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

Abstract

The present invention provides an alkaline developing resin composition capable of forming a solder resist layer having excellent adhesion and thermal shock resistance, a photocurable dry film thereof, a cured product thereof, and a printed wiring board formed using the same. The alkali developing resin composition is characterized by containing (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) a glass frit, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (E) an inorganic filler, the (E) inorganic filler comprising talc, the (C) glass frit comprising, in wt%, 60-65% of SiO2, 0.01-0.02% of Fe2O3, 14-20% of Al2O3, 6-9% of CaO, 1-2% of MgO, and 8-12% of B2O3, and the (D) compound having two or more ethylenically unsaturated groups in one molecule, and the (E) inorganic filler comprising talc, and the (C) glass frit comprising, in wt%, 20-30% of SiO2, 0.01-0.02% of Fe2O3, 14-20% of Al2O3, 6-9% of CaO, 1-2% of MgO, and 8-12% of B2O3. The glass powder (C) has a Mohs hardness of less than 6.5.

Description

[0001] This application is a divisional application of an application with a filing date of December 27, 2023, an application number of 202380017216.6, and an invention name of alkaline-developable resin composition, its photocurable dry film and its cured product, and a printed circuit board formed using the same. Technical Field

[0002] The present invention relates to an alkaline-developable resin composition suitable for forming a solder resist layer or the like of a printed circuit board, a photocurable dry film thereof, and a cured product thereof, and particularly relates to an alkaline-developable resin composition capable of forming a solder resist layer having excellent adhesion and resistance to thermal shock, a photocurable dry film thereof, and a cured product thereof, as well as a printed circuit board. Background Art

[0003] At present, in the formation of solder resist layers (solder resist films) of some civilian printed circuit boards and almost all industrial printed circuit boards, alkaline developing type solder resists are used, which are developed after ultraviolet exposure to form an image and are completely cured (main cure) by heat and / or light irradiation. In addition, in semiconductor devices used in transportation vehicles such as automobiles, trains, ships and airplanes, there is a tendency to use solder resists for high-reliability electronic materials as printed circuit board solder resists.

[0004] However, conventional alkali-developable solder resist inks usually have poor thermal shock cracking resistance due to thermal expansion and contraction, and poor reliability for ambient temperature changes. In addition, from the perspective of protecting copper circuits and aesthetics, the solder resist layer must have excellent adhesion. Although talc can be used as a filler to improve cracking, the adhesion is poor. Alternatively, when talc and silica are used as fillers, the thermal shock resistance requirements of the solder resist ink for automotive use may be met, but the adhesion is still insufficient.

[0005] For example, the fillers in the photocurable solder mask ink of Patent Document 1 use silicon dioxide, barium sulfate and talc. The curable resin composition for solder mask layer of Patent Document 2 contains a carboxyl resin, a thermosetting component, a flame retardant and an ion capture agent, wherein the ion capture agent is a mixture of a hydrotalcite-based ion capture agent and an ion capture agent other than the hydrotalcite-based ion capture agent, and the inorganic filler uses aluminum hydroxide. The curable resin composition of Patent Document 3 is used for a permanent mask for a printed circuit board, and it contains: a resin containing ethylenically unsaturated groups and carboxyl groups in the molecule, a photopolymerization initiator, a photopolymerizable monomer, titanium oxide surface-treated with aluminum oxide, barium sulfate and / or talc, and an organic solvent. The UV-curable liquid photosensitive solder mask soft board ink of Patent Document 4 records that the filler is barium sulfate, talc or silicon dioxide.

[0006] Patent document 1: CN114716868A

[0007] Patent Document 2: CN108137791A

[0008] Patent Document 3: CN101798432A

[0009] Patent Document 4: CN106380929A SUMMARY OF THE INVENTION

[0010] Problem that the invention aims to solve

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

[0012] Solutions for solving problems

[0013] The inventors of the present invention conducted repeated and in-depth studies to solve the above problems, and as a result, found that the type of filler has a great influence on the resistance to thermal shock. The alkali-developable resin composition described below can solve the above problems, and thus the present invention is completed. The alkali-developable resin composition is characterized by containing (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) glass powder, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (E) an inorganic filler. The (E) inorganic filler contains talc. Calculated by weight%, the (C) glass powder contains SiO 2 : 60 to 65%, Fe 2 O 3 : 0.01 to 0.02%, Al 2 O 3 : 14 to 20%, CaO: 6 to 9%, MgO: 1 to 2%, B 2 O 3 : 8 to 12%, and the Mohs hardness of the (C) glass powder is less than 6.5.

[0014] That is, the alkali-developable resin composition of the present invention is characterized by containing (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) glass powder, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (E) an inorganic filler. The (E) inorganic filler contains talc. Calculated by weight%, the (C) glass powder contains SiO 2 : 60 to 65%, Fe 2 O 3 : 0.01 to 0.02%, Al 2 O 3 : 14 to 20%, CaO: 6 to 9%, MgO: 1 to 2%, B 2 O 3: 8-12%, the Mohs hardness of the (C) glass powder is lower than 6.5.

