JP2002006488A - Photosensitive resin composition, photosensitive element using the same, method for producing resist pattern, resist pattern and resist pattern laminated substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of satisfying flame resistance (by which UL94-V0 is retained) when applied to a halogen-free and antimony-free flame-retardant substrate, developable with a dilute aqueous alkali solution and capable of forming a high reliability soldering resist excellent in resolution, heat resistance, TCT property, flexibility and mechanical characteristics and to provide a photosensitive element, a method for producing a resist pattern, a resist pattern and a resist pattern laminated substrate. SOLUTION: The photosensitive resin composition contains (A) a phosphorus- containing photosensitive resin and (B) a photopolymerization initiator. The photosensitive element is obtained by applying and drying the photosensitive resin composition on a base. In the method for producing a resist pattern, a layer of the photosensitive resin composition is disposed on a substrate and imagewise irradiated with active light, the exposed part is photo-cured and the unexposed part is removed by development. The resist pattern is produced by the method. The resist pattern laminated substrate has the resist pattern on a substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method for producing a resist pattern, a resist pattern, and a resist pattern laminated substrate.

[0002]

2. Description of the Related Art Conventionally, solder resist has been used in the manufacture of printed wiring boards, but in recent years it has also been used in new LSI packages such as BGA (ball grid array) and CSP (chip size package). Have been. Solder resist is an indispensable material as a protective film or a permanent mask for preventing solder from adhering to unnecessary parts in a soldering process. As a solder resist, for example, there is a method in which a thermosetting type is printed by a screen printing method and applied.

Although the present invention can be applied to such a method,
In recent years, as the density of wiring has increased, the screen printing method has a limit in terms of resolution, and a photo solder resist for forming a pattern by a photographic method has been actively used. Among them, an alkali developing type, which can be developed with a weak alkali solution such as sodium carbonate solution, has become mainstream from the viewpoint of working environment conservation and global environment conservation.

[0004] As such a device, those disclosed in JP-A-61-243869 and JP-A-1-141904 are known. However, these compositions have insufficient flame resistance, and recently, when applied to a non-halogen, non-antimony-based flame-retardant substrate that has attracted attention from the viewpoint of preventing dioxin contamination, the flame retardancy is reduced. There is a problem.

[0005]

According to the first, second and third aspects of the present invention, when applied to a non-halogen, non-antimony based flame-retardant substrate, flame retardancy (UL94-V0 is maintained) can be satisfied, and The present invention provides a photosensitive resin composition which can be developed with a dilute alkaline aqueous solution and which can form a highly reliable solder resist having excellent resolution, heat resistance, TCT properties, flexibility and mechanical properties. The invention according to claim 4 is a non-halogen,
When applied to non-antimony-based flame-retardant substrates, flame retardancy (UL
94-V0), and can be developed with a dilute aqueous alkali solution, and provide a highly reliable solder resist capable of forming a highly reliable solder resist having excellent resolution, heat resistance, TCT properties, flexibility and mechanical properties. It is to be.

The invention according to claim 5 is applicable to a non-halogen, non-antimony based flame-retardant substrate.
-V0) and developing a resist pattern that can be developed with a dilute alkaline aqueous solution and that can form a highly reliable solder resist with excellent resolution, heat resistance, TCT properties, flexibility and mechanical properties. To provide. The invention according to claim 6, when applied to a non-halogen, non-antimony-based flame-retardant substrate, can satisfy flame retardancy (retain UL94-V0), can be developed with a dilute alkaline aqueous solution, and has resolution, heat resistance, An object of the present invention is to provide a resist pattern capable of forming a highly reliable solder resist having excellent TCT properties, flexibility and mechanical properties.

