JP5448301B2 - Coating composition and resin laminate - Google Patents

Description

  The present invention relates to a cured film, a coating composition, and a resin laminate subjected to surface treatment with this composition.

  Thermoplastics, particularly polycarbonate resins, are widely used as structural materials to replace glass because they are excellent in transparency, lightweight and excellent in impact resistance. However, since it is inferior in scratch resistance, its use is limited, and it is desired to improve the surface characteristics of the polycarbonate resin substrate.

  As a method for improving the surface treatment, there is a method of coating the surface of a polycarbonate resin molded article with a surface treatment agent. For example, a method has been proposed in which a cured layer made of a polyfunctional acrylic photocurable resin or a melamine-based or organopolysiloxane-based thermosetting resin is formed on the surface of a polycarbonate resin substrate.

  Among these, those coated with organosiloxane are considered useful because they are excellent in scratch resistance and chemical resistance. However, the coating with the organosiloxane resin has a problem in adhesion to the polycarbonate resin, and particularly has a problem that the coating layer is peeled off when used outdoors for a long period of time. In order to improve adhesion and wear resistance, there is a problem that even if the thickness of the organosiloxane resin is increased, there is a problem that cracks are likely to occur at the time of curing, and improvement is desired.

  For improving the adhesion, a method of blending various polymers having good adhesion into the paint has been proposed in Patent Document 1 or the like, but the scratch resistance is sacrificed. If an organic solvent such as toluene or tetrahydrofuran is used to dissolve the polymer, the surface of the polycarbonate substrate or the like is attacked and whitened, and a transparent laminate cannot be formed. In some cases, the weather resistance of the paint is significantly reduced. Therefore, in applications requiring scratch resistance and weather resistance, a two-coat method is generally used in which an acrylic paint is applied as a primer on a polycarbonate resin substrate, and a coating layer is further applied thereon ( Patent Document 2). However, since the work process is long, there is a problem in productivity, and development of a one-coat method is eagerly desired.

  Patent Document 3 proposes a technique for forming a thermosetting film with a single coat on a polycarbonate resin from an aqueous emulsion and colloidal silica. Silica particles are dispersed inside an organic film formed by fusing organic fine particles. The formed film is formed. Although it is possible to impart adhesion to a resin base material, it is difficult to impart wear resistance.

  Patent Document 4 proposes a method for realizing scratch resistance and adhesion by a one-coat method. In this method, it is preferable to use at least one of an epoxy group-containing silane coupling agent and an amino group silane coupling agent as the silane coupling agent, and the silane coupling agent is a non-volatile component of paint (JIS K5401) 100. It is used in the range of 5 to 10 parts by weight with respect to parts by weight. It is described that when the amount of the silane coupling agent is less than 5 parts by weight, the film property and adhesion are lowered, and when the amount exceeds 10 parts by weight, the scratch resistance is lowered. As shown in Example 6 of Patent Document 4, the weather resistance of the polycarbonate resin laminate not subjected to UV resistance prescription or not so much is low, and the coating layer is peeled off.

On the other hand, Patent Document 5 discloses a composition containing silicone-containing polymer ultraviolet absorber particles and polyorganosiloxane. However, the dispersion cannot be stabilized only by mixing the polymer ultraviolet absorbent particles and the polyorganosiloxane.
JP-A-7-90224 JP 2004-131549 A JP 2003-82272 A JP 2000-272071 A JP 2004-1393 A

  In view of the above problems, the present invention has a cured film, a coating composition, and a resin laminate that have good adhesion to a resin substrate such as polycarbonate without using a primer, and have excellent scratch resistance and weather resistance. The purpose is to provide a body.

According to the present invention, the following cured film, coating composition, resin laminate and the like are provided.
1. Organic UV-absorbing particles having an average particle diameter of 1 to 200 nm and inorganic UV-absorbing particles and / or colloidal silica having an average particle diameter of 1 to 200 nm are dispersed in a matrix having Si—O bonds. A cured film.
2. 2. The cured film according to 1, wherein the volume fraction of the organic ultraviolet absorbing particles in the cured film is 0.5 to 70% by volume.
3. The cured film of 1 or 2 whose total conversion weight of the inorganic oxide contained in the said cured film is 30 to 80 weight% of the total weight of a cured film.
The resin laminated body which formed the cured film in any one of 4.1-3 on the resin base material.
5. 5. The resin laminate according to 4, wherein the haze is 10% or less.
6). 6. The resin laminate according to 5, wherein the visible light transmittance is 80% or more.
7). A coating composition comprising the following components (1) to (7).
(1) Alkoxysilane compound or polyalkoxysilane compound (2) Aminosilane compound (3) Epoxysilane compound (4) Polymer ultraviolet absorbent particles (5) Curing catalyst (6) Inorganic ultraviolet absorbent particles and / or colloidal silica (7) Solvent 8. 8. The coating composition according to 7, wherein the amount of the components (1) to (7) is in the following range.
Component (1): 10 to 90% by weight
Component (2): 1 to 55% by weight
Ingredient (3): 1 to 60% by weight
Ingredient (4): 0.1 to 65% by weight
Ingredient (5): 0.1 to 30% by weight
Ingredient (6):
When component (6) is only inorganic UV-absorbing particles, 0.1 to 50% by weight
When component (6) is only colloidal silica, 0.1 to 80% by weight
When the component (6) is inorganic ultraviolet absorbing particles and colloidal silica, the inorganic ultraviolet absorbing particles are 0.1 to 50% by weight, and the colloidal silica is 0.1 to 80% by weight.
Component (7): 10 to 1000 parts by weight when the total of components (1) to (6) is 100 parts by weight The coating composition according to 7 or 8, wherein the curing catalyst is an organic acid.
The cured film formed by hardening | curing the coating composition in any one of 10.7-9.
11. The manufacturing method of the coating composition prepared by mixing the following component (1)-(7).
(1) Alkoxysilane compound or polyalkoxysilane compound (2) Aminosilane compound (3) Epoxysilane compound (4) Polymer ultraviolet absorbent particles (5) Curing catalyst (6) Inorganic ultraviolet absorbent particles and / or colloidal silica (7) Solvent 12. 12. A method for producing a coating composition according to 11, wherein a mixed liquid containing at least component (1) and component (6) is prepared, and finally component (4) is mixed.
The manufacturing method of the cured film which heats and cures the coating composition in any one of 13.7-9.