[0015] Furthermore, it is preferred that (F) other additives be contained in addition to (B) the photopolymerization initiator and (C) the glass frit.

[0016] Furthermore, it is preferred that (G) an epoxy resin is contained.

[0017] Furthermore, it is preferred that (H) an organic solvent is contained.

[0018] Furthermore, the photocurable dry film of the present invention is characterized by being obtained by applying the alkaline developing resin composition on a carrier film and drying it.

[0019] In addition, the cured product of the present invention is characterized in that it is obtained by photocuring the following coating film, wherein the coating film is: a coating film obtained by applying the alkaline developing resin composition on copper and drying; or a coating film obtained by applying the alkaline developing resin composition on a carrier film and drying it, and laminating the obtained photocurable dry film on copper.

[0020] In addition, the printed circuit board of the present invention is characterized in that it is obtained by photocuring and then thermally curing the following coating film, wherein the coating film is: a coating film obtained by coating the alkaline developing resin composition on a substrate having a copper circuit and drying; or a coating film obtained by coating the alkaline developing resin composition on a carrier film and drying, and laminating the obtained photocurable dry film on a substrate having a copper circuit.

[0021] The most significant technical feature of the alkaline-developable resin composition of the present invention is that it comprises (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, wherein the (E) inorganic filler comprises talc, and the (C) glass powder comprises SiO 2 :60~65%,Fe 2 O 3 :0.01~0.02%,Al 2 O 3 : 14~20%, CaO: 6~9%, MgO: 1~2%, B 2 O 3 : 8-12%, the Mohs hardness of the (C) glass powder is lower than 6.5.

[0022] Based on the characteristic structure of the present invention, by using the soft composite glass powder and talc in combination and adjusting the ratio of the two, the adhesion can be improved while maintaining excellent thermal shock performance.

[0023] In contrast, in the prior art, talc and barium sulfate are used as fillers at the same time, which can meet the requirements of the thermal shock resistance of the solder resist ink, but the adhesion is poor (for example, Patent Document 1, etc.).

[0024] As described above, the inventors have found through repeated and in-depth research that talc as a filler has good flexibility and excellent crack resistance in the temperature cycle test (hereinafter sometimes referred to as the "TCT test"), but the adhesion becomes worse as the amount used increases. Although glass powder, especially soft composite glass powder, can provide excellent adhesion as a filler, it is not resistant to thermal shock. By using talc and glass powder as fillers at the same time, it is possible to maintain excellent thermal shock resistance and adhesion at the same time, thereby achieving the above-mentioned purpose of the present invention.

[0025] Effects of the Invention

[0026] As described above, the present invention can provide an alkali-developable resin composition capable of forming a solder resist having excellent adhesion and thermal shock resistance, a photocurable dry film thereof, a cured product thereof, and a printed wiring board. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a photograph showing cracks in the solder resist film used for evaluating thermal shock resistance in Examples (NG (cracks)).

[0028] Figure 2 This is a photograph showing that the solder resist film used for evaluating thermal shock resistance in Examples was not cracked (OK (no cracking)).

[0029] Figure 3 Schematic diagram of a spindle used for evaluating adhesion in the examples (spindle schematic diagram). DETAILED DESCRIPTION

[0030] Hereinafter, each constituent component in the alkali-developable resin composition of the present invention will be described.

[0031] The alkali-developable resin composition of the present invention is characterized by containing (C) glass powder and (E) an inorganic filler, wherein the (E) inorganic filler contains talc as an essential component. Therefore, (C) glass powder and (E) inorganic filler will be described first.

[0032] (C) Glass powder

[0033] The glass powder (C) used in the alkali-developable resin composition of the present invention refers to a powdery glassy amorphous inorganic substance, the main component of which is silicon dioxide, and is typically produced by sintering an inorganic mineral as a main raw material at a high temperature.

[0034] As the glass powder (C) used in the alkaline developing resin composition of the present invention, soft composite glass powder is preferred from the viewpoint of further facilitating the achievement of the object of the present invention. The glass powder (C) may be unsurface treated or surface treated.

[0035] The soft composite glass powder typically comprises SiO 2 :60~65%,Fe 2 O 3 :0.01~0.02%,Al 2 O 3 : 14~20%, CaO: 6~9%, MgO: 1~2%, B 2 O 3 : 8-12%, preferably SiO 2 :61~64%,Fe 2 O 3 :0.012~0.019%,Al 2 O 3 : 15~19%, CaO: 6.5~8.5%, MgO: 1.1~1.8%, B 2 O 3 : 9-11%, more preferably SiO 2 :62~63%,Fe 2 O 3 :0.014~0.018%,Al 2 O 3 : 16~18%, CaO: 7~8%, MgO: 1.2~1.6%, B 2 O 3 :9.5~10.5%.

