JP2011154363A - Colored laminate and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dyed laminate which has no primer layer between a substrate and a hard coat layer, and has the hard coat layer having a high hardness. <P>SOLUTION: The laminate is equipped with a substrate and a layer which is formed on the substrate and in which at least one of colloidal silica and organic fine particles is dispersed in a matrix having Si-O bond. The organic fine particles each contain an ultraviolet absorbing group. The layer is characterized in that the haze value is ≤10%; the transmittance of at least one wavelength of the wavelengths of 400 to 750 nm is ≤80%; when steel wool #0000 is reciprocated by ten times so as to scuff under conditions that the load is 9.8 N and the rate is 2,000 mm/sec, the number of flaws is zero after rubbing of 10 reciprocating; the haze difference before and after a Tabor abrasion test at a load of 4.9N and 500 revolutions, using a friction ring of CS-10F is <30; and no peeling is found on the layer in a cross-cut peeling test according to JIS K 5400. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a laminate in which a dyed hard coat layer is provided on a resin substrate and a method for producing the same.

  Plastic lenses, which are a type of transparent substrate, are superior to glass lenses in terms of safety, ease of processing, fashionability, lightness, etc. Also, by developing hard coat technology and antireflection technology for plastic lenses In recent years, it has spread rapidly. In particular, polycarbonate is promising as a plastic lens because of its excellent impact resistance. However, since it is difficult to color the polycarbonate, a plastic lens provided with a hard coat layer through which the dye can pass may be dyed.

  A coating composition for hard coat capable of allowing dye to pass therethrough is known (for example, Patent Documents 1 and 2). Patent Document 1 describes a coating composition comprising colloidal silica, epoxy silane, a crosslinking agent, and a curing catalyst. The hard coat film obtained by the coating composition described in Patent Document 1 has a high hardness before the dyeing process, but has a problem that the hardness decreases after the dyeing process.

  In order to solve the above problem, a coated plastic lens coated with a hard coat layer having high hardness capable of being dyed and a coating composition therefor have been proposed (Patent Document 2). However, in the coated plastic described in Patent Document 2, it is necessary to provide a primer layer between the resin substrate and the hard coat layer.

  On the other hand, Patent Document 3 discloses a laminate of a hard coat layer and a substrate made of an alkoxysilane compound, organic polymer fine particles, colloidal silica, silane compound-treated cerium oxide, and the like.

JP 58-80359 A JP 2004-175907 A International Publication 2009/099106 Pamphlet

  An object of the present invention is to obtain a dyed laminate that does not have a primer layer between a substrate and a hard coat layer, has a hard coat layer with high hardness, and is dyed.

According to this invention, the following laminated bodies and its manufacturing method are provided.
1. A substrate,
A layer in which at least one of colloidal silica and organic fine particles formed on the substrate is dispersed in a matrix having Si-O bonds;
With
The organic fine particles contain an ultraviolet absorbing group,
The layer has a haze value of 10% or less,
The transmittance of at least one wavelength among wavelengths of 400 to 750 nm is 80% or less,
The number of scratches when steel wool # 0000 was rubbed 10 reciprocations at 9.8 N load and 2000 mm / sec was 0,
The difference in haze between before and after a 4.9 N load, 500 rotation Taber abrasion test using a wear wheel of CS-10F is less than 30,
A laminate in which the layer does not peel in a cross-cut peel test in accordance with JIS K 5400.
2. 2. The laminate according to 1, wherein the layer is a layer in which the organic fine particles are dispersed in the matrix.
3. The layer according to 1 or 2, wherein the layer has a haze difference of less than 15 before and after the Taber abrasion test.
4). A substrate,
A layer in which at least one of colloidal silica and organic fine particles formed on the substrate is dispersed in a matrix having Si-O bonds;
With
The organic fine particles contain an ultraviolet absorbing group,
The layer has a haze value of 10% or less,
The number of scratches when steel wool # 0000 was rubbed 10 reciprocations at 9.8 N load and 2000 mm / sec was 0,
The difference in haze between before and after a 4.9 N load, 500 rotation Taber abrasion test using a wear wheel of CS-10F is less than 30,
A method for producing a colored laminate, wherein the laminate is immersed in a dye in a laminate in which the layer does not peel in a cross-cut peel test based on JIS K 5400.
5. (A) below
At least one of (B) and (C),
(D) and (E) composition I containing component, or the following (A ′),
Curing a composition II containing at least one of (B) and (C) and (D) to (G) components on a substrate to produce a laminate;
Immersing the laminate in a liquid in which a dye is dispersed to produce a colored laminate;
A method for producing a colored laminate comprising:
Composition I:
(A) Hydrolysis condensate of one or more compounds selected from the following (A-1) to (A-5).
(A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compound containing no amino group, epoxy group and isocyanate group (A-3) Silane compound having amino group and alkoxy group (A-4) Epoxy group And a silane compound having an alkoxy group (A-5) a blocked isocyanatosilane compound having an alkoxy group (B) an organic polymer fine particle comprising a copolymer containing a monomer unit having an ultraviolet absorbing group (C) colloidal silica (D) Curing catalyst (E) Dispersion medium composition II:
(A ′) Hydrolyzed condensate of silane compound having alkoxy group (B) Organic polymer fine particle comprising copolymer containing monomer unit having ultraviolet absorbing group (C) Colloidal silica (D) Curing catalyst (E ) Dispersion medium (F) Cerium oxide (G) dispersion stabilizer treated with silane compound The manufacturing method of the colored laminated body of 5 in which the said composition I or II contains the said (B) component.
7). The method for producing a colored laminate according to 5 or 6, wherein the composition I further comprises (F) cerium oxide treated with a silane compound and (G) a dispersion stabilizer.
8). (A) below
At least one of (B) and (C),
(D) as well as the step of obtaining the composition III using the component (E), or the following (A ′)
Obtaining composition IV using at least one of (B) and (C), and components (D) to (G);
Curing the composition III or the composition IV on a substrate to produce a laminate;
Immersing the laminate in a liquid in which a dye is dispersed to produce a colored laminate;
A method for producing a colored laminate comprising:
Composition III:
(A) Hydrolysis condensate of one or more compounds selected from the following (A-1) to (A-5).
(A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compound containing no amino group, epoxy group and isocyanate group (A-3) Silane compound having amino group and alkoxy group (A-4) Epoxy group And a silane compound having an alkoxy group (A-5) a blocked isocyanatosilane compound having an alkoxy group (B) an organic polymer fine particle comprising a copolymer containing a monomer unit having an ultraviolet absorbing group (C) colloidal silica (D) Curing catalyst (E) Dispersion medium composition IV:
(A ′) Hydrolyzed condensate of silane compound having alkoxy group (B) Organic polymer fine particle comprising copolymer containing monomer unit having ultraviolet absorbing group (C) Colloidal silica (D) Curing catalyst (E ) Dispersion medium (F) Cerium oxide (G) dispersion stabilizer treated with silane compound 9. 9. The method for producing a colored laminate according to 8, wherein in the step of obtaining the composition III or the step of obtaining the composition IV, the composition III or the composition IV is obtained using the component (B).
10. The method for producing a colored laminate according to 8 or 9, wherein in the step of obtaining the composition III, the composition III is further obtained using (F) a cerium oxide treated with a silane compound and (G) a dispersion stabilizer.
The colored laminated body manufactured by the manufacturing method in any one of 11.4-10.

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the laminated body which does not have a primer layer between a board | substrate and a hard-coat layer, has a hard-coat layer of high hardness, and was dye | stained.

It is a chart which shows the transmittance | permeability in wavelength 400-750nm of the colored laminated body obtained in Example 1. FIG. It is a chart which shows the transmittance | permeability in wavelength 400-750nm of the colored laminated body obtained in Examples 2-1 to 2-6. It is a chart which shows the transmittance | permeability in wavelength 400-750nm of the colored laminated body obtained in Example 3. FIG. It is a chart which shows the transmittance | permeability in wavelength 400-750nm of the colored laminated body obtained in Example 4-1 and 4-2. It is a chart which shows the transmittance | permeability in wavelength 400-750nm of the colored laminated body obtained in Examples 5-1 to 5-8. It is a chart which shows the transmittance | permeability in wavelength 400-750nm of the colored laminated body obtained in Examples 2-5 and 5-5 and Comparative Examples 1 and 2. FIG. It is a chart which shows the transmittance | permeability in wavelength 400-750nm of the colored laminated body obtained in Example 6. FIG. It is a chart which shows the transmittance | permeability in wavelength 400-750nm of the colored laminated body obtained in Example 7. FIG. It is a chart which shows the transmittance | permeability in wavelength 400-750nm of the colored laminated body obtained in Example 8. FIG. It is a chart which shows the transmittance | permeability in wavelength 400-750nm of the colored laminated body obtained in Example 9. FIG. It is a chart which shows the transmittance | permeability in the wavelength of 380-780 nm of the colored laminated body obtained in Examples 2-6 and 10-13. 4 is a TEM photograph of a laminate obtained in Reference Example 1. 4 is a TEM photograph of a laminate obtained in Example 3.

[Method for producing colored laminate]
In the method for producing a colored laminate of the present invention, the following composition I or composition II is cured on a substrate to produce a laminate, and then the laminate is immersed in a liquid in which a dye is dispersed.

[Composition I]
Composition I includes the following components:
(A) component,
At least one of component (B) and component (C),
(D) component, and (E) component.
Furthermore, the following (F) and (G) components can be included. Composition I preferably contains (B).

((A) component)
The component (A) is a hydrolysis condensate of one or more compounds selected from the following (A-1) to (A-5). The hydrolysis condensate may be a hydrolysis condensate of a single compound in (A-1) to (A-5), or any of (A-1) to (A-5). It may be a hydrolysis condensate of a mixture of two or more.
In the present invention, the alkoxy group-containing silane compound is an alkoxysilane compound and / or a partial condensate thereof, and the alkoxysilane compound partial condensate is a part of the alkoxysilane compound condensed into a siloxane in the molecule. A polyalkoxysilane compound or a polyorganoalkoxysilane compound formed by forming a bond (Si—O bond). (The same applies to the component (A ′) described later.)
The hydrolyzed condensate of the silane compound having an alkoxy group may include a silane compound having the alkoxy group before hydrolytic condensation in addition to the hydrolyzed condensate of the silane compound having an alkoxy group. (The same applies to the component (A ′) described later.)

<(A-1) Compound>
(A-1) The compound is a tetraalkoxysilane compound. Moreover, the partial condensate (polyalkoxysilane compound) couple | bonded by the siloxane bond (Si-O bond) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
(A-1) As a compound, a tetraalkoxysilane compound and its partial condensate can be represented by, for example, the following formula (1), and a compound represented by the following formula (6) is particularly preferable.
Si (OR ¹ ) ₄ (1)
[Wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group. A plurality of R ¹ may be the same or different. ]

[Wherein, R ¹ is the same as above, and n is an integer of 1 to 15.] ]

In the formulas (1) and (6), examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and various butyl groups. Examples of OR ¹ in which R ¹ is an alkoxyalkyl group having 1 to 4 carbon atoms include a 2-methoxyethoxy group and a 3-methoxypropoxy group.
Examples of the tetraalkoxysilane compound (A-1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetraisobutoxysilane.
Examples of the polyalkoxysilane compound include “M silicate 51”, “silicate 40”, and “silicate 45” manufactured by Tama Chemical Industries, Ltd., and “methyl silicate 51”, “methyl silicate 53A”, and “ethyl silicate 40” manufactured by Colcoat Co., Ltd. "Ethyl silicate 48" etc. are mentioned.

<(A-2) Compound>
The compound (A-2) is an organoalkoxysilane compound that does not contain an amino group, an epoxy group, or an isocyanate group. Moreover, the partial condensate can also be used. However, the compound (A-2) does not include the compound (A-1). These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
As the compound (A-2), the organoalkoxysilane compound and the partial condensate thereof are preferably bifunctional alkoxysilane and trifunctional alkoxysilane, and can be represented by, for example, the following formula (2). ) Is preferred.

R ² _a Si (OR ³ ) _4-a (2)
[Wherein, R ² represents an alkyl group having 1 to 10 carbon atoms; a fluorinated alkyl group having 1 to 10 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with a methacryloxy group, R ³ is an alkyl group or alkoxyalkyl group having 1 to 4 carbon atoms, and a is 1 or 2. When R ² are a plurality, the plurality of R ² may be the same or different, a plurality of OR ³ may be the same or different. ]

[Wherein R ² and R ³ are the same as above, and m is an integer of 1 to 15.] ]

In the formulas (2) and (7), the alkyl group having 1 to 10 carbon atoms may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and isopropyl. Groups, various butyl groups, various hexyl groups, various octyl groups, various decyl groups and the like, and examples of the fluorinated alkyl group include a trifluoroethyl group and a trifluoropropyl group. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. The alkyl group or alkoxyalkyl group having 1 to 4 carbon atoms is as described in the above formula (1). Preferably ^{R 2} is an alkyl group having 1 to 4 carbon atoms. R ³ is preferably an alkyl group having 1 to 4 carbon atoms. Preferably a is 1.

  Among the organoalkoxysilane compounds represented by formula (2), trifunctional alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, and methyl-tris (2-methoxyethoxy). ) Silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, ethyl-tris (2-methoxyethoxy) silane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltripropoxysilane, hexyl Fluorinated amines such as tributoxysilane, decyltrimethoxysilane, decyltriethoxysilane, decyltripropoxysilane, decyltributoxysilane, trifluoropropyltrimethoxysilane, etc. Kill (trialkoxy) silane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, .gamma.-methacryloxypropyltrimethoxysilane, and the like. Moreover, methyldimethoxy (ethoxy) silane, ethyl diethoxy (methoxy) silane, etc. which have two types of alkoxy groups are mentioned.

