TWI467322B - Photosensitive resin composition and sealant - Google Patents

Description

Photosensitive resin composition and sealant

The present invention relates to a photosensitive resin composition and a sealant.

In recent years, with the demand for thinner display panels such as liquid crystal televisions and mobile phones, display devices such as liquid crystal display panels have been required to be thinner. In order to reduce the thickness of the display device, a method of manufacturing a glass panel by bonding thin glass and a method of physically or chemically thinning a glass portion after manufacturing a glass panel are studied. Among them, in the method of manufacturing a glass panel by laminating thin glass, since the strength of the thin glass to be used is insufficient, it is considered that the possibility of breakage of the glass panel in the process is high. Therefore, there has been proposed a method of thinning the thickness of glass by laminating or etching a glass surface by laminating glass of a usual thickness to produce a glass panel. (Patent Documents 1 to 3).

The above-mentioned grinding method of the glass surface includes a physical grinding method such as polishing or a chemical grinding method (etching) using hydrofluoric acid or the like, and can easily control the thickness of the glass having sufficient strength and can be continuously processed. The reason for this is that an etching system using hydrofluoric acid or the like is widely used.

However, when etching using hydrofluoric acid or the like, if the glass panel is immersed in the etching liquid, the etching liquid may enter the inside of the glass panel and cause various defects. Therefore, there has been proposed a seal agent that prevents such an etching liquid from intruding (Patent Document 4).

[Patent Document 1] Japanese Patent No. 2722798

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-76640

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-317981

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2007-314660

Patent Document 4 proposes a sealant for preventing entry of an etchant when etching a glass substrate, which comprises: an epoxy resin (a) having an epoxy equivalent of 400 to 2500 eq/g and containing The oligomer (A) obtained by reacting the ethylenically unsaturated monocarboxylic acid (a2), the ethylenically unsaturated group-containing compound (B) other than the component (A), and the photopolymerization initiator (C). Here, in order to ensure resistance to etching using hydrofluoric acid, it is necessary to use a resin composition having a high molecular weight and a high viscosity as a sealing agent.

In recent years, due to the demand for thinning of display devices, it has been required to increase the etching time and the accuracy of the etching amount. However, if a sealant is applied to a glass panel having a narrow gap, the viscosity of the previous sealant must be long in order to penetrate into the gap of the glass panel, and the sealant has poor permeability to the gap and cannot be completely infiltrated. The sealant to the inside will bulge on the outside of the glass panel and form a convex bulge. Therefore, after the etching, the above-mentioned convex bulging is thicker than the glass panel, and the glass panel is broken. Therefore, a sealant having a low viscosity and excellent permeability to a gap is required, but a low-viscosity sealant has a drawback of low molecular weight and low hydrofluoric acid resistance. Further, when a solvent is used to adjust the viscosity, the density of the resin component in the sealant is lowered, and there is a problem that the hydrogen fluoride resistance is lowered when softened at the time of curing.

The present invention has been made in view of the above problems, and an object thereof is to provide a photosensitive resin composition having excellent hydrogen fluoride resistance and excellent permeability and a sealant using the photosensitive resin composition.

The present inventors have found that the present invention can be solved by solving the above problems by using a specific monomer component. In particular, the present invention provides the following.

(1) The present invention provides a photosensitive resin composition comprising: a terminal (meth) acrylate oligomer (A), a monomer (b1) and a formula selected from the following formula (1) ( 2) One or more monomers (B) of the group consisting of the monomers (b2) shown, and a photopolymerization initiator (C).

(In the formula, A represents a group having a cyclic guanamine group or a cyclic oximine group and these nitrogen atoms are bonded to a residue in the formula (1), and R ¹ , R ^{1 '} and R ² are Independently represents a hydrogen atom or a methyl group, and a and b each independently represent an integer from 1 to 3)

(2)

(wherein R ³ represents a hydrogen atom or a methyl group, B represents a single bond or an alkylene group having 1 to 5 carbon atoms, and R ⁴ represents a ring in which one bond is bonded to a monocyclic or polycyclic ring; a residue formed by a hydrogen atom on a carbon atom of a lactone compound).

(2) Further, the present invention provides a sealant obtained by using the above-described photosensitive resin composition.

The photosensitive resin composition of the present invention has excellent hydrofluoric acid resistance and has a lower viscosity than the conventional resin composition for a sealant. Therefore, the convex bulge which is excellent in permeability and which is applied to the outer peripheral portion of the glass panel is small. Thereby, it is possible to reduce the possibility of breakage when the glass panel is thinned. Further, it is possible to achieve an effect of preventing degradation of hydrogen fluoride resistance during curing.

Hereinafter, embodiments of the present invention will be described.

The photosensitive resin composition of the present invention contains an oligomer (A), a monomer (B), and a photopolymerization initiator (C). Further, any component as described below can be contained, and each component will be described below.

