JP2011053420A - Alkali-developable photocurable resin composition, dry film and cured product thereof, and printed wiring board using those - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkali-developable photocurable resin composition excellent in developability (particularly in a through-hole part), having high sensitivity and excellent in soldering heat resistance, electroless gold plating resistance, electric insulation and the like, a dry film and cured product of the composition, and a printed wiring board on which a cured coating such as a solder resist is formed with the dry film or cured product. <P>SOLUTION: The photocurable resin composition includes: a carboxylic acid resin derived from a compound represented by general formula (1); a compound having a plurality of ethylenically unsaturated groups in one molecule; and a photopolymerization initiator. The carboxylic acid resin is obtained by depolymerizing (a) a polyester with (b) a polyol having a plurality of hydroxyl groups in one molecule, and reacting the resulting product with (c) a saturated or unsaturated polybasic acid or an anhydride thereof. The photocurable resin composition preferably contains a thermocurable component. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photocurable resin composition that can be developed with an aqueous alkali solution, in particular, a composition for a solder resist that is photocured by ultraviolet exposure or laser exposure, a dry film and a cured product thereof, and a cured film formed using them. It is related with the printed wiring board which has.

  The solder resist is intended to protect the circuit of the printed circuit board, and is formed on the surface layer of the circuit board on which the circuit is formed. In general, the substrate on which the circuit is formed has not only a circuit on the surface layer but also numerous holes called through holes. In the production of printed wiring boards, photo solder resist is generally employed, and dry film type photo solder resist and liquid photo solder resist are being developed. Among these, in consideration of environmental problems, an alkali development type photosensitive resin composition using an aqueous alkali solution as a developing solution has become the mainstream, and several composition systems have been proposed (Patent Document 1). -3 etc.)

  Conventionally, when a solder resist is applied or laminated to a circuit board in which a through hole exists, the solder resist in the through hole portion flows into the through hole and is harder to develop than other places, and it is difficult to remove the resist. there were. On the other hand, the development time is extended or the cone shape of the spray is devised and removed, but the increase in the development time not only lowers the productivity but also forms the necessary fine line pattern of the resist. However, there is a problem that an excessive developer attack is caused, an undercut is generated in a necessary fine shape, and it cannot be finally formed. Further, in recent years, the printed wiring board has been increased in density, multilayered, and through-holes have been reduced in size due to the reduction in the thickness of electronic components, and the above problems have become serious.

JP 61-243869 (Claims) JP-A-11-288091 (Claims) JP-A-5-32746 (Claims)

The present invention has been made in view of the prior art as described above, has excellent developability (particularly through-hole portion), high sensitivity, excellent solder heat resistance, electroless gold plating resistance, electrical insulation, and the like. An object of the present invention is to provide an alkali-developable photocurable resin composition in consideration of the problem.
Furthermore, the object of the present invention is to obtain a dry film and a cured product excellent in various properties as described above obtained by using such a photocurable resin composition, and to cure a solder resist or the like with the dry film or the cured product. It is providing the printed wiring board by which a membrane | film | coat is formed.

式中、Ｒ^１は（ｍ＋１）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１０未満の整数であり、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（特にベンゼン環もしくはナフタレン環）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（特にベンゼン環もしくはナフタレン環）を表す。 In order to achieve the above object, according to the present invention, a carboxylic acid resin derived from a compound containing a structure represented by the following general formula (1), a compound having a plurality of ethylenically unsaturated groups in one molecule, And an alkali-developable photocurable resin composition comprising a photopolymerization initiator.

In the formula, R ¹ represents an (m + 1) -valent polyhydric alcohol derivative, m and n are integers of 1 or more and less than 10, l is an integer of 0 or 1 and less than 10, and R ² is CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , a substituted or unsubstituted aromatic ring (particularly a benzene ring or a naphthalene ring), and R ³ represents a substituted or unsubstituted aromatic ring ( In particular, it represents a benzene ring or a naphthalene ring.

  In a preferred embodiment, the carboxylic acid resin comprises (a) polyester (b) depolymerized with a polyol having a plurality of hydroxyl groups in one molecule, or (c) a saturated or unsaturated polybasic acid or its It was obtained by reacting an anhydride. In this case, the polyol (b) having a plurality of hydroxyl groups in one molecule is preferably at least trimethylolpropane and / or polycarbonate diol. In a more preferred embodiment, the photocurable resin composition further contains a thermosetting component, more preferably a carboxyl group-containing resin (however, derived from a compound having a structure represented by the general formula (1)). A carboxyl group-containing resin), and more preferably a colorant. Such a photocurable resin composition, in particular, a photocurable / thermosetting resin composition containing a thermosetting component can be suitably used as a solder resist.

