JP2013020047A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition that has excellent resolution in pattern formation and is superior in all of insulation, bending resistance and fire retardancy after the pattern formation, and a photosensitive dry film, a photosensitive laminate, a permanent pattern formation method and a printed circuit board using the photosensitive composition.SOLUTION: A photosensitive composition contains an acid modified ethylenically unsaturated group-containing polyurethane resin, an ethylenically unsaturated group-containing acryl resin, a polymerizable compound, a photopolymerization initiator, and phosphoric acid metal salt.

Description

  The present invention relates to a photosensitive composition, and a photosensitive dry film, a photosensitive laminate, a permanent pattern forming method, and a printed board using the photosensitive composition.

  Conventionally, when forming a permanent pattern such as a solder resist, a liquid resist or a photosensitive film having a photosensitive layer formed by applying a photosensitive composition on a support and drying it has been used. As a method for forming a permanent pattern such as a solder resist, for example, a laminate is formed by laminating a photosensitive layer using a liquid resist or a photosensitive film on a substrate such as a copper-clad laminate on which a permanent pattern is formed. A method of forming a permanent pattern by exposing the photosensitive layer, developing the photosensitive layer after the exposure to form a pattern, and then performing a curing process or the like is known.

  In the photosensitive composition that can be used for the solder resist, it is important to improve the resolution of pattern formation and the insulation, impact resistance, folding resistance, flame resistance, etc. after pattern formation. It is one and various studies have been made.

For example, photopolymerizable epoxy (meth) acrylate resin, photopolymerizable urethane (meth) acrylate resin, and photopolymerization having one terminal (meth) acrylate group having a molecular weight of 250 to 650 and no carboxyl group. A photocurable solder resist ink containing a functional compound has been proposed (see Patent Document 1).
A photosensitive resin composition comprising (A) an acrylic resin, (B) a polyurethane resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a phosphorus-containing compound. The (B) polyurethane resin is a photosensitive resin that is a reaction product of an epoxy acrylate compound having an ethylenically unsaturated group and two or more hydroxyl groups, a diisocyanate compound, and a diol compound having a carboxyl group. A composition has been proposed (see Patent Document 2).

  However, the performance of the photosensitive composition obtained by these proposed techniques is still not sufficient.

JP-A-61-103968 JP 2010-282001 A

  An object of the present invention is to provide a photosensitive composition that is excellent in resolution of pattern formation and excellent in insulation, folding resistance, and flame retardancy after pattern formation. Another object of the present invention is to provide a photosensitive dry film, a photosensitive laminate, a flexible wiring board, a method for manufacturing a flexible wiring board, and a method for forming a permanent pattern using the photosensitive composition.

一般式（ＵＥ１）において、Ｌ^ＵＥは下記一般式（１）〜（３）のいずれかの部分構造を有し、かつ主鎖の結合に−ＮＨＣ（＝Ｏ）Ｏ−もしくは−ＯＣ（＝Ｏ）ＮＨ−を含まない２価の連結基を表す；

一般式（１）において、Ｒ^１〜Ｒ^３は、それぞれ独立に水素原子又は１価の有機基を表す。Ｘは、酸素原子、硫黄原子、又は−Ｎ（Ｒ^１２）−を表す。ここで、Ｒ^１２は、水素原子、又は１価の有機基を表す；

一般式（２）において、Ｒ^４〜Ｒ^８は、それぞれ独立に水素原子又は１価の有機基を表す。Ｙは、酸素原子、硫黄原子、又は−Ｎ（Ｒ^１２）−を表す。ここで、Ｒ^１２は、水素原子、又は１価の有機基を表す；

一般式（３）において、Ｒ^９〜Ｒ^１１は、それぞれ独立に水素原子又は１価の有機基を表す。Ｚは、酸素原子、硫黄原子、−Ｎ（Ｒ^１３）−、又は置換基を有してもよいフェニレン基を表す。ここでＲ^１３は、水素原子、又は１価の有機基を表す。
＜５＞前記一般式（ＵＥ１）におけるＬ^ＵＥが、前記一般式（１）〜（３）のいずれかの部分構造を１つ有する、＜４＞に記載の感光性組成物。
＜６＞酸変性エチレン性不飽和基含有ポリウレタン樹脂が有するエチレン性不飽和基がアクリロイルオキシ基又はメタクリロイルオキシ基である、＜１＞〜＜５＞のいずれかに記載の感光性組成物。
＜７＞感光性組成物に含有される酸変性エチレン性不飽和基含有ポリウレタン樹脂及びエチレン性不飽和基含有アクリル樹脂の総量に占める前記酸変性エチレン性不飽和基含有ポリウレタン樹脂の割合が、５５質量％以上９５質量％以下である＜１＞〜＜６＞のいずれかに記載の感光性組成物。
＜８＞＜１＞〜＜７＞のいずれかに記載の感光性組成物を含む感光層を有する、感光性ドライフィルム。
＜９＞基材上に、＜１＞〜＜７＞のいずれかに記載の感光性組成物を含む感光層を有する、感光性積層体。
＜１０＞基材上に、＜１＞〜＜７＞のいずれかに記載の感光性組成物を含む感光層を光硬化して得られるレジストパターンを有してなる、フレキシブル配線基板。
＜１１＞＜８＞に記載の感光性ドライフィルムが有する感光層を基材上に転写し、転写した感光層を露光及び現像処理してレジストパターンを形成することを含む、フレキシブル配線基板の製造方法。
＜１２＞＜１＞〜＜７＞のいずれかに記載の感光性組成物を含む感光層に対して露光することを含む、永久パターン形成方法。 The object of the present invention has been achieved by the following means.
<1> A photosensitive composition containing an acid-modified ethylenically unsaturated group-containing polyurethane resin, an ethylenically unsaturated group-containing acrylic resin, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and a metal phosphate.
<2> The ethylenically unsaturated group-containing acrylic resin is a partial acid group of a copolymer of (meth) acrylic acid ester and a compound having an ethylenically unsaturated group and having at least one acid group <1> The photosensitive composition according to <1>, which is a modified copolymer obtained by adding (meth) acrylate having an epoxy group.
<3> The photosensitive composition according to <1> or <2>, wherein the ethylenically unsaturated group of the ethylenically unsaturated group-containing acrylic resin is an acryloyloxy group or a methacryloyloxy group.
<4> The acid-modified ethylenically unsaturated group-containing polyurethane resin has a mass average molecular weight of 2,000 to 60,000, an acid value of 20 mgKOH / g to 120 mgKOH / g, and an ethylenically unsaturated group equivalent of 0.05 mmol / g to 3. The photosensitive composition according to any one of <1> to <3>, which is 0 mmol / g and has a partial structure represented by the following general formula (UE1):

In the general formula (UE1), L ^UE has a partial structure of any one of the following general formulas (1) to (3), and -NHC (= O) O- or -OC (= O ) Represents a divalent linking group not containing NH-;

In General formula (1), R < ¹ > -R < ³ > represents a hydrogen atom or monovalent organic group each independently. X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Here, R ¹² represents a hydrogen atom or a monovalent organic group;

In General formula (2), R < ⁴ > -R < ⁸ > represents a hydrogen atom or monovalent organic group each independently. Y represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Here, R ¹² represents a hydrogen atom or a monovalent organic group;

In General formula (3), R < ⁹ > -R < ¹¹ > represents a hydrogen atom or monovalent organic group each independently. Z represents an oxygen atom, a sulfur atom, —N (R ¹³ ) —, or an optionally substituted phenylene group. Here, R ¹³ represents a hydrogen atom or a monovalent organic group.
<5> The photosensitive composition according to <4>, wherein L ^UE in the general formula (UE1) has one partial structure of any one of the general formulas (1) to (3).
<6> The photosensitive composition according to any one of <1> to <5>, wherein the ethylenically unsaturated group of the acid-modified ethylenically unsaturated group-containing polyurethane resin is an acryloyloxy group or a methacryloyloxy group.
<7> The ratio of the acid-modified ethylenically unsaturated group-containing polyurethane resin in the total amount of the acid-modified ethylenically unsaturated group-containing polyurethane resin and the ethylenically unsaturated group-containing acrylic resin contained in the photosensitive composition is 55. The photosensitive composition in any one of <1>-<6> which is the mass% or more and 95 mass% or less.
<8> A photosensitive dry film having a photosensitive layer containing the photosensitive composition according to any one of <1> to <7>.
<9> The photosensitive laminated body which has a photosensitive layer containing the photosensitive composition in any one of <1>-<7> on a base material.
A flexible wiring board having a resist pattern obtained by photocuring a photosensitive layer containing the photosensitive composition according to any one of <1> to <7> on a <10> base material.
<11> Production of a flexible wiring board, comprising: transferring a photosensitive layer of the photosensitive dry film according to <8> onto a substrate; and exposing and developing the transferred photosensitive layer to form a resist pattern. Method.
<12> A method for forming a permanent pattern, comprising exposing a photosensitive layer containing the photosensitive composition according to any one of <1> to <7>.

The photosensitive composition of the present invention is excellent in resolution of pattern formation by exposure / development, and is excellent in all of insulation, folding resistance, and flame retardancy after pattern formation.
The photosensitive film and photosensitive laminate of the present invention are excellent in resolution of pattern formation by exposure / development and excellent in insulation, folding resistance, and flame retardancy after pattern formation. Having a layer.
Further, according to the method for forming a permanent pattern of the present invention, an extremely fine pattern can be accurately formed on the photosensitive layer, and any of insulation, folding resistance, and flame resistance of the cured layer after pattern formation can be achieved. Also excellent.
Moreover, the printed circuit board of the present invention has high pattern shape accuracy and excellent durability.

(Photosensitive composition)
The photosensitive composition of the present invention includes an acid-modified ethylenically unsaturated group-containing polyurethane resin, an ethylenically unsaturated group-containing acrylic resin, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and a metal phosphate. And at least a salt. The photosensitive composition of the present invention may contain other components such as a curing accelerator.

<Acid-modified ethylenically unsaturated group-containing polyurethane resin>
The acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and can be appropriately selected according to the purpose. In the present invention, in particular, the acid-modified polyurethane resin having an ethylenically unsaturated bond in the side chain Is preferred. In the present invention, the side chain is a chain that is connected by substituting from a chain of atoms constituting the main chain of the polyurethane resin with a branched or substituted atom constituting the main chain, and has an ethylenically unsaturated group in the side chain. Means that an ethylenically unsaturated group is contained in such a side chain, or an atom constituting the main chain is directly substituted with an ethylenically unsaturated group. For example, a polyurethane resin obtained only by reaction of a diol of HOCH ₂ CH═CHCH ₂ OH and OCN (CH ₂ ) ₆ NCO contains an ethylenically unsaturated group in the main chain.
The ethylenically unsaturated group is a group having an ethylene bond that is consumed in the measurement of bromine value and iodine value, and is not a group showing aromaticity such as benzene. The ethylenically unsaturated group is preferably a vinyl group which may have a substituent.

  The preferred molecular weight, acid value, and ethylenically unsaturated group equivalent of the acid-modified ethylenically unsaturated group-containing polyurethane resin used in the present invention and the preferred content of the photosensitive composition will be described below.

<< Molecular weight >>
There is no restriction | limiting in particular as a mass mean molecular weight of acid-modified ethylenically unsaturated group containing polyurethane resin, Although it can select suitably according to the objective, 5,000-60,000 are preferable, 5,000-50 Is more preferable, and 5,000 to 30,000 is particularly preferable. When the weight average molecular weight is less than 5,000, when the photosensitive composition of the present invention is used for a photosensitive solder resist, a sufficiently low elastic modulus at a high temperature of the cured film may not be obtained. If it exceeds 60,000, coating suitability and developability may be deteriorated. In addition, when an inorganic filler is used, it is excellent in the dispersibility of the inorganic filler, excellent in crack resistance and heat resistance, and excellent in developability of non-image areas with an alkaline developer.
Here, the said mass mean molecular weight can be measured using a high-speed GPC apparatus (the Toyo Soda Co., Ltd. make, HLC-802A). Specifically, a 0.5 mass% THF solution is used as a sample solution, a column uses one TSKgel HZM-M, a 200 μL sample is injected, and the sample is eluted with the THF solution. It is measured by a detector or a UV detector (detection wavelength 254 nm). And a mass mean molecular weight can be calculated | required from the molecular weight distribution curve calibrated with the standard polystyrene.

<< Acid value >>
The acid value of the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. Is more preferable, and 35 mgKOH / g to 100 mgKOH / g is particularly preferable. If the acid value is less than 20 mg KOH / g, the developability may be insufficient, and if it exceeds 120 mg KOH / g, the development speed may be too high, and development control may be difficult.
Here, the acid value can be measured in accordance with, for example, JIS K0070. In addition, when a sample does not melt | dissolve, a dioxane or tetrahydrofuran is used as a solvent. The acid value is the solid content acid value of the resin.

