Alkaline developing type resin composition, photocurable dry film and cured product thereof, and printed wiring board formed using the same

Abstract

The present invention provides an alkali-developable resin composition capable of forming a solder resist layer having excellent adhesion and cold-heat shock resistance, a photocurable dry film thereof, a cured product thereof, and a printed circuit board formed using the same. The alkali-developable resin composition is characterized by containing (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) a glass powder, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (E) an inorganic filler, the (E) inorganic filler including talc, the (C) glass powder including, in terms of weight %, SiO2: 60 to 65 %, Fe2O3: 0.01 to 0.02 %, Al2O3: 14 to 20 %, CaO: 6 to 9 %, MgO: 1 to 2 %, B2O3: 8 to 12 %, the (C) glass powder having a Mohs hardness of less than 6.5.

Description

[0001] This application is a divisional application of the application with the application number 202380017216.6, the application date of December 27, 2023, and the invention title of Alkaline developing type resin composition, photocurability of dry film thereof and cured product thereof, and printed circuit board formed using the same. TECHNICAL FIELD

[0002] The present application relates to an alkaline developing type resin composition, photocurability of dry film thereof and cured product thereof, which are suitable for forming a solder resist layer of a printed circuit board, and particularly relates to an alkaline developing type resin composition, photocurability of dry film thereof and cured product thereof, which can form a solder resist layer having excellent adhesion and cold-heat shock resistance, and a printed circuit board. BACKGROUND

[0003] Nowadays, in the formation of a solder resist layer (solder resist film) of a part of a civil printed circuit board and almost all of an industrial printed circuit board, an alkaline developing type solder resist which forms an image after ultraviolet exposure and development, and is completely cured (main curing) by heat and / or light irradiation is used. In addition, in semiconductor devices for vehicles such as automobiles, trains, ships, and aircraft, there is a tendency to use a solder resist for a printed circuit board that is oriented toward high-reliability electronic materials.

[0004] However, a conventional alkali developing solder resist ink generally has poor cold-heat shock resistance and poor reliability against changes in environmental temperature due to thermal expansion and contraction and the like. In addition, from the perspectives of protecting copper circuits and aesthetics, the solder resist layer must have excellent adhesion. Although the use of talc as a filler can improve cracking, the adhesion is poor. Or when talc and silica are used as fillers, although the cold-heat shock resistance of the solder resist ink for vehicle use can be satisfied, the adhesion is still insufficient.

[0005] For example, the filler in the photocurable solder resist ink of Patent Document 1 uses silica, barium sulfate, and talc powder. The solder resist layer useable cured resin composition of Patent Document 2 contains a carboxyl-containing resin, a thermal curing component, a flame retardant, and an ion capturing agent, which is a mixture of a hydrotalcite-based ion capturing agent and an ion capturing agent other than a hydrotalcite, and an inorganic filler uses aluminum hydroxide. The cured resin composition of Patent Document 3 is used for a permanent mask of a printed circuit board, which contains: a resin having an ethylenically unsaturated group and a carboxyl group in the molecule, a photopolymerization initiator, a photopolymerizable monomer, titanium oxide subjected to surface treatment with alumina, barium sulfate and / or talc, and an organic solvent. The ultraviolet light curable liquid photosensitive solder resist soft board ink of Patent Document 4 describes that the filler is barium sulfate, talc powder, or silica.

[0006] Patent Document 1: CN114716868A

[0007] Patent Literature 2: CN108137791A

[0008] Patent Literature 3: CN101798432A

[0009] Patent Literature 4: CN106380929A SUMMARY

[0010] Problem to be solved by the invention

[0011] An object of the present application is to provide a positive resist resin composition capable of forming a solder resist layer having excellent adhesion and cold-heat shock resistance, a photocurable dry film thereof, and a cured product thereof, and a printed circuit board.

[0012] Solution to the problem

[0013] The present inventors have conducted intensive studies to solve the problems and as a result, found that the type of filler greatly affects the cold-heat shock resistance. The positive resist resin composition described below can solve the above problems and thus complete the present application, which is characterized by containing (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) a glass powder, (D) a compound having two or more ethylenic unsaturated groups in one molecule, and (E) an inorganic filler, the (E) inorganic filler containing talc, the (C) glass powder containing, in terms of mass%, SiO2: 60 to 65%, Fe2O3: 0.01 to 0.02%, Al2O3: 14 to 20%, CaO: 6 to 9%, MgO: 1 to 2%, B2O3: 8 to 12%, and the (C) glass powder having a Mohs hardness of less than 6.5.

[0014] That is, the positive resist resin composition of the present application is characterized by containing (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) a glass powder, (D) a compound having two or more ethylenic unsaturated groups in one molecule, and (E) an inorganic filler, the (E) inorganic filler containing talc, the (C) glass powder containing, in terms of mass%, SiO2: 60 to 65%, Fe2O3: 0.01 to 0.02%, Al2O3: 14 to 20%, CaO: 6 to 9%, MgO: 1 to 2%, B2O3: 8 to 12%, and the (C) glass powder having a Mohs hardness of less than 6.5.

[0015] Further, it is preferable to contain (F) another additive other than the (B) photopolymerization initiator and the (C) glass powder.

[0016] Further, it is preferable to contain (G) an epoxy resin.

[0017] Further, it is preferable to contain (H) an organic solvent.

[0018] Further, the photocurable dry film of the present application is characterized by being obtained by coating the alkali-developable resin composition on a support film and drying.

[0019] Further, the cured product of the present application is characterized by being obtained by photocuring a coating film obtained by coating the alkali-developable resin composition on copper and drying, or a coating film obtained by coating the alkali-developable resin composition on a support film, drying, and laminating the obtained photocurable dry film on copper.

