TW200912534A - Photocuring and thermosetting resin composition and printed wiring obtained using the same - Google Patents

Abstract

To provide a photocuring and thermosetting resin composition highly sensitive in ultraviolet and laser exposure, having excellent hardening depth, excelling in storage stability, work efficiency and developing property with a dilute alkaline aqueous solution and suitable for a solder resist. The photocuring and thermosetting resin composition contains (A) resin containing a carboxyl group, (B) mercapto butanoic acid or its derivative, (C) a photopolymerization initiator, (D) a compound having two or more ethylenic unsaturated groups in a molecule and (E) a thermosetting component. It is preferable that the resin (A) containing the carboxyl group has radically polymerizable unsaturated double bond. The photopolymerization initiator (C) is preferably an oxime-based photopolymerization initiator (C1), particularly an oxime ester photopolymerization initiator, an aminoacetophenone photopolymerization initiator and/or an acylphosphine oxide photopolymerization initiator.

Description

200912534 IX. Description of the Invention [Technical Field] The present invention relates to a photocurable resin which is developable with a dilute aqueous alkali solution, a thermosetting resin composition, a cured product thereof, and a photoresist pattern which is obtained by using the same A printed circuit board. [Prior Art] Recently, in the exposure of a solder resist for a printed circuit board, laser scanning exposure is generally used from the viewpoint of excellent position and accuracy. The laser exposure scans the solder resist on the patterned circuit board without using a photomask and forms an image at the same time. When using a conventional commercially available solder resist, the appropriate exposure amount is 200 mJ/cm2 or more. There are disadvantages in that exposure is very time consuming. Therefore, it is required to have high sensitivity for the solder resist system corresponding to the laser exposure. From the above viewpoints, there have been proposals for a composition of a fluorene-based photopolymerization initiator which exhibits high photopolymerization ability or a photopolymerization initiator thereof (for example, see Patent Document 1 and Patent Document 2). However, although these techniques do exhibit sufficient photopolymerization ability, they are partially photoreactive due to deactivation of the photopolymerization initiator (due to the reaction of oxime ester with metallic copper) on the circuit after heat treatment. The problem of peeling off the coating film on the copper circuit is reduced. On the other hand, as a method for promoting the photoreaction, there is a proposal to increase the sensitivity of the photoresist (ph 〇t 〇resist) by a chain reaction reaction using a sulfhydryl compound. Technique (refer to Patent Document 3 and Patent Document 4). However, the disclosure of 200912534 propyl propionic acid derivative is very highly active on the copper circuit existing on the printed circuit board and reacts with copper, so that it is confirmed that the residue which is supposed to be developed also has residual residue. Further, even in the storage of photoresist, the fluorenyl group derived from mercaptopropionic acid used in these documents is determined to be reactive with a compound having an unsaturated double bond, and it is determined that the photoresist is remarkably made reactive. The developability is lowered. [Patent Document 1] Japanese Patent Laid-Open Publication No. H02- 2 3 5 8 5 8 (Application Patent Field) [Patent Document 2] International Publication W Ο 0 2 / 0 9 6 9 6 9 (Application Patent Scope) [Patent Document 3] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 2006-259150 (Application No.) [Explanation] [Problems to be Solved by the Invention] The invention is to solve the problems of the prior art as described above, and its main object is to provide a photocurable thermosetting resin composition which has high sensitivity and good hardening depth in ultraviolet light and laser exposure, and further It has excellent storage stability and workability, and is excellent in developability of a dilute alkali aqueous solution, and is suitable for a solder resist. Further, an object of the present invention is to provide a printed circuit board having a photoresist pattern which is excellent in properties obtained by using such a photocurable thermosetting resin composition-5-200912534. And the graphics are excellent in precision. [Means for Solving the Problems] In order to achieve the object of the present invention, according to the present invention, a photocurable thermosetting resin composition can be provided which is characterized by containing (A) a carboxyl group-containing resin and (B) a mercapto group. An acid or a derivative thereof, (c) a photopolymerization initiator, a compound having two or more ethylenically unsaturated groups in the (D) molecule, and (E) a thermosetting component. In a preferred aspect, the aforementioned carboxyl group-containing resin (A) is a carboxyl group-containing resin (A1) having a radically polymerizable unsaturated double bond, especially one or all of the unsaturated double bonds. Acrylic acid or a derivative derived therefrom is preferred. In addition, the photopolymerization initiator (C) is preferably an oxime ester photopolymerization initiator (C'), particularly an oxime ester photopolymerization initiator (C1) represented by the formula (I) described later. Or the oxime ester photopolymerization initiator (C1) and the aminoacetophenone photopolymerization initiator (C2) and/or the formula (III) represented by the formula (II) described later. A mixture of a mercaptophosphine oxide photopolymerization initiator (C3) is preferred. In another preferred embodiment, the mercaptobutyric acid or a derivative thereof (B) has two or more 2-mercaptoisobutyric acid or 3-mercaptobutyric acid or a derivative thereof in one molecule. It is better. Further, the thermosetting component (E) is an epoxy resin, and is a 2-liquid type composition blended in a mixture different from the above-described mixture in which mercaptobutyric acid or a derivative (B) thereof is blended, or a mixture of at least the carboxyl group-containing resin (A) and the aforementioned mercaptobutyric acid or a derivative thereof (B), and a mixture of the above-described oxime ester photopolymerization initiator (C') and a thermosetting component (E) The resulting 2-liquid type 200912534 composition is preferred. Further, the compound (D) having two or more ethylenically unsaturated groups in the molecule may be added to the mixture of any of the above. Further, the solder resist containing a colorant is preferably a green or blue solder resist. Furthermore, according to the present invention, a photocurable thermosetting/hardenable resin film obtained by applying the photocurable thermosetting resin composition to a carrier film and drying it is provided. Further, in another aspect of the present invention, there is provided a cured product obtained by photohardening a photocurable thermosetting resin composition or a dry film coated on copper, particularly at 350 nm to 410 nm. The laser emitting light source is photohardened into a pattern. Further, a printed circuit board having a photoresist pattern in which the photocurable thermosetting resin composition or the dry film is directly imaged by ultraviolet rays having a wavelength of from 550 nm to 410 nm is used to form a pattern. After the shape, it is obtained by heat hardening. [Effect of the invention] The photocurable thermosetting resin composition of the present invention comprises (A) a carboxyl group-containing resin, (C) a photopolymerization initiator, and (D) a molecule having two or more ethylenically unsaturated groups. Since the compound (B) and the (E) thermosetting component contain (B) mercaptobutyric acid or a derivative thereof, the coating of the photocurable thermosetting resin composition can be obtained by the linkage reaction of the compound. High sensitivity. In particular, it can be used in combination with an oxime-based initiator as a photopolymerization initiator to exhibit high photopolymerization ability, and at the same time, thioglycolic acid or a derivative thereof is mild to a copper circuit existing on a printed circuit board ( The mild reaction, 200912534, inhibits the deactivation of the photopolymerization initiator (due to the reaction of the oxime ester with the metallic copper) on the circuit after the heat treatment. Therefore, it has high sensitivity and good depth of hardening in ultraviolet light and laser exposure, and has excellent storage stability and workability, and has excellent developability with a dilute aqueous alkali solution, and development residue does not occur during development. In addition, by using such a photocurable thermosetting resin composition, it is possible to provide a cured product having excellent properties and a resistive pattern printed circuit board having excellent pattern accuracy. [Best Mode for Carrying Out the Invention] As a result of intensive investigation into the above-mentioned problems, the present inventors have found that a mercaptopropionic acid derivative and a mercapto group used in the present invention are similarly obtained even in the case of an initiator which has a linkage shift reaction. Between butyric acid or its derivative (B), there are different differences in the copper circuit present on the printed circuit board or its compound having an unsaturated double bond. That is, the mercaptopropionic acid derivative is highly active on the copper circuit and reacts with copper, so that the portion which should be developed has a residue residue; and the thiol group used in the present invention is relatively The acid or its derivative (B) reacts mildly on the copper circuit, so that this problem can be suppressed, and even in the storage of the photoresist, the quinone gene derived from mercaptopropionic acid is reactive, so it has an unsaturated double The compound of the bond reacts and significantly reduces the development of the photoresist, but it is found that such a problem can be suppressed by using mercaptobutyric acid or a derivative thereof. Hereinafter, each constituent component of the photocurable thermosetting resin composition of the present invention will be described in detail. -8- 200912534 First, the mercaptobutyric acid or its derivative (B) used in the present invention means 2-mercaptoisobutyric acid or 3-mercaptobutyric acid or a derivative thereof, and further details are The acid is an esterified or amided compound. Preferably, it is preferred to esterify two or more mercapto groups in one molecule. Specific examples thereof include ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate), and diethylene glycol bis (3) in JP-A-2008-149755. - mercaptobutyrate), butanediol bis(3-mercaptobutyrate), octanediol bis(3-mercaptobutyrate), trimethylolpropane ginseng (3-mercaptobutyrate) ), pentaerythritol bismuth (3-mercaptobutyrate), dipentaerythritol hexa(3-mercaptobutyrate), or 1,3,5-gin (3-mercapto (Mercapto) butyloxyethyl) -1,3,5-triterpene-2,4,6(lH,3H,5H)-trione. In this case, by using, for example, 1,3,5-paraxyl (Mercapto butyloxyethyl)-1,3,5-three tillage-2,4,6(1H,3H , 5H) - Triketone alicyclic structure, which can be obtained by solder heat resistance, electroless gold plating, and also has a photocurability and thermosetting resin composition excellent in stability. Here, the effects of such mercaptobutyric acid or a derivative thereof are listed as follows: (1) improving sensitivity, (2) preventing peeling by deactivation of copper lower than that of the lanthanide initiator, and (3) improving (Extended) During the development of the photoresist (1 if e) (developable drying time). In particular, the effects of the above (2) and (3) are conventionally unknown effects. The effect of the above (2) will be described. 