TW201740200A - Photocurable resin composition, photocurable coating, and cured product - Google Patents

Abstract

An embodiment of the present invention relates to a photocurable resin composition that is used to protect at least a portion of an end of a glass substrate and has a viscosity of 0.4 to 20 Pa.s.

Description

Photocurable resin composition, photocurable paint, cured product, glass substrate, display device, mobile terminal, method for producing cured product, and method for producing protected glass substrate

The present disclosure relates to a photocurable resin composition, a photocurable paint, a cured product, a glass substrate, a display device, a mobile terminal, a method for producing a cured product, and a method for producing a protected glass substrate.

In a mobile terminal such as a smart phone or a tablet, it is thinned for the purpose of large screen and light weight. Along with this, the cover glass used is also thinned. Therefore, chemically strengthened glass having high strength is widely used in cover glass. There is a case where the cover glass is cracked at the end due to contact or impact in the manufacturing steps. In chemically strengthened glass, there is a tendency that the strength is remarkably lowered due to cracking.

Moreover, the design of the cover glass projection has recently been popular with respect to the housing of the mobile terminal. The end portion is exposed to an impact directly contacting the outside or coming from the outside due to the cover glass projection, and cracking easily occurs. Therefore, it is necessary to protect the cover glass from contact or impact by the end portion, and to prevent the occurrence of cracks (see, for example, Patent Document 1 and Patent Document 2). The protective film is formed, for example, by applying a liquid photocurable paint to the end of the cover glass. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-111688 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-527399

[Problems to be Solved by the Invention] However, in recent years, even in the case of a cover glass provided with a protective film, cracking has begun to occur. Accordingly, the present disclosure provides a photocurable resin composition, a photocurable coating material, and a cured product having excellent protective effects. Further, the present disclosure provides a glass substrate excellent in durability, a display element including the same, and a mobile terminal. Further, the present disclosure provides a method for producing the cured product and the glass substrate efficiently. [Means for solving the problem]

The invention encompasses various embodiments. Examples of the embodiments are listed below. The present invention is not limited to the following embodiments.

One embodiment relates to a photocurable resin composition for protecting at least a portion of an end portion of a glass substrate and having a viscosity of 0.4 Pa·s to 20 Pa·s.

The photocurable resin composition may also contain a colorant.

Further, another embodiment relates to a photocurable coating material using the photocurable resin composition.

Another embodiment relates to a cured product obtained by curing the photocurable resin composition or the photocurable paint.

Other embodiments are directed to a glass substrate that protects at least a portion of the ends by the cured product.

Other embodiments are directed to a display device or mobile terminal that includes the glass substrate.

Further, another embodiment relates to a method for producing a cured product comprising the step of curing the photocurable resin composition or the photocurable coating material by light irradiation.

Other embodiments relate to a method of producing a protected glass substrate, comprising: coating the photocurable resin composition or the photocurable coating onto at least a portion of an end of a glass substrate to form The step of coating the film and the step of curing the coating film by light irradiation to form a protective film.

The present application is related to the subject matter described in Japanese Patent Application No. Hei. No. 2016-093775, the entire disclosure of which is incorporated herein. [Effects of the Invention]

According to the present disclosure, a photocurable resin composition, a photocurable coating material, and a cured product having excellent protective effects are provided. Further, according to the present disclosure, a glass substrate excellent in durability, a display element including the same, and a mobile terminal are provided. Further, a method for producing the cured product and the glass substrate efficiently is provided by the present disclosure.

The embodiments of the present invention will be described. The present invention is not limited to the following embodiments. The inventors have found that the thickness of the glass substrate is reduced, and the portion where the protective film is provided is narrowed, and formation of a protective film that exhibits a sufficient protective effect is difficult, and even a specific photocurable resin composition is used. The protective film having an excellent protective effect can also be formed in a narrow portion, thereby completing the present invention.

<Photocurable Resin Composition> According to one embodiment, the photocurable resin composition is a composition for protecting at least a part of the end portion of the glass substrate and having a viscosity of 0.4 Pa·s to 20 Pa·s. Since the photocurable resin composition is easily applied to the end portion of the glass substrate, it can be preferably used as a material for protecting the glass substrate.

The inventors believe that one of the reasons why a sufficient protective effect cannot be obtained by the conventional photocurable resin composition is that the formation of the protective film is poor. Usually, the protective film is formed by applying a liquid photocurable resin composition to the end of the glass substrate and hardening it. The degree varies depending on the coating method and/or the curing method, but usually in any of the methods, a time difference occurs between the end time of the coating step and the start time of the hardening step. That is, the time elapses from the end of the coating step to the start of the hardening step. Therefore, the shape of the applied liquid photocurable resin composition may not be maintained until it is cured, and the shape in which the protective film exhibits a sufficient protective effect is not formed. As a result, it is considered that the glass substrate is cracked. Therefore, according to one embodiment, a photocurable resin composition is provided which can be formed into a good shape even in a narrow portion such as an end portion of a glass substrate which has been thinned.

In other words, when the photocurable resin composition has a low viscosity, an outflow of the photocurable resin composition occurs between the coating step and the curing step, and a cured product (protective film) cannot be formed in a favorable shape, and the protective property is changed. difference. On the other hand, in the coating step, if the photocurable resin composition has a high viscosity, coating becomes difficult, and the protective film cannot be obtained in a good shape. According to one embodiment, in the photocurable resin composition, by setting the liquid viscosity to a specific range, it is possible to form a protective film having an excellent protective effect. Further, by setting the liquid viscosity to a specific range, the workability is also improved, and the productivity of the glass substrate is improved.

