JP2009167245A - Photosensitive resin composition and acid group-containing polymerizable resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkali developable photosensitive resin composition having both high photosensitivity and excellent adhesion to a substrate. <P>SOLUTION: The photosensitive resin composition contains, as essential components, an acid group-containing polymerizable resin (A) having a molecular structure represented by structural formula (1) (wherein a plurality of symbols X each independently represents a radical polymerizable unsaturated double bond-containing structural moiety (i), a carboxy group-containing structural moiety (ii), a hydroxy group-containing structural moiety (iii) or a hydrogen atom), having both the radical polymerizable unsaturated double bond-containing structural moiety (i) and the carboxy group-containing structural moiety (ii), and further having a urethane bond in the structure of the radical polymerizable unsaturated double bond-containing structural moiety (i), a photopolymerization initiator (B) and an epoxy resin (C). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composition for resist ink and a novel acid group-containing polymerizable resin, which are particularly excellent in sensitivity to light and have good adhesion to a substrate.

Conventionally, the photosensitive resin composition for resist inks has excellent heat resistance due to the carboxyl group-containing photosensitive resin obtained by reacting a reaction product of a novolac type epoxy resin and an unsaturated monocarboxylic acid with a polybasic acid anhydride. It has been widely used because of its chemical resistance and electrical insulation. However, along with the recent miniaturization and higher precision of electric boards, further improvements in characteristics such as heat resistance, toughness, flexibility, water resistance, chemical resistance, and electrical insulation are essential. Various new carboxyl group-containing photosensitive resins have been developed.
In particular, as a carboxyl group-containing photosensitive resin with excellent heat resistance, toughness, flexibility, water resistance, chemical resistance, and electrical insulation, it contains unsaturated groups in the reaction product of novolac phenolic resins and cyclic carbonates. A carboxyl group-containing photosensitive resin obtained by reacting a monocarboxylic acid or its ester and further reacting with a polybasic acid anhydride is known (see Patent Document 1). Such a photosensitive resin does not go through general epoxidation using epichlorohydrin as a raw material, so it does not contain chlorine, and although the electrical insulation and water resistance are certainly improved, the UV sensitivity is sufficient. In addition, the toughness and flexibility of the coating film were not sufficient, and the adhesion to the substrate was poor. Here, in order to improve the adhesion to the substrate, means for introducing a functional group having a higher affinity with the substrate can be considered, but in this case, the concentration of unsaturated groups in the photosensitive resin is reduced. Therefore, the photosensitivity is lowered.

  Thus, a carboxyl group-containing photosensitive resin obtained by reacting a reaction product of a novolak-type phenol resin and a cyclic carbonate with an unsaturated group-containing monocarboxylic acid or its ester, and further reacting with a polybasic acid anhydride. However, the present situation is that both the photosensitivity and the adhesion to the substrate cannot be combined.

JP 2004-359728 A

  The problem to be solved by the present invention is an alkali development type photosensitive resin composition that combines high photosensitivity that exhibits excellent curability even with low exposure energy, and excellent adhesion to a substrate. It is another object of the present invention to provide an acid group-containing polymerizable resin capable of imparting such properties to an alkali-developable photosensitive resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have introduced a urethane bond at a position close to the unsaturated double bond in the photosensitive resin, thereby exhibiting excellent photosensitivity and a substrate. As a result, the present inventors have found that the adhesion to the resin is remarkably improved.

  That is, the present invention provides the following structural formula (1)

（Ｒ^１及びＲ^２はそれぞれ独立的に水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ^３は炭素原子数１〜４のアルキリデン基、又は脂肪族環状炭化水素基であり、Ｘはそれぞれ独立的にラジカル重合性不飽和二重結合含有構造部位（i）、カルボキシル基含有構造部位（ii）、水酸基含有構造部位（iii）、又は水素原子を表し、ｎは０以上の数を表す。）
で表される分子構造を有しており、かつ、ラジカル重合性不飽和二重結合含有構造部位（i）とカルボキシル基含有構造部位（ii）とを併有しており、更に該ラジカル重合性不飽和二重結合含有構造部位（i）の構造中にウレタン結合を有する酸基含有重合性樹脂（Ａ）、光重合開始剤（Ｂ）、及びエポキシ樹脂（Ｃ）を必須成分とすることを特徴とする感光性樹脂組成物に関する。

(R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ³ is an alkylidene group having 1 to 4 carbon atoms or an aliphatic cyclic hydrocarbon group; Each independently represents a radical polymerizable unsaturated double bond-containing structural moiety (i), a carboxyl group-containing structural moiety (ii), a hydroxyl group-containing structural moiety (iii), or a hydrogen atom, and n is a number of 0 or more. To express.)
And a radically polymerizable unsaturated double bond-containing structural part (i) and a carboxyl group-containing structural part (ii). An acid group-containing polymerizable resin (A) having a urethane bond in the structure of the unsaturated double bond-containing structural moiety (i), a photopolymerization initiator (B), and an epoxy resin (C) are essential components. It is related with the photosensitive resin composition characterized.

Furthermore, the present invention provides
The following structural formula (1)

（Ｒ^１及びＲ^２はそれぞれ独立的に水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ^３は炭素原子数１〜４のアルキリデン基、又は脂肪族環状炭化水素基であり、Ｘはそれぞれ独立的にラジカル重合性不飽和二重結合含有構造部位（i）、カルボキシル基含有構造部位（ii）、水酸基含有構造部位（iii）、又は水素原子を表し、ｎは０以上の数を表す。）
で表される分子構造を有しており、かつ、ラジカル重合性不飽和二重結合含有構造部位（i）とカルボキシル基含有構造部位（ii）とを併有しており、更に該ラジカル重合性不飽和二重結合含有構造部位（i）の構造中にウレタン結合を有することを特徴とする酸基含有重合性樹脂に関する。

(R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ³ is an alkylidene group having 1 to 4 carbon atoms or an aliphatic cyclic hydrocarbon group; Each independently represents a radical polymerizable unsaturated double bond-containing structural moiety (i), a carboxyl group-containing structural moiety (ii), a hydroxyl group-containing structural moiety (iii), or a hydrogen atom, and n is a number of 0 or more. To express.)
And a radically polymerizable unsaturated double bond-containing structural part (i) and a carboxyl group-containing structural part (ii). The present invention relates to an acid group-containing polymerizable resin characterized by having a urethane bond in the structure of the unsaturated double bond-containing structural moiety (i).

  According to the present invention, an alkali development type photosensitive resin composition that combines high photosensitivity expressing excellent curability even with low exposure energy, and excellent adhesion to a substrate, and An acid group-containing polymerizable resin that can impart such characteristics to an alkali-developable photosensitive resin composition can be provided.

