JP2013029780A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having excellent resolution for patterning and exhibiting excellent thermal shock resistance and insulating property of a cured layer after patterning, while containing an inorganic filler that is stably dispersed at a high density.SOLUTION: There is provided the photosensitive resin composition contains at least each one kind of (A) a polyurethane resin containing an acid-modified ethylene unsaturated group, (B) a radical polymerizable monomer, (C) a photoinitiator, (D) an inorganic filler, (E) a dispersant, and (F) a thermal crosslinking agent. The content of the component (D) in the whole volume of a non-volatile component is 20 vol.% or more; and the mass content of aromatic moieties in the structure of the component (A) is 30 mass% or more.

Description

  The present invention relates to a photosensitive resin composition suitably used for a solder resist or the like, a photosensitive film using the photosensitive resin composition, a photosensitive laminate, a printed board, a method for producing a printed board, and a method for forming a permanent pattern. .

  Conventionally, when forming a permanent pattern such as a solder resist, a photosensitive film having a photosensitive layer formed by applying a photosensitive resin composition on a liquid resist or 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. In addition, a method is known in which the photosensitive layer is subjected to exposure / development processing to form a pattern and then subjected to curing processing to form a permanent pattern.

In general, the performance of a solder resist can be further improved by lowering the coefficient of thermal expansion (thermal expansion coefficient). Therefore, an inorganic filler (inorganic fine particles) is dispersed in the photosensitive resin composition to reduce the thermal expansion coefficient of the resin (see, for example, Patent Document 1).
A dispersant for dispersing an inorganic filler in a photosensitive resin composition used for a solder resist is also known. For example, Patent Document 2 discloses a dispersant for dispersing silica fine particles, and Patent Document 3 discloses a dispersant composed of a styrene / maleic anhydride / butyl acrylate copolymer for dispersing barium sulfate. It is disclosed.

  On the other hand, with the recent miniaturization of semiconductor devices, the development of solder resists with smaller L / S (line space) patterns has been promoted, and further improvements in resolution, impact resistance, and insulation are strongly demanded. Has been. However, it cannot be said that the above-mentioned conventional solder resist can sufficiently satisfy these high-level requirements.

JP 2011-95705 A JP 2003-234439 A International Publication No. 2005-124462 Pamphlet

The present invention provides a photosensitive resin composition having high density and containing an inorganic filler stably, having excellent pattern resolution, and excellent thermal shock resistance and insulating properties of a cured product after pattern formation. The task is to do.
Moreover, this invention makes it a subject to provide the photosensitive film using the said photosensitive resin composition, the photosensitive laminated body, the printed circuit board, the manufacturing method of a printed circuit board, and the permanent pattern formation method.

一般式（１）〜（３）において、Ｒ^１〜Ｒ^１１は各々独立に、水素原子または１価の有機基を表す。ＸおよびＹは各々独立に、酸素原子、硫黄原子または−Ｎ（Ｒ^１２）−を表す。ここで、Ｒ^１２は、水素原子または１価の有機基を表す。Ｚは、酸素原子、硫黄原子、−Ｎ（Ｒ^１３）−また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、水素原子または１価の有機基を表す。
＜７＞（Ａ）成分が、下記一般式（ＵＢ）で表される部分構造を有し、該（Ａ）成分の構造中に占める下記一般式（ＵＢ）の芳香族部分の質量含有率が３０質量％以上である、＜１＞〜＜６＞のいずれかに記載の感光性樹脂組成物。

一般式（ＵＢ）において、Ｘ^Ｌ１は、単結合、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−Ｓ−、−Ｏ−または−Ｃ（＝Ｏ）−を表し、Ｒ^ｕ１〜Ｒ^ｕ８は各々独立に水素原子または置換基を表す。
＜８＞一般式（ＵＢ）において、Ｒ^ｕ１〜Ｒ^ｕ８がいずれも水素原子である、＜７＞に記載の感光性樹脂組成物。
＜９＞（Ａ）成分が、下記一般式（ＵＮＣＯ）で表される部分構造を有する、＜１＞〜＜８＞のいずれかに記載の感光性樹脂組成物。

一般式（ＵＮＣＯ）において、Ｘ^Ｌ１は、単結合、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−Ｓ−、−Ｏ−または−Ｃ（＝Ｏ）−を表す。Ｒ^ｕ１〜Ｒ^ｕ８は各々独立に水素原子または置換基を表す。
＜１０＞一般式（ＵＮＣＯ）において、Ｒ^ｕ１〜Ｒ^ｕ８がともに水素原子であり、かつＸ^Ｌ１が−ＣＨ_２−である、＜９＞に記載の感光性樹脂組成物。
＜１１＞（Ａ）成分が、下記一般式（ＵＥ１）で表される部分構造を有する、＜１＞〜＜１０＞のいずれかに記載の感光性樹脂組成物。

一般式（ＵＥ１）において、Ｌ^ＵＥは主鎖の結合に−ＮＨＣ（＝Ｏ）Ｏ−もしくは−ＯＣ（＝Ｏ）ＮＨ−を含まない２価の連結基であって、かつエチレン性不飽和基を有する基が少なくとも１つ置換した２価の連結基を表す。
＜１２＞一般式（ＵＥ１）が、下記一般式（Ｇ１）で表される、＜１１＞に記載の感光性樹脂組成物。

一般式（Ｇ１）において、Ｒ^１〜Ｒ^３は、それぞれ独立に水素原子又は１価の有機基を表し、Ａは２価の有機残基を表し、Ｘは、酸素原子、硫黄原子、又は−Ｎ（Ｒ^１２）−を表し、Ｒ^１２は、水素原子、又は１価の有機基を表す。
＜１３＞（Ａ）成分が、ポリマー主鎖の末端に少なくとも１つのカルボキシル基を有する、＜１＞〜＜１２＞のいずれかに記載の感光性樹脂組成物。
＜１４＞＜１＞〜＜１３＞のいずれかに記載の感光性樹脂組成物を含む感光層を有する、感光性フィルム。
＜１５＞基体上に、＜１＞〜＜１３＞のいずれかに記載の感光性樹脂組成物を含む感光層を有する、感光性積層体。
＜１６＞基体上に、＜１＞〜＜１３＞のいずれかに記載の感光性樹脂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、プリント基板。
＜１７＞＜１４＞に記載の感光性フィルムが有する感光層を基体上に転写し、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、プリント基板の製造方法。
＜１８＞＜１＞〜＜１３＞のいずれかに記載の感光性樹脂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) Acid-modified ethylenically unsaturated group-containing polyurethane resin, (B) radical polymerizable monomer, (C) photopolymerization initiator, (D) inorganic filler, (E) dispersant, (F) heat Each containing at least one crosslinking agent,
The photosensitive resin in which the content of the component (D) in the total capacity of the non-volatile component is 20% by volume or more and the mass content of the aromatic moiety in the structure of the component (A) is 30% by mass or more. Composition.
<2> The photosensitive resin composition according to <1>, wherein the component (E) is a polymer dispersant having a molecular weight of 3000 or more.
<3> The photosensitive resin composition according to <1> or <2>, wherein the component (E) has a basic group or an acidic group.
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the component (E) has a steric hindrance group.
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the component (D) contains silicon as a constituent atom.
<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the component (A) has a structure of any one of the following general formulas (1) to (3).

In the general formulas (1) to (3), R ^{1 to} R ¹¹ each independently represents a hydrogen atom or a monovalent organic group. X and Y each independently represent an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Here, R ¹² represents a hydrogen atom or a monovalent organic group. Z represents an oxygen atom, a sulfur atom, —N (R ¹³ ) — or a phenylene group which may have a substituent. Here, R ¹³ represents a hydrogen atom or a monovalent organic group.
<7> The component (A) has a partial structure represented by the following general formula (UB), and the mass content of the aromatic moiety of the following general formula (UB) in the structure of the (A) component is The photosensitive resin composition in any one of <1>-<6> which is 30 mass% or more.

In the general formula (UB), X ^L1 represents a single bond, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —O— or — C (= O)-, and R ^{u1 to} R ^u8 each independently represent a hydrogen atom or a substituent.
<8> The photosensitive resin composition according to <7>, wherein in the general formula (UB), R ^{u1 to} R ^u8 are all hydrogen atoms.
<9> The photosensitive resin composition according to any one of <1> to <8>, wherein the component (A) has a partial structure represented by the following general formula (UNCO).

