JPS5983152A - Photoresist composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive color development type photoresist material, especially a photoresist material giving easily recognizable patterns in exposed and unexposed parts by adding a specified methine compound to a photosensitive resin composition contg. a photosensitive resin and a photosensitizer. CONSTITUTION:A methine compound represented by the formula (where each of R and R<1> is H or alkyl, each of X and Y is H, lower alkyl, alkoxy or amino, and A is phenyl or naphthyl) is added as an essential component to a photosensitive resin composition contg. a photosensitive resin which can be cured when irradiated with ultraviolet rays in the presence of a photosensitizer and the photosensitizer which generates radicals when irradiated with ultraviolet rays. A nonvolatile org. halide may be added furthermore. When the composition is irradiated with ultraviolet rays, the resin is cured by polymn., and at the same time, a deep color is developed, so a cured resin layer assuming a fast deep color can be obtd. Said methine compound includes 4,4'-bis(dimethylamino)-4''-(N-methyl-N- benzylamino)-triphenylmethane.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photoresist compositions using novel phototropic materials.

More specifically, photosensitizers and novel diphenyl-β-
The present invention relates to a photoresist composition containing a styrylmethane derivative, which is colored and cured by irradiation with ultraviolet rays or electron beams.

In recent years, photoresists have been widely used for various purposes. This has the advantage of shortening the process and improving productivity due to the quick curing property of photosensitive resin, the advantage of saving resources and not causing environmental pollution due to being solvent-free, and the advantage of saving energy and forming precise patterns by curing with ultraviolet rays etc. This is due to the fact that it is extremely useful in practice compared to thermosetting resins.

Photoresists having such functions have recently come to be widely used in the processing of printed circuits and the advancement of integrated circuits such as R, C, and LSI, and even higher functionality has been required.

In particular, in the manufacture of printed circuit boards, one surface of a photopolymerizable film is adhered to the surface of a copper-clad laminate, the other side of said photopolymerizable film is adhered to a membrane support, and then the photopolymerizable film is adhered to a membrane support according to a predetermined pattern. After exposing the photopolymerizable layer to light, (A) the support is removed and the unexposed areas are washed away with a suitable organic solvent or alkaline aqueous solution to expose the copper layer.

Alternatively, (B) a so-called "dry-free" type in which the unexposed area or exposed area is removed and exposed together with the support by utilizing the difference in adhesiveness between the unexposed area and the exposed area and the support.

Typical examples include "lum" type photoresists, and "shi/ink" type photoresists that are applied on copper-clad laminates by screen printing, etc.

These include video, stereo, gaming machines, automobiles,
Applications are progressing to a wide range of industrial and consumer printed wiring boards, which are widely used in computers and the like.

Photoresist compositions such as those described above are generally used in colored form in many cases from the viewpoint of workability, and in particular, photoresists that produce a bright difference in hue or density between the cured areas and unexposed areas after exposure to ultraviolet rays, etc. is extremely convenient in terms of product management, such as controlling the exposure level, controlling the exposure position, and inspecting for scratches and disconnections when forming printed circuit boards. 3
No. 113024 and No. 3121632 describe a coloring system based on a leumetriphenylmethane dye and a sulfonyl halide, a sulfenyl halide, or an alkyl or aryl ketone, or a coloring system based on a free base of an aminoacridine dye and a halide, (3) JP-A No. Japanese Patent No. 55-13780 proposes a coloring system using a combination of a fluoran compound and a latent activator for a fluoran dye.

However, even with these prior art techniques, the problems have not been completely solved. For example, USP 3113
The compositions proposed in No. 024 and No. 3121632 are generally unstable, and only leuco crystal violet (blue-violet coloring system) has been applied to actual photoresist systems. This product also lacks stability against heat (thermal coloring tendency) and has a natural coloring tendency during long-term storage of the resist, so it does not completely satisfy the needs of consumers.

Also, disclosed in Japanese Patent Application Laid-Open No. 52-130701,
In systems using free bases of dyes, the free bases of the dyes themselves are colored, and it is difficult to obtain a large contrast between the colored and uncolored areas after exposure. The base itself has not been commercialized because it is expensive, unstable, and unstable.

