JPWO2012141124A1 - Curable resin composition, cured product thereof and printed wiring board using the same - Google Patents

Abstract

In order to achieve a good balance between flexibility and high reflectivity at a high level and to form a white cured film on a printed wiring board or the like with little decrease in reflectivity over time, the curable resin composition comprises (A) Carboxyl group-containing urethane resin obtained by using a compound having an isocyanate group which is not aromatic, (B) a carboxyl group-containing resin having no aromatic ring and (C) titanium oxide, and heating or irradiation with active energy rays The ratio of the carboxyl group-containing urethane resin (A) and the carboxyl group-containing resin (B) having no aromatic ring is in the range of 50 to 70:50 to 30 on a mass basis. In the case of a thermosetting resin composition, (D) a thermosetting component, and in the case of a photocurable thermosetting resin composition, (E) a monoacylphosphine oxide photopolymerization initiator alone, or Further, (F) a bisacylphosphine oxide photopolymerization initiator is contained.

Description

  The present invention relates to a curable resin composition, and more particularly to a curable resin composition capable of forming a white cured film having high flexibility and high reflectance and little decrease in reflectance over time, and more specifically, thermosetting. The present invention relates to a photocurable thermosetting resin composition that can be developed with a resin composition and a dilute alkaline aqueous solution and can form a cured film such as a solder resist having a high reflectance. The present invention also relates to a cured product of such a curable resin composition, and a printed wiring board having a cured film such as an insulating layer, a protective film, or a solder resist formed using the same.

  With recent rapid progress in semiconductor components, electronic devices tend to be smaller, lighter, higher performance, and multifunctional. Following this trend, printed wiring boards are also becoming increasingly dense and surface-mounted. In the production of high-density printed wiring boards, photo solder resist is generally employed, and dry film type photo solder resist and liquid photo solder resist have been developed. Among these, in consideration of environmental problems, an alkali developing type photosensitive composition using a dilute alkaline aqueous solution as a developing solution has become the mainstream, and several composition systems have been proposed (Patent Document 1). reference).

Conventionally, in the case of a thin-film printed board represented by a flexible wiring board (hereinafter abbreviated as FPC), it is desired to be flexible and excellent in folding resistance.
In recent years, printed wiring boards have applications that are directly mounted on light emitting diodes (LEDs) that emit light at low power, such as backlights for liquid crystal displays of portable terminals, personal computers, televisions, etc., and light sources of lighting fixtures. Increasing (see, for example, Patent Document 2). In that case, the insulating film that is formed on the printed wiring board as a solder resist film or protective film, in addition to the properties usually required for the solder resist film, such as solvent resistance, hardness, solder heat resistance, electrical insulation, etc. It is desirable that the light reflectance is excellent so that the light emission of the LED can be used effectively. That is, in order to efficiently use the light of the LED, there is a demand for a printed wiring board having a solder resist film that has high reflectivity and can increase the illuminance as a whole when the LED is mounted on the printed wiring board. .

  In order to efficiently use the light of the LED directly mounted on the printed wiring board, the solder resist film has a high reflectance as described above, and at the same time, this high reflectance is used over a period in which the LED is used as a light source. Need to keep. However, the conventionally used white solder resist composition includes a component having an aromatic ring as one means for improving heat resistance, and the aromatic ring has a property of gradually reacting with light or heat. For this reason, there is a problem in that the resin oxidizes and turns yellow due to light emitted from the LED and heat history due to heat generation, and the reflectance decreases with time.

In order to solve such a problem, Japanese Patent Application Laid-Open No. 2009-149878 (Patent Document 3) discloses (A) a rutile type titanium oxide produced by a chlorine method, and (B) a white cured material containing a curable resin. Resin compositions have been proposed.
When rutile type titanium oxide produced by the chlorine method is used as proposed above, it has almost no photoactivity, so the deterioration (yellowing) of the resin due to light caused by the photoactivity of titanium oxide is suppressed. And exhibits excellent stability to light. However, rutile titanium oxide is inferior in whiteness compared to anatase titanium oxide, which is the same titanium oxide, so when blended in a large amount to increase reflectivity, it balances flexibility and high reflectivity at a high level. There is a problem that it is difficult to achieve well.

  Furthermore, some white photocurable thermosetting solder resist compositions formulated by combining a carboxyl group-containing resin having no aromatic ring and rutile titanium oxide have been proposed (for example, Patent Documents 4 to 6). reference). However, since the carboxyl group-containing resin having no aromatic ring is generally inferior in flexibility, there is a problem that it is difficult to achieve a good balance between flexibility and high reflectance at a high level.

JP 61-243869 JP 2007-249148 A JP 2009-149878 A Japanese Patent No. 4538521 Japanese Patent No. 4538484 Japanese Patent No. 4340272

The present invention has been made to solve the above-mentioned problems of the prior art, and its main purpose is to achieve a high level of flexibility and high reflectivity in a well-balanced manner, and to achieve light degradation and thermal degradation. Providing curable resin compositions such as thermosetting resin compositions and photo-curable thermosetting resin compositions that can form a white cured film that is difficult to receive and has little decrease in reflectance over time (hereinafter referred to as low rate of change). There is to do.
Furthermore, the object of the present invention is to provide a white cured film having a high reflectance, a low change rate and excellent flexibility, and a cured film having such excellent characteristics by using such a curable resin composition. It is to provide a printed wiring board.

  In order to achieve the above object, according to the present invention, (A) a carboxyl group-containing urethane resin obtained by using a compound having an isocyanate group that is not aromatic, (B) a carboxyl group containing no aromatic ring A resin, and (C) a composition containing titanium oxide and cured by at least one of heating and active energy ray irradiation, the carboxyl group-containing urethane resin (A) and a carboxyl group containing no aromatic ring A curable resin composition is provided in which the ratio of the resin (B) is in the range of 50 to 70:50 to 30 on a mass basis.

  According to one embodiment of the present invention, (A) a carboxyl group-containing urethane resin obtained using a compound having an isocyanate group that is not aromatic, (B) a carboxyl group-containing resin having no aromatic ring, (C ) A composition containing titanium oxide and (D) a thermosetting component, wherein the ratio of the carboxyl group-containing urethane resin (A) and the carboxyl group-containing resin (B) having no aromatic ring is on a mass basis. A thermosetting resin composition characterized by being in the range of 50 to 70:50 to 30 is provided.

Moreover, according to this invention, the hardened | cured material obtained by apply | coating the said thermosetting resin composition on a base material and making it harden | cure is provided.
Furthermore, according to this invention, the printed wiring board which has an insulating layer or protective film which consists of this hardened | cured material is also provided.

According to another aspect of the present invention, (A) a carboxyl group-containing urethane resin obtained by using a compound having an isocyanate group that is not aromatic, (B) a carboxyl group-containing resin having no aromatic ring, (C ) A composition containing titanium oxide and (E) a monoacylphosphine oxide photopolymerization initiator, wherein the carboxyl group-containing urethane resin (A) and the carboxyl group-containing resin (B) having no aromatic ring A photocurable thermosetting resin composition is provided in which the ratio is in the range of 50 to 70:50 to 30 on a mass basis.
In the suitable aspect of the said photocurable thermosetting resin composition, the carboxyl group containing resin (B) which does not have the said aromatic ring is a carboxyl group containing (meth) acrylic-type copolymer resin, and in 1 molecule. It is a carboxyl group-containing copolymer resin obtained by a reaction between an oxirane ring and a compound having an ethylenically unsaturated group. Moreover, in another suitable aspect, (F) bisacyl phosphine oxide type photoinitiator and a thermosetting component (D) are contained further.

Moreover, according to this invention, the hardened | cured material obtained by photocuring the said photocurable thermosetting resin composition or thermosetting as needed is provided.
Furthermore, according to the present invention, there is also provided a printed wiring board having a cured film obtained by photocuring the photocurable thermosetting resin composition in a pattern and then thermosetting.

  The curable resin composition of the present invention comprises at least two kinds of carboxyl group-containing resins, that is, (A) a carboxyl group-containing urethane resin obtained by using a compound having an isocyanate group that is not aromatic, and (B) an aroma. Carboxy group-containing resin having no ring, (C) titanium oxide, or (D) thermosetting component or photopolymerization initiator alone, (E) monoacylphosphine oxide photopolymerization initiator alone, Or (E) a composition containing a monoacylphosphine oxide photopolymerization initiator and (F) a bisacylphosphine oxide photopolymerization initiator, which comprises the carboxyl group-containing urethane resin (A) and an aromatic ring. Since the ratio of the carboxyl group-containing resin (B) not present is in the range of 50 to 70:50 to 30 on a mass basis, both are aromatic rings Because it does not, flexibility and high reflectance can be achieved at a high level in a well-balanced manner, and it is less susceptible to light degradation and thermal degradation, has little decrease in reflectance over time, and achieves high reflectance over a long period of time. A white cured film can be formed.