In the general formula (UNCO), X ^L1 represents a single bond, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —O— or — C (= O)-is represented. R ^{u1 to} R ^u8 each independently represents a hydrogen atom or a substituent.
<10> The photosensitive resin composition according to <9>, wherein in the general formula (UNCO), R ^{u1 to} R ^u8 are all hydrogen atoms and X ^L1 is —CH ₂ —.
<11> The photosensitive resin composition according to any one of <1> to <10>, in which the component (A) has a partial structure represented by the following general formula (UE1).

In the general formula (UE1), L ^UE is a divalent linking group that does not contain —NHC (═O) O— or —OC (═O) NH— in the main chain bond, and is an ethylenically unsaturated group. Represents a divalent linking group in which at least one group having a substituent is substituted.
<12> The photosensitive resin composition according to <11>, wherein the general formula (UE1) is represented by the following general formula (G1).

In General Formula (G1), R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom, or — N (R ¹² ) — is represented, and R ¹² represents a hydrogen atom or a monovalent organic group.
<13> The photosensitive resin composition according to any one of <1> to <12>, in which the component (A) has at least one carboxyl group at the terminal of the polymer main chain.
<14> A photosensitive film having a photosensitive layer containing the photosensitive resin composition according to any one of <1> to <13>.
<15> A photosensitive laminate having a photosensitive layer containing the photosensitive resin composition according to any one of <1> to <13> on a substrate.
<16> A printed board having a resist pattern obtained by photocuring a photosensitive layer containing the photosensitive resin composition according to any one of <1> to <13> on a substrate.
<17> A method for producing a printed board, comprising: transferring a photosensitive layer of the photosensitive film according to <14> onto a substrate, and exposing and developing the transferred photosensitive layer to form a resist pattern.
<18> A method for forming a permanent pattern, comprising exposing a photosensitive layer containing the photosensitive resin composition according to any one of <1> to <13>.

The photosensitive resin composition of this invention is excellent in the resolution of pattern formation, and is also excellent in the impact resistance and insulation reliability of the cured layer after pattern formation.
Moreover, the photosensitive film and photosensitive laminated body of this invention have the photosensitive resin composition which has the said effect.
Moreover, the printed circuit board of this invention has a resist pattern obtained by hardening the photosensitive resin composition which has the said effect.
Further, according to the method for producing a printed wire board of the present invention, it is possible to produce a printed board having a cured layer having a desired pattern that is excellent in both impact resistance and insulation reliability.
Moreover, according to the method for forming a permanent pattern of the present invention, it is possible to form a cured layer having a desired pattern that is excellent in both impact resistance and insulation reliability.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention comprises (A) an acid-modified ethylenically unsaturated group-containing polyurethane resin, (B) a radical polymerizable monomer, (C) a photopolymerization initiator, (D) an inorganic filler, (E) Each contains at least one dispersant and (F) a thermal crosslinking agent. Content of the said (D) component in the photosensitive resin composition of this invention will be 20 volume% or more when the total capacity | capacitance of the non-volatile component in the photosensitive resin composition of this invention is 100 volume%. Moreover, the mass content rate of the aromatic part which occupies in the structure of the said (A) component will be 30 mass% or more when the whole structure of the said (A) component is 100 mass%.
The photosensitive resin composition of this invention may contain another component as needed.

<< Acid-modified ethylenically unsaturated group-containing polyurethane resin >>
The acid-modified ethylenically unsaturated group-containing polyurethane resin (component (A)) is not particularly limited and may be appropriately selected depending on the intended purpose. In the present invention, an acid-modified polyurethane resin having an ethylenically unsaturated bond in the side chain is particularly preferable. 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 resin composition will be described below.

<< Molecular weight >>
The mass average molecular weight 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 3,000 to 60,000 in terms of mass average molecular weight. Is more preferable, and 4,000 to 30,000 is particularly preferable. When the photosensitive resin composition of the present invention is used for a photosensitive solder resist, when it is in such a mass average molecular weight range, the heat resistance is excellent, and the developability of a non-image area by an alkaline developer is excellent.
When the mass average molecular weight is less than 3,000, sufficient heat resistance may not be obtained, and when it exceeds 60,000, coating suitability and developability may be deteriorated.
Here, the mass average molecular weight was measured using a high-speed GPC device (HLC-802A, manufactured by Toyo Soda Co., Ltd.), and the column was measured using one TSKgel HZM-M. Specifically, 200 μL of a sample solution prepared with a 0.5 mass% THF solution is injected, eluted with the THF solution, and eluted with a refractive index detector or UV detector (detection wavelength 254 nm) at 25 ° C. And obtained using a molecular weight distribution curve calibrated with 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, but is preferably 20 mgKOH / g to 120 mgKOH / g, and 30 mgKOH / g to 110 mgKOH / g 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 0.05 mmol / g to 3.0 mmol / g. Preferably, 0.5 mmol / g to 2.7 mmol / g is more preferable, and 0.5 mmol / g to 2.5 mmol / g is more preferable. When the ethylenically unsaturated group equivalent is less than 0.05 mmol / g, the heat resistance of the cured film may be inferior. The ethylenically unsaturated group equivalent is more preferably 1.2 mmol / g or more, and still more preferably 1.2 to 2.5 mmol / g.
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.

<< Mass content of aromatic part >>
In the present invention, the acid-modified ethylenically unsaturated group-containing polyurethane resin has a mass of an aromatic moiety in the polyurethane resin structure (hereinafter, the mass of the aromatic moiety) when the polyurethane resin is 100 mass%. Is sometimes 30% by mass or more, more preferably 32% by mass to 70% by mass, still more preferably 33% by mass to 60% by mass, and 35% by mass. It is particularly preferably 55 to 55% by weight, particularly preferably 35 to 50% by weight. When the mass content of the aromatic moiety is less than 30% by mass, the hardness may be reduced or the insulation reliability may be inferior.
Here, the term aromatic means the conventional concept of aromatics as defined in the literature, particularly Jerry MARCH, MARCH'S Advanced Organic Chemistry, 5th edition, John Wiley and Sons, 2001, page 37 and below. To do.
In the present invention, the mass of the aromatic moiety is the total mass of the atoms constituting the skeleton of the aromatic ring and the hydrogen atoms bonded to the atom, and the two aromatic rings are —CH ₂ —, —CH (CH ₃ ). When connected by-, -C (CH ₃ ) _2- , -SO _2- , -S-, -O- or -C (= O)-, it means the total mass including the mass of this connecting part. To do.
The case where two aromatic rings are connected by the above linking group is, for example, when the two aromatic rings are benzene rings, represented by the following general formula (UB), and X ^L1 is —CH ₂ —, — This is the case when CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —O— or —C (═O) —. R ^{u1 to} R ^u8 are a hydrogen atom or a substituent.

For example, in the case of (A), since X ^{L1 of} the connecting portion is —CH (CH ₃ ) —, the mass of —CH (CH ₃ ) — is added. On the other hand, in the case of (B), since X ^{L1 of} the connecting portion is —C (═O) —O—, which does not satisfy the above-mentioned definition of X ^L1 , this mass is changed to the mass of the aromatic portion. Do not add. In addition, the substituent substituted by an aromatic ring is not added to the mass of an aromatic part other than said coupling group.
Therefore, the mass of the aromatic moiety in the case of (A) is such that one benzene ring part has 6 carbon atoms, 3 hydrogen atoms, the connecting part has 2 carbon atoms, 4 hydrogen atoms, and the remaining benzene ring part Are 6 carbon atoms and 3 hydrogen atoms. As a result, the mass of the aromatic portion is considered to be a portion of 14 carbon atoms and 10 hydrogen atoms.
On the other hand, in the case of (B), since the —C (═O) —O— moiety is not added, the mass of the aromatic portion is considered to be the portion of 12 carbon atoms and 6 hydrogen atoms.

The aromatic moiety in the acid-modified ethylenically unsaturated group-containing polyurethane resin preferably has at least a partial structure represented by the general formula (UB), and among them, R ^{u1 to} R ^u8 are all hydrogen atoms. In which X ^L1 is —CH ₂ — is preferable.
In addition, the acid-modified ethylenically unsaturated group-containing polyurethane resin used in the present invention has a mass content of 30 in the aromatic portion of the partial structure represented by the general formula (UB) in the polyurethane resin structure. It is preferably at least mass%, more preferably from 30 to 70 mass%, even more preferably from 33 to 60 mass%, particularly preferably from 35 to 55 mass%, and from 35 to 50 mass%. It is particularly preferred that
The partial structure represented by the general formula (UB) is preferably incorporated in the acid-modified ethylenically unsaturated group-containing polyurethane resin as a partial structure represented by the following general formula (UNCO).

