Photosensitive, thermosetting, and developable resin compositions, their dry films and cured products, and printed circuit boards formed using them.

Abstract

The present invention provides a photosensitive, thermosetting, and developable resin composition capable of forming a solder resist layer with excellent printability, excellent hardness, and excellent resistance to thermal shock, a dry film thereof, a cured product thereof, and a printed circuit board formed using the same. [Solution] The photosensitive, thermosetting, and developable resin composition contains (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) a phosphate ester dispersant, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (E) an inorganic filler, wherein (C) the phosphate ester dispersant contains (C-1) a polymer having a phosphate ester structure in its main chain, and (E) the inorganic filler contains talc and silica, wherein the total amount of both talc and silica is 50 to 180 parts by weight per 100 parts by weight of (A) vinyl ester resin (on a solid content basis), and the proportion of talc is 20 to 80% by weight when the total amount of talc and silica is 100% by weight.

Description

[Technical Field]

[0001] The present invention relates to a photosensitive, thermosetting, and developable resin composition suitable for forming solder resist agents for printed circuit boards, a dry film thereof, and a cured product thereof, and more particularly to a photosensitive, thermosetting, and developable resin composition, a dry film thereof, and a cured product thereof, as well as a printed circuit board, that can form a solder resist layer with excellent printability and excellent hardness and thermal shock resistance. [Background technology]

[0002] Currently, some consumer printed circuit boards and most industrial printed circuit boards use alkaline developable solder resists that are exposed to ultraviolet light, developed to form a pattern, and then completely cured (primarily cured) by heat and / or light irradiation. Furthermore, in semiconductor devices used in vehicles such as automobiles, trains, ships, and aircraft, there is a tendency to use solder resists for high-reliability electronic materials as printed circuit board solder resists.

[0003] However, conventional alkaline-developable solder resists typically have poor crack resistance to thermal shock due to thermal expansion and other reasons, resulting in poor reliability against changes in ambient temperature. While crack resistance can be improved by selecting talc as a filler, printability and hardness are compromised. Furthermore, while talc and barium sulfate can be used as fillers to meet the thermal shock resistance requirements for automotive solder resists, printability and hardness are reduced.

[0004] For example, the photocurable solder resist described in Patent Document 1 uses silica, barium sulfate, and talc as fillers. The curable resin composition for solder resist layers described in Patent Document 2 contains a carboxyl group-containing resin, a thermosetting component, a flame retardant, and an ion scavenger, the ion scavenger being a mixture of a hydrotalcite-based ion scavenger and a non-hydrotalcite-based ion scavenger, and aluminum hydroxide as an inorganic filler. The curable resin composition described in Patent Document 3 is used as a permanent mask for printed circuit boards and contains a resin containing ethylenically unsaturated groups and carboxyl groups in its molecule, a photopolymerization initiator, a photopolymerizable monomer, titanium oxide surface-treated with alumina, barium sulfate and / or talc, and an organic solvent. Patent Document 4 describes a UV-curable liquid photosensitive solder resist flex ink in which the filler is barium sulfate, talc, or silica. [Prior art documents] [Patent Documents]

[0005] Patent document 1: CN114716868A Patent document 2: CN108137791A Patent document 3: CN101798432A Patent document 4: CN106380929A [Overview of the project] [Problems that the invention aims to solve]

[0006] The object of the present invention is to improve the printability of solder resist and the hardness of the dry film and cured product formed therefrom, as well as to further improve long-term reliability.

[0007] More specifically, the object of the present invention is to provide a photosensitive, thermosetting, and developable resin composition, a dry film thereof, and a cured product thereof, as well as a printed circuit board, that can form a solder resist layer having excellent printability and excellent hardness and thermal shock resistance. [Means for solving the problem]

[0008] The present inventors conducted extensive research to solve the above problems and found that the types of fillers and additives have a significant effect on thermal shock resistance. A photosensitive, thermosetting, and developable resin composition containing (A) vinyl ester resin, (B) photopolymerization initiator, (C) phosphate ester dispersant, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (E) inorganic filler, wherein the (C) phosphate ester dispersant contains (C-1) a polymer having a phosphate ester structure in its main chain, and the (E) inorganic filler contains talc and silica, and the total amount of both talc and silica is 50 to 180 parts by weight per 100 parts by weight of (A) vinyl ester resin (in terms of solid content), and the proportion of talc is 20 to 80% by weight when the total amount of talc and silica is 100% by weight, can solve the above problems and has led to the completion of the present invention.

[0009] In other words, the photosensitive, thermosetting, and developable resin composition of the present invention contains (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) a phosphate ester dispersant, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (E) an inorganic filler, wherein (C) the phosphate ester dispersant contains (C-1) a polymer having a phosphate ester structure in its main chain, and (E) the inorganic filler contains talc and silica, wherein the total amount of both talc and silica is 50 to 180 parts by weight per 100 parts by weight of (A) vinyl ester resin (on a solid content basis), and the proportion of talc is 20 to 80% by weight when the total amount of talc and silica is 100% by weight.

[0010] Furthermore, it is preferable to include (F) other additives other than (B) photopolymerization initiators and (C) phosphate ester dispersants.

[0011] Furthermore, it is preferable that (G) epoxy resin be included.

[0012] Furthermore, it is preferable that the material contains an organic solvent (H).

[0013] Furthermore, the (C) phosphate ester dispersant preferably further contains a polymer having a phosphate ester structure in its (C-2) side chain.

[0014] Furthermore, the dry film of the present invention is characterized by being obtained by applying the photosensitive, thermocurable, and developable resin composition to a carrier film and drying it.

[0015] Furthermore, the cured product of the present invention is characterized by being obtained by applying the photosensitive, thermocurable, and developable resin composition to copper and drying it to obtain a coating film, or by applying the photosensitive, thermocurable, and developable resin composition to a carrier film, drying it, and then laminating the resulting photocurable dry film onto copper to obtain a coating film, which is then photocured.

