Polycarbonate resin laminate, light-guiding member and lighting member using the same, and use of polycarbonate resin laminate for light-guiding member and lighting member applications

Abstract

To provide a polycarbonate resin laminate having excellent high-temperature and high-humidity resistance, a light guide member and an illumination member including the polycarbonate resin laminate, and applications of the polycarbonate resin laminate to a light guide member and an illumination member for high-output light-emitting diode sources.SOLUTION: A laminate for a light guide member of a high-output light-emitting diode has a polycarbonate resin, and a cured film directly formed on the polycarbonate resin, and the cured film is formed by using a coating liquid including the following components (A), (B) and (C). (A) a hydrolytic condensate of silane compounds having alkoxy groups, of the following components (A-1)-(A-4): (A-1) a tetraalkoxysilane compound, (A-2) an organoalkoxysilane compound free of an amino group, an epoxy group and an isocyanate group, (A-3) a silane compound having an amino group and an alkoxy group, and (A-4) a blocked isocyanate silane compound having an alkoxy group. (B) a curing catalyst. (C) a dispersion medium.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin laminate, a light guide member and a lighting member using the same, and the use of the polycarbonate resin laminate for light guide members and lighting members. [Background technology]

[0002] Polycarbonate resin is widely used as a structural material to replace glass in applications such as lighting covers and light-guiding components, due to its excellent transparency and moldability, as well as its light weight and excellent impact resistance.

[0003] Patent Document 1 describes the results of evaluating the illuminance of a polycarbonate plastic lens for light-emitting diode (LED) lighting, which is coated with a coating liquid to form a film. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2020 / 241745 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a polycarbonate resin laminate having excellent resistance to high temperatures and high humidity, a light-guiding member and an illumination member using the same, and use of the polycarbonate resin laminate in light-guiding members and illumination members for high-power light-emitting diode light sources. [Means for solving the problem]

[0006] According to the present invention, there are provided the following polycarbonate resin laminate, a light guide member and a lighting member using the same, and use of the polycarbonate resin laminate for a light guide member and a lighting member. 1. A laminate for a light-guiding component of a high-power light-emitting diode, comprising a polycarbonate resin and a cured film formed directly on the polycarbonate resin, the cured film being produced using a coating liquid containing the following components (A), (B), and (C): (A) A hydrolysis condensate of a silane compound having an alkoxy group, comprising the following components (A-1) to (A-4): (A-1) Tetraalkoxysilane Compound (A-2) Organoalkoxysilane compound containing no amino group, epoxy group, or isocyanate group (A-3) Silane Compound Having an Amino Group and an Alkoxy Group (A-4) Blocked isocyanatosilane compound having an alkoxy group (B) Curing catalyst (C) Dispersion medium 2. The laminate according to 1, 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 having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms and an ether bond. 1 may be the same or different.] 3. The laminate according to 1 or 2, wherein the component (A-2) is an organoalkoxysilane compound represented by the following general formula (2) which does not contain an amino group, an epoxy group, or an isocyanate group. R 2 a Si(OR 3 ) 4-a ···(2) [In the formula, R 2 represents an alkyl group having 1 to 10 carbon atoms or a fluorinated alkyl group having 1 to 10 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with a methacryloxy group. R 3 represents an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms and an ether bond. a represents 1 or 2. R 2If there are multiple R 2 may be the same or different, and multiple OR 3 may be the same or different.] 4. The laminate according to any one of 1 to 3, wherein the 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 having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from a methacryloxy group, an amino group (-NH2 group), an aminoalkyl group [-(CH2)x-NH2 group (where x is an integer of 1 to 3)], and an alkylamino group [-NHR group (where R is an alkyl group having 1 to 3 carbon atoms)]. R 4 At least one of represents an amino group, or an alkyl group having 1 to 3 carbon atoms substituted with either an aminoalkyl group or an alkylamino group. R 5 represents an alkyl group having 1 to 4 carbon atoms. b represents 1 or 2. R 4 If there are multiple R 4 may be the same or different, and multiple OR 5 may be the same or different.] 5. The laminate according to any one of 1 to 4, wherein the 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 having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from a methacryloxy group and a blocked isocyanate group, and R 8At least one of R represents an alkyl group having 1 to 3 carbon atoms substituted with a blocked isocyanate group. 9 represents an alkyl group having 1 to 4 carbon atoms, and d represents 1 or 2. 8 If there are multiple R 8 may be the same or different, and multiple OR 9 may be the same or different.] 6. The laminate according to any one of 1 to 5, further comprising (E) a silane compound having an epoxy group and an alkoxy group. 7. The laminate according to 6, 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 having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group; R 6 At least one of the groups represents an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. R 7 represents an alkyl group having 1 to 4 carbon atoms. c indicates 1 or 2. R 6 If there are multiple R 6 may be the same or different, and multiple OR 7 may be the same or different.] 8. The laminate according to any one of 1 to 7, wherein the thickness of the cured film is 5 μm or less. 9. A light-guiding member for a high-power light-emitting diode light source, comprising the laminate according to any one of 1 to 8. 10. A lighting component for a high-power light-emitting diode light source, comprising the laminate according to any one of 1 to 8. 11. Use of the laminate according to any one of 1 to 8 as a light guide member for a high-power light-emitting diode light source. 12. Use of the laminate according to any one of 1 to 8 for use as a lighting component for a high-power light-emitting diode light source. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a polycarbonate resin laminate having excellent resistance to high temperatures and high humidity, a light guide member and a lighting member using the same, and the use of the polycarbonate resin laminate for light guide members and lighting members. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 2 is a diagram showing the transmittance of the laminate produced in Example 1 and Comparative Example 1. [Figure 2] FIG. 1 is a diagram showing the transmittance of the laminate produced in Example 2 and Comparative Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0009] The polycarbonate resin laminate of the present invention will now be described. [Polycarbonate resin laminate] One embodiment of the polycarbonate resin laminate of the present invention comprises a polycarbonate resin and a cured film formed directly on the polycarbonate resin, The cured film is a laminate for a light guide member or lighting member of a high-power light-emitting diode, which is produced using a coating liquid containing the following components (A), (B), and (C): (A) A hydrolysis condensate of a silane compound having an alkoxy group, comprising the following components (A-1) to (A-4): (A-1) Tetraalkoxysilane Compound (A-2) Organoalkoxysilane compound containing no amino group, epoxy group, or isocyanate group (A-3) Silane Compound Having an Amino Group and an Alkoxy Group (A-4) Blocked isocyanatosilane compound having an alkoxy group (B) Curing catalyst (C) Dispersion medium

[0010] This makes it possible to obtain a polycarbonate resin laminate that is excellent in resistance to high temperatures and high humidity.

[0011] (1) Polycarbonate resin is transparent and has excellent impact resistance. It can be used as a lightweight substitute for glass, and can also be molded into shapes that are difficult to achieve with glass. Taking advantage of the above-mentioned properties, polycarbonate resin has excellent impact resistance and can be used to create light-guiding components with complex shapes. This has led to the use of DRLs (Daytime Running Lights), which illuminate using reflected and scattered light from a small number of light-emitting diode (LED) light sources. In this case, the end of the polycarbonate light guide member is disposed near the LED light source.

[0012] (2) LEDs are being improved year by year, and LEDs with increased output are now being put to practical use. Such high-output LEDs (e.g., power LEDs, high-power LEDs) (e.g., 1.5 W or more, 1.9 W or more, 2.0 W or more, or 2.1 W or more) (the upper limit is not particularly limited, but for example, 15 W or less) may cause problems such as deterioration and deformation of polycarbonate resin.