Below, the acid-modified urethane resin which has an ethylenically unsaturated bond in the side chain which is a preferable aspect 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 the general formulas (1) to (3), R ^{1 to} R ¹¹ each independently represents a hydrogen atom or a monovalent organic group. 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 , R ³ , R ^{4 to} R ⁸ , R ¹⁰ and R ¹¹ have a hydrogen atom, halogen atom, amino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group or substituent. An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkyl which may have a substituent An amino group, 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, and among them, the radical reactivity is high. , A hydrogen 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.
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.

X and Y each independently represent 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 in terms of high radical reactivity.
Z represents 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, and among them, a methyl group, an ethyl group, and an isopropyl group are more preferable in terms 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.

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 molecule There is 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). The polyurethane resin having an ethylenically unsaturated bond in the side chain includes both polyurethane resins (i) and (ii).
In the present invention, the polyurethane resin (i) obtained by the method (i) is preferred.

-Polyurethane resin (i)-
The polyurethane resin is synthesized by a reaction of a diisocyanate compound and a diol compound (a compound having at least two hydroxyl groups), and the polyurethane resin (i) is composed of at least one diisocyanate compound represented by the following general formula (4): It is a polyurethane resin having as a basic skeleton a structural unit represented by a reaction product of at least one diol compound represented by the following general formula (5).

^OCN-X 0 -NCO ··· general Formula (4)
HO-Y ⁰ -OH 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 at least one of the groups represented by the general formulas (1) to (3). If one is present, a polyurethane resin in which the groups represented by the general formulas (1) to (3) are introduced into the side chain is generated as a reaction product of the diisocyanate compound and the diol compound. The 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 ethylenically unsaturated group in a side chain, According to the objective, it can select suitably, The monofunctional compound which has a triisocyanate compound and an unsaturated group A diisocyanate compound obtainable by addition reaction with 1 equivalent of an alcohol or a monofunctional amine compound, for example, in the side chain described in paragraphs [0042] to [0049] of JP-A-2005-250438 And compounds having an unsaturated 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. A diisocyanate compound having a bisphenol F type skeleton is most preferable.
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. 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, such as a bisphenol A-type or bisphenol F-type skeleton. The diisocyanate compound is more preferable. 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.

  The diisocyanate compound is particularly preferably a compound represented by the following general formula (UB1), and the polyurethane resin has a partial structure of the general formula (UNCO).

In the general formulas (UB1) and (UNCO), X ^L1 represents a single bond, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, — O— or —C (═O) — is represented, and R ^{u1 to} R ^u8 each independently represent a hydrogen atom or a substituent.

  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 is used as a raw material for producing the polyurethane resin. The method is preferred. 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 easily produced by a reaction with a compound containing an unsaturated group, such as a carboxylic acid, an acid chloride, an isocyanate, an alcohol, an amine, a thiol, or an alkyl halide 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 is a divalent linking group that does not contain —NHC (═O) O— or —OC (═O) NH— in the main chain bond, It represents a divalent linking group having at least one ethylenically unsaturated group in the chain.
L ^UE preferably does not contain an aromatic ring in the shortest bond chain connecting two hydroxyl groups (HO groups), and may contain -O- and -S- in the shortest bond chain. The aliphatic group is more preferably a divalent aliphatic group, and an alkylene group is particularly preferable. Moreover, 2-12 are preferable, as for carbon number in the shortest bond chain which couple | bonds two hydroxyl groups (HO group), 2-6 are more preferable, 2-4 are more preferable, and 2 is the most preferable. The divalent linking group in L ^UE has one ethylenically unsaturated group as a substituent, but in addition to this, it may have a substituent that is not an ethylenically unsaturated group. It represents a monovalent organic groups listed ^R 1 ^{to R 11} in the general formula (1) to (3) below.

In the present invention, when a group having an ethylenically unsaturated group is a group represented by the general formula (1), the main chain of L ^UE, the α-position or β-position, having a hydroxyl group or an acyl group The case where it does not couple | bond with an alkyloxycarbonyl group is preferable.
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 General Formulas (G) and (G1), R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, 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. The “acid-modified” indicates that the polyurethane resin has an acid group. The “acid group” is not particularly limited, and examples thereof include carboxylic acid and sulfo group. From the viewpoint of developability, the polyurethane resin (i) preferably has a carboxyl group. 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 cyano group, a nitro group, a halogen atom such as —F, —Cl, —Br, —I, etc.), —CONH ₂ , —COOR ¹⁶ , —OR ¹⁶ , —NHCONHR ¹⁶ , —NHCOOR ¹⁶ , —NHCOR ¹⁶ , —OCONHR ¹⁶ (wherein 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 formulas (17) to (19), L ⁹ , L ¹⁰ and L ¹¹ may be the same or different from each other, and may be a single bond or a substituent (for example, an alkyl group, an aralkyl group or 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 etc. which were 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.
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), as the low molecular weight diol compounds, those having a mass average molecular weight of less than 400 are preferable, and are described, for example, in 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).

  There is no restriction | limiting in particular as said polyether diol compound, According to the objective, it can select suitably, For example, the compound etc. which were described in Paragraph [0068]-[0076] of Unexamined-Japanese-Patent No. 2005-250438 etc. are mentioned. It is done.

  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.

  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.

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 compounds described.

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 having an ethylenically unsaturated bond in the side chain, or between the photosensitive resin 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 between the resins, 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 3.0 mmol / g, 0.5 mmol / g to 2.7 mmol / g is more preferable, and 0.5 mmol / g to 2.5 mmol / g is particularly preferable. The ethylenically unsaturated group equivalent is more preferably 1.2 mmol / g or more, and still more preferably 1.2 to 2.5 mmol / g.

  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- Examples include 1,4-diol and polybutadiene diol.

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.
The divalent or more atoms in Y ^100, for example, an oxygen atom, a nitrogen atom, a carbon atom, 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 that can be introduced into Y ¹⁰⁰ include a substituent including an atom selected from a hydrogen atom, an oxygen atom, a sulfur atom, 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 diisocyanate and diol compound used for synthesis (M _a : M _b ) is not particularly limited and may be appropriately selected depending on the intended purpose, preferably 1: 1 to 1.2: 1. 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

OCN-R ₁ -NCO general formula (I)

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) Represents an aromatic hydrocarbon group. 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 to} R ₁₁ each independently represents a divalent aliphatic or aromatic hydrocarbon group. 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 group or carbon having 2 to 10 carbon atoms. Several to 10 arylene groups are more preferable. R ₈ represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, and an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms is More preferred. In addition, in R _{7 to} R ₁₁ , other functional groups that do not react with the isocyanate group, such as ether groups, carbonyl groups, ester groups, cyano groups, olefin groups, urethane groups, amide groups, ureido groups, halogen atoms, etc. There may be.

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 group having 7 to 15 carbon atoms, a cyano group, or a halogen atom is preferable, and a hydrogen atom or a carbon number of 1 An alkyl group having 6 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms are more preferable. 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 a number of 2 or more. The number of 2-100 is preferable. In the general formula (III-5), n ₆ represents 0 or a number of 2 or more, preferably 0 or a number of 2 to 100.

In the 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 a carbon atom having 1 to 10 carbon atoms. Represents a hydrogen group. p represents 0 or the number of 1-10.

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, the molar ratio of the diisocyanate and diol compound can be determined by treating with an alcohol or an amine. In the form in which no isocyanate group remains.

<< 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 resin 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% by mass is preferable, 20% by mass to 75% by mass is more preferable, and 30% by mass to 70% by mass is particularly 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.

<Radically polymerizable monomer>
There is no restriction | limiting in particular as a radically polymerizable monomer ((B) component), 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, dimethylol tricyclodecane di (meth) acrylate; (meth) acrylate after addition reaction of polyfunctional alcohols such as trimethylolpropane, glycerin and bisphenol with ethylene oxide and propylene oxide; Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dimethyloltricyclodecane di (meth) acrylate Particularly preferred.

  There is no restriction | limiting in particular as content in the said photosensitive resin composition solid content of the said radically polymerizable monomer, Although it can select suitably according to the objective, 3 mass%-50 mass% are preferable, and 5 mass % To 40% by mass is more preferable. When the content is less than 3% by mass, the exposure sensitivity is deteriorated. When the content is more than 50% by mass, the tackiness (adhesiveness) of the photosensitive layer may be too strong.