<End (meth) acrylate oligomer (A)>

The terminal (meth) acrylate oligomer (A) contained in the photosensitive resin composition of the present invention (hereinafter also referred to as (A) component) can have CH ₂ =CHCOO- at the end of the oligomer. The base or CH ₂ =CCH ₃ COO-based is suitably selected. In the present invention, for example, an oligomer obtained by reacting an epoxy resin (a1) with a vinyl group-containing monocarboxylic acid (a2) is preferred. By containing such a component (A), it is possible to achieve excellent hydrofluoric acid resistance and water resistance, and to impart appropriate elongation and hardness to the cured product obtained by curing the photosensitive resin composition. The components constituting the component (A) are as follows.

[Epoxy Resin (a1)]

Examples of the epoxy resin (hereinafter also referred to as "(a1) component)" include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, and N, N- Diepoxypropyl-O-toluidine, N,N-diepoxypropylaniline, resorcinol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, trishydroxyl Propane triepoxypropyl ether, polypropylene glycol diepoxypropyl ether, hexahydrophthalic anhydride diepoxypropyl ester, and the like. Among them, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferred, and bisphenol A type epoxy resin is particularly preferred. These epoxy resins may be used singly or in combination of plural kinds.

[vinyl-containing monocarboxylic acid (a2)]

Examples of the vinyl group-containing monocarboxylic acid (hereinafter also referred to as (a2) component) include (meth)acrylic acid, or a saturated or unsaturated dibasic acid and a vinyl group-containing monoepoxypropyl group. The reactant of the base compound. Examples of the (meth)acrylic acid include acrylic acid, methacrylic acid, β-styrylacrylic acid, β-mercaptoacrylic acid, a saturated or unsaturated dibasic acid anhydride, and one hydroxyl group in one molecule. The molar reactant of the (meth) acrylate derivative, that is, the half ester, the saturated or unsaturated dibasic acid, and the monoglycidyl (meth) acrylate derivative are also half Esters and the like.

Examples of the saturated or unsaturated dibasic acid anhydride used for the production of the above-mentioned half esters include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyl hexahydroanthracene. An acid anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, methyl endomethylenetetrahydrophthalic anhydride or the like. In addition, examples of the (meth) acrylate derivative having one hydroxyl group in one molecule include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. 4-hydroxybutyl acrylate, polyethylene glycol mono(meth) acrylate, glycerol di(meth) acrylate, trimethylolpropane (meth) acrylate, neopentyl alcohol tris (methyl) Acrylate, dipentaerythritol penta (meth) acrylate, phenyl epoxidized propyl ether (meth) acrylate, and the like.

Further, examples of the saturated or unsaturated dibasic acid used for the production of the above-mentioned half esters include succinic acid, maleic acid, adipic acid, decanoic acid, tetrahydrofurfuric acid, and hexahydroabietic acid. , itaconic acid, fumaric acid, and the like. Further, examples of the monoglycidyl (meth)acrylate derivative include glycidyl (meth)acrylate.

The component (a2) may be used singly or in combination of plural kinds. A particularly preferred component (a2) is (meth)acrylic acid.

The component (A) can be obtained by reacting the component (a1) with the component (a2). This synthesis reaction can be carried out by a generally known method. For example, acrylic acid or methacrylic acid, a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylphosphonium chloride) can be added to the epoxy resin by a predetermined equivalent ratio. Triphenylstibine) and polymerization inhibitors (eg, methoquinone, hydroquinone, methylhydroquinone, thiophene (dibutylhydroxytoluene, etc.), for example, is allowed to react at 80 to 110 ° C to obtain a component (A). The molecular weight of the component (A) to be synthesized in this manner is preferably from 300 to 6,000, more preferably from 500 to 3,000. By having such a molecular weight of the component (A), it is possible to have excellent hydrofluoric acid resistance and water resistance and an appropriate viscosity.

Further, in terms of adhesion improvement, the component (A) preferably has a hydroxyl group. Further, commercially available products corresponding to the component (A) include EBECRYL 600, EBECRYL605, EBECRYL645, EBECRYL648, EBECRYL860, EBECRYL1606, EBECRYL3105, EBECRYL3213, EBECRYL3420, EBECRYL3500, EBECRYL3608, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL6040, and the like. Epoxy acrylate; (meth)acrylic acid acrylate such as EBECRYL 303, EBECRYL 740-40TP, EBECRYL 745, EBECRYL 767, EBECRYL 1200; (any one is manufactured by DAICEL-CYTEC). Further, a polyester (meth) acrylate such as CNUVE 151 (manufactured by SARTOMER Co., Ltd.) or the like can be given.