  The acid group-containing polymerizable resin (A) used in the present invention has the following structural formula (1).

（Ｒ^１及びＲ^２はそれぞれ独立的に水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ^３は炭素原子数１〜４のアルキリデン基、又は脂肪族環状炭化水素基であり、Ｘはそれぞれ独立的にラジカル重合性不飽和二重結合含有構造部位（i）、カルボキシル基含有構造部位（ii）、水酸基含有構造部位（iii）、又は水素原子を表し、ｎは０以上の数を表す。）
で表される分子構造を有しており、かつ、ラジカル重合性不飽和二重結合含有構造部位（i）とカルボキシル基含有構造部位（ii）とを併有しており、更に該ラジカル重合性不飽和二重結合含有構造部位（i）の構造中にウレタン結合を有することを特徴としている。

(R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ³ is an alkylidene group having 1 to 4 carbon atoms or an aliphatic cyclic hydrocarbon group; Each independently represents a radical polymerizable unsaturated double bond-containing structural moiety (i), a carboxyl group-containing structural moiety (ii), a hydroxyl group-containing structural moiety (iii), or a hydrogen atom, and n is a number of 0 or more. To express.)
And a radically polymerizable unsaturated double bond-containing structural part (i) and a carboxyl group-containing structural part (ii). It is characterized by having a urethane bond in the structure of the unsaturated double bond-containing structural moiety (i).

  In the present invention, since it has a urethane bond in the structure of the radical polymerizable unsaturated double bond-containing structural site (i), it can form a remarkably strong coating film when cured by light irradiation, Excellent adhesion to the substrate can be expressed. Moreover, since unsaturated double bonds are close to each other at the time of preliminary drying due to the cohesive force between urethane bonds, good curability is exhibited at the time of light irradiation.

Here, R ¹ and R ² in the structural formula (1) are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically, a hydrogen atom, a methyl group, an ethyl group, A propyl group, n-butyl group, and t-butyl group are mentioned. Among these, a hydrogen atom or a methyl group is particularly preferable from the viewpoint of heat resistance and chemical resistance.

In addition, the radical polymerizable unsaturated double bond-containing structural moiety (i) constituting X in the structural formula (1) has a urethane bond in the structure as described above. Specifically, The following structural formula (2)
The following structural formula (2)

（式中、Ｒ^４は炭素原子数２〜１０のアルキレン基、Ｒ^５は炭素原子数１〜５のアルキレン基、Ａｃは（メタ）アクリロイル基、ｏは繰り返し単位で１〜５の数、ｐは１〜３の数である。）又は、下記構造式（３）

(In the formula, R ⁴ is an alkylene group having 2 to 10 carbon atoms, R ⁵ is an alkylene group having 1 to ⁵ carbon atoms, Ac is a (meth) acryloyl group, o is a repeating unit having a number of 1 to 5, p Is a number from 1 to 3) or the following structural formula (3)

（式中、Ｒ^４は炭素原子数２〜１０のアルキレン基、Ｒ^６は炭素原子数２〜５０の炭化水素基、Ｒ^７は多価の有機基、Ａｃは（メタ）アクリロイル基、ｏは繰り返し単位で１〜５の数、ｐは１〜３の数である。）
で表されるものが、フレキシブル基板に対しても優れた密着性を発現する点から好ましい。

Wherein R ⁴ is an alkylene group having 2 to 10 carbon atoms, R ⁶ is a hydrocarbon group having 2 to 50 carbon atoms, R ⁷ is a polyvalent organic group, Ac is a (meth) acryloyl group, and o is The number of repeating units is 1 to 5, and p is a number of 1 to 3.)
It is preferable from the point which expresses the outstanding adhesiveness also to a flexible substrate.

Here, in the structural formula (2) or the structural formula (3), the structural portion represented by R ⁴ is an alkylene group having 2 to 10 carbon atoms as described above, specifically, ethylene, Examples include propylene, butylene, pentylene, octane-1,8-diyl and butane-1,10-diyl. In the present invention, ethylene or propylene is preferable from the viewpoint of easy production and imparting appropriate flexibility to the cured product. In Structural Formula (2), o is a repeating unit, and is preferably in the range of 1 to 5 in terms of excellent flexibility. In particular, applications that require electrical insulation reliability such as package substrate applications. Is preferably 1-2 in terms of the balance between water absorption and flexibility.

Next, in the structural formula (2), R ⁵ is an alkylene group having 1 to ⁵ carbon atoms. Among them, an ethylene group or a propylene group makes the effect of the present invention remarkable. preferable.

In the structural formula (3), the polyvalent organic group represented by R ⁷ is an aliphatic carbon group having 1 to 10 carbon atoms such as an ethylene group, a propylene group, a butylene group, or a decane-1,10-diyl group. A hydrogen group;
Trivalent or tetravalent aliphatic hydrocarbon groups derived from polyhydric alcohols such as glycerol and pentaerythritol; phenyleneoxyalkylene groups such as phenyleneoxypropylene groups; heterocycle-containing polyvalent groups such as isocyanuric acid structure-containing polyvalent ethyl groups An alkyl group; a divalent organic group derived from a polyoxyalkylene structure such as an ethylene polyoxyalkylene group.

  Among these, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a trivalent or tetravalent aliphatic hydrocarbon group derived from the polyhydric alcohol are preferable, and in particular, there are a plurality of bonding sites with an acryloyl group. From the point that sensitivity to light is higher and curability is improved.

Next, R ⁶ in the structural formula (3) is a hydrocarbon group having 2 to 50 carbon atoms, and is a linear or branched alkylene group, an alkylene group having an alicyclic structure, or a divalent aromatic group. Any hydrocarbon group may be used. Specifically, a linear alkylene group such as a 1,4-butylene group, a 1,6-hexene group, a dodecane-1,12-diyl group; a 1,3-cyclohexene group, 1,4-cyclohexene group, other structural formulas al-1 to al-8

（上記各構造式中、破線部は他の構造部位との結合部を示す。）
で表される脂肪族環状構造を有する構造部位；

(In each of the structural formulas above, the broken line portion indicates a connecting portion with another structural portion.)
A structural moiety having an aliphatic cyclic structure represented by:

  Structural formulas ar-1 to ar-11 derived from aromatic diisocyanates

（上記各構造式中、破線部は他の構造部位との結合部を示す。）
で示される芳香族含有構造部位が挙げられる。

(In each of the structural formulas above, the broken line portion indicates a connecting portion with another structural portion.)
An aromatic-containing structural site represented by

  Among these, an aromatic-containing structural part is particularly desirable from the viewpoint of excellent mechanical strength, and a structural part having an aliphatic cyclic structure is particularly preferable from the viewpoint of excellent light resistance.

