TW202111039A - Coating liquid, cured film, multilayer body provided with said cured film, lighting component provided with said multilayer body, display, lens, component for solar cells, antireflective film, lighting cover, and lighting device - Google Patents

Abstract

A coating liquid which is characterized by containing components (A), (B) and (C) described below. (A) a hydrolysis-condensation product of components (A-1) to (A-4) described below, said components (A-1) to (A-4) being silane compounds having an alkoxy group (A-1) a tetraalkoxysilane compound (A-2) an organoalkoxysilane compound which does not contain an amino group, an epoxy group and an isocyanate group (A-3) a silane compound having an amino group and an alkoxy group (A-4) a blocked isocyanate silane compound having an alkoxy group (B) a curing catalyst (C) a dispersion medium.

Description

Coating liquid, cured film, and laminate provided with the cured film, and lighting member, display, lens, solar cell member, anti-reflection film, lighting cover, and lighting fixture provided with the laminate

The present invention relates to a coating solution, a cured film, a laminate provided with the cured film, and a lighting member, a display, a lens, a solar cell member, an antireflection film, a lighting cover, and a lighting fixture provided with the laminate.

Previously, in lighting covers, various displays (light guide plates), lenses (glasses, cameras, etc.), solar cell panels, anti-reflection films, etc., especially as substrates with excellent transparency, thermoplastic plastic substrates or glass substrates were widely used . In particular, thermoplastic plastic substrates made of polycarbonate resin and the like are not only excellent in transparency, but also light in weight and excellent in impact resistance. Therefore, they are widely used as structural materials instead of glass. To date, various substrate treatments have been researched and developed for these transparent substrates for the purpose of further improving substrate characteristics.

Patent Document 1 discloses a coating composition containing chain silica particles of a specific average particle size, a specific hydrolysis condensate of alkoxysilane, a specific silane compound, etc., which are contained in all solid components A fixed ratio of chain silica particles of the above average particle size. By applying the coating composition to a glass substrate or the like, excellent moisture and heat resistance is imparted to the glass substrate, and the decrease in transmittance is suppressed.

Patent Document 2 discloses a method for manufacturing a coating film as follows: preparing a polysiloxane resin composition containing organopolysiloxane containing specific structural units, preparing the coating solution and coating it on a substrate, and applying it at a specific temperature Carry out hardening. According to this method, a coating film with high refractive index, high heat resistance, and excellent transparency is formed without generating by-products such as water during the hard coating.

Patent Document 3 discloses a composition for forming a coating film containing a fluorine-containing polymer having a specific hydrolyzable silyl group, a silane compound and/or a partial condensate of the silane compound, and a specific metal alkoxide The chelating complex of the substance. The composition has excellent adhesion to various substrates, and efficiently forms a transparent cured film with excellent scratch resistance, excellent weather resistance, and low refractive index.

Patent Document 4 discloses a coating composition containing specific nonionic polymer particles and a hydrolyzable silane compound. The coating composition has excellent liquid stability over time, and has anti-reflective and resistant properties on the substrate. A film with excellent scratch resistance and antifouling properties.

In recent years, with the increasing development of technology, it is expected to further improve the characteristics required for the substrate, especially the transmittance of the substrate. Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2015-21029 Patent Document 2: Japanese Patent Laid-Open No. 2009-148670 Patent Document 3: Japanese Patent Laid-Open No. 10-147740 Patent Document 4: International Publication No. 2018/101277

The inventors of the present invention conducted intensive research on the formulation and manufacturing method of the coating liquid, and found that the following coating liquid can be obtained to complete the present invention: the storage stability is high, and it is difficult to dry the cured film after coating to produce streaks or For cracks, the adhesion between the cured film and the substrate is high, and the transmittance is improved by coating.

The object of the present invention is to provide a coating solution capable of providing a laminate with good transmittance by forming a film on a substrate, etc., a cured film formed on the substrate from the coating solution, a laminate provided with the cured film, and The lighting component, display, lens, solar battery component, anti-reflection film, lighting cover, and lighting equipment of the laminate.

According to the present invention, the following coating liquid, cured film, laminate, etc. are provided. 1. A coating liquid characterized by containing the following components (A), (B) and (C). (A) The hydrolysis condensate of the alkoxy-containing silane compound of the following components (A-1) to (A-4) (A-1) The tetraalkoxysilane compound (A-2) does not contain an amino group, Epoxy and isocyanate group organic alkoxysilane compound (A-3) amine group and alkoxy silane compound (A-4) alkoxy group blocked isocyanato silane compound (B) Hardening catalyst (C) dispersion medium 2. Coating liquid as in 1, which further contains (D) inorganic fine particles. 3. A coating liquid in which the following is added to the reaction product obtained by contacting the hydrolysis condensate of the following components (A-1) and (A-2) with the following components (B) to (C) (A-4) After the component is reacted, the following (A-3) component is added and reacted. (A-1) Tetraalkoxysilane compound (A-2) Organic alkoxysilane compound not containing amine group, epoxy group and isocyanate group (A-3) Silane compound having amine group and alkoxy group (A-2) A-4) Blocked isocyanatosilane compound with alkoxy group (B) hardening catalyst (C) dispersion medium 4. The coating liquid of 3, wherein the above (A-1) and (A- 2) Before adding the above-mentioned (A-4) component to the reaction product obtained by contacting the hydrolysis condensate of the component with the above-mentioned (B) to (C) components, inorganic fine particles are added as the (D) component and reacted. 5. A coating liquid in which the following (A-) is added to the reaction product obtained by contacting a mixture containing the following (A-1), (A-2), (B) and (C) components 4) After the component is reacted, the following (A-3) component is added and reacted. (A-1) Tetraalkoxysilane compound (A-2) Organic alkoxysilane compound not containing amine group, epoxy group and isocyanate group (A-3) Silane compound having amine group and alkoxy group (A-2) A-4) Blocked isocyanatosilane compound having an alkoxy group (B) Hardening catalyst (C) Dispersion medium 6. The coating liquid of 5, wherein the above-mentioned (A-4) is added to the above-mentioned reaction product ) Before the component, inorganic fine particles are added as the (D) component and reacted. 7. A coating liquid which is a reaction product obtained by contacting the hydrolysis condensate of the following components (A-1), (A-2) and (E) with the following components (B) to (C) After adding and reacting the following component (A-4), and then adding and reacting the following component (A-3). (A-1) Tetraalkoxysilane compound (A-2) Organic alkoxysilane compound not containing amine group, epoxy group and isocyanate group (A-3) Silane compound having amine group and alkoxy group (A-2) A-4) Blocked isocyanatosilane compound with alkoxy group (B) Hardening catalyst (C) Dispersion medium (E) Silane compound with epoxy group and alkoxy group 8. Coating liquid of 7 , Wherein the above (A-4) is added to the reaction product obtained by contacting the hydrolysis condensate of the above (A-1), (A-2) and (E) components with the above (B) to (C) components Before the components, inorganic fine particles are added as the (D) component to react. 9. A coating liquid characterized in that it is prepared with the following components (A), (B), and (C) as raw materials, and is used to hydrolyze the following components (A-1) and (A-2) The reaction product obtained by contacting the condensate with the above-mentioned components (B) to (C) is obtained by adding and reacting the following (A-4) component, and then further adding and reacting the above-mentioned (A-3) component. (A) The hydrolysis condensate of the alkoxy-containing silane compound of the following components (A-1) to (A-4) (A-1) The tetraalkoxysilane compound (A-2) does not contain an amino group, Epoxy and isocyanate group organic alkoxysilane compound (A-3) amine group and alkoxy silane compound (A-4) alkoxy group blocked isocyanato silane compound (B) Hardening catalyst (C) dispersion medium 10. The coating liquid of 9, wherein the hydrolysis condensate of the above-mentioned components (A-1) and (A-2) is obtained by contacting the above-mentioned components (B) to (C) Before adding the above-mentioned (A-4) component to the reaction product, inorganic fine particles are added as the (D) component to react. 11. A coating liquid prepared by using the following components (A), (B), and (C) as raw materials, and containing the following (A-1), (A-2), (B) by contact The reaction product obtained from the mixture of) and (C) components is obtained by adding and reacting the following (A-4) component, and then further adding and reacting the following (A-3) component. (A) The hydrolysis condensate of the alkoxy-containing silane compound of the following components (A-1) to (A-4) (A-1) The tetraalkoxysilane compound (A-2) does not contain an amino group, Epoxy and isocyanate group organic alkoxysilane compound (A-3) amine group and alkoxy silane compound (A-4) alkoxy group blocked isocyanato silane compound (B) Hardening catalyst (C) dispersion medium 12. The coating liquid of 11, in which inorganic fine particles are added as the component (D) to react before adding the component (A-4) to the reaction product. 13. A coating liquid characterized in that it is prepared using the following (A), (B), (C), and (E) components as raw materials, and is made of the following (A-1), (A-2) The reaction product obtained by contacting the hydrolysis condensate of component (E) and the above-mentioned (B) to (C) components is added with the following (A-4) component to react, and then the above-mentioned (A-3) is added The ingredients make it react. (A) The hydrolysis condensate of the alkoxy-containing silane compound of the following components (A-1) to (A-4) (A-1) The tetraalkoxysilane compound (A-2) does not contain an amino group, Epoxy and isocyanate group organic alkoxysilane compound (A-3) amine group and alkoxy silane compound (A-4) alkoxy group blocked isocyanato silane compound (B) Hardening catalyst (C) Dispersion medium (E) Silane compound having epoxy group and alkoxy group 14. The coating liquid of 13, wherein the above components (A-1), (A-2) and (E) are used Before adding the above-mentioned (A-4) component to the reaction product obtained by contacting the hydrolysis condensate with the above-mentioned components (B) to (C), inorganic fine particles are added as the (D) component and reacted. 15. The coating liquid according to any one of 1 to 14, wherein the component (A-1) is a tetraalkoxysilane compound represented by the following general formula (1). Si(OR ¹ ) ₄ ••• (1) [In the formula, R ¹ represents an alkyl group with 1 to 4 carbons or an alkyl group with 1 to 4 carbons with an ether bond; plural R ¹ may be the same or different ] 16. The coating liquid according to any one of 1 to 15, wherein the above-mentioned component (A-2) is an organic alkoxy group represented by the following general formula (2), which does not contain an amino group, an epoxy group, and an isocyanate group Silane compounds. R ² _a Si(OR ³ ) _4-a ••• (2) [In the formula, R ² represents an alkyl group with 1 to 10 carbons or a fluorinated alkyl group with 1 to 10 carbons, vinyl, phenyl, Or an alkyl group with 1 to 3 carbons substituted by a methacryloxy group; R ³ represents an alkyl group with 1 to 4 carbons or an alkyl group with an ether bond; a represents 1 or 2; when there are plural R ² In this case, a plurality of R ² may be the same or different, and a plurality of OR ³ may be the same or different] 17. The coating liquid of any one of 1 to 16, wherein the above-mentioned (A-3) component is the following A silane compound having an amino group and an alkoxy group represented by the formula (3). R ⁴ _b Si(OR ⁵ ) _4-b ••• (3) [In the formula, R ⁴ represents an alkyl group with 1 to 4 carbon atoms, a vinyl group, a phenyl group, or is selected from methacryloxy group, Amino group (-NH ₂ group), amino alkyl group [-(CH ₂ )x-NH ₂ group (wherein x is an integer of 1 to 3)]), and alkylamino group [-NHR group (wherein, R is an alkyl group with 1 to 3 carbons)] an alkyl group with 1 to 3 carbons substituted by one or more groups; at least one R ⁴ represents an amino group, or an aminoalkyl group or an alkylamino group An alkyl group with 1 to 3 carbons substituted by any one of them; R ⁵ represents an alkyl group with 1 to 4 carbons; b represents 1 or 2; when there are more than one R ⁴ , the plurality of R ⁴ may be the same It may be different, and a plurality of OR ⁵ may be the same or different] 18. The coating liquid according to any one of 1 to 17, wherein the above-mentioned component (A-4) is represented by the following general formula (4) and has an alkoxy The blocking isocyanato silane compound of the base. R ⁸ _d Si(OR ⁹ ) _4-d ••• (4) [In the formula, R ⁸ represents an alkyl group with 1 to 4 carbon atoms, a vinyl group, a phenyl group, or is selected from methacryloyloxy and An alkyl group with 1 to 3 carbons substituted by one or more of ^{the blocked isocyanate groups, at least one R 8} represents an alkyl group with 1 to 3 carbons substituted by a blocked isocyanate group; R ⁹ represents carbon An alkyl group with a number of 1 to 4, d represents 1 or 2; when there are a plurality of R ^8s , the plurality of R ^8s may be the same or different, and the plurality of OR ^9s may be the same or different] 19. As technical solution 7 The coating liquid of any one of ~8 and 13-14, wherein the component (E) is a silane compound having an epoxy group and an alkoxy group represented by the following general formula (5). R ⁶ _c Si(OR ⁷ ) _4-c ••• (5) [In the formula, R ⁶ represents an alkyl group with 1 to 4 carbon atoms, a vinyl group, a phenyl group, or is selected from methacryloxy group, An alkyl group with 1 to 3 carbons substituted by more than one of glycidoxy and 3,4-epoxycyclohexyl, at least one R ⁶ represents glycidoxy or 3,4-epoxy Cyclohexyl substituted alkyl with 1 to 3 carbons; R ⁷ represents alkyl with 1 to 4 carbons; c represents 1 or 2; when there are more than one R ⁶ , the plurality of R ⁶ may be the same Different, a plurality of OR ⁷ may be the same or different] 20. A cured film formed by curing the coating liquid of any one of 1-19. 21. A laminated body characterized by having a base material and a cured film such as 20 formed directly on the base material. 22. The laminate of 21, wherein the thickness of the cured film is 5 μm or less. 23. The layered body of 21 or 22, wherein the cured film is formed on one or both sides of the substrate. 24. The laminate according to any one of 21 to 23, wherein the substrate is made of resin. 25. The laminate according to any one of 21 to 24, wherein the substrate is made of polycarbonate resin. 26. An illuminating member, a display, a lens, a member for solar cells, or an anti-reflection film, which comprises a laminate of any one of 21-25. 27. A laminated body characterized by having: a substrate; and a cured film formed directly on the substrate and formed by curing a coating solution containing a hydrolyzed condensate of a silane compound having an alkoxy group; and the above The thickness of the cured film is 500 nm or less. 28. The layered product according to 27, wherein the base material contains a light diffusing agent. 29. A lighting cover or lighting fixture, which is provided with a laminated body such as 27 or 28. 30. A method for preparing a coating liquid, which is a reaction product obtained by contacting the hydrolysis condensate of the following components (A-1) and (A-2) with the following components (B) to (C) After adding and reacting the following (A-4) component, the following (A-3) component is further added and reacted. (A-1) Tetraalkoxysilane compound (A-2) Organic alkoxysilane compound not containing amine group, epoxy group and isocyanate group (A-3) Silane compound having amine group and alkoxy group (A-2) A-4) Blocked isocyanatosilane compound with alkoxy group (B) hardening catalyst (C) dispersion medium 31. The preparation method of the coating liquid of 30, wherein the above (A-1) and The reaction product obtained by contacting the hydrolysis condensate of component (A-2) with the above-mentioned components (B) to (C) before adding the above-mentioned component (A-4) is to add inorganic fine particles as the component (D) to react. 32. A method for preparing a coating liquid, which is added to the reaction product obtained by contacting a mixture containing the following components (A-1), (A-2), (B), and (C) After the above-mentioned (A-4) component was reacted, the following (A-3) component was further added and reacted. (A-1) Tetraalkoxysilane compound (A-2) Organic alkoxysilane compound not containing amine group, epoxy group and isocyanate group (A-3) Silane compound having amine group and alkoxy group (A-2) A-4) Blocked isocyanatosilane compound with alkoxy group (B) hardening catalyst (C) dispersion medium 33. The preparation method of the coating liquid of 32, wherein the above-mentioned (() is added to the above-mentioned reaction product A-4) Before the component, inorganic fine particles are added as the component (D) and reacted. 34. A method for preparing a coating liquid, which is obtained by contacting the hydrolysis condensate of the following components (A-1), (A-2) and (E) with the following components (B) to (C) After adding the following (A-4) component to the reaction product to react, the following (A-3) component is further added and reacted. (A-1) Tetraalkoxysilane compound (A-2) Organic alkoxysilane compound not containing amine group, epoxy group and isocyanate group (A-3) Silane compound having amine group and alkoxy group (A-2) A-4) Blocked isocyanatosilane compound with alkoxy group (B) Hardening catalyst (C) Dispersion medium (E) Silane compound with epoxy group and alkoxy group 35. Such as 34 coating liquid The method of preparation, wherein the above-mentioned (A) is added to the reaction product obtained by contacting the above-mentioned components (B) to (C) with the hydrolysis condensate of the above-mentioned (A-1), (A-2) and (E) -4) Before the component, the inorganic fine particles are added as the component (D) and reacted. 36. A method for preparing a coating liquid, characterized by contacting the hydrolysis condensate of the following components (A-1) and (A-2) with the above-mentioned components (B) to (C). After adding the following (A-4) component and reacting therewith, the above-mentioned (A-3) component is further added and reacted. (A) The hydrolysis condensate of the alkoxy-containing silane compound of the following components (A-1) to (A-4) (A-1) The tetraalkoxysilane compound (A-2) does not contain an amino group, Epoxy and isocyanate group organic alkoxysilane compound (A-3) amine group and alkoxy silane compound (A-4) alkoxy group blocked isocyanato silane compound (B) Hardening catalyst (C) dispersion medium 37. The preparation method of the coating liquid of 36, wherein the hydrolysis condensate of the above-mentioned (A-1) and (A-2) components is brought into contact with the above-mentioned (B) to (C) components Before adding the above-mentioned (A-4) component to the obtained reaction product, inorganic fine particles are added as the (D) component to react. 38. A method for preparing a coating liquid, which is added to the reaction product obtained by contacting a mixture containing the following components (A-1), (A-2), (B), and (C) After the above-mentioned (A-4) component was reacted, the following (A-3) component was further added and reacted. (A) The hydrolysis condensate of the alkoxy-containing silane compound of the following components (A-1) to (A-4) (A-1) The tetraalkoxysilane compound (A-2) does not contain an amino group, Epoxy and isocyanate group organic alkoxysilane compound (A-3) amine group and alkoxy silane compound (A-4) alkoxy group blocked isocyanato silane compound (B) The hardening catalyst (C) dispersion medium 39. The preparation method of the coating liquid of 38, wherein before adding the above-mentioned (A-4) component to the above-mentioned reaction product, inorganic fine particles are added as the (D) component to be reacted. 40. A method for preparing a coating liquid, which is a reaction obtained by contacting the hydrolysis condensate of the following components (A-1), (A-2) and (E) with the above components (B) to (C) After adding and reacting the following (A-4) component to the product, the above-mentioned (A-3) component is further added and reacted. (A) The hydrolysis condensate of the alkoxy-containing silane compound of the following components (A-1) to (A-4) (A-1) The tetraalkoxysilane compound (A-2) does not contain an amino group, Epoxy and isocyanate group organic alkoxysilane compound (A-3) amine group and alkoxy silane compound (A-4) alkoxy group blocked isocyanato silane compound (B) Hardening catalyst (C) Dispersion medium (E) Silane compound having epoxy group and alkoxy group 41. The preparation method of the coating liquid of 40, wherein the above-mentioned (A-1), (A-2) and ( E) The reaction product obtained by contacting the hydrolysis condensate of the component with the above-mentioned (B) to (C) components before adding the above-mentioned (A-4) component, and then adding inorganic fine particles as the (D) component to react. 42. The method for preparing a coating liquid according to any one of 30 to 41, wherein the component (A-1) is a tetraalkoxysilane compound represented by the following general formula (1). Si(OR ¹ ) ₄ ••• (1) [In the formula, R ¹ represents an alkyl group with 1 to 4 carbons or an alkyl group with 1 to 4 carbons with an ether bond, and multiple R ^1s may be the same or different ] 43. The method for preparing a coating liquid according to any one of 30 to 42, wherein the above-mentioned component (A-2) is an organic compound represented by the following general formula (2) that does not contain an amino group, an epoxy group, and an isocyanate group Alkoxysilane compounds. R ² _a Si(OR ³ ) _4-a ••• (2) [In the formula, R ² represents an alkyl group with 1 to 10 carbons or a fluorinated alkyl group with 1 to 10 carbons, vinyl, phenyl, Or an alkyl group with 1 to 3 carbons substituted by a methacryloxy group; R ³ represents an alkyl group with 1 to 4 carbons or an alkyl group with an ether bond; a represents 1 or 2; when there are plural R ² In this case, a plurality of R ² may be the same or different, and a plurality of OR ³ may be the same or different] 44. The method for preparing a coating liquid according to any one of 30 to 43, wherein the above component (A-3) is A silane compound having an amino group and an alkoxy group represented by the following general formula (3). R ⁴ _b Si(OR ⁵ ) _4-b ••• (3) [In the formula, R ⁴ represents an alkyl group with 1 to 4 carbon atoms, a vinyl group, a phenyl group, or is selected from methacryloxy group, Amino group (-NH ₂ group), amino alkyl group [-(CH ₂ )x-NH ₂ group (wherein x is an integer of 1 to 3)]), and alkylamino group [-NHR group (wherein, R is an alkyl group with 1 to 3 carbons)] an alkyl group with 1 to 3 carbons substituted by one or more groups; at least one R ⁴ represents an amino group, or an aminoalkyl group or an alkylamino group An alkyl group with 1 to 3 carbons substituted by any one of them; R ⁵ represents an alkyl group with 1 to 4 carbons; b represents 1 or 2; when there are more than one R ⁴ , the plurality of R ⁴ may be the same It may be different, and a plurality of OR ⁵ may be the same or different] 45. The method for preparing a coating liquid according to any one of 30 to 44, wherein the above-mentioned (A-4) component is represented by the following general formula (4) Blocked isocyanatosilane compound with alkoxy group. R ⁸ _d Si(OR ⁹ ) _4-d ••• (4) [In the formula, R ⁸ represents an alkyl group with 1 to 4 carbon atoms, a vinyl group, a phenyl group, or is selected from methacryloyloxy and An alkyl group with 1 to 3 carbons substituted by one or more of ^{the blocked isocyanate groups, at least one R 8} represents an alkyl group with 1 to 3 carbons substituted by a blocked isocyanate group; R ⁹ represents carbon An alkyl group with a number of 1 to 4, d represents 1 or 2; when there are a plurality of R ^8s , the plurality of R ^8s may be the same or different, and the plurality of OR ^9s may be the same or different] 46. Such as 34-35 And the method for preparing a coating liquid of any one of 40 to 41, wherein the component (E) is a silane compound having an epoxy group and an alkoxy group represented by the following general formula (5). R ⁶ _c Si(OR ⁷ ) _4-c ••• (5) [In the formula, R ⁶ represents an alkyl group with 1 to 4 carbon atoms, a vinyl group, a phenyl group, or is selected from methacryloxy group, An alkyl group with 1 to 3 carbons substituted by more than one of glycidoxy and 3,4-epoxycyclohexyl, at least one R ⁶ represents glycidoxy or 3,4-epoxy Cyclohexyl substituted alkyl with 1 to 3 carbons; R ⁷ represents alkyl with 1 to 4 carbons; c represents 1 or 2; when there are more than one R ⁶ , the plurality of R ⁶ may be the same Different, multiple OR ⁷ can be the same or different]