'The oxime-based photopolymerization initiator is inferior in sensitivity to contact with a metal and has a low sensitivity to a portion in contact with a copper circuit on a circuit substrate when the solder resist is used. . This phenomenon is more pronounced in heating. Further, it is confirmed that the portion where the solder resist is thinned (the edge of the loop -9 - 200912534 edge) is peeled off after development. This is considered to be a decomposition of the ruthenium compound due to the contact of copper with a ruthenium compound, and the reduction in the light-initiating ability of the ruthenium compound decomposition (deactivation) is a major problem for the solder resist. However, the presence of a mercapto group derived from mercaptobutyric acid which is relatively mildly reacted or coordinated with copper acts as a protective film to prevent deactivation of the antimony compound, and is to prevent peeling of the solder resist. The effect of the above (3) will be described, and the effect is particularly seen when the heat-curing component used in the solder resist is an epoxy resin. That is, in the case where an epoxy resin is present in the solder resist composition, and the epoxy resin and the mercaptobutyric acid derivative are simultaneously present in the solder resist composition, it is apparent that the composition is present in the presence of mercaptobutyric acid. It is extended during the development period. The detailed reason is not necessarily obvious, but the decrease in the development period is generally caused by the sudden reaction of the carboxyl group of the carboxyl group-containing resin with the epoxy group of the epoxy resin. In the case where a mercaptobutyric acid derivative is added here, it is considered that the mercapto group and the epoxy group start to react before the reaction of the carboxyl group with the epoxy group. Therefore, it is presumed that the carboxyl group which affects developability is not consumed. The amount of the above-mentioned mercaptobutyric acid or the derivative (B) thereof is preferably 0.05 parts by mass or more and 3.0 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (A). The ratio of 1 part by mass or more and 2 · 〇 by mass or less. In the resin (A) containing a carboxyl group contained in the photocurable thermosetting resin composition of the present invention, a conventionally used resin compound containing a carboxylic acid in the molecule can be used. Further, the carboxylic acid-containing photosensitive resin (A,) having an ethylenically unsaturated double bond in the molecule is preferably a layer of photohardenability or developability of -10-200912534. Therefore, the unsaturated group is preferably derived from acrylic acid or methyl acrylate or derivatives thereof, and is effective as a source derived from methacrylic acid from the viewpoint of preservation stability. (Mercaptoic acid or its derivative (Β)' has a tendency to have a Michael addition reaction with an ethylenically unsaturated double bond derived from acrylic acid, but is difficult to react with an ethylenically unsaturated double bond derived from methacrylic acid) . However, since the source derived from methacrylic acid is inferior to the point of sensitivity derived from the acrylic acid, it is preferred to have a compound derived from both acrylic acid and methacrylic acid. According to the inventors of the present invention, the introduction of the acrylic acid portion has little influence on the storage stability and can be highly sensitive. Further, since the introduction of a part of methacrylic acid has a small decrease in sensitivity and an effect on storage stability, it is considered to have an ethylenically unsaturated double bond derived from methacrylic acid and an ethylenic unsaturated derived from acrylic acid, respectively. The construction of the double bond is optimal. At this time, in terms of the balance between sensitivity and stability, the ethylenically unsaturated double bond derived from acrylic acid: the ratio of the ethylenically unsaturated double bond derived from methacrylic acid is 95 to 50: 5 to 5 〇. The ratio is better. The carboxyl group-containing resin (A) is specifically a resin as listed below. (1) to (9): (1) A carboxyl group-containing resin which is an unsaturated carboxylic acid such as (meth)acrylic acid or a compound having one or more other unsaturated double bonds The copolymerization is carried out to obtain '(2) a photosensitive carboxyl group-containing resin' which is a total of unsaturated decanoic acid such as (meth)acrylic acid and one or more compounds having other unsaturated double bonds. Polymer 'by a compound having an epoxy group and an unsaturated double bond such as glycidyl (meth) acrylate or -11 - 200912534 3,4-epoxycyclohexylmethyl (meth) acrylate Or (meth)acrylic acid chloride or the like, which is obtained by adding an ethylenically unsaturated group as a pendant, and (3) a photosensitive carboxyl group-containing resin which has glycidol Copolymerization of a compound of an epoxy group and an unsaturated double bond such as a (meth) acrylate or a 3,4-epoxycyclohexylmethyl (meth) acrylate with a compound having another unsaturated double bond Reacting with an unsaturated carboxylic acid such as (meth)acrylic acid, and causing it to be formed The hydroxyl group is determined by a polybasic acid anhydride reaction, and (4) a photosensitive carboxyl group-containing resin which is an acid anhydride having an unsaturated double bond such as maleic anhydride and a compound having another unsaturated double bond. The copolymer is obtained by reacting a compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate with an unsaturated double bond, and (5) a photosensitive carboxyl group-containing resin, which is The functional epoxy compound is reacted with an unsaturated monocarboxylic acid, and the resulting hydroxyl group is obtained by reacting a saturated or unsaturated polybasic acid anhydride. (6) A photosensitive resin having a hydroxyl group and a carboxyl group, which is a polyvinyl alcohol. A hydroxyl group-containing polymer such as a derivative is reacted with a saturated or unsaturated polybasic acid anhydride, and the resulting carboxylic acid is obtained by reacting a compound having an epoxy group and an unsaturated double bond in one molecule, (7) A photosensitive carboxyl group-containing resin which is a reactive group other than an alcoholic hydroxyl group which reacts a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, and at least one alcoholic hydroxyl group in one molecule with an epoxy group. The reaction product of the compound, A saturated or unsaturated polybasic acid anhydride is obtained by reacting (8) a photosensitive carboxyl group-containing resin which is a polyfunctional oxyhalide having at least 2 oxetane rings in one molecule of -12-200912534. a cyclobutane compound obtained by reacting an unsaturated monocarboxylic acid and reacting a first-order hydroxyl group in the obtained modified oxetane resin with a saturated or unsaturated polybasic acid anhydride, and (9) a photosensitive property a sulfhydryl group-containing resin which is a carboxyl group-containing resin obtained by reacting (a) a polyfunctional epoxy resin with (b) an unsaturated monocarboxylic acid, and (c) a polybasic acid anhydride, and further (f) a molecule In the case where one oxirane ring is reacted with one or more compounds having a bivalent unsaturated group, it is not limited thereto. Among the carboxyl group-containing resins exemplified above, the carboxyl group-containing resin of the above (2), (5), and (7) is preferred, and the carboxylic acid-containing photosensitive resin of the above (9) is photocurable and hardened. It is preferable in terms of the characteristics of the coating film. Further, in the present specification, the terms (meth)acrylates, which are collectively referred to as acrylates, methacrylates, and the like, have the same behaviors. The carboxyl group-containing resin (A) as described above is developed in a dilute aqueous alkali solution because it has a plurality of free carboxyl groups in the side chain of the backbone polymer. The acid salt of the carboxyl group-containing resin (A) is in the range of 40 to 200 mgKOH/g, more preferably 45 to 120 mgKOH/g. When the acid enthalpy of the thiol-containing resin is less than 40 mgKOH/g, alkali development is difficult. On the other hand, when it exceeds 200 mgKOH/g, in order to dissolve the exposed portion of the developer, it is necessary to make the line thin. In the case where the exposed portion and the unexposed portion are not distinguished from each other, the dissolution and peeling in the developer are facilitated, and the drawing of the normal photoresist pattern becomes difficult, which is not preferable. Further, the weight average molecular weight of the carboxyl group-containing resin (A) varies depending on the resin skeleton, but is generally 2, 〇〇〇 150,000, and further preferably 5,000 to 100,000. When the weight average molecular weight is less than 2,000, there is a case where the viscosity is poor. The film after exposure has poor moisture resistance and the film is reduced during development, and the resolution is poor. On the other hand, when the weight average molecular weight exceeds 1,500,000, the developability is remarkably deteriorated, and the storage stability is poor. The blending amount of the carboxyl group-containing resin (A) is from 20 to 60% by mass, preferably from 30 to 50% by mass, based on the total composition. In the case of less than the above range, the film strength is lowered, which is not preferable. On the other hand, in the case of more than the above range, the viscosity is high and the coatability and the like are lowered, which is not preferable. The photopolymerization initiator (C) is an oxime ester photopolymerization initiator (C1) having a group represented by the following formula (1), and has a group represented by the following formula (II). a group of OC-aminoacetophenone photopolymerization initiator (C2) and a mercaptophosphine oxide photopolymerization initiator (C3) having a group represented by the following formula (III) It is preferred to select one or more kinds of photopolymerization initiators. In particular, the 'oxime ester photopolymerization initiator (C1), or the oxime ester photopolymerization initiator (C1) and the α-aminoacetophenone photopolymerization initiator (C2) and/or decylphosphine A mixture of an oxide photopolymerization initiator (C 3 ) is preferred. -14- 200912534

