JP2001201870A - Pattern-forming laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pattern forming laminate which gives sharp patterns. SOLUTION: A negative or positive UV-sensitive resin coating layer (A), a sheet layer (B) which transmits UV and an energy beam sensitive coating layer (C) which shields UV are successively laminated on the surface of a substrate to obtain the objective pattern forming laminate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laminate for forming a pattern, a method for producing the same, and a method for forming a pattern using the laminate.

[0002]

2. Description of the Related Art Hitherto, lithography using an exposure technique has been used for a wiring board, a display panel, an etching and the like as a method of forming a pattern on, for example, a plastic or an inorganic substance.

As a method of forming a pattern, for example,
After forming a photosensitive insulating or conductive coating layer by applying a photosensitive insulating or conductive composition on the surface of the substrate, from the surface electron beam, ultraviolet light is irradiated through a photomask,
Then, a method is known in which the photosensitive insulating or conductive coating layer is subjected to a development treatment to obtain a desired pattern.
However, this method has a problem that a sharp pattern cannot be formed due to insufficient photosensitivity of the insulating or conductive coating layer.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, this time, by using a film obtained by laminating a specific photosensitive film, It has been found that the above problem can be solved, and the present invention has been completed.

Thus, according to the present invention,
Negative or positive type ultraviolet-sensitive resin coating layer (A),
There is provided a laminate for pattern formation, which is formed by sequentially laminating a sheet layer (B) transmitting ultraviolet rays and an energy-sensitive coating layer (C) shielding ultraviolet rays.

Hereinafter, the pattern forming laminate of the present invention, a method for producing the same, and a pattern forming method using the laminate will be described in more detail.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The substrate used in the laminate of the present invention is not particularly limited, and those conventionally used for pattern formation can be used in the same manner. A glass-epoxy plate; a plastic sheet or a plastic sheet such as a polyethylene terephthalate sheet or a polyimide sheet; by bonding a metal foil such as copper or aluminum to the surface of the plastic plate or the plastic sheet; or copper, nickel or silver Compounds such as metals or conductive oxides typified by indium-tin oxide (ITO) formed into a conductive film by a method such as vacuum deposition, chemical vapor deposition, plating, etc .; plastic plates provided with through holes, A conductive sheet as described above formed on the surface and through-holes of a plastic sheet; gold such as a copper plate Plate; copper through-hole printed wiring board is patterned, and the like.

In the negative or positive type ultraviolet-sensitive resin coating layer (A) used in the laminate of the present invention, a portion of the coating layer which has not been irradiated with ultraviolet rays is removed by dissolving or dispersing with a developing solution, and the ultraviolet rays are removed. A negative type coating layer (A-1) in which the irradiated portion of the coating layer does not dissolve or disperse in the developer and remains as a resist film, or a portion of the coating not irradiated with ultraviolet light is dissolved or dispersed in the developing solution. The positive coating layer (A-2), which remains as a resist coating without being removed and is exposed to ultraviolet rays, is decomposed by ultraviolet rays and dissolved or dispersed by a developer to be removed. Any material having such ultraviolet light-sensitive characteristics can be used without particular limitation.

As the resin composition for forming the negative type ultraviolet-sensitive film layer (A-1), for example, a known film-forming resin composition containing an ultraviolet curable resin and a photo-radical polymerization initiator can be used. Can be used.

The above-mentioned ultraviolet-curable resin includes, for example, a photosensitive unsaturated group capable of crosslinking and curing the resin by irradiation with ultraviolet light, and an ion having sufficient ion to dissolve or disperse the resin in an alkaline developing solution or an acidic developing solution. An ultraviolet curable resin having a functional group (anionic group or cationic group) is used.

[0011] Examples of the photosensitive unsaturated group that can be contained in the ultraviolet curable resin include an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, and an allyl group. Examples of the ionic group include, for example, a carboxyl group as a representative example of the anionic group, and the content of the carboxyl group is usually about 1 to about the acid value of the resin.
0-700 mgKOH / g, especially about 20-600 mgK
OH / g is preferred. As the cationic group,
An amino group is mentioned as a typical example, and the content of the amino group is preferably in the range of usually about 20 to 650, particularly about 30 to 600 in terms of the amine value of the resin.

As the anionic ultraviolet curable resin,
For example, a resin obtained by reacting an unsaturated monomer such as glycidyl (meth) acrylate with a carboxyl group-containing resin (polycarboxylic acid resin) to introduce an unsaturated group and a carboxyl group into the resin.

The cationic UV-curable resin includes, for example, a resin having a hydroxyl group and a tertiary amino group,
A resin obtained by subjecting a reaction product of a hydroxyl group-containing unsaturated compound and a diisocyanate compound to an addition reaction is exemplified.

The above-mentioned anionic and cationic ultraviolet-curable resins are described in JP-A-3-223759 (= US Pat. No. 5,045,434). Instead of a simple description.

Examples of the photo-radical polymerization initiator include, for example,
Aromatic carbonyl compounds such as benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzylxanthone, thioxanthone and anthraquinone; acetophenone, propiophenone, α-hydroxyisobutylphenone, α, α′-dichloro-4-phenoxyacetophenone, 1-hydroxy Acetophenones such as -1-cyclohexylacetophenone and diacetylacetophenone; benzoyl peroxide, t-
Butylperoxy-2-ethylhexanoate, t-butyl hydroperoxide, di-t-butyldiperoxyisophthalate, 3,3 ′, 4,4′-tetra (t
Organic peroxides such as -butylperoxycarbonyl) benzophenone; diphenylhalonium salts such as diphenyliodobromide and diphenyliodonium chloride; organic halides such as carbon tetrabromide, chloroform and iodoform; 3-phenyl-5-isoxazolone , 2,4,6-tris (trichloromethyl) -1,
Heterocyclic and polycyclic compounds such as 3,5-triazine and benzanthrone; 2,2′-azo (2,4-dimethylvaleronitrile), 2,2-azobisisobutyronitrile, 1,1 ′ Azo compounds such as -azobis (cyclohexane-1-carbonitrile) and 2,2'-azobis (2-methylbutyronitrile); iron-allene complexes (EP-A
-152377); titanocene compounds (JP-A-63
No. 221110 (= US Pat. No. 5,011,75)
No. 5)) Bisimidazole compounds; N-arylglycidyl compounds; acridine compounds; combinations of aromatic ketones / aromatic amines; peroxyketals (see JP-A-6-321895). Among the above radical photopolymerization initiators, di-t-
Butyldiperoxyisophthalate, 3,3 ', 4
Since 4'-tetra (t-butylperoxycarbonyl) benzophenone, iron-allene complex and titanocene compound generally have high activity for crosslinking or polymerization, they are preferably used.

