KR20170060534A - Photo-curable and Thermo-curable Resin Composition - Google Patents

Abstract

The present invention provides a photo-curable thermosetting resin composition comprising a heat-resistant resin containing an unsaturated double bond and a carboxyl group, a photoinitiator, a thermosetting component, and a reactive diluent having an aromatic ring, an unsaturated double bond, and a functional group capable of hydrogen bonding.

Description

[0001] The present invention relates to a photo-curable thermosetting resin composition,

The present invention relates to a photo-curable thermosetting resin composition capable of developing into an alkali aqueous solution capable of forming a cured film of a solder resist and a printed wiring board using the same.

At present, a solder resist of a printed wiring board is mainly made of an alkali developing type photo-solder resist using an aqueous alkaline solution as a developing solution, and is used in large quantities in the production of an actual printed wiring board.

In recent years, in response to the increase in the density of printed wiring boards due to the thinning and shortening of electric / electronic devices, workability and high performance are required for solder resist. However, current alkaline developing type photo-solder resists still have problems in terms of durability. That is, as compared with the conventional thermosetting and solvent-developing type solder resists, the resistance to alkalinity, water resistance, and heat resistance is poor.

Conventional acid-modified epoxy acrylates, photoinitiators, reactive diluents, and solder resist compositions containing a thermosetting component have no problem in reliability in a conventional package. However, in a package requiring a thin thickness and a high level of reliability, the heat resistance of the cured coating is insufficient The film may be deformed due to expansion in a manufacturing process requiring a high temperature. In order to improve this, conventionally, an attempt was made to increase the content of the reactive diluent including an aliphatic chain to increase the glass transition temperature to increase the heat resistance, but it was difficult to secure excellent heat resistance due to the poor heat resistance of the basic skeleton itself. In addition, when a reactive diluent containing an aliphatic chain alone is used to form a cured film, the adhesive force is low, resulting in problems such as peeling of the film or peeling of the film. As a result, the conventional cured coating of the solder resist is limited in its application to a package requiring a thin thickness and a high level of reliability.

Japanese Patent Laid-Open No. 1991-250012 Korean Patent Publication No. 10-2012-0022820

The present invention provides a photo-curable thermosetting resin composition capable of developing in an aqueous alkaline solution capable of forming a cured film of a solder resist excellent in heat resistance and adhesion to a substrate.

The present invention also provides a solder resist formed from the photo-curable thermosetting resin composition.

In addition, the present invention provides a printed wiring board comprising a patterned cured layer of the above-mentioned photocurable thermosetting resin composition.

The present invention provides a photo-curable thermosetting resin composition comprising a heat-resistant resin containing an unsaturated double bond and a carboxyl group, a photoinitiator, a thermosetting component, and a reactive diluent having an aromatic ring, an unsaturated double bond, and a functional group capable of hydrogen bonding.

In one embodiment of the present invention, the reactive diluent can be prepared by ring-opening reaction of an epoxy compound having an aromatic ring and a compound having an unsaturated double bond.

The epoxy compound having an aromatic ring may be a bisphenol A compound having an epoxy group, a bisphenol F compound, a phenol novolak compound, a cresol novolak compound, or a naphthalene compound.

In addition, the compound having an unsaturated double bond may be an acrylic derivative selected from the group consisting of acrylic acid, methacrylic acid, and itaconic acid.

On the other hand, the present invention provides a solder resist formed from the photo-curable thermosetting resin composition.

The photo-curable thermosetting resin composition according to the present invention uses a reactive diluent having an aromatic ring, an unsaturated double bond and a functional group capable of hydrogen bonding to increase the glass transition temperature of the cured film to thereby exhibit excellent heat resistance, It is possible. Therefore, the photo-curable thermosetting resin composition according to the present invention can be effectively used as a solder resist for a semiconductor package which is thin and requires excellent reliability.

Hereinafter, the present invention will be described in more detail.

The photo-curable thermosetting resin composition according to the embodiment of the present invention comprises a heat-resistant resin (A) containing an unsaturated double bond and a carboxyl group, a photoinitiator (B), a thermosetting component (C), and an aromatic ring, And a reactive diluent (D) having a functional group.

In the embodiment of the present invention, the heat-resistant resin (A) containing the unsaturated double bond and the carboxyl group may be derived from phenol, cresol or a derivative thereof capable of securing excellent heat resistance. The heat resistant resin (A) may have a softening point of 60 ° C to 120 ° C. More specifically, the softening point may be 70 ° C to 110 ° C. If the softening point is less than 60 ° C, the heat resistance of the composition may be poor, resulting in poor heat resistance such as heat resistance. If the softening point is more than 120 ° C, too high viscosity may result in lack of workability or yield have.

The unsaturated double bond of the heat-resistant resin may be derived from an ester containing a vinyl group, that is, an acrylic derivative in which two carbon atoms are double bonds and a carbonyl group is directly bonded to one of the carbon atoms. Acrylamide derivatives such as acrylamide, methyl acrylamide, glycidyl acrylate derivatives such as hydroxy glycidyl acrylate and glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, Hydroxyacrylate derivatives such as hydroxypropyl acrylate and hydroxypropyl methacrylate, acrylic acid derivatives such as acrylic acid, methacrylic acid and itaconic acid, and acrylic derivatives having functional groups capable of crosslinking. More preferably, an acrylic derivative having a functional group capable of crosslinking with a glycidyl ether such as acrylic acid, methacrylic acid or itaconic acid can be used.

Further, the heat-resistant resin may contain a carboxyl group to form a reaction group with excellent developability and a thermosetting component. The carboxyl group can be introduced by reacting a polybasic acid anhydride such as phthalic anhydride, maleic anhydride or the like.

Specific examples of the above heat-resistant resin (A) having an unsaturated double bond and a carboxyl group include phenol, cresol, or derivatives thereof. The product obtained by reacting a phenolic hydroxyl group of a novolac resin with epichlorohydrin is reacted with (meth) A heat-resistant resin obtained by reacting a monocarboxylic acid containing an unsaturated double bond and then reacting with a polybasic acid anhydride such as maleic anhydride or phthalic anhydride. Any of oligomers and polymers are possible.