  Therefore, by using the curable resin composition of the present invention, it is possible to form a cured film having a high reflectance, a low rate of change, and excellent flexibility. Protective films and insulating layers such as solder resists and interlayer insulation films used in the manufacture of tapes and tape carrier packages, or back electrodes of electroluminescent panels used in liquid crystal display backlights and information display displays It can be advantageously used for a protective film for a display, a protective film for a display panel of a mobile phone, a watch, a car stereo, etc., an IC or a VLSI sealing material.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have (A) a carboxyl group-containing urethane resin obtained by using a compound having an isocyanate group that is not aromatic, and (B) having an aromatic ring. In the curable resin composition containing at least two kinds of carboxyl group-containing resins, and (C) titanium oxide, and cured by at least one of heating or irradiation with active energy rays, the carboxyl group-containing urethane By setting the ratio of the resin (A) and the carboxyl group-containing resin (B) having no aromatic ring in the range of 50 to 70:50 to 30 on a mass basis, the flexibility and the high reflectance are balanced at a high level. It can be achieved well, can suppress light deterioration and thermal deterioration, and can form a white cured film with little decrease in reflectance over time. Out, which has led to the completion of the present invention.

According to the study by the present inventors, a carboxyl group-containing urethane resin (A) obtained by using a compound having an isocyanate group which is not aromatic but is effective for both high reflectance and low change rate. Is excellent in flexibility but inferior in solder heat resistance, etc. On the other hand, the carboxyl group-containing resin (B) having no aromatic ring is inferior in flexibility but effective in solder heat resistance, etc. By using two kinds of carboxyl group-containing resins at an appropriate ratio, and in the case of a photocurable thermosetting resin composition, a monoacylphosphine oxide photopolymerization initiator (E) is used alone as a photopolymerization initiator. Or in combination with the bisacylphosphine oxide-based photopolymerization initiator (F), the composition containing titanium oxide (C) as a white pigment also has a high reflectance (X Z color system of Y value: 80 or more), low change rate difference from the initial value even after accelerated deterioration is small (Delta] E * ^ab: while having a 3.0 or less), white cured film excellent in flexibility It was found that can be formed.
Hereinafter, each component of the curable resin composition of the present invention will be described in detail.

  As the carboxyl group-containing urethane resin (A) obtained by using a compound having an isocyanate group that is not aromatic, preferably (a) a compound having an isocyanate group that is not aromatic, and (b) in one molecule And a carboxyl group-containing urethane resin obtained by reacting a compound having two or more alcoholic hydroxyl groups with (c) a compound having one alcoholic hydroxyl group in one molecule. In the curable resin composition containing such a carboxyl group-containing urethane resin together with a thermosetting compound, the carboxyl group causes a crosslinking reaction with a functional group of the thermosetting compound, for example, an epoxy group of an epoxy resin, during thermosetting. The characteristics such as solder heat resistance can be improved. Generally, the lower the crosslink density of the resin, the greater the flexibility of the film formed, and the less the film warps after thermosetting. However, when the crosslink density is lowered, characteristics such as solder heat resistance, plating resistance, chemical resistance and the like of the obtained film are likely to be lowered. On the other hand, by using a carboxyl group-containing urethane resin obtained by using a compound having an isocyanate group that is not aromatic, the crystallinity of the urethane resin can be lowered, and as a result, warpage and folding resistance can be reduced. It is possible to use high-performance high glass transition point (Tg) epoxy resins and polyfunctional epoxies that have been difficult to use for the required solder resists for flexible substrates, while maintaining low warpage. It is possible to improve characteristics such as solder heat resistance.

  In addition, when the compound (c) having one alcoholic hydroxyl group in one molecule further has one or more phenolic hydroxyl groups, a urethane resin having a phenolic hydroxyl group at the molecular end is obtained. This urethane resin having a phenolic hydroxyl group at the molecular end causes a crosslinking reaction with the functional group of the thermosetting compound, for example, the epoxy group of the epoxy resin, at the time of thermosetting, and further heat resistance of the solder, etc. The characteristics of can be improved.

  The carboxyl group-containing urethane resin functions as a compound (a) having an isocyanate group that is not aromatic, a compound (b) having two or more alcoholic hydroxyl groups in one molecule, and a reaction terminator. It is preferably a urethane resin having a phenolic hydroxyl group introduced at the terminal by a reaction with the compound (c) having one alcoholic hydroxyl group and one or more phenolic hydroxyl groups in one molecule. In addition to this, the compound (a) having a non-aromatic isocyanate group and a compound (b) having two or more alcoholic hydroxyl groups in one molecule are obtained as the compound (b). Molecules using a compound having a phenolic hydroxyl group and two or more alcoholic hydroxyl groups Urethane resin with a phenolic hydroxyl group introduced into the chain, or a urethane resin with a carboxyl group introduced into the molecular side chain using a compound having a carboxyl group and two or more alcoholic hydroxyl groups in one molecule. Can do. In the latter urethane resin, the compound (c) having one alcoholic hydroxyl group and one or more phenolic hydroxyl groups in one molecule can be used as a terminal blocking agent (reaction terminator). , Monohydroxyl compounds such as aliphatic alcohols and monohydroxy mono (meth) acrylate compounds, monocarboxylic acids having functional groups capable of undergoing an addition reaction or condensation reaction with isocyanate groups such as alcoholic hydroxyl groups, amino groups, and thiol groups Various conventionally known reaction terminators can be used. During the synthesis of the resin, a compound having one hydroxyl group and one or more (meth) acrylic groups in the molecule such as hydroxyalkyl (meth) acrylate is added, or equimolar amounts of isophorone diisocyanate and pentaerythritol triacrylate are added. A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having one isocyanate group and one or more (meth) acrylic groups in the molecule, such as a reaction product, and terminal (meth) acrylated can also be used.

  For example, in the case of the preferred urethane resin, the urethane resin includes a compound (a) having an isocyanate group that is not aromatic, a compound (b) having two or more alcoholic hydroxyl groups in one molecule, and 1 The compound (c) having one alcoholic hydroxyl group in the molecule may be mixed and reacted, or the compound (a) having an isocyanate group that is not aromatic and two or more in one molecule May be reacted with the compound (b) having an alcoholic hydroxyl group, and then the compound (c) having one alcoholic hydroxyl group in one molecule which also functions as a reaction terminator may be reacted. In the case of the other urethane resins described above, the compound (a) having an isocyanate group which is not aromatic and the compound having a phenolic hydroxyl group and / or a carboxyl group and two or more alcoholic hydroxyl groups in one molecule (B) and the reaction terminator may be mixed and reacted together, but from the viewpoint of molecular weight adjustment, the compound (a) having an isocyanate group that is not aromatic and the compound (b) are reacted. It is preferable that the reaction stopper is subsequently reacted.

  The reaction proceeds without catalyst by stirring and mixing at room temperature to 100 ° C, but it is preferable to heat to 70 to 100 ° C in order to increase the reaction rate. The reaction ratio (molar ratio) of the components (a) to (c) is (a) :( b) = 1: 1 to 2: 1, preferably 1: 1 to 1.5: 1. A ratio of a + b) :( c) = 1: 0.01 to 0.5, preferably 1: 0.02 to 0.3 is appropriate.

  As the compound (a) having an isocyanate group that is not aromatic, any conventionally known compound having an isocyanate group that is not aromatic can be used, and is not limited to a specific compound. Specific examples of the compound (a) having an isocyanate group that is not aromatic include, for example, aliphatic diisocyanates such as hexamethylene diisocyanate, branched aliphatic diisocyanates such as trimethylhexamethylene diisocyanate, isophorone diisocyanate, (o, m, or p). )-(Hydrogenated) xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate and the like. Among these, hexamethylene diisocyanate which is an aliphatic diisocyanate and trimethylhexamethylene diisocyanate which is a branched aliphatic diisocyanate are preferable. These compounds having an isocyanate group that is not aromatic can be used alone or in admixture of two or more. When these diisocyanate compounds are used, a cured product excellent in low warpage can be obtained.

  Next, as the compound (b) having two or more alcoholic hydroxyl groups, conventionally known various polyols can be used and are not limited to specific compounds, but polycarbonate polyols such as polycarbonate diol, polyether polyols, Polyester polyol, polyolefin polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, hydrogenated isoprene polyol, phosphorus-containing diol, bisphenol A alkylene oxide adduct diol, carboxyl group and alcoholic properties A compound having a hydroxyl group, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, a phosphorus-containing polyol, or the like can be suitably used. The polycarbonate diol is derived from a polycarbonate diol (b-1) containing a repeating unit derived from one or more linear aliphatic diols as a constituent unit, derived from one or two or more alicyclic diols. Polycarbonate diol (b-2) containing a repeating unit as a constituent unit, or polycarbonate diol (b-3) containing a repeating unit derived from both a linear aliphatic diol and an alicyclic diol as a constituent unit. It is done. Further, when a compound (b-4) having a carboxyl group and two or more alcoholic hydroxyl groups, a compound (b-5) having a phenolic hydroxyl group and two or more alcoholic hydroxyl groups, and the like are used, A functional group (phenolic hydroxyl group or carboxyl group) can be imparted to the molecular side chain. When the phosphorus-containing polyol (b-6) is used, flame retardancy can be imparted to the urethane resin. These compounds (b-1) to (b-6) can be used alone or in admixture of two or more.

  Specific examples of the polycarbonate diol (b-1) containing as a constituent unit a repeating unit derived from one or more linear aliphatic diols are derived from 1,6-hexanediol, for example. Polycarbonate diol, polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol, polycarbonate diol derived from 1,4-butanediol and 1,6-hexanediol, 3-methyl-1,5 -Polycarbonate diol derived from pentanediol and 1,6-hexanediol, polycarbonate diol derived from 1,9-nonanediol and 2-methyl-1,8-octanediol, and the like.

