JPH09152713A - Photosensitive resin composition and photosensitive resin laminated film using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. having high sandblasting resistance and high sensitivity, hardly receive electrostatic charge and not causing the damage of a substrate to be processed by electric discharge due to electrostatic charge and the falling of a thunderbolt. SOLUTION: This resin compsn. contains a photopholymerizable urethane (meth)acrylate compd. having two or more (meth)acryloyl groups, an alkali- soluble high molecular compd. having 50-250mgKOH/g acid value, a photopolymn. initiator and a composite of an alkali salt of thiocyanic acid with a high molecular compd. having polyalkylene oxide segments.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel photosensitive resin composition and a photosensitive resin laminated film having a photosensitive layer formed of the photosensitive resin composition, and more particularly to a film having high elasticity and flexibility and alkali developability. The present invention relates to a photosensitive resin composition which is excellent and has good adhesion to a base material, and is free from discharge due to static electricity or lightning strike during sandblasting, and a photosensitive resin laminated film having a photosensitive layer made of the photosensitive resin composition.

[0002]

2. Description of the Related Art Conventionally, a sandblasting method has been known as one of the processing methods for forming a pattern on the surface of a substrate such as glass, marble, plastic, ceramics, leather, and wood. In the above-mentioned processing method, it is common to provide a sandblast resist on the surface of the base material and selectively polish it by spraying an abrasive or the like on the exposed portion of the resist or form a pattern by etching with a reagent. is there. In particular, a method of providing a photosensitive resin layer as a sandblast resist, forming a mask pattern by photolithography, and then selectively polishing by spraying an abrasive or the like, or etching with a reagent is a fine processing method with a metal pattern. It is applied to the formation of circuit boards in which insulating patterns are mixed, particularly metal wiring patterns of plasma displays and insulating patterns of ceramics, phosphors and the like. As the photosensitive resin composition used in the precision sandblasting method, the resin composition after curing has a sandblasting resistance and the mask is not damaged by sandblasting, and the development after the pattern exposure is a weak alkaline aqueous solution. Can be done easily, without causing problems in working environment, wastewater treatment, etc., and further damage to the base material due to static electricity charged or electrostatic discharge generated by friction of abrasive fine particles during processing or lightning strike, for example, Glass and marble are required to have no spots, chips, or cracks, and circuit boards are required to have no short circuit due to damage to the wiring pattern or insulating layer. As a photosensitive resin composition for sandblast resist that meets these requirements,
For example, a photosensitive resin composition containing an unsaturated polyester, an unsaturated monomer and a photopolymerization initiator is disclosed in JP-A-55-10.
3554, and a photosensitive resin composition comprising polyvinyl alcohol and a diazo resin is disclosed in JP-A-2-69754.
Each of them is proposed in the publication.

[0003]

However, although the above-mentioned photosensitive resin composition is excellent in sandblast resistance, etc., it has chargeability. Therefore, when microfabrication is performed using it, discharge due to charged static electricity is caused. However, a lightning strike occurred and the base material was damaged. In particular, in the formation of a circuit board, there is a defect that an irreparable defective portion is generated in a wiring pattern or an insulating layer, which often causes defective products.

Therefore, the present inventors have found that a photopolymerizable urethane (meth) acrylate compound having an acid value of 50 to 50 as a photosensitive resin composition for sandblasting that solves the above problems.
250 mg / KOH alkali-soluble polymer compound, photopolymerization initiator, and photosensitivity for sandblasting, which has an electric insulation resistance value after photocuring of 8.0 × 10 ^{9 to} 1.0 × 10 ¹⁴ Ω · cm A resin composition was proposed. The above-mentioned photosensitive resin composition for sandblasting is excellent not only in sandblasting resistance but also in electric resistance, but as a result of further intensive studies, the above-mentioned photosensitive resin composition for sandblasting was further treated with an alkali thiocyanate. By containing a complex of a salt and a polymer compound having a polyalkylene oxide segment, electrostatic charging during sandblasting is further reduced, and there is no occurrence of damage due to discharge or lightning strike, and the photosensitive resin composition. Furthermore, it was found that the addition of a Lewis acid salt soluble in an organic solvent and capable of generating a Lewis acid upon irradiation with light can provide a photosensitive resin composition for sandblasting which is further free from discharge and lightning strike. It was also found that when the above-mentioned photosensitive resin composition is laminated on a flexible film, a photosensitive laminated film which can be easily subjected to precision processing can be obtained. The present invention has been completed based on these findings.

