JP6129092B2 - 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, applied with excellent adhesion to a glass substrate. The present invention relates to a white curable resin composition capable of forming a decorative part, a cured film thereof, and a decorative glass plate provided with the same.

  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

  Usually, titanium oxide is used as a pigment in order to impart concealability to the decorative portion. However, the glass substrate that is the substrate of the touch panel is poorly wet, and the adhesion between the glass substrate and the decorative portion may not always be sufficient. Therefore, if the amount of titanium oxide added is increased so as to improve the concealing property of the decorative portion, the adhesion between the glass substrate and the decorative portion will be further deteriorated. On the other hand, if the amount of titanium oxide, which is a pigment, is reduced in order to improve the adhesion between the glass substrate and the decorative portion, a sufficient concealing effect cannot be obtained. Therefore, improving the adhesion between the decorative portion and the glass substrate is also important for improving the concealing property.

  Then, the objective of this invention provides the white curable resin composition which can form the decorating part excellent in adhesiveness with a glass substrate, its cured film, and a decorating glass plate provided with the same. There is.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that the above-mentioned problems can be solved by setting the resin component of the curable resin composition forming the decorative portion to a predetermined one. The present invention has been completed.

  That is, the curable resin composition of the present invention comprises (A) a carboxyl group-containing resin having a styrene skeleton, (B) an epoxy resin, (C) a rutile titanium oxide, and (D) a thermosetting catalyst. A curable resin composition to be contained, wherein (A) the carboxyl group-containing resin having a styrene skeleton has a weight average molecular weight of 10,000 to 30,000, and an acid value of 120 to 200 mgKOH / g. It is characterized by this.

  In the resin composition of the present invention, the (D) thermosetting catalyst is preferably triphenylphosphine. In the resin composition of the present invention, the (C) rutile titanium oxide is preferably a multi-processed rutile titanium oxide.

  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.

  ADVANTAGE OF THE INVENTION According to this invention, providing the white curable resin composition which can form the decorating part excellent in adhesiveness with a glass substrate, its cured film, and a decorative glass plate provided with the same. it can.

Hereinafter, embodiments of the present invention will be described in detail.
The curable resin composition of the present invention contains (A) a carboxyl group-containing resin having a styrene skeleton, (B) an epoxy resin, (C) a rutile-type titanium oxide, and (D) a thermosetting catalyst. . In the resin composition of the present invention, (A) the carboxyl group-containing resin having a styrene skeleton has a weight average molecular weight of 10,000 to 30,000, and an acid value of 120 to 200 mgKOH / g. By using the (A) carboxyl group-containing resin having a styrene skeleton as the resin component, the adhesion between the cured film of the resin composition and the glass substrate can be improved. Hereinafter, (A) a carboxyl group-containing resin having a styrene skeleton, (B) an epoxy resin, (C) a rutile type titanium oxide, and (D) a thermosetting catalyst will be described in detail.

<(A) Carboxyl group-containing resin having a styrene skeleton>
(A) A carboxyl group-containing resin having a styrene skeleton is a resin having a carboxyl group in the molecule and no photosensitive group such as an ethylenically unsaturated bond, having a styrene skeleton in the molecule, and a weight. The average molecular weight is 10,000 to 30,000, and the acid value is 120 to 200 mgKOH / g. The carboxyl group-containing resin having such a styrene skeleton can be synthesized by copolymerization using styrene as an essential monomer. By using the carboxyl group-containing resin having such physical properties, it is possible to improve the adhesion between the cured film made of the resin composition of the present invention and the glass substrate.

  (A) Specific examples of the carboxyl group-containing resin having a styrene skeleton are selected from, for example, unsaturated carboxylic acids such as (meth) acrylic acid, styrene, α-methylstyrene, lower alkyl (meth) acrylate, isobutylene, and the like. And a carboxyl group-containing resin (either an oligomer or a polymer) obtained by copolymerization with an unsaturated group-containing compound. The lower alkyl refers to an alkyl group having 1 to 5 carbon atoms.

  In the resin composition of the present invention, the weight average molecular weight of the (A) carboxyl group-containing resin having a styrene skeleton varies depending on the resin skeleton, but is generally preferably 10,000 or more and 30,000 or less. By setting the weight average molecular weight to 10,000 or more, transferability defects or pinholes during screen printing are less likely to occur. Further, when the weight average molecular weight is 30,000 or less, the storage stability is excellent. More preferably, it is 10,000 or more and 25,000 or less.