  Specific examples of the polycarbonate diol (b-2) containing a repeating unit derived from one or more alicyclic diols as a constituent unit include, for example, a polycarbonate derived from 1,4-cyclohexanedimethanol. Diol etc. are mentioned.

  Specific examples of the polycarbonate diol (b-3) containing as a constituent unit a repeating unit derived from both a linear aliphatic diol and an alicyclic diol include 1,6-hexanediol and 1 Polycarbonate diol derived from 1,4-cyclohexanedimethanol.

  Specific examples of the compound (b-4) having a carboxyl group and two or more alcoholic hydroxyl groups include dimethylolpropionic acid and dimethylolbutanoic acid. By using a compound having these carboxyl groups and two or more alcoholic hydroxyl groups, the carboxyl groups can be easily introduced into the urethane resin.

  Specific examples of the compound (b-5) having a phenolic hydroxyl group and two or more alcoholic hydroxyl groups include 6-hydroxy-5-methyl-1,3-benzenedimethanol, 2,4-dimethyl (Hydroxymethyl) -6-cyclohexylphenol, 3,3'-methylenebis (2-hydroxy-5-methyl-benzenemethanol), 4,4 '-(1-methylethylidene) bis [2-methyl-6-hydroxymethyl Phenol], 4,4 ′-[1,4-phenylenebis (1-methylethylidene) bis [2-methyl-6-hydroxymethylphenol], 2-hydroxy-5-fluoro-1,3-benzenedimethanol, 4,4′-methylenebis (2-methyl-6-hydroxymethylphenol), 4,4′-methylenebis (2,5- Methyl-4-hydroxymethylphenol), 4,4′-cyclohexylidenebis (2-methyl-6-hydroxymethylphenol), 4,4′-cyclohexylidenebis (2-cyclohexyl-6-hydroxymethylphenol) 2,6-bis [(2-hydroxy-3-hydroxymethyl-5-methylphenyl) methyl] -4-methylphenol, 2-hydroxy-5-ethyl-1,3-benzenedimethanol, 2-hydroxy- 4,5-dimethyl-1,3-benzenedimethanol, 2-hydroxy-5- (1-methylpropyl) -1,3-benzenedimethanol, 4- (1,1-dimethylethyl) -2-hydroxy- 1,3-benzenedimethanol, 2-hydroxy-5-cyclohexyl-1,3-benzenedimethanol, 2-hydride Xyl-5- (1,1,3,3-tetramethylbutyl) -1,3-benzenedimethanol, 2,6-bis [(4-hydroxy-3-hydroxymethyl-2,5-dimethylphenyl) methyl ] -3,4-dimethylphenol, 2,6-bis [(4-hydroxy-3-hydroxymethyl-2,5-dimethylphenyl) methyl] -4-cyclohexylphenol, 2-hydroxy-1,3,5- Benzene trimethanol, 3,5-dimethyl-2,4,6-trihydroxymethylphenol, 4,4 ′, 4 ″ -ethylidinetris (2-methyl-6-hydroxymethylphenol), 2,3,5 Examples include 6-tetra (hydroxymethyl) -1,4-benzenediol and 4,4′-methylenebis [2,6-bis (hydroxymethyl) phenol]. By using a compound having these phenolic hydroxyl group and alcoholic hydroxyl group, the phenolic hydroxyl group can be easily introduced into the urethane resin.

  A polycarbonate diol containing a repeating unit derived from the linear aliphatic diol as a constituent unit tends to be excellent in low warpage and flexibility. Moreover, the polycarbonate diol which contains the repeating unit derived from an alicyclic diol as a structural unit exists in the tendency which is excellent in tin plating resistance and solder heat resistance. From the above viewpoints, these polycarbonate diols may be used in combination of two or more, or a polycarbonate diol containing a repeating unit derived from both a linear aliphatic diol and an alicyclic diol as a constituent unit may be used. it can. In order to achieve a good balance between low warpage and flexibility, solder heat resistance and tin plating resistance, the copolymerization ratio of the linear aliphatic diol and the alicyclic diol is 3: 7 to 7 by mass ratio. : 3 polycarbonate diol is preferably used.

  The polycarbonate diol preferably has a number average molecular weight of 200 to 5,000, but the polycarbonate diol contains a repeating unit derived from a linear aliphatic diol and an alicyclic diol as a structural unit, and a linear aliphatic diol. When the copolymerization ratio of the alicyclic diol and the alicyclic diol is from 3: 7 to 7: 3, the number average molecular weight is preferably from 400 to 2,000.

  Specific examples of the phosphorus-containing polyol include FC-450 (manufactured by ADEKA Corp.), M-Ester (manufactured by Sanko Corp.), M-Ester-HP (manufactured by Sanko Corp.), and the like. By using this phosphorus-containing polyol, a phosphorus compound can be introduced into the urethane resin, and flame retardancy can be imparted.

Next, as the compound (c) having one alcoholic hydroxyl group, various conventionally known monohydroxy compounds can be used and are not limited to specific compounds, but include methanol, ethanol, n-propanol, isopropanol, and n-butanol. , Isobutanol, sec-butanol, t-butanol, amyl alcohol, hexyl alcohol, octyl alcohol, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) ) Acrylate, caprolactone or alkylene oxide adduct of each (meth) acrylate, glycerin di (meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri ( Data) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, allyl alcohol, allyloxy ethanol, glycolic acid, and the like hydroxypivalic acid, but is not limited thereto.
In the present specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  The compound (c) having a phenolic hydroxyl group and having one alcoholic hydroxyl group in one molecule is used for the purpose of introducing a phenolic hydroxyl group into polyurethane and also functions as an end-capping agent for polyurethane. In particular, a compound having one alcoholic hydroxyl group and phenolic hydroxyl group capable of reacting with isocyanate in the molecule functions as a reaction terminator. Specific examples of such a compound (c) include, for example, hydroxymethylphenol, hydroxymethylcresol, hydroxymethyl-di-t-butylphenol, p-hydroxyphenyl-2-methanol, p-hydroxyphenyl-3-propanol, p -Hydroxyphenyl-4-butanol, hydroxyethylcresol, 2,6-dimethyl-4-hydroxymethylphenol, 2,4-dimethyl-6-hydroxymethylphenol, 2,3,6-trimethyl-4-hydroxymethylphenol, 2-cyclohexyl-4-hydroxymethyl-5-methylphenol, 4-methyl-6-hydroxymethylbenzene-1,2-diol, 4- (1,1-dimethylethyl) -6-hydroxymethylbenzene-1,2 -Hydroxy such as diol Alkylphenol or hydroxyalkylcresol; phenol having a carboxyl group-containing substituent such as hydroxybenzoic acid, hydroxyphenylbenzoic acid, or hydroxyphenoxybenzoic acid, and ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene Examples thereof include, but are not limited to, esterified products with glycol and the like; monoethylene oxide adducts of bisphenol, monopropylene oxide adducts of bisphenol, p-hydroxyphenethyl alcohol, and the like. These compounds (c) can be used alone or in admixture of two or more.

The carboxyl group-containing urethane resin (A) obtained using a compound having an isocyanate group that is not aromatic as described above can be used alone or in combination of two or more.
Moreover, it is preferable that the weight average molecular weights of the said carboxyl group-containing urethane resin (A) are 500-100,000, and 8,000-50,000 are further more preferable. Here, the weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography. If the weight average molecular weight of the carboxyl group-containing urethane resin (A) is less than 500, the elongation, flexibility and strength of the cured film may be impaired. On the other hand, if it exceeds 100,000, the solubility in a solvent is low. In addition, since the viscosity becomes too high even if it is dissolved, restrictions on use are increased.

The carboxyl group-containing resin (B) having no aromatic ring is a photosensitive resin having one or more photosensitive unsaturated double bonds in itself as long as the resin has a carboxyl group not having an aromatic ring. Any of a carboxyl group-containing resin and a carboxyl group-containing resin having no photosensitive unsaturated double bond can be used, and the resin is not limited to a specific one. In particular, among the resins listed below, those having no aromatic ring (any of oligomers or polymers) can be suitably used. That is,
(1) Coordination of an aliphatic unsaturated carboxylic acid and an aliphatic polymerizable monomer having 2 to 20 carbon atoms (specifically, an aliphatic (meth) acryloyl compound, an aliphatic vinyl ether, a fatty acid vinyl ester, etc.) Carboxyl group-containing resin obtained by polymerization,
(2) A carboxyl group-containing (meth) acrylic copolymer resin produced from an aliphatic polymerizable monomer having 2 to 20 carbon atoms, and 4 to 20 carbon atoms having an oxirane ring and an ethylenically unsaturated group in one molecule. A photosensitive carboxyl group-containing resin obtained by reaction with an aliphatic polymerizable monomer of
(3) An aliphatic polymerizable monomer having 4 to 20 carbon atoms (for example, glycidyl (meth) acrylate) having one epoxy group and an unsaturated double bond in each molecule, and an unsaturated double bond The copolymer with an aliphatic polymerizable monomer having 2 to 20 carbon atoms (specifically, an aliphatic (meth) acryloyl compound, an aliphatic vinyl ether, a vinyl ester of a fatty acid, etc.) includes an aliphatic group. A photosensitive carboxyl group-containing resin obtained by reacting a saturated monocarboxylic acid and reacting the produced secondary hydroxyl group with a saturated or unsaturated aliphatic polybasic acid anhydride,
(4) After reacting an aliphatic hydroxyl group-containing polymer with a saturated or unsaturated aliphatic polybasic acid anhydride, the resulting carboxylic acid has one epoxy group and one unsaturated double bond in each molecule. It is a photosensitive hydroxyl group- and carboxyl group-containing resin obtained by reacting an aliphatic polymerizable monomer having 4 to 20 carbon atoms (such as glycidyl (meth) acrylate).
In the present specification, the term “aliphatic” includes a compound containing a cyclo ring such as a cyclohexane ring or a cyclohexene ring in the molecule.