[0016] Furthermore, the printed circuit board of the present invention is characterized by being obtained by applying the photosensitive, thermocurable, and developable resin composition to a substrate and drying it to obtain a coating film, or by applying the photosensitive, thermocurable, and developable resin composition to a carrier film, drying it, laminating the resulting photocurable dry film onto a substrate, photocuring the coating film, and then thermocuring it.

[0017] The most significant feature of the photosensitive, thermosetting, and developable resin composition of the present invention is that it comprises (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) a phosphate ester dispersant, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (C) a polymer having a phosphate ester structure in its main chain as the phosphate ester dispersant, and (E) an inorganic filler, the inorganic filler comprising talc and silica.

[0018] Based on the characteristic structure of the present invention, by using a polymer having a phosphate ester structure in the main chain, and by using talc and silica in combination instead of the conventional filler barium sulfate, and by optimizing the mixing ratio of the two, it is possible to improve printability and pencil hardness while effectively enhancing resistance to thermal shock.

[0019] On the other hand, as a filler, by using talc and barium sulfate in combination, the requirements for the thermal shock resistance of the solder resist can be satisfied, but the pencil hardness deteriorates (for example, Patent Document 1, etc.).

[0020] As described above, as a result of intensive research by the present inventors, it has been found that talc, as a filler, has good flexibility and excellent crack resistance in a thermal cycle test (Temperature Cycle Test, hereinafter sometimes abbreviated as "TCT test"), but the surface hardness is significantly reduced. In addition, since the oil absorption amount of talc is large, the printability of the ink is significantly deteriorated. On the other hand, silica has high hardness and low oil absorption amount. By using talc and silica in combination and optimizing the blending ratio of both, the object of the present invention has been achieved.

Effect of the Invention

[0021] As described above, according to the present invention, it is possible to provide a photosensitive, thermosetting, and developable resin composition, a dry film thereof, a cured product thereof, and a printed wiring board that can form a solder resist layer having excellent printability and excellent hardness and thermal shock resistance.

Brief Description of the Drawings

[0022] [Figure 1] It is a diagram showing a substrate for evaluating printability in an example. [Figure 2] It is an image diagram in which cracks occurred when evaluating thermal shock resistance in an example. [Figure 3] It is an image diagram in which no cracks occurred when evaluating thermal shock resistance in an example.

Mode for Carrying Out the Invention

[0023] Hereinafter, each constituent component of the photosensitive, thermosetting, and developable resin composition of the present invention will be described. The photosensitive, thermosetting, and developable resin composition of the present invention contains (E) an inorganic filler, and the (E) inorganic filler is characterized by containing talc and silica as essential components. Therefore, the (E) inorganic filler will be described first.

[0024] (E) Inorganic filler In the photosensitive, thermosetting, and developable resin composition of the present invention, (E) talc used as an inorganic filler is used to improve thermal shock resistance. Silica is used to improve printability.

[0025] The talc can be any one of the following: magnesium carbonate, serpentine, silica / silica-alumina, or magnesium deposits, or any of the so-called silicate minerals, and may be in massive or fine powder form. Surface treatment may or may not be performed. The oil absorption capacity of the talc should be 20-100 ml / 100 g, preferably 30-90 ml / 100 g, and more preferably 40-80 ml / 100 g. The average particle size of the talc should be 1.0-20.0 μm, more preferably 2.0-10 μm, and even more preferably 3.0-8.0 μm.

[0026] Examples of commercially available products include HD25 manufactured by Pingdu City Talc Mining Co., Ltd. in Shandong Province, and LMP-100 manufactured by Fuji Talc Industry Co., Ltd.

[0027] The silica may be amorphous, crystalline, or a mixture thereof. Particularly preferred is amorphous (fused) silica. Surface treatment may or may not be performed. The oil absorption capacity of the silica is appropriately 15-60 ml / 100g, preferably 20-50 ml / 100g, and more preferably 27-45 ml / 100g. The average particle size of the silica is appropriately 0.1-10.0 μm, more preferably 1.0-8.0 μm, and even more preferably 2.0-6.0 μm.

[0028] Examples of commercially available silica include CS1002 and CS1002A from Jiangsu Novoray New Materials Co., Ltd., A-8 from Sibelco Co., Ltd., SE-40 from Tokuyama Co., Ltd., MSV25G from Longsen Co., Ltd., MLV-2114 from Longsen Co., Ltd., SO-E5 from ADMATECHS, and SO-E2 from ADMATECHS.

[0029] Regarding the blending ratio of talc and silica, when the total amount of both is 100% by weight, the lower limit of the talc ratio should be 20% by weight or more, preferably 25% by weight or more, and more preferably 30% by weight or more. The upper limit of the talc ratio should be 80% by weight or less, preferably 75% by weight or less, and more preferably 70% by weight or less. If the talc ratio is within the above range, thermal shock resistance can be significantly improved. Below 20% by weight, sufficient thermal shock resistance cannot be obtained, while above 80% by weight, although thermal shock resistance remains excellent, printability and the surface hardness of the solder resist film tend to decrease. This is presumed to be because talc has a high oil absorption capacity, and if too much is used, the printability of the ink is greatly affected. In contrast, silica has high hardness and low oil absorption. By blending the two in an appropriate ratio, it is possible to achieve both printability and pencil hardness (at least 4H, preferably 6H or higher), as well as improved resistance to thermal shock (withstanding at least 1000 cycles under thermal cycling conditions from -40°C to 160°C).

[0030] Furthermore, it is appropriate that the total amount of talc and silica per 100 parts by weight of (A) vinyl ester resin (in terms of solid content) be 50 to 180 parts by weight, preferably 60 to 160 parts by weight, and more preferably 80 to 150 parts by weight. Within the above range, it is possible to ensure that excellent thermal shock resistance is obtained while maintaining both printability and hardness.

