JP2000063451A - Photopolymerizable composition, negative type photosensitive resist composition and formation of resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cured product which can be developed through using water or a diluted aqueous alkaline solution as a developing solution, has good curability and chemical resistance, and is capable of forming a fine resist pattern, by using a specific photopolymerizable urethane compound. SOLUTION: A resist pattern is formed by applying a negative type photosensitive resist composition comprising a photopolymerizable composition onto a base which is the photopolymerizable composition containing a photopolymerizable urethane compound represented by the formula (wherein A is a residue derived from a polyisocyanate compound; B is a residue derived from a hydroxy compound having at least two photopolymerizable unsaturated groups at molecular termini; R' is a residue derived from a polyol compound containing a carboxyl group and (n) is an integer of 1-10), drying the resultant product at a temperature of 50-130 deg.C to obtain a negative type photosensitive resist film having a thickness of 0.5-100 μm, irradiating a laser beam on the surface of the negative type photosensitive resist film through a negative mask to cure the film so as to form, a desired resist film, and then subjecting it to an alkaline development treatment.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerizable composition, and more particularly to a negative type photopolymerizable resin composition for producing a printed wiring board. The photopolymerizable composition of the present invention can be used as a solder resist, an etching resist, a plating resistant resist and the like.

[0002]

2. Description of the Related Art Conventionally, in order to form a conductor circuit such as a printed wiring board, a resist pattern is formed on a substrate coated with a photosensitive resist by exposure / development, and then an unnecessary portion is removed by etching. Is being done.

As such a photosensitive resist composition, for example, a photosensitive resist composition which can be developed with a dilute alkali using an unsaturated resin having a carboxylic acid group (see, for example, JP-A-3-223759). It is known.

The above-mentioned carboxyl group-containing unsaturated resin is usually prepared by radically copolymerizing an acid unsaturated monomer such as acrylic acid with a (meth) acrylic acid alkyl ester monomer as described in the publication. After producing a carboxylic acid resin, the resin and glycidyl (meth)
It is produced by subjecting an epoxy group-containing unsaturated monomer such as acrylate to an addition reaction of a part of a carboxyl group (meth) acrylic acid alkyl ester monomer and a glycidyl group.

When such a resin is used as an alkali-developing resist composition, the molecular weight distribution of the resin is generally broadened due to the radical polymerization reaction. Therefore, in the high molecular weight range, an alkali developer or an etching solution is used. Solubility by the resist solution becomes slower, while solubility in the alkaline developing solution or etching resist solution becomes faster in the low molecular weight range, and uniform developing treatment or etching resist treatment cannot be carried out. Since the radical copolymerization reaction rates of the and (meth) acrylic acid alkyl ester monomers are not the same, homopolymers of acrylic acid monomers and acrylic resin components with a small amount of acrylic acid components may be formed. Becomes non-uniform and the resist coating Remain, and the photo-curing film is eroded and washed away by the etching resist solution, so that a fine resist pattern cannot be formed.Addition reaction of polycarboxylic acid resin and epoxy group-containing unsaturated monomer When the reaction is carried out, the polycarboxylic acid resin is further increased in molecular weight because heating is performed, and in order to suppress the radical polymerization reaction between unsaturated groups during the addition reaction, a radical polymerization inhibitor is usually used. However, the photopolymerization reactivity is lowered because it is included in the resin as an unnecessary substance, and the film portion is eroded and washed away by the etching resist solution due to insufficient physical properties of the photocured film. Therefore, there is a problem that a fine resist pattern cannot be formed.

Further, as a method of introducing an unsaturated group into a resin, for example, JP-A-7-102037 discloses a polyhydroxy compound, a radical-polymerizable unsaturated group-containing polyhydroxy compound, and an anionic hydrophilic group-containing polyhydroxy compound. A method for producing a water-soluble active energy ray-curable resin obtained by neutralizing a polyurethane resin obtained by reacting a compound, a polyisocyanate compound and a radically polymerizable unsaturated group-containing monohydroxy compound with an amine is described. However, when the above water-soluble polyurethane resin is used as a resist composition, there is a problem that a fine resist pattern cannot be formed due to poor alkali developability and etching resist resistance.

As a method for introducing an unsaturated group, a reaction product of dimethylolpropionic acid and ε-caprolactone, an organic polyisocyanate compound and a hydroxyl group-containing (meth) acrylate are disclosed in JP-A-6-136077 in addition to the above. A radiation-curable resin composition obtained by reacting However, when the above-mentioned composition is used as a resist composition, there is a problem that the alkali developability and the etching resist resistance are poor.

[0008]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific photopolymerizable composition can be used as a resist to prevent water or rare water. The inventors have found that an aqueous alkaline solution can be used as a developer, and that the cured product is excellent in curability, chemical resistance, heat resistance, performance of forming a fine resist pattern, etc., and completed the present invention. .

That is, the present invention has the following structural units.