According to the present invention, there are provided a transparent cured film, a coating composition, and a resin laminate having good adhesion to a resin substrate (particularly a polycarbonate resin substrate) and having excellent scratch resistance and weather resistance. it can.
Furthermore, since the resin laminate of the present invention can be obtained without using a primer layer, in particular, a polycarbonate resin laminate is advantageous in terms of cost and useful as a structural member that replaces glass.

  The cured film of the present invention comprises organic ultraviolet absorbing particles having an average particle diameter of 1 to 200 nm, inorganic ultraviolet absorbing particles having an average particle diameter of 1 to 200 nm and / or colloidal silica having an average particle diameter of 1 to 200 nm. Are dispersed in a matrix having Si—O bonds. By dispersing organic ultraviolet absorbing particles, inorganic ultraviolet absorbing particles and / or colloidal silica as fine particles in the film, a cured film having excellent ultraviolet resistance and high transparency can be obtained.

A polymer ultraviolet absorber can be suitably used as the organic ultraviolet absorbing particles. Polymer ultraviolet absorbers, inorganic ultraviolet absorbing particles and colloidal silica will be described later. The average particle size of organic ultraviolet absorbing particles, inorganic ultraviolet absorbing particles and colloidal silica is a resin substrate by TEM (transmission electron microscope). It means an average value obtained by observing a cross section of the upper thermosetting film and obtained by image processing software. The average particle size of these particles is preferably 100 nm or less.

  Examples of the matrix having a Si—O bond include a Si—O condensate formed by hydrolysis / condensation reaction of an alkoxysilane compound. An organic substituent such as a Me (methyl) group may be covalently bonded to Si, or an OMe group or an OH group present due to non-condensation may be covalently bonded.

The volume ratio of the organic ultraviolet absorbing particles in the cured film is preferably 0.5 to 70% by volume, particularly 1 to 50% by volume. As a result, a cured film having high transparency and excellent ultraviolet absorption ability is obtained.
The volume fraction of the organic UV-absorbing particles is determined by observing the cross-section of the cured film on the resin substrate with a TEM (transmission electron microscope), obtaining the area% using image processing software, It means the value obtained by dividing by the value of “thickness of sample ÷ average particle diameter”.

In the cured film of the present invention, the total converted weight of the inorganic oxide derived from the Si compound, inorganic ultraviolet absorbing particles, colloidal silica and the like contained in the cured film is 30 to 80% by weight of the total weight of the cured film. It is preferable that it is and it is especially preferable that it is 40 to 80 weight%. By setting it within this range, a cured film having good film-forming properties (no cracks) and excellent scratch resistance can be obtained.
The ratio of the inorganic oxide was determined by thermogravimetrically measuring a cured film sample formed on a Teflon (registered trademark) petri dish (20 ° C./minute temperature increase under nitrogen, room temperature to 800 ° C.), and the residue at 800 ° C. Obtained from the quantity value.

The cured film of the present invention can be applied to various resin substrates to form a resin laminate. In particular, it can be suitably used for polycarbonate resin and polymethyl methacrylate (PMMA).
The polycarbonate resin base material is not particularly limited, but from a bisphenol compound represented by 2,2-bis (4-hydroxyphenyl) alkane or 2,2-bis (4-hydroxy-3,5-dihalogenophenyl) alkane. A polymer produced by a known method is used, and the polymer skeleton may contain a structural unit derived from a fatty acid diol or a structural unit having an ester bond. Although it does not specifically limit about molecular weight, From a viewpoint of extrusion moldability or mechanical strength, the thing of 10,000-50,000 is preferable at a viscosity average molecular weight, and the thing of 13,000-40,000 is more preferable. Although there is no restriction | limiting in particular about the thickness of a base material, Preferably it is the range of about 0.1-20 mm. The polycarbonate resin substrate is preferably a transparent substrate.

  In addition, you may add suitably a ultraviolet absorber, antioxidant, a heat stabilizer, a flame retardant, an inorganic filler, an antistatic agent, a heat ray shielding agent, etc. in a resin base material as needed.

  In the case of a polycarbonate laminate, in order to further improve the weather resistance, the surface of the polycarbonate resin substrate is preferably preliminarily 1 to 10 parts by weight, more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the polycarbonate resin. It is preferable to use a polycarbonate resin base material provided with 5 to 100 μm of a polycarbonate resin layer added in an amount of 5 parts by weight. Examples of the ultraviolet absorber to be used include conventionally known benzotriazole-based, benzophenone-based, salicylic acid phenyl ester-based, triazine-based, and the like. Generally, triazole-based is used.

  The method of providing the polycarbonate resin layer containing the ultraviolet absorber on the polycarbonate resin substrate is not particularly limited, but it is provided by a coextrusion method in which the polycarbonate resin and the polycarbonate resin containing the ultraviolet absorber are simultaneously melt extruded to form a sheet. It is preferable.

  In addition, although the resin laminated body of this invention is two layers of a resin base material and a coating layer, in the range which does not impair the effect of this invention, you may laminate | stack another layer suitably.

  The resin laminate of the present invention preferably has a visible light transmittance of 80% or more, more preferably 85% or more. The haze value is preferably 10% or less, more preferably 5% or less.

  The cured film of the present invention can be produced, for example, by curing the coating composition of the present invention described below.

The coating composition of the present invention includes the following components (1) to (7).
(1) Alkoxysilane compound or polyalkoxysilane compound (2) Aminosilane compound (3) Epoxysilane compound (4) Polymer ultraviolet absorbent particles (5) Curing catalyst (6) Inorganic ultraviolet absorbent particles and / or colloidal silica (7) Solvent

The alkoxysilane compound (1) is an alkoxysilane compound containing no amino group and no epoxy group, preferably a bifunctional alkoxysilane, a trifunctional alkoxysilane or a tetrafunctional alkoxysilane, more preferably a trifunctional alkoxysilane or a tetrafunctional alkoxy. Silane can be used. In addition, these may be used alone or in combination.
Trifunctional alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyl-tris (2-methoxyethoxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyl Tripropoxysilane, ethyltributoxysilane, ethyl-tris (2-methoxyethoxy) silane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltripropoxysilane, hexylriboxysilane, decyltrimethoxysilane, decyltriethoxysilane Fluorinated alkyl (trialkoxy) silanes such as decyltripropoxysilane, decyltributoxysilane, and trifluoropropyltrimethoxysilane with fluorine atoms introduced into the substituent Emissions, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, .gamma.-methacryloxypropyltrimethoxysilane, and the like. Moreover, methyldimethoxy (ethoxy) silane, ethyl diethoxy (methoxy) silane, etc. which have two types of alkoxy groups are mentioned.
Examples of the tetrafunctional alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetraisobutoxysilane.