<< Equivalent ethylenically unsaturated group >>
The ethylenically unsaturated group equivalent of the acid-modified ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.05 mmol / g to 2.0 mmol / g. 0.5 mmol / g to 1.9 mmol / g is more preferable, and 0.75 mmol / g to 1.8 mmol / g is particularly preferable. When the ethylenically unsaturated group equivalent is less than 0.05 mmol / g, the heat resistance of the cured film may be inferior, and when it exceeds 2.0 mmol / g, folding resistance may be deteriorated.
Here, the ethylenically unsaturated group equivalent can be determined, for example, by measuring the bromine number. The bromine number can be measured, for example, according to JIS K2605.
Here, the ethylenically unsaturated equivalent is typically a vinyl group equivalent, and the number of grams of bromine (Br ₂ ) added to 100 g of the resin to be measured obtained by the bromine number (gBr ₂ / 100 g) is converted to the number of moles of added bromine (Br ₂ ) per 1 g of resin.

Below, the preferable aspect of the acid-modified urethane resin which has an ethylenically unsaturated bond in a side chain in this invention is demonstrated.
There is no restriction | limiting in particular as acid-modified urethane resin which has an ethylenically unsaturated bond in a side chain, According to the objective, it can select suitably, For example, the following General formula (1)-(3) is included in the side chain. What has at least 1 among the functional groups represented by these is mentioned.

In General formula (1), R < ¹ > -R < ³ > represents a hydrogen atom or monovalent organic group each independently. Here, examples of the monovalent organic group include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group. , Amino group, alkylamino group, arylamino group, acylamino group, sulfonamido group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, carbamoyl group, sulfamoyl Group, hydroxyl group, mercapto group, cyano group, nitro group, carboxyl group, sulfo group, ureido group, urethane group and the like, and these groups may be further substituted with these substituents. In addition, the same group is mentioned also in each subsequent group and the monovalent organic group or substituent in each general formula.
R ¹ is preferably a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom or a methyl group is more preferable in terms of high radical reactivity. R ² and R ³ are each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an optionally substituted alkyl group, a substituted group An aryl group that may have a group, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, and an arylsulfonyl group which may have a substituent are preferable. Among them, a hydrogen atom, a carboxyl group, an alkoxy group are preferable because of high radical reactivity. A carbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable.

X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —, and R ¹² represents a hydrogen atom or a monovalent organic group. R ¹² is preferably an alkyl group which may have a substituent, and among them, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are more preferable from the viewpoint of high radical reactivity.
Here, the substituent that each of the above groups may have (substituent that may be present in an alkyl group that may have a substituent) is not particularly limited, and may be appropriately selected depending on the purpose. For example, the groups mentioned in the above-mentioned monovalent organic groups can be mentioned, and halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups Amino group, alkylamino group, arylamino group, acylamino group, carbamoyl group, alkoxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, carboxyl group, sulfo group, nitro group, and cyano group are preferred.

In General formula (2), R < ⁴ > -R < ⁸ > represents a hydrogen atom or monovalent organic group each independently. R ^{4 to} R ⁸ are not particularly limited and may be appropriately selected depending on the purpose. Here, examples of the monovalent organic group include those described as R ^{1 to} R ³ in the general formula (1). Groups. R ^{4 to} R ⁸ are a hydrogen atom, a halogen atom, an amino group, an alkylamino group which may have a substituent, a dialkylamino group which may have a substituent, or an arylamino which may have a substituent. Group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent , An aryloxy group which may have a substituent, an alkylsulfonyl group which may have a substituent, and an arylsulfonyl group which may have a substituent are preferable. An atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable.

Examples of the substituent that each of the above groups may have include the same as those in the general formula (1). Y represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. R ¹² has the same meaning as R ^{12 in the} general formula (1), and preferred examples thereof are also the same.

In General formula (3), R < ⁹ > -R < ¹¹ > represents a hydrogen atom or monovalent organic group each independently. Here, as a monovalent organic group, the group quoted by R < ¹ > -R < ³ > in the said General formula (1) is mentioned. R ⁹ is preferably a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom or a methyl group is more preferable in terms of high radical reactivity. R ¹⁰ and R ¹¹ are a hydrogen atom, a halogen atom, an amino group, an alkylamino group which may have a substituent, a dialkylamino group which may have a substituent, or an arylamino which may have a substituent. Group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent An aryloxy group which may have a substituent, an alkylsulfonyl group which may have a substituent, and an arylsulfonyl group which may have a substituent are preferable. An atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable.

Here, as a substituent which each said group may have, the thing similar to General formula (1) is mentioned. Further, Z is an oxygen atom, a sulfur atom, -N (R ¹³⁾ -, or a phenylene group which may have a substituent. R ¹³ represents a hydrogen atom or a monovalent organic group. R ¹³ is preferably an alkyl group which may have a substituent. Among them, a methyl group, an ethyl group, and an isopropyl group are more preferable from the viewpoint of high radical reactivity.

Of the groups represented by the general formulas (1) to (3), the group represented by the general formula (1) is preferable, and R ¹ in the general formula (1) is a methyl group from the viewpoint of forming a crosslinked cured film. And a group in which R ² and R ³ are hydrogen atoms, a group in which R ^{1 to} R ³ in the general formula (1) are all hydrogen atoms, and a styryl group in which Z in the general formula (3) is a phenylene group are preferable. A group in which R ¹ in the general formula (1) is a methyl group and R ² and R ³ are hydrogen atoms, and a group in which R ^{1 to} R ³ in the general formula (1) are all hydrogen atoms are more preferable. From the viewpoint of achieving both the formability of the cured film and the raw storage stability, a group in which R ¹ in the general formula (1) is a methyl group and R ² and R ³ are hydrogen atoms is particularly preferable. Here, X in the general formula (1) is preferably an oxygen atom, and the ethylenically unsaturated group is preferably a methacryloyloxy group or an acryloyloxy group, and most preferably a methacryloyloxy group.

In order to introduce an ethylenically unsaturated group into the side chain, (i) a method obtained by a polymerization reaction with a compound having an ethylenically unsaturated group in a diisocyanate compound or a diol compound, (ii) a carboxyl group-containing polyurethane, And a method obtained by reacting an epoxy group with a compound having an ethylenically unsaturated group.
Hereinafter, the polyurethane resin obtained by the method (i) is also referred to as polyurethane resin (i), and the polyurethane resin obtained by the method (ii) is also referred to as polyurethane resin (ii). Moreover, the polyurethane resin which has an ethylenically unsaturated bond in a side chain is the concept containing both polyurethane resin (i) and (ii).
In the present invention, the polyurethane resin (i) obtained by the method (i) is preferred.

-Polyurethane resin (i)-
A polyurethane resin is a resin synthesized by a reaction between a diisocyanate compound and a diol compound (a compound having at least two hydroxyl groups). The polyurethane resin (i) is represented by a reaction product of at least one diisocyanate compound represented by the following general formula (4) and at least one diol compound represented by the following general formula (5). A polyurethane resin having a structural unit as a basic skeleton.
^OCN-X 0 -NCO ··· general Formula (4)
^HO-Y 0 -OH ··· the general formula (5)
In the general formulas (4) and (5), X ⁰ and Y ⁰ each independently represent a divalent organic residue.

  At least one of the diisocyanate compound represented by the general formula (4) and the diol compound represented by the general formula (5) is a group represented by the general formulas (1) to (3). If it has at least one of them, as a reaction product of the diisocyanate compound and the diol compound, a polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain is provided. Generated. According to this method, a polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain is easier than substitution and introduction of a desired side chain after the reaction of the polyurethane resin is generated. Can be manufactured.

The diisocyanate compound represented by the general formula (4) is not particularly limited and can be appropriately selected depending on the purpose. For example, a triisocyanate compound and a monofunctional alcohol having an unsaturated group Or the product obtained by addition-reacting with 1 equivalent of monofunctional amine compounds is mentioned.
The triisocyanate compound is not particularly limited and can be appropriately selected depending on the purpose. For example, the compounds described in paragraphs [0034] to [0035] of JP-A-2005-250438, Etc.

  The monofunctional alcohol having an unsaturated group or the monofunctional amine compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paragraphs of JP-A-2005-250438 And the compounds described in [0037] to [0040].

  There is no restriction | limiting in particular as a diisocyanate compound in the method using the diisocyanate compound containing an unsaturated group in a side chain, It can select suitably according to the objective, Monofunctional alcohol which has a triisocyanate compound and an unsaturated group, or A diisocyanate compound obtained by addition reaction with 1 equivalent of a monofunctional amine compound, for example, unsaturated in the side chain described in paragraphs [0042] to [0049] of JP-A-2005-250438 And a compound having a group.

  The polyurethane resin (i) is a diisocyanate compound other than the diisocyanate compound containing an ethylenically unsaturated group, from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. It can also be copolymerized.

The diisocyanate compound to be copolymerized is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a diisocyanate compound represented by the following general formula (6).

OCN-L ¹ -NCO ··· general formula (6)

In General formula (6), L < ¹ > represents the bivalent aliphatic or aromatic hydrocarbon group which may have a substituent. If necessary, L ¹ may have another functional group that does not react with an isocyanate group, for example, an ester group, a urethane group, an amide group, or a ureido group.

  There is no restriction | limiting in particular as a diisocyanate compound represented by the said General formula (6), According to the objective, it can select suitably, For example, the dimer of 2, 4- tolylene diisocyanate and 2, 4- tolylene diisocyanate 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4 ' -Aromatic diisocyanate compounds such as diisocyanates; Aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; Isophorone diisocyanate, 4,4'-methyl Alicyclic diisocyanate compounds such as bis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; 1 mol of 1,3-butylene glycol and tolylene diisocyanate 2 A diisocyanate compound which is a reaction product of a diol such as an adduct with a mole and a diisocyanate;

The diisocyanate compound represented by the general formula (4) or (6) (particularly the diisocyanate compound represented by the general formula (6)) may be used in combination of different types, but the folding resistance can be improved. At least one of them is preferably an aromatic diisocyanate compound. The aromatic diisocyanate compound is preferably a diisocyanate compound having a bisphenol A type, bisphenol F type, biphenyl type, naphthalene type, phenanthrene type, or anthracene type skeleton, for example, a bisphenol A type or bisphenol F type skeleton. More preferred is a diisocyanate compound having
Each of these types of skeletons is represented by the following general formula.

In the above, R ^a and R ^b each independently represent a substituent, and the substituent is preferably an alkyl group having 2 to 5 carbon atoms. l ₁ and l ₂ each independently represents an integer of 0 to 4. l ₁ and l ₂ are preferably 0 or 1. l ₃ represents an integer of 0-6. l ₄ represents an integer of 0 to 8. l ₃ is preferably 0 to 2, and l ₄ is preferably 0 or 2. When l _{1 to} l ₄ is 2 or more, a plurality of R ^a and R ^b may be the same as or different from each other. The naphthalene type, the phenanthrene-type and anthracene type, may be a substituent of any of the rings R ^a are constituting a condensed ring.

  The diisocyanate compound is more preferably a combination of an aromatic diisocyanate compound and an aliphatic diisocyanate compound from the viewpoint of suppressing warping after curing and improving folding resistance. As the aliphatic diisocyanate compound, for example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate and dimer acid diisocyanate are preferable, and hexamethylene diisocyanate and trimethylhexamethylene diisocyanate are more preferable.

  There is no restriction | limiting in particular as a diol compound represented by the said General formula (5), According to the objective, it can select suitably, For example, a polyether diol compound, a polyester diol compound, a polycarbonate diol compound etc. are mentioned. .

  Here, as a method for introducing an ethylenically unsaturated group into the side chain of the polyurethane resin, in addition to the above-described method, a diol compound containing an ethylenically unsaturated group in the side chain may be used as a raw material for producing the polyurethane resin. The method used can be preferably used. The diol compound containing an ethylenically unsaturated group in the side chain may be a commercially available compound such as trimethylolpropane monoallyl ether, or a compound such as a halogenated diol compound, a triol compound, or an aminodiol compound. And a compound produced by a reaction with an unsaturated group-containing compound such as carboxylic acid, acid chloride, isocyanate, alcohol, amine, thiol, or halogenated alkyl compound.

  As such a diol compound having an ethylenically unsaturated group, a compound represented by the following general formula (UE) is preferable, and the polyurethane resin has a partial structure represented by the following general formula (UE1). become.

