JP2012211944A - Photosensitive composition, photosensitive film, photosensitive laminate, method for forming permanent pattern and printed board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition which is improved in surface hardness, cold impact properties, plating resistance and insulation properties and excellent in folding endurance and solder heat resistance.SOLUTION: A photosensitive composition contains at least an ethylenically unsaturated group-containing polyurethane resin, a polymerizable compound, a photopolymerization initiator and a thermal crosslinking agent. The ethylenically unsaturated group-containing polyurethane resin has an ethylenically unsaturated group equivalent weight of 1.2 mmol/g or more and 1.5 mmol/g or less and a mass composition ratio of aromatic groups of 30% by mass or more. The thermal crosslinking agent contains at least any of an epoxy compound, an oxetane compound, a compound obtained by reacting a blocking agent with an isocyanate compound and a melamine derivative. The ethylenically unsaturated group-containing polyurethane resin is a photosensitive composition containing a structural unit represented by the following general formula (I).

Description

  The present invention relates to a photosensitive composition, a photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printed circuit board suitable as a solder resist material for forming an image by exposure.

  Conventionally, when forming a permanent pattern such as a solder resist, a photosensitive film in which a photosensitive layer is formed by coating a photosensitive composition on a support and drying it has been used. As a method for forming a permanent pattern such as a solder resist, for example, a photosensitive laminate is formed by laminating a photosensitive film on a substrate such as a copper-clad laminate on which a permanent pattern is formed, and the photosensitive lamination A method is known in which a photosensitive layer in a body is exposed, and after the exposure, the photosensitive layer is developed to form a pattern, followed by a curing process or the like to form a permanent pattern.

In a photosensitive composition using a polyurethane resin as a binder for the solder resist, it is one of important issues to improve hardness and increase sensitivity, and various studies have been made.
For example, Patent Document 1 contains an ethylenically unsaturated bond group in an equivalent amount of 0.35 meq / g to 1.50 meq / g of an ethylenically unsaturated bond group in the side chain, and is aromatic. A polymerizable composition using a polyurethane resin containing 40% by mass or more of a group is disclosed.
Patent Document 2 has an ethylenically unsaturated bond group of 0.5 mmol / g to 5.0 mmol / g, and is suitable as a solder resist for a printed wiring board using a polyurethane resin containing an aromatic group. Elastomers are disclosed.

  However, the techniques of the above-mentioned prior art documents not only improve the surface hardness, thermal shock resistance, plating resistance, and insulation, but also sufficiently satisfy various characteristics such as folding resistance and solder heat resistance. The present situation is that further improvement and development are desired.

JP-A-2005-250438 JP 2007-002030 A

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention provides a photosensitive composition comprising an ethylenically unsaturated group-containing polyurethane resin that not only improves surface hardness, thermal shock resistance, plating resistance, and insulation, but also has excellent folding resistance and solder heat resistance. It is an object to provide a photosensitive film, a photosensitive laminate, a method for forming a permanent pattern, and a printed board using the photosensitive composition.