That is, the present invention is a photosensitive resin composition having high elasticity and flexibility, excellent alkali developability, good adhesion to a substrate, and no damage to the substrate due to electric discharge or lightning strike during sandblasting. The purpose is to provide things.

Another object of the present invention is to provide a photosensitive laminated film obtained by laminating the above photosensitive resin composition.

[0007]

Means for Solving the Problems The present invention which achieves the above objects, comprises: (A) a photopolymerizable urethane (meth) acrylate compound having at least two or more acryloyl groups or methacryloyl groups; 50-250m
A photosensitive material containing a complex of an alkali-soluble polymer compound of g / KOH, (C) a photopolymerization initiator, and (D) an alkali salt of thiocyanate and a polymer compound having a polyalkylene oxide segment. A photosensitive resin composition and a photosensitive laminated film having the photosensitive resin composition layer.

The photopolymerizable urethane (meth) acrylate compound having at least two acryloyl groups or methacryloyl groups of the component (A) of the present invention is a terminal isocyanate group (-) obtained by reacting a diol compound and a diisocyanate compound. A reaction product of a compound having an NCO group) with a (meth) acrylate compound having a hydroxyl group. Examples of the diol compound include polyesters having terminal hydroxyl groups, polyales, and the like. Examples of polyesters include ring-opening-polymerized polyesters of lactones, polycarbonates, ethylene glycol, propylene glycol, diethylene glycol, and triethylene. Examples thereof include polyesters obtained by a condensation reaction of an alkylene glycol such as glycol and dipropylene glycol with a dicarboxylic acid such as maleic acid, fumaric acid, glutaric acid and adipic acid. In particular, polyesters and polycarbonates obtained by ring-opening polymerization of lactones are suitable because they have a low insulation resistance value and discharge is unlikely to occur during sandblasting. Specific examples of the lactones include δ-valerolactone, ε-caprolactone, β-propiolactone, α-methyl-β propiolactone, β-methyl-β propiolactone, and α-methyl-β propiolactone. , Β-methyl-β-propiolactone, α, α-dimethyl-β-propiolactone,
Examples include β, β-dimethyl-β-propiolactone. Specific examples of the polycarbonates include reaction products of diols such as bisphenol A, hydroquinone and dihydroxycyclohexane, and carbonyl compounds such as diphenyl carbonate, phosgene and succinic anhydride.

Specific examples of the polyethers include polyethylene glycol, polypropylene glycol,
Examples thereof include polytetramethylene glycol and polypentamethylene glycol. 2,2-bis (hydroxymethyl) in the polyester and polyether
Propionic acid, 2,2-bis (2-hydroxyethyl)
When a residue of propionic acid or 2,2-bis (3-hydroxypropyl) propionic acid, especially a residue of 2,2-bis (hydroxymethyl) propionic acid is contained, a urethane compound having excellent solubility in an alkaline solution is synthesized. It is possible and preferable. The above-mentioned polyester or polyether may be used alone or in a mixture of two or more kinds.

Specific examples of the diisocyanate compound which reacts with the diol compound include dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate and 2,2-dimethylpentane-1, 5
-Diisocyanate, octamethylene diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate, 2,2,4-trimethylpentane-1,5-diisocyanate, nonamethylene diisocyanate, 2,
Examples thereof include aliphatic or alicyclic diisocyanate compounds such as 2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, and isophorone diisocyanate, and the compounds may be used alone or in a mixture of two or more kinds.

Further, it has a hydroxyl group (meth)
Specific examples of the acrylate compound include hydroxymethyl acrylate, hydroxymethyl methacrylate, and 2
-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, ethylene glycol monoacrylate, ethylene glycol monomethacrylate, glycerol acrylate, glycerol methacrylate, dipentaerythritol monoacrylate, dipentaerythritol monomethacrylate These may be used alone or in admixture of two or more.

The weight average molecular weight of the urethane (meth) acrylate compound, which is a reaction product of the above components, is preferably in the range of 1,000 to 10,000. When the weight average molecular weight is less than 1000, the bond strength of the coating after curing is increased to increase hardness and the sandblast resistance is lowered, and when the weight average molecular weight exceeds 10,000, the viscosity is increased and the coating property is deteriorated, resulting in poor workability. Is deteriorated and the electrical insulation resistance value is also increased, which is not preferable. The urethane (meth) acrylate compound may contain a carboxyl group, but its acid value is 70 mg / KOH or less, preferably 20 to 50 m.
It should be in the range of g / KOH.