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

[0037] The inventors of the present invention have found that, from the perspective of both the cold and hot shock resistance and adhesion of the solder mask layer, while using talc as a filler, further compounding (C) glass powder can significantly improve the adhesion while maintaining excellent cold and hot shock resistance. At this time, the mixing ratio of the two is based on a weight ratio, that is, talc: glass powder is 90:10 to 10:90 is appropriate, preferably 80:20 to 20:80, more preferably 75:25 to 25:75, and further preferably 70:30 to 30:70. In this way, an alkaline developing resin composition that can achieve a solder mask layer with excellent cold and hot shock resistance and adhesion can be obtained.

[0038] The mixing ratio of (C) glass powder is preferably 10 to 90 parts by weight, preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight, and further preferably 40 to 60 parts by weight, relative to 100 parts by weight of the (A) vinyl ester resin in terms of solid content. The amount of (C) glass powder used is within the above range, which ensures that the adhesion is improved while obtaining excellent thermal shock resistance. In the case of exceeding the above range, the properties as a solder resist are reduced, which is not preferred.

[0039] Commercially available products of the soft composite glass powder include K10 (manufactured by Suzhou Jinyi New Material Technology Co., Ltd.) and G2C (manufactured by Shanghai Sibelco Mining Co., Ltd.).

[0040] (E) Inorganic filler

[0041] In the alkaline developing resin composition of the present invention, talc used as (E) inorganic filler is used to improve thermal shock resistance. The (E) inorganic filler here does not include the above-mentioned (C) glass powder, especially soft composite glass powder.

[0042] As talc, the parent rock can be any one of magnesium carbonate, serpentine, silica / silicon dioxide-alumina, and magnesium sediment, and can be one of the so-called silicate minerals, and the shape can be block or fine powder. It may or may not be surface treated. The average particle size of talc is preferably 1.0-20.0 μm, more preferably 2.0 to 10 μm, and further preferably 3.0 to 8.0 μm. Examples of commercially available products include HD25 manufactured by Shandong Pingdu Talc Mining Co., Ltd. and LMP-100 manufactured by Fuji Talc Industry Co., Ltd.

[0043] The amount of talc is suitably 10 to 90 parts by weight, preferably 20 to 80 parts by weight, and more preferably 30 to 70 parts by weight, relative to 100 parts by weight of the (A) vinyl ester resin in terms of solid content. Within the above range, excellent thermal shock resistance can be ensured while improving adhesion.

[0044] As long as the purpose of the present invention is not affected, other fillers other than talc and the above-mentioned (C) glass powder, such as silica, may also be mixed. As the silica, it may be any one of amorphous and crystalline, or a mixture thereof. Amorphous (molten) silica is particularly preferred. Surface treatment may or may not be performed. The silica typically has a Mohs hardness of 6.5 or more. The average particle size of the silica is suitable for 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 Materials Co., Ltd., A-8 manufactured by Sibelco Co., Ltd., SE-40 manufactured by Tokuyama Co., Ltd., MSV25G manufactured by Longsen, MLV-2114 manufactured by Longsen, SO-E5 manufactured by ADMATECHS, SO-E2 manufactured by ADMATECHS, etc. can be cited.

[0045] (A) Vinyl ester resin

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

[0047] (1) Vinyl ester resins obtained by copolymerizing unsaturated carboxylic acids such as (meth)acrylic acid with one or more other compounds having unsaturated double bonds;

[0048] (2) Photosensitive vinyl ester resins obtained by adding an ethylenically unsaturated group as a pendant group to a copolymer of an unsaturated carboxylic acid such as (meth)acrylic acid and one or more other compounds having an unsaturated double bond, using a compound having an epoxy group and an unsaturated double bond such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, or (meth)acryloyl chloride;

[0049] (3) A photosensitive vinyl ester resin obtained by reacting a copolymer of a compound having an epoxy group and an unsaturated double bond such as glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate, and another compound having an unsaturated double bond with an unsaturated carboxylic acid such as (meth)acrylic acid, and reacting a polyacid anhydride with the generated secondary hydroxyl group;

[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 another compound having an unsaturated double bond with a compound having a hydroxyl group and an unsaturated double bond such as 2-hydroxyethyl (meth)acrylate;

[0051] (5) Vinyl ester resins obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting a saturated or unsaturated polyacid anhydride with the resulting hydroxyl group;

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

[0053] (7) a vinyl ester resin obtained by reacting a reaction product of a polyfunctional epoxy compound and an unsaturated monocarboxylic acid with a compound having at least one alcoholic hydroxyl group and one reactive group other than the alcoholic hydroxyl group that reacts with an epoxy group in one molecule, with 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 reacting an unsaturated monocarboxylic acid with a polyfunctional epoxy resin and then reacting the unsaturated monocarboxylic acid with a polyacid anhydride to obtain a carboxyl group-containing resin, ...;

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

[0057] Among these examples, particularly preferred are the vinyl ester resins (2), (5), (7) and (9).

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

[0059] Since the above-mentioned (A) vinyl ester resin has a plurality of free carboxyl groups on the side chains of the main chain polymer, it can be developed with a dilute alkaline aqueous solution.

