TWI333499B - - Google Patents

Description

(4) 1333499 The inventors and others, in order to achieve the above-mentioned purpose, were found to contain (A) a carboxylic acid-containing resin and (B) a hydrazine group having a general formula (I). Ester photopolymerization initiator, [Chemical 5] -C=N—·〇—C—R2 (I)

1 II R 0

(wherein R1 is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or a phenyl group, and R2 is an alkyl group having 1 to 7 carbon atoms or a phenyl group) (C) having a general formula (11) Aminoethyl benzene-based photopolymerization initiator of the structure, [Chemical 6]

C—C—N ...... (II) π l v OR κ

(wherein 'R3, R4 are an alkyl group or an aralkyl group having 1 to 12 carbon atoms, and R5 and R6 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a cyclic alkyl ether group having two combinations thereof. (D) a compound having one or more ethylenically unsaturated groups in the molecule (except for a compound containing a carboxylic acid) (E) a blue pigment, and a composition which can be imaged by a dilute alkali solution, The coating film has a photocurable resin composition having a light absorbance of 400 to 420 nm of 0.5 to 1.2 per 25 #m, and exhibits high photopolymerization ability and sufficient surface hardening for laser light of 400 to 420 nm. And deep hardenability (6) 1333499 Compounds having more than one ethylenically unsaturated group ' (except for compounds containing a carboxylic acid), (E) a blue pigment, which can be imaged by a dilute alkali solution The composition of the coating film having a absorbance at a wavelength of 400 to 420 nm is a composition of 0.5 to 1.2 per 25 jum.

In other words, the oxime ester-based photopolymerization initiator (B) containing the carboxylic acid-containing resin (A) and the oxime ester group represented by the general formula (I), and the amine group represented by the general formula (II) are found. An acetaminophen photopolymerization initiator (C) and a compound having one or more ethylenically unsaturated groups in the molecule (except for a compound containing a carboxylic acid) (D) can be converted into a dilute aqueous solution. The composition of the image can be coated on the film by the oxime ester photopolymerization initiator (B), the aminoacetamide photopolymerization initiator (C), and the blue pigment (E). The absorbance in the ~42 Onm wavelength is adjusted to 0.5 to 1.2 per 25/xm, and a coating film excellent in surface hardenability and deep hardenability can be formed.

Hereinafter, each constituent component of the resin composition of the photocuring property or the photocurability/thermosetting property of the present invention will be described in detail. In the carboxylic acid-containing resin (A) contained in the photocurable or photocurable thermosetting resin composition of the present invention, a known and customary resin compound containing a carboxyl group in the molecule can be used. Further, the carboxylic acid-containing photosensitive resin (A) having an ethylenically unsaturated double bond in the molecule is more preferable in terms of photocurability and development resistance. Specifically, the resins listed below can be mentioned. (1) A carboxylic acid-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with one or more of -9 - 1333499 (7) having a compound having another unsaturated double bond. (2) A photosensitive resin containing a carboxylic acid, which is a copolymer of an unsaturated carboxylic acid such as (meth)acrylic acid and one or more compounds having a compound having another unsaturated double bond, and (meth)acrylic acid a compound having an epoxy group and an unsaturated double bond, such as glycidyl ester and 3,4-epoxycyclohexylethyl (meth)acrylate, and (meth)acryloyl chloride, etc., having an ethylenically unsaturated group as a side Kigai became the income.

(3) A photosensitive resin containing a carboxylic acid characterized by having an epoxy group and an unsaturated group such as glycidyl (meth)acrylate and 3,4-epoxycyclohexylethyl (meth)acrylate. a compound of a double bond, a copolymer with a compound having another unsaturated double bond, reacting with an unsaturated carboxylic acid such as (meth)acrylic acid, and reacting the resulting secondary hydroxyl group with a polybasic acid anhydride

(4) A photosensitive resin containing a carboxylic acid, which is characterized in that an acid anhydride having an unsaturated double bond such as maleic anhydride and a copolymer having another compound having no double bond are (meth)acrylic acid. A compound obtained by reacting a compound having a hydroxyl group and an unsaturated double bond, such as 2-hydroxyethyl ester. (5) A photosensitive resin containing a carboxylic acid, which is characterized in that a polyfunctional epoxy compound is reacted with an unsaturated monocarboxylic acid such as (meth)acrylic acid, and the resulting hydroxyl group is reacted with a saturated or unsaturated polybasic acid anhydride. Income. (6) A photosensitive resin containing a hydroxy group and containing a hydroxy group, which is characterized in that a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative is reacted with a saturated or unsaturated polybasic acid anhydride, and then a carboxylic acid is formed. A reaction of a compound having an epoxy group and an unsaturated double bond in the molecule. -10- (8) 1333499 (7) A photosensitive resin containing a carboxylic acid characterized by having a polyfunctional epoxy compound, an unsaturated monocarboxylic acid such as (meth)acrylic acid, and at least one molecule A reaction product of an alcoholic hydroxyl group and a compound other than a reactive group reactive with an epoxy group (for example, dimethylolpropionic acid, etc.) is obtained by reacting a saturated or unsaturated polybasic acid anhydride.

(8) A photosensitive resin containing a carboxylic acid, characterized in that a polyfunctional butane compound having at least two abutane rings in one molecule is reacted with an unsaturated monocarboxylic acid such as (meth)acrylic acid. And the obtained primary hydroxyl group in the modified butane resin is obtained by reacting a saturated or unsaturated polybasic acid anhydride.