[0010]

[Chemical 2]

(Wherein A is a residue derived from a polyisocyanate compound, B is the same or different and is a residue derived from a hydroxy compound having two or more photopolymerizable unsaturated groups at each molecular end, and R1 Represents a residue derived from a carboxyl group-containing polyol compound, n is 1 to 10
Indicates an integer. The present invention relates to a photopolymerizable composition, a negative photosensitive resist composition and a method for forming a resist pattern.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The photopolymerizable polyurethane compound according to the present invention will be described below.

In the above formula, the polyisocyanate compound forming a residue, the hydroxy compound having two or more photopolymerizable unsaturated groups at the molecular ends, and the carboxyl group-containing polyol compound will be described.

Polyisocyanate compound: The polyisocyanate compound is used for binding a compound that introduces a carboxyl group into the molecule and a compound that introduces a photopolymerizable unsaturated group at the end of the molecule.

Examples of the aliphatic diisocyanate compound include hexamethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate, 1,
2-propylene diisocyanate, 1,2-butylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, lysine diisocyanate, 2,3-butylene diisocyanate, 1,3
Examples of the alicyclic diisocyanate compound such as butylene diisocyanate include isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or-
2,6--diisocyanate, 1,3- (or 1,4
-) Di (isocyanatomethyl) cyclohexane, 1,4
-Cyclohexane diisocyanate, 1,3-cyclopentane diisocyanate, 1,2-cyclohexane diisocyanate, etc .; Examples of aromatic diisocyanate compounds include xylylene diisocyanate, metaxylylene diisocyanate, tetramethylxylylene diisocyanate, tolylene diisocyanate, 4, 4'-
Diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 4,4'-toluidine diisocyanate, 4,
4'-diphenyl ether diisocyanate, (m- or p-) phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,
4'-biphenylene diisocyanate, bis (4-isocyanatophenyl) sulfone, isopropylidene bis (4-phenyl isocyanate); other polyisocyanates include, for example, triphenylmethane-
4,4 ', 4 "-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 4,4'-dimethyldiphenylmethane-
Polyisocyanate compounds having three or more isocyanate groups such as 2,2 ′, 5,5′-tetraisocyanate, ethylene glycol, propylene glycol,
Hexamethylene diisocyanate, an adduct obtained by reacting a polyisocyanate compound in an amount such that the isocyanate group is in excess with respect to the hydroxyl groups of polyols such as 1,4-butylene glycol, polyalkylene glycol, trimethylolpropane, and hexanetriol. , Isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) and other burette type adducts, isocyanuric ring type adducts and the like. These can be used alone or in combination of two or more. Among these compounds, the aromatic diisocyanate compound is particularly difficult to hydrolyze in an alkali developing solution and can form a photocured coating having a high resistance against an alkaline developing solution or an etching resist solution, and the coating itself. Is tough, so that it is preferable that the photo-cured resist film is sufficiently adhered without being peeled off from the substrate by an external force such as an etching resist solution until it is peeled off in the resist pattern forming method.

Hydroxy Compound Having Two or More Photopolymerizable Unsaturated Groups at the Molecular End: The compound is a compound used for introducing a photopolymerizable unsaturated group at the molecular end.

The photopolymerizable unsaturated group is an unsaturated group which forms a crosslinked structure by radical polymerization reaction by light.
It includes conventionally known unsaturated groups. Among the unsaturated groups, a (meth) acryloyl group is particularly preferable.

Examples of the compound include glycerin di (meth)
Acrylate, diglycerin di (meth) acrylate,
Diglycerin tri (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, hydroxyisocyanurate di (meth) acrylate, Examples thereof include hydroxy compounds containing two or more unsaturated groups in one molecule, such as sorbitol di (meth) acrylate. These can be used alone or in combination of two or more.

Carboxyl group-containing polyol compound: With this compound, an aqueous dispersion of the photopolymerizable composition can be obtained by introducing a carboxyl group into the molecule, and the unirradiated resist film portion can be removed by alkali development treatment. It is a component that becomes.

As the compound, a compound having at least one carboxyl group and at least two hydroxyl groups in the molecule can be used. Specifically, for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolacetic acid,
2,2-dimethylolpentanoic acid, or a half-ester compound obtained by the reaction of a triol compound and an acid anhydride compound, sodium dimethylsulfoisophthalate and glycols are subjected to transesterification under an excess of glycols. The obtained sulfonate diol compound etc. are mentioned, You may use these compounds 1 type or in combination of 2 or more types.

In the above formula of the photopolymerizable polyurethane compound, n is preferably in the range of 1-10, particularly 1-5. When n is less than 1, alkali development becomes impossible, while when n exceeds 10, the resist sensitivity is remarkably lowered. Usually, the number average molecular weight of this product is about 500-1.
The range is 0000.

The photopolymerizable polyurethane compound can be produced by a known method similar to general polyurethane resins. That is, the carboxyl group-containing polyol compound and the polyisocyanate compound have excess isocyanate groups (for example, isocyanate group / hydroxyl group = about 2.
(0 to 1.1 molar ratio, preferably about 2.0 to 1.2 molar ratio) is added to react with an isocyanate group and a hydroxyl group to produce a carboxyl group-containing isocyanate compound. A photopolymerizable unsaturated group-containing polyol compound was added to this, for example, in an isocyanate group / hydroxyl group ratio of about 0.8 to 1.0, preferably about 0.9 to 1.0. By subjecting the product to an addition reaction, the carboxyl group is blocked by esterifying with a lower alcohol such as methanol, ethanol, propanol, etc. before the reaction, and then the lower alcohol is heated by the reaction. It is also possible to remove and regenerate the carboxyl group.

