JPH0934109A - Photosensitive resin composition and hardened film forming method using that - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin compsn. easy for forming a symbol mark, capable of obtaining a pattern of high reliability and of good adhesion property, and suitable for a solder resist for a printed circuit board, and to provide a forming method for a hardened film by using this compsn. SOLUTION: This photosensitive resin compsn. consists of (A) a prepolymer having ethylene-type bonding groups and carboxyl groups, (B) a reactive diluent, (C) a thermosetting compd. (D) a radical polymn. initiator which is sensitive for 450-700nm absorption wavelength, (E) a radical polymn initiator which is sensitive for 200-400nm absorption wavelength, and (F) a dye which produces radicals by irradiation with light and develops a color. A coating film comprising this compsn. is formed on a base body, exposed to 450-700nm wavelength laser light for making, exposed to UV rays of 200-400nm wavelength for patterning, and then developed to form a hardened coating film.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel photosensitive resin composition and a method for forming a cured coating film using the same. More specifically, the present invention can form a symbol mark with visible light, and by curing with ultraviolet light, it is possible to give a pattern having high reliability and excellent adhesion to a substrate. The present invention relates to a photosensitive resin composition suitable as a solder resist for a printed wiring board and a method for easily forming a cured coating film with a symbol mark using the same.

[0002]

2. Description of the Related Art Solder resist is used to form a film on the entire surface of a printed wiring board other than the soldered portion of a circuit conductor when manufacturing a printed wiring board to be incorporated in various equipment. Electronic components are soldered to the printed wiring board. When soldering, prevent solder from adhering to unnecessary parts,
In addition, it serves as a protective film for preventing the circuit conductor from being directly exposed to air and corroded by oxygen or moisture.

Further, in the manufacture of this printed wiring board, a symbol mark is usually provided in order to clearly indicate a mark for mounting an electronic component, its manufacturing number and the like. Conventionally, the symbol mark is formed by forming a pattern using a solder resist, printing the marking ink with a silk printing machine or the like, and then thermosetting or ultraviolet curing the marking ink. However, such a method requires an additional step for printing the marking ink, which inevitably reduces productivity.

[0004]

The present invention overcomes the drawbacks of the prior art and allows the symbol mark to be formed by a simple operation, has high reliability, and is superior to the substrate. PROBLEM TO BE SOLVED: To provide a photosensitive resin composition suitable for a solder resist for a printed wiring board, which can give a pattern exhibiting adhesion, and a method for efficiently forming a cured coating film having a symbol mark using this composition. It was made for the purpose.

[0005]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above-mentioned object, the present inventors have found that a specific prepolymer, a reactive diluent, a thermosetting compound and visible light can be used. It was found that the object can be achieved by a composition containing as an essential component a radical polymerization initiator, a radical polymerization initiator that is sensitive to ultraviolet light, and a dye that develops color upon irradiation with light, and the present invention is based on this finding. Has been completed.

That is, the present invention comprises (A) a prepolymer having an ethylenic bond-containing group and a carboxyl group,
(B) a reactive diluent, (C) a thermosetting reactant,
(D) a radical polymerization initiator that is photosensitive in the light absorption wavelength region of 450 to 700 nm, and (E) a radical polymerization initiator that is photosensitive in the light absorption wavelength region of 200 to 400 nm,
(F) A photosensitive resin composition containing, as an essential component, a dye that develops a color upon irradiation with light and develops a color, and a coating film made of this photosensitive resin composition on a substrate. After providing it, the wavelength range 450-700n
A method for forming a cured coating film, which comprises irradiating a laser beam of m for marking exposure, and then irradiating ultraviolet light in a wavelength range of 200 to 400 nm for pattern formation exposure and developing treatment. Is.

