, various characteristic evaluation was performed similarly to Example 1, and the result was shown in Table 2-Table 4. —Comparative Example 3—

A laminated body (sample lens) in the same manner as in Example 1 except that TKA (aryl resin plastic lens) with a refractive index of 1.60 used in Example 1 was replaced with PC (polycarbonate resin lens) with a refractive index of 1.59. ) And the physical properties were evaluated. These results are shown in Table 2, Table 3 and Table 4.

O / iAVio9: /.!£ί ι.

Early

No. Coating composition Plastic lens substrate Appearance

Solvent resistance Scratch resistance Adhesion Weather resistance Heat shock resistance

30 lessons 50% RH 70 dragons

a TKA

,

b, TKA ® ◎ ◎ o A 100/100 100/100 A Example c TKB ◎ ◎ o A 100/100 100/100 A 5 ◎

G TKB ◎ ◎ ◎ o A 100/100 100/100 A Example d TKA A 100/100 100/100 A 6 ◎ ◎ ◎ o

d, TKA ◎ ◎ ◎ o A 100/100 100/100 A Example e

f, TKA ◎ ◎ ◎ o A 100/100 100/100 A Example TKB

h, SE ◎ ◎ o o A 100/100 100/100 A i SE

Example 1 1 ◎ ◎ ◎ o A 100/100 100/100 A

1 SE ◎ ◎ ◎ o A 100/100 100/100 A Example 1 2 i TKA ◎ ◎ ◎ o A 100/100 100/100 A

J TKA ◎ ◎ ◎ o A 100/100 100/100 A Example k TKA

14 ◎ ◎ ◎ 〇 A 100/100 100/100 A

1 'TKA ◎ ◎ ◎ 〇 A 100/100 100/100 A 莠 Example m TKA

1 5 ◎ ◎ o A 100/100 100/100 A m 'TKA ◎ ◎ ◎ o A 100/100 100/100 A Example n TKA

1 6 ◎ ◎ ◎-○ A 100/100 100/100 A n TKA ◎ ® ◎ o A 100/100 100/100 A

0 KR

P TKA ◎ ◎ ◎ o A 100/100 100/100 c Comparative example 2 q TKA o o o o A 100/100 0/100 A q TKA o o ○ o B 100/100 0/100 A Comparative example a

3 PC △ Δ 厶 X C 0/100

a PC 厶 Δ Δ XC 0/100 ― ―

Save 55M | #j later

No. Coating composition Plastic lens substrate Appearance Solvent resistance Scratch resistance Adhesion Weather resistance Heat shock resistance

30% RH 50% RH 70% RH

a TKA

Example 1 ◎ ◎ ◎ o A 100/100 100/100 A a, TKA ◎ ◎ ◎ o A 100/100 100/100 A Example 2 a SE ◎ ◎ ◎ o A 100/100 100/100 A a, SE ◎ ◎ O o A 100/100 100/100 A Example a KR

3 ◎ © © o A 100/100 100/100 A a KR ◎ ooo A 100/100 100/100 A Example 4 b TKA ◎ ◎ ◎ o A 100/100 100/100 A b, TKA ◎ ◎ oo A 100 / 100 100/100 A Example c TKB

5 ◎ ◎ ◎ o A 100/100 100/100 A c TKB ◎ ◎ ◎ o A 100/100 100/100 A Example d TKA

6 ◎ ◎ ◎ 〇 A 100/100 100/100 A

TKA ◎ ◎ o o A 100/100 100/100 A Example e TKA

7 ◎ ® ◎ o B 100/100 100/100 A e TKA ◎ ◎ o o B 100/100 100/100 A Example f TKA 100/100 100/100 A 8 ◎ ◎ ◎ o A

f TKA ◎ o o o A 100/100 100/100 A Example 9 g TKB ◎ ◎ ◎ ○ A 100/100 100/100 A

TKB ◎ ◎ o o A 100/100 100/100 A Example h SE 00/100 A 1 0 ◎ ◎ ◎ o A 100/100 1

h 'SE ◎ ○ o o A 100/100 100/100 A i SE ® ◎ ◎ o A 100/100 100/100 A Example 1 1

SE ◎ ◎ o o A 100/100 100/100 A Example 1 2 j TKA ® ◎ ◎ o A 100/100 100/100 A

■,

J TKA ◎ ◎ o A 100/100 100/100 A Example k TKA

0 KR

Example 1 7 ◎ ◎ ◎ 〇 A 100/100 100/100 A

P TKA ® ◎ ◎ o A 100/100 100/100 c Comparative example 2 q TKA o o o o B 100/100 0/100 A q TKA Δ X Xo B 100/100 0/100 A Comparative example a Δ