A suitable alkoxysilane compound (1) can be represented by the following formula (1).
(R ¹ ) _m Si (OR ² ) _4-m (1)
Wherein R ¹ may be the same or different and is an alkyl group having 1 to 6 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 6 carbon atoms substituted with a methacryloxy group, a ureido group or a fluoro group. R ² is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 0, 1, or 2.)

  The polyalkoxysilane compound (1) is a compound in which the above alkoxysilane compounds are connected by a siloxane bond (Si—O bond). As specific examples, “silicate 40”, “silicate 45”, “silicate 48”, “M silicate 51”, “MTMS-A”, “MTMS-A” manufactured by Tama Chemical Industry Co., Ltd., “SS-101” manufactured by Colcoat Co., Ltd. Examples thereof include polyalkoxysilane compounds (alkoxysilicate compounds) such as “AZ-6101”, “SR2402”, and “AY42-163” manufactured by Toray Dow Corning Co., Ltd.

  The aminosilane compound (amino group-containing silane compound) (2) is an alkoxysilane compound that contains an amino group but does not contain an epoxy group. Specific examples thereof include N- (2-aminoethyl) -3-aminopropylmethyldimethoxy. Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-amino Examples include propyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, and N-methylaminopropyltriethoxysilane.

A suitable aminosilane compound (2) can be represented by the following formula (2).
(R ¹¹ ) _n Si (OR ² ) _4-n (2)
(In the formula, R ¹¹ may be the same or different, and the alkyl group having 1 to 4 carbon atoms; vinyl group; phenyl group; or methacryloxy group, amino group (—NH ₂ group), aminoalkyl group (— (CH ₂ ) _x— NH ₂ group) and an alkylamino group (—NHR group), which is an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from the group consisting of an alkyl group (—NHR group), and at least one of R ¹¹ is an amino group , An aminoalkyl group, or an alkylamino group, and an alkyl group having 1 to 3 carbon atoms, wherein x in the alkylamino group is an integer of 1 to 3, and R in the alkylamino group is carbon. 1 to 3 alkyl groups, R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or 2.)

  The epoxy silane compound (epoxy group-containing silane compound) (3) is an alkoxy silane compound containing an epoxy group but no amino group. Specific examples thereof include 3-glycidoxypropylmethyldiethoxysilane, 3-glycol. Sidoxypropylmethyldimethoxysilane (dimethoxy-3-glycidoxypropylmethylsilane), 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Examples include trimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

A suitable epoxysilane compound (3) can be represented by the following formula (3).
(R ²¹ ) _n Si (OR ² ) _4-n (3)
Wherein R ²¹ may be the same or different and is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or one or more selected from the group consisting of a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group And at least one of R ²¹ is an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or 2.)

The polymer ultraviolet absorbent particle (4) is a polymer compound having in its molecule a skeleton having the function of an ultraviolet absorbent.
For example, an acrylic monomer and other ethylenically unsaturated compounds (acrylic acid, methacrylic acid and their derivatives, styrene, etc.) having a skeleton (benzophenone series, benzotriazole series, triazine series, etc.) acting as an ultraviolet absorber in the side chain Examples are those copolymerized with vinyl acetate and the like. While conventional UV absorbers are generally low molecular weight molecules having a molecular weight of 200 to 700, the polymer UV absorber particles generally have a weight average molecular weight exceeding 10,000. Disadvantages of conventional low molecular weight ultraviolet absorbers such as compatibility with plastics and heat resistance are improved, and weather resistance can be imparted over a long period of time. The shape includes a solution system using a powder or an organic solvent such as ethyl acetate as a dispersant, an emulsion system dispersed in water, and the like. As specific examples, coating ultraviolet ray absorbent ULS700, ULS-1700, ULS383MA, ULS-1383MA, ULS-383MG, ULS-1383MG, ULS-1385MG, ULS manufactured by Otsuka Oil Co., Ltd. -635MH, ULS-933LP, ULS-935LH, ULS-1935LH, HC-935UE, XL-504, XL-524, XL-547, XL-729, XL-730, etc. Examples thereof include molecular ultraviolet absorbing resin paints NCI-905-20EM and NCI-905-20EMA (polymer ultraviolet absorbers made of a copolymer of a styrene monomer and a benzotriazole monomer).
Preferably, the dispersion medium includes water, lower alcohols such as methanol, ethanol, propanol, and 1-methoxy-2-propanol, and cellosolves such as methyl cellosolve and ethyl cellosolve. By using such a dispersion medium, the dispersibility of the polymer ultraviolet absorber is improved and sedimentation can be prevented. More preferably, the dispersion medium is water. When the dispersion medium is water, it can be advantageously used for hydrolysis and condensation reactions of silane compounds, which are necessary for forming a matrix having Si—O bonds.

The curing catalyst (5) is a catalyst for hydrolyzing and condensing (curing) the silane compounds (1) to (3). Examples thereof include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, Examples thereof include inorganic acids such as sulfamic acid, and organic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, tartaric acid, succinic acid, maleic acid, glutamic acid, lactic acid, p-toluenesulfonic acid, and citric acid.
Lithium hydroxide, sodium hydroxide, potassium hydroxide, n-hexylamine, dimethylamine, tributylamine, diazabicycloundecene, ethanolamine acetate, dimethylaniline formate, tetraethylammonium benzoate, sodium acetate, potassium acetate Organic metal salts such as sodium propionate, sodium glutamate, potassium propionate, sodium formate, potassium formate, benzoyltrimethylammonium acetate, tetramethylammonium acetate, tin octylate, tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide , aluminum triisopropoxide, aluminum _{acetylacetonate,} SnCl _4, TiCl 4, etc. Lewis acids ZnCl ₄ and the like can be mentioned, et al That.

