JP5734604B2 - Curable resin composition, dry film and cured product thereof, and printed wiring board using them - Google Patents

Description

  The present invention provides a curable (photocurable and / or thermosetting) resin composition containing a curable resin derived from a specific polyester polyol and a layered double hydroxide, particularly a recovered polyester. The present invention relates to an alkali-developable photocurable resin composition containing a curable resin and a layered double hydroxide, a dry film and a cured product thereof, and a printed wiring board using them.

In recent years, from the viewpoint of environmental problems, printed wiring boards used for electronic devices have been required to use environmentally friendly materials. For example, due to the social problem of the generation of harmful gases such as dioxins during incineration, flame retardant materials and coloring materials used for prepregs, solder resist films, etc., have been changed from conventional halogen-containing systems such as bromine to non-halogen systems. Conversion is required.
For example, various studies have been made on non-halogenation of a flame retardant material of a printed wiring board composition (see, for example, Patent Document 1). However, due to growing interest in environmental issues, further consideration for the environment is required.
On the other hand, since a printed wiring board is used for an electronic device, insulation is required. In addition, heat resistance is required because an electronic component is attached to the interlayer resin insulation layer of the printed wiring board at a high temperature.

  In recent years, with the miniaturization of the pattern of the solder resist film formed on the outermost layer of the printed wiring board, a photolithography method is used for pattern formation. At this time, since the pattern is formed by irradiating active energy rays through the mask pattern, the resin composition for forming the solder resist film is further required to have photocurability. Thus, among such photosensitive resin compositions, non-halogen-type ones that are environmentally friendly have been proposed (see, for example, Patent Document 2).

Thus, in the resin composition for printed wiring boards, both consideration for the environment and maintenance and improvement of characteristics are required.
However, as a carboxyl group-containing resin used for a conventional solder resist, an epoxy acrylate-modified resin derived by modification of an epoxy resin is generally used. For example, Japanese Patent Application Laid-Open No. 61-243869 (Patent Document 3) discloses a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolak epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, and a diluent. And a solder resist composition comprising an epoxy compound is disclosed. Japanese Patent Laid-Open No. 3-250012 (Patent Document 4) adds (meth) acrylic acid to an epoxy resin obtained by reacting a reaction product of salicylaldehyde with a monohydric phenol with epichlorohydrin. Furthermore, a solder resist composition comprising a photosensitive resin obtained by reacting a polybasic carboxylic acid or an anhydride thereof, a photopolymerization initiator, an organic solvent and the like is disclosed. These epoxy acrylate modified resins contain halogen ions because epichlorohydrin is used as a raw material, and it has been difficult to make them halogen-free.

  On the other hand, the amount of PET bottles used in recent years has been increasing rapidly due to its light weight, transparency, gas barrier properties, and high strength, and its disposal method has become a social problem. For this reason, various studies have been made on the recycling of PET bottles (see Patent Documents 5 and 6). However, in the recycling process, there is a problem that the molecular weight of PET decreases due to hydrolysis of ester bonds, and the melt viscosity and mechanical strength of PET decrease. Such a decrease in quality is a factor in inhibiting the recycling of PET bottles. Therefore, at present, recycled PET resin is mainly used only in the field of fibers and industrial materials. However, as the amount of discarded PET bottles increases, a new effective method of using recycled PET resin is sought. ing.

  Examples of new methods for reclaiming waste polyester include the production of coating alkyd resins using a depolymerization reaction with glycols (see Patent Document 7), and the production of paint polyester resins using recycled polyester (Patent Documents 8 and 9). Further, the use of recycled polyester as a raw material for a photocurable urethane resin (see Patent Document 10) and the like has been studied, all of which are intended for use in coating compositions.

WO02 / 006399 Publication (Claims) JP 2000-7974 (Claims) JP 61-243869 (Claims) Japanese Patent Laid-Open No. 3-250012 (Claims) JP-A-10-287844 (Claims) JP-A-11-114961 (Claims) Japanese Patent No. 3310661 (Claims) Japanese Patent No. 3443409 (Claims) Japanese Patent No. 3256537 (Claims) JP 2004-307779 A (Claims, Examples)

The present invention has been made in view of the prior art as described above, is halogen-free, and has high sensitivity, excellent solder heat resistance, electroless gold plating resistance, moisture resistance, electrode corrosion resistance, and environmental problems. It aims at providing the curable resin composition in consideration.
Furthermore, an object of the present invention is to provide a dry film and a cured product excellent in various properties as described above obtained by using such a curable resin composition, and a cured film such as a solder resist by the dry film and the cured product. It is in providing the printed wiring board formed by.

（式中、Ｒ^１は（ｍ＋ｌ）価の多価アルコール誘導体を表し、ｍ及びｎは１以上、１０未満の整数であり、ｌは０もしくは１以上の整数であり、Ｒ^２はＣＨ_２、Ｃ_２Ｈ_４、Ｃ_３Ｈ_６、Ｃ_４Ｈ_８、置換もしくは無置換の芳香族環のいずれかを表し、Ｒ^３は置換もしくは無置換の芳香族環を表す。） In order to achieve the object, according to the present invention, (A) a curable resin derived from a compound including a structure represented by the following general formula (1), and (B) a layered double hydroxide is contained. A curable resin composition is provided.

(Wherein R ¹ represents an (m + 1) -valent polyhydric alcohol derivative, m and n are an integer of 1 or more and less than 10, l is an integer of 0 or 1 and R ² is CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , any of a substituted or unsubstituted aromatic ring, and R ³ represents a substituted or unsubstituted aromatic ring.

In a preferred embodiment, the compound having the structure represented by the general formula (1) is a polyol obtained by depolymerizing (a) polyester with (b) a polyol having two or more hydroxyl groups in one molecule. Resin. More preferably, the polyester of (a) is a recovered polyester, particularly polyethylene terephthalate (PET), and the polyol of (b) is trimethylolpropane, trimethylolethane, pentaerythritol, dipenta It is at least one selected from the group consisting of erythritol, ditrimethylolpropane, vegetable oil and glycerin, and trimethylolpropane is particularly preferable.
In another preferred embodiment, it further contains a thermosetting component, and preferably further contains a colorant. Such a curable resin composition, particularly a curable resin composition containing a thermosetting component, can be suitably used as a solder resist.

Further, according to the present invention, a curable dry film obtained by applying and drying the curable resin composition on a film, or a curable resin composition obtained by curing the curable resin composition or the dry film. In particular, a cured product obtained by photocuring on copper and a cured product obtained by photocuring in a pattern are also provided.
Furthermore, according to the present invention, there is also provided a printed wiring board characterized by having a cured film obtained by photocuring the photocurable resin composition or dry film in a pattern and then thermosetting.

The curable resin used in the curable resin composition of the present invention has a thermosetting property, a photocurable property, or a photocurable and thermosetting property. Further, since this curable resin is derived from a polyester polyol having a structure represented by the general formula (1), unlike a conventional epoxy acrylate-modified resin, a raw material not containing a halogen ion can be used. Therefore, it can be made halogen-free, and a cured film excellent in electrical insulation, heat resistance, and dryness to touch can be formed. Moreover, since a layered double hydroxide is contained together with the curable resin derived from the polyester polyol having the structure represented by the general formula (1), a cured film having extremely excellent electrode corrosion resistance can be formed.
In addition, when the compound having the structure represented by the general formula (1) is produced by depolymerization of polyester, the recovered polyester can be used as a starting material polyester, so that the resources can be effectively used. Can contribute. Furthermore, the depolymerized product obtained by depolymerizing the polyester with the polyol can be used for the next reaction as it is without separation, so that the recycled resin utilization rate is increased and the aroma in the recovered polyester depolymerized product is increased. Carboxylic acid having a ring (benzene ring), particularly terephthalic acid, can contribute to solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, etc. of the cured coating film of the curable resin composition.
Furthermore, by including a thermosetting resin, it is possible to form a cured film having further excellent solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, and the like.
Therefore, the curable resin composition of the present invention can be advantageously applied to the formation of a cured film such as a solder resist of a printed wiring board or a flexible printed wiring board.