(9) A photosensitive resin containing a carboxylic acid, characterized in that a polyfunctional epoxy resin (for example, a cresol novolak type epoxy resin or the like) is an unsaturated monocarboxylic acid (for example, (meth)acrylic acid or the like) After the reaction, the photosensitive resin containing a carboxylic acid obtained by reacting a polybasic acid anhydride (for example, tetrahydrophthalic anhydride or the like), and more preferably, has an oxirane ring and one or more ethylenically unsaturated groups in the molecule. The compound (for example, glycidol (meth) acrylate or the like) is obtained by a reaction, but is not limited thereto. In these examples, the photosensitive resin containing a carboxylic acid of the above (2), (5), (7), and (9) is preferably the light-sensitive resin containing the carboxylic acid of the above (9). It is preferable in terms of hardenability and hard coating properties. Further, in the present specification, the term "(meth)acrylate" is a term generally referred to as propionate, methacrylate, and a mixture thereof, and the same applies to other similar expressions. -11 - (9) 1333499 The above-mentioned carboxylic acid-containing resin (A) has a large number of free carboxyl groups in the side chain of the skeleton-polymer, and thus can be visualized by a dilute aqueous alkali solution.

Further, the acid hydrazide of the carboxylic acid-containing resin (A) is in the range of 40 to 200 mgKOH/g, more preferably in the range of 45 to 120 mgKOH/g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, alkali imaging is difficult. On the other hand, when it exceeds 200 mgKOH/g, the exposed portion is dissolved through the developing solution, so that the wire becomes thinner than necessary, as the case may be. Since the exposed portion and the unexposed portion cannot be distinguished and are dissolved and peeled off by the developing solution, it is difficult to draw a normal resist pattern, which is not preferable. Further, the weight average molecular weight of the carboxylic acid-containing resin (A) is preferably from 2,000 to 150,000, more preferably from 5,000 to 100,000, depending on the resin skeleton. When the weight average molecular weight is less than 2,000, the tack-removing property is poor, the moisture resistance of the coating film after exposure is poor, and film thinning occurs at the time of development, and the resolution is greatly deteriorated. On the other hand, if the weight average molecular weight is more than 1 50,000, the developability is remarkably deteriorated, and the storage stability is improved.

difference. The compounding amount of the carboxylic acid-containing resin (A) and/or the carboxylic acid-containing photosensitive resin (A') is 20 to 60% by mass, preferably 30 to 50% by mass based on the total composition. When the amount is less than the above range, the film strength is lowered, which is not preferable. On the other hand, when it is more than the above range, the viscosity is high, and the coatability and the like are lowered, which is not preferable. The oxime ester-based photopolymerization initiator (B) used in the invention of the present invention is an oxime ester-based photopolymerization initiator containing an oxime ester group represented by the following general formula (I), -12- 1333499

(10) [Chem. 7] - C = N - 0 - C - R2 丨 ll R1 0 (wherein R1 represents a hydrogen atom, a carbon number of 1 to 7 phenyl groups, and R2 represents a carbon number of 1 to 7) For example, the one described in the aforementioned Patent Document 1 can be cited. The photopolymerization initiator (B) is preferably an initiator of the following formula (III) (2-(ethyloxyimidomethyl) thioxanthene-9-one), [Chemical 8]

The photopolymerization of the photopolymerization initiator of the structure represented by the following general formula (V), or the photopolymerization of the oxime ester type represented by the following general formula (IV): (Ill) Agent, and ... (IV)

0

-13- ......(V) (11)1333499 (in the formula, R7 and R8 are alkyl groups each independently representing a carbon number '丨~丨," and Chinese 9, 111 (), 1111, and 12 are independently represented. A hydrogen atom or an alkyl group having a carbon number of 1 to 6 'n is an integer representing 0 to 5. R13 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R14 and R15 are each a carbon number of 1 to 12. alkyl). Commercially available products are CGI-325 ' Irugacure ΟΧΕΟ 1, Irugacure OXE 02 manufactured by Ciba Specialty Chemicals. These oxime ester photopolymerization initiators may be used alone or in combination of two or more.

The resin composition containing such an oxime ester-based photopolymerization initiator (B), which is photocurable or photocurable or thermosetting, is applied to copper of a printed wiring board alone or the like. The reaction with a copper atom has a problem of deactivating the function as a photopolymerization initiator, and must be used together with an aminoethylbenzene-based photopolymerization initiator (C) to be described later.

The amount of the oxime ester-based photopolymerization initiator (B) is 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the carboxylic acid-containing resin (A). When the amount of the oxime ester-based photopolymerization initiator (B) is less than 0.01 part by mass with respect to 100 parts by mass of the carboxylic acid-containing resin (A), one or more ethylenic unsaturations are contained in the photo-molecular molecule. The hardening of the compound (D) and the carboxylic acid-containing resin (A) is insufficient, the hygroscopicity of the cured film is high, and the PCT resistance is liable to be lowered, and the solder heat resistance and electroless plating resistance are also liable to become low. . On the other hand, when the amount of the oxime ester-based photopolymerization initiator (B) is more than 10 parts by mass based on 100 parts by mass of the carboxylic acid-containing resin (A), the shape of the cured coating film tends to be larger than that of the irradiation ray. The phenomenon that the part of the light is more sensitized (smooth) is more difficult to obtain the depth of hardening, so it is not good. -14- (12) 1333499 The following general formula benzene photopolymerization initiator (C) used in the present invention, [Chemical 1 0]

(In the formula, R3 and R4 are carbon atoms I to 'R5, and R6 is a cyclic alkyl ether group having a hydrogen atom and a carbon number of 1 to 6). For example, 2-methyl-1 - [4 · (A Street) Acetone-1,2-benzyl·2-dimethylamino-1-(z 嗣,2-(dimethylamino)-2-[(4-methylphenyl)linyl)phenyl]-1 - Butanone, anthracene, anthracene-dimethylamino group, Ciba Specialty Chemicals, Irugacure 369, Iurgacure 3 79, etc. The polymerization of such an aminoethyl benzene-based photopolymerization-initiating oxime ester-based photopolymerization initiator (B), The oxime ester photopolymerization initiator (B) acts on copper. The amide-based phthalocyanine photopolymerization initiator is 100 parts by mass, preferably 0.5 to 15 parts by mass of the carboxylic acid-containing resin (A). Proportion of shares

When the amount of the initiator (C) is less than 0.1 part by mass, the amount of the initiator (C) is less than 0.1 part by mass, and the coating film is peeled off, and the urethane is coated with the coating material -15-II).