[0020] Further, the printed circuit board of the present application is characterized by being obtained by photocuring and then heat-curing a coating film obtained by coating the alkali-developable resin composition on a substrate having a copper circuit, or a coating film obtained by coating the alkali-developable resin composition on a support film, drying, and laminating the obtained photocurable dry film on a substrate having a copper circuit.

[0021] The alkali-developable resin composition of the present application is characterized by comprising (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) a glass powder, (D) a compound having two or more ethylenic unsaturated groups in one molecule, and (E) an inorganic filler, the (E) inorganic filler comprising talc, the (C) glass powder comprising, in terms of mass%, Si02: 60 to 65%, Fe203: 0.01 to 0.02%, Al203: 14 to 20%, CaO: 6 to 9%, MgO: 1 to 2%, B203: 8 to 12%, the (C) glass powder having a Mohs hardness of less than 6.5.

[0022] Based on the characteristic configuration of the present application, by using a soft composite glass powder and talc in combination, and adjusting the ratio of the two, it is possible to improve the adhesion while maintaining excellent cold and hot shock resistance.

[0023] On the other hand, in the prior art, talc and barium sulfate are used as fillers at the same time, which can satisfy the requirement of cold and hot shock resistance of solder resist ink, but the adhesion is poor (for example, Patent Literature 1 and the like).

[0024] As described above, the present inventors and others have found through repeated and intensive studies that talc has good flexibility as a filler, and has excellent resistance to cracking in a temperature cycle test (hereinafter sometimes referred to as "TCT test"), but the adhesion becomes poor as the amount used increases. A glass powder, particularly a soft composite glass powder, as a filler can provide excellent adhesion, but is insufficient in terms of cold and hot shock resistance. By using talc and a glass powder as fillers at the same time, it is possible to maintain excellent cold and hot shock resistance and adhesion at the same time, thereby achieving the above-described object of the present application.

[0025] Effects of the invention

[0026] As described above, with the present application, it is possible to provide a positive resist resin composition capable of forming a solder resist layer having excellent adhesion and cold-heat shock resistance, a photocurable dry film thereof, and a cured product thereof, and a printed circuit board. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 A photograph showing that the solder resist film in the example for evaluating the cold-heat shock resistance was cracked (NG (cracked)).

[0028] Figure 2 A photograph showing that the solder resist film in the example for evaluating the cold-heat shock resistance was not cracked (OK (not cracked)).

[0029] Figure 3 A schematic view of a spindle used when evaluating the adhesion in the example (spindle schematic view). DETAILED DESCRIPTION

[0030] Hereinafter, each component in the positive resist resin composition of the present application will be described.

[0031] The positive resist resin composition of the present application is characterized by containing (C) glass powder and (E) inorganic filler, and the (E) inorganic filler contains talc as an essential component, and therefore, (C) glass powder and (E) inorganic filler will be described first.

[0032] (C) glass powder

[0033] The (C) glass powder used in the positive resist resin composition of the present application refers to a powder-shaped amorphous inorganic substance in a glass state, and the main component is silicon dioxide. It is typically formed by sintering an inorganic mineral as a main raw material at a high temperature.

[0034] As the (C) glass powder used in the positive resist resin composition of the present application, a soft composite glass powder is preferred from the viewpoint of further contributing to the achievement of the object of the present application. The (C) glass powder can be a glass powder without surface treatment or a glass powder with surface treatment.

[0035] As the component composition of the soft composite glass powder, it is typical that SiO2: 60 to 65%, Fe2O3: 0.01 to 0.02%, Al2O3: 14 to 20%, CaO: 6 to 9%, MgO: 1 to 2%, B2O3: 8 to 12%, preferably SiO2: 61 to 64%, Fe2O3: 0.012 to 0.019%, Al2O3: 15 to 19%, CaO: 6.5 to 8.5%, MgO: 1.1 to 1.8%, B2O3: 9 to 11%, more preferably SiO2: 62 to 63%, Fe2O3: 0.014 to 0.018%, Al2O3: 16 to 18%, CaO: 7 to 8%, MgO: 1.2 to 1.6%, B2O3: 9.5 to 10.5%.

[0036] As the soft composite glass powder, it has a Mohs hardness of less than 6.5, preferably in the range of 4.8 to 6.2, more preferably in the range of 5 to 6.

[0037] The present inventors have found that, from the viewpoint of both cold and hot impact resistance and adhesion of the solder resist layer, by further compounding the (C) glass powder while using talc as the filler, it is possible to significantly improve the adhesion while maintaining excellent cold and hot impact resistance. At this time, the compounding ratio of the two, i.e., talc: glass powder is 90:10 to 10:90 by weight is appropriate, preferably 80:20 to 20:80, more preferably 75:25 to 25:75, further preferably 70:30 to 30:70. In this way, it is possible to obtain an alkali development type resin composition that enables a solder resist layer having both excellent cold and hot impact resistance and adhesion.

[0038] As for the compounding ratio of the (C) glass powder, it is appropriate to be 10 to 90 parts by weight, preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight, further preferably 40 to 60 parts by weight, with respect to 100 parts by weight of the (A) vinyl ester resin in terms of solid content. The use amount of the (C) glass powder within the above range can ensure both excellent cold and hot impact resistance and improved adhesion. Outside the above range, the characteristics as a solder resist are reduced and thus are not preferred.

[0039] As a commercially available product of the soft composite glass powder, K10 (manufactured by Suzhou Jin Yi New Material Technology Co., Ltd.), G2C (manufactured by Shanghai Sibike Mining Co., Ltd.), and the like can be mentioned.

[0040] (E) inorganic filler

[0041] The talc used as the (E) inorganic filler in the alkali development type resin composition of the present application is used in order to improve the cold and hot impact resistance. The (E) inorganic filler here does not include the (C) glass powder described above, particularly the soft composite glass powder.