Examples of the bifunctional alkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, bis (2-methoxyethoxy) dimethylsilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.
Specific examples of the polyorganoalkoxysilane compound include “MTMS-A” manufactured by Tama Chemical Industry Co., Ltd., “SS-101” manufactured by Colcoat Co., Ltd., “AZ-6101” “SR2402” manufactured by Toray Dow Corning Co., Ltd. "AY42-163" and the like.

<(A-3) Compound>
(A-3) The compound is an silane compound having an amino group and an alkoxy group, and does not contain an epoxy group or an isocyanate group. Moreover, the partial condensate (amino group containing polyorganoalkoxysilane compound) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
As the compound (A-3), an amino group-containing organoalkoxysilane compound and a partial condensate thereof can be represented, for example, by the following formula (3).

R ⁴ _b Si (OR ⁵ ) _4-b (3)
[Wherein, R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms; vinyl group; phenyl group; or methacryloxy group, amino group (—NH ₂ group), aminoalkyl group [— (CH ₂ ) _x —NH ₂ group ( Wherein x is an integer of 1 to 3)]), an alkylamino group [—NHR group (where R is an alkyl group having 1 to 3 carbon atoms)], and the number of carbon atoms substituted with one or more groups 1 to 3 alkyl groups, and at least one of R ⁴ is an alkyl group having 1 to 3 carbon atoms substituted with any of an amino group, an aminoalkyl group, and an alkylamino group. R ⁵ is an alkyl group having 1 to 4 carbon atoms, and b is 1 or 2. If R ⁴ is plural, R ⁴ may be the same or different, the plurality of OR ⁵ may be the same or different. ]
In the above formula (3), the alkyl group having 1 to 3 carbon atoms and the alkyl group having 1 to 4 carbon atoms are as described in the above formula (1) or (2). R ⁴ is preferably an alkyl group having 1 to ⁴ carbon atoms or an alkyl group having 1 to 6 carbon atoms substituted with an amino group. R ⁵ is preferably an alkyl group having 1 to 4 carbon atoms. Preferably b is 1.

Specific examples of the amino group-containing organoalkoxysilane compound represented by the formula (3) include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and N- (2-aminoethyl) -3-aminopropyl. Trimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Examples include propyltriethoxysilane, N-methylaminopropyltrimethoxysilane, and N-methylaminopropyltriethoxysilane.
Examples of the amino group-containing polyorganoalkoxysilane compound include “KBP-90” manufactured by Shin-Etsu Silicone Co., Ltd.

<(A-4) Compound>
The compound (A-4) is an silane compound having an epoxy group and an alkoxy group, and does not contain an amino group and an isocyanate group. Moreover, the partial condensate (epoxy group containing polyorganoalkoxysilane compound) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
As the compound (A-4), an epoxy group-containing organoalkoxysilane compound and a partial condensate thereof can be represented, for example, by the following formula (4).

R ⁶ _c Si (OR ⁷ ) _4-c (4)
[Wherein R ⁶ is an alkyl group having 1 to 4 carbon atoms; vinyl group; phenyl group; or carbon substituted with one or more groups selected from a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. An alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms), and at least one of R ⁶ is 1 to ⁶ carbon atoms (preferably carbon atoms) substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. It is an alkyl group of formulas 1-4. R ⁷ is an alkyl group having 1 to 4 carbon atoms, and c is 1 or 2. If R ⁶ is plural, R ⁶ may be the same or different, a plurality of OR ⁷ may be the same or different. ]
In the above formula (4), the alkyl group having 1 to 3 carbon atoms and the alkyl group having 1 to 4 carbon atoms are as described in the above formula (1) or (2). R ⁶ preferably has 1 to ⁶ carbon atoms (preferably 1 to 4 carbon atoms) substituted with one or more groups selected from an alkyl group having 1 to 4 carbon atoms, a glycidoxy group, and a 3,4-epoxycyclohexyl group. And more preferably an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) substituted with an alkyl group having 1 to 4 carbon atoms or a glycidoxy group. R ⁷ is preferably an alkyl group having 1 to 4 carbon atoms. Preferably b is 2.

  Specific examples of the epoxy group-containing organoalkoxysilane compound represented by the formula (4) include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxysilane. , 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.

<(A-5) Compound>
The compound (A-5) is a blocked isocyanatosilane compound having an alkoxy group (generally also referred to as a blocked isocyanate silane compound), which contains a blocked isocyanate group, but has an amino group and an epoxy group. It is an alkoxysilane compound not included. Moreover, the partial condensate (blocked isocyanate group containing polyorganoalkoxysilane compound) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
The blocked isocyanatosilane compound is an isocyanatosilane compound in which an isocyanate group is protected by a blocking agent such as oxime to be inactive, and is deblocked by heating to activate (regenerate) the isocyanate group (general) Also referred to as an isocyanate silane compound).

As the compound (A-5), a blocked isocyanate group-containing organoalkoxysilane compound and a partial condensate thereof can be represented, for example, by the following formula (5).
R ⁸ _d Si (OR ⁹ ) _4-d (5)
[Wherein R ⁸ is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; Is an alkyl group having 1 to 4 carbon atoms, and at least one of R ⁸ is an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) substituted with a blocked isocyanate group. R ⁹ is an alkyl group having 1 to 4 carbon atoms, and d is 1 or 2. If R ⁸ is plural, R ⁸ may be the same or different, a plurality of OR ⁹ may be the same or different. ]
In the above formula (5), the alkyl group having 1 to 3 carbon atoms and the alkyl group having 1 to 4 carbon atoms are as described in the above formula (1) or (2). Preferably, R ⁸ is an alkyl group having 1 to 4 carbon atoms (preferably having 1 to 4 carbon atoms) substituted with an alkyl group having 1 to 4 carbon atoms or a blocked isocyanate group. R ⁹ is preferably an alkyl group having 1 to 4 carbon atoms. Preferably d is 1.

  Specific examples of the blocked isocyanate group-containing organoalkoxysilane compound represented by the formula (5) include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, What protected the isocyanate group in compounds, such as 3-isocyanatopropyl methyl diethoxysilane and 3-isocyanatopropyl ethyl diethoxysilane, with the blocking agent is mentioned. Among these, 3-blocked isocyanatopropyltriethoxysilane can be mentioned as a preferable compound.

  Examples of the blocking agent for isocyanate groups include oxime compounds such as acetooxime, 2-butanone oxime, cyclohexanone oxime, methyl isobutyl ketoxime, lactams such as ε-caprolactam, alkylphenols such as monoalkylphenol (cresol, nonylphenol, etc.), Active methylene compounds such as 3,5-xylenol, dialkylphenols such as di-t-butylphenol, trialkylphenols such as trimethylphenol, malonic acid diesters such as diethyl malonate, acetoacetates such as acetylacetone and ethyl acetoacetate , Alcohols such as methanol, ethanol, n-butanol, hydroxyl group-containing ethers such as methyl cellosolve and butyl cellosolve, hydroxyl groups such as ethyl lactate and amyl lactate Esters, mercaptans such as butyl mercaptan and hexyl mercaptan, acid amides such as acetanilide, acrylic amide and dimer acid amide, imidazoles such as imidazole and 2-ethylimidazole, pyrazoles such as 3,5-dimethylpyrazole, Triazoles such as 1,2,4-triazole, and acid imides such as succinimide and phthalimide can be used. In order to control the dissociation temperature of the blocking agent, a catalyst such as dibutyltin dilaurate may be used in combination.

((B) component)
The composition I contains at least one of the components (B) and (C). The composition I preferably contains the component (B).
Organic polymer fine particles comprising a copolymer containing a monomer unit having a UV-absorbing group as component (B) (hereinafter sometimes referred to as polymer UV-absorbing resin fine particles) For example, an acrylic monomer having a skeleton (benzophenone-based, benzotriazole-based, triazine-based, etc.) acting as an ultraviolet absorber in the side chain (hereinafter referred to as an ultraviolet absorbing acrylic monomer) and other ethylene Examples are those obtained by copolymerizing a series of unsaturated compounds (acrylic acid, methacrylic acid and derivatives thereof, styrene, vinyl acetate, etc.). While conventional ultraviolet absorbers are generally low molecular weight molecules having a molecular weight of 200 to 700, the weight average molecular weight of the polymer ultraviolet absorbing resin fine particles usually exceeds 10,000. Disadvantages of conventional low molecular weight ultraviolet absorbers such as compatibility with plastics and heat resistance are improved, and weather resistance can be imparted over a long period of time.

  The ultraviolet absorbing acrylic monomer is not particularly limited as long as it is a compound having at least one ultraviolet absorbing group and acryloyl group in the molecule. Examples of such compounds include benzotriazole compounds represented by the following formula (8) and benzophenone compounds represented by the formula (9).

[Wherein, X is a hydrogen atom or a chlorine atom, R ¹⁰ is a hydrogen atom, a methyl group, or a tertiary alkyl group having 4 to 8 carbon atoms, and R ¹¹ is a linear or branched carbon atom having 2 to 10 carbon atoms. An alkylene group, R ¹² represents a hydrogen atom or a methyl group, and p represents 0 or 1. ]

[Wherein R ¹³ is a hydrogen atom or a methyl group, R ¹⁴ is a substituted or unsubstituted linear or branched alkylene group having 2 to 10 carbon atoms, R ¹⁵ is a hydrogen atom or a hydroxyl group, and R ¹⁶ is hydrogen. An atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms is shown. ]

  Specific examples of the benzotriazole-based compound represented by the above formula (8) include, for example, 2- (2′-hydroxy-5 ′-(meth) acryloxyphenyl) -2H-benzotriazole, 2- (2 ′ -Hydroxy-3′-tert-butyl-5 ′-(meth) acryloxymethylphenyl) -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(2- (meth) acryloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(2- (meth) acryloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2 And '-hydroxy-3'-methyl-5'-(8- (meth) acryloxyoctyl) phenyl] -2H-benzotriazole.

Specific examples of the benzophenone compound represented by the above formula (9) include, for example, 2-hydroxy-4- (2- (meth) acryloxyethoxy) benzophenone, 2-hydroxy-4- (4- (meth)). Acryloxybutoxy) benzophenone, 2,2′-dihydroxy-4- (2- (meth) acryloxyethoxy) benzophenone, 2,4-dihydroxy-4 ′-(2- (meth) acryloxyethoxy) benzophenone, 2, 2 ′, 4-trihydroxy-4 ′-(2- (meth) acryloxyethoxy) benzophenone, 2-hydroxy-4- (3- (meth) acryloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4- And (3- (meth) acryloxy-1-hydroxypropoxy) benzophenone.
These ultraviolet-absorbing acrylic monomers may be used alone or in combination of two or more.

The content of the ultraviolet-absorbing acrylic monomer unit in the polymer ultraviolet-absorbing resin fine particles as the component (B) is from the viewpoint of the ultraviolet absorbing ability of the obtained cured film, other physical properties and economic balance, etc. Usually, it is about 5-70 mass%, Preferably it is about 10-60 mass%.
The polymer ultraviolet absorbing resin fine particles used as the component (B) have an average particle size in the range of 1 to 200 nm from the viewpoints of manufacturability, dispersibility in the composition, coating property of the composition, transparency of the cured film, and the like. What exists in is preferable, and what exists in the range of 1-100 nm is more preferable. The average particle diameter of the polymer ultraviolet absorbing resin fine particles can be measured by a laser diffraction scattering method or a dynamic light scattering method.

  In the present invention, the polymer ultraviolet absorbing resin fine particles are preferably used in a form dispersed in a dispersion medium. Examples of the dispersion medium include water, methanol, ethanol, propanol, 1-methoxy-2-propanol, and the like. Preferred examples include lower alcohols and cellosolves such as methyl cellosolve. By using such a dispersion medium, the dispersibility of the polymer ultraviolet absorbing resin fine particles is improved, and sedimentation can be prevented. More preferably, the dispersion medium is water. When the dispersion medium is water, it can be advantageously used for the hydrolysis and condensation reaction of the silane compound necessary for forming the matrix having Si-O bonds derived from the component (A).

There is no restriction | limiting in particular in the manufacturing method of the polymer ultraviolet rays absorption resin fine particle used as the said (B) component, A conventionally well-known method, for example, an emulsion polymerization method, a fine suspension polymerization method, etc. are employable.
In the emulsion polymerization method, a mixture of an ultraviolet-absorbing acrylic monomer as a monomer and an ethylenically unsaturated monomer copolymerized therewith is obtained from an aqueous dispersion medium, an anionic or nonionic surfactant. A method of obtaining a dispersion of fine polymer UV-absorbing resin fine particles by proceeding polymerization in a surfactant micelle layer emulsified into fine droplets and enclosing the monomer mixture using an emulsifier and a water-soluble polymerization initiator It is.
On the other hand, the fine suspension polymerization solution is first premixed in an aqueous medium by adding the monomer mixture, oil-soluble polymerization initiator, emulsifier and other additives as necessary, and homogenized by a homogenizer. Adjust the particle size of the oil droplets. Next, the homogenized liquid is sent to a polymerization vessel and a polymerization reaction is carried out to obtain a dispersion of polymer ultraviolet absorbing resin fine particles.
In any of the above methods, the polymerization temperature is about 30 to 80 ° C.