Furthermore, in the system using a fluoran compound disclosed in JP-A No. 55-13780, those having practically sufficient color-forming ability are limited to a limited number of compounds having a primary amine group in the molecule, making it difficult to put them into practical use. It is limited to 3-diethylamino-6-methoxy-7-amine-fluoran (which produces a red color).

As mentioned above, the prior art does not provide a perfect photoresist for printed wiring boards, which is currently advanced, but has the following characteristics:
There is a strong need for photoresist compositions that have excellent heat and storage stability prior to use. In particular, there is a strong desire for a phototropic photoresist composition that develops a color from green to blue that can be distinguished with good contrast when working under a yellow safety light.

In view of the above-mentioned requirements, the present inventors have conducted intensive studies on photosensitive color-forming four-resists, particularly on photoresist combinations that can facilitate pattern recognition in exposed and unexposed areas. ) A photosensitive resin that can be cured by irradiation with ultraviolet light in the presence of a photosensitizer, Φ)
A photosensitizer that generates radicals when irradiated with ultraviolet rays, (C
) General formula (1) (wherein, R and R'' represent a hydrogen atom or an alkyl group, and X and Y each represent a hydrogen atom, a lower argyl group, an alkoxy group, or an amino group (the amine group is a lower alkyl group as a substituent) , a cycloalkyl group, an alkylene group, a cyanoalkylene group, an oquindoalkylene group, or an aralkyl group substituted with a halogen atom or an alkyl group), and A is a phenyl group or a naphthyl group (these groups are substituted with may have an alkyl group, an alkoxy group, or a substituted amine group.When A is a phenyl group containing a substituted amine group, and X and Y are amino groups, 6 amines in the molecule At least one of the groups is an amine group substituted with an alkyl group and a benzyl group, and the benzyl group may have an alkyl group or a halogen atom. When only X is a substituted amino group (therefore, there are two amino groups in the molecule), Y is an alkoxy group and has an alkyl group or a cycloalkyl group in the ortho position of this alkoxy group. In the case of a naphthyl group, it is substituted with an alkoxy group.In addition, the substituents of A, X, Y
(if only one of them is an amine group, it has at least one alkoxy group in the molecule) as an essential component, and if necessary, (d) By also containing an emitting organic logenide, the resin is polymerized and cured at the same time as it is irradiated with ultraviolet rays, and is colored in a deep color to provide a strong, darkly colored cured resin layer.
Alternatively, it was discovered that when exposed through a photomask, an excellent photoresist composition can be obtained that allows for extremely easy pattern recognition using the difference in color density between the exposed and cured areas and the unexposed areas, resulting in the present invention. did.

In the presence of (a) a photosensitizer used in the composition of the present invention,
The photosensitive resin is a resin that can be polymerized by irradiation with electromagnetic waves or particle beams, such as ultraviolet rays,
Examples include (A) radical polymerization type photosensitive resins and (B) addition polymerization type photosensitive resins.