[0031] From the viewpoint of further satisfying thermal shock resistance, pencil hardness, and printability, the photosensitive, thermosetting, and developable resin composition of the present invention preferably does not contain barium sulfate.

[0032] (A) Vinyl ester resin

[0033] In the photocurable thermosetting resin composition of the present invention, a known resin having an ethylenically unsaturated double bond in its molecule can be used as the (A) vinyl ester resin to impart alkali developability. From the viewpoint of photocurability and developability, a carboxyl group-containing resin having an ethylenically unsaturated double bond in its molecule is particularly preferred. Furthermore, it is more preferable that the unsaturated double bond originates from acrylic acid or methacrylic acid or derivatives thereof. As the (A) vinyl ester resin, resins starting from epoxy resins, polyurethane resins having a urethane skeleton, copolymer resins having a copolymer structure of unsaturated carboxylic acids, and resins starting from phenolic compounds are preferred. Specific examples of the (A) vinyl ester resin are shown below.

[0034] (1) A vinyl ester resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with one or more other compounds having an unsaturated double bond. (2) A photosensitive vinyl ester resin obtained by adding an ethylenically unsaturated group as a side 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 compounds having epoxy groups and unsaturated double bonds such as glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate, or (meth)acrylic acid chloride, etc. (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 or 3,4-epoxycyclohexylmethyl (meth)acrylate, with an unsaturated carboxylic acid such as (meth)acrylic acid, and then reacting the resulting secondary hydroxyl group with a polybasic acid anhydride. (4) A photosensitive vinyl ester resin obtained by reacting a copolymer of an acid anhydride having an unsaturated double bond, such as maleic anhydride, with a compound having an unsaturated double bond, such as 2-hydroxyethyl (meth)acrylate, with a compound having a hydroxyl group and an unsaturated double bond. (5) A vinyl ester resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting the resulting hydroxyl group with a saturated or unsaturated polybasic acid anhydride. (6) A vinyl ester resin containing hydroxyl groups and carboxyl groups is obtained by reacting a saturated or unsaturated polybasic acid anhydride with a hydroxyl group-containing polymer such as a polyvinyl alcohol derivative, and then reacting the resulting carboxylic acid with a compound having an epoxy group and an unsaturated double bond in one molecule. (7) A vinyl ester resin obtained by reacting a saturated or unsaturated polybasic acid anhydride with a reaction product of a polyfunctional epoxy compound, an unsaturated monocarboxylic acid, and a compound having at least one alcoholic hydroxyl group and one reactive group other than the alcoholic hydroxyl group that reacts with the epoxy group in one molecule, (8) A vinyl ester resin obtained by reacting a polyfunctional oxetane compound having at least two oxetane rings in one molecule with an unsaturated monocarboxylic acid, and reacting the primary hydroxyl group in the resulting modified oxetane resin with a saturated or unsaturated polybasic acid anhydride, and (9) A vinyl ester resin obtained by reacting a polyfunctional epoxy resin with an unsaturated monocarboxylic acid, then reacting the carboxyl group-containing resin obtained by reacting it with a polybasic acid anhydride, and further reacting the carboxyl group-containing resin obtained by reacting it with a compound having one oxirane ring and one or more ethylenically unsaturated groups in the molecule. (10) A vinyl ester resin obtained by reacting an unsaturated monocarboxylic acid with a difunctional epoxy compound, and then reacting the resulting hydroxyl group with a saturated or unsaturated polybasic acid anhydride.

[0035] Of these examples, the vinyl ester resins described in (2), (5), (7), and (9) above are particularly preferred.

[0036] In this specification, (meth)acrylate is a general term referring to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions below.

[0037] The vinyl ester resin (A) described above has multiple free carboxyl groups in the side chains of the main chain polymer, and therefore can be developed using a dilute alkaline aqueous solution.

[0038] Furthermore, 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 carboxyl group-containing resin is less than 40 mgKOH / g, alkaline development becomes difficult. On the other hand, if it exceeds 200 mgKOH / g, the dissolution of the exposed areas by the developer progresses, causing the lines to thin more than necessary, or in some cases, the exposed and unexposed areas to dissolve and peel off indiscriminately with the developer, making it difficult to draw a normal resist pattern, which is undesirable.

[0039] Furthermore, the weight-average molecular weight of the vinyl ester resin (A) described above varies depending on the resin skeleton, but is generally preferred to be in the range of 2,000 to 150,000, and even more preferably in the range of 5,000 to 100,000. If the weight-average molecular weight is less than 2,000, the tack-free performance after coating and drying on the substrate may be poor, and the moisture resistance of the coating film after exposure may be poor, resulting in film thinning during development and significantly reduced resolution. On the other hand, if the weight-average molecular weight exceeds 150,000, the developability may be significantly poor and the storage stability may be poor.

[0040] (A) The amount of vinyl ester resin added is preferably in the range of 20 to 60% by mass of the total composition in terms of solid content, and more preferably 25 to 50% by mass. (A) If the amount of vinyl ester resin added is less than the above range, the strength of the coating film will decrease, which is undesirable. On the other hand, if it is more than the above range, the viscosity of the composition will increase or the applicability will decrease, which is undesirable.

[0041] (B) Photopolymerization initiator The photopolymerization initiator used in the photosensitive, thermosetting, and developable resin composition of the present invention is not particularly limited as long as it is a photopolymerization initiator commonly used in photosensitive, thermosetting, and developable resin compositions.

[0042] Known photopolymerization initiators can be used, including benzoin, benzoin methyl ether, benzoin ethyl ether, and their alkyl ethers; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; and 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone. Examples include antraquinones; thioxanthones such as isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; and oxoanthracenes.