[0042] As the talc, any one of magnesium carbonate, serpentine, silica / silica-alumina, magnesium deposit, or one of so-called silicate minerals can be used, and the shape can be in the form of a lump or a fine powder. Surface treatment can or can not be performed. The average particle diameter of the talc is preferably 1.0 to 20.0 μm, more preferably 2.0 to 10 μm, and further preferably 3.0 to 8.0 μm. As commercially available products, HD25 manufactured by Shandong Pingdu Talc Mine Co., Ltd., LMP-100 manufactured by Fuji Talc Industrial Co., Ltd., and the like can be mentioned.

[0043] The amount of the talc is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, and further preferably 30 to 70 parts by weight, relative to 100 parts by weight of the (A) vinyl ester resin based on the solid content. If the amount is within the above range, it is possible to improve the adhesion while ensuring excellent cold and hot impact resistance.

[0044] In a range not affecting the object of the present application, other fillers such as silica can be compounded in addition to the talc and the above-mentioned (C) glass powder. As the silica, any one of amorphous, crystal, or a mixture thereof can be used. Amorphous (fused) silica is particularly preferred. Surface treatment can or can not be performed. The silica is typically 6.5 or more in Mohs' hardness. The average particle diameter of the silica is preferably 0.1 to 10.0 μm, more preferably 1.0 to 8.0 μm, and further preferably 2.0 to 6.0 μm. As commercially available products of the silica, CS1002 and CS1002A manufactured by Jiangsu Lianrui New Material Co., Ltd., A-8 manufactured by Sibelco Co., Ltd., SE-40 manufactured by Tokuyama Co., Ltd., MSV25G manufactured by Longson, MLV-2114 manufactured by Longson, SO-E5 manufactured by ADMATECHS, SO-E2 manufactured by ADMATECHS, and the like can be mentioned.

[0045] (A) vinyl ester resin

[0046] As the (A) vinyl ester resin in the photocurable thermosetting resin composition of the present application, a publicly known resin having an ethylenic unsaturated double bond in the molecule can be used from the viewpoints of photocurability and resistance to development. In addition, in order to impart alkali development, a carboxyl-containing resin having an ethylenic unsaturated double bond in the molecule is particularly preferred. Furthermore, it is more preferred that the unsaturated double bond is derived from acrylic acid or methacrylic acid or a derivative thereof. As the (A) vinyl ester resin, a resin using an epoxy resin as a starting material, a polyurethane resin having a urethane skeleton, a copolymer resin having a copolymer structure of an unsaturated carboxylic acid, a resin using a phenol compound as a starting material is preferred. Specific examples of the (A) vinyl ester resin are shown below.

[0047] (1) a vinyl ester resin obtained by copolymerizing (meth)acrylic acid or the like unsaturated carboxylic acid and one or more kinds of compounds having an unsaturated double bond other than the same;

[0048] (2) a photosensitive vinyl ester resin obtained by adding an olefinic unsaturated group in the form of a side group to a copolymer of (meth)acrylic acid or the like unsaturated carboxylic acid and one or more kinds of compounds having an unsaturated double bond other than the same, using a compound having an epoxy group and an unsaturated double bond such as glycidyl (meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate, (meth)acryloyl chloride or the like;

[0049] (3) a photosensitive vinyl ester resin obtained by reacting a copolymer of glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate or the like compound having an epoxy group and an unsaturated double bond and one or more kinds of compounds having an unsaturated double bond other than the same, with an unsaturated carboxylic acid such as (meth)acrylic acid, and reacting a polybasic acid anhydride with a secondary hydroxyl group generated;

[0050] (4) a photosensitive vinyl ester resin obtained by reacting a copolymer of an acid anhydride having an unsaturated double bond such as maleic anhydride and one or more kinds of compounds having an unsaturated double bond other than the same, with a compound having a hydroxyl group and an unsaturated double bond such as 2-hydroxyethyl (meth)acrylate;

[0051] (5) a vinyl ester resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid, and reacting a saturated or unsaturated polybasic acid anhydride with a hydroxyl group generated;

[0052] (6) a vinyl ester resin containing a hydroxyl group and a carboxyl group obtained by reacting a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative with a saturated or unsaturated polybasic acid anhydride, and reacting a compound having an epoxy group and an unsaturated double bond in one molecule with a carboxylic acid generated;

[0053] (7) a vinyl ester resin obtained by reacting a polyfunctional epoxy compound and an unsaturated monocarboxylic acid with a reaction product of a compound having at least one alcoholic hydroxyl group and one reactive group other than the alcoholic hydroxyl group which reacts with an epoxy group in one molecule, and a saturated or unsaturated polybasic acid anhydride;

[0054] (8) a vinyl ester resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional oxetane compound having at least two oxetane rings in one molecule, and reacting a saturated or unsaturated polybasic acid anhydride with a primary hydroxyl group in the resulting modified oxetane resin; and

[0055] (9) a vinyl ester resin obtained by further reacting a carboxyl-containing resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional epoxy resin and then with a polybasic anhydride, with a compound having one oxirane ring and one or more ethylenic unsaturated groups in the molecule;

[0056] (10) a vinyl ester resin obtained by reacting a difunctional epoxy compound with an unsaturated monocarboxylic acid and reacting a saturated or unsaturated polybasic anhydride with the resulting hydroxyl group.

[0057] As particularly preferable substances among these examples, the vinyl ester resins of said (2), (5), (7), (9) are given.

[0058] Note that, in the present specification, (meth)acrylate is a term collectively referring to acrylate, methacrylate and mixtures thereof, and the same applies to other similar expressions.

[0059] The above-described (A) vinyl ester resin has a plurality of free carboxyl groups on the side chain of the main chain polymer, and thus can be developed using a dilute aqueous alkali solution.