In the general formulas (UE) and (UE1), L ^UE has one ethylenically unsaturated group in the side chain, and —NHC (═O) O— or —OC (═O) NH— in the main chain bond. And a divalent linking group having one ethylenically unsaturated group in the side chain.

  The compound represented by the general formula (UE) is preferably a compound represented by the following general formulas (UE-1) to (UE-6). In addition, the compound represented by the following general formula (UE-7) is a preferable compound other than the compound represented by the said general formula (UE).

In General Formulas (UE-1) to (UE-7), E ¹ represents a single bond or a divalent linking group (a divalent organic residue), and E ² represents a single bond or ₂ other than —CH ₂ —. Represents a valent linking group. A represents a divalent linking group. Q represents any group of the general formulas (1) to (3). Examples of the divalent linking group for E ¹ and E ² include —O—, —S—, —OCH (CH ₂ —Q) CH ₂ —, —CO ₂ —CH ₂ —, —OCH ₂ C (CH _{2 -Q) 2 CH 2 -,} - O-CONHCH 2 CH 2 -, - OC (= O) -, - CONHCH 2 CH 2 -, - CH 2 C (CH 2 -Q) 2 CH 2 -, - CH _{2 -, - NHCONHCH 2 CH 2} -, - NHCH (CH 2 -Q) CH 2 -, - NCH (CH 2 -Q) CH 2 -, - NHCH 2 C (CH 2 -Q) 2 CH 2 -, - _{NH-CH (CH 2 -Q)} CH 2 -, - C (= O) -, - CO 2 -CH 2 CH 2 -, - CO 2 -CH 2 CH 2 CH 2 - and the like. Here, Q represents any group of the general formulas (1) to (3).
Specific examples of these compounds include compounds described in paragraphs “0057” to “0060” of JP-A-2005-250438.

  Of the compounds represented by the general formulas (UE-1) to (UE-7), the compounds represented by the general formulas (UE-1) to (UE-6) are preferable, and the general formula (UE- The compound represented by 6) is more preferable. Of the compounds represented by the general formula (UE-6), compounds represented by the following general formula (G) are particularly preferable. Note that the compound represented by the general formula (G) has a partial structure represented by the following general formula (G1) in the polyurethane resin.

In the general formulas (G) and (G1), R ^{1 to} R ³ each independently represents a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom or sulfur. Represents an atom or —N (R ¹² ) —, and R ¹² represents a hydrogen atom or a monovalent organic group.
Incidentally, the general formula (G), R ¹ to R ³ and X in (G1) has the same meaning as R ¹ to R ³ and X in the general formula (1), preferred embodiments versa.
Examples of the compound represented by the general formula (G) include compounds described in paragraphs [0064] to [0066] of JP-A-2005-250438, and are preferable in the present invention.
By using the polyurethane resin derived from the diol compound represented by the general formula (G), the effect of suppressing the excessive molecular movement of the polymer main chain caused by the secondary alcohol having a large steric hindrance can be reduced. It is thought that improvement can be achieved.

  The polyurethane resin (i) of the present invention is acid-modified, and examples of the acid in the acid modification include carboxylic acid and sulfonic acid, and carboxylic acid is particularly preferable. For the synthesis of the polyurethane resin (i), it is preferable to use acid-modified by using a diol compound having a carboxyl group. Examples of the diol compound having a carboxyl group include those represented by the following formulas (17) to (19).

In the formulas (17) to (19), R ¹⁵ represents a hydrogen atom or a substituent (for example, a halogen atom such as a cyano group, a nitro group, —F, —Cl, —Br, —I, etc., —CONH ₂ , —COOR ¹⁶ , —OR ¹⁶ , —NHCONHR ¹⁶ , —NHCOOR ¹⁶ , —NHCOR ¹⁶ , —OCONHR ¹⁶ (where R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms. ) And the like, as long as it represents an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group that may have a substituent, and is appropriately selected depending on the purpose. A hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 15 carbon atoms are preferable. In the above formulas (17) to (19), L ⁹ , L ¹⁰ and L ¹¹ may be the same or different, and may be a single bond, a substituent (for example, an alkyl group, an aralkyl group, an aryl group). As long as it represents a divalent aliphatic or aromatic hydrocarbon group that may have an alkyl group, and an alkoxy group and a halogen atom are not particularly limited, and can be appropriately selected depending on the purpose. However, a C1-C20 alkylene group and a C6-C15 arylene group are preferable, and a C1-C8 alkylene group is more preferable. If necessary, the L ^{9 to} L ¹¹ may have another functional group that does not react with the isocyanate group, for example, a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, or an ether group. In addition, you may form a ring by two or three of said R < ¹⁵ >, L < ⁹ >, L < ¹⁰ >, L < ¹¹ >.
In the formula (18), Ar is not particularly limited as long as it represents a trivalent aromatic hydrocarbon group which may have a substituent, and can be appropriately selected according to the purpose. However, an aromatic group having 6 to 15 carbon atoms is preferable.

  The diol compound having a carboxyl group represented by the formulas (17) to (19) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 3,5-dihydroxybenzoic acid, 2, 2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxy Phenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) -3-carboxy-propionamide and the like. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as a diol compound which has a carboxyl group, According to the objective, it can select suitably, For example, the compound described in Paragraph [0047] of Unexamined-Japanese-Patent No. 2007-2030 etc. are mentioned.

  The presence of such a carboxyl group is preferable because the polyurethane resin can be provided with characteristics such as hydrogen bonding properties and alkali solubility. By introducing a carboxyl group in this way, the acid value can be adjusted to the preferred range in the present invention as described above.

  The presence of such a carboxyl group is preferable because the polyurethane resin can be provided with characteristics such as hydrogen bonding properties and alkali solubility. By introducing a carboxyl group in this way, the acid value can be adjusted to the preferred range in the present invention as described above.

Moreover, in the synthesis | combination of the polyurethane resin which has an ethylenically unsaturated bond in a side chain, the compound which ring-opened tetracarboxylic dianhydride with the diol compound other than the diol compound mentioned above can also be used together.
The compound obtained by ring-opening the tetracarboxylic dianhydride with a diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, JP-A-2005-250438, paragraph [0095] to And the compounds described in [0101].

The polyurethane resin (i) is, for example, a diol compound containing an ethylenically unsaturated group in the side chain from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. Or a diol compound other than a diol compound containing a carboxyl group can be copolymerized. In the present invention, it is particularly preferable to copolymerize such a diol compound.
Such a diol compound is not particularly limited and can be appropriately selected according to the purpose. For example, a low-molecular diol compound or a polymer diol compound such as a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, A polycarbonate compound of m-dihydroxybenzene can be exemplified.

  Such a diol compound is represented by the following general formula (U) and, when incorporated as a polyurethane resin, is represented by a partial structure represented by the following general formula (U1).

In the general formulas (U) and (U1), L ^U1 represents a divalent linking group that does not contain an ethylenically unsaturated group and a carboxyl group.

L ^U1 includes, for example, an alkylene group, an arylene group, and a divalent heterocyclic group, and the alkylene group includes —O—, —OCOO—, a phenylene group, and a carbon-carbon double bond in the chain of the alkylene group. , A carbon-carbon triple bond, -OCO-Z ¹ -COO- (Z ¹ represents an alkylene group, an alkenylene group, or an arylene group).

Of the diol compounds represented by the general formula (U), the low molecular weight diol compound preferably has a mass average molecular weight of less than 400, and is described in, for example, paragraph [0048] of JP-A-2007-2030. And the like.
In the present invention, a polymer diol compound is preferable and will be described in detail below.

-Polymer diol compound-
The polymer diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide block copolymer or random copolymer Polyether diols such as coalesced polytetramethylene glycol, block copolymer or random copolymer of tetramethylene glycol and neopentyl glycol; polyhydric alcohol or polyether diol and maleic anhydride, maleic acid, fumaric acid, Polyester diols that are condensates of polybasic acids such as itaconic anhydride, itaconic acid, adipic acid, terephthalic acid, isophthalic acid; reaction of glycol or bisphenol with carbonate Alternatively, polycarbonate diols obtained by reacting phosgene with glycol or bisphenol in the presence of alkali; caprolactone-modified polymer diols such as caprolactone-modified polytetramethylene diol, polybutadiene-based polymers such as polyolefin-based polymer diols and hydrogenated polybutadiene diols Examples thereof include polymer diols and silicone polymer diols. These may be used individually by 1 type and may use 2 or more types together.

In the present invention, preferred compounds and partial structures are such that L ^U1 in the general formulas (U) and (U1) is — (CH ₂ CH ₂ O) n ^U1 CH ₂ CH ₂ —, — [CH ₂ CH (CH ₃ ) O] _{^{n U1 -CH 2 CH (CH 3}} ) -, - (CH 2 CH 2 CH 2 O) n U1 -CH 2 CH 2 CH 2 -, - ^{_{[(CH 2) n U2 -OC (}} = O) ^{_{- (CH 2) n U3 -C}} (= O) O ] _{^{n U4 -O (CH 2) n}} U2 - or - ^{_{[(CH 2) n U5 -OC (}} = O) O ] ⁿ U6 - _(CH 2) n ^U7 −. Here, n ^{U1 to} n ^U7 each independently represents a number of 1 or more.
In addition, the compound represented by the general formula (U) is also preferably a diol compound represented by the following general formulas (III-1) to (III-6).

  The polyether diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraphs [0068] to [0076] of JP-A-2005-250438. Can be mentioned.

  The polyester diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paragraphs [0077] to [0079] and paragraphs [0083] to [0085] of JP-A-2005-250438. No. 1-No. 8 and no. 13-No. 18 and the like, and the like.

  There is no restriction | limiting in particular as said polycarbonate diol compound, According to the objective, it can select suitably, For example, Unexamined-Japanese-Patent No. 2005-250438 Paragraph [0080]-[0081] and Paragraph [0084] No. 9-No. 12 and the like, and the like.

In addition to the diol compound described above, a diol compound having a substituent that does not react with an isocyanate group can be used in combination.
There is no restriction | limiting in particular as a diol compound which has a substituent which does not react with the said isocyanate group, According to the objective, it can select suitably, For example, Paragraph [0087]-[0088] of Unexamined-Japanese-Patent No. 2005-250438 And the described compounds.

The mass average molecular weight of such a polymer diol compound is preferably 400 to 8,000, more preferably 500 to 5,000, still more preferably 600 to 3,000, and 800 to 2 Is particularly preferred. If the mass average molecular weight is less than 400, sufficient folding resistance may not be obtained, and if it exceeds 8,000, the glass transition temperature (Tg) of the resulting polyurethane resin will be too low. May deteriorate.
Here, the mass average molecular weight is determined using, for example, a high-speed GPC apparatus (HLC-802A, manufactured by Toyo Soda Co., Ltd.), a 0.5% by mass THF solution as a sample solution, and a column of one TSKgel HZM-M. In use, 200 μL of sample can be injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or UV detector (detection wavelength 254 nm).

  The mass ratio of the partial structure represented by the general formula (U1) in the acid-modified ethylenically unsaturated group-containing polyurethane resin is preferably 10 to 60%, more preferably 20 to 60%, and more preferably 25 to 25%. It is more preferable that it is 55%, and it is further more preferable that it is 30 to 50%. When the mass ratio is less than 10%, it may be difficult to suppress warping after curing, and when it exceeds 60%, the sensitivity of photocuring may be excessively lowered and resolution may be deteriorated.

  Moreover, as a polyurethane resin which has an ethylenically unsaturated bond in the side chain used by this invention, what has an unsaturated group in a polymer terminal and a principal chain is used suitably. Polyurethane resin having an ethylenically unsaturated bond in the side chain, or between the photosensitive composition and the polyurethane resin having an ethylenically unsaturated bond in the side chain, by having an unsaturated group at the polymer terminal and main chain Crosslinking reactivity is improved, and the strength of the photocured product is increased. Here, as an unsaturated group, it is especially preferable to have a carbon-carbon double bond from the viewpoint of easy occurrence of a crosslinking reaction.

As a method for introducing an unsaturated group into the polymer terminal, there are the following methods. That is, in the step of synthesizing the polyurethane resin having an ethylenically unsaturated bond in the side chain as described above, in the step of treating with the residual isocyanate group at the polymer end and the alcohol or amine, the alcohol having an unsaturated group. Alternatively, amines or the like may be used. Specific examples of such a compound include the same compounds as those exemplified above as the monofunctional alcohol or monofunctional amine compound having an unsaturated group.
The unsaturated group is preferably introduced into the polymer side chain rather than the polymer terminal from the viewpoint that the introduction amount can be easily controlled and the introduction amount can be increased, and that the crosslinking reaction efficiency is improved.
The ethylenically unsaturated bond group to be introduced is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of forming a crosslinked cured film, a methacryloyl group, an acryloyl group, and a styryl group are preferable, and methacryloyl Group and acryloyl group are more preferable, and methacryloyl group is particularly preferable in terms of both the formability of the crosslinked cured film and the raw storage stability.
The amount of methacryloyl group introduced is not particularly limited and may be appropriately selected depending on the intended purpose. The ethylenically unsaturated group equivalent is preferably 0.05 mmol / g to 2.0 mmol / g, 0.5 mmol / g to 1.90 mmol / g is more preferable, and 0.75 mmol / g to 1.80 mmol / g is particularly preferable.