[0060] The acid value of the vinyl ester resin (A) is preferably in the range of 40 to 200 mgKOH / g, and more preferably in the range of 45 to 120 mgKOH / g. If the acid value of the vinyl ester resin (A) is less than 40 mgKOH / g, alkali development is difficult. On the other hand, if it exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer is promoted, so that the line becomes thinner than necessary, and sometimes the exposed portion and the unexposed portion are dissolved and peeled by the developer indiscriminately, making it difficult to draw a normal resist pattern, which is not preferred.

[0061] The weight average molecular weight of the vinyl ester resin (A) described above varies depending on the resin skeleton, and is generally preferably in the range of 2,000 to 150,000, and more preferably in the range of 5,000 to 100,000. When the weight average molecular weight is less than 2,000, the coating on the substrate and the non-tackiness after drying may be deteriorated, and the moisture resistance of the coating film after exposure may deteriorate, the film may be reduced during development, and the resolution may be greatly deteriorated. On the other hand, when the weight average molecular weight exceeds 150,000, the developability may be significantly deteriorated and the storage stability may be deteriorated.

[0062] The blending amount of the vinyl ester resin (A) is preferably in the range of 20 to 60% by mass of the total composition in terms of solid content, and preferably in the range of 25 to 50% by mass. If the blending amount of the vinyl ester resin (A) is less than the above range, the coating film strength is reduced, which is not preferred. On the other hand, if the blending amount is more than the above range, the viscosity of the composition becomes high or the coating property is reduced, which is not preferred.

[0063] (B) Photopolymerization initiator

[0064] The photopolymerization initiator used in the alkali-developable resin composition of the present invention is not particularly limited as long as it is a photopolymerization initiator generally used in alkali-developable resin compositions.

[0065] As the photopolymerization initiator, a known substance can be used, and examples thereof include: benzoin and alkyl ethers thereof such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-tert-butyldioxy-1-methylethyl)acetophenone; 2-methylanthraquinone, 2-amylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone. Anthraquinones; thioxanthones such as isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diisopropyl thioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzophenones such as benzophenone, 4-(1-tert-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(tert-butyldioxycarbonyl)benzophenone; and xanthones, etc.

[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-aminoacetophenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a titanocene-based photopolymerization initiator, a phosphate-based photopolymerization initiator, or the like can be used.

[0067] Commercially available oxime ester photopolymerization initiators include Irgacure OXE01 and Irgacure OXE02 manufactured by BASF Japan, and N-1919 and NCI-831 manufactured by ADEKA CORPORATION. Photopolymerization initiators having two oxime ester groups in the molecule can be preferably used, and specifically, oxime ester compounds having a carbazole ring structure can be mentioned.

[0068] Examples of commercially available products of the alkylphenone-based photopolymerization initiator include α-hydroxyalkylphenone-based products such as Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 manufactured by IGM Resins B.V.

[0069] Specific examples of the α-aminoacetophenone-based photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-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] As the acylphosphine oxide-based photopolymerization initiator, specifically, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, trifunctional or higher acylphosphine-based photopolymerization initiators, etc. The trifunctional or higher acylphosphine-based photopolymerization initiator may be a photopolymerization initiator having three or more acylphosphine oxide skeletons in one molecule, and may be represented by the following formula (I).

[0071]

[0072] In the formula,

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

[0074] G is a multifunctional compound (core) G-(AH) m+n A residue of wherein AH each represents an alcohol group or an amino group or a thiol group;

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

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

[0077] R 1 and R 2 Independently of each other, C 1 -C 18 Alkyl, C 6 -C 12 Aryl and C 5 -C 12 The cycloalkyl groups are each not disconnected or are disconnected by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, or R 1 and R 2 are independently of one another a five- to six-membered heterocyclic group containing oxygen and / or nitrogen and / or sulfur atoms, wherein each of the aforementioned groups is optionally substituted by an aryl group, an alkyl group, an aryloxy group, an alkoxy group, a heteroatom and / or a heterocyclic group;

[0078] R 2 Can be R 1 -(C=O)-;

[0079] Y is O or S;

[0080] R 3 is hydrogen or C 1 ~C 4 The alkyl group;

[0081] 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-(AH) m+n is a polyhydroxy compound selected from the group consisting of monomeric polyols, oligomeric polyols, polymeric polyols and mixtures thereof. When A is sulfur, G-(AH) m+n is a polythiol compound. In formula (I), when A is nitrogen, G-(AH) m+n It is a linear or branched polyamine. When A is a mixture of oxygen and / or nitrogen and / or sulfur, G-(AH) m+n is a compound containing different functional groups, for example, a compound containing an amino group and a hydroxyl group. The residue G- suitable for the practice of the present invention does not contain a photocurable ethylenically unsaturated group. When A is a single bond, G- is G-(AH) listed above. m+n The residue after removing the hydroxyl group and / or amino group and / or thiol group.

[0084] G-(AH) is preferred m+n The number average molecular weight is 1500 or less, more preferably 800 or less, and further preferably 500 or less.