Examples of the method of applying the photocurable resin composition include a potting method, a dipping method, a spray method, and a roll coating method. A dispenser such as an injection dispenser or a jet dispenser can also be used for coating. The method of applying the photocurable resin composition is preferably a method of directly applying a liquid photocurable resin composition to a glass substrate. The method of using the dispenser is a preferred method for efficiently protecting the glass substrate.

Ultraviolet rays are preferably used in the hardening of the photocurable resin composition. The light source to be used is not particularly limited, and examples thereof include a light-emitting diode (LED) lamp, a mercury lamp (low-voltage, high-voltage, ultra-high pressure, etc.), a metal halide lamp, an excimer lamp, a xenon lamp, and the like. Good for LED lights, mercury lights, metal halide lamps, etc.

Usually, even when any coating method and/or hardening method is used, it takes time to put the coated photocurable resin composition into the hardening step. The photocurable resin composition exhibits an excellent protective effect in various coating methods and curing methods.

The viscosity of the photocurable resin composition is from 0.4 Pa·s to 20 Pa·s. When it is less than 0.4 Pa, the outflow of the photocurable resin composition occurs after application, and the photocurable resin composition cannot maintain a good shape. Moreover, the film thickness of the protective film becomes insufficient. If it exceeds 20 Pa·s, coating becomes difficult. Further, drawing, clogging, and the like occur, and workability is lowered. The viscosity of the photocurable resin composition is preferably 0.7 Pa·s or more, more preferably 1.0 Pa·s or more, still more preferably 1.3 Pa·s or more, and particularly preferably 1.5, from the viewpoint of obtaining a good protective effect. Pa·s or above. Moreover, the viscosity of the photocurable resin composition is preferably 10 Pa·s or less, more preferably 5 Pa·s or less, and still more preferably 3 Pa·s or less, from the viewpoint of obtaining a good protective effect. It is 2.5 Pa·s or less.

The viscosity of the photocurable resin composition can be measured using a single cylindrical rotary viscometer (B type viscometer). As a single cylindrical rotary viscometer, a "TVB-10 type viscometer" manufactured by Toki Sangyo Co., Ltd. is mentioned.

In one embodiment, the photocurable resin composition preferably contains (A) a monomer having a polymerizable unsaturated group and (B) an acrylic compound. The photocurable resin composition may contain any component such as (C) a phosphoric acid compound, (D) a photopolymerization initiator, and/or (E) a colorant. The photocurable resin composition may contain only one of these components, or may contain two or more types. The photocurable resin composition may contain a solvent, and may contain no solvent from the viewpoint of obtaining a good protective effect.

The viscosity of the photocurable resin composition can be adjusted, for example, by changing the content of each component. In the case where the viscosity is to be increased, the content of the (B) acrylic compound may be increased as long as the content of the (A) monomer is decreased. On the other hand, in the case where the viscosity is to be lowered, the content of the (B) acrylic compound may be decreased, and the content of the (A) monomer may be increased.

Hereinafter, each component will be described. ((A) Monomeric substance having a polymerizable unsaturated group) Examples of the polymerizable unsaturated group which the (A) monomeric body has include a vinyl group (ethenyl group), an ethynyl group, and an allyl group. A group having a carbon-carbon double bond such as a (meth) acrylonitrile group, a (meth) propylene fluorenyl group or a (meth) acryl fluorenyl group. The (A) monomer is preferably a (meth) acryloxy group or a (meth) acryl fluorenyl group. (A) The sizing body has at least one polymerizable unsaturated group in the molecule.

Examples of the (A) monomeric body include a compound having a (meth)acryl fluorenyl group, a compound having a (meth) acryloxy group, a compound having a (meth) acryl fluorenyl group, and the like. These compounds can be preferably used from the viewpoint of improving the protective effect. In the case of the (A) single-body "comprising a compound having a (meth)acryl fluorenyl group", it means at least one of a compound having an acryl fluorenyl group and a compound having a methacryl fluorenyl group. The term "(meth)" is similarly meant to include at least one of a compound having a (meth) acryloxy group and a compound having a (meth) acryl fluorenyl group.

Examples of the (A) monomeric body include (A-1) a (meth) acrylate monocomponent, and (A-2) a (meth) acrylamide monoamide. In the case of the (A) monomeric "including (meth) acrylate", it means at least one of acrylate and methacrylate. The same applies to "(meth)acrylamide". As the (A) monomeric body, a compound different from the (B) acrylic compound and the (C) phosphoric acid compound described later is used. The term "(meth)" is similarly meant to include at least one of the (B) acrylic compound and the (C) phosphoric acid compound.

Examples of the monofunctional (meth) acrylate-based monomer include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and isobutyl (meth)acrylate. Tert-butyl (meth)acrylate, butoxyethyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , (h) (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauric (meth) acrylate Ester, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, cetyl (meth)acrylate, (methyl) Stearyl acrylate, behenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-(methyl) acrylate Hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxylated polyethylene glycol (meth) acrylate, methoxypolypropylene glycol ( Methyl) acrylate, ethoxylated polypropylene glycol (methyl) Oleate, succinic acid mono(2-(meth)acryloxyethyl ester), (meth)acrylic acid and glycidyl ester (for example, "Kajula" manufactured by Momentive Performance Materials An aliphatic (meth) acrylate such as a reactant of Cardura) E-10"); cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, (methyl) Dicyclopentyl acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, mono(2-(methyl) propylene methoxyethyl) tetrahydrophthalate, six An alicyclic (meth) acrylate such as hydrogen (2-(meth) propylene methoxyethyl) monophthalate or the like.