The acid value range of the heat resistant resin (A) containing the unsaturated double bond and the carboxyl group may be 40-150 mgKOH / g, specifically 50-130 mgKOH / g. If the acid value of the heat resistant resin (A) containing an unsaturated double bond and a carboxyl group is less than 40 mgKOH / g, developability due to an aqueous alkali solution is lacking. If the acid value exceeds 150 mgKOH / g, the pattern line is thin Or in some cases, the exposed portion and the non-exposed portion are not distinguished from each other and dissolved and separated by the aqueous alkaline solution, so that normal pattern formation may become difficult.

The weight average molecular weight of the heat resistant resin (A) containing an unsaturated double bond and a carboxyl group varies depending on the skeleton of the base resin, but may be 2,000 to 150,000, especially 5,000 to 100,000. If the weight average molecular weight is less than 2,000, the moisture resistance and reliability of the cured coating after the exposure may be lost, and the appearance change such as the reduction in development and the lower resolution may be caused. If the weight average molecular weight exceeds 150,000, the developability may be significantly lowered and the storage stability may deteriorate.

The amount of the heat resistant resin (A) containing the unsaturated double bond and the carboxyl group may be 20 to 60% by weight, particularly 30 to 50% by weight, based on 100% by weight of the whole composition. When the blending amount of the heat resistant resin (A) containing the unsaturated double bond and the carboxyl group is less than 20% by weight, the strength of the film may be lowered. When the blending amount is more than 60% by weight, And the like.

In one embodiment of the present invention, the photoinitiator (B) comprises an oxime ester photoinitiator (B-1) represented by the following formula 1, an? -Aminoacetophenone photoinitiator (B-2) represented by the following formula And an acylphosphine oxide-based photoinitiator (B-3) represented by the general formula (3).

[Chemical Formula 1]

In Formula 1,

R ¹ is a hydrogen atom, a phenyl group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkanol group having 2 to 20 carbon atoms or a benzoyl group,

R ² is a phenyl group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkanol having 2 to 20 carbon atoms, or a benzoyl group.

(2)

In Formula 2,

R ³ and R ⁴ are each independently an alkyl or arylalkyl group having 1-12 carbon atoms,

R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1-6 carbon atoms, or R ⁵ and R ⁶ are bonded to each other to form an alkyl ether ring having 1-6 carbon atoms.

(3)

In Formula 3,

R ⁷ and R ⁸ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group, a halogen atom, or an aryl group substituted with an alkyl group or an alkoxy group.

Representative examples of the oxime ester-based photoinitiators include the compounds represented by the following formulas (4) and (5).

[Chemical Formula 4]

[Chemical Formula 5]

In Formula 5,

R ⁹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a phenyl group, a benzoyl group, an alkanol group having 2 to 12 carbon atoms, or an alkoxy group,

R ¹⁰ is a phenyl group, an alkyl group having a carbon number of 1-12, a cycloalkyl group having a carbon number of 5-8, an alkanol group having a carbon number of 2-20 or a benzoyl group,

R ¹¹ is a hydrogen atom, a phenyl group, an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 5-8 carbon atoms, an alkanol group having 2-20 carbon atoms or a benzoyl group,

R ¹² is a phenyl group, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkanol having 2 to 20 carbon atoms, or a benzoyl group.

Examples of the oxime ester photoinitiator include BASF's Irgacure OXE-01 and Irgacure OXE-02. These oxime ester-based photoinitiators may be used alone or in combination of two or more.

Representative examples of the? -Aminoacetophenone type photoinitiator include 2-methyl-1- [(4-methylthio) phenyl] -2- (4-morpholinyl) Amino) -4-morpholinobutyrophenone, and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one. Examples of the product of the? -Aminoacetophenone photoinitiator include BASF's Irgacure 907, Irgacure 369, Irgacure 379, and the like.

Representative examples of the acylphosphine oxide-based photoinitiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-2,4,6-trimethylbenzoyl-phenylphosphine oxide, bis-2,4,4- Trimethyl-benzyl-phosphine oxide, and the like. Examples of products of the acylphosphine oxide-based photoinitiator include Irgacure TPO or Irgacure 819 from BASF.

The blending amount of the photoinitiator (B) may be in the range of 0.01-10.0 wt%, especially 0.50-5.00 wt%, based on 100 wt% of the entire composition. If the blending amount of the photoinitiator is less than 0.01% by weight, the photo-curing may be insufficient and the film may peel off or the film properties such as chemical resistance may be deteriorated. On the other hand, when the compounding amount of the photoinitiator is more than 10.0 wt%, the absorption of light at the surface of the film becomes severe, which may cause a decrease in the hardness of the deep portion.

In one embodiment of the present invention, the thermosetting component (C) is for imparting heat resistance, and it is preferable that the thermosetting component (C) is a thermosetting thermosetting resin such as a block isocyanate compound, a benzoxazine resin, a cyclocarbonate compound, a polyfunctional epoxy compound, Resin can be used.

The thermosetting component (C) may be a compound having two or more ring-form ether groups or ring-form thioether groups in the molecule. Specific examples include multifunctional epoxy compounds having two or more epoxy groups in the molecule, and multifunctional episulfide compounds having two or more thioether groups in the molecule.

Examples of the polyfunctional epoxy compound include bisphenol A multifunctional epoxy resin, bisphenol F multifunctional epoxy resin, hydrogenated bisphenol A multifunctional epoxy resin, brominated multifunctional epoxy resin, halogen-free multifunctional epoxy resin, novolak multifunctional epoxy resin, And biphenyl multifunctional epoxy resins.

Examples of bisphenol A multifunctional epoxy resin products include YD-011 and YD-01 of Japan Epoxy Resins, such as JER828, JER834 and JER1001 of Japan Epoxy Resins, Epikuron 840, Epikuron 850 and Epikuron 1050, ESA-014, ESA-115, and ESA-128 of BASF, such as DER317, DER331, DER661 and DER664 of Dow Chemical such as YA-013, YD-127 and YD-128; AER330 and AER331 of Asahi Kasei Industries , AER661, AER664, and YD-012 of Kukdo Chemical.

Brominated multifunctional epoxy resin products include: JERYL903 of Japan Epoxy Resin, Epikuron 152 of Epoxy Resin Chemical Industry, Epikuron 165, etc., YDB-400 and YDB-500 of Dow Chemical, DER542 of Dow Chemical, and Alaldide 8011 of BASF.