Further, according to the present invention, the photocurable resin composition obtained by applying and drying the photocurable resin composition on a carrier film, the photocurable resin composition or the dry film is cured. In addition, a cured product obtained by photo-curing on copper, and a cured product obtained by photo-curing 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 photocurable resin composition of the present invention has, as a development aid, a carboxylic acid resin derived from a compound containing the structure represented by the general formula (1), particularly a polyester having a plurality of hydroxyl groups in one molecule. It contains a carboxylic acid resin obtained by further reacting a saturated or unsaturated polybasic acid or its anhydride with a polyol containing the structure represented by the general formula (1) obtained by depolymerization with a polyol. Therefore, it is possible to form a cured film excellent in alkali developability, particularly through-hole developability, and excellent in solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, and the like.
Therefore, the photocurable 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.

As described above, the photocurable resin composition of the present invention is characterized in that a carboxylic acid resin made from a compound containing the structure represented by the general formula (1) is used as a development aid. .
According to the study by the present inventors, the photocurable resin composition obtained by containing a carboxylic acid resin derived from a compound containing the structure represented by the general formula (1) can develop a dry coating film. Compared to the case where it does not contain the carboxylic acid resin, the developability of the through hole is good and the solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, etc. are excellent. I found it.

  In the carboxylic acid resin, (a) polyester is depolymerized with (b) a polyol having a plurality of hydroxyl groups in one molecule, and (c) a saturated or unsaturated polybasic acid or an anhydride thereof is reacted at the same time or later. Since it is a carboxyl group-containing resin obtained by making it, it is excellent in developability. In particular, by changing the molar balance of the component (a) and the component (b), an oligomer having both a carboxyl group and a hydroxyl group is obtained. Since it is an oligomer having a hydroxyl group and a carboxyl group at the same time, it is considered that developability is improved as compared with the case of using a conventional carboxylic acid resin. Furthermore, by using a trifunctional or higher functional polyol as the component (b), the resulting oligomer can have a multi-branched structure, which is also considered to be a factor for improving developability. On the other hand, for example, when a styrene-acrylic acid copolymer (trade name: Jonkrill 68, manufactured by Johnson Polymer Co., Ltd.) which is a typical carboxylic acid resin or trimellitic acid which is a low molecular carboxylic acid is used. On the contrary, the developability of the surface is increased without increasing the developability of the through hole, and a dull state is obtained after development. At this time, the performance as a solder resist is inferior in electrical characteristics and the appearance is also poor. This was surprising and unexpected.

  The polyester (a) used for the synthesis of the compound having the structure represented by the general formula (1) as a raw material of the carboxylic acid resin may be any conventionally known polyester, but polyethylene terephthalate, polytrimethylene terephthalate. , Polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and liquid crystal polyesters such as polycondensates of 4,4-dihydroxybiphenol, terephthalic acid and parahydroxybenzoic acid. In addition, PET bottles, PET films, and other PET products manufactured after pulverization, and recycled polyester recovered from waste and washed can be obtained from the market. be able to.

  As the polyol (b) having a plurality of hydroxyl groups in one molecule, all polyols having two or more functional groups can be used and are not limited to specific ones. Bifunctional polyols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, spiro glycol, dioxane glycol, adamantane Diol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methylpropanediol, 1,3,3-methylpentanediol, 1, Ethylene oxide modification of bifunctional phenols such as 5-hexamethylene glycol, octylene glycol, 9-nonanediol, 2,4-diethyl-1,5-pentanediol, bisphenol A A compound, a propylene oxide-modified compound of a bifunctional phenol such as bisphenol A, an ethylene oxide of a bifunctional phenol such as bisphenol A, a propylene oxide copolymer-modified compound, a copolymer polyether polyol of ethylene oxide and propylene oxide, a carbonate diol, Adamantanediol, polyether diol, polyester diol, hydroxyl-terminated polyalkanediene diols (e.g. elastomers such as 1,4-polyisoprenediol, 1,4- and 1,2-polybutadiene diols and their hydrogenated products) Is mentioned. As a commercially available product, for example, as an example of a commercially available product of the above hydroxyl group-terminated polyalkanedienediol, Epol (made by Idemitsu Petrochemical Co., Ltd., hydrogenated polyisoprene diol, molecular weight 1,860, average polymerization degree 26), PIP ( Idemitsu Petrochemical Co., Ltd., polyisoprene diol, molecular weight 2,200, average polymerization degree 34), polytail HA (Mitsubishi Chemical Corporation, hydrogenated polybutadiene diol, molecular weight 2,200, average polymerization degree 39), R-45HT (Idemitsu) Examples include polybutanediol, molecular weight 2,270, and average degree of polymerization 42) manufactured by Petrochemical Co., Ltd. Examples of the tri- or higher functional polyol include glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, adamantanetriol, and more. Ethylene oxide or propylene oxide modified products are also included. Examples of the polyol having an aromatic ring include ethylene oxide or propylene oxide modified products of trifunctional or higher functional phenol compounds, and examples of those having a heterocyclic ring include Sake manufactured by Shikoku Kasei Kogyo Co., Ltd. These polyols can be used alone or in combination of two or more. Among these, trifunctional polyols typified by trimethylolpropane are preferable because they are free of turbidity when converted to a depolymerized product and have high solubility in a solvent. Accordingly, among the above polyols, those having trimethylolpropane and / or a derivative thereof as an essential component are preferred, and those containing at least 50 mol% of trimethylolpropane and / or a derivative thereof are particularly preferred. .