[0007] The invention according to claim 7, when applied to a non-halogen, non-antimony based flame-retardant substrate, has a flame-retardant (UL94).
-V0) and develop with a dilute alkaline aqueous solution, and provide a resist pattern laminated substrate capable of forming a highly reliable solder resist excellent in resolution, heat resistance, TCT properties, flexibility and mechanical properties. It is to be.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a photosensitive resin composition containing (A) a phosphorus-containing photosensitive resin and (B) a photopolymerization initiator. In addition, the present invention provides (A) a reaction product of (a) a phosphorus-containing compound having at least one epoxy group in a molecule and (b) a reaction product of an unsaturated monocarboxylic acid with (c) a phosphorus-containing photosensitive resin. The present invention relates to the photosensitive resin composition obtained by an addition reaction of a saturated or unsaturated polybasic acid anhydride.

The present invention also relates to the photosensitive resin composition further comprising (C) a compound having at least one epoxy group. Further, the present invention relates to a photosensitive element obtained by applying and drying the photosensitive resin composition on a support.

The present invention also relates to a method of laminating a layer of the photosensitive resin composition on a substrate, irradiating the layer with an actinic ray in the form of an image, curing the exposed portion with light, and removing the unexposed portion by development. The present invention relates to a method for manufacturing a characteristic resist pattern. Also,
The present invention relates to a resist pattern manufactured by the method for manufacturing a resist pattern. The present invention also relates to a resist pattern laminated substrate having the resist pattern on a substrate.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto,
(Meth) acrylate means acrylate and its corresponding methacrylate, and (meth) acryloyl group means acryloyl and its corresponding methacryloyl group.

The photosensitive resin composition of the present invention comprises (A) a phosphorus-containing photosensitive resin and (B) a photopolymerization initiator. The (A) phosphorus-containing photosensitive resin is, for example, (a)
It can be obtained by adding (c) a saturated or unsaturated polybasic acid anhydride to a reaction product of a phosphorus-containing compound having at least one epoxy group in the molecule and (b) an unsaturated monocarboxylic acid.

Examples of the (a) phosphorus-containing compound having at least one epoxy group in the molecule include tris (2,3-epoxypropyl) phosphate, bis (2,3-epoxypropyl) phenylphosphoric acid Acid ester, tris [2- (2 ', 3'epoxypropyloxy) ethyl] phosphate ester and the like.
These are used alone or in combination of two or more.

Further, as the component (a), a phosphorus-containing epoxy resin obtained by reacting a phosphorus-containing compound having an active group with an epoxy resin can also be suitably used.
Examples of the phosphorus-containing epoxy resin include phosphoric acid (orthophosphoric acid), metaphosphoric acid, pyrophosphoric acid, phosphoric anhydride (diphosphorus pentoxide), orthophosphorous acid, metaphosphorous acid,
Pyrophosphorous acid, monoalkyl (C1-8) phosphate, (meth) acryloyloxyethyl acid phosphate, 9,8 described in JP-A-11-1666035
Phosphorus compounds having active hydrogen such as dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and cresol novolak epoxy resin, phenol novolak epoxy resin, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy Resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, tetraglycidyl xylenoyl ethane Resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, silicon-modified epoxy resin, ε-caprolactone-modified epoxy resin, dicyclope Tajien type epoxy resins, the reaction product of bisphenol A / dicyclopentadiene / 2,6-xylenol cocondensate type known epoxy resin having an epoxy resin. These are used alone or in combination of two or more.

The phosphorus-containing epoxy resin is preferably soluble in a solvent, and is preferably transparent to light of 300 to 400 nm, but the structure is not particularly limited.

The unsaturated monocarboxylic acid (b) includes, for example, (meth) acrylic acid, crotonic acid, cinnamic acid, a saturated or unsaturated polybasic anhydride and one hydroxyl group in one molecule ( (Meth) acrylates, a reaction product of a half-ester compound of a saturated or unsaturated dibasic acid and an unsaturated monoglycidyl compound, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid and hydroxyethyl (Meth) acrylate, hydroxypropyl (meth) acrylate, tris (hydroxyethyl) isocyanurate di (meth) acrylate, glycidyl (meth) acrylate reactants obtained by reacting in an equimolar ratio by a conventional method, and the like, Acrylic acid is preferred. These are used alone or in combination of two or more.