For the addition reaction of the isocyanate group and the hydroxyl group, the temperature of the reaction system is usually 50 to 150 ° C., but 100 ° C. to prevent the polymerization of the radically polymerizable unsaturated group.
The following is preferable, and a urethane-forming reaction catalyst may be used if necessary. Examples of the urethane-forming reaction catalyst include organotin compounds such as tin octylate and dibutyltin dilaurate. In addition, an organic solvent can be used as necessary for producing the polyurethane resin. As these organic solvents, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ethyl acetate, butyl acetate, toluene, xylene, N, N
-Dimethylformamide, N-methyl-2-pyrrolidone and the like can be mentioned.

The light used in the present invention means active energy rays such as electron rays, ultraviolet rays and visible rays. Also, ultraviolet rays,
In the case of irradiating with visible light to crosslink, a photopolymerization initiator and, if necessary, a photosensitizer can be provided.

As the photo-radical polymerization initiator, conventionally known ones can be used. Examples thereof include aromatic carbonyl compounds such as benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzylxanthone, thioxanthone and anthraquinone; acetophenone, propiophenone,
Acetophenones such as α-hydroxyisobutylphenone, α, α'-dichloro 4-phenoxyacetophenone, 1-hydroxy-1-cyclohexylacetophenone, diacetylacetophenone, acetophenone; benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t- Butyl hydroperoxide, di-t-butyl diperoxyisophthalate,
Organic peroxides such as 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; Diphenylhalonium salts such as diphenyliodobromide, diphenyliodonium chloride; Carbon tetrabromide, chloroform, iodoform, etc. Organic halides; heterocyclic and polycyclic compounds such as 3-phenyl-5-isoxazolone, 2,4,6-tris (trichloromethyl) -1,3,5-triazinebenzanthrone; 2,2 '
-Azo (2,4-dimethylvaleronitrile), 2,2-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2-methylbutyronitrile), etc. Compound;
Iron-allene complex (see European Patent No. 152377);
Titanocene compounds (see JP-A-63-221110), bisimidazole compounds; N-arylglycidyl compounds; acridine compounds; aromatic ketone / aromatic amine combinations; peroxyketals (JP-A-6-321895).
(See Japanese Patent Publication) and the like. Among the above photo-radical polymerization initiators, di-t-butyldiperoxyisophthalate, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, iron-allene complex and titanocene compound are crosslinked or It is preferred to use this because it is highly active for polymerization.

As the trade name, for example, Irgacure 651 (trade name, acetophenone-based photoradical polymerization initiator manufactured by Ciba Geigy), Irgacure 184
(Ciba Geigy, trade name, acetophenone-based photoradical polymerization initiator), Irgacure 1850 (Ciba Geigy, trade name, acetophenone-based photoradical polymerization initiator), Irgacure 907 (Ciba Geigy, trade name, aminoalkylphenone-based Photoradical polymerization initiator), Irgacure 369 (manufactured by Ciba Geigy, trade name, aminoalkylphenone-based photoradical polymerization initiator), Lucillin TPO (manufactured by BASF, trade name, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide), Kayacure DETXS (trade name, manufactured by Nippon Kayaku Co., Ltd.), CGI-784 (trade name, titanium complex compound manufactured by Ciba-Geigy), and the like. These can be used alone or in combination of two or more.

The photosensitizing dyes include, for example, thioxanthene type, xanthene type, ketone type, thiopyrylium salt type, base styryl type, merocyanine type, 3-substituted coumarin type, 3.4-substituted coumarin type, cyanine type, Acridine, thiazine, phenothiazine, anthracene, coronene, benzanthracene, perylene,
Examples thereof include merocyanine dyes, ketocoumarin dyes, fumarine dyes, and borate dyes. These can be used alone or in combination of two or more. Examples of the borate-based photosensitizing dye include those described in JP-A-5-241338, JP-A-7-5685, JP-A-7-225474 and the like.

In the photopolymerizable composition of the present invention, if necessary, unsaturated compounds other than those mentioned above, adhesion promoters, hydroquinone, 2,6-di-t-butyl-p-cresol, N, Polymerization inhibitors such as N-diphenyl-p-phenylenediamine, saturated resins, unsaturated resins, organic resin fine particles such as vinyl polymers (containing unsaturated groups), various pigments such as coloring pigments and extender pigments, cobalt oxide Metal oxides such as
It may contain a plasticizer such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, polyethylene glycol, polypropylene glycol, a cissing inhibitor, and a fluidity adjusting agent.