Specifically, (A) radical polymerizable photosensitive resins include (1) ■phthalic anhydride, isophthalic anhydride, terephthalic acid, adipic acid, cepatic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexa hydrophthalic acid, methylhexahydrophthalic acid, hymic acid,
Polybasic acids such as trimellitic acid, pyromellitic acid, het acid, etc. and @ethylene glycol, glopylene glycol, polybutylene glycol, polypropylene glycol, 1,3-butylene diglycol, 1,4-butylene diglycol , 1,6-hexanediglycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol,
Polyester (meth)acrylate resin obtainable by esterification reaction with polyhydric glycol such as dipentaerythritol, bisphenol A ethylene oxide addition, hydrogenated bisphenol A1 polybutylene glycol, polycaprolactone, etc. and (meth)acrylic acid,
Still (2) ■ Polyester obtained from the above polybasic acid and the above polyhydric glycol or @ polyethylene glycol, polybutylene glycol to polybutylene glycol,
Polyethers such as polycaprolactone and theta tolylene diisonanate, 4゜ediphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, etc.
4.4'-methylenebis(cyclohexylinoneane)
1.), hydrogenated tolylene diisocyanate 1-11.3
-(ynoneanatemethyl) cyclohexane, isophorone diiso/anate, trimethylhexamethylene diynonane-1, etc., and @
Polyurethane/(meth)acrylate obtained by reaction of a monomer having a hydroxyl group and a (meth)acryloyl group, such as 2-t-troki/ethyl (meth)acrylate, 2-hydroquinozolopyl (meth)azilylate, etc. Resins, and (6) ■Bisphenol Δ7 glycine ether, aliphatic glycine ethenopenoporac type epoxy resin/resin, evogated polybutazoene, epoxylated oil, fatty acid-modified epoxy resin, /・rogeno-containing epoxy position 1 fat, etc. Epoxy/Epoxy (meth)acrylate obtained by reacting resin and O(meth)acrylic acid], (rotate, etc.) (4) (a) Polyacetal, 02-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polyacetal (meth)acrylate resin obtained by reaction of active hydrogen such as (meth)acrylic acid with a monomer having a (meth)acryloyl group, (5) terminal or side chain of silicone oligomer Silicone (meth)acrylate resin with a (meth)acryloyl group introduced into it, (6) ■Methyl (meth)acryle-41, ethyl (meth)acrylate, butyl (meth)acrylate, inopropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-
Hydroxyethyl (meth)acrylate, 2-hydroxy/zolopyl (meth)acrylate, (meth)acrylic acid, maleic acid, itaconone, fumaric acid, acrylamide, glycidyl (meth)acrylate, styrene/,
Vinyl toluene, vinyl ^'1 acid, acrylonitrile,
Diethylaminoethyl (meth)acrylate: α, β unsaturated monomers such as diethylaminoethyl (meth)acrylate, morphonoethyl (meth)acrylate, etc.
Utilizing the functional groups of the side chains of vinyl copolymers obtained by vinyl copolymerization, for example, By reacting a monomer having an acryloyl group with the hydroxyl group of the vinyl copolymer, diynyanate and 2-hydroxyethyl (meth)acrylate, 2-hydroxyquinropyl (meth)acrylate, etc. ) By reacting a monomer having an acryloyl group, or (2) reacting a monomer having a hydroxyl group and a (meth)acryloyl group as described above with the acid anhydride group of the vinyl copolymer. (7) Vinyl copolymer (meth)acrylate (flank), (7) melamine (
Examples include meth)acrylate resin, (8) polybutadiene (meth)acrylate resin, and (9)/clopentadiene (meth)acrylate resin.

(B) Examples of addition polymerization type photosensitive resins include pentaerythritol tetrakis (thioglycole-1),
1- 'J 7' A polythiol compound such as tyrolpropane I-lis (β-mercaptopropionate), ethylene glycol dimercaptopropionate, etc., the above-mentioned radical polymerizable photosensitive resins, terminal allyl type urethane resin, terminal Combinations with unsaturated resins such as allyl type epoxy resins, terminal allyl type epoxy resins, terminal allyl type melamine resins, vinyl compounds, and diene compounds can be mentioned. These photosensitive resins may be used alone or in combination of two or more.

The photosensitizer (1) used in the composition of the present invention may be, for example, a compound that generates Rancar when irradiated with ultraviolet rays, but it is required to have good efficiency in generating U/C. Examples of such photosensitizers include (1)
Benzoin-type photosensitizers such as benzoin, benzoin ethyl ether, benzoin isoglobyl ether, benzoin inobutyl ether, benzoin inobutyl ether, benzoin octyl ether, (2) 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy7acetophenone/, P-phenoxy7-2,2-dichloroacetophenone, P-1-butyl-2,2,2-trichloroacetophenone, P-t-butyl-2,2-dichloroacetophenone Acetophenone type light such as tl
Sensitizing agent, (3) α-acylo of 1-phenyl-1,2-propanedione-2-(0-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(〇-bensoyl)oximnato Kimester type photosensitizer,
(4) 2-hydroxy-2-methylpropiophenone,
Biophenone-type photosensitizers such as /-isoprobyl-2-hydroxy-2-methylpropiophenone, (
5) benzophenone type photosensitization such as 7 sol, 4,4-bisdiethylaminobenzophenone, chlorinated benzophenone (<S) 2-1 tylanthraginone, 2-t-butylamino Traginone, 2-
Anthraquinone type photosensitizers such as amylanthraquino, 2-chloroanthraquinone, (7) 2-chlorothiogyzanthone, 2-methylthiogyzanthone, 2-isoglobilthioxanthone, 2,4-diisopropyl Thiogizanoton type photosensitizers such as thioxanthone, the dragon (8
) benzoate type photosensitizers such as methyl-orthobenzoyl benzene-1; and (9) benzaldehyde type sensitizers such as p-di-n-bropylaminobenzaldehyde. These photosensitizers may be used alone or in combination of two or more.