Examples of the water-soluble polymerization initiator used for emulsion polymerization include water-soluble peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide, these initiators or cumene hydroperoxide, t-butyl hydroperoxide, and the like. Redox initiators that combine hydroperoxides with reducing agents such as acidic sodium sulfite, ammonium sulfite, and ascorbic acid, water-soluble azo compounds such as 2,2′-azobis (2-methylpropionamidine) dihydrochloride, etc. Can be mentioned.
On the other hand, examples of oil-soluble polymerization initiators used for fine suspension polymerization include oil-soluble organic peroxides such as diacyl peroxides, ketone peroxides, peroxyesters, peroxydicarbonates, and the like. Examples include azo compounds such as' -azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile).

Specific examples of the polymer ultraviolet ray absorbing resin fine particles that can be used as the component (B) include, on the other hand, a polymer ultraviolet absorber for coating ULS-700, ULS-1700, ULS-383MA, ULS manufactured by Yufu Kogyo Co., Ltd. -1383MA, ULS-383MG, ULS-385MG, ULS-1383MG, ULS-1385MG, ULS-635MH, etc., a polymer ultraviolet ray absorbing resin paint NCI-905-20EM or NCI-905-20EMA manufactured by Nikko Chemical Laboratory, Inc. Polymer ultraviolet absorber made of a copolymer of a styrene monomer and a benzotriazole monomer).
As the component (B), the polymer ultraviolet absorbing resin fine particles may be used singly or in combination of two or more.

((C) component)
The (C) component colloidal silica is also called colloidal silica or colloidal silicic acid. In water, it refers to a colloidal suspension of silicon oxide having Si—OH groups on its surface by hydration, and is formed when hydrochloric acid is added to an aqueous solution of sodium silicate. Recently, new preparation methods have been developed one after another, and there are those dispersed in a non-aqueous solution and fine powders made by a gas phase method, and the particle diameters are various from several nm to several μm. The average particle size is preferably about 1 to 200 nm. The composition of the particles is indefinite, and some particles are polymerized by forming siloxane bonds (—Si—O—, —Si—O—Si—). The particle surface is porous and is generally negatively charged in water. The average particle diameter can be measured by a laser diffraction scattering method.

Commercially available products include “Ultra High-Purity Colloidal Silica” Quartron PL Series (product names: PL-1, PL-3, PL-7) manufactured by Fuso Chemical Industry Co., Ltd. “Colloidal silica” (Product name: Snowtex 20, Snowtex 30, Snowtex 40, Snowtex O, Snowtex O-40, Snowtex C, Snowtex N, Snowtex S, Snowtex 20L, Snowtex OL, etc. ) "Or" organosilica sol (product names: methanol silica sol, MA-ST-MS, MA-ST-L, IPA-ST, IPA-ST-MS, IPA-ST-L, IPA-ST-ZL, IPA-ST-) UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-MS, MIBK- T, XBA-ST, PMA-ST, DMAC-ST, PGM-ST, etc.) "can be mentioned.
(C) As said component, the said colloidal silica may be used individually by 1 type, and may be used in combination of 2 or more type.

((D) component)
The curing catalyst as component (D) is a catalyst for hydrolyzing and condensing (curing) the silane compounds (A-1) to (A-5) in component (A) described above. For example, hydrochloric acid, sulfuric acid, Inorganic acids such as nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, citric acid, tartaric acid, succinic acid, maleic acid, glutamic acid, lactic acid, p-toluenesulfone Organic acids such as acids can be mentioned.

Lithium hydroxide, sodium hydroxide, potassium hydroxide, n-hexylamine, dimethylamine, tributylamine, diazabicycloundecene, ethanolamine acetate, dimethylaniline formate, tetraethylammonium benzoate, sodium acetate, potassium acetate Organic metal salts such as sodium propionate, sodium glutamate, potassium propionate, sodium formate, potassium formate, benzoyltrimethylammonium acetate, tetramethylammonium acetate, tin octylate, tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide , aluminum triisopropoxide, aluminum _{acetylacetonate,} SnCl _4, TiCl 4, etc. Lewis acids ZnCl ₄ and the like can be mentioned, et al That.

Among these curing catalysts, an organic acid can be preferably used because it can be highly dispersed even if the blending amount of the components (B) and (C) is increased, and the transparency of the resulting film can be improved. In particular, organic carboxylic acids, especially acetic acid can be preferably used.
(D) As a component, the said curing catalyst may be used individually by 1 type, and may be used in combination of 2 or more type.

((E) component)
The composition is used in a state where the component particles are dispersed in a dispersion medium. The dispersion medium is not particularly limited as long as it can uniformly mix and disperse the respective component particles. For example, in addition to water, alcohols, aromatic hydrocarbons, ethers, ketones, esters, etc. The organic dispersion medium can be mentioned. Among these organic dispersion media, specific examples of alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n- Octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, 1-methoxy-2-propanol (propylene glycol monomethyl ether), propylene monomethyl ether acetate, diacetone Examples include alcohol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, and butyl cellosolve. That.

Specific examples of other dispersion media include cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, xylene, dichloroethane, toluene, methyl acetate, ethyl acetate, ethoxyethyl acetate. Etc.
Among these dispersion media, water and alcohols are preferable from the viewpoint of performance as a dispersion medium.
(E) As a component, the said dispersion medium may be used individually by 1 type, and may be used in combination of 2 or more type.

((F) component)
The composition preferably contains cerium oxide treated (pretreated) with a silane compound as the component (F) for improving dispersibility and imparting weather resistance.
The pretreatment here refers to changing the surface state of cerium oxide by reacting the OH group of cerium oxide with the silanol group of the silane compound to form a covalent bond. Silane-treated cerium oxide does not form aggregates or precipitates even when mixed with a sol (for example, colloidal silica) in which anionic particles are dispersed, and this silane-treated cerium oxide must be dispersed in both water and alcohol. Can do.
The cerium oxide to be used is not particularly limited, but is preferably in the form of particles and having an average particle diameter of 1 to 200 nm, and more preferably 1 to 100 nm from the viewpoint of transparency. Further, from the viewpoint of improving dispersibility, when adding the component (F), it is preferable to add the component after dispersing it in a dispersion medium such as water or alcohol.

“Dispersion” in component (F) refers to a state in which a dispersed phase (solid) is suspended and suspended in a dispersion medium (liquid). The “sol” is a colloid having a liquid as a dispersion medium and a solid as dispersed particles, and is sometimes referred to as a colloid solution. The average particle diameter of the cerium oxide fine particles can be measured by a laser diffraction scattering method.
As a dispersion medium, although it applies to the above-mentioned (E) component, water or alcohol is preferable. In particular, the alcohol refers to the alcohol generated from the silane compound described in the components (A-1) to (A-5) in the component (A) and the alcohol described in the component (E), particularly methanol and ethanol. , N-propyl alcohol, isopropyl alcohol, 1-methoxy-2-propanol and other lower alcohols are preferably dispersed. In addition, water and alcohol as a dispersion medium may be used individually by 1 type, and may be used in combination of 2 or more type.

  The component (F) is a dispersion obtained by reacting a surface-charged cerium oxide sol with a silane compound and modifying the surface, and can be suitably added to the composition without agglomeration, precipitation or gelation. is there. This silane compound includes all alkoxysilanes or their hydrolyzed condensates. Therefore, since the exact solid content concentration in the state of the dispersion cannot be obtained, the total amount of cerium oxide as a raw material and the total amount of the complete condensation product of alkoxysilane is divided by the total amount of charge, and expressed as a percentage. This was taken as the calculated solid content concentration.

<Method for producing component (F)>
The method for producing the raw material cerium oxide fine particles to be used is not particularly limited. However, since the reaction with the silane compound is difficult with the powder as it is, it is suitably used as a dispersion. As the stabilizer for dispersion, an acid stable cationic cerium oxide sol using an acidic dispersion stabilizer can be suitably used from the viewpoint of promoting the hydrolysis reaction of the silane compound, and the average particle size is 1 to 200 nm. In view of imparting transparency, the thickness is preferably 1 to 100 nm. Examples of the acidic dispersion stabilizer to be added include inorganic acids such as hydrochloric acid, nitric acid and perchloric acid, and organic carboxylic acids such as acetic acid, formic acid and lactic acid. These may be used alone or in combination. Among these, since the organic carboxylic acid has a coordination effect on the metal, the dispersion stabilizer is preferably an inorganic acid, more preferably cerium oxide sol using hydrochloric acid, from the viewpoint of further reacting cerium oxide with the silane compound. Examples of commercially available products include “Nidoral H-15” manufactured by Taki Chemical Co., Ltd.

  The raw material silane compound used can be defined in the same way as the component (A) described above, but in order to form a siloxane bond suitably with the silanol groups of the component (A) and the component (C) during the production of the cured film, (A-1) A compound is preferred. These may be used alone or in combination.

Moreover, as a silane compound in (F) component, in addition to said tetraalkoxysilane and its hydrolysis condensate or polyalkoxysilane, organoalkoxysilane or its hydrolysis condensate or polyorganoalkoxysilane is used together. You can also. Specific examples of the organoalkoxysilane include one or more organic substituents among the component (A), and more preferably the components (A-2) to (A-5).
The structure of the surface treatment may be a complete two-layer structure or a structure in which each alkoxysilane, its hydrolysis condensate or polyalkoxysilane is mixed.
Since the OH group on the surface layer of the cerium oxide particles has high reactivity, if only organoalkoxysilane is directly used for the surface treatment, there is a risk of promoting aggregation / gelation of only cerium oxide due to the difference in reaction rate. Therefore, as the surface treatment of cerium oxide in component (F), first, the cerium oxide surface layer is treated with a highly reactive tetraalkoxysilane or its hydrolysis condensate, and secondly, the organoalkoxysilane or its hydrolysis condensation. It is desirable to react with the product.
In this way, the silane-treated layer of component (F) has a structure in which some organic substituents are present, so that a siloxane bond is suitably formed with the silanol groups of component (A) and component (C) during the production of the cured film. At the same time, the flexibility of the cured film can be further improved.

It is difficult to add a general cationic cerium oxide sol after surface treatment with a silane compound because it causes aggregation and gelation with an anionic component in the composition. Therefore, in order to disperse stably in the composition, it is necessary to react the OH group of the surface layer of the cerium oxide fine particles of the cationic cerium oxide sol with the silanol group of the silane compound and use it after surface treatment.
In the component (F), the amount of the silane compound used for the surface treatment is considered by the mass of the silane compound as a metal oxide. The metal oxide of a silane compound is defined as the following formula, for example.
R ¹ _m R ² _n SiO _{((4-mn) / 2)}
Wherein R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms; a fluorinated alkyl group having 1 to 10 carbon atoms; a vinyl group; a phenyl group; or a methacryloxy group, an amino group, or an aminoalkyl group. , An alkylamino group, a glycidoxy group, a 3,4-epoxycyclohexyl group and a blocked isocyanate group, substituted with one or more groups having 1 to 3 carbon atoms, and m and n are each independently 0, 1 or 2 and m + n is 0, 1 or 2.)
The mass of the silane compound (R ¹ _m R ² _n SiO ² _{((4 −n−n) / 2)) in} the total mass of the metal oxide (the total amount of CeO ₂ and R ¹ _m R ² _n SiO ² _{((4-mn) / 2))} The ratio of _{mn) / 2)} ) is preferably 50% by mass or less, more preferably 2 to 40% by mass. If it is less than this, the cerium oxide itself may be aggregated and gelled, and if it is more than this, the silane compound itself may be reacted and aggregated and gelled.

The following method can be adopted as a specific method for producing the component (F).
A first liquid mixture composed of a cationic cerium oxide sol and the aforementioned component (E) is prepared, and then a second liquid is prepared by mixing one or more silane compound (A) components. After aging at room temperature, the mixture is further stirred at room temperature or heated to obtain component (F). The component (E) may be diluted by further adding the component (F) after preparation, or the dispersion medium may be replaced by adding another dispersion medium.
Furthermore, when an organoalkoxysilane is used in combination, the following method can be more preferably employed.
A first mixed liquid composed of a cationic cerium oxide sol and a component (E) described later is prepared, and then a tetraalkoxysilane (component (A)) is mixed to prepare a second liquid. After aging at room temperature, organoalkoxysilane (component (A)) is mixed to prepare a third mixed solution. Furthermore, it is set as (F) component by making it stir at room temperature or heating. The component (E) may be diluted by further adding the component (F) after preparation, or the dispersion medium may be replaced by adding another dispersion medium.
Even if the silane-treated cerium oxide sol added to the composition is allowed to stand at room temperature for 1 week after production, no aggregated sediment is visually observed at the bottom of the container. There is no restriction | limiting in particular about this sol stationary period until it adds to a composition.
(F) As a component, the said cerium oxide sol may be used individually by 1 type, and may be used in combination of 2 or more type.

((G) component)
The dispersion stabilizer which is the component (G) stably disperses the reactants of the silane compounds (A-1) to (A-5), the components (B), (C), and (F) in the composition. It is an additive for suppressing coagulation sedimentation and gelation. In the composition, the fine particles of the components (B), (C), and (F) are preferably maintained in a dispersed state without causing aggregation sedimentation or gelation. It is preferable.

Since the composition utilizes a condensation reaction at the time of thermal curing, it is desirable to keep the metal alkoxide in the OH form before coating. Therefore, it is desirable to maintain acidic conditions that promote the hydrolysis reaction and suppress the condensation reaction. Furthermore, since the carboxylic acid itself has not only an effect as an acid but also a coordination effect on a metal and is an effective additive for stabilizing an alkoxide, an organic acid, particularly an organic carboxylic acid, is used as the component (G). It can be preferably used. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and the like can be mentioned. In addition, since the composition forms a cured film by thermosetting, it preferably has a boiling point that does not remain in the cured film during thermosetting, and more preferably acetic acid can be used.
(G) As a component, the said dispersion stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type.