  In addition, a depolymerization catalyst can be used to promote the depolymerization. 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, particularly 0.05 to 3 parts by mass, with respect to 100 parts by mass of the total amount of the polyester (a) and polyol (b). It is desirable to be within.

  As the saturated or unsaturated polybasic acid or its anhydride (c) used for the synthesis of the carboxylic acid resin, a conventionally known polybasic acid or its anhydride can be used. Specific examples include phthalic anhydride, isophthalic acid, terephthalic acid, tetrabromophthalic anhydride, methyl hymic anhydride, tetrachlorophthalic anhydride and other aromatic polycarboxylic acids and their acid anhydrides, hexahydrophthalic anhydride , Cyclohydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and other alicyclic carboxylic acids and their anhydrides, maleic anhydride, fumaric acid, succinic anhydride, adipic acid, sebacine Examples thereof include aliphatic polyvalent carboxylic acids such as acids and azelaic acid and trifunctional or higher functional carboxylic acids such as acid anhydrides thereof, pyromellitic anhydride, trimellitic anhydride, and methylcyclohexene dicarboxylic acid anhydride.

  The blending ratio of the polyester (a) and the polyol (b) at the time of depolymerization is such that the ratio of the number of moles of polyol (B1) to the number of moles (A1) of the repeating unit of the polyester is (A1) / (B1). = 0.3 to 5, preferably 0.5 to 4.5. When the ratio is less than 0.3, polyol is excessively contained, and the ratio of aromatic rings derived from polyester is reduced. Therefore, dryness to touch when solder resist is used, solder heat resistance and electrical characteristics are reduced. Deteriorate. On the other hand, if the ratio is larger than 5, the polyester-derived crystallized product is almost present, which is not preferable because it is insoluble in a solvent. In addition, the reaction ratio (charge ratio) of the saturated or unsaturated polybasic acid or anhydride (c) with respect to the generated polyol is 0.1 mol to 3 mol of component (c) with respect to 1 mol of the generated polyol. A range is preferred.

The acid value of the carboxylic acid resin is desirably in the range of 10 to 200 mgKOH / g, preferably 20 to 120 mgKOH / g. When the acid value of the carboxylic acid resin is lower than 10 mgKOH / g, there is no effect of improving developability. On the other hand, when it is higher than 200 mgKOH / g, not only the through-hole but also the surface is developed, which is not preferable in terms of appearance. Insulation is also poor.
The weight average molecular weight of the carboxylic acid resin is preferably in the range of 600 to 50,000, more preferably 700 to 20,000. When the weight average molecular weight is less than 600, the touch-drying property (tack-free performance) of the coating film may be inferior, the moisture resistance of the coating film after exposure is poor, the film is reduced during development, and the resolution is greatly inferior. Sometimes. On the other hand, when the weight average molecular weight exceeds 50,000, developability may be remarkably deteriorated, and storage stability may be inferior.

  The blending amount of the carboxylic acid resin is 5 to 80% by mass in the solid content of the composition, more preferably 5 to 60% by mass. When used in combination with the carboxyl group-containing resin described later, the carboxyl group-containing resin and / or Or the range of 5-200 mass parts with respect to 100 mass parts of carboxyl group-containing photosensitive resin (when using 2 or more types, those total amounts, and the following similarly), The range of 10-100 mass parts is suitable. is there. If the amount of the carboxylic acid resin is more than the above range, not only the through-holes but also the surface is developed, which is not preferable in appearance and the electric insulation is also deteriorated.

  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 a carboxyl group-containing resin as described later is converted into an alkaline aqueous solution. Insolubilize or help insolubilization. Examples of such compounds include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, and the like. Polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts or propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycy Ethers, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates.

  Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further, 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 mass% in solid content of a composition, More preferably, it is 5-60 mass%, and carboxyl group-containing resin mentioned later When used together with 5 to 100 parts by mass, more preferably 5 to 70 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin and / or carboxyl group-containing photosensitive resin. When the compounding amount of the compound is less than the above range, the 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 above range is exceeded, the solubility in an alkaline aqueous solution is lowered and the coating film becomes brittle, which is not preferable.

式中、Ｒ^４は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基、もしくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基もしくはフェニル基で置換されていてもよい）を表し、
Ｒ^５は、フェニル基（炭素数１〜６のアルキル基、フェニル基もしくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基もしくはフェニル基で置換されていてもよい）を表し、
Ｒ^６及びＲ^７は、それぞれ独立に、炭素数１〜１２のアルキル基又はアリールアルキル基を表し、
Ｒ^８及びＲ^９は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、又は２つが結合した環状アルキルエーテル基を表し、
Ｒ^１０及びＲ^１１は、それぞれ独立に、炭素数１〜１０の直鎖状又は分岐状のアルキル基、シクロヘキシル基、シクロペンチル基、アリール基、又はハロゲン原子、アルキル基もしくはアルコキシ基で置換されたアリール基を表し、但し、Ｒ^１０及びＲ^１１の一方は、Ｒ−Ｃ（＝Ｏ）−基（ここでＲは、炭素数１〜２０の炭化水素基）を表してもよい。 As the photopolymerization initiator, an oxime ester photopolymerization initiator having a group represented by the following general formula (II), an α-aminoacetophenone photopolymerization initiator having a group represented by the following general formula (III) It is preferable to use one or more photopolymerization initiators selected from the group consisting of acylphosphine oxide photopolymerization initiators having a group represented by the following formula (IV).

