Radiation imagery chemistry: process – composition – or product th – Imaging affecting physical property of radiation sensitive... – Radiation sensitive composition or product or process of making
Reexamination Certificate
2001-08-14
2002-11-05
Baxter, Janet (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Imaging affecting physical property of radiation sensitive...
Radiation sensitive composition or product or process of making
C430S283100, C430S285100, C522S084000, C522S085000, C522S100000, C522S121000
Reexamination Certificate
active
06475702
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a photosensitive resin composition developable with water or a diluted alkali aqueous solution, and a photoresist ink for manufacturing printed wiring boards.
2. Disclosure of the Prior Art
In the past, photoresist inks developable with a diluted alkali aqueous solution have been used as inks for manufacturing printed wiring boards, screen printing stencils, color-filter pixels and color-filter protective films, or a photogravure ink. For example, such photoresist inks are disclosed in Japanese Patent Early Publications No. 5-224413 and No. 5-241340.
However, these photoresist inks contain various organic solvents such that they can be uniformly applied on substrates. The organic solvents are usually evaporated from the photoresist inks during a predrying step prior to a subsequent exposing step. Therefore, there are problems inherent in the use of the organic solvents such as a poor working condition, environmental pollution and the occurrence of a fire.
SUMMARY OF THE INVENTION
The present invention concerns a photosensitive resin composition developable with water or a diluted alkali aqueous solution, which is capable of improving the above problems. The photosensitive resin composition contains the following components (A) to (D). That is, the component (A) is a water-soluble photosensitive resin selected from the group consisting of a first resin obtained by introducing a styryl pyridinium group into a polyvinyl alcohol polymer, a second resin obtained by introducing a styryl quinolinium group into the polyvinyl alcohol polymer, and a third resin adding N-alkylol(meth)acrylamide to the polyvinyl alcohol polymer. The component (B) is a photosensitive prepolymer having a carboxyl group and at least two ethylenically unsaturated groups in molecule. The component (C) is a photopolymerization initiator. The component (D) is water.
It is preferred that the photosensitive resin composition further contains a photopolymerizable ethylenically-unsaturated monomer as the component (E).
It is particularly preferred to use the photosensitive resin composition of the present invention as a photoresist ink for manufacturing printed wiring boards.
These and still other objects and advantages will become apparent from the following detail descriptions of the preferred embodiments and examples of the invention.
DETAIL DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the present specification, “(meth)acrylic-” means “acrylic-” and “methacrylic-”. For example, (meth)acrylic acid means acrylic acid and methacrylic acid. In addition, (meth)acrylamide means acrylamide and methacrylamide.
A photosensitive resin composition of the present invention comprises a water-soluble photosensitive resin (A), photosensitive prepolymer (B), photopolymerization initiator (C) and water (D).
The water-soluble photosensitive resin (A) is selected from the group consisting of a water-soluble photosensitive resin (A1) obtained by introducing a styryl pyridinium group or a styryl quinolinium group into a polyvinyl alcohol polymer, and a water-soluble photosensitive resin (A2) obtained by adding N-alkylol(meth)acrylamide to the polyvinyl alcohol polymer.
As the polyvinyl alcohol polymer used to prepare the photosensitive resin (A), for example, it is possible to use a polyvinyl alcohol obtained by complete saponification or a partial saponification of polyvinyl acetate, or a water-soluble polyvinyl alcohol derivative obtained by a reaction of —OH group or —OCOCH
3
group of a completely-saponified or partially-saponified polyvinyl alcohol with an acid-anhydride containing compound, carboxy-group containing compound, epoxy-group containing compound, or an aldehyde-group containing compound. In addition, it is possible to use a vinyl alcohol copolymer having vinyl alcohol units, which is obtained by the complete saponification or the partial saponification of polyvinyl acetate. As the copolymer component of vinyl acetate, for example, it is possible to use (meth)acrylic acid, (meth)acrylamide, N-methylol(meth)acrylamide, styrene, ethylene, propylene, maleic anhydride, (meth)acrylonitrile, (meth)acrylic ester.