(Optional additive)
In addition to the components (A) [(A-1) to (A-5)] to (E), the above composition appropriately contains various known additive components used in conventional compositions as necessary. be able to.
Examples of the additive component that can be contained as necessary include leveling agents, flexibility imparting agents, lubricity imparting agents, antioxidants, bluing agents, antistatic agents, and antifoaming agents (antifoaming agents). ), A light stabilizer, a weather resistance imparting agent, a colorant, a fine particle dispersant (anti-settling agent), a fine particle surface activity modifier, and the like.

<Leveling agent>
A leveling agent can be added to the composition in order to improve the smoothness of the resulting cured film and the flowability during coating. Examples of these additives include silicone leveling agents and fluorine leveling agents. , Acrylic leveling agents, vinyl leveling agents, and leveling agents in which fluorine and acrylic are combined. All work on the surface of the coating and reduce the surface tension. Each has its own characteristics and can be used according to the purpose. The ability to lower the surface tension is strong in silicone and fluorine systems, but acrylic and vinyl systems are advantageous in that wetting defects are less likely to occur when recoating.

  As a specific example of the silicone leveling agent, a copolymer of polyoxyalkylene and polydimethylsiloxane can be used. Commercially available silicone leveling agents include FZ-2118, FZ-77, FZ-2161, etc. manufactured by Toray Dow Corning Co., Ltd., KP321, KP323, KP324, KP326, KP340, KP341, etc. manufactured by Shin-Etsu Chemical Co., Ltd., etc. -Performance Materials Japan GK TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, TSF4453, TSF4460, BYK-300, BYK-302, BYK-306, BYK-307, BYK, etc. -320, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-345, BYK-346, BY -348, may be mentioned BYK-377, BYK-378, BYK-UV3500, BYK-3510, BYK-3570 and the like polyether-modified silicone oil (polyoxyalkylene-modified silicone oil) and the like.

  Moreover, when heat resistance of 150 degreeC or more is required, the aralkyl modified silicone oil which has polyester modification and a benzene ring is suitable. As a commercially available product of polyester-modified silicone oil, BYK-310, BYK-315, BYK-370 manufactured by BYK Japan Japan Co., Ltd., as a commercially available product of aralkyl-modified silicone oil having a benzene ring, BYK manufactured by BYK Japan Japan Co., Ltd. -322, BYK-323, and the like.

As the fluorine leveling agent, a copolymer of polyoxyalkylene and fluorocarbon can be used.
Examples of commercially available fluorine leveling agents include MEGAFAC series manufactured by DIC Corporation, FC series manufactured by Sumitomo 3M Corporation, and the like.
Examples of commercially available acrylic leveling agents include BYK-350, BYK-352, BYK-354, BYK-355, BYK358N, BYK-361N, BYK-380N, BYK-382, BYK-392 manufactured by BYK-Chemie Japan. And BYK-340 into which fluorine is introduced.

By blending such a leveling agent, the finished appearance of the cured film is improved and can be uniformly applied as a thin film. The amount of the leveling agent used is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, based on the total amount of the composition.
As a method of blending the leveling agent, it may be blended when preparing the composition, or may be blended into the composition immediately before forming the cured film, and further, preparation of the composition and formation of the cured film. You may mix | blend in both the last steps.

<Flexibility imparting agent>
In order to improve the flexibility of the cured film obtained, the composition may contain a flexibility imparting agent as a stress relaxation agent.
As the flexibility imparting agent, for example, a silicone resin or the like can be used.
As a commercial product of silicone resin, Resin MK series manufactured by Wacker, for example, Belsil PMS MK (a polymer containing a repeating unit (unit T) of CH ₃ SiO _3/2 , up to 1% by mass (CH ₃ )) ₂ SiO _2/2 unit (including unit D), and KR-242A manufactured by Shin-Etsu Chemical Co., Ltd. (including 98% by mass of unit T and 2% by mass of dimethyl unit D and including Si—OH end groups) ), KR-251 (containing 88 mass% unit T and 12 mass% dimethyl unit D and containing Si—OH end groups), KR-220L (comprising unit T of formula CH ₃ SiO _3/2 , And those containing Si-OH (silanol) end groups).

(Content of each component in the composition containing the components (A) to (E))
Although content of each component in a composition can be selected suitably, it is preferable to select so that content of each component may become the range shown below, for example.
(E) Except the dispersion medium of a component, each component content with respect to the total amount of (A) [(A-1)-(A-5)]-(D) component is represented by the mass%. The components (B) and (C) preferably used as the dispersion state are calculated using only the respective solid contents, and the dispersion medium included in each component is included in the component (E).
(A-1) Content of a component is about 0.01-40 mass% normally, Preferably it is 0.1-20 mass%. (A-2) Content of a component is about 0.1-40 mass% normally, Preferably it is 1-30 mass%. (A-3) Content of a component is about 0.1-30 mass% normally, Preferably it is 0.3-20 mass%. (A-4) Content of a component is about 0.1-30 mass% normally, Preferably it is 0.3-20 mass%. The content of the component (A-5) is usually about 0.1 to 50% by mass, preferably 1 to 40% by mass.

When (B) component is included, content of (B) component is about 0.1-50 mass% normally, Preferably it is 1-40 mass%. Moreover, when (C) component is included, content of (C) component is about 0.1-70 mass% normally, Preferably it is 1-50 mass%.
(D) Content of a component is about 0.001-30 mass% normally, Preferably it is 0.001-20 mass%. The content of component (E) is usually about 5 to 1000 parts by mass, preferably 20 with respect to the total mass of components (A) [(A-1) to (A-5)] to (D). It is -800 mass parts.
The mixing molar ratio of the component (A-3) and the component (A-5) is not particularly limited, but is preferably 1: 1 to 1: 5, more preferably 1: 2 to 1: 4. is there. When the blending molar ratio of the component (A-3) and the component (A-5) is within the above range, the durability of the obtained cured film is further improved.

(Method for preparing composition containing components (A) to (E))
The composition comprises (A-1) component, (A-2) component and (A-4) hydrolysis condensate, (B) component and (C) at least one component, (D) component and (E) The reaction product obtained by bringing the component into contact with the component (A-5) is preferably reacted with the component (A-5) and then further reacted with the component (A-3).
A mixture containing at least one of the component (A-1), the component (A-2), the component (A-4), the component (B) and the component (C), the component (D) and the component (E). More preferably, the reaction product obtained by heating is added with the component (A-5) and reacted, and then the component (A-3) is added and reacted.

The composition is a reaction product obtained by contacting the hydrolysis condensate of the components (A-1), (A-2) and (A-4) with the components (B) to (E). More preferably, the component (A-5) is added to the product and reacted, and then the component (A-3) is further added and reacted.
Moreover, the reaction product obtained by heating the mixture containing (A-1) component, (A-2) component, (A-4) component, and (B)-(E) component is added to (A- 5) More preferably, the component (A-3) is added and reacted after the component is added and reacted.

Specifically, it is desirable to prepare the composition by performing the following operations.
First, a first mixed solution containing at least (A-1), (A-2), (A-4), (D), (E) and, if necessary, (B) component is prepared, and then If necessary, the component (C) is mixed to prepare the second mixed solution, and then the component (A-5) is mixed to prepare a third mixed solution. Finally, it is preferable to prepare the composition by mixing the component (A-3).
First, a first mixed solution containing at least the components (A-1), (A-2), (A-4), (B), (D) and (E) is prepared, and then (C) The components are mixed to produce a second mixed solution, and then the component (A-5) is mixed to prepare a third mixed solution. Finally, it is more preferable to prepare the composition by mixing the component (A-3).

Thus, it is preferable to prepare each component separately because the liquid storage stability (such as not gelation) of the composition is improved.
In particular, this effect is more exhibited when the amount of water in the liquid is increased by increasing the amount of the components (B) and (C). For example, after the components (A-1), (A-2), (A-4), (B), (D) and (E) are mixed, the component (C) is added. Next, the component (A-5) is mixed, and finally the component (A-3) is mixed. In addition, (E) component can dilute a composition by adding, after preparing a composition.

  It is known that the liquid storage stability of a mixed material such as the above composition is liable to affect the liquid pH (for example, “Application of the sol-gel method to nanotechnology / supervision: Sakuo Sakuo” MC Publishing). In the preparation of the composition, since the acidic component is mixed as the component (D) and the basic component is mixed as the component (A-3) and the component (D), the liquid pH changes depending on the mixing order. As the liquid pH value, for example, the liquid pH value evaluated with a portable pH meter (trade name: Checker 1) manufactured by a calibration pH standard solution, the above first mixed liquid and second mixed liquid are It is preferable that pH ≦ 6, the third mixed solution, and the final mixed solution have pH ≦ 7. In particular, when the liquid pH exceeds 8 when the third liquid mixture, that is, the component (A-3) is mixed, the liquid stability may be lowered. The liquid is preferably kept in an acidic state from the start of preparation of the composition to the end of preparation. That is, it is preferable to prepare the composition by a procedure in which such conditions are maintained.

  Moreover, it is preferable to heat-process said 1st liquid mixture, 2nd liquid mixture, and 3rd liquid mixture after mixing of each component. The temperature is preferably 30 ° C to 130 ° C, more preferably 50 ° C to 90 ° C, and the heat treatment time is preferably 30 minutes to 24 hours, more preferably 1 hour to 8 hours. The mixing and heating means is not particularly limited as long as it can uniformly mix and heat. By heating in this way, the condensation reaction of the components (A-1), (A-2), (A-3), (A-4) and (A-5) in the liquid proceeds, and the boiling resistance is increased. And other durability. Reactions of the components (A-1), (A-2), (A-3), (A-4), and (A-5) can be analyzed by solution Si-NMR, thereby achieving a suitable structure. Can design. The reaction is often extremely slow at less than 30 ° C. or less than 30 minutes, and when it exceeds 130 ° C. or more than 24 hours, (A-1), (A-2), (A-3), (A -4) and (A-5) reaction of the component proceeds too much, and the liquid may gel or become highly viscous and may not be applied.

The final liquid (composition) after mixing the component (A-3) is also preferably heat-treated. In the case of mixing at room temperature, it is easily affected by the stirring efficiency, and due to this, when the degree of dispersion of the component (A-3) is low, the transparency of the cured film (decrease in total light transmittance, increase in haze) May fall. The temperature is preferably 30 ° C to 130 ° C, more preferably 50 ° C to 90 ° C, and the time is preferably 5 minutes to 10 hours, more preferably 15 minutes to 6 hours. The mixing and heating means is not particularly limited as long as it can uniformly mix and heat. If the temperature is less than 30 ° C. or less than 5 minutes, the effect of the heat treatment is often poor, and if it exceeds 130 ° C. or more than 10 hours, the liquid may gel or become highly viscous and cannot be applied.
In the examples described later, the evaluation results of the cured film produced using the composition obtained after standing for 1 week are described, but there is no particular limitation on the liquid standing period until the cured film is produced.

(Content of each component in the composition containing the components (A) to (G))
Although the content of each component in the composition containing at least one of (A), (B) and (C) and the components (D) to (G) can be appropriately selected, (A) to ( E) Each content of component is the mass of each component content relative to the total amount of components (A) [(A-1) to (A-5)] to (G), excluding the dispersion medium of component (E). It can be the same as that of the case of the composition containing (A)-(E) component except expressing with%.

  (F) Content of a component is about 0.01-30 mass% normally, Preferably it is 0.1-20 mass%. (G) Content of a component is about 1-60 mass parts normally, Preferably it is about 10-50 mass parts.

(Method for preparing composition containing components (A) to (G))
The said composition is obtained by making the hydrolysis-condensation product of (A-1), (A-2), (A-4) and (A-5) component, and (B)-(G) component contact. The reaction product obtained by adding the component (A-3) to the reaction is preferable. Specifically, it is desirable to prepare the composition by performing the following operations. In the following preparation methods, at least one of (B) and (C) may be used.

First, a first mixed solution containing at least the components (A-1), (A-2), (A-4), (B), (D), (E), and (G) is prepared. The components (C) and (F) are mixed with the second mixture, and then the component (A-5) is mixed to prepare a third mixture. Finally, it is preferable to prepare the composition by mixing the component (A-3).
Thus, it is preferable to prepare each component separately because the liquid storage stability (such as not gelation) of the composition is improved. In particular, this effect is more exerted when the amount of water in the liquid is increased by increasing the amount of the components (B), (C), and (F) added.
For example, after mixing the components (A-1), (A-2), (A-4), (B), (D), (E), and (G), the components (C) and (F) Add Next, the component (A-5) is mixed, and finally the component (A-3) is mixed.
In addition, (E) component can dilute a composition by adding, after preparing a composition.

As a more preferable method for preparing the composition, hydrolysis condensates of the components (A-1), (A-2) and (A-4), (B), (C), (D), (E) and (G) Component (F) and (A-5) are added to the reaction product obtained by contacting component and reacted, and component (A-3) is added to the resulting reaction product. The composition can be prepared by reaction.
Specifically, the mixture containing the components (A-1), (A-2), (A-4), (B), (C), (D), (E), and (G) is heated. Components (F) and (A-5) are added to the reaction product obtained and heated, and then component (A-3) is added to the reaction product obtained and heated to obtain a composition. It is. By using such a preparation method, the dispersibility of the composition can be further improved, and the transparency of the cured film can be improved.