According to the present invention, it is possible to provide a coating solution capable of providing a laminate with good transmittance by forming a film on a substrate, etc., a cured film formed on the substrate from the coating solution, a laminate provided with the cured film, and The lighting component, display, lens, solar battery component, anti-reflection film, lighting cover, and lighting equipment of the laminate.

The coating liquid of the present invention will be described. [Coating Solution] One aspect of the coating liquid of the present invention contains the following components (A), (B) and (C). (A) Hydrolysis condensate of alkoxy-containing silane compound of the following components (A-1)～(A-4) (A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compounds that do not contain amine groups, epoxy groups and isocyanate groups (A-3) Silane compound with amine group and alkoxy group (A-4) Blocked isocyanatosilane compound with alkoxy group (B) Hardening catalyst (C) Dispersion medium

((A) component) One aspect of the coating liquid of the present invention is a hydrolysis-condensation product of four compounds of the following components (A-1) to (A-4) as component (A). Silane having an alkoxy group. Compound hydrolysis condensate.

In the present invention, the so-called alkoxysilane compound having an alkoxy group is an alkoxysilane compound and/or a partial condensate thereof. The so-called partial condensate of an alkoxysilane compound refers to a partial condensation of an alkoxysilane compound, Polyalkoxysilane compound or polyorganoalkoxysilane compound formed by forming siloxane bond (Si-O bond) inside. In addition, the so-called hydrolysis condensate of a silane compound having an alkoxy group is in the following state: in addition to the hydrolysis condensate of a silane compound having an alkoxy group, a silane compound having an alkoxy group before the hydrolysis condensation is included.

((A-1) Ingredient) (A-1) The component is a tetraalkoxysilane compound. In addition, a partial condensate (polyalkoxysilane compound) formed by bonding a siloxane bond (Si-O bond) can also be used. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The tetraalkoxysilane compound which is a component (A-1) can be represented by the following general formula (1), for example. In addition, as the polyalkoxysilane compound, a compound represented by the following general formula (6) is particularly preferable. Si(OR ¹ ) ₄ (1) [In the formula, R ¹ is an alkyl group with 1 to 4 carbons or an alkyl group with 1 to 4 carbons with an ether bond, and the plural R ¹ may be the same or different]

[式中，R¹ 與通式(1)相同，n為1～15之整數][化1]

[In the formula, R ^{1 is the} same as the general formula (1), and n is an integer of 1-15]

In the general formulas (1) and (6), examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and isobutyl. Group, tertiary butyl group, and as ^{OR 1 in which R 1} is an alkyl group having 1 to 4 carbon atoms with an ether bond, for example, 2-methoxyethoxy and 3-methoxypropoxy Wait.

As the tetraalkoxysilane compound of the component (A-1), tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane can be mentioned , Tetraisobutoxysilane, etc.

Also, as polyalkoxysilane compounds, "Silicate 40" and "Silicate 45" manufactured by Tama Chemical Industry Co., Ltd., and "Methyl Silicate 51", "Methyl Silicate 53A" manufactured by COLCOAT Co., Ltd., "Ethyl Silicate 40" and "Ethyl Silicate 48" etc.

((A-2) Ingredients) (A-2) The component is an organic alkoxysilane compound that does not contain an amino group, an epoxy group, and an isocyanate group. In addition, partial condensates of polyorganoalkoxysilane compounds can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

The organoalkoxysilane compound as the component (A-2) is preferably a bifunctional alkoxysilane or a trifunctional alkoxysilane, and can be represented by the following general formula (2), for example. In addition, as the partial condensate of the polyorganoalkoxysilane compound, a compound represented by the following general formula (7) is particularly preferred.

R ² _a Si(OR ³ ) _4-a ••• (2) [In the formula, R ² is an alkyl group with 1 to 10 carbons or a fluorinated alkyl group with 1 to 10 carbons, vinyl, phenyl, Or an alkyl group with 1 to 3 carbons substituted by a methacryloxy group; R ³ is an alkyl group with 1 to 4 carbons or an alkyl group with 1 to 4 carbons having an ether bond; a is 1 or 2; When there are a plurality of R ² , the plurality of R ² may be the same or different, and the plurality of OR ³ may be the same or different]

[式中，R² 及R³ 與通式(2)相同，m為1～15之整數][化2]

[In the formula, R ² and R ^{3 are the} same as the general formula (2), and m is an integer of 1-15]

In the general formulae (2) and (7), the alkyl group having 1 to 10 carbon atoms may be either linear or branched. For example, methyl, ethyl, n-propyl, Isopropyl, linear or branched various butyl groups, linear or branched various hexyl groups, linear or branched various octyl groups, or linear or branched various decyl groups As the fluorinated alkyl group having 1 to 10 carbon atoms, for example, trifluoroethyl group and trifluoropropyl group may be mentioned. Moreover, as the C1-C3 alkyl group, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group can be mentioned. The alkyl group having 1 to 4 carbon atoms or the alkyl group having 1 to 4 carbon atoms having an ether bond is the same as the description of the general formula (1).