[0013] (3) The inventors considered that when polycarbonate is used for light-guiding or lighting components that use LEDs as light sources, some parts may become extremely hot due to placement near LED light sources and the high output of LEDs. In Europe, some countries have made daytime running lights mandatory, and it is expected that long-term use of daytime running lights will become mainstream in the future. Also, in some countries (e.g., Southeast Asia), LEDs are sometimes used in high-humidity environments. The present inventors provide a solution to the serious problems of polycarbonate resin, such as deterioration and deformation of polycarbonate resin caused by high output, high temperature and humidity, and long-term use.

[0014] (4) Furthermore, Patent Document 1 aims to improve the storage stability of the coating material, the prevention of mottling and cracking of the cured film, the adhesion between the cured film and the substrate, and transmittance, and does not take into account the effect of heat from the LED light source on the polycarbonate resin as described in (3) above. Patent Document 1 does not recognize the issues that arise when using polycarbonate near high-output LEDs, and merely describes a wide range of uses and general applications.

[0015] (5) The laminate using the coating liquid of Patent Document 1 is not for special purposes like the present invention, but for general purposes. For the above reasons, a "laminate" limited to "for use as a light-guiding member or lighting member for a high-power light-emitting diode light source" means one that is particularly suitable for that use, and is a "laminate" that is meant by "for use as a light-guiding member or lighting member for a high-power light-emitting diode."

[0016] (6) In the present invention, the potential problem of deterioration and deformation occurring when polycarbonate is used near high-power light-emitting diodes is addressed by the idea that a laminate in which a cured film is formed using a specific coating material can be used to solve the problem. In the examples described below, an unknown attribute not found in Patent Document 1 has been discovered, namely, that the cured film suppresses the occurrence of deterioration and deformation of polycarbonate resin when placed in a high-temperature, high-humidity environment for a long period of time (conditions corresponding to light-guiding components or lighting applications for high-power light-emitting diode light sources). (7) In the present invention, it has been found that the film is suitable for a new application as a "light guide member or lighting member for a high-power light-emitting diode light source."

[0017] One embodiment of the laminate of the present invention is preferably used under high temperature and high humidity conditions. The time for use at high temperature and humidity, for example, 70°C or higher (preferably 75°C or higher, more preferably 80°C or higher, and even more preferably 82°C or higher) (there is no particular upper limit, but for example, 100°C or lower) and 70% relative humidity or higher (preferably 75% relative humidity or higher, more preferably 80% relative humidity or higher, and even more preferably 82% relative humidity or higher) (there is no particular upper limit, but for example, 100% relative humidity or lower), is preferably 1000 hours or higher, more preferably 1500 hours or higher, and even more preferably 2000 hours or higher. There is no particular upper limit, but 10,000 hours or lower is preferred.

[0018] (Component (A)) The above-mentioned coating liquid contains, as the hydrolysis condensation product of the component (A) of a silane compound having an alkoxy group, one or more of the hydrolysis condensation products of the following four compounds, components (A-1) to (A-4):

[0019] In the present invention, the silane compound having an alkoxy group refers to an alkoxysilane compound and / or a partial condensate thereof, and the partial condensate of the alkoxysilane compound refers to a polyalkoxysilane compound or a polyorganoalkoxysilane compound in which a portion of the alkoxysilane compound is condensed to form a siloxane bond (Si-O bond) within the molecule. Furthermore, the hydrolysis condensate of the silane compound having an alkoxy group refers to a state in which, in addition to the hydrolysis condensate of the silane compound having an alkoxy group, the silane compound having an alkoxy group before hydrolysis condensation is contained.

[0020] (Component (A-1)) The component (A-1) is a tetraalkoxysilane compound. A partial condensate (polyalkoxysilane compound) bonded with a siloxane bond (Si-O bond) can also be used. These compounds can be used alone or in combination of two or more.

[0021] The tetraalkoxysilane compound that is the component (A-1) can be represented, for example, by the following general formula (1): Furthermore, as the polyalkoxysilane compound, a compound represented by the following general formula (6) is particularly suitable. Si(OR 1 )4(1) [In the formula, R 1 is an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms and an ether bond. 1 may be the same or different.]

[0022] [ka] [In the formula, R 1 is the same as in general formula (1), and n is an integer of 1 to 15.

[0023] In the general formulas (1) and (6), examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. 1 is an alkyl group having 1 to 4 carbon atoms and an ether bond, OR 1 Examples of the methoxy group include a 2-methoxyethoxy group and a 3-methoxypropoxy group.

[0024] Examples of the tetraalkoxysilane compound of the component (A-1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetraisobutoxysilane.

[0025] Examples of polyalkoxysilane compounds include "Silicate 40" and "Silicate 45" manufactured by Tama Chemical Industry Co., Ltd., and "Methyl Silicate 51," "Methyl Silicate 53A," "Ethyl Silicate 40," and "Ethyl Silicate 48" manufactured by Colcoat Co., Ltd.

[0026] (Component (A-2)) The component (A-2) is an organoalkoxysilane compound that does not contain an amino group, an epoxy group, or an isocyanate group. A partial condensate of a polyorganoalkoxysilane compound can also be used. These compounds can be used alone or in combination of two or more.

[0027] The organoalkoxysilane compound of component (A-2) is preferably a difunctional alkoxysilane or a trifunctional alkoxysilane, and can be represented, for example, by the following general formula (2): Furthermore, as a partial condensate of a polyorganoalkoxysilane compound, a compound represented by the following general formula (7) is particularly suitable.

[0028] R 2 a Si(OR 3 ) 4-a ···(2) [In the formula, R 2 is an alkyl group having 1 to 10 carbon atoms or a fluorinated alkyl group having 1 to 10 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with a methacryloxy group, and R 3 is an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms and an ether bond, and a is 1 or 2. 2 If there are multiple R 2 may be the same or different, and multiple OR 3 may be the same or different.]

[0029] [ka] [In the formula, R 2 and R 3 is the same as in general formula (2), and m is an integer of 1 to 15.

[0030] In general formulas (2) and (7), the alkyl group having 1 to 10 carbon atoms may be either linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various linear or branched butyl groups, various linear or branched hexyl groups, various linear or branched octyl groups, and various linear or branched decyl groups. Examples of the fluorinated alkyl group having 1 to 10 carbon atoms include a trifluoroethyl group and a trifluoropropyl group. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. The alkyl group having 1 to 4 carbon atoms or the alkyl group having 1 to 4 carbon atoms and an ether bond are as described in general formula (1).

[0031] Among the organoalkoxysilane compounds represented by the general formula (2), the trifunctional alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltrippropoxysilane, methyltributoxysilane, methyltris(2-methoxyethoxy)silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrippropoxysilane, ethyltributoxysilane, ethyltris(2-methoxyethoxy)silane, hexyltrimethoxysilane, and hexyltriethoxysilane. Examples of suitable silanes include hexyl tripropoxysilane, hexyl tributoxysilane, decyl trimethoxysilane, decyl triethoxysilane, decyl tripropoxysilane, decyl tributoxysilane, fluorinated alkyl (trialkoxy)silanes such as trifluoropropyl trimethoxysilane, which have fluorine atoms introduced into the substituents, phenyl trimethoxysilane, phenyl triethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, γ-methacryloxypropyl trimethoxysilane, etc. Also suitable are methyl dimethoxy (ethoxy) silane and ethyl diethoxy (methoxy) silane, which have two types of alkoxy groups.