Examples of the bifunctional (meth) acrylate-based monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylic acid. Ester, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(a) Acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 1,3-butanediol di(methyl) Acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate 1,6-hexanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 1,9-nonanediol di(methyl) Acrylate, 1,10-decanediol di(meth)acrylate, glycerol di(meth)acrylate, tricyclodecane dimethanol (meth) acrylate, ethoxylated 2-methyl- Aliphatic (meth) acrylate such as 1,3-propanediol di(meth)acrylate; cyclohexane Dimethanol (meth) acrylate, ethoxylated cyclohexane dimethanol (meth) acrylate, propoxylated cyclohexane dimethanol (meth) acrylate, ethoxylated propoxylated ring Hexane dimethanol (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, ethoxylated tricyclodecane dimethanol (meth) acrylate, propoxylated tricyclodecane II Methanol (meth) acrylate, ethoxylated propoxylated tricyclodecane dimethanol (meth) acrylate, ethoxylated hydrogenated bisphenol A di(meth) acrylate, propoxylated hydrogenation Bisphenol A di(meth) acrylate, ethoxylated propoxylated hydrogenated bisphenol A di(meth) acrylate, ethoxylated hydrogenated bisphenol F di(meth) acrylate, propoxy An alicyclic (meth) acrylate such as hydrogenated bisphenol F di(meth)acrylate or ethoxylated propoxylated hydrogenated bisphenol F di(meth)acrylate.

Examples of the trifunctional or higher (meth) acrylate-based monomer include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and propoxygen. Trimethylolpropane tri(meth)acrylate, ethoxylated propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol Tris(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, ethoxylated propoxylated pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylate Pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated propoxylated pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(a) An aliphatic (meth) acrylate such as acrylate or dipentaerythritol hexa(meth) acrylate.

From the viewpoints of compatibility with other components such as an acrylic compound and a colorant, and hardness characteristics at the time of hardening, the (A-1) monocomponent is preferably a monofunctional (meth)acrylate series. It is more preferred to use a monofunctional alicyclic (meth) acrylate, and it is preferred to use isobornyl (meth) acrylate.

Examples of the (meth)acrylamide series monovalent body include (meth)acrylamide, methyl (meth) acrylamide, dimethyl (meth) acrylamide, and ethyl (meth) propylene. Guanamine, diethyl (meth) acrylamide, n-propyl (meth) acrylamide, di-n-propyl (meth) acrylamide, isopropyl (meth) acrylamide, diiso Propyl (meth) acrylamide, n-butyl (meth) acrylamide, di-n-butyl (meth) acrylamide, isobutyl (meth) acrylamide, diisobutyl (A Base acrylamide, tert-butyl (meth) acrylamide, di-tert-butyl (meth) acrylamide, n-pentyl (meth) acrylamide, di-n-pentyl (methyl) ) acrylamide, n-hexyl (meth) acrylamide, di-n-hexyl (meth) acrylamide, cyclohexyl (meth) acrylamide, dicyclohexyl (meth) acrylamide, (methyl) ) acryloyl morpholine and the like.

From the viewpoints of compatibility with other components such as an acrylic compound and a colorant, and hardness characteristics at the time of self-hardening, (A-2) a monovalent body is preferably a (meth) acrylonitrile morpholine.

(A) The single body may be used alone or in combination of two or more. From the viewpoints of compatibility with other components such as an acrylic compound and a colorant, and hardness characteristics at the time of curing, the (A) single body is preferably used in combination of two or more kinds, more preferably (A-1). The monocomponent is used in combination with the (A-2) unitary amount, and further preferably a monofunctional (meth) acrylate monomeric body as the (A-1) unitary body and (A-2) single The combination is used in combination.

The self-adhesive property is based on the compatibility with other components such as an acrylic compound or a colorant, and the workability, productivity, and hardness characteristics at the time of curing, based on the total mass of the photocurable resin composition. A) The content of the monomer is preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more. In addition, from the same viewpoint, the content of the (A) monomer is preferably 50% by mass or less, more preferably 45% by mass or less, based on the total mass of the photocurable resin composition. It is 40% by mass or less.

When the (A-1) unit is used in combination with the (A-2) unit, the ratio (mass ratio) of the (A-2) unit to the (A-1) unit is preferred. It is 0.02 or more, more preferably 0.05 or more, still more preferably 0.08 or more. Further, the ratio (mass ratio) of the (A-2) monomeric substance to the (A-1) unitary body is preferably 0.3 or less, more preferably 0.2 or less, still more preferably 0.15 or less.

((B) Acrylic Compound) (B) The acrylic compound is a compound having at least one (meth) acrylonitrile group or (meth) propylene fluorenyloxy group. For example, a (meth) acrylate compound having a urethane bond can be exemplified. (B) The acrylic compound is a compound different from the (C) phosphate compound described later. The (meth) acrylate compound having a urethane bond can be preferably used from the viewpoint of improving the protective effect.

Examples of the (meth) acrylate compound having a urethane bond include a (meth)acrylic monomer having an OH group at the β-position, isophorone diisocyanate, and 2,6-toluene diisocyanate. a reaction product of a diisocyanate compound such as 2,4-toluene diisocyanate or 1,6-hexamethylene diisocyanate, tris((meth)acryloxytetraethyleneethylene glycol isocyanate) hexamethylene isocyanocyanate Acid ester, EO modified di(meth)acrylic acid urethane, PO modified di(meth)acrylic acid urethane, EO and PO modified di(meth)acrylic acid urethane, A carboxyl group-containing (meth)acrylic acid urethane or the like. Further, a (meth) acrylate compound having a urethane bond may preferably use a urethane oligomer.