  Among these, (a) a carboxyl group-containing (meth) acrylic copolymer resin produced from an aliphatic polymerizable monomer having 2 to 20 carbon atoms, which is the photosensitive carboxyl group-containing resin of (2) above, (B) A photosensitive carboxyl group-containing resin obtained by a reaction between an oxirane ring and an ethylenically unsaturated group-containing aliphatic polymerizable monomer having 4 to 20 carbon atoms in one molecule is preferable.

  The carboxyl group-containing (meth) acrylic copolymer resin produced from the (a) aliphatic polymerizable monomer having 2 to 20 carbon atoms is composed of a (meth) acrylic acid ester having 4 to 20 carbon atoms and one molecule. And an aliphatic compound having one unsaturated group and at least one carboxyl group. Examples of the (meth) acrylic acid ester constituting the copolymer resin (a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl ( Hydroxyl groups such as (meth) acrylic acid alkyl esters such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate Containing (meth) acrylic acid esters, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, methoxy Triethylene glycol (meth) acrylate, glycol-modified (meth) acrylates such as methoxy polyethylene glycol (meth) acrylate. These may be used alone or in combination of two or more.

  Examples of the aliphatic compound having one unsaturated group and at least one carboxyl group in one molecule include acrylic acid, methacrylic acid, and a modified unsaturated monocarboxylic acid having a chain extended between the unsaturated group and the carboxylic acid. Carboxylic acid, for example, β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, unsaturated monocarboxylic acid having an ester bond due to lactone modification, etc., modification having an ether bond Examples thereof include unsaturated monocarboxylic acids and those containing two or more carboxyl groups in the molecule such as maleic acid. These may be used alone or in combination of two or more.

  Examples of the aliphatic polymerizable monomer having 4 to 20 carbon atoms having an oxirane ring and an ethylenically unsaturated group in one molecule of (b) include glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylbutyl (meth) acrylate, 3,4-epoxycyclohexylmethylamino acrylate, etc. it can. Among these, 3,4-epoxycyclohexylmethyl (meth) acrylate is preferable. These (b) C4-C20 aliphatic polymerizable monomers having an oxirane ring and an ethylenically unsaturated group in one molecule may be used alone or in admixture of two or more.

The carboxyl group-containing resin (B) having no aromatic ring as described above can be used alone or in combination of two or more.
Moreover, it is preferable that the weight average molecular weight of carboxyl group-containing resin (B) which does not have the said aromatic ring exists in the range of 5,000-100,000. When the weight average molecular weight is less than 5,000, the elongation, flexibility, and strength of the cured film may be impaired. On the other hand, when it exceeds 100,000, the solubility in a solvent is lowered and the cured film may be dissolved. Since the viscosity becomes too high, restrictions on use are increased.

Both the carboxyl group-containing urethane resin (A) and the carboxyl group-containing resin (B) having no aromatic ring preferably have an acid value in the range of 10 to 200 mgKOH / g, more preferably 20 to 100 mgKOH / g. preferable. When the acid value is less than 10 mgKOH / g, the reactivity with the thermosetting component is lowered, and the heat resistance may be impaired. On the other hand, when the acid value exceeds 200 mgKOH / g, the resist properties such as alkali resistance and electrical properties of the cured film may be deteriorated. The acid value of the resin is a value measured according to JIS K5407.
The blending amount (total amount) of the carboxyl group-containing urethane resin (A) and the carboxyl group-containing resin (B) having no aromatic ring as described above is 50 wt% or less, preferably 10 to 40 wt% of the total amount of the composition. A range of% is suitable.

  In the curable resin composition of the present invention, titanium oxide (C) is used to whiten the cured film. Examples of titanium oxide (C) include those manufactured by sulfuric acid method and chlorine method, titanium oxide that has been surface-treated with rutile-type titanium oxide, anatase-type titanium oxide, or hydrous metal oxide, or surface-treated with organic compounds. Can be used. Among these titanium oxides, rutile type titanium oxide is preferable. Anatase-type titanium oxide is often used because of its high whiteness compared to the rutile type. However, since anatase type titanium oxide has photocatalytic activity, it may cause discoloration of the resin in the curable resin composition. In contrast, rutile titanium oxide has a slightly lower whiteness than the anatase type, but has almost no photoactivity, so that a stable solder resist film can be obtained. As a rutile type titanium oxide, a well-known rutile type thing can be used. Specifically, TR-600, TR-700, TR-750, TR-840 manufactured by Fuji Titanium Industry Co., Ltd., R-550, R-580, R-630, R-820 manufactured by Ishihara Sangyo Co., Ltd., CR-50, CR-60, CR-90, CR-97, KR-270, KR-310, KR-380 manufactured by Titanium Industry Co., Ltd. can be used. Among these rutile titanium oxides, it is particularly preferable to use titanium oxide whose surface is treated with hydrous alumina or aluminum hydroxide from the viewpoint of dispersibility in the composition, storage stability, and flame retardancy.

  The compounding amount of these titanium oxides (C) ranges from 50 to 300 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (B) and the carboxyl group-containing resin (B) having no aromatic ring. Is preferably 100 to 250 parts by mass, more preferably 150 to 200 parts by mass. When the blending amount of titanium oxide is less than 50 parts by mass, it is difficult to form a good white cured film. On the other hand, when the compounding amount of titanium oxide exceeds 300 parts by mass, the viscosity of the composition becomes high, application and moldability are lowered, and the cured product becomes brittle, which is not preferable.

  Examples of the thermosetting component (D) used in the thermosetting resin composition of the present invention include amine resins such as melamine resins and benzoguanamine resins, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, Known and commonly used thermosetting resins such as episulfide resins, melamine derivatives, bismaleimides, oxazine compounds, and oxazoline compounds can be used. Preferred are the carboxyl group-containing urethane resin (A) and carboxyl groups having no aromatic ring. A plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as “cyclic (thio) ether groups”) in the molecule capable of reacting with the carboxyl group (or further phenolic hydroxyl group) of the resin (B). It is a thermosetting component.

  Such a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule includes either one of a three-, four- or five-membered cyclic ether group or a cyclic thioether group or two kinds of groups in the molecule. For example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a plurality of thioether groups in the molecule In other words, an episulfide resin or the like is preferable, and a polyfunctional epoxy compound is particularly preferable.

  Specific examples of the polyfunctional epoxy compound include, for example, a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a brominated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol S type epoxy. Resin, bixylenol type epoxy resin, biphenol type epoxy resin, and the like. Examples of the trifunctional or more polyfunctional epoxy resin include novolak type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, N-glycidyl type epoxy resin. Resin, bisphenol A novolac epoxy resin, bixylenol epoxy resin, biphenol novolac epoxy resin, chelate epoxy resin, glyoxal epoxy resin, amino group-containing epoxy Resin, rubber modified epoxy resin, dicyclopentadiene phenolic type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoyl yl ethane resins, silicone-modified epoxy resins, such as ε- caprolactone-modified epoxy resin. Further, as an epoxy resin that can easily obtain a cured product having a preferable high glass transition temperature Tg, N-glycidyl type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, tetraglycidyl xylenoyl ethane resin, tetrakisphenol ethane type epoxy Resin, dicyclopentadiene phenolic epoxy resin, naphthalene skeleton-containing epoxy resin, and the like. Specifically, tetrakisphenolethane type epoxy resin GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.), dicyclopentadiene phenolic Type epoxy resin HP-7200H (manufactured by DIC Corporation), epoxy resin having naphthalene skeleton HP-4032D, EXA-7240, EXA-4700, EXA-4770 (manufactured by DIC Corporation), naphthol ESN-175 (manufactured by Nippon Steel Chemical Co., Ltd.), an aralkyl type epoxy resin, EXA-7335 (manufactured by DIC Corporation), an epoxy resin having a xanthene skeleton, and NC-3000 (Japan), a biphenol novolac epoxy resin By using these polyfunctional epoxy resins and other trifunctional and tetrafunctional epoxy resins, characteristics such as solder heat resistance can be improved. In order to impart flame retardancy, an epoxy resin in which atoms such as halogen such as chlorine and bromine and phosphorus are introduced into the structure may be used.

  Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene), cardo-type bisphenol Le ethers, calixarenes, calix resorcin arenes, such as ethers of the resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  In the thermosetting resin composition of the present invention, the thermosetting component (D) can be used alone or in combination of two or more. The blending amount is 5 to 150 parts by mass, preferably 10 to 80 parts by mass with respect to 100 parts by mass of the total amount of the carboxyl group-containing urethane resin (A) and the carboxyl group-containing resin (B) having no aromatic ring. It is desirable that If it is less than 5 parts by mass, the solder heat resistance of the cured film of the thermosetting resin composition may be insufficient. On the other hand, if it exceeds 150 parts by mass, it is used as an insulating protective film for a flexible printed circuit board (FPC). In this case, various characteristics, particularly electrical insulation, tend to deteriorate.

  In the curable resin composition of the present invention, a thermosetting catalyst can be blended in order to promote the thermosetting reaction and further improve the properties such as adhesion, chemical resistance and heat resistance. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with a thermosetting catalyst.

  These thermosetting catalysts can be used alone or in admixture of two or more, and the compounding amount thereof is sufficient at a normal quantitative ratio, for example, having the carboxyl group-containing urethane resin (A) and an aromatic ring. Preferably 0.1 to 20 parts by mass, more preferably 100 parts by mass of the carboxyl group-containing resin (B) or thermosetting component (D) having a plurality of cyclic (thio) ether groups in the molecule. 0.5 to 15.0 parts by mass.

In the photocurable thermosetting resin composition of the present invention, the monoacylphosphine oxide photopolymerization initiator (E) alone or further a bisacylphosphine oxide photopolymerization initiator is used as the photopolymerization initiator. (F) is used in combination.
Examples of the monoacylphosphine oxide photopolymerization initiator (hereinafter abbreviated as “MAPO”) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2, Examples include 6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, and pivaloylphenylphosphine acid isopropyl ester. Of these, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF Japan Ltd., trade name: Lucillin TPO) is easily available.

    Examples of the bisacylphosphine oxide photopolymerization initiator (hereinafter abbreviated as “BAPO”) include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide and bis- (2,6-dichlorobenzoyl)-. 2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5- Dimethylphenylphosphine oxide, bis- (2, , 6-trimethyl benzoyl) phenyl phosphine oxide, (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide and the like. Among these, bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF Japan Ltd., trade name: Irgacure 819) is easily available.

  The present invention is a highly reflective coating film formed using a photocurable thermosetting resin composition containing a large amount of titanium oxide by using MAPO alone or in combination with BAPO and MAPO. Can be cured by a small amount of light passing through the coating. Therefore, even if such a photocurable thermosetting resin composition and a coating film thereof are used, it is possible to form a high-definition pattern having excellent resolution.

  And the photosensitivity of the photocurable thermosetting resin composition of this invention can be finely adjusted by changing the compounding ratio of BAPO and MAPO. That is, in the cross-sectional shape of the pattern formed on the base material, when the deep curability on the base material surface side is insufficient and undercut is likely to occur, the BAPO blending ratio is increased. Further, when the surface state of the pattern is poor after development due to insufficient surface curability of the coating film, the blending ratio of MAPO is increased. The blending ratio of BAPO and MAPO is preferably 90 to 10 to 1 to 99, and more preferably 80 to 20 to 2 to 98, by mass ratio. Outside the range of this blending ratio, the effect of the combined use of BAPO and MAPO is reduced, and it is difficult to obtain the photosensitivity necessary for curing the coating film, so that it becomes impossible to form a high-definition pattern.

  The blending amount when MAPO is used alone or the total blending amount of BAPO and MAPO is 100 parts by weight of the total amount of the carboxyl group-containing urethane resin (A) and the carboxyl group-containing resin (B) having no aromatic ring. The amount is preferably 1 to 30 parts by mass, more preferably 2 to 25 parts by mass. When the blending amount when MAPO is used alone or the total blending amount of BAPO and MAPO is less than 1 part by mass, the photocurability of the coating film is lowered, and pattern formation after exposure / development becomes difficult. Also, if the blending amount when MAPO is used alone or the total blending amount of BAPO and MAPO exceeds 30 parts by mass, the color of the coating film derived from the photopolymerization initiator is increased, which further increases the cost. It is not preferable.

  In the photocurable thermosetting resin composition of the present invention, a compound (photopolymerizable monomer) having an ethylenically unsaturated group in a conventionally known molecule can be blended as a reactive diluent. Such a compound having an ethylenically unsaturated group is photocured by irradiation with active energy rays to insolubilize or insolubilize the curable resin of the present invention or the carboxyl group resin in an alkaline aqueous solution. In order to make the composition photocurable when the carboxyl group-containing urethane resin (A) and the carboxyl group-containing resin (B) having no aromatic ring do not have an ethylenically unsaturated double bond, It is necessary to use a photosensitive compound having a plurality of ethylenically unsaturated groups in the molecule in an amount necessary for photocuring.

  Specific examples of such a photosensitive compound include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diglycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol. Acrylates; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate Hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate Polyhydric alcohols or polyethyl acrylates such as these ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene of these phenols Polyvalent acrylates such as oxide adducts; polyvalent acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; Polyols such as polycarbonate diol, hydroxyl-terminated polybutadiene, and polyester polyol are directly acrylated or diisocyanate. Examples thereof include acrylates and melamine acrylates that are urethane acrylated via a vinyl salt, and / or methacrylates corresponding to the above acrylates.

  Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  The compounding quantity of the compound which has an ethylenically unsaturated group in such a molecule | numerator is with respect to 100 mass parts of total amounts of said carboxyl group-containing urethane resin (A) and carboxyl group-containing resin (B) which does not have an aromatic ring. The ratio of 5 to 100 parts by mass, more preferably 5 to 70 parts by mass is appropriate. When the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle.

  A thermosetting component (D) can be blended with the photocurable thermosetting resin composition of the present invention in order to further improve the heat resistance. Thermosetting components include amine resins such as melamine resins and benzoguanamine resins as described above, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, bismaleimides, and oxazine compounds. Any known and commonly used thermosetting resin such as an oxazoline compound can be used, but preferably, the carboxyl group of the carboxyl group-containing urethane resin (A) and the carboxyl group-containing resin (B) having no aromatic ring (or more It is a thermosetting component having a plurality of cyclic (thio) ether groups in a molecule capable of reacting with (phenolic hydroxyl group).

  In the photocurable thermosetting resin composition of the present invention, the thermosetting component (D) can be used alone or in combination of two or more. The blending amount is 5 to 150 parts by mass, preferably 10 to 80 parts by mass with respect to 100 parts by mass of the total amount of the carboxyl group-containing urethane resin (A) and the carboxyl group-containing resin (B) having no aromatic ring. It is desirable that If it is less than 5 parts by mass, the solder heat resistance of the cured film of the photo-curable thermosetting resin composition may be insufficient. On the other hand, if it exceeds 150 parts by mass, the insulation protection of the flexible printed circuit board (FPC) may occur. Various characteristics when used as a film, particularly electrical insulation, tend to deteriorate.

  In the curable resin composition of the present invention, the carboxyl group-containing urethane resin, the carboxyl group-containing resin having no aromatic ring and the thermosetting component are easily dissolved or dispersed, or the viscosity is suitable for coating. An organic solvent can be used to adjust. Examples of the organic solvent include toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, carbitol acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, Diethylene glycol ethyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, N, N-dimethyl Formamide, N, N-dimethylacetamide, - it includes methyl pyrrolidone, .gamma.-butyrolactone, dimethyl sulfoxide, chloroform and methylene chloride. The blending amount of the organic solvent can be appropriately set according to the desired viscosity.

  The curable resin composition of this invention can contain a well-known and usual mercapto compound and an adhesion promoter in order to improve adhesiveness with base materials, such as a polyimide, as needed. Examples of mercapto compounds include 2-mercaptopropionic acid, trimethylolpropane tris (2-thiopropionate), 2-mercaptoethanol, 2-aminothiophenol, 3-mercapto-1,2,4-triazole, and 3-mercapto. -A mercapto group-containing silane coupling agent such as propyltrimethoxysilane. Examples of the adhesion promoter include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, Examples include 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, and vinyltriazine. These may be used alone or in combination of two or more. The blending amount is suitably in the range of 10 parts by mass or less per 100 parts by mass of the total amount of the carboxyl group-containing urethane resin (A) and the carboxyl group-containing resin (B) having no aromatic ring. When the compounding amount of these compounds exceeds the above range, it is not preferable because the epoxy group of the epoxy resin necessary for the crosslinking reaction is consumed (reacts with the epoxy group) and the crosslinking density is lowered.

  In many polymer materials, once oxidation starts, oxidative degradation occurs successively in a chain, resulting in functional degradation of the polymer material. Therefore, the curable resin composition of the present invention has a ( 1) Radical scavengers that invalidate the generated radicals and / or (2) Oxidation of peroxide decomposers that decompose the generated peroxides into harmless substances and prevent the generation of new radicals. An inhibitor can be added.

  Examples of the antioxidant acting as a radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2 -Methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2 , 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-t-butyl-4-hydroxybenzyl)- Phenolic compounds such as S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6-tetramethyl-4 -Piperidyl) -amine compounds such as sebacate and phenothiazine.

  The radical scavenger may be commercially available, for example, ADK STAB (registered trademark) AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, Adekastab LA-87 (all manufactured by ADEKA), IRGANOX (registered trademark) 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN (registered trademark) 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 152 And TINUVIN 5100 (both manufactured by BASF Japan Ltd.).