[0032] Examples of bifunctional alkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, bis(2-methoxyethoxy)dimethylsilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane.

[0033] Specific examples of polyorganoalkoxysilane compounds include "SS-101" manufactured by Colcoat Co., Ltd., and "SR2402" and "AY42-163" manufactured by Dow Toray Industries, Inc.

[0034] (Component (A-3)) The component (A-3) is a silane compound having an amino group and an alkoxy group, but not containing an epoxy group or an isocyanate group (hereinafter also referred to as an amino group-containing organoalkoxysilane compound). Its partial condensate (amino group-containing polyorganoalkoxysilane compound) can also be used. These may be used alone or in combination of two or more. As the component (A-3), the amino group-containing organoalkoxysilane compound can be represented, for example, by the following general formula (3): The partial condensate of the amino group-containing organoalkoxysilane compound can be, for example, a partial condensate of a silane compound having an amino group and an alkoxy group, represented by the following general formula (3):

[0035] R 4 b Si(OR 5 ) 4-b ···(3) [In the formula, R 4 is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from a methacryloxy group, an amino group (-NH group), an aminoalkyl group [-(CH)-NH group (where x is an integer of 1 to 3)], and an alkylamino group [-NHR group (where R is an alkyl group having 1 to 3 carbon atoms)], and R 4 At least one of R is an amino group or an alkyl group having 1 to 3 carbon atoms substituted with either an aminoalkyl group or an alkylamino group.5 is an alkyl group having 1 to 4 carbon atoms, and b is 1 or 2. 4 If there are multiple R 4 may be the same or different, and multiple OR 5 may be the same or different.] In the general formula (3), the alkyl group having 1 to 3 carbon atoms and the alkyl group having 1 to 4 carbon atoms are as explained in the general formula (1) or (2).

[0036] Specific examples of the amino group-containing organoalkoxysilane compound represented by general formula (3) include N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methylaminopropyltrimethoxysilane, and N-methylaminopropyltriethoxysilane. Furthermore, examples of amino group-containing polyorganoalkoxysilane compounds include "KBP-90" manufactured by Shin-Etsu Silicones Co., Ltd.

[0037] (Component (A-4)) The component (A-4) is a blocked isocyanatosilane compound (commonly referred to as a blocked isocyanate silane compound) having an alkoxy group, which contains a blocked isocyanate group but does not contain an amino group or an epoxy group (hereinafter referred to as a blocked isocyanate group-containing organoalkoxysilane compound). Its partial condensate (blocked isocyanate group-containing polyorganoalkoxysilane compound) can also be used. These compounds may be used alone or in combination of two or more.

[0038] The blocked isocyanatosilane compound is an isocyanatosilane compound (generally referred to as an isocyanate silane compound) in which the isocyanate group is protected with a blocking agent such as an oxime to render it inactive, and then deblocked by heating to activate (regenerate) the isocyanate group.

[0039] As the component (A-4), the blocked isocyanate group-containing organoalkoxysilane compound can be represented, for example, by the following general formula (4): Partial condensates of blocked isocyanate group-containing organoalkoxysilane compounds include, for example, partial condensates of blocked isocyanatosilane compounds having alkoxy groups represented by the following general formula (4): R 8 d Si(OR 9 ) 4-d ···(4) [In the formula, R 8 is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from a methacryloxy group and a blocked isocyanate group, and R 8 At least one of R is an alkyl group having 1 to 3 carbon atoms substituted with a blocked isocyanate group. 9 is an alkyl group having 1 to 4 carbon atoms, and d is 1 or 2. 8 If there are multiple R 8 may be the same or different, and multiple OR 9 may be the same or different.] In the general formula (4), the alkyl group having 1 to 3 carbon atoms and the alkyl group having 1 to 4 carbon atoms are as explained in the general formula (1) or (2).

[0040] Specific examples of the blocked isocyanate group-containing organoalkoxysilane compound represented by general formula (4) include compounds in which the isocyanate group in a compound such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, or 3-isocyanatopropylethyldiethoxysilane has been protected with a blocking agent. Among these, a preferred compound is 3-blocked isocyanatopropyltriethoxysilane.

[0041] Examples of blocking agents for isocyanate groups include oxime compounds such as acetoxime, 2-butanone oxime, cyclohexanone oxime, and methyl isobutyl ketoxime; lactams such as ε-caprolactam; alkylphenols such as monoalkylphenols (cresol, nonylphenol, etc.); dialkylphenols such as 3,5-xylenol and di-t-butylphenol; trialkylphenols such as trimethylphenol; malonic acid diesters such as diethyl malonate; and active methyl esters such as acetoacetate and ethyl acetoacetate. Examples of blocking agents that can be used include: alcohols such as methanol, ethanol, and n-butanol; hydroxyl-containing ethers such as methyl cellosolve and butyl cellosolve; hydroxyl-containing esters such as ethyl lactate and amyl lactate; mercaptans such as butyl mercaptan and hexyl mercaptan; acid amides such as acetanilide, acrylamide, and dimer acid amide; imidazoles such as imidazole and 2-ethylimidazole; pyrazoles such as 3,5-dimethylpyrazole; triazoles such as 1,2,4-triazole; and acid imides such as succinimide and phthalimide. A catalyst such as dibutyltin dilaurate may also be used in combination to control the dissociation temperature of the blocking agent.

[0042] ((B) component) The above-mentioned coating liquid contains a curing catalyst as component (B). This curing catalyst is a catalyst that hydrolyzes and condenses (cures) the silane compounds (A-1) to (A-4) in the component (A) described above, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, and sulfamic acid; and organic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, citric acid, tartaric acid, succinic acid, maleic acid, glutamic acid, lactic acid, and p-toluenesulfonic acid.

[0043] Also, lithium hydroxide, sodium hydroxide, potassium hydroxide, n-hexylamine, dimethylamine, tributylamine, diazabicycloundecene, ethanolamine acetate, dimethylaniline formate, tetraethylammonium benzoate; organic metal salts such as sodium acetate, potassium acetate, sodium propionate, sodium glutamate, potassium propionate, sodium formate, potassium formate, benzoyltrimethylammonium acetate, tetramethylammonium acetate, and stannous octylate; tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide, and aluminum triisopropyl ammonium benzoate. Examples of suitable Lewis acids include aluminum acetylacetonate, aluminum propoxide, aluminum acetylacetonate, SnCl4, TiCl4, and ZnCl4.

[0044] Among these curing catalysts, organic acids are preferred because they stably disperse the reaction products of the silane compounds (A-1) to (A-4) and component (D) in the coating solution, are useful as additives to suppress aggregation, sedimentation, and gelation, and can improve the transparency of the resulting film. In particular, organic carboxylic acids, especially acetic acid, are preferred. 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.

[0045] ((C) component) The above-mentioned coating liquid contains a dispersion medium as component (C). In one embodiment of the present invention, the coating liquid is used in a state in which the above-mentioned components are mixed and dispersed in a dispersion medium. The dispersion medium used in this embodiment of the present invention is not particularly limited as long as it can uniformly mix and disperse the above-mentioned components. Examples of the dispersion medium include water, as well as organic dispersion media such as alcohols, aromatic hydrocarbons, ethers, and esters. Specific examples of alcohols among these organic dispersion media include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, 1-methoxy-2-propanol (propylene glycol monomethyl ether), propylene glycol monomethyl ether acetate, diacetone alcohol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, and butyl cellosolve.