CMMO- ο- N =1cIR

2 R \^/ TX /_\

c =〇

3 - 4 R — C — R

-N F. 6 k \-'/ H I /\

7 R

OMM c-p: R8〇 (wherein R1 represents a hydrogen atom, a phenyl group (which may also be substituted by a substituent having a carbon number of 1 to 6, a phenyl group or a halogen atom), and an alkyl group having a carbon number of 1 to 20 (also It may be substituted by one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, or an alkanoyl group or a benzoic acid group having 2 to 20 carbon atoms. (Alternatively substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group); R2 represents a phenyl group (may also be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and has a carbon number of 1 to 20 The base of the hospital (can also be replaced by more than one kinky base, and may have more than one oxygen atom in the middle of the chain), the ring of the carbon number of 5~8, the base of the carbon number of 2~20 or the benzene A fluorenyl group (which may also be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group); R3 and R4 each independently represent an alkyl group having 1 to 12 carbon atoms or an aralkyl group-15-200912534 R5 and R6 systems Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 2 is bonded to form a cyclic alkyl ether group; and R7 and R8 each independently represent a linear or branched chain having 1 to 10 carbon atoms; Alkyl group, linear or branched with 1 to 10 carbon atoms An alkoxy group, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl group substituted by a halogen atom, an alkyl group or an alkoxy group, but one of R7 and R8 may also represent 11_(:(;==〇) _ base (wherein R is a hydrocarbon group having 1 to 20 carbon atoms). The oxime ester-based photopolymerization initiator (C 1) of the group represented by the above formula (1) is preferably a formula (IV) The compound represented by the following formula (V) and the compound represented by the following formula (VI) are shown in the following formula: 2-(ethylideneoxyiminomethyl) salid-9-oxime. [Chemical 2] 〇II .C, N-0-C-CHq (IV) -16- 200912534

(wherein R9 represents a hydrogen atom, a halogen atom, a group having a carbon number of 1 to 2, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzamidine group, an alkyl 2 group having 2 to 12 carbon atoms, The alkoxycarbonyl group having 2 to 12 carbon atoms (when the carbon number of the alkyl group constituting the alkoxy group is 2 or more, the alkyl group may be substituted by one or more hydroxyl groups, and the alkyl chain may have one or more oxygen atoms in the middle of the alkyl chain. ), or phenoxycarbonyl;

Rl〇 and R12 each independently represent a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 2 carbon atoms (may be one or more). The hydroxy group may have one or more oxygen atoms in the middle of the alkyl chain), the cycloalkyl group having 5 to 8 carbon atoms, the alkyl fluorenyl group having 2 to 20 carbon atoms or the benzhydryl group (may also be a carbon number of 1~) 6 alkyl or phenyl substituted); R11 is a hydrogen atom, a phenyl group (which may also be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and a carbon number of 1 to 20 (may also be One or more kinds of radical substitution, one or more oxygen atoms in the middle of the chain, a cycloalkyl group having 5 to 8 carbon atoms, an alkylene group having 2 to 20 carbon atoms, or a benzoyl group (may also be Alkyl or phenyl substituted with 1 to 6 carbon atoms)) -17- 200912534 [Chemical 4]