......(丨丨) 12 alkyl or aralkyl alkyl groups or a combination of two yl) phenyl]-2-morpholinamine μmorpholine phenyl)-butane-1-S) Iso[4-(4-o-ethyl benzene, etc.. Irugacure 907, !l (C) which can be manufactured by the commercial product does not hinder the above-mentioned phenomenon, and compensates for the phenomenon of inactivation by the aforementioned heat ( The amount of C), the amount of the phase t, is 〇·1 to 30. The amino acetonitrile is a photopolymer containing a carboxylic acid resin (the photocurable film on the ketone is degraded, so it is not (13) 1333499. When the amount of the aminoethyl benzene-based photopolymerization agent (C) is more than 30 parts by mass based on 100 parts by mass of the carboxylic acid-containing resin (A), It is not preferable because the heat resistance and electrical properties are lowered.

Further, the photocurable or photocurable thermosetting resin composition of the present invention may contain a tertiary amine compound and a benzophenone compound as a light-emitting auxiliary. Examples of such tertiary amines include ethanolamines, 4,4·-dimethylaminobenzophenone (Nissocure MABP manufactured by Nippon Soda Co., Ltd.), and 4,4·-diethylaminobenzophenone (Zokuto Valley Chemical Industry) EAB), 4-dimethylaminobenzoic acid ethyl vinegar (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylaminobenzoic acid ethyl vinegar (Quantacure DMB manufactured by International Biosynthetic Co., Ltd.), 4-dimethylaminobenzene Formic acid (n-butoxy)ethyl ester (Quantacure BEA, manufactured by I nternati ο na 1 B i 〇synthetic)

Isoamyl ethyl p-dimethylaminobenzoate (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (Esolol 507 manufactured by Van Dyk Co., Ltd.), and the like. These well-known conventional tertiary amine compounds may be used singly or in combination of two or more. Among them, dialkylamino benzophenone (F) such as 4,4'-dimethylaminobenzophenone and 4,4'-diethylaminobenzophenone is particularly preferred. In particular, 4,4'-diethylaminobenzophenone is less toxic and is preferably used. The reason for this is that the region having a wavelength of 400 to 42 Onm has a large absorption, and has a large influence on the absorbance to be described later and achieves the surface hardenability and the hardening depth of the object of the present invention. The amount of the dialkylamino benzophenone (F) to be added is 5 parts by mass or less, preferably 0.01 to 5 parts by mass, more preferably 0.1% by mass based on 100 parts by mass of the carboxylic acid-containing resin (A). ~ 2 parts by mass ratio. When the amount of the dialkylamine-16-(14)1333499 benzophenone (F) is more than 5 parts by mass based on 1 part by mass of the resin of the residual acid (A), the electrical properties are lowered. Therefore, it is not good.

The photocurable or photocurable/thermosetting resin composition of the present invention may further contain benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, etc., as needed. Benzoin and benzoin alkyl ether; acetophenone, 2,2-dimethoxy-2-phenylethyl benzene, 2,2-diethoxy-2-phenylethyl benzene, Acetylbenzenes such as 1,1-dichloroethyl benzene and the like: 2-methyl hydrazide '2-ethyl hydrazine' 2-tert-butyl fluorene, 1-chloroindole and the like; Thiophenones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; a ketal such as dimethyl ketal or benzyl dimethyl ketal; benzophenone, 4-benzhydryl dithiobenzene, 4-benzylidene-4-methyldithiobenzene, 4-benzoic acid二_4'-ethyldithiobenzene, 4-benzothymol- 4'-propyldithiobenzene, etc., benzophenones or xanthones; 2,4,6-trimethylbenzoate A known photopolymerization initiator such as a phosphine oxide such as phenylphosphine oxide.

Among them, the most preferred one is 4-benzylformin-4'-methyldithiobenzene, more preferably 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2 A thioxanthone-based photopolymerization initiator such as chlorothioxanthone or 2,4-diisopropylthioxanthone is preferred from the viewpoint of high sensitivity. The amount of the photopolymerization initiator and the photoinitiator is the same as the above-described oxime ester photopolymerization initiator (B), amino acetophenone photopolymerization initiator (C), or alkylaminobenzophenone ( The total amount of F) is in the range of 20 parts by mass or less based on 1 part by mass of the carboxylic acid-containing resin (A). When it is more than the above range, the electrical properties are lowered, which is not preferable. -17- (15) 1333499 The compound (D) having one or more ethylenically unsaturated groups in the molecule used for the photocurable or photocurable/thermosetting resin composition of the present invention (however, the above-mentioned carboxylic acid is contained) The photosensitive resin (except for the carboxylic acid-containing compound of A◦) is photocured by irradiation with an active energy ray, and the carboxylic acid-containing resin (A) is insolubilized in an alkaline aqueous solution or helps to dissolve. substance.

Examples of such a compound (D) include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; Mono- or diacrylates of diols; acrylamides such as hydrazine, hydrazine, dimethyl methacrylamide, hydrazine-hydroxymethyl acrylamide, hydrazine, hydrazine-dimethylaminopropyl acrylamide; acrylic acid Anthracene amides such as hydrazine, hydrazine-dimethylamine ethyl ester, hydrazine acrylate, hydrazine-dimethylaminopropyl propyl ester; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, trishydroxyethyl isocyanurate a polyvalent acrylate such as an acid ester or the like thereof or an ethylene oxide adduct thereof or a propylene oxide adduct; a phenoxy acrylate, a bisphenol fluorene diacrylate, and a phenolic epoxy An acrylate such as an alkane adduct or a propylene oxide adduct; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate or the like Acrylic acid of glycidyl ether; and melamine acrylate, and/or methacrylic acid corresponding to each of the above acrylates Class. Among them, a polyfunctional (meth) acrylate compound having a compound having two or more ethylenically unsaturated groups in the molecule is particularly excellent in photocurability. • Further, a polyfunctional epoxy resin such as bisphenol A, bisphenol F epoxy resin, phenol or cresol novolak epoxy resin, or epoxy reacted with acrylic-18-(16)1333499 may be mentioned. An acrylate resin, and a base of the oxy acrylate resin, an epoxy reacted with a hydroxy acrylate such as pentaerythritol triacrylate or a melamine compound of a diisocyanate such as isophor or diisocyanate. A urethane acrylate compound. Such an epoxy acryl vine resin does not deteriorate the dryness of the finger touch and can improve the photocurability.

