KR101698209B1 - Photosensitive resin composition and sealant - Google Patents

Abstract

assignment

(EN) Disclosed is a photosensitive resin composition and an encapsulating agent which are excellent in hydrofluoric acid resistance and permeability.

Solution

The photosensitive resin composition according to the present invention is a photosensitive resin composition comprising a terminal (meth) acrylate oligomer (A), a monomer (b1) represented by the formula (1) and a monomer (b2) represented by the formula At least one monomer (B) selected and a photopolymerization initiator (C).

(Wherein A represents a group having a cyclic amide group or a cyclic imide group and the nitrogen atom thereof is bonded to the residue in the formula (1), R ¹ , R ^{1 '} and R ² are independently a hydrogen atom or a methyl group , And a and b independently represent an integer of 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 hydrogen atom bonded to the carbon atom of the monocyclic or polycyclic lactone compound Represents residues formed except for the dog.)

Description

[0001] PHOTOSENSITIVE RESIN COMPOSITION AND SEALANT [0002]

The present invention relates to a photosensitive resin composition and an encapsulating agent.

2. Description of the Related Art In recent years, display devices such as liquid crystal display panels have been required to be thinned due to the demand for thinner display panels such as liquid crystal televisions and cellular phones. In order to make the display thinner, a method of manufacturing a glass panel by sticking a thin glass to it and a method of physically or chemically thinning a glass portion after manufacturing the glass panel have been studied. Among them, in the method of manufacturing a glass panel by sticking a thin glass, it is considered that the possibility that the glass panel is broken during the process becomes high due to the lack of strength due to the use of the thin glass. For this reason, there has been proposed a method of grinding or etching a glass surface after manufacturing a glass panel by attaching a glass having a thickness normally used to reduce the thickness of the glass (Patent Documents 1 to 3).

There are physical grinding methods such as grinding and chemical grinding (etching) using hydrofluoric acid. However, it is difficult to control the thickness of glass having sufficient strength, Etching using hydrofluoric acid or the like is widely used.

However, in the etching using hydrofluoric acid or the like, if the glass panel is immersed in the etching solution, the etching solution may get into the glass panel and cause various problems. Therefore, an encapsulant (encapsulant) that prevents the penetration of such an etchant has been proposed (Patent Document 4).

Patent Document 1: Japanese Patent No. 2722798

Patent Document 2: JP-A-2004-77640

Patent Document 3: Japanese Patent Application Laid-Open No. 2004-317981

Patent Document 4: Japanese Patent Application Laid-Open No. 2007-314660

Japanese Patent Publication 4 discloses an oligomer (A) obtained by reacting an epoxy resin (a) having an epoxy equivalent of 400 to 2,500 eq / g with a monocarboxylic acid (a2) containing an ethylenic unsaturated group, an ethylenically unsaturated An encapsulating agent containing a group-containing compound (B) and a photopolymerization initiator (C) and used for preventing the penetration of an etching agent at the time of etching the glass substrate has been proposed. 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 an encapsulating agent.

Recently, according to the demand for thinning of the display device, the etching time is required to be prolonged and the etching amount is required to be high. However, when an encapsulating agent is applied to a glass panel having a narrow gap, it takes a long time to infiltrate the sealing agent into the gap of the glass panel in the viscosity of the conventional encapsulating agent, and the permeability to the gap of the encapsulating agent is poor, The sealant that did not infiltrate into the glass panel bulged up from the outside of the glass panel, and piled up the convex shaped bulge. For this reason, after the etching, the bulge of the convex shape becomes thicker than the glass panel, and the glass panel may be broken. Therefore, a sealing agent having a low viscosity and excellent permeability to the gap has been demanded, but the sealing agent having a low viscosity has a drawback that the molecular weight is low and the hydrofluoric acid resistance is deteriorated. Further, when a solvent is used to adjust the viscosity, the density of the resin component in the sealing agent is lowered, and when the resin is cured, there is a problem that the hydrofluoric acid resistance is lowered.

The present invention has been made in view of the above problems, and it is an object of the present invention to provide a photosensitive resin composition having excellent hydrofluoric acid resistance and excellent permeability and an encapsulating agent using the photosensitive resin composition.