Also, hydrolysis condensates of the components (A-1), (A-2), (A-4) and (A-5), and (B), (C), (D), (E) and (E (G) Component (F) is added to the reaction product obtained by contacting component G) and reacted, and the resulting reaction product is reacted by adding component (A-3). You can also
Specifically, for example, (A-1), (A-2), (A-4), (A-5), (B), (C), (D), (E) and (G) components (F) component (F) is added to the reaction product obtained by heating the mixture containing the mixture and heated, and then the component (A-3) is added to the reaction product obtained and heated to obtain a composition. It is. By using such a preparation method, the dispersibility of the composition can be further improved, and the transparency of the cured film can be improved.

Furthermore, the reaction product obtained by bringing the hydrolysis condensate of components (A-1), (A-2) and (A-4) and the components (B) to (G) into contact with (A) The component can also be prepared by adding the component (A-3) and reacting the obtained reaction product with the component (5).
Specifically, for example, a reaction product obtained by heating a mixture containing the components (A-1), (A-2), (A-4) and (B) to (G) is added to the reaction product (A- 5) A component is added and heated, and then the component (A-3) is added to the obtained reaction product and heated to obtain a composition. By using such a preparation method, the dispersibility of the composition can be further improved, and the transparency of the cured film can be improved.

It is known that the liquid storage stability of a mixed material such as the above composition is liable to affect the liquid pH (for example, “Application of the sol-gel method to nanotechnology / supervision: Sakuo Sakuo” MC Publishing). In the preparation of the composition, since the acidic component is mixed as the components (D) and (G) and the basic component is mixed as the components (A-3) and (D), the liquid pH changes depending on the mixing order.
As the liquid pH value, for example, the liquid pH value evaluated with a portable pH meter (trade name: Checker 1) manufactured by a calibration pH standard solution, the above first mixed liquid and second mixed liquid are It is preferable that pH ≦ 6, the third mixed solution, and the final mixed solution have pH ≦ 7. In particular, when the liquid pH exceeds 8 when the third liquid mixture, that is, the component (A-3) is mixed, the liquid stability may be lowered. The liquid is preferably kept in an acidic state from the start of preparation of the composition to the end of preparation. That is, it is preferable to prepare the composition by a procedure in which such conditions are maintained.

  Moreover, it is preferable to heat-process said 1st liquid mixture, 2nd liquid mixture, and 3rd liquid mixture after mixing of each component. The temperature is preferably 30 ° C to 130 ° C, more preferably 50 ° C to 90 ° C, and the heat treatment time is preferably 30 minutes to 24 hours, more preferably 1 hour to 8 hours. The mixing and heating means is not particularly limited as long as it can uniformly mix and heat. By heating in this way, the condensation reaction of the components (A-1), (A-2), (A-3), (A-4), and (A-5) in the liquid proceeds and durability is increased. (Boiling resistance) and other properties are improved. Reactions of the components (A-1), (A-2), (A-3), (A-4), and (A-5) can be analyzed by solution Si-NMR, and thereby have a suitable structure. Can be designed. The reaction is often extremely slow at less than 30 ° C. or less than 30 minutes, and when it exceeds 130 ° C. or more than 24 hours, (A-1), (A-2), (A-3), (A -4) and (A-5) reaction of the component proceeds too much, and the liquid may gel or become highly viscous and may not be applied.

Moreover, it is preferable to heat-process also the last liquid (composition) after mixing (A-3) component. In the case of mixing at room temperature, it is easily affected by the stirring efficiency, and due to this, when the degree of dispersion of the component (A-3) is low, the transparency of the cured film (decrease in total light transmittance, increase in haze) May fall. The temperature is preferably 30 ° C to 130 ° C, more preferably 50 ° C to 90 ° C, and the time is preferably 5 minutes to 10 hours, more preferably 15 minutes to 6 hours. The mixing and heating means is not particularly limited as long as it can uniformly mix and heat. If the temperature is less than 30 ° C. or less than 5 minutes, the effect of the heat treatment is often poor, and if it exceeds 130 ° C. or more than 10 hours, the liquid may gel or become highly viscous and cannot be applied.
In the examples described later, the evaluation results of the cured film produced using the composition obtained after standing for 1 week are described, but there is no particular limitation on the liquid standing period until the cured film is produced.

  Furthermore, since the component (F) used in the present invention is an acid stable type, when mixed with other dispersions, it is better to mix them in acidic sols in order to prevent aggregation, precipitation and gelation during mixing. preferable. For example, when the sol of the basic stable anionic fine particles and the component (F) are directly mixed, there is a possibility that the dispersion cannot be maintained because it is out of the pH range where it can be stably dispersed.

[Composition II]
Composition II includes the following components:
(A ′) component,
(B) at least one of component and (C) component, and (D)-(G) component.
Composition II preferably contains component (B).
(A ′) Hydrolyzed condensate of silane compound having alkoxy group (B) Organic polymer fine particle comprising copolymer containing monomer unit having ultraviolet absorbing group (C) Colloidal silica (D) Curing catalyst (E ) Dispersion medium (F) Cerium oxide (G) dispersion stabilizer treated with silane compound The above components (B) to (G) are the same as in composition I.

((A ′) component)
This composition contains a hydrolysis condensate of a silane compound having an alkoxy group as the component (A ′).
There is no restriction | limiting in particular as a silane compound which has the alkoxy group used as a raw material of the said hydrolysis-condensation product, For example, various things are mentioned, for example, following formula (10)
R ¹ _m R ² _n Si (OR ³ ) _4-mn (10)
Wherein R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms; a fluorinated alkyl group having 1 to 10 carbon atoms; a vinyl group; a phenyl group; or a methacryloxy group, an amino group, or an aminoalkyl group. , An alkylamino group, a glycidoxy group, a 3,4-epoxycyclohexyl group, and a blocked isocyanate group, and an alkyl group having 1 to 3 carbon atoms substituted with one or more groups, and R ³ has 1 carbon atom. -4 alkyl group or alkoxyalkyl group, m and n are each independently 0, 1 or 2, and m + n is 0, 1 or 2.) Mention may be made of partial condensates.

  In the formula (10), the alkyl group having 1 to 10 carbon atoms may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and various butyl groups. Groups, various hexyl groups, various octyl groups, various decyl groups and the like, and examples of the fluorinated alkyl group include a trifluoroethyl group and a trifluoropropyl group. Moreover, as a C1-C3 alkyl group, a methyl group, an ethyl group, n-propyl group, and an isopropyl group are mentioned.

As a particularly preferred hydrolysis condensate of a silane compound having an alkoxy group, a hydrolysis condensate of one or more compounds selected from the following (A-2) to (A-5) is preferably used.
(A-2) Organoalkoxysilane compound not containing amino group, epoxy group and isocyanate group (A-3) Silane compound having amino group and alkoxy group (A-4) Silane compound having epoxy group and alkoxy group (A -5) Blocked isocyanatosilane compounds having an alkoxy group
Said (A-2)-(A-5) is the same as the composition I.

(Content of each component in Composition II)
Although content of each component in a composition can be selected suitably, it is preferable to select so that content of each component may become the range shown below, for example.
(E) Except the dispersion medium of a component, each component content with respect to the total amount of (A) [(A-2)-(A-5)]-(G) component is represented by the mass%. The components (B), (C), and (F) that are preferably used as the dispersion state are calculated using only the respective solid contents, and the dispersion medium included in each component is included in the component (E). And
(A-2) Content of a component is about 0.1-50 mass% normally, Preferably it is 0.5-30 mass%. (A-3) Content of a component is about 0.1-40 mass% normally, Preferably it is 0.5-20 mass%. (A-4) Content of a component is about 0.1-30 mass% normally, Preferably it is 0.3-20 mass%. The content of the component (A-5) is usually about 0.1 to 50% by mass, preferably 0.5 to 30% by mass.

When (B) component is included, content of (B) component is about 0.1-50 mass% normally, Preferably it is 1-40 mass%. Moreover, when (C) component is included, content of (C) component is about 0.1-50 mass% normally, Preferably it is 1-40 mass%. (F) Content of a component is about 0.01-30 mass% normally, Preferably it is 0.1-20 mass%. (D) Content of a component is about 0.001-40 mass% normally, Preferably it is 0.003-30 mass%. (G) Content of a component is about 1-60 mass% normally, Preferably it is 10-50 mass%.
The content of the component (E) is usually about 5 to 1000 parts by mass, preferably about 100 parts by mass in total of the components (A) [(A-2) to (A-5)] to (G). Is about 20 to 800 parts by mass.
The molar ratio of the component (A-3) and the component (A-5) is not particularly limited, but is preferably 1: 1 to 1: 5, more preferably 1: 2 to 1: 4. is there. When the molar ratio of the component (A-3) and the component (A-5) is within the above range, the durability (boiling resistance) of the obtained cured film is further improved.

(Method for preparing composition II)
The composition is obtained by bringing the hydrolysis condensate of components (A-2), (A-4) and (A-5) and the components (B) to (E) into contact with each other, (A-3) A component obtained by adding a component and reacting is preferable. Specifically, it is desirable to prepare a composition by performing the following operations. In the following preparation methods, at least one of (B) and (C) may be used.

First, a first mixed solution containing at least the components (A-2), (A-4), (B), (D), (E) and (G) is prepared, and then (C) and (F ) Components are mixed to produce a second mixed solution, and subsequently (A-5) component is mixed to prepare a third mixed solution. Finally, it is preferable to prepare the composition by mixing the component (A-3).
Thus, it is preferable to prepare each component separately because the liquid storage stability (such as not gelation) of the composition is improved. In particular, this effect is more exerted when the amount of water in the liquid is increased by increasing the amount of the components (B), (C), and (F) added.
For example, the components (A-2), (A-4), (B), (D), (E) and (G) are mixed, and then the components (C) and (F) are added. Next, the component (A-5) is mixed, and finally the component (A-3) is mixed.
In addition, (E) component can dilute a composition by adding, after preparing a composition.

As a more preferable method for preparing the composition, hydrolysis condensates of the components (A-2) and (A-4) and the components (B), (C), (D), (G) and (E) The components (F) and (A-5) are added to the reaction product obtained by contact and reacted, and the component (A-3) is added to the obtained reaction product for reaction. Can be prepared.
Specifically, for example, a reaction product obtained by heating a mixture containing the components (A-2), (A-4), (B), (C), (D), (G) and (E). The components (F) and (A-5) are added to the product and heated, and then the component (A-3) is added to the obtained reaction product and heated to obtain a composition. By using such a preparation method, the dispersibility of the composition can be further improved, and the transparency of the cured film can be improved.

Further, the hydrolysis condensate of components (A-2), (A-4) and (A-5) is contacted with components (B), (C), (D), (G) and (E). The component (F) can be added to the reaction product obtained by the reaction and reacted, and the component (A-3) can be added to the reaction product and reacted to prepare the composition.
Specifically, for example, a mixture containing the components (A-2), (A-4), (A-5), (B), (C), (D), (G) and (E) is heated. The component (F) is added to the reaction product obtained and heated, and then the component (A-3) is added to the reaction product obtained and heated to obtain a composition. By using such a preparation method, the dispersibility of the composition can be further improved, and the transparency of the cured film can be improved.

Further, the component (A-5) is added to the reaction product obtained by bringing the hydrolysis condensate of components (A-2) and (A-4) into contact with the components (B) to (G). It is possible to prepare a composition by adding the component (A-3) to the reaction product obtained by the reaction and reacting the resulting product.
Specifically, for example, the component (A-5) is added to the reaction product obtained by heating a mixture containing the components (A-2), (A-4) and (B) to (G). The composition is obtained by heating and then adding the component (A-3) to the resulting reaction product and heating. By using such a preparation method, the dispersibility of the composition can be further improved, and the transparency of the cured film can be improved.

It is known that the liquid storage stability of a mixed material such as the above composition is liable to affect the liquid pH (for example, “Application of the sol-gel method to nanotechnology / supervision: Sakuo Sakuo” MC Publishing). In the preparation of the composition, since the acidic component is mixed as the components (D) and (G) and the basic component is mixed as the components (A-3) and (D), the liquid pH changes depending on the mixing order.
The liquid pH value, for example, the liquid pH value evaluated with a portable pH meter (manufactured by Hannah: trade name checker 1) corrected with a pH standard solution for calibration, It is preferable that pH ≦ 6, the third mixed solution, and the final mixed solution have pH ≦ 7. In particular, when the liquid pH exceeds 8 when the third liquid mixture, that is, the component (A-3) is mixed, the liquid stability may be lowered. The liquid is preferably kept in an acidic state from the start of preparation of the composition to the end of preparation. That is, it is preferable to prepare the composition by a procedure in which such conditions are maintained.

  Moreover, it is preferable to heat-process said 1st liquid mixture, 2nd liquid mixture, and 3rd liquid mixture after mixing of each component. The temperature is preferably 30 ° C to 130 ° C, more preferably 50 ° C to 90 ° C, and the heat treatment time is preferably 30 minutes to 24 hours, more preferably 1 hour to 8 hours. The mixing and heating means is not particularly limited as long as it can uniformly mix and heat. By heating in this way, the condensation reaction of the components (A-2), (A-3), (A-4), and (A-5) in the liquid proceeds and durability (boiling resistance) and Other characteristics are improved. Reactions of the components (A-2), (A-3), (A-4), and (A-5) can be analyzed by solution Si-NMR, and thus can be designed to have a suitable structure. The reaction is often extremely slow at less than 30 ° C. or less than 30 minutes, and when it exceeds 130 ° C. or more than 24 hours, (A-2), (A-3), (A-4), and ( A-5) The reaction of the component proceeds too much, and the liquid may gel or become highly viscous and may not be applied.