[0046] Specific examples of other dispersion media include tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, xylene, dichloroethane, toluene, methyl acetate, ethyl acetate, and ethoxyethyl acetate. Among these dispersion media, water and alcohols are preferred from the viewpoint of performance as a dispersion medium. 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.

[0047] ((D) component) The above-mentioned coating liquid preferably contains inorganic fine particles as component (D) for the purpose of controlling the refractive index, etc. Examples of inorganic fine particles include colloidal silica, magnesium fluoride, aluminum oxide, antimony pentoxide, tin oxide, zirconium oxide, niobium oxide, cerium oxide, titanium oxide, etc. These may be used alone or in combination of two or more. The average particle size of the inorganic fine particles is preferably, for example, about 1 to 200 nm from the viewpoints of ease of handling and ease of control of the refractive index.

[0048] The inorganic fine particles are preferably dispersed in a dispersion medium. Suitable dispersion media include water, lower alcohols such as methanol, ethanol, propanol, and 1-methoxy-2-propanol, and cellosolves such as methyl cellosolve. These dispersion media may be used alone or in combination of two or more.

[0049] Colloidal silica, also known as colloidal silica or colloidal silicic acid, is a colloidal suspension of silicon oxide with Si-OH groups on its surface due to hydration in water. It is produced by adding hydrochloric acid to an aqueous solution of sodium silicate. Recently, new preparation methods have been developed, resulting in dispersions in non-aqueous solutions and fine powders produced by vapor phase deposition, with particle sizes ranging from several nanometers to several micrometers. Hollow silica particles with internal voids have also been developed and are suitable for use. Average particle sizes of approximately 1 to 200 nm are preferred. The particle composition is variable, and some particles are polymerized through the formation of siloxane bonds (-Si-O-, -Si-O-Si-). The particle surface is porous, and in water, they are generally negatively charged.

[0050] Commercially available colloidal silica products include, for example, the "Ultra-High Purity Colloidal Silica" Quattron PL series and the "High-Purity Organosol" Quattron PL series manufactured by Fuso Chemical Co., Ltd., and "Colloidal Silica (product name: Snowtex)" and "Organosilica Sol (product names: Methanol Silica Sol, MA-ST-L, IPA-ST, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, PGM-ST, etc.)" manufactured by Nissan Chemical Co., Ltd. One type of colloidal silica may be used alone, or two or more types may be used in combination.

[0051] In addition to the above, commercially available inorganic fine particles include "Nanouse ZR (zirconia aqueous sol)," "Alumina sol AS-200," and "Alumina sol AS-520-A" manufactured by Nissan Chemical Co., Ltd., "CATALOID (alumina aqueous dispersion sol)," "OPTOLAKE (titanium oxide organosol)," and "ELCOM-V4566 (antimony pentoxide organosol)" manufactured by JGC Catalysts and Chemicals Co., Ltd., and "Needral (cerium oxide sol)" and "Ceramace (tin oxide sol)" manufactured by Taki Chemical Co., Ltd. These inorganic fine particles may be used alone or in combination of two or more.

[0052] ((E) component) The coating liquid may contain, as component (E), a silane compound having an epoxy group and an alkoxy group. Component (E) is a silane compound having an epoxy group and an alkoxy group, but not containing an amino group or an isocyanate group (hereinafter also referred to as an epoxy group-containing organoalkoxysilane compound). Its partial condensate (epoxy group-containing polyorganoalkoxysilane compound) can also be used. These may be used alone or in combination of two or more. As the (E) compound, an epoxy group-containing organoalkoxysilane compound can be represented, for example, by the following general formula (5): An example of a partial condensate of an epoxy group-containing organoalkoxysilane compound is a partial condensate of a silane compound having an epoxy group and an alkoxy group, represented by general formula (5).

[0053] R 6 c Si(OR 7 ) 4-c ···(5) [In the formula, R 6 is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group; R 6 At least one of them is an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. R 7 is an alkyl group having 1 to 4 carbon atoms, and c is 1 or 2. 6 If there are multiple R 6 may be the same or different, and multiple OR 7 may be the same or different.] In the general formula (5), the alkyl group having 1 to 3 carbon atoms and the alkyl group having 1 to 4 carbon atoms are as explained in the general formula (1) or (2).

[0054] Specific examples of the epoxy group-containing organoalkoxysilane compound represented by general formula (5) include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

[0055] (Optional addition ingredient) In addition to the components (A), (B), (C), (D), and (E), the coating liquid may contain various additives conventionally used in coating liquids. Examples of additives that may be added as needed (hereinafter also referred to as optional additives) include organic polymer fine particles, ultraviolet absorbers, leveling agents, flexibility-imparting agents, lubricity-imparting agents, antioxidants, bluing agents, antistatic agents, defoamers (antifoaming agents), light stabilizers, weather resistance-imparting agents, colorants, fine particle dispersants (antisettling agents), and fine particle surface activity modifiers.

[0056] (Organic polymer fine particles) In one embodiment of the present invention, organic polymer fine particles may or may not be contained in the coating liquid. If they are contained, they may or may not have an ultraviolet absorbing group. The inclusion of organic polymer particles can sometimes allow for better control of the refractive index. Furthermore, when the organic polymer particles have UV-absorbing groups, they can also function as UV absorbers. Examples of UV absorbers include polymeric UV-absorbing resin particles obtained by copolymerizing an acrylic monomer (hereinafter referred to as a UV-absorbing acrylic monomer) having a side chain skeleton (e.g., benzophenone, benzotriazole, triazine) that functions as a UV absorber with other ethylenically unsaturated compounds (e.g., acrylic acid, methacrylic acid and their derivatives, styrene, vinyl acetate, etc.). While conventional UV absorbers generally have low molecular weights of 200 to 700, the weight-average molecular weight of the polymeric UV-absorbing resin particles typically exceeds 10,000. These particles overcome the shortcomings of conventional low-molecular-weight UV absorbers, such as compatibility with plastics and heat resistance, and can provide long-term weather resistance.

[0057] The ultraviolet absorbing acrylic monomer is not particularly limited as long as it is a compound having at least one ultraviolet absorbing group and one acryloyl group in the molecule. Examples of such compounds include benzotriazole compounds represented by the following general formula (8) and benzophenone compounds represented by the following general formula (9).

[0058] [ka]

[0059] [wherein X is a hydrogen atom or a chlorine atom, R 10 is a hydrogen atom, a methyl group, or a tertiary alkyl group having 4 to 8 carbon atoms; R 11 is a linear or branched alkylene group having 2 to 10 carbon atoms, R 12 represents a hydrogen atom or a methyl group, and p represents 0 or 1.]

[0060] [ka]

[0061] [In the formula, R 13 is a hydrogen atom or a methyl group, R 14 is a substituted or unsubstituted linear or branched alkylene group having 2 to 10 carbon atoms, R 15 is a hydrogen atom or a hydroxyl group, R 16 represents a hydrogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.

[0062] Specific examples of the benzotriazole-based compound represented by general formula (8) include 2-(2'-hydroxy-5'-(meth)acryloxyphenyl)-2H-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-(meth)acryloxymethylphenyl)-2H-benzotriazole, 2-[2'-hydroxy-5'-(2-(meth)acryloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(2-(meth)acryloxyethyl)phenyl]-5-chloro-2H-benzotriazole, and 2-[2'-hydroxy-3'-methyl-5'-(8-(meth)acryloxyoctyl)phenyl]-2H-benzotriazole.