Examples of commercially available products include Irgacure 651 (trade name, acetophenone-based photo-radical polymerization initiator, manufactured by Ciba Geigy), Irgacure 184 (trade name, acetophenone-based photo-radical polymerization initiator, manufactured by Ciba-Geigy), Irgacure 1850 (Ciba-Geigy, trade name, acetophenone-based photoradical polymerization initiator), Irgacure 907 (Ciba-Geigy, trade name, aminoalkylphenone-based photoradical polymerization initiator), Irgacure 369 (Ciba-Geigy, trade name, Aminoalkylphenone-based photo-radical polymerization initiator), lucilin TPO (trade name, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide), Kayacure DETX-S (Nippon Kayaku Co., Ltd.)
Manufacture, trade name, thioxanthone compound), CGI-78
4 (manufactured by Ciba-Geigy Corporation, trade name, titanium complex compound) and the like. These can be used alone or in combination of two or more.

The mixing ratio of the photo-radical polymerization initiator is generally 0.1 to 25 per 100 parts by weight of the ultraviolet curable resin.
Parts by weight, preferably in the range of 0.2 to 10 parts by weight.

The resin composition for forming the ultraviolet-sensitive coating layer (A-1) may optionally contain a saturated resin. The saturated resin is used to suppress the solubility of the resin composition (the solubility of the resist film in an alkali developing solution or the solubility used in removing a photocured film, for example, the solubility in a strong alkaline solution). For example, polyester resin, alkyd resin, (meth) acrylic resin, vinyl resin, epoxy resin, phenol resin, natural resin, synthetic rubber, silicone resin, fluororesin,
Polyurethane resins and the like are included. These resins can be used alone or in combination of two or more.

The resin composition can be dissolved or dispersed in a solvent such as an organic solvent, water or a mixture thereof and applied to the surface of a substrate. Examples of the organic solvent include ketones, esters, ethers, cellosolves, aromatic hydrocarbons, alcohols, halogenated hydrocarbons, and the like. The resin composition dissolved or dispersed in a solvent is, for example, a roller,
It can be applied by means such as a roll coater, a spin coater, a curtain roll coater, spray, electrostatic coating, dip coating, silk printing, spin coating and the like. The coating film to be formed is then set as necessary,
For example, by drying at a temperature of about 50 to about 130 ° C., a negative type ultraviolet-sensitive resin coating layer (A-1) can be obtained.

The aqueous negative-type ultraviolet-sensitive resin composition can be obtained by dissolving or dispersing the above-mentioned negative-type ultraviolet-sensitive resin composition in water.

The water-soluble or water-dispersible negative UV-sensitive resin composition is obtained by neutralizing an anionic group (for example, a carboxyl group) in the UV-curable resin with an alkali (neutralizing agent), or This is performed by neutralizing a cationic group (for example, an amino group) in the ultraviolet-curable resin composition with an acid (neutralizing agent).

In addition to the above, a conventionally known water-developable ultraviolet-curable resin composition can be used as the negative-type ultraviolet-sensitive resin composition. Examples of such a resin include an aqueous resin obtained by introducing an ultraviolet-curable unsaturated group and an ion-forming group into a novolak phenol type epoxy resin. The aqueous resin, for example,
Photopolymerization is imparted to the resin by adding (meth) acrylic acid to some epoxy groups of the novolak phenol type epoxy resin, and a reaction of at least some other epoxy groups with a tertiary amine compound, for example. To form a water-soluble onium base. In the aqueous resin thus obtained, the portion exposed to ultraviolet light hardens and becomes insoluble in water, and the unexposed portion is removed by water development. In addition, the coating film can be made hydrophobic by heating after water development (for example, at about 140 to 200 ° C. for 10 to 30 minutes) to volatilize the ion-forming groups remaining in the cured coating film. Thereby, like a resist coating film formed from the above-described alkali-developable and acid-developable photosensitive composition, a hydrophilic group (carboxyl group,
It is possible to form a film having excellent resist properties without amino groups or the like (salts by a developer). In addition to the novolak phenol type epoxy resin, for example, homopolymers of epoxy group-containing radically polymerizable unsaturated monomers such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylalkyl (meth) acrylate, and vinyl glycidyl ether; Copolymers of one or more monomers with other radically polymerizable unsaturated monomers (eg, alkyl or cycloalkyl (meth) acrylates having 1 to 24 carbon atoms, radically polymerizable unsaturated aromatic compounds, etc.) In the same manner as described above, an aqueous polymer obtained by reacting (meth) acrylic acid with, for example, a tertiary amine compound can also be used.

Negative UV-sensitive resin coating layer (A-1)
Is performed using an alkaline developer when the negative type ultraviolet-sensitive resin composition forming the coating layer is anionic, and using an acidic developer when the negative type ultraviolet-sensitive resin composition is cationic. Done. In the case where the resin itself is soluble in water (for example, the above-mentioned onium base-containing resin or the like), a water development treatment can be performed.