（式中、Ｒ^１は（ｍ＋ｌ）価の多価アルコール誘導体を表し、ｍ及びｎは１以上、１０未満の整数であり、ｌは０もしくは１以上の整数であり、Ｒ^２はＣＨ_２、Ｃ_２Ｈ_４、Ｃ_３Ｈ_６、Ｃ_４Ｈ_８、置換もしくは無置換の芳香族環のいずれかを表し、Ｒ^３は置換もしくは無置換の芳香族環を表す。） As described above, the curable resin composition of the present invention is characterized by (A) a curable resin derived from a compound containing a structure represented by the following general formula (1), and (B) a layered double hydroxide. It is in use.

(Wherein R ¹ represents an (m + 1) -valent polyhydric alcohol derivative, m and n are an integer of 1 or more and less than 10, l is an integer of 0 or 1 and R ² is CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , any of a substituted or unsubstituted aromatic ring, and R ³ represents a substituted or unsubstituted aromatic ring.

According to the studies by the present inventors, such a resin composition can form a cured film excellent in electrode corrosion resistance, heat resistance, and touch dryness, and the polyester is recovered from waste materials such as PET bottles. In the case of recycled polyester and recycled polyester, it is possible to provide an environmentally friendly composition.
Hereinafter, each component of the curable resin composition of the present invention will be described in detail.

  When the polyester is depolymerized with a polyol component according to a known method, a mixture of a component having a carboxyl group and a component having a hydroxyl group generated by depolymerization of the polyester, or a mixture further containing a remaining polyol component depending on the amount of the polyol component added. Any of these can be used for the reaction with an alicyclic polybasic acid or an anhydride thereof or the reaction with a compound having one or more ethylenically unsaturated groups in the molecule.

When the curable resin (A) derived from the compound having the structure represented by the general formula (1) used in the present invention is a carboxylic acid resin, (a) polyester (b) two or more in one molecule It is obtained by depolymerizing with a polyol having a hydroxyl group and reacting the depolymer with (c ) a polybasic acid or its anhydride.

  When the curable resin (A) derived from the compound containing the structure represented by the general formula (1) used in the present invention is a photosensitive resin, (a) polyester (b) two or more in one molecule It is obtained by depolymerizing with a polyol having a hydroxyl group and reacting the depolymer with a functional group capable of reacting with a hydroxyl group or a carboxyl group in the molecule and a compound having one or more ethylenically unsaturated groups. It is done.

When the curable resin (A) derived from the compound having the structure represented by the general formula (1) used in the present invention is a carboxyl group-containing photosensitive resin capable of alkali development, (a) polyester (b) 1 Depolymerized with a polyol having two or more hydroxyl groups in the molecule, and (d) the depolymer has a functional group capable of reacting with a hydroxyl group or a carboxyl group and one or more ethylenically unsaturated groups in the molecule. It is obtained by reacting a compound and further reacting with (c ) a polybasic acid or an anhydride thereof.

  The ratio of the polyester and the polyol having two or more hydroxyl groups in one molecule is the ratio of the number of moles of repeating units (α) of the polyester and the number of moles of polyol having two or more hydroxyl groups in one molecule (β). However, (α) / (β) = 0.5 to 3 is appropriate, and preferably within the range of 0.8 to 2. When the ratio is less than 0.5, the polyol component is excessively contained, the ratio of the aromatic ring derived from the polyester is decreased, and the effect of improving heat resistance and chemical resistance is decreased, which is not preferable. On the other hand, when the ratio is greater than 3, the depolymerized product is crystallized in most cases and is insoluble in the solvent, which is not preferable.

  The polyester (a) may be any conventionally known polyester, and examples thereof include polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene phthalate, and liquid crystal polymer. Recycled PET and recycled PET recovered from waste such as PET bottle waste are more preferable from the viewpoint of environmental protection. The collected PET can be crushed and washed, and the recycled PET can be obtained from the market after being washed and pelletized. The shape of the polyester is not particularly limited, but is preferably in the form of pellets and / or flakes. Moreover, although it is not necessary to grind | pulverize finely in powder form, the grind | pulverized thing may be used.

  As the polyol (b) having two or more hydroxyl groups in one molecule, any bifunctional polyol or trifunctional or higher polyol can be used, and these can be used alone or in combination of two or more. .

  Examples of the bifunctional polyol include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, 1,3-butanediol, Neopentyl glycol, spiro glycol, dioxane glycol, adamantanediol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methylpropanediol 1, Bifunctional phenols such as 3,3-methylpentanediol 1,5, hexamethylene glycol, octylene glycol, 9-nonanediol, 2,4-diethyl-1,5-pentanediol, bisphenol A Ethylene oxide modified compound of bisphenol A, propylene oxide modified compound of bifunctional phenol such as bisphenol A, ethylene oxide of bisphenol A, propylene oxide copolymer modified compound, copolymer polyether polyol of ethylene oxide and propylene oxide, polycarbonate diol, Adamantanediol, polyether diol, polyester diol, polycaprolactone diol (e.g., Plaxel 205, Plaxel L205AL, Plaxel 205U, Plaxel 208, Plaxel L208AL, Plaxel 210, Plaxel 210N, Plaxel 212, Plaxel L212AL, Plaxel 220, Plaxel 220N, Plaxel 220NP1, Plaxel L220AL, Plaque 230, Plaxel 240, Plaxel 220EB, Plaxel 220EC; all manufactured by Daicel Chemical Industries, Ltd .; trade name), hydroxyl group-terminated polyalkanediene diols (eg, 1,4-polyisoprenediol, 1,4- and 1,2-polybutadiene diols and elastomers such as hydrogenated products thereof. Examples of commercially available products of the above hydroxyl group-terminated polyalkanediene diols include EPOL (registered trademark; hydrogenated polyisoprene diol, molecular weight). 1,860, average polymerization degree 26, manufactured by Idemitsu Kosan Co., Ltd.), PIP (polyisoprene diol, molecular weight 2,200, average polymerization degree 34, manufactured by Idemitsu Kosan Co., Ltd.), polytail H (hydrogenated polybutadiene diol, molecular weight) 2,200, average degree of polymerization 39, Mitsubishi Chemical Corporation Product), R-45HT (polybutanediol, molecular weight 2,270, average polymerization degree 42, manufactured by Idemitsu Kosan Co., Ltd.), and the like.

  Examples of the tri- or higher functional polyol include glycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, adamantanetriol, polycaprolactone triol (for example, plaxel 303, plaxel 305, Plaxel 308, Plaxel 312, Plaxel L312AL, Plaxel 320ML, Plaxel L320AL; all of which are manufactured by Daicel Chemical Industries, Ltd .; trade names), and those having aromatic rings include ethylene oxides and propylene oxides of trifunctional or higher phenol compounds Sake manufactured by Shikoku Kasei Kogyo Co., Ltd. is exemplified as a modified product or a compound having a heterocyclic ring. In particular, when trimethylolpropane is used, it is preferable because an amorphous semi-solid fluid product that does not become turbid when obtained as a depolymerized product is obtained and the solubility in a solvent is further increased.