The methine compound used in the present invention has the general formula (
A general term for a group of novel compounds represented by 1), in which one amine group is substituted with a methyl group and a benzyl group which may have a substituent, 4 They are broadly classified into noaminotriphenylmethane compounds having an -alkoxy-3-5 substituted phenyl group, monoaminotriphenylmethane compounds containing at least one alkoxy group, substituted naphthyl-diphenylmethane compounds, and the like.

Specific compounds include (1) l-lyaminotriphenylmethane compounds such as 4.4#-bis-(dimethylamino)=4''-(N-methyl-N-benzyl-
amino)-triphenylmethane, 4,4'-bis-(N
-Methyl-N=benodylamino)-41'-trimethylamino-triphenylmethane, 4.4'-bis-(dimethyl)-4"-N-p-chlorobennol-N-methylamine)-triphenylmethane, 4° Ebis-(dimethylamino)-4″-(N-p-methylbenzyl-N
-Methylamine)-triphenylmethane, 4,4'-bis-(N-1)-methylbenzyl-N-methyl)amino-4''-dimethylamine-triphenylmethane, 4.4
'-bis-(dimethylamino)-4''-(N-0-chlorobe/zyl-14-methylamino)-triphenylmethane, 4.4'-bis-(dimethylamino>ah-mol polytwotriphenylmethane , 4,4-bis-(dimethylamino)-4″=(N-shihendylamino)-1-
I7 phenylmethane etc., f2) diaminotriphenylmethane type compounds, 4.4'-bis-(dimethyla</)-4"-methoxyro"-methyl-triphenylmethane, 4.4'--bis-( dimethylamino)-4
N-Engineering]・xy-somethyl-triphenylmethane, 4
,4'-bis-(dimethylamino)-49-methoxy/-
3"-1er naphthyl-triphenylmethane, 4.4
'-bis-(dimethylamino)-47-medoxy 6#
-cyclohexyl 1-rephenylmethane, 4.4'
-bis-(N-bearazyl-N-methylamino)-4#-
Methoxy-triphenylmethane, 4.4'-bis-pyrrolidino-4#-ethoxy-3#-methyl-triphenylmethane, 4.4'-bis-(N-methyl-N-benzylamino)-4"- Ethoxy-6"-methyl-triphenylmethane, 4,4'-bis-morpholino-4''-methoxy-ro'-tert-butyl-triphenylmethane,
3.5: 3'-trimethyl-4,4'-bis-methylamino-4#-methoxytriphenylmethane etc., (6
) As a monoaminotriphenylmethane compound, 4-
Dimethylamino-4'-methoxy-triphenylmethane, 4,4'-dimethoxy-4"-dimethylamine-triphenylmethane, 4,4'-dimethoxy-41-methylamino-6'-methyl-triphenylmethane, 4,4'
-dimethoxy-4Q-(N-methyl-14=benzyl)
-triphenylmethane, 4,4'-jethoxy-4n-
Dimethylamino-triphenylmethane, 6,5'-dimethyl-4,4'-dimethoxy-41-dimethylamine-
Triphenylmethane, (4) Naphthyl-diphenylmethane compounds include bis-(4-dimethylaminophenyl), I-methoxynaphthyl-1-methane, bis-
(4-dimethylaminophenyl)-4'-methoxynaphthyl-1-methane, bis-(4-dimethyladanophenyl)-418'-dimethoxynaphthyl-1-methane, and the like.