  In addition, the carboxyl group-containing structural moiety (i) present in the acid group-containing polymerizable resin (A) may have any carboxyl group at the end of the structural moiety. )

（式中、Ｒ^４は炭素原子数２〜１０のアルキレン基、Ｒ^８は炭素原子数２〜２０の炭化水素基、ｏは繰り返し単位で１〜５の数である。）
で表されるものが、硬化物に適度な柔軟性を付与できフレキシブル基板用途において優れた密着性を発現すると共にアルカリ現像性にも優れた性能を発現する点から好ましい。

(In the formula, R ⁴ is an alkylene group having 2 to 10 carbon atoms, R ⁸ is a hydrocarbon group having 2 to 20 carbon atoms, and o is a number of 1 to 5 as a repeating unit.)
Is preferable from the viewpoint of imparting appropriate flexibility to the cured product and exhibiting excellent adhesion in flexible substrate applications and also exhibiting excellent performance in alkali developability.

In the structural formula (4), the structural site represented by R ⁴ has the same meaning as in the structural formula (2).

In the structural formula (4), the structural portion represented by R ⁸ is a divalent structural portion derived from a polybasic acid anhydride as a raw material. , Maleic anhydride, succinic anhydride, itaconic anhydride, dodecyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-methylhexahydroanhydride Phthalic acid, 4-methylhexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride, 3-butenyl-5,6-dimethyltetrahydrophthalic anhydride Acid, 3,6-endomethylene-tetrahydrophthalic anhydride, 7-methyl-3,6-endomethylenetetrahydrophthalic anhydride Acid, aliphatic acid anhydrides such as benzophenone tetracarboxylic anhydride; phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride Aromatic acid anhydrides such as products.

The acid group-containing polymerizable resin (A) comprises a radical polymerizable unsaturated double bond-containing structural moiety (i) and the carboxyl group-containing structural moiety (ii) in a molar ratio of [(ii) / (i)]. The ratio of 90/10 to 30/70 is preferable from the viewpoint of a good balance between photosensitivity and developability.

In addition, the structural site represented by R ³ in the structural formula (1) is an alkylidene group having 1 to 4 carbon atoms such as a methylene group, an ethylidene group, a 2,2-propylidene group, or a 2,2-butylidene group, Divalent aliphatic cyclic hydrocarbon groups derived from unsaturated alicyclic compounds such as dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorborna-2-ene, α-pinene, β-pinene and limonene Can be mentioned. Among these, a methylene group, a 2,2-propylidene group, or a divalent aliphatic cyclic hydrocarbon group derived from dicyclopentadiene is preferable, and a methylene group is particularly preferable because of excellent adhesion to a substrate. .

In addition to the structural moiety (i) or the structural moiety (ii), the structural moiety represented by X in the structural formula (I) may also include a hydroxyl group-containing structural moiety (iii) or a hydrogen atom.
Examples of the hydroxyl group-containing structural site (iii) include those in which the hydroxyl group-containing structural site produced when the cyclic carbonate compound is reacted with the raw material phenol resin (a) remains in the final product as it is. Further, the case where the structural site represented by X in the structural formula (I) is a hydrogen atom means that the phenolic hydroxyl group in the raw material phenol resin (a) is left unreacted in the final product. Can be mentioned.

  When X in the structural formula (I) has a hydroxyl group-containing structural moiety (iii) or a hydrogen atom, the content of the hydroxyl group-containing structural moiety (iii) in the acid group-containing polymerizable resin (A) is X Less than 20%, especially less than 10% of the total number is preferable from the viewpoint of good photosensitivity. On the other hand, the content of hydrogen atoms in the acid group-containing polymerizable resin (A) is preferably less than 10%, more preferably less than 5%, based on the total number of X from the viewpoint of good photosensitivity. .

  The acid group-containing polymerizable resin (A) preferably has an unsaturated double bond equivalent in the range of 250 to 2000 from the viewpoint of photosensitivity. In the present invention, since the urethane bond exists in the vicinity of the unsaturated double bond in the chemical structure of the acid group-containing polymerizable resin (A), excellent photocuring is possible even if the number of unsaturated double bonds is not so large. Expresses sex.

  In addition, the acid group-containing polymerizable resin (A) is preferable in that the developability is excellent when the solid content acid value is in the range of 30 to 150 KOH / g.

  Furthermore, the acid group-containing polymerizable resin (A) preferably has an average number of nuclei of aromatic rings in the structural formula (1) in the range of 3 to 15 from the viewpoint of the strength of the cured product.

Specifically, the above acid group-containing polymerizable resin (A) can be industrially produced through the following step 1 and then through the following step 2.
Step 1: Structural formula (a) below

（Ｒ^１及びＲ^２はそれぞれ独立的に水素原子又は炭素原子数１〜４のアルキル基であり、Ｒ^３は炭素原子数１〜４のアルキリデン基、又は脂肪族環状炭化水素基であり、ｎは０以上の数を表す。）
フェノール樹脂（ａ）に触媒の存在下で環状カーボネート化合物（ｂ）を脱炭酸反応させアルコール性水酸基を有するポリオール樹脂（ｃ）を製造する工程。
工程２：工程１で得られたポリオール樹脂（ｃ）に不飽和基含有イソシアネート化合物（ｄ）、及び、多塩基酸無水物（ｅ）を反応させて、目的とするアルカリ現像型感光性樹脂（Ａ）を得る工程。

(R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ³ is an alkylidene group having 1 to 4 carbon atoms or an aliphatic cyclic hydrocarbon group; Represents a number of 0 or more.)
A step of producing a polyol resin (c) having an alcoholic hydroxyl group by decarboxylating the cyclic carbonate compound (b) in the presence of a catalyst with the phenol resin (a).
Step 2: Unsaturated group-containing isocyanate compound (d) and polybasic acid anhydride (e) are reacted with the polyol resin (c) obtained in Step 1, and the desired alkali-developable photosensitive resin ( A) obtaining step.