Examples of the antioxidant acting as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3′-thiodipro Sulfur compounds such as pionate can be mentioned.
The peroxide decomposing agent may be a commercially available one. For example, Adeka Stub TPP (manufactured by ADEKA), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd.), Sumilyzer (registered trademark) TPS (manufactured by Sumitomo Chemical Co., Ltd.) Etc.
The above antioxidants can be used individually by 1 type or in combination of 2 or more types.

The curable resin composition of the present invention can use an ultraviolet absorber in addition to the antioxidant.
Examples of such ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like.

  Examples of the benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and 2 , 4-dihydroxybenzophenone and the like.

  Examples of the benzoate derivative include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl- Examples include 4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.

  Examples of the benzotriazole derivatives include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) enzotriazole, 2- (2′- Hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, Examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole.

  Examples of the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.

  Ultraviolet absorbers may be commercially available, for example, TINUVI PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460. , TINUVIN 479 (both manufactured by BASF Japan) and the like.

  The curable resin composition of the present invention further includes at least one filler selected from the group consisting of an inorganic filler and an organic filler for the purpose of improving properties such as adhesion, hardness, and heat resistance, if necessary. Can be contained. Examples of inorganic fillers include barium sulfate, calcium carbonate, barium titanate, silicon oxide, amorphous silica, talc, clay, hydrotalcite, and mica powder. Examples of organic fillers include silicon powder, nylon powder, and fluorine powder. Etc. Among the fillers, silica is particularly excellent in low hygroscopicity and low volume expansion. Silica may be a mixture of these materials regardless of melting or crystallinity, but in particular, silica surface-treated with a coupling agent or the like is preferable because it can improve electrical insulation. The average particle size of the filler is desirably 25 μm or less, more preferably 10 μm or less, and still more preferably 3 μm or less. The blending amount of these inorganic and / or organic fillers is suitably 300 parts by mass or less per 100 parts by mass of the total amount of the carboxyl group-containing urethane resin (A) and the carboxyl group-containing resin (B) having no aromatic ring. The ratio is preferably 5 to 150 parts by mass. If the blending amount of the filler exceeds the above ratio, the folding resistance of the cured film is lowered, which is not preferable.

  Furthermore, you may add other additives other than the said component in the curable resin composition of this invention, unless the effect of this invention is impaired. Additives include known and commonly used thickeners such as fine silica, organic bentonite, montmorillonite, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, glass fibers, carbon fibers, boron nitride fibers And fiber reinforcing materials such as Furthermore, if necessary, known and commonly used thermal polymerization inhibitors, silane coupling agents such as imidazole series, thiazole series and triazole series, plasticizers, foaming agents, flame retardants, antistatic agents, antiaging agents, antibacterial / antibacterial agents A glaze etc. can be added.

  The thermal polymerization inhibitor can be used for preventing thermal polymerization or polymerization with time of the polymerizable compound. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

  The thermosetting resin composition having the above composition is prepared by dissolving each of the above-described components or further components described later as necessary using a mixer such as a disper, a kneader, a three-roll mill, a bead mill, or the like. Obtained by dispersing. In that case, you may use the solvent inactive with respect to an epoxy group or a phenolic hydroxyl group. As such an inert solvent, the organic solvent mentioned above is preferable.

  The thermosetting resin composition of the present invention can be applied to a printed circuit board by various conventionally known methods such as curtain coating method, roll coating method, spray coating method and dip coating method, as well as various types such as dry film or prepreg. It can be used for the form and application. Various solvents can be used depending on the method of use and application, but in some cases, not only good solvents but also poor solvents can be used.

  The thermosetting resin composition of the present invention is applied to a flexible printed wiring board, a tape carrier package or an electroluminescent panel on which a circuit is formed by a screen printing method, and heated to a temperature of 120 to 180 ° C., for example. By thermosetting, there is no warping due to curing shrinkage and cooling shrinkage, in addition to properties such as adhesion to the substrate, folding resistance, low warpage, electroless gold plating resistance, solder heat resistance, electrical insulation, A white cured film is formed in which a high level of flexibility and high reflectance is achieved in a well-balanced manner, and a decrease in reflectance over time is small.

  The photocurable thermosetting resin composition of the present invention is adjusted to a viscosity suitable for the coating method with, for example, the organic solvent, and on the substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (temporary drying) at a temperature of about 60 to 100 ° C. Moreover, a resin insulation layer can be formed by apply | coating the said composition on a carrier film, and drying and winding up as a film together on a base material. Thereafter, by contact type (or non-contact type), exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 to A resist pattern is formed by development with a 3 wt% sodium carbonate aqueous solution. Further, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group (or further phenolic hydroxyl group) of the carboxyl group-containing urethane resin or carboxyl group-containing resin, and a thermosetting component, for example, The epoxy group of the epoxy resin (or the cyclic (thio) ether group of another thermosetting component if it is contained) reacts to adhere to the substrate, bend resistance, low warpage, electroless gold In addition to properties such as plating resistance, solder heat resistance, electrical insulation, etc., a white cured film is formed in which a high level of flexibility and high reflectance is achieved in a well-balanced manner, and there is little decrease in reflectance over time.

  As the substrate, in addition to a printed circuit board and a flexible printed circuit board in which circuits are formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, copper-clad laminate of all grades (FR-4 etc.) using polyimide, polyethylene, PPO, cyanate ester, etc., polyimide film, PET A film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.

  Volatile drying performed after applying the photocurable thermosetting resin composition of the present invention is performed using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, or the like (equipped with an air heating heat source using steam). And a method in which hot air in the dryer is brought into countercurrent contact and a method in which the hot air in the dryer is blown onto the support from the nozzle).

  As mentioned above, after apply | coating the photocurable thermosetting resin composition of this invention and evaporating and drying, exposure (irradiation of an active energy ray) is performed with respect to the obtained coating film. In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.

As the exposure apparatus used for the active energy ray irradiation, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer), an exposure apparatus equipped with a metal halide lamp, and an (ultra) high pressure mercury lamp. , An exposure machine equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high pressure mercury lamp. As the active energy ray, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. Further, the exposure amount varies depending the thickness or the like, generally 5~800mJ / cm ^2, preferably be in the range of 5~500mJ / cm ^2. As the direct drawing device, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any device may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .

  The developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

  The photo-curable thermosetting resin composition of the present invention is not a liquid and directly applied to a substrate, but also a dry resist layer formed by applying and drying a solder resist on a film of polyethylene terephthalate or the like in advance. It can also be used in the form of a film. The case where the photocurable thermosetting resin composition of this invention is used as a dry film is shown below.

  The dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film used as necessary are laminated in this order. A soldering resist layer is a layer obtained by apply | coating and drying a photocurable thermosetting resin composition on a carrier film or a cover film, for example. After forming a solder resist layer on the carrier film, a cover film is laminated thereon, or a solder resist layer is formed on the cover film, and this laminate is laminated on the carrier film to obtain a dry film.

As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used.
The solder resist layer is formed by uniformly applying a photocurable thermosetting resin composition to a carrier film or a cover film with a thickness of 10 to 150 μm using a blade coater, lip coater, comma coater, film coater or the like, and then drying. The
As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but a cover film having a smaller adhesive force than the solder resist layer is preferable.

  To produce a protective film (permanent protective film) on a printed wiring board using a dry film, peel off the cover film, layer the solder resist layer and the substrate on which the circuit is formed, and bond them together using a laminator, etc. A solder resist layer is formed on the formed substrate. If the formed solder resist layer is exposed, developed, and heat cured in the same manner as described above, a cured coating film can be formed. The carrier film may be peeled off either before exposure or after exposure.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, “parts” and “%” are based on mass unless otherwise specified.

<Synthesis example of carboxyl group-containing urethane resin (A) obtained by using a compound having an isocyanate group that is not aromatic>
Synthesis example 1
A polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol as a compound having two or more alcoholic hydroxyl groups in a reaction vessel equipped with a stirrer, a thermometer and a condenser (Asahi Kasei Chemicals Corporation) ) 2400 g (3.0 mol) of T5650J, number average molecular weight 800), 603 g (4.5 mol) of dimethylolbutanoic acid, and 238 g (2.6 mol) of 2-hydroxyethyl acrylate as a monohydroxyl compound . Next, 1887 g (8.5 mol) of isophorone diisocyanate is added as a compound having an isocyanate group which is not aromatic, and the mixture is heated to 60 ° C. with stirring and stopped, and when the temperature in the reaction vessel starts to decrease. It heated again and stirring was continued at 80 degreeC, it confirmed that the absorption spectrum (2280cm < ^-1 >) of the isocyanate group disappeared in the infrared absorption spectrum, and reaction was complete | finished. Subsequently, carbitol acetate was added so that a solid content might be 50 wt%, and the viscous liquid carboxyl group-containing urethane resin (A-1) containing a diluent was obtained. The acid value of the solid content of the obtained carboxyl group-containing urethane resin was 51.0 mgKOH / g.