Among these curing catalysts (5), an organic acid can be preferably used because it can be highly dispersed even when the blending amount of the polymeric ultraviolet absorbent particles (4) is increased and the transparency of the resulting film can be improved. In particular, organic carboxylic acids, especially acetic acid can be preferably used.
In addition, a curing catalyst may be used independently and may be used in combination of multiple.

  A semiconductor can be illustrated as an inorganic type ultraviolet absorptive particle (6). A semiconductor absorbs light having energy greater than the band gap, that is, ultraviolet light, and generates electrons in the conduction band and holes in the valence band. It is thought that the energy release process is converted into energy such as heat by these recombination. Titanium oxide, zinc oxide, cerium oxide, iron oxide, zirconium oxide, tungsten trioxide, strontium titanate, and the like are generally known inorganic ultraviolet absorbing particles. For example, the band gap energy of titanium oxide is 3 eV for the rutile type and 3.2 eV for the anatase type, which corresponds to light energy having wavelengths of about 410 nm and 390 nm, respectively. Light of a shorter wavelength than that, that is, ultraviolet rays can be absorbed. A rutile type is often used because it can cut longer wavelength ultraviolet rays. Conversely, light having a wavelength longer than that, that is, visible light is not essentially absorbed.

  Commercially available products can be used according to the application and production method, but as titanium oxide, "Neutral titania sol TSK-5" manufactured by Ishihara Sangyo Co., Ltd., cerium oxide is a cerium oxide-based ultraviolet ray manufactured by Taki Chemical. As the zinc oxide, such as the absorbent “Nidoral”, the aqueous dispersion type anionic emulsion Niedral P-10, the water dispersion type cationic emulsion Niedral U-15, the powder type, etc., “ZS-” manufactured by Sumitomo Osaka Cement Co., Ltd. 303 ”,“ ultrafine zinc oxide FZO ”manufactured by Ishihara Sangyo Co., Ltd., and the like. The inorganic ultraviolet absorbing particles convert ultraviolet energy into weak energy by the action of the electrons and release it. At this time, since the inorganic ultraviolet absorbing particles themselves do not cause a substance change, the effect is maintained for a long time.

  Colloidal silica (6) is also called colloidal silica or colloidal silicic acid. In water, it refers to a colloidal suspension of silicon oxide having Si—OH groups on the surface by hydration. Formed when hydrochloric acid is added to an aqueous solution of sodium silicate. Recently, new preparation methods have been developed one after another, and there are those dispersed in a non-aqueous solution and fine powders made by a gas phase method, and the particle diameters are various from several nm to several μm. In the present invention, those having an average particle diameter of 1 to 200 nm are used. In some cases, the composition of the particles is indefinite, and a siloxane bond (—Si—O—, —Si—O—Si—) is formed to form a polymer. The particle surface is porous and is generally negatively charged in water.

  Commercially available products include “Ultra High-Purity Colloidal Silica” Quartron PL Series (product names: PL-1, PL-3, PL-7) manufactured by Fuso Chemical Industry Co., Ltd. "Aqueous silica sol" (Product name: Snowtex 20, Snowtex 30, Snowtex 40, Snowtex O, Snowtex O-40, Snowtex C, Snowtex N, Snowtex S, Snowtex 20L, Snowtex OL) Etc. "or" organosilica sol (product names: methanol silica sol, MA-ST-MS, IPA-ST, IPA-ST-MS, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-MS, MIBK-ST, XBA-ST PMA-ST, DMAC-ST) or the like "are mentioned.

  Although the polymer ultraviolet absorber particles alone are excellent in ultraviolet resistance, there is a method of increasing the polymer ultraviolet absorber particle content in the cured film when durability is further required. However, it is expected that the abrasion resistance will decrease significantly. In addition, it is possible to produce a cured film only with inorganic UV-absorbing particles and / or colloidal silica, but since the flexibility of the cured film is reduced, it is difficult to prevent cracks during thermal curing. It becomes difficult to increase the thickness of the film. As a result, sufficient ultraviolet absorbing ability cannot be exhibited. In the present invention, by using both an organic ultraviolet absorber and an inorganic ultraviolet absorber and / or colloidal silica, excellent ultraviolet absorptivity can be obtained without deteriorating other properties.

The coating composition of this invention is used in the state mixed with water and / or the organic solvent. The solvent (7) used in the present invention is not particularly limited as long as the above components can be mixed uniformly. For example, water, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like can be used. Can be mentioned. Among these organic solvents, specific examples of alcohol include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, and n-octyl. Alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene monomethyl ether acetate, diacetone alcohol , Methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve and the like.
Specific examples of other solvents include cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, xylene, dichloroethane, toluene, methyl acetate, ethyl acetate, ethoxyethyl acetate, and the like. Is mentioned.
One of these may be used alone, or two or more of these may be used in combination.

Although the compounding quantity of each component (1)-(7) can be set suitably, it is as follows, for example.
Alkoxysilane compound (1): preferably 5 to 90% by weight (more preferably 10 to 90% by weight, more preferably 15 to 75% by weight) (further, tetrafunctional alkoxysilane 5 to 50% by weight (more preferably 5 to 45% by weight) trifunctional alkoxysilane 5 to 80% by weight (more preferably 5 to 40% by weight))
Aminosilane compound (2): preferably 1 to 55% by weight (more preferably 2 to 45% by weight)
Epoxysilane compound (3): preferably 1 to 60% by weight (more preferably 5 to 45% by weight)
Polymer ultraviolet absorbent particles (4): preferably 0.1 to 65% by weight (more preferably 0.1 to 50% by weight)
The curing catalyst is (5): preferably 0.1 to 30% by weight (more preferably 0.1 to 20% by weight)
When component (6) is only inorganic UV-absorbing particles: preferably 0.1 to 50% by weight (more preferably 0.1 to 30% by weight)
When component (6) is only colloidal silica: preferably 0.1 to 80% by weight (more preferably 0.1 to 50% by weight)
When component (6) is inorganic UV-absorbing particles and colloidal silica: preferably 0.1 to 50% by weight (more preferably 0.1 to 30% by weight) of inorganic UV-absorbing particles and 0 to colloidal silica .1 to 80% by weight (more preferably 0.1 to 50% by weight)
In addition, the compounding quantity of said (1)-(6) is the weight% with respect to the total amount of (1)-(6).