Examples of the novolac multifunctional epoxy resin product include JER152 and JER154 of Japanese epoxy resin and Epikuron N-730, Epikuron N-770 and Epikuron N-865 of Dainippon Ink and Chemicals Industries; YDCN- EOCN-1020, EOCN-104S, RE-306 and the like of Japanese explosives, such as DEN431 and DEN438 of Dow Chemical Co., Ltd., Alaldehyde ECN1235 of BASF, Alaldide ECN1273, have.

These polyfunctional epoxy resins may be used alone or in combination of two or more. As an example, novolac epoxy resins or mixtures thereof may be used.

Examples of products of episulfide compounds having two or more ring-form thioether groups in the molecule include YL7000 of Japan Epoxy Resin and YSLV-120TE of Tokto Chemicals. An episulfide resin in which the oxygen atom of the epoxy group in the novolak epoxy resin is replaced by a sulfur atom can also be used.

The blending amount of the thermosetting component (C) may be in the range of 1.00 to 20.0% by weight, particularly 5.00 to 15.0% by weight based on 100% by weight of the whole composition. When the blending amount of the thermosetting component is less than 1.00 wt%, a carboxyl group is left in the composition film and the heat resistance, alkali resistance, electric insulation, etc. may be lowered. When the blending amount of the thermosetting component exceeds 20.0 wt% (Thio) ether groups remain in the dried film, and the strength and the like of the film may be lowered.

Heating the composition containing the thermosetting component (C) to a temperature of 130 to 160 캜 to form the carboxyl group of the heat-resistant resin (A) containing the unsaturated double bond and the carboxyl group and the carboxyl group of the thermosetting component (C) Group reacts to form a cured film excellent in heat resistance, chemical resistance, hygroscopicity, adhesion, electrical characteristics and the like.

In an embodiment of the present invention, the reactive diluent (D) having a functional group capable of forming an aromatic ring, an unsaturated double bond and a hydrogen bond may be used alone or in combination with another reactive diluent.

A conventional cured film obtained by using a reactive diluent having an aliphatic chain or an unsaturated double bond has a low glass transition temperature and thus requires a cured film of a thick thickness, It is not desirable for a package requiring a high level of reliability. In addition, when a reactive diluent having an aliphatic chain or an unsaturated double bond is applied alone, the adhesion of the solder resist cured coating is poor, which may lead to coating film peeling, coating film peeling, and peeling of the coating film.

In the present invention, all or a part of a reactive diluent (D) having an aromatic ring and an unsaturated double bond and a functional group capable of forming a hydrogen bond with the substrate is used in combination to increase the glass transition temperature of the cured film due to the aromatic ring, And it is also possible to exhibit excellent adhesion between the substrate and the substrate through the hydrogen bonding of the functional group capable of hydrogen bonding and the substrate.

The reactive diluent having a functional group capable of forming an aromatic ring, an unsaturated double bond and a hydrogen bond can be prepared through a ring-opening reaction with a reaction catalyst under specific temperature conditions of an epoxy compound having an aromatic ring and a compound having an unsaturated double bond.

The epoxy compound having an aromatic ring may be a bisphenol A compound having an epoxy group, a bisphenol F compound, a phenol novolak compound, a cresol novolak compound, a naphthalene compound, or the like. The softening point of the epoxy compound having an aromatic ring may be 60 ° C to 120 ° C, particularly 70 ° C to 110 ° C. If the softening point of the epoxy compound is less than 60 캜, the heat resistance of the composition may be poor, resulting in poor heat resistance such as solder heat resistance. If it is more than 120 캜, the viscosity of the reactive diluent is too high, Resulting in a decrease in the yield.

The number of epoxy groups may include 1 to 8. The epoxy equivalent of the epoxy compound having an aromatic ring may be 100 to 800 g / eq. If the amount is outside the above range, the number of hydrogen-bonded bonds may decrease, resulting in a decrease in adhesion with the substrate or an increase in viscosity, which may result in deterioration in workability or degradation of storage stability.

The compound having an unsaturated double bond may be an ester containing a vinyl group, that is, an acrylic derivative in which two carbon atoms are double bonds and carbonyl group is directly bonded to one of the carbon atoms. Acrylamide derivatives such as acrylamide, methyl acrylamide, glycidyl acrylate derivatives such as hydroxy glycidyl acrylate and glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, Hydroxyacrylate derivatives such as hydroxypropyl acrylate and hydroxypropyl methacrylate, acrylic acid derivatives such as acrylic acid, methacrylic acid and itaconic acid, and acrylic derivatives having functional groups capable of crosslinking. More preferably, acrylic derivatives having functional groups capable of crosslinking with glycidyl ethers such as acrylic acid, methacrylic acid and itaconic acid can be used singly or in combination.

The acid value of the unsaturated double bond-containing compound may be 130 mgKOH / g or more, particularly 150 mgKOH / g or more and 500 mgKOH / g or less. If the acid value of the compound having an unsaturated double bond is less than 130 mgKOH / g, the reaction with the epoxy compound having an aromatic ring can not be carried out and sufficient unsaturated double bonds can not be secured, resulting in poor curing density due to light, / g, the storage stability is deteriorated, undercuts may occur during the development process, and the developing margin may be decreased to deteriorate adhesion to the substrate and lower reliability.

The functional group generated by the ring-opening reaction of the epoxy compound having an aromatic ring and the compound having an unsaturated double bond can induce hydrogen bonding with the substrate to exhibit excellent adhesion. Examples of such functional groups include an amine group, a hydroxyl group, and a carboxyl group. The number of functional groups generated may vary depending on the amount of the acrylic compound introduced and the progress of the ring-opening reaction.

In the ring-opening reaction of the epoxy compound having an aromatic ring and the compound having an unsaturated double bond, the amount of the compound having an unsaturated double bond may be used in an amount of 100% by weight to 500% by weight based on 100% by weight of the epoxy compound having an aromatic ring . If the amount of the compound having an unsaturated double bond is less than the above range, there may be a problem that the curing density due to the light of the composition is lowered and the adhesion force is impaired. On the contrary, when the amount is exceeded, the compound having an unsaturated double bond The reliability of the cured coating of the solder resist can be lowered.