In the formula, R ⁴ represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ⁵ is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups). Well, it may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 6 carbon atoms) Which may be substituted with an alkyl group or a phenyl group of
R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,
R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded,
R ¹⁰ and R ¹¹ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl substituted with a halogen atom, an alkyl group or an alkoxy group. Represents one group, but one of R ¹⁰ and R ¹¹ may represent an R—C (═O) — group (where R is a hydrocarbon group having 1 to 20 carbon atoms).

The oxime ester photopolymerization initiator having a group represented by the general formula (II) is preferably 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (V), The compound represented by the following general formula (VI) and the compound represented by the following general formula (VII) are mentioned.

式中、Ｒ^１２は、水素原子、ハロゲン原子、炭素数１〜１２のアルキル基、シクロペンチル基、シクロヘキシル基、フェニル基、ベンジル基、ベンゾイル基、炭素数２〜１２のアルカノイル基、炭素数２〜１２のアルコキシカルボニル基（アルコキシル基を構成するアルキル基の炭素数が２以上の場合、アルキル基は１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、又はフェノキシカルボニル基を表し、
Ｒ^１３、Ｒ^１４は、それぞれ独立に、フェニル基（炭素数１〜６のアルキル基、フェニル基もしくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基もしくはフェニル基で置換されていてもよい）を表し、
Ｒ^１５は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基もしくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基もしくはフェニル基で置換されていてもよい）を表す。

In the formula, R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or 2 to 2 carbon atoms. 12 alkoxycarbonyl groups (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and one or more oxygen atoms are placed in the middle of the alkyl chain. Which may have), or a phenoxycarbonyl group,
R ¹³ and R ¹⁴ are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ¹⁵ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (substituted with one or more hydroxyl groups). And may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having a carbon number). 1-6 alkyl groups or phenyl groups optionally substituted).

式中、Ｒ^１６、Ｒ^１７及びＲ^２２は、それぞれ独立に、炭素数１〜１２のアルキル基を表し、
Ｒ^１８、Ｒ^１９、Ｒ^２０及びＲ^２１は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表し、Ｍは、Ｏ、Ｓ又はＮＨを表し、ｐ及びｑは、それぞれ独立に０〜５の整数を表す。

In the formula, R ¹⁶ , R ¹⁷ and R ²² each independently represent an alkyl group having 1 to 12 carbon atoms,
R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, M represents O, S or NH, and p and q each independently Represents an integer of 0 to 5;

  Among the oxime ester photopolymerization initiators, 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the general formula (V) and a compound represented by the formula (VI) are more preferable. Examples of commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Specialty Chemicals, N-1919 manufactured by ADEKA, and the like. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

  As the α-aminoacetophenone photopolymerization initiator having a group represented by the general formula (III), 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. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.

  Examples of the acylphosphine oxide photopolymerization initiator having the group represented by the general formula (IV) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine. Examples thereof include oxides and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

The blending amount of such a photopolymerization initiator is 0.01 to 20% by mass, more preferably 0.5 to 10% by mass in the solid content of the composition, and when used in combination with a carboxyl group-containing resin described later. The range of 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass is appropriate for 100 parts by mass of the carboxyl group-containing resin and / or the carboxyl group-containing photosensitive resin. When the blending amount of the photopolymerization initiator is less than the above range, the photocurability on copper is insufficient, and the coating film is peeled off or the coating film properties such as chemical resistance are deteriorated. On the other hand, when the above range is exceeded, light absorption on the surface of the solder resist coating film of the photopolymerization initiator becomes violent, and the deep curability tends to decrease, which is not preferable.
In the case of the oxime ester-based photopolymerization initiator having a group represented by the formula (II), the blending amount is preferably 0.01 to 20 mass with respect to 100 mass parts of the carboxyl group-containing resin described later. Parts, more preferably in the range of 0.01 to 5 parts by mass.

  Other photopolymerization initiators, photoinitiator assistants, and sensitizers 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. A compound, a xanthone compound, a tertiary amine compound, etc. can be mentioned.

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, and 1,1-dichloroacetophenone.

Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.
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, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyldiphenyl. Sulfide.

  Specific examples of the tertiary amine compound include, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylamino. Dialkylamino benzophenone such as benzophenone (EAB manufactured by Hodogaya Chemical Co.), and dialkylamino groups such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin) Containing coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylaminobenzoic acid ( -Butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (manufactured by Van Dyk) Esolol 507), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).