In the composition of the present invention, the prepolymer used as the component (A) has an ethylenic bond-containing group and a carboxyl group. The prepolymer preferably has an acid value in the range of 40 to 150 mgKOH / g. This acid value is 40mgKOH /
If it is less than g, it becomes difficult to develop, and 150 mgKOH / g
If it exceeds, the hydrophilicity of the resin becomes too high, which adversely affects the electrical characteristics. Such a prepolymer is obtained by, for example, reacting an oligomer or polymer having an epoxy group with an unsaturated monocarboxylic acid having an ethylenic bond, and then reacting with an unsaturated or saturated polycarboxylic acid anhydride, or a carboxyl group. It can be obtained by reacting an oligomer or polymer having a group with an unsaturated compound having an ethylenic bond and an epoxy group in one molecule.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned oligomer or polymer having an epoxy group usually has an epoxy equivalent of 1,0.
00 or less, preferably 100 to 500 epoxy resin,
For example, bisphenol A type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, bisphenol F type epoxy resin, brominated epoxy resin,
Alicyclic epoxy resin, heterocyclic epoxy resin, aliphatic epoxy resin, phenol novolac epoxy resin,
Cresol novolac type epoxy resin, naphthol novolac type epoxy resin, glycidyl amine type epoxy resin, bisphenol S modified novolac type polyfunctional epoxy resin, polyfunctional modified novolac type epoxy resin, condensation of phenols with aromatic aldehyde having phenolic hydroxyl group Examples include epoxy resins, copolymers of alkyl esters of acrylic acid or methacrylic acid, and epoxy group-containing acrylates or methacrylates.

Examples of the unsaturated monocarboxylic acid having an ethylenic bond which is reacted with the oligomer or polymer having an epoxy group include acrylic acid, methacrylic acid, crotonic acid and cinnamic acid. The amount of the unsaturated monocarboxylic acid used is 0.8 to 1 per equivalent of the epoxy group of the oligomer or polymer having an epoxy group.
A range of 3.0 equivalents is preferred. When the unsaturated monocarboxylic acid is used in a stoichiometric amount or more, the excess amount of the unsaturated monocarboxylic acid will be further added to the ethylene bond of the previously added unsaturated monocarboxylic acid group. Then, as the saturated or unsaturated polycarboxylic acid anhydride to be reacted with the reaction product, for example, succinic anhydride, glutaric anhydride, adipic anhydride, maleic anhydride, itaconic anhydride, hexahydrophthalic anhydride, etc. Is mentioned. The amount of these polycarboxylic acid anhydrides used is selected such that the acid value of the prepolymer usually obtained is in the range of 40 to 150 mgKOH / g.

Examples of the above-mentioned oligomer or polymer having a carboxyl group include a copolymer of an alkyl ester of acrylic acid or methacrylic acid and acrylic acid or methacrylic acid. Examples of the unsaturated compound having an ethylenic bond and an epoxy group in a molecule to be reacted with this compound include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether,
Examples thereof include methallyl glycidyl ether. The amount of these unsaturated compounds used is selected so that the acid value of the prepolymer usually obtained is in the range of 40 to 150 mgKOH / g.

In the composition of the present invention, the reactive diluent used as the component (B) has acid resistance, heat resistance, alkali resistance and the like, which makes the photopolymerization of the prepolymer of the component (A) more sufficient. It is used to obtain a coating film. Examples of such reactive diluents include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hydroxy acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl. Glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol adipate diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, dicyclopentanyl diacrylate, caprolactone modified dicyclopentenyl diacrylate, ethylene oxide modified phosphoric acid diacrylate, allylated cyclohexyl Diacrylate, isocyanurate diacrylate, trimethylolpropane triacrylate, dipentaene Thritol triacrylate, propionic acid-modified dipentaerythritol triacrylate, pentaerythritol triacrylate, propylene oxide-modified trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, propionic acid-modified dipentaerythritol pentaacrylate, dipentaerythritol hexa Examples thereof include acrylates, caprolactone-modified dipentaerythritol hexaacrylate, and corresponding methacrylates. Among these, those having an acryloyl group or a methacryloyl group in the molecule are preferable.

