JP6192556B2 - Curable resin composition, cured film thereof, and decorated glass plate provided with the same - Google Patents

Description

  The present invention relates to a curable resin composition (hereinafter also simply referred to as “resin composition”), a cured film thereof, and a decorative glass plate provided with the same, and more specifically, lamination of a decorative layer formed by screen printing. It is related with the white curable resin composition which can form the decorating part which has sufficient light-shielding property, reducing the number and laminated film thickness, its cured film, and the decorating glass plate provided with this.

  2. Description of the Related Art In recent years, touch panel type input devices (hereinafter also simply referred to as “touch panels”) have been adopted for operation units of various electronic devices such as mobile phones, portable information terminals, and car navigation systems. The touch panel is used as an input device that detects a contact position of a fingertip or a pen tip on a display surface of a display panel such as a liquid crystal display device. There are various types of touch panels such as a resistance film type and a capacitance type depending on the structure and detection method.

  A capacitive touch panel has a matrix-like translucent conductive film formed on a single glass substrate, and is sensitive to changes in capacitance induced by the contact of a finger or the like between the electrodes. The position to be touched on the touch panel is specified by detecting it as a current change, and there is an advantage that it has a higher transmittance than the resistance film type input device conventionally used.

  A liquid crystal display device including a touch panel is generally mounted and fixed on a polarizing plate of a display panel of the liquid crystal display device. A method of fixing a touch panel by laying cushion rubber with an adhesive or a display panel A method of sticking the entire surface of the touch panel with a transparent adhesive or the like is employed (for example, see Patent Document 1).

  By the way, when viewing the display unit from the user side in a mobile phone or the like, information and images are not displayed on the entire surface of the cover glass. There is a display in this frame. This frame part is called a decoration part, and the display part is formed in a predetermined shape such as a quadrangular shape, and parts that are inconvenient if the touch panel wiring part or the wiring part of the display device are visible are not visible. A concealing function is required.

  Conventionally, the cover glass decorated and the touch panel sensor are manufactured separately, and finally pasted and integrated. On the other hand, in recent years, a decorative cover that provides a touch panel sensor to a cover glass by forming a transparent conductive film such as ITO (indium tin oxide) after forming a decorative part on the cover glass for the purpose of thinning the touch sensor. A glass-integrated touch panel sensor structure has been proposed (see, for example, Patent Document 2).

JP 09-274536 A JP 2012-226688 A

  As described above, the decoration part formed on the glass substrate is required to play a role of hiding the wiring part of the display device. Is also required. For this reason, when forming a decoration part by screen printing, in order to improve light-shielding property, the light-shielding characteristic requested | required by laminating | stacking several decoration layers is seen. In particular, with white decoration, it is difficult to ensure light-shielding properties, so it is necessary to increase the thickness of the decoration layer. For example, when an optical density characteristic value OD (optical density) value of about 4 to 5 or more is required, a white decorative ink formed by a screen printing method needs to be stacked about 80 to 120 μm or more.

  However, when a plurality of decorative layers are stacked, the thickness of the decorative part increases, and the step of the decorative part becomes a barrier during resist application in each process by spin coating in the touch panel sensor formation process. Kelamula and the like occur in the film, making it difficult to ensure good coating quality. Moreover, when light-shielding property is implement | achieved combining a light-shielding layer, the white decorating layer needs the high concealment property which cannot see through the color of a light-shielding layer. Furthermore, in the touch panel sensor formation process, if various resists are not uniformly applied over the entire glass substrate, the touch panel sensor cannot be normally operated as a result of the wiring formation of the touch panel sensor failing and disconnection. Furthermore, when heat treatment is performed in a subsequent process such as ITO deposition, there is a problem that the concealment problem becomes remarkable.

  Accordingly, an object of the present invention is to provide a white curable resin composition capable of forming a decorative portion having sufficient light shielding properties while reducing the number of decorative layers to be formed by screen printing and the laminated film thickness. It is providing a decorative film board provided with the thing, its cured film, and this.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a predetermined titanium oxide as a white pigment, and have completed the present invention.

  That is, the curable resin composition of the present invention comprises (A) a carboxyl group-containing resin, (B) a thermosetting component, (C) a multi-processed rutile titanium oxide, and (D) a thermosetting catalyst. And containing.

  In the resin composition of the present invention, the oil absorption amount of the (C) multi-processed rutile type titanium oxide is preferably 25 mL / 100 g or more. Moreover, it is preferable that the said (B) thermosetting component is an epoxy compound.