In the organoalkoxysilane compound represented by the general formula (2), as the trifunctional alkoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and methyltripropoxysilane can be exemplified , Methyltributoxysilane, Methyl-tris(2-methoxyethoxy)silane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Ethyltripropoxysilane, Ethyl Tributoxysilane, ethyl-tris(2-methoxyethoxy)silane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltripropoxysilane, hexyltributoxysilane, decane Fluorinated alkanes such as trimethoxysilane, decyltriethoxysilane, decyltripropoxysilane, decyltributoxysilane, trifluoropropyltrimethoxysilane with a fluorine atom introduced into the substituent Group (trialkoxy) silane, phenyl trimethoxy silane, phenyl triethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, γ-methacryloxy propyl trimethyl Oxysilane and so on. In addition, methyldimethoxy (ethoxy) silane, ethyl diethoxy (methoxy) silane, etc. having two kinds of alkoxy groups can also be exemplified.

The bifunctional alkoxysilane may, for example, be dimethyldimethoxysilane, dimethyldiethoxysilane, bis(2-methoxyethoxy)dimethylsilane, diethyldiethyl Oxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, etc.

Specific examples of polyorganoalkoxysilane compounds include "SS-101" manufactured by COLCOAT Co., Ltd., "SR2402" manufactured by Dow Toray Co., Ltd., and "AY42-163".

((A-3) Ingredients) (A-3) The component is a silane compound having an amino group and an alkoxy group, and is an alkoxysilane compound that does not contain an epoxy group and an isocyanate group (hereinafter, also referred to as an organic alkoxysilane compound containing an amino group) ). In addition, a partial condensate thereof (a polyorganoalkoxysilane compound containing an amino group) can also be used. These may be used individually by 1 type, and may be used in combination of 2 or more types. As the component (A-3), an amino group-containing organic alkoxysilane compound and a partial condensate thereof can be represented by the following general formula (3), for example.

R ⁴ _b Si(OR ⁵ ) _4-b ••• (3) [In the formula, R ⁴ is an alkyl group with 1 to 4 carbons, a vinyl group, a phenyl group, or is selected from methacryloxy group, Amino (-NH ₂ group), aminoalkyl [-(CH ₂ )x-NH ₂ group (wherein x is an integer of 1 to 3)], and alkylamino group [-NHR group (where R Is an alkyl group with 1 to 3 carbons)] an alkyl group with 1 to 3 carbons substituted by one or more groups; at least one R ⁴ is an amino group, or an aminoalkyl group or an alkylamino group Any one of the substituted C1-C3 alkyl groups; R ⁵ is C1-C4 alkyl groups; b is 1 or 2; when there are more than one R ⁴ , the plurality of R ⁴ may be the same May be different, plural OR ⁵ may be the same or different] In the general formula (3), for an alkyl group with 1 to 3 carbons and an alkyl group with 1 to 4 carbons, the same as the general formula (1) or (2) The description is the same.

As a specific example of the amino group-containing organoalkoxysilane compound represented by the general formula (3), N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane can be mentioned , N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyl diethoxysilane, N- (2-Aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methylamino Propyl trimethoxysilane, N-methylaminopropyl triethoxysilane, etc. In addition, as an amine group-containing polyorganoalkoxysilane compound, for example, "KBP-90" manufactured by Shin-Etsu Silicone Co., Ltd. can be mentioned.

((A-4) Ingredient) (A-4) The component is a blocked isocyanate silane compound having an alkoxy group (usually also called a blocked isocyanate silane compound), and it contains a blocked isocyanate group, but does not contain an amine group and a ring Alkoxysilane compound of oxy group (hereinafter, also referred to as organic alkoxysilane compound containing blocked isocyanate group). Moreover, its partial condensate (polyorganoalkoxysilane compound containing blocked isocyanate group) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more types.

Furthermore, the so-called blocked isocyanatosilane compound is the following isocyanatosilane compound (usually also called isocyanate silane compound): the isocyanate group is protected by a blocking agent such as oxime to make it inert, and it is removed by heating Blocking and isocyanate group activation (regeneration).

As the component (A-4), a blocked isocyanate group-containing organoalkoxysilane compound and a partial condensate thereof can be represented by the following general formula (4), for example. R ⁸ _d Si(OR ⁹ ) _4-d ••• (4) [In the formula, R ⁸ is an alkyl group with 1 to 4 carbons, a vinyl group, a phenyl group, or is selected from methacryloxy and An alkyl group with 1 to 3 carbons substituted by one or more of ^{the blocked isocyanate groups, at least one R 8} is an alkyl group with 1 to 3 carbons substituted by a blocked isocyanate group; R ⁹ is carbon An alkyl group with a number of 1 to 4, d is 1 or 2. When there are plural R ^8s , the plural R ^8s may be the same or different, and the plural OR ^9s may be the same or different] in the general formula (4) Here, the alkyl group having 1 to 3 carbon atoms and the alkyl group having 1 to 4 carbon atoms are the same as the description of the general formula (1) or (2).

As a specific example of the organoalkoxysilane compound containing a blocked isocyanate group represented by the general formula (4), a blocking agent can be used to protect 3-isocyanatopropyltrimethoxysilane, 3-isocyanate Cyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropyl It is formed from the isocyanate group of compounds such as ethyl diethoxysilane. Among them, as a preferable compound, 3-blocked isocyanatopropyltriethoxysilane can be exemplified.

As a blocking agent for isocyanate groups, oxime compounds such as acetoxime, 2-butanone oxime, cyclohexanone oxime, and methyl isobutyl ketoxime can be used; internal amines such as ε-caprolactam; monoalkanes Alkylphenols (cresol, nonylphenol, etc.); Dialkylphenols such as 3,5-xylenol and di-tert-butylphenol; Trialkylphenols such as trimethylphenol; Propylene Malonic acid diesters such as diethyl diacid; active methylene compounds such as acetone, acetyl acetate and ethyl acetate; alcohols such as methanol, ethanol, and n-butanol; methyl soluble Cellulose, butyl cellosolve, etc. containing hydroxyl ethers; ethyl lactate, pentyl lactate and other hydroxyl containing esters; butane mercaptan; hexyl mercaptan and other mercaptans; acetaniline, acrylamide, dimer acid Amines such as amide; imidazoles such as imidazole and 2-ethylimidazole; pyrazoles such as 3,5-dimethylpyrazole; triazoles such as 1,2,4-triazole; succinimidazole, Phthalimines and other imines. In addition, in order to control the dissociation temperature of the blocking agent, a catalyst such as dibutyl tin dilaurate may be used in combination.

((B) ingredient) One aspect of the coating liquid of the present invention contains a hardening catalyst as the (B) component. The hardening catalyst is a catalyst that hydrolyzes and condenses (hardens) the silane compounds (A-1) to (A-4) of the above component (A). Examples include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and Inorganic acids such as nitric acid, perchloric acid, and aminosulfonic acid; formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, citric acid, tartaric acid, succinic acid, maleic acid, glutamic acid, lactic acid, p-toluenesulfonic acid And other organic acids.

In addition, lithium hydroxide, sodium hydroxide, potassium hydroxide, n-hexylamine, dimethylamine, tributylamine, diazabicycloundecene, ethanolamine acetate, dimethylaniline formate, Benzoic acid tetraethylammonium salt; sodium acetate, potassium acetate, sodium propionate, sodium glutamate, potassium propionate, sodium formate, potassium formate, benzyltrimethylammonium acetate, tetramethylammonium acetate, caprylic acid Organic metal salts such as tin, Lewis acids such as tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide, aluminum triisopropoxide, aluminum acetone acetone, SnCl ₄ , TiCl ₄ , ZnCl _{4 and the like.}

In these hardening catalysts, it is used to stably disperse the reactants of the silane compounds (A-1) to (A-4) and the (D) component in the coating solution to prevent aggregation, precipitation or gelation The additive is also useful and can improve the transparency of the obtained film, an organic acid can be preferably used. In particular, acetic acid among organic carboxylic acids can be preferably used. In the present invention, as the component (B), one type of curing catalyst may be used alone, or two or more types may be used in combination.

((C) Ingredient) One aspect of the coating liquid of the present invention contains a dispersion medium as the (C) component. In one aspect of the present invention, the coating liquid is used in a state where the above-mentioned components are mixed and dispersed in a dispersion medium. The dispersion medium used in one aspect of the present invention is not particularly limited as long as it can uniformly mix and disperse the above-mentioned components. For example, in addition to water, alcohols, aromatic hydrocarbons, ethers, Organic dispersion media such as esters. Specific examples of alcohols in these organic dispersion media include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol, and n-octanol. , 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 glycol monomethyl ether acetate, diacetone alcohol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, etc.

As specific examples of other dispersion media, tetrahydrofuran, 1,4-diethane, 1,2-dimethoxyethane, xylene, dichloroethane, toluene, methyl acetate, ethyl acetate, Ethoxy ethyl acetate and so on. Among these dispersion media, from the viewpoint of performance as a dispersion medium, water and alcohols are preferred. In the present invention, as the component (C), one type of dispersion medium may be used alone, or two or more types may be used in combination.

((D) Ingredient) One aspect of the coating liquid of the present invention preferably contains inorganic fine particles as the (D) component for the purpose of controlling the refractive index and the like. As the inorganic fine particles, for example, colloidal silica, magnesium fluoride, aluminum oxide, antimony pentoxide, tin oxide, zirconium oxide, niobium oxide, cerium oxide, titanium oxide, etc. may be mentioned. These may be used individually by 1 type, and may combine 2 or more types. The average particle diameter of the inorganic fine particles is preferably about 1 to 200 nm in terms of handling properties, ease of control of the refractive index, and the like.

The inorganic fine particles are preferably used after being dispersed in a dispersion medium. As the dispersion medium, for example, lower alcohols such as water, methanol, ethanol, propanol, 1-methoxy-2-propanol, cellosolves such as methyl cellosolve, and the like can be preferably used. These dispersion media may be used individually by 1 type, and may use 2 or more types together.

Colloidal silica is also called colloidal silica and colloidal silicic acid. In water, it refers to a colloidal suspension of silica having Si-OH groups on the surface by hydration, which is generated by adding hydrochloric acid to an aqueous solution of sodium silicate. Recently, novel preparation methods have been developed one after another, including those dispersed in a non-aqueous solution or fine powder prepared by a gas phase method, and the particle size ranges from several nm to several μm. As colloidal silica, it has also been developed to have a hollow space inside and can be preferably used. The average particle diameter is preferably about 1 to 200 nm. The composition of the particles is not fixed, and there are also those that form siloxane bonds (-Si-O-, -Si-O-Si-) and polymerize. The surface of the particles is porous and is usually negatively charged in water.

As commercial products of colloidal silica, for example, Fuso Chemical Industry Co., Ltd. "ultra-high purity colloidal silica" Quartron PL series, the company’s "high-purity organosol" Quartron PL series, or Nissan Chemical Colloidal silica (product name: Snowtex) or organic silica sol (product name: Methanol Silicasol, MA-ST-L, IPA-ST, IPA-ST-L, IPA-ST-ZL, IPA- ST-UP, EG-ST, NPC-ST-30, PGM-ST, etc.)". The colloidal silica can be used alone or in combination of two or more.

As commercial products of inorganic fine particles, in addition to the above-mentioned inorganic fine particles, "NANOUSE ZR (Zirconium Oxide Aqueous Sol)" manufactured by Nissan Chemical Co., Ltd., "ALUMINASOL AS-200", and "ALUMINASOL AS-520-A" can be mentioned. , "CATALOID (aluminum oxide water dispersible sol)", "OPTOLAKE (titanium oxide organosol)", "ELCOM-V4566 (antimony pentoxide organosol)" manufactured by Nippon Catalytic Chemicals Co., Ltd., Taki Chemical Co., Ltd. Manufactured "NEEDRAL (cerium oxide sol)", "CERAMACE (tin oxide sol)" and so on. These inorganic fine particles may be used singly or in combination of two or more kinds.

((E) Ingredient) One aspect of the coating liquid of the present invention may also include a silane compound having an epoxy group and an alkoxy group as the (E) component. (E) Component is a silane compound having an epoxy group and an alkoxy group, and is an alkoxysilane compound that does not contain an amine group and an isocyanate group (hereinafter, also referred to as an epoxy group-containing organic alkoxysilane compound) . Moreover, its partial condensate (epoxy group-containing polyorganoalkoxysilane compound) can also be used. These may be used individually by 1 type, and may be used in combination of 2 or more types. As the compound (E), an epoxy group-containing organoalkoxysilane compound and a partial condensate thereof can be represented by the following general formula (5), for example.

R ⁶ _c Si(OR ⁷ ) _4-c ••• (5) [In the formula, R ⁶ is an alkyl group with 1 to 4 carbons, a vinyl group, a phenyl group, or is selected from methacryloxy group, An alkyl group with 1 to 3 carbons substituted by one or more of glycidyloxy and 3,4-epoxycyclohexyl; at least one R ⁶ is glycidyloxy or 3,4-epoxy Cyclohexyl substituted alkyl with 1 to 3 carbons; R ⁷ is alkyl with 1 to 4 carbons; c is 1 or 2; when there are more than one R ⁶ , the plurality of R ⁶ may be the same Different, a plurality of OR ⁷ may be the same or different.] In the general formula (5), the alkyl group with 1 to 3 carbons and the alkyl group with 1 to 4 carbons are the same as those of the general formula (1) or (2). The description is the same.

As specific examples of the epoxy-containing organoalkoxysilane compound represented by the general formula (5), 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl Methyl diethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl triethoxy silane, 2-(3,4-epoxycyclohexyl) ethane Trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, etc.