These reactive diluents may be used alone or in combination of two or more. The content thereof is preferably in the range of 2.0 to 50 parts by weight with respect to 100 parts by weight of the prepolymer as the component (A). If this amount is less than 2.0 parts by weight, the photocurability is insufficient, and the effect of improving the acid resistance and heat resistance of the cured coating film is not sufficiently exerted, and if it exceeds 50 parts by weight, the surface is too hardened. Therefore, the desired cured coating film cannot be obtained because the internal curing is not sufficiently performed. The content of the reactive diluent is particularly preferably from 3.0 to 20 parts by weight from the viewpoint of having an appropriate photocurability and obtaining a good cured coating film.

In the composition of the present invention, the thermosetting reaction substance used as the component (C) is either one which can be thermoset by itself or one which reacts with other components to be thermoset, and after post cure, Used to obtain a sufficiently tough coating. Examples of the thermosetting reaction substance include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, propylene or polypropylene glycol. Diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexane Diol diglycidyl ether, ethylene or propylene glycol diglycidyl ether, sorbitol polyglycidyl ether,
Compounds having two or more epoxy groups in one molecule such as sorbitan polyglycidyl ether, pentaerythritol polyglycidyl ether, tris (2,3-epoxypropyl) isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, etc. Is preferred. These may be used alone or in combination of two or more. Further, a known epoxy curing accelerator such as a melamine compound as a reaction accelerator, an imidazole compound and a phenol compound is used in combination, and by post-curing the coating film, the heat resistance of the cured coating film,
It is possible to improve various properties such as acid resistance, solvent resistance, adhesion and hardness.

The content of the epoxy thermosetting agent as the component (C) is such that a sufficiently tough coating film can be obtained after post-curing, so that the prepolymer 100 as the component (A) is used.
The range of 0.1 to 50 parts by weight is preferable, and the range of 0.5 to 30 parts by weight is particularly preferable.

In the composition of the present invention, as the component (D), a radical polymerization initiator which is photosensitive in the light absorption wavelength region of 450 to 700 nm, that is, the visible light region is used. A titanocene derivative is particularly suitable as the radical polymerization initiator. Examples of the titanocene derivative include bis (cyclopentadienyl) -bis [2,6-difluoro-3- [2- (1-pyr-1-yl) ethyl]
Phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- [3- (1-pyr-1-
Iyl) propyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-[(1
-Pyr-1-yl) methyl] phenyl] titanium, bis (methylcyclopentadienyl) -bis [2,6-difluoro-3-[(1-pyr-1-yl) methyl] phenyl] titanium, bis ( Cyclopentadienyl) -bis [2,6-difluoro-3-[(2,5-dimethyl-1
-Pyr-1-yl) methyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-[(2-isopropyl-5-methyl-1-pyr-
1-yl) methyl] phenyl] titanium, bis (cyclopentadienyl) -bis {2,6-difluoro-3-
[[2- (2-Methoxyethyl) -5-methyl-1-pyr-1-yl] methyl] phenyl} titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-
[(3-Trimethylsilyl-2,5-dimethyl-1-pyr-1-yl) methyl] phenyl] titanium, bis (cyclopentadienyl) -bis <2,6-difluoro-3-
{[2,5-Dimethyl-3- [bis (2-methoxyethyl) aminomethyl] -1-pyr-1-yl] methyl} phenyl> titanium, bis (cyclopentadienyl) -bis {2,6- Difluoro-3-[[2,5-bis (morpholinomethyl) -1-pyr-1-yl] methyl] phenyl} titanium, bis (cyclopentadienyl) -bis {2,6-difluoro-3-[[[ 2,5-dimethyl-3
-(1,3-Dioxolan-2-yl) -1-pill-1
-Yl] methyl] phenyl} titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-4-
[(2,5-Dimethyl-1-pyr-1-yl) methyl]
Phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-methyl-4- [2- (1
-Pyr-1-yl) ethyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-[(2,3,4,5-tetramethyl-1-pyr-
1-yl) methyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,3,5,6-tetrafluoro-4- [3- (1-pyr-1-yl) propyl] phenyl] titanium , Bis (cyclopentadienyl) -bis [2,6-difluoro-3- [2- (1-pyr-1-yl) propyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6 -Difluoro-3- [1-methyl-2- (1-pyr-1-yl) ethyl] phenyl]
Titanium, bis (cyclopentadienyl) -bis [2,6
-Difluoro-3- [3- (2-isoindol-2-yl) propyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- [2-
(4,5,6,7-Tetrahydro-2-isoindole-
2-yl) ethyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- [6
-(9-carbazol-9-yl) hexyl] phenyl]
Titanium, bis (cyclopentadienyl) -bis [2,6
-Difluoro-3- [3- (2,3,4,5,6,7,
8,9-Octahydro-1-carbazol-9-yl) propyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- [3- (4
5,6,7-Tetrahydro-2-methyl-1-indol-1-yl) propyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-
[(Acetylamino) methyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-[(2-propionylamino) ethyl] phenyl] titanium, bis (cyclopentadienyl)- Bis [2,6-difluoro-3- [3- (acetylamino)
Propyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- [4- (pivaloylamino) butyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6- Difluoro-3-
[2- (2,2-dimethylpentanoylamino) ethyl] phenyl] titanium, bis (cyclopentadienyl)
-Bis [2,6-difluoro-3- [3- (benzoylamino) propyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-
[(2,2-Dimethylpentanoylamino) methyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- [2- (2,2-dimethyl-3-chloropropanoyl) Amino) ethyl] phenyl]
Titanium, bis (cyclopentadienyl) -bis [2,6
-Difluoro-3-[(2,2-dimethyl-3-ethoxypropanoylamino) methyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2-lauroylamino) Ethyl] phenyl]
Titanium, bis (cyclopentadienyl) -bis [2,6
-Difluoro-3- [2- (N-allylmethylsulfonylamino) ethyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- [3
-(N-isobutylphenylsulfonylamino) propyl] phenyl] titanium, bis (cyclopentadienyl)
-Bis [2,6-difluoro-3-[(methylsulfonylamino) methyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- [3
-(Ethylsulfonylamino) propyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-
Difluoro-3- [2- (butylsulfonylamino) ethyl] phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- [3- (4-tolylsulfonylamino) propyl] phenyl] Examples include titanium. These titanocene derivatives are prepared by known methods [Journal of Organometallic Chemistry, Vol. 2, pp. 206-212 (1964).
, "Journal of Organometallic Chemistry," Vol. 4, 445-446 (1965).
Year)].