The reaction temperature for the ring-opening reaction of the epoxy compound having an aromatic ring and the compound having an unsaturated double bond may be 60 to 150 ° C. There are no particular restrictions on the pressure conditions, and the reaction can be carried out under all conditions such as reduced pressure, atmospheric pressure, and pressure. As the polymerization inhibitor, hydroquinone, methylhydroquinone, hydro-monomethylquinone, catechol, pyrocalcohol and the like can be suitably used.

The epoxy equivalent of the reactive diluent having the aromatic ring, unsaturated double bonds and hydrogen bondable functional groups may be 25,000 g / eq or less, particularly 1000 g / eq or more and 20,000 g / eq or less. When the epoxy equivalent of a reactive diluent having an aromatic ring, an unsaturated double bond and a functional group capable of hydrogen bonding is less than 1,000 g / eq, the reliability of the cured coating of the solder resist may be lowered due to the residual unsaturated double bond, And when it is more than 20,000 g / eq, the viscosity becomes high and workability is deteriorated and the developability is deteriorated, so that it is difficult to obtain a uniform pattern because resolution is low.

In one embodiment of the present invention, the reactive diluent (D) having a functional group capable of forming an aromatic ring, an unsaturated double bond and a hydrogen bond may include at least one selected from the compounds represented by the following formulas (6) to (8).

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the above formula, R represents a hydrogen atom or an alkylene group having 1 to 10 carbon atoms,

F represents an amine group, a hydroxyl group or a carboxyl group

When a reactive diluent is used to improve reliability, heat resistance and adhesion, a reactive diluent (D) having functional groups capable of forming an aromatic ring, an unsaturated double bond and a hydrogen bond may be used in whole or in part.

The reactive diluent having a functional group capable of forming an aromatic ring, an unsaturated double bond and a hydrogen bond may be mixed with a reactive diluent having an aliphatic chain and an unsaturated double bond.

Specific examples of the reactive diluent having an aliphatic chain and an unsaturated double bond include caprolactone acrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, dimethylpropane tetraacrylate, Trimethylolpropane triacrylate, trimethylolpropane triacrylate, tricyclodecane dimethanol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, dipentaerythritol caprolactone acrylate, and the like. Examples of the aliphatic reactive diluent include DPHA, DPCA-30, Miramer M200, Miramer M300, Miramer M340, and Miramer M600 manufactured by Miwa Corporation.

The amount of the reactive diluent having the aromatic ring, the unsaturated double bond and the functional group capable of hydrogen bonding may be from 0.50 to 10.0% by weight, particularly from 2.00 to 8.00% by weight based on 100% by weight of the total composition. If the blending amount of the reactive diluent is less than 0.50 wt%, the photocurability is lowered, and pattern formation may become difficult due to the development of the alkali aqueous solution after irradiation of the activation energy. On the other hand, when the blending amount of the reactive diluent is more than 10.0% by weight, the solubility in an aqueous alkali solution may be lowered.

The photo-curable thermosetting resin composition according to one embodiment of the present invention may further comprise a colorant (E).

The colorant (E) may be any one of pigments, dyes, pigments, and colorants, but may not contain a halogen in view of environmental load reduction and effects on the human body.

Examples of the yellow colorant include azo, disazo, condensed azo, benzoimidazole, isoindolinone, anthraquinone, and the like.

Pigment Yellow 001, 002, 003, 004, 005, 006, 009, 010, 012, 061, 062, 065, 073, 074, 075, 097, 100, 104, 105, 111, 116, 1671 169;

Disazo-Pigment Yellow 012, 013, 014, 016, 017, 055, 063, 081, 083, 087, 126, 127, 152, 170, 172, 174, 176, 188, 198;

Pigment Yellow 093, Pigment Yellow 095, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180;

Benzoimidazole-based pigments such as Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181;

Isoindolinone-Pigment Yellow 109, Pigment Yellow 110, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185;

Anthraquinone-Solvent Yellow 163, Pigment Yellow 024, Pigment Yellow 108, Pigment Yellow 147, Pigment Yellow 193, Pigment Yellow 199, Pigment Yellow 222.

Examples of the blue colorant include phthalocyanine type and anthraquinone type, and specific examples include the following.

Pigment Blue 15: 1, Pigment Blue 15: 1, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 60:00.

In addition, a metal substituted or unsubstituted phthalocyanine compound may be used.

The blending amount of the colorant (E) is not particularly limited, but may be 0.10-5.00% by weight, particularly 0.10-3.00% by weight, based on 100% by weight of the total composition.

The photo-curable thermosetting resin composition according to an embodiment of the present invention may further include a filler (F) to improve the physical strength and the like of the film.

As the filler (F), an inorganic or organic filler can be used, and in particular, barium sulfate and nano silica can be used. A metal oxide such as titanium oxide or a metal hydroxide such as aluminum hydroxide may be used as a filler in order to obtain a white appearance and flame retardancy.

The amount of the filler (F) may be 70 wt% or less, specifically 5.00-50.0 wt%, more specifically 10.0-40.0 wt%, based on 100 wt% of the entire composition. When the amount of the filler is more than 70% by weight, the viscosity of the composition becomes high, which results in poor workability, deteriorating printing properties or rendering the cured product to be unfavorable.

The photo-curable thermosetting resin composition according to an embodiment of the present invention may further include an additive (for example, antifoaming agent) which is usually used in the curable resin composition, if necessary, in addition to the above components. Further, an organic solvent may be further added to suitably adjust the viscosity upon application of the composition.

The photo-curable thermosetting resin composition according to one embodiment of the present invention can be prepared, for example, by adjusting the viscosity with an organic solvent to a suitable viscosity for the application method, and applying a dip coating method, a flow coating method, a roll coating method, A curtain coating method or the like, and the organic solvent contained in the composition is volatilized and dried at a temperature of about 60-120 캜. Then, the photoresist is selectively exposed to active energy through a photomask having a pattern formed by a contact or a non-contact method, or a direct pattern is exposed using a laser direct exposure machine or the like, and the exposed portion is exposed to an aqueous alkali solution (0.1-3.0% Aqueous solution) to form a pattern.