Further, a negative type ultraviolet-sensitive resin coating layer (A
-1) may be electrically conductive or insulative in itself. Thus, in order to impart conductivity or insulation to the coating, the ultraviolet-sensitive resin composition may be optionally provided with a conductive material. Conductive materials (conventionally known conductive pigments such as silver, copper,
Metals such as iron, manganese, nickel, aluminum, cobalt, chromium, lead, zinc, bismuth and ITO, one or more of these alloys and their oxides, and these conductive materials are coated on the surface of the insulating material. Or, an insulating material (plastic fine powder, insulating inorganic powder, etc.) can be compounded. The insulating film usually has a volume resistivity of 1 to be finally formed.
More than ⁰⁹ Ω · cm, especially 10 ¹⁰ Ω · cm to 10
^In the range of ¹⁸ Ω · cm, the conductive coating usually has a volume resistivity of 10 ⁹ Ω of the finally formed coating.
・ Cm, particularly preferably in the range of 1 Ω · cm to 10 ⁸ Ω · cm.

On the other hand, a positive type ultraviolet-sensitive resin coating layer (A
As the resin composition forming -2), for example, a resin composition containing a photoacid generator component and a resin component can be used. The resin component is decomposed by an acid generated from the photoacid generator component upon irradiation with ultraviolet rays, thereby changing the physical properties such as the polarity and molecular weight of the resin component, whereby an alkaline or acidic aqueous developer, a water developer, an organic solvent A film-forming resin which becomes soluble in a developing solution such as a developing solution is used. The resin composition may further contain other resins for adjusting the solubility in a developing solution, if necessary.

As the resin component used in the positive type ultraviolet-sensitive resin composition, for example, quinonediazidesulfonic acid is bonded to a base resin such as an acrylic resin having an ion-forming group via a sulfonic ester bond. Composition containing resin as a main component (Japanese Patent Laid-Open No. 61-20629)
No. 3 (= U.S. Pat. No. 4,673,458) and JP-A-7-133449 (= U.S. Pat.
No. 781), that is, a naphthoquinonediazide-sensitive energy ray composition utilizing a reaction in which a quinonediazide group is photolyzed by irradiation with ultraviolet light to form indenecarboxylic acid via ketene; Or to form a crosslinked film insoluble in acidic developer,
Further, a positive active energy ray-sensitive composition utilizing a mechanism in which a crosslinked structure is cut by an acid generated from a photoacid generator by ultraviolet irradiation so that an irradiated portion becomes soluble in an alkaline developing solution or an acidic developing solution (Japanese Unexamined Patent Application Publication No. 6-2950
No. 64, JP-A-6-308733, JP-A-6-308733
No. 3,313,134 (= US Pat. No. 5,527,65)
No. 6), JP-A-6-313135 (= U.S. Pat. Nos. 5,527,656 and 5,702,872).
JP-A-6-313136 (= U.S. Pat. Nos. 5,527,656 and 5,702,872).
No.) and JP-A-7-146552)). Since the above-mentioned positive type ultraviolet-sensitive resin is described in the above-mentioned publication, the detailed description will be replaced with the citation here.

The photoacid generator is a compound which generates an acid upon exposure to light and decomposes the resin using the generated acid as a catalyst. Conventionally known photoacid generators can be used. Specifically, for example, a sulfonium salt,
Onium salts such as ammonium salts, phosphonium salts, iodonium salts and selenium salts, iron-allene complexes, ruthenium allene complexes, silanol-metal chelate complexes, triazine compounds, diazidonaphthoquinone compounds, sulfonic acid esters, sulfones Examples thereof include acid imide esters and halogen compounds. Further, in addition to the above, JP-A-7-146552,
Photoacid generators described in JP-A-11-237731 can also be used. The photoacid generator component may be in the form of a mixture with the above-described resin, or may be bonded to the resin body. The mixing ratio of the photoacid generator component is generally about 0.1 to about 40 parts by weight, preferably about 0.2 to about 20 parts by weight, based on 100 parts by weight of the resin component.

The resin composition is dissolved or dispersed in a solvent such as an organic solvent, water or a mixture thereof and applied to the surface of a substrate. Examples of the organic solvent include ketones, esters, ethers, cellosolves, aromatic hydrocarbons, alcohols, halogenated hydrocarbons, and the like. The resin composition dissolved or dispersed in a solvent may be applied by, for example, a roller, a roll coater, a spin coater, a curtain roll coater, a spray, an electrostatic coating, a dip coating, a silk printing, a spin coating, or the like. Can be. The coating film to be formed is then set, if necessary, and then dried at a temperature of, for example, about 50 to about 130 ° C., to obtain a positive-type ultraviolet-sensitive resin coating layer (A-2). .

The aqueous positive-type ultraviolet-sensitive resin composition can be obtained by dissolving or dispersing the above-mentioned positive-type ultraviolet-sensitive resin composition in water.

The water-soluble or water-dispersible positive UV-sensitive resin composition is prepared by neutralizing an anionic group (for example, a carboxyl group) in the resin with an alkali (neutralizing agent) or in the resin. This is performed by neutralizing a cationic group (for example, an amino group) with an acid (neutralizing agent).

Positive UV-sensitive resin coating layer (A-2)
Is carried out using an alkali developer when the positive-type ultraviolet-sensitive resin composition forming the coating layer is anionic, and using an acid developer when it is cationic. Done. In addition, those in which the resin itself dissolves in water (for example, an onium base-containing resin or the like) can be subjected to water development treatment.

Further, a positive type ultraviolet-sensitive resin coating layer (A
-2) may be conductive or insulating in itself. Thus, in order to impart conductivity or insulation to the film, a conductive material may be added to the ultraviolet-sensitive resin composition, if necessary. (Conventionally known conductive pigments such as silver, copper, iron, manganese, nickel, aluminum, cobalt, chromium,
Metals such as lead, zinc, bismuth, and ITO, one or more of these alloys and their oxides, and those in which these conductive materials are coated or vapor-deposited on the surface of an insulating material; Plastic fine powder, insulating inorganic powder, etc.). The insulating coating usually has a volume resistivity of 10 ⁹ Ω of the finally formed coating.
.Cm, especially 10 ¹⁰ Ω · cm to 10 ¹⁸ Ω
cm, while the conductive coating usually has a volume resistivity of the final coating film of less than 10 ⁹ Ω · cm, especially in the range of 1 Ω · cm to 10 ⁸ Ω · cm. Some are preferred.