As the alkali-soluble polymer compound as the component (B) contained in the photosensitive resin composition of the present invention, a copolymer of acrylic acid or methacrylic acid, a carboxyl group-containing cellulose resin and the like are suitable. The acid value of the component (B) is 50 to 250 mg / KOH, preferably 80 to 2
A range of 00 mg / KOH is good. Acid value is 50mg / KO
If it is less than H, defective development may occur.
When it exceeds mg / KOH, the flexibility is lost and the water resistance is poor.

As the copolymerization component of the acrylic acid or methacrylic acid copolymer, fumaric acid, maleic acid, crotonic acid, cinnamic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid Butyl, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monomethyl maleate, monoethyl maleate, monopropyl maleate, sorbic acid, hydroxymethyl acrylate,
Hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, ethylene glycol monoacrylate, ethylene glycol monomethacrylate, glycerol acrylate, glycerol methacrylate, dipentaerythritol monoacrylate, Examples thereof include dipentaerythritol monomethacrylate, acrylic acid dimethylaminoethyl ester, methacrylic acid dimethylaminoethyl ester, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, acrylic acid amide, methacrylic acid amide, acrylonitrile and methacrylonitrile. Particularly preferred are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, and isobutyl methacrylate.

Specific examples of the carboxyl group-containing cellulose resin include hydroxyethyl carboxymethyl cellulose and cellulose acetate phthalate. The carboxyl group-containing cellulose resin is suitable because it hardly increases the electric insulation resistance value after curing of the photosensitive resin composition of the present invention and has the property of not being charged with static electricity. Of these, cellulose acetate phthalate is preferable. The cellulose acetate phthalate is preferable because it has good compatibility with the urethane (meth) acrylate compound, has excellent film-forming ability when formed into a dry film, and has good alkali developability. When a copolymer of (meth) acrylic acid and (meth) acrylic acid ester is used as the alkali-soluble polymer compound, urethane (meth) acrylate compound: (meth) acrylic acid and (meth) acrylic It is preferable that the blending amount of the acid ester + photopolymerizable monomer is in the range of 5:95 to 95: 5 by weight.

Examples of the photopolymerization initiator which is the component (C) of the present invention include 1-hydroxycyclohexyl phenyl ketone and 2,2-dimethoxy-1,2-diphenylethane-
1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane -1-one, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, 2,4,6
-Trimethylbenzoyldiphenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl]
-2-hydroxy-2-methyl-1-propan-1-one, 2,4-diethylthioxanthone, 2-chlorothioquinton, 2,4-dimethylthioxanthone, 3,3-
Dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanthone, 1-
(4-Isopropylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethyl Methyl aminobenzoate, ethyl 4-dimethylaminobenzoate,
Butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2,2-diethoxyacetophenone, benzyldimethylketal, benzyl-β-
Methoxyethyl acetal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, 4,4′-bisdiethylaminobenzophenone 4,4'-dichlorobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether,
p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldiloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, α, α-dichloro-4-phenoxyacetophenone, Mention may be made of pentyl-4-dimethylaminobenzoate and the like. The above compounds may be used alone or in combination of two or more. The photopolymerization initiator may be contained in the range of 0.1 to 20 parts by weight in 100 parts by weight of the solid content of the photosensitive resin.

The photosensitive resin composition of the present invention has the above (A)
The component and the component (B) are contained in a weight ratio of 5:95 to 95: 5, preferably 10:90 to 85:15, and the component (C) is contained in the photosensitive resin composition. It is contained in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the solid content. If the content of the component (B) in the photosensitive resin composition exceeds 95% by weight, the blast resistance is lowered, and if it is less than 5% by weight, the film-forming ability is insufficient when formed into a film and problems such as cold flow occur. Dots occur.

The photosensitive resin composition of the present invention has the above (A)
~ (C) component, in addition to (D) thiocyanate
Having potassium salt and polyalkylene oxide segment
It contains a complex with a polymer compound. Component (D)
Incorporation of the photosensitive resin composition after photocuring
Insulation resistance value (specific volume resistance value) is 1.0 x 10⁹~ 1.
0x10¹²Ω · cm Due to static electricity discharge
It can prevent lightning strikes and damages.