  The cured film of the present invention is obtained by curing the curable resin composition of the present invention.

  The decorative glass plate of the present invention comprises the cured film of the present invention.

  According to the present invention, a white curable resin composition capable of forming a decorative part having sufficient light-shielding properties while reducing the number of laminated decorative layers formed by screen printing and the laminated film thickness, The cured film and a decorative glass plate provided with the same can be provided. Furthermore, good concealment can be obtained even if heat treatment is performed.

It is a graph which shows (DELTA) E * ab of Examples 1-4 and Comparative Examples 1-4 with and without the light shielding layer. It represents the level of concealment.

Hereinafter, embodiments of the present invention will be described in detail.
The curable resin composition of the present invention includes (A) a carboxyl group-containing resin, (B) a thermosetting component, (C) a multi-processed rutile titanium oxide, (D) a thermosetting catalyst, Containing. By including (C) multi-processed rutile-type titanium oxide as a white pigment, even if it is a thin layer, a decorative layer having sufficient shielding properties and light shielding properties can be formed. Hereinafter, (A) carboxyl group-containing resin, (B) thermosetting component, (C) multi-processed rutile titanium oxide, and (D) thermosetting catalyst will be described in detail.

<(A) Carboxyl group-containing resin>
In the curable resin composition of the present invention, as the (A) carboxyl group-containing resin, a resin having a carboxyl group in the molecule and not having a photosensitive group such as an ethylenically unsaturated bond is preferably used. Can do.

  Specific examples of such carboxyl group-containing resins include, for example, the following compounds (any of oligomers and polymers). Of these, styrene copolymers are preferred. For example, containing non-photosensitive carboxyl group obtained by copolymerization of unsaturated carboxylic acid such as (meth) acrylic acid and unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, isobutylene Resin. The lower alkyl refers to an alkyl group having 1 to 5 carbon atoms.

<(B) thermosetting component>
In the curable resin composition of the present invention, the thermosetting component (B) is a component for imparting heat resistance, and for example, an epoxy compound, a polyfunctional oxetane compound, or an oxazoline compound can be used. In particular, epoxy compounds are preferred. In the resin composition of the present invention, only one thermosetting component may be used, or two or more thermosetting components may be used in combination.

  Epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, cresol novolac type epoxy compounds, phenol novolac type epoxy compounds, glycidyl ester type epoxy compounds obtained by reacting polybasic acid compounds with epichlorohydrin. And known and commonly used epoxy resins such as glycidyl ether type epoxy compounds and alicyclic epoxy compounds. From the viewpoint of further increasing the strength of the cured film and heat yellowing resistance, the epoxy compound is preferably a bisphenol A type epoxy resin or a hydrogenated bisphenol A type epoxy resin.

  The epoxy equivalent of the epoxy compound is preferably 100 or more and 1,000 or less. By setting the epoxy equivalent to 100 or more, workability is improved with less thickening during printing. Moreover, the intensity | strength of a cured film can be raised further by making an epoxy equivalent into 1,000 or less.

  Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3- Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3- In addition to polyfunctional oxetanes such as oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin , Poly (p-hydroxystyrene), cardo-type bis Phenol ethers, calixarenes, calix resorcin arenes, etherified products such as the resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the oxazoline compound include 2-methyloxazoline, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2. -Oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2,2,4-trimethyl- 2-oxazoline, 2-isopropyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,2′-bis (2-oxazoline), 2,2 ′-(1,3-phenylene) bis (2-oxazoline) Etc. Examples of commercially available products include K-2010E, K-2020E, K-2030E, WS-500, WS-700, and RPS-1005 of Epocross (manufactured by Nippon Shokubai Co., Ltd.).

  (B) The compounding quantity of a thermosetting component is suitably adjusted so that it may harden | cure moderately by provision of heat, and is not specifically limited. (A) The blending amount of the thermosetting component (B) is preferably 10 parts by mass or more and 100 parts by mass or less, more preferably 20 parts by mass or more and 90 parts by mass or less, more preferably 100 parts by mass of the carboxyl group-containing resin. Is 25 parts by mass or more and 85 parts by mass or less. (B) If the compounding quantity of a thermosetting component shall be said range, a resin composition will harden | cure more effectively by heating and the heat resistance of a cured film will become still higher.

