JP2003050463A - Pattern formation method - Google Patents

Abstract

The present invention relates to a method for forming a partition of a plasma display panel (PDP), an electrode, and a pattern forming method for manufacturing a printed wiring board and the like. Provided is a novel pattern forming method which is excellent in pattern forming ability. SOLUTION: An alkali-resistant photosensitive resin composition layer (1) and an alkali-developable photosensitive resin composition layer (2) are sequentially provided on a substrate surface, and the photosensitive resin composition layer is interposed through a pattern mask. After exposure, the photosensitive resin composition layer (2)
Is subjected to alkali development, and then the unexposed portion of the photosensitive resin composition layer (1) and the substrate surface under the unexposed portion are sandblasted to form an uneven pattern. Pattern formation method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for stably forming a pattern for forming barrier ribs and electrodes of a plasma display panel (PDP), and further for manufacturing a printed wiring board and the like. Provided is a pattern forming method including a novel sandblasting process which is excellent in the ability to form an uneven pattern.

[0002]

2. Description of the Related Art Pattern formation by a sandblasting method can meet the demands for finer unevenness and larger panel size. Therefore, pattern formation for manufacturing barrier ribs, electrodes, etc. of a plasma display panel (PDP). Has been put to practical use. After such a processing method, the photosensitive resin composition layer provided on the substrate surface is exposed through a pattern mask to form an image composed of a cured part (exposed part) and an uncured part (unexposed part), The unexposed portion is developed and removed with an alkaline solution, and the exposed surface of the base material is ground by sandblasting to form an uneven pattern.

However, in the conventional sandblasting method, even if it is advantageous for forming a fine line pattern, the line width of about 70 μm is limited, and a clearer panel screen is required. The current market demand cannot always be satisfied, and countermeasures against it are desired. Particularly, in the prior art, in the space portion between the fine line patterns, that is, the space portion ground by sandblasting, the grinding distance is 100 μm or more, and further 20
The deeper the depth is from 0 μm to 300 μm, the more the target line width and its shape are likely to be misaligned, and the effect is more serious as the pitch width is made smaller. Therefore, it is extremely useful to form a fine line pattern having a line width of 70 μm or less, preferably about 10 μm to 50 μm, without adversely affecting the shape of the convex portion formed even if the sandblasting of the base material is deepened.

Therefore, the present inventor has conducted diligent research in view of such circumstances, and after exposing the photosensitive resin composition layer provided on the substrate surface through a pattern mask, an unexposed portion or an unexposed portion is formed. It was found that the object can be achieved when the surface of the base material under the unexposed portion is sandblasted to form an uneven pattern, and a patent application was filed previously. The method peels off the film on the resist after exposure,
The feature is that the unexposed part is directly sandblasted, and this method does not adversely affect the shape of the convex portion even if the sandblasting of the substrate is deepened, and it is possible to form a thin line pattern with a small line width or space width. It is possible to form. Further, in such a method, a part of the unexposed portion is soda carbonate from the viewpoint of usefulness such as shortening of development time and recovery of powder used for sandblasting.
We also proposed a method in which alkaline development is performed using an alkaline aqueous solution such as potassium carbonate, and then sandblasting is performed.

[0005]

However, in the industrial implementation of alkali development in the combination of alkali development and sandblasting, a large number of printed wiring boards are continuously treated while circulating the developing solution.
With the lapse of development time, the activity of the developer decreases, so-called loose developer fatigue occurs, and it becomes difficult to adjust the degree of development in the partial development of the above-mentioned unexposed portion to a certain range, and as a result, it is not developed. It was found that the height of the remaining unexposed portion was not uniform, and the blast grinding distance during the final blasting process fluctuated, which could cause variations in the product.

[0006]

However, as a result of further studies to solve the above-mentioned problems, the present inventor has found that the alkali-resistant photosensitive resin composition layer (1) and the alkali-developable photosensitive material are formed on the surface of the base material. Of the photosensitive resin composition layer (2) are sequentially provided, the photosensitive resin composition layer is exposed through a pattern mask, and then the unexposed portion of the photosensitive resin composition layer (2) is alkali-developed, preferably 80 ˜100% by weight alkali development, and then sandblasting the unexposed portion of the photosensitive resin composition layer (1) and the substrate surface below the unexposed portion,
The present invention has been completed by finding that a pattern forming method for generating an uneven pattern can achieve such an object.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
First, the base material used in the present invention is not particularly limited, and any material such as glass, low melting point glass paste laminated glass, copper clad printed wiring board, and various other ceramics can be used.

The photosensitive resin composition layers (1) and (2) provided on such a substrate are compositions containing a base polymer, an ethylenically unsaturated compound and a photopolymerization initiator, and other additives as main components. is there. In the above, as the base polymer, urethane acrylic resin, acrylic resin, polyester resin, cellulose derivative and the like can be used alone or in combination of two or more.

Since the photosensitive resin composition layer (1) of the present invention is directly provided on the substrate side, it must be alkali resistant so that it cannot be dissolved by an alkali developing solution. In particular, urethane acrylic resin (A) containing no carboxyl group
A composition containing as a base polymer, a photopolymerization initiator and, if necessary, an ethylenically unsaturated compound is preferably used. The urethane acrylic resin (A) containing no carboxyl group is not particularly limited, but a compound (I) obtained by reacting a polyol compound and a diisocyanate compound at a molar ratio of n: n + 1 is added to an acryloyl group-containing hydroxy compound (II). The thing obtained by adding) is preferable.