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

[0086] Representative trifunctional or higher acylphosphine 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, and PI-17 are particularly preferred. By including such trifunctional or higher acylphosphine photopolymerization initiators, a cured product with suppressed outgassing and better insulation reliability can be obtained.

[0087] Table 1

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

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

[0096] As commercially available products of the acylphosphine oxide-based photopolymerization initiator, Omnirad TPO manufactured by IGM Resins, Omnirad 819 and Omnipol TP manufactured by IGM Resins BV, and the like can be used.

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

[0098] The compounding ratio of the photopolymerization initiator (B) is preferably 0.01 to 30 parts by weight, preferably 5 to 25 parts by weight, and more preferably 10 to 20 parts by weight, relative to 100 parts by weight of the (A) vinyl ester resin in terms of solid content. When the amount of the photopolymerization initiator used is less than the above range, the photocurability of the composition deteriorates, while when it is too much, the properties as a solder resist are deteriorated, which is not preferred.

[0099] It should be noted that, in this specification, polymer is a term that collectively refers to homopolymers, copolymers, and mixtures thereof, and the same applies to other similar expressions.

[0100] (D) Compounds having two or more ethylenically unsaturated groups in one molecule

[0101] The compound (D) having two or more ethylenically unsaturated groups in one molecule used in the alkaline-developable resin composition of the present invention is a compound that makes the aforementioned (A) vinyl ester resin insoluble in an alkaline aqueous solution or contributes to making the aforementioned vinyl ester resin insoluble in an alkaline aqueous solution by photocuring by irradiation with active energy rays. Specific examples of such compounds include:

[0102] Hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate;

[0103] Monoacrylates or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol;

[0104] Acrylamides such as N,N-dimethylacrylamide, N-hydroxymethylacrylamide, and N,N-dimethylaminopropylacrylamide;

[0105] Aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate;

[0106] Polyacrylates of polyols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, trishydroxyethyl isocyanurate, or their ethylene oxide adducts or propylene oxide adducts;

[0107] Acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols;

[0108] Acrylic esters of glycidyl ethers such as glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate;

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

[0110] Furthermore, epoxy acrylate resins obtained by reacting a polyfunctional epoxy resin such as a cresol novolac epoxy resin with acrylic acid, and epoxy urethane acrylate compounds obtained by reacting a hydroxyl group of the epoxy acrylate resin with a hydroxy acrylate such as pentaerythritol triacrylate and a half urethane compound of a diisocyanate such as isophorone diisocyanate, etc. can also be mentioned.

[0111] The compound (D) having two or more ethylenically unsaturated groups in one molecule is preferably added in an amount of 5 to 100 parts by weight, more preferably 10 to 70 parts by weight, relative to 100 parts by weight of the aforementioned (A) vinyl ester resin in terms of solid content. When the amount is less than 5 parts by weight relative to 100 parts by weight of the aforementioned (A) vinyl ester resin, the photocurability of the obtained alkaline developing type resin composition is reduced, and it is difficult to form a pattern by alkaline development after irradiation with active energy rays, so it is not preferred. On the other hand, when it exceeds 100 parts by weight, the solubility in alkaline aqueous solution is reduced and the cured coating film becomes brittle, so it is not preferred.

[0112] (F) Other additives

[0113] As described above, the other additives in the present invention refer to additives other than the (B) photopolymerization initiator and the (C) glass frit.

[0114] Examples of such additives include known and commonly used colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black; known and commonly used thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, and phenothiazine; known and commonly used thickeners such as fine powder silica, organic bentonite, and montmorillonite; at least one of silicone-based, fluorine-based, and polymer-based defoamers and leveling agents; imidazole-based, thiazole-based, and triazole-based adhesion-imparting agents; silane coupling agents; phenol-based, phosphorus-based, and sulfur-based antioxidants; hindered amine-based light stabilizers; and dispersants.

[0115] The compounding ratio of such (F) other additives is preferably 0.01 wt % or more and 20 wt % or less of the total amount of the alkaline developing resin composition. If it is less than 0.01 wt %, the corresponding effect cannot be fully obtained, and if it exceeds 20 wt %, the printability and hardness of the alkaline developing resin composition deteriorate, which is not preferred.

[0116] (G) Epoxy resin

[0117] In order to impart heat resistance, it is preferred that the alkali-developable resin composition used in the present invention contains an epoxy resin having at least two epoxy groups in a molecule, that is, a multifunctional epoxy resin (G).