Synthesis example 2
A polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol as a compound having two or more alcoholic hydroxyl groups in a reaction vessel equipped with a stirrer, a thermometer and a condenser (Asahi Kasei Chemicals Corporation) ) 2400 g (3.0 mol) of T5650J, number average molecular weight 800), 603 g (4.5 mol) of dimethylolbutanoic acid, and 238 g (2.6 mol) of 2-hydroxyethyl acrylate as a monohydroxyl compound . Next, 1512 g (6.5 mol) of hexamethylene diisocyanate was added as a compound having an isocyanate group which is not aromatic, and the mixture was heated to 60 ° C. with stirring and stopped, and the temperature in the reaction vessel began to decrease. Then, the mixture was heated again and stirred at 80 ° C., and it was confirmed that the absorption spectrum (2280 cm ⁻¹ ) of the isocyanate group disappeared in the infrared absorption spectrum, and the reaction was completed. Subsequently, carbitol acetate was added so that a solid content might be 50 wt%, and the viscous liquid carboxyl group-containing urethane resin (A-2) containing a diluent was obtained. The acid value of the solid content of the obtained carboxyl group-containing urethane resin was 49.8 mgKOH / g.

Synthesis example 3
A polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol as a compound having two or more alcoholic hydroxyl groups in a reaction vessel equipped with a stirrer, a thermometer and a condenser (Asahi Kasei Chemicals Corporation) ) 2400 g (3.0 mol) of T5650J, number average molecular weight 800), 603 g (4.5 mol) of dimethylolbutanoic acid, and 238 g (2.6 mol) of 2-hydroxyethyl acrylate as a monohydroxyl compound . Next, 1554 g (7.0 mol) of trimethylhexamethylene diisocyanate was added as a compound having an isocyanate group which is not aromatic, and the mixture was heated to 60 ° C. with stirring and stopped, and the temperature in the reaction vessel began to decrease. At that time, the mixture was heated again and stirred at 80 ° C., and it was confirmed that the isocyanate group absorption spectrum (2280 cm ⁻¹ ) had disappeared in the infrared absorption spectrum, and the reaction was terminated. Subsequently, carbitol acetate was added so that a solid content might be 50 wt%, and the carboxyl group-containing urethane resin (A-3) which has a phenolic hydroxyl group at the terminal of the viscous liquid containing a diluent was obtained. The acid value of the solid content of the carboxyl group-containing urethane resin having a phenolic hydroxyl group at the terminal was 48.8 mgKOH / g.

<Synthesis example of a carboxyl group-containing urethane resin obtained using a compound having an aromatic isocyanate group>
Comparative Synthesis Example 1
A polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol as a compound having two or more alcoholic hydroxyl groups in a reaction vessel equipped with a stirrer, a thermometer and a condenser (Asahi Kasei Chemicals Corporation) ) 2400 g (3.0 mol) of T5650J, number average molecular weight 800), 603 g (4.5 mol) of dimethylolpropionic acid, and 238 g (2.6 mol) of 2-hydroxyethyl acrylate as a monohydroxyl compound. . Next, 1879 g (6.5 mol) of tolylene diisocyanate is added as an aromatic isocyanate, heated to 60 ° C. with stirring and stopped, and heated again when the temperature in the reaction vessel begins to decrease. Stirring was continued at 0 ° C., and the reaction was terminated after confirming that the absorption spectrum (2280 cm ⁻¹ ) of the isocyanate group had disappeared in the infrared absorption spectrum. Subsequently, carbitol acetate was added so that a solid content might be 50 wt%, and the viscous liquid carboxyl group-containing urethane resin (A ') containing a diluent was obtained. The acid value of the solid content of the obtained carboxyl group-containing urethane resin was 49.5 mgKOH / g.

<Synthesis example of carboxyl group-containing resin (B) having no aromatic ring>
Synthesis example 4
In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introducing tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate (Nippon Yushi) as a polymerization initiator 21.4 g of Perbutyl O manufactured by Co., Ltd. was added and heated to 90 ° C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (Dacel Chemical Industries, Ltd., Plaxel FM1) were added to the bis ( 4-t-butylcyclohexyl) peroxydicarbonate (Perroyl TCP manufactured by Nippon Oil & Fats Co., Ltd.) was added dropwise over 3 hours, and further aged for 6 hours to obtain a carboxyl group-containing copolymer resin. It was. The reaction was performed under a nitrogen atmosphere.
Next, 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (Daicel Chemical Co., Ltd. Cyclomer A200), 3.6 g of dimethylbenzylamine as a ring-opening catalyst, polymerization inhibition were added to the obtained carboxyl group-containing copolymer resin. As an agent, 1.80 g of hydroquinone monomethyl ether was added, heated to 100 ° C., and stirred to carry out an epoxy ring-opening addition reaction. After 16 hours, a solution containing 53.8% by weight (nonvolatile content) of a carboxyl group-containing resin having no aromatic ring and having an acid value of solids of 108.9 mgKOH / g and a weight average molecular weight of 25,000 was obtained. . Hereinafter, this reaction solution is called resin (B-1).

Synthesis example 5
A flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser is charged with diethylene glycol monoethyl ether acetate as a solvent and azobisisobutyronitrile as a catalyst, heated to 80 ° C. in a nitrogen atmosphere, and methacrylic acid. And methyl methacrylate mixed at a molar ratio of 0.40: 0.60 was added dropwise over about 2 hours. After further stirring for 1 hour, the temperature was raised to 115 ° C. and deactivated to obtain a resin solution.
After cooling the resin solution, tetrabutylammonium bromide was used as a catalyst, and butyl glycidyl ether was equivalence of butyl glycidyl ether at a molar ratio of 0.40 under conditions of 95 to 105 ° C. for 30 hours. And the reaction was cooled.
Furthermore, tetrahydrophthalic anhydride was subjected to addition reaction at a molar ratio of 0.26 under the condition of 95 to 105 ° C. for 8 hours with respect to the OH group of the obtained resin. The solution was taken out after cooling to obtain a solution containing 50% by mass (nonvolatile content) of a carboxyl group-containing resin having no aromatic ring having a solid content acid value of 78.1 mgKOH / g and a weight average molecular weight of 35,000. Hereinafter, this reaction solution is called resin (B-2).

<Synthesis example of carboxyl group-containing resin having an aromatic ring>
Comparative Synthesis Example 2
Orthocresol novolak type epoxy resin [DIC Corporation, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] 1070 g (number of glycidyl groups (total number of aromatic rings)) to 600 g of diethylene glycol monoethyl ether acetate : 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 4 hours. After cooling, the solid content acid value 89 mgKOH / G, a resin solution having a solid content of 65% was obtained. Hereinafter, this is referred to as a resin (B ′).

Examples 1-6 and Comparative Examples 1-6
Various components shown in Table 1 below were blended in the proportions (parts by mass) shown in Table 1, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a thermosetting resin composition paste.
The obtained paste of the thermosetting resin composition was applied to a substrate by screen printing so that the film thickness of the cured film was about 15 μm, and thermosetting was performed at 150 ° C. for 60 minutes to prepare a test substrate.

About the cured film of each said thermosetting resin composition, the following various characteristics were evaluated with the following method.
<Heat resistance>
For each test board, using a color difference meter CR-400 manufactured by Konica Minolta, the initial value of the Y value of the XYZ color system and the initial value of L ^* , a ^* , b ^* of the L ^* a ^* b ^* color system Was measured. After that, each test substrate was allowed to stand in a hot air circulation drying oven at 150 ° C. for 50 hours for accelerated deterioration, and again, each value was measured with a Minolta color difference meter CR-400, and the change in Y value and ΔE ^* ab were evaluated. did. The results are shown in Table 2 together with the result of visual discoloration evaluation.

The Y value is the Y value of the XYZ color system, and the higher the value, the higher the reflectance. ΔE ^* ab is the difference between the initial value and the value after accelerated deterioration in the L ^* a ^* b ^* color system, and the larger the value, the greater the color change. The calculation formula of ΔE ^* ab is as follows.
^{ΔE * ab = [(L *} 2 -L * 1) 2 + (a * 2 -a * 1) 2 + (b * 2 -b * 1) 2] 1/2
In the formula, L ^{* 1} , a ^{* 1} , and b ^{* 1} represent initial values of L ^* , a ^* , and b ^* , respectively, and L ^{* 2} , a ^{* 2} , and b ^{* 2} represent L after acceleration deterioration, respectively. ^* , A ^* , b ^* values are represented.

The criteria for visual evaluation are as follows.
○: No discoloration at all.
Δ: There is a slight discoloration.
X: There is discoloration.

<Bending resistance>
The paste of each thermosetting resin composition was applied to a 12.5 μm-thick polyimide film [Kapton (registered trademark) 50H, manufactured by Toray DuPont Co., Ltd.] with a 100 mesh polyester plate by screen printing, and 30 at 150 ° C. Partial heat curing. The paste film thickness after curing was adjusted to about 15 μm.
The polyimide film on which the paste was applied and heat-cured in this way was wound so that the coated surface was in the outer side and in close contact with a 5.0 mmφ cylinder, and the results of visual observation were evaluated for bending properties according to the following criteria.
○: There is no crack in the cured film.
X: The cured film has cracks.