[0060] In addition, the acid value of the above-described (A) vinyl ester resin is preferably in the range of 40 to 200 mgKOH / g, and more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the (A) vinyl ester resin is less than 40 mgKOH / g, it is difficult to perform alkali development, on the other hand, when it exceeds 200 mgKOH / g, the exposed portion is dissolved in the developer, and thus the line becomes finer than desired, and sometimes the exposed portion and the unexposed portion are dissolved and peeled off by the developer without distinction, and thus it is difficult to draw a normal resist pattern, and thus it is not preferable.

[0061] Further, the weight average molecular weight of the above-described (A) vinyl ester resin varies depending on the resin skeleton, and is generally preferably in the range of 2000 to 150000, and further preferably in the range of 5000 to 100000. When the weight average molecular weight is less than 2000, sometimes the non-tacky property after coating and drying on a substrate deteriorates, and further, sometimes the moisture resistance of the coating film after exposure deteriorates, and film reduction occurs during development, and the resolution greatly deteriorates. On the other hand, when the weight average molecular weight exceeds 150000, sometimes the developability significantly deteriorates, and the storage stability deteriorates.

[0062] The compounding amount of the (A) vinyl ester resin is desirably in the range of 20 to 60% by mass of the total composition based on the solid content, and is preferably in the range of 25 to 50% by mass. When the compounding amount of the (A) vinyl ester resin is less than the range, the strength of the coating film decreases, and thus it is not preferable. On the other hand, when it is more than the range, the viscosity of the composition becomes high, or the coatability and the like deteriorate, and thus it is not preferable.

[0063] (B) photopolymerization initiator

[0064] As the photopolymerization initiator used in the alkali developing type resin composition of the present application, there is no particular limitation as long as it is a photopolymerization initiator generally used in alkali developing type resin compositions.

[0065] As the photopolymerization initiator, known substances can be used, and examples of which can be given: benzoin, benzoin methyl ether, benzoin ethyl ether and the like benzoin and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-tert-butyldioxy-1-methylethyl)acetophenone and the like acetophenones; 2-methylanthraquinone, 2-pentylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and the like anthraquinones; isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone and the like thioxanthones; acetophenone dimethyl ketal, benzil dimethyl ketal and the like ketals; benzophenone, 4-(1-tert-butyldioxy-1-methylethyl)benzophenone, 3,3',4,4'-tetra(tert-butyldioxycarbonyl)benzophenone and the like benzophenones; and xanthone and the like.

[0066] In addition, as the photopolymerization initiator, an oxime ester-based photopolymerization initiator having an oxime ester group, an alkylphenone-based photopolymerization initiator, an α-aminophenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a titanocene-based photopolymerization initiator, a phosphate-based photopolymerization initiator and the like can also be used.

[0067] As the oxime ester-based photopolymerization initiator, commercially available products can be given: Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan Co., Ltd., N-1919, NCI-831 manufactured by ADEKA CORPORATION and the like. A photopolymerization initiator having 2 oxime ester groups within the molecule can be preferably used, and specifically, an oxime ester compound having a carbazole ring structure can be given.

[0068] As the alkylphenone-based photopolymerization initiator, commercially available products can be given: α-hydroxyalkylphenone-based Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 and the like manufactured by IGM Resins B.V. Co.

[0069] As α-aminoacetophenone-based photopolymerization initiators, specific examples include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone, and N,N-dimethylaminoacetophenone. Commercially available products include Omnirad 907, Omnirad 369, and Omnirad 379 manufactured by IGM Resins BV.

[0070] Examples of acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and acylphosphine oxide photopolymerization initiators with three or more functional groups. These acylphosphine oxide photopolymerization initiators can be photopolymerization initiators having three or more acylphosphine oxide skeletons in one molecule, and can be represented by the following formula (I).

[0071]

[0072] In the formula,

[0073] A represents a single bond, O, S, or NR independently of each other. 3 ;

[0074] G is a multifunctional compound (core) G-(AH) m+n The residues, where AH each represent an alcohol group, an amino group, or a thiol group;

[0075] Both m and n are integers, and m+n is an integer between 3 and 10;

[0076] m is an integer between 3 and 8;

[0077] R1 and R2 are independently C1-C 18 Alkyl, C6-C 12 aryl and C5-C 12 The cycloalkyl group is either not broken or is cleaved by the following groups: one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, or R1 and R2 are independently five- to six-membered heterocyclic groups containing oxygen and / or nitrogen and / or sulfur atoms, wherein the aforementioned groups are optionally substituted by aryl, alkyl, aryloxy, alkoxy, heteroatom and / or heterocyclic groups.

[0078] R2 can be R1-(C=O)-;

[0079] Y is either O or S;

[0080] R3is hydrogen or a C1-C4alkyl group;

[0081] wherein the photopolymerization initiator of formula (I) does not contain a photocurable ethylenically unsaturated group.

[0082] Preferably, in formula (I), m + n is an integer between 3 and 8, more preferably an integer between 3 and 6. For example, in formula (I), m is an integer between 3 and 6, more preferably an integer between 3 and 5.

[0083] In formula (I), when A is oxygen, G-(A-H) m+n is a polyhydroxy (polyol) compound selected from the group consisting of monomeric polyols, oligomeric polyols and polymeric polyols, and mixtures thereof. When A is sulfur, G-(A-H) m+n is a polythiol compound. When A is nitrogen, in formula (I), G-(A-H) m+n is a linear or branched polyamine. When A is a mixture of oxygen and / or nitrogen and / or sulfur, G-(A-H) m+n is a compound comprising different functional groups, for example a compound comprising amino groups and hydroxyl groups. The residue G- suitable for the practice of the present application does not contain a photocurable ethylenically unsaturated group. When A is a single bond, G- is the residue G-(A-H) listed above. m+n after removal of the hydroxyl and / or amino and / or mercapto groups.