(wherein R13 and R14 each independently represent an alkyl group having 1 to 12 carbon atoms; and R15, R16, R17 and R18 each independently represent a hydrogen atom or a group having a carbon number of 1 to 6, and η represents In the above-mentioned oxime ester photopolymerization initiator (C1), 2-(ethylideneoxyiminomethyl)thioxanthene-9-one represented by the above formula (IV) And the compound represented by the formula (V) is more preferable. CGI-3 2 5 , IRGACURE OXEO1, IRGACURE 0^02, etc., which are commercially available from Ciba Specialty Chemicals Co., Ltd., may be used. These oxime ester photopolymerization initiators may be used alone or in combination of two or more. The α-aminoacetophenone photopolymerization initiator (C2) having a group represented by the above formula (II) is exemplified by 2-methyl-1-[4-(methylthio)phenyl group. ]_2_morpholinopropane-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2 -[(4-Methylphenyl)methyl]·1-[4-(4-morpholinyl)phenyl]-1-butanone, hydrazine, hydrazine-dimethylaminoacetophenone, and the like. Commercially available IRGACURE 907 'IGGACURE 369, 3 79, etc., manufactured by Ciba Specialty Chemicals, Inc., may be mentioned. The mercaptophosphine oxide-based light-18-200912534 polymerization initiator (C3) having the group represented by the above formula (ΙΠ) may, for example, be 2,4,6-trimethylbenzimidyl diphenyl. Phosphonium oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-tri Methyl monopentylphosphine oxide and the like. For example, Lucirin TPO manufactured by BASF Corporation, IRGACURE 819 manufactured by Ciba Specialty Chemicals Co., Ltd., and the like can be cited. The blending amount of the photopolymerization initiator (C) is preferably in the range of 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). When the amount of the film is less than 1 part by mass, the photocurability on the copper is insufficient, and the film properties such as peeling of the coating film and chemical resistance are lowered, which is not preferable. On the other hand, when the amount is more than 30 parts by mass, the light absorption on the surface of the solder resist film of the photopolymerization initiator (C) is intense, and the deep hardenability is lowered, which is not preferable. Further, in the case of the oxime ester-based photopolymerization initiator (C 1) having the group represented by the above formula (I), the blending amount is 10 parts by mass based on the carboxyl group-containing resin (A). It is preferably selected from the range of 0.01 to 20 parts by mass, more preferably 0.01 to 5 parts by mass. In addition to the photopolymerization initiator (C), a photopolymerization initiator, a photoinitiator, and a sensitizer which are suitable for use in the photocurable thermosetting resin composition of the present invention, Examples thereof include a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a diphenylketone compound, a xanthone compound, and a tertiary amine compound. Specific examples of the benzoin compound such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether are listed. Specific examples of the acetophenone compound, such as acetophenone, 2,2-dimethyl-19-200912534 oxy-2-phenylacetophenone, 2,2-diethoxy-2-phenyl benzene Ketone, l,l-dichloroacetophenone. Specific examples of the ruthenium compound are exemplified by, for example, 2 - methyl hydrazine, 2-ethyl hydrazine, 2-t-butyl hydrazine, and chloropurine. Specific examples of thioxanthone are exemplified, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylpropargone. Specific examples of the ketal compound are exemplified as acetophenone dimethyl ketal and benzyl dimethyl ketal. Specific examples of the diphenyl ketone compound 'e.g. 'diphenyl ketone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, 4-phenylene Mercapto-4,-ethyldiphenyl sulfide 4-benzylidene-4'-propyldiphenyl sulfide. Specific examples of the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4'-dimethylaminodiphenyl ketone (Nissocure MABP, manufactured by Nippon Soda Co., Ltd.), 4, Dialkylaminodiphenyl ketone such as 4'-diethylaminodiphenyl ketone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7-(diethylamino)-4-methyl-2H-1-benzene a dialkylamino group-containing coumarin compound such as pyran-2-one (7-(diethylamino)-4-methylcoumarin), ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics Co., Ltd.), 4-dimethylaminobenzoic acid (η-butoxy)ethyl (International) Quantacure BE A) manufactured by Bio-Synthetics Co., Ltd., isoamylethyl p-dimethylaminobenzoate (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (Van Dyk) Company-made -20- 200912534 ES〇1〇1507), 4,4'-diethylaminodiphenyl ketone (EAB made by Hodogaya Chemical Co., Ltd.). Among the above compounds, a thioxanthone compound and a tertiary amine compound are also preferred. In the composition of the present invention, it is preferable to contain a thioxanthone compound in the form of a deep hardenability, and also 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2 A thioxanthone compound such as chlorothioxanthone or 2,4-diisopropylthioxanthone is preferred. The blending amount of the sulfonate compound is preferably 20 parts by mass or less, more preferably 1 part by mass or less, per 100 parts by mass of the carboxyl group-containing resin (A). When the amount of the thioxanthone compound is too large, the thick film hardening property is lowered, which is associated with the cost up of the product, which is not preferable. As the tertiary amine compound, a compound having a dialkylaminobenzene structure, preferably a dialkylaminodiphenyl ketone compound, and a dialkylamine having a maximum absorption wavelength of 3 50 to 41 Onm; The coumarin compound is particularly preferred. As the dialkylaminodiphenyl ketone compound, the 4,4'-diethylaminodiphenyl ketone is preferably low in toxicity. A dialkylamine group-containing coumarin compound having a maximum absorption wavelength of from 3 to 50 to 41 〇nm, which is a photocurable and thermosetting resin composition having a maximum absorption wavelength in the ultraviolet field and having little coloration and being colorless and transparent The coloring pigment is originally used, so that a colored solder resist film reflecting the color of the coloring pigment itself can be provided. In particular, since 7-(diethylamino)_4_methyl-2H-1-benzopyran-2-one exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm, it is preferable. The blending amount of the tertiary amine compound is preferably from 1 to 20 parts by mass, more preferably from 21 to 200912534, from 0.1 to 10 parts by mass per 100 parts by mass of the carboxyl group-containing resin (A). proportion. When the blending amount of the tertiary amine compound is 0.1 part by mass or less, a sufficient sensitizing effect may not be obtained. On the other hand, when the amount is more than 20 parts by mass, the light absorption on the surface of the dry solder resist coating film of the tertiary amine compound becomes intense, and the deep hardenability tends to be lowered. The photopolymerization initiator, photoinitiator, and sensitizer as described above may be used singly or in combination of two or more. The total amount of the photopolymerization initiator, the photoinitiator, and the sensitizer is preferably in the range of 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (A). When the amount of light exceeds 35 parts by weight, the deep curing property tends to decrease. The compound (D) having two or more ethylenically unsaturated groups in the molecule used in the photocurable thermosetting resin composition of the present invention is photocured by irradiation of an active energy ray to be unexposed. Partially insoluble in aqueous alkali solution, or help insoluble. Examples of such a compound include diacrylates of ethylene glycol such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, and dipentaerythritol; a polyhydric alcohol such as a polyhydric alcohol such as hydroxyethyl isocyanurate or such an ethylene oxide adduct or a propylene oxide adduct; a phenoxy acrylate, a bisphenol A diacrylate, and a phenolic ethylene oxide adduct or a propylene oxide adduct of a propylene oxide; a polyacrylate of a glycidyl ether such as glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether or triglycidyl isocyanurate; and melamine acrylate-22- 200912534, and/or corresponding to each methacrylate of the above acrylate. Further, an epoxy acrylate resin in which a polyfunctional epoxy resin such as a cresol novolac type epoxy resin is reacted with acrylic acid, or a hydroxyl group such as pentaerythritol triacrylate or the like in which the hydroxyl group of the epoxy acrylate resin is further reacted An epoxy urethane acrylate compound obtained by reacting an ester with a semi-carbamate compound of a diisocyanate such as isophorone diisocyanate. Such an epoxy acrylate-based resin does not deteriorate the finger-drying property and can improve the light hardenability. The blending amount of the compound (D) having two or more ethylenically unsaturated groups in the molecule is 5 to 100 by mass based on 100 parts by mass of the carboxylic acid-containing resin (A) containing the ethylenically unsaturated group. The ratio is preferably from 1 to 70 parts by mass. When the blending amount is less than 5 parts by mass, the photocurability is lowered, and the alkali development after irradiation with the active energy ray is difficult to form a pattern, which is not preferable. On the other hand, in the case of more than 1 part by mass, the solubility in the aqueous alkali solution is lowered, and the coating film becomes brittle, which is not preferable. The photocurable thermosetting composition of the present invention imparts heat resistance and can be added with a thermosetting component (D). The thermosetting resin (D) is particularly preferably a thermosetting resin having two or more cyclic ether groups and/or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule. . The thermosetting resin having two or more cyclic (thio)ether groups in such a molecule is a cyclic ether group having two or more 3, 4 or 5 membered rings in the molecule, or a cyclic thioether. a compound of any one or two of the groups ', for example, a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (D-1); having at least two or more oxygens in the molecule Heterocyclic -23-200912534 oxetanyl compound, that is, a polyfunctional oxetane compound (D-2); a compound having two or more thioether groups in the molecule, that is, an episulfide Resin (D-3), etc. Examples of the polyfunctional epoxy compound (D-1) include JER828, JER834, JER1001, and JER1 004 manufactured by Japan Epoxy Resins Co., Ltd., EPICLON 840, EPICLON 850, EPICLON 1050, and EPICLON 2055 manufactured by Dainippon Ink and Chemicals. EPOTOHTO YD-011, YD-013, YD-127, YD-128 manufactured by Dongdu Chemical Co., Ltd., DER317, DER331, DER661, DER664 manufactured by Dow Chemical Co., Ltd.; Araldite 6071 and Araldite 6084 from Ciba Specialty Chemicals Araldite GY250, Araldite GY260, Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Industries Co., Ltd.; AER3 30, AER331, AER661, AER664, etc. manufactured by Asahi Kasei Kogyo Co., Ltd. ( Bisphenol A type epoxy resin of the product name; YL903 manufactured by Japan Epoxy Resins Co., Ltd., EPICLON 152, EPICLON 165 manufactured by Otsuka Ink Chemical Industry Co., Ltd., EPOTOHTO YDB-400 and YDB-500 manufactured by Dongdu Chemical Co., Ltd. DER542 manufactured by Dow Chemical Co., Ltd., Araldite 8011 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Industries, Asahi Kasei Company's A · E · R. 7 1 1 , AER714 (both trade names) brominated epoxy resin; Japan Epoxy Resins company's JER152, JER154, Dow Chemical Company's DEN431, DEN438, large EPICLON N-73, manufactured by Nippon Ink Chemical Industry Co., Ltd., EPICLON N-770 ' EPICLON N- 8 65, East-24- 200912534 EPOHOTO YDCN-701, YDCN-704, manufactured by Duhua Chemical Co., Ltd., Araldite, manufactured by Ciba Specialty Chemicals ECN1235, Araldite ECN 1 273, Araldite ECN1 299, Araldite XPY3 07, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, manufactured by Nippon Kayaku Co., Ltd., Sumi-epoxy, Sumitomo Chemical Industries, Ltd. ESCN-195X, ESCN-220 > AER ECN-23 manufactured by Rising Sun Chemical Co., Ltd. 5, ECN-2 99, etc. (all trade names), novolac type epoxy resin: EPICLON 8 3 manufactured by Dainippon Ink Chemical Industry Co., Ltd. 0, JER 807 manufactured by Japan Epoxy Resins Co., Ltd., EPOTOHTO YDF-170, YDF-175, YDF-200 1, YDF-2004 manufactured by Dongdu Chemical Co., Ltd., and Araldite XPY306 (all trade names) manufactured by Ciba Specialty Chemicals Co., Ltd. Phenol F epoxy resin Hydrogenated biguanide A epoxy resin such as EPOTOHTO ST-2004, ST-2007, ST-3000 (trade name) manufactured by Dongdu Chemical Co., Ltd.; JER 604 manufactured by Japan Epoxy Resins Co., Ltd., EPOTOHTO YH-made by Dongdu Chemical Co., Ltd. 434, Araldite MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., glycidylamine type epoxy resin of Sumi-epoxy ELM-120 (all trade name) manufactured by Sumitomo Chemical Industries, Ltd.; Araldite CY-3 5 manufactured by Ciba Specialty Chemicals Co., Ltd. Hydantoin type epoxy resin such as 0 (trade name); CELLOXIDE 202 manufactured by DAICEL Chemical Industry Co., Ltd., alicyclic epoxy resin of Araldite CY175, CY179, etc. (all trade names) manufactured by Ciba Specialty Chemicals Co., Ltd. YL- 9 3 3 manufactured by Japan Epoxy Resins Co., Ltd., TEN, EPPN-501, EPPN-502, etc. (all trade names) manufactured by Dow Chemical Co., Ltd.; -25- 200912534