The self-adhesive property is preferably 800 or more in terms of compatibility with other components such as a monomer or a colorant, workability, productivity, hardness characteristics at the time of curing, and the like. (B) The weight average molecular weight of the acrylic compound is preferably 800 or more. More preferably, it is 2,000 or more, More preferably, it is 4,000 or more. Further, from the same viewpoint, the weight average molecular weight of the (B) acrylic compound is preferably 10,000 or less, more preferably 9,000 or less, still more preferably 7,000 or less. The weight average molecular weight can be measured by gel permeation chromatography (GPC) using a value in terms of standard polystyrene.

For example, "UA-306H", "UA-306T", and "UA-306I" manufactured by Kyoeisha Chemical Co., Ltd.; "Artresin UN" manufactured by Gensei Industrial Co., Ltd. -904", "A Tao Laijin UN-6060S"; "Biscoat #700HV" manufactured by Osaka Organic Chemical Industry Co., Ltd.; "KAYARAD" manufactured by Nippon Kayaku Co., Ltd. DPHA-40H", "KAYARAD UX-5000", etc.

(B) The acrylic compound may be used alone or in combination of two or more.

The self-adhesive property is based on the compatibility with other components such as a single body or a colorant, and the workability, productivity, and hardness characteristics at the time of curing, based on the total mass of the photocurable resin composition. B) The content of the acrylic compound is preferably 35% by mass or more, more preferably 40% by mass or more, and still more preferably 45% by mass or more. In addition, from the same viewpoint, the content of the (B) acrylic compound is preferably 70% by mass or less, more preferably 65% by mass or less, based on the total mass of the photocurable resin composition. It is 60% by mass or less.

((C) Phosphoric acid compound) The (C) phosphoric acid compound is a compound having any at least one selected from the group consisting of a phosphate group and a phosphate group, and at least one polymerizable unsaturated group. (C) The polymerizable unsaturated group which the phosphoric acid compound has may, for example, be a vinyl group (ethenyl group), an ethynyl group, an allyl group, a (meth)acryl fluorenyl group or a (meth) acryloxy group. A group having a carbon-carbon double bond such as a (meth) acryloylamino group. The (C) phosphoric acid compound preferably has a (meth) propylene fluorenyloxy group. (C) the phosphoric acid compound is preferably ethylene oxide modified di(meth)acrylate and/or propylene oxide modified di(meth)acrylate, more preferably ethylene oxide modified phosphoric acid (Meth) acrylate.

(C) Examples of the phosphoric acid compound include: Acid Phosphooxy Ethyl Methacrylate, (meth) acrylate acid phosphonium propyl ester, (meth)acrylic acid Esters of phosphonium oxybutyl acrylate, (meth) acrylate acid phosphonium pentoxide, acid phosphonium oxy ethoxylate monomethacrylate, acid phosphonium oxy group A compound represented by the following formula (1) such as polyoxypropylene glycol ester monomethacrylate.

[Chemical 1]

In the formula, R ¹ represents hydrogen or a methyl group, R ² represents a linear, branched or cyclic alkyl group, n represents a number of 1 or more, and m represents a number of 1 to 3. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 9 carbon atoms, still more preferably 1 to 6 carbon atoms. n is preferably from 1 to 12, more preferably from 1 to 6, still more preferably from 1 to 3. m is preferably from 1 to 2.

Further, examples of the (C) phosphoric acid compound include 3-chloro-2-acid phosphonoxypropyl (meth) acrylate and phenyl phosphate (2-(methyl) propylene methoxyethyl ester). , diphenyl phosphate (2-(methyl) propylene methoxyethyl ester), acid (meth) propylene decyloxy-2-hydroxypropyl ester, acid phosphate (methyl) propylene methoxy group - 3-hydroxypropyl ester, (meth)acryloyloxy-3-chloro-2-hydroxypropyl phosphate, acid allyl phosphate, and the like.

Further, the (C) phosphoric acid compound may be a salt such as a monomethanolamine salt or a monoethanolamine salt of these compounds.

The (C) phosphoric acid compound is preferably a compound represented by the formula (1), more preferably in the formula (1), R ¹ is a methyl group, R ² is a dimethylene group or a pentamethylene group, and n is 1 to 2, m is a compound of 1 to 2, and further preferably a compound of the formula (1), wherein R ¹ is a methyl group, R ² is a dimethylene group, n is 1 to 2, and m is 1 or 2.

(C) The phosphoric acid compound may be used alone or in combination of two or more.

From the viewpoint of the good adhesion to the glass substrate, the content of the (C) phosphate compound is preferably 0.01 with respect to 100 parts by mass of the total of the (A) monomer and the (B) acrylic compound. The amount by mass or more is more preferably 0.1 part by mass or more, and still more preferably 0.3 part by mass or more. In addition, the content of the (C) phosphoric acid compound is preferably 100 parts by mass based on 100 parts by mass of the total of the (A) monolith and the (B) acrylic compound, from the viewpoint of the stability of the photocurable resin composition. 10 parts by mass or less, more preferably 5 parts by mass or less, further preferably 3 parts by mass or less.