(C) Examples of the saturated or unsaturated polybasic anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride,
And succinic anhydride, trimellitic anhydride and the like. These are used alone or in combination of two or more.

The acid value of the (A) phosphorus-containing photosensitive resin is as follows:
From the viewpoint of the balance between alkali developability and electrical properties, 4
0 to 250 mgKOH / g, preferably 50 to 15 mgKOH / g.
More preferably, it is 0 mgKOH / g.

The phosphorus content of the (A) phosphorus-containing photosensitive resin is preferably in the range of 0.6 to 3% by weight. When the content is less than 0.6% by weight, the flame retardancy of the obtained photosensitive resin composition tends to decrease, and when it exceeds 3% by weight, properties such as adhesion and heat resistance tend to decrease.

The (A) phosphorus-containing photosensitive resin further includes a diisocyanate compound such as tolylene diisocyanate and isophorone diisocyanate and a (meth) acrylate having one or more hydroxyl groups in one molecule such as hydroxyethyl (meth) acrylate. May be reacted with isocyanate ethyl (meth) acrylate or the like to introduce an unsaturated group via a urethane bond.

Examples of the photopolymerization initiator (B) include benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2. -Phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2
-Methyl-1- [4- (methylthio) phenyl] -2-
Acetophenones such as morpholinopropan-1-one, 2,2-diethoxyacetophenone, N, N-dimethylaminoacetophenone, 2-methylanthraquinone,
Anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4
Thioxanthones such as diisopropylthioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, methylbenzophenone, 4,4'-bis (diethylamino) benzophenone, Michler's ketone, 4-benzoyl-4 '
Benzophenones such as -methyldiphenyl sulfide, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl)
-4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5
2,4,5-triarylimidazole dimer such as -diphenylimidazole dimer, acridine derivative such as 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide. These are used alone or in combination of two or more.

In the photosensitive resin composition of the present invention, as a photopolymerization initiation aid, for example, ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, pentyl-4-dimethyl Tertiary amines such as aminobenzoate, dimethylethanolamine, triethylamine and triethanolamine can be blended in the range of about 0.1 to 20% by weight of the total amount of the photosensitive resin composition.

Examples of the compound (C) having at least one epoxy group include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F
Epoxy resin, bisphenol S epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, bixylenol epoxy resin, biphenol epoxy resin, tetraglycidyl xylenoyl ethanene resin, chelate epoxy resin, glyoxal epoxy resin , Amino group-containing epoxy resin, rubber-modified epoxy resin, silicon-modified epoxy resin, ε-caprolactone-modified epoxy resin, cresol novolak-type epoxy resin, phenol novolak-type epoxy resin, dicyclopentadiene-type epoxy resin, bisphenol A / dicyclopentadiene / 2,6-xylenol co-condensation type epoxy resin, hydantoin type epoxy resin, triglycidyl isocyanurate, the phosphorus-containing epoxy resin, the following general formula (I)

Embedded image (Wherein, a plurality of Rs and a plurality of R's each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
A cycloalkyl group, an aryl group having 6 to 18 carbon atoms, an amino group, an alkylamino group having 1 to 10 carbon atoms, and 2 carbon atoms
A dialkylamino group, a nitro group, a cyano group, a carbonyl group, a mercapto group, an alkylmercapto group having 1 to 10 carbon atoms, an allyl group, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group and an alkyl group A carboxyalkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms in the alkyl group, an alkoxy group having 1 to 20 carbon atoms or a group containing a heterocyclic ring, and n is an integer of 0 to 3 And the like. These are used alone or in combination of two or more.

In the general formula (I), a plurality of R's and a plurality of R ''s may be the same or different and each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or 6 carbon atoms. ~ 1
And a plurality of R's are preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms. Further, n is an integer of 0 to 3, and when n exceeds 3, the epoxy equivalent becomes large and the heat resistance tends to be inferior.