Japan Epoxy Resins YL-605 6, ΥΧ-4000, γ[_ 6 1 2 1 (all trade names), etc., bi-xylenol type or bisphenol type epoxy resin or a mixture thereof; Japanese chemical Epp S-2 00, manufactured by Asahi Kasei Kogyo Co., Ltd., EPX-3 0 manufactured by Dainippon Ink Chemical Industries Co., Ltd., EXA-1514 (trade name) manufactured by Dainippon Ink Chemical Industry Co., Ltd.; Jap an Epoxy Resins Co., Ltd. Bisphenol A novolac type epoxy resin such as JER 15 7S (trade name); YL-931 manufactured by Japan Epoxy Resins Co., Ltd., Araldite 163 (all trade name) manufactured by Ciba Specialty Chemicals Co., Ltd. Oxygen resin; Araldite PT810 manufactured by Ciba Specialty Chemicals Co., Ltd., heterocyclic epoxy resin of TEPIC (all trade name) manufactured by Nissan Chemical Industries Co., Ltd.; diglycidyl phthalate resin such as BLEMMER DGT manufactured by Nippon Oil Co., Ltd.; Glycidyl xylenoyl ethane resin, such as ZX- 1 063, manufactured by Kasei Co., Ltd.; ESN-190, ESN-3 60 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032 manufactured by Dainippon Ink Chemical Industry Co., Ltd. , EXA-4750, EXA-4700, etc. An epoxy resin having a naphthyl group; an epoxy resin having a dicyclopentadiene skeleton such as HP-7200 or HP-7200H manufactured by Dainippon Ink Chemical Industry Co., Ltd.; CP-50S, CP-5〇M, etc. manufactured by Nippon Oil & Fats Co., Ltd. Glycidyl methacrylate copolymerized epoxy resin; further copolymerized epoxy resin of cyclohexylmethylene iodide and glycidyl methacrylate; epoxy modified polybutadiene rubber A derivative (for example, PB-3 600 manufactured by DAICEL Chemical Industry Co., Ltd.), a CTBN modified epoxy resin (for example, YR-102 manufactured by Tosho Kasei Co., Ltd., YR-45 0, etc.), and the like, but is not limited thereto. These epoxy resins may be used alone or in combination of two or more. Among these, a novolak type epoxy resin, a heterocyclic epoxy resin, a -26-200912534 bisphenol A type epoxy resin or a mixture thereof is preferable. The polyfunctional oxetane compound (D-2) may, for example, be bis[(3-methyl-3-oxetanylmethoxy)methyl]ether or bis[(3-ethyl-3-) Oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-) 3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxetanyl)methacrylic acid Ester, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, or oligomerization thereof Polyfunctional oxetane such as a substance or a copolymer, and other oxetane and novolak resins, poly(P-hydroxystyrene), cardo type bisphenol a calixarene type, a calixarene (a calixresorcinarene) type, or an ether compound of a resin having a hydroxyl group such as a silsesquioxane or the like. Other examples thereof include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate. The compound (D-3) having two or more cyclic thioether groups in the above-mentioned molecule may, for example, be a bisphenol A-type surface sulfide resin YL7 000 manufactured by Japan Epoxy Resins Co., Ltd., or the like. Further, by using the same synthesis method, an episulfide resin in which an oxygen atom of an epoxy group of a novolac type epoxy resin is substituted with a sulfur atom may be used. The amount of the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is 1 equivalent to the carboxyl group of the carboxyl group-containing resin (A), preferably 0.6 to 2.5. The equivalent weight is more preferably in the range of 0.8 to 2.0 equivalents. The amount of the thermosetting component -27-200912534 (D) having two or more cyclic (thio)ether groups in the molecule is less than 〇.6, and the carboxyl group remains in the solder resist film, and heat resistance, Alkali resistance, electrical insulation, etc. are lowered, so it is not good. On the other hand, when it exceeds 2.5 eq., the strength of the coating film due to the low molecular weight cyclic (thio)ether group remaining on the dried coating film is lowered, which is not preferable. When the thermosetting component (D) having two or more cyclic (thio)ether groups in the above molecule is used, it is preferred to contain a thermosetting catalyst. The thermosetting catalyst 'is, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano group Imidazole derivatives such as ethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, dicyandiamide, benzylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc. An amine compound; a ruthenium compound such as diammonium adipate or bismuth sebacate; a phosphorus compound such as triphenylphosphine; and a commercially available product such as 2MZ-A and 2MZ manufactured by Shikoku Chemical Industry Co., Ltd. OK, 2PHZ, 2P4BHZ, 2P4MHZ (trade name of imidazole-based compound), U-CAT3 5 03N, U-CAT3 5 02T (trade name of block isocyanate compound of dimethylamine) manufactured by SAN-APRO Co., Ltd., DBU , DBN, U-CATSA102, U-CAT5002 (all bicyclic guanidine compounds and their salts). In particular, it is not limited thereto, and a thermosetting catalyst of an epoxy resin or an oxetane compound may be used, or a reaction for promoting an epoxy group and/or an oxetanyl group and a carboxyl group may be used. It is also possible to use two or more kinds alone or in combination. Further, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-tris- 2 -ethylene can also be used. Base-4,6-diamino-S-triazine, 2_vinyl-4,6-diamino-S-three tillage. Heterotrimeric-28- 200912534 Cyanate adduct, 2,4- An S-triterpene derivative such as a diamino-6-methacryloxyethyl-S-trisole/iso-cyanuric acid addition product, preferably used as an adhesion imparting agent It is sufficient that the compounding amount of the functional compound and the above-mentioned thermosetting catalyst is a ratio of the amount of the above-mentioned thermosetting catalyst to a general amount, for example, for the carboxyl group-containing resin (A) or a molecule having two or more rings 100 parts by mass of the thermosetting component (D) of the (thio)ether group is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass. The photocurable thermosetting resin composition of the present invention is formed by increasing the physical strength of the coating film and the like, and blending the chelating agent as needed. As such a chelating agent, a well-known inorganic or organic chelating agent can be used, and strontium sulphate, spheroidal cerium oxide and talc are particularly preferably used. Further, a compound having one or more ethylenically unsaturated groups or a NANOCRYL (trade name) XP 03 manufactured by Hanse-Chemie Co., Ltd. in which the nano silica is dispersed in the polyfunctional epoxy resin (D-1) may be used. 96, XP 05 96 ' XP 073 3, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP1045 (all product grade name) or Hanse-Chemie N ANOPOX (trade name) XP 0516, XP 0525 , XP 0314 (all product grade name). These may be used alone or in combination of two or more. The blending amount of the above-mentioned chelating agent is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, even more preferably 0.1 to 150 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin (A). When the blending amount of the chelating agent exceeds 300 parts by mass, the viscosity of the photocurable thermosetting resin composition becomes high, the printability is lowered, and the cured product becomes brittle. -29-200912534 Further, the photocurable thermosetting resin composition of the present invention is prepared by synthesizing or synthesizing the carboxyl group-containing resin (A) or adjusting the viscosity of the substrate or the carrier film. Solvent. Examples of such an organic solvent include ketones, aromatic hydrocarbons, ethylene glycols, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and stone solvents. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as xylene and tetramethylbenzene; cellosolve, methyl agent, butyl cellosolve, carbitol, and A Glycol ethers such as carbitol, butyl carbitol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl triethylene glycol monoethyl ether; ethyl acetate, acetic acid And esters such as dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propyl ethyl ether acetate, propylene glycol butyl ether acetate; alcohols such as ethanol alcohol, ethylene glycol, and propylene glycol; octane, Fat such as decane; stone solvent 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 photocurable thermosetting resin composition of the present invention may further be blended with hydroquinone, hydroquinone monomethyl ether, t-butyl ketone, pyrogallol, phenothiazine, etc. Thermal polymerization inhibiting agent; known viscosifying polyoxyalkylene series such as micro cerium oxide, organic bentonite, montmorillonite, etc., fluorine-based, polymer-based defoaming agent and/or leveling imidazole, thiazole A well-known additive such as a decane coupling agent such as a triazole system, an antioxidant, or a solvent. The photocurable and thermosetting resin composition of the present invention may be an alcohol-soluble ether-based toluene-soluble fiber, a propyl ether, a butyl ester diol, or a glycerin-based oil. The rust-preventing agent is in the form of a dry film comprising a carrier film and a layer of the photocurable thermosetting resin composition formed on the carrier film. In the dry film formation, the photocurable thermosetting resin composition of the present invention is diluted to an appropriate viscosity with the above-mentioned organic solvent, and coated with a squeegee (comma coater) or a squeegee. Blade coater, lip coater, rod coater, squeeze coater 'reverse coater', transfer roll coat A transfer roll coater, a gravure coater, and a spray coater are equal to a uniform thickness applied to the support, and are generally dried at a temperature of 50 to 130 ° C for 1 to 30 minutes to obtain a film. The coating film thickness is not particularly limited, but the film thickness after drying is suitably selected in the range of 10 to 150 μm, preferably 20 to 60 μm. As the carrier film, a plastic film can be used, and a polyester film such as polyethylene terephthalate, a polyimide film, a polyimide film, a polypropylene film, a polystyrene film, or the like can be used. Plastic film is preferred. The thickness of the carrier film is not particularly limited, but is generally suitably selected in the range of 10 to 150 μm. After the film is formed on the carrier film, it is preferable to laminate the peelable protective film on the surface of the film for the purpose of preventing adhesion of the surface of the film or the like. As the peelable protective film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface treated paper, or the like can be used, and if the protective film is peeled off, the adhesion of the film to the protective film is higher than that of the film and the support. Those who are still young are better. -31 - 200912534 The photocurable thermosetting resin composition of the present invention having the above composition is diluted to a viscosity suitable for the coating method as needed, and is formed on a circuit board forming a circuit. Coating by a method such as screen printing, curtain coating, spray coating, roll coating, or the like, for example, a temperature of about 60 to 1 〇〇 ° C by volatilizing and drying the organic solvent contained in the composition. A tack-free coating film is formed. After the coating film is formed on the printed circuit board forming the circuit (in the case of using the dry film described above, after the laminate is formed on the printed circuit board forming the circuit, the support cannot be peeled off), the active energy rays of the laser light or the like are along the pattern. Directly irradiated, or selectively formed by a pattern of photomasks by active energy rays, and unexposed portions are developed with a dilute aqueous solution to form a photoresist pattern (in the case of using the above-described dry film, it is peeled off after exposure) The support is developed). Thereafter, only heat-hardening or heat-hardening after irradiation with an active energy ray or heat-hardening and then irradiating the active energy ray to cause final hardening (true hardening) can form electrical insulation, PCT resistance, and denseness. Excellent cured film (cured material) such as solderability, solder heat resistance, chemical resistance, and electroless gold plating resistance. The photocurable thermosetting resin composition of the present invention is adjusted to have a viscosity suitable for a coating method by using the organic solvent, for example, by dip coating, flow coating, roll coating, or bar coating on a substrate. Method, screen printing method, curtain coating method, etc., coating the 'organic solvent contained in the composition to dry (false dry) at a temperature of about 60 to 1 〇〇X: to form a non-sticky Coating film. In the case of the "form of the dry film", the substrate is bonded to the substrate by a hot roll laminator or the like (the photocurable thermosetting resin composition layer is bonded to the -32 to 200912534 substrate). ). In the case of a dry film having a peelable protective film on the photocurable and thermosetting resin composition layer of the film, the photocurable heat hardening is performed by using a hot roll laminator or the like after peeling off the protective film. The resin composition layer is bonded in contact with the substrate. Thereafter, the obtained coating film (photocurable thermosetting resin composition layer) is exposed (irradiated active energy ray). The exposure system can be a contact pattern (or a non-contact method), a pattern by using a mask, a method of selectively exposing by an active energy line, or a direct direct drawing by a laser direct exposure machine. Any of the methods of exposure. By exposure, the exposed portion of the coating film (the portion irradiated by the active energy ray) is hardened. Next, the unexposed portion is developed by an aqueous alkali solution (e.g., 0.3 to 3% aqueous alkali carbonate solution) to form a photoresist pattern. Further, for example, heating at a temperature of about 1 40 to 180 ° C by thermal curing causes the carboxyl group of the carboxyl group-containing resin (A) to have two or more cyclic ether groups in the molecule and/or The thermosetting component of the cyclic thioether group reacts to form a cured coating film having excellent properties such as heat resistance and chemical resistance, such as moisture absorption resistance, adhesion, and electrical properties. As the above substrate, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimine, glass cloth/non-woven fabric-epoxy resin, glass cloth/paper-epoxy resin can be used. a copper-clad laminate or a polyimide film of all grades (FR-4, etc.) of a composite material such as a synthetic fiber-epoxy resin, a fluororesin, a polyethylene, a PPO, a cyanoate, or the like. PET film, glass substrate, ceramic substrate, wafer board, and the like. After applying the photocurable thermosetting resin composition of the present invention, the volatile drying of -33-200912534 is carried out, and a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection furnace, etc. can be used (the use of steam is used) The heat source of the air heating method is either a method of bringing the hot air in the dryer into contact with the flow or a method of spraying the nozzle onto the support. As the exposure machine used for illuminating the above-mentioned active energy ray, a direct drawing device (e.g., a laser direct imaging (i m a g i g) device that directly draws a picture image via CAD data from a computer) can be used. The laser beam using the maximum wavelength in the range of 350 to 410 nm for the active energy ray may be either a gas laser or a solid laser. Further, the exposure amount varies depending on the thickness of the film or the like, and is usually in the range of 5 to 200 mJ/cm 2 , preferably 5 to 100 mJ/cm 2 , and more preferably 5 to 50 mJ/cm 2 . For the above-described direct drawing device ’, for example, a product manufactured by Nippon Technologies Co., Ltd., PENTAX Co., Ltd., or the like, and a device having a maximum wavelength of 3 50 to 41 Onm of laser light can be used, and any device can be used. The developing method may be a dipping method, a shower method, a spray method, a brushing method, or the like; as the developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia, or an amine may be used. An aqueous solution such as an alkali. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described by way of examples and comparative examples, and the present invention is not limited to the following examples. Synthesis Example 1 -34- 200912534 A cresol novolac type epoxy resin (manufactured by Sakamoto Chemical Co., Ltd.) was introduced into a 2-liter separable flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube. EOCN-104S, softening point 92 ° C, epoxy equivalent 220) 660 g, carbitol acetate 4213 g and solvent naphtha 18 〇 6 g, heated at 9 ° C. Stir and dissolve. Then, it was temporarily cooled to 6 (rc, propylene, 216 g of tribasic acid, 4 〇g of triphenylphosphine, and methyl hydroquinone) were reacted at 100 ° C for 12 hours to obtain cesium 〇 2 mg KOH / The reaction product of g. 241.7 g of tetrahydrophthalic anhydride was added thereto, and the mixture was heated at 90 ° C to react for 6 hours. Thus, the acid hydrazine was found to be 50 mg KOH/g, and the double bond equivalent (per a solution of a carboxyl group-containing resin (A) having a weight average molecular weight of 7,000 and a solution of the carboxyl group-containing resin (A). Hereinafter, the solution of the carboxyl group-containing resin is referred to as A-1 varnish. A 2 liter separable flask of a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube was charged with a cresol-cresol novolac type epoxy resin (epoxy equivalent 215, an average of 6 phenol cores per molecule) 430 g And 144 g of acrylic acid (2 moles), heated to 120 ° C while stirring, and kept at 10 ° C for 10 hours. Once the reaction product was cooled to room temperature, 190 g (1.9 m) of succinic anhydride was added. The reaction was heated for 4 hours at 80 ° C. The reaction product was again cooled to room temperature. Zhi acid solids component was 139mgKOH / g.

