JP2002287349A - Sandblast resistant photosensitive resin composition exposable with visible light, dry film using the same and method for cutting body processed using these - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sandblast resistant photosensitive resin composition which can be directly and patternwise exposed with visible light, particularly argon laser light whose wavelength peak is at about 488 nm or YAG(yttrium aluminum garnet) second harmonic laser light whose wavelength peak is at about 532 nm and has superior profitability and high sensitivity and to provide a dry film using the composition and a method for cutting a body processed using these. SOLUTION: The sandblast resistant photosensitive resin composition exposable with visible light comprises a photopolymerizable urethane (meth) acrylate compound (A) having at least two (meth)acryloyl groups, an alkali- soluble high molecular compound (B) having 50-250 mg/KOH acid value and a photopolymerization initiating system (C) comprising a specified compound such as tetramethylammonium-ethyltributyl borate, tetra-n-butylammonium- phenetyltrimethyl borate or tetraethylammonium-phenyltriisobutyl borate and a sensitizing dye.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sandblast-resistant photosensitive resin composition that can be exposed to visible light, and more particularly, to a material having suitable properties as a mask material when cutting an object to be processed by sandblasting, Highly sensitive, visible-exposure-resistant sandblasting that enables direct drawing exposure with visible light such as argon laser light having a peak near 488 nm or YAG-SHG (second harmonic) laser light having a wavelength peak near 532 nm. The present invention relates to a photosensitive photosensitive resin composition, a Drafti film using the same, and a method for cutting an object to be processed using the same.

[0002]

2. Description of the Related Art Conventionally, in forming a relief by cutting glass, marble, plastic or the like, processing by sandblasting has been performed. In recent years, in the production of circuit boards in which metal patterns and insulating patterns are mixed, particularly, metal wiring patterns for plasma displays, and insulating patterns such as ceramics and phosphors, patterning is performed by using a photolithography method or the like as a mask material on an object to be processed. There has been proposed a sandblasting method in which a photosensitive resin layer is provided, and then a non-mask portion is selectively cut by spraying an abrasive.

As a photosensitive resin composition used as a mask material for the sandblast treatment, for example, an unsaturated polyester, an unsaturated monomer and a photopolymerization initiator as disclosed in JP-A-55-103554 are used. And a photosensitive resin composition comprising polyvinyl alcohol and a diazo resin as disclosed in JP-A-2-69754. Also, Japanese Patent Application Laid-Open Nos. 6-161097 and 6-16
No. 1098 discloses that the basic performance as a sandblast-resistant photosensitive resin composition is (1) that it has high elasticity and flexibility and can be used as a sandblast mask material;
(2) excellent developability with an aqueous alkali solution;
Photosensitive resin compositions for the purpose of (3) good adhesion to the object to be processed, (4) being able to be formed into a dry film, etc. are disclosed. Direct drawing exposure could not be performed by visible light exposure.

[0004]

By the way, recently, due to the development of electronic device technology, the use of FA has been advanced, and the cutting work by sand blasting and the like has also tended to be automated. In order to reduce the cost, a photosensitive resin composition that can be directly drawn and exposed by a visible laser beam or the like is required as a mask material. For example, a practical wavelength peak is around 488 nm from the intensity of exposure intensity. There is a demand for a sandblast-resistant photosensitive resin composition that can be exposed by drawing with a certain argon laser beam and a YAG-SHG (second harmonic) laser beam having a wavelength peak near 532 nm. JP-A-10-
JP-A-293400 discloses a sandblast-resistant photosensitive resin composition which can be exposed to light by using a titanocene compound, an acridine compound, a triazine compound, a rhodamine compound, and a coumarin compound as a photopolymerization initiator component. However, the photopolymerization initiator system used for this is very expensive and economically inferior. .

The present invention solves the above-mentioned conventional problems and has the following basic properties as a sandblast-resistant photosensitive resin composition: (1) it has high elasticity and flexibility and can be used as a sandblast mask material; In addition to (2) excellent alkali developability in consideration of the environment, (3) good adhesion to the object to be processed, and (4) being able to form a dry film, (5) visible light Especially 4 wavelength peaks
Requirements for direct drawing exposure with visible light such as argon laser light near 88 nm and YAG second harmonic laser light with a wavelength peak near 532 nm, and (6) excellent economical efficiency It is an object of the present invention to provide a highly sensitive sandblast-resistant photosensitive resin composition which satisfies all of the above conditions, a dry film using the same, and a method for cutting an object using these.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by combining a specific compound as a photopolymerization initiation component into a composition. And completed the present invention.

That is, the present invention relates to a photopolymerizable urethane (meth) acrylate compound (A) having at least two (meth) acryloyl groups, and having an acid value of 50 to 25.
0-mg / KOH alkali-soluble polymer compound (B), and a visible-exposure-resistant, sandblast-resistant photosensitive composition comprising a photopolymerization initiation component (C) comprising a compound represented by the following general formula (1) and a sensitizing dye: The present invention relates to a water-soluble resin composition.

Embedded image (Wherein, R ₁ , R ₂ , R ₃ and R ₄ each independently represent an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a heterocyclic group, or an alicyclic group, and R ₁ , R ₂ , R ₃
And R ₄ may be the same or different. Z is 4
Quaternary ammonium cation, quaternary pyridinium cation,
Represents a quaternary quinolium cation, a phosphonium cation, a sulfonium cation, an oxonium cation, an iodonium cation, or a metal cation. )

The photopolymerization initiator component (C) preferably comprises a compound represented by the following general formula (2) and a sensitizing dye.

Embedded image (Wherein, R ₅ and R ₆ each independently represent hydrogen, an alkyl group, an alkenyl group, an alkoxyl group, an aryl group, an aralkyl group, a heterocyclic group, or an alicyclic group, and R ₅ and R ₆
May be the same or different. The substitution position of R ₅ may be on any ring of naphthalene. Z is 4
Quaternary ammonium cation, quaternary pyridinium cation,
Represents a quaternary quinolium cation, a phosphonium cation, a sulfonium cation, an oxonium cation, an iodonium cation, or a metal cation. )

It is preferable that the composition further contains a chain transfer agent (D) in addition to the components (A) to (C).