[0043] Furthermore, oxime ester-based photopolymerization initiators having an oxime ester group, alkylphenone-based photopolymerization initiators, α-aminoacetophenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, titanocene-based photopolymerization initiators, etc., can also be used as photopolymerization initiators.

[0044] Commercially available oxime ester-based photopolymerization initiators include Irgacure OXE01 and Irgacure OXE02 from BASF Japan, and N-1919 and NCI-831 from ADEKA CORPORATION. Photopolymerization initiators having two oxime ester groups in the molecule can be suitably used, specifically oxime ester compounds having a carbazole structure.

[0045] Commercially available alkylphenone-based photopolymerization initiators include α-hydroxyalkylphenone-based products such as Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 from IGM Resins BV.

[0046] Examples of α-aminoacetophenone-based photopolymerization initiators include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and N,N-dimethylaminoacetophenone. Commercially available products include Omnirad 907, Omnirad 369, and Omnirad 379 from IGM Resins BV.

[0047] Examples of acylphosphine oxide-based photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and acylphosphine-based photopolymerization initiators with three or more functions. These acylphosphine-based photopolymerization initiators with three or more functions may be photopolymerization initiators having three or more acylphosphine oxide skeletons in one molecule, and can be represented by the following formula (I). JPEG2026090389000001.jpg28168In formula, A is independent of each other, consisting of single bonds, O, S, or NR. 3 This represents, G is a polyfunctional compound (core) G-(AH) m+n These are residues (where AH represents an alcohol group, an amino group, or a thiol group, respectively), Both m and n are integers, and m+n is an integer between 3 and 10. m is an integer between 3 and 8. R1 and R2 are each independently an unbroken C1-C alkyl group, an aryl group of C6-C, or a cycloalkyl group of C5-C, or are each independently interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, or R1 and R2 are each independently a 5- to 6-membered heterocyclic group containing oxygen and / or nitrogen and / or sulfur atoms, which may be substituted by an aryl group, an alkyl group, an aryloxy group, an alkoxy group, a heteroatom and / or a heterocyclic group. 18 of the alkyl group, C6-C 12 of the aryl group and C5-C 12 of the cycloalkyl group, or R1 and R2 may be each independently a 5- to 6-membered heterocyclic group containing oxygen and / or nitrogen and / or sulfur atoms, which may be substituted by an aryl group, an alkyl group, an aryloxy group, an alkoxy group, a heteroatom and / or a heterocyclic group. R2 may be R1-(C=O)-. Y is O or S. R 3 is hydrogen or a C1-C4 alkyl group.

[0048] Here, the photoinitiator represented by formula (I) does not contain a photocurable ethylenically unsaturated group.

[0049] 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.

[0050] In formula (I), when A is oxygen, G-(A-H) m+n is a polyhydroxy compound selected from the group consisting of monomer polyols, oligomer polyols, polymer polyols and mixtures thereof. When A is sulfur, G-(A-H) m+n is a polythiol compound. In formula (I), when A is nitrogen, 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 containing different functional groups, for example a compound containing an amino group and a hydroxy group. The residue G- suitable for the implementation of the present invention does not contain a photocurable ethylenically unsaturated group. When A is a single bond, G- is the G-(A-H) exemplified above. m+nThese are residues from which a hydroxyl group and / or an amino group and / or a mercapto group have been removed.

[0051] Preferably, G-(AH) m+n The number average molecular weight is 1,500 or less, more preferably 800 or less, and even more preferably 500 or less.

[0052] If n is not 0, the compound represented by formula (I) has an alcoholic free radical and / or an amino group and / or a mercapto group.

[0053] Table 1 shows representative acylphosphine-based photopolymerization initiators with three or more functions included in formula (I). Among these, PI-3, PI-4, PI-10, PI-11, PI-12, PI-14, and PI-17 are particularly preferred. By including such acylphosphine-based photopolymerization initiators with three or more functions, outgassing is suppressed, and a cured product with superior insulation reliability can be obtained.

[0054] [Table 1] JPEG2026090389000003.jpg226169JPEG2026090389000004.jpg227169JPEG2026090389000005.jpg183169 JPEG2026090389000006.jpg131169JPEG2026090389000007.jpg218169JPEG2026090389000008.jpg105169

[0055] Such trifunctional or more acylphosphine-based photopolymerization initiators can be produced, for example, by the method described in Japanese Patent No. 6599446.

[0056] Commercially available acylphosphine oxide-based photopolymerization initiators include Omnirad TPO from IGM Resins, Omnirad 819 and Omnipol TP from IGM Resins BV, etc.

[0057] Examples of the titanocene-based photopolymerization initiators include bis(cyclopentadienyl)(diphenyl)titanium(IV), bis(cyclopentadienyl)titanium(IV) dichloride, bis(cyclopentadienyl)-bis(2,3,4,5,6-pentafluorophenyl)titanium(IV), and bis(cyclopentadienyl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium(IV). A commercially available example is Omnirad 784 from IGM Resins BV.

[0058] The appropriate blending ratio of these photopolymerization initiators (B) is 0.01 to 30 parts by weight, preferably 5 to 25 parts by weight, and more preferably 10 to 20 parts by weight, per 100 parts by weight (in terms of solid content) of the vinyl ester resin (A). If the amount of photopolymerization initiator used is less than the above range, the photocurability of the composition will be poor, while if it is too much, the properties as a solder resist will be reduced, which is undesirable.

[0059] (C) Phosphate ester dispersant The (C) phosphate ester dispersant used in the photosensitive, thermosetting, and developable resin composition of the present invention refers to a compound or polymer having a phosphate ester structure represented by the following formula (II) in its main chain or side chain. JPEG2026090389000009.jpg36169

[0060] Among these, polymers having a phosphate ester structure represented by formula (II) in the main chain or side chain are preferred because they have good affinity with pigments, can be used in solvent-free and solvent-based inks, and are suitable for stabilizing pigments in low-polarity systems (e.g., alkyd resins, acrylate resins, thermoplastic acrylic acid resins, and epoxy resins).