As the polyol-based compound, any of polyether-based polyol, polyester-based polyol, polycarbonate-based polyol, acrylic-based polyol, polybutadiene-based polyol, polyolefin-based polyol and the like can be used. Specifically, ethylene glycol,
Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1,4-butanediol, polybutylene glycol, 1,6-hexanediol, neopentyl glycol, cyclohexanedi Methanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, arabitol, xylitol, galactitol, glycerin, polyglycerin, polytetramethylene glycol Such as polyhydric alcohols, polyethylene oxide, polypropy Polyether, polyol having at least one structure of block copolymer or random copolymer of ethylene oxide / propylene oxide, maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, and itacone Examples thereof include polyester polyols that are condensates with polybasic acids such as acids, adipic acid, and isophthalic acid, caprolactone-modified polyols such as caprolactone-modified polytetramethylene polyol, and polyolefin-based polyols. Among these, those having a molecular weight of 500 or more, particularly those having a molecular weight of 500 to 4000 are used, and if the molecular weight is less than 500, the sandblast resistance is deteriorated, which is not preferable.

Specific examples of the diisocyanate compound include hexamethylene diisocyanate, heptamethylene diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, octamethylene diisocyanate and 2,5-dimethylhexane-1,6-. Diisocyanate, 2,2,4-trimethylpentane-1,5
-Diisocyanate, nonamethylene diisocyanate,
2,2,4-Trimethylhexane diisocyanate, decamethylene diisocyanate, undecamethylene diisocyanate, dodecamethylene diisocyanate, tridecamethylene diisocyanate, pentadecamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2-butyl Nylene diisocyanate, 2,4-tolylene diisocyanate,
Examples thereof include isophorone diisocyanate, 1,3-xylylene diisocyanate and 1,4-xylylene diisocyanate, and hexamethylene diisocyanate, 2,4-tolylene diisocyanate and isophorone diisocyanate are preferably used. The molecular weight of the diisocyanate compound is advantageously 300 or less, and the molecular weight is 3 or less.
If it exceeds 00, the reactivity with the polyol-based compound decreases, which is not preferable.

In reacting such a polyol compound with a diisocyanate compound, a known reaction means can be used. For example, the diisocyanate compound is reacted in a stable solvent (ethyl acetate or the like) at a temperature of 60 to 90 ° C. You can do it. However, in the present invention, it is preferable to set the reaction molar ratio of the polyol compound and the diisocyanate compound to 1: 2 as a theoretical value (in the actual charging, an error of about several percent is allowed), and such a condition is preferable. If it deviates, an isocyanate group cannot be added to both terminals, and the introduction of an ethylenically unsaturated group described later becomes difficult, which is not preferable.

Then, the compound (I) obtained by reacting the polyol compound and the diisocyanate compound as described above is added to the acryloyl group-containing hydroxy compound (II).
Although a known method can be adopted, for example, the acryloyl group-containing hydroxy compound (II) may be added to the solution of the compound (I), and the reaction may be performed at a temperature of 50 to 80 ° C. Also, a known catalyst such as dibutyltin tin laurate can be added to accelerate the reaction.

Examples of the acryloyl group-containing hydroxy compound (II) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate.
(Meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate,
2-hydroxy-3-acryloyloxypropyl (meth) acrylate, a compound obtained by ring-opening addition of ε-captolactone to the above acryloyl group-containing hydroxy compound, and the like, and preferably 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate is used.

In the photosensitive resin composition layer (1) of the present invention, as a base polymer, not only a urethane acrylic resin (A) not containing a carboxyl group alone but also other than such a resin as long as alkali resistance is not impaired. Polymer compounds having a softening temperature of 30 ° C. or higher, particularly carboxyl group-containing acrylic resin, carboxyl group-containing cellulose derivative and the like can be used alone or in combination. When the photosensitive resin composition layer is used in the form of dry film photoresist (DFR) by such combination,
Especially when the film is rolled up and stored,
It can be expected that the edge fusion of the photosensitive resin composition layer from the roll end can be efficiently prevented. When a carboxyl group-containing acrylic resin or a carboxyl group-containing cellulose derivative is used in combination, the mixing amount is 50% by weight or less, preferably 3 to 40% by weight based on the urethane acrylic resin not containing a carboxyl group.

The carboxyl group-containing acrylic resin mentioned above is mainly a copolymer of (meth) acrylic acid alkyl ester and ethylenically unsaturated carboxylic acid. As the (meth) acrylic acid alkyl ester, methyl (meth) acrylate, ethyl (meth) acrylate,
n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-
Butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate and the like can be mentioned, and preferably methyl (meth) acrylate and ethyl ( (Meth) acrylate, n-
Use of butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate is useful.

As the ethylenically unsaturated carboxylic acid, (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, aconitic acid, cinnamic acid, monoalkylmalate, monoalkylfumarate,
Monoalkyl itaconate, citraconic anhydride, citraconic acid and the like can be mentioned, preferably (meth) acrylic acid,
Maleic acid and maleic anhydride.

When the acrylic resin is produced by copolymerization, other copolymerizable monomers can be used in combination,
Examples of the monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and 2-hydroxy-3-. Phenoxypropyl (meth) acrylate, N-methylol (meth) acrylamide and other hydroxyl group-containing unsaturated monomers, glycidyl (meth) acrylate, allylglycidyl (meth) acrylate and other glycidyl group-containing unsaturated monomers, (meth) acrylamide, N- (Meth) acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, N
-Vinylpyrrolidone, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, vinyl acetate,
Styrene etc. are mentioned, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, vinyl acetate and styrene are useful. The adjustment of the softening temperature is achieved by adjusting the type and degree of polymerization of the copolymerized monomer. The softening temperature was measured by a thermomechanical analyzer (Perkin Elmer Co .: T
MA7) is used, and it is measured in a temperature range of 0 to 200 ° C., a temperature increase of 10 ° C., and a load of 110 mN.