<Photopolymerization initiator>
The photopolymerization initiator (component (C)) is not particularly limited as long as it has the ability to initiate the polymerization of the radical polymerizable monomer, and can be appropriately selected according to the purpose. Those having photosensitivity to visible light are preferable, and may be an activator that generates an active radical by causing some action with a photoexcited sensitizer, and initiates cationic polymerization according to the type of monomer. Such an initiator may be used.

  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 thio compounds. Etc. 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.

A 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 resin composition solid content of the said photoinitiator, Although it can select suitably according to the objective, 0.1 mass%-30 mass% are preferable, 0.5 mass%-20 mass% are more preferable, and 0.5 mass%-15 mass% are especially preferable.

<Inorganic filler>
The photosensitive resin composition of the present invention contains an inorganic filler (component (D)). Since the inorganic filler can improve the surface hardness of the permanent pattern, or suppress the coefficient of linear expansion, increase the thermal conductivity, or suppress the dielectric constant or dielectric loss tangent of the cured film itself, Can be selected / used.
Examples of the inorganic filler include kaolin, barium sulfate, barium titanate, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica. As a commercial item of the said barium sulfate, B-30 (made by Sakai Chemical Industry Co., Ltd.) etc. are mentioned, for example.
Among these, compounds having a silicon atom such as silica (compounds containing silicon as a constituent atom), barium sulfate, talc and aluminum hydroxide are preferable, compounds having a silicon atom are more preferable, and silica is particularly preferable.

  There is no restriction | limiting in particular as an average particle diameter of an inorganic filler, Although it can select suitably according to the objective, 5 micrometers or less, Preferably it is 1 micrometer or less, More preferably, 0.5 micrometer or less is suitable. When the average particle size is 5 μm or more, resolution may be deteriorated due to light scattering.

In the photosensitive resin composition of this invention, content of an inorganic filler is 20 volume% or more in the non volatile component total capacity | capacitance (100 mass%) in the photosensitive resin composition. Thereby, the effect of this invention can be show | played effectively and a thermal expansion coefficient can be lowered | hung. The content of the inorganic filler is preferably 25 to 60% by volume, more preferably 30 to 60% by volume, based on the total volume of the nonvolatile components of the photosensitive resin composition. If it is less than 20% by volume, the effect of lowering the coefficient of thermal expansion is small, and the effect of improving the impact resistance becomes insufficient. On the other hand, if it exceeds 60% by volume, the resolution is greatly deteriorated.
In the present invention, the nonvolatile component in the photosensitive resin composition means a component that does not volatilize even when heated to 150 ° C. under a reduced pressure of 20 mbar (a component that remains as a solid content). Specifically, in the photosensitive resin composition of the present invention, at least the components (A) to (F) are nonvolatile components. Examples of the volatile component include organic solvents (for example, cyclohexanone, propylene glycol monomethyl ether acetate, carbitol acetate) and the like that can be included in the photosensitive resin composition of the present invention.

<Dispersant>
The photosensitive resin composition used in the present invention contains a dispersant (component (E)) for dispersing the inorganic filler. For this reason, the polymer dispersing agent which has the group which interacts with the surface of an inorganic filler, and does not have an ethylenically unsaturated group is preferable. Examples of the group that interacts with the surface of the inorganic filler include a basic group or an acidic group, and a basic group is particularly preferable. In addition, it is preferable that these interacting groups interact with each other on the surface of the inorganic filler and do not associate between the molecules of the dispersant. In order to suppress this association, there is a group that causes steric hindrance in the molecule. It is preferable to do. Further, the mass average molecular weight is preferably 1,000 to 100,000.
In addition, when the dispersant does not contain a basic functional group, but contains an acidic functional group or a salt structure, a sufficient adsorption amount for an inorganic filler such as silica may not be obtained. In the case of a film, the viscosity may not decrease because aggregation of silica cannot be suppressed.

The basic group is not particularly limited, and examples thereof include a primary amino group, a secondary amino group, a tertiary amino group, and a nitrogen-containing heterocyclic group. Heterocyclic groups are preferred, and tertiary amino groups are particularly preferred.
The basic group is adsorbed on the surface of an inorganic or organic filler or pigment, particularly on the surface of silica fine particles, for example, by ionic interaction.

  Any nitrogen-containing heterocyclic group may be used as long as it contains a nitrogen atom as a ring-constituting atom and the nitrogen atom exhibits basicity. The heterocyclic ring in the nitrogen-containing heterocyclic group is preferably a 5- or 6-membered heterocyclic group, and may be an aromatic ring or an unsaturated or saturated ring. The nitrogen-containing heterocycle may be further condensed with an aromatic ring, a heterocycle or an alicyclic ring, and the nitrogen-containing heterocycle may have a substituent. Examples of such substituents include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, aryl groups or heterocyclic groups, halogen atoms, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, amino groups, alkylaminos. 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.

  Examples of the nitrogen-containing heterocycle include pyrrolidine ring, pyrroline ring, piperidine ring, piperazine ring, morpholine ring, imidazolidine ring, imidazoline ring, imidazole ring, pyrazolidine ring, pyrrolidine ring, pyrazole ring, pyrrole ring, pyridine ring, pyrazine Ring, pyrimidine ring, pyridazine ring, indole ring, indazole ring, purine ring, quinoline ring, quinoxaline ring, quinazoline ring, indoline ring, quinuclidine ring.

The acidic group is not particularly limited, and examples of the acid group of the acidic group include a carboxyl group, a sulfo group, a phosphonyl group, —COCH ₂ CO—R ^B , —CONHCO—R ^B , —COCH ₂ CN, Examples thereof include a phenolic hydroxyl group, -R _F CH ₂ OH,-(R _F ) ₂ CHOH, an alkyl or aryl sulfonamide group. Here, R ^B represents a hydrocarbon group having 1 to 10 carbon atoms, and R _F represents a perfluoroalkyl group. The hydrocarbon group is a saturated, unsaturated or cyclic hydrocarbon group, preferably a cyclic hydrocarbon group.
Of the acidic groups, a carboxyl group, a sulfo group, and a phosphonyl group are preferable, and a carboxyl group is particularly preferable in terms of developability.
In addition, the acid part of the acid group is an aliphatic group (alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, cycloalkynyl group, etc.), an aromatic group, a heterocyclic group, and a group of the above acid part. It may have, and the group of the said acid part may become an acidic group directly.

The amine value of the dispersant preferably used in the present invention is preferably 0.65 mmol / g or more, more preferably 0.75 mmol / g or more, and further preferably 0.9 mmol / g or more. The upper limit of the amine value is not particularly limited, but is preferably 4 mmol / g or less, and more preferably 3 mmol / g or less.
Here, the amine value is measured, for example, by weighing a sample in a beaker, adding acetic acid, stirring and dissolving, adjusting the measurement temperature to 25 ° C., and then adding 0.1N perchloric acid acetic acid as a titration reagent. And can be determined by titrating with a titration apparatus.
The amine value is the amount of perchlorate consumed when titrated, expressed in moles per gram of dispersant resin (solid content).

The acid value of the dispersant preferably used in the present invention is preferably 0.3 mmol / g or more, more preferably 0.45 mmol / g or more, and still more preferably 0.5 mmol / g or more. Although the upper limit of an acid value is not specifically limited, Preferably it is 3.5 mmol / g or less, More preferably, it is 2.5 mmol / g or less.
Here, for the measurement of the acid value, for example, a sample is weighed in a beaker, a solution of THF / water = 5/1 (volume ratio) is added, dissolved by stirring, and the measurement temperature is adjusted to 25 ° C. Thereafter, the acid value can be determined by titrating with a titration apparatus using a 0.1N NaOH aqueous solution as a titration reagent.
The acid value is the amount of NaOH consumed when titrated, expressed in moles per gram of dispersant resin (solid content).

The dispersant preferably used in the present invention preferably has at least one of a basic group and a polymer steric hindrance group as described above.
The steric hindrance group includes a branched alkyl group, a bicycloalkyl group, an aryl group, a heterocyclic group (in particular, the aryl group and the heterocyclic group preferably have two or more substituents), and a number average molecular weight of 500. Examples include ˜50,000 side chain polymer chains, with polymer dispersants having a graph and chains being preferred.
Among these, if the steric protecting group is not high molecular weight but low molecular weight, sufficient steric repulsion may not be obtained. In some cases, repulsion cannot be obtained. When a film is formed, aggregation of inorganic fillers cannot be suppressed, and the viscosity may not decrease.