[0084] Preferably G-(A-H) m+n has a number average molecular weight of 1500 or less, more preferably 800 or less, further preferably 500 or less.

[0085] When n is not 0, the compound of formula (I) has an alcoholic free radical and / or an amino group and / or a mercapto group.

[0086] Representative 3 or more functional acylphosphine-based photopolymerization initiators included in formula (I) are shown in Table 1. Among these, PI-3, PI-4, PI-10, PI-11, PI-12, PI-14, PI-17 are particularly preferred. By including such 3 or more functional acylphosphine-based photopolymerization initiators, a cured product can be obtained which has inhibited outgassing and which has even more excellent insulation reliability.

[0087] Table 1

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095] Such a 3 or more functional acylphosphine-based photopolymerization initiator can be produced, for example, by the method described in Japanese Patent No. 6599446.

[0096] As a commercially available product of an acyloxyphosphine-based photopolymerization initiator, Omnirad TPO manufactured by IGM Resins Co., Ltd., Omnirad 819 manufactured by IGM Resins B.V., Omnipol TP, and the like can be used.

[0097] As the aforementioned titanocene-based photopolymerization initiator, specifically, bis(cyclopentadienyl)-diphenyltitanium, bis(cyclopentadienyl)-dichlorotitanium, bis(cyclopentadienyl)-bis(2,3,4,5,6-pentafluorophenyl)titanium, bis(cyclopentadienyl)-bis(2,6-difluoro-3-(pyrrol-1-yl)phenyl)titanium, and the like can be given. As a commercially available product, Omnirad 784 manufactured by IGM Resins B.V., and the like can be given.

[0098] As to the compounding ratio of these photopolymerization initiators (B), 0.01 to 30 parts by weight, preferably 5 to 25 parts by weight, and more preferably 10 to 20 parts by weight, is suitable with respect to 100 parts by weight of the aforementioned (A) vinyl ester resin in terms of solid content. In the case where the amount of the photopolymerization initiator used is less than the aforementioned range, the photocurability of the composition becomes poor, and on the other hand, in the case where it is excessive, the properties as a solder resist are reduced and thus are not preferable.

[0099] Note that in the present specification, polymer is a term collectively referring to homopolymers, copolymers, and mixtures thereof, and the same applies to other similar expressions.

[0100] (D) compound having two or more ethylenic unsaturated groups in one molecule

[0101] The (D) compound having two or more ethylenic unsaturated groups in one molecule used in the alkali development type resin composition of the present application is a compound which makes the aforementioned (A) vinyl ester resin insoluble in an aqueous alkali solution or contributes to the insolubility of the aforementioned vinyl ester resin in an aqueous alkali solution by light curing with irradiation of active energy rays. As specific examples of such a compound, the following can be given:

[0102] 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and the like hydroxyalkyl acrylates;

[0103] mono- or di-acrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, and the like;

[0104] acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, N,N-dimethylamino propyl acrylamide, and the like;

[0105] aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate, and the like;

[0106] polyacrylates of polyols such as hexanediol, trimethylolpropane, pentaerythritol, di-pentaerythritol, trihydroxyethyl isocyanurate, and the like, or their oxirane adducts or propylene oxide adducts, and the like;

[0107] acrylates such as phenoxy acrylate, bisphenol A diacrylate, and oxirane adducts or propylene oxide adducts of these phenols, and the like;

[0108] acrylates of glycidyl ethers such as glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, trisglycidyl isocyanurate, and the like;

[0109] and at least any one of melamine acrylate, and each methacrylate corresponding to the above acrylates, and the like.

[0110] Further, examples include: an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as a cresol novolak type epoxy resin and the like with acrylic acid, an epoxy urethane acrylate compound obtained by further reacting a hydroxyl group of the epoxy acrylate resin with a half urethane compound of a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate, and the like.

[0111] The compounding amount of such a compound (D) having two or more ethylenic unsaturated groups in one molecule is desirably in a proportion of 5 to 100 parts by weight, and more desirably in a proportion of 10 to 70 parts by weight, relative to 100 parts by weight of the aforementioned (A) vinyl ester resin calculated as a solid content. In a case where the compounding amount is less than 5 parts by weight relative to 100 parts by weight of the (A) vinyl ester resin, the obtained alkali development type resin composition has a reduced photocurability, and it is difficult to form a pattern by alkali development after irradiation with active energy rays, and thus is not preferable. On the other hand, in a case where the compounding amount exceeds 100 parts by weight, the solubility in an aqueous alkali solution is reduced, and the cured coating film becomes brittle, and thus is not preferable.

[0112] (F) other additives

[0113] As described above, the other additive in the present application means an additive other than the (B) photopolymerization initiator and the (C) glass powder.

[0114] As such an additive, at least any one of the following can be cited: phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, and the like, which are well-known and commonly used colorants; hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, pyrogallol, phenothiazine, and the like, which are well-known and commonly used thermal polymerization inhibitors; finely powdered silica, organic bentonite, montmorillonite, and the like, which are well-known and commonly used thickeners; defoaming agents and leveling agents of silicone type, fluorine type, high molecular type, and the like; adhesion-imparting agents of imidazole type, thiazole type, triazole type, and the like; silane coupling agents; phenol type, phosphorus type, sulfur type, and the like, which are well-known and commonly used antioxidants; hindered amine light stabilizers; dispersants; and the like.

[0115] The compounding ratio of such (F) other additive is preferably 0.01% by weight or more and 20% by weight or less of the total amount of the alkali developing type resin composition. When less than 0.01% by weight, the corresponding effect cannot be sufficiently obtained, and when more than 20% by weight, the printability and hardness of the alkali developing type resin composition are deteriorated, and thus are not preferable.