The above-mentioned electrical insulation resistance value means a PZT wiring on a glass-epoxy laminate with a thickness of 45 μm and a line width of 625 μm.
m with a pitch of 1825 μm, and a coating film of 50 μm formed by coating and drying a photosensitive resin composition thereon is exposed by an ultra-high pressure mercury lamp and cured to obtain high resistance.
Meter (High Resistance Mete)
r) The value measured with a 4339 A (manufactured by Hewlett Packard) measuring device.

Specific examples of the alkali thiocyanate salt constituting the component (D) include lithium thiocyanate, sodium thiocyanate, potassium thiocyanate, rubidium thiocyanate, calcium thiocyanate, ammonium thiocyanate, cesium thiocyanate, and thiocyanate. Magnesium acid, zinc thiocyanate, copper thiocyanate,
Examples thereof include lead thiocyanate. Among them, sodium thiocyanate, magnesium thiocyanate and ammonium thiocyanate are preferable because they have a high effect of suppressing an increase in electric insulation resistance value, and are suitable for forming barrier ribs and a flattening film of a plasma display panel.

Specific examples of the polyalkylene oxide segment of the polymer compound having the polyalkylene oxide segment include the segments of Chemical formulas 1 to 17.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

[Chemical 6]

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

Embedded image (In the above formula, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m represents an integer of 1 to 10, and n represents an integer of 5 to 250.)

In the component (D), the ratio of the alkali thiocyanate salt to the polymer compound having a polyalkylene oxide segment is 0.001 part by weight of the thiocyanate alkali salt to 1 part by weight of the polymer compound having a polyalkylene oxide segment. ˜1 part by weight. If the mixing ratio of the thiocyanic acid alkali salt is less than 0.001 part by weight, the desired effect cannot be achieved, and if it exceeds 1 part by weight, the long-term storage stability decreases. The component (D) is (A)
The range of 0.1 to 20 parts by weight is preferable with respect to 100 parts by weight of the total amount of the component (C).

To the photosensitive resin composition of the present invention, a Lewis acid salt soluble in an organic solvent and capable of generating a Lewis acid after irradiation with light can be added as the component (E) for the purpose of further lowering the electrical insulation resistance. As the Lewis acid salt, specifically,
27 compounds may be mentioned.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

Embedded image (In the above formula, R ₁ , R ₂ , R ₅ , and R ₈ represent an alkyl group having 1 to 3 carbon atoms, and R ₃ , R ₄ , R ₆ , and R ₇ are alkyl groups or alkoxy groups having 1 to 5 carbon atoms. Represents a group, and X ⁻ represents BF ⁻
₄ , AsF ^- ₆ , SbF ^- ₆ or PF ^- ₆ . )

The content of the Lewis acid salt is preferably in the range of 0.05 to 10 parts by weight with respect to 100 parts by weight of the solid content of the photosensitive resin composition. When the content is less than 0.05 parts by weight, the effect of lowering the electric insulation resistance value is not obtained, and when it exceeds 10 parts by weight, the storage stability becomes poor.

The photosensitive resin composition of the present invention may further contain a photopolymerizable monomer in order to further improve the sensitivity and prevent film loss and swelling during development. Examples of the photopolymerizable monomer include acrylic acid, methacrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol. Monofunctional monomers such as monomethyl ether methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol Tetramethacrylate, dipentaerythritol penta It can be mentioned polyfunctional monomers such as acrylates. These compounds may be used alone or in combination of two or more.

The photopolymerizable monomer is urethane (meth).
It is advisable to add it in an amount not exceeding 20 parts by weight with respect to 100 parts by weight of the acrylate compound. If the blending amount exceeds 20 parts by weight, cold flow is likely to occur in the dry film form, and the elasticity of the photosensitive resin composition after ultraviolet ray curing is reduced and the sandblast resistance is deteriorated.

The present invention can be dissolved in a solvent before use. Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and 2-methoxybutyl acetate. , 3-methoxybutyl acetate, 4-methoxybutyl acetate,
2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-
Examples thereof include, but are not limited to, methoxybutyl acetate, 2-ethoxybutyl acetate and 4-ethoxybutyl acetate.

Further, a dye, a polymerization inhibitor, a conductive substance such as carbon for adjusting the electric insulation resistance value, a cation system,
Anionic or amphoteric surfactants and the like can be optionally added.

The photosensitive resin composition of the present invention may be applied in a liquid state on a base material, screen-printed on the base material, or the like, depending on the application, but it may be used for manufacturing electronic parts. In the technical field requiring precision processing, it is preferable to use a photosensitive resin laminated film obtained by coating the photosensitive resin composition on a flexible supporting film and drying. By using the photosensitive resin laminated film, precise positioning can be facilitated and highly accurate cutting can be realized.