Here, the reaction temperature in Step 1 is in the range of 150 to 250 ° C., and particularly preferably in the range of 160 to 200 ° C. from the viewpoint of reaction control. The decarboxylation reaction in Step 1 can use a basic catalyst, and specific examples include tris-substituted organic phosphine, imidazole, and tertiary amine.
In the step 2, the polyol resin (c) may be reacted with the unsaturated group-containing isocyanate compound (d), and then the polybasic acid anhydride (e) may be reacted, or the polyol resin (c) may be reacted. The polybasic acid anhydride (e) may be reacted, and then the unsaturated group-containing isocyanate compound (d) may be reacted. Further, the novolac type polyol resin (c), the unsaturated group-containing isocyanate compound (d), and the polybasic acid anhydride (e) may be charged and reacted together.
The reaction temperature in step 2 is in the range of 50 to 120 ° C, and particularly preferably in the range of 70 to 110 ° C from the viewpoint of reaction control.

  The novolak type phenol resin (a) used in Step 1 is, for example, specifically a phenol novolak resin, a cresol novolak resin, a halogenated phenol novolak resin, or a phenol novolak having an alkyl group having 2 to 4 carbon atoms as a substituent. Examples thereof include resins.

  Among these, a phenol novolac resin and a cresol novolac resin are particularly preferable because the obtained cured product has good heat resistance and chemical resistance.

  Further, the phenol resin (a) has a good balance between the photosensitivity and developability of the finally obtained acid group-containing polymerizable resin (A), and further includes an acid group-containing polymerizable resin ( The viscosity of A) is suitably low, and it is preferably one having an average number of nuclei of 3 to 15 from the viewpoint of excellent workability when a resist ink is used and excellent drying properties during preliminary drying.

  Further, the cyclic carbonate compound (b) used in Step 1 is specifically ethylene carbonate, 1,3-propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 2,4-pentylene carbonate. 1,3-pentylene carbonate and the like. Among these, ethylene carbonate and 1,3-propylene carbonate are particularly preferable from the viewpoint of reactivity, and ethylene carbonate is particularly preferable.

  Next, the unsaturated group-containing isocyanate compound (d) used in Step 2 specifically includes a reaction product of a diisocyanate compound and a hydroxy group-containing acrylate compound. Specifically, the diisocyanate compound used here is 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- or 1,4-diisocyanate, Isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate; IPDI), bis- (4-isocyanatocyclohexyl) methane (hydrogenated MDI), 2- or 4-isocyanatocyclohexyl-2 Aliphatic diisocyanates such as' -isocyanatocyclohexylmethane, 1,3- or 1,4-bis- (isocyanatomethyl) -cyclohexane, bis- (4-isocyanato-3-methylcyclohexyl) methane, 2,4-tolylene diisocyanate Anate, 2,6-tolylene diisocyanate, 2,2′-, 2,4′- or 4,4′-diisocyanatodiphenylmethane (MDI), 1,5-naphthalene diisocyanate, p- or m-phenylene diisocyanate, Examples thereof include aromatic diisocyanates such as xylene diisocyanate, diphenyl-4,4′-diisocyanate, 1,3- or 1,4-α, α, α ′, α′-tetramethylxylene diisocyanate.

  Among these, an aromatic diisocyanate compound is preferable from the viewpoint of excellent mechanical strength, and an alicyclic diisocyanate compound is preferable from the viewpoint of excellent light resistance.

  On the other hand, specific examples of hydroxy group-containing acrylate compounds include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, acryloyloxyethyl hydroxyethylphthalic acid, hydroxyphenoxypropyl (meth) ) Acrylates, monofunctional acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate; hydroxyacryloyloxypropyl (meth) acrylate, (meth) acrylic acid adducts of hydroxyl group-containing polyesters, ethylene isocyanurate Oxide-modified di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, glycerol di (meth) acrylate, glyce Bifunctional acrylates such Lumpur acrylate methacrylate, trifunctional acrylates such as pentaerythritol tri (meth) acrylate.

In addition, when making the said diisocyanate compound and a hydroxyl group containing acrylate compound react, it is preferable to make a hydroxyl group containing acrylic monomer and a diisocyanate compound react by the mole number by which an isocyanate group becomes excess with respect to a hydroxyl group.
As the unsaturated group-containing isocyanate compound (d), commercially available (meth) acryloyloxyethyl isocyanate (“Karenz MOI, AOI” manufactured by Showa Denko) may be used.

  Specific examples of the polybasic acid anhydride (e) include maleic anhydride, succinic anhydride, itaconic anhydride, dodecyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 4- (4-methyl-3-pentenyl) tetrahydrophthalic anhydride Acid, 3-butenyl-5,6-dimethyltetrahydrophthalic anhydride, 3,6-endomethylene-tetrahydrophthalic anhydride, 7-methyl-3,6-endomethylenetetrahydrophthalic anhydride, benzophenone tetracarboxylic anhydride, etc. Aliphatic acid anhydrides; phthalic anhydride, tetrachlorophthalic anhydride, Raburomo phthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, aromatic monoacid anhydride such as benzophenone tetracarboxylic acid anhydride.

  Among these, tetrahydrophthalic anhydride or hexahydrophthalic anhydride is preferable from the viewpoint of good solvent solubility of the acid group-containing polymerizable resin (A). In addition, succinic anhydride is preferable from the viewpoint that the thermal management width and alkali developability when used as a resist ink are particularly excellent. Therefore, succinic anhydride and tetrahydrophthalic anhydride or hexahydrophthalic anhydride may be used in combination as the polybasic acid anhydride (e).

  The acid group-containing polymerizable resin (A) synthesized in this way was cured by light irradiation because it had a urethane bond in the structure of the radical polymerizable unsaturated double bond-containing structural moiety (i). It is possible to form a remarkably strong coating film, and to exhibit excellent adhesion to the base material, and that the unsaturated double bond is close at the time of preliminary drying due to the cohesive force between the urethane bonds. Thus, a resist ink that exhibits good curability upon light irradiation can be obtained.

  Next, the photopolymerization initiator (B) used in the present invention is, for example, acetophenone, 2,2-diethoxy-2-phenylacetophenone, p-dimethylaminopropiophenone, cycloacetophenone, 2-methyl-1- [ Acetophenones such as 4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; benzophenone, 2-chlorobenzophenone, benzophenones such as p, p-bisdiethylaminobenzophenone, p, p-bisdiethylaminobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isobutyl ether; Ketals such as tilketal; thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone; anthraquinone, 2,4,5-triarylimidazole dimer, 2,4,6- Examples include tris-S-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Among these, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 Is preferred because of its high reactivity. These photopolymerization initiators (B) can be used alone or in combination of two or more.