The compounding amount of the compound (D) having one or more ethylenically unsaturated groups in the molecule is from 5 to 100 parts by mass, more preferably from 10 to 100 parts by mass, based on 100 parts by mass of the carboxylic acid-containing resin (A). 70 parts by mass. When the amount of the above-mentioned compounding amount is less than 5 parts by mass, the photocurability is lowered, and it is difficult to form a pattern by alkaline development after irradiation with an active amount line, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the solubility in the alkaline aqueous solution is lowered and the coating film becomes brittle, which is not preferable.

The blue pigment (E) which is one of the features of the present invention is a conventional coloring pigment, but when a laser light of 400 to 42 Onm is used in the present invention, it is found that a blue pigment (for example, phthalocyanine blue) is added. Gloss sensitivity can be achieved at lower exposure levels. The reason for the sensitizing effect of the blue pigment (for example, a phthalocyanine blue pigment) is not clarified, but it is known, for example, in a resin composition having a absorbance of 0.5 μm per z 25; In the case of phthalocyanine blue, the absorbance is only 〇·5 or more, and sufficient surface hardenability and hardening depth can be obtained at a low exposure amount at the same time. Further, this sensitizing effect has an effect on the surface reactivity (gloss improvement), and the hardening depth is inversely deteriorated. That is, the action of reacting the laser light is performed. This action is also effective for the stabilization of the shape of the photoresist. For example, when observing the cross-sectional shape of the photoresist, the compound which does not contain phthalocyanine blue and which absorbs -19-(18)1333499 two or more butadiene groups, that is, the polyfunctional butane compound (G-2), intramolecular A compound having two or more thioether groups, that is, an episulfide resin or the like.

Examples of the polyfunctional epoxy compound (G-1) include Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1 004 manufactured by Japan Epoxy Resin Co., Ltd., Epiclione 8 40 manufactured by Dainippon Ink and Chemicals, and Epiclione 8 5 0. , Epiclione 1 05 0, Epiclione 2055, ugly by Dongdu Chemical Co., Ltd. (^〇16丫0-011, 丫0-013, 丫0-127 'YD- 1 28 > DER 317, D by Dow Chemical Co., Ltd. .

ER33 1, D. E_R.66 1. DER664, Ararudide 6071, Ararudide 6084, Ararudide GY 250, Ararudide GY 260 from Ciba Specialty Chemicals, Sumiepoxy ESA-011, ESA-014, ELA manufactured by Sumitomo Chemical Industries -115, ELA-128, A.E_R.330, AER331, AER661, AER664, etc. (all trade names) manufactured by Asahi Kasei Kogyo Co., Ltd. (both trade names) bisphenol A type epoxy tree; Japan Epoxy Resin Co., Ltd. Epicoat YL 903, Epiclone 152 manufactured by Dainippon Ink and Chemicals Co., Ltd., Epiclone 165, Epotote YDB-40 manufactured by Dongdu Chemical Co., Ltd., YDB-500, DER 542 manufactured by Dow Chemical Co., Ltd., Ararudide 8011 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumitomo Sumiepoxy ESB-400, ESB-700 manufactured by Chemical Industry Co., Ltd., AER 711 manufactured by Asahi Kasei Kogyo Co., Ltd., AER 714, etc. (both trade names) brominated epoxy resin; Epicoat 152, Epicoat 154 manufactured by Japan Epory Resin Co., Ltd. DEN 431, DEN 438, -21 - (19) 1333499 manufactured by Dow Chemical Co., Ltd. Epiclone N-730, Epiclone N-770, Epiclone manufactured by Dainippon Ink Chemical Industry Co., Ltd. N-865, Epotate YDCN-701, YDCN-704, manufactured by Dongdu Chemical Co., Ltd., Ararudide ECN 1 23 5 manufactured by Ciba Specialty Chemicals, Ararudide ECN 1 273, Ararudide ECN 1 299, Ararudide XPY 307, manufactured by Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1 025, EOCN-1 020, EOCN-104S, RE-

3 06. Sumiepoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Industries Co., Ltd., AERECN-23 5 manufactured by Asahi Kasei Kogyo Co., Ltd., ECN-2 99 (all are trade names), novolak-type epoxy resin; Epiclone 830 manufactured by Ink Chemical Industry Co., Ltd. Epicoat 8 07 manufactured by Japan Epoxy Resin Co., Ltd., Epotote YDF-170, YDF-175, YDF-2004 manufactured by Dongdu Chemical Co., Ltd., Ararudide XPY 3 manufactured by Ciba Specialty C h em i cal s Bisphenol F type epoxy resin such as 06 (all trade names); hydrogenated bisphenol A type epoxy resin such as Epotote ST-2004, ST-2007, ST-^OOG (trade name) manufactured by Dongdu Chemical Co., Ltd.: Epicoat 604 manufactured by Japan Epoxy Resin Co., Ltd., Epotote YH-43 manufactured by Tosho Kasei Co., Ltd., Ararudide MY 720 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumiepoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (all trade names) Amine type epoxy resin; Ararudide CY-350 (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd., etc. Ethylene ureide type epoxy resin: Seroxide 202 manufactured by Diace Chemical Industry Co., Ltd., Ciba Specialty C Ararudide CY175, CY179, etc. (all trade names) of hemicals, alicyclic epoxy resin: YL-933, Dow -22- (20) 1333499, manufactured by Japan Epoxy Resin Co., Ltd.