The present inventors have found out what can solve the above problems by using a specific monomer component, and accomplished the present invention. Specifically, the present invention provides the following.

(1) In the present invention, the terminal (meth) acrylate oligomer (A) is selected from the group consisting of a monomer (b1) represented by the following formula (1) and a monomer (b2) represented by the following formula And at least one monomer (B) and a photopolymerization initiator (C).

(Wherein A represents a group having a cyclic amide group or a cyclic imide group and such a nitrogen atom is bonded to the residue in formula (1), and R ¹ , R ^{1 '} and R ² independently represent a hydrogen atom or a methyl group And a and b independently represent an integer of 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 hydrogen atom bonded to the carbon atom of the monocyclic or polycyclic lactone compound Represents residues formed except for the dog.)

(2) The present invention also provides an encapsulating agent using the above photosensitive resin composition.

The photosensitive resin composition according to the present invention has excellent hydrofluoric acid resistance and has a viscosity lower than that of the conventional resin composition for encapsulant. For this reason, it has excellent penetrability and less bulge in convex shape when applied to the outer periphery of the glass panel. Thereby, the possibility of breakage when the glass panel is thinned can be reduced. Furthermore, the effect of preventing the hydrofluoric acid resistance from being lowered when cured is exhibited.

Hereinafter, embodiments of the present invention will be described.

The photosensitive resin composition according to the present invention contains an oligomer (A), a monomer (B) and a photopolymerization initiator (C). It may contain an optional component as described below. Each component will be described below.

<Terminal (meth) acrylate oligomer (A)>

(Meth) acrylate oligomer (hereinafter also referred to as &quot; component (A) &quot;) contained in the photosensitive resin composition according to the present invention has a structure in which a CH ₂ ═CHCOO- group or CH ₂ ═CCH ₃ COO- It can be selected appropriately from having a flag. In the present invention, for example, an oligomer obtained by reacting an epoxy resin (a1) with a vinyl group-containing monocarboxylic acid (a2) is preferable. By containing such component (A), excellent hydrofluoric acid resistance and water resistance can be exhibited, and a suitable elongation and hardness can be imparted to the cured product after 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 &quot; component (a1) &quot;) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, N, N-diglycidyl- N, N-diglycidyl aniline, resorcinol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylol propane triglycidyl ether, polypropylene glycol diglycidyl ether, hexahydro anhydride Phthalic acid diglycidyl ester, and the like. Among them, a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are preferable, and a bisphenol A type epoxy resin is particularly preferable. These epoxy resins may be used alone or in combination of plural kinds.

[Vinyl group-containing monocarboxylic acid (a2)]

Examples of the vinyl group-containing monocarboxylic acid (hereinafter also referred to as "component (a2)") include (meth) acrylic acid or a reaction product of a saturated or unsaturated dibasic acid and a vinyl group-containing monoglycidyl compound . Examples of the (meth) acrylic acid include acrylic acid, methacrylic acid,? -Styryl acrylic acid,? -Furfuryl acrylic acid, a saturated or unsaturated dibasic acid anhydride and (meth) acrylates having one hydroxyl group in one molecule Semi-esters which are equimolar reactants of the derivatives, and half-esters which are equimolar reactants of saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives.

Examples of the saturated or unsaturated dibasic acid anhydrides used in the production of the above-described half-esters include maleic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Phthalic anhydride, itaconic anhydride and methyl endmethylene tetrahydrophthalic anhydride. Examples of the (meth) acrylate derivative having one hydroxyl group in one molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerin di ) Acrylate, (meth) acrylate of phenyl glycidyl ether, and the like.

Examples of the saturated or unsaturated dibasic acid used in the production of the above-described half ester include succinic acid, maleic acid, adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, itaconic acid, . Examples of monoglycidyl (meth) acrylate derivatives include glycidyl (meth) acrylate and the like.

The component (a2) may be used alone or in combination of plural kinds. 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 is carried out by a generally known method. For example, an epoxy resin may be mixed with acrylic acid or methacrylic acid in a predetermined equivalent ratio, a catalyst (e.g., benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.) (A) is obtained by adding a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.) . The molecular weight of the component (A) thus synthesized is preferably 300 to 6,000, more preferably 500 to 3,000. The component (A) has such a molecular weight that it can have excellent hydrofluoric acid resistance, water resistance and suitable viscosity.