Before The Kio dibasic acid or anhydride thereof (c), it is possible to use conventional known polybasic acid or its anhydride. Specific examples include aromatic polycarboxylic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, tetrabromophthalic anhydride, methyl hymic anhydride, tetrachlorophthalic anhydride, and anhydrides thereof, hexahydrophthalic anhydride Acids, tetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, alicyclic carboxylic acids such as 1,3-cyclohexanedicarboxylic acid and their anhydrides, maleic anhydride, fumaric acid, succinic anhydride, adipic acid, sebacine Examples thereof include aliphatic polyvalent carboxylic acids such as acid and azelaic acid, and anhydrides thereof, pyromellitic anhydride, trimellitic anhydride, trifunctional or higher carboxylic acid such as methylcyclohexenedicarboxylic acid anhydride, alone or Two or more types can be used in combination.

  Compound (d) having a functional group capable of reacting with a hydroxyl group or a carboxyl group in the molecule and one or more ethylenically unsaturated groups is a compound having one carboxyl group and one or more ethylenically unsaturated groups A (meth) acrylic monomer having an isocyanate group, a compound having one cyclic ether group and one or more ethylenically unsaturated groups, a compound having one hydroxyl group and one or more ethylenically unsaturated groups, etc. Is mentioned.

Examples of the compound having one carboxyl group and one or more ethylenically unsaturated groups include acrylic acid, dimer of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, crotonic acid, α -Half ester compounds of cyanocinnamic acid, cinnamic acid, (meth) acrylic acid caprolactone adduct, and saturated or unsaturated dibasic acid anhydride and (meth) acrylates having one hydroxyl group in one molecule Can be mentioned. Examples of (meth) acrylates having a hydroxyl group for producing a half ester compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, Examples include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and phenylglycidyl (meth) acrylate. Examples of the dibasic acid anhydride for producing the half ester compound include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenetetrahydro Phthalic anhydride etc. are mentioned, It can use individually or in combination of 2 or more types.
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 (meth) acrylic monomer having an isocyanate group is not particularly limited as long as it is an isocyanate compound having one isocyanate group and one or more ethylenically unsaturated groups in one molecule. Specific examples include, for example, (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxyethoxyethyl isocyanate, bis (acryloxymethyl) ethyl isocyanate, or modified products thereof, alone or in combination of two or more. Can be used in combination. Commercially available products include “Karenz MOI” (methacryloyloxyethyl isocyanate), “Karenz AOI” (acryloyloxyethoxyethyl isocyanate), “Karenz MOI-EG” (methacryloyloxyethoxyethyl isocyanate), “Karenz MOI BM” (Karenz MOI isocyanate block), "Karenz MOI-BP" (Karenz MOI isocyanate block), and "Karenz BEI" (1,1-bis (acryloxymethyl) ethyl isocyanate) are commercially available from Showa Denko K.K. ing. These trade names are registered trademarks. Furthermore, a half urethane compound of a compound having one hydroxyl group and one or more ethylenically unsaturated groups in one molecule and a diisocyanate such as isophorone diisocyanate, toluylene diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate is also used. can do.

  Examples of the compound having one cyclic ether group and one or more ethylenically unsaturated groups in one molecule include 2-hydroxyethyl (meth) acrylate glycidyl ether, 2-hydroxypropyl (meth) acrylate glycidyl ether, 3-hydroxy Propyl (meth) acrylate glycidyl ether, 2-hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxypentyl (meth) acrylate glycidyl ether, 6-hydroxyhexyl (meth) acrylate glycidyl Examples include ether or glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl acrylate, and the like can be used alone or in combination of two or more.

Examples of the compound having one hydroxyl group and one or more ethylenically unsaturated groups in one molecule include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meta ) Hydroxyalkyl (meth) acrylates such as acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like, and may be used alone or in combination of two or more.
The (meth) acrylic monomer having a functional group capable of reacting with a hydroxyl group or a carboxyl group as described above can be used alone or in combination of two or more.

  In order to promote the depolymerization, a depolymerization catalyst can be used. Examples of the depolymerization catalyst include monobutyltin hydroxide, dibutyltin oxide, monobutyltin-2-ethylhexanoate, dibutyltin dilaurate, stannous oxide, tin acetate, zinc acetate, manganese acetate, cobalt acetate, and calcium acetate. , Lead acetate, antimony trioxide, tetrabutyl titanate, tetraisopropyl titanate and the like. The amount of these depolymerization catalysts used is usually in the range of 0.005 to 5 parts by mass, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the polyester and polyhydric alcohol. is there.

  Although not a depolymerization catalyst, water is a compound that promotes depolymerization. This is present as an impurity in, for example, recycled PET, and causes a decrease in molecular weight when PET is recycled. Therefore, it is usually necessary to remove it by a very energy-consuming process such as drying. is there. However, in the application of the present invention, it is not necessary. Rather, the use of recycled PET pellets once melted and kneaded in a pellet manufacturing machine such as an extruder with water added has a lower molecular weight of the recycled PET. Since the reaction temperature at the time of superposition | polymerization can be lowered | hung and the viscosity at the time of a fusion | melting is low, it is preferable at the point that reaction can be performed with high concentration.

  In general, commercially available polyester pellets (virgin) have an IV value (intrinsic viscosity) of about 1.0 to 1.2, but recycled PET and recycled PET have an IV value of 0.6 to 0.7. For this reason, there is an effect that the time required for depolymerization can be shortened when recycled PET and recycled PET are used. Further, when the PET was regenerated without repelling moisture with an extruding machine, the IV value was low and around 0.1, but there was no particular problem when used in the present invention.

  The layered double hydroxide (B) used in the present invention is known as an ion adsorbent. It is also known as an antacid in the pharmaceutical field. The inventors of the present invention have found that the curable resin composition of the present invention containing a layered double hydroxide is remarkably excellent in electrode corrosion resistance as compared with the case of not containing a layered double hydroxide. The effect that the layered double hydroxide improves the electrode corrosion resistance of the composition containing it is thought to be due to the layered double hydroxide adsorbing halogen, and therefore usually contains halogen. Even when layered double hydroxide was added to the composition that did not, there was no effect of improving electrode corrosivity. However, when layered double hydroxide was added to the curable resin composition of the present invention which is halogen-free, dramatic improvement in electrode corrosivity was confirmed. This is considered to be an effect obtained by suppressing the acid such as a catalyst when the layered double hydroxide acts as an acid acceptor and synthesizes the curable resin used in the present invention.

Specific examples of the layered double hydroxide (B) used in the present invention include Indigirite Mg ₂ Al ₂ [(CO ₃ ) ₄ (OH) ₂ ] · 15H ₂ O, Fe ²⁺ ₄ Al ₂ [(OH) ₁₂ CO ₃ ] · 3H ₂ O, Quintinite Mg ₄ Al ₂ (OH) ₁₂ CO ₃ · H ₂ O, Manasseite Mg ₆ Al ₂ [(OH) ₁₆ CO ₃ ] · 4H ₂ O, SjOegrenite Mg ₆ Fe ^{3 +} ₂ [(OH _{) 16 CO 3] · 4H 2} O, Zaccagnaite Zn 4 Al 2 (CO 3) (OH) 12 · 3H 2 O, Desautelsite Mg 6 Mn 3+ 2 [(OH) 16 CO 3] · 4H 2 O, hydrotalcite Mg 6 Al ₂ [(OH) ₁₆ CO ₃ ] · 4H ₂ O, Pyroaurite Mg ₆ Fe ^{3 +} ₂ [(OH) ₁₆ CO ₃ ] · 4H ₂ O, Reevesite Ni ₆ Fe ³⁺ ₂ [(OH) ₁₆ CO ₃ ] · 4H ₂ O, Stichtite Mg ₆ Cr ₂ [(OH) ₁₆ CO ₃ ] · 4H ₂ O, Takovite Ni ₆ Al ₂ [(OH) ₁₆ CO ₃ ] · 4H ₂ O, and the like may be mentioned alone or in combination of two or more. Can be used.