  When the tetrafunctional alkoxysilane exceeds 50% by weight, the film-forming property is lowered and cracking may occur. If it is less than 5% by weight, the scratch resistance may be lowered. When the trifunctional alkoxysilane is mixed in an amount exceeding 80% by weight, the scratch resistance is lowered, and when it is less than 5% by weight, the coating liquid stability may be lowered.

  When the aminosilane compound (2) is mixed in an amount exceeding 55% by weight, the film forming property is lowered, and there is a possibility that cracking occurs. If it is less than 1% by weight, adhesion, scratch resistance, and stability of the coating solution may be significantly reduced. Furthermore, about the minimum of compounding quantity, as shown in an Example, using 5 weight% or more is preferable for abrasion-resistant expression. More preferably, it is 8% by weight or more.

  When the epoxysilane compound (3) exceeds 60% by weight, the transparency, adhesion, scratch resistance, and coating solution stability of the film are deteriorated. May decrease and cracks may occur. Furthermore, about a minimum of compounding quantity, as shown in an Example, it is preferable to use 5 weight% or more for film forming property (no crack) expression. More preferably, it is 10% by weight or more.

  When the polymer ultraviolet absorbent particles (4) are mixed in an amount exceeding 65% by weight, the scratch resistance is lowered, and when it is less than 0.1% by weight, sufficient weather resistance may not be exhibited.

  When the curing catalyst (5) exceeds 30% by weight, the stability of the coating liquid may be lowered, and when it is less than 0.1% by weight, it may cause poor curing.

  If the inorganic ultraviolet absorbing particles (6) are mixed in an amount exceeding 50% by weight, the film forming property may be deteriorated. If the amount is less than 0.1% by weight, sufficient weather resistance may not be exhibited. There is.

  If the colloidal silica (6) exceeds 80% by weight, the film-forming property may be deteriorated or uniform dispersion may be difficult. If it is less than 0.1% by weight, sufficient scratch resistance is obtained. There is a risk that the effect of imparting sex may not be obtained.

  The blending amount of the solvent (7) is preferably 10 to 1000 parts by weight, more preferably 10 to 800 parts by weight, and particularly preferably 50 to 600 parts by weight with respect to 100 parts by weight of the total of the components (1) to (6). Used in part range.

In addition, the coating composition of the present invention can also contain a leveling agent and a lubricant for the cured film. Examples of such additives include a copolymer of polyoxyalkylene and polydimethylsiloxane, and polyoxyalkylene. A copolymer of fluorocarbon and the like can be used.
In addition, a light stabilizer, a weather resistance imparting agent, a colorant, or an antistatic agent can be added as necessary.

The coating composition is prepared by mixing the components (1) to (7).
Preferably, a mixed solution containing at least component (1) and component (6) is prepared, and finally component (4) is mixed.
Thus, it is preferable to prepare it separately, since the storage stability (such as non-gelling) of the coating composition is improved.

The coating composition of the present invention can be made into a cured film (cured film) by curing by a conventional method.
Specifically, a coating composition is sprayed, dipped, curtain flow, bar coater, roll coating or the like on a substrate such as a resin molded product (injection molded product, film, sheet, or the like) that is a target for forming a cured film. Is applied by a known method to form a coating film. The thickness of the coating film is adjusted so that the thickness of the cured film is preferably 1 to 15 μm, more preferably 2 to 10 μm.
Then, a cured film is obtained by heat curing for 30 to 120 minutes at appropriate curing conditions, usually 80 to 140 ° C., preferably 110 to 140 ° C.

In the cured film obtained from the coating composition of the present invention, organic ultraviolet absorbing particles (component (4)), inorganic ultraviolet absorbing particles and / or colloidal silica (component (6)) are dispersed in the film. ing. The cured film of the present invention preferably has a visible light transmittance of 80% or more, more preferably 85% or more. Moreover, Preferably a haze value is 10% or less, More preferably, it is 5% or less. Such a cured film is excellent in ultraviolet resistance and is a highly transparent cured film.
The matrix having Si—O bonds in which organic particles (component (4)) and inorganic particles and / or colloidal silica (component (6)) are dispersed is (1), (2), (3 ) Derived from ingredients.

In the examples and comparative examples, the following components were used.
Ingredient (1):
MTMS-A (Trifunctional polyalkoxysilane compound)
(Tama Chemical Industry Co., Ltd.) Lot. 030601
Solid content (non-volatile content) 67% (from manufacturer analysis table)
M silicate 51 (tetrafunctional polyalkoxysilane compound)
(Tama Chemical Industry Co., Ltd.) Lot. 03070
Solid content (non-volatile content) 51% (from manufacturer analysis table)

Ingredient (4):
ULS-1385MG (Ultraviolet absorbing skeletal species: benzotriazole)
On the other hand, manufactured by Yushi Kogyo Co., Ltd. (water dispersion / solid concentration 30%)

Ingredient (6):
Niedral U-15 (Inorganic UV-absorbing particles)
Manufactured by Taki Chemical Co., Ltd. (water dispersion, cerium oxide concentration 15% by weight, particle size manufacturer catalog value 8nm or less)
Snowtex O-40 (Colloidal Silica)
Made by Nissan Chemical Industries, Ltd. (water dispersion, colloidal silica concentration 40 wt%, particle size manufacturer catalog value 10-20 nm)

Polycarbonate substrate:
Idemitsu Kosan Co., Ltd. (formerly Idemitsu Petrochemical Co., Ltd.) IV2200R (weatherproof grade), 3 mm thick (visible light transmittance 90%, haze value 1%)