When the component (A) has a hydroxyl group, it is preferable from the viewpoint of improving the adhesion. As a commercially available product corresponding to component (A), EBECRYL 600, EBECRYL 605, EBECRYL 645, EBECRYL 648, EBECRYL 860, EBECRYL1 606, EBECRYL 3105, EBECRYL 3213, EBECRYL 3420, EBECRYL 3500, EBECRYL 3608, EBECRYL 3700, EBECRYL 3701 , EBECRYL 3702, EBECRYL 3703, EBECRYL 3708, and EBECRYL 6040; Acrylic (meth) acrylates such as EBECRYL 303, EBECRYL 740-40TP, EBECRYL 745, EBECRYL 767 and EBECRYL 1200; (All available from Daicel-Cotech). In addition, polyester type (meth) acrylates such as CNUVE 151 (manufactured by SARTOMER) and the like may be mentioned.

The content of the component (A) is preferably 15 to 60% by weight, more preferably 17 to 50% by weight, and still more preferably 20 to 40% by weight based on the photosensitive resin composition. When the amount is less than the upper limit, permeability of the photosensitive resin composition is improved. The hydrofluoric acid resistance is improved by setting it to the lower limit value or more. In addition, within the above range, the effect of imparting an appropriate elongation and hardness to the cured product is obtained, which is an improvement in water resistance.

&Lt; Monomer (B) &gt;

The monomer (hereinafter also referred to as &quot; component (B) &quot;) contained in the photosensitive resin composition according to the present invention can be obtained by copolymerizing a monomer (b1) represented by the following formula (1) and a monomer represented by the following formula b2). &lt; / RTI &gt; The components constituting the component (B) are as follows.

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

The monomer (b1) (hereinafter also referred to as &quot; component (b1) &quot;) is represented by the following formula (1). The term "residue in the formula (1)" represents "- [- (CHR ¹ -CHR ^{1 '} ) _a -O-] _b -CO-CR ² ═CH ₂ ".

(Wherein A represents a group having a cyclic amide group or a cyclic imide group and the nitrogen atom thereof is bonded to the residue in the formula (1), and R ¹ , R ^{1 '} and R ² independently represent a hydrogen atom or a methyl group And a and b independently represent an integer of 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, more preferably 1.

In the formula (1), the cyclic skeleton in A may be monocyclic or polycyclic, and may be a phytocyclic ring or an unsaturated ring. The above A is preferably a cyclic amide group or a cyclic imide group having 5 to 10 membered ring cyclic skeletons alone or in combination of two or more, and is preferably a cyclic amide group or a cyclic amide group having 5 to 6 membered rings, More preferably an imide group.

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

Among them, monomers represented by formulas (1-5) to (1-20) and formulas (1-25) to (1-40) having cyclic imide are preferable from the viewpoint of improvement of adhesion. In view of improving the etching resistance, the monomers represented by formulas (1-9) to (1-20) and (1-29) to (1-40) are preferable. Particularly preferred are N-acryloyloxyethylhexahydrophthalimide (1-9) or N-methacryloyloxyethylhexahydrophthalimide (1-10). The component (b1) may be used alone, or a plurality of components may be used in combination. By containing the component (b1), the shrinkage upon curing can be reduced, and the adhesion can be enhanced.

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

The monomer b2 (hereinafter also referred to as &quot; component (b2) &quot;) 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 hydrogen atom bonded to the carbon atom of the monocyclic or polycyclic lactone compound Represents residues formed except for the dog.)

When B is an alkylene group, the alkylene group may be linear or branched. By containing the component (b2), the shrinkage upon curing can be reduced and the heat resistance is improved. Examples of such component (b2) include monomers 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, a fluorine atom or a fluorinated alkyl group Branched or cyclic alkyl group having 1 to 15 carbon atoms, m is 0 or 1, Q is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or Sulfur atom.)