The content of the component (A) is preferably 15 to 60% by mass, more preferably 17 to 50% by mass, even more preferably 20 to 40% by mass, based on the photosensitive resin composition. By the upper limit or less, the permeability of the photosensitive resin composition is improved. By being above the lower limit value, the hydrogen fluoride resistance is improved. Further, by the above range, the water resistance is improved and the effect of imparting appropriate elongation and hardness to the cured product can be achieved.

<Monomer (B)>

The monomer (hereinafter also referred to as component (B)) contained in the photosensitive resin composition of the present invention is selected from the monomer (b1) represented by the following formula (1) and the following formula (2). One or more types of the group consisting of the monomers (b2) are shown. The components constituting the component (B) are as follows.

[Monomer (b1) represented by formula (1)]

The monomer (b1) (hereinafter also referred to as the component (b1)) is represented by the following formula (1). Further, "residue in the formula (1)" means "-[-(CHR ¹ -CHR ^1' ) _a -O-] _b -CO-CR ² =CH ₂ "".

(In the formula, A represents a group having a cyclic guanamine group or a cyclic oximine group and these nitrogen atoms are bonded to a residue in the formula (1), and R ¹ , R ^{1 '} and R ² are Independently represents a hydrogen atom or a methyl group, and a and b each independently represent an integer from 1 to 3)

In the formula (1), R ¹ is preferably a hydrogen atom. R ^{1 '} is preferably a hydrogen atom, b is preferably 1 to 2, and more preferably 1 is used.

Further, in the formula (1), the cyclic skeleton in A may be a single ring or a polycyclic ring, or may be a saturated ring or an unsaturated ring. It is preferable that the above-mentioned A has a cyclic amidino group or a cyclic quinone imine group having a ring skeleton of 5 to 10 member rings alone or in combination of two or more, so that 5 to 6 member rings are individually or in combination 2 More preferably, a cyclic guanamine group or a cyclic quinone imine group is preferred.

Examples of the component (b1) include a monomer represented by the following formulas (1-1) to (1-40) (wherein b' represents 1 or 2).

[Chemical 4]

Among them, in terms of adhesion improvement, it is preferred that the monomers represented by the formula (1-5) to (1-20) and the formula (1-25) to (1-40) having a cyclic quinone imine group are preferred. . Further, in terms of improvement in etching resistance, a monomer represented by the formulae (1-9) to (1-20) and formulas (1-29) to (1-40) is more preferable, and N-acrylonitrile is preferable. Ethoxyethyl hexahydroimine (1-9) or N-methylpropenyloxyethyl hexahydroimine (1-10) is particularly preferred. The component (b1) may be used singly or in combination of plural kinds. By containing such a component (b1), shrinkage at the time of hardening can be reduced and adhesion can be improved.

[Monomer (b2) represented by formula (2)]

The monomer (b2) (hereinafter also referred to as the component (b2)) is represented by the following formula (2).

(wherein R ³ represents a hydrogen atom or a methyl group, B represents a single bond or an alkylene group having 1 to 5 carbon atoms, and R ⁴ represents a ring in which one bond is bonded to a monocyclic or polycyclic ring; a residue formed by a hydrogen atom on a carbon atom of a lactone compound).

When the B chain is alkyl, the alkyl group may be linear or branched. By containing such a component (b2), shrinkage at the time of hardening can be reduced, and heat resistance is improved. The component (b2) may, for example, be a monomer represented by the following formulas (b2-1) to (b2-5).

(wherein R ³ is as defined above, R' is a hydrogen atom, a lower alkyl group, an alkoxy group having 1 to 5 carbon atoms or COOR", and R" is a hydrogen atom or may be a fluorine atom or a fluorinated atom. The alkyl group has a linear, branched chain or cyclic alkyl group having 1 to 15 carbon atoms, m is 0 or 1, and the Q system may contain an oxygen atom or a sulfur atom having a carbon number of 1 to 5. Alkyl, oxygen or sulfur atom)

When R' is a lower alkyl group, the lower alkyl group preferably has a carbon number of from 1 to 5. When R" is a linear or branched chain alkyl group, the alkyl group preferably has a carbon number of from 1 to 10 and more preferably has a carbon number of from 1 to 5. When R" is a cyclic alkyl group, The alkyl group preferably has a carbon number of from 3 to 15 and more preferably has a carbon number of from 4 to 12, more preferably from 5 to 10 carbon atoms. Specifically, R" is exemplified by removing one or more hydrogens from a polycyclic alkane such as a cycloalkane, a bicycloalkane, a tricycloalkane or a tetracycloalkane which may be substituted by a fluorine atom or a fluorinated alkyl group. More specifically, a cycloalkane such as cyclopentane or cyclohexane, or adamantane, Alkane, different A polycyclic alkane such as an alkane, a tricyclodecane or a tetracyclodecane is a group obtained by removing one or more hydrogen atoms. In the formulae (b2-1) to (b2-5), it is considered that it is industrially easy to obtain, and R' is preferably a hydrogen atom.