To this solution, 85.2 g (0.6 mol) of glycidyl methacrylate and 45.9 g of propylene glycol methyl ether acetate were added, and heated to ii (TC -35-200912534) while maintaining at 1 1 0 °C while stirring. The reaction was continued for 6 hours, and the reaction product was cooled to room temperature to obtain a viscous solution. In this manner, a solution of a carboxyl group-containing resin (A) having a nonvolatile content of 65 % by mass and a solid content of cesium 86 mg KOH / g was obtained. The solution of the carboxyl group-containing resin is referred to as A-2 varnish. Synthesis Example 3 A solution of the carboxyl group-containing resin (A) was obtained in the same manner except that methacrylic acid was used instead of the acrylic acid of the above Synthesis Example 1. The solution of the carboxyl group-containing resin is referred to as A-3 varnish. Examples 1 to 7 and Comparative Examples 1 and 2 The resin solutions of the respective synthesis examples described above were used, and the various components shown in Table 1 were blended (to simultaneously The ratio (parts by mass) shown in 1 is prepared by mixing with a mixer, and then kneading with a three-roller honing machine to prepare a photocurable and thermosetting resin composition for a solder resist. Here, the resulting photocurability is obtained. Thermosetting resin composition When the degree of dispersion was evaluated by the particle size measurement of a grindmeter manufactured by Erichsen Co., Ltd., it was 15 μm or less. -36- 200912534 [Table 1] Composition (parts by mass) Example Comparative Example 1 2 3 4 5 6 7 1 2 A component varnish A-1*1 154 varnish A-2*1 154 154 154 154 154 154 154 154 B component B1*2 1 B2*3 1 B3*4 1 1 1 1 B4*5 1 DPHA&quot;6 20 20 20 20 20 20 20 20 20 Lanthanide photopolymerization initiator (C-1)*7 1.0 1.0 1.0 (C-2)*8 0.8 0.8 0.8 0.8 Photopolymerization initiator (C-3)*9 other than lanthanide 6 10 10 (C-4)*10 6 Epoxy resin DEN-431*1] 15 15 15 15 15 15 15 15 15 YX-4000*12 25 25 25 25 25 25 25 25 25 Thermal curing catalyst dicyandiamide Icyandiamide 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 melamine 5 5 5 5 5 5 5 5 5 barium sulfate*13 100 100 100 100 100 100 100 100 100 dipropylene glycol monomethyl ether 5 5 5 5 5 5 5 5 5 Polyoxyalkylene defoamer 3 3 3 3 3 3 3 3 3 Phthalocyanine blue*14 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 氺1 : Solid component just *2 : I,4-double (3- Succinyloxy Butane*3: pentaerythritol bismuth (3-mercaptobutyrate) * 4 : 1,3,5-gin (3-mercapto (methcapto) butyloxyethyl)-1,3,5-three哄-2,4,6(1min 311,511)-trione*5: thiol isobutyric acid*6: Japanese chemical medicine (stock) dipentaerythritol hexa-propyl citrate *7 : 2-(ethyl hydrazine Hydroxyimidomethyl)thioxan-9-one*8: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-carbazole _3·yl] Ethyl ketone) *9 : 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide * 10 : IRGACURE 907 (manufactured by Ciba. Specialty. Chemicals) * 11 : manufactured by Dow Chemical Co., Ltd. Phenolic novolak type epoxy resin *12 : Japan Epoxy Resins (bixylenol) type epoxy tree month *13: barium sulfate B30 堺H: C.LPigmentBlue 15: 0.3 parts of 3 parts and 0.8 parts of CIPigment yelI〇wl47-37-200912534 Evaluation performance: &lt;Optimum exposure amount&gt; Buff roll honing a circuit pattern substrate with a copper thickness of 35 μm, washed with water, dried After that, the photocurable and thermosetting resin composition of the above examples and comparative examples were uniformly coated by a screen printing method at a heat of 80 ° C. Circulating drying oven and dried for 60 minutes. After drying, a direct drawing device equipped with a semiconductor laser having a maximum wavelength of 355 nm, a direct drawing exposure machine equipped with a high-pressure mercury lamp, or an exposure device equipped with a high-pressure mercury lamp is used, and exposure is performed by a Step tablet (Kodak No. 2). When the pattern of the step tablet remaining in development for 30 seconds (30 ° C, 0.2 Μ P a, 1% by mass aqueous sodium carbonate solution) was 7 segments, the optimum exposure amount was obtained. <Resolution> After the polishing roll honing line/the circuit pattern substrate having a distance of 300/300 μm and a copper thickness of 35 μm, after washing with water and drying, the photocuring properties of the examples and the comparative examples were applied by screen printing. The thermosetting resin composition was dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, exposure was carried out using a direct drawing device equipped with a semiconductor laser having a maximum wavelength of 355 nm. The exposure pattern is used for direct drawing data of lines of 20/30/40/50/60/70/80/90/ ΙΟΟμιη at the pitch. The exposure amount is such that the active energy ray is irradiated to an optimum exposure amount of the photohardenable/thermosetting resin composition. After the exposure, development was carried out by using a 1% by mass aqueous sodium carbonate solution at 30 ° C, and a pattern was drawn, and a hardened coating film was obtained by a heat hardening treatment at 150 ° C for 60 minutes. -38- 200912534 The minimum residual line (resolution) of the cured coating film of the photocurable/thermosetting resin composition for solder resist obtained was determined by an optical microscope adjusted to 200 times. Characteristic test: On the copper foil substrate on which the pattern was formed, the compositions of the above examples and comparative examples were completely coated by screen printing, and dried at 8 (TC for 20 minutes, and allowed to cool to room temperature. The substrate is directly exposed to a semiconductor laser equipped with a maximum wavelength of 355 nm, and the resist pattern is exposed at an optimum exposure amount, and an aqueous solution of 1% Na2C03 at 30 ° C is developed for 60 seconds under the conditions of a spray pressure of .2 MPa. The resist pattern was obtained, and the substrate was irradiated with ultraviolet light under the conditions of a cumulative exposure amount of 1 000 mJ/cm 2 in a UV transfer furnace, and then heated at 150 ° C for 60 minutes to be hardened. The obtained printed substrate (evaluation substrate) was obtained. The evaluation characteristics were as follows. <Color of coating film> The color of the cured product was visually judged for the alkali-developing type solder resist of the above-described examples and comparative examples. <Solder heat resistance> The rosin was coated with The evaluation of the flux is immersed in a solder bath set at 260 ° C in advance, and after the flux is washed with denatured alcohol, the expansion and peeling of the photoresist layer which is visually observed are evaluated. The criteria are as follows: 39 - 200912534 ◎: No peeling occurred even if it was immersed for 6 times or more for 1 sec. ◦: No peeling occurred even if it was immersed for 10 times or more for 10 seconds. △: If it was repeated three times or more for 10 seconds, there was a slight peeling. X: When it is immersed for 10 times within 10 seconds, it is swelled and peeled off in the photoresist layer. <Anti-electroless gold plating resistance> For the evaluation substrate, a commercially available electroless nickel plating bath and an electroless gold plating bath are used, and nickel is used. The conditions of 0.5 μΐη and gold 0·03 μΐη were plated, and the peeling of the photoresist layer or the presence or absence of plating penetration was evaluated by tape stripping, and then peeling of the photoresist layer was performed to evaluate the presence or absence of peeling of the photoresist layer. The judgment criteria are as follows: ◎: No infiltration or peeling was observed. 〇: Some infiltration after plating, but no peeling after peeling off the tape. △: Only a little infiltration was observed after plating, and peeling was also observed after tape stripping. X: peeling after plating. <Electrical characteristics> A comb-shaped electrode B sample of IPC B-25 was used instead of the copper foil substrate, and an evaluation substrate was produced under the above conditions, and DC 1 was applied to the comb-shaped electrode. 0 0 V bias voltage, constant temperature at 85 ° C, 8 5 % R. Η. In the constant humidity tank, the migration (migrati ο η) after 1,0 hour is confirmed. The criteria are as follows. 〇: There is no change at all △: Only a few changers -40 - 200912534 X : Migration generators - Acid resistant The evaluation substrate was immersed in a 10 v 〇 1% H 2 SO 4 aqueous solution at room temperature for 30 minutes, and the elution or coating film was confirmed to be eluted, and the peeling by tape removal was confirmed. The criteria were as follows: 〇: no penetration, dissolution, or peeling ' △: Confirm that there is little infiltration, dissolution or peeling. X : A large amount of infiltration, dissolution or peeling was confirmed. &lt;Maximum development period &lt;&gt; The composition of the above examples and comparative examples was completely applied by screen printing on a copper foil substrate on which a pattern was formed, and dried at 8 ° C for 20 to 80 minutes. The substrate was taken out and allowed to cool to room temperature every 10 minutes. To the substrate, a 1% Na2C03 aqueous solution of 3 °C was developed under the conditions of 2MP a for 60 seconds, and p was the maximum allowable drying time without residual residue as the maximum development period. The results of the above respective evaluation tests are shown in Table 2. -41 - 200912534