Means for solving the problems are as follows. That is,
<1> An ethylenically unsaturated group-containing polyurethane resin comprising at least an ethylenically unsaturated group-containing polyurethane resin, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent. The equivalent is 1.2 mmol / g or more and 1.5 mmol / g or less, and the mass composition ratio of the aromatic group is 30% by mass or more, and the thermal crosslinking agent is blocked by an epoxy compound, an oxetane compound and an isocyanate compound. A photosensitive resin comprising at least one of a compound obtained by reacting an agent and a melamine derivative, wherein the ethylenically unsaturated group-containing polyurethane resin contains a structural unit represented by the following general formula (I): Composition.
However, in said general formula (I), R < ¹ >, R < ² > and R < ³ > may mutually be the same and may differ, respectively, and each represents a hydrogen atom or monovalent organic group, A is Represents a divalent organic residue, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, and R ¹² represents a hydrogen atom or a monovalent organic group.
<2> The ethylenically unsaturated group-containing polyurethane resin contains an aromatic group represented by the following general formula (1-1), and the mass composition ratio of the aromatic group represented by the general formula (1-1) is It is a photosensitive composition as described in said <1> which is 30 mass% or more.
However, in the general formula (1-1), X represents a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —CO—, or —O—. To express. R ¹ , R ² , R ³ , and R ⁴ may be the same as or different from each other, and each represents a hydrogen atom, a monovalent organic group, a halogen atom, —OR ⁵ , —N ( R ⁶ ) (R ⁷ ) or —SR ⁸ , and R ⁵ , R ⁶ , R ⁷ , and R ⁸ each represent a hydrogen atom or a monovalent organic group.
<3> The ethylenically unsaturated group-containing polyurethane resin contains an aromatic group represented by the following general formula (1-2), and the mass composition ratio of the aromatic group represented by the general formula (1-2) Is a photosensitive composition according to any one of <1> to <2>, wherein is 30% by mass or more.
However, in the general formula (1-2), X represents a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —CO—, or —O—. .
<4> The ethylenically unsaturated group-containing polyurethane resin contains a structural unit represented by a reaction product of a compound having a monofunctional or polyfunctional alcohol group and 4,4′-diphenylmethane diisocyanate (MDI). The photosensitive composition according to any one of <1> to <3>, which is a polyurethane resin.
<5> The ethylenically unsaturated group-containing polyurethane resin contains a structural unit represented by a reaction product of a compound having a monofunctional or polyfunctional alcohol group and 4,4′-diphenylmethane diisocyanate (MDI). It is a polyurethane resin, The photosensitive composition according to any one of <1> to <4>, wherein the mass composition ratio of the MDI in the ethylenically unsaturated group-containing polyurethane resin is 30% by mass or more.
<6> A photosensitive film comprising a photosensitive layer containing the photosensitive composition according to any one of <1> to <5> on a support.
<7> A photosensitive laminate comprising a photosensitive layer containing the photosensitive composition according to any one of <1> to <5> on a substrate.
<8> A method for forming a permanent pattern, comprising at least exposing the photosensitive layer formed of the photosensitive composition according to any one of <1> to <5>.
<9> A printed circuit board wherein a permanent pattern is formed by the method for forming a permanent pattern according to <8>.

  According to the present invention, various problems in the prior art can be solved, and not only the surface hardness, thermal shock resistance, plating resistance, and insulation are improved, but also containing an ethylenically unsaturated group that is excellent in folding resistance and solder heat resistance. The photosensitive composition containing a polyurethane resin, the photosensitive film using this photosensitive composition, the photosensitive laminated body, the permanent pattern formation method, and a printed circuit board can be provided.

(Photosensitive composition)
The photosensitive composition of this invention contains an ethylenically unsaturated group containing polyurethane resin, a polymeric compound, a photoinitiator, and a thermal crosslinking agent at least, and also contains another component as needed.

<Ethylene unsaturated group-containing polyurethane resin>
The ethylenically unsaturated group-containing polyurethane resin is not particularly limited as long as the ethylenically unsaturated group equivalent is 1.2 mmol / g or more and 1.5 mmol / g or less, and can be appropriately selected according to the purpose. However, the ethylenically unsaturated group equivalent is preferably 1.3 mmol / g or more and 1.5 mmol / g or less. When the ethylenically unsaturated group equivalent is less than 1.2 mmol / g, heat resistance and sensitivity may be lowered, and when it exceeds 1.5 mmol / g, folding resistance may be deteriorated.
In addition, as a calculation method of the said ethylenically unsaturated group equivalent, the method of calculating by measuring a bromine number is mentioned, for example. In addition, as a measuring method of the said bromine number, the method etc. which measure based on JISK2605 are mentioned, for example.

  The ethylenically unsaturated group is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably a methacryloyl group, an acryloyl group, or a vinylphenyl group from the viewpoint of forming a crosslinked cured film, a methacryloyl group, An acryloyl group is more preferable, and a methacryloyl group is particularly preferable in terms of both the formability of the crosslinked cured film and the raw storage stability.

The ethylenically unsaturated group-containing polyurethane resin is not particularly limited as long as the mass composition ratio of the aromatic group is 30% by mass or more, and can be appropriately selected according to the purpose. The mass composition ratio is preferably 30% by mass to 70% by mass, more preferably 32% by mass to 70% by mass, and particularly preferably 35% by mass to 70% by mass. If the mass composition ratio is less than 30% by mass, the hardness may decrease.
Here, the term “aromatic” refers to a 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. means.