<Bendability>
Each thermosetting resin composition paste was applied to a 12.5 μm-thick polyimide film (Kapton 50H, manufactured by Toray DuPont Co., Ltd.) with a 100 mesh polyester plate and thermally cured at 150 ° C. for 30 minutes. . The paste film thickness after curing was adjusted to about 15 μm.
Thus, the polyimide film which apply | coated and thermosetting the paste was bent 180 degree | times by making the application surface outside, and the result of having observed visually was evaluated by the following references | standards.
○: There is no crack in the cured film.
X: The cured film has cracks.

<Pencil hardness>
A pencil of B to 9H, which was sharpened so that the tip of the core was flattened, was pressed against each test substrate at an angle of about 45 °, and the hardness of the pencil at which the cured film did not peel off was recorded.

<Solder heat resistance>
The test substrate coated with the rosin flux was allowed to flow for 10 seconds in a solder bath set at 260 ° C. in advance. Then, after washing with propylene glycol monomethyl ether acetate and drying, a peel test with a cellophane adhesive tape was performed to evaluate the peeling of the cured film. The judgment criteria are as follows.
○: Peeling of the cured film is not recognized.
Δ: Some peeling of the cured film.
X: There exists peeling of a cured film.

<Adhesion>
The paste of each thermosetting resin composition was printed on the entire surface by screen printing on Kapton 200H (polyimide film manufactured by Toray DuPont Co., Ltd., thickness: 50 μm), and heat cured at 150 ° C. for 60 minutes. The paste film thickness after curing was adjusted to about 15 μm. The adhesion of the cured film was evaluated according to JIS D 0202 according to the following criteria.
○: Peeling of the cured film is not recognized.
Δ: Some peeling of the cured film.
X: There exists peeling of a cured film.

The results of each evaluation test are summarized in Table 2.

  As is clear from the results shown in Table 2 above, in each example using the thermosetting resin composition of the present invention, white curing having high reflectivity, low change rate, and excellent flexibility. A film could be formed. On the other hand, in the case of Comparative Example 1 using a carboxyl group-containing urethane resin obtained by using a compound having an aromatic isocyanate group and Comparative Example 2 using a carboxyl group-containing resin having an aromatic ring, the present invention Could not achieve the desired high reflectivity and low rate of change. On the other hand, a carboxyl group-containing urethane resin (A) obtained using a compound having an isocyanate group that is not aromatic and a carboxyl group-containing resin that does not have an aromatic ring are used. In the case of Comparative Examples 3 and 4 that are out of the range, the ratio of the carboxyl group-containing resin having no aromatic ring is too high in Comparative Example 3, which is inferior in bending resistance and bendability, and on the contrary, in Comparative Example 4 which is too low in soldering It was inferior in heat resistance. Moreover, in the case of the comparative example 5 which did not mix | blend a thermosetting component, it was inferior to pencil hardness, solder heat resistance, and adhesiveness. On the other hand, in the case of the comparative example 6 which did not mix | blend a titanium oxide, the high reflectance and low change rate which this invention aimed could not be achieved, and also pencil hardness and solder heat resistance were inferior.

Examples 7 to 13 and Comparative Examples 7 to 12
The various components shown in Table 3 below were blended in the proportions (parts by mass) shown in Table 3, premixed with a stirrer, kneaded with a three-roll mill, and a photocurable thermosetting resin composition paste. Prepared.

Characteristic test:
Each of the photocurable thermosetting resin compositions of Examples and Comparative Examples was applied on the entire surface of the patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Using this exposure apparatus equipped with a high-pressure mercury lamp on this substrate, the solder resist pattern is exposed at an optimum exposure amount, and developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 90 seconds. Obtained. This substrate was cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed board (test board) were evaluated as follows. The evaluation methods for heat resistance, pencil hardness, and solder heat resistance are as described above.

<Resolution>
A negative pattern having a via opening diameter of 300 μm was used as a negative mask for resolution evaluation, and the cross section of the solder resist opening was observed and measured with a 200 × optical microscope, and evaluated according to the following evaluation criteria. The undercut amount indicates an amount obtained by subtracting the bottom diameter from the upper diameter of the solder resist opening.
A: The undercut amount is less than 20 μm.
X: The undercut amount is 20 μm or more.

<Bending resistance>
A photocurable thermosetting resin composition was applied to and cured on a 12.5 μm-thick polyimide film [Kapton (registered trademark) 50H, manufactured by Toray DuPont Co., Ltd.] to prepare each test substrate. . The paste film thickness after curing was adjusted to about 15 μm.
The coated surface of each test substrate was placed outside, wound so as to be in close contact with a 5.0 mmφ cylinder, and the results of visual observation were evaluated for bending properties according to the following criteria.
○: There is no crack in the cured film.
X: The cured film has cracks.

<Adhesion>
The adhesion of each test substrate was evaluated according to JIS D 0202 according to the following criteria.
○: Peeling of the cured film is not recognized.
Δ: Some peeling of the cured film.
X: There exists peeling of a cured film.

The results of the evaluation tests are summarized in Table 4.

  As is apparent from the results shown in Table 4 above, in each of the examples using the photocurable thermosetting resin composition of the present invention, it has a high reflectance, and has a low change rate and excellent flexibility. A white cured film could be formed. In contrast, Comparative Example 7 using a carboxyl group-containing urethane resin (A ′) obtained using a compound having an aromatic isocyanate group and a carboxyl group-containing resin (B ′) having an aromatic ring were used. In the case of Comparative Example 8, the high reflectivity and low change rate intended by the present invention could not be achieved. On the other hand, a carboxyl group-containing urethane resin obtained by using a compound having an isocyanate group that is not aromatic and a carboxyl group-containing resin that does not have an aromatic ring are used. In Comparative Examples 9 and 10, the ratio of the carboxyl group-containing resin not having an aromatic ring is too high in Comparative Example 9, while the comparatively low Comparative Example 10 is inferior in solder heat resistance. It was. Moreover, in the case of the comparative example 11 using photoinitiators other than a bisacyl phosphine oxide type photoinitiator and a monoacyl phosphine oxide type photoinitiator, it was inferior to resolution and pencil hardness. On the other hand, in the case of the comparative example 12 which did not mix | blend a titanium oxide, the high reflectance and low change rate which this invention aimed could not be achieved, and pencil hardness and solder heat resistance were also inferior.

  The curable resin composition of the present invention or the dry film thereof is a protective film such as a solder resist or an interlayer insulating film used for manufacturing a printed wiring board, particularly a flexible printed wiring board or a tape carrier package, an insulating layer, Or a protective film for a back electrode of an electroluminescent panel used for a backlight of a liquid crystal display or a display for information display, a protective film for a display panel of a mobile phone, a watch, a car stereo, etc. It can be advantageously used as a stopping material.

Claims (10)

  (A) a carboxyl group-containing urethane resin obtained by using a compound having an isocyanate group that is not aromatic, (B) a carboxyl group-containing resin that does not have an aromatic ring, and (C) titanium oxide, A composition that is cured by at least one of irradiation with active energy rays, wherein the ratio of the carboxyl group-containing urethane resin (A) and the carboxyl group-containing resin (B) having no aromatic ring is 50 to 70 on a mass basis: It is in the range of 50-30, The curable resin composition characterized by the above-mentioned.   (A) Carboxyl group-containing urethane resin obtained using a compound having an isocyanate group that is not aromatic, (B) Carboxyl group-containing resin having no aromatic ring, (C) Titanium oxide, and (D) Thermosetting The ratio of the carboxyl group-containing urethane resin (A) and the carboxyl group-containing resin (B) having no aromatic ring is in the range of 50 to 70:50 to 30 on a mass basis. There is a thermosetting resin composition.   The hardened | cured material obtained by apply | coating the curable resin composition of Claim 1 or 2 on a base material, and making it harden | cure.   The printed wiring board which has an insulating layer or protective film which consists of hardened | cured material of the curable resin composition of Claim 1 or 2.   (A) Carboxyl group-containing urethane resin obtained using a compound having an isocyanate group that is not aromatic, (B) Carboxyl group-containing resin having no aromatic ring, (C) Titanium oxide, and (E) Monoacyl A composition containing a phosphine oxide photopolymerization initiator, wherein the ratio of the carboxyl group-containing urethane resin (A) and the carboxyl group-containing resin (B) having no aromatic ring is 50 to 70 on a mass basis: It exists in the range of 50-30, The photocurable thermosetting resin composition characterized by the above-mentioned.   The carboxyl group-containing resin (B) having no aromatic ring is obtained by a reaction between a carboxyl group-containing (meth) acrylic copolymer resin and a compound having an oxirane ring and an ethylenically unsaturated group in one molecule. 6. The photocurable thermosetting resin composition according to claim 5, wherein the photocurable thermosetting resin composition is a carboxyl group-containing copolymer resin.   The photocurable thermosetting resin composition according to claim 5 or 6, further comprising (F) a bisacylphosphine oxide photopolymerization initiator.   Furthermore, (D) a thermosetting component is contained, The photocurable thermosetting resin composition as described in any one of Claim 5 thru | or 7 characterized by the above-mentioned.   Hardened | cured material obtained by photocuring or thermosetting as needed the photocurable thermosetting resin composition as described in any one of the said Claims 5 thru | or 8.   A printed wiring board having a cured film obtained by photocuring the photocurable thermosetting resin composition according to any one of claims 5 to 8 in a pattern and then thermosetting.