Typical examples of the carboxyl group-containing cellulose derivative include hydroxypurpyrmethylcellulose acetate, hydroxypurpyrumethylcellulose acetate succinate, cellulose acetate hexahydrophthalate, hydroxypurpyrumethylcellulose acetate phthalate, hydroxypurpyrumethylcellulose hexahydrophthalate and the like. It is illustrated.

Since the photosensitive resin composition layer (2) of the present invention must be alkali-developed, a carboxyl group-containing resin is preferably used as the base polymer in the composition, and a carboxyl group-containing urethane acrylic resin, Any one of carboxyl group-containing acrylic resin, carboxyl group-containing polyester resin, carboxyl group-containing cellulose derivative and the like can be used alone or in combination of two or more kinds. Acid value of carboxyl group-containing resin is 10-2
50 mg KOH / g is suitable. In the above, the carboxyl group-containing urethane acrylic resin (B) is particularly useful from the viewpoint of the balance between the sandblast resistance and the alkali developing property, and it is solely or mainly composed of (B) and the carboxyl group-containing acrylic resin or It is advantageous to use a carboxyl group-containing cellulose derivative together. When the carboxyl group-containing acrylic resin or the carboxyl group-containing cellulose derivative is used in combination, the mixing amount thereof is 50% by weight or less, preferably 3 to 40% by weight based on (B).

The carboxyl group-containing urethane acrylic resin (B) used in the photosensitive resin composition layer (2) is not particularly limited, but as described in the carboxyl group-containing diol compound and the photosensitive resin composition layer (1). To the compound (IV) obtained by reacting the same diisocyanate compound in a molar ratio of 1: 2, the same polyol compound (II) as described in the photosensitive resin composition layer (1) is added, and further, Similarly, the same (meth) acryloyl group-containing hydroxy compound (II as described in the above-mentioned photosensitive resin composition layer (1) (II
I) is preferably added, and the carboxyl group-containing diol compound has a molecular weight of 500.
Below, the weight ratio of the compound (IV) in (B) is preferably 15 to 65% by weight. When the molecular weight of such a diol compound exceeds 500, the solubility in the reaction solvent decreases and the reactivity with the diisocyanate compound decreases.
Further, the molecular weight of the diisocyanate compound is 30.
When it exceeds 0, the reactivity with the diol compound is lowered, which is not preferable, as described in the photosensitive resin composition layer (1).

Specific examples of the carboxyl group-containing diol compound having a molecular weight of 500 or less include tartaric acid, 2,
4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) butanoic acid,
2,2-bis (hydroxyethyl) butanoic acid, 2,2-
Bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, dihydroxymethylacetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-
Examples thereof include bis (4-hydroxyphenyl) pentanoic acid and homogentisic acid, and preferably 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2- Bis (hydroxymethyl) butanoic acid is used.

In reacting such a diol compound and a diisocyanate compound, a known reaction means can be used, and for example, the reaction may be carried out at a temperature of 60 to 90 ° C. in a solvent (ethyl acetate or the like) stable to diisocyanate. . However, in the present invention, it is preferable to set the reaction molar ratio of the diol compound and the diisocyanate compound to 1: 2 as a theoretical value (the error of about several percent is allowed in the actual charging) as described above. If it deviates from the above range, isocyanate cannot be added to both ends, and introduction of an ethylenically unsaturated group described later becomes difficult, which is not preferable.

Then, the compound (IV) obtained by reacting the diol compound and the diisocyanate compound as described above
Then, the polyol compound (II) is subjected to an addition reaction. In the addition reaction, a known method can be adopted. For example, the polyol compound (II) is added to the compound (I) solution obtained by reacting the diol compound and the diisocyanate compound as described above, The reaction may be performed at a temperature of 60 to 90 ° C. Also, a known catalyst such as dibutyltin laurate can be added to accelerate the reaction.

Further, a carboxyl group-containing urethane acrylic resin (B) can be obtained by adding a (meth) acryloyl group-containing hydroxy compound (III) to the compound obtained above. As described above, the weight ratio of the compound (IV) in (B) is 15 to
It is preferably 65% by weight, and the content is 15
If it is less than 10% by weight, sufficient strength of the cured resist cannot be obtained,
On the other hand, if it exceeds 65% by weight, the sandblast resistance of the cured resist decreases, which is not preferable. To adjust the weight ratio of the compound (IV), the compound (IV) in the above reaction is used.
The ratio of (II) and (III) may be controlled.
The acid value of (B) is preferably 10 to 90 mgKOH / g, and more preferably 20 to 70 mgKOH / g in terms of the balance between sandblast resistance and alkali developability.
In adjusting the acid value, the number of reaction moles of each of the above-mentioned agents and the molecular weight of the polyol compound may be selected.

Examples of the carboxyl group-containing resin that can be used in the present invention include, in addition to (B), a carboxyl group-containing acrylic resin and a carboxyl group-containing cellulose derivative. The carboxyl group-containing acrylic resin is mainly a copolymer of (meth) acrylic acid alkyl ester and ethylenically unsaturated carboxylic acid. The acid value of acrylic resin is 5
A range of 0 to 250 mg KOH / g is suitable. As the (meth) acrylic acid alkyl ester, methyl (meth) acrylate, ethyl (meth) acrylate,
n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-
Butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate and the like can be mentioned, and preferably methyl (meth) acrylate and ethyl ( (Meth) acrylate, n-
Butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are useful.