When R 'is a lower alkyl group, the lower alkyl group preferably has 1 to 5 carbon atoms. When R "is a linear or branched alkyl group, the alkyl group preferably has 1 to 10 carbon atoms and more preferably 1 to 5. In the case where R" is a cyclic alkyl group, the alkyl group has 3 to 15 carbon atoms More preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, R "represents a group in which at least one hydrogen atom is removed from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane, or a tetracycloalkane, which may be substituted with a fluorine atom or a fluorinated alkyl group More specifically, a monocycloalkane such as cyclopentane or cyclohexane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane, or a mixture of at least one hydrogen Among the groups (b2-1) to (b2-5), R 'is preferably a hydrogen atom in consideration of industrial availability.

When Q is an alkylene group of 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, specific examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, -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 formulas (b2-1) to (b2-5) are shown below.

Among them, lactone of the group represented by the formulas (b2-1) and (b2-3) and lactone of the group represented by the formulas (b2-2-8) to (b2-2-9) from the viewpoint of improving the adhesion and heat resistance Monomers are preferred. In particular, the monomers represented by the formulas (b2-1-1) to (b2-1-2) and (b2-2-8) to (b2-2-9) are more preferable, (b2-1-1) to (b2-1-2) are more preferable, and? -methacryloxy-gamma -butyrolactone and? -methacryloxy-gamma -butyrolactone are particularly preferable Do. The component (b2) may be used alone or in combination of plural kinds.

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

The photosensitive resin composition according to the present invention preferably contains a hydroxyl group-containing (meth) acrylate (hereinafter also referred to as "component (b3)"). By containing such component (b3), the shrinkage upon curing can be reduced, and the adhesion can be further enhanced.

Examples of the component (b3) include monomers 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 in R ⁶ is preferably a hydroxyalkyl group having 10 or less carbon atoms, and is preferably a linear or branched chain, more preferably a hydroxyalkyl group having 2 to 8 carbon atoms, A hydroxyethyl group, or a hydroxypropyl group. The number of hydroxyl groups is not particularly limited, but is preferably 1 or 2, more preferably 1. The bonding position is not particularly limited, but is preferably bonded to the terminal of the alkyl group.

The hydroxyalkyl group of R ⁶ may have a phenoxy group or a phenoxyalkyl group as a substituent. The phenoxyalkyl group is preferably a phenoxymethyl group, a phenoxyethyl group or a phenoxypropyl group. It is preferable that one of the hydrogen atoms of the carbon atoms to which the hydroxyl group of R &lt; ⁶ &gt; is bonded is substituted with a phenoxyalkyl group.

An example of the preferable component (b3) represented by the above formula (3-1) is a monomer represented by the following formula (3-2).

(Wherein R ⁵ is as defined above, R ⁷ is a hydrogen atom or a phenoxyalkyl group, and c is 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 preferable.

As the component (b3), a monomer in which the hydrogen atom of the hydroxyl group in the formula (3-1) is further substituted with a hydroxyl group-containing organic group or a carboxyl group-containing organic group as a monomer other than the above may be mentioned. The organic group preferably contains an ester bond. As the monomer substituted with the hydroxyl group-containing organic group, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate is suitably used. Examples of the monomer substituted with the carboxyl group-containing organic group include 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylhexahydrophthalic acid and monoacryloyloxyethylhexahydrophthalate.

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

The content of the component (B) is preferably from 20 to 95% by weight, more preferably from 30 to 85% by weight, based on the photosensitive resin composition. By setting the thickness to the above range, high adhesion to the glass panel and heat resistance at the time of etching can be exhibited. The blending amount of the components (b1), (b2) and (b3) may be appropriately changed according to the desired values of the adhesion and heat resistance of the photosensitive resin composition. For example, the component (b1) (B2) is preferably from 15 to 70% by weight, more preferably from 20 to 65% by weight, based on the photosensitive resin composition, based on the weight of the photosensitive resin composition, , And the amount of the component (b3) is preferably from 1 to 55% by weight, more preferably from 3 to 50% by weight, based on the photosensitive resin composition.

Examples of the monomer constituting the component (B) include:

(1) When only the component (b1) is composed

(2) When only the component (b2) is composed

(3) In the case of the component (b1) and the component (b2)

(4) In the case of the component (b1) and the component (b3)

(5) A composition comprising the component (b2) and the component (b3)

(6) the component (b1), the component (b2), and the component (b3).