  It is preferable that the compounding quantity of the said photoinitiator (B) is the range of 0.5-50 mass parts normally with respect to 100 mass parts of acid group containing polymeric resin (A). That is, at 0.5 parts by mass or more, the photocuring reaction of the acid group-containing polymerizable resin (A) proceeds well, and at 50 parts by mass or less, the mechanical properties of the cured product are good. From the point which is excellent in the sensitivity with respect to light, the mechanical physical property of hardened | cured material, etc., as a more preferable compounding quantity of a photoinitiator (B), 2-30 mass parts with respect to 100 mass parts of acid group containing polymeric resin (A). Range.

  The epoxy resin (C) used in the present invention is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, bisphenol S novolak. Type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, resorcinol / cresol co-condensation novolak type epoxy resin, alicyclic epoxy resin, trisphenol methane type epoxy resin, rubber modified epoxy resin, tris (2,3- Epoxypropyl) isocyanurate, diphenyldiglycidyl ether, tetramethyldiphenyldiglycidyl ether, epoxy resin containing oxazolidone ring, dicyclopentadiene Polyglycidyl ethers of the polyaddition reaction product of an unsaturated alicyclic compound and phenols of.

  Among these, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin from the aspect of having a wide thermal management range when used as a resist ink and excellent heat resistance of the cured product after heat curing, Resorcin / cresol co-condensed novolak type epoxy resin, epoxy resin containing oxazolidone ring, polyglycidyl ether of polyaddition reaction product of unsaturated cycloaliphatic compound such as dicyclopentadiene and phenols is preferable and used as resist ink It is preferable to use bisphenol A type epoxy resin or tris (2,3-epoxypropyl) isocyanurate from the viewpoint of excellent photosensitivity and reactivity. These resins can be used alone or in combination of two or more according to the application.

  The epoxy resin containing the oxazolidone ring is not particularly limited, and examples thereof include an epoxy resin obtained by reacting a polyfunctional epoxy resin with aromatic monoisocyanates.

  In the present invention, it is further preferable to use a curing accelerator. Examples of the curing accelerator include various curing accelerators for epoxy resins such as melamine and derivatives thereof, imidazole and derivatives thereof, dicyandiamide, phenol and derivatives thereof, and the like.

  As a compounding quantity of an epoxy resin (C), 5-40 mass parts is preferable with respect to 100 mass parts of said acid group containing polymeric resin (A). That is, by using 5 parts by mass or more, the cured product finally obtained has excellent physical properties such as heat resistance, solvent resistance, acid resistance, and adhesion, and is sufficient for electrical characteristics such as insulation resistance. On the other hand, when the amount is 40 parts by mass or less, the sensitivity to light is excellent, and the sensitivity and developability when used as a resist ink are excellent.

  In particular, when used as a resist ink resin composition, the photosensitive resin composition of the present invention preferably contains a diluent (D) in addition to the above components.

  The diluent (D) is not particularly limited, and examples thereof include ketones such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; methyl cellosolve, butyl cellosolve, Glycol ethers such as methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether; ethyl acetate, butyl acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Esters such as acetate; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; Octane, decane, etc. Aliphatic hydrocarbons; organic solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc., 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-vinyl Pyrrolidone, N-vinylcaprolactam, acryloylmorpholine, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, N, N-dimethylacrylamide, melamine (meth) acrylate, diethylene glycol di (Meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, glyce Polyglycidyl ether di (meth) acrylate, isobornyl (meth) acrylate, hexanediol, trimethylolpropane, pentaerythritol ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate, or these ethylene oxides, And photopolymerizable reactive diluents such as polyvalent (meth) acrylates of propylene oxide adducts. Among these, from the point that the smoothness after preliminary drying when used as a resist ink is good, the use of esters alone, the combined use of esters and petroleum solvents are preferred, and these are photopolymerizable reactive diluents The combined product is more preferable. Among the esters, propylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate are preferably used.

  The diluent (D) is used alone or as a mixture of two or more thereof, and the blending amount thereof is preferably 30 to 300 parts by mass, particularly 50 parts per 100 parts by mass of the acid group-containing polymerizable resin (A). It is preferable that it is -200 mass parts.

  In order to use the photosensitive resin composition of the present invention as a resist ink resin composition, the acid group-containing polymerizable resin (A), photopolymerization initiator (B), epoxy resin (C), and diluent ( It is obtained by mixing D) and mixing them uniformly by means of a three-roll or rotating / revolving stirrer.

  Here, the blending amount of the acid group-containing polymerizable resin (A) is not particularly limited, but the effect of improving the photosensitivity of the resist ink and the drying property after preliminary drying becomes favorable, and further heat It is preferable that it is 10-70 mass% in the resin composition for resist inks from the point which is excellent in the heat resistance of the coating film obtained after hardening, and solvent resistance, and it is especially preferable that it is the range used as 30-60 mass%.

  In the photosensitive resin composition of the present invention, pigments, fillers, additives and the like can be used depending on the application. Specifically, organic pigments such as quinacridone, azo, and phthalocyanine; inorganic pigments such as titanium oxide, metal foil pigments, rust preventive pigments; barium sulfate, calcium carbonate, spherical fused silica, crushed fused silica, crystals Fillers such as silica, alumina, silicon nitride, aluminum hydroxide, carbon black, talc and clay; UV absorbers such as hindered amines, benzotriazoles, benzophenones; hindered phenols, phosphoruss, sulfurs, hydrazides Antioxidants such as silanes, coupling agents such as titanium, leveling agents such as fluorine surfactants, rheology control agents such as Aerosil, pigment dispersants: anti-repellent agents, additives such as antifoaming agents, etc. Is mentioned. Moreover, reinforcing materials, such as glass fiber, glass cloth, and carbon fiber, can be contained as needed. Moreover, a flame retardant imparting agent can be added as necessary. Various flame retardants can be used as the flame retardant, such as halogen compounds such as decabromodiphenyl ether and tetrabromobisphenol A; phosphorus atom-containing compounds such as red phosphorus and various phosphate compounds; melamine or derivatives thereof Nitrogen atom-containing compounds; inorganic flame retardant compounds such as aluminum hydroxide, magnesium hydroxide, zinc borate and calcium borate can be exemplified.