(Optionally add ingredients) As one aspect of the coating liquid of the present invention, in addition to the above-mentioned components (A), (B), (C), (D), and (E), if necessary, it may appropriately contain the well-known ones previously used in the coating liquid. Various additives. As additional components that may be contained as needed, for example, organic polymer particles, ultraviolet absorbers, leveling agents, flexibility imparting agents, lubricity imparting agents, antioxidants, bluing agents, antistatic agents, and defoaming agents may be mentioned. Agent (anti-foaming agent), light stabilizer, weather resistance imparting agent, coloring agent, fine particle dispersant (anti-precipitation agent), fine particle surface active modifier, etc.

(Organic polymer particles) In one aspect of the present invention, organic polymer particles may or may not be included in the coating liquid. When the coating liquid contains organic polymer microparticles, it may have an ultraviolet absorbing group, or may not have an ultraviolet absorbing group. By containing fine organic polymer particles, the refractive index can be controlled well in some cases. In addition, when the organic polymer fine particles have ultraviolet absorbing groups, they also function as ultraviolet absorbers and the like. As the ultraviolet absorber, for example, acrylic monomers (hereinafter referred to as Ultraviolet absorbing acrylic monomer) and other ethylenically unsaturated compounds (acrylic acid, methacrylic acid and its derivatives, styrene, vinyl acetate, etc.) copolymerized with polymer ultraviolet absorbing resin particles. Conventional ultraviolet absorbers are usually low molecular weights with a molecular weight of 200 to 700. In contrast, the weight average molecular weight of the above-mentioned polymer ultraviolet absorbing resin particles usually exceeds 10,000. The above-mentioned polymer ultraviolet absorbing resin microparticles are those that have been improved to have the disadvantages of low-molecular-weight ultraviolet absorbers such as compatibility with plastics or heat resistance, and can continue to impart weather resistance for a long 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 an acryl group in the molecule, respectively. As such a compound, for example, a benzotriazole-based compound represented by the following general formula (8) and a benzophenone-based compound represented by the general formula (9) may be mentioned.

[化3]

[In the formula, X represents a hydrogen atom or a chlorine atom; R ¹⁰ represents a hydrogen atom, a methyl group, or a tertiary alkyl group with 4 to 8 carbons; R ¹¹ represents a linear or branched chain with 2 to 10 carbons Alkylene; R ¹² represents a hydrogen atom or a methyl group; p represents 0 or 1]

[化4]

[In the formula, R ¹³ represents a hydrogen atom or a methyl group; R ¹⁴ represents a substituted or unsubstituted linear or branched alkylene group having 2 to 10 carbon atoms; R ¹⁵ represents a hydrogen atom or a hydroxyl group; R ¹⁶ represents a hydrogen atom, a hydroxyl group, or an alkoxy group with 1 to 6 carbon atoms]

As a specific example of the benzotriazole compound represented by the general formula (8), for example, 2-(2'-hydroxy-5'-(meth)acryloyloxyphenyl)-2H-benzo Triazole, 2-(2'-hydroxy-3'-tertiary butyl-5'-(meth)acryloyloxymethylphenyl)-2H-benzotriazole, 2-[2'-hydroxy -5'-(2-(meth)acryloyloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tertiary butyl-5'-(2 -(Meth)acryloyloxyethyl)phenyl]-5-chloro-2H-benzotriazole, 2-[2'-hydroxy-3'-methyl-5'-(8-(methyl ) Allyloxyoctyl) phenyl]-2H-benzotriazole and the like.

As a specific example of the benzophenone compound represented by the general formula (9), for example, 2-hydroxy-4-(2-(meth)acryloyloxyethoxy)benzophenone, 2 -Hydroxy-4-(4-(meth)acryloxybutoxy)benzophenone, 2,2'-dihydroxy-4-(2-(meth)acryloxyethoxy) Benzophenone, 2,4-dihydroxy-4'-(2-(meth)acryloyloxyethoxy)benzophenone, 2,2',4-trihydroxy-4'-(2 -(Meth)acryloxyethoxy)benzophenone, 2-hydroxy-4-(3-(meth)acryloxy-2-hydroxypropoxy)benzophenone, 2- Hydroxy-4-(3-(meth)acryloxy-1-hydroxypropoxy)benzophenone and the like. These ultraviolet absorbing acrylic monomers may be used individually by 1 type, and may be used in combination of 2 or more types.

From the viewpoint of the UV absorption capacity of the obtained cured film, the balance of other physical properties and economic efficiency, the content of the UV-absorbing acrylic monomer unit of the polymer UV-absorbing resin particles is usually about 5 to 70% by mass, preferably About 10-60% by mass.

In one aspect of the present invention, in the coating liquid, from the viewpoints of manufacturability, dispersibility in the coating liquid, coatability of the coating liquid, and transparency of the cured film, the polymer ultraviolet absorbing resin particles are preferred Those whose average particle diameter is in the range of 1 to 200 nm, and more preferably those in the range of 1 to 100 nm.

In the present invention, the organic polymer fine particles are preferably used in a form dispersed in a dispersion medium. As the dispersion medium, for example, lower alcohols such as water, methanol, ethanol, propanol, 1-methoxy-2-propanol, cellosolves such as methyl cellosolve, and the like can be preferably exemplified. By using such a dispersion medium, the dispersibility of the organic polymer particles is improved, and precipitation can be prevented. Furthermore, the dispersion medium is preferably water. If the dispersion medium is water, it can also be used for the hydrolysis and condensation reaction of the silane compound required when forming a matrix having the Si-O bond derived from the above-mentioned component (A).

The method for producing the organic polymer particles is not particularly limited, and a previously known method, such as emulsion polymerization method or fine suspension polymerization method, can be used.

As a specific example of organic polymer microparticles, there can be mentioned ULS-700, ULS-1700, ULS-383MA, ULS-1383MA, ULS-383MG, ULS-385MG for coating polymer UV absorbers manufactured by Lion Specialty Chemicals Co., Ltd. , ULS-1383MG, ULS-1385MG, etc., functional polymer NCI-905-20NPF manufactured by NIKKO Chemical Research Institute Co., Ltd., etc. In addition, the BESTEX HR-84, HCR-120, VANATEX HG-9HN, NEWCOAT 9306, UVA-101, etc. of New Nakamura Chemical Industry Co., Ltd. can be cited. The organic polymer microparticles may be used singly or in combination of two or more kinds.

(Leveling agent) As one aspect of the coating liquid of the present invention, in order to improve the smoothness of the cured film obtained and the fluidity during coating, a leveling agent may be added. As these additives, a silicone-based leveling agent, a fluorine-based leveling agent, an acrylic-based leveling agent, an ethylene-based leveling agent, and a compounded fluorine-based and acrylic-based leveling agent, etc. may be mentioned. Both act on the surface of the coating film to reduce the surface tension. Each has its own characteristics and can be used depending on the purpose. Silicone-based and fluorine-based have strong surface tension reduction capabilities, while acrylic and vinyl-based systems are less likely to cause poor wetting during recoating, which is more advantageous.

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

In addition, when heat resistance above 150°C is required, polyester-modified or aralkyl-modified polysiloxane oil with a benzene ring is suitable. As commercial products of polyester-modified silicone oil, BYK-310, BYK-315, BYK-370, etc. manufactured by BYK-Chemie Japan Co., Ltd. can be cited as examples of aralkyl-modified polysiloxane with benzene ring. Commercially available silicone oils can be BYK-322 and BYK-323 manufactured by BYK-Chemie Japan Co., Ltd., etc.

As the fluorine-based leveling agent, a copolymer of polyoxyalkylene and fluorocarbon or the like can be used. As commercial products of fluorine-based leveling agents, MEGAFAC series manufactured by DIC Co., Ltd., FC series manufactured by Sumitomo 3M Co., Ltd., etc. can be cited. Commercial products of acrylic leveling agents include BYK-350, BYK-352, BYK-354, BYK-355, BYK358N, BYK-361N, BYK-380N, BYK manufactured by BYK-Chemie Japan Co., Ltd. -381, BYK-392, etc., the introduction of fluorine BYK-340, etc.

By blending this leveling agent, the final appearance of the cured film is improved, and it can be evenly coated as a thin film. The amount of the leveling agent used is preferably 0.01 to 10% by mass relative to the total amount of the coating liquid, and more preferably 0.02 to 5% by mass. As a method of blending the leveling agent, it can be blended when the coating liquid is prepared, or it can be blended in the coating solution immediately before the cured film is formed, and furthermore, it can also be blended in the two stages of preparing the coating solution and forming the cured film.

(Flexibility-imparting agent) As one aspect of the coating liquid of the present invention, in order to improve the flexibility of the cured film obtained, a flexibility imparting agent may be contained as a stress relaxation agent. As the flexibility imparting agent, for example, silicone resin or the like can be used.

As a commercially available product of polysiloxane resin, for example, the Resin MK series manufactured by Wacker Company, for example, Belsil PMS MK contains a _{polymer of (CH 3} SiO _3/2 ) repeating unit (unit T), and the polymer is also Contains up to 1% by mass of (CH ₃ ) ₂ SiO _2/2 ) units (unit D)), or KR-242A manufactured by Shin-Etsu Chemical Co., Ltd. (contains 98% by mass of unit T and 2% by mass of dimethyl Base unit D and including Si-OH end group), KR-251 (including 88% by mass of unit T and 12% by mass of dimethyl unit D and including Si-OH end group), KR-220L includes (CH ₃ SiO _3/2 ) unit T and includes Si-OH (silanol group) and the like.

In one aspect of the present invention, the content of each component of the coating liquid can be appropriately selected. For example, it is preferable to select the content of each component so as to be in the range shown below.

Except for the dispersion medium of (C) component, each component is expressed in mass% relative to the total amount of (A)[(A-1)～(A-4)] component, (B) component, and (E) component content. Furthermore, when component (D) (inorganic fine particles) is used, only the solid components are used to calculate the (D) component (inorganic fine particles) used in a dispersed state, and the dispersion medium contained in each component is set to be contained in (C) Ingredients.

(A-1) The content of the component is usually about 0.01 to 40% by mass, and preferably 0.1 to 20% by mass. (A-2) The content of the component is usually about 0.1 to 50% by mass, and preferably 1 to 40% by mass. (A-3) The content of the component is usually about 0.1 to 30% by mass, preferably 0.3 to 20% by mass. (A-4) The content of the component is usually about 0.1 to 50% by mass, and preferably 1 to 40% by mass.

(B) The content of the component is usually about 0.001 to 30% by mass, and preferably 0.001 to 20% by mass.

The content of (C) component is usually about 5 to 5000 parts by mass relative to the total mass parts of (A)[(A-1)～(A-4)] component, (B) component, and (E) component, Preferably it is 20-3500 mass parts. When the component (D) is contained, its content is usually about 0.1 to 70% by mass, and preferably 1 to 50% by mass.

Furthermore, there is no particular limitation on the molar ratio of the component (A-3) and the component (A-4), but it is preferably 1:1 to 1:5, more preferably 1:2 to 1:4 . If the molar ratio of the component (A-3) and the component (A-4) is in the above range, the durability of the cured film obtained will be further improved.

(Preparation method of coating liquid) In one aspect of the present invention, the coating liquid is preferably in the reaction product obtained by contacting the hydrolysis condensate of (A-1) component and (A-2) component with (B) and (C) component After adding and reacting the component (A-4), the component (A-3) is further added and reacted.

Moreover, it is also preferable to add (A) to the reaction product obtained by contacting the hydrolysis condensate of (A-1) component, (A-2) component and (E) component with (B) and (C) component -4) After the component is reacted, the component (A-3) is further added and reacted.

Furthermore, it is more preferable to add (A-4) to the reaction product obtained by contacting and heating a mixture containing (A-1) component, (A-2) component, (B) component, and (C) component ) After the component is reacted, the component (A-3) is further added and reacted.

Furthermore, it is also preferable to add (A-4) to the reaction product obtained by heating a mixture containing (A-1) component, (A-2) component, (E) component, and (B) to (C) components After the components are reacted, the component (A-3) is further added and reacted.

Specifically, it is preferable to perform the following operations to prepare a coating liquid. First, a first mixed liquid containing at least the components (A-1), (A-2), (B), and (C) is prepared. Next, when the component (D) (inorganic fine particles, such as colloidal silica) is used in the coating liquid to be produced, (D) is mixed to produce a second mixed liquid. Furthermore, the component (A-4) was continuously mixed to prepare a third mixed liquid. Finally, it is preferable to mix the component (A-3) to prepare a coating liquid. Here, you may optionally contain (E) component in the 1st mixed liquid.

As described above, if each component is prepared separately, the liquid storage stability (non-gelation, etc.) of the coating liquid is improved, which is preferable. In particular, when the amount of water in the liquid increases due to the increase in the amount of component (D) added, the effect is further exhibited. For example, after mixing (A-1), (A-2), (E), (B), and (C) components, add (D) component. Next, the component (A-4) is mixed, and finally the component (A-3) is mixed. Furthermore, the coating liquid can be diluted by adding the component (C) after preparing the coating liquid.

It is known that the liquid storage stability of the mixed material of the coating liquid of the present invention is likely to affect the pH value of the liquid (for example, "Application of Sol-Gel Method in Nanotechnology/Supervision: Zuohua Zio" CMC publication). In one aspect of the present invention, when preparing the coating liquid, since the acidic component is mixed as the (B) component, and the alkaline component is mixed as the (A-3) component and (B) component, the pH of the liquid will be based on The mixing sequence changes.

As the pH value of the liquid, for example, the pH value of the liquid evaluated by a portable pH meter (manufactured by Hanna Corporation, trade name: Checker 1) corrected with a pH standard liquid after calibration, preferably the first mixed liquid and The second mixed liquid is set to pH ≦6, and the third mixed liquid and the final mixed liquid are set to pH ≦7. In particular, if the pH of the third liquid mixture, that is, when the component (A-3) is mixed, exceeds 8, the stability of the liquid may decrease. It is preferable that the liquid maintains an acidic state from the beginning of the preparation of the coating liquid to the end of the preparation. That is, it is preferable to prepare the coating liquid in the order of maintaining such conditions.