-Graft chain-
The polymer dispersant preferably has a graft chain on the side chain or at least one of the ends of the main chain.
Examples of the graft chain include a polyester chain, a polyalkyl acrylate chain, a polyalkyl methacrylate chain, a polyalkylene oxide chain (preferably a polyethylene oxide chain, a polypropylene oxide chain), a polycarbonate chain, a polystyrene chain, or a combination thereof. The chain | strand of which is included in partial structure is mentioned. Among these, a graft chain having a polyester moiety (polyester graft chain) is preferable in terms of resolution.
The degree of polymerization of the graft chain is preferably 1 to 100, more preferably 1 to 80, and particularly preferably 1 to 60.
The content of the graft is preferably 10% by mass to 60% by mass, and more preferably 20% by mass to 50% by mass with respect to the entire polymer dispersant resin.

  In the present invention, the amine value, the acid value, or the amine value and the acid value are preferably in the above range, the amine value and the acid value are more preferably in the above range, and the amine value and the acid value are as described above. More preferred are those having a graft chain.

A commercial product of the dispersant is not particularly limited and may be appropriately selected depending on the purpose. Solsperse 32000, Solsperse 33000, Solsperse 38500, Solsperse 39000, Solsperse 41000, Solsperse 55000, Solsperse 56000, Solsperse 71000, Solsperse 76500 (all manufactured by Lubrizol); Disperbyk-161, Disperbyk-167, Disperbyk-182y, Disperbyk-182k 2155, Disperbyk- 02, Disperbyk-111, Disperbyk-106, Disperbyk-108, Disperbyk-112, Disperbyk-2000, Disperbyk-2001, Disperbyk-2008, Disperbyk-202009, Disperbyk-20D, 20D (All manufactured by BYK Chemie); Efka-4008, Efka-4009, Efka-4010, Efka-4015, Efka-4020, Efka-4046, Efka-4047, Efka-4400, Efka-4401, Efka-4002, Efka -4003, Efka-4480, Efka-4300, Efka- 310, Efka-4320, Efka-4330, Efka-4340, Efka-4061, Efka-5044, Efka-5244, Efka-5054, Efka-5055, Efka-5063, Efka-5065, Efka-5066, Efka-5070 Examples include Efka-5071, Efka-5207, Efka-6220, and Efka-6225 (all manufactured by BASF).
Among these, those having a basic group and those having a steric hindrance group are preferred.

There is no restriction | limiting in particular as content with respect to the inorganic filler of a dispersing agent, Although it can select suitably according to the objective, 0.1-10 mg per 1 m < ² > of surface area of an inorganic filler is preferable, and 1-3 mg is more preferable.
When the content is less than 0.1 mg, the dispersibility of the inorganic filler is insufficient, and when it exceeds 10 mg, the tackiness of the film may be deteriorated. On the other hand, when the content is within the more preferable range, it is advantageous in terms of both dispersibility and tackiness.
<Thermal crosslinking agent>
The thermal crosslinking agent (component (F)) is not particularly limited and may be appropriately selected depending on the intended purpose. In order to improve the film strength after curing of the photosensitive layer, it adversely affects developability and the like. For example, 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, a polyisocyanate compound, a polyisocyanate or a derivative thereof. Examples include compounds obtained by reacting isocyanate groups with blocking agents (blocked polyisocyanate compounds).

  There is no restriction | limiting in particular as content in the said photosensitive resin 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% is preferable. -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.

<Elastomer>
By adding an elastomer to the photosensitive resin composition of the present invention, heat resistance, flexibility and toughness can be imparted to the photosensitive resin composition, which is preferable.

  There is no restriction | limiting in particular as an elastomer, According to the objective, it can select suitably, For example, a styrene-type elastomer, an olefin-type elastomer, a urethane-type elastomer, a polyester-type elastomer, a polyamide-type elastomer, an acrylic elastomer, a silicone-type elastomer etc. Is mentioned. These elastomers are composed of a hard segment component and a soft segment component. In general, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness. Moreover, there is no restriction | limiting in particular as a property of an elastomer, According to the objective, it can select suitably, For example, it is preferable that it is alkali-soluble or swellable in terms of the production efficiency of a image development process.

There is no restriction | limiting in particular as a styrene-type elastomer, According to the objective, it can select suitably, For example, a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butylene-styrene block copolymer, Examples include styrene-ethylene-propylene-styrene block copolymers.
In addition to styrene, which is a component constituting the styrene-based elastomer, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used. Specifically, as commercially available products, Tufprene, Solprene T, Asaprene T, Tuftec (above, manufactured by Asahi Kasei Co., Ltd.), Elastomer AR (made by Aron Kasei), Kraton G, Over Reflex (above, made by Shell Japan), JSR-TR, TSR-SIS, Dynalon (manufactured by Nippon Synthetic Rubber Co., Ltd.), Denka STR (manufactured by Denki Kagaku Kogyo Co., Ltd.), Quintac (manufactured by Zeon Corporation), TPE-SB series (Sumitomo Chemical Co., Ltd.) )), Lavalon (Mitsubishi Chemical Co., Ltd.), Septon, Hibler (above, Kuraray Co., Ltd.), Sumiflex (Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimer (above, Riken Vinyl Industry) It is done.

There is no restriction | limiting in particular as an olefin type elastomer, According to the objective, it can select suitably, For example, C2-C20 alpha, such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene, etc. -Olefin copolymers, for example, ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM) and the like, and dicyclopentadiene, 1,4-hexadiene, cyclohexane Examples thereof include non-conjugated dienes having 2 to 20 carbon atoms such as octadiene, methylene norbornene, ethylidene norbornene, butadiene, and isoprene, and α-olefin copolymers. Moreover, the carboxy modified NBR which copolymerized methacrylic acid to the butadiene-acrylonitrile copolymer is mentioned. Specifically, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, propylene / α-olefin copolymer rubber, butene / α-olefin copolymer rubber, etc. Can be mentioned.
Specifically, as a commercial product, Miralastoma (Mitsui Chemicals), EXACT (Exxon Chemical), ENGAGE (Dow Chemical), hydrogenated styrene-butadiene rubber (DYNABON HSBR, Nippon Synthetic Rubber Co., Ltd.) , Butadiene-acrylonitrile copolymer (NBR series manufactured by Nippon Synthetic Rubber Co., Ltd.), or both terminal carboxyl group-modified butadiene-acrylonitrile copolymer having a crosslinking point (XER series manufactured by Nippon Synthetic Rubber Co., Ltd.). .

  The urethane-based elastomer is not particularly limited and can be appropriately selected according to the purpose. For example, a hard segment composed of a low molecular glycol and a diisocyanate and a soft segment composed of a high molecular (long chain) diol and a diisocyanate. It consists of structural units, and as a polymer (long chain) diol, polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene / 1,4-butylene adipate), polycaprolactone, poly (1, 6-hexylene carbonate), poly (1,6-hexylene neopentylene adipate), etc.

  The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000, and short chain diols such as propylene glycol, 1,4-butanediol and bisphenol A can be used in addition to ethylene glycol. The number average molecular weight of the short-chain diol is preferably 48 to 500. Examples of commercially available urethane elastomers include PANDEX T-2185, T-2983N (manufactured by DIC Corporation), and sylactolan E790.

There is no restriction | limiting in particular as a polyester-type elastomer, According to the objective, it can select suitably, For example, what is obtained by polycondensing dicarboxylic acid or its derivative (s) and a diol compound or its derivative (s) is mentioned.
Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which hydrogen atoms of these aromatic nuclei are substituted with a methyl group, an ethyl group, a phenyl group, and the like. Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These may be used alone or in combination of two or more.
Examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol. And dicyclic phenols represented by the following structural formulas.

In the above formula, Y ^DO represents any one of an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, —O—, —S—, and —SO ₂ —, or benzene. Represents a direct bond (single bond) between rings. R ^DO1 and R ^DO2 each independently represent a halogen atom or an alkyl group having 1 to 12 carbon atoms. p ^do1 and p ^do2 each independently represent an integer of 0 to 4, and n ^do1 represents 0 or 1.

Specific examples of the polyester elastomer include bisphenol A, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) propane, and resorcin. These may be used alone or in combination of two or more.
Also, as the polyester elastomer, a multi-block copolymer having an aromatic polyester (for example, polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) portion as a soft segment component should be used. You can also.
The multi-block copolymer includes various grades depending on the kind, ratio, and molecular weight of the hard segment and the soft segment. Specific examples include Hytrel (manufactured by DuPont-Toray Industries, Inc.), Perprene (manufactured by Toyobo Co., Ltd.), Espel (manufactured by Hitachi Chemical Co., Ltd.), and the like.