An example of the above-mentioned photosensitive resin laminated film is shown in FIG. In FIG. 1, reference numeral 1 denotes a flexible support film, on which the photosensitive resin composition of the present invention is applied to form a photosensitive resin composition layer 2. Further, a release film 3 is attached and integrated on the photosensitive resin composition layer 2.

The flexible support film 1 is a layer for supporting the photosensitive resin composition layer 2 of the present invention and has a film thickness of 15 to 12
A 5 μm film is good. Specific examples of the film include synthetic resin films of polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, polyvinyl chloride and the like. In particular, a polyethylene terephthalate (PET) film is preferable in terms of flexibility and strength. The photosensitive resin composition layer 2 is an applicator which is a solution prepared by dissolving the photosensitive resin composition in the above solvent.
It can be formed by coating using a bar coater, a roll coater, a curtain flow coater or the like so as to have a dry film thickness of 10 to 100 μm.

The release film 3 is a layer that stably protects the photosensitive resin composition layer 2 when not in use, and has a proper releasability that can be easily peeled off when used, but does not peel off when not used. Film is used. As the release film 3, 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 suitable.

In the above-mentioned photosensitive resin laminated film, in order to prevent the oxygen desensitizing action and prevent the adhesion of the mask pattern adhered at the time of exposure, a water-soluble resin is used between the flexible support film and the photosensitive resin composition layer. A resinous layer can be provided. The water-soluble resin layer is preferably a layer obtained by applying a 5-20 wt% aqueous solution of a water-soluble polymer of polyvinyl alcohol or partially saponified polyvinyl acetate to a dry film thickness of 1-10 μm and drying. When ethylene glycol, propylene glycol, polyethylene glycol or the like is further added to the water-soluble polymer solution forming the water-soluble resin layer,
This is preferable because the flexibility of the water-soluble resin layer is increased and the releasability is improved. Further, in the preparation of the water-soluble polymer solution, methanol, ethylene glycol monomethyl ether, acetone, the viscosity of the liquid by adding an aqueous defoaming agent,
The defoaming property and the like can be improved.

Next, one example of a suitable usage of the photosensitive resin laminated film is shown in FIGS. 2 (a) to 2 (e). The release film 3 in FIG. 1 is peeled off as shown in FIG. 2 (a), and the exposed photosensitive resin composition layer is adhered onto the substrate 4. It is preferable to employ a so-called thermocompression bonding method in which the base material 4 is heated in advance and a dry film is placed on and pressed against the base material 4 in the contact. After pressing, the flexible supporting film 1 is peeled off, and a mask 7 having a predetermined mask pattern is adhered onto the exposed photosensitive resin layer 2 as shown in FIG. 2 (b). Exposure is performed from above by using a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an arc lamp, a xenon lamp, or the like. As the exposure light beam, excimer laser, X-ray, electron beam or the like can be used in addition to ultraviolet light. After exposure, the mask pattern 7 is removed and development is performed. By the development, as shown in FIG. 2C, the unexposed portion of the photosensitive resin layer 2 to the ultraviolet rays is removed, and only the resin layer 9 of the exposed portion remains. A general-purpose alkaline developer can be used as the developer used for the development. The developed substrate is sandblasted and polished as shown in FIG. 2 (d) to form a pattern faithful to the pattern. As the blasting material used in the sandblasting process, glass beads of _{2 to} 500 μm, inorganic fine particles such as SiC, SiO ₂ , Al ₂ O ₃ , and ZrO are preferably used.

The resin layer 9 remaining from the sandblasted base material is dissolved in an alkaline aqueous solution to form a pattern on the surface of the base material as shown in FIG. 2 (e).