The thickness of the negative or positive type ultraviolet-sensitive resin coating layer (A) described above is not strictly limited, and may be appropriately selected according to the use of the final laminate. In general, the thickness is preferably in the range of about 1 μm to about 5 mm, particularly preferably about 2 μm to about 500 μm.

The ultraviolet-permeable sheet layer (B) used in the laminate of the present invention is a resin sheet that transmits at least about 90%, preferably about 99% or more of ultraviolet rays to be irradiated. The material and the like are not particularly limited, and those known per se can be used. For example, polyethylene terephthalate, polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, cellulosic,
A sheet made of a polymer such as polyurethane, polyacrylate, aramid, Kapton, polymethylpentene, polyethylene, and polypropylene can be used, and it is particularly preferable to use a polyethylene terephthalate sheet. The thickness of the sheet layer (B) is usually about 1
It is preferably in the range from 0 μm to about 5 mm, especially from about 15 μm to about 500 μm.

The energy-sensitive coating layer (C) for shielding ultraviolet rays used in the laminate of the present invention is formed on the surface of the sheet layer (B) and becomes the uppermost layer. When an active energy ray is irradiated from the upper surface of the coating layer (C), and then the coating layer (C) is developed, a pattern is formed on the coating layer (C), and then the patterned surface of the coating layer (C) is formed. When irradiated with ultraviolet light from above, the coating layer (C) blocks (absorbs and / or reflects) the ultraviolet light, so that the lower ultraviolet-sensitive resin coating layer (A) corresponds to the pattern formed on the coating layer (C). This is a layer provided to form a positive or negative pattern.

As described above, the energy-sensitive radiation coating layer (C) shields (absorbs and / or reflects) the ultraviolet rays emitted from the upper surface of the coating layer (C), thereby forming the lower layer by the irradiation of ultraviolet rays. The film layer (A) serves to prevent a substantial change (hardening or decomposition) of the film layer (A), and at the same time, irradiates water, an organic solvent,
A substance which becomes soluble or dispersible in a treatment liquid such as an alkali or an acid and can form the same pattern as desired by being incorporated into the coating layer (A), or water by irradiation with the active energy ray itself. , Organic solvents, alkalis,
It becomes insoluble or non-dispersible in a treatment liquid such as an acid and can form the same pattern as desired for the coating layer (A).

As the energy-sensitive radiation coating layer (C), a layer absorbing ultraviolet rays, for example, a layer containing an ultraviolet absorber, a coloring agent (color pigment, coloring dye, etc.), a filler or the like in the coating layer is used. Can be used.

As the above-mentioned ultraviolet absorber, specifically,
For example, benzophenones such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone; 2 (2'hydroxy-5-methylphenyl)
Benzotriazoles such as benzotriazole; anilide oxalates; ultraviolet absorbers such as cyanoacrylates; and others, BEDNERET et al., Farbe + Lacke, 89, 84
0 (1983); HJ HELLER et al., Pure and Applied, Ch
em, 30, 145 (1972); Ibid, 36, 141 (1973); A. VALET, F
arbe + Lacle, 96, 189 (1990) and the like.

Examples of the coloring agent include titanium oxide, zinc white, lead white, basic lead sulfate, lead sulfate, lithopone,
White pigments such as zinc sulfide and antimony white; black pigments such as carbon black, acetylene black, lamp black, bone black, graphite, iron black, and aniline black; orange pigments such as naphthol yellow S, Hansa yellow 10G, permanent yellow and permanent orange ;
Brown pigments such as iron oxide and amber; red pigments such as red iron oxide, lead red, permanent red, and quinacridone red pigments; purple pigments such as cobalt purple, manganese purple, fast violet B, and methyl violet lake;
Blue pigments such as navy blue, cobalt blue, cerulean blue, phthalocyanine blue, and fast sky blue; and green pigments such as chrome green and phthalocyanine green.

As the filler, for example, barita powder,
Precipitated barium sulfate, barium carbonate, calcium carbonate,
Examples include gypsum, clay, silica, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, and mica powder.

The proportions of the ultraviolet absorbers, coloring agents and fillers to be used can be appropriately selected according to the intensity of the ultraviolet rays to be irradiated, the thickness of the energy-sensitive ray coating layer (C), etc. Usually, in the case of an ultraviolet absorber, 0.01% by weight to 50% by weight, preferably 0.02% by weight based on the coating layer (C).
% To 30% by weight, and in the case of a colorant and a filler, 0.5% to 90% by weight based on the coating layer (C).
%, Preferably in the range of 1% to 50% by weight.

As the energy-sensitive ray coating layer (C) for shielding ultraviolet rays, a layer containing a reflecting agent for reflecting ultraviolet rays (flake metal pigment or the like) or the like can be used.

Examples of the above-mentioned reflecting agent include (scale-like)
Metal powder pigments such as aluminum powder, bronze powder, copper powder, tin powder, lead powder, zinc powder, iron phosphide, pearl-like metal-coated mica powder, and mica-like iron oxide, and metallic luster pigments.

The proportion of the reflecting agent used can be appropriately selected according to the intensity of the ultraviolet ray to be irradiated, the thickness of the energy-sensitive coating layer (C), and the like. It is desirably in the range of 0.5% to 90% by weight, preferably 1% to 50% by weight.

The above-mentioned ultraviolet absorbers and reflectors can be used in combination.

The resin for forming the energy-sensitive ray coating layer (C) may be either a negative type or a positive type, and the energy-sensitive rays to be irradiated include ultraviolet rays, visible rays, electron rays and heat rays. Any one may be used.