In addition, it is preferable that the first mixed liquid, the second mixed liquid, and the third mixed liquid be heated after mixing the components. 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. There are no particular restrictions on the mixing and heating method as long as it can be uniformly mixed and heated. By heating as described above, the condensation reaction of the components (A-1), (A-2), (A-3), (E) and (A-4) in the liquid proceeds, boiling resistance or other Durability is improved. The reactions of components (A-1), (A-2), (A-3), (E) and (A-4) can be analyzed by solution Si-NMR (Nuclear Magnetic Resonance), thereby Can be designed into a suitable structure. When the temperature is less than 30°C or less than 30 minutes, the reaction is often extremely slow, and when it exceeds 130°C or more than 24 hours, there are (A-1), (A-2), (A- 3) The reaction of the components (E) and (A-4) progresses excessively, and the liquid may gel or become highly viscous, and may become uncoated.

It is also preferable to heat-process the final liquid (coating liquid) after mixing (A-3) component. When mixing at room temperature, it is easily affected by the stirring efficiency. When the dispersion of the component (A-3) is low due to the stirring efficiency, the transparency of the cured film may decrease (the total light transmittance decreases, The haze rises). 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 method is not particularly limited as long as it can be uniformly mixed and heated. When the temperature is less than 30°C or less than 5 minutes, the effect of heat treatment is often lacking, and if it exceeds 130°C or more than 10 hours, the liquid will gel or become highly viscous and become uncoated. Yu. In the examples described below, the evaluation results of the cured film manufactured using the coating liquid obtained after standing for 1 week are described, but the liquid standing time until the cured film is manufactured is not particularly limited.

(Use of coating fluid, etc.) In one aspect of the present invention, the coating liquid system liquid has good stability and handling properties, and can be cured by drying at a relatively low temperature. The formed cured film has a good appearance and a small thickness. It is coated on the base material to form a laminate, thereby effectively increasing the transmittance. Therefore, the coating liquid according to one aspect of the present invention is useful as a material capable of modifying various substrate properties by coating on various substrates with high transparency.

In one aspect of the present invention, the coating liquid can be preferably used for lighting components such as facilities, shops, outdoor lighting or residential lighting, street lamps, etc., for the purpose of expecting an effective increase in transmittance or transparency. Headlights, fog lights, rear lights, overhead lights, interior lighting and other automotive lighting components, corrective glasses, sunglasses, sports goggles, safety glasses, etc. eyeglass lenses, digital still cameras, mobile phones, smart models Mobile phone cameras, projectors, optical readers, CCD (Charge Coupled Device) cameras and other optical lenses, infrared camera sensors, visible light camera sensors, driving recorders, etc., vehicle-mounted camera lenses, liquid crystals Displays, organic EL (Electroluminescence, electroluminescence) displays, anti-reflection films, light guide plates, optical fibers, touch panels, solar battery panels, and other coating materials in various displays, LEDs (Light Emitting Diode, light-emitting diodes) Parts for displays (digital signage, street TV) or micro LED displays, etc.

In addition, the coating liquid of the present invention can be preferably used for the manufacture of various transparent parts such as resin-made car windows, resin windows of buildings, road soundproof walls, arcades and other large-area transparent parts, instrument panels and other instruments, buildings Resin windows, transparent plastic components, etc. In particular, in terms of being able to form a laminated body with high light transmittance, it can be preferably used in the manufacture of lighting lamps, display lamps, traffic lights, fluorescent tubes, domes for daylighting, ceiling lights, arcades , Road side wall panels and other lighting equipment lighting covers or lighting lenses, especially can be preferably used to manufacture LED lighting covers or lenses with high brightness and high directivity LED light sources, laser lighting covers or lenses, etc. Components for lighting. Furthermore, it can be preferably used for coating interior and exterior parts of automobiles, industrial machinery, furniture, interior and exterior parts for construction, home appliances, plastic products, etc.

the following. The cured film of one aspect of the present invention will be described. [Cured film] One aspect of the cured film of the present invention is formed by curing the above-mentioned coating liquid of one aspect of the present invention. Specifically, spray, curtain-type flat surface, bar coating, roll coating, dip coating, etc. are used to form the base of the resin molded product (injection molded product, film, sheet, glass, etc.) that is the object of the cured film. The material is formed by coating the coating liquid as one aspect of the present invention. Among these coating methods, in terms of being able to efficiently realize the coating of the coating liquid with relatively simple equipment, dip coating is preferred. Generally, dip coating may also cause uneven coating, but as long as it is dip coating using the coating solution of one aspect of the present invention, it is difficult to produce foreign matter, streaks, cracks, etc. on the appearance, and it is efficiently formed on the appearance. Good hardened film. On the other hand, in dip coating, for example, it is difficult to achieve uniform coating due to the shape of the substrate due to the shape of the substrate, such as accumulating the coating liquid in the concave portion of the substrate having unevenness, and spray coating is preferable.

As the substrate, at least any one of resin, glass, acrylic glass, strengthened glass, metal, wood, rubber, concrete, stone, ceramics, leather, paper, cloth, and fiber can be used, and transparency is preferred. The higher one is, among them, a resin-made substrate (resin substrate) is preferred. In particular, in terms of excellent various substrate properties such as transparency, mechanical properties, and heat resistance, a base material made of a polycarbonate resin is preferred.

The thickness of the cured film is preferably 5 μm or less, more preferably 2 μm or less, and still more preferably 500 nm or less. Furthermore, it is preferably 50 to 110 nm, more preferably 60 to 95 nm or less. If the thickness of the above-mentioned cured film exceeds 5 μm, the transmittance of the formed laminate may not increase.

The drying temperature when forming the cured film may be relatively low, and specifically, it is preferably from room temperature to 190°C, more preferably from 80 to 120°C. When the drying temperature is relatively high, for example, if it exceeds 120°C, when polycarbonate is used in the substrate, the polycarbonate may be thermally deformed.

The refractive index of the cured film is preferably 1.1 to 1.59. By setting the refractive index of the cured film as the refractive index between the air and the substrate, the reflectance can be reduced and the transmittance can be increased.

Hereinafter, a laminated body of one aspect of the present invention will be described. [Layered body] As one aspect of the present invention, the laminate includes a base material and the above-mentioned cured film of the present invention directly formed on the base material. The resin layer formed on the substrate may be one layer, or two or more layers. Hereinafter, the laminate of the present invention will be described in detail. One aspect of the laminated body of the present invention is a laminated body having the above-mentioned cured film of the present invention on a substrate.

The method of forming the above-mentioned cured film using the coating liquid of one aspect of the present invention is the same as the content shown in the description of the above-mentioned cured film of the present invention. The laminate of the present invention is not particularly limited as long as it has a good transmittance and has the above-mentioned structure. Therefore, it can be preferably used in various applications as shown below.

As the use of the laminated body, for example, it can be used for windshields of two-wheeled vehicles and three-wheeled vehicles, windows for automobiles, railway vehicles, construction machinery vehicles, roofs for construction machinery vehicles, automotive interior parts, automotive exterior parts, locomotives Parts, loading platform covers of trucks, internal and external decoration parts of various vehicles such as trams, aircrafts, ships, etc.; AV (Audio Visual) machines, washing machines, electric pots, electric kettles, IH (Induction Heat) cooking Household electrical appliances such as heaters, furniture and other components; mobile phones, notebook computers, remote controls, etc.; furniture exterior materials, building materials, car windows, windows of buildings and other light-shielding films, walls, ceilings, and floors Interior decorations, wall panels and other exterior walls, enclosures, roofs, door leaves, gables and other architectural exterior decorations, window frames, doors, handrails, thresholds, door lintels and other furniture surface decoration materials; street lamps and other lighting Components, facilities, shops, outdoor lighting, residential lighting, headlights and other automotive lighting, various displays such as plasma, liquid crystal, and organic EL, components for solar cells, anti-reflection films, optical lenses, optical discs, mirrors, corrective glasses , Sunglasses, sports goggles, safety glasses and other optical parts, camera lenses, window glass and other optical components; bottles, cosmetic containers, lotions, body soap, hand soap, etc., desserts or snacks, beverages, etc. Various packaging containers and packaging materials such as containers and storage boxes; other parts such as slot machines; suitcases and other bags; toilet seats; table mats; clocks and watches; whiteboards; protective shields and groceries, etc.

In terms of having high light transmittance, the laminated body of the present invention can be preferably used to manufacture lighting lamps, display lamps, traffic lights, fluorescent tubes, domes for daylighting, ceiling lights, arcades, road side walls Lighting covers or lighting lenses for lighting fixtures such as panels, especially, can be preferably used for manufacturing LED lighting covers or lenses with high brightness and high directivity LED light sources, laser lighting covers or lenses, etc. member.

Examples of automotive interior parts include: instrument panels, console boxes, instrument covers, instrument panels, indicator panels, door trims, door lock rings, steering wheels, power window switch seats, central instrument clusters, and meters Discs, shift lever covers, switches, soot dishes, etc.

Examples of automotive exterior parts include weather strips, bumpers, bumper guards, side fenders, body panels, door panels, spoilers, hoods, body guards, and trunks. Covers, front grilles, decompression covers, rim covers, center pillars, door mirrors, center decorations, side bumpers, door bumpers, window bumpers, windows, headlights, taillights, lamp reflectors , Door sun visors, windshield components, etc. In addition, as the component for the locomotive described above, for example, a fairing, a fender, a box shell, a carrying box cover, etc. may be mentioned.

As AV equipment, washing machines, electric pots, electric kettles, IH cooking heaters and other household electrical appliances, furniture and other components, for example, front panels, control panels, touch panels, membrane switch panels, buttons, signs, and surface decorations Materials and so on. Examples of building materials include road light-transmitting sound insulation panels, sound insulation panels around railways or factories, arcades, wind panels, snow shelters, carports or parking lots, bus stops, sun rooms, corridors, etc., roofs, entrances, etc. Lighting materials such as dome roofs, windows of buildings, etc., plastic sheds, etc. As components of mobile phones, notebook computers, remote controllers, etc., for example, casings, display windows, keyboards, buttons, etc. can be cited.

(Substrate) As the substrate, at least any one of resin, glass, acrylic glass, strengthened glass, metal, wood, rubber, concrete, stone, ceramics, leather, paper, cloth, and fiber can be used, and transparency is preferred. The higher one is, among them, a resin-made substrate (resin substrate) is preferred. In particular, in terms of excellent various substrate properties such as transparency, mechanical properties, and heat resistance, a base material made of a polycarbonate resin is preferred.

In one aspect of the present invention, the substrate may contain a light diffusing agent for the purpose of imparting a light diffusing effect or the like. The light diffusing agent is not particularly limited, and known ones can be used. For example, crosslinked acrylic resins, crosslinked polystyrene resins, silicone resins, fluorine resins, silica, quartz, titanium oxide, zinc oxide, etc. may be mentioned. These may be used individually by 1 type, and may use 2 or more types together. Among them, it is preferable to include organic fine particles including polysiloxane resin in terms of good retention thermal stability during molding and the like and an effect of improving flame retardancy. The particle size (D ₅₀ ) of the light diffusing agent is not particularly limited, but from the viewpoint of improving the retention thermal stability during molding, flame retardancy, etc., it is preferably 0.5 to 10 μm, more preferably 1 ~5 μm. _{Here, the particle size (D 50} ) of the light diffusing agent is measured by a laser diffraction type particle size distribution measuring device (volume basis).

When the base material is made of resin, the type of resin is not particularly limited, and can be appropriately selected from various resins according to the purpose of the laminate. In addition, the base material of the present invention is manufactured using a known molding method such as an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a pressure molding method, a vacuum molding method, and a foam molding method. It has unevenness on the surface, and, in addition to the plate shape, it may have a cylindrical shape, an elliptic cylindrical shape, a square pillar shape, a cylindrical shape, and the like.

In the case of a substrate manufactured by an injection molding method, the surface of the substrate becomes a mirror surface due to the transfer of the mold. On the other hand, when the substrate is manufactured by, for example, an extrusion molding method, irregularities may be formed on the surface of the substrate. If unevenness is formed on the surface of the substrate, the haze may increase due to diffuse reflection. In this respect, in the laminate of the present invention formed by forming a cured film on a substrate using the coating liquid of one aspect of the present invention, regardless of the manufacturing method of the substrate, even if the haze is slightly higher In the case of the base material, it can also be made into a laminate and reduce the haze.

In the present invention, as the resin that can be used for the substrate, for example, polyethylene, polypropylene, and cycloolefin-based resin (for example, "ARTON" manufactured by JSR Co., Ltd., "Zeon Co., Ltd." ZEONOR”, “ZEONEX”), polyolefin resins such as polymethylpentene, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, Cellulose resins such as diacetyl cellulose, triacetyl cellulose, cellulose acetyl butyrate, polystyrene, parapolystyrene, acrylonitrile-butadiene-styrene resin (ABS resin) and other benzene Vinyl resins, polyimides, polyetherimides, polyimide resins such as polyimide resins, polyamide resins such as nylon, ketone resins such as polyether ketone, polyether ether ketone, poly Tungsten resins such as waste, polyether waste, vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride, acrylic resins such as polymethyl methacrylate, polycarbonate resins, polyphenylene sulfide, polyacetal, Modified polyacetal ether, polyvinyl alcohol, ethoxy resin, fluororesin, etc., may also be a polymer alloy-polymer blend formed by mixing a plurality of the above-mentioned polymers. Moreover, it may be a laminated structure formed by laminating a plurality of the above-mentioned resins. Among the above resins, polyester resins, polyolefin resins, and polycarbonate resins are preferred.

The base material using these resins as a material may be either transparent or translucent, and may be colored or uncolored, and may be appropriately selected according to the application. When used in optical applications, those with excellent transparency and uncolored are preferred. Among the above resins, polycarbonate which is excellent in transparency, mechanical properties, and heat resistance is particularly preferred. The thickness of the substrate is not particularly limited, and is appropriately selected according to the situation, but is usually about 5 μm to 30 mm, preferably 15 μm to 10 mm.

In one aspect of the present invention, the substrate may be a substrate that has been micro-processed on the surface of the substrate, such as a ridge layer, a microlens layer, or a functional layer such as a hard coat layer, a light diffusion layer, and an ink layer. Especially when the substrate has a microlens array, it can control the light-gathering-diffusion property, and it is preferable as a display material by combining with an LED light source such as a microLED.