  The polyamide-based elastomer is not particularly limited and can be appropriately selected according to the purpose. For example, a polyether block amide type and a polyether ester block using a polyamide as a hard phase and a polyether or polyester as a soft phase. The polyamide is roughly classified into two types, polyamide-6, 11, 12 and the like are used as the polyamide, and polyoxyethylene, polyoxypropylene, polytetramethylene glycol and the like are used as the polyether. Specifically, as commercially available products, UBE polyamide elastomer (manufactured by Ube Industries), Daiamide (manufactured by Daicel Huls), PEBAX (manufactured by Toray Industries, Inc.), Grilon ELY (manufactured by MMS Japan Co., Ltd.) ), Nopamid (Mitsubishi Chemical Co., Ltd.), Gla Relax (DIC Co., Ltd.) and the like.

  The acrylic elastomer is not particularly limited and can be appropriately selected depending on the purpose.For example, an acrylic ester as a main component, ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, and the like can be given. Examples of the crosslinking point monomer include glycidyl methacrylate and allyl glycidyl ether. Furthermore, acrylonitrile and ethylene can be copolymerized. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like.

  The silicone elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, the silicone elastomer is mainly composed of organopolysiloxane, such as polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Is mentioned. Specific examples of commercially available products include the KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), the SE series, the CY series, and the SH series (manufactured by Toray Dow Corning Silicone Co., Ltd.).

  In addition to the elastomer, a rubber-modified epoxy resin can be used. The rubber-modified epoxy resin includes, for example, a part or all of the epoxy groups of the bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac type epoxy resin or cresol novolac type epoxy resin. It is obtained by modifying with a terminal carboxylic acid-modified butadiene-acrylonitrile rubber, a terminal amino-modified silicone rubber or the like. Among these elastomers, both end carboxyl group-modified butadiene-acrylonitrile copolymers and polyester elastomers having hydroxyl groups, Espel (manufactured by Hitachi Chemical Co., Ltd., Espel 1612, 1620) in terms of shear adhesiveness Is preferred.

The content of the elastomer is preferably 1 part by mass to 50 parts by mass, more preferably 2 parts by mass to 20 parts by mass, and more preferably 3 parts by mass to 10 parts by mass with respect to 100 parts by mass of the photosensitive resin composition. Particularly preferred.
When the content is less than 2 parts by mass, the elastic modulus in the high temperature region of the cured film tends not to decrease, and when it exceeds 50 parts by mass, the unexposed part tends not to elute with the developer.

<Coloring pigment>
It is preferable to contain a color pigment in the photosensitive resin composition of the present invention.
There is no restriction | limiting in particular as a coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat black HB ( CI.26150), Monolite Yellow G
T (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), C.I. I. Pigment Yellow 55, Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) Fastel Pink B Supra (CI Pigment Red 81) Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (CI Pigment Black 1), carbon, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64 and the like. These may be used alone or in combination of two or more. Moreover, the dye suitably selected from well-known dye can be used as needed.

  The solid content of the colored pigment in the photosensitive resin composition can be determined in consideration of the exposure sensitivity and resolution of the photosensitive layer during permanent pattern formation, and varies depending on the type of the colored pigment. However, generally 0.01-10 mass% is preferable, and 0.05-5 mass% is more preferable.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, and a surface treatment agent, and further, the surface of the substrate. Adhesion promoters and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc. ) May be used in combination.
By appropriately containing these components, it is possible to adjust properties such as stability, photographic properties, and film properties of the target photosensitive resin composition.
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 surface treatment agent include silane coupling agents described in paragraphs [0017] to [0022] of JP-A-2008-102486.
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 resin composition, According to the objective, it can select suitably, You may use it in a liquid state and may use it as a photosensitive film.

<Photosensitive film>
The said photosensitive film has a support body and the photosensitive layer which contains the photosensitive resin composition of this invention on this support body at least, and also has another layer as needed.

-Support-
The support 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. Is more preferable.

  There is no restriction | limiting in particular as said support body, According to the objective, it can select suitably, For example, the support body of Paragraph [0115]-[0117] of Unexamined-Japanese-Patent No. 2008-250074 etc. are mentioned.

-Photosensitive layer-
If the said photosensitive layer is a layer which consists of the said photosensitive resin 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, a photosensitive resin composition solution is prepared by dissolving, emulsifying or dispersing the photosensitive resin 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 resin 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 120 ° 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 film may have these layers individually by 1 type, and may have 2 or more types.

--Protective film--
The photosensitive 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. .

  There is no restriction | limiting in particular as the length of the said photosensitive film, and a storage method, According to the objective, it can select suitably, For example, the length and storage as described in Paragraph [0120] of Unexamined-Japanese-Patent No. 2008-250074. The method etc. are mentioned.

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

<Substrate>
The substrate is a substrate to be processed on which a photosensitive layer is formed, or a substrate to which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited, and is appropriately selected depending on the purpose. For example, it can be arbitrarily selected from those having high surface smoothness to those having a rough surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include known printed wiring board manufacturing substrates (printed substrates), glass plates (soda glass plates, etc.), synthetic resin films, paper, metal plates, and the like.

<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 film of the present invention is performed. And a method of transferring and laminating.

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 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 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 can be particularly suitably used for forming a permanent pattern on a printed circuit board.

(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 by the photosensitive resin composition of the present invention, and can be appropriately selected according to the purpose. For example, the present invention The process of exposing with respect to the photosensitive layer in the said photosensitive laminated body is mentioned.

  The subject of the exposure is not particularly limited as long as it is the photosensitive layer, and can be appropriately selected according to the purpose, but while performing at least one of heating and pressurizing the photosensitive film on the substrate. It is preferable to be performed on a laminated body 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 by the permanent pattern forming method. Then, 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 exhibits a function as a protective film, an insulating film (interlayer insulating film), or a solder resist, and prevents external impact and conduction between adjacent electrodes.

(Printed board)
The printed circuit board of the present invention comprises at least a substrate and a permanent pattern formed by the permanent pattern forming method, and further has other configurations appropriately selected as necessary.
There is no restriction | limiting in particular as another structure, According to the objective, it can select suitably, For example, the buildup board | substrate etc. in which the insulating layer was further provided between the base material and the said permanent pattern are mentioned.

  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 sample did not dissolve, dioxane or tetrahydrofuran was used as a solvent.

<Mass average molecular weight>
The mass average molecular weight was measured using a high-speed GPC apparatus (HLC-802A, manufactured by Toyo Soda Co., Ltd.), and the column was measured using one TSKgel HZM-M. Specifically, 200 μL of a sample solution prepared with a 0.5 mass% THF solution is injected, eluted with the THF solution, and eluted with a refractive index detector or UV detector (detection wavelength 254 nm) at 25 ° C. And obtained using a molecular weight distribution curve calibrated with standard polystyrene.

<Equivalent ethylenically unsaturated group>
The ethylenically unsaturated group equivalent was determined by measuring the bromine number according to JIS K2605.

(Synthesis Example 1)
<Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resin 1>
In a 500 mL three-necked round bottom flask equipped with a condenser and a stirrer, 17.71 g (0.132 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and glycerol monomethacrylate (GLM) 34. 6 g (0.216 mol) was dissolved in 140 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 0.2 g, as a catalyst, 0.4 g of trade name: Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) was added, and the mixture was heated and stirred at 75 ° C. for 5 hours. Thereafter, the mixture was diluted with 32.04 mL of methyl alcohol and stirred for 30 minutes to obtain 272 g of an acid-modified ethylenically unsaturated group-containing polyurethane resin 1 solution (solid content: 45% by mass).
The obtained acid-modified ethylenically unsaturated group-containing polyurethane resin 1 had an acid value of 60 mgKOH / g and an ethylenically unsaturated group equivalent of 1.75 mmol / g (all in terms of solid content). Moreover, the mass average molecular weight was 8,000, and the mass content of the aromatic moiety converted from the composition was 32 mass% (see Table 1 below).

(Synthesis Examples 2 to 6)
<Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resins 2 to 6>
In the same manner as in Synthesis Example 1, acid-modified ethylenically unsaturated group-containing polyurethane resins 2 to 6 were synthesized using diisocyanate compounds and diol compounds shown in Table 1 below as monomers. Table 1 also shows the mass content (% by mass) of the aromatic moiety of the acid-modified ethylenically unsaturated group-containing polyurethane resins 2 to 6 (corresponding to Synthesis Examples 2 to 6, respectively).