[0063] Specific examples of the benzophenone-based compound represented by general formula (9) include 2-hydroxy-4-(2-(meth)acryloxyethoxy)benzophenone, 2-hydroxy-4-(4-(meth)acryloxybutoxy)benzophenone, 2,2'-dihydroxy-4-(2-(meth)acryloxyethoxy)benzophenone, 2,4-dihydroxy-4'-(2-(meth)acryloxyethoxy)benzophenone, 2,2',4-trihydroxy-4'-(2-(meth)acryloxyethoxy)benzophenone, 2-hydroxy-4-(3-(meth)acryloxy-2-hydroxypropoxy)benzophenone, and 2-hydroxy-4-(3-(meth)acryloxy-1-hydroxypropoxy)benzophenone. These ultraviolet absorbing acrylic monomers may be used alone or in combination of two or more.

[0064] The content of the ultraviolet absorbing acrylic monomer unit in the polymeric ultraviolet absorbing resin particles is usually about 5 to 70% by mass, and preferably about 10 to 60% by mass, from the viewpoint of the balance between the ultraviolet absorbing ability of the resulting cured film, other physical properties, and economic efficiency.

[0065] In one embodiment of the present invention, in the coating liquid, the polymeric ultraviolet-absorbing resin fine particles preferably have an average particle size in the range of 1 to 200 nm, more preferably in the range of 1 to 100 nm, from the viewpoints of manufacturability, dispersibility in the coating liquid, coatability of the coating liquid, transparency of the cured film, and the like.

[0066] In the present invention, the organic polymer fine particles are preferably used in a form dispersed in a dispersion medium. Examples of the dispersion medium include water, lower alcohols such as methanol, ethanol, propanol, and 1-methoxy-2-propanol, and cellosolves such as methyl cellosolve. The use of such a dispersion medium improves the dispersibility of the organic polymer fine particles and prevents sedimentation. Furthermore, the dispersion medium is preferably water. Water is preferable as the dispersion medium because it can also be used for the hydrolysis and condensation reactions of the silane compound, which are necessary for forming a matrix having Si-O bonds derived from the aforementioned component (A).

[0067] There are no particular limitations on the method for producing the organic polymeric fine particles, and conventionally known methods such as emulsion polymerization and fine suspension polymerization can be used.

[0068] Specific examples of organic polymeric fine particles include polymeric ultraviolet absorbers for coating such as ULS-700, ULS-1700, ULS-383MA, ULS-1383MA, ULS-383MG, ULS-385MG, ULS-1383MG, and ULS-1385MG manufactured by Lion Specialty Chemicals Co., Ltd., and functional polymer NCI-905-20NPF manufactured by Nikko Chemical Research Institute Co., Ltd. Other examples include Bestex HR-84, HCR-120, Vanatex HG-9HN, Newcoat 9306, and UVA-101 manufactured by Shin-Nakamura Chemical Co., Ltd. One type of organic polymeric fine particle may be used alone, or two or more types may be used in combination.

[0069] (Leveling agent) A leveling agent can be added to the coating liquid to improve the smoothness of the resulting cured film and the flow properties during coating. Examples of such additives include silicone-based leveling agents, fluorine-based leveling agents, acrylic leveling agents, vinyl-based leveling agents, and leveling agents that are a combination of fluorine and acrylic. All of these act on the coating surface to reduce surface tension. Each has its own unique characteristics and can be used according to the purpose. While silicone-based and fluorine-based agents have strong surface tension reduction capabilities, acrylic-based and vinyl-based agents are advantageous in that they are less likely to cause poor wetting when recoating.

[0070] Specific examples of silicone-based leveling agents include copolymers of polyoxyalkylene and polydimethylsiloxane. Commercially available silicone-based leveling agents include FZ-2118, FZ-77, FZ-2161, etc. manufactured by Toray Dow Corning Co., Ltd., KP321, KP323, KP324, KP326, KP340, KP341, etc. manufactured by Shin-Etsu Chemical Co., Ltd., TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, TSF4453, TSF4460, etc. manufactured by Momentive Performance Materials Japan, LLC, and TSF4452, TSF4453, TSF4460, etc. manufactured by BYK-Chemie Japan K.K. Examples of such polyether-modified silicone oils (polyoxyalkylene-modified silicone oils) include BYK-300, BYK-302, 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, and BYK-3570 manufactured by Co., Ltd.

[0071] Furthermore, when heat resistance of 150°C or higher is required, polyester-modified or aralkyl-modified silicone oils having a benzene ring are suitable. Commercially available polyester-modified silicone oils include BYK-310, BYK-315, and BYK-370 manufactured by BYK Japan Co., Ltd. Commercially available aralkyl-modified silicone oils having a benzene ring include BYK-322 and BYK-323 manufactured by BYK Japan Co., Ltd.

[0072] As the fluorine-based leveling agent, a copolymer of polyoxyalkylene and fluorocarbon can be used. Commercially available fluorine-based leveling agents include the MEGAFAC series manufactured by DIC Corporation and the FC series manufactured by Sumitomo 3M Limited. Commercially available acrylic leveling agents include BYK-350, BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380N, BYK-381, BYK-392, and fluorinated BYK-340, all manufactured by BYK Japan Co., Ltd.

[0073] The addition of such a leveling agent improves the finished appearance of the cured film and enables it to be applied uniformly as a thin film. The amount of the leveling agent used is preferably 0.01 to 10 mass %, more preferably 0.02 to 5 mass %, based on the total amount of the coating liquid. The leveling agent may be added when preparing the coating liquid, or may be added to the coating liquid immediately before forming a cured film, or may be added both at the stage of preparing the coating liquid and immediately before forming a cured film.

[0074] (Flexibility imparting agent) The above-mentioned coating liquid may contain a flexibility-imparting agent as a stress relaxation agent in order to improve the flexibility of the resulting cured film. As the flexibility imparting agent, for example, a silicone resin or the like can be used.

[0075] Commercially available silicone resins include the Resin MK series manufactured by Wacker, such as Belsil PMS MK (CHSiO 3 / 2 ) repeating units (units T) of the formula (CH3)2SiO 2 / 2 ) units (unit D)), Shin-Etsu Chemical Co., Ltd.'s KR-242A (containing 98 mass% of unit T and 2 mass% of dimethyl unit D and containing Si-OH end groups), KR-251 (containing 88 mass% of unit T and 12 mass% of dimethyl unit D and containing Si-OH end groups), KR-220L (CHSiO 3 / 2 ) units T and containing Si-OH (silanol) terminal groups).

[0076] In one embodiment of the present invention, the content of each component in the coating liquid can be selected as appropriate, but it is preferable to select the content of each component so that it falls within the range shown below, for example.

[0077] The content of each component is expressed in mass % relative to the total amount of components (A) [(A-1) to (A-4)], (B), and (E), excluding the dispersion medium for component (C). When component (D) (inorganic fine particles) is used, the amount of component (D) (inorganic fine particles) used in a dispersed state is calculated using only the solid content of each component, and the dispersion medium contained in each component is considered to be included in component (C).