((D) Photopolymerization initiator) (D) The photopolymerization initiator also includes a substance called a sensitizer. Specific examples of the (D) photopolymerization initiator include acridine; an acridine compound having at least one acridinyl group in the molecule; benzophenone; N, N'-tetramethyl-4, 4' N,N-tetraalkyl-4,4'-diaminobenzophenone, such as diaminobenzophenone (micilenone); 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)-butanone-1, 2-methyl-1-(4-methylphenylthio)-2-morpholinoacetone-1, (1-hydroxycyclohexyl)benzene An aromatic ketone such as a ketone; an anthracene such as an alkyl hydrazine; a benzoin ether compound such as benzhydryl alkyl ether; a benzoin compound; a benzoin compound such as an alkyl benzoin; and a benzoin derivative derived from a benzoin dimethyl ketal 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2 -(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyl) 2,4,5-triarylimidazole dimer such as phenyl)-4,5-diphenylimidazole dimer; N-phenylglycine; N-phenylglycine derivative; coumarin a compound; a guanidine salt or the like. From the viewpoint of the balance between the deep hardenability and the surface hardenability of the resin composition, an aromatic ketone can be preferably used.

(D) The photopolymerization initiator may be used alone or in combination of two or more.

(D) Light from the total of 100 parts by mass of the (A) monolith and (B) acrylic compound, from the viewpoint of suppressing the viscosity of the cured product, the surface of the photocurable resin composition is sufficiently cured. The content of the polymerization initiator is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, still more preferably 5 parts by mass or more. In addition, (D) photopolymerization initiator is used for 100 parts by mass of the total of (A) the monolith and the (B) acrylic compound, from the viewpoint of the sufficient hardenability and the adhesion to the deep portion. The content is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 12 parts by mass or less.

((E) Colorant) As the (E) colorant, a coloring agent having a small absorption of light used for curing is used. The coloring agent (E) may, for example, be a dye or a pigment. From the viewpoint of obtaining a uniform photocurable resin composition, it is preferred to use a dye, and it is more preferred to use a dye dissolved in the (A) monomer.

It was confirmed by the following method that the dye was dissolved in the (A) monomer. 10 mL (A) of a single body (temperature 25 ° C) was added to a 50 mL beaker, and then 10 mg (solid content) dye was added and stirred using a glass rod for 1 minute. After the stirring, the solid matter of the dye could not be confirmed by visual observation, and it was judged that the dye was dissolved in the (A) monomer.

In one embodiment, the transmittance of the peak wavelength of light irradiated for curing (hereinafter also referred to as "irradiation transmittance") is higher than the average transmittance of visible light (hereinafter also referred to as "visible transmittance"). 10% or more of the coloring agent is used as the (E) coloring agent. More preferably, it is 20% or more, further preferably 30% or more, and particularly preferably 40% or more. The upper limit is not particularly limited, and it is preferred that the difference between the two is large. In the case of 10% or more, the protection and light blocking properties of the end portion can be considered in a good condition.

Further, in one embodiment, a coloring agent having an irradiation light transmittance of 60% or more and a visible light transmittance of 50% or less is used as the (E) coloring agent. The transmittance of the irradiation light is more preferably 65% or more, and still more preferably 70% or more. The visible light transmittance is more preferably 45% or less, further preferably 40% or less. When the irradiation light transmittance is 60% or more and the visible light transmittance is 50% or less, the protection of the end portion and the light blocking property can be achieved in a favorable state.

The peak wavelength of the light to be irradiated for hardening refers to the wavelength at which the intensity is maximum when the light is applied to the photocurable resin composition at the time of curing. In the case of using an LED lamp as a light source, the peak wavelength is, for example, 365 nm, 385 nm, or the like.

In one embodiment, a coloring agent having a transmittance of light of 365 nm and a transmittance higher than a visible light transmittance of 10% or more is used as the (E) coloring agent. More preferably, it is 20% or more, further preferably 30% or more, and particularly preferably 40% or more. The upper limit is not particularly limited, and it is preferred that the difference between the two is large. In the case of 10% or more, the protection and light blocking properties of the end portion can be considered in a good condition.

Further, in one embodiment, a coloring agent having a transmittance of light of 365 nm and a transmittance of 60% or more and a visible light transmittance of 50% or less is used as the (E) coloring agent. The transmittance of light having a wavelength of 365 nm is more preferably 65% or more, and still more preferably 70% or more. The visible light transmittance is more preferably 45% or less, further preferably 40% or less. When the transmittance of light having a wavelength of 365 nm is 60% or more and the visible light transmittance is 50% or less, both end protection and light blocking properties can be achieved in a favorable state.

(E) Irradiation light transmittance of the colorant can be measured by the following method. 0.1 parts by mass of the (E) coloring agent was added to 100 parts by mass of the solvent for dissolving the (E) coloring agent to obtain a coloring agent solution. Using the obtained coloring agent solution, the transmittance of the peak wavelength of light irradiated for hardening was measured by a visible ultraviolet spectrophotometer (for example, "UV-2400PC" manufactured by Shimadzu Corporation). The decomposition wavelength was 1 nm and the measurement was carried out in the range of 300 nm to 780 nm. It can be confirmed that the (E) colorant is dissolved in the solvent by the same method as the "dye dissolved in (A) single body". (E) The transmittance of light having a wavelength of 365 nm of the colorant can also be measured by the same method as the transmittance of the light.

The "average transmittance of visible light" refers to the average transmittance of light having a wavelength of 400 nm to 700 nm. The average transmittance of visible light can be measured by the following method. Using a coupler solution prepared in the same manner as described above, a spectrophotometer (for example, "CM-3700A" manufactured by Konica Minolta Co., Ltd.) is used, and a wavelength range of 400 nm to 700 nm is used. The transmittance was measured every 1 nm. The average value of each of the obtained values was obtained as the average transmittance.