Other unsaturated compounds include, for example:
A compound having preferably 1 to 4 radical-polymerizable unsaturated groups, wherein a monomer, a dimer, a trimer and other oligomers which cause insolubilization in the exposed area by addition polymerization upon exposure are Can be mentioned. Specific examples of such compounds include acrylic acid, methacrylic acid, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetra or higher poly (4 to 1).
6) ethylene glycol di (meth) acrylate, propylene glycol di (meth) (acrylate, trimethylolpropane tri (meth) acrylate, pentaerythril tetra (meth) acrylate, ethylene glycol diitaconate, ethylene glycol dimaleate, Hydroquinone di (meth) acrylate, resorcinol di (meth) acrylate, pyrogallol (meth)
Examples thereof include acrylate, oligourethane acrylate, oligoepoxy acrylate, divinylbenzene and the like. The above ethylenically unsaturated compound is 1
They may be used alone or in combination of two or more.

The amount of these ethylenically unsaturated compounds used can be generally 200 parts by weight or less, preferably 3 to 50 parts by weight, per 100 parts by weight of the photopolymerizable polyurethane compound.

The above-mentioned adhesion promoters are added to improve the adhesion of the coating film to the substrate, and include, for example, tetrazole, 1-phenyltetrazole, 5-aminotetrazole and 5-amino-1-. Methyltetrazole, 5-amino-2-phenyltetrazole, 5-mercapto-1-phenyltetrazole, 5-
Examples thereof include trazoles such as mercapto-1-methyltetrazole, 5-methylthiotetrazole, and 5-chloro-1-phenyl-1H-tetrazole. These may be used alone or in combination of two or more.

As the saturated resin, in order to suppress the solubility of the photopolymerizable composition (inhibitor of the solubility of the resist coating in an alkaline developing solution or the solubility used in the removal of the photocured coating, for example, a strong alkaline solution). Can be used for Examples thereof include polyester resin, alkyd resin, (meth) acrylic resin, vinyl resin, epoxy resin, phenol resin, natural resin, synthetic rubber, silicone resin, fluorine resin, polyurethane resin and the like. These resins may be used alone or in combination of two or more.

The unsaturated resin is preferably the above-mentioned resin containing an average of about 1 to 10, particularly about 1 to 4 unsaturated groups in one molecule.

The amount of these saturated or unsaturated resins used can be generally 200 parts by weight or less, preferably 3 to 50 parts by weight, per 100 parts by weight of the photopolymerizable polyurethane compound.

The composition of the present invention is a known photosensitive material that is generally used, for example, paints, inks, adhesives, resist materials, printing plate materials (plate-making materials for flat plates and letterpress, PS plates for offset printing). Although it can be used for a wide variety of applications such as recording materials and relief image-forming materials, it is particularly preferably used as a resist composition.

As the resist composition, for example, a liquid resist (organic solvent-based resist, water-based resist, resist for electrodeposition paint, etc.) or a dry film resist can be used. Among these, it is particularly preferable to use as an organic solvent-based liquid resist.

As the organic solvent type liquid resist, the above photopolymerizable composition is used as an organic solvent (ketones, esters, ethers, cellosolves, aromatic hydrocarbons, alcohols, halogenated hydrocarbons, etc.). It is obtained by dissolving or dispersing in. The composition is a support (eg,
Sheets of metals such as aluminum, magnesium, copper, zinc, chrome, nickel, iron or alloys containing them, or printed circuit boards surface-treated with these metals, plastic, glass or silicone wafers, carbon, etc.), rollers, rolls Coater, spin coater,
A resist film can be obtained by applying by a means such as a curtain roll coater, spraying, electrostatic coating, dip coating, silk printing, etc., setting if necessary, and drying.

Further, the resist coating may be provided with a cover coat layer on the surface of the material before it is exposed to light and cured. This cover coat layer is formed in order to block oxygen in the air to prevent radicals generated by exposure from being deactivated by oxygen and to smoothly cure the photosensitive material by exposure.

As the cover coat layer, for example, a resin film (film thickness of about 1 to 70 μm) of polyester resin such as polyethylene terephthalate, acrylic resin, polyethylene, polyvinyl chloride resin or the like is coated on the surface of the coating film. Polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl alcohol-vinyl acetate copolymer, partially saponified polyvinyl acetate-vinyl acetate copolymer, polyvinylpyrrolidone, water-soluble polysaccharide polymers such as pullulan, basic group , An aqueous solution containing an acidic group or a base, such as an acrylic resin, a polyester resin, a vinyl resin or an epoxy resin, which is dissolved or dispersed in water, is applied to the surface of the coating film (dry film thickness: about 0.5
˜5 μm), and a cover coat layer can be formed by drying. This cover coat layer is preferably removed after exposing the surface of the photosensitive material and before developing. The cover coat layer of the water-soluble polysaccharide polymer or the aqueous resin can be removed with a solvent such as water, an acidic aqueous solution or a basic aqueous solution which dissolves or disperses these resins.

The aqueous liquid resist composition can be obtained by dissolving or dispersing the above-mentioned photocurable composition in water. This material can be handled in the same manner as a normal photosensitive material for electrodeposition coating and can be used as a coating material for electrodeposition coating. Water-solubilization or water-dispersion of the aqueous photosensitive resin composition is carried out by neutralizing the carboxyl groups in the photopolymerizable composition with an alkali (neutralizing agent).