The compound (C) having at least one epoxy group may have a photosensitive group, for example, a reaction product of the epoxy resin and the unsaturated monocarboxylic acid, A reaction product with an isocyanate containing a (meth) acryl group can be used.

The amount of the component (A) is preferably 20 to 90% by weight, more preferably 40 to 70% by weight, based on the total solid content of the photosensitive resin composition. If the amount is less than 20% by weight, the flame retardancy tends to be inferior, and if it exceeds 90% by weight, the adhesive heat resistance and the hardness tend to be inferior.

The amount of the component (B) is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight, based on the total solid content of the photosensitive resin composition. If the amount is less than 0.1% by weight, the photoreactivity tends to be inferior, and if it exceeds 20% by weight, the curability of the resist bottom tends to be inferior.

The amount of the component (C) is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, based on the total solid content of the photosensitive resin composition.
If the amount is less than 1% by weight, the adhesion tends to be poor, and if it exceeds 40% by weight, the developability tends to be poor.

The flame-retardant photosensitive resin of the present invention includes, for example,
For the purpose of improving characteristics such as light sensitivity and heat resistance, JP-A-61
No. 3,243,869, JP-A-5-32746, and the like, a carboxyl group-containing photosensitive resin containing no phosphorus can be contained up to 70% by weight of the total amount of the flame-retardant photosensitive resin composition. If the amount exceeds 60% by weight, the flame retardancy tends to decrease.

The photosensitive resin composition of the present invention may contain a curing accelerator for an epoxy resin for the purpose of improving adhesion, chemical resistance, heat resistance, etc., for example, melamine, acetoguanamine, benzoguanamine, and the like. Melamine-phenol-formalin resin, 2MZ-A manufactured by Shikoku Chemical Industry Co., Ltd.
ZINE, 2E4MZ-AZINE, C11Z-AZI
Examples thereof include melamine derivatives such as NE and 2MA-OK, and triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, and 2,4-diamino-6-xylyl-S-triazine. These are used alone or in combination of two or more.

[0031] The compounding amount depends on the adhesion to the copper circuit and the PC resistance.
From the viewpoint of T properties and electrolytic corrosion, the content is preferably 0.1 to 10% by weight based on the total amount of the photosensitive resin composition,
More preferably, it is 5% by weight. When the blending amount is 0.
If it is less than 1% by weight, the adhesion tends to be poor, and 10% by weight
If it exceeds, the developability tends to be poor.

Further, in the photosensitive resin composition of the present invention, other curing agents or thermosetting accelerators can be used in the range of about 0.01 to 10% by weight based on the total amount of the photosensitive resin composition.

Examples of the curing agent include alkylated melamine resins such as dicyandiamide, organic acid hydrazide, diaminomaleonitrile, urea, amine imide and hexamethoxymethylated melamine, and salts of polyamines.
Diaminodiphenylmethane, metaphenylenediamine,
Aromatic amines such as diaminodiphenylmethane, metaxylenediamine, diaminodiphenylsulfone, hardener HT972 manufactured by Ciba-Geigy, phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate) Tet), aromatic acid anhydrides such as benzophenonetetracarboxylic anhydride, aliphatic acid anhydrides such as maleic anhydride and tetrahydrophthalic anhydride, and polyphenols such as polyvinylphenol, phenol novolak and alkylphenol novolak. These are used alone or in combination of two or more.

Examples of the thermosetting accelerator include metal salts of acetylacetone such as acetylacetonate Zn.
Enamine, tin octylate, quaternary phosphonium salt,
Tertiary phosphines such as triphenylphosphine,
Dimethylbenzylamine, 1,8-diazabicyclo [5,4,0] undecene, m-aminophenol,
Tertiary amines such as 2,4,6-tris (dimethylaminophenol) and tetramethylguanidine, 2-ethyl-4-methylimidazole, 2-methylimidazole,
Imidazoles such as 1-benzyl-2-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole; These are used alone or in combination of two or more.