  The photosensitive resin composition thus obtained can obtain a cured product by irradiation with light such as ultraviolet rays. In particular, when used as a resin composition for resist ink, for example, a thickness of 10 to 150 μm (liquid film thickness) on a printed board by screen printing, curtain coating method, roll coating method, spin coating method, dip coating method or the like. After coating, it is pre-dried at 60-90 ° C. for 15-90 minutes to volatilize volatile components such as organic solvents (the coating and pre-drying steps may be repeated multiple times) and desired for the dried coating film A negative film of the mask pattern is brought into close contact, and ultraviolet light is irradiated thereon to perform exposure (or the pattern may be directly exposed using laser light or the like, in which case the mask pattern is not required), and thereafter. By developing with a dilute alkaline aqueous solution as a developing solution, the coating film in the non-exposed area is removed, and the coating film in the exposed part is not removed because it is photocured The Rukoto, it is possible to form a pattern. In this case, the dilute alkaline aqueous solution is generally 0.5 to 5% by mass of sodium carbonate aqueous solution or sodium hydroxide aqueous solution, but other alkaline solutions can also be used. Subsequently, the cured coating film excellent in electrical characteristics, migration resistance, heat resistance, solvent resistance, and the like can be obtained by thermosetting with a hot air dryer or the like at 130 to 160 ° C. for 20 to 90 minutes.

  The photosensitive resin composition of the present invention is, for example, a resin composition for solder resist ink of a circuit board such as a printed wiring board, an interlayer insulating layer, a resist material for a liquid crystal color filter, such as an overcoat, a spacer for liquid crystal, and a color filter. It is preferably used for pigment resist, black matrix resist and the like.

Hereinafter, the present invention will be described more specifically with reference to examples. Unless otherwise indicated, the middle part and% in the examples are based on mass. In addition, < ¹³ > C-NMR and IR spectrum were measured on condition of the following.
[ ¹³ C-NMR measurement conditions]
Device: AL-400 manufactured by JEOL Ltd.
Measurement mode: SGBCM (1H complete decoupling method)
Solvent: Dimethyl sulfoxide Pulse angle: 30 ° C pulse Sample concentration: 30 wt%
Integration count: 60000 times [IR spectrum]
Apparatus: FT / IR-500 manufactured by JASCO Corporation.
The resin solution obtained in each synthesis example was applied to a KBr plate and measured.

[Synthesis of unsaturated group-containing isocyanate compound (c1)]
222 g (1.0 mol) of isophorone diisocyanate and 0.29 g of methoquinone were heated to 85 ° C., and 357 g of pentaerythritol tri / tetraacrylate [“Aronix M-305” manufactured by Toagosei Co., Ltd., hydroxyl equivalent 357] Mol) was added dropwise and further reacted at 85 ° C. for 6 hours to obtain an unsaturated group-containing isocyanate compound (c1). The NCO equivalent of the obtained compound (c1) was 579 g / eq.

Example 1 [Synthesis of Photosensitive Resin (A)]
In a nitrogen atmosphere reaction kettle, 26.4 g (0.3 mol) of ethylene carbonate and phenol novolac resin [“Phenolite TD-2131” manufactured by Dainippon Ink & Chemicals, Inc., softening point 80 ° C., hydroxyl group equivalent 104 g / eq. 104 g (1.0 mol) was charged and dissolved at 130 ° C. Triphenylphosphine 0.56g was prepared here, and it heated up at 170 degreeC, and reacted for 1 hour. The solution was further charged with 57.2 g (0.65 mol) of ethylene carbonate and reacted at 170 ° C. for 3 hours. During the reaction, carbon dioxide desorbed from ethylene carbonate is generated and removed from the system as needed. To this reaction solution, 180 g of diethylene glycol monoethyl ether acetate, 0.22 g of methoquinone, and 76.0 g (0.5 mol) of tetrahydrophthalic anhydride were reacted and reacted at 120 ° C. for 4 hours. Furthermore, after making the reaction kettle into an air atmosphere, 220 g (0.38 mol) of an unsaturated group-containing isocyanate compound (c1) was charged into the reaction solution and reacted at 85 ° C. for 3 hours. After the reaction, the IR spectrum of the reaction solution was measured to confirm the disappearance of the 2240 cm ⁻¹ peak derived from the NCO group. The obtained resin had a double bond equivalent of 388 solids and an acid value of 67 mgKOH / g. This is designated as resin solution A-1. FIG. 1 shows a ¹³ C-NMR chart of this resin solution, and FIG. 2 shows an IR chart.

Example 2 [same as above]
In a nitrogen atmosphere reaction kettle, 26.4 g (0.3 mol) of ethylene carbonate and phenol novolac resin [“Phenolite TD-2131” manufactured by Dainippon Ink & Chemicals, Inc., softening point 80 ° C., hydroxyl group equivalent 104 g / eq. 104 g (1.0 mol) was charged and dissolved at 130 ° C. Triphenylphosphine 0.56g was prepared here, and it heated up at 170 degreeC, and reacted for 1 hour. The solution was further charged with 57.2 g (0.65 mol) of ethylene carbonate and reacted at 170 ° C. for 3 hours. During the reaction, carbon dioxide desorbed from ethylene carbonate is generated and removed from the system as needed. To this reaction solution, 121 g of diethylene glycol monoethyl ether acetate, 0.14 g of methoquinone, and 45.6 g (0.3 mol) of tetrahydrophthalic anhydride were reacted, and reacted at 120 ° C. for 4 hours. Furthermore, after making the reaction kettle into an air atmosphere, 91.7 g (0.65 mol) of an unsaturated group-containing isocyanate compound [manufactured by Showa Denko, Karenz AOI-VM, NCO equivalent 141] was charged into the reaction solution at 85 ° C. The reaction was carried out for 3 hours. After the reaction, the IR spectrum of the reaction solution was measured to confirm the disappearance of the 2240 cm-1 peak derived from the NCO group. The resulting resin had a double bond equivalent of 435 solid content and a solid content acid value of 62 mgKOH / g. This is designated as resin solution A-2.

Example 3 [same as above]
In a reaction vessel in a nitrogen atmosphere, 26.4 g (0.3 mol) of ethylene carbonate and an orthocresol novolak resin [“Phenolite MC-2663” manufactured by Dainippon Ink & Chemicals, Inc., softening point 107 ° C., hydroxyl group equivalent 120 g / eq. 120 g (1.0 mol) was charged and dissolved at 150 ° C. The triphenylphosphine 0.64g was prepared here, and it heated up at 170 degreeC, and reacted for 1 hour. The solution was further charged with 66.0 g (0.75 mol) of ethylene carbonate and reacted at 170 ° C. for 3 hours. During the reaction, carbon dioxide desorbed from ethylene carbonate is generated and removed from the system as needed. To this reaction solution, 202 g of diethylene glycol monoethyl ether acetate, 0.24 g of methoquinone, and 91.2 g (0.6 mol) of tetrahydrophthalic anhydride were reacted, and reacted at 120 ° C. for 4 hours. Furthermore, after making the reaction kettle into an air atmosphere, 214 g (0.37 mol) of an unsaturated group-containing isocyanate compound (c1) was charged into the reaction solution and reacted at 85 ° C. for 3 hours. After the reaction, the IR spectrum of the reaction solution was measured to confirm the disappearance of the 2240 cm ⁻¹ peak derived from the NCO group. The resulting resin solid content had a double bond equivalent of 425 and a solid content acid value of 73 mgKOH / g. This is designated as resin solution A-3.