  As a method of introducing an unsaturated group into the main chain, there is a method of using a diol compound having an unsaturated group in the main chain direction for the synthesis of a polyurethane resin. The diol compound having an unsaturated group in the main chain direction is not particularly limited and may be appropriately selected depending on the purpose. For example, cis-2-butene-1,4-diol, trans-2-butene- 1,4-diol, polybutadiene diol, and the like.

In the present invention, as the acid-modified polyurethane resin having an ethylenically unsaturated bond in the side chain used in the present invention, those having at least one carboxyl group at the terminal of the polymer main chain may be used as non-images by an alkaline developer. It is preferably used because it is excellent in developability of part. It has at least one carboxyl group at the terminal of the polymer main chain and preferably has 2 or more and 5 or less carboxyl groups, and having two carboxyl groups is excellent in developability and has a fine pattern forming property. Is particularly preferable.
The polyurethane resin has two main chain ends, but preferably has at least one carboxyl group at one end, and may have at least one carboxyl group at both ends.

  It is preferable that the terminal of the main chain of the polyurethane resin has a structure represented by the following general formula (AD).

General formula (AD)
-L ^100- (COOH) _n

In the general formula (AD), L ¹⁰⁰ represents an (n + 1) -valent organic linking chain, n represents an integer of 1 or more, preferably 1 to 5, and particularly preferably 2.
The organic linking group represented by L ¹⁰⁰ is configured to include one or more atoms selected from a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom, specifically, represented by L ^100. The number of atoms constituting the main skeleton of the organic linking group is preferably 1 to 30, more preferably 1 to 25, still more preferably 1 to 20, and particularly preferably 1 to 10.
The “main skeleton of the organic linking group” means an atom or an atomic group used only for linking the main chain of the polyurethane resin and the terminal COOH, and when there are a plurality of linking paths, The atom or atomic group which comprises the path | route with the fewest number of atoms used is pointed out.

  The method for introducing at least one carboxyl group at the end of the main chain of the polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, as a raw material for producing a polyurethane resin, at least one Examples include a method using a carboxylic acid compound having a carboxyl group.

  Examples of the carboxylic acid compound include a monocarboxylic acid compound having one carboxyl group, a dicarboxylic acid compound having two carboxyl groups, a tricarboxylic acid compound having three carboxyl groups, a tetracarboxylic acid compound having four carboxyl groups, and a carboxyl group. Examples thereof include pentacarboxylic acid compounds having five groups. Among these, a dicarboxylic acid compound having two carboxyl groups is particularly preferable in terms of excellent developability and fine pattern formability.

  The carboxylic acid compound is not particularly limited as long as it has at least one carboxyl group, and can be appropriately selected according to the purpose. However, a compound represented by the following general formula (ADH) is preferable.

General formula (ADH)
^{H-O-L 200 -Y 100} -L 100 - (COOH) n

In the general formula (ADH), L ¹⁰⁰ and n represent the same meaning as in the general formula (AD). Y ¹⁰⁰ represents a divalent or higher valent atom. L ²⁰⁰ represents a single bond or an alkylene group which may have a substituent.
Examples of the divalent or higher atom in Y ¹⁰⁰ include an oxygen atom, a nitrogen atom, a carbon atom, and a silicon atom. Among these, a nitrogen atom and a carbon atom are particularly preferable. Here, the atom represented by Y ¹⁰⁰ being divalent or more means that at least Y ¹⁰⁰ has two bonds in which the terminal —COOH is bonded via L ¹⁰⁰ and L ²⁰⁰ , Y ¹⁰⁰ may further have a hydrogen atom or a substituent.
Examples of the substituent which can be introduced into Y ^100, a hydrogen atom, an oxygen atom, a sulfur atom, a substituted group configured to include an atom selected from a nitrogen atom and a halogen atom. Among these, a hydrocarbon group having 1 to 50 carbon atoms is preferable, a hydrocarbon group having 1 to 40 carbon atoms is more preferable, and a hydrocarbon group having 1 to 30 carbon atoms is particularly preferable.

The alkylene group for L ^200, preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms. Examples of the substituent that can be introduced into the alkylene group include a halogen atom (—F, —Br, —Cl, —I), an alkyl group that may have a substituent, and the like.

  The carboxylic acid compound represented by the general formula (ADH) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include lactic acid, malic acid, hydroxyhexanoic acid, citric acid, and a diol compound. Examples include a reaction product of an acid anhydride. These may be used individually by 1 type and may use 2 or more types together. Among these, malic acid is particularly preferable.

  Specific examples of the polyurethane resin (i) used in the present invention include, for example, polymers P-1 to P-31 shown in paragraphs [0293] to [0310] of JP-A-2005-250438. Can be mentioned. Among these, the polymers of P-27 and P-28 shown in paragraphs [0308] and [0309] are preferable.

The polyurethane resin having an ethylenically unsaturated bond in the side chain used in the present invention is prepared by adding the above-mentioned diisocyanate compound and diol compound to an aprotic solvent and adding a known catalyst having an activity corresponding to each reactivity. To be synthesized. The molar ratio of the diisocyanate used in the synthesis and the diol _compound: As the (M a M _b), is not particularly limited and may be appropriately selected depending on the intended purpose, 1: 1 to 1.2: 1 are preferred, By treating with alcohols or amines, a product having desired physical properties such as molecular weight or viscosity is synthesized in a form in which no isocyanate group remains finally.

  The polyurethane resin having an ethylenically unsaturated bond in the side chain used in the present invention is, in particular, the aforementioned diisocyanate compound and a diol compound, a (meth) acrylate compound having two hydroxyl groups in the molecule, and two in the molecule. It is preferably obtained by reacting a carboxylic acid having a hydroxyl group with the above-mentioned polymer diol compound, and in addition, obtained by reacting a compound having one hydroxyl group and a carboxyl group represented by the general formula (ADH). Is preferred.

-Polyurethane resin (ii)-
The polyurethane resin (ii) is a polyurethane resin obtained by reacting a carboxyl group-containing polyurethane with a compound having an epoxy group and an ethylenically unsaturated group in the molecule.
The polyurethane resin (ii) is a polyurethane resin obtained by reacting a carboxyl group-containing polyurethane resin containing diisocyanate and a carboxyl group-containing diol as essential components and a compound having an epoxy group and an ethylenically unsaturated group in the molecule. It is. Depending on the purpose, as the diol component, a low molecular diol having a mass average molecular weight of 300 or less or a low molecular diol having a mass average molecular weight of 500 or more may be added as a copolymer component.
By using this, the polyurethane resin (ii) has excellent dispersibility, crack resistance, and impact resistance with an inorganic filler, so that it has heat resistance, moist heat resistance, adhesion, mechanical properties, and electrical properties. improves.
In addition, as the polyurethane resin (ii), a diisocyanate of a divalent aliphatic and aromatic hydrocarbon which may have a substituent, a COOH group and two carbon atoms via any one of a C atom and an N atom. A reaction product comprising a carboxyl group-containing diol having an OH group as an essential component, the reaction product obtained, and a compound having an epoxy group and an ethylenically unsaturated group in the molecule via a -COO- bond It may be obtained by reaction.
Moreover, as said polyurethane resin (ii), the diisocyanate shown by the following general formula (I), and the carboxyl group containing diol compound represented by Formula (17)-(19) demonstrated in the above-mentioned polyurethane resin (i) are mentioned. A high molecular diol having a mass average molecular weight of 800 to 3,000 represented by the following general formulas (III-1) to (III-6) according to the purpose: A reaction product with at least one selected from the group consisting of an epoxy group and an ethylenically unsaturated group in a molecule represented by the following general formulas (IV-1) to (IV-16): It may be obtained by reacting a compound having

In the general formula (I), R ₁ is a divalent aliphatic which may have a substituent (for example, any of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogen atom is preferable) or Represents an aromatic hydrocarbon. If necessary, R ₁ may have any other functional group that does not react with an isocyanate group, such as an ester group, a urethane group, an amide group, or a ureido group.

In the general formulas (III-1) to (III-3), R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ may be the same or different from each other, and may be divalent aliphatic. Or represents an aromatic hydrocarbon. R ₇ , R ₉ , R ₁₀ and R ₁₁ are each preferably an alkylene group having 2 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, and an alkylene or carbon number having 2 to 10 carbon atoms. 6 to 10 arylene groups are more preferred. R ₈ represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms. preferable. In addition, in R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ , other functional groups that do not react with isocyanate groups, such as ether groups, carbonyl groups, ester groups, cyano groups, olefin groups, urethane groups, There may be an amide group, a ureido group, or a halogen atom.

In General Formula (III-4), R ₁₂ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a cyano group, or a halogen atom. A hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl having 7 to 15 carbon atoms, a cyano group, or a halogen atom is preferable, and a hydrogen atom or one carbon atom is preferable. More preferred are ˜6 alkyl and aryl groups having 6 to 10 carbon atoms. R ₁₂ may contain other functional groups that do not react with isocyanate groups, such as alkoxy groups, carbonyl groups, olefin groups, ester groups, or halogen atoms. m represents an integer of 2 to 4.

In General Formula (III-5), R ₁₃ represents an aryl group or a cyano group, and preferably an aryl group or a cyano group having 6 to 10 carbon atoms.
In the general formulas (III-1) to (III-6), n ₁ , n ₂ , n ₃ , n ₄ , n ₅ , n ₇ , n ₈ and n ₉ each represents an integer of 2 or more. , An integer of 2 to 100 is preferable. In General Formula (III-5), n ₆ represents 0 or an integer of 2 or more, and 0 or an integer of 2 to 100 is preferable.

In General Formulas (IV-1) to (IV-16), R ₁₄ represents a hydrogen atom or a methyl group, R ₁₅ represents an alkylene group having 1 to 10 carbon atoms, and R ₁₆ represents 1 to 1 carbon atoms. 10 hydrocarbon groups are represented. p represents 0 or an integer of 1 to 10.

Incidentally, when reacted with a compound having an epoxy group or an oxetane group in the carboxyl group-containing polyurethane and the molecule, X, the partial structure Y or Z is linked to the polyurethane backbone, -CO 2 - _{(beta-position} or γ-position It has a structure having an aliphatic group)-(*) substituted with a hydroxyl group or an acyloxy group. Here, the partial structures of the general formulas (1) to (3) exist on the (*) side.

The polyurethane resin (ii) may further be copolymerized with a carboxyl group-free low molecular weight diol as a fifth component. Examples of the low molecular weight diol compound include those represented by the general formulas (III-1) to (III) III-6) having a mass average molecular weight of 500 or less. The carboxyl group-free low molecular weight diol can be added as long as the alkali solubility is not lowered and the elastic modulus of the cured film can be kept sufficiently low.
As said low molecular weight diol compound, the compound described in the paragraph [0048] of Unexamined-Japanese-Patent No. 2007-2030 etc. are mentioned, for example.

  As the polyurethane resin (ii), in particular, the diisocyanate represented by the general formula (I) and at least one selected from the carboxyl group-containing diols represented by the above formulas (17) to (19) are essential. As a component, depending on the purpose, at least one selected from polymer diols having a weight average molecular weight of 800 to 3,000, represented by general formulas (III-1) to (III-6), A reaction product with a low molecular weight diol having a mass average molecular weight of 500 or less and represented by formulas (III-1) to (III-6) is further added to the general formulas (IV-1) to (IV-16). The acid value obtained by reacting a compound having one epoxy group and at least one (meth) acrylic group in the molecule represented by any one of the following, is 20 mg KOH / g to 120 mg KOH / An alkali-soluble photocrosslinkable polyurethane resin g is preferred.

  In addition, also in the said polyurethane resin (ii), it replaced with the compound represented by the said general formula (III-1)-(III-6), or used together, and the general demonstrated by the above-mentioned polyurethane resin (i). It is preferable to use the diol compound represented by the formula (U), and the mass ratio of the partial structure represented by the general formula (U1) in the acid-modified ethylenically unsaturated group-containing polyurethane resin is the above-mentioned polyurethane. The same as in the case of the resin (i).