Example 1
[Preparation of coating solution]
It prepared according to the preparation amount of Table 1.
In a sample tube having a volume of 50 g, an inorganic ultraviolet absorbing particle dispersion (component (6): Nidral U-15 (water dispersion, cerium oxide concentration 15% by weight) manufactured by Taki Chemical, ethyl cellosolve (component (7)), Charge ion-exchanged water (component (7)) and stir at 700 rpm while acetic acid (component (5)), tetramethoxysilane (component (1)), 20% p-toluenesulfonic acid methanol solution (component (5)). ) In each order over 1 minute, followed by stirring at room temperature for 10 minutes to obtain solution A.
A sample tube having a volume of 20 g is charged with methyltrimethoxysilane (component (1)), ethyl cellosolve (component (7)), and 3-glycidoxypropyltrimethoxysilane (component (3)) at 500 rpm for 10 minutes. The mixture was stirred and this was designated as solution B.
After A liquid was dripped at B liquid over 2 minutes, it stirred at room temperature for 30 minutes at 700 rpm. Subsequently, 3-aminopropyltrimethoxysilane (component (2)) was added dropwise over 2 minutes, followed by stirring at room temperature for 24 hours.
Finally, while stirring, polymer ultraviolet absorbent particle nanoparticle dispersion (component (4): ULS-1385MG, manufactured by Yushi Kogyo Co., Ltd., ultraviolet absorbing skeleton species: benzotriazole, water dispersion, solid content concentration: 30% by weight The UV-absorbing monomer copolymerization ratio in the solid content: about 50% by weight) was added dropwise over 3 minutes. Then, it left still for one week at 25 degreeC in the dark place.

[Production of resin laminate]
The coating solution obtained above was applied to the surface of a polycarbonate molded body having a thickness of 3 mm with a bar coater so that the cured film had a thickness of 6 μm, and was thermally cured at 130 ° C. for 2 hours. The physical properties of the cured film thus obtained are shown in Table 1.
In the table, the content (% by weight) of the polymer ultraviolet absorber particles in the solid content is the ratio of the polymer ultraviolet absorber particles in the solid content in the coating composition.
As a result of measuring the volume fraction of the organic particles of the cured coating produced in Example 1 by the following method, it was 6% by volume. Moreover, as a result of measuring the total conversion mass of the inorganic oxide derived from Si compound and an inorganic type ultraviolet absorptive particle by the following method, it was 58 weight%.

[Evaluation method]
(1) Average particle diameter of organic particles in the cured film (in the solid content): Cross-sectional observation of the thermosetting film with TEM (transmission electron microscope), and select 10 particles present in the 1 μm square, The average particle size was determined using free software NIH Image 1.63 manufactured by NIH (National Institute of Health). In addition, the average particle diameter in Example 1-14 was 40-60 nm. Moreover, the cross-sectional photograph (magnification: 100,000 times) of the thermosetting film produced in Example 1 and Example 12 is shown in FIG.1 and FIG.2. This photograph is a TEM cross-sectional photograph of the cured film of Example 1 and Example 12. Black dots are inorganic ultraviolet absorbing particles, and white dots are organic ultraviolet absorbing particles. From the photograph, it can be seen that both particles are dispersed with a particle size of 200 nm (= 0.2 μm) or less.

(2) Average particle size of inorganic ultraviolet absorbing particles and colloidal silica in the cured film (in the solid content): measured by the same method as for organic fine particles. Both are black spots in the TEM picture. In addition, the average particle diameter of the inorganic ultraviolet absorbing particles in Examples 1 to 7, 13, and 14 was 5 to 10 nm. The average particle size of the colloidal silica in Examples 13 and 14 was 23 nm.

(3) Volume fraction of organic particles in the cured film: The volume fraction of organic particles is obtained by observing the cross section of the thermosetting film on the resin substrate with a TEM (transmission electron microscope), The area of the existing particles was obtained by calculating the area% using free software manufactured by NIH USA, and dividing the value by the value of “thickness of observation sample ÷ average particle diameter of organic particles”.

(4) Total converted weight of inorganic oxide contained in the cured film: The ratio of the oxide is determined by thermogravimetric measurement of a sample obtained by thermosetting the coating liquid on a Teflon (registered trademark) petri dish ( Under nitrogen, the temperature was raised at 20 ° C./min, room temperature to 800 ° C., and the amount was determined from the amount of residue at 800 ° C.

(5) Liquid stability: Sealed and stored for 14 days at room temperature, and the presence or absence of gelation was determined visually. About the thing which is not gelatinized, the viscosity was measured by A & D tuning fork type vibration viscometer SV-10, and the thing whose change rate from the initial stage was less than 3 times was made favorable.

(6) Appearance of the cured film: The appearance of the cured film (presence or absence of foreign matter or mottled pattern) and the presence or absence of cracks were confirmed visually.

(7) Visible light transmittance and haze of resin laminate: Measured in a state of a laminate with a polycarbonate substrate using a direct reading haze computer (manufactured by Suga Test Instruments Co., Ltd., HGM-2DP).

(8) Scratch resistance of the cured film: After 10 reciprocations with steel wool # 0000, load 500 g, 20 mm / sec, the surface damage state was visually evaluated in 4 stages.
1: Not scratched at all 2: Slightly scratched 3: Scratched half of the rubbed area 4: Scratched on the entire rubbed area

(9) Adhesion between the cured film and the resin base material: In accordance with JIS K5400, the sample was cut into 11 grids at intervals of 2 mm at intervals of 2 mm with a razor blade to make 100 grids, and a commercially available cellophane tape ( “CT-24 (width 24 mm)” (manufactured by Nichiban Co., Ltd.) was closely adhered to the belly of the finger, and then peeled off rapidly at an angle of 90 °, and the film remained without peeling off the film ( X) was displayed in X / 100.

(10) Organic chemical resistance of the cured film: 1 cc of acetone was dropped onto the cured film, and after wiping with a cloth after 5 minutes, the state of the film was visually observed to be good.

(11) Heat resistance: It was carried out under the conditions of 110 ° C. and 720 hours with a heat resistance tester (manufactured by Tabai, PS-222). The heat resistance was evaluated by the change in adhesion before and after the test.

(12) Thermal shock resistance: A thermal shock test (manufactured by ESPEC, TSA-200D-W, -30 ° C for 1 hour, 110 ° C for 1 hour for 100 cycles) was performed. The heat resistance test was evaluated by the change in adhesion between before and after the test.

(13) Weather resistance: A xenon weather test (Atlas Ci165, output 6.5 kW, black panel temperature 63 ° C., humidity 50%, 1020 hours and 1440 hours) was performed. The heat resistance was evaluated by the change in adhesion before and after the test.