As the ethylenically unsaturated carboxylic acid, (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, aconitic acid, cinnamic acid, monoalkylmalate, monoalkylfumarate,
Monoalkyl itaconate, citraconic anhydride, citraconic acid and the like can be mentioned, preferably (meth) acrylic acid,
Maleic acid and maleic anhydride.

When the acrylic resin is produced by copolymerization, other copolymerizable monomers may be used in combination,
Examples of the monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and 2-hydroxy-3-. Phenoxypropyl (meth) acrylate, N-methylol (meth) acrylamide and other hydroxyl group-containing unsaturated monomers, glycidyl (meth) acrylate, allylglycidyl (meth) acrylate and other glycidyl group-containing unsaturated monomers, (meth) acrylamide, N- (Meth) acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, N
-Vinylpyrrolidone, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, vinyl acetate,
Styrene etc. are mentioned, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, vinyl acetate and styrene are useful.

As the carboxyl group-containing cellulose derivative, hydroxypropyl methylcellulose acetate,
Typical examples are hydroxypurpyrumethyl cellulose acetate succinate, cellulose acetate hexahydrophthalate, hydroxypurpyrumethyl cellulose acetate phthalate and hydroxypurpyrumethyl cellulose hexahydrophthalate. The acid value of the derivative is suitably in the range of 50 to 250 mgKOH / g.

Further, in the present invention, the sandblast resistance of the cured part can be improved by using a resin containing no carboxyl group in combination with the resin containing a carboxyl group within the range not impairing the alkali developability. The effect is that the carboxyl group-containing urethane acrylic resin (B)
It is remarkable that the urethane acrylic resin (A) containing no carboxyl group is used together. Practically, a carboxyl group-containing urethane acrylic resin (B) / a carboxyl group-free urethane acrylic resin (A),
Carboxyl group-containing urethane acrylic resin (B) / carboxyl group-containing acrylic resin / carboxyl group-free urethane acrylic resin (A), carboxyl group-containing urethane acrylic resin (B) / carboxyl group-containing cellulose derivative / carboxyl group Consists of a combination of urethane acrylic resin not containing (A), urethane acrylic resin containing carboxyl group (B) / acrylic resin containing carboxyl group / cellulose derivative containing carboxyl group / urethane acrylic resin containing no carboxyl group (A), etc. It is desirable to do.

In the present invention, in both cases of the photosensitive resin composition layer (1) and the photosensitive resin composition layer (2), when the urethane acrylic resin is used as a base polymer, a photopolymerization initiator ( C) is used in combination.
There are no particular restrictions on (C), and known photopolymerization initiators can be used, but benzophenone, P, P′-bis (dimethylamino) benzophenone, P, P′-bis (diethylamino) benzophenone, P, P'-bis (dibutylamino) benzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoylbenzoic acid, methyl benzoylbenzoate, benzyldiphenyl disulfide, Benzyl dimethyl ketal, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-
Methoxybenzophenone, benzophenone, dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone,
2,2-diethoxyacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibezosparone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1 -Propanone, 2-methyl-
[4- (methylthio) phenyl] -2-morpholino-
1-propanone, tribromophenyl sulfone, tribromomethylphenyl sulfone can be mentioned.

2,4,6- [Tris (trichloromethyl)]-1,3,5-triazine, 2,4- [bis (trichloromethyl)]-6- (4'-methoxyphenyl)
-1,3,5-triazine, 2,4- [bis (trichloromethyl)]-6- (4'-methoxynaphthyl) -1,
3,5-triazine, 2,4- [bis (trichloromethyl)]-6- (piperonyl) -1,3,5-triazine, 2,4- [bis (trichloromethyl)]-6-
Triazine derivatives such as (4′-methoxystyryl) -1,3,5-triazine, acridine and acridine derivatives such as 9-phenylacridine, 2,2′-bis (o-
Chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (o-
Chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis (o-
Fluorophenyl) -4,5,4 ', 5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis (o
-Methoxyphenyl) -4,5,4 ', 5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis (p-methoxyphenyl) -4,5,4', 5'-tetra Phenyl-1,1'-biimidazole, 2,4
2 ', 4'-bis [bi (p-methoxyphenyl)]-
5,5'-diphenyl-1,1'-biimidazole,
2,2'-bis (2,4-dimethoxyphenyl) -4,
5,4 ', 5'-diphenyl-1,1'-biimidazole, 2,2'-bis (p-methylthiophenyl) -4,
5,4 ', 5'-diphenyl-1,1'-biimidazole, bis (2,4,5-triphenyl) -1,1'-biimidazole and the like and disclosed in Japanese Kokai No. 45-37377. , 2'-, 1,4'-, 2,4'-covalently bound tautomers, hexaarylbiimidazole derivatives, triphenylphosphine, triphenylphosphine oxide, 2,4,6- Examples thereof include trimethylbenzoyldiphenylphosphine oxide and 2-benzoyl-2-dimethylamino-1- [4-morpholinophenyl] -butane, and it is preferable to use a hexaarylbiimidazole derivative. .