Of these, (3) to (5) are preferable in view of favorable balance of adhesion and heat resistance in addition to hydrofluoric acid resistance, and (3) or (5) is particularly preferable.

(B1) / (b2) of the polymer (3) is preferably from 1/99 to 99/1, more preferably from 10/90 to 90/10, and still more preferably from 20/80 to 65/35.

(B1) / (b3) of the polymer (4) is preferably from 1/99 to 99/1, more preferably from 10/90 to 90/10, and still more preferably from 20/80 to 80/20.

(B2) / (b3) of the polymer (5) is preferably from 1/99 to 99/1, more preferably from 5/95 to 95/5, and further preferably from 10/90 to 90/10.

(6) is preferably 45/55 to 99/1 (the sum of (b1) and (b2)] / (b3). The ratio of (b1) to (b2) is preferably the same as in the case of (3).

&Lt; Bifunctional Monomer (E) &gt;

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

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

(In formula (e1), R ⁸ is independently the same as R ² , R ⁹ is independently an alkylene group having 1 to 3 carbon atoms, and R ¹⁰ is a divalent cyclic group having 6 to 20 carbon atoms.)

R ⁹ in the formula (e1) is specifically a methylene group, an ethylene group, a propylene group or an isoprene group. From the viewpoint of improving the heat resistance, a methylene group and an ethylene group are preferable, and a methylene group is more preferable. The divalent cyclic group of R &lt; ¹⁰ &gt; in the formula (e1) is preferably an aliphatic cyclic group. The carbon number of the cyclic group is preferably 7 to 15, more preferably 8 to 12. The cyclic group may have an alkyl group having 1 to 5 carbon atoms as a substituent.

Examples of the cyclic group include a monocycloalkane or a group excluding two hydrogen atoms from a polycycloalkane such as a bicycloalkane, a tricycloalkane or a tetracycloalkane. Specific examples thereof include monocycloalkylene groups such as cyclopentylene group and cyclohexylene group; And polycycloalkylene groups such as an adamantylene group, a norbornylene group, an isobornylene group, a tricyclodecanylene group and a tetracyclododecanylene group. From the viewpoint of improving the heat resistance and the etching resistance, the poly A cycloalkylene group, and more preferably a tricyclodecanylene group and a tetracyclododecanylene group.

As the bifunctional (meth) acrylate (e1), tricyclodecane dimethanol diacrylate, tricyclodecane diethanol diacrylate, tetracyclododecanediacrylate and the like are preferable. Particularly preferred is tricyclodecane dimethanol diacrylate.

The component (E) may be used alone or in combination of plural species.

The content of the component (E) is in the range of 10 to 50% by weight with respect to the photosensitive resin composition. Within the above range, heat resistance and etching resistance can be improved.

(E), examples of combinations with the component (B) are:

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

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

(3 ') In the case of the component (b1), the component (b2) and the component (e1)

(4 '), (b1), (b3) and (e1), particularly preferably (1').

&Lt; Photopolymerization initiator (C) &gt;

The photopolymerization initiator (C) is not particularly limited, but is preferably dissolved in the monomer (B). Examples of the photopolymerization initiator (C) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) Methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethane Yl] -1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide , 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, , 4-dimethylamino-2-isoamylbenzoic acid, benzyl benzyldimethylketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4- , 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2-methylthioxanthone, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, Benzoyl peroxide, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o- chlorophenyl) Methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone , 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin Ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, P-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, alpha, alpha -methylpyrrolidone, Dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine , 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) 2-yl) ethenyl] -4,6-bis (trichloromethyl) -s- (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4- dimethoxyphenyl) ethenyl] (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s- triazine, 2,4-bis- trichloromethyl-6- 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4- Bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4- ) Styrylphenyl-s-triazine. Among them, it is particularly preferable to use a photopolymerization initiator of the morpholino system in terms of sensitivity. These photopolymerization initiators may be used alone or in combination of plural kinds.