Chemicals company's TEN, EPPN-501, EPPN-502 (all trade names) of trishydroxyphenylmethane epoxy resin; Japan Epoxy Resin company's YL-6045, YX-4000, YL-6121 (both Dimethyl diol type or biphenol type epoxy resin or a mixture thereof, such as a product name; EBPS-200 manufactured by Nippon Chemical Co., Ltd., EPX_30 manufactured by Asahi Kasei Kogyo Co., Ltd., EXA-made by Dainippon Ink Chemical Industry Co., Ltd. Double 酣S type epoxy resin such as 1 514 (trade name); bisphenol A novolac type epoxy resin such as Epicoat 157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd.; Epicoat YL-931 manufactured by Japan Epoxy Resin Co., Ltd. Ciba

Four products of Ararudide 163, etc. (both trade names) manufactured by Specialty Chemicals Co., Ltd.; Ararudide PT810 manufactured by Ciba Specialty Chemicals Co., Ltd., TEP 1C manufactured by Nissan Chemical Industries Co., Ltd. (all trade names) Heterocyclic epoxy resin; diglycidyl acrylate resin such as Brenmer DGT manufactured by Nippon Oil & Fats Co., Ltd.; tetraglycidyl xylenol ethane resin such as ZX-1063 manufactured by Dongdu Chemical Co., Ltd.; Nippon Steel Chemical Co., Ltd. Company-made ESN-190, ESN-360, Nippon Ink Chemical Industry Co., Ltd. HP-4032, EXA-4750, EXA-4700, etc. Naphthalene-based epoxy resin: HP-7200, HP manufactured by Dainippon Ink Chemical Industry Co., Ltd. Epoxy resin having a dicyclopentadiene skeleton such as -7200H; glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil Co., Ltd.; and cyclohexylmaleimide Copolymer epoxy resin with glycidyl methacrylate; epoxy modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Diacel Chemical Industry Co., Ltd.), CTBN modified epoxy resin (for example, Dongdu Chemical Company) The YR-102, YR-450 -23- (21) 1333499, etc.) and the like, but are not limited thereto. Among them, a novolak type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.

The polyfunctional butane compound (G-2) may, for example, be bis[3-methyl-3_indolylmethoxy]methyl]ether or bis[(3-ethyl-3-tert-butylmethoxy)methyl] Ether, 1,4-bis[(3-methyl-3-indolyl methoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-indolylmethoxy)methyl]benzene, (3-Methyl-3-indene butyl) methacrylate '(3-ethyl-3-hydrazinobutyl) methacrylate, (3-methyl-3-P-butyl butyl) methyl group Polyacrylates of (meth) acrylate, (3-ethyl-3- crotonyl) methyl methacrylate and oligomers or copolymers thereof, and butyl alcohol and novolak resins, poly An ether compound of a resin having a hydroxyl group such as (p-hydroxystyrene), a card type bisphenol, a calixarene, a cup-containing resorcinol arene, or a sesquiterpene. Further, a copolymer of an unsaturated monomer having a sulfonate ring and an alkyl (meth) acrylate may, for example, be mentioned.

The compound having two or more cyclic thioether groups in the above molecule may be exemplified by a biguanide type A episulfide resin YL 7000 manufactured by Japan Epoxy Resin Co., Ltd., and the like. Further, the same synthesis method may be used, and an epoxy sulfide resin in which an oxygen atom of an epoxy group of a phenolic stomach paint type epoxy resin is substituted with a sulfur atom may be used. The amount of the cyclic (thio)ether (G) to be added to the heat resistance is from 0.6 to 2.0 equivalents, preferably from 0.8 to 1.5 equivalents, per equivalent of the carboxyl group of the carboxylic acid-containing resin. . When the amount of the cyclic (thio)ether (G) is less than the above range, the carboxyl group remains, and the heat resistance is less than 24 (22) 1333499, and the testability and electrical insulating properties are lowered. On the other hand, when the above range is exceeded, the low molecular weight cyclic (thio)ether (G) remains as a result of a decrease in the strength of the coating film and the like, which is not preferable.

When the above cyclic (thio)ether compound (G) is used, it is preferred to contain a thermosetting catalyst. Examples of such a thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1-cyanoethylidene. Imidazole derivatives such as 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethylamino) Anthracene, hydrazine-dimethylbenzylamine, 4-methoxy-indole, hydrazine-dimethylbenzylamine, 4-methyl-hydrazine, hydrazine-dimethylbenzylamine, etc., adipic acid An antimony compound such as diterpene or azelaic acid; a phosphorus compound such as triphenylphosphine; or a commercially available substance such as 2ΜΖ-Α, 2ΜΖ-0Κ, 2ΡΗΖ, 2Ρ4ΒΗΖ, 2Ρ4ΜΗΖ manufactured by Shikoku Chemical Industrial Co., Ltd. ( It is a trade name of a bismuth compound), U-CAT3 5 03N, U-CAT 3 5 0 2 T (a trade name of a block isocyanate compound of dimethylamine), DBU, DBN, manufactured by Sunapplo Co., Ltd.

U-CATSA102, U-CAT5002 (both bicyclic guanidine compounds and their salts). In particular, it is not limited thereto, and it may be a thermosetting catalyst of an epoxy resin and a butyl compound, or a reaction promoting an epoxy group and/or a butyl butyl group and a residue, and may be used singly or in combination. The above is also fine. Further, as the adhesion-imparting agent, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-three tillage can also be used. ' 2_Ethyl group _ 2,4-diamino-S-three tillage, 2-vinyl-4,6-diamino-S-triterpene isoformate addition, 2,4- An S-trinyl derivative such as a diamino-6-methylpropenyloxyethyl-S-triterpene-isophthalic acid adduct or the like, preferably as a dense-25- (23 1333499 A compound of a viscosity-imparting agent is used in combination with the aforementioned thermosetting catalyst. The amount of the thermosetting catalyst is sufficient in a usual proportion, for example, 0.1 to 20 by mass based on 100 parts by mass of the carboxylic acid-containing resin (A) or the cyclic (thio)ether compound (G). The fraction is preferably a ratio of 0.5 to 1 5.0 parts by mass.