[0063]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0064]

【Example】

Example 1 Preparation of Photosensitive Resin Composition The compounds shown below were thoroughly stirred and kneaded to prepare a solution of the photosensitive resin composition.・ Daicel Chemical Co., Ltd. carboxyl group-containing urethane acrylate "KRM7222" (weight average molecular weight 10,000, acid value 20, containing 20% ethyl acetate as a solvent) 35 parts by weight ・ Nippon Gosei Chemical Co., Ltd. carboxyl group-containing urethane acrylate "Shikou UT- 9510 "(weight average molecular weight about 20,000, acid value 32 containing 30% ethyl acetate as solvent) 32 parts by weight-Cellulose acetate phthalate" KC-71 "(manufactured by Wako Pure Chemical Industries, Ltd .: acid value 120, containing 75% methyl ethyl ketone as solvent) ) 30 parts by weight, 2,4-dimethylthioxanthone 2 parts by weight, 4-dimethylaminobenzoic acid-2-isoamyl 1 part by weight, dimethylbenzyl ketal 0.05 parts by weight, a composite of polyethylene oxide and ammonium thiocyanate (polyethylene). The molecular weight of oxide is about 50 0, weight = 1 / 0.05 of the polyethylene oxide / ammonium thiocyanate) 3 parts by weight of ethyl acetate 30 parts by weight

Regarding the prepared photosensitive resin composition,
After measuring the electrical insulation resistance after
Is the volume resistivity of 3.47 × 10^TenΩ · cm Met.

The above-mentioned photosensitive resin composition solution was applied onto a polyethylene terephthalate (PET) support film so that the film thickness after drying was 50 μm, and dried to form a photosensitive resin composition layer. A PET release film was applied on the photosensitive resin composition layer to prepare a photosensitive resin laminated film. The release film of the photosensitive resin laminated film was peeled off, and the exposed photosensitive resin composition layer was thermocompression bonded onto a glass substrate at 80 ° C. Then, the PET support film was peeled off, and 60 μm was formed on the exposed photosensitive resin composition layer.
With a line / space of 100 mJ / cm through this mask using an ultra-high pressure mercury lamp
^The exposure was performed with an energy dose of ² . 0.2% after exposure
Develop with an aqueous solution of sodium carbonate at a spray pressure of 1.5 kg / cm ² , use the resulting resist pattern as a mask, and use abrasive glass beads # 800 to perform sandblasting for 180 seconds at a blast pressure of 4 kg / cm ^2. went. When the glass substrate after processing was observed, the base material was not damaged at all, and the film reduction of the resist pattern was small.

Example 2 Preparation of Photosensitive Resin Composition The compounds shown below were well stirred and kneaded to prepare a solution of the photosensitive resin composition. * Daicel Chemical Co., Ltd. carboxyl group-containing urethane acrylate "KRM7222" (above) 35 parts by weight-Nippon Gosei Chemical Co., Ltd. carboxyl group-containing urethane acrylate "Shikou UT-9510" (above) 32 parts by weight-Cellulose acetate phthalate "KC" -71 "(above) 30 parts by weight-2,4-dimethylthioxanthone 2 parts by weight-2-dimethylaminobenzoic acid-2-isoamyl 1 part by weight-Dimethylbenzyl ketal 0.05 parts by weight A complex of a polymer having a polyalkylene oxide segment represented by and sodium thiocyanate (the molecular weight of the polymer having a polyalkylene oxide segment is about 6000, the weight of the polymer having a polyalkylene oxide segment and sodium thiocyanate = 1 / 0.005 ) 3 parts by weight-Ethyl acetate 30 parts by weight

Regarding the prepared photosensitive resin composition,
After measuring the electrical insulation resistance after
Is the volume resistivity 8.86 × 10¹¹Ω · cm Met.

The above photosensitive resin composition solution was formed into a photosensitive laminated film in the same manner as in Example 1, the release film was peeled off, and the glass substrate was thermocompression bonded at 80 ° C. to form a photosensitive resin composition layer. The PET support film is then peeled off, 60
A mask capable of reproducing a line / space of μm was brought into close contact, exposed and developed in the same manner as in Example 1 to form a mask pattern, and then glass beads # 800 were used, and a blast pressure of 4 kg / cm ² for 180 seconds. Sandblasting was performed, but during processing, no phenomena such as electric discharge and lightning were observed on the glass substrate, no damage was observed on the glass substrate after processing, and no reduction in the resist pattern film was observed. .

Example 3 Preparation of Photosensitive Resin Composition The compounds shown below were well stirred and kneaded to prepare a solution of the photosensitive resin composition. * Daicel Chemical Co., Ltd. carboxyl group-containing urethane acrylate "KRM7222" (above) 35 parts by weight-Nippon Gosei Chemical Co., Ltd. carboxyl group-containing urethane acrylate "Shikou UT-9510" (above) 32 parts by weight-Cellulose acetate phthalate "KC" -71 "(above) 30 parts by weight-2,4-dimethylthioxanthone 2 parts by weight-2-dimethylaminobenzoic acid-2-isoamyl 1 part by weight-Dimethylbenzyl ketal 0.05 parts by weight A complex of a polymer having a polyalkylene oxide segment represented by and magnesium thiocyanate (the molecular weight of the polymer having a polyalkylene oxide segment is about 5500, the weight of the polymer having a polyalkylene oxide segment and magnesium thiocyanate = 1 / 0.5 ) 2.5 parts by weight-ethyl acetate 30 parts by weight

Regarding the prepared photosensitive resin composition,
After measuring the electrical insulation resistance after
Is the volume resistivity 5.29 × 10⁹Ω · cm Met.