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

&Lt; Colorant (D) &gt;

The photosensitive resin composition according to the present invention preferably further contains a colorant (hereinafter also referred to as &quot; component (D) &quot;). It is easy to visually confirm the amount of penetration into the coated portion and the glass panel when the photosensitive resin composition according to the present invention is applied to the glass panel by including the colorant. Although such a colorant is not particularly limited, it may be dissolved in the photosensitive resin composition according to the present invention without using a solvent, so that there is no discoloration over time and does not overlap with the absorption wavelength of the photopolymerization initiator (component (C)) . Of these, organic dyes are preferred. The organic dyes may be used singly or in combination of two or more as necessary.

The wavelength of the maximum absorbance in the organic dye added to the photosensitive resin composition according to the present invention is preferably 450 to 750 nm, more preferably 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, (CI 42535), Rhodamine B (CI 45170B), Malachite Green (CI 42000), and Rhodamine B (CI 42535) Methylene blue (CI 52015), and the like.

The organic dye can be appropriately dissolved in the photosensitive resin composition by a known method. Examples of such a method include a method using a high-speed stirrer such as a dissolver. The amount of the organic dye to be added is appropriately adjusted according to the environment (conditions and applications) in which the photosensitive resin composition is used, preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight based on the entire photosensitive resin composition.

<Other components>

The photosensitive resin composition according to the present invention may contain additives as required. Examples of the additive include a heat polymerization inhibitor, a defoaming agent, a sensitizer, a curing accelerator, a photo-crosslinking agent, a photosensitizer, a dispersant, a dispersing aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti-

<Organic solvents>

In the photosensitive resin composition according to the present invention, an organic solvent may suitably be used for improving the solubility of each component and for assisting in dissolution uniformity.

As the organic solvent,

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono- -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- Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri Propylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol di (Poly) alkylene glycol alkyl ethers such as ethyl ether;

(Propylene glycol monomethyl ether acetate), ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA) Alkylene glycol alkyl ether acetates;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone;

Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate;

Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, propylene glycol monomethyl ether Propionate, propylene glycol monoethyl ether propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, Propyl acetate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, methyl carbonate, carbon tetrachloride, ethyl lactate, ethyl lactate, ethyl lactate, butyl lactate, Acetate, other esters such as propyl carbonate, butyl carbonate, and the like;

Aromatic hydrocarbons such as benzene, toluene and xylene;

Amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide,

(DMSO), methanol, ethanol, propanol, butanol, 3-methoxybutanol (BM), hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin,? -Butyrolactone,? - terpineol (terpineol), and the like.

The amount of the organic solvent to be used is not particularly limited and may be suitably set in accordance with the coating film thickness at a coatable concentration. Is preferably 20% by weight or less, more preferably 10% by weight or less, further preferably 5% by weight or less of the entire photosensitive resin composition from the viewpoints of maintaining the density of the resin component and maintaining the hydrofluoric acid resistance upon curing , And particularly preferably 1% by weight or less. In the present invention, it is most preferable that the material is substantially 0 wt% (that is, a non-solvent-sensitive photosensitive resin composition).

&Lt; Preparation method of photosensitive resin composition &gt;

The photosensitive resin composition according to the present invention can be obtained by mixing all the above components with a stirrer. Further, the mixture may be filtered using a filter so as to be 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, particularly preferably a viscosity of 1.0 to 1.8 Pa · s Do. By having the viscosity in this range, permeability to the inside of the glass panel is improved, and breakage of the glass panel after etching can be prevented. By setting the viscosity to 0.5 Pa · s or more depending on the size of the gap (gap) between the glass panels, the coating property of the photosensitive resin composition can be maintained satisfactorily, the glass panel can be sufficiently sealed, Or less, it is possible to maintain good permeability to the inside of the glass panel and to prevent breakage of the glass panel after etching.

When the photosensitive resin composition according to the present invention is cured, the density of the resin component is not lowered and the hydrofluoric acid resistance is not lowered.

[Method of sealing glass panel]

Examples of the application of the photosensitive resin composition according to the present invention as an encapsulating agent are shown below.