As the above-mentioned alkali neutralizing agent, for example, monoethanolamine, diethanolamine, triethylamine, diethylamine, dimethylaminoethanol, cyclohexylamine, ammonia and the like can be used. Neutralization is generally carried out per equivalent of carboxyl group,
0.2 to 1.0 equivalent, particularly 0.3 to 0.8 equivalent is preferable.

The electrodeposition coating composition is, for example, a cationic electrodeposition coating composition having a pH range of 4 to 7 and a pH of 7 to 7 adjusted to a bath concentration (solid content concentration) of 3 to 25% by weight, particularly 5 to 15% by weight.
Anion electrodeposition paints in the range of 9 can be used.

The electrodeposition coating composition can be applied to the surface of the conductor to be coated, for example, as follows. That is, first, the pH and bath concentration of the bath are adjusted within the above ranges, and the bath temperature is controlled at 15 ° C to 40 ° C, preferably 15 ° C to 30 ° C. Then, the conductor to be coated is soaked in an electrodeposition coating bath controlled in this way as an anode when the electrodeposition coating is an anion type and as a cathode when the electrodeposition coating is a cation type.
A direct current of up to 200 V is applied. Energization time is 10 seconds ~
5 minutes is appropriate.

In the electrodeposition coating method, a method of applying an electrodeposition coating having a low glass transition temperature to an object to be coated, then washing with water or washing with water and drying, and then applying an electrodeposition coating having a glass transition temperature of 20 ° C. or higher (See Japanese Patent Application Laid-Open No. 2-20873), that is, double coat electrodeposition coating may be performed.

The film thickness obtained is a dry film thickness, generally 0.5
The range of ˜50 μm, particularly 1 to 15 μm is preferable.

After the electrodeposition coating, the object to be coated is pulled out from the electrodeposition bath and washed with water, and then the water content contained in the electrodeposition coating film is dried and removed by hot air or the like. As the conductor, a conductive material such as metal, carbon or tin oxide, or a material obtained by laminating these and fixing them to a plastic or glass surface by plating or the like can be used.

A cover coat layer may be previously provided on the surface of the electrodeposition coating film before exposure and curing.
Examples of the cover coat layer include those mentioned above. This cover coat layer is preferably removed before the electrodeposition coating film is developed. The cover coat layer using a water-soluble polysaccharide polymer or an aqueous resin can be removed with a solvent such as water, an acidic aqueous solution or a basic aqueous solution which dissolves or disperses these resins.

The dry film resist is prepared, for example, by roll-coating the above-mentioned aqueous or organic solvent resist composition on a transparent resin film such as polyester resin such as polyethylene terephthalate, acrylic resin, polyethylene, polyvinyl chloride resin, etc., which becomes the base film layer. Coater, blade coater, curtain flow coater, etc. and dry to form a resist film (dry film thickness of about 0.5 to 50 μm).
m, particularly preferably 1 to 15 μm) and then used as a dry film resist in which a protective film is attached to the surface of the coating film.

Such a dry film resist can be adhered by a method such as thermocompression bonding to a support similar to the above so that the resist film comes into face-to-face contact after the protective film is peeled off to form a resist film. . The resulting resist coating is either stripped of the base film layer or not stripped, and then exposed to visible light and cured according to the image in the same manner as in the above-mentioned electrodeposition coating film, and then the base film is cured. An image can be formed by peeling off the layer when there is a layer and developing the layer when there is no layer. Further, in the dry film resist, the above-mentioned cover coat layer can be provided between the base film layer and the resist film, if necessary. The cover coat layer may be formed by coating on the resist coating or may be formed by pasting on the resist coating.
The cover coat layer may or may not be removed before the development treatment.

Examples of the light source used for photocuring include ultra-high pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, tungsten lamps and the like. Further, various lasers having an oscillation line in the visible region can also be used. Among these, an argon laser (488 nm) or a YAG-SHG laser (532 nm) is preferably a laser having an oscillation line.

The negative photosensitive resist composition of the present invention comprises
For example, a base material such as a plastic sheet, metal, glass, paper or wood can be coated and printed. Further, it is preferable to use the composition for forming a resist pattern film.

Next, a method for forming a resist pattern on a substrate using this negative photosensitive resist composition will be described below.

A negative photosensitive resist composition is coated (1) on a substrate to form a photosensitive coating, and a laser beam is applied so that a desired resist coating (image) can be obtained on the surface of the coated photosensitive coating. It is cured by exposing (2) directly or through a light beam through a negative mask, and then developing treatment (3) is performed on the uncured portion of the photosensitive film with an aqueous solution of alkali to form a resist film on the substrate, which is protected by the resist film. It is obtained by removing the copper layer in the non-existing portion and further removing the resist film.

As the above-mentioned substrate, a plastic film or a plastic plate such as an electrically insulating glass-epoxy plate, a polyethylene terephthalate film or a polyimide film; and a metal foil such as copper or aluminum on the surface of the plastic plate or the plastic film. A conductive film was formed by adhesion or by a metal such as copper, nickel, silver or a compound such as a conductive oxide represented by indium-tin oxide (ITO) by a method such as vacuum deposition, chemical vapor deposition, and plating. Material: A plastic plate or a plastic film provided with a through hole portion and a conductive film formed on the surface of the through hole portion: a metal plate such as a copper plate.