In order to effectively develop color at the same time as curing the photoresist using the novel phototropic triarylmethane derivative of the present invention upon exposure, preferred embodiments include (1) having a halogen atom in the molecule as a photosensitizer; When irradiated with ultraviolet rays, the polymerization or crosslinking reaction of photosensitive resins progresses, and halogen radicals are provided, allowing triarylmethane derivatives to undergo a rapid and effective color-forming chemical reaction. Sensitizers, e.g.
p-f, ert-butyl-2,2゜2-trichloroacetophenone, p-phenoxy-2,2-dichloroacetophenone, 4,4'-dichlorobenzophenone, 2-
A method in which chloranthraquinone, 2-chlorothioxant 7, etc. are used as at least one component of a photosensitizer, (2) (a) a photosensitive resin, Φ) a photosensitizer, and (c) a triarylmethane derivative; (d) A method in which halogen free radicals are generated by ultraviolet rays or the like and a nonvolatile organic halogen compound that can effectively convert the triarylmethane derivative into a color-forming type is used in combination.

Nonvolatile organic halides include α,′α′-hexabromoxylene, α, (χ, α,<α;α′-hexachloroxylene, hexabromobenzene, hexabromobenzene, hexachlorocyclohexane, hexachlorocyclohexane, Hexachlorocyclopentadiene, hexabromodiphenino, etc.

--40-α, α, α-tribromoacetophenone, α
, α, α-α; α; α′-hexabromo-p~diacetylhensen, moy, y-triflomoxaldine, 2-/
, W-tribromomethyl-quinoline, hexabromodimethyl sulfoxide, pentabromodimethyl sulfoxide, hexabromodimethyl sulfone, 2-trichloromethyl-benozothiazolyl sulfonate, atrabromodimethyl sulfone, 2,4 monodichlorophenyltrichloromethylsulpone, trichloroacetic acid phenyl ester, trichloroacetic acid pentachlorophenyl ester, 4,4-dibro-5-imo-2,6-hexanedione, 2,2,4,47-trabromocyclobutanone, 2-chlorocyclo One+? 7.2
-iodo-1,3-cyclopentadione, 2,5-dichloro-3,6-cyr-toxycarbonyl-hydroquinone, 2,5-dibromo-3,6-d-n-phthoxycarbonyl-hydroquinone, 2,6-cyclohydroquinone and the like are used.

In addition, among these organic halides, compounds containing a large amount of halogen atoms, especially bromine, in the molecule also have a flame retardant effect, and photoresist compositions using such compounds have flame retardant properties. and is industrially useful.

The amount of these organic halides to be used is determined experimentally depending on the generation of radicals by ultraviolet rays, etc. and the coloring ability of the triarylmethane derivative, but it is usually 0.1 to 10 parts by weight per 1 part by weight of the triarylmethane compound. This is within the scope of the department.

The composition of the present invention is used as a photoresist material for printed circuit boards as follows.

(A) Use as a dry film resist, after dissolving and diluting the composition of the present invention in a low boiling point solvent such as methyl ethyl ketone, various films such as polyamide, polyolefin, polyester, vinyl polymer, cellulose ester (hereinafter referred to as "support film") are prepared. '') is coated with a continuous web coating machine, etc., and dried with hot air to form a thin resist layer.A protective film of polyolefin, polyester, etc. is laminated on top of the resist layer using a pressure roller, etc. This is a so-called dry film resist with a Sanderutsch structure.

In actual use, the protective film is removed, and the resist film is superimposed on the clean copper surface of the copper-coated laminate and irradiated with ultraviolet light to form a colored, cured resist film. Furthermore, if necessary, ultraviolet a! is applied through a mask that transmits light from desired pattern areas. A colored image of triarylmetal is drawn on the copper plate at the same time as the resin hardens in the exposed area, while the unexposed area remains uncured and colorless or light-colored, and the exposed area and unexposed area are separated. can be easily recognized with the naked eye due to its colored pattern.

(B) Use as a liquid resist A method in which the composition of the present invention is painted or printed on a material such as metal, plastic, paper, glass, etc. by various methods, and then cured with ultraviolet rays to form a colored image. Alternatively, a film coated with the above composition using a roll coater, knife coater, flow coater, etc. is pressure-bonded to a copper-coated laminate, or by roll coulter, spray, flow coater, screen printing, or clavier printing on a copper-coated laminate. It is applied by offset printing, dipping, etc., and then exposed to the entire surface or irradiated with ultraviolet rays through a mask that transmits the light of the desired pattern, to create a fully colored cured coating or a colored image that can be recognized with the naked eye on the copper plate. Method.