The photosensitive resin composition of the present invention includes, for example,
A photopolymerizable compound can be added and used for the purpose of improving characteristics such as photosensitivity.

As the photopolymerizable compound, for example, 2
-Hydroxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, N, N-dimethyl (meth) acrylate, N-methylol (meth) Acrylamide, urethane (meth) acrylate, or polyethylene glycol, polypropylene glycol, polyethylene glycol or propylene glycol of bisphenol A, tris (2-hydroxyethyl) isocyanuric acid mono- or polyfunctional (meth) acrylates, triglycidyl isocyanurate, etc. (Meth) acrylates of glycidyl ether, diallyl phthalate,
A photopolymerizable compound such as 1,3,5-triacryloyl-hexahydro-S-triazine is used. These may be used alone or in combination of two or more.

Further, the photosensitive resin composition of the present invention includes, for example, ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene Glycol monomethyl ether, dipropylene glycol monoethyl ether,
Glycol ethers such as triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, alcohols such as ethanol, propanol, ethylene glycol and propylene glycol, and aliphatics such as octane and decane The solid content of the photosensitive resin composition is reduced to 80 by organic solvents such as hydrocarbons, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, petroleum solvents such as solvent naphtha, etc.
It can be used as a solution of about 90% by weight.
These are used alone or in combination of two or more.

Further, the photosensitive resin composition of the present invention may be prepared from the viewpoints of adhesion, hardness and the like, for example, barium sulfate, barium titanate, powdery silicon oxide, amorphous silica, talc, clay, calcined kaolin, magnesium carbonate , Calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder, etc., in an amount of from 0 to 60 with respect to the total amount of the photosensitive resin composition.
% By weight. These are used alone or in combination of two or more.

Further, the photosensitive resin composition of the present invention may be, for example, phthalocyanine blue, iodine green, disazo yellow, crystal violet, titanium oxide,
Coloring agents such as carbon black and naphthalene black,
Polymerization inhibitors such as methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, and phenothiazine;
Thixotropic agents such as montmorillonite, aerosil and amide wax; antifoaming agents such as silicone, fluorine, and polymer; leveling agents; adhesives such as imidazole, thiazole, triazole, and silane coupling agents And other additives.

The photosensitive resin composition of the present invention is prepared, for example, by uniformly mixing the raw materials blended in the above ratio by a roll mill, a bead mill or the like, and forming the mixture on a substrate such as a printed wiring board, an electric circuit board such as a BGA or a CSP. 10 to 16 by a method such as a screen printing method, a spray method, an electrostatic spray method, an airless spray method, a curtain coater method, and a roll coating method.
Laminate by applying the photosensitive resin composition of the present invention at a film thickness of about 0 μm, and after drying the coating film at about 60 to 110 ° C., place a negative film on the coating film and apply radiation such as ultraviolet rays. By irradiating an actinic ray such as an image in an image form, light-curing the exposed portion, and then dissolving or dispersing and removing (developing) the unexposed portion with a dilute alkaline aqueous solution such as a 0.5 to 2% by weight aqueous sodium carbonate solution. After obtaining a resist pattern, it is possible to obtain a cured film by sufficiently curing by usually irradiating ultraviolet rays or heating at 100 to 200 ° C. for about 0.5 to 1 hour. Obtainable.

The photosensitive resin composition of the present invention comprises a sodium carbonate aqueous solution to which a surfactant having an HLB of 13 to 15 is added, and an organic amine-based developer (manufactured by Mitsubishi Gas Chemical Co., Ltd.)
F-105A) can also be suitably used.

The photosensitive resin composition of the present invention is useful as a solder resist composition for printed wiring boards and packages such as BGA and CSP, and is also used for coating materials such as paints, glass, ceramics, plastics, and paper. it can.

[0043]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments.