  Moreover, as a commercial item of synthetic hydrotalcite, Kyowa Chemical Industry Co., Ltd. product; Alkamizer, DHT-4A, Kyoward 500, Kyoward 1000, Sakai Chemical Co., Ltd. STABIACE series HT-1, HT -7, HT-P and the like.

  Particularly preferred are synthetic hydrotalcites having an average particle size of 2 μm or less, more preferably 1 μm or less. Further, these hydrotalcites can be used in the anhydrous state as they are in the form of hydrates or after baking.

  It is preferable that the compounding quantity of a layered double hydroxide (B) shall be 0.1-30 wt% of the whole composition amount. The range is preferably 0.5-30 wt%, more preferably 0.1-25 wt%. If the blended amount of the layered double hydroxide (B) is more than the above range, the viscosity and thixotropy of the composition will be too high, the printability may be lowered, and the cured product may be brittle. Absent. On the other hand, if it is less than 0.1 wt%, the effect of electrode corrosion resistance is impaired, which is not preferable.

When the curable resin composition of the present invention is formed into a photocurable resin composition, the composition further contains a photopolymerization initiator.
The photopolymerization initiator used in the present invention is at least selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. One type of photoinitiator can be used.

（式中、Ｘは、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数1〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数1〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、結合か、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルで表し、ｎは０か１の整数である。） Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Japan, N-1919, NCI-831 manufactured by Adeka, and the like as commercially available products. Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.

(In the formula, X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms). A group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms), Represents an amino group, an alkylamino group having a C 1-8 alkyl group or a dialkylamino group, and Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, and a carbon number of 1 Alkyl group having ˜8 alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms) Or substituted with a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkyl group) Anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar is a bond or alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, Anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1)

  In particular, in the above general formula, X and Y are each a methyl group or an ethyl group, Z is a methyl group or a phenyl group, n is 0, Ar is a bond, phenylene, naphthylene, thiophene or thienylene. It is preferable that

  The blending amount of such an oxime ester photopolymerization initiator is preferably 0.02 to 10 wt% of the total amount of the composition. When it is less than 0.02 wt%, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are deteriorated. On the other hand, when it exceeds 10 wt%, light absorption on the surface of the solder resist coating film becomes intense, and the deep curability tends to be lowered.

  Specific examples of the α-aminoacetophenone photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1. -(4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like can be mentioned. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Japan.

  Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6- And dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by Ciba Japan.

  The blending amount of these α-aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.5 to 15 wt% of the total amount of the composition. If it is less than 0.5 wt%, the photocurability on copper is similarly insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are lowered. On the other hand, when it exceeds 15 wt%, the effect of reducing the outgas cannot be obtained, and the light absorption on the surface of the solder resist coating film becomes intense and the deep curability tends to be lowered.

  In addition, examples of the photopolymerization initiator, photoinitiator assistant, and sensitizer that can be suitably used in the photocurable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenones. Compounds, tertiary amine compounds, and xanthone compounds.

  Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.

  Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, and the like.

  Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

  Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

  Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyl. And diphenyl sulfide.

  Specific examples of the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.). Dialkylaminobenzophenone such as 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4 Dimethylamino group-containing coumarin compounds such as -methylcoumarin), ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics) ) 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamylethyl ester (Nippon Kayaku Co., Ltd. Kayacure DMBI), 4-dimethylamino Examples include 2-ethylhexyl benzoate (Esolol 507 manufactured by Van Dyk), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), and the like.

  Of the above photopolymerization initiator, photoinitiator assistant and sensitizer, thioxanthone compounds and tertiary amine compounds are preferred. In particular, the inclusion of a thioxanthone compound is preferable from the viewpoint of deep curability. Among them, it is preferable to include a thioxanthone compound such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

  The amount of such a thioxanthone compound is preferably 15 wt% or less of the total amount of the composition. When the blending amount of the thioxanthone compound exceeds 15 wt%, the thick film curability is lowered and the cost of the product is increased. More preferably, it is 10 wt% or less.

  As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.

  As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm and is in the ultraviolet region, so it is less colored and uses not only a colorless and transparent photosensitive composition but also a colored pigment, which reflects the color of the colored pigment itself. A colored solder resist film can be provided. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  As a compounding quantity of such a tertiary amine compound, it is preferable to set it as 0.1-15 wt% of the whole composition amount. When the compounding amount of the tertiary amine compound is less than 0.1 wt%, a sufficient sensitizing effect tends not to be obtained. If it exceeds 15 wt%, light absorption on the surface of the dried solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to be lowered.

These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
The total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the curable resin of the present invention. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  In addition, since these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, in some cases, the sensitivity is lowered, and the photopolymerization initiator, the photoinitiator assistant, and the sensitizer may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to improve the photoreactivity of the surface, change the resist line shape and opening to vertical, tapered, reverse taper, and processing accuracy of line width and opening diameter Can be improved.

  The curable resin composition of the present invention can further contain a compound having a carbodiimide group. By containing the compound which has a carbodiimide group, it can bridge | crosslink with the unreacted hydroxyl group and unreacted carboxyl group which remain | survive in hardened | cured material, and a coating-film intensity | strength can be improved. Furthermore, coating film deterioration due to hydrolysis of ester bonds can be suppressed.

  The compound having a carbodiimide group used in the present invention can be easily obtained from the market. Specific examples include Carbodilite V-03, Carbodilite V-06, Carbodilite 10M-SP, Carbodilite 9010, etc., manufactured by Nisshinbo Co., Ltd. Carbodilite series.

  The compounding amount of the compound having a carbodiimide group is suitably 0.5 to 40 wt%, preferably 1 to 30 wt% of the total amount of the composition. When the compounding quantity of the compound which has a carbodiimide group is too much than the said range, since the intensity | strength of a coating film falls, it is unpreferable. On the other hand, when it is less than 0.5 wt%, the effect of hydrolysis resistance is impaired, which is not preferable.

  In the photocurable resin composition of the present invention, known and commonly used N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, and the like can be used as chain transfer agents in order to improve sensitivity. Specific examples of chain transfer agents include, for example, chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol, Chain transfer agents having a hydroxyl group such as mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclope Tanchioru, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol like.

  Further, examples of the heterocyclic compound having a mercapto group acting as a chain transfer agent include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, and 2-mercapto. -4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4- Butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) Ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5-va Lolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto- Examples include 5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, and 2-mercapto-6-hexanolactam.

  In particular, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2,4-triazole as a heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the photocurable resin composition 5-methyl-1,3,4-thiadiazole-2-thiol and 1-phenyl-5-mercapto-1H-tetrazole are preferred. These chain transfer agents can be used alone or in combination of two or more.

  Further, the photocurable resin composition of the present invention may contain a conventionally known carboxyl group-containing photosensitive resin for the purpose of improving photosensitivity, developability, heat resistance, and electrical characteristics. As specific examples of the carboxyl group-containing photosensitive resin, compounds listed below (any of oligomers and polymers) may be preferable.

  (1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene. A carboxyl group-containing photosensitive resin obtained by reacting a compound having one or more ethylenically unsaturated groups and one epoxy group in a molecule.

  (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (3) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

  (4) During the synthesis of the resin of the above (2) or (3), a compound having one hydroxyl group and one or more (meth) acryl groups in the molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing photosensitive urethane resin.

  (5) During the synthesis of the resin of the above (2) or (3), one isocyanate group and one or more (meth) acryl groups are added in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal (meth) acrylate.

  (6) Carboxyl group-containing photosensitivity in which (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin as described later and a dibasic acid anhydride is added to the hydroxyl group present in the side chain. Resin.

  (7) A polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. Added carboxyl group-containing photosensitive resin.

  (8) A cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenol compound such as novolak, and the resulting hydroxyl group is partially esterified with (meth) acrylic acid, and a polybasic acid is added to the remaining hydroxyl group. A carboxyl group-containing photosensitive resin obtained by reacting an anhydride.