In the present invention, the titanocene derivative may be used alone or in combination of two or more kinds. Further, if desired, a photosensitizer having an optical absorption wavelength of 450 to 700 nm, that is, an absorption wavelength in the visible light region can be used together. Examples of such a photosensitizer include coumarin derivatives, xanthene dyes, triarylmethane dyes, methine dyes, azo dyes, cyanine dyes, thiopyrylium salts, and diphenyliodonium salts. Of these, coumarin derivatives are particularly preferable. Examples of the coumarin derivatives include 7-diethylamino-3- (2-benzothiazyl) coumarin and 7-diethylamino-3- (2
-Benzimidazoyl) coumarin, 7-diethylamino-3-benzoylcoumarin, 7-diethylamino-3-
Thianoylcoumarin, 7-diethylamino-3,3'-
Carbonyl biscoumarin, 7-diethylamino-3-
(4-tert-Butyldioxycarbonylmethoxybenzoyl) coumarin, 5,7-dimethoxy-3- (4-
tert-butyldioxycarbonylmethoxybenzoyl) coumarin and the like.

This photosensitizer may be used alone, or 2
You may use it in combination of 2 or more types. As described above, the triplet energy of the photosensitizer used in combination with the radical polymerization initiator must be larger than the triplet energy of the radical polymerization initiator. If this condition is not satisfied, the energy of absorbing visible light will not be transmitted to the radical polymerization initiator, so that the effect of using the photosensitizer together cannot be sufficiently exhibited.

The content of the radical polymerization initiator of the component (D) is usually 0.5 to 50 parts by weight, preferably 2.0 to 30 parts, per 100 parts by weight of the prepolymer of the component (A).
It is selected in the range of parts by weight. The photosensitizer is used in a proportion of 1 to 50% by weight with respect to the radical polymerization initiator.