As the negative type and positive type ultraviolet-sensitive type, the same type as the resin composition for forming the coating layer (A) can be used.

As the negative-type and positive-type visible light-sensitive types, those obtained by blending a photosensitizer with the resin composition described above for forming the coating layer (A) may be used. it can. As the photosensitizer, conventionally known photosensitizing dyes can be used, and specifically, for example, thioxanthene-based, xanthene-based, ketone-based, thiopyrylium salt-based, basestyryl-based, merocyanine-based ,
3-substituted coumarins, 3.4-substituted coumarins, cyanines, acridines, thiazines, phenothiazines,
Anthracene, coronene, benzanthracene,
Dyes of perylene type, ketocoumarin type, fumaline type, borate type and the like can be mentioned. These are one or two
It can be used in combination of more than one species. Examples of the borate-based photosensitizing dye include, for example, JP-A-5-241338.
And Japanese Patent Application Laid-Open No. 7-5885 (= U.S. Pat.
498,641) and JP-A-7-225474 (= U.S. Pat. No. 5,498,641). The mixing ratio of these photosensitizers can be in the range of about 0.1 to 20% by weight, preferably about 0.2 to 10% by weight, based on the coating layer (C) (solid content).

The heat-sensitive resin composition is a composition containing a resin which is crosslinked or decomposed by heat rays such as infrared rays. As the resin composition, a conventionally known resin composition can be used. For example, a combination of a hydroxyl group-containing resin / amino resin, a combination of a hydroxyl group-containing resin / blocked isocyanate, a melamine resin, a silicon resin or an acrylic resin containing a hydrolyzable group (eg, an alkoxysilyl group, a hydroxysilyl group, etc.), epoxy Combination of resin / phenolic resin, combination of epoxy resin / (anhydride) carboxylic acid, combination of epoxy resin / polyamine,
Examples thereof include a combination of an unsaturated resin and a radical polymerization catalyst (for example, peroxide and the like), and an olefinically unsaturated compound containing a carboxyl group and / or a hydroxyphenyl group and an ether bond. In addition, a thermal acid generator (for example, the same as the above-mentioned photoacid generator) may be blended with these to be used as a positive type.

The resin composition forming the energy-sensitive radiation coating layer (C) can be dissolved or dispersed in, for example, an organic solvent, water or a mixture thereof and applied to the surface of the sheet layer (B). .

Examples of the above-mentioned organic solvent include ketones, esters, ethers, cellosolves, aromatic hydrocarbons, alcohols, halogenated hydrocarbons and the like. Can be performed by, for example, a roller, a roll coater, a spin coater, a curtain roll coater, spray, electrostatic coating, dip coating, silk printing, spin coating, or the like. Then, after setting as necessary, for example, about 50 to
By drying at a temperature of about 130 ° C., the energy-sensitive radiation coating layer (C) can be obtained.

The thickness of the energy-sensitive radiation coating layer (C) is usually about 1 μm to about 500 μm, especially about 2 μm to about 100 μm.
It is preferably in the range of μm.

A cover coat layer can be provided on the surface of the energy-sensitive coating layer (C) of the laminate thus formed, if necessary. This cover coat layer is effective for blocking oxygen in the air to prevent radicals generated by exposure from being deactivated by oxygen, and to smoothly cure the photosensitive material by exposure. Such a cover coat layer is made of, for example, a resin film (thickness of about 1 to about 70 μm) of polyester resin such as polyethylene terephthalate, acrylic resin, polyethylene, polyvinyl chloride resin and the like.
m) on the surface of the laminate to form polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl alcohol-vinyl acetate copolymer, partially saponified polyvinyl acetate-vinyl acetate copolymer, polyvinyl pyrrolidone Aqueous liquid containing or dispersing in water water-soluble resins such as acrylic resins, polyester resins, vinyl resins, and epoxy resins containing water-soluble polysaccharide polymers such as pullulan, basic groups, acidic groups or bases Is applied to the surface of the laminate (dry film thickness: about 0.5 to about 5 μm) and dried.

The laminate for pattern formation of the present invention can be produced, for example, by any one of the following methods 1 to 4.

1. A negative or positive type ultraviolet-sensitive resin coating layer (A) is formed on the surface of the substrate, a sheet layer (B) that transmits ultraviolet light is formed, and an energy-sensitive ray coating layer (C) that blocks ultraviolet light is further formed. A method consisting of laminating: The coating layer (A) is formed by coating or laminating a resin composition for forming the coating layer (A) as described above on the surface of the base material, or from the resin composition. Can be formed by adhering a film formed on a substrate surface via a photosensitive or heat-sensitive adhesive (adhesive) layer, and the sheet layer (B) is formed on the surface of the film layer (A). The sheet as described above can be thermally laminated, or the sheet can be attached to the coating layer (A) via a pressure-sensitive or heat-sensitive adhesive (adhesive) layer. Further, the energy-sensitive ray coating layer (C) is formed by coating or laminating a resin composition for forming the energy-sensitive ray coating layer (C) on the surface of the sheet layer (B), or by coating the resin composition. Film-sensitive or heat-sensitive adhesive (adhesive)
It can be laminated by attaching to the sheet layer (B) via a layer.

2. A negative or positive type UV-sensitive resin coating layer (A) is formed on the surface of the base material, and then a UV-transmitting sheet layer (B) formed on the surface of the coating layer (A) is coated with the UV light. A method comprising laminating such that the surface on the sheet layer (B) side of the two-layer laminate with the energy-sensitive ray coating layer (C) to be shielded and the coating layer (A) are in contact with each other: the coating layer (A) Can be formed on the surface of the substrate in the same manner as in the above method 1. The two-layer laminate provided on the coating layer (A) is obtained by coating or laminating a resin composition for forming the energy-sensitive radiation coating layer (C) on one surface of the sheet layer (B), or It can be obtained by attaching a film made of the composition via a photosensitive or heat-sensitive adhesive (adhesive) layer. Further, the lamination of the surface of the laminate on the sheet layer (B) side to the coating layer (A) can be performed by, for example, a heat lamination method or a method using a pressure-sensitive or heat-sensitive adhesive (adhesive) layer. it can.