Production Example 1 Phosphorus-Containing Photosensitive Resin (A-1) In a flask equipped with a stirrer, a reflux condenser and a thermometer,
(A) Tris- [2- (2 ′, 3′-epoxypropyloxy) ethyl] phosphate (epoxy equivalent: 12
4) 248 parts by weight, (b) 144 parts by weight of acrylic acid, 1 part by weight of methylhydroquinone, 2 parts by weight of triphenylphosphine, 200 parts by weight of carbitol acetate and 50 parts by weight of solvent naphtha, and heated to 100 ° C. The reaction was carried out until the acid value became 1 mgKOH / g or less.

Next, the obtained solution was cooled to 50 ° C.
(C) 117 parts by weight of tetrahydrophthalic anhydride, 20 parts by weight of carbitol acetate and 20 parts of solvent naphtha
A part by weight was charged and reacted at 80 ° C. for a predetermined time to obtain a phosphorus-containing photosensitive resin (A-1) having a solid content of an acid value of 85 mgKOH / g and a solid content of 64% by weight.

Production Example 2: Phosphorus-containing photosensitive resin (A-2) In a flask equipped with a stirrer, a reflux condenser and a thermometer,
(A) EOCN-4400 (cresol novolak type epoxy resin manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 190) / phosphoric anhydride (acid equivalent / epoxy equivalent ratio: 0.2) reaction product (epoxy equivalent: 246; 246 parts by weight of phosphorus content 1%)
(B) 72 parts by weight of acrylic acid, 0.4 parts by weight of methylhydroquinone, 1 part by weight of triphenylphosphine, 200 parts by weight of carbitol acetate and 50 parts by weight of solvent naphtha were charged, and the solid content acid value was 2 mgKOH / g at 100 ° C.
The reaction was carried out until the following.

Next, the obtained solution is cooled to 50 ° C.
(C) 76 parts by weight of tetrahydrophthalic anhydride, 20 parts by weight of carbitol acetate and 6 parts by weight of solvent naphtha were charged and reacted at 80 ° C. for a predetermined time to obtain a solid acid value of 7
A phosphorus-containing photosensitive resin (A-2) having 1 mgKOH / g and a solid content of 60% by weight was obtained.

Examples 1 to 3 and Comparative Example 1 The components shown in Table 1 below and the components shown in Table 2 below were kneaded using three rolls according to the compositions, and then mixed to prepare a photosensitive resin composition. .

[0049]

[Table 1]

[0050]

[Table 2]

A copper-clad laminate (MCL-RO67G, Hitachi Chemical Co., Ltd., thickness 0%) was dried by a screen printing method using a 100-mesh polyester screen so that the film thickness after drying was 25 to 35 μm. .2 mm), the coating film was dried at 80 ° C. for 20 minutes, and a negative mask film having a resist pattern was adhered thereto, and then irradiated with ultraviolet rays for a predetermined time using an ultraviolet exposure apparatus. Next, 1%
Spray development (spray pressure: 0.2 MPa) was performed with an aqueous solution of sodium carbonate for 60 seconds to dissolve and remove unexposed portions, and the developability was evaluated. Next, using a circulation hot air dryer, 15
Heat curing was performed at 0 ° C. for 1 hour, and the obtained cured film was evaluated.

Next, a 0.2 mm thick non-halo flame-retardant substrate (MCL-RO67G was etched to remove copper foil) so that the photosensitive resin composition had a dried film thickness of 50 μm. And cured in the same way as above,
The flame retardancy of the obtained substrate was evaluated. Table 3 summarizes the evaluation results.

[0053]

[Table 3]

The evaluation items in Table 3 are shown below. * 1: UL-94 vertical test was performed. * 2: Cross-cut test of JIS D0202 (1 × 1 mm square,
100). * 3: The sample base material was alternately placed in a constant temperature bath at −65 ° C. and a constant temperature bath at 125 ° C. for 30 minutes to perform a cooling / heating cycle test. It was evaluated as good when no appearance abnormality occurred in 100 cycles. * 4: The undeveloped portion of the undeveloped portion was observed.