The substrate may be a printed wiring board or a flexible printed wiring board on which a circuit is previously formed, a glass fiber impregnated with a phenol resin, a glass fiber impregnated with an epoxy resin, a glass fiber impregnated with a bismaleimide triazine resin, A PET film, a glass substrate, a ceramic substrate, a wafer substrate, or the like.

The volatile drying after the photocurable thermosetting resin composition of the present invention is applied to a substrate can be carried out by using a hot air circulating drying furnace, an infrared drying furnace, a hot plate, or the like.

The photocurable thermosetting resin composition of the present invention is applied on a substrate, and after volatilization and drying, the resulting film is exposed to active energy, whereby the film is cured. Examples of the exposure apparatus used for the irradiation of active energy include a direct drawing apparatus (for example, a laser direct image apparatus that expresses a pattern directly with a laser by a computer using CAD data), an exposure apparatus equipped with a metal halide lamp, A direct exposure apparatus using an ultraviolet lamp such as a (high) pressure mercury lamp, or the like can be used.

The range of the active energy may be laser light and ultraviolet lamp light in the range of the maximum wavelength of 340-420 nm, and either gas laser or solid laser may be used.

Examples of the developing method include a dipping method, a shower method, a spraying method, a brushing method and the like. As the developer, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, .

The photocurable thermosetting resin composition of the present invention can be used in the form of a dry film having a solder resist layer formed by applying a solder resist to a base film such as polyethylene terephthalate and drying it, in addition to a method of directly applying the composition to a substrate in a liquid phase. The case where the photocurable thermosetting resin composition of the present invention is used as a dry film will be described below.

A dry film is a structure in which a base film, a solder resist layer, and a peelable cover film to be used, if necessary, are laminated in the above order. The solder resist layer is a layer obtained by applying a developable photocurable thermosetting resin composition to an alkali aqueous solution to a base film or a cover film and drying the same. A solder resist layer is formed on a base film and then a cover film is laminated, or a solder resist layer is formed on a cover film, and a base film is laminated to obtain a dry film.

As the base film, a thermoplastic film such as a polyester film in a thickness range of 1 to 200 mu m may be used. The solder resist layer is formed by uniformly applying a photo-curable thermosetting resin composition to a base film or a cover film by a blade coater, a lip coater, a comma coater, a film coater or the like in a thickness range of 5-200 占 퐉 and drying.

When a protective film is formed on a printed wiring board using a dry film, the cover film is peeled off, the solder resist layer and the substrate on which the circuit is formed are overlapped and a solder resist layer is formed on the circuit formed substrate by pasting them together using a laminator. When the exposure process, the development process, and the heat curing process are performed on the formed solder resist layer in the same manner as described above, a cured coating film can be obtained. The base film may be peeled off either before or after exposure.

Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples and Experimental Examples. It should be apparent to those skilled in the art that these examples, comparative examples and experimental examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Synthetic example  1: Preparation of reactive diluent (A-1)

500 g of an epoxy resin (phenol novolac type, Printec, VG3101L, epoxy equivalence = 210, softening point = 61 캜) having three epoxy functional groups was added to a four-necked flask having a capacity of 5 L and then gradually heated to 100 캜. Subsequently, 2 g of hydroquinone, which is a polymerization inhibitor, and 1500 g of acrylic acid (acid value = 320 mgKOH / g) were sequentially added and the temperature was raised again to 120 ° C. After the temperature was elevated, 2 g of triphenylphosphate as a catalyst was added. The temperature was raised to 150 ° C., and the mixture was reacted for about 24 hours. The mixture was cooled to room temperature and extracted to obtain an unsaturated double bond and hydrogen bond To obtain a reactive diluent (A-1) having a functional group.

(Epoxy equivalent = 18,000 g / eq)

Synthetic example  2: Preparation of reactive diluent (A-2)

In a four-necked flask having a capacity of 5 L, an epoxy resin having four epoxy functional groups (naphthalene type, DIC, EXA-4700, epoxy equivalent = 162, softening point = 92 占 폚), and the temperature was gradually raised to 100 占 폚. Subsequently, 2 g of hydroquinone, which is a polymerization inhibitor, and 1500 g of acrylic acid (acid value = 320 mgKOH / g) were sequentially added and the temperature was raised again to 120 ° C. After the temperature was elevated, 2 g of triphenylphosphate as a catalyst was added. The temperature was raised to 150 ° C., and the mixture was reacted for about 24 hours. The mixture was cooled to room temperature and extracted to obtain an unsaturated double bond and hydrogen bond To obtain a reactive diluent (A-2) having a functional group.

(Epoxy equivalent = 17,900 g / eq)

Synthetic example  3: Preparation of reactive diluent (A-3)

In a four-neck flask having a capacity of 5 L, two epoxy functional groups 500 g of an epoxy resin (bisphenol A type, available from Kukdo Chemical Co., Ltd., YD-011, epoxy equivalent = 475, softening point = 65 ° C) Subsequently, 2 g of hydroquinone, which is a polymerization inhibitor, and 1500 g of acrylic acid (acid value = 320 mgKOH / g) were sequentially added and the temperature was raised again to 120 ° C. After the temperature was elevated, 2 g of triphenylphosphate as a catalyst was added. The temperature was raised to 150 ° C., and the mixture was reacted for about 24 hours. The mixture was cooled to room temperature and extracted to obtain an unsaturated double bond and hydrogen bond To obtain a reactive diluent (A-3) having a functional group.

(Epoxy equivalent = 17,900 g / eq)

Example 1: Preparation of photocurable thermosetting resin composition .