  These high molecular compounds may be used individually by 1 type, and may use 2 or more types together.

  Also in the polyurethane resin (ii), those having at least one carboxyl group at the terminal of the polymer main chain are preferable for obtaining the same effect as the polyurethane resin (i), and are described in the polyurethane resin (i). The terminal block method of the polymer main chain and the group represented by the general formula (A) are preferable, and the preferable range is the same as that of the polyurethane resin (i).

  Examples of the polyurethane resin (ii) include epoxy group and vinyl group-containing compounds in polymers U1 to U4 and U6 to U11 shown in paragraphs [0314] to [0315] of JP-A-2007-2030. Glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate (trade name: Cyclomer A400, manufactured by Daicel Chemical Industries), 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M400, Daicel Chemical Corporation) Polymer) in place of (manufactured).

—Synthesis Method of Polyurethane Resin (ii) Obtained by Reacting Carboxyl Group-Containing Polyurethane with Compound Having Epoxy Group and Ethylenically Unsaturated Group in the Molecule—
As a method for synthesizing the polyurethane resin (ii), the diisocyanate compound and the diol compound are synthesized in an aprotic solvent by adding a known catalyst having an activity corresponding to each reactivity and heating. The molar ratio of the diisocyanate and diol compound to be used is preferably 0.8: 1 to 1.2: 1. When an isocyanate group remains at the end of the polymer, it is finally treated with alcohols or amines. Synthesized with no isocyanate groups remaining.

<< Content of acid-modified ethylenically unsaturated group-containing polyurethane resin (i), (ii) >>
The acid-modified ethylenically unsaturated group-containing polyurethane resin (i) or (ii) used in the present invention can be used in combination with an alkali-soluble polymer containing a polyurethane resin having a structure different from that of the specific polyurethane resin. is there. For example, the polyurethane resin having an ethylenically unsaturated bond in the side chain can be used in combination with a polyurethane resin containing an aromatic group in the main chain and / or side chain.
There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the polyurethane resin (i) and (ii) used by this invention, Although it can select suitably according to the objective, 5 mass%- 80 mass% is preferable, 20 mass%-75 mass% is more preferable, and 30 mass%-70 mass% is especially preferable. The photosensitive resin composition of the present invention may contain both of the polyurethane resins (i) and (ii). In that case, the total amount of the polyurethane resins (i) and (ii) is within the above concentration range. It is preferable.
When the content is less than 5% by mass, the folding resistance may not be kept good. When the content exceeds 80% by mass, the heat resistance may be broken. When the content is within the particularly preferable range, it is advantageous in terms of achieving both good folding resistance and heat resistance.
The ratio of the acid-modified ethylenically unsaturated group-containing polyurethane resin in the total amount of the acid-modified ethylenically unsaturated group-containing polyurethane resin and the ethylenically unsaturated group-containing acrylic resin in the photosensitive composition is particularly limited. However, it can be appropriately selected according to the purpose, but 55% by mass to 95% by mass is preferable, and 65% by mass to 75% by mass is more preferable. When the ratio is less than 55% by mass, the thermal shock resistance may be lowered, and when it exceeds 95% by mass, the insulation may be lowered. When the ratio is within the more preferable range, it is advantageous in that both insulation and thermal shock resistance are very excellent.

<Ethylenically unsaturated group-containing acrylic resin>
The ethylenically unsaturated group-containing acrylic resin used in the present invention is not particularly limited as long as it is an acrylic resin containing an ethylenically unsaturated group that can be polymerized by radicals generated by a photopolymerization initiator. It can be selected appropriately. Examples of the functional group having an ethylenically unsaturated group include an acryloyl group, a methacryloyl group, an allyl group, a vinyl ether group, and a vinylphenyl group.
Examples of the ethylenically unsaturated group-containing acrylic resin include a (meth) acrylic acid ester (A) and a copolymer obtained from the compound (B) having an ethylenically unsaturated group and having at least one acid group. A modified copolymer obtained by adding (meth) acrylate (C) having an epoxy group to a part of acid groups of a polymer (hereinafter sometimes referred to as “copolymer”) (hereinafter referred to as “modified copolymer”). It is preferable that the heat resistance is excellent.
In the present invention, (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester, and (meth) acrylate means acrylate and / or methacrylate.

-(Meth) acrylic acid ester (A)-
Examples of the (meth) acrylic acid ester (A) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate. (Meth) acrylic acid alkyl esters such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprocactone-modified 2-hydroxyethyl (meth) acrylate and other hydroxyl groups ( Meth) acrylic acid esters; benzyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (me ) Acrylate, phenoxy triethyleneglycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, etc. (meth) acrylates such as methoxy polyethylene glycol (meth) acrylate. Among these, benzyl (meth) acrylate is preferable in terms of low water absorption.

-Compound (B) containing an ethylenically unsaturated group and having at least one acid group-
Examples of the compound (B) containing an ethylenically unsaturated group and having at least one acid group include acrylic acid, methacrylic acid, vinylphenol, chain extended between an ethylenically unsaturated group and a carboxyl group. Modified unsaturated monocarboxylic acid.
Examples of the modified unsaturated monocarboxylic acid include β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and lactone modification. And an unsaturated monocarboxylic acid having an ester bond and a modified unsaturated monocarboxylic acid having an ether bond.
These may be used individually by 1 type and may use 2 or more types together.

--Lactone modified unsaturated monocarboxylic acid--
Specific examples of the lactone-modified unsaturated monocarboxylic acid include compounds obtained by lactone modification of (meth) acrylic acid and represented by the following formula (15).

_{^{CH 2 = C (-R 1)}} CO- [O (CR 2 R 3) m CO] n -OH ·· (15)

Moreover, it is a lactone modified product obtained by acid-modifying a terminal hydroxyl group with an acid anhydride, and includes a compound represented by the following formula (16).

CH ₂ ═C (—R ¹ ) COO—CH ₂ CH ₂ O [CO (CR ² R ³ ) _m O] _n COR ⁴ COOH (16)

However, the equation (15), in (16), ^{R 1} represents a hydrogen atom or a methyl group. m R ² and R ³ each independently represent any of a hydrogen atom, a methyl group, and an ethyl group, and may be different from each other. R ⁴ is a C 1-10 divalent aliphatic saturated hydrocarbon group, a C 2-10 divalent unsaturated hydrocarbon group, a C 3-6 divalent alicyclic saturated hydrocarbon. Represents any of a group, an unsaturated hydrocarbon group having 3 to 6 carbon atoms, a p-xylylene group, and a phenylene group. m represents an integer of 4 to 8, and n represents an integer of 1 to 10.

--Modified unsaturated monocarboxylic acid having an ether bond--
As the modified unsaturated monocarboxylic acid having an ether bond, for example, an epoxy compound such as ethylene oxide is added to (meth) acrylic acid, and the molecular terminal hydroxyl group of the adduct is an acid-modified product with an acid anhydride. The compound represented by Formula (17) is mentioned.

_{^{CH 2 = C (-R 1)}} COO - [(CR 2 R 3) m O] n -COR 4 COOH (17)

However, in the above formula (17), ^{R 1} represents a hydrogen atom or a methyl group. m R ² and R ³ each independently represents any of a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a butyl group, and may be different from each other. R ⁴ is a C 1-10 divalent aliphatic saturated hydrocarbon group, a C 2-10 divalent unsaturated hydrocarbon group, a C 3-6 divalent alicyclic saturated hydrocarbon. A group, and a C 3-6 divalent unsaturated hydrocarbon group, p-xylylene, and a phenylene group. m and n represent an integer of 1 to 10.

-(Meth) acrylate having epoxy group (C)-
The (meth) acrylate (C) having an epoxy group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth). An acrylate etc. are mentioned. Among these, glycidyl (meth) acrylate is preferable.

-Method for producing modified copolymer-
As a method for producing the ethylenically unsaturated group-containing acrylic resin, an example of the method for producing the modified copolymer will be described below.
First, the copolymer is produced. There is no restriction | limiting in particular as a manufacturing method of the said copolymer, According to the objective, it can select suitably, For example, the manufacturing methods of well-known acrylic resins, such as solution polymerization, are mentioned.
Subsequently, the modified copolymer is produced by adding the (meth) acrylate (C) having the epoxy group to some of the acid groups of the copolymer.
There is no restriction | limiting in particular as said additional amount, According to the objective, it can select suitably.
In the addition, it is preferable to use a solvent and a catalyst.
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, the solvent etc. of Paragraph [0020] of Unexamined-Japanese-Patent No. 2009-086376 are mentioned.
There is no restriction | limiting in particular as said catalyst, According to the objective, it can select suitably, For example, the catalyst etc. of Paragraph [0021]-[0025] of Unexamined-Japanese-Patent No. 2009-086376 are mentioned.

  There is no restriction | limiting in particular as an acid value of the said ethylenically unsaturated group containing acrylic resin, Although it can select suitably according to the objective, 10 mgKOH / g-150 mgKOH / g is preferable, 50 mgKOHg / g-150 mgKOH / g is More preferred. When the acid value is less than 10 mgKOH / g, it may be difficult to remove the uncured film with a dilute alkaline aqueous solution, and when it exceeds 150 mgKOH / g, the water resistance and electrical characteristics of the cured film may be inferior. is there.

  There is no restriction | limiting in particular as a mass average molecular weight of the said ethylenically unsaturated group containing acrylic resin, Although it can select suitably according to the objective, 5,000-100,000 are preferable. When the mass average molecular weight is less than 5,000, tack-free performance is inferior, and the moisture resistance of the coated film after exposure is poor, resulting in film slippage during development, resulting in greatly inferior resolution. When the mass average molecular weight exceeds 100,000, developability may be remarkably deteriorated and storage stability may be inferior.

  There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said ethylenically unsaturated group containing acrylic resin, Although it can select suitably according to the objective, 1 mass%-30 mass% are preferable, 2 mass%-25 mass% are more preferable.

<Polymerizable compound>
There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, The compound which has one or more functional groups which have an ethylenically unsaturated group is preferable.

  Examples of the functional group having an ethylenically unsaturated group include a (meth) acryloyl group, a (meth) acrylamide group, a vinylphenyl group, a vinyl ester group, a vinyl ether group, an allyl ether group, and an allyl ester group.

  There is no restriction | limiting in particular as a compound which has one or more functional groups which have the said ethylenically unsaturated group, Although it can select suitably according to the objective, At least 1 selected from the monomer which has a (meth) acryl group. Species are preferred.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin Tri (meth) acrylate; polyfunctional alcohols such as trimethylolpropane, glycerin, bisphenol, etc., after addition reaction of ethylene oxide and propylene oxide, (meth) acrylate; reaction reaction of epoxy resin and (meth) acrylic acid Examples thereof include polyfunctional acrylates such as epoxy acrylates and methacrylates. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said polymeric compound, Although it can select suitably according to the objective, 5 mass%-50 mass% are preferable, and 10 mass%- 40 mass% is more preferable. When the content is 5% by mass or more, developability and exposure sensitivity are good, and when the content is 50% by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong.

<Photopolymerization initiator>
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected according to the purpose. Those having photosensitivity are preferable, and may be an activator that generates an active radical by generating some action with a photoexcited sensitizer, and is an initiator that initiates cationic polymerization according to the type of monomer. May be.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a wavelength range of about 300 nm to 800 nm. The wavelength is more preferably 330 nm to 500 nm.
As said photoinitiator, a neutral photoinitiator is preferable. Moreover, the other photoinitiator may be included as needed.

  The neutral photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a compound having at least an aromatic group, such as (bis) acylphosphine oxide or an ester thereof. More preferred are acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds. Two or more neutral photopolymerization initiators may be used in combination.

  Examples of the photopolymerization initiator include (bis) acylphosphine oxide or esters thereof, acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime derivatives, organic peroxides, and thiols. Compound etc. are mentioned. Among these, from the viewpoints of the sensitivity and storage stability of the photosensitive layer and the adhesion between the photosensitive layer and the printed wiring board forming substrate, oxime derivatives, (bis) acylphosphine oxide or esters thereof, acetophenone compounds, benzophenone Compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds are preferred.

  Examples of the (bis) acylphosphine oxide, the acetophenone compound, the benzophenone compound, the benzoin ether compound, the ketal derivative compound, and the thioxanthone compound include, for example, paragraph [0042] of JP 2010-256399 A Examples thereof include (bis) acylphosphine oxides, acetophenone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, and thioxanthone compounds.

  Examples of the oxime derivative include oxime derivatives described in paragraphs [0043] to [0059] of JP2010-256399A.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said photoinitiator, Although it can select suitably according to the objective, 0.1 mass%-30 mass% are preferable, 0 More preferably, the content is more preferably 5% by mass to 20% by mass, and particularly preferably 0.5% by mass to 15% by mass.