When the Q system may further contain an alkylene group having 1 to 5 carbon atoms of an oxygen atom or a sulfur atom, the alkylene group may specifically be a methylene group, an exoethyl group, a n-propyl group, an exo-propyl group, or O-CH ₂ -, -CH ₂ -O-CH ₂ -, -S-CH ₂ -, -CH ₂ -S-CH ₂ -, and the like.

Specific examples of the monomers represented by the above (b2-1) to (b2-5) are shown below.

Among them, in terms of adhesion and heat resistance improvement, the lactones of the group represented by the formulas (b2-1) and (b2-3), and the formula (b2-2-8) to (b2-2-9) The monomer shown is preferred. In particular, in terms of adhesion improvement, the monomers represented by the formulas (b2-1-1) to (b2-1-2) and the formulas (b2-2-8) to (b2-2-9) are Preferably, the monomers of (b2-1-1) to (b2-1-2) are more preferred, and α-methacryloxy-γ-butyrolactone and β-methacryloxyloxy group are used. -γ-butyrolactone is particularly preferred. The component (b2) may be used singly or in combination of plural kinds.

[Hydroxyl group-containing (meth) acrylate (b3)]

Further, the photosensitive resin composition of the present invention preferably contains a hydroxyl group-containing (meth) acrylate (hereinafter also referred to as a component (b3)). By containing such a component (b3), shrinkage at the time of hardening can be reduced, and adhesion can be further improved.

The component (b3) is a monomer represented by the following formula (3-1).

(wherein R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a hydroxyalkyl group which may have a substituent)

The hydroxyalkyl group of R ⁶ is preferably a hydroxyalkyl group having a carbon number of 10 or less, preferably a linear or branched chain, and more preferably a hydroxyalkyl group having 2 to 8 carbon atoms. Methyl, hydroxyethyl or hydroxypropyl is particularly preferred. The number of the hydroxyl groups is not particularly limited, and 1 or 2 is preferred, and 1 is more preferred. The bonding position is not particularly limited, and it is preferably bonded to the terminal of the alkyl group.

Further, the hydroxyalkyl group of R ⁶ may have a phenoxy group or a phenoxyalkyl group as a substituent. As the phenoxyalkyl group, a phenoxymethyl group, a phenoxyethyl group or a phenoxypropyl group is preferred. It is preferred that one of the hydrogen atoms of the carbon atom to which the hydroxyl group of R ⁶ is bonded is substituted by a phenoxyalkyl group.

Examples of the preferable component (b3) shown in the above (3-1) include a monomer represented by the following formula (3-2).

(wherein R ⁵ is the same as defined above, R ⁷ represents a hydrogen atom or a phenoxyalkyl group, and c represents an integer of 1 or more and 3 or less)

Among them, hydroxyethyl methacrylate, hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate and 2-hydroxy-3-phenoxypropyl methacrylate are preferred.

In addition, as the component (b3), a monomer other than the above may be a monomer in which a hydrogen atom of a hydroxyl group of the above formula (3-1) is further substituted with a hydroxyl group-containing organic group or a carboxyl group-containing organic group. . The organic group preferably contains an ester bond. As the monomer substituted with the hydroxyl group-containing organic group, 2-methylpropenyloxyethyl-2-hydroxypropyl phthalate can be suitably used. The monomer substituted with the carboxyl group-containing organic group may, for example, be 2-methylpropenyloxyethyl succinic acid, 2-methylpropenyloxyethyl hexahydrophthalic acid or hexahydroquinone. Acid-propylene methoxyethyl ester.

The component (b3) may be used singly or in combination of plural kinds.

The content of the component (B) is preferably from 20 to 95% by mass, more preferably from 30 to 85% by mass, based on the photosensitive resin composition. By the above range, it is possible to achieve both high adhesion to a glass panel and heat resistance at the time of etching. In addition, the amount of the components (b1), (b2), and (b3) can be appropriately changed depending on the values required for the adhesion and heat resistance of the photosensitive resin composition. For example, the component (b1) is sensitive to photosensitivity. The resin composition is preferably from 10 to 95% by mass, more preferably from 15 to 85% by mass, and the component (b2) is preferably from 15 to 70% by mass based on the photosensitive resin composition, and is preferably from 20 to 70% by mass. The range of 65 mass% is more preferable, and the component (b3) is preferably from 1 to 55% by mass, more preferably from 3 to 50% by mass, based on the photosensitive resin composition.