[Table 2] Characteristic Example Comparative Example 1 2 3 4 5 6 7 1 2 Tone Green Green Green Green Green Green Green Green High Pressure Mercury Lamp Exposure Sensitivity (mJ/cm2) 30 30 30 50 40 50 100 70 250 High Pressure Mercury Lamp Direct Exposure Sensitivity (mJ /cm2) 30 30 30 50 40 50 100 70 250 355 nm laser exposure sensitivity (mJ/cm2) 30 30 30 50 50 60 150 110 300 Resolving power (μιη) 50 50 50 50 60 60 70 100 100 Solder heat resistance 〇 〇 ◎ ◎ ◎ 〇〇 Δ 〇 Electrical characteristics 〇〇〇〇〇〇〇 Δ 〇 Electroless gold plating ◎ ◎ ◎ 〇〇 Δ 〇 Acid resistance 〇〇〇〇〇〇〇 〇 〇 Maximum development period 70 minutes 70 minutes 70 Minute 70 minutes 70 minutes 50 minutes 60 minutes 50 minutes 50 minutes Remarks High pressure mercury lamp exposure device: ORC company exposure machine equipped with mercury short arc lamp

Direct-pressure exposure of high-pressure mercury lamp: Direct-exposure exposure machine equipped with ultra-high pressure gold and silver lamp (lamp) DAINIPPON SCREEN company Marquex 35511111 laser exposure machine: 〇1'1) (^.11 company system? &amp; melon §〇]18000 Comparative Example 1 caused peeling of the presumed photoresist on the copper circuit after development due to deactivation of the photopolymerization initiator. Stability test = According to the blending example shown in Table 3, the main component and the hardening In the mixture, the components are blended in a ratio (parts by mass) shown in Table 3, and the mixture is mixed with a mixer, and then kneaded by a three-roll honing machine to prepare a photocurable and thermosetting resin composition for a solder resist. Then, when the degree of dispersion of the obtained photocurable *thermosetting resin group -42 - 200912534 was evaluated by the particle size measurement of a grindmeter manufactured by Erichsen Co., Ltd., it was 15 μηι or less. 〇 [Table 3 Composition (parts by mass) Blending 1 column 1 1 2 3 4 5 6 7 8 9 10 Main agent Α varnish A-1*1 154 154 154 Varnish A-2*1 154 154 154 154 Varnish A-3*1 154 154 154 B component B1*2 1 1 1 B2*3 1 1 1 B3*4 1 1 1 B5*5 1 dipentaerythritol hexaacrylate 20 20 20 20 20 20 20 20 20 20 phthalocyanine blue 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 dicyandiamide 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 melamine 5 5 5 5 5 5 5 5 5 5 Polyoxane defoamer 3 3 3 3 3 3 3 3 3 3 DPM 10 10 10 10 10 10 10 10 10 10 Barium sulphate 80 80 80 80 80 80 80 80 80 80 Hardener (C) Lanthanide photopolymerization initiator (C-2) 1 1 1 1 1 1 1 1 1 1 (C) Photopolymerization initiator other than 肟 (C-4) ” 5 5 5 5 5 5 5 5 5 5 phenol awake lacquer type epoxy resin 15 15 15 15 15 15 15 15 1S 15 _ bis xylenol type epoxy resin 25 25 25 25 25 25 25 25 DPV S5 [ 5 5 5 5 5 5 5 5 S 5 钡20 20 20 20 20 20 20 20 9〇2〇Remarks*1: Solid content 100 parts*2 : 1,4-Bis(3-sulfenylbutoxy)butane*3: Pentaerythritol 肆 (3- Mercaptobutyrate) *4 : 1,3,5-gin (3-Mercapto butyloxyethyl)-1,3,5·tris-2,4,6(1H,3H5] *5 : Mercaptopropionic acid derivative (trimethylol propyl thiopropionate) ^ ? ' *6 : Ethyl ketone, H9 · ethyl each (2 - methyl Benzene oxime)-9H-咔哩·3·yl]-χο- 乙醒基) *7 : IRGACURE907 (manufactured by Ciba Specialty Chemical Co., Ltd.) Triketone-43- 200912534 About the main agent and hardener obtained The sensitivity of the 355 5 nm laser exposure machine as shown in Table 4 and the evaluation of the maximum development period were carried out. For the preservation stability, the obtained main component and the curing agent were placed in a sealed container made of polyethylene, and placed in a thermostat of 3 (TC), and evaluated after 60 days and 60 days later. The results obtained are shown in Table 4. [Table 4] Example 8 Example 9 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Comparative Example 3 Blending Example 1 Blending Example 2 Blending Example 3 Blending Example 4 Blending Example 5 Blending Example 6 Blending Example 7 Blending Example 8 Blending Example 9 Blending Example 10 Immediately after the preparation of the main homogenizing agent, the characteristics were evaluated. Sensitivity 50 mJ 50 mJ 50 mJ 40 mJ 40 mJ 40 mJ 60 mJ 60 mJ 60 mJ 40 mJ max During the development period, 60 minutes, 70 minutes, 70 minutes, 60 minutes, 70 minutes, 70 minutes, 70 minutes, 70 minutes, 70 minutes, 20 minutes, the main agent, the hardener, was stored at 3 ° C for 30 days, and then mixed and evaluated. Sensitivity 50 mJ 50 mJ 50 mJ 40 mJ 40mJ 40mJ 60mJ 60mJ 60mJ Maximum development period 50 minutes 60 minutes 70 minutes 60 minutes 70 minutes 70 minutes 70 minutes 70 minutes 70 minutes Can not be developed as a main agent, hardener, and then stored at 3 ° C for 60 days after ί 昆合And evaluation "Jia. Sensitivity 50mJ 50mJ 50mJ 40mJ 40mJ 40mJ 60mJ 60mJ 60mJ Maximum development period 40 minutes 50 minutes 60 minutes 50 minutes 70 minutes 70 minutes 60 minutes 70 minutes 70 minutes can not be developed Comparative Example 4 Mixture shown in Table 3 5, after the main agent and the curing agent were adjusted, they were immediately mixed and stored at 30 ° C for 60 days, and the development period was significantly shortened to 30 minutes - 44 - 200912534. Comparative Example 5 In the blending example 5 shown in Table 3, Blending (B2) pentaerythritol bismuth (3-mercaptobutyrate) on the side of the hardener, after 30 days of storage at 30 ° C for 30 days, the test was carried out 'but not developed. Example 1 8 will be in accordance with The photohardenability of the thermosetting resin composition prepared in Example 3 shown in Table 1 was diluted with methyl ethyl ketone, and then applied to a carrier film and dried by heating to form a photocurable thermosetting layer having a thickness of 20 μm. The resin composition layer is bonded to the protective film to obtain a dry film. Thereafter, the protective film is peeled off and the film is bonded to the patterned copper foil substrate, and then the carrier film is peeled off at 80 ° C. Dryer drying 30 points Thereafter, hardened by heating 60 minutes in a hot air dryer to produce a test substrate of l5〇 ° C. To obtain the test substrate having the cured coating film to the test methods and evaluation methods of various characteristics of the test were evaluated. The result is the same as in Example 3. -45-