(E) The color tone of the colorant is not particularly limited. A photocurable resin composition conforming to the hue of the bezel can be prepared by using a coloring agent having various color tones. By using the photocurable resin composition containing the (E) coloring agent, a display device and a mobile terminal excellent in design can be manufactured. For example, a black colorant such as a black dye can be used.

Examples of the (E) colorant include indigo blue, indocyanine green, iodine green, diazo yellow, nigrosine, and ruthenium.

As the commercial item, for example, "elixa black 850" manufactured by Orient Chemical Industries Co., Ltd., or the like can be cited. "Eriksa Black 850" is a transmittance of light having a wavelength of 365 nm which is 10% higher than the average transmittance of visible light, and a transmittance of light having a wavelength of 365 nm of 60% or more and a visible light transmittance of 50%. Less than % of the coloring agent.

(E) The coloring agents may be used alone or in combination of two or more.

The content of the (E) colorant is preferably 0.1 parts by mass or more based on 100 parts by mass of the total of the (A) monolith and the (B) acrylic compound, from the viewpoint of the effect of the light-shielding of the visible light. It is more preferably 0.3 parts by mass or more, still more preferably 0.5 parts by mass or more. Furthermore, from the viewpoint of the curability of the photocurable resin composition, in particular, from the viewpoint of sufficiently curing the deep portion, the total mass of the (A) monolith and the (B) acrylic compound is 100 parts by mass. The content of the colorant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less.

(Additive) The photocurable resin composition may contain various additives as needed. Examples of the additives include an adhesion improver such as a coupling agent, a polymerization inhibitor, a light stabilizer, an antifoaming agent, a filler, an antioxidant, a chain transfer agent, a thixotropic agent, a plasticizer, a flame retardant, and a release agent. , surfactants, lubricants, antistatic agents, etc. Known additives can be used for these additives. The additives may be used alone or in combination of two or more.

As the coupling agent, for example, a titanate coupling agent, a decane coupling agent, or the like can be used. Examples of the titanate coupling agent include a titanate coupling agent having at least an alkylating group having 1 to 60 carbon atoms, a titanate coupling agent having an alkylphosphite group, and an alkyl phosphate group. A titanate coupling agent, a titanate coupling agent having an alkyl pyrophosphate group, and the like.

Examples of the decane coupling agent include an amine decane coupling agent, a urea decane coupling agent, a vinyl decane coupling agent, a methacrylic decane coupling agent, an epoxy decane coupling agent, a decyl decane coupling agent, and an isocyanate. A decane coupling agent or the like.

The polymerization inhibitor may, for example, be hydroquinone, hydroquinone monomethyl ether, benzoquinone, p-tert-butylcatechol, 2,6-di-tert-butyl-4-methylphenol, ortho-benzene. Anthraquinones such as trisphenol. Examples of the antifoaming agent include an anthrone-based oil, a fluorine-based oil, and a polycarboxylic acid-based polymer.

(Manufacturing Method) According to one embodiment, the photocurable resin composition can be photopolymerized by (A) a monolith and (B) an acrylic compound and, if necessary, a (C) phosphoric acid compound and (D) by stirring. The initiator, (E) colorant and/or additive are mixed and produced. Stirring can be carried out by a known method such as stirring, stirring, or the like. The temperature at the time of stirring is preferably a temperature at which the coloring agent (E) can be sufficiently dissolved, and for example, it can be set to 60 to 90 °C.

<Photocurable Coating Material> One embodiment relates to a photocurable coating material using the photocurable resin composition. The photocurable coating material contains at least (A) a monolith and (B) an acrylic compound, and may optionally contain (C) a phosphoric acid compound, (D) a photopolymerization initiator, (E) a colorant, and/or an additive. The photocurable coating material may contain a solvent, and may contain no solvent from the viewpoint of obtaining a good protective effect. When the photocurable coating material has a light-shielding property, it can be preferably used as a coating material for light-shielding.

<The cured product and the method for producing the same> One embodiment relates to a cured product obtained by curing a cured product of the photocurable resin composition or the photocurable paint. The cured product is obtained by curing the photocurable resin composition or the photocurable coating material. The cured product is provided on at least a portion of the end portion of the glass substrate, and can be used as a protective film for protecting the glass substrate.

The cured product can be obtained by a production method including the step of hardening the photocurable resin composition or the photocurable coating material by light irradiation. The light source can be used for light illumination. Ultraviolet light is preferably used in light irradiation. The wavelength of the ultraviolet light is not particularly limited, and is, for example, 365 nm.

<Glass Substrate and Method of Producing the Same> One embodiment relates to a glass substrate which protects at least a part of an end portion by the cured product. The material of the glass substrate is not particularly limited. Examples of the glass include alkali-free glass, low alkali glass, alkali glass, and quartz glass. It may also be a glass substrate which is chemically strengthened by an ion exchange method.

The size and thickness of the glass substrate are also not particularly limited, and can be appropriately determined depending on the use. For example, the photocurable resin composition is suitable for a glass substrate having a thickness of 1 mm or less, preferably 0.8 mm or less, more preferably 0.7 mm or less. Further, the lower limit is not particularly limited. For example, the photocurable resin composition is suitable for a glass substrate having a thickness of 0.2 mm or more, preferably 0.3 mm or more, more preferably 0.4 mm or more.

As an example, when a glass substrate is used in a mobile phone, the size is about 60 mm × 120 mm and the thickness is about 0.55 mm.