In the coating step (1), when the negative photosensitive resin composition is an organic solvent type, spray coating, electrostatic coating, spin coating, dip coating, roller coating, curtain flow coating on the surface of the substrate, Paint by means such as silk printing, set as necessary, etc.
The photosensitive resin film can be formed by drying at a temperature in the range of 130 ° C. The film thus formed is then exposed in the step (2). If necessary, it is conventionally known to block oxygen on the surface of the film to prevent the curing of the photosensitive film by exposure. A non-photosensitive cover coat layer can be provided.

When the negative photosensitive resist composition is an electrodeposition coating, it is subjected to electrodeposition coating, followed by draining, air blowing, etc., and if necessary at a temperature in the range of about 50 to 130 ° C. A negative photosensitive resist film can be formed by drying.

The film thickness of the negative type photosensitive resist film described above is preferably in the range of about 0.5 to 100 μm, particularly preferably about 1 to 50 μm.

The light rays used in the exposure step (2) include
In particular, visible light having an emission spectrum wavelength of a light source of 488 nm (argon laser) or 532 nm (YAG-SHG laser) has been put into practical use, and it is preferable to use this, but it is not limited to this. .

In the developing treatment (3), the uncured film is usually washed out with a weak alkaline aqueous solution prepared by diluting caustic soda, sodium carbonate, caustic potash, ammonia, amine and the like in water. When the cover coat is provided, it is preferable to remove the cover coat before the development processing. When used as an etching resist substrate, the exposed copper layer (non-circuit portion) is then removed by etching with an aqueous solution of ferric chloride or cupric chloride. The resist coating is removed by a strong alkali such as caustic soda or a solvent such as methylene chloride.

The substrate on which the resist pattern thus obtained is formed is a solder resist substrate for decoration,
It can be used as an etching resist substrate.

[0061]

EXAMPLES The present invention will be described in more detail by way of examples. Hereinafter, “part” and “%” mean “part by weight” and “% by weight”, respectively.

Production of Photocurable Resin Example 1 Photopolymerizable Polyurethane Compound A (*) 100 parts Polymerization initiator (**) 3 parts Sensitizer (***) 1.5 parts Ethyl acetate 400 parts The formulation was mixed to obtain the photopolymerizable composition of Example 1.

(*) Photopolymerizable polyurethane compound A: A product obtained by adding 2 mol of trimethylolpropane diacrylate to a reaction product of 1 mol of dimethylolbutanoic acid and 2 mol of tolylene diisocyanate.

[0064]

[Chemical 3]

(**) Polymerization initiator: titanocene compound, trade name, CGI-784, manufactured by Ciba-Geigy Co., Ltd. (***) Sensitizer: coumarin-based photosensitizer, trade name, NKX
-1595, manufactured by Nippon Senshoku Co., Ltd. The photopolymerizable composition obtained above was applied to a bar coater on a copper-clad glass fiber reinforced epoxy substrate having a thickness of 2 mm and a size of 350 × 460 mm having a copper layer having a thickness of 18 μm on the surface. Was applied and dried at 60 ° C. for 10 minutes to obtain a resist film having a dry film thickness of 10 μm.

A wavelength of 488n is applied to the resist film forming substrate.
The irradiation amount was 3 mJ / cm ² with an argon ion laser irradiation device of m and the resolution was 100 μm / 100 μm (line (μm) / space (μm)) with a visible light laser. Then, the exposed resist film-formed substrate was heated at 60 ° C. for 10 minutes, and then immersed in a 1% sodium carbonate aqueous solution at 30 ° C. for 1 minute for development to remove the uncured portion of the resist film. As a result, the resolution was good at 100 μm / 100 μm.

After alkali development, 20 ° C., 2
The copper layer on the exposed part was removed by immersing in a 4% ferric chloride aqueous solution for 2 minutes for etching. As a result, the resolution was good at 100 μm / 100 μm.

Example 2 Polymerization initiator CGI-784 and sensitizer N in Example 1 were used.
Polymerization initiator Irgacure 90 instead of KX-1595
7. The composition of Example 2 using Kayacure DETX-S was obtained.

Photopolymerizable polyurethane compound A 100 parts Polymerization initiator A (****) 10 parts Polymerization initiator B (*****) 2 parts Ethyl acetate 400 parts Examples prepared by mixing the above-mentioned compounds. A photopolymerizable composition of No. 2 was obtained.

(****) Polymerization initiator A: Aminoalkylphenone type photoradical polymerization initiator, trade name, Irgacure 907, manufactured by Ciba-Geigy (*****) Polymerization initiator B: Thioxanthone type photoradical polymerization Initiator, trade name Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd. The photopolymerizable composition obtained above has a copper layer having a thickness of 18 μm on the surface, a plate thickness of 2 mm, a size of 350 × 460 mm copper-clad glass A fiber reinforced epoxy substrate was coated with a bar coater and dried at 60 ° C. for 10 minutes to obtain a resist film having a dry film thickness of 10 μm.