Moreover, it is preferable to heat-process also the last liquid (composition) after mixing (A-3) component. In the case of mixing at room temperature, it is easily affected by the stirring efficiency, and due to this, when the degree of dispersion of the component (A-3) is low, the transparency of the cured film (decrease in total light transmittance, increase in haze) May fall. The temperature is preferably 30 ° C to 130 ° C, more preferably 50 ° C to 90 ° C, and the time is preferably 5 minutes to 10 hours, more preferably 15 minutes to 6 hours. The mixing and heating means is not particularly limited as long as it can uniformly mix and heat. If the temperature is less than 30 ° C. or less than 5 minutes, the effect of the heat treatment is often poor, and if it exceeds 130 ° C. or more than 10 hours, the liquid may gel or become highly viscous and cannot be applied.
In the examples described later, the evaluation results of the cured film produced using the composition obtained after standing for 1 week are described, but there is no particular limitation on the liquid standing period until the cured film is produced.

  Composition III is obtained by a production method similar to the production method of composition I described above. The composition IV is obtained by the same production method as the production method of the composition II.

  Furthermore, since the component (F) used in the present invention is an acid stable type, when mixed with other dispersions, it is better to mix them in acidic sols in order to prevent aggregation, precipitation and gelation during mixing. preferable. For example, when the sol of the basic stable anionic fine particles and the component (F) are directly mixed, there is a possibility that the dispersion cannot be maintained because it is out of the pH range where it can be stably dispersed.

The above composition is applied onto a substrate to form a coating film. For example, it is applied by a known method such as spraying, dipping, curtain flow, bar coater or roll coating.
The thickness of the coating film depends on the final form of the cured film to be formed.
As a 1st aspect (composition I), it adjusts as thickness of a coating film so that the thickness of a cured film becomes like this. Preferably it is 0.5-30 micrometers, More preferably, it is 0.5-15 micrometers. Then, a desired cured film is obtained by heating and curing at appropriate curing conditions, usually room temperature to 190 ° C., preferably 80 to 140 ° C. for about 10 minutes to 24 hours, preferably 30 minutes to 3 hours. It is done.
In the second embodiment (Composition II), the thickness of the coating film is adjusted so that the thickness of the cured film is preferably 1 to 50 μm, more preferably 2 to 20 μm. Then, a desired cured film is obtained by heat curing at appropriate curing conditions, usually 80 to 190 ° C., preferably 100 to 140 ° C., for about 10 minutes to 24 hours, preferably 30 minutes to 3 hours. .

In the cured film obtained from the composition, organic polymer fine particles (component (B)) and / or colloidal silica (component (C)) are dispersed in the film. When the composition contains cerium oxide particles (component (F)), these particles are also dispersed.
The dispersed state is preferably an inorganic-organic hybrid sea-island structure. The particle size of the organic fine particles corresponding to the islands having a sea-island structure is preferably 200 nm or less, more preferably 100 nm or less, and the particles are uniformly dispersed without agglomeration. The component (A) or (A ′) corresponds to the sea of sea-island structure.

  The average particle diameter of the organic polymer fine particles in the film is defined as follows. The cross section of the cured film is observed under a condition of an acceleration voltage of 200 kV with a TEM (field emission transmission electron microscope). The value of the biaxial average diameter of each organic polymer fine particle present in 1 μm square is calculated. 10 organic polymer fine particles having a large biaxial average diameter are selected. The number average value of the biaxial average diameter values (that is, the value obtained by dividing the sum of the biaxial average diameters by 10) is defined as the average particle diameter.

  Moreover, the average particle diameter of the colloidal silica in the film is defined in the same manner as the average particle diameter of the organic polymer fine particles in the film. That is, the cross section of the cured film is observed under a condition of an acceleration voltage of 200 kV with a TEM (field emission transmission electron microscope). The value of the biaxial average diameter of each colloidal silica present in a 1 μm square is calculated. Select 10 colloidal silicas with a large biaxial average diameter. The number average value of the biaxial average diameter values (that is, the value obtained by dividing the sum of the biaxial average diameters by 10) is defined as the average particle diameter.

  Examples of the resin that can be used for the substrate include polyethylene, polypropylene, cycloolefin resins (eg, “ARTON” manufactured by JSR Corporation, “ZEONOR” “ZEONEX” manufactured by Nippon Zeon Corporation), and polyolefins such as polymethylpentene. Resin, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, cellulose resin such as diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, polystyrene, syndiotactic polystyrene, acrylonitrile butadiene styrene resin ( Styrene resins such as ABS resin), imide resins such as polyimide, polyetherimide, and polyamideimide, polyamide resins such as nylon, and polyether , Ketone resins such as polyetheretherketone, sulfone resins such as polysulfone and polyethersulfone, vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride, acrylic resins such as polymethyl methacrylate, polycarbonate resins , Polyphenylene sulfide, polyacetal, modified polyphenylene ether, polyvinyl alcohol, epoxy resin, fluorine resin, plastic lens resin polymethyl methacrylate, alicyclic polyolefin, acrylonitrile styrene copolymer, methacryl styrene copolymer, alicyclic acryl, di Examples include glycol diallyl carbonate, diallyl phthalate, polyurethane, polythiourethane, episulfide, etc., and polymer alloys and polymers in which a plurality of the above polymers are mixed It may be a blend. Further, a laminated structure in which a plurality of the above resins are laminated may be used. Among the above resins, polyester resins, polyolefin resins, and polycarbonate resins are preferable.

The substrate made of these resins may be transparent or translucent, may be colored, or may be uncolored, and may be appropriately selected according to the application. It is excellent in transparency and preferably has no color. Among the resins, polycarbonates that are excellent in transparency, mechanical properties, heat resistance, and the like are particularly suitable.
There is no restriction | limiting in particular in the thickness of a board | substrate, Although it selects suitably according to a condition, Usually, it is about 5 micrometers-30 mm, Preferably it is 15 micrometers-10 mm.

  The composition can form a cured film with good adhesion on the substrate, but in order to further improve the adhesion, an oxidation method or the like may be applied to at least the surface of the substrate on the side where the cured film is formed. Surface treatment can be performed by an uneven method or the like. Examples of the oxidation method include corona discharge treatment, plasma treatment such as low pressure plasma method and atmospheric pressure plasma method, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, electron beam treatment, and intro treatment. In addition, examples of the roughening method include a sand blast method and a solvent treatment method. These surface treatment methods are appropriately selected according to the type of the substrate, but in general, the corona discharge treatment method is preferably used from the viewpoints of curing and operability. Further, a surface treatment with a silane coupling agent or a primer layer can be provided. However, since it is not necessary to provide a primer layer in the present invention, the structure can be simplified.

  Moreover, you may provide an inorganic hard material layer, a transparent conductive film, a photocatalyst layer, etc. on the hardened | cured material layer formed on the board | substrate. These layers can be provided after dyeing.

  The composition I and its laminate are described in PCT / JP2009 / 051897, and the composition II and its laminate are described in the international publication 2009/099106 pamphlet.

  In the present invention, a laminate obtained by coating and curing the above composition on a substrate or a laminate of the present invention described later is further dyed. By dyeing, the organic fine particles contained in the coat layer and / or the substituents bonded to Si atoms contained in the coat layer are affected in some way, and the cured film is considered to be colored. The laminate of the present invention has little coloring unevenness. Since the laminate of the present invention is dyed without providing a primer layer between the substrate and the coat layer, there is no need to provide a primer layer. For example, when producing a color lens for spectacles from the laminate of the present invention, dyeing is performed before forming the antireflection layer.

A general disperse dye can be used for dyeing.
Examples of dyes include nitroso dyes, nitro dyes, azo dyes, stilbene azo dyes, ketoimine dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, methine dyes, polymethine dyes, thiazole dyes, indamine dyes, indophenols. Examples include dyes, azine dyes, oxazine dyes, thiazine dyes, sulfur dyes, aminoketone dyes, oxyketone dyes, anthraquinone dyes, indigoid dyes, and phthalocyanine dyes, and at least one of them can be used. Specific examples include p-anisidine, aniline, p-aminoacetanilide, p-aminophenol, 1-chloro-2,4-dinitrobenzene, 2-chloro-4-nitroaniline, o-chloronitrobenzene, diphenylamine, m- Nitroaniline, p-nitroaniline, N, N-bis (2-hydroxyethyl) aniline, 1-phenyl-3-methyl-5-pyrazolone, benzene-based intermediates such as phenol, p-cresidine (6-methoxy-m -Toluidine), m-cresol, p-cresol, m-toluidine, 2-nitro-p-toluidine, toluene-based intermediates such as p-nitrotoluene, 1-naphthylamine, naphthalene-based intermediates such as 2-naphthol, 1- Amino-4-bromoanthraquinone-2-sulfonic acid (bromamic acid), 1-ant Quinonesulfonic acid, 1,4-diaminoanthraquinone, 1,5-dichloroanthraquinone, 1,4-dihydroxyanthraquinone (quinizarin), 1,5-dihydroxyanthraquinone (anthralphine), 1,2,4-trihydroxyanthraquinone (purpurine) ), Phthalic anhydrides such as 2-methylanthraquinone, anthraquinone-based intermediates, N- [4-[(2-hydroxy-5-methylphenyl) azo] phenyl] acetamide, 2,2 ′-[[3-chloro- 4-[(2,6-dichloro-4-nitrophenyl) azo] phenyl] imino] bisethanol, 1- (methylamino) -4- (2-hydroxyethylamino) anthraquinone, 5,8-dihydroxy-1, 4-Bis [(2-hydroxyethyl) amino] -9,10-anthraquino And photochromic materials such as diarylethene compounds, spiropyran compounds, spiroperimidine compounds, viologen compounds, 2,5-norbornadiene, 3,3-diphenyl-3H-naphtho [2,1-b] pyran, azobenzene, thioindigo, etc. Can be mentioned.

  Moreover, you may use a disperse dye individually or in mixture of 2 or more types. The disperse dye is usually dispersed in water to form a dye bath, but an organic solvent such as methanol, ethanol, benzyl alcohol or the like may be used in combination as a solvent.

  Further, a surfactant may be further added to the dyeing bath as a dispersant for the dye. Examples of the surfactant include alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate, aromatic sulfonic acid formalin condensate, lauryl sulfate, and other anionic surfactants, polyoxyethyl alkyl ether, alkyl Nonionic surfactants such as amine ethers and polyoxyethylene sorbitan fatty acid esters are listed.

  A dyeing bath is prepared by dispersing the dye in a solvent, and the laminate is immersed in the dyeing bath, and dyeing is performed at a predetermined temperature for a predetermined time. The dyeing temperature and time vary depending on the desired color density, but are usually 40 to 100 ° C, preferably 70 to 99 ° C, and may be about 1 to 60 minutes. The dye concentration in the dyeing bath is usually about 0.01 to 30% by weight.

  As the carrier agent, a water-soluble organic solvent is often used. Various types are presented in Japanese Patent No. 83501, Japanese Patent Laid-Open No. 04-41785, and the like. An example is benzyl alcohol.

[Laminate]
The laminate of the present invention comprises a substrate and a layer (coat layer) on the substrate, and this layer is formed in a matrix in which organic fine particles containing an ultraviolet absorbing group and / or colloidal silica has a Si—O bond. Is distributed.
The laminated body of this invention can be manufactured by said method. That is, when manufacturing using the said composition I and II, an organic fine particle corresponds to (B) component, and the matrix which has a Si-O bond corresponds to (A) or (A ') component. About 0.1-50 mass% of organic fine particles are contained. Further, inorganic fine particles of the component (C) and the component (F) are also dispersed.
The organic fine particles dispersed in the coat layer preferably have an average particle diameter of 1 to 200 nm, and the average particle diameter can be measured by the method described above.

  The haze value of the coat layer of the laminate obtained by the above method is 10% or less, preferably 5% or less. In addition, it has excellent hardness and the number of scratches when steel wool # 0000 is rubbed for 10 reciprocations at 9.8 N load and 2000 mm / sec is 0, and the load is 4.9 N using a wear ring of CS-10F. The difference in haze before and after the Taber abrasion test of 500 revolutions is less than 30, preferably less than 15 (more preferably 10 or less). Furthermore, it is excellent in adhesiveness, and the coating layer does not peel in a cross-cut peel test in accordance with JIS K 5400.

The coat layer of the laminate is colored by dyeing, and the transmittance of at least one wavelength of wavelengths in the visible light region of 400 to 750 nm (preferably 420 to 680 nm or 420 to 650 nm) is 80% or less.
Preferably, in the visible light region of 400 to 750 nm (preferably 420 to 680 nm or 420 to 650 nm), the transmittance of at least one wavelength is 80% or less, and the transmittance is 400% other than the wavelength of 80% or less. Among the wavelengths of ˜750 nm, the transmittance of at least one wavelength is 1% or more.
More preferably, the transmittance of at least one of the wavelengths in the visible light region of 400 to 750 nm (preferably 420 to 680 nm or 420 to 650 nm) is 80% or less, and the transmittance is other than the wavelength of 80% or less. Among the wavelengths of 400 to 750 nm, the transmittance of at least one wavelength is 10% or more.

  Here, “at least one wavelength transmittance is 80% or less” means, for example, that the transmittance at a specific wavelength (for example, a wavelength of 400 nm) is 80% or less. Further, for example, it means that the transmittance of both the wavelength of 500 nm and the wavelength of 600 nm is 80% or less. Further, for example, it may be 80% or less continuously within the above range and over a wavelength width of 100 nm, 150 nm, or 200 nm, or over 420 to 650 nm.