<(C) Multi-processed rutile titanium oxide>
The curable resin composition of the present invention contains (C) multi-processed rutile titanium oxide as a white pigment. Here, multi-processing means that the surface of rutile titanium oxide is coated with alumina or silica. Since this (C) multi-processed rutile type titanium oxide has a large amount of oil absorption, a cured film using this has high concealability due to the dry hide effect. Therefore, the thickness of the decoration part can be made thin. Here, the dry hydride effect means that the layer surrounding the titanium oxide particles, which are white pigments, contains air (refractive index 1.0) and resin (refractive index of about 1.4 to 1.6). This means that the refractive index (apparent refractive index) is greatly reduced and the light diffusion performance is improved. In addition, the concealability that causes a problem when heat treatment is performed can also be improved by using the titanium oxide.

  In the resin composition of the present invention, the oil absorption of (C) multi-processed rutile titanium oxide is preferably 25 mL / 100 g or more. By setting the oil absorption amount to 25 mL / 100 g or more, the concealing property of the decorative part due to the dry hide effect can be obtained particularly well. Here, the oil absorption is the consumption capacity of refined sesame oil with respect to 100 g of the sample pigment in the test method of JIS K5101-13-1.

  In the resin composition of the present invention, a rutile type is used as multi-processed titanium oxide. Anatase-type titanium oxide has higher reflectivity on the short wavelength side in the ultraviolet region than rutile type, so it is desirable as a reflectivity, but it has photocatalytic activity and therefore causes discoloration of the resin in the composition. There is. On the other hand, rutile titanium oxide has a lower whiteness than the anatase type but has a lower reflectance on the short wavelength side of the ultraviolet region, but has almost no photoactivity, so it can suppress deterioration of the resin. And a stable cured film can be obtained. In the resin composition of the present invention, the rutile type titanium oxide may be either produced by the chlorine method or produced by the sulfuric acid method. As the multi-processed rutile type titanium oxide, Taipure R-931 (manufactured by DuPont), TITON R-7E (manufactured by Sakai Chemical Industry Co., Ltd.) or the like can be used.

  (C) The compounding quantity of the multi-processed rutile type titanium oxide is preferably 50 to 350 parts by mass, more preferably 100 to 300 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. By making a compounding quantity into 350 mass parts or less, it can prevent that a hardened film becomes weak, preventing the deterioration of a dispersibility. Further, when the amount is 50 parts by mass or more, a sufficient hiding power can be obtained and the color of the light shielding layer can be prevented from being seen through.

<(D) Thermosetting catalyst>
The resin composition of the present invention contains (D) a thermosetting catalyst. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2 Imidazole derivatives such as -cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, Examples include amine compounds such as 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Besides these, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl- S-triazine derivatives such as 4,6-diamino-S-triazine / isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used. In particular, it is preferable to use triphenylphosphine as a thermosetting catalyst because yellowing can be prevented even when the cured film is exposed to a high temperature of 200 ° C. or higher.

  Examples of commercially available thermosetting catalysts include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N manufactured by San Apro, U -CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. These may be used alone or in admixture of two or more.

  In the resin composition of this invention, the compounding quantity of (D) thermosetting catalyst has preferable 0.1-10 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin. (D) By making the compounding quantity of a thermosetting catalyst into the said range, the stability at the time of storage and the hardening characteristic of a resin composition can be made compatible with balance. More preferably, it is 0.1-5.0 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin.

<Photopolymerization initiator>
The resin composition of the present invention may contain a photopolymerization initiator. By adding a photopolymerization initiator, the resin composition of the present invention can be used not only for heat curing but also for photocuring. As the photopolymerization initiator, any known photopolymerization initiator can be used. Among them, an α-aminoacetophenone photopolymerization initiator and an acylphosphine oxide photopolymerization initiator are preferable. A photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type.

<Photopolymerization initiation aid or sensitizer>
In addition to the photopolymerization initiator, in the resin composition of the present invention, a photoinitiator aid or a sensitizer may be used. Examples of the photoinitiation assistant or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. These compounds may be used as a photopolymerization initiator in some cases, but are preferably used in combination with a photopolymerization initiator. Moreover, a photoinitiator auxiliary or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

<Filler>
In order to increase the physical strength of the resulting cured product, the resin composition of the present invention may contain a filler as necessary. As such a filler, a well-known inorganic or organic filler can be used, for example, barium sulfate, spherical silica, or talc can be used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as metal oxides and aluminum hydroxide can be used as extender pigment fillers.