(14) Organic UV-absorbing particles, inorganic UV-absorbing particles, colloidal silica (nanoparticle) dispersion structure: each particle having an average particle size of 200 nm or less is ◯, and average particle size is larger than 200 nm X, and particles having a particle size of 200 nm or less are present, but those having an amoeba shape having a particle size of 200 nm or more are indicated by Δ.

Examples 2-7
In the same manner as in Example 1, it was prepared and evaluated according to the components and preparation amounts shown in Table 1. The evaluation results are shown in Table 1.

Example 8
As the component (6), 1.25 g of colloidal silica (Snowtex O-40 manufactured by Nissan Chemical Industries, Ltd. (water dispersion, colloidal silica concentration 40% by weight)) is used instead of 3.3 g of the inorganic ultraviolet absorbing particles. The other components were prepared according to Table 2, except that a coating solution was prepared and a resin laminate was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
In the table, the inorganic oxide content (% by weight) in the solid content is the ratio of the inorganic oxide (eg, SiO ₂ , CeO ₂ ) to the solid content in the coating composition. The polymer ultraviolet absorber particle content (% by weight) in the solid content is a ratio obtained from the charging ratio of the polymer ultraviolet absorber particles in the solid content in the coating composition.
The volume fraction of the organic particles in the cured film produced in Example 8 was 8% by volume, and the total converted mass of the inorganic oxide derived from the Si compound and colloidal silica was 59% by weight.

Examples 9-12
In the same manner as in Example 8, it was prepared and evaluated according to the components and preparation amounts shown in Table 2. The evaluation results are shown in Table 2.

Example 13
As component (6), 1.25 g of colloidal silica and 2.6 g of inorganic ultraviolet absorbing particles were used in place of 3.3 g of inorganic ultraviolet absorbing particles, and other components were prepared according to Table 2 except that they were prepared according to Table 2. In the same manner as in Example 1, a coating solution was prepared, and a resin laminate was prepared and evaluated. The evaluation results are shown in Table 2.
The volume fraction of the organic particles in the cured film produced in Example 13 was 6% by volume, and the total converted mass of the inorganic oxide derived from the Si compound, colloidal silica, and inorganic ultraviolet absorbing particles was 63% by weight. .

Example 14
In the same manner as in Example 13, it was prepared and evaluated according to the components and preparation amounts shown in Table 2. The evaluation results are shown in Table 2.

Comparative Examples 1-8
In the same manner as in Example 1, it was prepared and evaluated according to the components and preparation amounts shown in Tables 3 and 4. The evaluation results are shown in Tables 3 and 4. In Comparative Example 4 and Comparative Example 8, the visible light transmittance and haze could not be measured.

  From Examples 1-14, it can be seen that the coating compositions of the present invention have good storage stability. In addition, the cured film of the present invention formed by applying and curing this on a polycarbonate resin substrate has no cracks or mottled patterns, and has transparency, scratch resistance, adhesion to the resin substrate, and organic chemical resistance. It turns out that it is excellent in property. Furthermore, the cured film has an adhesion property to the resin base material even when left at 110 ° C. for 720 hours, when the low temperature / high temperature environment is alternately cycled (−30 ° C. to 110 ° C.) for 100 cycles, and when left for a long time. It was confirmed that there was no change.

  The cured films of Comparative Examples 1 and 6, which were formed by applying a coating composition containing no polymer ultraviolet absorbent particles (component (4)) on a polycarbonate resin substrate and curing, were impacted many times at -30 ° C. When cracked, cracking occurred and the thermal shock resistance was poor.

  A cured film of Comparative Examples 2 and 5 formed by applying a coating composition not containing inorganic ultraviolet absorbing particles and colloidal silica (component (6)) on a polycarbonate resin substrate and curing the coating composition was 1440 hours, It was confirmed that the adhesiveness was lowered when held in an environment of Atlas Ci165, output 6.5 kW, black panel temperature 63 ° C., humidity 50%).

  The cured films of Comparative Examples 3 and 7 formed by applying and curing a coating composition not containing an aminosilane compound (component (2)) on a polycarbonate resin substrate are inferior in terms of haze and scratch resistance. there were.

  The cured film of Comparative Examples 4 and 8 formed by applying a coating composition not containing an epoxy silane compound (component (3)) on a polycarbonate resin substrate and curing it was cracked immediately after curing, Transparency and adhesion could not be measured. Moreover, since the film-forming property (cracking) was poor, it was not possible to prepare a sample for observing the cross section of the cured film, and the average particle size of particles in the cured film could not be measured.

  The present invention includes automobile interior parts such as meter covers, windshields for motorcycles and tricycles, resin automobile windows (various vehicle windows), plastic building material windows, roofs for construction machinery, road light transmission boards (sound insulation boards), and corrections. In addition to eyeglass lenses such as sunglasses, sports, safety glasses, etc., optical discs, displays, mobile phone parts, lighting parts such as street lights, windshields, various resin materials for protective shields, especially polycarbonate materials Development is possible, and it can be suitably used as a glass substitute member.

2 is a cross-sectional photograph of a cured film produced in Example 1. 2 is a cross-sectional photograph of a cured film produced in Example 12.

Claims (17)