  In the resin composition of the present invention, (A) the acid value of the carboxyl group-containing resin having a styrene skeleton is preferably 120 to 200 mgKOH / g, and more preferably 140 to 180 mgKOH / g. (A) By setting the acid value of the carboxyl group-containing resin having a styrene skeleton to 200 mgKOH / g or less, the crosslinking density becomes appropriate, and no stress is generated during curing, and a good coating film is obtained. On the other hand, when the acid value of the (A) carboxyl group-containing resin is 120 mgKOH / g or more, the coating properties such as adhesion are improved, which is preferable.

  In the resin composition of the present invention, (A) the carboxyl group-containing resin having a styrene skeleton preferably has a styrene skeleton ratio of 30 to 60 mol% in the molecule. That is, it is preferable to use 30 to 60 mol% of styrene with respect to the total amount of monomers when synthesizing (A) a carboxyl group-containing resin having a styrene skeleton. By setting it as 30 mol% or more, it becomes a cured film with high adhesiveness with respect to a base material. On the other hand, by setting it to 60 mol% or less, it becomes a cured film with little thermal discoloration.

  (A) The carboxyl group-containing resin having a styrene skeleton is a resin having a high molecular weight when produced by suspension polymerization. In general, when (A) a carboxyl group-containing resin having a styrene skeleton is produced by suspension polymerization, the polymer has a high molecular weight. However, in consideration of screen printing suitability, it is necessary to keep the weight average molecular weight in the range of 10,000 to 30,000. is there. Therefore, in controlling the molecular weight, it is preferable to use a chain transfer agent during the synthesis of (A) a carboxyl group-containing resin having a styrene skeleton.

  Examples of the chain transfer agent include MSD (α-methylstyrene dimer) and n-DM (n-dodecyl mercaptan) in addition to the chain transfer agents listed below. Of these, MSD (α-methylstyrene dimer) is preferable. The compounding amount of the chain transfer agent is 1 to 10 parts by mass in 100 parts by mass of the (A) carboxyl group-containing resin having a styrene skeleton in terms of solid content when synthesizing the (A) carboxyl group-containing resin having a styrene skeleton. Is preferred.

  Moreover, in order to accelerate | stimulate superposition | polymerization, it is preferable to use a polymerization initiator at the time of (A) carboxyl group-containing resin synthesis | combination which has a styrene skeleton. Examples of the polymerization initiator include BPO (benzoyl peroxide), t-butylperoxy-2-ethylhexanate, AMBN (2,2'-azobis (2-methylbutyronitrile)) and the like. Of these, BPO (benzoyl peroxide) is preferable. The blending amount of the polymerization initiator is preferably 0.1 to 10 parts by mass in 100 parts by mass of the resin in terms of solid content when synthesizing (A) a carboxyl group-containing resin having a styrene skeleton, It is more preferable that it is 1-4 mass parts in 100 mass parts of resin.

<(B) Epoxy resin>
In the resin composition of the present invention, the (B) epoxy resin is a component for imparting heat resistance. In the resin composition of the present invention, the epoxy compound may be used alone or in combination of two or more.

  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 having an aromatic skeleton. From the viewpoint of further enhancing the strength of the cured film and the heat-resistant yellowing prevention property, 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.

  (B) The compounding quantity of an epoxy compound 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 epoxy compound (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, relative to 100 parts by mass of the carboxyl group-containing resin having a styrene skeleton. More preferably, it is 25 mass parts or more and 85 mass parts or less. (B) When the compounding quantity of an epoxy compound 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) Rutile type titanium oxide>
In the resin composition of the present invention, (D) rutile titanium oxide is used as the white pigment. Anatase-type titanium oxide is often used because of its high whiteness compared to the rutile type. However, since anatase-type titanium oxide has photocatalytic activity, it may cause discoloration of the cured film. On the other hand, although rutile type titanium oxide is slightly inferior in whiteness to anatase type titanium oxide, it has almost no photoactivity, so that a stable cured film can be obtained. (D) As a rutile type titanium oxide, a well-known rutile type thing can be used, and what was manufactured by the chlorine method or what was manufactured by the sulfuric acid method may be used.

  In the resin composition of the present invention, there is no particular limitation as long as it is a rutile type titanium oxide, but a multi-processed rutile type titanium oxide is particularly preferable. Here, multi-processing means that the surface of rutile titanium oxide is coated with alumina or silica. Since this multi-processed rutile 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 order to obtain a dry hydride effect, it is necessary that a large number of air micropores exist in the matrix phase. However, if a large number of air micropores exist, the cured film may become brittle. However, when a styrene-based copolymer is used as the carboxyl group-containing resin, the cured film does not become brittle even if a large number of air micropores are present, and therefore these resins can be preferably used.