[0078] The content of component (A-1) is usually about 0.01 to 40% by mass, preferably 0.1 to 20% by mass. The content of component (A-2) is usually about 0.1 to 50% by mass, preferably 1 to 40% by mass. The content of component (A-3) is usually about 0.1 to 30% by mass, preferably 0.3 to 20% by mass. The content of component (A-4) is usually about 0.1 to 50% by mass, preferably 1 to 40% by mass.

[0079] The content of the component (B) is usually about 0.001 to 30% by mass, and preferably 0.001 to 20% by mass.

[0080] The content of component (C) is usually about 5 to 5,000 parts by mass, preferably 20 to 3,500 parts by mass, based on the total mass of components (A) [(A-1) to (A-4)], (B), and (E). When component (D) is included, its content is usually about 0.1 to 70% by mass, preferably 1 to 50% by mass.

[0081] The molar ratio of the (A-3) component to the (A-4) component is not particularly limited, but is preferably 1:1 to 1:5, and more preferably 1:2 to 1:4. When the molar ratio of the (A-3) component to the (A-4) component is within the above range, the durability of the resulting cured film is further improved.

[0082] In the laminate of the present invention, the coating liquid essentially consists of components (A), (B), and (C), and optionally components (E) and (D), and optionally additional components, and may contain other inevitable impurities within a range that does not impair the effects of the present invention. In the laminate of the present invention, for example, 80 to 100 mass%, 90 to 100 mass%, 95 to 100 mass%, 98 to 100 mass%, or 100 mass% of the coating liquid is Components (A), (B) and (C), Components (A), (B), (C) and (E), Components (A), (B), (C), and (E), and optionally component (D) and any additional components; or It may consist of components (A), (B) and (C), and optionally components (E), (D) and optional additional components.

[0083] (Method for preparing coating liquid) In one embodiment of the present invention, the coating liquid is preferably prepared by contacting a hydrolysis condensate of the components (A-1) and (A-2) with the components (B) and (C) to obtain a reaction product, adding the component (A-4) to the reaction product, and then further adding the component (A-3) to the reaction product.

[0084] Also preferred is a product obtained by contacting a hydrolysis condensate of components (A-1), (A-2), and (E) with components (B) and (C), adding component (A-4) to the resulting reaction product, and then further adding and reacting component (A-3).

[0085] Furthermore, a more preferred product is obtained by contacting and heating a mixture containing the components (A-1), (A-2), (B), and (C), adding the component (A-4) to the resulting reaction product, and then further adding and reacting the component (A-3).

[0086] Furthermore, a product obtained by heating a mixture containing the components (A-1), (A-2), (E), and (B) to (C), adding the component (A-4) to the reaction product, and then adding and reacting the component (A-3) thereto is also preferred.

[0087] Specifically, it is preferable to prepare the coating liquid by carrying out the following operations. First, a first mixture containing at least components (A-1), (A-2), (B), and (C) is prepared. Next, if component (D) (inorganic fine particles, e.g., colloidal silica) is used in the coating liquid to be prepared, (D) is mixed to prepare a second mixture. Subsequently, component (A-4) is mixed to prepare a third mixture. Finally, component (A-3) is preferably mixed to prepare the coating liquid. Here, component (E) may optionally be added to the first mixture.

[0088] In this way, it is preferable to prepare each component separately, since this improves the storage stability of the coating liquid (prevention of gelation, etc.). This effect is particularly pronounced when the amount of water in the liquid increases due to an increase in the amount of component (D) and other additives. For example, components (A-1), (A-2), (E), (B), and (C) are mixed, and then component (D) is added. Next, component (A-4) is mixed, and finally component (A-3) is mixed. Note that component (C) can be further added after the coating liquid has been prepared to dilute the coating liquid.

[0089] In the laminate of the present invention, it is known that the liquid storage stability of a mixed material such as a coating liquid is easily affected by the liquid pH (for example, "Application of the Sol-Gel Method to Nanotechnology / Edited by Sakuhana Sumio," CMC Publishing). In one aspect of the present invention, in preparing the coating liquid, an acidic component is mixed as component (B), and basic components are mixed as components (A-3) and (B), so the liquid pH changes depending on the mixing order.

[0090] The liquid pH values, for example, as evaluated using a portable pH meter (manufactured by Hanna: product name Checker 1) calibrated with a calibration pH standard solution, are preferably pH ≦6 for the first and second mixed liquids, and pH ≦7 for the third and final mixed liquids. In particular, if the liquid pH of the third mixed liquid, i.e., during mixing of component (A-3), exceeds 8, the liquid stability may decrease. It is preferable to maintain the liquid in an acidic state from the start to the end of preparation of the coating liquid. In other words, it is preferable to prepare the coating liquid using a procedure that maintains these conditions.

[0091] Furthermore, the first, second, and third mixed liquids are preferably heat-treated 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. The mixing and heating methods are not particularly limited as long as they can achieve uniform mixing and heating. Heating in this manner promotes the condensation reaction of components (A-1), (A-2), (A-3), (E), and (A-4) in the liquid, improving boiling resistance and other durability. The reaction of components (A-1), (A-2), (A-3), (E), and (A-4) can be analyzed by solution Si-NMR, which allows for the design of an appropriate structure. If the temperature is below 30°C or if the reaction time is less than 30 minutes, the reaction is often extremely slow. If the temperature is above 130°C or if the reaction time is longer than 24 hours, the reaction of components (A-1), (A-2), (A-3), (E), and (A-4) may proceed too quickly, causing the liquid to gel or become highly viscous, making it impossible to apply.

[0092] The final liquid (coating liquid) obtained after mixing component (A-3) is also preferably heat-treated. Mixing at room temperature is susceptible to the effects of stirring efficiency, which can lead to low dispersion of component (A-3), potentially resulting in reduced transparency of the cured film (reduced total light transmittance and increased haze). 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. There are no particular restrictions on the mixing and heating means, as long as they ensure uniform mixing and heating. Heat treatment at temperatures below 30°C or for less than 5 minutes is often ineffective, while heat treatment above 130°C or for more than 10 hours can cause the liquid to gel or become highly viscous, potentially making it impossible to apply. In the examples described below, the evaluation results of a cured film produced using the coating liquid obtained after standing for one week are described, but there is no particular limit to the period for which the liquid is left standing before producing a cured film.

[0093] (Applications of coating liquid, etc.) In one aspect of the present invention, the coating liquid has good stability and handleability, and can be cured by drying at a relatively low temperature. The cured film formed has a good appearance and a small thickness, and by applying the coating liquid to a polycarbonate resin to form a laminate, the high-temperature and high-humidity resistance can be effectively improved.

[0094] [Cured film] Specifically, the above-mentioned cured film is formed by applying the above-mentioned coating liquid to the polycarbonate resin on which the cured film is to be formed by methods such as spraying, curtain flow, bar coating, roll coating, and dip coating. Among these coating methods, dip coating is preferred because it allows the coating liquid to be applied efficiently with relatively simple equipment. Dip coating usually results in uneven coating, but dip coating using the above-mentioned coating liquid is less likely to result in the appearance of foreign matter, mottled patterns, cracks, etc., and efficiently forms a cured film with a good appearance. On the other hand, with dip coating, it may be difficult to achieve a uniform coating depending on the shape of the polycarbonate resin, for example, the coating liquid may accumulate in the recesses of the uneven polycarbonate resin, and spray coating may be preferred in some cases.