As an example of a monomer constituting the component (B):

(1) A situation consisting only of (b1) components

(2) Cases consisting only of (b2) components

(3) The condition consisting of (b1) and (b2)

(4) Cases consisting of (b1) and (b3) components

(5) Cases consisting of (b2) and (b3) components

(6) Cases consisting of (b1) component, (b2) component, and (b3) component

Among the above, (3) to (5) are preferable, and (3) or (5) is particularly preferable because the hydrogen fluoride resistance is good and the balance between adhesion and heat resistance is good.

The ratio (b1)/(b2) of (3) is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and still more preferably 20/80 to 65/35.

The ratio (b1)/(b3) of (4) is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and still more preferably 20/80 to 80/20.

The ratio (b2)/(b3) of (5) is preferably 1/99 to 99/1, more preferably 5/95 to 95/5, and still more preferably 10/90 to 90/10.

(6) The system [total of (b) and (b2)] / (b3) is preferably 45/55 to 99/1. Further, the ratio of (b1) to (b2) is preferably the same as in the case of the above (3).

<difunctional monomer (E)>

The photosensitive resin composition of the present invention preferably further contains a difunctional monomer (E) having a cyclic group having 6 to 20 carbon atoms (hereinafter also referred to as a component (E)). By containing the (E) component, heat resistance or etching resistance is improved.

The difunctional monomer (E) is preferably a difunctional (meth) acrylate. The component (E) is preferably a difunctional (meth) acrylate (e1) represented by the following formula (e1).

(In the formula (e1), R ⁸ is independently the same as the above R ^{2 .} R ⁹ each independently represents an alkylene group having 1 to 3 carbon atoms. R ¹⁰ is a divalent ring having 6 to 20 carbon atoms; base)

R ⁹ in the formula (e1) specifically has a methylene group, an ethyl group, a propyl group, and an isoproterenyl group. In terms of heat resistance improvement, a methylene group and an ethyl group are preferred, and a methylene group is more preferred. The divalent cyclic group of R ¹⁰ in the formula (e1) is preferably an aliphatic cyclic group. The number of carbon atoms of the cyclic group is preferably from 7 to 15, more preferably from 8 to 12. The cyclic group may have an alkyl group having 1 to 5 carbon atoms as a substituent.

The cyclic group may be a group obtained by removing two or more hydrogen atoms from a monocyclic alkane or a polycyclic alkane such as a bicycloalkane, a tricycloalkane or a tetracycloalkane, and specifically Examples of the exocycloalkyl group, the exo-adamantyl group, and the extension of the cyclopentyl group, the cyclohexyl group, and the like Alkyl A polycycloalkyl group such as an alkyl group, a tricyclodecylalkyl group or a tetracyclododecyl group, and the like, in terms of heat resistance and etching resistance, a polycycloalkyl group is preferred, and a tricyclic ring is preferred. A decyl group or a tetracyclododecyl group is more preferred.

As the above difunctional (meth) acrylate (e1), tricyclodecane dimethanol diacrylate, tricyclodecane diethanol diacrylate, tetracyclododecane dimethanol diacrylate is preferred, and Cyclodecane dimethanol diacrylate is particularly preferred.

The component (E) may be used singly or in combination of plural kinds.

The content of the component (E) is in the range of 10 to 50% by mass based on the photosensitive resin composition. By the above range, heat resistance and etching resistance can be improved.

When the component (E) is contained, it can be suitably used as an example of the combination with the component (B).

(1') A condition consisting only of (b1) and (e1) components

(2') A condition consisting only of (b2) and (e1) components

(3') A condition consisting of (b1) component, (b2) component, and (e1) component component

(4') A condition consisting of (b1) component, (b3) component, and (e1) component component

It is particularly good to (1').

<Photopolymerization initiator (C)>

The photopolymerization initiator (C) is not particularly limited, and is preferably dissolved in the above monomer (B). The photopolymerization initiator (C) may, for example, be 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2- Hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1- Ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1- Ketone, bis(4-dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2- Tropicpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butan-1-one, 1-[9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]-ethanone-1-(0 -acetamidine), 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 4-benzylidene-4'-methyldimethyl sulfide, 4-dimethylaminobenzene Formic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethylketal, 1-phenyl-1,2-propanedione-2 -(0-ethoxycarbonyl)anthracene, methyl 0-benzylidenebenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone , 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2- Ethyl hydrazine, octamethyl hydrazine, 1,2-benzopyrene, 2,3-diphenyl fluorene, azobisisobutyronitrile, benzammonium peroxide, cumene peroxide, 2 -Hexylthiobenzimidazole, 2-hydrothiobenzoate Oxazole, 2-hydrothiobenzothiazole, 2-(0-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, diphenyl ketone, 2-chlorodi Phenyl ketone, p-, p-di-dimethylaminodiphenyl ketone, 4,4'-bisdiethylaminodiphenyl ketone, 4,4'-dichlorodiphenyl ketone, 3,3- Dimethyl-4-methoxydiphenyl ketone, benzoin, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl Ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyethyl benzene, p-dimethyl acetophenone, p-dimethylamino propyl benzene, Dichloroethyl benzene, trichloro ethane benzene, p-tert-butyl acetophenone, p-dimethylamino acetophenone, p-butyl butyl trichloro ethane benzene, p-butyl butyl dichloro ethane Benzene, α,α-dichloro-4-phenoxyethyl benzene, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, pentyl-4 -dimethylaminobenzoate, 9-phenyl acridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinyl)pentane, 1,3 - bis(9-acridinyl)propane, p-methoxy III , 2,4,6-para (trichloromethyl)-s-three 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three 2-(4-ethoxyphenyl)-4,6-bis(trichloromethyl)-s-three ,2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-three 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-three 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-three 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-three Wait. Among them, in terms of sensitivity, to use A morpholine photopolymerization initiator is particularly preferred. These photopolymerization initiators may be used singly or in combination of plural kinds.