Further, for example, the difference between the maximum transmittance and the minimum transmittance of wavelengths in the visible light region of 400 to 750 nm is 50% or less, preferably 30% or less.
The transmittance may be, for example, 70%, 60%, 50%, or 40% or less.
Although it changes with colors, specifically, it may be continuously below a predetermined transmittance at 420 to 470 nm, 470 to 520 nm, 520 to 570 nm, 570 to 620 nm, or 620 to 670 nm.

Further, for example, the following transmittance may be provided.
-It has the minimum value of transmittance at 400-600 nm. The minimum value is 80% or less.
-It has the minimum transmittance at 400-450 nm. The minimum value is 80% or less.
It has a minimum value of transmittance at 400 to 450 nm and a maximum value of transmittance at 450 to 550 nm. The minimum value is 80% or less, and the maximum value is 95% or less.
The difference between the maximum value and the minimum value of transmittance at 400 to 650 nm is 10% or more.
The difference between the maximum value and the minimum value of transmittance at 400 to 650 nm is 20% or more.

  The transmittance of the wavelength can be appropriately changed depending on the type and amount of the dye used. When used for sunglasses, brown or gray is usually preferred. Moreover, it can change suitably with the kind of dye to use also the wavelength whose transmittance | permeability is 80% or less.

Various characteristics in each example were determined according to the following.
(1) Organic polymer fine particle content (% by mass) in the cured film
Calculated by calculation. Specifically, components (A-1) to (A-5) in which hydrolysis / condensation reaction has completely progressed (component (A) or component (A ′)), organic polymer fine particles (component (B)) And the mass% of the organic polymer fine particles in the total mass of other components was calculated.

(2) Film appearance The appearance of the cured film was visually observed to confirm foreign matters and mottled patterns.

(3) Total light transmittance The total light transmittance of the laminate was measured with a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.).

(4) Haze With a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.), the haze value of the substrate and the laminate is measured, and the difference between the haze value of the laminate and the haze value of the substrate is determined from the haze value of the dyed layer. did.

(5) Abrasion resistance Using a wear wheel CS-10F and a Taber abrasion tester (rotary abrasion tester) (Toyo Seiki Co., Ltd., model: TS), a 500 rotation Taber abrasion test was performed at a load of 4.9 N, and Taber abrasion When the difference (ΔH) between the haze before the test and the haze after the Taber abrasion test was less than 15, “◎” was given, “15” was given 15 or more and less than 30 and “x” was given 30 or more.

(6) Scratch resistance Using steel wool # 0000 (load 9.8 N), after 10 reciprocations at 2000 mm / sec, the surface damage was visually evaluated. “1” indicates that there is no scratch, “2” indicates that the scratch is slightly scratched, and “3” indicates that the scratch is present on more than half of the rubbed area.

(7) Adhesiveness In accordance with JIS K 5400, a sample (cured film) was cut with a razor blade every 11 mm in length and width to make 100 grids, and a commercially available cellophane tape ("CT-24" (Width 24 mm) ", made by Nichiban Co., Ltd.), and then closely peeled with the belly of the finger, and then peeled off rapidly at an angle of 90 °, and the cured film did not peel off, and the remaining number (X) remained, Displayed by X / 100, the adhesion of the cured film was evaluated.

(8) Organic fine particle dispersion structure The cross-section of the cured film was observed with a TEM (transmission electron microscope), 10 organic fine particles present in the 1 μm square were selected, and the average particle size was determined. Specifically, a protective film of carbon and tungsten is sequentially formed on the cured film surface by coating, and accelerated by an FIB microsampling system (manufactured by Hitachi High-Technologies Corporation, FB-2000A type focused ion beam processing observation apparatus). The film was thinned at a voltage of 30 kV. The thinned sample was cured with TEM (manufactured by Hitachi High-Technologies Corporation, HF-2100 field emission type transmission electron microscope) under the conditions of acceleration voltage 200 kV, direct magnification × 5000, × 10000, × 30000, and × 50000. The cross section of was observed. The value of the biaxial average diameter of each organic polymer fine particle present in 1 μm square was calculated. Ten organic polymer fine particles having a large biaxial average diameter were selected. The number average value of the biaxial average diameter values (that is, the value obtained by dividing the sum of the biaxial average diameters by 10) was defined as the average particle diameter.
The organic fine particles having an average particle diameter of 200 nm or less are indicated by “◯”, the average particle diameter of greater than 200 nm is indicated by “X”, and those having a particle diameter of 200 nm or less are present. In the case where there is an amoeba having a thickness of 200 nm or more, “Δ” was given. Further, “−” indicates that organic fine particles are not present.

(9) Inorganic fine particle dispersion structure Carbon and tungsten protective films are sequentially formed on the cured film surface by coating, and using FIB microsampling system (manufactured by Hitachi High-Technologies Corporation, FB-2000A type focused ion beam processing observation apparatus) The film was thinned at an acceleration voltage of 30 kV. The thinned sample was cured with TEM (manufactured by Hitachi High-Technologies Corporation, HF-2100 field emission type transmission electron microscope) under the conditions of acceleration voltage 200 kV, direct magnification × 5000, × 10000, × 30000, and × 50000. The cross section of was observed. The value of the biaxial average diameter of each inorganic fine particle present in 1 μm square was calculated. Ten inorganic fine particles having a large biaxial average diameter were selected. The number average value of the biaxial average diameter values (that is, the value obtained by dividing the sum of the biaxial average diameters by 10) was defined as the average particle diameter.

  The average particle size of the colloidal silica fine particles and cerium oxide fine particles in the cured film was determined in the same manner as in (8) above. Samples with an average particle size of 200 nm or less were marked with “◯”, and those with an average particle size larger than 200 nm were marked with “x”. Further, “−” indicates that no inorganic fine particles exist.

Moreover, the detail of the raw material described with the brand name is as follows.
(A-1) Component: M silicate 51 “polyalkoxysilane which is a partial condensate (average 3 to 5 mer) of tetramethoxysilane” manufactured by Tama Chemical Industry Co., Ltd. (A-2) Component: MTMS-A “Methyl” Polyorganoalkoxysilane which is a partial condensate of trimethoxysilane ”(B) component manufactured by Tama Chemical Industry Co., Ltd .: ULS-1385MG (ultraviolet absorption skeleton type: benzotriazole) (Concentration 30% by mass, average particle size 55 to 170 nm)
(B) Component: ULS-385MG (ultraviolet ray absorbing skeleton species: benzophenone series), manufactured by Yushi Kogyo Co., Ltd. (water dispersion / solid content concentration 30% by mass, average particle size 55 to 170 nm)
(B) Component: ULS-1383MG (ultraviolet ray absorbing skeleton species: benzotriazole), manufactured by Yushi Kogyo Co., Ltd. (water dispersion / solid content concentration 30% by mass, average particle size 55 to 170 nm)
(B) Component: ULS-383MG (ultraviolet ray absorbing skeleton type: benzophenone), manufactured by Yushi Kogyo Co., Ltd. (water dispersion / solid content concentration 30% by mass, average particle size average particle size 55-170 nm)

  In addition, the average particle diameter of the above (B) was measured as follows. The liquid diluted 100 times with ion-exchanged water is measured using a dynamic light scattering particle size distribution analyzer (Beckman Coulter, Co., Ltd., Coulter Counter N5), and the average particle is obtained by unimodal analysis (monodisperse mode analysis). The diameter was determined. This was repeated 5 times, and the average value of the average particle size for 5 times was defined as the average particle size.

Component (C): IPA-ST-L (Colloidal silica)
Made by Nissan Chemical Industries, Ltd. (isopropanol dispersion, colloidal silica concentration 30% by mass, average particle size 40-50 nm (manufacturer published value))
The average particle size of (C) was measured as follows.
After drying, firing, and pulverizing the sample, the BET specific surface area measuring device (Monosorb MS-17) was used to determine the BET specific surface area by the nitrogen adsorption method, and converted to the particle diameter when assumed to be true particles. The average particle size was taken.

Example 1
(1) Manufacture of coating liquid (composition I) It prepared according to the component and compounding quantity which are shown in Table 1.
Into a sample tube with a volume of 50 ml, 0.80 g of organic polymer fine particles: ULS-1385MG (component (B) + component (E)) was charged and stirred at 500 rpm while 1-methoxy-2-propanol (component (E)). 4.25 g, water (component (E)) 0.50 g, acetic acid (component (D)) 0.50 g, M silicate 51 (component (A-1)) 0.40 g, MTMS-A ((A-2) Component) 1.10 g, dimethoxy-3-glycidoxypropylmethylsilane (component (A-4)) 0.55 g, 20 mass% p-toluenesulfonic acid methanol solution (component (D) + component (E)) 0 In the order of .05 g, each was added dropwise over 1 minute. Subsequently, after stirring for 60 minutes at room temperature and 500 rpm, the mixture was allowed to stand for one day, which was designated as solution A.

A sample tube with a volume of 20 ml was charged with 1.10 g of 3-isocyanatopropyltriethoxysilane and 0.35 g of 2-butanone oxime (isocyanate group blocking agent), stirred at room temperature at 500 rpm for 10 minutes, and then allowed to stand for one day. This was designated as solution C. The blocking of the isocyanate group was confirmed by the disappearance of the isocyanate group signal by ¹³ C-NMR. The total amount of 3-isocyanatopropyltriethoxysilane and 2-butanone oxime was defined as the amount of the blocked isocyanatosilane compound: (A-5) component.

Into a 200 ml three-necked flask equipped with a condenser, put A solution and a stirring bar, and stir at 500 rpm. The solution was added dropwise and stirred at room temperature for 60 minutes. Then, it heated at 600 rpm and 80 degreeC under nitrogen stream for 3 hours. Then, C liquid was added, and it stirred at 80 degreeC on the same conditions for 4 hours, Then, it left still at room temperature overnight.
Furthermore, 0.40 g of 3-aminopropyltrimethoxysilane ((A-3) component) was added dropwise thereto over 2 minutes as a D solution. After stirring at room temperature for 10 minutes, the mixture was further heated at 700 rpm and 80 ° C. for 3 hours under a nitrogen stream.
Subsequently, it was left to stand for 1 week to obtain a coating solution.

(2) Preparation of laminate As a substrate, polycarbonate substrate [manufactured by Idemitsu Kosan Co., Ltd., trade name: Toughlon, product number: IV2200R (anti-glare grade), thickness 3 mm (total light transmittance 90%, haze value 0.5%)] Was used.
The coating liquid obtained in the above (1) is applied to the surface of a polycarbonate molded body having a thickness of 3 mm with a bar coater so that the cured film has a thickness of 3 μm, and is thermally cured at 130 ° C. for 2 hours. A laminate composed of a substrate and a cured film was produced.

(3) Dyeing and Evaluation of Laminate 10 parts of BPI Gray (made by Brain Power Inc., gray) was added to 100 parts of pure water, and kept at 60 to 70 ° C. for 1 hour to prepare a dye solution. Thereafter, the dyeing solution was heated to 90 ° C., and the laminate was immersed in it for 30 minutes for dyeing. The evaluation results such as the total light transmittance of the dyed laminate are shown in Table 2, and the transmittance curve is shown in FIG.

  Further, the cross section of the laminate was polished using a precision polishing machine (ML-150P: manufactured by MARUTO), and the polished surface was taken out using CP (SM-09010: manufactured by JEOL) to obtain an optical microscope (BX51). : Manufactured by OLYMPUS Co.) was observed, and it was confirmed that the layer formed on the substrate was stained. Furthermore, the cross section of the laminate was subjected to line analysis using a microscopic Raman apparatus (ALMEGA: manufactured by THERMO), and the dye was not detected on the substrate, but only on the cured film layer. It was confirmed that the layer was stained.

Examples 2-1 to 2-6
A coating solution was produced in the same manner as in Example 1 according to the components and blending amounts shown in Table 1, and a laminate was produced. This laminate was dyed with the following dyes. The laminate after dyeing was evaluated, and the results are shown in Table 2, and the transmittance curve is shown in FIG. Further, it was confirmed that the layer was dyed in the same manner as in Example 1 instead of the substrate.
Example 2-1 BPI Gray manufactured by Brain Power Inc.
Example 2-2: Brain Power Inc. BPI Apricot
Example 2-3: AOMeadow manufactured by Brain Power Inc.
Example 2-4: AOTeak manufactured by Brain Power Inc.
Example 2-5: Brain Power Inc. BPI Rodenstock Rose
Example 2-6: BPI Brown manufactured by Brain Power Inc.

Example 3
In the same manner as in Example 1, a coating solution was produced according to the components and blending amounts shown in Table 1, and a laminate was produced and dyed. The laminated body after dyeing was evaluated, the results are shown in Table 2, and the transmittance curve is shown in FIG. It was also confirmed that the layer was dyed, not the substrate.
Moreover, the average particle diameter of the inorganic fine particles in the cured film obtained in Example 3 was measured. The average particle size was 200 nm or less.

Example 4-1
(1) Manufacture of coating liquid (Composition II) It manufactured according to the component and preparation amount shown in Table 3.
Into a 100 ml Erlenmeyer flask, 25.0 g of organic polymer fine particles: ULS-1385MG (component (B)) was charged and stirred at 500 rpm, while 7.8 g of 1-methoxy-2-propanol (component (E)), acetic acid ((G) component) 20.0 g, methyltrimethoxysilane ((A-2) component) 1.0 g, dimethoxy-3-glycidoxypropylmethylsilane ((A-4) component) 0.5 g, 5 mass % P-toluenesulfonic acid methanol solution (component (D)) was added dropwise in the order of 0.1 g. Subsequently, the mixture was stirred at room temperature and 500 rpm for 60 minutes, and then allowed to stand for one day. The mixture was transferred to a 200 ml three-necked flask equipped with a condenser, and 28.5 g of IPA-ST-L (component (C)) was added dropwise over 5 minutes while stirring at 500 rpm, followed by stirring at room temperature for 10 minutes. Subsequently, the mixture was heated and stirred at 650 rpm and 80 ° C. for 7 hours under a nitrogen stream, and then allowed to stand overnight at room temperature.