  In the resin composition of the present invention, the oil absorption of the multi-processed rutile type 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.

  Examples of the rutile type titanium oxide include, for example, Typek R-820, Typek R-830, Typek R-930, Typek R-550, Typek R-630, Typek R-680, Typek R-670, Typek R-680, R-670, Typek R-780, Typek R-780-2, Typek R-850, Typek R-855, Typek R-953, Typek CR-50, Typek CR-57, Typek CR-80, Typek CR-90 , Type CR-90-2, Type CR-93, Type CR-95, Type CR-97, Type CR-60, Type CR-63, Type CR-67, Type CR-58, Type CR-85, Type UT771 (Ishihara Manufactured by Taipure R-100, Taipure R-101, Taipure R-102, Taipure R-103, Taipure R-104, Taipure R-105, Taipure R-108, Taipure R-900, Taipure R-902, Taipure R-960, Taipure R-706, Taipure R-931 (manufactured by DuPont), TITON R-25, TITON R-21, TITON R-32, TITON R-7E, TITON R-5N, TITON R-61N, TITON R-62N, TITON R-42, TITON R-45M, TITON R-44, TITON R-49S, TITON GTR-100, TITON GTR-300 TITON D-918, TITON TCR-29, TITON TCR-52, TITO N FTR-700 (manufactured by Sakai Chemical Industry Co., Ltd.), TITANIX JR-300, TITANIX JR-403, TITANIX JR-405, TITANIX JR-600A, TITANIX JR-600E, TITANIX JR-602, TITANIX JR-602X, TITANIX JR-602X 603, TITANIX JR-805 (manufactured by Teika) or the like can be used.

  (C) The compounding quantity of a rutile type titanium oxide becomes like this. Preferably it is 50-350 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin which has a styrene skeleton, More preferably, it is 100-300 mass parts. By making a compounding quantity into 350 mass parts or less, the fall of a dispersibility and the embrittlement of a cured film can be prevented. 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 the present invention, the blending amount of the (D) thermosetting catalyst is preferably 0.1 to 10.0 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin having a styrene skeleton. (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 comprises (A) a carboxyl group-containing resin having a styrene skeleton, (B) an epoxy resin, (C) a rutile titanium oxide, and (D) a thermosetting catalyst. It is a resin composition, and it is only important that (A) the carboxyl group-containing resin having a styrene skeleton has a weight average molecular weight of 10,000 to 30,000 and an acid value of 120 to 200 mgKOH / g. 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 (A) a carboxyl group-containing resin having a styrene skeleton is used in the resin composition of the present invention, the resin composition of the present invention is excellent in adhesion between the cured film and the glass substrate. . Therefore, the cured film of this invention can be used suitably for the decorating part of touchscreens, 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 1>
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 methacrylic acid, 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 is a high speed 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. Measured by liquid chromatography.

<Synthesis of carboxyl group-containing resin solution 2>
In a 2,000 ml flask equipped with a stirrer and a condenser, 502 g of tripropylene glycol monomethyl ether was placed and heated to 90 ° C. under a nitrogen stream. A mixture of 108.1 g of styrene, 363.4 g of methacrylic acid, and 28.1 g of dimethyl 2,2′-azobis (2-methylpropionate) (Wako Pure Chemical Industries, Ltd .: V-601) was mixed and dissolved for 4 hours. Over the flask. In this way, a carboxyl group-containing resin solution 2 was obtained. This carboxyl group-containing resin solution 2 has a solid content acid value of 160 mgKOH / g, a solid content of 50%, and a molecular weight of 17,000. 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.

<Synthesis of carboxyl group-containing resin solution 3>
A flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser is charged with methyl methacrylate and methacrylic acid in a molar ratio of 0.87: 0.13, dipropylene glycol monomethyl ether as a solvent, and azobis as a catalyst. Isobutyronitrile was added and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere to obtain a carboxyl group-containing resin solution 3. This carboxyl group-containing resin had a mass average molecular weight of about 10,000 and an acid value of 74 mgKOH / g. 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. In this way, a carboxyl group-containing resin solution 3 was obtained.