Two glass plates having a thickness of 0.5 to 1.0 mm are aligned so that a gap of 2 to 20 占 퐉 is formed and the photosensitive resin composition is applied to the outer peripheral portion by a manual or dispenser or the like. At this time, the amount of penetration of the photosensitive resin composition is preferably 1 to 10 mm from the outer peripheral portion. In a preferred embodiment of the present invention, since the photosensitive resin composition contains a colorant, the amount of penetration can be easily confirmed by eyes.

Subsequently, the coated photosensitive resin composition is exposed to active energy rays such as ultraviolet rays and excimer laser rays. The energy dose to be irradiated varies depending on the composition of the photosensitive resin composition, but is preferably, for example, 200 to 5,000 mJ / cm 2.

Subsequently, the glass panel is subjected to etching by immersion or shower using a hydrofluoric acid etching solution such as hydrofluoric acid or ammonium fluoride at 20 to 80 ° C for 30 to 200 minutes. The total thickness of the glass plate fitted by this etching is reduced to 0.2 to 1.0 mm.

In the case of encapsulating using a 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 has not penetrated the interior of the glass panel is located outside And piles up the bulge of the convex shape. Therefore, after the etching, the bulge of the convex shape becomes thicker than the glass panel, and there is a high possibility that the glass panel is broken. However, since the photosensitive resin composition according to the present invention has a low viscosity, the permeability is high and it is difficult to cause a bulge in a convex shape. Therefore, the possibility of damaging the glass panel can be greatly reduced. Further, since the photosensitive resin composition according to the present invention contains the specific monomer (B), it exhibits the effect of reducing the curing shrinkage and improving the adhesiveness and heat resistance.

Example

Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to the following examples.

&Lt; Examples 1 to 12, Comparative Examples 1 to 5 &gt;

As the component (A), the component (B) and the component (C), the compounds shown in Table 1 were compounded in the ratios shown in Table 1 to prepare photosensitive resin compositions. The viscosity at this time (25 ° C) is shown in the table.

(A) -1 in the table represents EBECRYL 3701: a modified epoxy acrylate having a bisphenol A skeleton (manufactured by Daicel-Cotech), (A) -2 represents CNUVE 151: polyester acrylate ). Acrylonitrile, N-acryloyloxyethylhexahydrophthalimide (tolactic acid), GBLMA, alpha -methacryloxy-gamma -butyrolactone (Osaka Organic Chemicals), HEMA, hydroxyethyl methacrylate, PHA refers to 3-phenoxy-2-hydroxyacrylate, and MAHP refers to monoacryloyloxyethylhexahydrophthalate.

As the bifunctional monomer (E), SR833 represents tricyclodecane dimethanol diacrylate (made by SARTOMER).

IR907 (manufactured by Ciba Specialty Chemicals) was used as the photopolymerization initiator (C).

As the colorant (D), (D) -1 represents Oil Blue 613 (manufactured by Orient Chemical).

The numerical values in parentheses in the tables indicate weight%.

<Evaluation>

The coating properties, curability, adhesion, heat resistance, etching resistance, and peeling after drying of the prepared samples were evaluated as follows. The results are shown in Table 2.

[Application property]

Two glass plates having a thickness of 0.7 mm were fitted so as to give a clearance of about 10 탆 and a sample was manually applied to the outer circumferential portion to visually confirm whether or not the sample had penetrated into the clearance of the glass plate. It is ○ that penetration is recognized, and × that it is not admitted.

[Surface hardening property]

The sample was coated on a glass plate having a thickness of 0.7 mm so as to have a thickness of 12 占 퐉 by using a spin coater (made by Mikasa), and then cured by irradiating ultraviolet rays at an exposure amount of 2,000 mJ / cm2. The hands were checked to see if there was any hardening. When nothing is attached by touching, ○ is indicated as hardened and × is attached.

[Adhesion]

The sample was coated on a glass plate having a thickness of 0.7 mm so as to have a thickness of 12 占 퐉 by using a spin coater (made by Mikasa), and then cured by irradiating ultraviolet rays at an exposure amount of 2,000 mJ / cm2. Then, relative comparison was carried out based on JIS K5600-5-7. The evaluation criteria are as follows;

?: At least 110;?: At least 80;?: At least 40;

[Heat resistance]

Test specimens of 250 mm x 3 mm x 200 m were prepared by irradiating ultraviolet rays at an exposure amount of 2,000 mJ / cm &lt; 2 &gt; The test film was subjected to TMA measurement by a tensile test method using a thermomechanical analyzer (manufactured by Seiko). And those having a softening point at 60 to 100 占 폚 and those having a softening point at 25 to 60 占 폚.