It is preferable that the composition further contains a photopolymerizable monomer (E) in addition to the components (A) to (D).

Further, the present invention provides a method for forming a sandblast-resistant photosensitive resin layer by applying the above-mentioned visible-light-exposed sandblast-resistant photosensitive resin composition on a support and drying the composition.
The present invention relates to a sandblast-resistant dry film capable of being exposed to light, comprising a protective material layer laminated on the layer.

Further, the present invention provides a method for applying the above-mentioned sandblast-resistant photosensitive resin composition capable of being exposed to visible light on an object to be processed.
After drying to form a sandblast-resistant photosensitive resin layer, this sandblast-resistant photosensitive resin layer is directly exposed to visible light for image drawing, and then developed to selectively remove the photosensitive resin layer. The present invention relates to a method for cutting an object to be processed, wherein a pattern is formed, and thereafter, the object is cut by sandblasting using the pattern as a mask.

Further, the present invention provides a method for removing a dry film by peeling off a protective material layer from the above-mentioned visible light-exposed sandblast-resistant dry film so that the exposed surface of the photosensitive resin layer is in contact with the surface of the object to be processed. After being deposited on the object to be processed, the sandblast-resistant photosensitive resin layer of this dry film is directly subjected to image drawing exposure with visible light, and then the support is peeled off and developed, and the photosensitive resin layer is selectively removed. To form a photosensitive resin pattern, and thereafter, the object is cut by sandblasting using the pattern as a mask.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The photopolymerizable urethane (meth) acrylate compound (A) used in the present invention comprises:
It has at least two (meth) acryloyl groups. This urethane (meth) acrylate compound (A) has a diisocyanate compound and a diol compound at both ends of -N.
It can be obtained by reacting such that a CO group (isocyanate group) remains, and reacting a (meth) acrylate compound having a hydroxyl group with the -NCO group. This urethane (meth) acrylate compound (A)
May be a carboxy-modified urethane (meth) acrylate compound by introducing a carboxyl group. In this case,
The acid value is preferably 70 mg / KOH or less, more preferably 20 to 50 mg / KOH. Acid value 70
When the amount exceeds mg / KOH, flexibility is lost and water resistance is poor, which is not preferable.

In addition, when the photosensitive resin composition of the present invention capable of being exposed to visible light is applied to the cutting of a non-conductive object such as glass, marble, porcelain, various plastics, etc. The urethane (meth) acrylate compound (A) has an electric (volume resistivity) electric insulation resistance value after curing by ultraviolet irradiation of 1.0 × 10 ¹⁰ Ω · cm or more and less than 2.0 × 10 ¹² Ω · cm. Is preferable, and more preferably 1.0 × 10 ¹⁰ Ω · cm or more,
It is 5.0 × 10 ¹¹ Ω · cm or less. When the electrical insulation resistance value is 2.0 × 10 ¹² Ω · cm or more, static electricity tends to be easily charged during sandblasting, and discharge or lightning is likely to occur, which may damage the workpiece.

The urethane (meth) acrylate compound (A) preferably has a mass average molecular weight of about 5,000 to 30,000, more preferably 8,000 to 25,000.
It is about. If the weight average molecular weight is less than 5000, the formed photosensitive resin pattern may be hard,
If the weight average molecular weight exceeds 30,000, the solubility in an alkaline aqueous solution tends to decrease.

As the alkali-soluble polymer compound (B) used in the present invention, a copolymer of (meth) acrylic acid and (meth) acrylate, a carboxyl group-containing cellulose resin, and the like are preferably used.
As the copolymer of (meth) acrylic acid and (meth) acrylic acid ester, a combination of acrylic acid or methacrylic acid / methyl acrylate, methyl methacrylate, ethyl acrylate or ethyl methacrylate is preferred, and particularly preferred is a further combination. , N-butyl acrylate or n-butyl methacrylate / acrylonitrile or methacrylonitrile in combination. Also, glycidyl methacrylate is obtained by copolymerizing (meth) acrylic acid and another (meth) acrylic acid ester, or (meth) acrylic acid and a (meth) acrylic acid ester having a hydroxyl group, or (meth) acrylic acid ester. Methacryloyloxyethyl isocyanate, etc., to which a double bond has been added. As the carboxyl group-containing cellulose resin, hydroxyethyl carboxymethylcellulose, hydroxyacetate hexahydrophthalate, hydroxypropylmethylcellulose hexahydrophthalate, cellulose acetate phthalate, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose acetate succinate and the like are preferable. Cellulose acetate phthalate, hydroxypropylmethylcellulose phthalate, etc., which have good compatibility with the above-mentioned carboxy-modified urethane (meth) acrylate compound, have excellent film forming ability when formed into a dry film, and have good developability with an aqueous alkali solution, are preferred. Used.

The compounding mass ratio of the component (A) and the component (B) is preferably from 5:95 to 95: 5, more preferably from 10:90 to 85:15. When the blending amount of the component (B) exceeds 95% by mass, the electrical insulation resistance value increases and the sandblast resistance may decrease. On the other hand, when the amount is less than 5% by mass, the film-forming ability is lacking. , Cold flow and the like.

The acid value of the alkali-soluble polymer compound (B) in the present invention is from 50 to 250 mg / KOH, preferably from 80 to 200 mg / KOH. Acid value is 50
When the amount is less than mg / KOH, poor development may occur. On the other hand, when the amount exceeds 250 mg / KOH, it is not preferable because flexibility is lowered and water resistance during development is poor.

Photopolymerization initiation system used in the present invention
The minute (C) is a compound represented by the above general formula (1) (C-
1) and a sensitizing dye (C-2). In general formula (1)
Compound (C-1) shown and an appropriate sensitizing dye (C-2)
In combination, light irradiation causes initiator decomposition.
The polymerization starts. R in the above general formula (1)₁,
R ₂, R₃And R₄Is each independently an alkyl group,
Alkenyl, aryl, aralkyl, heterocyclic,
Represents an alicyclic group. Where R₁, R₂, R₃And R₄Is the same
Or different.