In the composition of the present invention, as the component (E), a radical polymerization initiator which is sensitive to the light absorption wavelength range of 200 to 400 nm, that is, the ultraviolet range is used.
Examples of such a radical polymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone,
2,2-dimethoxy-2-phenylacetophenone,
2,2-diethoxy-2-phenylacetophenone, 2
-Hydroxy-2-methyl-1-phenylpropane-1
-One, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]
2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy- 2-propyl) ketone, benzophenone, p-phenylbenzophenone,
4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylamino benzoic acid ester and the like can be mentioned.

These may be used alone or in combination of two or more. The content is usually 0.1 per 100 parts by weight of the prepolymer of the component (A).
It is selected in the range of 5 to 50 parts by weight, preferably 2.0 to 30 parts by weight.

These radical polymerization initiators can also be used, if desired, in combination with a photosensitizer capable of being photosensitive in the light absorption wavelength region of 200 to 400 nm.

In the composition of the present invention, it is necessary to use, as the component (F), a dye which generates a radical by irradiation of light and develops a color. The component (F) is used to form a symbol mark, and particularly, a leuco dye that generates a radical by irradiation of light and develops a color by an oxidation reaction is suitable. Examples of such leuco dyes include 4,4 ', 4 "-methylidine tris (N, N-dimethylbenzenamine), 4,4', 4"-
Methylidine tris (N, N-diethyl-3-methylbenzenamine), 4,4 '-(phenylmethylene) bis (N, N-diethylbenzenamine), 4,4'-(phenylmethylene) bis (N, N-dimethylbenzenamine), 9-diethylamino-12- (2-methoxycarbonylphenyl) -benzoxanthene and the like.

These dyes may be used alone or 2
You may use it in combination of 2 or more types. The content is usually selected in the range of 0.5 to 10 parts by weight per 100 parts by weight of the component (A).

The photosensitive resin composition of the present invention contains the above-mentioned components (A), (B), (C), (D), (E) and (F) as essential components, but is necessary. Depending on the organic solvent, various additional components, for example, inorganic pigments such as silica, alumina, talc, calcium carbonate, barium sulfate, phthalocyanine-based, azo-based organic pigments, defoaming agents, leveling agents, etc. Additives and the like can be included.

Next, the method for forming a cured coating film of the present invention will be described. First, the photosensitive resin composition is applied onto a suitable substrate to form a coating film having a thickness of about 1 to 100 μm. . Then, this coating film has a wavelength range of 450 to 700 nm.
After performing marking exposure by irradiating the laser light of
For example, pattern formation exposure is performed by irradiating ultraviolet light having a wavelength range of 200 to 400 nm through a negative film having a desired pattern. After that, development treatment is performed using an alkaline aqueous solution or the like, the unexposed portion is dissolved and removed, and then post-exposure is performed with ultraviolet light if necessary, whereby a cured coating film with a symbol mark is obtained.

[0026]

INDUSTRIAL APPLICABILITY The photosensitive resin composition of the present invention can form a symbol mark by a simple operation and, at the same time, gives a pattern having high reliability and excellent adhesion to a substrate, and printing. As a solder resist for wiring boards,
Alternatively, it is preferably used for forming an insulating layer. In addition to this, it can be used for a wide range of applications such as paints, photosensitive adhesives, plastic relief materials, printing plate materials and the like.

Further, according to the method for forming a cured coating film of the present invention, a cured coating film having a desired pattern with a symbol mark can be efficiently formed by an extremely simple operation.