Example  1-1: Preparation of Resin Composition 1-1

(KCC, SR90-B3T4, solid content = 65%, acid value = 57, weight average molecular weight = 7,300) containing an unsaturated double bond and a carboxyl group in a mixing tank equipped with a stirrer and a thermosetting component of bisphenol A type , YD-012, softening point = 80 占 폚, equivalent weight: 650) were charged and stirred at 500 rpm for 10 minutes. After stirring, 10 g of a reactive diluent (A-1) having an aromatic ring and having a functional group capable of forming an unsaturated double bond and a hydrogen bond with the substrate and 30 g of a photoinitiator (BASF, Irgacure 369,? -Aminoacetophenone system) Subsequently, 2 g of a yellow colorant (BASF, Pigment Yellow 147) and 2 g of a blue colorant (BASF, Pigment Blue 16:00) And the mixture was stirred at 500 rpm for 10 minutes. After the stirring was completed, 250 g of filler (Sakai, B-30, barium sulfate, D (50) = 0.3 탆) was dividedly added three to six times. After completion of the addition, the mixture was stirred at 700 rpm for 20 minutes at high speed. At this time, the internal temperature was prevented from exceeding 45 ° C due to the heat generated by the high-speed agitation. When stirring was completed, the mixture was dispersed with a 3 roll mill. After completion of the dispersion, the level of the particle size was checked, and dispersion was repeated when the particle size was 10 μm or more. The solid content of the photo-curable thermosetting resin composition which can be developed in the alkali aqueous solution thus obtained was 75% and the viscosity was 13,000 mPa · s.

Example  1-2: Preparation of Resin Composition 1-2

(KCC, SR90-B3T4, solid content = 65%, acid value = 57, weight average molecular weight = 7,300) containing an unsaturated double bond and a carboxyl group in a mixing tank equipped with a stirrer and a thermosetting component of bisphenol A type , YD-012, softening point = 80 占 폚, equivalent weight: 650) were charged and stirred at 500 rpm for 10 minutes. After stirring, 10 g of a reactive diluent (A-2) having an aromatic ring and a functional group capable of forming an unsaturated double bond and a hydrogen bond with a substrate and 30 g of a photoinitiator were added thereto, followed by sequentially adding 2 g of a yellow colorant and 6 g of a blue colorant The mixture was stirred at 500 rpm for 10 minutes. When the stirring was completed, 250 g of the filler was divided into three to six times. When the addition was completed, the mixture was stirred at 700 rpm for 20 minutes at high speed. At this time, the internal temperature was prevented from exceeding 45 ° C due to the heat generated by the high-speed agitation. When stirring was completed, the mixture was dispersed with a 3-roll mill. After completion of the dispersion, the level of the particle size was checked, and dispersion was repeated when the particle size was 10 μm or more. The solid content of the photo-curable thermosetting resin composition that can be developed in the alkali aqueous solution thus obtained was 73% and the viscosity was 12500 mPa · s.

Example  1-3: Preparation of Resin Composition 1-3

(KCC, SR90-B3T4, solid content = 65%, acid value = 57, weight average molecular weight = 7,300) containing an unsaturated double bond and a carboxyl group in a mixing tank equipped with a stirrer and a thermosetting component of bisphenol A type , YD-012, softening point = 80 占 폚, equivalent weight: 650) were charged and stirred at 500 rpm for 10 minutes. After stirring, 10 g of a reactive diluent (A-3) having an aromatic ring and a functional group capable of forming an unsaturated double bond and a hydrogen bond with a substrate and 30 g of a photoinitiator were added thereto, followed by sequentially adding 2 g of a yellow colorant and 6 g of a blue colorant The mixture was stirred at 500 rpm for 10 minutes. When the stirring was completed, 250 g of the filler was divided into three to six times. When the addition was completed, the mixture was stirred at 700 rpm for 20 minutes at high speed. At this time, the internal temperature was prevented from exceeding 45 ° C due to the heat generated by the high-speed agitation. When stirring was completed, the mixture was dispersed with a 3-roll mill. After completion of the dispersion, the level of the particle size was checked, and dispersion was repeated when the particle size was 10 μm or more. The solid content of the photo-curable thermosetting resin composition that can be developed in the obtained alkali aqueous solution was 75% and the viscosity was 12500 mPa · s.

Comparative Example  1-1: Preparation of Resin Composition 2-1

(KCC, SR90-B3T4, solid content = 65%, acid value = 57, weight average molecular weight = 7,300) containing an unsaturated double bond and a carboxyl group in a mixing tank equipped with a stirrer and a thermosetting component of bisphenol A type , YD-012, softening point = 80 占 폚, equivalent weight: 650) were charged and stirred at 500 rpm for 10 minutes. After stirring, 10 g of an aliphatic reactive diluent (M600, 6-functional) and 30 g of a photoinitiator were added thereto. Subsequently, 2 g of a yellow colorant and 6 g of a blue colorant were added thereto, followed by stirring at 500 rpm for 10 minutes. When the stirring was completed, 250 g of the filler was divided into three to six times. When the addition was completed, the mixture was stirred at 700 rpm for 20 minutes at high speed. At this time, the internal temperature was prevented from exceeding 45 ° C due to the heat generated by the high-speed agitation. When stirring was completed, the mixture was dispersed with a 3-roll mill. After completion of the dispersion, the level of the particle size was checked, and dispersion was repeated when the particle size was 10 μm or more. The solid content of the photo-curable thermosetting resin composition that can be developed in the alkali aqueous solution thus obtained was 74% and the viscosity was 14,000 mPa · s.

Comparative Example  1-2: Preparation of Resin Composition 2-2

(KCC, SR90-B3T4, solid content = 65%, acid value = 57, weight average molecular weight = 7,300) containing an unsaturated double bond and a carboxyl group in a mixing tank equipped with a stirrer and a thermosetting component of bisphenol A type , YD-012, softening point = 80 占 폚, equivalent weight: 650) were charged and stirred at 500 rpm for 10 minutes. After stirring, 10 g of an aliphatic reactive diluent (M300, trifunctional) and 30 g of a photoinitiator were added, followed by 2 g of a yellow colorant and 6 g of a blue colorant, followed by stirring at 500 rpm for 10 minutes. When the stirring was completed, 250 g of the filler was divided into three to six times. When the addition was completed, the mixture was stirred at 700 rpm for 20 minutes at high speed. At this time, the internal temperature was prevented from exceeding 45 ° C due to the heat generated by the high-speed agitation. When stirring was completed, the mixture was dispersed with a 3-roll mill. After completion of the dispersion, the level of the particle size was checked, and dispersion was repeated when the particle size was 10 μm or more. The solid content of the photo-curable thermosetting resin composition that can be developed in the alkali aqueous solution thus obtained was 75% and the viscosity was 13,500 mPa · s.