A coating composition comprising the following components (1) to (7).
(1) An alkoxysilane compound represented by the following formula (1) or a polyalkoxysilane compound in which the alkoxysilane compound is connected by a siloxane bond (Si—O bond)
(R ¹ ) _m Si (OR ² ) _4-m (1)
Wherein R ¹ may be the same or different and is an alkyl group having 1 to 6 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 6 carbon atoms substituted with a methacryloxy group, a ureido group or a fluoro group. R ² is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 0, 1, or 2.)
(2) Aminosilane compound represented by the following formula (2)
(R ¹¹ ) _n Si (OR ² ) _4-n (2)
(In the formula, R ¹¹ may be the same or different and is an alkyl group having 1 to 4 carbon atoms; vinyl group; phenyl group; or methacryloxy group, amino group, aminoalkyl group represented by NH ₂ — (CH ₂ ) _x —. , R 1 -NH- represents an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from the group consisting of alkylamino groups, and at least one of R ¹¹ is an amino group, an aminoalkyl group , An alkyl group having 1 to 3 carbon atoms substituted with any of the alkylamino groups, x in the alkylamino group is an integer of 1 to 3, and R in the alkylamino group is an alkyl group having 1 to 3 carbon atoms. An alkyl group, R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or 2.)
(3) Epoxysilane compound represented by the following formula (3)
(R ²¹ ) _n Si (OR ² ) _4-n (3)
Wherein R ²¹ may be the same or different and is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or one or more selected from the group consisting of a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group And at least one of R ²¹ is an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or 2.)
(4) Polymer ultraviolet absorbent particles (5) Curing catalyst (6) Inorganic ultraviolet absorbent particles and / or colloidal silica (7) Solvent R in formula (1) ¹ May be the same or different and is an alkyl group having 1 to 6 carbon atoms,
  R in formula (2) ¹¹ , Which may be the same or different, an alkyl group having 1 to 4 carbon atoms; or an amino group, NH ₂ -(CH ₂ ) _x An alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from the group consisting of an alkylamino group represented by R-NH-; ¹¹ At least one of these is an alkyl group having 1 to 3 carbon atoms substituted with any of an amino group, an aminoalkyl group, and an alkylamino group,
  R in formula (3) ²¹ , Which may be the same or different, and an alkyl group having 1 to 4 carbon atoms; or an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from the group consisting of a glycidoxy group and a 3,4-epoxycyclohexyl group R and R ²¹ 2. The coating composition according to claim 1, wherein at least one of is a C 1-3 alkyl group substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. The coating composition according to claim 1 or 2, wherein a blending amount of the components (1) to (7) is in the following range.
Component (1): 10 to 90% by weight
Component (2): 1 to 55% by weight
Ingredient (3): 1 to 60% by weight
Ingredient (4): 0.1 to 65% by weight
Ingredient (5): 0.1 to 30% by weight
Ingredient (6):
When component (6) is only inorganic UV-absorbing particles, 0.1 to 50% by weight
When component (6) is only colloidal silica, 0.1 to 80% by weight
When the component (6) is inorganic ultraviolet absorbing particles and colloidal silica, the inorganic ultraviolet absorbing particles are 0.1 to 50% by weight, and the colloidal silica is 0.1 to 80% by weight.
Component (7): 10 to 1000 parts by weight when the total of components (1) to (6) is 100 parts by weight The coating composition according to claim 1 , wherein the curing catalyst is an organic acid. The coating composition according to claim 1, wherein the curing catalyst is acetic acid. 6. The polymer ultraviolet absorber particle is obtained by copolymerizing an acrylic monomer having a benzophenone-based, benzotriazole-based, or triazine-based skeleton in a side chain with another ethylenically unsaturated compound. A coating composition according to any of the above. The coating composition according to any one of claims 1 to 6, wherein the polymer ultraviolet absorber particles have a weight average molecular weight exceeding 10,000. The polymer ultraviolet absorber particles have an average particle size of 1 to 200 nm,
  The coating composition according to any one of claims 1 to 7, wherein the inorganic ultraviolet absorbing particles and / or colloidal silica has an average particle size of 1 to 200 nm. A cured film obtained by curing the coating composition according to claim 1 . The cured film according to claim 9 , wherein the volume fraction of the polymer ultraviolet absorbent particles in the cured film is 0.5 to 70% by volume. The resin laminated body which formed the cured film of Claim 9 or 10 on the resin base material. The resin laminate according to claim 11 , wherein the haze is 10% or less. The resin laminate according to claim 12 , which has a visible light transmittance of 80% or more. The manufacturing method of the coating composition in which the following component (4) and (6) are disperse | distributing prepared by mixing the following component (1)-(7).
(1) An alkoxysilane compound represented by the following formula (1) or a polyalkoxysilane compound in which the alkoxysilane compound is connected by a siloxane bond (Si—O bond)
(R ¹ ) _m Si (OR ² ) _4-m (1)
Wherein R ¹ may be the same or different and is an alkyl group having 1 to 6 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 6 carbon atoms substituted with a methacryloxy group, a ureido group or a fluoro group. R ² is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 0, 1, or 2.)
(2) Aminosilane compound represented by the following formula (2)
(R ¹¹ ) _n Si (OR ² ) _4-n (2)
(In the formula, R ¹¹ may be the same or different and is an alkyl group having 1 to 4 carbon atoms; vinyl group; phenyl group; or methacryloxy group, amino group, aminoalkyl group represented by NH ₂ — (CH ₂ ) _x —. , R 1 -NH- represents an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from the group consisting of alkylamino groups, and at least one of R ¹¹ is an amino group, an aminoalkyl group , An alkyl group having 1 to 3 carbon atoms substituted with any of the alkylamino groups, x in the alkylamino group is an integer of 1 to 3, and R in the alkylamino group is an alkyl group having 1 to 3 carbon atoms. An alkyl group, R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or 2.)
(3) Epoxysilane compound represented by the following formula (3)
(R ²¹ ) _n Si (OR ² ) _4-n (3)
Wherein R ²¹ may be the same or different and is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or one or more selected from the group consisting of a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group And at least one of R ²¹ is an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or 2.)
(4) Polymer ultraviolet absorbent particles (5) Curing catalyst (6) Inorganic ultraviolet absorbent particles and / or colloidal silica (7) Solvent R in formula (1) ¹ May be the same or different and is an alkyl group having 1 to 6 carbon atoms,
  R in formula (2) ¹¹ , Which may be the same or different, an alkyl group having 1 to 4 carbon atoms; or an amino group, NH ₂ -(CH ₂ ) _x An alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from the group consisting of an alkylamino group represented by R-NH-; ¹¹ At least one of these is an alkyl group having 1 to 3 carbon atoms substituted with any of an amino group, an aminoalkyl group, and an alkylamino group,
  R in formula (3) ²¹ , Which may be the same or different, and an alkyl group having 1 to 4 carbon atoms; or an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from the group consisting of a glycidoxy group and a 3,4-epoxycyclohexyl group R and R ²¹ The method for producing a coating composition according to claim 14, wherein at least one of these is a C 1-3 alkyl group substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. Producing a mixed solution containing at least component (1) and component (6);
The method for producing a coating composition according to claim 14 or 15 , wherein the component (4) is finally mixed. The manufacturing method of the cured film which heats and cures the coating composition in any one of Claims 14-16 .