3 PC △ Δ X C 0/100 ― One

PC △ Δ △ XC 0/100 ― ―

As apparent from Table 2 to Table 4, when the coating film was laminated on the surface of the synthetic resin lens substrate using the coating composition of the present invention in Examples 1 to 15, the initial appearance (white turbidity) Degree), solvent resistance, scratch resistance, adhesion, weather resistance, and heat shock resistance were all good. In addition, the storage stability is good, and the physical properties such as appearance, solvent resistance, scratch resistance, adhesion, weather resistance, and heat shock resistance after 3 weeks and 5 weeks after storage are the same as the coating composition. It was the same as the initial preparation. Furthermore, even when a coating composition in which 10% by mass of water is added to the coating composition is used, the appearance of the laminate is very good, and the coating composition of the present invention is hardly affected by moisture. I understand that.

On the other hand, in Comparative Example 1, as shown in Tables 2 to 4, the initial appearance, solvent resistance, scratch resistance, adhesion, and weather resistance are good, but the heat shock resistance is poor. It turns out that it is enough. In addition, the storage stability is the same as the initial preparation of the coating composition after 3 weeks and 5 weeks of storage, and the physical properties such as appearance, solvent resistance, scratch resistance, adhesion, and weather resistance are good. However, the heat shock resistance was insufficient. Furthermore, even when a coating composition in which 10% by mass of water was added to the coating composition was used, the heat shock resistance was insufficient. In Comparative Example 2, the initial appearance, solvent resistance, scratch resistance, adhesion, heat shock resistance and the like were good, but the weather resistance was insufficient. This inferior weather resistance was also observed in the storage stability test. In addition, in the case of using a coating composition in which 10% by mass of water is added to the coating composition, the appearance is remarkably poor and these coating compositions are sensitive to moisture. It can be understood that it can only be used.

In Comparative Example 3, physical properties such as solvent resistance, scratch resistance, and adhesion were insufficient even when the initial and storage stability tests were performed, because a poly force-ponate was used for the base material. . In Comparative Example 3, since the physical properties were insufficient from the beginning, weather resistance and heat shock resistance were not evaluated. Further, as for the appearance, the polycarbonate resin lens surface was clouded by contact with the epoxy group-containing silicon compound. '

Claims

The scope of the claims

1. In a laminate in which a cured layer of a coating composition is formed on the surface of a resin substrate,

The coating composition contains the following components (A) to (E):

(A) antimony pentoxide sol;

(B) The following general formula (1) or the following general formula (2):

R ¹ R ² _a S i (OR ³ ) ₃ -a… (1)

X [S i R ⁵ _b (OR ⁶ ) ₃ — _b ] ₂ … (2)

X is a divalent organic residue or an oxygen atom, b is an integer of 0 to 2,

And at least one silicon compound selected from the group consisting of these compounds and hydrolysates thereof;

(C) an epoxy group-containing silicon compound or a hydrolyzate thereof;

(D) an organic solvent; and

(E) Acetylacetonate complex;

The said resin base material consists of a (meth) acryl resin, an aryl resin, or an epoxy resin, The laminated body characterized by the above-mentioned.

2. The coating composition comprises (B) component and (C) total amount of 100 parts by mass, (A) 25 to 250 parts by mass, and (D) 100 to 2500 parts by mass. And (E) 0.1 to 15 parts by mass of component, (B) component and (C) component The laminate according to claim 1, which is contained in an amount of mass ratio (BZC) = 0.01 to 1.

3. The laminate according to claim 1, wherein the refractive index of the resin base material is 1.55 or more.

4. A plastic lens comprising the laminate according to claim 3.