  In addition, the acid value of the acid-modified ethylenically unsaturated group-containing polyurethane resins 2 to 6, the ethylenically unsaturated group equivalent (all in terms of solid content), and the mass average molecular weight were as follows.

Polyurethane resin 2: acid value 70 mgKOH / g, ethylenically unsaturated group equivalent 1.83 mmol / g, mass average molecular weight 4500.
Polyurethane resin 3: acid value 71 mgKOH / g, ethylenically unsaturated group equivalent 1.37 mmol / g, mass average molecular weight 5000
Polyurethane resin 4: acid value 70 mgKOH / g, ethylenically unsaturated group equivalent 1.34 mmol / g, mass average molecular weight 4800
Polyurethane resin 5: acid value 74 mgKOH / g, ethylenically unsaturated group equivalent 1.55 mmol / g, mass average molecular weight 6500
Polyurethane resin 6: acid value 86 mgKOH / g, ethylenically unsaturated group equivalent 1.66 mmol / g, mass average molecular weight 4300

(Synthesis Example 7)
<Synthesis of acid-modified ethylenically unsaturated group-containing polyurethane resin 7>
In a 500 mL three-necked round bottom flask equipped with a condenser and a stirrer, 32.00 g (0.216 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMBA) and polypropylene glycol (molecular weight 1,000) 9.0 g (0.009 mol) of (PPG1000) was dissolved in 118 mL of propylene glycol monomethyl ether monoacetate. To this, 37.54 g (0.15 mol) of 4,4-diphenylmethane diisocyanate (MDI), 0.1 g of 2,6-di-t-butylhydroxytoluene, 0.2 g of Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) After stirring at 75 ° C. for 5 hours, 9.61 g of methyl alcohol was added. Thereafter, 17.91 g (0.126) of glycidyl methacrylate (GMA) as a vinyl group-containing epoxy and 5,000 ppm of catalyst triphenylphosphine were further added, stirred at 110 ° C. for 5 hours, and then cooled to room temperature. , 214 g of acid-modified ethylenically unsaturated group-containing polyurethane resin 7 solution (solid content: 40% by mass) was obtained.
The acid-modified ethylenically unsaturated group-containing polyurethane resin 7 obtained above had an acid value of 75 mgKOH / g and an ethylenically unsaturated group equivalent of 1.3 mmol / g (all in terms of solid content). Moreover, the mass average molecular weight was 12,000, and the mass content of the aromatic moiety converted from the composition was 27% by mass.

(Synthesis Example 8)
<Synthesis of dispersant>
<Synthesis of macromonomer>
250 g of ε-caprolactone, 14.3 g of 2-ethylhexanol, and 0.125 g of monobutyltin oxide were placed in a 500 mL three-necked round bottom flask, stirred at 90 ° C. for 4 hours, and stirred at 110 ° C. for 4 hours, and then at 80 ° C. Then, 17.3 g of MOI manufactured by Showa Denko KK and 0.07 g of 2,6-di-t-butylhydroxytoluene were added and stirred for 2 hours. Dilution with 650 g of cyclohexanone gave a polyester macromonomer. The molecular weight of the macromonomer was Mn3100.

<Synthesis of Dispersant P-4>
After putting 36 g of cyclohexanone into a three-necked flask, 21.6 g of methacrylic acid 2- (dimethylamino) ethyl ester, 8.0 g of methacrylic acid, 17.6 g of methyl methacrylate, 109 g of a macromonomer solution, dimethyl 2,2′- A solution prepared by mixing 1.28 g of azobis (isobutyrate) and 3.2 g of 3-mercaptopropionic acid 2-ethylhexyl ester was added dropwise at 80 ° C. in a nitrogen stream over 1 hour and a half, followed by stirring for 3 hours, and then cyclohexanone. 200 g was added to obtain a dispersant solution P-4.
The solid content concentration of the dispersant solution P-4 was 20% by mass.
Dispersant solution P-4 obtained above had an acid value of 65 mgKOH / g and an amine value of 1.72 mmol / g (all in terms of solid content). The mass average molecular weight was 8,000.

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

-Composition of photosensitive resin composition solution-
-Acid-modified ethylenically unsaturated group-containing urethane resin 1 solution of Synthesis Example 1 (solid content 40% by mass) ... 86.6 parts by mass-Polymerizable compound (DCP-A, manufactured by Kyoei Chemical Co., Ltd.) ... 18 .97 parts by mass Thermal crosslinking agent (Epototo YDF-170, manufactured by Tohto Kasei Co., Ltd., bisphenol F type epoxy resin) ... 10.34 parts by mass
... 29.27 parts by mass-Irgacure-907 ... 2.07 parts by mass-EAB-F (made by Hodogaya Chemical Co., Ltd.) ... 0.069 parts by mass-DETX-S (made by Nippon Kayaku)- -0.020 parts by mass-Pigment dispersion (hereinafter referred to as "G-1") ... 77.10 parts by mass-Cyclohexanone (solvent) ... 6.76 parts by mass The pigment dispersion (G- 1) is 35.0 parts by mass of silica (manufactured by Admatechs, SO-C2), 29.05 parts by mass of the acid-modified ethylenically unsaturated group-containing urethane resin 1 solution of Synthesis Example 1, and phthalocyanine blue 0.074. 1 part by weight, 0.021 part by weight of anthraquinone yellow pigment (CI PY24), 0.57 part by weight of melamine, 28.35 parts by weight of cyclohexanone and 2.8 parts by weight of the dispersant of Synthesis Example 8 After mixing, It was prepared by dispersing for 3 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 1.0 mm using Lu M-250 (manufactured by Eiger).
Content of the inorganic filler (silica) in the non-volatile component total capacity | capacitance in the said photosensitive resin composition became 21 volume% (35 mass%).

-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 (manufactured by Nichigo Morton Co., Ltd., VP130) was used on the copper-clad laminate while peeling off the protective film from the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper-clad laminate. Thus, a photosensitive laminate was prepared in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated 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.

-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.

-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.

<Evaluation>
Insulation, thermal shock resistance, and resolution were evaluated as follows. The results are shown in Table 1.

<< Insulation >>
In the lamination to the substrate, the lamination on the substrate, the exposure step, the development step, and the like, except that the copper-clad laminate was replaced with a comb substrate having a copper thickness of 12 μm and L / S = 25 μm / 25 μm. A curing process was performed to produce an evaluation substrate.
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

<< Thermal shock resistance (crack resistance) >>
An insulating layer was formed on the line pattern of L / S = 75 μm / 125 μm using the photosensitive resin composition obtained above so that the film thickness on copper was 15 μm. Thereafter, 200 μm, 300 μm, and 400 μm round hole patterns were formed to obtain test plates. The obtained test plate is left in a liquid phase at −65 ° C. and 150 ° C. for 5 minutes each, and this is regarded as one cycle, and a 1,000 cycle test is performed, and a crack generated along the line pattern is observed. The occurrence of cracks was evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
◎: No occurrence of crack ○: Generation of crack is 5% or less with respect to all round hole pattern △: Generation of crack exceeds 5% with respect to all round hole pattern, and 20% or less ×: Generation of crack However, it exceeds 20% and is less than 50% for all round hole patterns.

<< Resolution >>
The photosensitive laminate was allowed to stand at 55% RH for 10 minutes at room temperature (23 ° C.). Photomask having a round hole pattern with a width of 50 μm to 200 μm in diameter using a circuit board exposure machine EXM-1172 (manufactured by Oak Manufacturing Co., Ltd.) from the obtained polyethylene terephthalate film (support) of the photosensitive laminate. The exposure was carried out at 40 mJ / cm ² .
The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the photosensitive film in the sensitivity evaluation. 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 sodium carbonate aqueous solution at 30 ° C. as the developer at a spray pressure of 0.15 MPa for twice the shortest development time to dissolve the uncured region. Removed.
The surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, there is no residue at the bottom of the round hole of the pattern, there are no abnormalities such as blistering / peeling of the pattern, and space The minimum round hole pattern width that can be formed 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 70 μm or less can be formed and has excellent resolution. ○: A round hole with a diameter exceeding 70 μm can be formed and the resolution is good. Δ: A diameter exceeding 90 μm and 120 μm. The following round holes can be formed, and the resolution is slightly inferior. X: A round hole having a diameter exceeding 120 μm and not more than 200 μm can be formed, and the resolution is inferior.