On the resist film-formed substrate, an exposure amount of 100 mJ / cm ² was obtained by an ultra-high pressure mercury lamp, and a resolution of 100 μm / 100 μm (line (μm) /
It irradiated so that it might become a space (micrometer). Then, the exposed resist film-formed substrate was heated at 60 ° C. for 10 minutes, and then immersed in a 1% sodium carbonate aqueous solution at 30 ° C. for 1 minute for development to remove the uncured portion of the resist film. As a result, the resolution was good at 100 μm / 100 μm.

After alkali development, 20 ° C., 2
The copper layer on the exposed part was removed by immersing in a 4% ferric chloride aqueous solution for 2 minutes for etching. As a result, the resolution was good at 100 μm / 100 μm.

Comparative Example 1 Instead of the photopolymerizable urethane compound A in Example 1, a photopolymerizable urethane compound B (2 mol of hydroxyethyl acrylate was added to a reaction product of 1 mol of dimethylolbutanoic acid and 2 mol of tolylene diisocyanate). The composition of Comparative Example 1 was obtained by blending in the same manner as in Example 1 except that the above composition was used.

[0074]

[Chemical 4]

Using the photopolymerizable composition obtained above, a resist film was obtained in the same manner as in Example 1.

A wavelength of 48 is applied to the obtained resist film forming substrate.
The exposure dose was set to 3 mJ / cm ² by an 8 nm argon ion laser irradiation device, and the visible light laser was set to a resolution of 100 μm / 100 μm (line (μm) /
It irradiated so that it might become a space (micrometer). Then, the resist film-formed substrate after the above exposure was heated at 60 ° C. for 10 minutes, then immersed in a 1% sodium carbonate aqueous solution at 30 ° C. for 1 minute for development to remove the uncured portion of the resist film. No membrane could be obtained.

Comparative Example 2 40 parts of methyl methacrylate, 40 parts of butyl acrylate
Part, 20 parts of acrylic acid, and 2 parts of azobisisobutyronitrile were mixed under a nitrogen gas atmosphere to give 1
It was added dropwise to 90 parts of propylene glycol monomethyl ether kept at 10 ° C. over 3 hours. After the dropping is completed,
The mixture was aged for 1 hour, a mixed solution containing 1 part of azobisdimethylvaleronitrile and 10 parts of propylene glycol monomethyl ether was added dropwise over 1 hour, and then aged for 5 hours to obtain a high acid value acrylic resin (resin acid value: 155 mgKOH
/ G) solution was obtained. Next, 24 parts of glycidyl methacrylate, 0.12 part of hydroquinone and 0.6 part of tetraethylammonium bromide were added to this solution, and the mixture was reacted at 110 ° C. for 5 hours while blowing air, and photocured with a solid content of about 55.4%. A resinous solution was obtained. The resulting photocurable resin had a resin acid value of about 50 mgKOH / g and a number average molecular weight of about 20,000.

A composition of Comparative Example 2 was prepared in the same manner as in Example 1 except that the above photocurable resin was used in the same portion (as solid content) in place of the photopolymerizable urethane compound A in Example 1. Obtained.

A wavelength of 48 was added to the obtained resist film forming substrate.
The exposure dose was set to 3 mJ / cm ² by an 8 nm argon ion laser irradiation device, and the visible light laser was set to a resolution of 100 μm / 100 μm (line (μm) /
It irradiated so that it might become a space (micrometer). Then, the exposed resist film-formed substrate was heated at 60 ° C. for 10 minutes, and then immersed in a 1% sodium carbonate aqueous solution at 30 ° C. for 1 minute for development to remove the uncured portion of the resist film.

After alkali development, 20 ° C., 2
It was immersed in a 4% ferric chloride aqueous solution for 2 minutes for etching, but the film peeled during the process, so 100 μm / 100
Resolution of μm was not possible.

Comparative Example 3 A comparative example was prepared in the same manner as in Example 1 except that the following water-soluble photocurable resin was used in place of the photopolymerizable urethane compound A in Example 1 (in terms of solid content). A composition of 3 was obtained.

Water-soluble photocurable resin: 334 parts of polyester diol (polymethylpentane adipate manufactured by Kuraray Co., Ltd., number average molecular weight of 2000), 24.3 parts of glycerol monoacrylate, 44.7 of 2,2-dimethylolpropionic acid. Part, hydroquinone monomethyl ether 0.
Charge 52 parts and 0.26 parts of dibutyltin dilaurate 4
At 0 ° C., while stirring and blowing dry air,
Add 185 parts of isophorone diisocyanate, 80 ° C
And then reacted for 6 hours to obtain an isocyanate group content of 1.
30% by weight of intermediate was obtained. Next, 34.8 parts of 2-hydroxyethyl acrylate was added and reacted at 80 ° C. for 15 hours to give a radically polymerizable unsaturated group- and anionic hydrophilic group-containing polyurethane resin having an isocyanate group content of 0.16% by weight. Obtained. After cooling to 40 ° C., 33.7 parts of triethylamine was added, stirred and homogenized, and the above resin solution was added to a 5 liter four-necked flask containing 1503 parts of deionized water heated to 50 ° C. to dissolve in water. Was made. Next, the solvent was removed (methyl ethyl ketone) under reduced pressure to obtain a light yellow transparent water-soluble photocurable resin. The nonvolatile content of this resin was 30% by weight.