Claims (1)

200912534 X. Patent Application No. 1 · A photocurable thermosetting resin composition characterized by containing (A) a carboxyl group-containing resin, (B) mercaptobutyric acid or a derivative thereof, and (C) photopolymerization a starting agent, a compound having two or more ethylenically unsaturated groups in the (D) molecule, and (E) a thermosetting component. The photocurable and thermosetting resin composition of the first aspect of the invention, wherein the photopolymerization initiator (C) is an oxime ester photopolymerization initiator (C,). 3. The photocurable thermosetting resin composition according to claim 1, wherein the carboxyl group-containing resin (A) is a carboxyl group-containing resin (A 1 ) having a radically polymerizable unsaturated double bond. . 4. The photocurable thermosetting resin composition according to claim 3, wherein a part or all of the unsaturated double bond of the carboxyl group-containing resin (A 1 ) is derived from methacrylic acid or a derivative thereof Things. 5. The photocurable thermosetting resin C composition according to the first aspect of the invention, wherein the mercaptobutyric acid or a derivative thereof (B) has two or more 2-mercaptoisoindoles in one molecule. Acid or 3-mercaptobutyric acid or a derivative thereof. 6. The photocurable thermosetting resin composition of the first aspect of the invention, wherein the photopolymerization initiator (C) is an oxime ester photopolymerization initiator represented by the following formula (I) (C1), or a mixture of the oxime ester photopolymerization initiator (C1) and an aminoacetophenone photopolymerization initiator (C2) represented by the following formula (II), the oxime ester light a mixture of a polymerization initiator (C1) and a photopolymerization initiator (C3) represented by the following formula (III): -46-200912534, a decyl phosphine oxide photopolymerization initiator (C1) And an amino acetophenone-based photopolymerization initiator (C2) represented by the following formula (II) and a mercaptophosphine oxide-based photopolymerization initiator represented by the following formula (III) (C) 3) Mixture, [Chem. 1] - C = N - 0 - c - R2 (I) II R1 Ο 3* 4 RHC — R - CMMO R7 Rc d OII c- (III) (wherein R1 represents a hydrogen atom, a phenyl group (may also be substituted by an alkyl group having a carbon number of i to 6, a phenyl group or a halogen atom), and an alkyl group having 1 to 20 carbon atoms (Alternatively, it may be substituted by one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), a ring group having a carbon number of 5 to 8, and an alkanoyl group having a carbon number of 2 to 20 (alkanoyl: or benzoquinone) a group (which may also be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group); R2 represents a phenyl group (which may also be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen-47-200912534 atom), An alkyl group having 1 to 20 carbon atoms (may be substituted by one or more hydroxyl groups, or one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 2 to 20 An alkanoyl or phenylhydrazine group (which may also be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group); R3 and R4 each independently represent an alkyl group or an aralkyl group having 1 to 12 carbon atoms; R5 and R6 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 2 is bonded to form a cyclic alkyl ether group; and R7 and R8 each independently represent a linear chain having a carbon number of 1 to 1 〇. Or branched alkyl, carbon number 1~1 a linear or branched alkoxy group, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl group substituted by a halogen atom, an alkyl group or an alkoxy group, but one of 'R7 and R8' It can represent RC(=0)-based (here, R is a hydrocarbon group having a carbon number of 1 to 20). 7- Photohardenability according to item 6 of the patent application. Thermosetting resin composition 'where the aforementioned The oxime ester photopolymerization initiator (C1) represented by the formula (1) is an oxime ester photopolymerization initiator represented by the following formula (IV), 化II C, N—Ο — C — CH3 II II, c ο Η IV IV IV IV IV IV IV IV IV IV IV IV IV IV IV IV IV IV IV IV IV IV IV 热 热 热 热 热 热 热 热 热 热 热 热 热 热 ( ( ( ( ( ( ( ( ( ( 1) is an oxime ester photopolymerization initiator represented by the following formula (ν), -48- 200912534 (wherein R9 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoinyl group, an alkylene group having 2 to 12 carbon atoms, and a carbon number; 2 to 12 alkoxycarbonyl groups (when the carbon number of the alkyl group constituting the alkoxy group is 2 or more, the alkyl group may be substituted by one or more hydroxyl groups, and the alkyl chain may have one or more oxygen atoms in the middle) Or phenoxycarbonyl; RIO, R12 each independently represents a phenyl group (which may also be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and an alkyl group having 1 to 20 carbon atoms (may also be 1). More than one hydroxy group substituted, one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkyl fluorenyl group having 2 to 20 carbon atoms or a benzoquinone group (may also be carbon number) 1 to 6 alkyl or phenyl substituted); R11 is a hydrogen atom, a phenyl group (which may also be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and an alkyl group having 1 to 20 carbon atoms (also It may be substituted by one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), a ring-shaped base having a carbon number of 5 to 8, a bromo or a benzoic acid group having a carbon number of 2 to 20 (may also be Cyan number ~ 6 alkyl Phenyl substituted)). 9. The composition of the photocurable thermosetting resin-49-200912534 of claim 1, wherein the thermosetting component (E) is an epoxy resin and is blended with a sulfhydryl group as described above. A 2-liquid type composition in a mixture of butyric acid or a derivative thereof (B). 10. The photocurable thermosetting resin composition of claim 2, which is a mixture of at least a carboxyl group-containing resin (A) and the aforementioned mercaptobutyric acid or a derivative thereof (B), and A two-component composition of a mixture of the above-described oxime ester photopolymerization initiator (C') and a thermosetting component (£). 1 1 The photocurable thermosetting resin composition of claim 1 is a solder resist further containing a coloring agent (F). 1 2 · Photohardenability/thermosetting resin composition as in item n of the patent application' is a green or blue solder resist. And a photocurable/thermosetting resin composition according to any one of the above claims 1 to 12, which is coated on a carrier film. And it is dried. A cured product of the photocurable thermosetting resin composition according to any one of claims 1 to 12, or the dry film of the above-mentioned Patent Application No. 13 or It is obtained by photohardening on copper. A cured product of the photocurable thermosetting resin composition according to any one of claims 1 to 12, or the dry film of the first or third aspect of the patent application, The laser emission source of 3 5 Onm~ 4 I Onm is photohardened into a pattern. 1 6 _ - A printed circuit board having a resistive pattern, characterized by the photocurable thermosetting -50-200912534 chemical resin composition according to any one of the above claims 1 to 12, Or the above-mentioned coating film, after having a wavelength of 350 nm to 410 nm as a pattern, and being thermally hardened, the dry type thin ultraviolet light of the patent range No. 13 is directly drawn to light harden -51 - 200912534 VII. Designated representative figure: a) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None