[Etching resistance]

The sample was ejected using an automatic dispenser (manufactured by Musashi Engineering Co., Ltd.) so as to have a square of 3.5 cm on a glass plate having a thickness of 10 cm and a thickness of 0.7 mm, followed by curing by irradiating ultraviolet rays at an exposure amount of 2,000 mJ / cm 2. Subsequently, the glass plate was immersed in 20 wt% hydrofluoric acid at 25 DEG C to observe the peeling of the cured product visually, and the time until partial peeling occurred was measured. ◎ for thing which took more than 55 minutes, ◎ for thing which took less than 40 minutes and less than 55 minutes, △ for thing that took less than 30 minutes and less than 40 minutes for less than 30 minutes.

[Peeling after drying]

After completion of the above etch resistance test, drying was carried out, and the presence or absence of peeling was visually observed. &Quot; &quot; indicates that no peeling occurred, and &quot; x &quot;

Yes Application property surface
Hardenability Adhesiveness Heat resistance Etchability after drying
Exfoliation Example 1 ○ ○ △ ○ ◎ × Example 2 ○ ○ ◎ × △ × Example 3 ○ ○ ○ ○ ◎ ○ Example 4 ○ ○ ○ ○ ◎ ○ Example 5 ○ ○ ○ ○ ◎ ○ Example 6 ○ ○ ○ × △ × Example 7 ○ ○ △ ○ ○ ○ Example 8 ○ ○ ○ ○ ◎ ○ Example 9 ○ ○ ○ ○ ◎ ○ Example 10 ○ ○ ○ × △ × Example 11 ○ ○ △ × △ × Example 12 ○ ○ ○ ○ ○ ○ Comparative Example 1 ○ ○ ◎ × × - Comparative Example 2 ○ ○ × - - - Comparative Example 3 ○ ○ ◎ × × - Comparative Example 4 ○ ○ × ○ - - Comparative Example 5 ○ ○ ○ × × -

For the evaluation, the adhesion was too high to evaluate the etching resistance, and the result was &quot; - &quot;. In addition, the reason why the result of the etching resistance is not good is that the peeling after drying is not confirmed, so the evaluation is "-".

In Table 2, it was found that the curable property can be maintained even when the photosensitive resin composition has a low viscosity in order to improve the coating property, and the etching resistance is also improved (Examples 1 to 12). (b1) and (b2), it was found that all evaluation items were satisfactory (Examples 3 to 5, Example 12). It was also found that by combining the components (E) (Example 9), good characteristics can be obtained.

As to Examples 3 and 9, the same evaluation was also conducted for the case where 5 wt% of PGMEA was further added without changing the weight ratio of each component. As a result, it was confirmed that all evaluation items were satisfactory.

Claims (6)

At least one monomer selected from the group consisting of a terminal (meth) acrylate oligomer (A), a monomer (b1) represented by the following formula (1) and a monomer (b2) represented by the following formula (2) B), a photopolymerization initiator (C), and a bifunctional monomer (E) represented by the following formula (e1) And a viscosity of 0.5 to 3.0 Pa · s.

(Wherein A represents a group having a cyclic amide group or a cyclic imide group and the nitrogen atom thereof is bonded to the residue in the formula (1), R ¹ , R ¹ 'and R ² are independently a hydrogen atom or a methyl group , And a and b independently represent an integer of 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 hydrogen atom bonded to the carbon atom of the monocyclic or polycyclic lactone compound Represents residues formed except for the dog.)

(Wherein R ⁸ independently represents a hydrogen atom or a methyl group, each R ⁹ independently represents an alkylene group having 1 to 3 carbon atoms, and R ¹⁰ represents a divalent cyclic group having 6 to 20 carbon atoms.) delete delete The method according to claim 1, And a hydroxyl group-containing (meth) acrylate (b3). The method according to claim 1, And a colorant (D). An encapsulating agent using the photosensitive resin composition according to any one of claims 1 to 5.