  (9) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth) acryl groups in one molecule to the resins (1) to (8).

  Among these, the resins mentioned in (1), (2), modified products thereof (4) and (5), and (8) can be used without using an epoxy compound (resin) made of epichlorohydrin as a raw material. Since a carboxylic acid-containing resin can be synthesized, it is particularly preferable from the viewpoint of halogen-free. In addition, even if it is an epoxy compound (resin), halogen-free can also be achieved by using the epoxy compound (resin) which does not use epichlorohydrin. Furthermore, as long as the isocyanate compound used in the resin synthesis is possible, one using an isocyanate which is not a phosgene method as a raw material is preferable.

  Since the carboxyl group-containing photosensitive resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.

  The acid value of the carboxyl group-containing photosensitive resin is suitably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.

  Moreover, although the weight average molecular weight of the said carboxyl group-containing photosensitive resin changes with resin frame | skeleton, what is generally in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

The amount of such a carboxyl group-containing photosensitive resin is 50 wt% or less, preferably 10 to 40 wt% of the total composition.
These carboxyl group-containing photosensitive resins are not limited to those listed above, and can be used singly or in combination of two or more.

  The curable resin composition of the present invention can contain a thermosetting component in order to impart heat resistance or to form a thermosetting resin composition. Examples of thermosetting components used in the present invention include amine resins such as melamine resins and benzoguanamine resins, blocked isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, bismaleimides, and oxazine compounds. In addition, a known and commonly used thermosetting resin such as an oxazoline compound can be used. Particularly preferred is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as “cyclic (thio) ether groups”) in the molecule.

  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 The compound which has this, ie, an episulfide resin etc. are mentioned.

  Examples of the polyfunctional epoxy compounds include epoxidized vegetable oils such as Adeka Sizer O-130P, Adeka Sizer O-180A, Adeka Sizer D-32, and Adeka Sizer D-55 manufactured by Asahi Denka; jER828 and jER834 manufactured by Japan Epoxy Resin Co., Ltd. , JER1001, jER1004, EHPE3150 manufactured by Daicel Chemical Industries, Epicron 840, Epicron 850, Epicron 1050, Epicron 1505, Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Tohto Kasei Co., Ltd. D. Chemicals manufactured by Dow Chemical Company. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R. 664, Ciba Japan's Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo A . E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., Dow Chemical Company D. E. R. 542, Araldide 8011 manufactured by Ciba Japan, Sumi-epoxy ESB-400 and ESB-700 manufactured by Sumitomo Chemical Co., Ltd. E. R. 711, A.I. E. R. 714 (both trade names) brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resin, D.C. E. N. 431, D.D. E. N. 438, Epicron N-730 manufactured by DIC, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., Araldide ECN1235, Araldide ECN1273, Araldide ECN1299 manufactured by Ciba Japan Araldide XPY307, Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo Co., Ltd. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170, YDF-175 manufactured by Toto Kasei Co., YDF- 2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Japan Co., Ltd. (all trade names); hydrogenated bisphenol such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Tohto Kasei Co., Ltd. Type A epoxy resin: jER604 manufactured by Japan Epoxy Resin, Epototo YH-434 manufactured by Tohto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Japan, Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. ) Glycidylamine type epoxy resin; Hydantoin type epoxy resins such as Araldide CY-350 (trade name) manufactured by Bread; Celoxide 2021 manufactured by Daicel Chemical Industries, and alicyclic epoxy such as Araldide CY175 and CY179 manufactured by Ciba Japan Resin; YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Bisphenol S type epoxy resins such as xylenol type or biphenol type epoxy resins or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by DIC Co., Ltd .; Bisphenol A novolak type epoxy resin such as epoxy resin jER157S (trade name); Tetraphenylolethane type such as jERYL-931 from Japan Epoxy Resin, Araldide 163 from Ciba Japan Co., Ltd. (all trade names) Epoxy resin; Aral made by Ciba Japan Id PT810, a heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries (all trade names); a diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; a tetraglycidyl xyleno such as ZX-1063 manufactured by Tohto Kasei Co., Ltd. Irethane resin; Nippon Steel Chemical Co., Ltd. ESN-190, ESN-360, DIC Corporation HP-4032, EXA-4750, EXA-4700 and other naphthalene group-containing epoxy resins; DIC Corporation HP-7200, HP-7200H Epoxy resins having a dicyclopentadiene skeleton such as CP-50S and CP-50M glycidyl methacrylate copolymer epoxy resins manufactured by Nippon Oil &Fats; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene Rubber derivatives (eg Iseru Chemical Co. PB-3600, etc.), CTBN modified epoxy resin (e.g., Tohto Kasei Co. YR-102, YR-450, etc.) and others as mentioned, is not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these, epoxide-modified compounds by the peracetic acid method such as EHPE3150, PB-3600, and Celoxide 2021 (all manufactured by Daicel Chemical Industries, Ltd.) are preferable because they do not contain halogen ions as impurities. Also, epoxidized vegetable oils such as Adeka Sizer D-32, Adeka Sizer D-55, Adeka Sizer O-130P, Adeka Sizer O-180A (all manufactured by ADEKA) and the like are preferable because they do not contain halogen.

  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, or the like ethers of a 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 Japan Epoxy Resins. 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.

  The amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents, more preferably, relative to 1 equivalent of carboxyl groups in the composition. A range of 0.8 to 2.0 equivalents is appropriate. When the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is less than 0.6 equivalent, the carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation, etc. Since it falls, it is not preferable. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.

  As another thermosetting component, a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be added. Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule. The compound which has, ie, a blocked isocyanate compound, etc. are mentioned.

  As said polyisocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.

  The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.

  As such a blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As this isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam. Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, milk Alcohol blocking agents such as methyl and ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine I can get lost.

  The block isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS- 2117, Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nippon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B -846, B-870, B-874, B-882 (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (trade name, manufactured by Asahi Kasei Chemicals Corp.) and the like. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

The compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.
The compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is appropriately 1 wt% to 50 wt%, more preferably 2 to 40 wt% of the total amount of the composition. When the blending amount is less than 1 wt%, it is not preferable because sufficient toughness of the coating film cannot be obtained. On the other hand, when it exceeds 50 wt%, storage stability falls and it is not preferable.

  Furthermore, examples of other thermosetting components include melamine derivatives and benzoguanamine derivatives. Examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.

  Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx -290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw -750LM, (above, manufactured by Sanwa Chemical Co., Ltd.) and the like. The said thermosetting component can be used individually or in combination of 2 or more types.

  When using the thermosetting component which has a some cyclic | annular (thio) ether group in the said molecule | numerator, it is preferable to contain a thermosetting catalyst. 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 the thermosetting catalyst.

  The blending amount of these thermosetting catalysts is sufficient in the usual quantitative ratio. It is 20 mass parts, More preferably, it is 0.5-15.0 mass parts.

  In the curable resin composition of the present invention, an adhesion promoter can be used in order to improve adhesion between layers or adhesion between the photosensitive resin layer and the substrate. Specific examples include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione. , 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent, etc. .

  The photocurable resin composition of the present invention can contain a compound having a plurality of ethylenically unsaturated groups in the molecule. The compound having a plurality of ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention is photocured by irradiation with active energy rays, and the curable resin of the present invention or the carboxyl group-containing photosensitivity. The insoluble resin is insolubilized in the aqueous alkali solution or helps insolubilization. As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth) acrylate can be used. Hydroxyalkyl acrylates such as hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; N, N-dimethylacrylamide, N-methylolacrylamide, N Acrylamides such as N, N-dimethylaminopropyl acrylamide; N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate Aminoalkyl acrylates such as alcohols; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or their ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone Polyvalent acrylates such as adducts; polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; glycerin diglycidyl ether, glycerin triglycidyl ether, tri Polyvalent acrylates of glycidyl ethers such as methylolpropane triglycidyl ether, triglycidyl isocyanurate; Not limited to the above, it corresponds to acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, and / or the above acrylates. Each methacrylate is mentioned.