The content of the photopolymerization initiator (C) is preferably from 0.5 to 30% by mass, more preferably from 1 to 20% by mass, based on the photosensitive resin composition. By the above range, sufficient heat resistance, hydrofluoric acid resistance, and water resistance can be obtained, and photohardening failure can be suppressed.

<Colorant (D)>

The photosensitive resin composition of the present invention preferably further contains a coloring agent (hereinafter also referred to as "(D) component"). When the photosensitive resin composition of the present invention is applied to the surface of a glass panel by containing a coloring agent, the amount of penetration of the coated portion and the inside of the glass panel can be easily visually observed. The coloring agent is not particularly limited, and can be dissolved in the photosensitive resin composition without using a solvent, and is preferably not discolored by time and does not overlap with the absorption wavelength of the photopolymerization initiator (component (C)). Among them, organic dyes are preferred. The organic dye may be used singly or in combination of two or more kinds as necessary.

The wavelength of the organic dye to be added to the maximum absorbance of the photosensitive resin composition is preferably from 450 to 750 nm, more preferably from 600 to 750 nm. Examples of such organic dyes include OIL YELLOW #101, OIL YELLOW #130, OIL PINK #312, OIL GREEN #BG, OIL BLUE #BOS, OIL BLUE #603, OIL BLUE #613, OIL BLACK BY, OIL. BLACK BS, OIL BLACK T-505 (above, ORIENT Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI (Color Index Number) 42555), Methyl Violet (CI42535), Rhodamine B (CI45170B), Malachite Green (CI42000), Methylene Blue ((CI52015), etc.

The organic dye can be appropriately dissolved by a method well known in the photosensitive resin composition. As such a method, a method using a high-speed agitator such as a dissolver or the like can be mentioned. The amount of the organic dye to be added may be appropriately adjusted according to the environment (conditions and uses) of the photosensitive resin composition, and is preferably 0.01 to 1% by mass, and preferably 0.05 to 0.5% by mass based on the entire photosensitive resin composition. For better.

<Other ingredients>

The photosensitive resin composition of the present invention can contain an additive as necessary. Specific examples of the additive include a thermal polymerization inhibitor, an antifoaming agent, a sensitizer, a hardening accelerator, a photocrosslinking agent, a photosensitizer, a dispersing agent, a dispersing aid, a filler, an adhesion promoter, and an antioxidant. UV absorbers, anti-agglomerates, etc.

<organic solvent>

In the photosensitive resin composition of the present invention, an organic solvent can be suitably used in order to improve the solubility of each component and to assist in the uniformity of dissolution.

Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol monomethyl ether. , diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, di-propylene glycol monomethyl ether, di-propylene glycol monoethyl ether, di-propylene glycol mono-n-propyl ether, di-propylene glycol-n-butyl (poly)alkylene glycol monoalkyl ethers such as alkylene ether, tri-propylene glycol monomethyl ether, tri-propylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (poly)alkylene glycol monoalkyl ether acetates such as ester (PGMEA), propylene glycol monoethyl ether acetate, etc.; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, two Glycol diethyl ether, four Other ethers such as furan; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexane, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, 2- Alkyl lactate such as ethyl hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Methyl propyl propionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate ( MA), 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, propylene glycol monomethyl propionate, propylene glycol monoethyl propionate, Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate , isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate , other esters such as methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate; benzene, toluene, An aromatic hydrocarbon such as toluene; N-methylpyrrolidone, N,N-dimethylformamide, and guanamine such as N,N-dimethylacetamide; Methyl hydrazine (DMSO), methanol, ethanol, propanol, butanol, tri-methoxybutanol (BM), hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerol, γ-butane Ester, α-terpineol (onion alcohol), and the like.