The alkyl group is preferably a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, Examples include pentyl, hexyl, heptyl, octyl, 3-methoxypropyl, 4-chlorobutyl, and 2-diethylaminoethyl.

The alkenyl group is specifically a substituted or unsubstituted alkenyl group having preferably 2 to 12 carbon atoms, for example, a vinyl group, a propenyl group, a butenyl group,
Examples include a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a dodecynyl group, and a prenyl group.

The aryl group is specifically a substituted or unsubstituted aryl group, for example, phenyl, tolyl,
Xylyl, 4-ethylphenyl, 4-butylphenyl,
4-tert-butylphenyl, 4-methoxyphenyl, 4-diethylaminophenyl, 2-methylphenyl, 2-methoxyphenyl, 1-naphthyl, 2-naphthyl, 6-methoxy-2-naphthyl, 4-methyl-1-naphthyl Phenanthryl, anthryl and the like.

The aralkyl group is a substituted or unsubstituted aralkyl group, such as benzyl, phenethyl, propiophenyl, 1-naphthylmethyl, 2-naphthylmethyl, 4-methoxybenzyl and the like. Can be

The heterocyclic group is a substituted or unsubstituted heterocyclic group, for example, a pyridyl group, a quinolyl group, a methylpyridyl group, an indolyl group and the like. The alicyclic group is a substituted or unsubstituted alicyclic group, for example, a cyclohexyl group, a 4-methylcyclohexyl group, a cyclopentyl group,
And a cycloheptyl group.

The compound represented by the above general formula (1) (C
As the cation moiety (Z) of -1), specifically, for example, a quaternary ammonium cation, a quaternary pyridinium cation, a quaternary quinolium cation, a phosphonium cation,
Examples include a sulfonium cation, an oxonium cation, and a metal cation such as sodium, potassium, lithium, magnesium, and calcium.

The compound represented by the general formula (1) (C-
Specific examples of 1) include tetramethylammonium-ethyltributylborate, tetra-n-butylammonium-phenethyltrimethylborate, tetraethylammonium-phenyltriisobutylborate, and tetra-n-butylammonium-phenethyltri (4- Methylphenyl) borate, tetramethylammonium / ethyltriphenylborate, (2-hydroxyethyl)
Trimethylammonium / n-butyltri (4-methylphenyl) borate, tetraethylammonium / n-
Octyltri (4,5-diethylphenyl) borate,
Tetra-n-butylammonium / n-pentyltri (4-methoxyphenyl) borate, tetra-n-butylammonium / n-butyltri (6-methoxy-2-
(Naphthyl) borate, (2-hydroxyethyl) trimethylammonium / methyltri (1-naphthyl) borate, (2-hydroxyethyl) trimethylammonium / n-butyltri (6-methoxy-2-naphthyl) borate, pyridinium / n-butyltri Naphthyl borate, diphenyliodonium n-butyl tri (4-methylnaphthyl) borate, triethylsulfonium
Examples thereof include n-octyl tri (4,5-diethyl naphthyl) borate and sodium ethyl triacenaphthyl borate. These can be used alone or in combination of two or more.

The compound represented by the general formula (1) (C-
Among 1), in particular, a compound represented by the above general formula (2)
Photopolymerization-initiating component comprising an appropriate sensitizing dye (C-2)
The use of (C) makes it possible to obtain photosensitivity, heat stability, and visible light.
Significantly higher photosensitivity in terms of the magnitude of the absorption wavelength in the region
Is particularly preferred because In the above general formula (2)
R₅, R₆Is independently hydrogen, an alkyl group,
Lucenyl group, alkoxyl group, aryl group, aralkyl
Represents a group, a heterocyclic group or an alicyclic group. Where R₅And R ₆Is the same
Or different. In the above general formula (2)
The cation moiety (Z) is a quaternary ammonium cation, a quaternary
Pyridinium cation, quaternary quinolium cation, phos
Honium cation, sulfonium cation, oxonium
Cation, iodonium cation or sodium, potassium
Gold, such as lithium, lithium, magnesium and calcium
Represents a genus cation.

The alkyl group is preferably a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and pentyl. , Hexyl, heptyl, octyl, 3-methoxypropyl, 4-chlorobutyl, 2-diethylaminoethyl and the like.

The alkenyl group is a substituted or unsubstituted alkenyl group, preferably having 2 to 12 carbon atoms, such as vinyl, propenyl, butenyl, pentenyl, hexenyl and heptenyl. Octenyl group, dodecynyl group, prenyl group and the like.

The alkoxyl group specifically has 1 carbon atom.
To 10 substituted or unsubstituted linear or branched alkoxyl groups are preferred, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy,
sec-butoxy, pentyloxy, hexyloxy,
tert-butoxy, 2-methoxypropoxy, 3-diethylaminobutoxy and the like.

The aryl group is a substituted or unsubstituted aryl group. Specifically, for example, phenyl, tolyl,
Xylyl, 4-ethylphenyl, 4-butylphenyl,
4-tert-butylphenyl, 4-methoxyphenyl, 4-diethylaminophenyl, 2-methylphenyl, 2-methoxyphenyl, naphthyl, 4-methylnaphthyl and the like.

The aralkyl group is a substituted or unsubstituted aralkyl group, specifically, for example, a benzyl group, a phenethyl group, a propiophenyl group, a 1-naphthylmethyl group,
Examples thereof include a 2-naphthylmethyl group and a 4-methoxybenzyl group.

The heterocyclic group is a substituted or unsubstituted heterocyclic group, and specific examples include a pyridyl group, a quinolyl group, a methylpyridyl group and an indolyl group.

The alicyclic group is a substituted or unsubstituted alicyclic group, and specific examples include a cyclohexyl group, a 4-methylcyclohexyl group, a cyclopentyl group and a cycloheptyl group.