[0095] The thickness of the cured film is preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 500 nm or less. Also, it is preferably 50 to 110 nm, and more preferably 60 to 95 nm. If the thickness of the cured film exceeds 5 μm, the transmittance of the formed laminate may not be improved.

[0096] The drying temperature during the formation of the cured film may be relatively low, specifically, preferably room temperature to 190° C., and more preferably 80 to 120° C. If the drying temperature is relatively high, for example, above 120° C., the polycarbonate resin may be thermally deformed.

[0097] The refractive index of the cured film is preferably 1.1 to 1.59. By making the refractive index of the cured film between the refractive indexes of air and polycarbonate resin, the reflectance can be reduced and the transmittance can be improved.

[0098] (Polycarbonate resin) Examples of polycarbonate resins include those generally used for light guide members or lighting members, such as Toughlon LEV1700KL (manufactured by Idemitsu Kosan Co., Ltd.).

[0099] In one embodiment of the present invention, the polycarbonate resin may contain a light diffusing agent for the purpose of imparting a light diffusing effect, etc. The light diffusing agent is not particularly limited, and known agents can be used. Examples include cross-linked acrylic resin, cross-linked polystyrene resin, silicone resin, fluorine-based resin, silica, quartz, titanium oxide, zinc oxide, etc. These may be used alone or in combination of two or more. Among these, it is preferable to contain organic fine particles made of silicone resin, as they have good retention heat stability during molding, etc., and have the effect of improving flame retardancy. The particle size (D 50 ) is not particularly limited, but from the viewpoint of improving the retention heat stability during molding and the flame retardancy, it is preferably 0.5 to 10 μm, more preferably 1 to 5 μm. Here, the particle size of the light diffusing agent (D 50 ) is measured using a laser diffraction particle size distribution analyzer (volume basis).

[0100] The polycarbonate resin may be produced using a known molding method such as injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, or foam molding, and may have an uneven surface. The polycarbonate resin may be in the form of a plate, a column, an elliptical column, a rectangular column, a cylinder, or the like.

[0101] In the case of polycarbonate resin produced by injection molding, the mold is transferred, so the polycarbonate resin surface becomes a mirror finish. On the other hand, when polycarbonate resin is produced by, for example, extrusion molding, unevenness may be formed on the polycarbonate resin surface. When unevenness is formed on the polycarbonate resin surface, the haze may increase due to diffuse reflection. In this regard, the laminate of the present invention, in which a cured film is formed on a polycarbonate resin using the above-mentioned coating liquid, can reduce the haze of the laminate, regardless of the method of producing the polycarbonate resin, even if a polycarbonate resin with a somewhat high haze is used.

[0102] There is no particular limitation on the thickness of the polycarbonate resin, and it may be appropriately selected depending on the situation, but it is usually about 5 μm to 30 mm, and preferably 15 μm to 10 mm.

[0103] In one embodiment of the present invention, the polycarbonate resin may be one in which the surface of the polycarbonate resin is subjected to microfabrication such as a prism layer or a microlens layer, or one provided with a functional layer such as a hard coat layer, a light diffusion layer or an ink layer.

[0104] In one embodiment of the present invention, the coating liquid can form a cured film with good adhesion on a polycarbonate resin. To further improve this adhesion, at least the surface of the polycarbonate resin on which the cured film is to be formed can be subjected to a surface treatment, such as an oxidation method or a roughening method, as desired. Examples of the oxidation method include corona discharge treatment, plasma treatment such as low-pressure plasma treatment or atmospheric-pressure plasma treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, electron beam treatment, and itro treatment. Examples of the roughening method include sandblasting and solvent treatment. These surface treatment methods are appropriately selected depending on the type of polycarbonate resin, but corona discharge treatment is generally preferred in terms of curing and operability. Surface treatment with a silane coupling agent or the formation of a primer layer can also be performed.

[0105] The present invention also provides a method for producing a cured film, which comprises the step of heating and curing the above-mentioned coating liquid, and a method for producing a laminate, which comprises the steps of applying the above-mentioned coating liquid onto a polycarbonate resin and drying and curing the coating liquid to provide a coating layer.

[0106] Another embodiment of the laminate of the present invention comprises a polycarbonate resin and a cured film formed directly on the polycarbonate resin by curing a coating liquid containing a hydrolysis condensate of a silane compound having an alkoxy group, the cured film having a thickness of 500 nm or less. The coating liquid and polycarbonate resin may be any of those described above in connection with the embodiment of the laminate of the present invention. The cured film may also be any of those described above in connection with the embodiment of the laminate of the present invention.

[0107] The laminate is preferably used at temperatures of 70° C. or higher and 70% relative humidity or higher, and is preferably used near a high-power light-emitting diode. One embodiment of the laminate of the present invention may be included in a high-power light-emitting diode. Examples of the high-power light-emitting diode include a power LED and a high-power LED.

[0108] Examples of power LEDs and high-power LEDs include: LED lighting sources such as straight tube lamps, LED lighting fixtures for residential or industrial use, such as downlights, ceiling lights, base lights, pendant lights, brackets, spotlights, stand lights, exterior lighting, etc. Outdoor lighting such as security lights, street lights, road lights, tunnel lights, floodlights, etc. LED lamps for plant factories, Examples of LED applications include automotive applications such as headlight systems, rear lamp systems, and DRLs (Daytime Running Lamps).

[0109] A light-guiding member or a lighting member for a high-power light-emitting diode according to one aspect of the present invention includes the above-described laminate. One embodiment of the use of the light guide member of the present invention is the use of the above-mentioned polycarbonate resin laminate in a light guide member for a high-power light-emitting diode or a lighting member. [Example]

[0110] The present invention will be explained in more detail by way of examples, but the present invention is not limited to these examples in any way.

[0111] In this specification, details of raw materials described by trade names are as follows: (A-1) Component: Silicate 40 (a mixture of ethyl polysilicate, ethyl orthosilicate tetraethyl silicate, and ethanol) manufactured by Tama Chemicals Co., Ltd. (D) Component: IPA-ST-L ((colloidal silica) manufactured by Nissan Chemical Co., Ltd. (isopropyl alcohol dispersion, colloidal silica concentration 30% by mass, average particle size 40-50 nm (manufacturer's published value))

[0112] Production Example 1 (Production of Coating Liquid 1) According to the ingredients and blending amounts shown in Production Example 1 in Table 1, a coating liquid was prepared as follows. Into a 50 ml sample tube, 8.5 g of 1-methoxy-2-propanol (component (C) dispersion solvent), 2.4 g of water (component (C)), 1.0 g of acetic acid (component (B)), 1.0 g of silicate 40 (component (A-1)), 3.0 g of methyltrimethoxysilane (component (A-2)), 1.1 g of dimethoxy-3-glycidoxypropylmethylsilane (component (E)), and 0.1 g of a 20 mass % p-toluenesulfonic acid methanol solution (component (B) + component (C)) were added dropwise in this order over one minute. The mixture was then stirred at 500 rpm at room temperature for 60 minutes, and then allowed to stand for one day. This was designated Liquid 1.

[0113] 2.2 g of 3-isocyanatopropyltriethoxysilane and 0.8 g of 2-butanone oxime (a blocking agent for isocyanate groups) were placed in a 20 ml sample tube, stirred at room temperature at 500 rpm for 10 minutes, and then left to stand for one day. This was used as the third liquid. Regarding the blocking of the isocyanate group, 13 This was confirmed by the disappearance of the isocyanate group signal in C-NMR. The total amount of 3-isocyanatopropyltriethoxysilane and 2-butanone oxime was taken as the amount of the blocked isocyanatosilane compound: component (A-4).