The resin composition of the photocurable or photocurable thermosetting resin of the present invention may be added with a sizing agent as needed in order to increase the physical strength of the coating film and the like. As the above-mentioned admixture, an inorganic or organic hydrating agent known in the art can be used, and particularly, barium sulfate, spheroidal cerium oxide and talc are preferably used. Further, it can also be used in the above-mentioned compound (D) having one or more ethylenically unsaturated groups and NANOCRYL (trade name) manufactured by Hanse-Chemie Co., Ltd. in which nano-cerium oxide is dispersed in the above-mentioned polyfunctional epoxy resin (G-1). ) XP 0396,

XP 0596, XP 0733, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all product grade names), and NANOPOX (trade name) XP 0516, XP 0525, XP made by Hanse-Chemie 03 14 (all product grade names). They may be used alone or in combination of two or more. The amount of the above-mentioned hydrazine-containing resin is 300 parts by mass or less, preferably 0.1 to 300 parts by mass, more preferably 0.1 to 150 parts by mass, per 100 parts by mass of the carboxylic acid-containing resin (A). When the amount of the above-mentioned filler is more than 300 parts by mass, the viscosity of the composition is high and the printability is lowered, and the curability is brittle, which is not preferable. Further, the photocurability or photocurability of the present invention or the thermosetting The resin composition may be an organic solvent in order to synthesize the carboxylic acid-containing resin (A) and the adjustment -26-(24) 1333499 composition, or to adjust the viscosity of the substrate and the carrier film.

Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, it is a ketone such as methyl ethyl ketone or cyclohexanone; an aromatic hydrocarbon such as toluene, xylene or tetramethylbenzene; a cellosolve, a methyl cellosolve, or a butyl cellosolve. a glycol ether of carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc.; ethyl acetate, Esters such as butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; aliphatic groups such as octane and decane; Hydrocarbons; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha, and the like. Such an organic solvent may be used singly or in combination of two or more.

The resin composition of the photocuring property, photocurability, and thermosetting property of the present invention may be combined with hydrogen awake, hydrogen awake monomethyl ether, tert-butyl catechol, pyrogallol, and fluorene. Known conventionally used thermal inhibitors, fine powdered cerium oxide, organic bentonite, montmorillonite, and the like, known conventional tackifiers, polyfluorene-based, fluorine-based, polymer-based antifoaming agents and/or leveling agents A known and customary additive such as a decane coupling agent such as an imidazole type, a thiazole type or a triazole type. Further, the photocurable or photocurable thermosetting resin composition of the present invention may contain a coloring pigment other than a blue pigment insofar as it does not adversely affect resolution or the like. -27- (25)1333499

The resin composition of the photocurability or photocurability and thermosetting property of the present invention is adjusted, for example, to a viscosity suitable for the coating method by the organic solvent, and is applied to a substrate by a dip coating method or a flow coating method. Coating by a roll coating method, a bar coating method, a screen printing method, a curtain coating method, and the like, and drying and drying (false drying) of the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. A tack-free coating film can be formed. Further, when the composition is coated on a carrier film, dried, and attached to a substrate by a film type winder, a resin insulating layer can be formed. Thereafter, the pattern is drawn by a direct drawing device (laser direct drawing device), or in a contact (or non-contact manner), selectively exposed by the active energy line through the patterned mask, and the unexposed portion is diluted with alkali An aqueous solution (for example, a 0.3 to 3% aqueous solution of soda carbonate) is developed to form a photoresist pattern. Further, when the thermosetting component is contained, it is thermally cured by, for example, heating at a temperature of about 140 to 180 r, so that the carboxyl group of the carboxylic acid-containing resin (A) and the molecule have two or more cyclic ethers. The thermosetting component (G) of the group and/or the cyclic (thio)ether group reacts to form a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. The substrate may be exemplified by paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, woven/nonwoven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluorine/polyethylene. - Copper-clad laminates of all grades (FR-4, etc.), such as PPO, cyanate, etc., such as copper-clad laminates for high-frequency circuits, and other polyimine films, PET films, glass substrates, and ceramic substrates. , wafer board, etc. The hot air circulating drying oven, the IR furnace, the hot plate, and the volatilization drying after the photocurable or photocurable thermosetting resin -28-(26) 1333499 composition of the present invention is applied. A convection oven or the like (a method in which a heat source having a steam-heating method is used to bring the hot air in the dryer into contact with the flow and a method in which the nozzle is blown to the support) is performed.

The exposure machine used for the active energy ray irradiation is as described above, and a direct drawing device (for example, a laser directly drawing an image by laser light from a computer to directly image the active energy line of the image can be used, and the maximum wavelength is 400 to 420 nm. The laser light of the range is sufficient. Further, the exposure amount varies depending on the film thickness, etc., and is generally 2 to 100 mJ/cm 2 , preferably 5 to 60 mJ/cm 2 , more preferably 10 to 30 mJ/cm 2 . For the above-mentioned direct drawing device, for example, a product manufactured by Pentax, manufactured by Hitachi Viamecanix, manufactured by Ball. Semiconductor, or the like can be used, and any of the devices can be used.