Comparative Example  1-3: Preparation of Resin Composition 2-3

(KCC, SR90-B3T4, solid content = 65%, acid value = 57, weight average molecular weight = 7,300) containing an unsaturated double bond and a carboxyl group in a mixing tank equipped with a stirrer and a thermosetting component of bisphenol A type , YD-012, softening point = 80 占 폚, equivalent weight: 650) were charged and stirred at 500 rpm for 10 minutes. After stirring, 10 g of an aliphatic reactive diluent (M340, trifunctional) and 30 g of a photoinitiator were added, followed by 2 g of a yellow colorant and 6 g of a blue colorant, followed by stirring at 500 rpm for 10 minutes. When the stirring was completed, 250 g of the filler was divided into three to six times. When the addition was completed, the mixture was stirred at 700 rpm for 20 minutes at high speed. At this time, the internal temperature was prevented from exceeding 45 ° C due to the heat generated by the high-speed agitation. When stirring was completed, the mixture was dispersed with a 3-roll mill. After completion of the dispersion, the level of the particle size was checked, and dispersion was repeated when the particle size was 10 μm or more. The solid content of the photo-curable thermosetting resin composition that can be developed in the alkali aqueous solution thus obtained was 74% and the viscosity was 13,500 mPa · s.

Experimental Example  One:

The glass transition temperature was measured using dynamic mechanical analysis (DMA) based on the standard JPCA standard of the photocurable thermosetting resin composition prepared in the above Examples and Comparative Examples, and the adhesive force was also evaluated through a cross-cutting method. The evaluation results are shown in Table 1 below.

The degree of dispersion of the produced photo-curable thermosetting resin composition was 10 mu m or less as a result of evaluation with a grindmeter.

The glass transition temperature and adhesion test result of the composition Raw material name Example  1-1 Example  1-2 Example  1-3 Comparative Example  1-1 Comparative Example  1-2 Comparative Example  1-3 Glass transition temperature 134 ℃ 141 ℃ 128 ° C 126 ℃ 125 ℃ 127 ℃ Adhesion 100/100 100/100 100/100 71/100 70/100 69/100

As can be seen in Table 2, the compositions of Examples 1-1, 1-2, and 1-3, in which a reactive diluent having an aromatic ring and having an unsaturated double bond and a functional group capable of hydrogen bonding with a substrate were applied, It can be seen that the glass transition temperature is relatively high as compared with the compositions of Comparative Examples 1-1, 1-2 and 1-3 in which a reactive diluent having a ring and an unsaturated double bond is applied. The compositions of Comparative Examples 1-1, 1-2, and 1-3, which do not contain a reactive diluent having an aromatic ring and having a functional group capable of forming an unsaturated double bond and a hydrogen bond with the substrate even though they have similar glass transition temperatures, It shows a remarkable decrease in adhesion in a harsh environment in which high temperature or high pressure such as solder or PCT is required. Such a low glass transition temperature and a poor adhesion force are undesirable because they impair reliability. Therefore, in order to obtain an excellent adhesion while obtaining a cured film having excellent heat resistance, it is necessary to introduce a reactive diluent having both an aromatic ring, a fluorinated double bond, and a functional group capable of hydrogen bonding with the substrate. The glass transition temperature or the viscosity of the solder resist shows a slight difference depending on the type of aromatic ring or the number of functional groups generated by the ring-opening reaction in the reactive diluent having an aromatic ring and having an unsaturated double bond and a base and hydrogen bonding .

Experimental Example  2: Characteristic evaluation

After the surface of the circuit pattern substrate was subjected to washing with water and drying, the photocurable thermosetting resin compositions prepared in Examples and Comparative Examples were coated by a screen printing method and dried at 80 ° C for 30 minutes. An exposure apparatus equipped with a high-pressure mercury lamp was used as an exposure apparatus for the exposure process after the drying, and a 41-step tablet (manufacturer: Hitachi Chemical) was used for sensitivity evaluation. The exposure process was performed as described above, and developed for 90 seconds in 30% aqueous 1% sodium carbonate solution. Optimum exposure conditions were selected based on the sensitivity of the step tablet (sensitivity = 6).

When the photo-curable thermosetting resin compositions of the above Examples and Comparative Examples were applied on a substrate by screen printing, the film thickness after drying was about 25 mu m.

(1) Evaluation of developing margin

The photocurable thermosetting resin compositions of the above Examples and Comparative Examples were applied on a substrate by screen printing, dried at 80 DEG C, taken out at intervals of 10 minutes from 30 minutes to 100 minutes, and cooled at room temperature. Thereafter, the resultant was developed with a 1% aqueous solution of sodium carbonate at 30 DEG C for 90 seconds, and the maximum allowable drying time at which no residue remained was defined as a developing margin.

(2) whether TACKY

The photocurable thermosetting resin compositions of the above Examples and Comparative Examples were applied on a substrate by screen printing, dried at 80 DEG C for 30 minutes, and cooled at room temperature. When a pattern mask film made of a polyester material was pressed on this substrate for 1 minute and the pattern mask film was peeled off, the film was evaluated for TACKY on the basis of the following criteria.

○: No transfer when peeling off the film

△: When the film is peeled, there is a part of the transfer, and a fine force is required when peeling off

X: When the film is peeled, there is a transfer, and force is required when peeling off

(3) Resolution

The photocurable thermosetting resin compositions of the above Examples and Comparative Examples were applied on a substrate by screen printing, dried at 80 DEG C for 30 minutes, and cooled at room temperature. The pattern mask film was pressed on the substrate, exposed at 600 mJ / cm ² through an exposure device equipped with a high-pressure mercury lamp, developed with a 30% aqueous 1% sodium carbonate solution for 90 seconds, and washed with water to form a pattern. The spacing between the formed patterns was measured and called the resolution.

(4) Solder heat resistance

The photocurable thermosetting resin compositions of the above Examples and Comparative Examples were applied on a substrate by screen printing, dried at 80 DEG C for 30 minutes, and cooled at room temperature. After exposure of this substrate to 600mJ / cm ² through an exposure machine with a high pressure mercury lamp was exposed to the further 1100mJ / cm ^2. Thereafter, the mixture was heated at 150 DEG C for 60 minutes to complete the final curing. The thus obtained substrate was immersed in a solder bath set at 260 DEG C for 10 seconds. The immersion step was repeated three times. At this time, visual appearance change and peeling of the solder resist layer were visually evaluated. The criteria are as follows.