The amount of the photopolymerization initiator (C) blended is 0.1 to 20 relative to 100 parts by weight of the above base polymer.
Parts by weight, more preferably 1 to 7 parts by weight. If the amount is less than 0.1 parts by weight, the sensitivity is remarkably reduced and good workability cannot be obtained. On the contrary, if the amount exceeds 20 parts by weight, the photosensitive resin composition is mixed with dry film photoresist (DF).
It is not preferable because the storage stability is lowered when it is commercialized as R).

Further, in the present invention, a leuco dye (D)
It is also preferable that the leuco dye (D) contains bis (4-N, N-diethylamino-o-tolyl) methylenedylthiophenylmethane and bis (4-N,
N-diethylamino-o-tolyl) benzylthiophenylmethane, leuco crystal violet, leucomalachite green, leuco diamond green and the like can be mentioned. Among them, leuco crystal violet, leucomalachite green, leuco diamond green are preferably used alone or in combination of two or more. Used for. The content of the leuco dye (D) is 0.05 to 3 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the base polymer. If the amount is less than 0.05 parts by weight, the sensitivity is remarkably reduced and good workability cannot be obtained. On the contrary, if the amount is more than 3 parts by weight, the storage stability when converted to DFR is lowered, which is not preferable.

The photosensitive resin composition used in the present invention includes
In addition to the above (A) to (D), an ethylenically unsaturated compound may be used in combination, and specific examples of such a compound include 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl Phthalate,
3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate,
Examples thereof include monofunctional monomers such as phthalic acid derivative half (meth) acrylate and N-methylol (meth) acrylamide.

Further, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate , Ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diphthalic acid Bifunctional monomers such as lysidyl ester di (meth) acrylate and hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) ) Ethylenically unsaturated compounds such as trifunctional or higher functional monomers such as acrylate, tri (meth) acryloyloxyethoxy trimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, etc. may be blended.

The amount of the ethylenically unsaturated compound is preferably 0 to 20 parts by weight, more preferably 0 to 10 parts by weight, based on 100 parts by weight of the base polymer. The cured resist becomes too hard, which leads to deterioration of the sandblast resistance, which is not preferable.

In addition, crystal violet,
Coloring dyes such as malachite green, brilliant green, patent blue, methyl violet, Victoria blue, rose aniline, parafuchsin, ethylene violet, adhesion promoters, plasticizers, antioxidants, thermal polymerization inhibitors, solvents, surface tension modification Materials, stabilizers, chain transfer agents,
Additives such as defoaming agents and flame retardants can be added as appropriate. In particular, when light is exposed from both upper and lower surfaces of a transparent substrate such as glass in order to form irregular concave and convex patterns on both upper and lower surfaces, light on one surface is prevented from passing through the photosensitive resin composition layer on the other surface. , P'-bis (diethylamino) benzophenone, butylmethoxydibenzoylmethane and the like, and it is desirable to add an ultraviolet absorber in particular, and the amount of the optical absorber to be added is 365 nm at a film thickness of 40 μm.
It may be adjusted so that the transmittance of the photosensitive resin composition phase at m is 65% or less. Some of the UV absorbers overlap the photopolymerization initiator (C) described above, but those having both the functions of the initiator and the absorber may be appropriately used.

The method for providing the above-mentioned photosensitive resin composition layers (1) and (2) on the surface of the substrate is not particularly limited, but the photosensitive resin composition may be provided with a polyester film, polypropylene film, polystyrene film or the like. It is advantageous to use it in the shape of DFR after coating on the surface of the base film, and then covering the coated surface with a protective film such as a polyethylene film and a polyvinyl alcohol film. Specific embodiments thereof include a DFR obtained by coating the base film surface with the photosensitive resin composition layer (1) and then laminating a protective film on the coated surface, and a photosensitive resin composition on the base film surface. After applying layer (2),
Each DFR having a protective film laminated on the coated surface is manufactured, and (1) and (2) are sequentially provided on the base material surface,
Photosensitive resin composition layers (1) and (2) on the base film surface
It is possible to apply DFR in which a protective film is laminated on the base material surface after the coating is performed by directly laminating. Of course, dip coating method, flow coating method,
It is also possible to directly coat the base material by a conventional method such as a screen printing method. Methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate,
Cyclohexane, methyl cellosolve, methylene chloride,
A solvent such as 1,1,1-trichloroethane can also be used in combination. The thickness of the photosensitive resin composition layer (1) is 2 to 50.
μm, preferably 5 to 25 μm, and the thickness of the photosensitive resin composition layer (2) is 10 to 100 μm, preferably 30 to 1
00 μm is suitable for each.

To provide a photosensitive resin composition layer on the surface of a substrate for forming an image using DFR, the adhesive force between the base film and the photosensitive resin composition layer and the protective film and the photosensitive resin composition are used. The adhesive strength with the layer is compared, the film having the lower adhesive strength is peeled off, and then the side of the photosensitive resin composition layer is attached to the substrate side in one or two steps.

Then, a pattern mask is brought into close contact with the other film for exposure. When the photosensitive resin composition does not have tackiness, the other film may be peeled off and then the pattern mask may be brought into direct contact with the photosensitive resin composition layer for exposure. The exposure is usually carried out by ultraviolet irradiation, and as the light source at that time, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp and the like are used. 50 exposure
A practical value is about 0 to 30,000 J / m ² . After irradiation with ultraviolet rays, heating can be performed as necessary to achieve complete curing.