In the composition of the present invention, (a), (b) and (C
) or (d) The content of the component is (a) 100 parts by weight of the photosensitive resin, (b) 0.05 to 20 parts by weight of the photosensitizer,
Preferably, the triarylmethane compound (C) is 0.05 to 15 parts by weight, preferably 01 to 5 parts by weight.
This is a serious danger section. When component (d) is used, it is generally 0.
05 to 20 parts by weight are used.

The compositions of the present invention include (a), ←), (C) and (
In addition to component d), if necessary, (a) the following unsaturated compounds, such as (1) 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cellosolve (meth)acrylate , methyl cellosolve (meth)acrylate, butyl cellosolve (
meth)acrylate, carpitol (meth)acrylate, methylcarpitol (meth)acrylate, butylcarpitol (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentagenyl ( meta) acrylate,
Dicyclopentadienyloxyethyl (meth)acrylate, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl (meth)acrylate, nonylphenoxyethyl (meth)acrylate-1-12-hydroxy-6-
Monofunctional (
meth)acrylate, (2) neopentyl glycol di(meth)acrylate), 1.6 hexane glycol di(
meth)acrylate, 1,4-butylene glycol di(
meth)acrylate), 1,3-butylene glycol di(
meth)acrylate, diethylene glycol di(meth)
Acrylate, polyethylene glycol, di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polycaprolactone di(meth)acrylate, bisphenol A Dioxydiethylene glycol ether diacrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

Furthermore, the photoresist composition of the present invention contains (b) an extender pigment with good ultraviolet transmittance, (C) a plasticizer, (d) a leveling agent, and (e) in order to adjust its physical properties depending on the intended use.
) antifoaming agent, (e) thixotropant, (f)
A clean adhesive component such as phosphoric acid esters to improve adhesion to the substrate, and (g) dyes to color the resist layer in advance can be added.

The novel photoresist composition of the present invention thus obtained has better storage stability than photoresist compositions using known leucotriphenylmethane compounds, such as leuco crystal violet and leucomalachite green. It is a composition that has excellent heat resistance stability (less tendency to spontaneous color development when light is cut off during heating) and extremely excellent ability to instantly develop color upon exposure to light.

In particular, when applied to dry film type photoresists, the heating conditions for removing volatile solvents such as methyl ethyl ketone and toluene can be raised to high temperatures, thereby greatly improving coating production speed.

In addition, compared to compositions using known leucotriarylmethane dyes or fluoran compounds, it has superior UV coloring ability from blue to green, making it easier to distinguish colors under safety lights.
It also has the effect of reducing the amount of expensive dyes used.

The photosensitive resin composition of the present invention can be applied to metals, plastics,
After being painted on paper, wood, glass, etc. using a roll coater, spray, knife coater, etc., or printed using screen printing, offset printing, gravure printing, flexo printing, letterpress, etc., it is coated with ultraviolet rays. etc. to form a cured colored film.

In order to improve printability and coating suitability during printing or painting, colorless extender pigments with good ultraviolet transmittance, leveling agents, antifoaming agents, thixotropic agents, adhesive components, etc. are added to the composition of the present invention. can be used.

Alternatively, the composition of the present invention can be applied by applying a film using a roll coater, knife coater, flow coater, etc. onto a metal plate, or by applying the composition onto a metal plate using a roll coater, a spray coater, a flow coater, etc. The metal plate is coated by dipping, irradiated with ultraviolet rays through a mask that allows light to pass through the desired pattern, a colored image that can be recognized as a pattern is drawn on the metal plate, and the unexposed areas are washed away with a solvent or alkaline aqueous solution. By removing the exposed and unexposed areas using the difference in adhesion to the support, a colored pattern is formed, thereby forming a relief image on a photosensitive printing plate or a pattern image in printing substrate processing. It can be applied to normal usage such as.

The photosensitive resin composition of the present invention can be colored and polymerized using electromagnetic waves or particle beams.

Light rays such as ultraviolet rays, near ultraviolet rays, gamma rays, X-rays, and beta rays (
Electronic i! 1m) Radiation with mass such as alpha rays can be mentioned. Practical examples include 550-4OO/I high-pressure mercury lamps, ultra-high-pressure mercury lamps, metallolide lamps, carbon arcs, fluorescent lamps with ultraviolet radiation phosphors, argon glow lamps, solar lamps, electronic flash devices, and photographic flashes. Irradiation with ultraviolet light from lamps or β-rays (electron beams) is often used.