[0028]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The performance of the cured coating film was evaluated according to the following method. (1) Solder heat resistance According to the test method of JIS C-6481, after immersing in a solder bath at 260 ° C. for 10 seconds, a peeling test with cellophane tape was performed for 1 to 3 cycles, and the state of the coating film was evaluated. The evaluation was made according to the following criteria. ⊚: No change in coating film after 3 cycles ◯: Slight change after 3 cycles Δ: Change after 2 cycles x: Peeling after 1 cycle

(2) Chemical resistance The cured coating film was dipped in 10% by weight of hydrochloric acid for 30 minutes, and the state of the coating film was evaluated according to the following criteria. ⊚: No change observed ○: Slightly changed Δ: Remarkably changed ×: Swelled and peeled coating film

(3) Solvent resistance The state of the coating film after dipping the cured coating film in methylene chloride for 30 minutes was evaluated according to the following criteria. ⊚: No change observed ○: Slightly changed Δ: Remarkably changed ×: Swelled and peeled coating film

(4) Pencil Hardness The pencil hardness was evaluated according to the test method of JIS K-5400.

(5) Adhesion According to the test method of JIS D-0202, cross-cuts are put on the cured coating film in a grid pattern, and then the state of peeling after a peeling test with cellophane tape is visually evaluated according to the following criteria. did. ⊚: No change was observed at 100/100 ◯: Cross-cut portion was slightly peeled off at 100/100 Δ: 50/100 to 90/100 ×: 0/100 to 50/100

(6) Coloring Marking Property The coloring property of the marking on the cured coating film was observed and evaluated according to the following criteria. ◎: Vivid color development ○: Color development enough to read text △: Color difference barely noticeable ×: No color development

Production Example 1 Cresol novolac type epoxy resin (epoxy equivalent 2
07) 207 parts by weight of acrylic acid, 72 parts by weight of acrylic acid and 155 parts by weight of carbitol acetate as a solvent were reacted under reflux at 110 ° C. for 5 hours to obtain a cresol novolac type epoxy acrylate. To this epoxy acrylate, 76 parts by weight of hexahydrophthalic anhydride was added and reacted under reflux until the acid value reached a theoretical value to obtain a prepolymer having an acid value of 81 mgKOH / g and a solid content of 70% by weight.

Production Example 2 60 parts by weight of a monomer mixture containing methyl methacrylate, ethyl methacrylate and methacrylic acid in a molar ratio of 1: 1: 2 was added to 40 parts by weight of ethyl cellosolve as a solvent, and azobis was used as a catalyst. Using isobutyronitrile, solution polymerization was carried out at 60 ° C. in a nitrogen gas atmosphere. Then, glycidyl methacrylate was added at a ratio of 20 mol% to obtain a prepolymer having an acid value of 120 mgKOH / g.

Example 1 8.0 parts by weight of polyethylene glycol diacrylate (A-200 manufactured by Shin Nakamura Chemical Co., Ltd.) as the component (B) was added to 100 parts by weight of the prepolymer as the component (A) obtained in Production Example 1. ,
(C) component biphenyl-4,4'-diglycidyl ether 8.0 parts by weight, (D) component bis (cyclopentadienyl) -bis [2,6-difluoro-3-[(1-pill- 1.0 parts by weight of 1-yl) methyl] phenyl] titanium, 2-benzyl-2-dimethylamino-of the component (E)
1- (4-morpholinophenyl) -butan-1-one (Ciba Geigy Co., Irger Cure 369) 8.0
Parts by weight, 1.0 part by weight of component (F) 4,4 ', 4 "-methylidine tris (N, N-dimethylbenzenamine) (A-DMA manufactured by Hodogaya Chemical Co., Ltd.), phthalocyanine green A photosensitive resin composition was prepared by blending 5 parts by weight and 8.0 parts by weight of talc under a red lamp and further mixing and dispersing with a triple roll.

Next, this photosensitive resin composition was applied by screen printing to a substrate having a copper foil pattern formed thereon in a thickness of 30 to 40 μm. Then, after drying for 20 minutes by a hot air circulation dryer at 70 ° C., a drawing pixel is 10 μm, a beam diameter is 40 μm, and an exposure amount is 20 mJ / cm ^2.
In the above, symbol mark exposure was performed with an argon laser having a wavelength of 488 nm. Then, a negative film having a desired pattern is adhered, and an exposure amount of 1000 mJ /
After irradiating with cm ² of ultraviolet rays, develop with a 1.0 wt% sodium carbonate aqueous solution for 60 seconds, and further apply 80 W
/ Cm, 3 lights, 3 m / min, the cured coating film was obtained by passing through a UV oven. The physical properties of this product are shown in Table 1.