Suitable sensitizing dyes (C-
2) is a cationic dye such as cyanine, xanthene, oxazine, thiazine, diarylmethane, triarylmethane, pyrylium, or an electrically neutral dye, that is, an organic dye which is not composed of a counter ion,
It refers to those containing + and-due to resonance in the same molecule, and examples thereof include merocyanine, coumarin, indigo, aromatic amine, phthalocyanine, azo, and quinone dyes. Counter anion if the cation dye is any anion, such as chlorine, bromine, halogen anions, benzenesulfonate anions, p- toluenesulfonate anion, methanesulfonic acid anion such as iodine anion, PF ₆ anion, organic And boron anions.

Specific examples of the sensitizing dye (C-2) include crystal violet (CI42555), methyl violet (CI42535), malachite green (CI42000), fuchsin (CI42510),
Crystal Violet-Carbinol Base (CI4
2555: 1), parafuchsin (CI42500), rhodamine B (CI45170), Victoria blue B
(CI44045), Victoria Pure Blue BOH
(CI42595), Brilliant Green (CI42
040), Night Blue BX (CI51185), Neutral Red (CI50040), Safranin O (C
I50240), Basic Orange 21 (CI480
35), Basic Orange 22, Basic Yellow 11, Basic Yellow 22, Basic Yellow 3
6, Basic Red 1 (CI45160), Basic Red 5 (CI50040), Basic Red 13
P-toluenesulfonate of Victoria Blue B, such as (CI48015), Basic Red 14, Basic Violet 7 (CI48020), Basic Violet 11 (CI45175), p-toluenesulfonate of crystal violet, or naphthalenesulfonate; Tetrafluoroboron salt, tetraphenylboron salt, etc., p-toluenesulfonate of Basic Orange 21, tetrafluoroboron salt, tetraphenylboron salt, etc., naphthalenesulfonate, tetrafluoroboron salt of Basic Red 5, or 3-allyl-1-carboxymethyl-5- [2- (3-ethyl-2 (3H) benzoxazolylidene) -2-thiohydantoin, 4- [2-
(3-Ethyl-2 (3H) benzothiazolylidene) ethylidene] -3-phenyl-2-isoxazoline-5-
On, 3- (2-benzothiazoline) -7- (diethylamino) coumarin, 3- (2-benzimidazolyl)-
7- (diethylamino) coumarin, 2,3,6,7-tetrahydro-11-oxo-1H, 5H, 11H-
[1] Benzopyrano [6,7,8-ij] quinaridine-
Examples thereof include ethyl 10-carboxylate, N, N'-diethylindigo, thioxoindigo, 2-dimethylaminoanthraquinone, 4-hydroxyazobenzene, and 4-phenylamino-4'-nitroazobenzene. These sensitizing dyes (C-2) may be used as a mixture of two or more as necessary. The content of the sensitizing dye (C-2) in the photopolymerization initiation system component (C) of the present invention is arbitrary, but based on the photosensitive resin composition of the present invention.
It is preferably from 0.01 to 5% by mass.

The amount of the photopolymerization initiation component (C) constituting the photosensitive resin composition of the present invention is 0.1 to 10% by mass, preferably 0.1 to 10% by mass, based on the photosensitive resin composition of the present invention. , 0.3 to 5% by mass. Photopolymerization initiation component (C)
If the compounding amount of is less than 0.1% by mass, poor exposure curing may occur, and a pattern may not be formed.
On the other hand, even if the blending amount of the photopolymerization initiation component (C) exceeds 10% by mass, no improvement in photosensitivity is observed. It may not be possible, which is not preferable.

The compound represented by the general formula (1) (C
-1) and the sensitizing dye (C-2) in terms of mass ratio.
It is desirable that the compound (C-1) / sensitizing dye (C-2) represented by the general formula (1) be set in a range of 0.01 to 100. When the use ratio of these two components is less than 0.01, the photosensitivity is reduced. On the other hand, when the use ratio exceeds 100, no improvement in the photosensitivity is observed.

In the present invention, in addition to the above components (A) to (C), if necessary, N-phenylglycine compounds such as N-phenylglycine and Np-hydroxyphenylglycine, phenoxyacetic acid, trimethylbarbituric acid ,
2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole,
N, N-dialkyl benzoic acid alkyl ester, N, N
-Photopolymerization initiation ability can be further enhanced by adding a chain transfer agent (D) comprising an active hydrogen donor such as dialkylaniline.

In the present invention, a photopolymerizable monomer (E) can be added, if necessary, in addition to the above components (A) to (D). By adding the component (E),
Sensitivity can be improved, and film loss and swelling during development can be prevented. As such a photopolymerizable monomer (E), specifically, methyl acrylate, methyl methacrylate,
Ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, Glycerol acrylate, glycerol methacrylate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, 2-
Monofunctional monomers such as ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, and benzyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and tetraethylene glycol Dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate , Tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate ,
In addition to polyfunctional monomers such as 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardo epoxy diacrylate, and cardo epoxy dimethacrylate, "-acrylate" of these compounds,
`` ~ Methacrylate '' is replaced with `` ~ fumarate '', `` ~ maleate '', `` ~ crotonate '', `` ~ itaconate '', fumaric acid ester, maleic acid ester, crotonic acid ester, itaconic acid ester, acrylic acid,
Methacrylic acid, fumaric acid, maleic acid, crotonic acid, itaconic acid, hydroquinone monoacrylate, hydroquinone monomethacrylate, hydroquinone diacrylate,
Hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol diacrylate, pyrogallol triacrylate, condensates of acrylic acid with phthalic acid and diethylene glycol,
Condensates of acrylic acid with maleic acid and diethylene glycol, condensates of methacrylic acid with terephthalic acid and pentaerythritol, condensates of acrylic acid with adipic acid and butanediol with glycerin, ethylenebisacrylamide, ethylenebismethacrylamide, phthalate Examples thereof include allyl esters of diallyl acid and divinyl phthalate. Among them, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate and the like are preferably used.