The photosensitive resin composition solution was formed into a photosensitive laminated film in the same manner as in Example 1, the release film was peeled off, and the glass substrate was thermocompression bonded at 80 ° C. to form a photosensitive resin composition layer. The PET support film is then peeled off, 60
A mask capable of reproducing a line / space of μm was brought into close contact, exposed and developed in the same manner as in Example 1 to form a mask pattern, and then glass beads # 800 were used, and a blast pressure of 4 kg / cm ² for 180 seconds. Sandblasting was performed, but during processing, no phenomena such as electric discharge and lightning were observed on the glass substrate, no damage was observed on the glass substrate after processing, and no reduction in the resist pattern film was observed. .

Comparative Example 1 Preparation of Photosensitive Resin Composition The compounds shown below were thoroughly stirred and kneaded to prepare a solution of the photosensitive resin composition. * Daicel Chemical Co., Ltd. carboxyl group-containing urethane acrylate "KRM7222" (above) 35 parts by weight-Nippon Gosei Chemical Co., Ltd. carboxyl group-containing urethane acrylate "Shikou UT-9510" (above) 32 parts by weight-Cellulose acetate phthalate "KC" -71 "(above) 30 parts by weight-2,4-dimethylthioxanthone 2 parts by weight-2-dimethylaminobenzoic acid-2-isoamyl 1 part by weight-Dimethylbenzyl ketal 0.05 parts by weight

Regarding the prepared photosensitive resin composition,
After measuring the electrical insulation resistance after
Is the volume resistivity 1.23 × 10¹⁴Ω · cm Met.

The photosensitive resin composition solution was formed into a photosensitive laminated film in the same manner as in Example 1, the release film was peeled off, and the glass substrate was thermocompressed at 80 ° C. to form a photosensitive resin composition layer. The PET support film is then peeled off, 60
A mask capable of reproducing a line / space of μm was brought into close contact, exposed and developed in the same manner as in Example 1 to form a mask pattern, and then glass beads # 800 were used, and a blast pressure of 4 kg / cm ² for 180 seconds. Although sandblasting was performed, discharge and lightning were observed on the glass substrate during processing, and glass through holes due to discharge were observed on the glass substrate after processing.

Example 4 Preparation of Photosensitive Resin Composition The compounds shown below were thoroughly stirred and kneaded to prepare a solution of the photosensitive resin composition. * Daicel Chemical Co., Ltd. carboxyl group-containing urethane acrylate "KRM7222" (above) 35 parts by weight-Nippon Gosei Chemical Co., Ltd. carboxyl group-containing urethane acrylate "Shikou UT-9510" (above) 32 parts by weight-Cellulose acetate phthalate "KC" -71 "(above) 30 parts by weight-2,4-dimethylthioxanthone 2 parts by weight-2-isoamyl 2-dimethylaminobenzoate 1 part by weight-Dimethylbenzyl ketal 0.05 parts by weight-Polyethylene oxide and ammonium thiocyanate (Compound having a polyalkylene oxide segment having a molecular weight of about 5,000, weight of polyethylene oxide and ammonium thiocyanate = 1 / 0.05) 2 parts by weight-ethyl acetate 30 parts by weight

Regarding the prepared photosensitive resin composition,
After measuring the electrical insulation resistance after
Is the volume resistivity 2.75 × 10^TenΩ · cm Met.

The photosensitive resin composition solution was formed into a photosensitive laminated film in the same manner as in Example 1, the release film was peeled off, and the glass substrate was thermocompressed at 80 ° C. to form a photosensitive resin composition layer. The PET support film is then peeled off, 60
A mask capable of reproducing a line / space of μm was brought into close contact, exposed and developed in the same manner as in Example 1 to form a mask pattern, and then glass beads # 800 were used, and a blast pressure of 4 kg / cm ² for 180 seconds. Although sandblasting was performed, no phenomena such as electric discharge and lightning were observed on the glass substrate during the processing, no damage was observed on the glass substrate after processing, and no reduction of the resist pattern film was observed.