[0118] Examples of commercially available products include bisphenol A type epoxy resins such as jER828, jER834, jER1001, and jER1004 manufactured by Mitsubishi Chemical Corporation, EPICLON 840, 850, 850S, 1050, and 2055 manufactured by DIC Corporation, EPOTOTE YD-011, YD-013, YD-127, and YD-128 manufactured by NIPPON STEEL Chemical & Material Co., Ltd., DER317, DER331, DER661, and DER664 manufactured by Dow Chemical Company, and Sumi-Epoxy ESA-011, ESA-014, ELA-115, and ELA-128 manufactured by Sumitomo Chemical Industries, Ltd. (all trade names); jERYL903 manufactured by Mitsubishi Chemical Corporation, and EPICLON 152 and EPICLON 153 manufactured by DIC Corporation. 165. EPOTOTE YDB-400 and YDB-500 manufactured by NIPPONSTEEL Chemical & Material Co., Ltd., DER542 manufactured by Dow Chemical Company, Sumi-Epoxy ESB-400 and ESB-700 manufactured by Sumitomo Chemical Industries, Ltd. (all trade names) brominated epoxy resins; jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, DEN431 and DEN438 manufactured by Dow Chemical Company, EPICLON N-730, EPICLON N-770 and EPICLON N-865 manufactured by DIC Corporation, EPOTOTE manufactured by NIPPON STEEL Chemical & Material Co., Ltd. YDCN-701, YDCN-704, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000 manufactured by Nippon Kayaku Co., Ltd., Sumi-Epoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Industries, Ltd., NIPPON STEELChemical&Material Co., Ltd.YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704A manufactured by DIC Corporation, EPICLON N-680, N-690, N-695 and the like (all trade names) novolac type epoxy resins manufactured by DIC Corporation; EPICLON 830 manufactured by DIC Corporation, jER807 manufactured by Mitsubishi Chemical Corporation, EPOTOTE YDF-170, YDF-175, YDF-2004 and the like (all trade names) bisphenol F type epoxy resins manufactured by NIPPON STEEL Chemical & Material Co., Ltd.; Co., Ltd., EPOTOTEST-2004, ST-2007, ST-3000 (trade names), YX8034 manufactured by Mitsubishi Chemical Corporation, etc., hydrogenated bisphenol A type epoxy resins; jER604 manufactured by Mitsubishi Chemical Corporation, EPOTOTE YH-434 manufactured by NIPPONSTEEL Chemical & Material Co., Ltd., Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Industries, Ltd., etc. (all trade names) glycidylamine type epoxy resins; hydantoin type epoxy resins; CELLOXIDE manufactured by Daicel Corporation 2021P and other (trade names) alicyclic epoxy resins; YL-933 manufactured by Mitsubishi Chemical Corporation, EPPN-501, EPPN-502 and other (all trade names) trihydroxyphenylmethane type epoxy resins manufactured by Nippon Kayaku Co., Ltd.; YL-6056, YX-4000, YL-6121 (all trade names) and other biphenylphenol type or biphenol type epoxy resins or mixtures thereof manufactured by Mitsubishi Chemical Corporation; EBPS-200, ADE EPX-30 manufactured by KACORPORATION, EXA-1514 (trade name) manufactured by DIC Corporation, etc., bisphenol S type epoxy resins; jER157S (trade name) manufactured by Mitsubishi Chemical Corporation, etc., bisphenol A novolac type epoxy resins; jERYL-931 (trade name) manufactured by Mitsubishi Chemical Corporation, etc., tetrahydroxyphenylethane type epoxy resins; TEPIC (trade name) manufactured by Nissan Chemical Industries, Ltd., etc., heterocyclic epoxy resins; BRENMAR DGT (trade name) manufactured by NOF Corporation, etc., diglycidyl phthalate resins; ZX-1063 (trade name) manufactured by NIPPON STEEL Chemical & Material Co., Ltd., etc., tetraglycidyl ditoluoyl ethane resins; NIPPON STEEL Chemical & Material Co., Ltd., etc.Naphthalene skeleton epoxy resins such as ESN-190, ESN-360, HP-4032, EXA-4750, and EXA-4700 manufactured by DIC Corporation; methacrylate glycidyl copolymer epoxy resins such as CP-50S and CP-50M manufactured by NOF Corporation; and copolymer epoxy resins of cyclohexylmaleimide and methacrylate glycidyl; CTBN modified epoxy resins (such as YR-102 and YR-450 manufactured by NIPPON STEEL Chemical & Material Co., Ltd.), but not limited to these. These epoxy resins can be used alone or in combination of two or more. .

[0119] The content of the epoxy resin (G) is preferably 10 to 100 parts by weight, more preferably 20 to 90 parts by weight, and even more preferably 30 to 80 parts by weight, based on 100 parts by weight of the vinyl ester resin (A) in terms of solid content.

[0120] (H) Organic solvents

[0121] The organic solvent (H) that can be used in the alkali-developable resin composition of the present invention can be used to synthesize the vinyl ester resin (A), prepare the composition, or adjust the viscosity for coating on a substrate or a carrier film.

[0122] Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. More specifically, they include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; 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, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha. The above organic solvents may be used alone or in the form of a mixture of two or more.