As one aspect of the present invention, the coating liquid can form a cured film with good adhesion on the substrate. However, in order to further improve the adhesion of the cured film, the substrate may be exposed to the substrate by an oxidation method or a concave-convex method as needed. At least the surface on the side where the cured film is formed is subjected to surface treatment. As the above-mentioned oxidation method, for example, plasma treatment such as corona discharge treatment, low-pressure plasma method or atmospheric pressure plasma method, chromic acid treatment (wet), flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, electronic Beam treatment, ITRO treatment, etc., and as the roughening method, for example, sandblasting method, solvent treatment method, etc. may be mentioned. These surface treatment methods can be appropriately selected according to the type of substrate, but in general, the corona discharge treatment method is preferably used in terms of hardening and handling properties. In addition, surface treatment or primer coating using silane coupling agent can also be provided.

In addition, the present invention also provides a method for manufacturing a cured film and a method for manufacturing a laminate. The method for manufacturing a cured film is characterized by including a step of heating and curing the above-mentioned coating liquid according to one aspect of the present invention. The manufacturing method of the laminated body is characterized by including: the step of applying the above-mentioned coating liquid of one aspect of the present invention on the substrate; and the step of drying and hardening the above-mentioned coating liquid to provide a coating layer.

In addition, one aspect of the laminate of the present invention has a substrate and a cured film formed directly on the substrate and cured by curing a coating solution containing a hydrolyzed condensate of a silane compound having an alkoxy group. The curing The thickness of the film is below 500 nm. For the coating liquid and the substrate, any one of the above-mentioned aspects of the laminate of the present invention can be used. Regarding the cured film, the cured film shown in one aspect of the above-mentioned laminate of the present invention can also be exemplified. Example

The present invention will be described in further detail based on examples, but the present invention is not limited to these examples at all. In addition, unless otherwise mentioned, the characteristics of each example are determined based on the following points (1) to (6).

(1) Liquid stability of coating liquid They were sealed and stored at room temperature for 14 days and 270 days respectively, and whether they were gelled or not was judged visually. For those that are not gelled, measure the viscosity with a tuning fork vibrating viscometer (model: SV-10) manufactured by A&D Co., Ltd., and set the viscosity change rate from the initial (before sealed storage) to within 3 times As "good", set the value of more than 3 times as "bad".

(2) Film appearance Visually observe the appearance of the laminated body to confirm whether there are foreign objects, markings, or cracks. If the foreign objects, markings, or cracks are not confirmed, set it as "good", and if the foreign objects, markings, or cracks are confirmed, set it as "bad".

(3) Film thickness A reflection spectroscopic film thickness meter (Asumi Giken Co., Ltd., model: AFW-100W) was used to measure the film thickness of the cured film of the laminate including the formed film.

(4) Transmittance Use UV-VIS-NIR (Ultraviolet-Visible-Near Infrared, ultraviolet-visible-near infrared) spectrophotometer (manufactured by Shimadzu Corporation, model: UV-3600) to measure the laminated body in the wavelength region of 250～800 nm Transmittance.

(5) Relative visible light transmittance Integrate the transmittance of the 380-780 nm wavelength region of the laminate measured with a UV-VIS-NIR spectrophotometer (manufactured by Shimadzu Corporation, model: UV-3600), and the integrated value of the laminate is compared to only The ratio of the integral value (1.000) of the substrate is set as the relative visible light transmittance.

(6) Refractive index A spectroscopic ellipsometer (manufactured by J.A. Woollam Company, model: М-2000D) was used to measure the refractive index of the cured film formed on the substrate. At this time, analyze using a common dispersion model to find the refractive index in the wavelength range of 200 to 1600 nm. Represents the refractive index at a wavelength of 450 nm.

(7) Adhesion Carry out the grid peeling test and evaluate the adhesion. Use the blade of the cutter to form 6 cut marks on the hardened film at 2 mm intervals to make 25 grids. Use your fingertips to make a commercially available transparent tape (manufactured by Miqibang Co., Ltd., model: CT-24) After good adhesion, it peeled off sharply in the forward direction at an angle of 90°. X/25 represents the number of squares (X) remaining without peeling of the cured film, and the adhesion of the cured film is evaluated.

(8) Heat cycle resistance Using a small thermal shock test device (manufactured by Espec, model: TSE-11-A), 1 hour at -30°C and 1 hour at 110°C were set as 1 cycle and 100 cycles were performed. After that, a grid peeling test was performed to perform close adhesion. Sexual assessment. Use the blade of the cutter to form 6 cut marks on the hardened film at 2 mm intervals to make 25 grids. Use your fingertips to make a commercially available transparent tape (manufactured by Miqibang Co., Ltd., model: CT-24) After the close bonding, it peeled off sharply in the front direction at an angle of 90°. X/25 represents the number of squares (X) remaining without peeling of the cured film, and the heat cycle resistance of the cured film is evaluated.

(9) Humidity and heat resistance Using the environmental testing machine SH-221 manufactured by Espec, the samples were stored in a testing machine set to a temperature of 65°C and a humidity of 95% for 120 days, and then the grid peeling test was performed to evaluate the adhesion. Use the blade of the cutter to form 6 cut marks on the hardened film at 2 mm intervals to form 25 grids. Use your fingertips to make a commercially available scotch tape (manufactured by Miqibang Co., Ltd., model: CT-24) After a good adhesion, it peels off sharply in the front direction at an angle of 90°. X/25 represents the number of squares (X) that the cured film is not peeled off and the remaining squares (X), and the heat and humidity resistance of the cured film is evaluated .

In addition, in this manual, the details of the raw materials described by the trade names are as follows. (A-1) Ingredients: Silicate 40 (a mixture of polyethyl silicate, ethyl orthosilicate, tetraethyl silicate, and ethanol), manufactured by Tama Chemical Industry Co., Ltd. (D) Ingredient: IPA-ST-L (colloidal silica), manufactured by Nissan Chemical Co., Ltd. (isopropanol dispersion, colloidal silica concentration 30% by mass, average particle size 40-50 nm (manufacturer’s published value)) (D) Ingredient: IPA-ST (colloidal silica), manufactured by Nissan Chemical Co., Ltd. (isopropanol dispersion, colloidal silica concentration 30% by mass, average particle size 10-15 nm (manufacturer’s published value))

Manufacturing example 1 (manufacturing of coating solution 1) According to the components and the blending amounts shown in Production Example 1 of Table 1, the coating liquid was prepared in the following manner. According to 1-methoxy-2-propanol ((C) dispersion solvent component) 8.5 g, water ((C) component) 2.4 g, acetic acid ((B) component) 1.0 g, Silicate 40 ((A-1) Ingredients) 0.40 g, methyltrimethoxysilane ((A-2) ingredient) 3.0 g, dimethoxy-3-glycidoxypropylmethylsilane ((E) ingredient) 1.1 g, 20% by mass 0.1 g of p-toluenesulfonic acid methanol solution (component (B) + component (C)) was added dropwise to a 50 ml sample tube in the order of 1 minute. Then, it was stirred at 500 rpm at room temperature for 60 minutes, and then it was allowed to stand for one day to make it the first liquid.

Add 2.2 g of 3-isocyanatopropyltriethoxysilane and 0.8 g of 2-butanone oxime (blocking agent for isocyanate groups) to a 20 ml sample tube, and stir at 500 rpm at room temperature After 10 minutes, it was allowed to stand for one day and set as the third solution. It was confirmed that the isocyanate group was blocked by ¹³ C-NMR based on the disappearance of the signal of the isocyanate group. The sum of the blending amounts of 3-isocyanatopropyltriethoxysilane and 2-butanone oxime was set as the amount of the blocked isocyanatosilane compound: (A-4) component.

Put the first liquid and the stir bar into a 200 ml three-necked flask equipped with a cooling tube, stir at 500 rpm, and add 9.1 g of isopropanol ((C) component) dropwise over 5 minutes as the second liquid. Stir at room temperature for 60 minutes. Then, it was heated at 600 rpm and 80°C for 3 hours under a nitrogen stream. Then, the third liquid was added, stirred at 80°C for 4 hours under the same conditions, and then allowed to stand overnight at room temperature. Furthermore, 0.80 g of 3-aminopropyltrimethoxysilane ((A-3) component) was dripped here over 2 minutes as a 4th liquid. After stirring for 10 minutes at room temperature, it was further heated at 700 rpm and 80°C for 3 hours under a nitrogen stream. Then, it was left to stand for 1 week, and it was diluted with 240 g of isopropanol as a dilution solvent, and the coating liquid 1 was produced.

Manufacturing examples 2 to 5 (manufacturing of coating solutions 2 to 5) In the same manner as in Production Example 1, a coating liquid was produced based on the components and blending amounts shown in Production Examples 2 to 5 in Table 1. According to the above content, the coating liquids 1 to 5 obtained in the above manner were evaluated for (1) liquid stability. The results are shown in Table 1.

In addition, the blending (mass% and mass parts) of each component at the time of preparing each coating liquid is shown in Table 2.

Examples 1-13 Use a coater (dip coater (manufactured by Asumi Giken Co., Ltd., model: M300) in Examples 1-12, and a bar coater (automatic coating device manufactured by Tester Sangyo Co., Ltd.) in Example 13 (PI-1210)) For each coating solution obtained in the production example, each coating solution was applied to both sides or one side of each substrate as described in Tables 3 to 4. After that, in Examples 1 to 11 and implementation In Example 13 it was dried at 120°C for 10 minutes, and in Example 12 it was dried at 60°C for 10 minutes to produce each laminate. According to the above (2) to (5) and (7) to (9) The laminate was evaluated (in Examples 2, 5, and 6, the evaluation was based on the above (2) to (9), and in Examples 9 to 12, the evaluation was based on the above (2) to (5)), and the results Shown in Tables 3 to 4. In Tables 3 to 4, the transmittance represents the transmittance of the laminate at a wavelength of 450 nm.

[Table 1] ingredient Manufacturing example 1 Manufacturing example 2 Manufacturing example 3 Manufacturing example 4 Manufacturing example 5 Coating liquid 1 Coating liquid 2 Coating liquid 3 Coating liquid 4 Coating solution 5 1-methoxy-2-propanol (g) Ingredients (C) 8.5 8.5 8.5 8.5 8.5 Water (g) Ingredients (C) 2.4 2.4 2.4 2.4 2.4 Acetic acid (g) Ingredients (B) 1.0 1.0 1.0 1.0 1.0 Silicate 40(g) Ingredients (A-1) 1.0 1.0 1.0 1.0 1.0 Methyltrimethoxysilane (g) Ingredients (A-2) 3.0 3.0 3.0 3.0 3.0 Dimethoxy-3-glycidoxypropylmethylsilane (g) Ingredients (E) 1.1 1.1 1.1 1.1 1.1 20% by mass p-toluenesulfonic acid methanol solution (g) Ingredients (B) (C) 0.1 0.1 0.1 0.1 0.1 IPA(g) Ingredients (C) 9.1 6.0 0.7 0.7 9.1 IPA-ST(g) Ingredients (C) (D) - 4.4 - - - IPA-ST-L(g) Ingredients (C) (D) - - 12.0 12.0 - 3-isocyanatopropyl triethoxysilane (g) Ingredients (A-4) 2.2 2.2 2.2 2.2 2.2 2-Butanone oxime (isocyanate-based blocking agent) (g) Ingredients (A-4) 0.8 0.8 0.8 0.8 0.8 3-aminopropyl trimethoxysilane (g) Ingredients (A-3) 0.8 0.8 0.8 0.8 0.8 IPA(g) Ingredients (C) 240 282 403 144 - (1) Liquid stability of coating liquid Sealed for 14 days good good good good good Sealed for 270 days good good good good good

[Table 2] ingredient Coating liquid 1 Coating liquid 2 Coating liquid 3 Coating liquid 4 Coating solution 5 quality% quality% quality% quality% quality% Ingredients (A) 78.67(%) 69.45(%) 57.75(%) 57.75(%) 78.67(%) Ingredients (D) 0.00(%) 11.72(%) 26.59(%) 26.59(%) 0.00(%) Ingredients (B) 10.26(%) 9.06(%) 7.53(%) 7.53(%) 10.26(%) Ingredients (E) 11.07(%) 9.77(%) 8.12(%) 8.12(%) 11.07(%) 100(%) 100(%) 100(%) 100(%) 100(%) Mass parts Mass parts Mass parts Mass parts Mass parts Ingredients (C) 2616.50 (parts) 2682.77 (parts) 3124.67 (parts) 1211.82 (parts) 202.01 (parts)

[table 3] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Coating liquid Coating liquid 1 Coating liquid 1 Coating liquid 1 Coating liquid 2 Coating liquid 2 Coating liquid 3 Coating liquid 4 Substrate PC PC PC PC PC PC PC Coated surface Two sides Two sides Two sides Two sides Two sides Two sides Two sides (2) Film appearance good good good good good good good (3) Film thickness 65 nm 80 nm 110 nm 50 nm 70 nm 85 nm 335 nm (4) Transmittance @450 nm 93.8% 94.1% 91.6% 93.2% 94.3% 93.8% 90.8% (5) Relative visible light transmittance 1.035 1.045 1.038 1.030 1.045 1.045 1.029 (6) Refractive index@450 nm - 1.49 - - 1.49 1.48 - (7) Adhesion 25/25 25/25 25/25 25/25 25/25 25/25 25/25 (8) Heat cycle resistance 25/25 25/25 25/25 25/25 25/25 25/25 25/25 (9) Humidity and heat resistance 25/25 25/25 25/25 25/25 25/25 25/25 25/25

[Table 4] Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Coating liquid Coating solution 5 Coating liquid 1 Coating liquid 2 Coating liquid 3 Coating liquid 3 Coating liquid 3 Substrate PC glass glass glass Acrylic PC2 Coated surface Two sides Two sides Two sides Two sides Two sides Single side (2) Film appearance good good good good good good (3) Film thickness 1.9 μm 80 nm 70 nm 85 nm 70 nm 225 nm (4) Transmittance @450 nm 91.5% 92.7% 93.1% 92.9% 92.4% 92.1% (5) Relative visible light transmittance 1.021 1.021 1.023 1.027 1.006 1.015 (6) Refractive index@450 nm - - - - - - (7) Adhesion 25/25 - - - ~ 25/25 (8) Heat cycle resistance 25/25 - - - - 25/25 (9) Humidity and heat resistance 25/25 - - - - 25/25

Comparative examples 1 to 4 (4) Transmittance and (5) Relative visible light transmittance were measured for each substrate used in Examples 1-13, and shown in Table 5.