The photosensitive resin composition of the present invention can form a cured film with the same thickness and coloring as thermosetting resins, and also has the various advantages of photosensitive resins mentioned above, such as fast curing. This is an extremely excellent photosensitive resin composition.

The present invention will be explained below with reference to Examples and Comparative Examples.

Example-1 Polypropylene/glycol (molecular weight 1ooo) 500 g, 2-hydroxyethyl acrylate 116v1 (hexamethylene diisocyaner) 16B fi' were placed in a flask equipped with a stirrer, and urethane acrylate was obtained at 80°C.

The urethane acrylate 100 r, 4 as a sensitizer
．． /-dichlorobenzophenone 6.02 and 0.5 P of 4,4'-bis(N-methyl-N-benzyl aξ))-/-methoxy-61-methyl-triphenylmethane as a dye precursor were mixed and dissolved. A green transparent liquid resist composition was obtained.

The composition was screen printed to a thickness of 50 μm on a copper-clad laminated board to form a substantially colorless and transparent resist layer, and then irradiated with ultraviolet rays for 10 seconds using a 100 W/- high pressure mercury lamp. The layer was completely cured and colored a dark green (Macbeth densitometer reflection density value 1.02).

The cured film thus obtained had good bendability, surface hardness, and adhesion, and was excellent in fastness to heat and light.

Example-2 Pentaerythritol'-lutetraacrylate 2゜p 60 copolymer of 75 parts by weight of styrene and 25 parts by weight of methacrylic acid
-phenoxy-2,2-dichloroacetophenone
A composition containing 6 methyl ethyl ketone 200 g was applied to a 1 mil thick polyester film to give a dry thickness of 12 microns, air dried, and the dried film was covered with a 1 mil thick polyethylene film.

The polyethylene cover film of the dry film resist with the above-mentioned sand inch structure was removed, the exposed surface of the photoresist was laminated on the clean copper surface of a copper clad laminate (manufactured by Universal Oil Products), and a rubber cover roll was formed. I pressed it to make it stick.

Transparent 12< with conductive pattern on opaque background
When a high-contrast silver halide film was closely attached to the top of a polyester film, and UV light was irradiated for 1 minute using an ultra-high pressure mercury beam of 250 W/cm, the UV transmitting area was completely reduced to one area and a deep blue color developed. 3, [
Macbeth reflection density value 081] The ultraviolet opaque area (uncured and colorless and transparent, and the hue of the copper surface was directly observed.

The UV opaque areas were removed by conventional methods to obtain the desired blue cured color pattern.

Example-6 Bisphenol type epoxy (product name Ko Picoat 828,
(manufactured by Yuka Ciel Epoxy Co., Ltd.) 1951i' with acrylic acid 7
22. Epoxy acrylate was obtained by ring-opening addition reaction of epoxy groups by adding triethylamine 7, Q, 51 as a promoter.

The epoxy acrylate 807, neopentyl glycol diacrylate 20f! , benzoin butyl ether 20y1 as a sensitizer, and 2-chlorothioxanthone 1. Of and 4. Edimethylamino-ro”-
Methyl-4”-ethquinetrife,=lumethane 1.1
1i' was mixed and dissolved to obtain a liquid nometresist composition.

The composition was coated on a bonded steel plate with a bar coater for 10 minutes.
When applied to a thickness of 0μ and irradiated for 15 seconds with a 100W/C□ metalloid lamp, it was completely cured to the inside. Concentration value 0
．． 84:] was colored.

The cured film showed no change in color even when immersed in a 260° C. solder bath for 10 seconds, and could be practically used as a solder mask resist.

Comparative example-1 4,4'-bis-dimethylamino-3# to methyl-47
Example-6 except that known leucomalachite green (4,4'-bis-dimethylamino-triphenylmethane) was used in place of -el xy-triphene and -lumethane.
A liquid photoresist was prepared in the same manner as above, applied, and exposed, but the cured film was only colored pale green.
(Macbeth reflection density 062), green solder resist m
However, the hue and density were insufficient.