<Antioxidant>
In the resin composition of the present invention, in order to prevent oxidation, a radical scavenger that invalidates the generated radicals and the generated peroxide are decomposed into harmless substances so that no new radicals are generated. An antioxidant such as a peroxide decomposing agent can be contained. The antioxidant used in the present invention can prevent oxidative deterioration of a resin or the like and suppress yellowing. An antioxidant may be used individually by 1 type and may be used in combination of 2 or more type.

<Ultraviolet absorber>
In general, a polymer material absorbs light, thereby causing degradation / degradation. Therefore, in addition to an antioxidant, an ultraviolet absorber is added to the resin composition of the present invention in order to take a countermeasure against stabilization of ultraviolet rays. Can be used. In addition, a ultraviolet absorber may be used individually by 1 type, and may be used in combination of 2 or more type. The combined use of the ultraviolet absorber and the antioxidant can stabilize the cured film obtained from the resin composition of the present invention.

<Additives>
The resin composition of the present invention may further include, as necessary, known and commonly used colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, and hydroquinone. , Hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine and other known and conventional thermal polymerization inhibitors, fine silica, organic bentonite, montmorillonite and other known and commonly used thickeners, silicone-based, fluorine-based, polymer-based, etc. One or more known and commonly used additives such as an anti-foaming agent, a leveling agent, an adhesion imparting agent such as an imidazole, thiazole, triazole, or silane coupling agent can be blended.

<Organic solvent>
The resin composition of the present invention can use an organic solvent for adjusting the viscosity when adjusting the composition. Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propanol Ethylene glycol, or propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, petroleum solvents such as solvent naphtha. Such an organic solvent may be used individually by 1 type, and may be used as a 2 or more types of mixture.

  The resin composition of the present invention contains (A) a carboxyl group-containing resin, (B) a thermosetting component, (C) a multi-processed rutile titanium oxide, and (D) a thermosetting catalyst. It is only important to do so, and there are no other restrictions. For example, the resin composition of the present invention may be used as a one-component resin composition in which the components (A) to (D) are mixed. From the viewpoint of storage stability, the component (A) and the component (B) It is preferable to separate the components into a two-component resin composition.

Next, the cured film of the present invention will be described.
The cured film of the present invention is obtained by curing the curable resin composition of the present invention. Since the resin composition of the present invention contains (C) multi-processed rutile-type titanium oxide, the resulting cured film is excellent in concealability and light shielding properties. Therefore, the resin composition of this invention can be used suitably for the decorating part of touchscreen parts, such as an electronic device. In addition, the cured film of the present invention includes not only those obtained by thermally curing the cured composition of the present invention, but also includes a photographic development method in which unnecessary unexposed portions are removed by development by selective photocuring. Even if it is a case, it is preferable to carry out thermosetting after photocuring. This is because the curable resin composition of the present invention can exhibit sufficient curing characteristics by thermosetting.

  When the resin composition of the present invention is thermally cured, the resin composition may be about 100 to 250 ° C., preferably about 100 to 200 ° C. When photocured, an exposure machine equipped with a metal halide lamp, ( An exposure machine equipped with an ultra-high pressure mercury lamp, an exposure machine equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high-pressure mercury lamp can be used.

  As an adherend of the resin composition of the present invention, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin, glass cloth / paper-epoxy resin, Synthetic fiber-epoxy resin, copper-clad laminates of all grades (FR-4 etc.) using composite materials such as fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide and cyanate ester, polyimide film, PET film, glass substrate, A ceramic substrate, a wafer plate, or the like can be used.

  As described above, since the resin composition of the present invention is excellent in concealing property and light shielding property, it can be suitably used for a decoration part of a touch panel part such as an electronic device. Therefore, a glass plate is used as an adherend. Is preferred. In this case, the glass substrate can be made of a glass having a good transparency equivalent to that of a substrate glass for a flat display device such as a general float glass or a liquid crystal panel. Thus, it is desirable to use a tempered glass having a high surface compressive stress. Tempered glass has a compressive stress layer formed on the surface by ion exchange or air-cooling tempering methods, etc., but it has an asymmetric cut surface in the thickness direction by processing from one side with a diamond cutter or laser cutter. If made, cracks are likely to occur. For this reason, it is desirable to devise further in the process of dividing the cover glass described later.