[0061] Furthermore, the inventors have found that, in order to improve thermal shock resistance while achieving both ink printability and surface hardness of the solder resist layer, it is more preferable to blend silica with talc as a filler, and to use in combination a polymer having a phosphate ester structure in the main chain (i.e., a polyphosphate ester polymer) and a polymer having a phosphate ester structure in the side chain as a (C) phosphate ester dispersant. In this case, the appropriate weight ratio of the two is, i.e., (C-1) polymer having a phosphate ester structure in the main chain : (C-2) polymer having a phosphate ester structure in the side chain is 1:10 to 10:1, preferably 1:5 to 5:1, more preferably 1:3 to 3:1, and even more preferably 1:2 to 2:1. In this way, a photosensitive, thermosetting, and developable resin composition with excellent ink printability, surface hardness of the solder resist layer, and thermal shock resistance can be obtained.

[0062] (C) The appropriate blending ratio of the phosphate ester dispersant is 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, and more preferably 1 to 10 parts by weight, per 100 parts by weight (in terms of solid content) of the vinyl ester resin (A). If the amount of (C) phosphate ester dispersant used is within the above range, it is possible to ensure that excellent thermal shock resistance is obtained while maintaining both printability and hardness. If it exceeds the above range, the properties as a solder resist agent will deteriorate, which is undesirable.

[0063] Examples of commercially available phosphate ester dispersants include Tech-5011 (manufactured by Shanghai Tigge Compound Technology Co., Ltd.), BYK-102, BYK-103, BYK-106, BYK-110, BYK-111, BYK-118, BYK-142, and BYK-145 (manufactured by Bic Chemie).

[0064] In this specification, "polymer" is a general term encompassing homopolymers, copolymers, and mixtures thereof, and the same applies to other similar expressions.

[0065] (D) Compounds having two or more ethylenically unsaturated groups in one molecule The compound (D) having two or more ethylenically unsaturated groups in one molecule, used in the photosensitive, thermocurable, and developable resin composition of the present invention, is a compound that can be photocured by irradiation with active energy rays to insolubilize the vinyl ester resin (A) in an alkaline aqueous solution, or to assist in the insolubilization of the vinyl ester resin in an alkaline aqueous solution. Specific examples of such compounds include: Hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate, Glycol monoacrylates or diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol, Acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, and N,N-dimethylaminopropylacrylamide, Aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate, Polyols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris(2-hydroxyethyl) isocyanurate, or polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts thereof, Phenoxyacrylate, bisphenol A diacrylate, and acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols, Glycidyl ether acrylates such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate, Examples include melamine acrylate and at least one of each of the methacrylates corresponding to the above acrylate.

[0066] Furthermore, examples include epoxy acrylate resins obtained by reacting a polyfunctional epoxy resin such as a cresol novolac type epoxy resin with acrylic acid, and epoxy urethane acrylate compounds obtained by reacting the hydroxyl groups of this epoxy acrylate resin with a half-urethane compound of a hydroxyacrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate.

[0067] The amount of compound (D) having two or more ethylenically unsaturated groups in one molecule is preferably 5 to 100 parts by weight, and more preferably 10 to 70 parts by weight, relative to 100 parts by weight (solid content) of the vinyl ester resin (A). If the amount of compound (D) is less than 5 parts by weight relative to 100 parts by weight of the vinyl ester resin (A), the photocurability of the resulting photosensitive, thermosetting, and developable resin composition decreases, making it difficult to form a pattern by alkaline development after irradiation with active energy rays, which is undesirable. On the other hand, if it exceeds 100 parts by weight, the solubility in alkaline aqueous solution decreases, and the cured coating film becomes brittle, which is undesirable.

[0068] (F) Other additives As described above, other additives in the present invention refer to additives other than (B) photopolymerization initiators and (C) phosphate ester dispersants.

[0069] Examples of such additives include well-known and conventional colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium dioxide, carbon black, and acid black; well-known and conventional thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, and phenothiazine; well-known and conventional thickeners such as fine silica, organic bentonite, and montmorillonite; at least one of silicone-based, fluorine-based, or polymer-based defoaming and leveling agents; adhesion promoters such as imidazole-based, thiazole-based, and triazole-based agents; silane coupling agents; antioxidants such as phenol-based, phosphorus-based, and sulfur-based agents; and well-known and conventional additives such as hindered amine-based light stabilizers.

[0070] The appropriate proportion of such (F) other additives is 0.01% by weight or more and 20% by weight or less of the total amount of the photosensitive, thermosetting, and developable resin composition. If it is less than 0.01% by weight, the effect will not be sufficiently obtained, while if it exceeds 20% by weight, the printability and hardness of the photosensitive, thermosetting, and developable resin composition will deteriorate, which is undesirable.

[0071] (G) Epoxy resin To impart heat resistance, it is preferable to incorporate an epoxy resin having at least two epoxy groups in its molecule, i.e., a polyfunctional epoxy resin (G), into the photosensitive, thermosetting, and developable resin composition used in the present invention.