The "end portion of the glass substrate" means a portion including at least a side surface of the glass substrate, and may be a portion including not only the side surface of the glass substrate but also the edge of one or both surfaces of the glass substrate. Fig. 1(a) is a plan view showing a glass substrate, and Fig. 1(b) is a schematic cross-sectional view showing the glass substrate. In Fig. 1 (a) and Fig. 1 (b), 1 denotes a glass substrate, 2 denotes a side surface of the glass substrate, and 3 denotes an end portion of the glass substrate.

Fig. 2 shows a glass substrate provided with a cured product on its side. 4 is a hardened substance. The thickness of the cured product 4 may be uniform or non-uniform, and the maximum thickness t of the cured product 4 is also not particularly limited. For example, the photocurable resin composition is suitable for a cured product having a maximum thickness t of 150 μm or more, preferably 200 μm or more, and more preferably 100 μm or more. Further, for example, the photocurable resin composition is suitable for a cured product having a maximum thickness t of 600 μm or less, preferably 500 μm or less, more preferably 400 μm or less.

As an example, when a glass substrate is used for a mobile phone, the maximum thickness t of the cured product 4 is 300 μm to 400 μm. The cured product may be provided at all of the ends of the glass substrate, or may be provided in a part thereof.

The protected glass substrate can be obtained by a production method including the step of applying the photocurable resin composition or the photocurable coating material to at least a part of the end portion of the glass substrate to form a coating film. And a step of forming the protective film by hardening the coating film by light irradiation. The coating method can be used in coating, and the light source can be used in light irradiation.

<Display Device> An embodiment relates to a display device including the glass substrate. A glass substrate is used for the display portion of the display device. The display device may, for example, be a flat panel display (FPD), and specific examples thereof include a liquid crystal display (LCD), a plasma display panel (PDP), and an organic electroluminescence panel (Organic). Electro-Luminescence Panel (OELP), Field Emission Display (FED), Cathode-Ray Tube (CRT), electronic paper, and the like.

<Mobile Terminal> By an embodiment, there is a mobile terminal including the glass substrate. A glass substrate is used for the display portion of the mobile terminal. Mobile terminals include mobile phones, smart phones, personal computers, electronic dictionaries, calculators, game consoles, and the like. [Examples]

Embodiments of the present invention will be specifically described by way of examples. The embodiments of the present invention are not limited to the following embodiments.

<Preparation of Photocurable Resin Composition> [Example 1] 37.8 parts by mass of isobornyl acrylate as component (A-1) and 4.2 parts by mass of propylene hydrazinomorpholine as component (A-2) 29.0 parts by mass of the urethane urethane-based compound of the component (B-1) (Ataolaijin "UN-904" manufactured by Kokusai Industrial Co., Ltd., and 29.0 parts by mass of the amine amide group as the component (B-2) a formate compound ("UN-6060S" manufactured by Kokusai Industrial Co., Ltd.), 0.5 parts by mass of ethylene oxide-modified phosphoric acid dimethacrylate as component (C), and 10.0 mass as component (D) (1-hydroxycyclohexyl) phenyl ketone, and 0.8 parts by mass of black dye as the component (E) ("Elixa Black 850" manufactured by Oriental Chemical Industry Co., Ltd.) at 60 ° C The photocurable resin composition was obtained by stirring, and the viscosity of the photocurable resin composition was measured using a B-type viscometer (rotor No. 22, rotation number: 30 rpm), and it was 1.8 Pa·s.

[Comparative Example 1] The component (A-1) was changed to 18.0 parts by mass, the component (A-2) was changed to 2.0 parts by mass, the component (B-1) was changed to 40.0 parts by mass, and the component (B-2) was changed to A photocurable resin composition was obtained in the same manner as in Example 1 except that the amount was changed to 40.0 parts by mass. The viscosity of the photocurable resin composition was 23.4 Pa·s (rotor No. 22, rotation speed: 3 rpm).

[Comparative Example 2] The component (A-1) was changed to 52.0 parts by mass, the component (A-2) was changed to 6.0 parts by mass, the component (B-1) was changed to 20.0 parts by mass, and the component (B-2) was changed to A photocurable resin composition was obtained in the same manner as in Example 1 except that the amount was changed to 20.0 parts by mass. The viscosity of the photocurable resin composition was 0.2 Pa·s (rotor No. 21, and the number of revolutions was 100 rpm).

[Viscosity of Photocurable Resin Composition] The viscosity was measured using a B-type viscometer ("TVB-10 type viscometer" manufactured by Toki Sangyo Co., Ltd.). The measurement conditions are described below. Temperature: 25 °C Rotor: No. 21 or No. 22 Rotational speed: 100 rpm when rotor No. 21 is used, 3 rpm or 30 rpm when rotor No. 22 is used, and rotor No. is used. When the measurement was performed to obtain a value of less than 1 Pa·s, the value obtained by using the rotor No. 21 was used. Further, when the rotor No. 22 was used and measured at a number of revolutions of 30 rpm to obtain a value of 10 Pa·s or less, the value obtained by measuring at a number of revolutions of 30 rpm was used.

[(E) Solubility of Colorant] (E) The solubility of the colorant was confirmed by the following method. Add 10 mL of (A) single body in a 50 mL beaker (temperature 25 ° C, mass ratio of isobornyl acrylate to acryl morpholine 37.8:4.2), then add 10 mg black dye (solid mass) Stir using a glass rod for 1 minute. After stirring, the solid matter of the black dye could not be confirmed by visual observation.