Among the above-mentioned compounds, thioxanthone compounds and tertiary amine compounds are preferable. The composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep curable properties. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone A thioxanthone compound such as
The amount of such a thioxanthone compound is 10% by mass or less, more preferably 5% by mass or less, based on the solid content of the composition. When used in combination with a carboxyl group-containing resin described later, a carboxyl group-containing resin and / or Alternatively, a ratio of preferably 20 parts by mass or less, more preferably 10 parts by mass or less is appropriate for 100 parts by mass of the carboxyl group-containing photosensitive resin. If the amount of the thioxanthone compound is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.

  As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has a maximum absorption wavelength in the ultraviolet region, so that it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition. A colored solder resist film reflecting the color 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.

  The compounding amount of such a tertiary amine compound is 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on the solid content of the composition. When used in combination with a carboxyl group-containing resin described later. Is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin and / or the carboxyl group-containing photosensitive resin. When the amount of the tertiary amine compound is less than the above range, a sufficient sensitizing effect tends not to be obtained. On the other hand, when the above range is exceeded, light absorption on the surface of the dry 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 in the range of 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin described later. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  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.

Furthermore, 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, 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.

A thermosetting component can be added to the photocurable resin composition of the present invention in order to impart heat resistance. Examples of thermosetting components used in the present invention include amine resins such as melamine resins and benzoguanamine resins, block isocyanate compounds, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, and the like. A curable resin 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 compounds in the molecule Examples thereof include compounds having a thioether group, that is, episulfide resins.

  Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, and Epoto manufactured by Tohto Kasei Co., Ltd. YD-011, YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Specialty Chemicals' Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. 664 etc. (all trade names) bisphenol A type epoxy resin; jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd. D. Chemicals manufactured by Dow Chemical Company. E. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. 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, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 from Toto Kasei Co., Ltd., Araldide ECN1235 from Ciba Specialty Chemicals, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumi-epoxy ESCN-195X, ESCN- manufactured by Sumitomo Chemical Co., Ltd. 220, manufactured by Asahi Kasei Corporation. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink and Chemicals, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170 manufactured by Toto Kasei Co., Ltd., YDF- 175, YDF-2004, Araldide XPY306 manufactured by Ciba Specialty Chemicals, etc. (both trade names); Epototo ST-2004, ST-2007, ST-3000 (trade names, manufactured by Toto Kasei) Hydrogenated bisphenol A type epoxy resin such as JER604 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumi-Epoxy ELM manufactured by Sumitomo Chemical Co., Ltd. -120 etc. (both Product name) Glycidylamine type epoxy resin; Ardandide type epoxy resin such as araldide CY-350 (trade name) made by Ciba Specialty Chemicals; Celoxide 2021 made by Daicel Chemical Industries, Araldide made by Ciba Specialty Chemicals CY175, CY179, etc. (both trade names); 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. Xylenol type or biphenol type epoxy resin or a mixture thereof; bisphenol S type such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin; jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals (all trade names) Tetraphenylolethane type epoxy Fatty; heterocyclic epoxy resins such as Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; Toto Kasei Co., Ltd. Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Nippon Steel; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. Naphtalene group-containing epoxy such as HP-4032, EXA-4750, EXA-4700 manufactured by Dainippon Ink & Chemicals, Inc. Resin; Epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink &Chemicals; Glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil &Fats; Cyclohexylmaleimide and glycidyl methacrylate Relate copolymerized epoxy resins; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.) and the like. However, it is not limited to these. These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.

  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 blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.6 to 2 with respect to 1 equivalent of the carboxyl group of the carboxylate resin and the carboxyl group-containing resin described later. A range of 0.5 equivalent, more preferably 0.8 to 2.0 equivalent 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.

  Moreover, the compound which has a some isocyanate group or blocked isocyanate group in 1 molecule as a thermosetting component can be added to the photocurable resin composition of this invention. 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 the 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, lactic acid And alcohol-based blocking agents such as ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methylethyl 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 It is.

  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, Nihon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B- 846, B-870, B-874, B-882 (above, Mitsui Takeda Chemicals, trade name), TPA-B80E, 17B-60PX, E402-B80T (above, Asahi Kasei Chemicals, trade name), etc. Can be mentioned. 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 1 to 100 parts by mass, more preferably 2 to 70 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. The ratio is appropriate. When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 mass parts, 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 compounding amount of these thermosetting catalysts is sufficient in a normal quantitative ratio, and is preferably, for example, with respect to 100 parts by mass of a carboxyl group-containing resin or a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule. Is 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.

As the carboxyl group-containing resin, various conventionally known carboxyl group-containing resins having a carboxyl group in the molecule can be used. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is more preferable in terms of photocurability and development resistance. And the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof.
Specific examples of the carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule and the carboxyl group-containing resin having no ethylenically unsaturated double bond in the molecule include the compounds listed below. (Either oligomer and polymer may be used).

  (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.

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

  (4) 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.

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

  (6) During the synthesis of the resin of (2) or (4) above, one isocyanate group and one or more (meth) acryloyl groups are present in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. The carboxyl group-containing photosensitive urethane resin which added the compound which has and was terminally (meth) acrylated.