[0055]

According to the photosensitive resin composition of the present invention, when applied to a non-halogen, non-antimony-based flame-retardant substrate, it can satisfy the flame retardancy (retain UL94-V0),
And it can be developed with dilute alkaline aqueous solution,
It has excellent TCT properties, flexibility and mechanical properties, and can form a solder resist with high reliability. When the photosensitive element according to the fourth aspect is applied to a non-halogen, non-antimony based flame-retardant substrate, it can satisfy flame retardancy (retain UL94-V0), can be developed with a dilute alkaline aqueous solution, and has high resolution and heat resistance. It has excellent properties, TCT properties, flexibility and mechanical properties, and enables formation of a highly reliable solder resist.

In the method for producing a resist pattern according to the fifth aspect, when applied to a non-halogen, non-antimony-based flame-retardant substrate, the flame retardancy (retaining UL94-V0) can be satisfied, and the resist pattern can be developed with a dilute alkaline aqueous solution. Yes, resolution, heat resistance, T
It has excellent CT properties, flexibility, and mechanical properties, and can form a highly reliable solder resist. The resist pattern according to claim 6, when applied to a non-halogen, non-antimony-based flame-retardant substrate, can satisfy flame retardancy (retain UL94-V0), can be developed with a dilute alkaline aqueous solution, and has high resolution and heat resistance. It has excellent TCT properties, flexibility, and mechanical properties, and can form a solder resist with high reliability.

When the resist pattern laminated substrate according to the present invention is applied to a non-halogen, non-antimony based flame-retardant substrate, it can satisfy flame retardancy (retain UL94-V0) and can be developed with a dilute alkaline aqueous solution. , Resolution, heat resistance, T
It has excellent CT properties, flexibility, and mechanical properties, and can form a highly reliable solder resist.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05K 3/28 H05K 3/28 D (72) Inventor Kuniaki Sato Gobanichi, Hasaki-cho, Kashima-gun, Kashima-gun, Ibaraki Pref. Hitachi Chemical Co., Ltd.Kashima Plant (72) Inventor Takao Hirayama, Ozaki, Hajima-cho, Kashima-gun, Ibaraki Pref. Banichi Hitachi Chemical Co., Ltd. Kashima Plant F-term (reference) 2H025 AA02 AA04 AA10 AB15 AC01 AD01 BC14 BC74 BC83 BC85 FA17 4J011 QB19 SA02 SA14 SA15 SA16 SA18 SA20 SA22 SA23 SA24 SA28 SA29 SA32 SA34 SA54 SA61 SA63 SA01 SA82 SA84 WA01 WA02 4J027 AE02 AE03 AE04 AE05 AE07 BA01 CB10 CC05 CD08 CD10 4J036 AA01 AB19 CA19 CA21 CA22 CC02 EA03 HA02 JA01 JA10 5E31 4 AA27 AA32 CC02 CC03 CC07 DD07 FF05 GG08 GG26

Claims (7)

[Claims] 1. A photosensitive resin composition comprising (A) a phosphorus-containing photosensitive resin and (B) a photopolymerization initiator. 2. A method according to claim 1, wherein (A) the phosphorus-containing photosensitive resin is obtained by reacting (a) a phosphorus-containing compound having at least one epoxy group in a molecule with (b) an unsaturated monocarboxylic acid;
2. The photosensitive resin composition according to claim 1, which is obtained by an addition reaction of a saturated or unsaturated polybasic acid anhydride. 3. The photosensitive resin composition according to claim 1, further comprising (C) a compound having at least one epoxy group. 4. A photosensitive element obtained by coating and drying the photosensitive resin composition according to claim 1, 2 or 3 on a support. 5. A layer of the photosensitive resin composition according to claim 1, 2, 3 or 4, which is laminated on a substrate, irradiated with actinic rays in an image-like manner, photo-cured on exposed portions, and exposed on unexposed portions. A method for producing a resist pattern, wherein the resist pattern is removed by development. 6. A resist pattern produced by the method for producing a resist pattern according to claim 5. 7. A resist pattern laminated substrate having the resist pattern according to claim 6 on a substrate.