This photopolymerizable monomer (E) can be used as the above (A)
It is preferable to mix the component (E) in a range not exceeding 20 parts by mass with respect to 100 parts by mass in total. If the amount exceeds 20 parts by mass, cold flow is likely to occur when the film is formed into a dry film, and the elasticity of the photosensitive resin composition after the visible light exposure curing is reduced, resulting in a decrease in sandblasting, which is not preferable. Further, as the alkali-soluble polymer compound (B), (meth) acrylic acid and (meth) acrylic acid are used.
When using a copolymer with acrylic acid ester,
Urethane (meta) from the consideration of the rise in electrical insulation resistance
Acrylate compound (A): The compounding mass ratio of (copolymer of (meth) acrylic acid and (meth) acrylic acid ester + photopolymerizable monomer) is preferably in the range of 5:95 to 95: 5. , More preferably from 10:90 to 90:10.
It is.

A solvent can be added to the photosensitive resin composition of the present invention, which is capable of performing visible light exposure, for the purpose of adjusting viscosity and the like. Such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether,
Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether,
Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monophenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl Ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomer Ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-
Methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3
-Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3 -Methoxypentyl acetate, 4-methoxypentyl acetate,
2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-
4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, tetrahydrofuran, cyclohexanone, methyl propionate, ethyl propionate, propyl propionate, propionic acid Isopropyl, 2-
Methyl hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl, methyl-
3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate,
Ethyl-3-propoxypropionate, propyl-3
-Methoxypropionate, isopropyl-3-methoxypropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isoamyl lactate , Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate,
Isoamyl acetate, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, benzyl methyl ether, benzyl ethyl ether, dihexyl ether, Benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, benzene, toluene, xylene, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin, etc. Can be.

The solvent comprises a total of 10 components (A) to (E).
2000 parts by mass or less, preferably 10 parts by mass with respect to 0 parts by mass
It can be blended in a range of not more than 00 parts by mass. In addition, hydroquinone, hydroquinone monoethyl ether,
p-methoxyphenol, pyrogallol, catechol,
2,6-di-tert-butyl-p-cresol, β-
Thermal polymerization inhibitors such as naphthol, dioctyl phthalate,
Plasticizers such as didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin; anionic, cationic, and nonionic surfactants; Various antifoaming agents such as a silicone type and a fluorine type can be appropriately added as needed.

The method for forming the sandblast-resistant photosensitive resin composition of the present invention on a substrate as a sandblast mask material can be appropriately selected according to the intended use. A method of forming a sandblast-resistant photosensitive resin layer by coating and drying on the
Any method such as a method of forming by a screen printing method, a method of forming a sandblast-resistant photosensitive resin layer between plastic films in advance and drying to form a dry film, and attaching the dry film to an object to be processed and sandblasting It may be. In particular, when used as a dry film, when precise alignment of electronic components or the like is required, it is not necessary to transfer a resin pattern formed in advance, so that a resin pattern can be formed at an accurate position, Higher precision cutting can be realized. Further, when the paste layer or the like is cut, the photosensitive resin composition is not penetrated into the paste layer, which is preferable.

The sandblast-resistant dry film capable of performing visible exposure using the photosensitive resin composition of the present invention is described below.
Description will be made with reference to FIG. 1, that is, as shown in FIG. 1, a sand blast-resistant dry film 1 of the present invention capable of visible exposure includes a support 2, a sand blast-resistant photosensitive resin layer 3, and a protective material layer. 4 are sequentially laminated and formed integrally. The support 2 supports the sandblast-resistant photosensitive resin layer 3 and needs to have appropriate flexibility. Specifically, for example, 1
A polyethylene terephthalate (PET) film having a thickness of about 5 to 125 μm is preferably used, and a synthetic resin film such as polyethylene, polypropylene, polycarbonate, and polyvinyl chloride is also preferably used. The protective material layer 4 is for stably protecting the surface of the photosensitive resin layer 3 when not in use, and is peeled off and removed in use. Therefore, it is necessary to have an appropriate releasability that is difficult to peel off when not in use and easy to peel off when used. As a material that satisfies such conditions, a PET film, a polypropylene film, a polyethylene film, or the like having a thickness of about 15 to 125 μm coated or baked with silicone is preferably used. The photosensitive resin composition layer 3 is formed by applying a solution obtained by dissolving each component of the above-described sandblast-resistant photosensitive resin composition in a solvent using an applicator, a bar coater, a roll coater, a curtain flow coater, or the like.
It is obtained by coating the support 2 so as to have a thickness of 0 to 100 μm.

Next, a method for cutting a treated body of the present invention using the dry film 1 will be described with reference to FIG. First, the protective material layer 4 is peeled off, and the exposed photosensitive resin layer 3 having sandblast resistance is applied to the object 5 to be processed, and the dry film 1 is applied on the object 5 (FIG. 2A). . At the time of application, a so-called thermocompression bonding method, in which the object 5 is usually heated in advance and the dry film 1 is placed thereon and pressed, is used.
The urethane (meth) acrylate compound is added to the photosensitive resin layer 3, so that even if the photosensitive resin layer 3 is processed into a dry film, the adhesion to the object 5 is extremely good. In particular, by using a carboxy-modified urethane (meth) acrylate compound, the adhesion can be further improved.

Next, as shown in FIG.
Is exposed to the visible light such as argon laser light having a wavelength peak near 488 nm or YAG-SHG laser light having a wavelength peak near 532 nm on the sandblast-resistant photosensitive resin layer 3 on which is laminated. The conductive resin layer 3 is selectively exposed. It is needless to say that the photosensitive resin layer 3 can be selectively cured by irradiating not only visible light but also ultraviolet light, an excimer laser or the like through a negative mask (not shown).

After the above-mentioned exposure, the support 2 is peeled off and developed to selectively remove the unexposed portions of the photosensitive resin layer 3 to form a pattern in which the exposed portion of the photosensitive resin layer 3 remains (FIG. 9). 2 (c)). Examples of the developer include alkali developers, that is, hydroxides, carbonates, bicarbonates, phosphates, and pyrophosphates of alkali metals such as lithium, sodium, and potassium;
Primary amines such as benzylamine and butylamine; secondary amines such as dimethylamine, dibenzylamine and diethanolamine; tertiary amines such as trimethylamine, triethylamine and triethanolamine; cyclic amines such as morpholine, piperazine and pyridine; Polyamines such as ethylenediamine and hexamethylenediamine; ammonium hydroxides such as tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide and trimethylphenylbenzylammonium hydroxide; trimethylsulfonium hydroxide, diethylmethylsulfonium hydroxide, dimethylbenzylsulfonium hydroxide and the like Aqueous solution consisting of sulfonium hydroxides; It can be used potassium developer.