The ethylenically unsaturated group-containing polyurethane resin is not particularly limited as long as it is a compound containing a structural unit represented by the following general formula (I), and can be appropriately selected according to the purpose. Examples include polyurethane resins containing a structural unit represented by a reaction product of a compound and a compound having a monofunctional or polyfunctional alcohol group having an ethylenically unsaturated group, and other copolymerization components. Also good.
The polyurethane resin having an ethylenically unsaturated group is not particularly limited as long as it is a compound containing the structural unit represented by the general formula (I), and can be appropriately selected depending on the purpose. In addition, the crosslinking reactivity is improved, the photocured product strength is increased, and when the resin is used for a solder resist or the like, it becomes a material having excellent toughness, and it can impart properties such as hydrogen bonding property and alkali solubility. A polyurethane resin having a carboxyl group and an ethylenically unsaturated group is preferable because it can be used.
However, in said general formula (I), R < ¹ >, R < ² > and R < ³ > may mutually be the same and may differ, respectively, and each represents a hydrogen atom or monovalent organic group, A is Represents a divalent organic residue, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, and R ¹² represents a hydrogen atom or a monovalent organic group.

<< Diisocyanate Compound >>
There is no restriction | limiting in particular as said diisocyanate compound, According to the objective, it can select suitably, For example, the compound etc. which are represented with following General formula (1) are mentioned.
However, in the general formula (1), R ₁ may have a substituent (for example, any of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogeno group is preferable). Represents an aliphatic or aromatic hydrocarbon. If necessary, R ₁ may have any other functional group that does not react with an isocyanate group, such as an ester group, a urethane group, an amide group, or a ureido group.

  There is no restriction | limiting in particular as a diisocyanate compound represented by the said General formula (1), According to the objective of improving compatibility with the other component in polymeric composition and improving storage stability suitably For example, a diisocyanate, a triisocyanate compound (a compound described in paragraphs [0034] to [0035] of JP-A-2005-250438), and a monofunctional alcohol having an ethylenically unsaturated group Alternatively, a product obtained by addition reaction of 1 equivalent of a monofunctional amine compound (compound described in paragraphs [0037] to [0040] of JP-A-2005-250438) and the like can be used.

There is no restriction | limiting in particular as a diisocyanate compound represented by the said General formula (1), Although it can select suitably according to the objective, The following general formula (1-1) is included in the said ethylenically unsaturated group containing polyurethane resin. It is preferable that the group represented by the following general formula (1-1) is included in that the group represented by formula (1-1) can be included.
However, in the general formula (1-1), X represents a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —CO—, or —O—. To express. R ¹ , R ² , R ³ , and R ⁴ may be the same as or different from each other, and each represents a hydrogen atom, a monovalent organic group, a halogen atom, —OR ⁵ , —N ( R ⁶ ) (R ⁷ ) or —SR ⁸ , and R ⁵ , R ⁶ , R ⁷ , and R ⁸ each represent a hydrogen atom or a monovalent organic group.

As the X in the general formula (1-1), in view of developing property, _-CH 2 -, - O-is preferable, -CH ₂ - is more preferable.
The monovalent organic group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (1-1) is an alkyl having 1 to 20 carbon atoms. Group, an alkenyl group having 1 to 20 carbon atoms, —OR ⁹ (wherein R ⁹ represents a monovalent organic group (preferably an alkyl group having 1 to 20 carbon atoms)), an aryl group, an aryloxy group, an aryl An amino group, a diarylamino group, etc. are mentioned.
Wherein in the general formula ^{(1-1) R 1, R 2} , R 3, and as ^{R 4,} from the viewpoint of resolution, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, -OR ⁹ are preferred, A hydrogen atom and an alkyl group having 1 to 20 carbon atoms are more preferable, and a hydrogen atom is particularly preferable.
Examples of the halogen atom in the general formula (1-1) include fluorine, chlorine, bromine and the like.

There is no restriction | limiting in particular as a diisocyanate compound represented by the said General formula (1), Although it can select suitably according to the objective, The following general formula (1-2) is included in the said ethylenically unsaturated group containing polyurethane resin. It is more preferable that the group represented by the following general formula (1-2) is included in that the group represented by formula (1-2) can be included.
However, in the general formula (1-2), X represents a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —CO—, or —O—. represents, _-CH 2 -, - O- are preferable, -CH ₂ - is particularly preferred.