Using the photopolymerizable composition obtained above, a resist film was obtained in the same manner as in Example 1.

A wavelength of 48 was added to the obtained resist film forming substrate.
The exposure dose was set to 3 mJ / cm ² by an 8 nm argon ion laser irradiation device, and the visible light laser was set to a resolution of 100 μm / 100 μm (line (μm) /
It irradiated so that it might become a space (micrometer). Then, the resist film-formed substrate after the above exposure was heated at 60 ° C. for 10 minutes, then immersed in a 1% sodium carbonate aqueous solution at 30 ° C. for 1 minute for development to remove the uncured portion of the resist film. No membrane could be obtained.

Comparative Example 4 Comparative Example 4 was prepared in the same manner as in Example 1 except that the following photocurable resin was used in place of the photopolymerizable urethane compound A in Example 1 in the same amount (as solid content). A composition was obtained.

Photocurable resin: charged with 134 parts of dimethylolpropionic acid, 366 parts of ε-caprolactone and 0.15 part of stannous chloride, heated to 110 ° C., reacted for about 10 hours, cooled to 60 ° C., Next, 333.4 parts of isophorone diisocyanate and polyethylene glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAY) as a diluent.
ARAD PEG400DA) 409.4 parts were charged,
After reacting at 80 ° C. for about 10 hours, 121.8 parts of 2-hydroxyethyl acrylate and 0.6 part of p-methoxyphenol were charged and reacted at 80 ° C. for about 15 hours to obtain urethane acrylate containing 30% polyethylene glycol diacrylate. Obtained.

Using the photopolymerizable composition obtained above, a resist film was obtained in the same manner as in Example 1.

A wavelength of 48 was added to the obtained resist film-formed substrate.
The exposure dose was set to 3 mJ / cm ² by an 8 nm argon ion laser irradiation device, and the visible light laser was set to a resolution of 100 μm / 100 μm (line (μm) /
It irradiated so that it might become a space (micrometer). Then, the resist film-formed substrate after the above exposure was heated at 60 ° C. for 10 minutes, then immersed in a 1% sodium carbonate aqueous solution at 30 ° C. for 1 minute for development to remove the uncured portion of the resist film. No membrane could be obtained.

[0089]

EFFECTS OF THE INVENTION The present invention has a narrow molecular weight distribution due to the above-mentioned constitution, so that the solubility in an alkali developing solution is uniform and the etching resistance to an etching resist solution is excellent. Since it is introduced, the solubility in an alkaline developer is uniform and the etching resistance to an etching resist solution is excellent, the coating has good polyurethane physical properties because it has a polyurethane bond, and the etching resistance is excellent. A polyester component in the molecule (for example, Since it does not contain ε-caprolactone), it exhibits a remarkable effect such as excellent resistance to etching resist.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Osamu Isozaki             Seki, 4-17-1, Higashi-Hachiman, Hiratsuka City, Kanagawa Prefecture             West Paint Co., Ltd. F term (reference) 2H025 AA06 AB15 AC08 AD01 BC14                       BC66 FA17                 2H096 AA26 BA05 EA04 GA09                 4J011 AC04 QA02 QA03 QA07 QA13                       QA17 QA18 QA19 QA23 QA24                       QA25 QB16 QB20 QB23 RA03                       RA07 RA10 SA02 SA06 SA07                       SA22 SA32 SA33 SA52 SA62                       SA63 SA64 SA74 SA76 SA78                       SA79 SA88 UA01 UA02 UA03                       VA01 WA01 WA02 WA06                 4J027 AC03 AC06 AE01 AG01 AG04                       AG12 AG13 AG14 AG15 AG23                       AG24 AG27 AG32 AG34 AJ02                       BA01 BA03 BA06 BA10 BA18                       BA19 BA20 BA21 BA26 BA27                       CA03 CA04 CA06 CA08 CA10                       CA25 CB10 CC04 CC05 CC06                       CC07 CD08 CD09 CD10

Claims (3)

[Claims] 1. The following structural units: (In the formula, A is a residue derived from a polyisocyanate compound, and B is the same or different and is 2 at each molecular end.
A residue derived from a hydroxy compound having one or more photopolymerizable unsaturated groups and R1 represents a residue derived from a carboxyl group-containing polyol compound. n shows 1-10 integer. A photopolymerizable composition comprising a photopolymerizable polyurethane compound having a). 2. A negative photosensitive resist composition comprising the above photopolymerizable polyurethane compound as a resin component for a negative photopolymerizable resist. 3. A step of (1) applying the negative photosensitive resist composition according to claim 3 on a substrate to form a photosensitive film, and (2) a photosensitive film formed on the substrate. A step of exposing the resist film formed by the above step (2) to an alkali so as to obtain a desired resist film (image) on the surface, which is directly exposed to a laser beam or exposed to a light beam through a negative mask to be cured. A method of forming a resist pattern, comprising the step of forming a resist pattern on the resist pattern.