[0116] (G) epoxy resin

[0117] In order to impart heat resistance, it is preferable that an epoxy resin having at least two epoxy groups in the compounding molecule of the alkali developing type resin composition used in the present application, i.e., a multifunctional epoxy resin (G).

[0118] As commercially available products, for example, the following can be mentioned: bisphenol A type epoxy resins such as jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, EPICLON 840, 850, 850S, 1050, 2055 manufactured by DIC Corporation, EPOTOTE YD-011, YD-013, YD-127, YD-128 manufactured by NIPPON STEEL Chemical & Material Co., Ltd., D.E.R. 317, D.E.R. 331, D.E.R. 661, D.E.R. 664 manufactured by Dow Chemical Company, Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Company Limited (all trade names); brominated epoxy resins such as jERYL903 manufactured by Mitsubishi Chemical Corporation, EPICLON 152, EPICLON 165 manufactured by DIC Corporation, EPOTOTE YDB-400, YDB-500 manufactured by NIPPON STEEL Chemical & Material Co., Ltd., D.E.R. 542 manufactured by Dow Chemical Company, Sumi-Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Company Limited (all trade names); epoxy resins such as jER152, jER154 manufactured by Mitsubishi Chemical Corporation, D.E.N. 431, D.E.N. 438 manufactured by Dow Chemical Company, EPICLON N-730, EPICLON N-770, EPICLON N-865 manufactured by DIC Corporation, EPOTOTE YDCN-701, YDCN-704 manufactured by NIPPON STEEL Chemical & Material Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000 manufactured by Japan Epoxy Resin Corporation, Sumi-Epoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Company Limited, EPOTOTE YDCN-701, YDCN-704 manufactured by NIPPON STEEL Chemical & Material Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000 manufactured by Japan Epoxy Resin Corporation, Sumi-Epoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Company Limited,YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704A, EPICLON N-680, N-690, N-695 (all trade names) manufactured by DIC Corporation, phenol novolak type epoxy resins; EPICLON 830 manufactured by DIC Corporation, jER807 manufactured by Mitsubishi Chemical Corporation, EPOTOTE YDF-170, YDF-175, YDF-2004 (all trade names) manufactured by NIPPON STEEL Chemical & Material Co., Ltd., bisphenol F type epoxy resins; EPOTOTE ST-2004, ST-2007, ST-3000 (trade name) manufactured by NIPPON STEEL Chemical & Material Co., Ltd., YX8034 manufactured by Mitsubishi Chemical Corporation, hydrogenated bisphenol A type epoxy resins; jER604 manufactured by Mitsubishi Chemical Corporation, EPOTOTE YH-434 manufactured by NIPPON STEEL Chemical & Material Co., Ltd., Sumi-Epoxy ELM-120 (all trade names) manufactured by Sumitomo Chemical Co., Ltd., glycidyl amine type epoxy resins; hydantoin type epoxy resins; CELLOXIDE 2021P (trade name) manufactured by Daicel Corporation, alicyclic epoxy resins; YL-933 manufactured by Mitsubishi Chemical Corporation, EPPN-501, EPPN-502 (all trade names) manufactured by Japan Epoxy Resin Co., Ltd., trihydroxyphenylmethane type epoxy resins; YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation, or a mixture thereof; EBPS-200 manufactured by Japan Epoxy Resin Co., Ltd., EPX-30 manufactured by ADEKA CORPORATION, EXA-1514 (trade name) manufactured by DIC Corporation, bisphenol S type epoxy resins; jER157S (trade name) manufactured by Mitsubishi Chemical Corporation, bisphenol A novolak type epoxy resins; jERYL-931 (trade name) manufactured by Mitsubishi Chemical Corporation, tetrahydroxyphenylethane type epoxy resins; TEPIC (trade name) manufactured by Nissan Chemical Industries, Ltd., heterocyclic epoxy resins; BRENMAR DGT manufactured by Nippon Oil Corporation, phthalic acid diglycidyl ester resins; ZX-1063 manufactured by NIPPON STEEL Chemical & Material Co., Ltd., tetraglycidyl xylene acyl ethane resins;ESN-190, ESN-360, HP-4032 manufactured by DIC Corporation, EXA-4750, EXA-4700, and the like, glycidyl methacrylate copolymer-based epoxy resins such as CP-50S, CP-50M manufactured by Nippon Oil Corporation, further, copolymer epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by NIPPON STEEL Chemical & Material Co., Ltd., and the like), and the like, but are not limited to these. These epoxy resins can be used alone or in combination of two or more.

[0119] (G) The content of the epoxy resin is preferably 10 to 100 parts by weight, more preferably 20 to 90 parts by weight, and further more preferably 30 to 80 parts by weight, with respect to 100 parts by weight of the (A) vinyl ester resin on a solid content basis.

[0120] (H) organic solvent

[0121] As the organic solvent (H) usable in the alkali developing type resin composition of the present application, an organic solvent can be used for the purpose of synthesizing the aforementioned vinyl ester resin (A), preparing the composition, or adjusting the viscosity so as to be coated on a substrate, a support film.

[0122] As such an organic solvent, there can be mentioned ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum-based solvents, and the like. More specifically, there are ketones such as methyl ethyl ketone, cyclohexanone, and the like; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, and the like; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, and the like; esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, and the like; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol, and the like; aliphatic hydrocarbons such as octane, decane, and the like; petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha, and the like. The aforementioned organic solvents can be used alone or in the form of a mixture of two or more.