  When the resin composition of the present invention is applied to an adherend, for example, the viscosity is adjusted to an application method with an organic solvent, and a dip coating method, a flow coating method, a roll coating method, a bar coater is formed on a substrate. The organic solvent contained in the composition may be volatilized and dried (temporarily dried) at a temperature of about 60 to 100 ° C.

Next, the decorative glass plate of the present invention will be described.
The decorated glass plate of the present invention is provided with the cured film of the resin composition of the present invention on a glass substrate, and is suitably suitable as a cover glass for touch panels of electronic devices and the like as described above. . The decoration pattern can be easily formed by using a printing method, and an arbitrary pattern can be formed on one side of the cover glass 1 by a screen printing method using a screen ink. The screen printing method is most suitable for forming a thick film with high light shielding properties such as a frame pattern. However, the present invention is not limited to this, and other printing methods, photolithography methods, transfer methods, etc. can be used if necessary. .

  The decorated glass plate of the present invention is not particularly limited except that it is formed by forming a cured film of the resin composition of the present invention on a glass substrate, and can be used for any application. In particular, since the resin composition of the present invention is excellent in concealability and light shielding properties, the decorative glass plate of the present invention is suitable for touch panels such as electronic devices, but when it contains a photopolymerization initiator. However, the present invention is not necessarily limited to this, and it can also be used for decoration applications that do not require high temperatures.

  Hereinafter, the present invention will be described in more detail with reference to examples.

<Synthesis of carboxyl group-containing resin solution>
In a 2,000 ml flask equipped with a stirrer and a condenser, 377 g of tripropylene glycol monomethyl ether was placed and heated to 90 ° C. under a nitrogen stream. A mixture of 100.7 g of styrene, 246.5 g of methacrylic acid, and 20.7 g of dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd .: V-601) was dissolved for 4 hours. Over the flask. In this way, a carboxyl group-containing resin solution was obtained. This carboxyl group-containing resin solution has a solid content acid value of 120 mgKOH / g, a solid content of 50%, and a molecular weight of 20,000. In addition, the mass average molecular weight of the obtained carboxyl group-containing resin was obtained by connecting three pumps LC-6AD manufactured by Shimadzu Corporation and columns Shodex (registered trademark) KF-804, KF-803, and KF-802 manufactured by Showa Denko. It was measured by high performance liquid chromatography.

<Examples 1-4 and Comparative Examples 1-4>
Curable resin compositions having the compositions shown in Tables 1 and 2 below were prepared. In addition, the unit of each component in the table | surface is a mass part, and what was synthesize | combined by the synthesis | combination of said carboxyl group containing resin solution was used as carboxyl group containing resin. Next, each obtained curable resin composition was apply | coated by the screen method on the soda-lime glass (made by Central Glass Co., Ltd.) of thickness 1.0mm. Thereafter, the organic solvent was removed by drying at 90 ° C. for 10 minutes. This operation was repeated twice, and the white decorative layer was printed on the glass substrate.

  Next, a black light shielding layer was printed on the white decorative layer by a screen method and dried at 90 ° C. for 10 minutes. Thereafter, heat was applied at 150 ° C. for 60 minutes to produce a decorative glass plate for evaluation. In addition, the composition of the composition used for the black light shielding layer is as follows.

(A) Carboxyl group-containing resin: manufactured by <Synthesis of carboxyl group-containing resin solution> (solid content 50% by mass)
(B) Thermosetting component 1: JER828 (bisphenol A type) manufactured by Mitsubishi Chemical Corporation
(B) Thermosetting component 2: Mitsubishi Chemical Corporation YX-8034 (hydrogenated bisphenol A type)
(C) Multi-processed rutile titanium oxide 1: Oil absorption 35.9 ml / 100 g
(C) Multi-processed rutile titanium oxide 2: Oil absorption 27-31 ml / 100 g
Rutile type titanium oxide 1: Oil absorption 19ml / 100g
Rutile-type titanium oxide 2: Oil absorption 19-21 ml / 100 g
(D) Thermosetting catalyst 1: Dicyandiamide (D) Thermosetting catalyst 2: Melamine (D) Thermosetting catalyst 3: Triphenylphosphine Antifoaming agent: Shin-Etsu Chemical Co., Ltd .: KS-66 (silicon-based antifoaming agent)
Wetting and dispersing agent: BYK-111 manufactured by Big Chemie
Antioxidant: IRGANOX1010 manufactured by BASF
Solvent: MFTG (methylpropylene triglycol) manufactured by Nippon Emulsifier Co., Ltd.