Next, after removing the film on the resist after exposure, the unexposed portion of the photosensitive resin composition layer (2) is treated with an alkali concentration of sodium carbonate, potassium carbonate or the like of 0.1 to 0.1.
Alkali development is performed using a dilute aqueous solution of about 2% by weight.
If the unexposed part is completely developed and removed, there is no variation in the quality of the product after sandblasting, but if 80% by weight or more, preferably 90% by weight or more of the unexposed part is developed, it is practical. Is no problem. Through this process, even if a large number of substrates are continuously developed while the alkaline developer is recycled and reused, there is no change in the degree of development over time, and the operating conditions for sandblasting in the next step are special. Stable processing can be performed without strict adjustment. Therefore, by sandblasting the photosensitive resin composition layer (1) and the base material, even if the sandblasting of the base material is deepened, the shape of the convex portion is not adversely affected, and the pitch width and space width are not adversely affected. It is possible to continuously form a product of uniform quality having a fine line pattern with a small size.

In the sandblasting, the particle size is 0.1 to 1
It is carried out by using SiC, SiO ₂ , Al ₂ O ₃ or the like having a diameter of about 00 μm and spraying at a blast pressure of 0.05 to 10 MPa. Depending on the final application, only the unexposed portion of the photosensitive resin composition layer (1) is sandblasted, or not only the unexposed portion but also the substrate therebelow is ground. The former is for manufacturing printed wiring boards, the latter is for P
It is used in the formation of DP partition walls and electrodes, ceramic processing, SiC substrate processing, silicon wafer dicing and PZT (piezoelectric element) processing, glass etching, and the like.

By such processing, an uneven pattern is formed on the surface of the base material, and then the cured resist (exposed portion) remaining on the surface of the convex portion is peeled off. Stripping and removing the pattern of the cured resist is performed with 0.1% sodium hydroxide, potassium hydroxide, etc.
It is carried out using an alkaline stripping solution consisting of an alkaline aqueous solution having a concentration of about 5% by weight. Further, instead of peeling with an alkaline aqueous solution, the pattern of the cured resist can be burned off.

[0045]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, "%" and "parts" mean weight basis unless otherwise specified. First, a DFR having a photosensitive resin composition layer was prepared by the following procedure. (I) DFR having an alkali-resistant photosensitive resin composition layer
(A-1) (Preparation of Urethane Acrylic Resin Not Containing Carboxyl Group) In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas blowing port, 200 g (0.9 mol) of isophorone diisocyanate and an average molecular weight of 10 were added.
Ethylene glycol / adipic acid of 00 (reaction molar ratio 1.02 / 0.5), 600 g (0.6 mol) of reaction product,
After charging 373 g of ethyl acetate and reacting at 80 ° C. under a nitrogen atmosphere, the temperature starts to be lowered when the residual isocyanate group becomes 2.3%, and after reaching 60 ° C., 71 g of 2-hydroxyethyl acrylate (0.6 mol ),
When the residual isocyanate group reached 0.3%, the reaction was terminated to obtain a urethane acrylic resin containing no carboxyl group. The urethane acrylic resin thus obtained had an isocyanate content of 0.3%, an acid value of 0 mgKOH / g and a resin content of 72%.

(Preparation of Dope) 139 parts of the above urethane acrylic resin solution containing no carboxyl group [100 parts of urethane acrylic resin in terms of solid content], 1.0 part of p, p'-bis (diethylamino) benzophenone, hexaary 3 parts of rubiimidazole and 45 parts of methyl ethyl ketone were mixed and mixed well to prepare a dope. The transmittance of this composition at a film thickness of 40 μm at 365 nm was 4.8%.

(Preparation of DFR) Next, the dope was coated on a polyester film having a thickness of 20 μm using an applicator having a gap of 1.5 mil, and allowed to stand at room temperature for 1 minute and 30 seconds, then at 60 ° C. and 90 ° C. And dried in an oven at 110 ° C. for 2 minutes each to form a photosensitive resin composition layer having a film thickness of 10 μm.
DFR (However, no protective film is provided).

(Ii) DFR (A-2) having an alkali-resistant photosensitive resin composition layer (preparation of urethane acrylic resin containing no carboxyl group) 4 equipped with thermometer, stirrer, water-cooled condenser, nitrogen gas blowing port Hexamethylene diisocyanate 168 g (1.0 mol) and ethyl acetate 3
30 g and a molecular weight of 650 polytetramethylene glycol 487.5 g (0.75 mol) were charged and reacted at 80 ° C. under a nitrogen atmosphere, and the residual isocyanate group was 2.5.
%, The temperature starts to decrease, and when the temperature decreases to 60 ° C., ε-captolactone-modified 2-hydroxyacrylate (“Placcel FA-” manufactured by Daicel Chemical Industries, Ltd.
1 ") 115 g (0.5 mol) was added and the reaction was continued at 60 ° C. When the residual isocyanate group reached 0.3%, the reaction was terminated to obtain a urethane acrylic resin containing no carboxyl group. The carboxyl group-free urethane acrylic resin solution obtained above had an isocyanate content of 0.3% and an acid value of 0 mgKOH / g%. DFR was obtained by the same operation as (A-1) using the above resin solution. The transmittance of the above composition at 365 nm at a film thickness of 40 μm was 4.6%.