  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 several ethylenically unsaturated groups in such a molecule | numerator is 1-70 wt% in the solid content of a composition, More preferably, it is 5-60 wt%, The said carboxyl group containing photosensitive resin and When using together, the ratio of 5-100 mass parts with respect to 100 mass parts of carboxyl group-containing photosensitive resin, More preferably, the ratio of 5-70 mass parts is suitable. 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.

  The curable resin composition of the present invention can contain a colorant. As the colorant, conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.

Red colorant:
Examples of red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. -Index (CI; issued by The Society of Dyers and Colorists) number.
Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
Disazo: Pigment Red 37, 38, 41.
Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1,68.
Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.
Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.
Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
Condensed azo series: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242.
Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.
Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:
Blue colorants include phthalocyanine-based and anthraquinone-based pigments, and pigment-based compounds such as Pigment Blue 15 and Pigment Blue 15 are listed below. : 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, and Pigment Blue 60.
The dye systems include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:
Similarly, green colorants include phthalocyanine, anthraquinone, and perylene. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:
Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
Isoindolinone type: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
Condensed azo series: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.
Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.
Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183.
Disazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.
Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black And the like.

  The mixing ratio of the colorant as described above is not particularly limited, but 5 wt% or less, more preferably 0.1 to 3 wt% is sufficient in the solid content of the composition.

  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 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, ADK STAB LA-87 (all manufactured by Asahi Denka), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, all manufactured by TINUVIN 5100 ) And the like.

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 commercially available, and examples thereof include ADK STAB TPP (manufactured by Asahi Denka Co., Ltd.), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd.), and Sumilizer TPS (manufactured by Sumitomo Chemical Co., Ltd.). It is done.
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 Ciba Japan).

  The ultraviolet absorbers as described above can be used singly or in combination of two or more. By using in combination with an antioxidant, the stability of the molded product obtained from the curable resin composition of the present invention can be improved. Can be achieved.

  The curable resin composition of the present invention can contain a filler as necessary in order to increase the physical strength of the coating film. As such a filler, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica and talc are preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers. The blending amount of the filler is preferably 75 wt% or less, more preferably 0.1 to 60 wt% of the total amount of the composition. When the blending amount of the filler exceeds 75 wt% of the total amount of the composition, the viscosity of the insulating composition becomes high, the coating and moldability are lowered, and the cured product becomes brittle.

  Further, the curable resin composition of the present invention is a viscosity adjustment for the synthesis of the curable resin of the present invention and the carboxyl group-containing photosensitive resin, for the preparation of the composition, or for application to a substrate or a carrier film. Therefore, an organic solvent can be used.

  Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Such as propylene glycol butyl ether acetate, methyl 2-hydroxyisobutyrate Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

  If necessary, the curable resin composition of the present invention may be a known thermal polymerization inhibitor, a known conventional thickener such as finely divided silica, organic bentonite, or montmorillonite, a silicone type, a fluorine type, a polymer type, or the like. Known additives such as antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, rust inhibitors, and the like can be blended.

  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 curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method with the organic solvent, for example, on the substrate, dip coating method, flow coating method, roll coating method, bar coater method, screen printing 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 (preliminary 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, in the case of a photo-curable resin composition, by a contact method (or non-contact method), exposure is selectively performed with an active energy ray through a photomask on which a pattern is formed or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion Is developed with a dilute alkali aqueous solution (for example, 0.3 to 3 wt% sodium carbonate aqueous solution) to form a resist pattern. Furthermore, in the case of a composition containing a thermosetting component, for example, by heating and curing at a temperature of about 140 to 180 ° C., the carboxyl of the curable resin of the present invention or the carboxyl group-containing photosensitive resin is obtained. The group and a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups in the molecule reacted, and were excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. A cured coating film can be formed. In addition, even when it does not contain a thermosetting component, by performing heat treatment, the ethylenically unsaturated bond of the photocurable component remaining in an unreacted state at the time of exposure undergoes thermal radical polymerization, and the coating film characteristics are improved. Therefore, heat treatment (thermosetting) may be performed depending on the purpose and application.

  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 the application of the curable resin composition of the present invention includes a hot-air circulating drying furnace, an IR furnace, a hot plate, a convection oven, etc. (with a heat source of an air heating method using steam) It is possible to use a method in which hot air is brought into countercurrent contact and a method in which a hot air is blown onto a support.

  As mentioned above, after apply | coating the photocurable 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 curable resin composition of the present invention is in the form of a dry film having a solder resist layer formed by applying and drying a solder resist in advance on a film of polyethylene terephthalate or the like, in addition to a method of directly applying to a substrate in a liquid state. It can also be used. The case where the curable 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. The solder resist layer is a layer obtained by, for example, applying and drying an alkali-developable photocurable resin composition on a carrier film or a cover film. 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 an alkali-developable photocurable 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, and 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.

Carboxyl group-containing acrylate synthesis example 1
Charged 384 parts of recycled PET flakes having an IV value of 0.6 to 0.7 to a 500 ml four-necked round bottom separable lasco equipped with a stirrer, nitrogen introduction tube, and cooling tube, and the atmosphere in the flask was changed to 300 ° C. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 1.30 parts of dibutyltin oxide was added. Next, 134 parts of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Then, the salt bath was replaced with an oil bath that had been heated to 240 ° C. in advance, and the temperature inside the flask was kept at 220 ° C. ± 10 ° C. and reacted for 5 hours. Next, 150 parts of this reaction product was placed in a 500 mL four-necked flask equipped with a stirrer, an air introduction tube, a fractionation tube, and a cooling tube, and 31.2 parts of acrylic acid, 1.82 parts of paratoluenesulfonic acid, paramethoxy 0.17 parts of phenol, 76 parts of methyl isobutyl ketone and 38 parts of toluene were added and dissolved uniformly by stirring, then immersed in an oil bath heated to 115 ° C. ± 5 ° C., and the reaction was continued for a predetermined time. After completion of the reaction, the acid value of the reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask and stirred to neutralize. Next, brine (20 wt%) was added and stirred. Thereafter, the solution was transferred to a separatory funnel, the same amount of methyl ethyl ketone as the reaction solution was added, and the aqueous phase was discarded. The oil phase was washed twice with brine (5 wt%) and the aqueous phase was discarded. Furthermore, the oil phase was washed twice with a small amount of tap water, and the aqueous phase was discarded. Next, the reaction solution was transferred to a beaker, the oil phase was stirred with hexane in the beaker, and the supernatant was discarded after standing. Finally, it concentrated by the evaporator and PET containing acrylate resin A was obtained. Next, 50 parts of PET-containing acrylate resin A and 30 parts of carbitol acetate were charged into a 300 mL four-necked round bottom flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, and the inside of the flask was made into a nitrogen atmosphere. It was immersed in an oil bath heated to ± 5 ° C. Next, 20 parts of tetrahydrophthalic anhydride was added to 2.5 parts while gradually adding dropwise a carbitol acetate solution prepared by dissolving 0.8 parts of triphenylphosphine and 0.4 parts of methoquinone in 7.8 parts of carbitol acetate. The reaction was carried out for 10 hours while adding in four portions every time to obtain a resin solution of carboxyl group-containing acrylate having a solid content of 65% and a solid content acid value of 119 mgKOH / g. This resin solution is designated as varnish A.