[0123] In the case where the alkali developing type resin composition of the present application is used in forming a solder resist layer of a printed wiring board, after adjusting the viscosity as required to be compatible with the coating method, it is coated on, for example, a printed wiring board on which a circuit has been formed in advance by a screen printing method, a curtain printing method, a spray coating method, a roll coating method or the like, and a non-tacky coating film can be formed by drying as required, for example, at a temperature of about 60 to 100°C. Then, exposure is performed selectively using active light through a photomask on which a prescribed exposure pattern has been formed, and the unexposed portions are developed by an aqueous alkali solution, and a resist pattern can be formed, and further, heat curing at a temperature of about 140 to 180°C, for example, is performed, whereby the curing reaction of the (G) epoxy resin and the polymerization of the (A) vinyl ester resin are promoted, and the adhesion, cold and heat shock resistance, heat resistance, solvent resistance, acid resistance, moisture absorption resistance, PCT resistance, adhesion, electrical properties and the like of the obtained resist coating film are improved.

[0124] As the aqueous alkali solution used at the time of development, an aqueous alkali solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines or the like can be used. Further, as the irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a semiconductor laser, a solid laser, a xenon lamp or a metal halide lamp or the like is suitable.

[0125] The alkali developing type resin composition of the present application can be used not only in the method of directly coating the liquid in a state on a substrate having a copper circuit, but also in the form of a photocurable dry film obtained by previously coating the alkali developing type resin composition on a support film and drying. The case where the alkali developing type resin composition of the present application is used in the form of a photocurable dry film is shown below.

[0126] The photocurable dry film has a structure in which a support film, a resin layer and, as required, a peelable cover film are laminated in this order. The resin layer is a layer obtained by coating the alkali developing type resin composition of the present application on a support film and drying. After the resin layer is formed on the support film, the cover film is laminated thereon, and thus a photocurable dry film is obtained.

[0127] As the support film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm can be used. The resin layer is formed by uniformly coating the alkali developing type resin composition on the support film with a thickness of 10 to 150 μm using a doctor blade coater, a lip coater, a comma coater, a film coater or the like and drying. As the cover film, a polyethylene film, a polypropylene film or the like can be used, and a cover film having an adhesion to the resin layer smaller than the adhesion of the support film to the resin layer is preferable.

[0128] The cured product of the present application is obtained by photocuring a coating film obtained by applying an alkali-developable resin composition to copper and drying it, or a coating film obtained by applying the alkali-developable resin composition to a support film, drying it, and laminating the obtained photocurable dry film to copper.

[0129] For producing a cured product on a substrate having a copper circuit using a photocurable dry film, the covering film is peeled off, the resin layer is overlaid on the substrate having a copper circuit, and the resin layer is formed on the substrate having a copper circuit by using a laminator or the like. The formed resin layer is subjected to exposure, development, and heat curing as described above, whereby a cured product can be formed. The support film can be peeled off before exposure or after exposure.

[0130] The alkali-developable resin composition is suitably used for forming a cured coating film on a printed circuit board. As the cured coating film, a permanent insulating coating film is preferred, and a solder resist layer is particularly preferred.

[0131] Examples

[0132] The present application is described in more detail based on Examples and Comparative Examples, but the scope of the present application and the embodiments thereof are not limited to these. The "parts" or "%" in the Examples and Comparative Examples are weight-based unless otherwise specified. The property value test of the composition of the present Examples was performed by the following described method.

[0133] Synthesis example

[0134] Into a four-necked flask equipped with a stirrer and a reflux condenser, 214 parts of cresol novolak-type epoxy resin EPICLON N-695 (manufactured by DIC, epoxy equivalent weight = 214) was charged, and 103 parts of carbitol acetate and 103 parts of petroleum hydrocarbon solvent (manufactured by Japan Energy Corporation, trade name: Cactus Fines SF-01) were added and heated to dissolve. Subsequently, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95 to 105°C, and 72 parts of acrylic acid was slowly added dropwise, and allowed to react for 16 hours. The resulting reaction product was cooled to 80 to 90°C, and 91.2 parts of tetrahydrophthalic anhydride was added and allowed to react for 8 hours, and then taken out after cooling. The nonvolatile content of the carboxyl group-containing vinyl ester resin thus obtained was 65%, and the acid value of the solid content was 87.5 mgKOH / g.

[0135] The alkali-developable resin composition was prepared by using the vinyl ester resin solution (varnish) of the Synthesis Example, compounding various components and proportions (parts by weight) shown in Table 1, pre-mixing with a stirrer, and then three-roll-mixing. The adhesion and cold-heat shock resistance were evaluated according to the following methods.

[0136] Table 1

[0137]

[0138] "-" means not added

[0139] A carboxyl group-containing vinyl ester resin of a synthesis example, solid content 65%, carboxyl group-containing vinyl ester resin corresponding to (5)

[0140] F pigment: phthalocyanine green, Pigment A manufactured by Dainippon Ink and Chemicals, Incorporated F defoaming agent: KS-66, manufactured by Shin-etsu Chemical Co., Ltd.

[0141] F dispersant: BYK-110, polymeric phosphate, manufactured by BYK-Chemie G light polymerization initiator: Omnirad 369E (chemical name: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone), manufactured by IGM Inc.

[0142] C soft composite glass powder: K10, manufactured by Suzhou Jin Yi New Material Technology Co., Ltd. (SiO2: 62.3-62.8%, Fe2O3: 0.0149-0.017%, Al2O3: 16.9-17.6%, CaO: 7.35-7.66%, MgO: 1.4-1.54%, B2O3: 9.6-10.3%), Mohs hardness: 5-6

[0143] E talc: LMP-100, manufactured by FUJI TALC INDUSTRIAL Co., Ltd.

[0144] Silica: A-8, manufactured by Sibelco

[0145] H solvent: PGMEA, propylene glycol monomethyl ether acetate

[0146] G epoxy resin: N-770-75EA, manufactured by DIC Corporation, multifunctional epoxy resin of novolak type, solid content 75%

[0147] D compound having two or more ethylenically unsaturated groups in one molecule: MT-3501G, manufactured by Zhangjiagang Dongya Di'aisi Chemical Co., Ltd.