[0072] Commercially available products include, for example, jER828, jER834, jER1001, jER1004 from Mitsubishi Chemical Corporation, EPICLON 840, 850, 850S, 1050, 2055 from DIC Corporation, EPOTOTE YD-011, YD-013, YD-127, YD-128 from NIPPON STEEL Chemical & Material Co., Ltd., DER317, DER331, DER661, DER664 from Dow Chemical Company, and Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128 from Sumitomo Chemical Co., Ltd. (all are product names) bisphenol A type epoxy resin; jERYL903 from Mitsubishi Chemical Corporation, EPICLON 152, EPICLON 165 from DIC Corporation, and NIPPON STEEL Chemical & Material Brominated epoxy resins such as EPOTOTE YDB-400, YDB-500 from Co., Ltd., DER542 from Dow Chemical Company, Sumi-Epoxy ESB-400, ESB-700 from Sumitomo Chemical Co., Ltd. (all are product names); jER152, jER154 from Mitsubishi Chemical Corporation, DEN431, DEN438 from Dow Chemical Company, EPICLON N-730, EPICLON N-770, EPICLON N-865 from DIC Corporation, EPOTOTE YDCN-701, YDCN-704 from NIPPON STEEL Chemical & Material Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000 from Nippon Kayaku Co., Ltd., and Sumi-Epoxy from Sumitomo Chemical Co., Ltd. ESCN-195X, ESCN-220, NIPPON STEEL Chemical & Novolac-type epoxy resins such as YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704A from Material Co., Ltd., and EPICLON N-680, N-690, N-695 etc. (all product names) from DIC Corporation; EPICLON 830 from DIC Corporation, jER807 from Mitsubishi Chemical Corporation, and bisphenol F-type epoxy resins such as EPOTOTE YDF-170, YDF-175, YDF-2004 etc. (all product names) from NIPPON STEEL Chemical & Material Co., Ltd.; EPOTOTE Hydrogenated bisphenol A epoxy resins such as ST-2004, ST-2007, ST-3000 (product name), and YX8034 manufactured by Mitsubishi Chemical Corporation; jER604 manufactured by Mitsubishi Chemical Corporation; and NIPPON STEEL Chemical & Material Co., Ltd.Glycidylamine-type epoxy resins such as EPOTOTE YH-434 from [company name] and Sumi-Epoxy ELM-120 from Sumitomo Chemical Co., Ltd. (all trade names); hydantoin-type epoxy resins; alicyclic epoxy resins such as CELLOXIDE 2021P from Daicel Corporation (trade names); trihydroxyphenylmethane-type epoxy resins such as YL-933 from Mitsubishi Chemical Corporation and EPPN-501, EPPN-502 from Nippon Kayaku Co., Ltd. (all trade names); bixylenol-type or biphenol-type epoxy resins or mixtures thereof such as YL-6056, YX-4000, YL-6121 from Mitsubishi Chemical Corporation (all trade names); EBPS-200 from Nippon Kayaku Co., Ltd., ADEKA Bisphenol S type epoxy resins such as EPX-30 from CORPORATION and EXA-1514 (product name) from DIC Corporation; Bisphenol A novolac type epoxy resins such as jER157S (product name) from Mitsubishi Chemical Corporation; Tetraphenyloleethane type epoxy resins such as jERYL-931 (product name) from Mitsubishi Chemical Corporation; Heterocyclic epoxy resins such as TEPIC (product name) from Nissan Chemical Industries, Ltd.; Diglycidyl phthalate resins such as BRENMAR DGT from NOF Corporation; Tetraglycidyl xylenolethane resins such as ZX-1063 from NIPPON STEEL Chemical & Material Co., Ltd.; NIPPON STEEL Chemical & Material Co., Naphthalene skeleton-containing epoxy resins such as ESN-190 and ESN-360 from Ltd., and HP-4032, EXA-4750, and EXA-4700 from DIC Corporation; glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M from NOF Corporation; further, copolymer epoxy resins of cyclohexyl maleimide and glycidyl methacrylate; and CTBN-modified epoxy resins (e.g., NIPPON STEEL Chemical). Examples include, but are not limited to, YR-102, YR-450, etc., manufactured by & Material Co., Ltd. These epoxy resins may be used individually or in combination of two or more types.

[0073] (G) The epoxy resin content is preferably 10 to 100 parts by weight, preferably 20 to 90 parts by weight, and more preferably 30 to 80 parts by weight, per 100 parts by mass (in terms of solid content) of (A) vinyl ester resin.

[0074] (H) Organic solvent Regarding the organic solvent (H) used in the photosensitive, thermosetting, and developable resin composition of the present invention, an organic solvent can be used for purposes such as the synthesis of the carboxyl group-containing resin (A), the preparation of the composition, or the adjustment of viscosity when applying it to a substrate or carrier film.

[0075] Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. More specifically, these 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, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. The above organic solvents can be used individually or as mixtures of two or more.

[0076] When using the photosensitive, thermosetting, and developable resin composition of the present invention to form a solder resist for printed circuit boards, the viscosity can be adjusted as needed to suit the application method. After that, it can be applied to a printed circuit board with pre-formed circuits, for example, by methods such as screen printing, curtain coating, spray coating, or roll coating, and dried at a temperature of approximately 60 to 100°C as needed to form a tack-free coating. Next, the coating can be selectively exposed to active light through a photomask with a predetermined exposure pattern, and the unexposed areas can be developed with an alkaline aqueous solution to form a resist pattern. Furthermore, by heating to a temperature of approximately 140 to 180°C to allow for thermosetting, the curing reaction of the epoxy resin and the polymerization of the vinyl ester resin can be promoted, improving various properties of the resulting resist film, such as hardness, thermal shock resistance, heat resistance, solvent resistance, acid resistance, moisture resistance, PCT resistance, adhesion, and electrical properties.