3. Three layers of a negative or positive type ultraviolet-sensitive resin coating layer (A), a sheet layer that transmits ultraviolet rays (B), and an energy-sensitive ray coating layer that blocks ultraviolet rays (C) formed on the surface of the base material in advance. A method of laminating so that the surface of the laminate on the side of the coating layer (A) and the surface of the substrate are in contact with each other: the negative or positive type ultraviolet-sensitive resin coating layer (A);
The three-layer laminate of a sheet layer (B) that transmits ultraviolet light and an energy-sensitive coating layer (C) that shields ultraviolet light is, for example,
After coating the resin composition for forming the coating layer (A) on one surface of the sheet layer (B) and drying as necessary, a coating layer (C) is formed on the other surface of the sheet layer (B). It can be produced by coating the resin composition (the coating order of the coating layer (A) and the coating layer (C) may be reversed). Further, lamination of the three-layer laminate on the surface of the substrate on the side of the coating layer (A) can be performed by, for example, a thermal lamination method.

4. A surface on the coating layer (A) side of a two-layer laminate of a negative or positive type ultraviolet-sensitive resin coating layer (A) and a sheet layer (B) that transmits ultraviolet light formed on the surface of the base material in advance. And laminated so that the substrate surface is in contact,
Next, a method comprising forming an energy-sensitive coating layer (C) for shielding ultraviolet rays as described above on the surface of the resulting three-layer laminate on the sheet layer (B) side: negative or positive ultraviolet light sensitivity The two-layer laminate of the resin coating layer (A) and the sheet layer (B) that transmits ultraviolet light is obtained by, for example, painting a resin composition that forms the coating layer (A) on the surface of the sheet layer (B). be able to. The lamination of the two-layer laminate on the surface of the substrate on the side of the coating layer (A) can be performed, for example, by a thermal lamination method. Further, the coating layer (C) may be formed by coating or laminating the resin composition forming the coating layer, or by applying a heat-sensitive or heat-sensitive adhesive (adhesive) to the coating made of the resin composition. It can be performed by pasting through a layer.

The pattern formation using the laminate of the present invention produced as described above may be performed, for example, by the following step (i): The active energy ray is irradiated through a mask or directly according to a pattern, and (ii) the energy-sensitive ray coating layer (C) is developed to remove the irradiated or non-irradiated portion of the coating layer (C). After forming a pattern film, (iii) then irradiating the entire surface with ultraviolet rays, (iv)
The ultraviolet-sensitive resin coating layer (A) is removed from the ultraviolet-sensitive resin coating layer (A) of the laminate except for the sheet layer (B) and the energy-sensitive radiation coating layer (C) that transmit ultraviolet light.
And (v) Then, the coating layer (A) is developed with a developing solution.

The light source used for the active energy ray irradiation includes, for example, an ultrahigh pressure, high pressure, medium pressure or low pressure mercury lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, tungsten lamp, etc., and argon laser. (488 nm), YAG-SHG laser (5
Laser (wavelength of oscillation line in parentheses) such as UV laser (351 nm to 364 nm). Examples of the heat ray source include a semiconductor laser (830 nm), a YAG laser (1.06 μm), and infrared rays.

As the light source for irradiating ultraviolet rays, those conventionally used, for example, ultrahigh-pressure, high-pressure, medium-pressure or low-pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, fluorescent lamps, Each light source such as a tungsten lamp and sunlight can be used.

The development processing of the coating (A) and the coating (C)
When the coating is anionic, the coating is performed using an alkaline developer, and when the coating is cationic, the coating is performed using an acidic developer. Further, depending on the properties of the film, development can be performed using an organic solvent or water.

In the development processing, for example, the developer is heated at a solution temperature of about 10 to about 80 ° C., preferably about 15 to about 50 ° C. for about 1 hour.
It can be performed by spraying or dipping for 0 seconds to about 60 minutes, preferably for about 30 seconds to about 30 minutes.

Examples of the alkaline developer include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, and the like.
Monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, diethylaminoethanol, ammonia, caustic soda, caustic potash, sodium metasilicate, potash metasilicate, carbonic acid Aqueous liquids such as soda and tetraethylammonium hydroxide.

Examples of the acidic developer include aqueous solutions of formic acid, crotonic acid, acetic acid, propionic acid, lactic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like.

Examples of the organic solvent include hydrocarbons such as hexane, heptane, octane, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, and trichloroethylene; alcohols such as methanol, ethanol, propanol and butanol; diethyl ether; Ethers such as dipropyl ether, dibutyl ether, ethyl vinyl ether, dioxane, propylene oxide, tetrahydrofuran, cellosolve, methyl cellosolve, butyl cellosolve, methyl carbitol, diethylene glycol monoethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone Ketones, such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc., pyridine, formamide , N, other solvents such as N- dimethylformamide.

The laminate for pattern formation of the present invention includes, for example, a black matrix pattern, a color filter pattern, an electronic component coating pattern (solder coating), a ceramic or phosphor pattern, a display panel partition pattern and the like. The present invention can be applied to the formation of a pattern formed on the surface of a base material, an insulating base material such as a wiring plastic substrate, a build-up plastic substrate, and the like, and a conductive pattern provided thereon.

The present invention will be described more specifically with reference to examples. Parts and percentages are by weight unless otherwise specified.