[0148] Performance evaluation:

[0149] (1) Adhesion (Pull off test)

[0150] The alkaline developing resin compositions of the examples and comparative examples were screen-printed onto a substrate with a 2 mm copper wire pattern to a thickness of 40 μm. The substrate was then dried in a hot air circulating drying oven at 80°C for 30 minutes. After cooling to room temperature, an exposure apparatus equipped with a high-pressure mercury lamp was used at 300 mJ / cm². 2 The pattern was exposed, then developed in a 1 wt% sodium carbonate aqueous solution at a pressure of 0.2 MPa and a liquid temperature of 30°C for 60 seconds, and then cured in a hot air circulating drying oven at 150°C for 60 minutes. This produced a copper circuit board with a cured film.

[0151] In addition, a DeFelsko PosiTest AT digital pull-out adhesion tester (capable of measuring the adhesion of coatings on metals, concrete, and other materials) was prepared. Using Emerson Cummins adhesive (LOCTITE ABLESTIK 2332-17 high-strength structural adhesive), the spindle (1cm in bottom diameter) was attached (e.g., [example missing]). Figure 3 (As shown in the schematic diagram) The curing film is adhered and fixed (heated at 120°C for 1 hour) to the surface of the above-mentioned curing film, and the pull force required to separate the curing film per unit area from the copper substrate is measured, expressed in MPa, according to ATSM D4541.

[0152] ○: Tensile strength above 6.0MPa

[0153] ×: Tensile strength less than 6.0 MPa

[0154] (2) Resistance to thermal shock

[0155] The alkaline developable resin compositions of the examples and comparative examples were screen-printed onto a substrate with a 2 mm copper wire pattern to a thickness of 40 μm. The substrate was then dried in a hot air circulating dryer at 80°C for 30 minutes. After cooling to room temperature, the pattern was exposed using an exposure apparatus equipped with a high-pressure mercury lamp at 400 mJ / cm². Following this, development was performed for 60 seconds in a 1 wt% sodium carbonate aqueous solution at 0.2 MPa pressure and 30°C, followed by curing in a hot air circulating dryer at 150°C for 60 minutes. A thermal shock resistance evaluation substrate with 17 right-angled resist patterns was fabricated by irradiating the substrate with ultraviolet light at a cumulative exposure of 2000 mJ / cm² in a UV transport oven. Multiple evaluation substrates prepared as described above were placed in a thermal shock cycler that cyclically rotated between -40°C and 160°C for different number of cycles to conduct thermal shock resistance tests (TCT tests). Then, observe the appearance at each cycle number and record the maximum number of cycles without cracking (for information on the presence or absence of cracks, please refer to...). Figure 1 and Figure 2 The evaluation criteria are as follows.

[0156] o: no cracks after 1000 cycles or more

[0157] Δ: no cracks after 700 or more and less than 1000 cycles

[0158] x: cracks at less than 700 cycles

[0159] As is apparent from the above, by adjusting the composition to that of Examples 1 to 3, a positive resist resin composition capable of obtaining a solder resist layer excellent in both cold and heat shock resistance and adhesion can be obtained. In contrast, in Comparative Examples 1 and 2, since the filler is only talc and silica, the adhesion is low, and in Comparative Example 2 in which the amount of talc is further reduced, the cold and heat shock resistance is also reduced. In Comparative Example 3, only soft composite glass powder is used, and although the adhesion is improved, the cold and heat shock resistance is low. In Comparative Example 4, only silica is used, and similarly although the adhesion is improved, the cold and heat shock resistance is low. In Comparative Example 5, soft composite glass powder and silica are used together, and similarly although the adhesion is improved, the cold and heat shock resistance is low.

Claims

1. An alkali developing type resin composition, characterized by comprising: A basic development type resin composition containing (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) a glass powder, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (E) an inorganic filler, the (E) inorganic filler including talc, The (C) glass powder contains, in weight%, SiO2: 60 to 65%, Fe2O3: 0.01 to 0.02%, Al2O3: 14 to 20%, CaO: 6 to 9%, MgO: 1 to 2%, B2O3: 8 to 12%, and the (C) glass powder has a Mohs hardness of less than 6.5, The (A) vinyl ester resin contains: A vinyl ester resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting a saturated or unsaturated polybasic anhydride with the resulting hydroxyl group.

2. The alkali developing resin composition according to claim 1, characterized by The polyfunctional epoxy compound is a difunctional epoxy compound.

3. The alkali developing resin composition according to claim 1, characterized by It further contains (F) another additive other than the (B) photopolymerization initiator and the (C) glass powder.

4. The alkali developing resin composition according to any one of claims 1 to 3, characterized by It further contains (G) an epoxy resin.

5. The alkali developing resin composition according to any one of claims 1 to 3, characterized by It further contains (H) an organic solvent.

6. The alkali developing resin composition according to claim 4, characterized by It further contains (H) an organic solvent.

7. A photocurable dry film, characterized by It is obtained by coating the basic development type resin composition described in any one of claims 1 to 6 on a support film and drying.

8. A cured product, characterized by, It is obtained by photo-curing a coating film obtained by coating the basic development type resin composition described in any one of claims 1 to 6 on copper and drying, or a coating film obtained by coating the basic development type resin composition on a support film, drying the obtained photo-curable dry film, and laminating it on copper.

9. A printed circuit board, characterized by It is obtained by photo-curing a coating film obtained by coating the basic development type resin composition described in any one of claims 1 to 6 on a substrate having a copper circuit and drying, or a coating film obtained by coating the basic development type resin composition on a support film, drying the obtained photo-curable dry film, and laminating it on a substrate having a copper circuit, and then heat-curing the photo-cured product.

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