(Iii) DFR (A-3) having an alkali-resistant photosensitive resin composition layer (preparation of urethane acrylic resin containing no carboxyl group) 4 equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port Isophorone diisocyanate 200 g (0.9 mol), ethyl acetate 51
6.2 g and a molecular weight of 2000 polycaprolactone diol (“Placcel 220 manufactured by Daicel Chemical Industries, Ltd.
N ") 900 g (0.45 mol) was charged and reacted at 80 ° C under a nitrogen atmosphere, and the residual isocyanate group was 2.
When the temperature reached 7%, the temperature started to decrease, and when the temperature fell to 60 ° C, 2-hydroxyethyl acrylate 104.4.
g (0.9 mol) was added and the reaction was continued at 60 ° C.
When the residual isocyanate group reached 0.3%, the reaction was terminated to obtain a urethane acrylic resin solution containing no carboxyl group. The obtained resin had an isocyanate content of 0.3% and an acid value of 0 mgKOH / g. DFR was obtained by the same operation as (A-1) using the above resin solution. In addition, 365 nm when the film thickness of the above composition is 40 μm
The transmittance was 4.9%.

(A) DFR having a photosensitive resin composition layer capable of alkali development (B-1) (Preparation of carboxyl group-containing urethane acrylic resin) 4 equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port In a two-necked flask, 119.5 g (0.89 mol) of 2,2-bis (hydroxymethyl) propionic acid
And isophorone diisocyanate 396.2 g (1.78 g)
(mol) ethyl acetate (435 g) was charged, and under a nitrogen atmosphere,
When reacted at 80 ° C. and the residual isocyanate group became 8.3%, ethylene glycol / adipic acid having an average molecular weight of 1000 (reaction molar ratio 1.02 / 0.5) reactant molecular weight 445.6 g (0.45 mol ) Was added, and 0.15 g of dibutyltin laurylate was added for further reaction.
55 ° C when the residual isocyanate group reaches 3.0%
After cooling to 2, 2-hydroxyethyl acrylate 10
2.1 g (0.88 mol) was added and reacted, and when the residual isocyanate group became 0.3%, the reaction was terminated,
A carboxyl group-containing urethane acrylic resin was obtained. The carboxyl group-containing urethane acrylic resin solution thus obtained had an isocyanate content of 0.3% and an acid value of 30.5 mgK.
It was OH / g.

(Preparation of Dope) 142.9 parts of the above urethane-acrylic resin solution containing a carboxyl group [100 parts of urethane acrylic resin in terms of solid content], 4.0 parts of hexaarylbiimidazole, 0.4 parts of leuco crystal violet, 0.05 parts of Diamond Green and 45.0 of methyl ethyl ketone were mixed and mixed well to prepare a dope.

(Preparation of DFR) Next, the dope was applied on a polyester film having a thickness of 20 μm using an applicator having a gap of 8 mils, and left at room temperature for 1 minute and 30 seconds, then at 60 ° C., 90 ° C. and 110 ° C. 3 in the oven at ℃
After being dried for a minute, the photosensitive resin composition layer having a film thickness of 50 μm D
FR (however, no protective film is provided).

(B) DFR (B-2) having a photosensitive resin composition layer capable of alkali development (Preparation of carboxyl group-containing urethane acrylic resin) 4 equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port In a one-necked flask, 85.14 g (0.63 mol) of 2,2-bis (hydroxymethyl) propionic acid
And hexamethylene diisocyanate 213.66 g
(1.27 mol) and 450.23 g of ethyl acetate were charged and reacted at 78 ° C. under a nitrogen atmosphere. When residual isocyanate groups reached 7.6%, polyethylene glycol (II) having a molecular weight of 600, 569.75 g (0 .95mo
l) is added, and 0.15 g of dibutyltin laurylate is further added.
Was added and the reaction was continued for about 5 hours. When the residual isocyanate group became 0.5%, 107.40 g (0.64 mol) of hexamethylene diisocyanate was newly added to continue the reaction, and when the residual isocyanate group became 2.3%, the temperature was raised to 60 ° C. After that, 77.00 g (0.66 mol) of 2-hydroxyethyl acrylate was added and reacted, and when the residual isocyanate group reached 0.3%, the reaction was terminated to obtain a carboxyl group-containing urethane acrylic resin solution. The obtained carboxyl group-containing urethane acrylic resin had an isocyanate content of 0.3% and an acid value of 23.0 mgKOH / g. Using the above carboxyl group-containing urethane acrylic resin solution, DFR was obtained by the same operation as described above.

(C) DFR (B-3) having a photosensitive resin composition layer capable of alkali development A hydroxypropyl methylcellulose acetate succinate (Shin-Etsu) with 75 parts of the carboxyl group-containing urethane acrylic resin used in (B-1). Chemical industry "HPMCAS AS-L", acid value is 109mgKOH
/ G) DFR in the same manner as above except that 25 parts were also used
Got (D) D having an alkali-developable photosensitive resin composition layer
FR (B-4) A mixture of the carboxyl group-containing urethane acrylic resin used in (B-1) and the carboxyl-free urethane acrylic resin used in (A-1), and the blending amount in terms of solid content is the former. / DFR was obtained using the latter composition = 65/35.

Example 1 DFR (A-1) was laminated on a glass substrate preheated to 60 ° C. in an oven at a laminating roll temperature of 70 ° C., a roll pressure of 0.3 MPa and a laminating speed of 2 m / min. Further, the polyester film of DFR (A-1) was peeled off, DFR (B-1) was laminated under the same conditions, and left at room temperature for 10 minutes to remove heat.
Exposure was performed using a parallel exposure machine “EXM-1201” manufactured by Oak Manufacturing Co., Ltd. The pattern mask used has a line / space of 50 μm / 150 μm and a line / space of 2
0 μm / 100 μm, exposure dose is 4000 J / m ²
Met. This operation is 100 for each
This was performed on one substrate.