[0077] As the alkaline aqueous solution used during the development process, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines can be used. Furthermore, as the irradiation light source used for photocuring, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, semiconductor lasers, solid-state lasers, xenon lamps, or metal halide lamps are suitable. In addition to being applied directly to a substrate in liquid form, the photosensitive, thermocurable, and developable resin composition of the present invention can also be used in the form of a photocurable dry film obtained by pre-coating the photosensitive, thermocurable, and developable resin composition onto a carrier film and drying it. The following describes how the photosensitive, thermocurable, and developable resin composition of the present invention can be used as a photocurable dry film. A photocurable dry film has a structure in which a carrier film, a resin layer, and a peelable cover film, used as needed, are laminated in this order. The resin layer is obtained by applying and drying the photosensitive, thermocurable, and developable resin composition of the present invention onto the carrier film or cover film. A dry film can be obtained by forming a resin layer on the carrier film and then laminating the cover film on top of it, or by forming a resin layer on the cover film and then laminating this laminate onto the carrier film. As the carrier film, a thermoplastic film such as polyester film with a thickness of 2 to 150 μm is used. The resin layer is formed by uniformly applying a photosensitive, thermosetting, and developable resin composition to the carrier film or cover film to a thickness of 10 to 150 μm using a blade coater, lip coater, comma coater, film coater, etc., and then drying it. As the cover film, polyethylene film, polypropylene film, etc. can be used, but it is preferable that the adhesive strength to the resin layer is weaker than that of the carrier film. The cured product of the present invention is obtained by applying a photosensitive, thermocurable, and developable resin composition to copper and drying it to obtain a coating film, or by applying the photosensitive, thermocurable, and developable resin composition to a carrier film, drying it, and then laminating the resulting photocurable dry film onto copper to obtain a coating film, which is then photocured. To produce a cured product on a printed circuit board with copper circuits using a photocurable dry film, the cover film is peeled off, the resin layer and the circuit-formed substrate are placed on top of each other, and they are bonded together using a laminator or the like to form a resin layer on the circuit-formed substrate. The formed resin layer is then exposed, developed, and heat-cured in the same manner as described above to form a cured product. The carrier film can be peeled off either before or after exposure. Photosensitive, thermosetting, and developable resin compositions are suitably used to form a cured film on printed circuit boards. The cured film is preferably a permanent insulating film, and particularly preferably a solder resist.

[0078] The present invention will be described more specifically by examples and comparative examples, but the scope of rights and embodiments of the present invention are not limited thereto. Unless otherwise specified, "parts" or "%" in the examples and comparative examples are based on weight. The properties of the composition of this example will be tested by the method described later.

[0079] Example of synthesis 214 parts of cresol novolac type epoxy resin EPICLON N-695 (manufactured by DIC, epoxy equivalent = 214) were added to a four-necked flask equipped with a stirrer and reflux condenser, along with 103 parts of diethylene glycol monoethyl ether acetate and a petroleum hydrocarbon solvent (manufactured by Japan Energy Corporation, trade name: Cactus Fines). 103 parts of SF-01) were added and heated to dissolve. Next, 0.1 parts of hydroquinone were added as a polymerization inhibitor and 2.0 parts of triphenylphosphine as a reaction catalyst. This mixture was heated to 95-105°C, and 72 parts of acrylic acid were slowly added dropwise, and the mixture was reacted for 16 hours. The resulting reaction product was cooled to 80-90°C, 91.2 parts of tetrahydrophthalic anhydride were added, and the mixture was reacted for 8 hours. After cooling, the product was removed. The carboxyl group-containing vinyl ester resin thus obtained had a non-volatile content of 65% and a solids acid value of 87.5 mgKOH / g.

[0080] Using the vinyl ester resin solution (varnish) from the above synthesis example, the components and proportions (parts by weight) shown in Table 1 were blended, pre-mixed with a stirrer, and then kneaded in a three-roll mill to prepare a photosensitive, thermosetting, and developable resin composition. Furthermore, the printability, pencil hardness, and thermal shock resistance were evaluated by the following methods.

[0081] [Table 1]

[0082] A. Cresol novolac type epoxy-modified acrylic resin (65% solids content) prepared using the above synthesis example. F Pigment: Phthalocyanine Green, manufactured by DIC Corporation. Defoaming agent: KS-66, manufactured by Shin-Etsu Chemical Co., Ltd. C-1 Phosphate ester dispersant: BYK-110, polymerized phosphate ester, polyphosphate ester polymer, manufactured by Bic Chemie, solids content 52% by mass, oil absorption capacity 63 ml / 100 g C-2 Phosphate ester dispersant: BYK-142, a compound of polyethylene polypropylene glycol monobutyl ether phosphate, a reaction product of 2-ethylhexyl 2-acrylate and (ethylenediamine / ethyleneimine polymer), manufactured by Bic Chemie, solids content 60% by mass, oil absorption 29 ml / 100 g B Photoinitiator: Omnirad 369 E, manufactured by IGM E Talc: LMP-100, manufactured by FUJI TALC INDUSTRIAL Silica: A-8, manufactured by Sibelco. Barium sulfate: B-30, manufactured by Sakai Chemical Industry Co., Ltd. H Solvent: PGMEA, propylene glycol monomethyl ether acetate CC G Epoxy resin: N-770-75EA, manufactured by DIC Corporation, novolac-type polyfunctional epoxy resin, solids content 75% by mass D Compound having two or more ethylenically unsaturated groups in one molecule: MT-3501G, manufactured by Zhangjiagang Dongyadiai Biochemical Co., Ltd.

[0083] Performance evaluation

[0084] (1) Printability A substrate with a copper thickness of 100 μm and an aperture pattern of φ400 μm and a pitch of 600 μm was formed on it. The photosensitive, thermosetting, and developable resin compositions of the examples and comparative examples were screen-printed over the entire surface, left to stand at room temperature for 30 minutes, and then dried in a hot air circulating drying oven at 80°C for 30 minutes to prepare printability evaluation substrates. The printability evaluation substrates were observed using a 100x optical microscope, and the rate of bubble generation in the copper apertures was evaluated (see Figure 1). The evaluation criteria are shown below. ○: Bubble generation rate is less than 40%. △: Bubble generation rate is between 40% and 50%. ×: Bubble generation rate is 50% or higher.