Comparative Example-2 4,4'-bis-dimethylamino-3'-methyl-4''
A green photoresist composition was obtained by processing in the same manner as in Example 6, except that an organic green pigment (phthalocyanine green) was dispersed and used in place of xy-triphenylmethane.

The composition was coated on a bonded steel plate with a bar coater for 10 minutes.
When it was applied to a thickness of 0μ and exposed under the same conditions as in Example 3, the surface layer was hardened, but the lower layer (near the steel plate) was not hardened and remained plate-like, giving an unsatisfactory result. Ta.

Example-4 1) 100 parts by weight of an acrylic resin containing 50 units of toluene (trade name Almatex L-1044 manufactured by Mitsui Toatsu Chemical Co., Ltd.) 2) Compound δ SOZ parts represented by the following formula (trade name BP4EA) Kyoeisha oil and fat 3) Photosensitizer (A) 2-Hydroxy-2-methylpropiofenono (trade name Darocure 1173) 1 Electrical switch manufactured by Merck & Co. 4) Bis(4-p+-methyl-N-benzylamino)-
Mix and dissolve 3"-methyl-41-ethoxy-triphenylmethane and toluene 507 in a room protected from ultraviolet rays to form a colorless and transparent solution.
Dry for 0 minutes and evaporate the solvent. After drying, the resist was adhered to a 15 μm thick polyethylene film (protective layer) according to a conventional method to prepare a three-layer dry film resist.

At this point the photoresist layer was clear and colorless. While the protective layer of the Dojii Film was peeled off, it was heated and laminated onto the clean copper surface of a glass epoxy copper-clad laminate, and then allowed to cool to room temperature. A silver salt photomask was attached to the top, and 2DD was performed using an ultra-high pressure mercury lamp (Oak Seisakusho 1R3KWX1 lamp).
When exposed under the exposure condition of mj x 15 sec, the transparent part of the photomask turned dark green (λrnax625
Colored and cured to mμ Macbeth densitometer reflection density value 081),
Opaque parts are uncured and uncolored! , i, and the pattern recognition of the exposed and unexposed areas was extremely clear.

When this was sprayed with 1,1,1-trichloroethane according to a conventional method, the unexposed areas were completely removed, the copper surface was exposed, and the green/zeta-turn of the exposed and hardened areas remained.

Comparative Example-6 Bis(4-N-methyl-N-benzylamino)-6"-
When treated in the same manner as in Example 4, except that leuco crystal violet (4,a':4"-tris-dimethylamino-triphenylmethane) was used in place of methyl-4"-ethquintriphenylmethane, 160 ℃×10
Under the dry conditions of m1n, the photoresist layer was colored blue, and the contrast between the exposed and unexposed areas after exposure was not good.

12 to prevent coloring of the photoresist layer when drying
The coating required long-time drying at 0° C. or lower9, and the coating workability (work speed) was insufficient.

Example 5-8 Bis-(4-N-methyl-N-benzylamino)-39
-A dry film resist was prepared in the same manner as in Example 4 using the following compound instead of methyl-41-ethoxytriphenylmethane, and an exposure test was conducted.

Claims (1)

[Scope of Claims] 1) A photosensitive resin composition containing (a) a photosensitive resin, (b) a photosensitizer, and (C) the general formula (1) (in the formula, R, R
' is a hydrogen atom or an alkyl group; (having an oxide alkylene group or an aralkyl group substituted with a halogen atom or an alkyl group), A is a phenyl group, a naphthyl group (these groups have an alkyl group,
may have an alkoxy group or a substituted amino group). A is a phenyl group containing a substituted amine group, x,
When Y is an amine group, at least one of the six amino groups in the molecule is an amine group substituted with an alkyl group and a benzyl group, and the benzyl group is substituted with an alkyl group or a benzyl group. It may have a gen atom. Further, when A is a phenyl group containing a substituted amine group and only X is a substituted amine group, Y is alkoxy and has an alkyl group or a cycloalkyl group at the orno position of the alkoxy group. Furthermore, when A is a naphthyl group, it is substituted with an alkoxy group. Furthermore, any one of the substituents of A, X, Y
1. A photoresist composition containing a methine-based compound represented by the following formula (when only one is an amino group, the molecule has at least one alkoxy group).