It is preferred that the polyvinyl alcohol polymer contains 60 mol % or more of the vinyl alcohol units within its polymerization unit. In particular, when using the polyvinyl alcohol polymer containing 80 mol % or more of the vinyl alcohol units, or the polyvinyl alcohol obtained by the complete saponification of polyvinyl acetate, there is an advantage that the photosensitive resin composition of the present invention is excellent in the water-solubility.
The photosensitive resin (A1) can be prepared by a conventional method disclosed in, for example, Japanese Patent Early Publication [KOKAI] No. 55-23163, No. 55-62905, or No. 56-11906.
Concretely, for example, the photosensitive resin (A1) can be obtained by adding a formyl styryl pyridinium salt or a formyl styryl quinolinium salt to the polyvinyl alcohol polymer according to an acetal reaction applying an alcoholic —OH group of the polyvinyl alcohol polymer.
The general formula (1) shows a typical structure of an introduced portion of the styryl pyridinium group in the photosensitive resin (A1). The general formula (2) shows a typical structure of an introduced portion of the styryl quinolinium group in the photosensitive resin (A 1).
In these formulas (1) and (2), each of R1 and R2 is hydrogen atom, alkyl group, or aralkyl group, “X
−
” is a conjugate base of an acid, “m” is an integer of 1~6, and “n” is 0 or 1.
It is preferred that an introduction rate of the styryl pyridinium group or the styryl quinolinium group in the photosensitive resin (A1) is within a range of 0.3 to 20 mol %, and more preferably 0.5 to 10 mol %, per vinyl alcohol polymerization unit constructing the photosensitive resin (A1). In the range of 0.3 to 20 mol % of the introduction rate, the photosensitive resin (A1) is good in the water-solubility, and has a suitable photo-bridging capability.
The water-soluble photosensitive resin (A2) can be prepared by a conventional method disclosed in, for example, Japanese Patent Publication [KOKOKU] No. 49-5923, or Japanese Patent Early Publication [KOKAI] No. 62-267302.
Concretely, for example, the photosensitive resin (A2) can be obtained by an etherification reaction between a polyvinyl alcohol polymer and N-alkylol(meth)acrylamide in the presence of an acid catalyst such as inorganic acid or sulfonic acid derivative in a good solvent of the polyvinyl alcohol polymer such as water or a N-methyl pyrrolidone solution, or a suspension of a bad solvent of the polyvinyl alcohol polymer.
As the N-alkylol(meth)acrylamide, for example, it is possible to use N-methylol(meth)acrylamide, N-ethylol(meth)acrylamide, N-propylol(meth)acrylamide, or N-butylol(meth)acrylamide. The N-alkylol(meth)acrylamide can be one of these materials or can be a combination of two or more of these materials, if necessary.
It is preferred that an addition ratio of the N-alkylol(meth)acrylamide is within a range of 0.05 to 25 mol %, and more preferably 0.05 to 15 mol %, per vinyl alcohol polymerization unit constructing the photosensitive resin (A2). In the above range of the addition ratio, better water-solubility and photo-curability of the photosensitive resin (A2) can be obtained.
The photosensitive prepolymer (B) is a photosensitive prepolymer having a carboxyl group and at least two ethylenically unsaturated groups in molecule. The photosensitive prepolymer is characterized in that a plurality of groups having photopolymerizable ethylenically-unsaturated groups branch from a main chain of the prepolymer. Since the photosensitive prepolymer contains the carboxyl group, it can be swelled, dispersed or dissolved in a diluted alkali aqueous solution. However, when the photosensitive prepolymer is exposed in the presence of the photopolymerization initiator, the ethylenically unsaturated groups of the prepolymer molecules react each other to increase the m
Baxter Janet
Goo Chemical Co., Ltd.
Lee Sin J.
Rader & Fishman & Grauer, PLLC
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