[0123] When the alkaline developing resin composition of the present invention is used to form a solder resist layer of a printed circuit board, after adjusting the viscosity to be suitable for the coating method as needed, it is coated on, for example, a printed circuit board on which a circuit is previously formed by a method such as screen printing, curtain printing, spray coating, or roll coating, and dried at a temperature of about 60 to 100° C. as needed to form a non-tack coating film. Then, it is selectively exposed to active light through a photomask having a predetermined exposure pattern, and the unexposed portion is developed with an alkaline aqueous solution to form an etching resist pattern. Furthermore, it is heat-cured by, for example, heating to a temperature of about 140 to 180° C. to promote the curing reaction of the epoxy resin (G) and the polymerization of the vinyl ester resin (A), thereby improving various properties of the obtained etching resist film, such as adhesion, thermal shock resistance, heat resistance, solvent resistance, acid resistance, moisture absorption resistance, PCT tolerance, adhesion, and electrical properties.

[0124] As the alkaline aqueous solution used in the above-mentioned development, there can be used an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. In addition, as the irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a semiconductor laser, a solid-state laser, a xenon lamp, or a metal halide lamp is suitable.

[0125] In addition to the method of directly applying the alkaline developing type resin composition of the present invention to the substrate having the copper circuit in a liquid state, the alkaline developing type resin composition can also be used in the form of a photocurable dry film obtained by applying the alkaline developing type resin composition on a carrier film in advance and drying. The following shows the case where the alkaline developing type resin composition of the present invention is used in the form of a photocurable dry film.

[0126] The photocurable dry film has a structure in which a carrier film, a resin layer, and a peelable cover film used as needed are sequentially laminated. The resin layer is a layer obtained by coating the alkaline developing resin composition of the present invention on a carrier film and drying it. After the resin layer is formed on the carrier film, the cover film is laminated thereon to obtain a photocurable dry film.

[0127] As the carrier 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 alkaline developing resin composition on the carrier film with a thickness of 10 to 150 μm using a knife coater, a lip coater, a comma coater, a film coater, etc. and drying. As the covering film, a polyethylene film, a polypropylene film, etc. can be used. A covering film having a smaller adhesive force to the resin layer than the adhesive force to the carrier film and the resin layer is preferred.

[0128] The cured product of the present application is obtained by photocuring the following coating film, wherein the coating film is: a coating film obtained by coating an alkaline developing resin composition on copper and drying it; or a coating film obtained by coating the alkaline developing resin composition on a carrier film and drying it, and laminating the obtained photocurable dry film on copper.

[0129] When a cured product is produced on a substrate having a copper circuit using a photocurable dry film, the cover film is peeled off, the resin layer is overlapped with the substrate having a copper circuit, and a laminator is used to bond the resin layer on the substrate having a copper circuit. The formed resin layer is exposed, developed, and heat-cured in the same manner as described above to form a cured product. The carrier film can be peeled off before or after exposure.

[0130] The alkaline developing resin composition is suitably used for forming a cured film on a printed circuit board. The cured film is preferably a permanent insulating film, and particularly preferably a solder resist layer.

[0131] Example

[0132] The present invention is described in more detail based on the examples and comparative examples, but the protection scope of the present invention and its implementation mode are not limited to these. "Part" or "%" in the examples and comparative examples is a weight basis unless otherwise specified. The property value test of the composition of this example was carried out by the method described below.

[0133] Synthesis example

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

[0135] The vinyl ester resin solution (varnish) of the synthesis example was mixed with the various components and proportions (parts by weight) shown in Table 2, premixed with a stirrer, and kneaded with a three-roll mill to prepare an alkaline-developable resin composition. Adhesion and thermal shock resistance were evaluated according to the following methods.

[0136] Table 2

[0137]

[0138] "-" means not added

[0139] The carboxyl vinyl ester resin of Synthesis Example A has a solid content of 65%, which is equivalent to the carboxyl vinyl ester resin of (5).

[0140] Pigment F: Phthalocyanine green, Pigment AF, manufactured by Dainippon Ink & Chemicals Co., Ltd. Defoamer: KS-66, manufactured by Shin-Etsu Chemical Co., Ltd.

[0141] F Dispersant: BYK-110, polyphosphate ester, manufactured by BYK Chemicals B Photopolymerization initiator: Omnirad 369E (chemical name: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone), manufactured by IGM

[0142] C soft composite glass powder: K10, manufactured by Suzhou Jinyi New Material Technology Co., Ltd. (SiO 2 :62.3~62.8%,Fe 2 O 3 :0.0149~0.017%,Al 2 O 3 : 16.9~17.6%, CaO: 7.35~7.66%, MgO: 1.4~1.54%, B 2 O 3 : 9.6~10.3%), Mohs hardness: 5~6

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

[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, novolac type multifunctional epoxy resin, solid content 75%

[0147] D Compounds with two or more ethylenically unsaturated groups in one molecule: MT-3501G, manufactured by Zhangjiagang Dongya DIC Chemical Co., Ltd.