Next, as shown in FIG. 2D, the workpiece 5 is subjected to sandblasting using the patterned residual photosensitive resin layer 3 as a mask to form a cut portion 7. Since the photosensitive resin layer 3 has the same level of sandblast resistance as a conventional ultraviolet-exposed photosensitive resin composition,
Before the etching to the desired depth is completed, the object under the resin layer 3 is not damaged by the film thickness reduction. As the blast material used in the sand blasting process, fine particles having a particle size of about 2 to 500 μm such as glass beads, alumina, silica, silicon carbide, and zirconium oxide are used. Processing is performed. The photosensitive resin composition layer 3 has higher elasticity and flexibility than ordinary photosensitive resin, and has high abrasion resistance due to sand blasting. It will not be lost.

After the sand blast treatment, as shown in FIG. 2E, the photosensitive resin composition layer 3 is made of sodium hydroxide,
PH 12 to potassium hydroxide or organic amines
The desired relief 8 is formed on the object 5 by being peeled off with about 14 aqueous solutions. In the above description of the cutting method, a dry film as a mask material has been described as an example, but instead of a dry film,
It is a matter of course that the sandblast-resistant photosensitive resin composition of the present invention may be applied directly onto the object to be processed and dried to form a photosensitive resin layer, and the resultant may be used as a mask material for sandblasting.

[0052]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

(Examples 1-4, 8-11, 15-18,
22-25) a-1 to a-5 are used as the urethane (meth) acrylate compound (A), and b-1 to b-3 are used as the alkali-soluble polymer compound (B). Using c-1 to c-4 as C), a solution of a photosensitive resin composition for sandblasting having a composition (% by mass) shown in Tables 1 and 2 was prepared.
The prepared photosensitive resin composition for sand blasting capable of visible exposure was processed into a dry film and used for cutting an insulating layer of a plasma display panel. First, the photosensitive resin composition for sandblasting that can be exposed to light prepared as described above is applied on a PET film so as to have a thickness of 30 μm after drying, and dried in a hot air heater at 80 ° C. for 6 minutes. A photosensitive resin layer was formed, and then a PET film was applied on the photosensitive resin layer at 40 ° C. to form a dry film. Next, after peeling off one side of the PET film of the dry film, the exposed photosensitive resin layer surface is placed on a plasma display panel substrate provided with a barrier rib layer (lead borosilicate glass frit layer) covering the electrode pattern. At 80 ° C. and laminated. Next, an argon laser exposure machine (“LPS plotter”,
Sync Laboratories Co., Ltd.) and 2 m of light having a wavelength of 488 nm was irradiated with argon laser in an atmosphere of 20 ° C.
Irradiation was performed at an energy amount of J / cm ² to perform image drawing exposure. After that, peel off the PET film on the other side,
1.5 kg / c using 0.2% sodium carbonate aqueous solution
Spray development was performed at a spray pressure of m ² for 60 seconds. After washing with water, drying was performed at 80 ° C. for 10 minutes, and the entire surface was irradiated with ultraviolet rays of 200 mJ / cm ² using an ultra-high pressure mercury lamp to completely cure the pattern. The obtained pattern was visually observed, but no chipping or peeling was observed in the pattern, and the pattern was excellent in reproducibility with little film loss. Next, the obtained pattern was used as an anti-sandblast mask, glass beads # 800 were used as an abrasive, and the blast pressure was 3 kg / c.
m ² at 5 minutes sandblasted, 150 of glass layer
The electrode pattern was exposed when the μm was cut, but no chipping or peeling of the pattern was observed at all during sandblasting, and the film was hardly reduced. After leaving this laminated film in a dark place for 6 months, it was similarly used for cutting the barrier rib layer, but there was no deterioration such as discoloration or curing of the photosensitive resin composition, and the film of the resist pattern at the time of sandblasting was used. There was little decrease.

Urethane (meth) acrylate compound (A); a-1: Carboxyl group-containing urethane acrylate ("KRM 7222"; manufactured by Daicel Chemical Industries, Ltd., mass average molecular weight 10,000, acid value 20, containing 20% ethyl acetate as solvent) A-2) Carboxyl group-containing urethane acrylate ("Shikko UT-2313"; manufactured by Nippon Synthetic Chemical Company, mass average molecular weight: about 20,000, acid value: 0, and ethyl acetate: 30% as a solvent)
A-3: Carboxyl group-containing urethane acrylate ("Shikko UV-9510EA"; manufactured by Nippon Synthetic Chemical Co., Inc., mass average molecular weight: about 20,000, acid value: 32, ethyl acetate as solvent: 30%) a-4: Carboxyl group Containing urethane acrylate ("Shikko UV-9532"; manufactured by Nippon Synthetic Chemical Co., Ltd., mass average molecular weight: about 20,000, acid value: 50, ethyl acetate: 30 as a solvent)
A-5: Carboxyl group-containing urethane acrylate ("UAS-C-9PMA"; manufactured by Kyoeisha Chemical Co., Ltd., mass average molecular weight about 10,000, acid value 21, containing 30% of propylene glycol monoethyl ether acetate as a solvent)

B-1: cellulose acetate phthalate (“KC-7”)
1 "; Wako Pure Chemical Industries, acid value 120) b-2: Hydroxypropyl methylcellulose phthalate (" HP-55 ", Shin-Etsu Chemical Co., Ltd., acid value 120) b-3: Methacrylic acid / methyl acrylate copolymer Coalescing (mass average molecular weight 100,000, acid value 60, methanol 50% as solvent)