Example 4 [same as above]
In a nitrogen atmosphere reaction kettle, 26.4 g (0.3 mol) of ethylene carbonate and an orthocresol novolak resin [Dainippon Ink & Chemicals, Phenolite MC-2663, softening point 107 ° C., hydroxyl group equivalent 120 g / eq. 120 g (1.0 mol) was charged and dissolved at 150 ° C. The triphenylphosphine 0.64g was prepared here, and it heated up at 170 degreeC, and reacted for 1 hour. The solution was further charged with 66.0 g (0.75 mol) of ethylene carbonate and reacted at 170 ° C. for 3 hours. During the reaction, carbon dioxide desorbed from ethylene carbonate is generated and removed from the system as needed. To this reaction solution, 125 g of diethylene glycol monoethyl ether acetate, 0.15 g of methoquinone, and 56.2 g (0.37 mol) of tetrahydrophthalic anhydride were charged and reacted at 120 ° C. for 4 hours. Furthermore, after making the reaction kettle into an air atmosphere, an unsaturated group-containing isocyanate compound [“Karenz AOI-VM” manufactured by Showa Denko, NCO equivalent 141] 84.6 (0.6 mol) was charged into the reaction solution at 85 ° C. The reaction was carried out for 3 hours. After the reaction, the IR spectrum of the reaction solution was measured to confirm the disappearance of the 2240 cm ⁻¹ peak derived from the NCO group. The double bond equivalent of the obtained resin solid content was 485, and the solid content acid value was 73 mgKOH / g. This is designated as Resin Solution A-4.

Comparative Example 1 (Production of Comparative Photosensitive Resin)
120 g of ethylene carbonate 88.0 g (1.0 mol) and orthocresol novolak resin [“Phenolite MC-2663” manufactured by Dainippon Ink & Chemicals, Inc., softening point 107 ° C., hydroxyl group equivalent 120] in a nitrogen atmosphere reaction kettle 1.0 mol) and 0.62 g of triphenylphosphine were charged, and the reaction was carried out at 170 ° C. for 4 hours. During the reaction, carbon dioxide desorbed from ethylene carbonate is generated and removed from the system as needed. After cooling this reaction solution to 80 ° C., the reaction kettle was brought to an air atmosphere, and charged with 115 g of toluene, 0.13 g of methoquinone, 43.2 g (0.6 mol) of acrylic acid, and 1.26 g of paratoluenesulfonic acid, 110 ° C. For 7 hours. Water produced by the reaction was distilled out of the system as an azeotrope with toluene, and the amount was 10.8 g. Thereafter, the resulting reaction solution was washed with water and distilled off while replacing toluene with 115 g of diethylene glycol monoethyl ether acetate by an evaporator. Next, 45.6 g (0.3 mol) of tetrahydrophthalic anhydride and 0.31 g of triphenylphosphine were charged into the obtained resin solution and reacted at 110 ° C. for 4 hours to obtain the desired resin solution. The double bond equivalent of the obtained resin solid content was 403, and the solid content acid value was 71 mgKOH / g. This is designated as resin solution A′-1.

Comparative Example 2 (Production of Comparative Control Epoxy Acrylate)
Orthocresol novolac type epoxy resin [Dainippon Ink Chemical Industries, EPICLON N-680, softening point 86 ° C., epoxy equivalent 211 g / eq. ] 211 g (1.0 mol), 72.0 g (1.0 mol) of acrylic acid, and 0.14 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve. Next, 1.09 g of triphenylphosphine was charged, the temperature was raised to 130 ° C., and the reaction was performed for 8 hours. The obtained reaction solution was charged with 103 g of aromatic hydrocarbon (Sorvesso 150) and 83.6 g (0.55 mol) of tetrahydrophthalic anhydride, and reacted at 110 ° C. for 3 hours to obtain the desired resin solution. The double bond equivalent of resin solid content was 367, and the acid value of solid content was 84 mgKOH / g. This is designated as resin solution A′-2.

Synthesis example (Preparation of heat-reactive curing agent)
90.4 g of diethylene glycol monoethyl ether acetate was heated to 100 ° C., and an orthocresol novolac type epoxy resin [“Epicron N-680” manufactured by Dainippon Ink & Chemicals, Inc., softening point 95 ° C., epoxy equivalent 211 g / eq. 211 g was uniformly dissolved to obtain a resin solution having a solid content of 70%. This resin solution is designated as B-1.

Examples 5-8, Comparative Examples 3-4
A photosensitive resin composition was blended in accordance with the blending composition shown in Tables 1 and 2 (numerical values are parts by mass), and mixed with a rotating and rotating stirrer equipped with a cooling device to prepare a resist ink resin solution. . Table 3 shows the drying property, photosensitivity, alkali developability, and coating film performance of the resulting resist ink resin composition. In addition, the drying property of the resist composition for resist ink, photosensitivity, alkali developability, and coating-film performance were evaluated by the method shown below. However, the coating performance is that the resist ink resin composition is applied to a polyimide film substrate to a thickness of 60 μm (before drying), pre-dried at 80 ° C. for 30 minutes, and then irradiated with ultraviolet rays at an exposure amount of 200 mJ / cm ^2. Then, using a 1% by weight aqueous sodium carbonate solution at 30 ° C., after developing for 60 seconds at a spray pressure of 2.0 kg / cm ² , a cured coating film was prepared by post-curing at 150 ° C. for 30 minutes. Evaluation was performed.

Test Method and Evaluation Method (1) Dryability The coating film was pre-dried at 80 ° C. for 30 minutes. Next, with the coating film cooled to room temperature, the solder mask pattern was brought into contact with the coating film surface, the solder mask pattern was peeled off from the coating film, and the state was evaluated.
○: The coating film and the pattern do not adhere at all and can be easily removed ×: The coating adheres to the solder mask pattern at the time of peeling

(2) Photosensitivity A 21-step tablet (manufactured by Kodak Co., Ltd.) is brought into intimate contact with the coating film preliminarily dried at 80 ° C. for 30 minutes. It was exposed to 200 mJ / cm ² ultraviolet rays. Subsequently, the number of the unexposed portions of the exposed portion after development for 60 seconds at a spray pressure of 2.0 kg / cm ² using a 1 mass% aqueous sodium carbonate solution at 30 ° C. is indicated by a number. Higher numbers indicate higher sensitivity.