[0148] Performance evaluation:

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

[0150] The alkaline developing resin composition of the example and the comparative example was applied to the entire surface of a substrate having a 2 mm copper wire pattern formed thereon by screen printing so as to have a thickness of 40 μm, and dried in a hot air circulation drying oven at 80° C. for 30 minutes. After cooling to room temperature, an exposure device equipped with a high pressure mercury lamp was used to expose the substrate at 300 mJ / cm 2 After pattern exposure, the film was 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 circulation drying oven at 150° C. for 60 minutes. Thus, a copper circuit board having a cured film was produced.

[0151] In addition, prepare the PosiTest AT digital display pull-off adhesion tester (which can measure the adhesion of metal, concrete and other material coatings) from DeFelsko, USA. Use the American Emmason Cumming adhesive (LOCTITE ABLESTIK2332-17 high-strength structural adhesive) to fix the ingot (size bottom diameter 1 cm) (e.g. Figure 3 The cured film was adhered and fixed (heated at 120° C. for 1 hour) to the surface of the cured film, and the tensile force required to separate the cured film per unit area from the copper substrate was measured, expressed in MPa, and measured in accordance with ATSMD4541.

[0152] ○: Tensile force 6.0MPa or more

[0153] ×: Tensile force less than 6.0 MPa

[0154] (2) Resistance to thermal shock

[0155] The alkaline developing resin composition of the embodiment and the comparative example was applied to the substrate with a 2mm copper wire pattern by screen printing so that the thickness was 40μm, and dried at 80°C for 30 minutes in a hot air circulation drying oven. After cooling to room temperature, the pattern was exposed at 400mJ / cm2 using an exposure device equipped with a high-pressure mercury lamp, and then developed for 60 seconds in a 1wt% sodium carbonate aqueous solution, a pressure of 0.2MPa, and a liquid temperature of 30°C, and then cured at 150°C for 60 minutes in a hot air circulation drying oven. By irradiating ultraviolet rays under the condition of a cumulative exposure of 2000mJ / cm2 in a UV conveyor furnace, 17 hot and cold cycle crack resistance evaluation substrates with a right-angled resist pattern were prepared. A plurality of evaluation substrates prepared as above were placed in a hot and cold cycle machine that cycles the temperature between -40°C and 160°C and set different numbers of cycles, and a hot and cold shock cycle test (TCT test) was carried out. Then, observe the appearance at each cycle number and record the maximum number of cycles without cracks (for the presence or absence of cracks, see Figure 1 and Figure 2), and its evaluation criteria are as follows.

[0156] ○: No cracks after more than 1000 cycles

[0157] △: No cracks after 700 or more and less than 1000 cycles

[0158] ×: Cracks occurred when the number of cycles was less than 700

[0159] From the above, it can be seen that by adjusting the composition to Examples 1 to 3, an alkaline developing resin composition that can obtain a solder mask layer with excellent cold and heat shock resistance and adhesion can be obtained. In contrast, in Comparative Examples 1 and 2, since only talc and silica are used as fillers, the adhesion is low, and in Comparative Example 2 with a smaller amount of talc, the cold and heat shock resistance is also reduced. Comparative Example 3 uses only soft composite glass powder, and although the adhesion is improved, the cold and heat shock resistance is low. Comparative Example 4 uses only silica, and although the adhesion is also improved, the cold and heat shock resistance is low. Comparative Example 5 uses both soft composite glass powder and silica, and although the adhesion is also improved, the cold and heat shock resistance is low.

Claims

1. An alkaline-developable resin composition, characterized in that, it contains (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) glass powder, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (E) an inorganic filler, and the (E) inorganic filler contains talc, In terms of weight percentage, the (C) glass powder contains SiO 2 : 60 to 65%, Fe 2 O 3 : 0.01 to 0.02%, Al 2 O 3 : 14 to 20%, CaO: 6 to 9%, MgO: 1 to 2%, B 2 O 3 : 8 to 12%, and the Mohs hardness of the (C) glass powder is less than 6.5 the alkaline-developable resin composition contains at least one of a novolac-type epoxy resin and an alicyclic epoxy resin as (G) an epoxy resin.

2. The alkaline-developable resin composition according to claim 1, characterized in that, it further contains (F) other additives except (B) the photopolymerization initiator and (C) the glass powder.

3. The alkaline-developable resin composition according to claim 1 or 2, characterized in that, it further contains (H) an organic solvent.

4. A photocurable dry film, characterized in that, it is obtained by coating the alkaline-developable resin composition according to any one of claims 1 to 3 on a carrier film and drying.

5. A cured product, characterized in that, it is obtained by photocuring the following coating film: a coating film obtained by coating the alkaline-developable resin composition according to any one of claims 1 to 3 on copper and drying; or a coating film obtained by coating the alkaline-developable resin composition on a carrier film and drying, and laminating the obtained photocurable dry film on copper.

6. A printed circuit board, characterized in that, it has a cured product obtained by photocuring and then thermally curing the following coating film: a coating film obtained by coating the alkaline-developable resin composition according to any one of claims 1 to 3 on a substrate having a copper circuit and drying; or a coating film obtained by coating the alkaline-developable resin composition on a carrier film and drying, and laminating the obtained photocurable dry film on a substrate having a copper circuit.

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