Example 5 Preparation of Photosensitive Resin Composition The compounds shown below were thoroughly stirred and kneaded to prepare a solution of the photosensitive resin composition. * Daicel Chemical Co., Ltd. carboxyl group-containing urethane acrylate "KRM7222" (above) 35 parts by weight-Nippon Gosei Chemical Co., Ltd. carboxyl group-containing urethane acrylate "Shikou UT-9510" (above) 32 parts by weight-Cellulose acetate phthalate "KC" -71 "(above) 30 parts by weight-2,4-dimethylthioxanthone 2 parts by weight-2-isoamyl 2-dimethylaminobenzoate 1 part by weight-Dimethylbenzyl ketal 0.05 parts by weight-Polyethylene oxide and ammonium thiocyanate Complex with (molecular weight of polymer having polyalkylene oxide segment of about 5,000, weight of polyethylene oxide and ammonium thiocyanate = 1 / 0.05) 2 parts by weight 4-morpholino-2,5-dibutoxybenzenediazonium Kisa fluorophosphate 0.5 part by weight of ethyl acetate 30 parts by weight

Regarding the prepared photosensitive resin composition,
After measuring the electrical insulation resistance after
Is the volume resistivity of 3.82 × 10⁹Ω · cm Met.

The photosensitive resin composition solution was formed into a photosensitive laminated film in the same manner as in Example 1, the release film was peeled off, and the glass substrate was thermocompression bonded at 80 ° C. to form a photosensitive resin composition layer. The PET support film is then peeled off, 60
A mask capable of reproducing a line / space of μm was brought into close contact, exposed and developed in the same manner as in Example 1 to form a mask pattern, and then glass beads # 800 were used, and a blast pressure of 4 kg / cm ² for 180 seconds. Sandblasting was performed, but during processing, no phenomena such as electric discharge and lightning were observed on the glass substrate, no damage was observed on the glass substrate after processing, and no reduction in the resist pattern film was observed. .

[0082]

EFFECTS OF THE INVENTION The photosensitive resin composition of the present invention has high sandblast resistance, high sensitivity and is less likely to be charged with static electricity, so that the treated substrate is not damaged by discharge due to static electricity or lightning strike. In particular, when the photosensitive resin laminated film formed by using the photosensitive resin composition of the present invention is used, fine processing of electronic parts and the like can be performed without static electricity discharge and lightning strike, and thus products can be manufactured with high yield.

[Brief description of the drawings]

FIG. 1 is an enlarged cross-sectional view of a photosensitive resin laminated film of the present invention.

FIG. 2 is an explanatory view showing a procedure of a surface etching method of the present invention.

[Explanation of symbols]

 1 flexible film 2 photosensitive resin composition layer 3 release film 4 insulating layer 5 conductor pattern 6 base material

Claims (5)

[Claims] 1. A photopolymerizable urethane (meth) acrylate compound having (A) at least two or more acryloyl groups or methacryloyl groups, and (B) an acid value of 50 to 25.
0 mg / KOH alkali-soluble polymer compound,
A photosensitive resin composition comprising (C) a photopolymerization initiator, and (D) a complex of an alkali salt of thiocyanate and a polymer compound having a polyalkylene oxide segment. 2. The photosensitive resin composition according to claim 1, further comprising (E) a Lewis acid salt which is soluble in an organic solvent and generates a Lewis acid upon irradiation with light. . 3. The photosensitive resin composition according to claim 1, wherein the thiocyanic acid alkali salt forming the component (D) is ammonium thiocyanate, sodium thiocyanate or magnesium thiocyanate. 4. A photopolymerizable urethane (meth) acrylate compound having (A) at least two acryloyl groups or methacryloyl groups on a flexible film,
(B) Contains an alkali-soluble polymer compound having an acid value of 50 to 250 mg / KOH, (C) a photopolymerization initiator, and (D) a complex of an alkali salt of thiocyanate and a polymer compound having a polyalkylene oxide segment. A photosensitive resin laminated film, comprising a photosensitive layer of the photosensitive resin composition, and a release film layer further laminated thereon. 5. A photosensitive resin composition for forming a photosensitive layer provided on a flexible film is soluble in an organic solvent (E) in addition to components (A) to (D) and generates a Lewis acid after light irradiation. The photosensitive resin laminated film according to claim 4, further comprising a Lewis acid salt.