[0069]

EXAMPLES Production Examples of Energy- Sensitive Radiation Composition a As an energy-ray-curable resin (polymer binder),
Acrylic resin (resin acid value 155 mg KOH / g, methyl methacrylate / butyl acrylate / acrylic acid = 4
(0/40/20 weight ratio) 60 parts of glycidyl methacrylate reacted with 24 parts of an ultraviolet curable resin (resin solid content 55%, propylene glycol monomethyl ether organic solvent, resin acid value 50 mg KOH / g, number average molecular weight about 2) 100 parts (solid content), 1 part of a photoradical polymerization initiator (CGI-784, trade name, manufactured by Ciba Geigy, titanocene compound), and an ultraviolet absorber (Tinuvin 326, trade name, manufactured by Ciba Specialty Chemicals) Benzotriazole-based composition a (solid content 1)
5%).

Production Example of UV-Sensitive Composition b As an ultraviolet-curable resin (polymer binder), an acrylic resin (resin acid value: 155 mg KOH / g, methyl methacrylate / butyl acrylate / acrylic acid = 40/4)
(0/20 weight ratio) 60 parts of glycidyl methacrylate 2
4 parts of a photocurable resin (resin solid content 55
%, Propylene glycol monomethyl ether organic solvent, resin acid value 50 mgKOH / g, number average molecular weight about 2
100 parts (solid content), 10 parts of a photoradical polymerization initiator (Irgacure 907, trade name, manufactured by Ciba Geigy, acetophenone compound) and 10 parts of a photoradical polymerization initiator (Kayacure DETX-S, trade name, Nippon Kayaku Co., Ltd.) 1 part of thioxanthone-based compound), 1 part of phthalocyanine green, 50 parts of talc and 20 parts of epoxy resin (Epicoat 828, trade name, Yuka Shell Co., bisphenol A type liquid epoxy resin) The composition was dissolved in a diethylene glycol dimethyl ether solvent to obtain a composition b (solid content: 30%).

Example 1 (1) An ultraviolet-sensitive composition b was coated on a copper foil (200 × 200 × 1.1 mm) with a bar coater,
Preliminary drying was performed for 0 minutes to form an ultraviolet-sensitive resin coating layer (I) having a thickness of about 30 μm. Next, a polyethylene terephthalate sheet (38 μm) was adhered to the surface of the formed film to obtain a sheet layer (II). Next, the energy-sensitive ray composition a was roller-coated so that the dry film thickness became 6 μm, and dried at 65 ° C. for 10 minutes to form an energy-sensitive ray coating layer (III). (2) Next, the coating layer (III) was directly irradiated with an argon ion laser (5 mj / cm ² ) in a pattern to expose. Then, it was immersed in an alkali developer a (aqueous sodium carbonate solution: 0.25%) at 25 ° C. for 60 seconds to remove the coating layer (III) on the exposed portion. (3) Then, a super-high pressure mercury lamp (300 mj
/ Cm ² ). (4) Next, the energy-sensitive ray coating layer (III) and the sheet layer (II) are peeled off from the ultraviolet-sensitive resin coating layer (I) to form a laminate of a copper foil and the ultraviolet-sensitive resin coating layer (I). I got (5) Next, the laminate was immersed in a 0.75% aqueous sodium carbonate solution at 25 ° C. for 60 seconds to remove the uncured (unexposed portion) ultraviolet-sensitive resin coating layer (I). The obtained pattern is line (pattern width) / space = 100 μm
It was patterned into a stripe pattern of / 20 μm, which was good.

Example 2 Energy Sensitive Radiation Coating Layer (III) and Sheet Layer (II)
Was carried out in the same manner as in Example 1 except that the above-mentioned was laminated in advance on the ultraviolet-sensitive resin coating layer (I). The obtained pattern was patterned in a stripe shape of line (pattern width) / space = 100 μm / 20 μm, and was good.

Example 3 An energy-sensitive coating layer (III) was formed after laminating an ultraviolet-sensitive resin coating layer (I) and a sheet layer (II) in advance on a substrate. The same processing as in No. 1 was performed. The obtained pattern was patterned in a stripe shape of line (pattern width) / space = 100 μm / 20 μm, and was good.

Example 4 The same procedure as in Example 1 was carried out except that a laminate of the ultraviolet-sensitive resin coating layer (I), the sheet layer (II) and the energy-sensitive radiation coating layer (III) was laminated on the substrate. Processing was performed. The obtained pattern is line (pattern width) /
The pattern was formed in a stripe pattern of space = 100 μm / 20 μm, which was good.

Comparative Example 1 A laminate was formed and developed in the same manner as in Example 1 except that the coating layer (III) did not contain an ultraviolet absorber. As a result, all of the films obtained had poor line survivability and poor space developability.

Comparative Example 2 A laminate was formed and developed in the same manner as in Example 2 except that the coating layer (III) did not contain an ultraviolet absorber. As a result, all of the films obtained had poor line survivability and poor space developability.

Comparative Example 3 A laminate was formed and developed in the same manner as in Example 3 except that the coating layer (III) did not contain an ultraviolet absorber. As a result, all of the films obtained had poor line survivability and poor space developability.

Comparative Example 4 A laminate was formed and developed in the same manner as in Example 4 except that the coating layer (III) did not contain an ultraviolet absorber. As a result, all of the films obtained had poor line survivability and poor space developability.