Example 2 In Example 1, as the component (D), bis (cyclopentadienyl) -bis [2,6-difluoro-3-
[(1-Pyr-1-yl) methyl] phenyl] titanium together with 1.0 part by weight of 7-diethylamino-3- (2-
A cured coating film was formed in the same manner as in Example 1 except that 1.0 part by weight of benzothiazyl) coumarin was used. The physical properties of this product are shown in Table 1.

Example 3 A cured coating film was prepared in the same manner as in Example 1 except that the prepolymer obtained in Production Example 2 was used in place of the prepolymer obtained in Production Example 1. Formed. The physical properties of this product are shown in Table 1.

Example 4 A cured coating film was prepared in the same manner as in Example 2 except that the prepolymer obtained in Production Example 2 was used in place of the prepolymer obtained in Production Example 1. Formed. The physical properties of this product are shown in Table 1.

Comparative Example 1 A photosensitive resin composition was prepared in the same manner as in Example 1 except that the component (D) was not used. Table 1 shows the physical properties of a cured coating film obtained in the same manner as in Example 1 using this photosensitive resin composition.

Comparative Example 2 A photosensitive resin composition was prepared in the same manner as in Example 1 except that the component (E) was not used.

Table 1 shows the physical properties of a cured coating film obtained by using this photosensitive resin composition in the same manner as in Example 1.

[0045]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03F 7/20 521 G03F 7/20 521 H05K 3/28 H05K 3/28 D

Claims (10)

[Claims] 1. A prepolymer having (A) an ethylenic bond-containing group and a carboxyl group, (B) a reactive diluent, (C) a thermosetting reaction substance, and (D) 450 to 700 n.
Radical polymerization initiator that is photosensitive in the light absorption wavelength region of m, (E) Radical polymerization initiator that is photosensitive in the light absorption wavelength region of 200 to 400 nm, and (F) Radicals are generated by irradiation with light to develop color. A photosensitive resin composition, which comprises as an essential component a dye. 2. The component (A) has an acid value of 40 to 150 mg KO.
The photosensitive resin composition according to claim 1, which is a H / g prepolymer. 3. The component (A) is a prepolymer obtained by reacting an oligomer or polymer having an epoxy group with an unsaturated monocarboxylic acid having an ethylenic bond and a polycarboxylic acid anhydride. 2. The photosensitive resin composition according to item 2. 4. The photosensitive resin composition according to claim 1, wherein the component (A) is a prepolymer obtained by reacting an oligomer or polymer having a carboxyl group with a compound having an ethylenic bond and an epoxy group. 5. The photosensitive resin composition according to claim 3, wherein the component (A) is a prepolymer obtained by reacting at a ratio of 0.8 to 3.0 equivalents of carboxyl groups per equivalent of epoxy groups. . 6. The component (B) has an acryloyl group or a methacryloyl group in the molecule, and the content thereof is 2.0 to 50 parts by weight per 100 parts by weight of the component (A). The photosensitive resin composition according to any one of 1 to 5. 7. The photosensitive resin composition according to claim 1, wherein the component (C) is a compound having two or more epoxy groups in one molecule. 8. The radical polymerization initiator of the component (D) is 4
The photosensitive resin composition according to any one of claims 1 to 7, which is a titanocene derivative that is photosensitive at a light absorption wavelength of 50 to 700 nm. 9. The photosensitive resin composition according to claim 1, wherein the component (F) is a leuco dye that produces a radical upon irradiation with light and develops a color by an oxidation reaction. 10. A coating film comprising the photosensitive resin composition according to claim 1 is provided on a substrate, and then a wavelength range of 450 to 450 is applied to the coating film.
Marking exposure by irradiating 700 nm laser light,
Subsequently, a method for forming a cured coating film, which comprises irradiating ultraviolet light having a wavelength range of 200 to 400 nm to perform pattern formation exposure and developing treatment.