Carboxyl group-containing acrylate synthesis example 2
384 parts of recycled PET flakes having an IV value of 0.6 to 0.7 were charged in a 1000 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen introducing tube, and a cooling tube. It was immersed in a heated salt bath. When PET was dissolved, stirring was started and 1.6 parts of dibutyltin oxide was added. Next, 134 parts of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Then, the salt bath was replaced with an oil bath that had been heated to 240 ° C. in advance, and the temperature inside the flask was kept at 220 ° C. ± 10 ° C. and reacted for 5 hours. Next, 518 parts of this reaction product was placed in a 1000 mL four-necked flask equipped with a stirrer, an air introduction tube, a fractionation tube, and a cooling tube, 81 parts of acrylic acid, 2.4 parts of paratoluenesulfonic acid, and paramethoxyphenol 0. 8 parts, 212 parts of methyl isobutyl ketone and 112 parts of toluene were stirred and dissolved uniformly, then immersed in an oil bath heated to 115 ° C. ± 5 ° C., and the reaction was continued for a predetermined time. After completion of the reaction, the acid value of the reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask and stirred to neutralize. Next, brine (20 wt%) was added and stirred. Thereafter, the solution was transferred to a separatory funnel, the same amount of methyl ethyl ketone as the reaction solution was added, and the aqueous phase was discarded. The oil phase was washed twice with brine (5 wt%) and the aqueous phase was discarded. Furthermore, the oil phase was washed twice with a small amount of tap water, and the aqueous phase was discarded. Next, the reaction solution was transferred to a beaker, the oil phase was stirred with hexane in the beaker, and the supernatant was discarded after standing. Finally, it concentrated by the evaporator and PET containing acrylate resin B was obtained. Next, 50 parts of PET-containing acrylate resin B and 27 parts of carbitol acetate were charged into a 300 mL four-necked round bottom flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, and the flask was filled with nitrogen atmosphere. It was immersed in an oil bath heated to + 5 ° C. Next, 20 parts of tetrahydrophthalic anhydride was added every 2.5 hours while gradually adding a carbitol acetate solution prepared by dissolving 0.8 part of triphenylphosphine and 0.4 part of methoquinone in 10 parts of carbitol acetate. The reaction was carried out for 10 hours while adding in 4 portions to obtain a resin solution of carboxyl group-containing acrylate having a solid content of 65% and a solid content acid value of 128 mgKOH / g. This resin solution is designated as varnish B.

Carboxyl group-containing acrylate synthesis example 3
Orthocresol novolak epoxy resin (600 parts by diethylene glycol monoethyl ether acetate, DIC Corporation, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 parts (number of glycidyl groups (total number of aromatic rings) ): 5.0 moles), 360 parts (5.0 moles) of acrylic acid, and 1.5 parts of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved. Next, 4.3 parts of triphenylphosphine was added, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction liquid, 415 parts of aromatic hydrocarbon (Sorvesso 150) and 456.0 parts (3.0 mol) of tetrahydrophthalic anhydride (THPA) were charged, reacted at 110 ° C. for 4 hours, cooled, A resin solution having a solid content acid value of 89 mgKOH / g and a solid content of 65% was obtained. This resin solution is named Varnish C.

Example of Synthesis of Carboxylic Acid Resin 192 parts of recycled PET flakes having an IV value of 0.6 to 0.7 were charged in a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen introduction tube and a cooling tube, and the inside of the flask was made a nitrogen atmosphere. Then, it was immersed in a salt bath heated to 300 ° C. When PET was dissolved, stirring was started and 0.65 part of dibutyltin oxide was added. Next, 134 parts of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Next, the oil bath was preliminarily heated to 240 ° C. from the salt bath, the flask internal temperature was kept at 220 ° C. ± 10 ° C., the reaction was performed for 5 hours, and then cooled to room temperature. Next, 121.6 parts of THPA and 240 parts of carbitol acetate were charged, the atmosphere in the flask was changed to a nitrogen atmosphere, and then immersed in an oil bath heated to 125 ± 5 ° C. Stirring was started gradually and the reaction was performed for 3 hours to obtain a carboxylic acid resin varnish having a non-volatile content of 65% and a solid content acid value of 103 mgKOH / g. This is varnish D.

Example of photosensitive resin synthesis 192 parts of recycled PET flakes having an IV value of 0.6 to 0.7 were charged in a 500 ml four-necked round bottom separable lasco equipped with a stirrer, a nitrogen introducing tube, and a cooling tube, and the inside of the flask was made a nitrogen atmosphere. Then, it was immersed in a salt bath heated to 300 ° C. When the PET flakes were dissolved, stirring was started and 0.65 part of dibutyltin oxide was added.
Next, 134 parts of trimethylolpropane previously heated and dissolved at 130 ° C. was added little by little while being careful not to solidify the PET. During this time, the stirring speed was increased to 150 rpm when the viscosity decreased. Then, the salt bath was replaced with an oil bath that had been heated to 240 ° C. in advance, and the temperature inside the flask was kept at 220 ° C. ± 5 ° C. and reacted for 5 hours. The reaction product was transparent yellow and soft viscous at room temperature.
To 100 parts of the obtained reaction product, 37 parts of toluene and 74 parts of methyl isobutyl ketone were introduced and mixed. Next, 65 parts of acrylic acid, 1.94 parts of paratoluenesulfonic acid, and 0.26 part of paramethoxyphenol were added and reacted at 110 ° C. for 100 hours, and cooled to room temperature. The acid value of the obtained reaction solution was measured, and an acid equivalent alkaline aqueous solution was added to the flask and stirred to neutralize. Next, 50 parts of brine was added and stirred.
Thereafter, the solution was transferred to a separating funnel, the aqueous phase was discarded, and the oil phase was washed twice with 100 parts of a 5 wt% NaCl solution. After washing, the solvent was distilled off with an evaporator to obtain a reaction product having a nonvolatile content of 100%. The obtained reaction product was a brown transparent soft liquid at room temperature. This is Resin E

Examples 1-6 and Comparative Examples 1-3
Using the resins obtained in the above synthesis examples, blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1 below, premixed with a stirrer, and then kneaded in a three-roll mill, A photosensitive resin composition for a solder resist was prepared.

上記表１中の符号の意味は以下のとおりである。
＊１ ハイドロタルサイト化合物：アルカマイザー 協和化学工業（株）製
＊２ ジペンタエリスリトールヘキサアクリレート：日本化薬（株）製
＊３ イルガキュアＯＸＥ０２ チバ・ジャパン社製
＊４ カルボジイミド化合物：カルボジライト１０Ｍ−ＳＰ 日清紡（株）製
＊５ ＥＨＰＥ３１５０（ダイセル化学工業（株）製）
＊６ ブロックイソシアネート（ＴＰＡ−Ｂ８０Ｅ；旭化成ケミカルズ（株）製）
＊７ トリグリシジルイソシアヌレート
＊８ メラミン
＊９ Ｉｒｇａｎｏｘ１０１０（チバ・ジャパン社製）
＊１０ ２-メルカプトベンゾチアゾール（アクセルＭ；川口化学工業（株）製）
＊１１ C.I.Pigment Blue 15:3
＊１２ C.I.Pigment Ｙellow 147
＊１３ 硫酸バリウム(Ｂ−３０：堺化学（株）製)
＊１４ ＫＳ−６６（信越シリコーン（株）製）
＊１５ ジプロピレングリコールモノメチルエーテル

The meanings of the symbols in Table 1 are as follows.
* 1 Hydrotalcite compound: Alkamizer Kyowa Chemical Industry Co., Ltd. * 2 Dipentaerythritol hexaacrylate: Nippon Kayaku Co., Ltd. * 3 Irgacure OXE02 Ciba Japan Co., Ltd. * 4 Carbodiimide compound: Carbodilite 10M-SP Nisshinbo * 5 EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.)
* 6 Block isocyanate (TPA-B80E; manufactured by Asahi Kasei Chemicals Corporation)
* 7 Triglycidyl isocyanurate * 8 Melamine * 9 Irganox 1010 (Ciba Japan)
* 10 2-mercaptobenzothiazole (Accel M; manufactured by Kawaguchi Chemical Co., Ltd.)
* 11 CIPigment Blue 15: 3
* 12 CIPigment Yellow 147
* 13 Barium sulfate (B-30: manufactured by Sakai Chemical Co., Ltd.)
* 14 KS-66 (Shin-Etsu Silicone Co., Ltd.)
* 15 Dipropylene glycol monomethyl ether

Performance evaluation:
<Recycled polyester content>
In the compositions of the examples and comparative examples, the content of the regenerated polyester resin relative to the total organic matter in the cured coating film was calculated.