[(E) Transmittance of Colorant] The irradiation light transmittance of the colorant (E) was measured by the following method. 0.1 part by mass of the colorant was added to 100 parts by mass of the solvent to obtain a colorant solution. Using the obtained coloring agent solution, the transmittance was measured by a visible ultraviolet spectrophotometer ("UV-2400PC" manufactured by Shimadzu Corporation). The decomposition wavelength was 1 nm, and the transmittance at a wavelength of 365 nm was measured, and the result was 74%.

The average transmittance of visible light of (E) colorant was determined by the following method. Using the colorant solution prepared in the same manner as described above, the transmission was measured every 1 nm with respect to the wavelength range of 400 nm to 700 nm by a spectrophotometer ("CM-3700A" manufactured by Konica Minolta). rate. The arithmetic mean of the obtained values was found and found to be 38%.

The content and viscosity of each component in the photocurable resin composition produced in Example 1 and Comparative Example 1 and Comparative Example 2 are shown in Table 1. [Table 1] Table 1

<Evaluation> The photocurable resin composition was applied onto the end surface of the glass substrate to be cured, and a protective film was formed on the end portion of the glass substrate.

[Formation of Protective Film] A photocurable resin composition was applied to an end surface of a glass substrate (60 mm × 120 mm, thickness: 0.55 mm) simulating a smart phone using a dispenser device. After the application, the photocurable resin composition was cured by using an ultraviolet irradiation device (light source: metal halide lamp, 1,000 mJ/cm ² ).

The workability of formation of a protective film, the outflow after coating, the film thickness after hardening, etc. were evaluated.

[Workability] The workability of the coating step was evaluated by the following criteria. A: It does not cause drawing and clogging, and can be applied well. B: Drawing or clogging occurred, and coating was not good.

[Outflow] The outflow from the end of coating to ultraviolet irradiation was evaluated by the following criteria. A: The coated photocurable resin composition does not flow out and stays at the end of the glass substrate. B: The coated photocurable resin composition was discharged.

[Four-point bending strength] As a shock model from the outside, a sandpaper (No. 320) was pulled while applying a weight of 1.65 gf/mm to apply damage to the end surface of the glass substrate on which the protective film was formed. The pulling distance is 10 mm. The damaged glass substrate was placed in a four-point bending tester with the damaged portion located between the upper punches (the distance between the upper punches was 10 mm, the distance between the lower punches was 30 mm, and the press-in speed was 5 mm). /min), the breaking strength until the glass substrate was broken.

[Protection Effect] The protective effect was evaluated by the following criteria as compared with the glass substrate on which the protective film was formed but not damaged. The four-point bending strength of the glass substrate which was not damaged was 600 MPa. A: After the damage, the four-point bending strength is maintained at 500 MPa or more. B: After the damage, the four-point bending strength is reduced to less than 500 MPa.

The evaluation results are shown in Table 2. [Table 2] Table 2

As shown in Table 2, the workability in Example 1 was good, and the photocurable resin composition was applied to the glass end surface. On the other hand, in Comparative Example 1, since the photocurable resin composition had a high viscosity, application by a dispenser was difficult, and as a result, the resin could not be applied to the glass end surface. Further, in Comparative Example 2, since the photocurable resin composition had a low viscosity, it was not possible to apply a sufficient amount to the glass end surface.

In the first embodiment, the photocurable resin composition was sufficiently applied to the glass end surface in the first embodiment and hardened, so that the glass end surface was not damaged and the four-point bending strength was maintained. On the other hand, in Comparative Example 2, the photocurable resin composition was not sufficiently applied to the glass end surface, and the glass end surface was damaged. Therefore, the four-point bending strength was remarkably lowered.

The present invention has been described with reference to the specific embodiments, and various changes and substitutions are possible without departing from the spirit and scope of the invention. Therefore, the present invention has been described by way of illustration and not by limitation.

1‧‧‧glass substrate
2‧‧‧Side side of glass substrate
3‧‧‧End of glass substrate
4‧‧‧ hardened material
t‧‧‧Maximum thickness of hardened material

Fig. 1(a) is a plan view schematically showing an example of a glass substrate according to an embodiment, and Fig. 1(b) is a schematic cross-sectional view showing an example of a glass substrate according to an embodiment. Fig. 2 (a) is a plan view schematically showing an example of a glass substrate of a preferred embodiment in which a cured product is provided on the side surface, and (b) of Fig. 2 and (c) of Fig. 2 show that a cured product is provided on the side surface. A schematic cross-sectional view of an example of a glass substrate of one embodiment.

1‧‧‧glass substrate

4‧‧‧ hardened material

t‧‧‧Maximum thickness of hardened material

Claims (9)

A photocurable resin composition for protecting at least a part of an end portion of a glass substrate and having a viscosity of 0.4 Pa·s to 20 Pa·s. The photocurable resin composition according to claim 1, which contains a coloring agent. A photocurable coating material using the photocurable resin composition according to the first or second aspect of the invention. A cured product obtained by curing the photocurable resin composition according to the first or second aspect of the invention or the photocurable coating material according to claim 3 of the patent application. A glass substrate which protects at least a portion of an end portion by a cured product as described in claim 4 of the patent application. A display device comprising the glass substrate as described in claim 5 of the patent application. A mobile terminal comprising the glass substrate as described in claim 5 of the patent application. A method for producing a cured product, which comprises curing a photocurable resin composition according to item 1 or 2 of the patent application or curing the photocurable coating material according to claim 3 of the patent application by light irradiation. A step of. A method for producing a protected glass substrate, which comprises coating a photocurable resin composition as described in claim 1 or 2 or a photocurable coating as described in claim 3 The step of forming a coating film by coating at least a part of the end portion of the glass substrate, and the step of curing the coating film by light irradiation to form a protective film.