The amount of the organic solvent to be used is not particularly limited, and may be appropriately set according to the thickness of the coating film, and the photosensitive resin composition may be used from the viewpoint of maintaining the density of the resin component and maintaining the hydrofluoric acid resistance after curing. 20% by mass or less is more preferable, and 10% by mass or less is more preferable, and 5% by mass or less is more preferable, and 1% by mass or less is particularly preferable. In the present invention, it is preferably 0% by mass (i.e., a solvent-free photosensitive resin composition).

<Method of Preparing Photosensitive Resin Composition>

The photosensitive resin composition of the present invention can be obtained by mixing all of the above components using a stirrer. Further, it is also possible to filter by using a filter to make the obtained mixture uniform.

The photosensitive resin composition thus obtained preferably has a viscosity of 0.5 to 3.0 Pa s, more preferably 0.7 to 2.0 Pa s, and preferably 1.0 to 1.8 Pa s. . By having the viscosity in this range, the permeability to the inside of the glass panel is improved, and damage to the glass panel after etching can be prevented. Further, depending on the size of the gap between the glass panels, the viscosity of the photosensitive resin composition can be improved by the viscosity of 0.5 Pa ‧ or more, and the glass panel can be sufficiently sealed, and it is 3.0 Pa·s or less. The permeability to the inside of the glass panel can be favorably maintained, and the glass panel can be prevented from being damaged.

Further, in the photosensitive resin composition of the present invention, after curing, the density of the resin component does not decrease and the hydrofluoric acid resistance does not decrease.

[Method of sealing glass panel]

An application example of the sealant which is a photosensitive resin composition of the present invention is shown below.

Two sheets of a glass panel having a thickness of 0.5 to 1.0 mm were attached so as to form a gap of 2 to 20 μm, and a photosensitive resin composition was applied to the outer portion by a coating device such as a manual or a dispenser. In this case, the amount of penetration of the photosensitive resin composition is preferably from 1 to 10 mm from the outer peripheral portion. In a preferred embodiment of the present invention, since the photosensitive resin composition contains a coloring agent, the amount of permeation can be easily visually confirmed.

Next, the applied photosensitive resin composition is exposed to an active energy ray such as excimer laser light. The energy line to be irradiated differs depending on the composition of the photosensitive resin composition, and is preferably, for example, 200 to 5000 mJ/cm ² .

Next, the glass panel is etched by immersing or spraying at 20 to 80 ° C for 30 to 200 minutes using a hydrofluoric acid-based etching solution such as hydrofluoric acid or ammonium fluoride. By this etching, the overall thickness of the laminated glass panel is reduced by 0.2 to 1.0 mm.

When the sealing treatment is performed using the conventional photosensitive resin composition, since the viscosity of the photosensitive resin composition is high (for example, about 6.0 Pa ‧ s), the photosensitive resin composition that cannot penetrate completely inside is embossed outside the glass panel and Construct a convex bulge. Therefore, after the etching, the convex bulging becomes thicker than the glass panel, and the glass panel is likely to be damaged. However, since the photosensitive resin composition of the present invention has a low viscosity, the permeability is high, and a convex bulge is unlikely to occur. Therefore, the possibility of breakage of the glass panel is greatly reduced. Further, since the photosensitive resin composition of the present invention contains a specific monomer (B), it is possible to achieve an effect of reducing hardening shrinkage and improving adhesion and heat resistance.

[Examples]

Hereinafter, the present invention will be described in detail with reference to examples. Further, the present invention is not limited at all to the embodiments.

<Examples 1 to 12 and Comparative Examples 1 to 5>

Each of the components (A), (B) and (C) was prepared by mixing the compounds described in Table 1 in accordance with the ratios shown in Table 1 to prepare a photosensitive resin composition. The viscosity (25 ° C) at this time is shown in the table.

Further, (A)-1 in the table indicates EBECRYL 3701: a modified epoxy acrylate having a bisphenol A skeleton (manufactured by DAICEL-CYTEC), and (A)-2 is a CNUVE 151: polyester acrylate (manufactured by SARTOMER) ). M140 represents N-propylene methoxyethyl hexahydroindenimide (manufactured by Toagosei Co., Ltd.), GBLMA represents α-methacryloxy-γ-butyrolactone (Osaka has a mechanism), and HEMA represents hydroxy Ethyl methacrylate, PHA means 3-phenoxy-2-hydroxy acrylate, and MAHP means hexahydrophthalic acid-acryloxyethyl ester.

Further, as the difunctional monomer (E), SR833 represents tricyclodecane dimethanol diacrylate (manufactured by SARTOMER).

As the photopolymerization initiator (C), IR907 (manufactured by CIBA SPECIALTY CHEMICALS) was used.

As the coloring agent (D), (D)-1 means OIL BLUE-613 (manufactured by ORIENT Chemical Co., Ltd.).

Moreover, the numerical values in parentheses in the table indicate the mass %.

<evaluation>

The applicability, hardenability, adhesiveness, heat resistance, etching resistance, and peeling after drying of the prepared sample were evaluated in the following manner. The results are shown in Table 2.