[0114] Liquid 1 and a stirrer were placed in a 200 ml three-neck flask equipped with a condenser. While stirring at 500 rpm, 0.7 g of isopropyl alcohol (IPA) (component (C)) and 12.0 g of IPA-ST-L (component (C) + component (D)) were added dropwise over 5 minutes as Liquid 2, and the mixture was stirred at room temperature for 60 minutes. The mixture was then heated at 600 rpm and 80°C for 3 hours under a nitrogen stream. Liquid 3 was then added, and the mixture was stirred at 80°C under the same conditions for 4 hours, after which it was left to stand at room temperature overnight. Then, 0.80 g of 3-aminopropyltrimethoxysilane (component (A-3)) was added dropwise to the mixture over 2 minutes as a fourth liquid. After stirring at room temperature for 10 minutes, the mixture was heated at 700 rpm and 80°C for 3 hours under a nitrogen stream. The mixture was allowed to stand for one week, and then diluted with 403 g of isopropyl alcohol as a dilution solvent to prepare coating liquid 1.

[0115] The blending amounts of the obtained coating solution 1 are summarized in Table 1. Furthermore, for Coating Liquid 1, Table 2 shows the composition of each component (% by mass and parts by mass).

[0116] [Table 1]

[0117] [Table 2]

[0118] Example 1 (Manufacturing of laminates) Coating Liquid 1 obtained in Production Example 1 was applied to both sides of Toughlon LEV1700KL (Idemitsu Kosan Co., Ltd., polycarbonate resin, thickness 5 mm) using a dip coater (Asumi Giken Co., Ltd., model: M300). Thereafter, the coating was dried at 120°C for 10 minutes to produce a laminate including a cured film of Coating Liquid 1.

[0119] (Film thickness measurement 1) The thickness of each of the cured films on both sides of the resulting laminate was measured using a spectroscopic reflection film thickness meter (manufactured by Asumi Giken Co., Ltd., model: AFW-100W), and the average film thickness was calculated. The film thickness per side was approximately 85 nm. The results are shown in Table 3.

[0120] (Haze value measurement 1) The haze value of the entire laminate obtained was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) The results are shown in Table 3.

[0121] (Transmittance measurement 1) The transmittance of the obtained laminate in the wavelength range of 350 to 800 nm was measured using a UV-VIS-NIR spectrophotometer (manufactured by Shimadzu Corporation, model: UV-3600). The results are shown in FIG.

[0122] (High temperature and humidity test) The obtained laminate was treated for 3000 hours under conditions of 85°C and 85% RH (relative humidity) using a small environmental tester SH-221 (manufactured by Espec Corporation).

[0123] (Haze value measurement 2) After the high-temperature, high-humidity test, the laminate was subjected to haze value measurement in the same manner as in Haze Value Measurement 1. The results are shown in Table 3.

[0124] (Transmittance measurement 2) After the high-temperature, high-humidity test, the laminate was subjected to transmittance measurement in the same manner as in Transmittance Measurement 1. The results are shown in FIG.

[0125] Comparative Example 1 A test was carried out in the same manner as in Example 1, except that Toughlon LEV1700KL was used instead of the laminate of Example 1 and no coating was performed. The results are shown in Table 3 and FIG.

[0126] [Table 3]

[0127] Example 2 A laminate was produced and evaluated in the same manner as in Example 1, except that PC1600 (manufactured by CI Takiron Co., Ltd., thickness: 3 mm) was used instead of Toughlon LEV1700KL. The results are shown in Table 4 and FIG.

[0128] Comparative Example 2 A test was carried out in the same manner as in Example 2, except that PC1600 was used instead of the laminate of Example 2 and no coating was performed. The results are shown in Table 4 and FIG.

[0129] [Table 4] [Industrial Applicability]

[0130] The laminate of the present invention and the light guide member or lighting member of the present invention can be used in members that use high-power light-emitting diodes as light sources.

Claims

1. Polycarbonate resin, a cured film formed directly on the polycarbonate resin; and and The cured film is prepared using a coating liquid containing the following components (A), (B), and (C): A laminate for use as a light-guiding member of a DRL (Daytime Running Lamp), which guides light emitted from a light-emitting diode light source while internally reflecting the light. (A) Hydrolysis and condensation products of silane compounds having an alkoxy group, which are the following components (A-1) to (A-4): (A-1) Tetraalkoxysilane compound (A-2) Organoalkoxysilane compound containing no amino group, no epoxy group, and no isocyanate group (A-3) Silane compound having an amino group and an alkoxy group (A-4) Blocked isocyanatosilane compound having an alkoxy group (B) Curing catalyst (C) Dispersion medium

2. 2. The laminate according to claim 1, 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 having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms and an ether bond. １ may be the same or different.]

3. 3. The laminate according to claim 1, wherein the component (A-2) is an organoalkoxysilane compound containing no amino group, no epoxy group, and no isocyanate group, and is represented by the following general formula (2): R ２ ａ Si(OR ３ ) ４－ａ ・・・(2) [In the formula, R ２ represents an alkyl group having 1 to 10 carbon atoms or a fluorinated alkyl group having 1 to 10 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with a methacryloxy group. R ３ represents an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms and an ether bond. a represents 1 or 2. R ２ If there are multiple R ２ may be the same or different, and multiple OR ３ may be the same or different.]

4. 4. The laminate according to claim 1, wherein the 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 having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or a methacryloxy group, an 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 an alkyl group having 1 to 3 carbon atoms)]. R ４ At least one of the groups represents an amino group or an alkyl group having 1 to 3 carbon atoms substituted with either an aminoalkyl group or an alkylamino group. R ５ represents an alkyl group having 1 to 4 carbon atoms. b represents 1 or 2. R ４ If there are multiple R ４ may be the same or different, and multiple OR ５ may be the same or different.]

5. The laminate according to any one of claims 1 to 4, wherein the 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 having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from a methacryloxy group and a blocked isocyanate group, and R ８ At least one of R represents an alkyl group having 1 to 3 carbon atoms substituted with a blocked isocyanate group. ９ represents an alkyl group having 1 to 4 carbon atoms, and d represents 1 or 2. ８ If there are multiple R ８ may be the same or different, and multiple OR ９ may be the same or different.]

6. The laminate according to any one of claims 1 to 5, further comprising (E) a silane compound having an epoxy group and an alkoxy group.

7. 7. The laminate according to claim 6, 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 having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group; R ６ At least one of the groups represents an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. R ７ represents an alkyl group having 1 to 4 carbon atoms. c represents 1 or 2. R ６ If there are multiple R ６ may be the same or different, and multiple OR ７ may be the same or different.]

8. The laminate according to any one of claims 1 to 7, wherein the thickness of the cured film is 5 µm or less.

9. A laminate described in any one of claims 1 to 8, which is used at 70°C or higher and 70% relative humidity or higher.

10. A light guide member for a DRL (Daytime Running Lamp), comprising the laminate according to any one of claims 1 to 8.

11. A DRL (Daytime Running Lamp) comprising the laminate according to any one of claims 1 to 8.

12. Use of the laminate according to any one of claims 1 to 8 in a light guide member for a DRL (Daytime Running Lamp).

13. Use of the laminate according to any one of claims 1 to 8 for use as a DRL (Daytime Running Lamp).

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