[table 5] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Coating liquid - - - - Substrate PC glass Acrylic PC2 Coated surface - - - - (2) Film appearance - - - - (3) Film thickness - - - - (4) Transmittance @450 nm 89.1% 90.6% 92.0% 89.6% (5) Relative visible light transmittance 1.000 1.000 1.000 1.000 (6) Refractive index@450 nm - - - -

In addition, in Tables 3 to 5, "PC" is a polycarbonate plate (manufactured by C.I. TAKIRON Co., Ltd., trade name: PC1600, thickness: 3 mm). In addition, "glass" is a glass slide (manufactured by Matunami Glass Industrial Co., Ltd., trade name: S1112, white edge frosted No. 1, thickness 1.0 to 1.2 mm), and "acryl" is an acrylic sheet (Sumika Manufactured by Acryl Sales Co., Ltd., trade name: Sumipex E, thickness 2 mm), and "PC2" is a polycarbonate sheet (manufactured by Idemitsu Kosan Co., Ltd., trade name: Tarflon LEV1700KL, thickness 1 mm).

(the study) Among the produced coating liquids 1 to 5, it was found that even if diluted, gelation was not confirmed for a relatively long period of time, and the storage stability of the liquid was excellent. The coating liquids 1 to 5 have good handling properties, and all are efficiently coated on the substrate by a dip coater. In addition, the laminates of each of Examples 1 to 13 were efficiently obtained by drying treatment at 120°C, which is a relatively low temperature. Upon visual observation, the appearance of the film of the laminates of Examples 1 to 13 obtained was good without confirming foreign matter, streaks, and cracks.

The transmittance is obtained by measuring the transmittance at a wavelength of 450 nm, but according to Tables 3 to 5, it can be seen that in any of the laminates produced in Examples 1 to 13, the transmittance is higher than that of the polycarbonate used as the base material. The rate (89.1%) increased. In particular, for the laminates produced in Examples 1, 2, 5, and 6, the transmittance is also about 5% higher than the transmittance of the substrate (PC1600). Here, the graph of the transmittance of the laminated body of Example 2 in the comparative wavelength region of 250-800 nm and the transmittance of the substrate (PC1600) in the wavelength region is shown in FIG. 1. According to Fig. 1, it can be seen that if the laminated system of Example 2 has a wavelength of 420 nm or more, it will greatly contribute to the increase in the transmittance of the substrate (PC1600) as a whole up to the wavelength of 800 nm.

Example 14 As a base material, a polycarbonate resin containing a light diffusing agent was molded by a uniaxial cast molding machine equipped with a T-die at an extrusion temperature of 270°C to produce a milky white sheet (thickness 750 μm) (below, There are cases where this substrate is called "PC3"). Except that the substrate (PC3) was used instead of the substrate (PC), the laminate of Example 14 was produced in the same manner as in Example 2. The above-mentioned (2), (3) and (6), and (10) and (11) were evaluated for each characteristic of the obtained laminate, and the results are shown in Table 6.

Evaluation of each characteristic (10) Transmittance An ultraviolet-visible-near-infrared spectrophotometer (manufactured by JASCO Corporation, model: V-670) equipped with integrating sphere unit ISN-723 manufactured by JASCO Corporation was used to measure the transmittance of the laminate in the wavelength region of 250-800 nm. Table 6 shows the transmittance of the laminate at a wavelength of 450 nm.

(11) Total light transmittance A haze meter (manufactured by Nippon Denshoku Industry Co., Ltd., model: NDH5000) was used, and JIS (Japanese Industrial Standard) (JIS K 7361-1: 1997) was selected in the measurement mode for measurement.

Comparative example 5 For the substrate (PC3) used in Example 14, (10) transmittance and (11) total light transmittance were measured. The results are shown in Table 6.

[Table 6] Example 14 Comparative example 5 Coating liquid Coating liquid 1 - Substrate PC3 PC3 Coated surface Two sides - (2) Film appearance good - (3) Film thickness 80 nm - (6) Refractive index@450 nm 1.49 - (10) Transmittance @450 nm 78.0% 74.3% (11) Total light transmittance 91.7% 88.2%

Furthermore, as the material of the substrate (PC3) of Example 14 and Comparative Example 5, a polycarbonate resin containing a light diffusing agent (trade name: Tarflon LZ2510V (manufactured by Idemitsu Kosan Co., Ltd.)) was used.

(the study) According to the results of Example 14 and Comparative Example 5 (Table 6), it can be seen that the transmittance of the laminate made using the base material (PC3) (transmittance 74.1%) is 78.0%. In particular, it can be used as a lighting Layered body with sufficient transmittance for cover or lighting equipment.

Example 15 Use a plastic lens for LED lighting (manufactured by Optical Solutions Co., Ltd., model: HSC-06-107W-1-A943, material: PC) (hereinafter, the substrate may be referred to as "PC4") instead of the substrate (PC), in this lens, the LED light emitting surface (flat lens surface) is set perpendicular to the liquid surface of the immersed coating liquid for dip coating, except that it is made in the same manner as in Example 6. The laminate of Example 15. The obtained laminate was evaluated based on evaluation items (2) film appearance, (12) film thickness, and (13) illuminance. The results are shown in Table 7.

Evaluation of each characteristic (12) Film thickness Using a spectroscopic ellipsometer (manufactured by J.A. Woollam Co., Model: M-2000D), a Cauchy model was used to analyze the measurement results in the wavelength range of 600 to 1600 nm to obtain the film thickness.

(13) Illumination The lens and the LED chip (J-A8 manufactured by CREE) are embedded in the LED lens folding device and set in the light distribution measuring device (made by Asahi Spectroscopy Co., Ltd., model: IMS-5000), and 10 mA is circulated to the LED chip Current. The platform angle is fixed, and the light receiving angle is set to θ=-90°～90° (with a measuring interval of 1°) for measurement, and the illuminance obtained at each light receiving angle of the light receiving angle θ=-90°～90° is accumulated, and set as Illumination in Table 7.

Example 16 The coating machine was changed from a dip coating machine to a spray coating machine (manufactured by Shimada Appli Co., Ltd., model: FSCC06 Selective Spray Coater), and coating liquid 3 was used to coat only the lens (PC4) under the spray coating film forming conditions shown in Table 8 Except for the exit surface, the laminate of Example 16 was produced in the same manner as in Example 15. The obtained laminates were evaluated based on evaluation items (2) film appearance and (13) illuminance, and the results are shown in Table 7.

Comparative example 6 The illuminance (13) was measured for the substrate (PC4) used in Examples 15 and 16, and the results are shown in Table 7.

[Table 7] Example 15 Example 16 Comparative example 6 Coating liquid Coating liquid 3 Coating liquid 3 - Substrate PC4 PC4 PC4 Coated surface Whole face Only the exit side of the lens - (2) Film appearance Bad: Spots are found in the recessed part of the lens of the incident LED light good - (12) Film thickness (the exit surface of the lens) 85 nm - - (13) Illumination 88001x 88001x 84001x

[Table 8] Film forming conditions Example 16 Atomization air pressure (MPa) 0.35 Spray gun distance (mm) 40 Needle opening (mm) 0.76 Spray gun speed (mm/sec) 300 Hydraulic (kpas) 20 Coating spacing (mm) 1 [Industrial availability]

By using the coating liquid of the present invention, it can be applied to automobile interior parts such as instrument covers, windshields of two-wheeled or three-wheeled vehicles, resin-made windows (various types of vehicle windows), resin-made building materials windows, ceilings for construction machinery, and road light transmission Panels (insulation panels), corrective glasses, sunglasses, sports glasses, safety glasses, etc., camera lenses, plasma or liquid crystal, organic EL displays, optical discs, mobile phone components, touch panels, solar batteries and other electronics Machine parts, lighting parts such as street lights, facilities, shops, outdoor lighting, residential lighting, headlights and other automotive lighting, windshields, and protective shields are made of various resin materials, especially polycarbonate materials. Ideally used as glass replacement parts, etc. In particular, by using the coating liquid of the present invention, it is possible to form a laminated body with high light transmittance, so it can be preferably used in the manufacture of lighting lamps, display lamps, traffic lights, fluorescent tubes, lighting domes, Lighting covers or lighting lenses for lighting fixtures such as ceiling lights, arcades, and road sidewall panels. In addition, it can be suitably used to manufacture LED lighting cover or lens, laser lighting cover or lens and other lighting components with high brightness and high directivity LED light source, and it is extremely useful in industry.

Above, several embodiments and/or examples of the present invention have been described in detail, but it is easy for the industry to make many changes to the illustrated embodiments and/or examples without materially deviating from the novelty of the present invention. The teaching and effect. Therefore, these many changes are included in the scope of the present invention. All the contents of the documents recorded in this manual and the application that became the basis of the priority of the Paris Treaty in this case are cited.

Fig. 1 is a graph showing the measurement results of the transmittance of the laminate obtained in Example 2 and the base material of the laminate in the wavelength region (250-800 nm).

Claims (46)