[Coating property]

Two sheets of a glass plate having a thickness of 0.7 mm were attached so as to form a gap of about 10 μm, and a sample was manually coated on the outer peripheral portion, and it was visually confirmed whether or not the sample penetrated into the gap of the glass plate. It will be confirmed that the infiltrant is marked as ○ and the unrecognizable person is marked as ×.

[Surface hardening]

The sample was applied to a thickness of 12 μm on a glass plate having a thickness of 0.7 mm by a spin coater (manufactured by MIKASA Co., Ltd.), and then irradiated with ultraviolet rays at an exposure amount of 2000 mJ/cm ² to harden it. With or without hardening by hand touch. The hardened material that is completely non-adhesive when touched is marked as ○, and the adherent is marked as ×.

[adhesion]

The sample was applied to a thickness of 12 μm on a glass plate having a thickness of 0.7 mm by a spin coater (manufactured by MIKASA Co., Ltd.), and then irradiated with ultraviolet rays at an exposure amount of 2000 mJ/cm ² to harden it. Subsequently, a relative comparison was made in accordance with JIS K5600-5-7. The evaluation criteria are as follows. ◎: 110 or more, ○: 80 or more, Δ: 40 or more, and ×: less than 40.

[heat resistance]

The test sample prepared above was irradiated with ultraviolet rays at an exposure amount of 2000 mJ/cm ² to be cured, and a test film of 250 mm × 3 mm × 200 μm was produced. The test film was subjected to TMA measurement by a tensile test method using a thermomechanical analyzer (manufactured by SEIKO). The softening point at 60 to 100 ° C is marked as ○, and the softening point at 25 to 60 ° C is marked as ×.

[etching resistance]

On a glass plate having a thickness of 0.7 mm on a square of 10 cm, the sample was spouted by a dispenser (manufactured by Musashi Engineering Co., Ltd.) in a manner of 3.5 cm square, and then irradiated with ultraviolet rays at an exposure amount of 2000 mJ/cm ^{2 .} It hardens. Subsequently, the glass plate was immersed in hydrofluoric acid of 20% by mass and 20% by mass, and the peeling of the cured product was visually observed, and the time until partial peeling occurred was measured. 55 minutes or more is marked as ◎, 40 minutes or more and less than 55 minutes are marked as ○, 30 minutes or more and less than 40 minutes are marked as Δ, and less than 30 minutes, and peeling is marked as ×.

[Peeling after drying]

After the above etching resistance test, it was dried and visually observed for peeling. The person who did not peel off was marked as ○, and even if a part was peeled off, it was marked as ×.

Regarding the evaluation, those who were too poor in adhesion and could not be evaluated for etching resistance were referred to as "-". Moreover, the result of the etching resistance was not good, since the peeling after drying was not confirmed, it was not evaluated as "-".

From Table 2, it was found that the photosensitive resin composition has a low viscosity in order to improve the coating property, and the curability can be maintained and the etching resistance can be improved (Examples 1 to 12). When it was found that both of (b1) and (b2) were present, all the evaluation items were good (Examples 3 to 5 and Example 12). Further, good characteristics can also be obtained by combining the component (E) (Example 9).

Further, in the examples 3 and 9, when the mass ratio of each component was not changed and 5 mass% of PGMEA was further added, the same evaluation results were also obtained, and it was confirmed that any of the evaluation items was good.

Claims (5)

A photosensitive resin composition comprising: a terminal (meth) acrylate oligomer (A), a monomer selected from the group consisting of the following formula (1) (b1) and a formula (2) One or more monomers (B) and a photopolymerization initiator (C) of the group consisting of the body (b2), and the photosensitive resin composition has a viscosity of 0.5 to 3.0 Pa·s at 25 ° C. (In the formula, A represents a group having a cyclic guanamine group or a cyclic oximine group and these nitrogen atoms are bonded to a residue in the formula (1), and R ¹ , R ^{1 '} and R ² are Independently represents a hydrogen atom or a methyl group, and a and b each independently represent an integer from 1 to 3) (wherein R ³ represents a hydrogen atom or a methyl group, B represents a single bond or an alkylene group having 1 to 5 carbon atoms, and R ⁴ represents a ring which is bonded to a monocyclic or polycyclic ring. a residue formed by a hydrogen atom on a carbon atom of a lactone compound). The photosensitive resin composition according to claim 1, further comprising a difunctional monomer (E) having a cyclic group having 6 to 20 carbon atoms. The photosensitive resin composition according to claim 1, further comprising: a hydroxyl group-containing (meth) acrylate (b3). The photosensitive resin composition according to claim 1, further comprising a colorant (D). A sealant is obtained by using the photosensitive resin composition according to any one of claims 1 to 4.