[0085] (2) Pencil hardness The photosensitive, thermosetting, and developable resin compositions of the above examples and comparative examples were applied to the entire surface of a copper foil-clad laminate substrate that had been pre-treated by polishing using screen printing. The substrate was dried at 80°C for 30 minutes, cooled to room temperature, and a 40 μm thick resin layer was formed. The resin layer was then exposed to 400 mJ / cm² of light using an exposure apparatus equipped with a high-pressure mercury lamp. 2 Pattern exposure was performed, and development was carried out for 50 seconds using a 1% by mass sodium carbonate aqueous solution at 30°C under a spray pressure of 0.15 MPa. The pencil hardness of the resin surface after heat curing of the obtained resin coating was measured according to JIS K 5600-5-4. The evaluation criteria are shown below. ○: Pencil hardness of 6H or higher. △: Pencil hardness is between 4H and 6H. ×: Pencil hardness less than 4H.

[0086] (3) Resistance to thermal shock The photosensitive, thermosetting, and developable resin compositions of the examples and comparative examples were coated over the entire surface of a substrate on which a 2 mm copper wire pattern had been formed by screen printing, to a thickness of 40 μm, and dried in a hot air circulating drying oven at 80°C for 30 minutes. After cooling to room temperature, exposure was performed using an exposure apparatus equipped with a high-pressure mercury lamp at 400 mJ / cm². 2 Pattern exposure was performed, followed by development with a 1 wt% sodium carbonate aqueous solution at a pressure of 0.2 MPa and a liquid temperature of 30°C for 60 seconds. Then, it was cured in a hot air circulating drying oven at 150°C for 60 minutes. The cumulative exposure dose in the UV transport oven was 2000 mJ / cm². 2 Seventeen evaluation substrates for crack resistance during thermal cycling, each with a right-angle resist pattern, were fabricated by irradiating them with ultraviolet light under the specified conditions. Multiple evaluation substrates fabricated in this manner were placed in a temperature cycling machine that performs thermal cycling from -40°C to 160°C, and thermal shock cycling (TCT) tests were conducted with different cycle counts. Next, the appearance was observed at each cycle count, and the maximum number of cycles without cracking was recorded. The evaluation criteria are shown below (see Figures 2 and 3 for illustrative images of cracked and non-cracked substrates). ○: No cracks have appeared even after 1000 cycles. ×: Cracks occurred in less than 1000 cycles.

[0087] As can be seen from the above, by adjusting the composition to that of Examples 1 to 6, a photosensitive, thermosetting, and developable resin composition with excellent printability, pencil hardness, and thermal shock resistance can be obtained. In contrast, in Comparative Example 1, only barium sulfate was used as a filler, so while printability and pencil hardness were excellent, thermal shock resistance was extremely low. In Comparative Example 2, only talc was used as a filler, so while thermal shock resistance was excellent, printability and pencil hardness deteriorated significantly. In Comparative Example 3, a combination of talc and barium sulfate was used, and in Comparative Example 4, a combination of silica and barium sulfate was used, but in either case, it was not possible to achieve excellent thermal shock resistance while simultaneously achieving both printability and pencil hardness. In Comparative Examples 5 to 8, talc and silica were used in combination, and in Comparative Example 5, the mixing ratio of the two was outside the range of the present application, and in Comparative Examples 6 to 8, the total amount of both was increased to 200 parts by weight. As a result, thermal shock resistance could not be satisfied in any of the cases, and in Comparative Examples 6 and 8, the printability and pencil hardness were sometimes adversely affected. In Comparative Example 9, using the same amount of the phosphate ester dispersant BYK-145 as in Example 2 resulted in a significant deterioration of printability and pencil hardness.

Claims

1. (A) vinyl ester resin, (B) photopolymerization initiator, (C) phosphate ester dispersant, (D) compound having two or more ethylenically unsaturated groups in one molecule, and (E) inorganic filler, The (C) phosphate ester dispersant comprises (C-1) a polymer having a phosphate ester structure in its main chain, and the (E) inorganic filler comprises talc and silica, wherein the total amount of both talc and silica is 50 to 180 parts by weight per 100 parts by weight of the (A) vinyl ester resin (on a solids basis), and when the total amount of talc and silica is 100% by weight, the proportion of talc is 20 to 80% by weight. The vinyl ester resin (A) is A vinyl ester resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid, and then reacting the resulting hydroxyl group with a saturated or unsaturated polybasic acid anhydride, and Vinyl ester resin obtained by reacting an unsaturated monocarboxylic acid with a difunctional epoxy compound, and then reacting the resulting hydroxyl group with a saturated or unsaturated polybasic acid anhydride. A photosensitive, thermosetting, and developable resin composition characterized by containing at least one of the following.

2. The photosensitive, thermosetting, and developable resin composition according to claim 1, further comprising (F) other additives other than (B) the photopolymerization initiator and (C) the phosphate ester dispersant.

3. (G) The photosensitive, thermosetting, and developable resin composition according to claim 1, further comprising an epoxy resin.

4. (H) The photosensitive, thermosetting, and developable resin composition according to claim 1, further comprising an organic solvent.

5. The photosensitive, thermosetting, and developable resin composition according to any one of claims 1 to 4, further comprising a polymer having a phosphate ester structure in its (C-2) side chain.

6. A photocurable dry film characterized by being obtained by applying a photosensitive, thermocurable, and developable resin composition according to any one of claims 1 to 4 to a carrier film and drying it.

7. A coating film obtained by applying the photosensitive, thermocurable, and developable resin composition according to any one of claims 1 to 4 to copper and drying it, or a coating film obtained by applying the photosensitive, thermocurable, and developable resin composition to a carrier film, drying it, and laminating the resulting photocurable dry film onto copper, is light-cured. A cured product characterized by being obtained by hardening.

8. A printed circuit board characterized by having a coating film obtained by applying the photosensitive, thermocurable, and developable resin composition described in any one of claims 1 to 4 to a substrate and drying it, or a cured product obtained by applying the photosensitive, thermocurable, and developable resin composition to a carrier film, drying it, laminating the resulting photocurable dry film onto a substrate, photocuring the coating film, and then thermocuring it.

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