(3) the coating film after pre-drying the development time 80 ° C. 30 minutes to contact a solder mask pattern was irradiated exposed to ultraviolet rays of 200 mJ / cm ^2. Next, development was performed using a 1% by mass aqueous sodium carbonate solution at 30 ° C. with a spray pressure of 2.0 kg / cm ² . At the time of development, the development state of the unexposed part was visually determined with a magnifying glass every 15 seconds, and the time when the ink was completely removed and development was complete was defined as the development time.

(4) Thermal management width Each coating film whose pre-drying time was changed at intervals of 10 minutes from 80 ° C. for 20 minutes to 80 ° C. for 90 minutes was subjected to the same evaluation as (3) development time, and the maximum development possible in 60 seconds The pre-drying time (min) was defined as the thermal management width.

(5) Solder heat resistance According to the test method of JIS C 6481, the cured coating film was repeatedly immersed in a solder bath at 260 ° C. for 10 seconds at a maximum of 3 times, and the maximum number of appearances without appearance change was noted.

(6) Pencil hardness The cured coating film was tested according to the test method of JIS K 5400, and the highest hardness at which the coating film was not damaged was observed.

(7) Adhesiveness A 10 × 10 crosscut with a width of 1 mm was put into the cured coating film, and a peel test was performed with a cellophane tape, and the peeled state was visually observed.
○: No peeling is observed Δ: 1-10 peeling is observed x: 10 or more peeling

(8) Chemical resistance The state of the coating film after the cured coating film was immersed in 10% by mass of hydrochloric acid for 30 minutes was evaluated.
○: No change at all ×: The film was swollen and peeled

(9) Solvent resistance The state of the coating film after the cured coating film was immersed in methylene chloride for 30 minutes was evaluated.
○: No change at all ×: The film was swollen and peeled

(10) PCT resistance The cured coating film was evaluated under the conditions of 121 ° C. and 50 hours in saturated steam.
○: No change is observed at all ×: The coating film is swollen, peeled off, or discolored

(11) Resistance to gold plating Electroless gold plating was applied to a test substrate, and the appearance of the substrate and a peel test using a cellophane tape were evaluated.
○: No discoloration or peeling of the substrate is observed at all. Δ: No discoloration of the substrate, but slight peeling is observed. ×: There is discoloration of the substrate, paint film is lifted, plating peeling is observed, peeling A large degree

(12) Durability Reliability As the durability reliability, the electrical insulation of the cured coating film was evaluated under the following conditions.
Humidification conditions: temperature 120 ° C., humidity 95% RH, applied voltage 30 V, 100 hours Measurement conditions: measurement time 60 seconds, applied voltage 500 V
○: Insulation resistance value after humidification of 10 ⁻¹⁰ Ω or more, no copper migration Δ: Insulation resistance value after humidification of 10 ⁻¹⁰ Ω or more, with copper migration ×: Insulation resistance value after humidification of 10 ⁻⁹ Ω or less, With copper migration

It is a ¹³ C-NMR chart of the resulting resin solution (A-1) in Example 1. 3 is an FT-IR chart of the resin solution (A-1) obtained in Example 1. FIG.

Claims (8)

The following structural formula (1)

(R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ³ is an alkylidene group having 1 to 4 carbon atoms or an aliphatic cyclic hydrocarbon group; Each independently represents a radical polymerizable unsaturated double bond-containing structural moiety (i), a carboxyl group-containing structural moiety (ii), a hydroxyl group-containing structural moiety (iii), or a hydrogen atom, and n is a number of 0 or more. To express.)
And a radically polymerizable unsaturated double bond-containing structural part (i) and a carboxyl group-containing structural part (ii). An acid group-containing polymerizable resin (A) having a urethane bond in the structure of the unsaturated double bond-containing structural moiety (i), a photopolymerization initiator (B), and an epoxy resin (C) are essential components. A photosensitive resin composition. The acid group-containing polymerizable resin (A) comprises a radically polymerizable unsaturated double bond-containing structural moiety (i) and the carboxyl group-containing structural moiety (ii) in a molar ratio of [(ii) / (i)]. The photosensitive resin composition according to claim 1, having a ratio of 90/10 to 30/70. The radical polymerizable unsaturated double bond-containing structural moiety (i) is represented by the following structural formula (2)

(Wherein R ⁴ is an alkylene group having 2 to 10 carbon atoms, R ⁵ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, Ac is a (meth) acryloyl group, o is a repeating unit of 1 to 5) Number, p is a number from 1 to 3) or the following structural formula (3)

(Wherein R ⁴ is an alkylene group having 2 to 10 carbon atoms, R ⁶ is a hydrocarbon group having 2 to 50 carbon atoms, R ⁷ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Ac is ( (Meth) acryloyl group, o is a repeating unit of 1 to 5 and p is 1 to 3)
And the carboxyl group-containing structural moiety (ii) is represented by the following structural formula (4):

(In the formula, R ⁴ is an alkylene group having 2 to 10 carbon atoms, R ⁸ is a hydrocarbon group having 2 to 20 carbon atoms, and o is a number of 1 to 5 as a repeating unit.)
The photosensitive resin composition of Claim 1 or 2 which is represented by these. The photosensitive resin composition according to claim 1, wherein the acid group-containing polymerizable resin (A) has a double bond equivalent of 250 to 2,000. The photosensitive resin composition according to claim 1, wherein the acid group-containing polymerizable resin (A) has a solid content acid value of 30 to 150 mgKOH / g. The photosensitive resin composition according to any one of claims 1 to 5, wherein the acid group-containing polymerizable resin (A) has an average number of nuclei of aromatic rings in the range of 3 to 15. The photosensitivity according to any one of claims 1 to 6, further comprising a diluent (D) in addition to the acid group-containing polymerizable resin (A), the photopolymerization initiator (B), and the epoxy resin (C). Resin composition.

(R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ³ is an alkylidene group having 1 to 4 carbon atoms or an aliphatic cyclic hydrocarbon group; Each independently represents a radically polymerizable unsaturated double bond-containing structural moiety (i), a carboxyl group-containing structural moiety (ii), a hydroxyl group-containing structural moiety (iii), or a hydrogen atom, and n represents a number of 0 or more. .)
And having both a carboxyl group-containing structural moiety (i) and a radical polymerizable unsaturated double bond-containing structural moiety (ii), and further comprising the radical polymerizable property An acid group-containing polymerizable resin characterized by having a urethane bond in the structure of the unsaturated double bond-containing structural moiety (ii).

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