Photopolymerization initiation component (C) c-1: tetra-n-butylammonium butyltriphenylborate / 1,3,3-trimethyl-2- [2
-(1-Methyl-2-phenyl-3-indolyl) vinyl] -3H-indolium tetraphenylborate =
4/1 (wt / wt) c-2: tetra-n-butylammonium / butyltritolylborate / basic yellow 36 = 4/1 (w
c-3: tetra-n-butylammonium / butyltri (1-naphthyl) borate / basic orange 22 =
4/1 (wt / wt) c-4: tetra-n-butylammonium butyltri (4-methyl-1-naphthyl) borate / 1,3,3-
Trimethyl-2- [2- (1-methyl-2-phenyl-
3-indolyl) vinyl] -3H-indolium tetraphenylborate / 1,3,3-trimethyl-2-
[2- (2,3-methoxy-1-anilino) vinyl]-
3H-indolium tetraphenylborate = 4/1
/ 1 (wt / wt / wt) c-5: tetra-n-butylammonium / butyltriphenylborate / basic red 1 = 3/1 (wt
/ Wt) c-6: tetra-n-butylammonium butyltri (1-naphthyl) borate / 3,7-diamino-2,8
-Dimethyl-5-phenylphenazinium tetrafluoroborate = 3/1 (wt / wt) c-7: Tetra-n-butylammonium / butyltri (4-methyl-1-naphthyl) borate / basic red 14 = 3/1 (wt / wt) c-8: dimethylthioxanthone / 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine / coumarin 6 = 30/6/1 ( w
t / wt / wt)

[0057]

[Table 1]

[0058]

[Table 2]

(Examples 5 to 7, 12 to 14, 19 to 2)
1,26-28) Urethane (meth) acrylate compounds
A-1 to a-5 are used as (A) and alkali-soluble
Using b-1 to b-3 as the polymer compound (B),
Using c-5 to c-7 as the combination initiation system component (C),
1. Visible light exposure having the composition (% by mass) shown in Table 2
A solution of the photosensitive resin composition for sandblasting was prepared.
Prepared photosensitive resin set for visible light exposure for sandblasting
Process the product into a dry film and use it for plasma display
Used for cutting the insulating layer of the panel. First, PET fill
Visible exposure sand brass prepared above
Film thickness of the photosensitive resin composition for drying becomes 30 μm
And dried in a hot air heater at 80 ° C for 6 minutes.
To form a photosensitive resin layer.
A PET film on the layer at 40 ° C
Lum created. Next, the PET film of this dry film
After removing one side of the film, remove the exposed photosensitive tree.
The surface of the resin layer is covered with a barrier rib layer (borosilicate
Plasma display with lead oxide glass frit layer)
On a lay panel substrate, it was closely adhered at 80 ° C. and laminated. Next
With a YAG-SHG laser exposure machine (“DPSS 53
2) Coherent) and in an atmosphere of 20 ° C
YAG secondary peak having a peak around 532 nm
Harmonic laser light 2mJ / cm²Irradiation with energy amount of
The image was exposed. After that, the PET side on the other side
Remove the film and use 0.2% sodium carbonate aqueous solution
1.5kg / cm²Spray for 60 seconds at a spray pressure of
Developed. After washing with water, dry at 80 ° C for 10 minutes.
200mJ / cm using high pressure mercury lamp ²UV rays on the whole surface
Irradiation allowed the pattern to completely cure. The resulting pattern
Was visually observed, but no chipping or peeling was observed in the pattern.
In addition, it was excellent in reproducibility with little film loss.
Next, the obtained pattern is used as a sandblast-resistant mask.
Using glass beads # 800 as abrasive
Strike pressure 3kg / cm²And sand blast for 5 minutes,
When the glass layer is cut by 180 μm, the electrode pattern is
It was exposed, but chipping or peeling of the pattern during sandblasting
No peeling was seen and there was almost no film loss. this
After leaving the laminated film in a dark place for 6 months,
Discoloration of the photosensitive resin composition used for cutting the rear rib layer
No deterioration such as heat and hardening
The film loss of the pattern was also small.

Comparative Example 1 A solution of the photosensitive resin composition for sandblasting capable of visible exposure was prepared in the same manner as in Example 1 except that c-8 was added instead of c-1. Prepared and formed a dry film. This dry film was processed and used for cutting the insulating layer of the plasma display panel. First, P on one side of the dry film
After peeling and removing the ET film, the exposed photosensitive resin layer surface was placed at 80 ° C. on a plasma display panel provided with a barrier rib layer (lead borosilicate glass frit layer) covering the electrode pattern and the dielectric pattern. They were adhered and laminated. Thereafter, the apparatus was set in the above-described argon laser exposure machine, and was irradiated with light having a wavelength of 488 nm by an argon laser at an energy amount of ² mJ / cm ² in an atmosphere of 20 ° C. to perform image drawing exposure. After that, the other side PE
The T film was peeled off, and the film was spray-developed with a 0.2% aqueous solution of sodium carbonate at a spray pressure of 1.5 kg / cm ² for 45 seconds, but the photosensitive resin layer was completely discharged due to poor exposure. Exposure-curable energy amount is 15
It was 0 mJ / cm ² and was not suitable for exposure with an argon laser.

(Comparative Example 2) B-3 was used as the alkali-soluble polymer compound (B), c-1 was used as the photopolymerization initiation component (C), and visible light having the composition (% by mass) shown in Table 3 A solution of the photosensitive resin composition for sandblasting that can be exposed was prepared. The prepared photosensitive resin composition for sand blasting capable of visible exposure was processed into a dry film and used for cutting an insulating layer of a plasma display panel. First, the photosensitive resin composition for sandblasting that can be exposed to light prepared as described above is applied on a PET film so as to have a thickness of 30 μm after drying, and dried in a hot air heater at 80 ° C. for 6 minutes. A photosensitive resin layer was formed, and then a PET film was applied on the photosensitive resin layer at 40 ° C. to form a dry film. Next, after peeling off one side of the PET film of the dry film, the exposed photosensitive resin layer surface is placed on a plasma display panel provided with a barrier rib layer (lead borosilicate glass frit layer) covering the electrode pattern. At 80 ° C. and laminated. Then, it was set in the above-mentioned argon laser exposure machine, and was irradiated with light having a wavelength of 488 nm by an argon laser at an energy amount of ² mJ / cm ² in an atmosphere of 20 ° C. to perform image drawing exposure. After that, the other side PE
The T film was peeled off and spray-developed with a 0.2% aqueous sodium carbonate solution at a spray pressure of 1.5 kg / cm ² for 45 seconds. After washing with water, drying at 80 ° C. for 10 minutes, the entire pattern was irradiated with ultraviolet rays of 200 mJ / cm ² using an ultra-high pressure mercury lamp, and the pattern was completely cured. The obtained pattern was used as a sandblast-resistant mask, and glass beads were used as an abrasive. Using # 800, ² at blast pressure 4kg / cm 2
After sandblasting for 120 minutes, the glass layer was
At the time of cutting, the pattern disappeared due to film thickness reduction.