<Thermal crosslinking agent>
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. An epoxy compound (for example, an epoxy compound having at least two oxirane groups in one molecule), an oxetane compound having at least two oxetanyl groups in one molecule can be used, and is described in JP-A-2007-47729. A compound obtained by reacting a blocking agent with an isocyanate group of an epoxy compound having an oxirane group, an epoxy compound having an alkyl group at the β-position, an oxetane compound having an oxetanyl group, a polyisocyanate compound, a polyisocyanate or a derivative thereof ( Blocked polyisocyanate compound).

  Moreover, a melamine derivative can be used as the thermal crosslinking agent. Examples of the melamine derivative include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl or the like). These may be used individually by 1 type and may use 2 or more types together. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is particularly preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

  There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said thermal crosslinking agent, Although it can select suitably according to the objective, 1 mass%-50 mass% are preferable, and 3 mass%- 30 mass% is more preferable. If the said content is 1 mass% or more, the film | membrane intensity | strength of a cured film will be improved, and if it is 50 mass% or less, developability and exposure sensitivity will become favorable.

  Examples of the epoxy compound include epoxy compounds described in paragraphs [0071] to [0073] of JP2010-256399A.

  Examples of the oxetane compound include oxetane compounds described in paragraph [0074] of JP2010-256399A.

  Examples of the polyisocyanate compound include the polyisocyanate compounds described in paragraph [0075] of JP2010-256399A.

  Examples of the blocked polyisocyanate compound include the blocked polyisocyanate compound described in paragraph [0076] of JP2010-256399A.

  Examples of the melamine derivative include melamine derivatives described in paragraph [0077] of JP 2010-256399 A.

ただし、前記一般式（１８）中、Ａ^Ｐ及びＢ^Ｐは、それぞれ独立に、直鎖状の炭素数１〜６のアルキル基、分岐状の炭素数１〜６のアルキル基、及びアリール基のいずれかを表す。Ｍは、Ｍｇ、Ｃａ、Ａｌ、Ｓｂ、Ｓｎ、Ｇｅ、Ｔｉ、Ｚｎ、Ｆｅ、Ｚｒ、Ｃｅ、Ｂｉ、Ｓｒ、Ｍｎ、Ｌｉ、Ｎａ、及びＫのいずれかを表す。ｍは、１〜４の整数を表す。 <Metallic phosphates>
The metal phosphate used in the present invention is preferably a metal phosphate represented by the following general formula (18). The metal phosphate not only improves the flame retardancy of the photosensitive layer, but can also minimize the decrease in folding resistance of the photosensitive layer after curing.

However, in the general formula (18), ^AP and ^BP are each independently a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 1 to 6 carbon atoms, or an aryl group. Represents either. M represents any of Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, and K. m represents an integer of 1 to 4.

As said ^AP and ^BP , a linear C1-C6 alkyl group is preferable, a methyl group, an ethyl group, and n-propyl group are more preferable, and an ethyl group is especially preferable.
As said M, Al is preferable.
The m is preferably 3.

  A commercially available product can be used as the metal phosphate represented by the general formula (18). Examples of the commercially available products include Exolite OP-935, Exolite OP-930, Exolite OP1230, Exolite OP-1240, and Exolite OP-1312 (all manufactured by Clariant Japan), which are aluminum phosphinates.

The average particle size of the metal phosphate represented by the general formula (18) is not particularly limited, but is preferably 2.0 μm or less, more preferably 1.0 μm or less, and 0.5 μm or less. Is more preferable, and 0.3 μm or less is particularly preferable. If the average particle diameter is too large, the folding resistance is lowered and the folding resistance is insufficient. There is no restriction | limiting in particular as a lower limit of the said average particle diameter, Although it can select suitably according to the objective, 0.01 micrometer or more is preferable.
The maximum particle size of the metal phosphate represented by the general formula (18) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 μm or less, more preferably 3 μm or less, and 1 μm. The following are particularly preferred:
The average particle size and the maximum particle size can be measured using, for example, a concentrated particle size analyzer (trade name FPAR1000, manufactured by Otsuka Electronics Co., Ltd.). Specifically, the measurement principle is a dynamic light scattering method, and the size distribution analysis method is a cumulant method and / or a histogram method.
The average particle size is defined as a particle size having an integrated value of 50% when expressed as an integrated (cumulative) weight percentage, and is defined as d50 (D50) or the like.
The maximum particle size is defined as a particle size having an integrated value of 100% and is defined as d100 (D100) or the like.

  The method for making the metal phosphate represented by the general formula (18) into the average particle size and the maximum particle size is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a method using a three-roll mill, a two-roll mill, a sand mill, a bead mill, a kneader, and an attritor.

  There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the metal phosphate represented by the said General formula (18), Although it can select suitably according to the objective, 5-40 masses % Is preferable, and 5 to 25% by mass is more preferable. When the content is less than 5% by mass, sufficient flame retardancy may not be obtained, and when it exceeds 40% by mass, folding resistance may be deteriorated.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include fillers, thermal polymerization inhibitors, plasticizers, colorants (color pigments or dyes), and further groups. Adhesion promoters and other auxiliaries to the material surface (for example, conductive particles, fillers, antifoaming agents, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) May be used in combination.
By appropriately containing these components, properties such as stability, photographic properties, and film properties of the intended photosensitive composition can be adjusted.
However, in this invention, it is preferable that content of the inorganic fine particle which is an inorganic filler in a photosensitive composition is 0-20 mass% in solid content ratio of a photosensitive composition, and is 0-10 mass%. More preferably it is.
Examples of the thermal polymerization inhibitor include thermal polymerization inhibitors described in paragraphs [0101] to [0102] of JP-A-2008-250074.
Examples of the thermosetting accelerator include the thermosetting accelerator described in paragraph [0093] of JP-A-2008-250074.
Examples of the plasticizer include the plasticizers described in paragraphs [0103] to [0104] of JP-A-2008-250074.
Examples of the colorant include the colorants described in paragraphs [0105] to [0106] of JP-A-2008-250074.
Examples of the adhesion promoter include adhesion promoters described in paragraphs [0107] to [0109] of JP-A-2008-250074.

  There is no restriction | limiting in particular as a usage form of the said photosensitive composition, According to the objective, it can select suitably, You may use it in a liquid state and may use it as a photosensitive dry film.

(Photosensitive dry film)
The photosensitive dry film of the present invention has at least a carrier film (support) and a photosensitive layer containing the photosensitive composition of the present invention on the carrier film, and further comprises other layers as necessary. Have.

<Carrier film>
The carrier film is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance, and further has a smooth surface. It is more preferable that it is good.
There is no restriction | limiting in particular as a carrier film, According to the objective, it can select suitably, For example, the support body as described in Paragraph [0115]-[0117] of Unexamined-Japanese-Patent No. 2008-250074 etc. are mentioned.

<Photosensitive layer>
If the said photosensitive layer is a layer containing the said photosensitive composition of this invention, there will be no restriction | limiting in particular, According to the objective, it can select suitably.
Further, the number of laminated photosensitive layers is not particularly limited and may be appropriately selected depending on the purpose. For example, it may be one layer or two or more layers.

  As the method for forming the photosensitive layer, for example, a photosensitive composition solution is prepared by dissolving, emulsifying or dispersing the photosensitive composition of the present invention in water or a solvent on the support. The method of laminating | stacking by apply | coating directly and drying is mentioned.

  There is no restriction | limiting in particular as a solvent used for the said photosensitive composition solution, According to the objective, it can select suitably.

The application method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, using a spin coater, slit spin coater, roll coater, die coater, curtain coater, etc. The method of apply | coating etc. are mentioned.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 seconds to 110 ° C. for about 30 seconds to 15 minutes.

  There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, 1 micrometer-100 micrometers are preferable, 2 micrometers-50 micrometers are more preferable, and 4 micrometers-30 micrometers are especially preferable.

<Other layers>
The other layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a protective film, a thermoplastic resin layer, a barrier layer, a release layer, an adhesive layer, a light absorbing layer, a surface protective layer, etc. Layer. The said photosensitive dry film may have these layers individually by 1 type, and may have 2 or more types.

-Protective film-
The photosensitive dry film may form a protective film on the photosensitive layer.
There is no restriction | limiting in particular as said protective film, According to the objective, it can select suitably, For example, the protective film as described in Paragraph [0118] of Unexamined-Japanese-Patent No. 2008-250074 etc. are mentioned.
There is no restriction | limiting in particular as a combination of the said protective film and the said support body, According to the objective, it can select suitably, For example, the combination as described in Paragraph [0118] of Unexamined-Japanese-Patent No. 2008-250074 etc. are mentioned. It is done.

Moreover, 0.3-1.4 are preferable and the static friction coefficient of the said support body and the said protective film has more preferable 0.5-1.2.
If the static friction coefficient is 0.3 or more, it is possible to prevent the occurrence of winding misalignment when it is made into a roll shape due to excessive slip, and if it is 1.4 or less, it can be wound into a good roll shape. .

  The length and storage method of the photosensitive dry film are not particularly limited and can be appropriately selected depending on the purpose. For example, the length described in paragraph [0120] of JP-A-2008-250074, Examples include storage methods.

  The protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying it at 30 to 150 ° C. for 1 to 30 minutes. As for the temperature in the case of the said drying, 50 to 120 degreeC is especially preferable.

(Photosensitive laminate)
The photosensitive laminate of the present invention comprises at least a substrate (substrate) and a photosensitive layer on the substrate, and further laminates other layers as necessary.
The photosensitive layer is a layer containing the photosensitive composition of the present invention.
The photosensitive layer is, for example, transferred from the photosensitive dry film produced by the above-described manufacturing method, and has the same configuration as described above.

<Base material>
The base material is a substrate to be processed on which a photosensitive layer is formed, or a material to be transferred onto which at least the photosensitive layer of the photosensitive dry film of the present invention is transferred, and is not particularly limited. For example, a material having a high surface smoothness to a material having an uneven surface can be arbitrarily selected, but a plate-like base material, a so-called substrate is preferable. Specific examples include known printed wiring board manufacturing substrates (printed substrates), glass plates (soda glass plates, etc.), synthetic resin films, paper, metal plates, etc. In the present invention, polyimide film is used. Particularly preferred.

<Method for producing photosensitive laminate>
The method for producing the photosensitive laminate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one of heating and pressing at least the photosensitive layer in the photosensitive dry film of the present invention. For example, a method of transferring and laminating while performing.

An example of the manufacturing method of the said photosensitive laminated body is the method of laminating | stacking the photosensitive film of this invention on the surface of the said base | substrate, performing at least any one of a heating and pressurization. In addition, when the said photosensitive dry film has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.
There is no restriction | limiting in particular as said heating temperature, According to the objective, it can select suitably, For example, 15 to 180 degreeC is preferable and 60 to 140 degreeC is more preferable.
There is no restriction | limiting in particular as a pressure of the said pressurization, According to the objective, it can select suitably, For example, 0.1 MPa-1.0 MPa are preferable and 0.2 MPa-0.8 MPa are more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator Co., Ltd. make, VP-II, Nichigo Morton Co., Ltd. make, VP130) is preferable.

  The photosensitive dry film and the photosensitive laminate of the present invention can be widely used for forming a high-definition permanent pattern in the field of electronic materials, and are preferably used for forming a permanent pattern of a printed circuit board, particularly a flexible wiring board. be able to.

(Permanent pattern forming method)
The permanent pattern forming method of the present invention includes at least an exposure step, and further includes other steps as necessary.

<Exposure process>
The exposure step is not particularly limited as long as it is a step of exposing the photosensitive layer formed of the photosensitive composition of the present invention, and can be appropriately selected according to the purpose. The process etc. which expose with respect to the photosensitive layer in the said photosensitive laminated body are mentioned.

  The exposure target is not particularly limited as long as it is the photosensitive layer, and can be appropriately selected according to the purpose. However, at least one of heating and pressurizing the photosensitive dry film on the substrate is performed. However, it is preferably performed on a laminate formed by laminating.

  There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, For example, digital exposure, analog exposure, etc. are mentioned.

<Other processes>
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, the surface treatment process of a base material, a development process, a hardening process process, a post exposure process etc. are mentioned.

-Development process-
The developing step is a step of removing an unexposed portion of the photosensitive layer.
There is no restriction | limiting in particular as a removal method of the said exposed part, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  There is no restriction | limiting in particular as said developing solution, According to the objective, it can select suitably, For example, the developing solution as described in Paragraph [0171]-[0173] of Unexamined-Japanese-Patent No. 2008-250074 etc. are mentioned.