  (7) (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin as described later, and phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride are added to the hydroxyl group present in the side chain. A carboxyl group-containing photosensitive resin to which a dibasic acid anhydride such as

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

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

  (10) The resin of the above (1) to (9) further has one epoxy group and one or more (meth) acryloyl groups in the molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. A carboxyl group-containing photosensitive resin obtained by adding a compound.

The carboxyl group-containing resin can be used without being limited to those listed above, and can be used by mixing one kind or plural kinds. In this specification, (meth) acrylate means acrylate, methacrylate. And a mixture thereof, and the same applies to other similar expressions.

Since the carboxyl group-containing 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.
Moreover, the acid value of the said carboxyl group-containing resin is the range of 40-200 mgKOH / g, More preferably, it is the range of 45-120 mgKOH / g. When the acid value of the carboxyl group-containing resin exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line becomes thinner than necessary. In some cases, the developer is not distinguished between the exposed portion and the unexposed portion. It is not preferable because the resist pattern is dissolved and peeled, and it becomes difficult to draw a normal resist pattern.

  Moreover, although the weight average molecular weight of the said carboxyl group containing resin changes with resin frame | skeletons, what is generally in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. If the weight average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, the film may be reduced during development, and the 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 resin is 20 to 60% by mass, preferably 30 to 50% by mass in the entire composition. When the amount of the carboxyl group-containing resin is less than the above range, the film strength is lowered, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity of the composition is increased or the coating property is lowered, which is not preferable.
These carboxyl group-containing resins can be used without being limited to those listed above, and can be used by mixing one kind or plural kinds.

  The photocurable resin composition of this invention can mix | blend a coloring agent. 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 the red colorant 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 blending ratio of the colorant as described above is not particularly limited, but is 0 to 5% by mass, more preferably 0.01 to 3% by mass in the solid content of the composition, and is used in combination with a carboxyl group-containing resin described later. In this case, the ratio is preferably 0 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin and / or the carboxyl group-containing photosensitive resin.

  The photocurable resin composition of the present invention can be blended with a filler as necessary in order to increase the physical strength of the coating film. As such a filler, at least one selected from the group consisting of known and commonly used inorganic fillers and organic fillers can be used, but inorganic fillers, particularly barium sulfate, spherical silica and talc are preferably used. Furthermore, it is good also as a white resist by adding a titanium oxide as a white filler. In order to further impart flame retardancy, metal oxide fine particles may be added, and specific examples include aluminum hydroxide, magnesium hydroxide, boehmite and the like. These fillers can be blended alone or in combination of two or more.

  The blending amount of these fillers is 1 to 70% by mass in the solid content of the composition, more preferably 0.1 to 50% by mass. When used in combination with the carboxyl group-containing resin described later, the carboxyl group-containing resin and / or Or it is 300 mass parts or less with respect to 100 mass parts of carboxyl group-containing photosensitive resin, More preferably, it is 0.1-300 mass parts, Most preferably, it is 0.1-150 mass parts. When the blending amount of the filler exceeds the above range, the viscosity of the solder resist composition becomes high, the printability is lowered, and the cured product becomes brittle, which is not preferable.

  In the resin composition of the present invention, a binder polymer can be used for the purpose of improving dryness to touch and improving handling properties. For example, polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyester amide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, phenoxy polymers, and the like can be used. These binder polymers can be used alone or as a mixture of two or more.

  Furthermore, the solder resist composition of the present invention can use an elastomer for the purpose of imparting flexibility and improving brittleness of the cured product. For example, a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyesteramide elastomer, an acrylic elastomer, or an olefin elastomer can be used. Moreover, the resin etc. which modified the one part or all part of the epoxy resin which has various frame | skeleton with the both-ends carboxylic acid modified butadiene-acrylonitrile rubber | gum can be used. Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers, and the like can also be used. These elastomers can be used alone or as a mixture of two or more.

  Furthermore, the photocurable resin composition of the present invention has a viscosity for synthesis of the carboxylic acid resin, carboxyl group-containing resin or carboxyl group-containing photosensitive resin, preparation of the composition, or application to a substrate or carrier film. An organic solvent can be used for adjustment.

  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; methyl lactate, ethyl lactate, butyl lactate, ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol Methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, etc. Esters; ethanol, propanol, ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether, and the like petroleum naphtha, hydrogenated petroleum naphtha, petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

  Generally, in many polymer materials, once oxidation starts, oxidative degradation occurs successively in a chain, resulting in a decrease in the function of the polymer material. Therefore, in the resin composition of the present invention, in order to prevent oxidation ( 1) Radical scavengers that invalidate the generated radicals and / or (2) oxidation of peroxide decomposers that decompose the generated peroxides into innocuous substances and prevent new radicals from being generated. An inhibitor can be added.

  Specific examples of the antioxidant that acts 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) -S-triazine-2,4,6- (1H, 3H, 5H) trione and other phenolic compounds, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6) Tetramethyl-4-piperidyl) - sebacate, and the like amine compounds such as 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 (above, manufactured by Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 152, TINUVIN 152, TINUVIN 292, TINUVIN 5100 Special Product name).