A coating liquid characterized by containing the following components (A), (B) and (C): (A) Hydrolysis condensate of alkoxy-containing silane compound of the following components (A-1)～(A-4) (A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compounds that do not contain amine groups, epoxy groups and isocyanate groups (A-3) Silane compound with amine group and alkoxy group (A-4) Blocked isocyanatosilane compound with alkoxy group (B) Hardening catalyst (C) Dispersion medium. Such as the coating liquid of claim 1, which further contains (D) inorganic fine particles. A coating liquid in which the following (A-1) and (A-2) components are added to the reaction product obtained by contacting the following (B) to (C) components with the hydrolysis condensate of the following components (A-1) and (A-2). -4) After the components are reacted, the following (A-3) components are further added and reacted: (A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compounds that do not contain amine groups, epoxy groups and isocyanate groups (A-3) Silane compound with amine group and alkoxy group (A-4) Blocked isocyanatosilane compound with alkoxy group (B) Hardening catalyst (C) Dispersion medium. The coating liquid of claim 3, wherein the above-mentioned (A) is added to the reaction product obtained by contacting the above-mentioned (A-1) and (A-2) components with the above-mentioned (B) to (C) components. -4) Before the component, the inorganic fine particles are added as the component (D) and reacted. A coating liquid in which the following (A-4) is added to a reaction product obtained by contacting a mixture containing the following (A-1), (A-2), (B), and (C) components ) After the components are reacted, the following (A-3) components are added to react to form: (A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compounds that do not contain amine groups, epoxy groups and isocyanate groups (A-3) Silane compound with amine group and alkoxy group (A-4) Blocked isocyanatosilane compound with alkoxy group (B) Hardening catalyst (C) Dispersion medium. The coating liquid of claim 5, wherein before adding the above-mentioned (A-4) component to the above-mentioned reaction product, inorganic fine particles are added as the (D) component to be reacted. A coating liquid which is a reaction product obtained by contacting the hydrolysis condensate of the following components (A-1), (A-2), and (E) with the following components (B) to (C) It is obtained by adding the following (A-4) component to react, and then adding the following (A-3) component to react: (A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compounds that do not contain amine groups, epoxy groups and isocyanate groups (A-3) Silane compound with amine group and alkoxy group (A-4) Blocked isocyanatosilane compound with alkoxy group (B) Hardening catalyst (C) Dispersion medium (E) Silane compounds having epoxy groups and alkoxy groups. The coating liquid according to claim 7, wherein the hydrolysis condensate of the above-mentioned components (A-1), (A-2), and (E) is brought into contact with the above-mentioned components (B) to (C). Before adding the above-mentioned (A-4) component, inorganic fine particles are added as the (D) component to react. A coating liquid characterized in that it is prepared with the following (A), (B), and (C) components as raw materials, and is The following (A-4) component is added to the reaction product obtained by contacting the hydrolysis condensate of the following (A-1) and (A-2) components with the above-mentioned (B) to (C) components to react Then, add the above-mentioned (A-3) component to react to form: (A) Hydrolysis condensate of alkoxy-containing silane compound of the following components (A-1)～(A-4) (A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compounds that do not contain amine groups, epoxy groups and isocyanate groups (A-3) Silane compound with amine group and alkoxy group (A-4) Blocked isocyanatosilane compound with alkoxy group (B) Hardening catalyst (C) Dispersion medium. The coating liquid of claim 9, wherein the above-mentioned (A) is added to the reaction product obtained by contacting the above-mentioned (A-1) and (A-2) components with the above-mentioned (B) to (C) components. -4) Before the component, the inorganic fine particles are added as the component (D) and reacted. A coating liquid prepared with the following components (A), (B), and (C) as raw materials, and is After adding the following (A-4) component to the reaction product obtained by contacting a mixture containing the following (A-1), (A-2), (B), and (C) components to react , And then add the following (A-3) components to react to form: (A) Hydrolysis condensate of alkoxy-containing silane compound of the following components (A-1)～(A-4) (A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compounds that do not contain amine groups, epoxy groups and isocyanate groups (A-3) Silane compound with amine group and alkoxy group (A-4) Blocked isocyanatosilane compound with alkoxy group (B) Hardening catalyst (C) Dispersion medium. The coating liquid of claim 11, wherein before adding the above-mentioned (A-4) component to the above-mentioned reaction product, inorganic fine particles are added as the (D) component to be reacted. A coating liquid characterized in that it is prepared with the following (A), (B), (C), and (E) components as raw materials, and is The following (A-4) is added to the reaction product obtained by contacting the hydrolysis condensate of the following components (A-1), (A-2) and (E) with the above components (B) to (C) After the components are reacted, the above-mentioned (A-3) component is added and reacted to form: (A) Hydrolysis condensate of alkoxy-containing silane compound of the following components (A-1)～(A-4) (A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compounds that do not contain amine groups, epoxy groups and isocyanate groups (A-3) Silane compound with amine group and alkoxy group (A-4) Blocked isocyanatosilane compound with alkoxy group (B) Hardening catalyst (C) Dispersion medium (E) Silane compounds having epoxy groups and alkoxy groups. The coating liquid of claim 13, wherein the reaction product obtained by contacting the hydrolysis condensate of the above-mentioned components (A-1), (A-2), and (E) with the above-mentioned components (B) to (C) Before adding the above-mentioned component (A-4), inorganic fine particles are added as the component (D) and reacted. The coating liquid of any one of claims 1 to 14, wherein the above-mentioned component (A-1) is a tetraalkoxysilane compound represented by the following general formula (1): Si(OR ¹ ) ₄ ••• ( 1) [In the formula, R ¹ represents an alkyl group with 1 to 4 carbons or an alkyl group with 1 to 4 carbons having an ether bond; plural R ¹ may be the same or different]. The coating liquid of any one of claims 1 to 14, wherein the above-mentioned component (A-2) is represented by the following general formula (2) and does not contain an amine group, an epoxy group, and an isocyanate group. Compound: R ² _a Si(OR ³ ) _4-a ••• (2) [In the formula, R ² represents an alkyl group with 1 to 10 carbons or a fluorinated alkyl group with 1 to 10 carbons, vinyl, benzene Group, or an alkyl group with 1 to 3 carbons substituted by a methacryloxy group; R ³ represents an alkyl group with 1 to 4 carbons or an alkyl group with an ether bond; a represents 1 or 2; when R ² of the case, a plurality of R ² may be identical or different, a plurality of OR ³ may be the same or different]. The coating liquid according to any one of claims 1 to 14, wherein the above-mentioned component (A-3) is a silane compound having an amino group and an alkoxy group represented by the following general formula (3): R ⁴ _b Si(OR ⁵ ) _4-b ••• (3) [In the formula, R ⁴ represents an alkyl group, vinyl group, phenyl group having 1 to 4 carbon atoms, or selected from methacryloxy group, amino group (-NH ₂ Group), aminoalkyl group [-(CH ₂ )x-NH ₂ group (where x is an integer of 1 to 3)]), and alkylamino group [-NHR group (where R is a carbon number of 1 to Alkyl of 3)] an alkyl group of 1 to 3 carbons substituted by one or more groups; at least one R ⁴ is substituted by either an amino group, or an aminoalkyl group or an alkylamino group The alkyl group with 1 to 3 carbon atoms; R ⁵ represents the alkyl group with 1 to 4 carbon atoms; b represents 1 or 2; when there are plural R ⁴ , the plural R ⁴ may be the same or different, plural OR ⁵ can be the same or different]. The coating liquid according to any one of claims 1 to 14, wherein the above-mentioned component (A-4) is a blocked isocyanatosilane compound having an alkoxy group represented by the following general formula (4): R ⁸ _d Si(OR ⁹ ) _4-d ••• (4) [In the formula, R ⁸ represents an alkyl group with 1 to 4 carbon atoms, a vinyl group, a phenyl group, or is selected from methacryloxy group and blocked An alkyl group of 1 to 3 carbons substituted by one or more of the isocyanate groups, at least one R ⁸ represents an alkyl group of 1 to 3 carbons substituted by a blocked isocyanate group; R ⁹ represents a carbon number of 1 The alkyl group of ~4, d represents 1 or 2; when there are plural R ⁸ , the plural R ⁸ may be the same or different, and the plural OR ⁹ may be the same or different]. The coating liquid according to any one of claims 7 to 8 and 13 to 14, wherein the above-mentioned component (E) is a silane compound having an epoxy group and an alkoxy group represented by the following general formula (5): R ⁶ _c Si(OR ⁷ ) _4-c ••• (5) [In the formula, R ⁶ represents an alkyl group with 1 to 4 carbon atoms, a vinyl group, a phenyl group, or is selected from methacryloxy group, glycidoxy group An alkyl group with 1 to 3 carbons substituted by at least one of the 3,4-epoxycyclohexyl group ^{, and at least one of R 6 represents a glycidyloxy group or a 3,4-epoxy group} Cyclohexyl substituted alkyl with 1 to 3 carbons; R ⁷ represents alkyl with 1 to 4 carbons; c represents 1 or 2; when there are more than one R ⁶ , the plural R ⁶ may be the same or different , A plurality of OR ⁷ may be the same or different]. A cured film formed by curing the coating liquid according to any one of claims 1 to 19. A laminated body characterized by having: a base material; and the cured film of claim 20, which is directly formed on the base material. The laminate of claim 21, wherein the thickness of the above-mentioned cured film is 5 μm or less. The laminate of claim 21 or 22, wherein the cured film is formed on one or both sides of the substrate. The laminate of claim 21 or 22, wherein the base material is made of resin. The laminate of claim 21 or 22, wherein the substrate is made of polycarbonate resin. An illuminating member, a display, a lens, a member for solar cells, or an anti-reflection film, which is provided with a laminate according to any one of claims 21 to 25. A laminated body characterized by having: a substrate; and a cured film formed directly on the substrate and formed by curing a coating solution containing a hydrolyzed condensate of a silane compound having an alkoxy group; and the cured film The thickness is below 500 nm. The laminate of claim 27, wherein the base material contains a light diffusing agent. Or lighting fixtures, which have a laminated body such as claim 27 or 28. A method for preparing a coating solution, which is to add the following components (A-1) and (A-2) to the reaction product obtained by contacting the hydrolysis condensate of the following components (B) to (C) After the component (A-4) is reacted, the following component (A-3) is further added to react: (A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compounds that do not contain amine groups, epoxy groups and isocyanate groups (A-3) Silane compound with amine group and alkoxy group (A-4) Blocked isocyanatosilane compound with alkoxy group (B) Hardening catalyst (C) Dispersion medium. The method for preparing a coating liquid according to claim 30, wherein the reaction product obtained by contacting the hydrolysis condensate of the above-mentioned components (A-1) and (A-2) with the above-mentioned components (B) to (C) is added Before the above-mentioned (A-4) component, inorganic fine particles are added as the (D) component and reacted. A method for preparing a coating liquid by adding the following (A-1), (A-2), (B), and (C) to the reaction product obtained by contacting a mixture containing the following components (A-1), (A-2), (B), and (C) A-4) After the component is reacted, the following (A-3) component is further added to react: (A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compounds that do not contain amine groups, epoxy groups and isocyanate groups (A-3) Silane compound with amine group and alkoxy group (A-4) Blocked isocyanatosilane compound with alkoxy group (B) Hardening catalyst (C) Dispersion medium. The method for preparing a coating liquid according to claim 32, wherein before adding the above-mentioned (A-4) component to the above-mentioned reaction product, inorganic fine particles are added as the (D) component to be reacted. A method for preparing a coating liquid, in which the hydrolysis condensate of the following components (A-1), (A-2), and (E) is reacted by contacting the following components (B) to (C) After adding the following (A-4) component to react, and then adding the following (A-3) component to react: (A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compounds that do not contain amine groups, epoxy groups and isocyanate groups (A-3) Silane compound with amine group and alkoxy group (A-4) Blocked isocyanatosilane compound with alkoxy group (B) Hardening catalyst (C) Dispersion medium (E) Silane compounds having epoxy groups and alkoxy groups. The method for preparing a coating liquid according to claim 34, wherein the hydrolysis condensate of the above-mentioned components (A-1), (A-2), and (E) is obtained by contacting the above-mentioned components (B) to (C) Before adding the above-mentioned (A-4) component to the reaction product, inorganic fine particles are added as the (D) component to react. A method for preparing a coating liquid, characterized by adding to the reaction product obtained by contacting the hydrolysis condensate of the following components (A-1) and (A-2) with the above components (B) to (C) After the following (A-4) component is reacted, the above-mentioned (A-3) component is further added to react: (A) Hydrolysis condensate of alkoxy-containing silane compound of the following components (A-1)～(A-4) (A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compounds that do not contain amine groups, epoxy groups and isocyanate groups (A-3) Silane compound with amine group and alkoxy group (A-4) Blocked isocyanatosilane compound with alkoxy group (B) Hardening catalyst (C) Dispersion medium. The method for preparing a coating liquid according to claim 36, wherein the reaction product obtained by contacting the hydrolysis condensate of the above-mentioned components (A-1) and (A-2) with the above-mentioned components (B) to (C) is added Before the above-mentioned (A-4) component, inorganic fine particles are added as the (D) component and reacted. A method for preparing a coating liquid by adding the following (A-1), (A-2), (B), and (C) to the reaction product obtained by contacting a mixture containing the following components (A-1), (A-2), (B), and (C) A-4) After the component is reacted, the following (A-3) component is further added to react: (A) Hydrolysis condensate of alkoxy-containing silane compound of the following components (A-1)～(A-4) (A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compounds that do not contain amine groups, epoxy groups and isocyanate groups (A-3) Silane compound with amine group and alkoxy group (A-4) Blocked isocyanatosilane compound with alkoxy group (B) Hardening catalyst (C) Dispersion medium. The method for preparing a coating liquid according to claim 38, wherein before adding the above-mentioned (A-4) component to the above-mentioned reaction product, inorganic fine particles are added as the (D) component to be reacted. A method for preparing a coating liquid, which is a reaction product obtained by contacting the hydrolysis condensate of the following components (A-1), (A-2) and (E) with the above components (B) to (C) After adding the following (A-4) component to make it react, add the above (A-3) component to make it react: (A) Hydrolysis condensate of alkoxy-containing silane compound of the following components (A-1)～(A-4) (A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compounds that do not contain amine groups, epoxy groups and isocyanate groups (A-3) Silane compound with amine group and alkoxy group (A-4) Blocked isocyanatosilane compound with alkoxy group (B) Hardening catalyst (C) Dispersion medium (E) Silane compounds having epoxy groups and alkoxy groups. The method for preparing a coating liquid according to claim 40, wherein the hydrolysis condensate of the above-mentioned components (A-1), (A-2), and (E) is obtained by contacting the above-mentioned components (B) to (C) Before adding the above-mentioned (A-4) component to the reaction product, inorganic fine particles are added as the (D) component to react. The method for preparing a coating liquid according to any one of claims 30 to 41, wherein the above-mentioned component (A-1) is a tetraalkoxysilane compound represented by the following general formula (1): Si(OR ¹ ) ₄ • •• (1) [In the formula, R ¹ represents an alkyl group with 1 to 4 carbons or an alkyl group with 1 to 4 carbons having an ether bond; plural R ¹ may be the same or different]. The method for preparing a coating liquid according to any one of claims 30 to 41, wherein the above-mentioned component (A-2) is an organic alkane represented by the following general formula (2) that does not contain an amine group, an epoxy group, and an isocyanate group Oxysilane compound: R ² _a Si(OR ³ ) _4-a ••• (2) [In the formula, R ² represents an alkyl group with 1 to 10 carbons or a fluorinated alkyl group with 1 to 10 carbons, ethylene R ³ represents an alkyl group with 1 to 4 carbon atoms or an alkyl group with an ether bond; a represents 1 or 2; When there are a plurality of R ² , the plurality of R ² may be the same or different, and the plurality of OR ³ may be the same or different]. The method for preparing a coating liquid according to any one of claims 30 to 41, wherein the above-mentioned component (A-3) is a silane compound having an amino group and an alkoxy group represented by the following general formula (3): R ⁴ _b Si(OR ⁵ ) _4-b ••• (3) [In the formula, R ⁴ represents an alkyl group with 1 to 4 carbon atoms, a vinyl group, a phenyl group, or is selected from a methacryloxy group, an amino group ( -NH ₂ group), aminoalkyl [-(CH ₂ )x-NH ₂ group (wherein x is an integer of 1 to 3)]), and alkylamino group [-NHR group (where R is carbon Alkyl group of 1 to 3)] An alkyl group of 1 to 3 carbons substituted by one or more groups; at least one R ⁴ represents any of an amino group, an amino alkyl group or an alkyl amino group One substituted alkyl group with 1 to 3 carbon atoms; R ⁵ represents an alkyl group with 1 to 4 carbon atoms; b represents 1 or 2; when there are more than one R ⁴ , the plurality of R ⁴ may be the same or different , A plurality of OR ⁵ may be the same or different]. The method for preparing a coating liquid according to any one of claims 30 to 41, wherein the above-mentioned component (A-4) is a blocked isocyanatosilane compound having an alkoxy group represented by the following general formula (4) : R ⁸ _d Si(OR ⁹ ) _4-d ••• (4) [In the formula, R ⁸ represents an alkyl group with 1 to 4 carbon atoms, a vinyl group, a phenyl group, or a methacryloyloxy group And an alkyl group with 1 to 3 carbons substituted by one or more of ^{the blocked isocyanate groups, at least one R 8} represents an alkyl group with 1 to 3 carbons substituted by a blocked isocyanate group; R ⁹ represents For an alkyl group having 1 to 4 carbon atoms, d represents 1 or 2; when there are a plurality of R ⁸ , the plurality of R ⁸ may be the same or different, and the plurality of OR ⁹ may be the same or different]. The method for preparing a coating liquid according to any one of claims 34 to 35 and 40 to 41, wherein the above-mentioned component (E) is a silane compound having an epoxy group and an alkoxy group represented by the following general formula (5): R ⁶ _c Si(OR ⁷ ) _4-c ••• (5) [In the formula, R ⁶ represents an alkyl group with 1 to 4 carbon atoms, a vinyl group, a phenyl group, or is selected from methacryloxy group, An alkyl group with 1 to 3 carbons substituted by one or more of the glycidyloxy and 3,4-epoxycyclohexyl groups, at least one R ⁶ represents a glycidyloxy group or a 3,4-ring An alkyl group of 1 to 3 carbons substituted by oxycyclohexyl; R ⁷ represents an alkyl group of 1 to 4 carbons; c represents 1 or 2; when there are more than one R ⁶ , the plurality of R ⁶ may be the same May be different, and plural OR ⁷ may be the same or different].

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