-Curing process-
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed pattern after the development step is performed.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

  The method for the entire surface exposure treatment and the entire surface heat treatment is not particularly limited and may be appropriately selected depending on the purpose. For example, in paragraphs [0176] to [0177] of JP-A-2008-250074 The method of description is mentioned.

When the permanent pattern forming method is a permanent pattern forming method for forming at least one of a protective film, an interlayer insulating film, and a solder resist pattern, the permanent pattern is formed on a printed circuit board, preferably on a flexible wiring board. A permanent pattern can be formed by the forming method, and soldering can be performed as follows.
That is, by the development, a hardened layer that is the permanent pattern is formed, and the metal layer is exposed on the surface of the printed board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer functions as a protective film, an insulating film (interlayer insulating film), a solder resist, particularly a flexible solder resist, and prevents external impact and conduction between adjacent electrodes. The

(Flexible wiring board)
The flexible wiring board of the present invention has at least a base (base material) and a permanent pattern formed by the permanent pattern forming method, and further includes other electronic members appropriately selected as necessary. Have.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not restrict | limited to these Examples at all.

In addition, the acid value, the mass average molecular weight, and the ethylenically unsaturated group equivalent in the synthesis examples were measured by the following methods.
(Acid value)
The acid value was measured according to JIS K0070. However, when the acid-modified ethylenically unsaturated group-containing polyurethane resin did not dissolve, dioxane or tetrahydrofuran was used as a solvent.
(Mass average molecular weight)
The mass average molecular weight is determined by using a high-speed GPC device (HLC-802A manufactured by Toyo Soda Industry Co., Ltd.), a 0.5% by mass THF solution as a sample solution, and a column using one TSKgel HZM-M, 200 μL. The sample was injected, eluted with the THF solution, and measured with a refractive index detector at 25 ° C. Next, the mass average molecular weight was determined from the molecular weight distribution curve calibrated with standard polystyrene.
(Ethylenically unsaturated group equivalent)
The ethylenically unsaturated group equivalent was determined by measuring the bromine number according to JIS K2605.

(Preparation Example 1) Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resin PU1 Into a 1 L three-necked round bottom flask equipped with a condenser and a stirrer was added 2,2-bis (hydroxymethyl) butyric acid (DMBA) 11 .11 g (0.075 mol), glycerol monomethacrylate (GLM) 35.44 g (0.221 mol), polypropylene glycol (molecular weight 1000) (PPG1000) 78.75 g (0.079 mol) and malic acid 6.03 g ( 0.045 mol) was dissolved in 300 mL of cyclohexanone. To this, 23.46 g (0.094 mol) of 4,4-diphenylmethane diisocyanate (MDI), 47.30 g (0.281 mol) of hexamethylene diisocyanate (HMDI), 2,6-di-t-butylhydroxytoluene 0 As a catalyst, 0.6 g of a trade name: Neostan U-600 (manufactured by Nitto Kasei Co., Ltd., inorganic bismuth) was added and stirred at 75 ° C. for 5 hours. After cooling to room temperature, the concentration was adjusted with cyclohexanone to obtain an acid-modified ethylenically unsaturated group-containing polyurethane resin (PU1) solution having a solid concentration of 40% by mass.
Mass average molecular weight: 7000
Acid value: 46 [mg KOH / g]
Equivalent ethylenically unsaturated group: 1.1 [mmol / g]

(Preparation Example 2) Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resin PU2 In Preparation Example 1, 11.11 g (0.075 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA), glycerol monomethacrylate ( GLM) 35.44 g (0.221 mol), polypropylene glycol (molecular weight 1000) (PPG1000) 78.75 g (0.079 mol) and malic acid 6.03 g (0.045 mol) Bis (hydroxymethyl) butyric acid (DMBA) 15.00 g (0.101 mol), Glycerol monomethacrylate (GLM) 31.83 g (0.199 mol), Polytetramethylene glycol (molecular weight 1000) (PTMG1000) 75 g (0. 075 mol) and 6.03 g (0.045 mol) of malic acid Except that instead of the combination of A, in the same manner as in Preparation Example 1, a solid concentration of 40 wt% of acid-modified ethylene unsaturated group-containing polyurethane resin (PU2) solution was synthesized.
Mass average molecular weight: 8600
Acid value: 54 [mg KOH / g]
Ethylenically unsaturated group equivalent: 1 [mmol / g]

(Preparation Example 3) Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resin PU3 <Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resin PU3>
In Preparation Example 1, 11.11 g (0.075 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA), 35.44 g (0.221 mol) of glycerol monomethacrylate (GLM), polypropylene glycol (molecular weight 1000) (PPG1000) 78.75 g (0.079 mol) and 6.03 g (0.045 mol) of malic acid were combined with 15.00 g (0.101 mol) of 2,2-bis (hydroxymethyl) butyric acid (DMBA). Glycerol monomethacrylate (GLM) 31.83 g (0.199 mol), polylite OD-X-240 (DIC Corporation, molecular weight 1000) 75 g (0.075 mol) and malic acid 6.03 g (0.045 mol) ), Except that the combination was changed to a solid content concentration of 40% by mass in the same manner as in Preparation Example 1. Acid modified ethylene unsaturated group-containing polyurethane resin (PU3) solution was synthesized.
Mass average molecular weight: 8300
Acid value: 54 [mg KOH / g]
Ethylenically unsaturated group equivalent: 1 [mmol / g]

Preparation Example 4 Synthesis of Ethylenically Unsaturated Group-Containing Acrylic Resin 1 159 g of 1-methoxy-2-propanol was placed in a 1,000 mL three-necked flask and heated to 85 ° C. under a nitrogen stream. To this, a solution of 159 g of 1-methoxy-2-propanol containing 63.4 g of benzyl methacrylate, 72.3 g of methacrylic acid, and 3.0 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over 2 hours. After completion of the dropwise addition, the reaction was further continued by heating for 5 hours. Subsequently, the heating was stopped to obtain a copolymer of benzyl methacrylate / methacrylic acid (30 mol% / 70 mol%).
Next, 120.0 g of the copolymer solution was transferred to a 300 mL three-necked flask, and 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added and dissolved by stirring. After dissolution, 3.0 g of triphenylphosphine was added while performing air bubbling, heated to 100 ° C., and after 20 minutes, glycidyl methacrylate was added to carry out an addition reaction. The disappearance of glycidyl methacrylate was confirmed by gas chromatography, and heating was stopped. 1-methoxy-2-propanol is added, an ethylenically unsaturated group-containing acrylic resin represented by the following structural formula (a) having a solid content of 40% by mass, and an ethylenically unsaturated group represented by the following structural formula (b) The ethylenically unsaturated group containing acrylic resin 1 solution containing the containing acrylic resin was obtained.

Preparation Example 5 Synthesis of Urethane Resin 1 To a 300 mL three-necked round bottom flask equipped with a condenser and a stirrer was added 21.73 g (0.162 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA). ), 30.00 g (0.030 mol) of polypropylene glycol (Mw 1,000, PPG 1000) and 12.78 g (0.168 mol) of propylene glycol (PG) were dissolved in 202 mL of propylene glycol monomethyl ether monoacetate. To this, 60.06 g (0.24 mol) of 4,4-diphenylmethane diisocyanate (MDI), 10.09 g (0.06 mol) of hexamethylene diisocyanate (HMDI), 2,6-di-t-butylhydroxytoluene 0 As a catalyst, 0.4 g of a trade name: Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) was added and stirred at 75 ° C. for 5 hours. Next, the mixture was stirred at room temperature for 30 minutes to obtain 336 g of a urethane resin 1 solution (solid content: 40% by mass).
The obtained urethane resin 1 had a solid content acid value of 67 mgKOH / g, and a mass average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) was 8,000.

(Preparation Example 6) Synthesis of Acrylic Resin 1 In a five-neck reaction vessel with an internal volume of 2 L, 800 g of propylene glycol monomethyl ether acetate, 140 g of butyl methacrylate (BMA), 30 g of methacrylic acid (MAA), hydroxyethyl methacrylate (HEMA) 30 g and 4 g of methyl azobisisobutyrate (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) were added and heated at 80 ° C. for 6 hours while blowing nitrogen to obtain an acrylic resin 1 solution. Then, it concentrated and obtained the acrylic resin 1 solution with a solid content of 40 mass%. The obtained acrylic resin 1 had a mass average molecular weight of 10,000.

Preparation Example 7 Synthesis of Acrylic Resin 2 A propylene glycol monomethyl ether acetate solution of a copolymer of methacrylic acid / ethyl acrylate / methyl methacrylate / styrene (mass ratio: 14/21/45/20) was prepared by a conventional method. (Mass average molecular weight: 90,000, solid content: 40% by mass).

(Preparation example 8) Preparation of metal phosphate salt dispersion 13.13 parts by mass of metal phosphate salt (trade name: OP-935, manufactured by Clariant Japan) and specific mixing of each resin prepared in each of the above preparation examples 75.40 parts by mass of a solution (solid content concentration: 40% by mass), 0.66 parts by mass of a dispersant (trade name: BYK-W903, manufactured by Big Chemie Japan), and 10.82 parts by mass of cyclohexanone were weighed. Dispersed using a Motor Mill M-50 (Eiger) dispersing machine filled with zirconia beads having a diameter of 0.65 mm, and a metal phosphate having an average particle diameter of 0.1 μm and a maximum particle diameter of 2 μm is dispersed in the resin. A metal phosphate dispersion was obtained.

The average particle size and the maximum particle size were measured by the following methods.
A solution obtained by diluting the above metal phosphate dispersion by a factor of 50 was measured using a concentrated particle size analyzer (trade name FPAR1000, manufactured by Otsuka Electronics Co., Ltd.). The measurement principle was a dynamic light scattering method, and the size distribution analysis method was measured as a cumulant method and / or a histogram method.
The average particle size is defined as a particle size of 50% integrated value when expressed in terms of integrated (cumulative) weight percentage, and is defined as d50 (D50), etc. The maximum particle size is 100% integrated value And is defined as d100 (D100) or the like.

Example 1
<Production of photosensitive dry film>
On a 16 μm thick polyethylene terephthalate film (16FB50, manufactured by Toray Industries, Inc.) as a support, a photosensitive composition solution having the following composition is applied and dried to form a 30 μm thick photosensitive layer on the support. did. On the photosensitive layer, as a protective layer, a polypropylene film having a thickness of 20 μm (manufactured by Oji Specialty Paper Co., Ltd., Alphan E-200) was laminated to produce a photosensitive dry film.

-Composition of photosensitive composition solution-
-Phosphate metal salt dispersion of Preparation Example 8 ... 54.42 parts by mass-Polymerizable compound (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) ... 8.96 parts by mass-Thermal crosslinking agent (Epototo YDF- 170, manufactured by Tohto Kasei Co., Ltd., bisphenol F type epoxy resin) ... 9.77 parts by mass-Acid-modified ethylenically unsaturated group-containing polyurethane resin PU1 (solid content concentration 40% by mass)
... 8.21 parts by mass-Ethylenically unsaturated group-containing acrylic resin 1 (solid content concentration 40% by mass)
... 5.47 parts by mass-Irgacure 907 ... 0.98 parts by mass-EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) ... 0.033 parts by mass-DETX-S (manufactured by Nippon Kayaku) -0.009 parts by mass-Pigment dispersion (hereinafter referred to as "G-1") ... 8.36 parts by mass The pigment dispersion (G-1) is 0.42 parts by mass of phthalocyanine blue. , 0.12 parts by mass of an anthraquinone yellow pigment (CI PY24), 12.85 parts by mass and 86.62 parts by mass of cyclohexanone were mixed in advance, and then with a motor mill M-250 (manufactured by Eiger) A zirconia bead having a diameter of 1.0 mm was used and dispersed for 3 hours at a peripheral speed of 9 m / s.
The metal phosphate dispersion used in the photosensitive composition solution was prepared in the manner shown in Table 1 below in which the PU 1 of Preparation Example 1 and the ethylenically unsaturated group-containing acrylic resin 1 of Preparation Example 4 were used in the photosensitive composition. It was prepared so as to be contained at the ratio shown in Example 1.

-Lamination on substrate-
A substrate was prepared by subjecting the surface of a copper-clad laminate (no through holes, copper thickness 12 μm) to chemical polishing treatment. A vacuum laminator (VP130, manufactured by Nichigo Morton Co., Ltd.) is peeled off on the copper clad laminate while peeling off the protective film on the photosensitive dry film so that the photosensitive layer of the photosensitive dry film is in contact with the copper clad laminate. The photosensitive laminate was prepared by laminating the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) in this order.
The pressure bonding conditions were as follows: vacuuming time 40 seconds, pressure bonding temperature 70 ° C., pressure bonding pressure 0.2 MPa, and pressure time 10 seconds.