Continuing from the front page (72) Inventor Takanobu Komatsu 4-171-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Paint Inside Kansai Paint Co., Ltd. (72) Inventor Genji 4-171-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Paint Kansai Paint In-house F term (reference) 2H025 AA20 AB15 AB20 AC01 AC08 AD01 AD03 BC13 BC73 BC83 BC86 BE00 BE02 CA18 CA39 CB41 CC02 CC08 CC11 DA01 DA13 DA14 DA33 DA40 FA06 FA17 FA30 FA39 2H096 AA26 AA30 BA06 BA10 CA20 EA04 GA08 HA03 HA30

Claims (24)

[Claims] 1. A negative or positive type ultraviolet-sensitive resin coating layer (A), a sheet layer (B) that transmits ultraviolet rays, and an energy-sensitive ray coating layer (C) that blocks ultraviolet rays are sequentially formed on a substrate surface. A laminate for forming a pattern, characterized by being laminated. 2. The negative-type ultraviolet-sensitive resin coating layer (A-), wherein the ultraviolet-sensitive resin coating layer (A) is formed from a film-forming resin composition containing an ultraviolet-curable resin and a photo-radical polymerization initiator. The laminate according to claim 1, which is 1). 3. The ultraviolet-curable resin is a resin having a photosensitive unsaturated group capable of crosslinking and curing the resin by irradiation with ultraviolet light and an ionic group sufficient for dissolving or dispersing the resin in an alkaline or acidic developer. The laminate according to claim 2. 4. A photo-radical polymerization initiator comprising di-t-butyldiperoxyisophthalate, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, an iron-allene complex and a titanocene compound The laminate according to claim 2, which is selected from the group consisting of: 5. The laminate according to claim 2, wherein the photo-radical polymerization initiator is contained within a range of 0.1 to 25 parts by weight based on 100 parts by weight of the ultraviolet curable resin. 6. The UV-sensitive resin coating layer (A) according to claim 1, wherein the UV-sensitive resin coating layer comprises an aqueous resin obtained by introducing a UV-curable unsaturated group and an ion-forming group into a novolak phenol type epoxy resin. Laminate. 7. A positive-type ultraviolet-sensitive resin coating layer (A-2) wherein the ultraviolet-sensitive resin coating layer (A) is formed from a resin composition containing a photoacid generator component and a resin component. The laminate according to claim 1, which is: 8. The laminate according to claim 7, wherein the resin component is a resin in which quinonediazidesulfonic acid is bonded to a base resin having an ion-forming group via a sulfonic ester bond. 9. The laminate according to claim 7, wherein the photoacid generator component is contained in the range of 0.1 to 40 parts by weight based on 100 parts by weight of the resin component. 10. The laminate according to claim 1, wherein the ultraviolet-sensitive resin coating layer (A) is conductive or insulating. 11. An ultraviolet-sensitive resin coating layer (A) comprising about 1
The laminate according to claim 1, having a thickness of from about μm to about 5 mm. 12. The laminate according to claim 1, wherein the sheet layer (B) transmitting the ultraviolet rays comprises a resin sheet that transmits at least about 90% of the irradiated ultraviolet rays. 13. The laminate according to claim 1, wherein the sheet layer (B) that transmits ultraviolet light comprises a polyethylene terephthalate sheet. 14. The laminate according to claim 1, wherein the sheet layer (B) that transmits ultraviolet light has a thickness of about 10 μm to about 5 mm. 15. The laminate according to claim 1, wherein the energy-sensitive radiation coating layer (C) comprises an ultraviolet absorber, a coloring agent, a filler, a metal powder pigment or a metal luster pigment. 16. An energy-sensitive radiation-sensitive coating layer (C) comprising a negative resin composition which becomes soluble or dispersible in a treatment liquid such as water, an organic solvent, an alkali or an acid upon irradiation with active energy rays. 2. The laminate according to 1. 17. The method according to claim 1, wherein the energy-sensitive ray coating layer (C) comprises a positive resin composition which becomes insoluble or non-dispersible in a treatment liquid such as water, an organic solvent, an alkali or an acid upon irradiation with active energy rays. Item 7. The laminate according to Item 1. 18. An energy-sensitive radiation-sensitive coating layer (C) having a thickness of about 1 μm.
2. The laminate of claim 1 having a thickness from m to about 500 [mu] m. 19. The laminate according to claim 1, further comprising a cover coat layer on the energy-sensitive radiation coating layer (C). 20. A negative- or positive-type ultraviolet-sensitive resin coating layer (A) is formed on the surface of a base material, then a sheet layer (B) that transmits ultraviolet light is formed, and further, an energy-sensitive ray coating that blocks ultraviolet light. The method according to claim 1, wherein the layers (C) are sequentially laminated. 21. A negative or positive type ultraviolet-sensitive resin coating layer (A) is formed on the surface of a base material, and then a previously formed ultraviolet-permeable sheet layer (A) is formed on the surface of the coating layer (A). B) and an energy-sensitive radiation-sensitive coating layer (C) for shielding ultraviolet rays, which is characterized in that the layer on the sheet layer (B) side and the coating layer (A) are laminated so as to be in contact with each other. The method for producing a laminate for pattern formation according to claim 1. 22. A negative- or positive-type ultraviolet-sensitive resin coating layer (A), a sheet layer (B) that transmits ultraviolet rays, and an energy-sensitive ray-coating layer that blocks ultraviolet rays (A). The method for producing a laminate for pattern formation according to claim 1, wherein the three-layer laminate (C) is laminated so as to be in contact with the surface on the coating layer (A) side and the substrate surface. 23. The coating layer of a two-layered laminate of a negative or positive type ultraviolet-sensitive resin coating layer (A) and a sheet layer (B) transmitting ultraviolet rays formed on a base material surface in advance. A) Laminated so that the side of the side and the surface of the substrate are in contact,
2. The pattern-forming laminate according to claim 1, wherein an energy-sensitive coating layer (C) for shielding ultraviolet rays is formed on the surface of the obtained three-layer laminate on the sheet layer (B) side. Method. 24. The following step (i): applying an active energy ray to the surface of the energy-sensitive coating layer (C) of the pattern-forming laminate according to claim 1 through a pattern-wise mask or (Ii) developing the energy-sensitive radiation coating layer (C) to remove the irradiated or non-irradiated portion of the coating layer (C) to form a resist pattern coating; and (iii) ultraviolet rays. And (iv) removing the sheet layer (B) and the energy-sensitive ray coating layer (C), which transmit ultraviolet rays, from the ultraviolet-sensitive resin coating layer (A) of the laminate to form an ultraviolet-sensitive resin coating. Layer (A)
And (v) developing the coating layer (A) with a developer.