Composition of black light shielding layer Carboxyl group-containing resin solution: 100 parts by mass (solid content 50% by mass) of carboxyl group-containing resin solution produced in <Synthesis of carboxyl group-containing resin solution>
Thermosetting component: JER828 (bisphenol A type) 8 parts by mass Triphenylphosphine 0.6 parts by mass Black pigment: 75 parts by mass of cobalt trioxide powder Rutile type titanium oxide: CR-58 (by Ishihara Sangyo Co., Ltd.) Chlorine method rutile type titanium oxide) 75 parts by mass Solvent: MFTG (methylpropylene triglycol) 12 parts by mass manufactured by Nippon Emulsifier Co., Ltd. BYK-111 6 parts by mass manufactured by Big Chemie

  Using the obtained decorative glass plate for evaluation, the shielding property of the light shielding layer, the adhesion of the cured film, and the heat resistance were evaluated. In addition, the following procedure evaluated the concealability of the light shielding layer, and the adhesiveness of the cured film.

<Concealment of light shielding layer>
The color difference ΔE * ab was calculated when the sample was viewed from the glass substrate side with and without the black light-shielding layer (before and after the black decorative layer was formed). ΔE ^* ab is a difference between the L ^* a ^* b ^* color system with and without the light-shielding layer, and the smaller the value, the more transparent the light-shielding layer cannot be seen. The calculation formula of ΔE ^* ab is as follows.
ΔE ^* ab = [(L ^{* 2−} L ^{* 1} ) ² + (a ^{* 2−} a ^{* 1} ) ² + (b ^{* 2−} b ^{* 1} ) ² ] ^1/2
In the formula, L ^{* 1} , a ^{* 1} , and b ^{* 1} represent L ^* , a ^* , and b ^* , respectively, when there is a light shielding layer, and L ^{* 2} , a ^{* 2} , and b ^{* 2} each represent a light shielding layer. The values of L ^* , a ^* , and b ^{* when} no is present. The case where ΔE * ab <0.5 (corresponding to the case where the black light-shielding layer is not visible) was marked with ◯, and the case where ΔE * ab> 2.0 (corresponding to the case where the black light-shielding layer was visible) was marked with ×. The obtained results are also shown in Tables 3 and 4. Incidentally, in calculating the Delta] E * ab, first, using a Konica Minolta color difference meter ^{CR-400, L * a *} b * color system sample in the absence of the sample and the light shielding layer in the case where there is a light shielding layer Each L ^* , a ^* , b ^* value was measured.

<Adhesion (cross-cut adhesion)>
Based on JISK5400, 100 mm grids (10 × 10) of 1 mm are made on the film of each sample, and a transparent adhesive tape (made by Nichiban Co., width: 18 mm) is completely attached on the grids, and the tape is immediately applied. While keeping one end of the substrate at a right angle to the glass substrate, it was pulled away instantaneously, and the number of grids remaining without being completely peeled was examined. The evaluation criteria are as follows. The obtained results are also shown in Tables 3 and 4.
○: No peeling occurred on the grid.
X: Peeling occurred on the grid.

As can be seen from Tables 3 and 4, the examples using the multi-processed rutile-type titanium oxide exhibit a sufficient hiding property even if the white decorative layer is a thin layer. Also, a multi-processing processed rutile titanium oxide, when used in combination with triphenyl phosphine as a thermosetting catalyst, change in color of the cured film by heating (Delta] E * ^ab- before heat treatment Delta] E * ^ab after heat treatment) It can be seen that it is possible to significantly reduce. In addition, in FIG. 1, the graph which shows (DELTA) E * ab with and without the light shielding layer of Examples 1-4 and Comparative Examples 1-4 is shown.

Claims (4)

(A) a carboxyl group-containing resin, (B) a thermosetting component, (C) a rutile-type titanium oxide surface-treated with alumina and / or silica, and (D) a thermosetting catalyst .
As said (B) thermosetting component, it contains any one or more of an epoxy compound, a polyfunctional oxetane compound and an oxazoline compound,
(C) A curable resin composition, wherein the rutile-type titanium oxide surface-treated with alumina and / or silica has an oil absorption of 25 mL / 100 g or more (excluding 25 mL / 100 g) . The (B) thermosetting component, the curable resin composition of claim 1 wherein the epoxy compound. Cured film curable tree composition of claim 1 or 2 wherein, characterized in that the formed by curing. A decorative glass plate comprising the cured film according to claim 3 .

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