After the exposure, the polyester film is peeled off,
After the exposure, use a 0.3% sodium carbonate aqueous solution for the substrate 3
Alkali development was performed at 0 ° C. and a spray pressure of 0.1 MPa for 45 seconds to develop 100% of the unexposed portion of (A-1). This developing solution was reused and the remaining 199 substrates were also developed.

Regarding and in each case, "PNEUMA BLASTER" (hyper nozzle, air pressure: 0.4 MPa, cutting agent: SiC) manufactured by Fuji Manufacturing Co., Ltd. was used for the first, 50th and 100th substrates. # 600
[Average particle size: 23 μm], powder supply amount: 200 g / mi
n), the gun height is 2 cm, the gun moving width is 20 cm,
Sand blasting was performed under a condition of 4 pass at a gun moving speed of 20 m / min to develop the unexposed portion (B-1) and grind the base material. The sandblasting distance (processing depth) and the length of the fine line portion (fine line portion distance) were evaluated for each substrate. The results are shown in Table 1.

Examples 2 to 9 Experiments were carried out according to Example 1 with combinations of DFR (A) and DFR (B) shown in Table 1. The results are shown in Table 1.

Comparative Example 1 In Example 1, the use of DFR (A-1) was omitted and D
The same experiment was conducted using only FR (B-1) (however, the film thickness of the photosensitive resin composition layer was 60 μm) and the developing time was 30 seconds. The results are shown in Table 1.

[Table 1] DFR processing depth / fine line portion distance (μm) used 1st sheet 50th sheet 100th sheet Example 1 (A-1) (B-1) 168/47 165/46 169 / 47 115/18 113/18 112/47 2 (A-1) (B-2) 168/54 168/52 166/52 113/21 112/21 113/22 3 (A-1) (B- 3) 169/44 169/44 168/44 114/11 114/11 112/11 〃 4 (A-1) (B-4) 166/51 167/50 165/50 114/20 115/20 113/19 〃 5 (A-2) (B-1) 143/47 141/47 144/45 104/15 103/13 103/13 〃 6 (A-2) (B-2) 142/53 142/53 142 / 54 103/20 104/20 102/20 〃 7 (A-2) (B-3) 143/42 142/44 143/42 103/10 103/11 104/9 〃 8 (A-3) (B- 2) 151/54 152/53 150/53 107/20 108/21 107/21 9 (A-3) (B-4) 150/50 150/50 152/50 107/20 107/19 110/19 Comparative Example 1 (B-1) 156/45 149/46 99/47 115/16 111/17 80/19

[0061]

According to the present invention, the alkali-resistant photosensitive resin composition layer and the alkali-developable photosensitive resin composition layer provided on the surface of the substrate are exposed to light through a pattern mask and then alkali-developable. The unexposed portion of the photosensitive resin composition layer is subjected to alkali development, and then the unexposed portion of the alkali-resistant photosensitive resin composition layer and the substrate surface under the unexposed portion are sandblasted to form an uneven pattern. By generating the fine line pattern, it is possible to continuously and stably form a fine line pattern having a small pitch width without adversely affecting the shape of the convex portion even if the sandblasting of the base material is deepened.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 15, 2002 (2002.7.1)
5)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction content]

[Table 1]

Continued front page    F-term (reference) 2H025 AA03 AA04 AB11 AB14 AB15                       AC01 AD01 BC13 BC42 BC66                       BC81 BJ01 CA00 DA01 FA17                       FA42                 2H096 AA26 BA05 EA02 GA08 HA23                       HA30 JA04 KA02 KA15 KA30

Claims (9)

[Claims] 1. An alkali-resistant photosensitive resin composition layer (1) and an alkali-developable photosensitive resin composition layer (2) are sequentially provided on a substrate surface, and the photosensitive resin composition layer is provided with a pattern mask therebetween. And then exposed, the photosensitive resin composition layer (2)
Of the photosensitive resin composition layer (1) and then sandblasting the unexposed portion of the photosensitive resin composition layer (1) and the substrate surface below the unexposed portion to produce an uneven pattern. Pattern formation method. 2. After exposing through a pattern mask, the unexposed portion of the photosensitive resin composition layer (2) is exposed to 80 to 1
Photosensitive resin composition layer (1), which was developed by using 100 wt% alkali.
2. The pattern forming method according to claim 1, wherein the unexposed portion and the base material surface below the unexposed portion are sandblasted. 3. The pattern forming method according to claim 1, wherein the photosensitive resin composition layer (2) is a photosensitive resin composition layer containing a carboxyl group-containing resin. 4. The pattern forming method according to claim 3, wherein the carboxyl group-containing resin is a carboxyl group-containing urethane acrylic resin. 5. A composition comprising a carboxyl group-containing resin mainly composed of a carboxyl group-containing urethane acrylic resin, and a combination of this and one or two of a carboxyl group-containing acrylic resin and a carboxyl group-containing cellulose derivative. The pattern forming method according to claim 4, which is characterized in that. 6. The pattern forming method according to claim 1, wherein the photosensitive resin composition layer (1) is a photosensitive resin composition layer containing a resin containing no carboxyl group. 7. The pattern forming method according to claim 6, wherein the resin containing no carboxyl group is a urethane acrylic resin containing no carboxyl group. 8. The photosensitive resin composition layer (1) has a film thickness of 40.
8. The pattern forming method according to claim 1, wherein the transmittance at a wavelength of 365 nm in μm is 65% or less. 9. The pattern forming method according to claim 1, wherein the photosensitive resin composition layer is a dry film photoresist.