The developing method is a dipping method, a rinsing method, a spraying method, a brushing method, etc., and a developing solution can use potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia, or hydric hydroxide. An alkaline aqueous solution such as tetramethylammonium. [Examples] Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited by the following examples. Synthesis Example 1 A 2-liter separable flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen gas introduction tube was charged with a cresol novolak type -29-(27)1333499

Epoxy resin (made by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C, epoxy equivalent = 2 20 g / equivalent) 660 g, carbitol acetate 42 丨. 3 g, and solvent stone brain The oil was 180.6 g and heated at 90 ° C to stir and dissolve. Next, the mixture was temporarily cooled to 60 ° C, and 216 g of acrylic acid, triphenylphosphine 4·g, and methyl hydrazine 1.3 g were added and reacted at 100 ° C for 12 hours to obtain a reaction product of acid oxime of 0.2 mg KOH / g. Thereto was charged 241.7 g of tetrahydrophthalic anhydride, and heated at 90 ° C for 6 hours. Thus, 65% by mass of the nonvolatile component was obtained, and the solid content of the acid was 77=77 mgKOH/g, the double bond equivalent (the weight of the resin of the unsaturated group per 1 mole of the resin) = 400 g/eq, and the weight average molecular weight = 7,000. A solution of a carboxylic acid photosensitive resin (A'). Hereinafter, the solution containing the carboxylic acid-based photosensitive resin is referred to as A-1 varnish. Synthesis Example 1

In a 2 liter separable flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, an o-cresol novolac type epoxy resin (epoxy equivalent = 2 15 g / equivalent, in one) was charged. There are an average of 6 phenol cores in the molecule of 430 grams and 144 grams of acrylic acid (2 moles). While heating to 120 ° C while stirring, the reaction was maintained at 120 t and the reaction was continued for 10 hours. The reaction product was temporarily cooled to room temperature, 190 g of succinic anhydride (1.9 mol) was added, and the reaction was heated at 80 ° C for 4 hours. Again, the reaction product was cooled to room temperature. The acid hydrate of this product solid component was 139 mg KOH/g. To this solution was added 85.2 g of glycidyl methacrylate (0.6 -30-(31) 1333499 performance evaluation: <absorbance>

For the measurement of the absorbance, an ultraviolet-visible spectrophotometer (Ubest-V-5100DS manufactured by JASCO Corporation) and an integrating sphere device (ISN-470 manufactured by JASCO Corporation) were used. The photocurable and thermosetting resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7 were applied on a glass plate by an applicator, and then dried in a hot air circulating drying oven at 8 (TC drying for 30 minutes). A dry coating film of a photocurable and thermosetting resin composition is formed on a glass plate, and a glass plate of a photocurable or thermosetting resin composition is applied by using an ultraviolet visible light spectrophotometer and an integrating sphere device. The same glass plate was used to measure the absorbance at 500 to 300 nm. The absorbance of the prepared glass plate with the dried coating film was measured, and the absorbance of the dried coating film was calculated from the baseline to obtain the target light wavelength of 405 nm. Absorbance. In order to prevent the absorbance from being uneven due to the thickness of the coating film, the operation was carried out by changing the coating thickness of the applicator in four stages, and a blank group of the coating thickness and the absorbance at 40 5 nm was prepared. The absorbance of the dried coating film having a film thickness of 25 μm was calculated as the approximate absorbance. The evaluation results are shown in Table 2. <Optimum Exposure Amount> The copper-clad laminate substrate was honed roller After pondering, After washing and drying, the photocurable and thermosetting resin compositions of the above Examples 1 to 7 and Comparative Examples 1 to 7 were applied by screen printing, and were subjected to a hot air circulating drying oven at 80 °C. Dry for 30 minutes. After drying, pass through the mask (Eastman -34- (32) 1333499

Coduct, Step Tablet Νο·2), was exposed using a direct drawing device equipped with blue-violet laser light with a wavelength of 405 nm. The irradiated person was regarded as a test piece, and after development for 60 seconds with a developing solution (sodium carbonate aqueous solution) of a spray pressure of 2 MPa, the number of remaining coating films was visually determined. The exposure amount in which the number of the remaining coating film is six segments is regarded as the optimum exposure amount. The evaluation results are shown in Table 2.

&lt;Surface hardening&gt;

The substrate produced by the above optimum exposure amount was not exposed by a photomask, and a development coating film was obtained in the same manner as the above development. The exposure amount was an exposure amount obtained by evaluating the above optimum exposure amount. The developed coating film was irradiated with ultraviolet rays of 1 000 mJ/crn2 with a high pressure mercury lamp, and then hardened at 150 ° C for 60 minutes to obtain a hard coating film. The surface hardenability of the obtained cured coating film was evaluated by using a gloss meter Microtriglose (manufactured by Biggadoner Co., Ltd.) to evaluate the gloss at 60°. The evaluation criteria were deemed to be good when the glossiness of 50 or more after development was good, and the glossiness of less than 50 was regarded as bad. The evaluation results are shown in Table 2. &lt;Cross-section shape&gt; The resin composition of the photocurable and thermosetting resins of Examples 1 to 7 and Comparative Examples 1 to 7 was a circuit pattern having a line/space of 300/300 and a copper thickness of 50/zm. The substrate was honed by a honing roll, washed with water, dried, and coated by screen printing, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, it was exposed using a direct drawing device -35-(33)1333499 equipped with a blue-violet laser light having a wavelength of 405 nm. The exposure pattern is a pattern for drawing a 20/30/40/50/60/70/80/90/100/zm line for the base. The exposure amount was evaluated by the above-mentioned optimum exposure amount. After the exposure, a developing pattern was formed with an aqueous solution of sodium carbonate, and ultraviolet rays of 10 〇〇m J/cm were irradiated with a high-pressure mercury lamp, and then cured at 150 ° C for 60 minutes to obtain a cured coating film. Observe the intersection of the design of the hardened coating film 値ΙΟΟμιη line.