[0062]

[Table 3]

[0063]

As described in detail above, the photosensitive resin composition for sandblasting according to the present invention has the following basic properties: (1) it has high elasticity and flexibility and can be used as a sandblasting mask material; In addition to (2) excellent alkali developability in consideration of the environment, (3) good adhesion to the object to be processed, (4) formation on a dry film, and (5) visible light, In particular, the wavelength peak is 488 nm.
Argon laser light and wavelength peak near 532n
m can be directly drawn and exposed by visible light such as YAG second harmonic laser light near m. (6)
It is a composition excellent in economy. In addition, by using the composition or using a dry film using the composition, the object to be processed can be cut easily, at low cost, and with high accuracy.

[Brief description of the drawings]

FIG. 1 is a longitudinal side view of a sandblast-resistant dry film capable of visible exposure according to the present invention.

FIG. 2 is an explanatory diagram of a method of grinding a workpiece using the dry film of FIG. 1;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Dry film 2 Support 3 Sandblast-resistant photosensitive resin layer 4 Protective material layer 5 Workpiece 7 Cutting part 8 Relief

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 299/06 C08F 299/06 4J027 C08K 5/00 C08K 5/00 5/55 5/55 C08L 75/14 C08L 75/14 101/00 101/00 G03F 7/004 501 G03F 7/004 501 511 511 512 512 7/027 513 7/027 513 7/031 7/031 7/032 7/032 7/40 521 7 / 40 521 F-term (reference) 2H025 AA00 AA01 AB11 AB20 AC01 AC08 AD01 BC14 BC45 CA41 CA50 CB43 CB51 FA03 FA17 FA39 2H096 AA00 AA30 BA05 BA20 CA20 EA02 EA04 GA08 HA30 JA04 4J002 AB01X BG01X BG04X BG05 EB04 BG04 EB04 BG04 EB04 FD207 FD208 GP03 4J011 AA05 BA04 DA02 DA04 FA07 FB01 PA53 PA69 QA03 QA05 QA06 QA07 QA12 QA13 QA21 QA22 QB24 SA86 SA88 UA06 VA01 WA01 4J026 AB03 BA26 BA 27 BA28 BA31 BA32 DB05 DB06 DB17 DB36 FA05 GA07 GA10 4J027 AG01 BA01 BA03 BA04 BA07 BA13 BA14 BA19 BA20 BA23 BA24 BA25 BA26 CB10 CC04 CD10

Claims (7)

[Claims] 1. A photopolymerizable urethane (meth) acrylate compound (A) having at least two (meth) acryloyl groups, an alkali-soluble polymer compound (B) having an acid value of 50 to 250 mg / KOH, and A sandblast-resistant photosensitive resin composition capable of visible exposure, comprising a photopolymerization initiation system component (C) comprising a compound represented by the following general formula (1) and a sensitizing dye. Embedded image (Wherein, R ₁ , R ₂ , R ₃ and R ₄ each independently represent an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a heterocyclic group, or an alicyclic group, and R ₁ , R ₂ , R ₃
And R ₄ may be the same or different. Z is 4
Quaternary ammonium cation, quaternary pyridinium cation,
Represents a quaternary quinolium cation, a phosphonium cation, a sulfonium cation, an oxonium cation, an iodonium cation, or a metal cation. ) 2. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator component (C) comprises a compound represented by the following general formula (2) and a sensitizing dye. object. Embedded image (Wherein, R ₅ and R ₆ each independently represent hydrogen, an alkyl group, an alkenyl group, an alkoxyl group, an aryl group, an aralkyl group, a heterocyclic group, or an alicyclic group, and R ₅ and R ₆
May be the same or different. The substitution position of R ₅ may be on any ring of naphthalene. Z is 4
Quaternary ammonium cation, quaternary pyridinium cation,
Represents a quaternary quinolium cation, a phosphonium cation, a sulfonium cation, an oxonium cation, an iodonium cation, or a metal cation. ) 3. The photosensitive resin composition according to claim 1, further comprising a chain transfer agent (D). 4. The photosensitive resin composition according to claim 1, further comprising a photopolymerizable monomer (E). 5. A sandblast-resistant photosensitive resin layer according to any one of claims 1 to 4, which is coated on a support and dried to form a sandblast-resistant photosensitive resin layer. Thereafter, a sandblast-resistant dry film capable of being exposed to light, which is obtained by laminating a protective material layer on the layer. 6. A sandblast-resistant photosensitive resin composition capable of being exposed to light according to any one of claims 1 to 4, which is applied to an object to be processed and dried to form a sandblast-resistant photosensitive resin layer. After that, this sandblast-resistant photosensitive resin layer is directly exposed to visible light for image drawing, and then developed to selectively remove the photosensitive resin layer to form a photosensitive resin pattern, and thereafter, the pattern is masked. Characterized in that the object to be processed is cut by sandblasting,
The method of cutting the workpiece. 7. After peeling and removing the protective material layer from the sand blast resistant dry film capable of performing visible exposure according to claim 5,
After applying the dry film on the object to be processed so that the exposed photosensitive resin layer surface is in contact with the surface of the object to be processed,
The sandblast-resistant photosensitive resin layer of the dry film is directly image-drawn and exposed to visible light, then the support is peeled off and developed, and the photosensitive resin layer is selectively removed to form a photosensitive resin pattern. Thereafter, the object to be processed is cut by sandblasting using the pattern as a mask.