Photosensitive composition for sandblasting and...

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

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C430S284100, C430S905000, C430S911000, C430S913000

Reexamination Certificate

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06322947

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to a novel photosensitive composition for sandblasting. More particularly it relates to a photosensitive composition for sandblasting which exhibits excellent alkali developability, sufficient adhesion to a substrate, and photosensitivity and, after patterning, has high elasticity and softness and excellent resistance to sandblasting and therefore enables fine and precise patterning and to a photosensitive film laminate comprising the same.
BACKGROUND OF THE INVENTION
Sandblasting is known as one of the techniques for patterning the surface of a substrate such as glass, stone, plastics, ceramics, leather, and wood. Sandblasting is carried out by a process using a stencil in which a rubber sheet, paper, etc. is stuck to the substrate and cut with a cutter, etc. to form a stencil pattern, and an abrasive is made to strike against the substrate to selectively abrade the substrate or a process using a photomask in which a photosensitive layer of a photosensitive composition is provided on the substrate, a mask pattern is formed by photolithography, and an abrasive is made to strike against the substrate to selectively abrade the substrate. The former process involves troublesome operations with low working efficiency. On the other hand, the latter photolithographic process achieves high working efficiency, enables fine processing, and is effective for producing circuit boards composed of a metallic pattern and an insulating pattern, particularly for the formation of a metallic wiring pattern and an insulating pattern made of ceramics, fluorescence substances, etc. of a plasma display panel.
Photosensitive compositions which have been proposed to date for use in the lithographic sandblasting include a composition comprising a urethane prepolymer having an ethylenically unsaturated group at the terminal, a monofunctional ethylenically unsaturated compound, and a polymerization initiator (see JP-A-60-10242), a composition comprising an unsaturated polyester, an unsaturated monomer, and a photopolymerization initiator (see JP-A-55-103554), and a composition comprising polyvinyl alcohol and a diazo resin (see JP-A-2-69754). The term “JP-A” as used herein means an unexamined published Japanese patent application. However, these photosensitive resin compositions are disadvantageous in that film thickness control is difficult, sensitivity, adhesion to a substrate and resistance to sandblasting are insufficient, and fine processing is difficult. In order to overcome these disadvantages, JP-A-6-161098 proposed a photosensitive composition for sandblasting which comprises a urethane prepolymer terminated with an ethylenically unsaturated group as a main component, a cellulose derivative, and a polymerization initiator. Although this composition is excellent in not only alkali developability but sensitivity, adhesion to a substrate, and elasticity and softness after patterning and is superior in sandblasting resistance to conventional photosensitive compositions, it is still unsatisfactory in performance in fine pattern formation for practical use. It has therefore been keenly demanded to develop a photosensitive composition having improved properties.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a photosensitive composition for sandblasting which is excellent in alkali developability, sensitivity, adhesion to a substrate, and elasticity, softness and resistance to sandblasting after patterning and is suited to formation of fine metallic or insulating patterns.
Another object of the invention is to provide a photosensitive film laminate having a photosensitive layer comprising the above-described photosensitive composition.
The inventors have continued their study and reached the finding that a photosensitive composition for sandblasting which is freed of the above-mentioned disadvantages of conventional photosensitive compositions and is capable of forming a fine pattern can be obtained by using a photopolymerizable urethane (meth) acrylate oligomer containing, as an essential structural unit, a reaction product between a diisocyanate compound and 1,4-butanediol. The present invention has been completed based on this finding.
The present invention relates to a photosensitive composition for sandblasting comprising (A) a photopolymerizable urethane (meth)acrylate oligomer having at least two acryloyl groups and/or methacryloyl groups and a structural unit represented by formula:
(B) an alkali-soluble compound, and (C) a photopolymerization initiator.
The present invention also relates to a photosensitive film laminate having a photosensitive layer comprising the photosensitive composition.
The photosensitive composition for sandblasting according to the present invention has excellent alkali developability, sensitivity, and adhesion and, after pattern formation, exhibits elasticity and softness and resistance to sandblasting and is suited to formation of fine patterns such as metallic patterns and insulating patterns. The photosensitive film laminate according to the present invention is easy to position and is preferred for fine patterning on electronic components.
DETAILED DESCRIPTION OF THE INVENTION
The photopolymerizable urethane (meth)acrylate oligomer, which can be used as a component characteristic of the photosensitive composition of the invention, contains a reaction product between a diisocyanate compound and 1,4-butanediol as an essential structural unit. The photopolymerizable urethane (meth)acrylate is a product obtained by the reaction of the structural unit with a (meth) acrylate compound having a hydroxyl group or a carboxyl group. Containing the diisocyanate compound/1,4-butanediol reaction product as an essential structural unit, the photosensitive composition of the invention exhibits improved adhesion to a substrate and improved sandblasting resistance and therefore realizes precise formation of fine patterns such as a metallic wiring pattern and an insulating pattern, particularly a metallic wiring pattern and a ceramic or fluorescent insulating pattern for a plasma display panel. In particular, a urethane (meth)acrylate oligomer having four or more urethane bonds in the molecule thereof is preferred. If the number of urethane bonds in the urethane (meth)acrylate oligomer is less than 4, the resistance to sandblasting is reduced considerably.
The diisocyanate compound which can be used for the preparation of the urethane (meth)acrylate oligomer includes aliphatic or alicyclic diisocyanate compounds, such as dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, octamethylene diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate, 2,2,4-trimethylpentane-1,5-diisocyanate, nonamethylene diisocyanate, 2,2,4-trimethylhexane diicoayanate, decamethylene diisocyanate, and isophorone diisocyanate. They can be used either individually or as a combination of two or more thereof.
If desired, 1,4-butanediol, which reacts with the diisocyanate compound to form the essential structural unit, can be used in combination with one or more of other diol compounds. Useful other diol compounds include alkylene glycols (e.g., ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, and neopentyl glycol) and compounds having a hydroxyl group at both terminals thereof that are obtained by allowing such an alkylene glycol to react with maleic acid, fumaric acid, glutaric acid, adipic acid, &dgr;-valerolactone, &egr;-caprolactone, &bgr;-propiolactone, &agr;-methyl-&bgr;-propiolactone, &bgr;-methyl-&bgr;-propiolactone, &agr;-methyl-&bgr;-propiolactone, &bgr;-methyl-&bgr;-propiolactone, &agr;,&agr;-dimethyl-&bgr;-propiolactone, &bgr;,&bgr;-dimethyl-&bgr;-propiolactone, bisphenol A, hydroquinone, dihydroxycyclohexane, diphenyl carbonate, phosgene, succinic anhydride, etc.
The (meth)acrylate compound having a hydroxyl group or a carboxyl group wh

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