As shown in the figure, the model diagram of this shape is divided into five stages of evaluation. The figure is a model diagram showing the following phenomenon. In particular, in the case of A evaluation, the deviation from the design is less than 5^m in the upper and lower parts. The result is not in Table 2. A evaluation: If the design is ideal for wide state B evaluation: erosion of surface layer due to insufficient imaging resistance C evaluation: evaluation of the downward rotation state D: line thickness due to blooming effect, etc. E evaluation: line of surface layer Thickening and lowering

-36- (34)1333499

Comparative example 1.25 Good, W v 〇 1.32 100 &lt; Good 1 0.39 K* 寸 0.87 100 &lt; Bad unmagifiable 0.35 100 &lt; Bad U CN 0.66 Good m 0.29 Good Q Poor &lt;Example Bu 0.75 Good &lt; Ό 0.74 〇 Good &lt; ” 0.72 〇S &lt; inch 0.71 § good &lt; m 0.92 good &lt; 0.82 1 &lt; r - H 0.63 Good &lt; Absorbance Appropriate Exposure (mJ/cm2) Surface Harden Shape -37-

Claims (1)

1333499 ^0. υι 丨丨1 r 丨 Announcement P Year 曰 曰 曰 本 本 本 95 132 95 Patent No. 95132758 Patent Application Chinese Patent Application Scope Republic of China January 28, 1999 Revision 1. A photohardenable resin composition An oxime ester-based photopolymerization initiator containing (A) a carboxylic acid-containing resin and (B) an oxime ester group represented by the following general formula (I): [C=N-0] —C—R 2 I, II R1 0 (wherein R 1 represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or a phenyl group “R 2 is an alkyl group having 1 to 7 carbon atoms, or a phenyl group” ( C) an aminoethyl benzene-based photopolymerization initiator having the structure represented by the following general formula (π), [Chemical 2] (wherein, r3 and r4 are an alkyl group or an aralkyl group having a carbon number of i to 12, and R5 and R6 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a two-bonded cyclic alkyl ether; (D) a compound having more than one ethylenically unsaturated group in the molecule (but excluding a compound containing a carboxylic acid) and (E) an indigo blue pigment, 1333499, which can be imaged by a dilute alkali solution And the absorbance of the coating film at a wavelength of 400 to 420 nm is 25 to 1.2 per um, and the carboxylic acid-containing resin (A) is contained in the total composition of 20 to 60% by mass, and relative to the foregoing 100 parts by mass of the carboxylic acid-containing resin (a), 0.01 to 10 parts by mass of the oxime ester-based photopolymerization initiator (B), and 0.1 to 30 parts by mass of the aminoethyl benzene-based photopolymerization initiator (C). The compound (D) is in a proportion of 5 to 100 parts by mass, and the indigo blue pigment (e) is in the range of 0.5 to 1.2 per 25 in which the dry coating film has a wavelength at a wavelength of from 400 to 420 nm. 2. The photocurable resin composition of claim 1, wherein the carboxylic acid-containing resin (A) is obtained by reacting (a) a polyfunctional epoxy resin with (b) an unsaturated monocarboxylic acid; a carboxylic acid-containing resin obtained by reacting (c) a polybasic acid anhydride with a carboxylic acid-containing photosensitive resin obtained by reacting (d) a compound having one oxirane ring and one or more ethylenically unsaturated groups in the molecule ( A'). [Chemical Formula 3] The photocurable resin composition of the invention of claim 1 wherein the oxime ester photopolymerization initiator (B) is a photopolymerization initiator containing the following formula (III). —C—CH3 4. The photocurable resin composition -2- 1333499 according to the first aspect of the invention, wherein the oxime ester photopolymerization initiator (B) is a photopolymerization having a structure represented by the following general formula (IV) Initiator, and/or have the following general Photopolymerization initiator of the formula (V) (IV) (wherein R 1 2 3 and R 4 are each independently represent an alkyl group having 1 to 12 carbon atoms; 115, 111 (), 117, and 1112 are independently represented by a hydrogen atom or a carbon number of 1 to 6; The alkyl group, η is an integer representing 0 to 5, R13 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R14 and R15 are an alkyl-3- 1 group having 1 to 12 carbon atoms. The photocurable resin composition 2 of the first aspect of the invention, wherein the compound 3 (D) having one or more ethylenically unsaturated groups in the molecule is an epoxy acrylate resin. 4 6. The photocurable resin composition 5 of claim 1, wherein the blue pigment (yttrium) is a phthalocyanine blue pigment. 6 7. The photocurable resin composition 7' of the scope of claim 1 is re-ordered (F) dialkylamino benzophenone relative to the carboxylic acid-containing tree 1333499 lipid (A) 100 parts by mass It contains 5 parts by mass or less. 8. The photocurable resin composition of the first application of the patent scope of the first aspect of the invention is a thermosetting component having two or more cyclic ether groups and/or cyclic thioether groups in the molecule. It is contained in an amount of 0.6 to 2.0 equivalents per 1 equivalent of the carboxyl group of the carboxylic acid-containing resin (A). A photocurable dry film obtained by coating and drying a resin composition according to any one of claims 1 to 8 on a carrier film. A light-curable and thermosetting dry film which is obtained by coating and drying a resin composition according to any one of claims 1 to 8 on a carrier film. A cured product obtained by photohardening a resin composition according to any one of claims 1 to 8 or a dried film according to claim 9 or claim 2 on a copper. 12. A hardened material characterized by a resin composition as claimed in any one of claims 1 to 8 or a dry film of a laser as claimed in claim 9 or 10 A hardened material obtained by photohardening, characterized by a resin composition according to any one of claims 1 to 8, or a hardened film of a dried film according to claim 9 or 10 of the patent application. It is 5~100a m. A printed wiring board characterized by being a resin composition according to any one of claims 1 to 8 or a dried film according to claim 9 or 10 of the patent application, having a wavelength of 350 ~420nm laser light -4- 1333499 After photohardening, it is obtained by heat hardening. A printed wiring board characterized by a resin composition according to any one of claims 1 to 8 or a cured film of a dried film according to claim 9 or 10 of the patent application 5~ 100/zm. -5-