<Optimum exposure amount>
A circuit pattern substrate having a copper thickness of 35 μm was polished with buffalo, washed with water and dried, and then the photo-curable thermosetting resin compositions of the examples and comparative examples were applied to the entire surface by a screen printing method, and hot air at 80 ° C. It was dried for 60 minutes in a circulation drying oven. After drying, exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and development (30 ° C., 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution) is performed at 60. When the pattern of the step tablet remaining when performing in seconds was 7 steps, the optimum exposure amount was set.

<Developability>
The photocurable thermosetting resin compositions of the examples and comparative examples were applied to a solid copper substrate by a screen printing method so that the film thickness after drying was about 25 μm, and a hot air circulation drying oven at 80 ° C. For 30 minutes. After drying, development was performed with a 1 wt% Na ₂ CO ₃ aqueous solution, and the time until the dried coating film was removed was measured with a stopwatch.

<Dry touch dryness>
The photocurable thermosetting resin compositions of the examples and comparative examples were each coated on the patterned copper foil substrate by screen printing, dried in a hot air circulation drying oven at 80 ° C. for 30 minutes, and brought to room temperature. Allowed to cool. A PET film was pressed against this substrate, and then the sticking state of the film when the negative film was peeled off was evaluated. The judgment criteria are as follows.
(Double-circle): When peeling a film, there is no resistance and a trace is not left in a coating film.
○: When the film is peeled off, there is no resistance, but the coating film has a slight mark.
(Triangle | delta): When peeling a film, there exists resistance slightly and the coating film has a trace.
X: When the film is peeled off, there is resistance and the coating film is clearly marked.

<Resolution>
A circuit pattern substrate having a line / space of 300/300 and a copper thickness of 35 μm was coated with the photocurable thermosetting resin compositions of Examples and Comparative Examples by buffing, washing with water and drying, followed by screen printing. , And dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. After drying, exposure was performed using an exposure apparatus equipped with a high-pressure mercury lamp. For the exposure pattern, a negative was used to draw a 20/30/40/50/60/70/80/90/100 μm line in the space. The active energy ray was irradiated so that the exposure amount became the optimal exposure amount of the photosensitive resin composition. After the exposure, a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa, and cured at 150 ° C. for 60 minutes to obtain a cured coating film. It determined using the optical microscope which adjusted the minimum residual line of the cured coating film of the obtained photosensitive resin composition for solder resists 200 times, and made this resolution.

<Halogen content>
Using the resin solutions obtained in each of the above synthesis examples, the various components shown in Table 1 above were blended in the proportions (parts by mass) shown in Table 1, premixed with a stirrer, and then kneaded with a three-roll mill. A photocurable thermosetting resin composition was prepared. The obtained photocurable thermosetting resin composition was quantified in terms of halogen ion impurity content (total of chlorine and bromide) by using a flask combustion treatment ion chromatograph method based on the JPCA standard. The results are shown in Table 2. In addition, the description regarding the thing whose halogen concentration is 20 ppm or less is set to [-].

Characteristic test:
The compositions of Examples and Comparative Examples were applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. This substrate is exposed to a solder resist pattern at an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and developed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. for 60 seconds under a spray pressure of 0.2 MPa. And a resist pattern was obtained. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
A: Peeling is not observed even after 10 seconds of immersion for 6 or more times.
○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more.
(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated 3 times or more.
X: The resist layer swells and peels off within 3 times for 10 seconds.

<Electroless gold plating resistance>
Using commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 0.5 μm and gold 0.03 μm, and the tape peeling causes the presence or absence of resist layer peeling or plating penetration. After evaluating the presence or absence, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
A: No soaking or peeling is observed.
○: Slight penetration is confirmed after plating, but does not peel off after tape peeling.
Δ: Slight penetration after plating and peeling after tape peel.
X: There is peeling after plating.

<Alkali resistance>
The evaluation substrate was immersed in a 10 wt% NaOH aqueous solution at room temperature for 30 minutes, and soaking, dissolution of the coating film, and peeling by tape beer were confirmed. The judgment criteria are as follows.
○: No soaking, melting or peeling.
Δ: Slight penetration, dissolution or peeling is confirmed.
X: Significant infiltration, dissolution or peeling.

<Electrode discoloration resistance>
An evaluation substrate was produced under the above conditions using a comb / electrode pattern of line / space = 50/50 μm instead of the copper foil substrate. H. A bias voltage of DC 305 V was applied under the heating and humidification conditions, and the degree of discoloration of the coating film around the electrode after 100 hours was evaluated. The judgment criteria are as follows.
○: No discoloration of the coating film.
(Triangle | delta): Discoloration of a coating film is confirmed slightly.
X: Discoloration of coating film is present.

<Dry film production>
After appropriately diluting each of the photosensitive resin compositions for solder resist of Example 1 and Comparative Example 2 with methyl ethyl ketone, using an applicator, a PET film (Toray FB-50: Toray FB-50: having a thickness of 30 μm after drying) 16 μm) and dried at 40 to 100 ° C. to obtain a dry film.

<Board fabrication>
After the circuit-formed substrate is buffed, the dry film produced by the above method is pressurized using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho): 0.8 MPa, 70 ° C., 1 minute, vacuum degree The substrate (unexposed substrate) having an unexposed solder resist layer was obtained by heat lamination under the condition of 133.3 Pa. Each of the obtained substrates was tested in the same manner as in the above evaluation method for optimum exposure, developability, resolution, solder heat resistance, gold plating resistance, and alkali resistance.
The evaluation results are shown in Table 2.

  As described above, the curable resin composition of the present invention is excellent in electrode corrosion resistance, and can reduce the burden on the environment by using PET bottle waste as a raw material. In particular, it was found to be useful as a solder resist.

Claims (6)

(A) A curable resin derived from a compound containing a structure represented by the following general formula (1), (B) a curable resin composition containing a layered double hydroxide , wherein the general formula (1) (B) a polyol having two or more hydroxyl groups in one molecule, and the number of moles (α) of repeating units of the polyester and the number of moles of the polyol (β ) Is a polyol resin obtained by depolymerization at a ratio such that (α) / (β) = 0.5-3 .

(Wherein R ¹ represents an (m + 1) -valent polyhydric alcohol derivative, m and n are an integer of 1 or more and less than 10, l is an integer of 0 or 1 and R ² is CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , any of a substituted or unsubstituted aromatic ring, and R ³ represents a substituted or unsubstituted aromatic ring. The curable resin composition according to claim 1 , wherein the polyester (a) is a recycled polyester. The curable resin composition according to claim 1 or 2, characterized by containing a compound having a carbodiimide group. A curable dry film obtained by applying and drying the curable resin composition according to any one of claims 1 to 3 on a film. A curable resin composition according to any one of claims 1 to 3 , or a curable dry film obtained by applying and drying the curable resin composition on a film, and obtained by curing in a pattern. Cured product. A curable resin composition according to any one of claims 1 to 3 , or a photocurable dry film obtained by applying and drying the curable resin composition on a film, photocured in a pattern. A printed wiring board having a cured film obtained by heat curing.