<Examples 1-4 and Comparative Examples 1 and 2>
A curable resin composition having the composition shown in Table 1 below was 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 once to print a white decorative layer 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 1: <Carboxyl group-containing resin solution having a styrene skeleton produced in <Synthesis of carboxyl group-containing resin solution 1> (solid content: 50% by mass)
(A) Carboxyl group-containing resin 2: A carboxyl group-containing resin solution having a styrene skeleton produced in <Synthesis of carboxyl group-containing resin 2> (solid content 50% by mass)
Carboxyl group-containing resin 3: Carboxyl group-containing resin solution having a styrene skeleton produced in <Synthesis of carboxyl group-containing resin solution 3> (solid content: 43% by mass)
(B) Epoxy resin 1: JER828 (bisphenol A type) manufactured by Mitsubishi Chemical Corporation
(B) Epoxy resin 2: Mitsubishi Chemical Corporation YX-8034 (hydrogenated bisphenol A type)
(C) Multi-processed rutile titanium oxide 1: DuPont R931 (chlorine rutile titanium oxide)
(C) Multi-processed rutile titanium oxide 2: R-7E (sulfuric acid method rutile titanium oxide) manufactured by Sakai Chemical Industry Co., Ltd.
(D) Thermosetting catalyst: 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
Organic 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 of carboxyl group-containing resin solution synthesized by synthesis of the above-mentioned carboxyl group-containing resin solution 1 (solid content 50% by mass)
Epoxy resin: Mitsubishi Chemical Corporation JER828 (bisphenol A type) 8 parts by mass Triphenylphosphine 0.6 parts by mass Black pigment: Tribasic cobalt oxide powder 60 parts by mass Rutile type titanium oxide: CR-58 by Ishihara Sangyo Co., Ltd. (chlorine method) Rutile type titanium oxide) 90 parts by mass Organic solvent: MFTG (methylpropylene triglycol) 12 parts by mass manufactured by Nippon Emulsifier Co., Ltd. Antifoaming agent: Silicone type antifoaming agent KS-66 3 parts by mass manufactured by Shin-Etsu Chemical Co., Ltd. BYK-111 6 parts by mass

  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>
When the sample was viewed from the glass substrate side with or without the light-shielding layer, the case where the black light-shielding layer was not visible was indicated as ◯, and the case where the black light-shielding layer was visible as x. The obtained results are also shown in Tables 2 and 3.

<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 2 and 3.
○: No peeling occurred on the grid.
X: Peeling occurred on the grid.

<Heat resistance>
About each sample, the initial value of L ^* , a ^* , b ^* of the L ^* a ^* b ^* color system was measured using Konica Minolta color difference meter CR-400. Thereafter, each sample was allowed to stand in a 230 ° C. hot-air circulating box drying furnace for 3 hours for accelerated deterioration, and each numerical value was again measured with a color difference meter CR-400 manufactured by Konica Minolta and evaluated by ΔE ^* ab. . The obtained results are also shown in Tables 2 and 3.

ΔE ^* ab is the difference between the initial value and the value after accelerated deterioration in the L ^* a ^* b ^* color system, and the larger the value, the greater the color change. 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 initial values of L ^* , a ^* , and b ^* , respectively, and L ^{* 2} , a ^{* 2} , and b ^{* 2} represent L after acceleration deterioration, respectively. ^* , A ^* , b ^* values are represented.

  As can be seen from Tables 2 and 3, in the examples using the carboxyl group-containing resin having a styrene skeleton, both the cured film and the glass substrate are excellent in adhesion. In addition, hydrogenated bisphenol A type resin is used as an epoxy resin, rutile type titanium oxide that has been multi-processed as titanium oxide, and triphenylphosphine is used as a thermosetting catalyst. Even when heat was applied for 3 hours, no yellowing of the cured film was observed. Since the carboxyl group-containing resins used in Comparative Examples 1 and 2 did not have a styrene skeleton, the adhesion was poor.

Claims (5)

(A) For forming a cured film on a decorative glass plate containing a carboxyl group-containing resin having a styrene skeleton, (B) an epoxy resin, (C) a rutile-type titanium oxide, and (D) a thermosetting catalyst . A thermosetting resin composition comprising:
(A) The carboxyl group-containing resin having a styrene skeleton has a weight average molecular weight of 10,000 to 30,000, and an acid value of 120 to 200 mgKOH / g . A thermosetting resin composition for forming a cured film . Wherein (D) a thermosetting catalyst, thermosetting resins composition according to claim 1, wherein triphenylphosphine. Wherein (C) rutile type titanium oxide, a multi-processing processed rutile titanium claim 1 or 2 thermosetting resin composition. Cured film thermosetting resins composition of any one of claims 1 to 3, characterized in that formed by curing.   A decorated glass plate comprising the cured film according to claim 4.