A 20-ml sample tube was charged with 4.4 g of 3-isocyanatopropyltriethoxysilane and 1.6 g of 2-butanone oxime (isocyanate group blocking agent), stirred at room temperature at 500 rpm for 10 minutes, and then allowed to stand for one day. This was designated as solution C. The blocking of the isocyanate group was confirmed by the disappearance of the isocyanate group signal by ¹³ C-NMR. The total amount of 3-isocyanatopropyltriethoxysilane and 2-butanone oxime was defined as the amount of the blocked isocyanatosilane compound: (A-5) component.

  A sample tube having a volume of 50 ml was charged with 10.0 g of Niedral H-15 (cerium oxide) and stirred at 500 rpm, 7.0 g of 1-methoxy-2-propanol (component (E)), tetraethoxysilane ((A ') Ingredients) were dropped in the order of 2.23 g over 1 minute each. Subsequently, the mixture was stirred at room temperature for 90 minutes and then allowed to stand at room temperature for 90 minutes. This and a stirring bar were charged into a 100 ml three-necked flask equipped with a condenser, and heated at 80 ° C. for 4 hours under a nitrogen stream while stirring at 500 rpm. Then, it left still at room temperature for one week, and obtained the dispersion liquid ((F) component) (B component) which consists of a reaction product of a silane compound and cerium oxide.

  Into a sample tube with a volume of 10 ml, 1.0 g of IPA-ST-L ((C) component, IPA dispersion sol in which anionic colloidal silica was dispersed) and a stirrer were charged, and the silane compound and cerium oxide were stirred while stirring at 400 rpm. 1.0 g of a dispersion (component (F)) consisting of the reaction product was added dropwise over 1 minute, followed by stirring at room temperature for 1 hour. It was visually confirmed that the dispersion state after stirring was dispersed without aggregation, precipitation, or gelation.

  To liquid A, 14.5 g of a dispersion (component (F)) composed of a reaction product of a silane compound and cerium oxide, and liquid C were added dropwise over 5 minutes, and stirred at room temperature for 10 minutes. Then, it heated at 750 rpm and 80 degreeC under nitrogen stream for 4 hours, and left still at room temperature overnight.

Further, 0.8 g of 3-aminopropyltrimethoxysilane (component (A-3)) was added dropwise as a D solution over 2 minutes. After stirring at room temperature for 10 minutes, the mixture was further heated at 750 rpm and 80 ° C. for 3 hours under a nitrogen stream.
Subsequently, it was left to stand for 1 week to obtain a coating solution.

(2) Production of Laminate Polycarbonate substrate (made by Idemitsu Kosan Co., Ltd., trade name: Toughlon, product number: IV2200R (anti-glare grade), thickness 3 mm (total light transmittance 90%, haze value 0.5%) ] Was used. The coating solution obtained above is applied to the surface of a polycarbonate molded body having a thickness of 3 mm with a bar coater so that the cured film has a thickness of 7 μm, and thermally cured at 130 ° C. for 2 hours to obtain a laminate. Produced.

(3) Dyeing and Evaluation of Laminate Dyeing and evaluation were performed in the same manner as in Example 1. The results are shown in Table 4. Further, as in Example 1, it was confirmed that not the substrate but the layer was dyed. The transmittance curve is shown in FIG.

Example 4-2
A laminate was prepared in the same manner as in Example 4-1, and the laminate was dyed and evaluated in the same manner as in Example 4-1, except that BPI Brown manufactured by Brain Power Inc. was used as the dye. The results are shown in Table 4, and the transmittance curve is shown in FIG.

Examples 5-1 to 5-8
A coating solution was produced in the same manner as in Example 4 according to the components and blending amounts shown in Table 3, and a laminate was produced. This laminate was dyed with the following dyes. The laminated body after dyeing was evaluated, the results are shown in Table 4, and the transmittance curve is shown in FIG. It was also confirmed that the layer was dyed, not the substrate.
Example 5-1: Brain Power Inc. BPI Gray
Example 5-2: BPI Apricot manufactured by Brain Power Inc.
Example 5-3: AOMeadow manufactured by Brain Power Inc.
Example 5-4: AOTeak manufactured by Brain Power Inc.
Example 5-5: BPI Rodenstock Rose manufactured by Brain Power Inc.
Example 5-6: BPI Violet manufactured by Brain Power Inc.
Example 5-7: BPI Blue manufactured by Brain Power Inc.
Example 5-8: BPI Brown manufactured by Brain Power Inc.

Comparative Example 1
Dyeing was performed in the same manner as in Example 1 except that “Polyca Ace EC100XX” manufactured by Sumitomo Bakelite was used as the laminate. The transmittance curve is shown in FIG.
Polycarbonate ACE EC100XX is a laminate in which a polycarbonate substrate is coated with a thermosetting silicone hard coat material.

Comparative Example 2
On the surface of the same substrate as in Example 1, as a primer layer, a primer PH91 manufactured by Momentive Performance Materials Japan G.K. was applied with a bar coater so as to have a thickness of 10 μm. Dried. Furthermore, as a hard coat layer, Momentive Performance Materials Japan GK Hard Coating Liquid Tosguard 510 was applied with a bar coater so that the cured film would be 2 μm, and heated at 130 ° C. for 2 hours. Cured to prepare a laminate composed of a substrate, a primer layer, and a hard coat layer. This laminate was dyed in the same manner as in Example 1. The transmittance curve is shown in FIG.

Examples 6-13
A coating solution was produced in the same manner as in Example 1 according to the components and blending amounts shown in Table 5, and a laminate was produced. This laminate was dyed with BPI Brown dye manufactured by Brain Power Inc. in the same manner as in Example 1.
The laminate after dyeing was evaluated in the same manner as in Examples 1 and 2. The results are shown in Table 6 and the transmittance curves are shown in FIGS. Further, it was confirmed that the layer was dyed in the same manner as in Example 1 instead of the substrate.

Reference example 1
In the same manner as in Example 12, a coating liquid was produced according to the following components and blending amounts to produce a laminate. The average particle diameter of the organic polymer fine particles was measured for this laminate. As a result, the average particle size was 200 nm or less. A TEM photograph is shown in FIG.

・ ULS-1385MG ・ ・ ・ 7.0g
・ 1-Methoxy-2-propanol ... 21.25g
・ Ion exchange water: 2.5g
・ Acetic acid ... 2.5g
・ Methyltrimethoxysilane ... 10g
・ Dimethoxy-3-glycidoxypropylmethylsilane ... 4.75g
・ 20% by mass p-toluenesulfonic acid methanol solution ... 0.25g
・ 3-isocyanatopropyltriethoxysilane ... 5.5g
・ 2-butanone oxime: 1.75 g
・ 3-Aminopropyltrimethoxysilane ... 2.0g

For the following reasons, there is no difference in the average particle size of the organic fine particles in the cured film between Reference Example 1 and Example 12.
The difference between Reference Example 1 and Example 12 is whether or not tetrafunctional tetraalkoxysilane is used. The tetrafunctional tetraalkoxysilane does not react with the organic fine particles in the cured film, but reacts with another silane compound to form a part of the Si—O matrix. Even if tetraalkoxysilane is contained, the physical influence of the Si-O matrix on the organic fine particles is not changed. The presence or absence of tetrafunctional tetraalkoxysilane does not affect the average particle size of the organic fine particles.
Therefore, the organic fine particles in the cured film of Example 12 have an average particle size of 200 nm or less. Further, as in Example 12, the example containing no inorganic fine particles also has an average particle size of 200 nm or less.

Furthermore, even if inorganic fine particles are included, the inorganic fine particles and the organic fine particles do not react. In addition, even if inorganic fine particles are included, it does not give physical deformation such that the average particle diameter of the organic fine particles changes. Therefore, examples including inorganic fine particles can be said to have an average particle diameter of 200 nm or less.

Moreover, it is thought that there is no difference in the average particle diameter of inorganic fine particles in Example 3 and other Examples for the following reasons.
Example 3 includes both organic fine particles and inorganic fine particles. Therefore, like Example 3, the example containing both organic fine particles and inorganic fine particles can be said to have an average particle size of 200 nm or less. A TEM photograph of Example 13 is shown in FIG.

Organic fine particles and inorganic fine particles do not react. Further, even if inorganic fine particles are included, it does not give physical deformation that changes the average particle size of the organic fine particles. Therefore, even in an embodiment that does not include organic fine particles and includes only inorganic fine particles, the average particle size is 200 nm or less. It can be said.

  The colored laminate of the present invention can be particularly developed into a polycarbonate material. The colored laminate of the present invention can be suitably used as a glass substitute member for sunglasses, sports, eyeglass lenses such as safety glasses, particularly sunglasses.

Claims (11)

A substrate,
A layer in which at least one of colloidal silica and organic fine particles formed on the substrate is dispersed in a matrix having Si-O bonds;
With
The organic fine particles contain an ultraviolet absorbing group,
The layer has a haze value of 10% or less,
The transmittance of at least one wavelength among wavelengths of 400 to 750 nm is 80% or less,
The number of scratches when steel wool # 0000 was rubbed 10 reciprocations at 9.8 N load and 2000 mm / sec was 0,
The difference in haze between before and after a 4.9 N load, 500 rotation Taber abrasion test using a wear wheel of CS-10F is less than 30,
A laminate in which the layer does not peel in a cross-cut peel test in accordance with JIS K 5400.   The laminate according to claim 1, wherein the layer is a layer in which the organic fine particles are dispersed in the matrix.   The laminate according to claim 1, wherein the layer has a haze difference of less than 15 before and after the Taber abrasion test. A substrate,
A layer in which at least one of colloidal silica and organic fine particles formed on the substrate is dispersed in a matrix having Si-O bonds;
With
The organic fine particles contain an ultraviolet absorbing group,
The layer has a haze value of 10% or less,
The number of scratches when steel wool # 0000 was rubbed 10 reciprocations at 9.8 N load and 2000 mm / sec was 0,
The difference in haze between before and after a 4.9 N load, 500 rotation Taber abrasion test using a wear wheel of CS-10F is less than 30,
A method for producing a colored laminate, wherein the laminate is immersed in a dye in a laminate in which the layer does not peel in a cross-cut peel test based on JIS K 5400. (A) below
At least one of (B) and (C),
(D) and (E) composition I containing component, or the following (A ′),
Curing a composition II containing at least one of (B) and (C) and (D) to (G) components on a substrate to produce a laminate;
Immersing the laminate in a liquid in which a dye is dispersed to produce a colored laminate;
A method for producing a colored laminate comprising:
Composition I:
(A) Hydrolysis condensate of one or more compounds selected from the following (A-1) to (A-5).
(A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compound containing no amino group, epoxy group and isocyanate group (A-3) Silane compound having amino group and alkoxy group (A-4) Epoxy group And a silane compound having an alkoxy group (A-5) a blocked isocyanatosilane compound having an alkoxy group (B) an organic polymer fine particle comprising a copolymer containing a monomer unit having an ultraviolet absorbing group (C) colloidal silica (D) Curing catalyst (E) Dispersion medium composition II:
(A ′) Hydrolyzed condensate of silane compound having alkoxy group (B) Organic polymer fine particle comprising copolymer containing monomer unit having ultraviolet absorbing group (C) Colloidal silica (D) Curing catalyst (E ) Dispersion medium (F) Cerium oxide (G) dispersion stabilizer treated with silane compound   The manufacturing method of the colored laminated body of Claim 5 in which the said composition I or II contains the said (B) component.   The method for producing a colored laminate according to claim 5 or 6, wherein the composition I further comprises (F) cerium oxide treated with a silane compound and (G) a dispersion stabilizer. (A) below
At least one of (B) and (C),
(D) as well as the step of obtaining the composition III using the component (E), or the following (A ′)
Obtaining composition IV using at least one of (B) and (C), and components (D) to (G);
Curing the composition III or the composition IV on a substrate to produce a laminate;
Immersing the laminate in a liquid in which a dye is dispersed to produce a colored laminate;
A method for producing a colored laminate comprising:
Composition III:
(A) Hydrolysis condensate of one or more compounds selected from the following (A-1) to (A-5).
(A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compound containing no amino group, epoxy group and isocyanate group (A-3) Silane compound having amino group and alkoxy group (A-4) Epoxy group And a silane compound having an alkoxy group (A-5) a blocked isocyanatosilane compound having an alkoxy group (B) an organic polymer fine particle comprising a copolymer containing a monomer unit having an ultraviolet absorbing group (C) colloidal silica (D) Curing catalyst (E) Dispersion medium composition IV:
(A ′) Hydrolyzed condensate of silane compound having alkoxy group (B) Organic polymer fine particle comprising copolymer containing monomer unit having ultraviolet absorbing group (C) Colloidal silica (D) Curing catalyst (E ) Dispersion medium (F) Cerium oxide (G) dispersion stabilizer treated with silane compound   The method for producing a colored laminate according to claim 8, wherein in the step of obtaining the composition III or the step of obtaining the composition IV, the composition III or the composition IV is obtained using the component (B).   The colored laminate according to claim 8 or 9, wherein in the step of obtaining the composition III, the composition III is further obtained using (F) a cerium oxide treated with a silane compound and (G) a dispersion stabilizer. Method.   The colored laminated body manufactured by the manufacturing method in any one of Claims 4-10.