(Example 2)
Evaluation was performed in the same manner as in Example 1 except that the composition of the photosensitive resin composition solution of Example 1 was blended so that the inorganic filler (silica) was 25% by volume in the total volume of the nonvolatile components.
(Example 3)
Evaluation was performed in the same manner as in Example 1 except that the composition of the photosensitive resin composition solution of Example 1 was blended so that the inorganic filler (silica) was 33% by volume in the total nonvolatile component volume.
Example 4
In Example 1, evaluation was performed in the same manner as in Example 1 except that the acid-modified ethylenically unsaturated group-containing polyurethane resin was replaced with the resin of Synthesis Example 2.
(Example 5)
In Example 2, evaluation was performed in the same manner as in Example 2 except that the acid-modified ethylenically unsaturated group-containing polyurethane resin was replaced with the resin of Synthesis Example 2.
(Example 6)
In Example 3, evaluation was performed in the same manner as in Example 3 except that the acid-modified ethylenically unsaturated group-containing polyurethane resin was replaced with the resin of Synthesis Example 2.
(Example 7)
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the acid-modified ethylenically unsaturated group-containing polyurethane resin was replaced with the resin of Synthesis Example 3.
(Example 8)
In Example 2, the evaluation was performed in the same manner as in Example 2 except that the acid-modified ethylenically unsaturated group-containing polyurethane resin was replaced with the resin of Synthesis Example 3.
Example 9
In Example 3, evaluation was performed in the same manner as in Example 3 except that the acid-modified ethylenically unsaturated group-containing polyurethane resin was replaced with the resin of Synthesis Example 3.
(Example 10)
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the acid-modified ethylenically unsaturated group-containing polyurethane resin was replaced with the resin of Synthesis Example 4.
(Example 11)
In Example 2, evaluation was performed in the same manner as in Example 2 except that the acid-modified ethylenically unsaturated group-containing polyurethane resin was replaced with the resin of Synthesis Example 4.
(Example 12)
In Example 3, the evaluation was performed in the same manner as in Example 3 except that the acid-modified ethylenically unsaturated group-containing polyurethane resin was replaced with the resin of Synthesis Example 4.
(Comparative Example 1)
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the acid-modified ethylenically unsaturated group-containing polyurethane resin was replaced with the resin of Synthesis Example 5.
(Comparative Example 2)
In Example 2, evaluation was performed in the same manner as in Example 2 except that the acid-modified ethylenically unsaturated group-containing polyurethane resin was replaced with the resin of Synthesis Example 5.
(Comparative Example 3)
In Example 3, evaluation was performed in the same manner as in Example 3 except that the acid-modified ethylenically unsaturated group-containing polyurethane resin was replaced with the resin of Synthesis Example 5.
(Comparative Example 4)
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the acid-modified ethylenically unsaturated group-containing polyurethane resin was replaced with the resin of Synthesis Example 6.
(Comparative Example 5)
In Example 2, evaluation was performed in the same manner as in Example 2 except that the acid-modified ethylenically unsaturated group-containing polyurethane resin was replaced with the resin of Synthesis Example 6.
(Comparative Example 6)
In Example 3, evaluation was performed in the same manner as in Example 3 except that the acid-modified ethylenically unsaturated group-containing polyurethane resin was replaced with the resin of Synthesis Example 6.
(Comparative Example 7)
In Example 1, evaluation was performed in the same manner as in Example 1 except that the inorganic filler (silica) was blended so as to be 19% by volume in the total volume of the nonvolatile components.
(Comparative Example 8)
In Example 4, the evaluation was performed in the same manner as in Example 4 except that the inorganic filler (silica) was blended so as to be 19% by volume in the total volume of the nonvolatile components.
(Comparative Example 9)
In Example 1, evaluation was performed in the same manner as in Example 1 except that the acid-modified ethylenically unsaturated group-containing resin was replaced with the resin of Synthesis Example 7.
(Comparative Example 10)
In Comparative Example 7, evaluation was performed in the same manner as in Comparative Example 7 except that the acid-modified ethylenically unsaturated group-containing resin was replaced with the resin of Synthesis Example 7.
The results are shown in Table 2.

If any of the above evaluation items is evaluated as Δ or ×, the practicality is inferior, which is not preferable. From the results of Table 2 above, it was found that in Comparative Examples 1 to 10 using the photosensitive resin composition not included in the present invention, Δ was evaluated in at least one of insulation and thermal shock resistance, and the practicality was inferior. It was.
On the other hand, in Examples 1 to 12 using the photosensitive resin composition of the present invention, ◎ or ○ evaluation in any of the resolution of pattern formation, insulation of the cured layer after pattern formation, and thermal shock resistance Thus, it has been found that it has excellent characteristics for practical use.

Claims (18)

(A) acid-modified ethylenically unsaturated group-containing polyurethane resin, (B) radical polymerizable monomer, (C) photopolymerization initiator, (D) inorganic filler, (E) dispersant, (F) thermal crosslinking agent Each containing at least one,
The photosensitive resin in which the content of the component (D) in the total capacity of the non-volatile component is 20% by volume or more and the mass content of the aromatic moiety in the structure of the component (A) is 30% by mass or more. Composition.   (E) The photosensitive resin composition of Claim 1 whose component is a polymeric dispersing agent with a molecular weight of 3000 or more.   (E) The photosensitive resin composition of Claim 1 or 2 in which a component has a basic group or an acidic group.   (E) The photosensitive resin composition of any one of Claims 1-3 in which a component has a steric hindrance group.   (D) The photosensitive resin composition of any one of Claims 1-4 in which a component contains silicon in a constituent atom. (A) The photosensitive resin composition of any one of Claims 1-5 in which a component has the structure in any one of the following general formula (1)-(3).

In the general formulas (1) to (3), R ^{1 to} R ¹¹ each independently represents a hydrogen atom or a monovalent organic group. X and Y each independently represent an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Here, R ¹² represents a hydrogen atom or a monovalent organic group. Z represents an oxygen atom, a sulfur atom, —N (R ¹³ ) — or a phenylene group which may have a substituent. Here, R ¹³ represents a hydrogen atom or a monovalent organic group. The component (A) has a partial structure represented by the following general formula (UB), and the mass content of the aromatic moiety of the following general formula (UB) in the structure of the component (A) is 30% by mass. It is the above, The photosensitive resin composition of any one of Claims 1-6.

In the general formula (UB), X ^L1 represents a single bond, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —O— or — C (= O)-, and R ^{u1 to} R ^u8 each independently represent a hydrogen atom or a substituent. The photosensitive resin composition according to claim 7, wherein in the general formula (UB), R ^{u1 to} R ^u8 are all hydrogen atoms. (A) The photosensitive resin composition of any one of Claims 1-8 in which a component has the partial structure represented by the following general formula (UNCO).

In the general formula (UNCO), X ^L1 represents a single bond, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —O— or — C (= O)-is represented. R ^{u1 to} R ^u8 each independently represents a hydrogen atom or a substituent. The photosensitive resin composition according to claim 9, wherein in the general formula (UNCO), R ^{u1 to} R ^u8 are all hydrogen atoms, and X ^L1 is —CH ₂ —. (A) The photosensitive resin composition of any one of Claims 1-10 in which a component has the partial structure represented by the following general formula (UE1).

In the general formula (UE1), L ^UE is a divalent linking group that does not contain —NHC (═O) O— or —OC (═O) NH— in the main chain bond, and is an ethylenically unsaturated group. Represents a divalent linking group in which at least one group having a substituent is substituted. The photosensitive resin composition according to claim 11, wherein the general formula (UE1) is represented by the following general formula (G1).

In General Formula (G1), R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom, or — N (R ¹² ) — is represented, and R ¹² represents a hydrogen atom or a monovalent organic group.   (A) The photosensitive resin composition of any one of Claims 1-12 in which a component has at least 1 carboxyl group at the terminal of a polymer principal chain.   The photosensitive film which has a photosensitive layer containing the photosensitive resin composition of any one of Claims 1-13.   The photosensitive laminated body which has a photosensitive layer containing the photosensitive resin composition of any one of Claims 1-13 on a base | substrate.   A printed circuit board comprising a resist pattern obtained by photocuring a photosensitive layer containing the photosensitive resin composition according to any one of claims 1 to 13 on a substrate.   A method for producing a printed circuit board, comprising: transferring a photosensitive layer of the photosensitive film according to claim 14 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 resin composition of any one of Claims 1-13.