  Specific examples of the antioxidant that acts as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 ′. -Sulfur compounds such as thiodipropionate.

The peroxide decomposing agent may be a commercially available one. For example, ADK STAB TPP (manufactured by Asahi Denka Co., Ltd., trade name), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd., trade name), Sumilizer TPS (Sumitomo Chemical) Company name, product name).
Said antioxidant can be used individually by 1 type or in combination of 2 or more types.

  In general, since the polymer material absorbs light and thereby decomposes and deteriorates, the resin composition of the present invention includes an ultraviolet ray in addition to the above-mentioned antioxidant in order to take a countermeasure against stabilization against the ultraviolet ray. Absorbents can be used.

  Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like. Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone. Is mentioned. Specific examples of benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t. -Butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like. Specific examples of the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.

Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, manufactured by Ciba Specialty Chemicals, Inc., trade name).
Said ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, By using together with the said antioxidant, stabilization of the molding obtained from the resin composition of this invention can be aimed at.

  The photo-curable resin composition of the present invention may further comprise known and commonly used thixotropic agents such as known and commonly used thermal polymerization inhibitors, fine silica, organic bentonite, montmorillonite and hydrotalcite, silicone, fluorine Known and conventional additives such as antifoaming agents and / or leveling agents such as styrene and polymer, silane coupling agents such as imidazole, thiazole and triazole, and rust preventives can be blended. .

  The thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization 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, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

  The solder resist composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and on the substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain A tack-free coating film can be formed by coating by a method such as a coating method and volatilizing and drying (temporary drying) an organic solvent contained in the composition at a temperature of about 60 to 100 ° C. Moreover, a resin insulation layer can be formed by apply | coating the said composition on a carrier film, and drying and winding up as a film together on a base material. Thereafter, by a contact method (or non-contact method), exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3). The resist pattern is formed by development with a ~ 3% sodium carbonate aqueous solution). Further, in the case of a composition containing a thermosetting component, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxylic acid resin or carboxyl group-containing resin, and in the molecule A thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups reacts to form a cured coating film having excellent characteristics such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. can do. 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 photocurable / thermosetting resin composition of the present invention is applied may be a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, or the like (having a heat source of an air heating method using steam). It is possible to use a method in which the hot air in the dryer is brought into countercurrent contact and a method in which the hot air is blown onto the support from the nozzle.

  After applying the photocurable resin composition of the present invention and evaporating and drying as follows, the obtained coating film is exposed (irradiated with active energy rays). In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.

As an exposure apparatus used for the active energy ray irradiation, an ultraviolet exposure apparatus equipped with a high-pressure mercury lamp or a metal halide lamp or a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a CAD data from a computer) is used. Can do. The active energy ray may be any one of a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gas laser, a solid state laser, and a semiconductor laser as long as 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 10 to 500 mJ / cm ^2, more preferably be in the range of 10 to 300 mJ / cm ^2.

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

  The photo-curable 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 the method of directly applying the liquid curable resin composition to a substrate. Can also be used. The case where the photocurable 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 applying and drying the solder resist 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 the photocurable resin composition to a carrier film or a cover film with a thickness of 10 to 150 μm using a blade coater, a lip coater, a comma coater, a film coater, or the like, and then drying it.
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.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the following examples do not limit the present invention, and all modifications may be made without departing from the spirit of the present invention. It is included in the technical scope of the present invention. In the following description, “part” represents “part by mass” and “%” represents “% by mass” unless otherwise specified.

Synthesis example 1
After charging 192 parts of PET flakes (Mitsubishi Chemical Co., Ltd .: Novavex (trade name)) into a 500 ml four-necked round bottom separable lasco equipped with a stirrer, nitrogen introducing tube, and cooling tube, and making the flask atmosphere nitrogen atmosphere, 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. Subsequently, 134 parts of trimethylolpropane previously heated to 130 ° C. and dissolved were 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, 91.2 parts of tetrahydrophthalic anhydride (hereinafter abbreviated as THPA) and 225 parts of carbitol acetate were charged, and after the atmosphere in the flask was set to a nitrogen atmosphere, the oil bath was heated to 125 ± 5 ° C. Soaked. Stirring was started gradually and the reaction was carried out for 3 hours to obtain a carboxylic acid resin varnish A having a non-volatile content of 65% and a solid content acid value of 83 mgKOH / g.

Synthesis example 2
After charging 192 parts of PET flakes (Mitsubishi Chemical Co., Ltd .: Novavex (trade name)) into a 500 ml four-necked round bottom separable lasco equipped with a stirrer, nitrogen introducing tube, and cooling tube, and making the flask atmosphere nitrogen atmosphere, 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. Subsequently, 134 parts of trimethylolpropane previously heated to 130 ° C. and dissolved were 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 carried out for 3 hours to obtain a carboxylic acid resin varnish B having a non-volatile content of 65% and a solid content acid value of 103 mgKOH / g.

Examples 1-10 and Comparative Examples 1-4
Using the resin solutions of the above synthesis examples, blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and used for solder resist A photosensitive resin composition was prepared. Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.