○: No external change and no peeling

DELTA: Micro-contour change and micro-exfoliation

X: Existence of appearance change and existence of film peeling

(5) PCT (Pressure Cooker Test)

The substrate prepared through the above process was treated under the conditions of a temperature of 121 占 폚, a humidity of 100%, a pressure of 2 atm and 168 hours by using a PCT equipment (manufacturer: Ileatech, model name: PCT-80) Respectively. The criteria are as follows.

○: No external change, no discoloration and no elution

DELTA: Microstructure change and some discoloration and elution

X: Excessive change in appearance and excessive discoloration and elution

(6) HAST  (Highly Accelerated Stress Test)

An evaluation substrate was prepared on the BT substrate on which the electrode (line space 30 mu m) was formed according to the above-described process. A voltage of 5 V was applied to the substrate under conditions of high temperature and high humidity at a temperature of 130 DEG C and a humidity of 85%, and HAST evaluation was performed for 168 hours. After 168 hours, the insulation resistance was evaluated by the following criteria.

○: more than 10 ⁸ Ω

Δ: 10 ⁶ to 10 ⁸ Ω

X: Less than 10 ⁶ Ω

The evaluation results of the properties of the photocurable thermosetting resin compositions prepared in Examples and Comparative Examples are summarized in Table 2 below.

Photocurable  Evaluation results of the characteristics of the thermosetting resin composition - Liquid type Evaluation items Example  1-1 Example  1-2 Example  1-3 Comparative Example  1-1 Comparative Example  1-2 Comparative Example  1-3 Developing margin 90 minutes 90 minutes 90 minutes 90 minutes 90 minutes 90 minutes Sensitivity 7th stage 8 stage 6 stages 6 stages 6 stages 6 stages Resolution 71 탆 68 탆 75 m 78 탆 78 탆 77 탆 Whether Tacky ○ ○ ○ ○ ○ ○ Solder heat resistance ○ ○ ○ △ △ △ PCT ○ ○ △ X X X HAST ○ ○ △ X X X

Example  2: Preparation of dry film

Each of the photo-curable thermosetting compositions prepared in the above Examples and Comparative Examples was diluted with methyl ethyl ketone and then applied onto a PET film made of a polyester material and dried at 80 캜 for 30 minutes to form a solder resist layer having a thickness of 25 탆 . Further, a cover film was laminated thereon to complete the dry film production.

Experimental Example  3: Characterization of dry film

The cover film was peeled off from the dry film prepared in the above Examples and Comparative Examples, and the film was laminated on the substrate. Then, the film was exposed at 600 mJ / cm ² through an exposure device equipped with a high pressure mercury lamp as in the process described in Experimental Example 2 And further exposed at 1100 mJ / cm ² . Thereafter, the mixture was heated at 150 DEG C for 60 minutes to complete the final curing. The substrate thus obtained was evaluated for its characteristics according to the characteristic evaluation method described in Experimental Example 2 above. The results are shown in Table 3 below.

Photocurable  Evaluation results of the properties of the thermosetting resin composition - Film type Evaluation items Example  1-1 Example  1-2 Example  1-3 Comparative Example  1-1 Comparative Example  1-2 Comparative Example  1-3 Developing margin 90 minutes 90 minutes 90 minutes 90 minutes 90 minutes 90 minutes Sensitivity 7th stage 8 stage 6 stages 6 stages 6 stages 6 stages Resolution 69 탆 65 탆 72 탆 75 m 76 탆 74 탆 Whether Tacky ○ ○ ○ ○ ○ ○ Solder heat resistance ○ ○ ○ △ △ △ PCT ○ ○ △ X X X HAST ○ ○ △ X X X

As can be seen from Tables 2 and 3, the photocurable thermosetting resin composition of the present invention can be produced by applying a reactive diluent having an aromatic ring and an unsaturated double bond and a functional group capable of hydrogen bonding with the substrate, And glass transition temperature, but the heat resistance was improved by increasing the glass transition temperature.

In addition, due to the functional group capable of hydrogen bonding with the substrate, the adhesive exhibits excellent adhesion even though the curing density is increased, and problems such as delamination can be solved. As a result, excellent reliability was exhibited even under severe conditions such as high temperature and high pressure, and problems such as film damage and film peeling were suppressed in the semiconductor manufacturing process.

As a result, it has been confirmed that the defects such as deterioration of the coating film are improved in the manufacturing process in which the reliability such as the PCT resistance and the HAST resistance is high and the high temperature is required. It has been confirmed that this is useful as a photo-curable thermosetting resin composition having the PCT resistance, heat resistance, HAST resistance and further a high glass transition temperature which are indispensably required for a solder resist for a semiconductor package.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Do. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the actual scope of the invention is defined by the appended claims and their equivalents.

Claims (7)

1. A photocurable thermosetting resin composition comprising a heat-resistant resin containing an unsaturated double bond and a carboxyl group, a photoinitiator, a thermosetting component, and a reactive diluent having an aromatic ring, an unsaturated double bond, and a functional group capable of hydrogen bonding. The photocurable thermosetting resin composition according to claim 1, wherein the reactive diluent is produced by a ring-opening reaction between an epoxy compound having an aromatic ring and a compound having an unsaturated double bond. The photocurable thermosetting resin composition according to claim 2, wherein the epoxy compound having an aromatic ring is a bisphenol A compound having an epoxy group, a bisphenol F compound, a phenol novolac compound, a cresol novolak compound, or a naphthalene compound. 3. The photocurable thermosetting resin composition according to claim 2, wherein the compound having an unsaturated double bond is an acrylic derivative selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid. The photocurable thermosetting resin composition according to claim 1, wherein the functional group capable of hydrogen bonding is an amine group, a hydroxyl group or a carboxyl group. The photocurable thermosetting resin composition according to claim 1, wherein the reactive diluent comprises at least one compound selected from the group consisting of compounds represented by the following formulas (6) to (8):
[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the above formula, R represents a hydrogen atom or an alkylene group having 1 to 10 carbon atoms,
F represents an amine group, a hydroxyl group or a carboxyl group A solder resist formed from the photo-curable thermosetting resin composition according to any one of claims 1 to 6.