-Exposure process-
A predetermined pattern is obtained with a parallel light exposure machine (ultra-high pressure mercury lamp) from the polyethylene terephthalate film (support) side through a glass mask having a predetermined pattern with respect to the photosensitive layer in the prepared photosensitive laminate. Irradiation was performed with an energy amount of 60 mJ / cm ² to cure a part of the photosensitive layer. This exposure process was defined as a standard exposure process.

-Development process-
After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the photosensitive laminate, and a 1% by mass sodium carbonate aqueous solution is used as an alkaline developer on the entire surface of the photosensitive layer on the copper clad laminate. Was spray-developed at 30 ° C. for 60 seconds at a pressure of 0.18 MPa (1.8 kgf / cm ² ) to dissolve and remove unexposed areas. Thereafter, it was washed with water and dried to form a permanent pattern. This development process was defined as a standard development process.

-Curing process-
The entire surface of the laminate on which the permanent pattern is formed is subjected to a heat treatment at 150 ° C. for 1 hour, and then subjected to post-exposure under the condition of 1 J / cm ² to cure the surface of the permanent pattern and to improve the film strength. Raised and produced a test plate. This curing process was defined as a standard curing process.

  Insulation, folding resistance, resolution, and flame retardancy were evaluated as follows. The results are shown in Table 1.

<Insulation>
In the lamination to the substrate, the copper-clad laminate was laminated to the substrate by the above standard steps, except that the copper-clad laminate was replaced with a comb-shaped substrate having a copper thickness of 12 μm and L (line) / S (space) = 25 μm / 25 μm. An exposure process, a development process, and a curing process were performed to produce a substrate for evaluation.
Using the evaluation substrate, a super accelerated high temperature high humidity life test (HAST) was performed under the conditions of 130 ° C., 85% RH, 50 V, 200 hours.
Thereafter, the degree of migration of solder resist on the evaluation substrate was observed with a 100 × optical microscope.
〔Evaluation criteria〕
A: No short circuit. Furthermore, the occurrence of migration cannot be confirmed, and the insulation is excellent. ○: No short circuit. However, the occurrence of migration is confirmed slightly on copper. The occurrence of migration is confirmed slightly on copper. The occurrence of migration is also confirmed

<Folding resistance>
A dry film resist is laminated to a substrate for flexible printed wiring boards (made by Nippon Steel Chemical Co., Ltd., trade name “ESPANEX” M series) in which a copper foil (copper foil thickness 18 μm) is laminated on a polyimide base material (polyimide thickness 25 μm), and 18 mJ After exposure at / cm ² , development was performed under the condition of 0.15 MPa / 40 s to produce a line pattern of L / S = 100/100 μm. After etching the substrate for flexible printed wiring board to which the line pattern of the dry film resist is applied, the dry film resist is peeled off by 3% by mass aqueous sodium hydroxide / 0.1 MPa / 120 s, so that L / S = 100 A wiring pattern of / 100 μm was created.
Therefore the obtained wiring pattern polyimide, a photosensitive layer of the photosensitive dry film prepared in the laminated wiring pattern side, after 10 minutes standing at room temperature, to a super-high pressure mercury lamp, the amount of energy 150 mJ / cm ² Is exposed to light to cure the photosensitive layer, and after heat treatment at 160 ° C. for 1 hour, the photosensitive layer is cured by irradiating with an energy amount of 1,000 mJ / cm ² to obtain film strength. The laminated body for evaluation was obtained by raising.
The obtained laminate for evaluation was cut into 5 mm × 10 cm squares, bent 180 ° in the long side direction with the wiring pattern on the outside, a predetermined weight was placed on the bent part for 3 seconds, and the folding resistance was evaluated according to the following criteria. .
〔Evaluation criteria〕
◎: No crack at 400 g ○: No crack at 200 g Δ: 200 g crack length is 10% or less of the bent side length ×: 200 g crack length is the bent side length More than 10%

<Resolution>
The photosensitive laminate produced above was allowed to stand at 55% RH for 10 minutes at room temperature (23 ° C.). From the obtained polyethylene terephthalate film (support) of the photosensitive laminate, a round hole pattern is used to form a round hole with a diameter of 30 μm to 100 μm at a diameter of 60 mJ / cm using a pattern forming apparatus. ² was exposed.
After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate.
The entire surface of the photosensitive layer on the copper clad laminate is sprayed with a 1% by weight aqueous sodium carbonate solution at 30 ° C. as a developer at a spray pressure of 0.15 MPa for a time twice as long as the development time in the standard development step, thereby uncured areas. Was dissolved and removed.
The surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, and there is no abnormality such as pattern residue, undercut, or peeling, and the smallest round hole pattern that can form a space The width was measured, and this was taken as the resolution and evaluated according to the following criteria. The smaller the numerical value, the better the resolution.
〔Evaluation criteria〕
A: A round hole with a diameter of 50 μm or less can be resolved, and the resolution is excellent. ○: A round hole with a diameter of 70 μm or less can be resolved, and the resolution is good. Δ: A round hole with a diameter of 100 μm or less. Can be resolved and resolution is slightly inferior ×: Round hole is not resolvable and resolution is inferior

<Flame retardance>
Etching a substrate for flexible printed wiring boards (made by Nippon Steel Chemical Co., Ltd., trade name “ESPANEX” M series), which is made by laminating a copper foil (copper foil thickness 12 μm) on a polyimide substrate (polyimide thickness 12.5 μm), and removing the copper foil As a result, a polyimide substrate having a thickness of 12.5 μm was obtained.
The photosensitive layer (thickness 38 μm) of the photosensitive dry film prepared above was adhered to both surfaces of this polyimide substrate by lamination. After standing at room temperature for 10 minutes, an exposure was performed by irradiating with an ultra high pressure mercury lamp with an energy amount of 150 mJ / cm ² , the photosensitive layer was cured, and after heat treatment at 160 ° C. for 1 hour, an energy amount of 1, The photosensitive layer was cured by irradiating with 000 mJ / cm ² to increase the film strength.
A composite sample was obtained by cutting the polyimide base material on which the cured photosensitive layer obtained above was formed into a size of 20 cm × 5 cm. The obtained composite sample was wound around a cylindrical rod having a diameter of 1 cm × 20 cm, and the position of 12.5 cm from the end of the composite sample was fixed with heat-resistant tape, and then the rod was removed to obtain a length of 20 cm and a diameter of 1 cm. A flame retardant test sample was obtained.
The obtained flame retardant test sample was hung with a clamp, and a flame test was conducted by indirect flame with a 3 cm flame for 3 seconds.
〔Evaluation criteria〕
○: Satisfies UL94 VTM-0 ×: Does not meet UL94 VTM-0

(Examples 2 to 6)
In Example 1, while maintaining the total content of the acid-modified ethylenically unsaturated group-containing polyurethane resin and the ethylenically unsaturated group-containing acrylic resin in the photosensitive composition, the type of resin and the acid-modified ethylenically unsaturated group were maintained. Except having changed the content ratio of a saturated group containing polyurethane resin and an ethylenically unsaturated group containing acrylic resin into the ratio of Table 1, it carried out similarly to Example 1, and the photosensitive composition, the photosensitive dry film, and A photosensitive laminate was obtained.
Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
In Example 3, a photosensitive composition, a photosensitive dry film, a photosensitive laminate, and the like were obtained in the same manner as in Example 3 except that PU1 in the photosensitive composition was replaced with urethane resin 1.
Evaluation was performed in the same manner as in Example 3. The results are shown in Table 1.

(Comparative Example 2)
In Example 3, except that PU1 in the photosensitive composition was changed to the ethylenically unsaturated group-containing acrylic resin 1, a photosensitive composition, a photosensitive dry film, and a photosensitive laminate were obtained in the same manner as in Example 1. Etc.
Evaluation was performed in the same manner as in Example 3. The results are shown in Table 1.

(Comparative Example 3)
In Example 3, except that the ethylenically unsaturated group-containing acrylic resin 1 in the photosensitive composition was replaced with the acrylic resin 1, the photosensitive composition, the photosensitive dry film, and the photosensitive property were obtained in the same manner as in Example 3. A laminate was obtained.
Evaluation was performed in the same manner as in Example 3. The results are shown in Table 1.

(Comparative Example 4)
In Example 3, except that the ethylenically unsaturated group-containing acrylic resin in the photosensitive composition was replaced with the acrylic resin 2, the photosensitive composition, the photosensitive dry film, and the photosensitive laminate were the same as in Example 3. I got a body.
Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

  The numerical value in Table 1 shows the ratio (mass%) of each resin when the total amount of the urethane resin and the acrylic resin in the photosensitive composition is 100 mass%.

  In Comparative Example 1 using a urethane resin other than the urethane resin defined in the present invention, and Comparative Examples 3 and 4 using an acrylic resin other than the acrylic resin defined in the present invention, insulation, folding resistance and resolution are provided. It became inferior result. Moreover, in Comparative Example 2 in which no urethane resin was used, the folding resistance was inferior. On the other hand, in Examples 1-6 using the photosensitive composition of this invention, it became a result excellent in all of insulation, folding resistance, resolution, and a flame retardance.

Claims (12)

  A photosensitive composition containing an acid-modified ethylenically unsaturated group-containing polyurethane resin, an ethylenically unsaturated group-containing acrylic resin, a polymerizable compound, a photopolymerization initiator, a thermal crosslinking agent, and a metal phosphate.   An ethylenically unsaturated group-containing acrylic resin has an epoxy group on some acid groups of a copolymer of (meth) acrylic acid ester and a compound having an ethylenically unsaturated group and having at least one acid group. The photosensitive composition according to claim 1, which is a modified copolymer to which a (meth) acrylate having a group is added.   The photosensitive composition of Claim 1 or 2 whose ethylenically unsaturated group which an ethylenically unsaturated group containing acrylic resin has is an acryloyloxy group or a methacryloyloxy group. Acid-modified ethylenically unsaturated group-containing polyurethane resin has a mass average molecular weight of 5,000 to 60,000, an acid value of 20 mgKOH / g to 120 mgKOH / g, and an ethylenically unsaturated group equivalent of 0.05 mmol / g to 2.0 mmol / g. The photosensitive composition according to any one of claims 1 to 3, wherein the photosensitive composition has a partial structure represented by the following general formula (UE1):

In the general formula (UE1), L ^UE has a partial structure of any one of the following general formulas (1) to (3), and -NHC (= O) O- or -OC (= O ) Represents a divalent linking group not containing NH-;

In General formula (1), R < ¹ > -R < ³ > represents a hydrogen atom or monovalent organic group each independently. X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Here, R ¹² represents a hydrogen atom or a monovalent organic group;

In General formula (2), R < ⁴ > -R < ⁸ > represents a hydrogen atom or monovalent organic group each independently. Y represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Here, R ¹² represents a hydrogen atom or a monovalent organic group;

In General formula (3), R < ⁹ > -R < ¹¹ > represents a hydrogen atom or monovalent organic group each independently. Z represents an oxygen atom, a sulfur atom, —N (R ¹³ ) —, or an optionally substituted phenylene group. Here, R ¹³ represents a hydrogen atom or a monovalent organic group. The photosensitive composition of Claim 4 in which L ^UE in the said general formula (UE1) has one partial structure in any one of the said General formula (1)-(3).   The photosensitive composition of any one of Claims 1-5 whose ethylenically unsaturated group which acid-modified ethylenically unsaturated group containing polyurethane resin has is an acryloyloxy group or a methacryloyloxy group.   The ratio of the acid-modified ethylenically unsaturated group-containing polyurethane resin in the total amount of the acid-modified ethylenically unsaturated group-containing polyurethane resin and the ethylenically unsaturated group-containing acrylic resin contained in the photosensitive composition is 55% by mass or more. It is 95 mass% or less, The photosensitive composition of any one of Claims 1-6.   The photosensitive dry film which has a photosensitive layer containing the photosensitive composition of any one of Claims 1-7.   The photosensitive laminated body which has a photosensitive layer containing the photosensitive composition of any one of Claims 1-7 on a base material.   The flexible wiring board which has a resist pattern obtained by photocuring the photosensitive layer containing the photosensitive composition of any one of Claims 1-7 on a base material.   A method for producing a flexible wiring board, comprising: transferring a photosensitive layer of the photosensitive dry film according to claim 8 onto a substrate; and exposing and developing the transferred photosensitive layer to form a resist pattern.   The permanent pattern formation method including exposing with respect to the photosensitive layer containing the photosensitive composition of any one of Claims 1-7.