<Optimum exposure amount>
The photocurable thermosetting resin compositions of the examples and comparative examples were coated on the entire surface by screen printing after the circuit pattern substrate having a copper thickness of 35 μm was buffed, washed with water, dried, and heated 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 at the second time 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.

<Developability of through hole>
A 1.0 mmt copper-clad laminate was drilled with a Φ200 μm drill, and through-hole plating was performed by a conventional method to prepare a substrate on which 400 through-holes having a measured value of about Φ150 μm were formed. The substrate was filled with the photocurable thermosetting resin composition by printing the photocurable thermosetting resin compositions of the Examples and Comparative Examples twice on the substrate by screen printing, and filling the hole with 80 ° C. It dried for 30 minutes with the hot-air circulation type drying furnace, and cooled to room temperature. Thereafter, development was performed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. for 120 seconds under the condition of a spray pressure of 0.2 MPa, and evaluation was performed according to the following criteria.
A: 100% through-hole development is possible by developing once or twice.
○: 100% through-hole development is possible by performing development 3 to 5 times.
Δ: 50-99% through-hole development is possible by performing development 3 to 5 times.
X: The through hole developability is 50% or less even after five developments.

<Resolution and resolution when through-hole development is possible>
A circuit pattern substrate having a line / space of 300/300 μm and a copper thickness of 35 μm was applied to the photocurable thermosetting resin compositions of Examples and Comparative Examples by buffing, washing with water, drying and then applying by screen printing. And dried for 30 minutes in a hot air circulation drying oven at 80 ° C. 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.
Moreover, the same test as described above was performed for the photocurable thermosetting resin compositions of the respective examples and comparative examples at a time during which the through hole can be developed. The remaining minimum line of the cured coating film of the obtained photosensitive resin composition for solder resist was similarly determined using an optical microscope adjusted to 200 times, and this was defined as the resolution when through-hole development was possible. In addition, a case where all lines have been developed and disappeared is described as “−”.

<Surface condition of coating film>
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. The substrate is exposed to a solder resist pattern at an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. is applied for 60 seconds under a spray pressure of 2 kg / cm ^2. Development was performed, and the state of the coating film surface after development was observed and evaluated according to the following criteria.
○: Surface gloss and film thickness are unchanged.
Δ: No change in film thickness, but the surface is slightly developed and the surface is cloudy.
X: The film thickness is reduced by development and the surface gloss is lost.

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.

<Dry film production>
Each of the photosensitive resin compositions for solder resists of Example 4 and Comparative Example 1 was appropriately diluted with methyl ethyl ketone, and then, using an applicator, a PET film (FB manufactured by Toray Industries, Inc.) so that the film thickness after drying was 30 μm. −50: 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 Co., Ltd.): 0.8 MPa, 70 ° C., 1 minute The substrate was heated and laminated under the condition of a degree of vacuum of 133.3 Pa to obtain a substrate (unexposed substrate) having an unexposed solder resist layer. About the obtained board | substrate, the characteristic was evaluated like the above.
The evaluation results are summarized in Table 2.

  As shown in Table 2 above, in the case of Examples 1 to 10, the developability, in particular, the developability of the through hole is better than those of Comparative Examples 1 to 4, solder heat resistance, electroless gold plating resistance, and moisture resistance. It was recognized that the resin was useful as an alkali development type photosensitive resin composition because of its excellent properties and electrical insulation.

Claims (7)

A carboxylic acid resin derived from a compound containing a structure represented by the following general formula (1):
An alkali-developable photocurable resin composition comprising a compound having a plurality of ethylenically unsaturated groups in one molecule and a photopolymerization initiator.

In the formula, R ¹ represents an (m + 1) -valent polyhydric alcohol derivative, m and n are integers of 1 or more and less than 10, l is an integer of 0 or 1 and less than 10, and R ² is CH ₂ , C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , a substituted or unsubstituted aromatic ring, and R ³ represents a substituted or unsubstituted aromatic ring.   When the carboxylic acid resin depolymerizes (a) polyester (b) with a polyol having a plurality of hydroxyl groups in one molecule, (c) reacts with a saturated or unsaturated polybasic acid or anhydride thereof at the same time or later. The photocurable resin composition according to claim 1, which is obtained.   The photocurable resin composition according to claim 2, wherein the polyester (a) is a recycled polyester.   Furthermore, it is a photocurable thermosetting resin composition containing a thermosetting component, The photocurable resin composition as described in any one of Claim 1 thru | or 3 characterized by the above-mentioned.   The photocurable dry film obtained by apply | coating and drying the photocurable resin composition as described in any one of the said Claims 1 thru | or 4 to a carrier film.   A photocurable resin film according to any one of claims 1 to 4, or a photocurable dry film obtained by applying and drying the photocurable resin composition on a carrier film, in a pattern shape. Hardened product obtained by photocuring.   A photocurable resin film according to any one of claims 1 to 4, or a photocurable dry film obtained by applying and drying the photocurable resin composition on a carrier film, in a pattern shape. A printed wiring board having a cured film obtained by photocuring and heat curing.