  There is no restriction | limiting in particular as a mass composition ratio of the aromatic group represented by the said General formula (1-1)-(1-2), Although it can select suitably according to the objective, 30 mass% or more is Preferably, 30% by mass to 70% by mass is more preferable, 32% by mass to 70% by mass is further preferable, and 35% by mass to 70% by mass is particularly preferable. In addition, when the mass composition ratio of the aromatic group includes the structural units represented by the general formulas (1-1) to (1-2), X represents a ratio calculated by including the aromatic unit. .

There is no restriction | limiting in particular as a specific example of the diisocyanate compound represented by the said General formula (1), According to the objective, it can select suitably, For example, 2, 4-tolylene diisocyanate, 2, 4-tolylene diene. Dimer of isocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, 3,3 ' -Aromatic diisocyanate compounds such as dimethylbiphenyl-4,4'-diisocyanate; Aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; Isophorone diisocyanate Alicyclic diisocyanate compounds such as 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; 1,3-butylene glycol 1 mol And a diisocyanate compound which is a reaction product of diol and diisocyanate such as an adduct of 2 mol of tolylene diisocyanate. These may be used individually by 1 type and may use 2 or more types together.
Among these, 4,4′-diphenylmethane diisocyanate (MDI) is preferable from the viewpoint of hardness. The ethylenically unsaturated group-containing polyurethane resin contains a structural unit represented by a reaction product of the compound having a monofunctional or polyfunctional alcohol group and the 4,4′-diphenylmethane diisocyanate (MDI). Thus, a resin having excellent hardness can be obtained.

  There is no restriction | limiting in particular as a mass composition ratio in the said ethylenically unsaturated group containing polyurethane resin of the said MDI which is a diisocyanate compound represented by the said General formula (1), Although it can select suitably according to the objective. 30 mass% or more is preferable, and 40 mass%-70 mass% is more preferable. If the mass composition ratio is less than 30% by mass, the hardness may decrease.

<< Compound having monofunctional or polyfunctional alcohol group having ethylenically unsaturated group >>
The compound having a monofunctional or polyfunctional alcohol group having an ethylenically unsaturated group is not particularly limited as long as it can contain at least a compound represented by the following general formula (2-1), depending on the purpose. A diol compound having an ethylenically unsaturated group is preferred, and specific examples include compounds described in paragraphs [0064] to [0066] of JP-A-2005-250438. It is done. These may be used alone or in combination of two or more. By using the compound represented by the general formula (2-1), the coating strength of the layer is improved by suppressing the excessive molecular motion of the polymer main chain caused by the secondary alcohol having a large steric hindrance. be able to.
However, in said general formula (2-1), R < ¹ > -R < ³ > represents either a hydrogen atom and a monovalent organic group each independently, A represents a bivalent organic residue, X is , oxygen atom, sulfur atom, and -N ^{(R 12)} - represents one of the ^{R 12} represents a hydrogen atom or a monovalent organic group.

R ¹ in the general formula (2-1) is preferably an alkyl group, more preferably a methyl group, and R ^{2 to} R ³ are each preferably a hydrogen atom.
As A in the general formula (2-1), an alkylene group is preferable, and a methylene group is more preferable.
X in the general formula (2-1) is preferably an oxygen atom.

<< Molar ratio between diisocyanate compound and compound having monofunctional or polyfunctional alcohol group having ethylenically unsaturated group >>
The molar ratio (M _a : M _b ) between the diisocyanate and the compound having a monofunctional or polyfunctional alcohol group having an ethylenically unsaturated group is not particularly limited and may be appropriately selected depending on the purpose. 1: 1 to 1.2: 1 are preferred, and by treatment with alcohols or amines, a product having desired physical properties such as molecular weight or viscosity is finally synthesized in a form in which no isocyanate group remains. The

<< Other copolymer components >>
The other copolymer component is not particularly limited and may be appropriately selected depending on the purpose. For example, it contains a carboxyl group in that a polyurethane resin having a carboxyl group and an ethylenically unsaturated group is used for synthesis A diol compound is preferably exemplified, and examples thereof include a carboxyl group-free diol compound, an epoxy group, and a compound having an ethylenically unsaturated group. These may be used alone or in combination of two or more.

-Carboxyl group-containing diol compound-
The carboxyl group-containing diol compound is not particularly limited as long as it is a carboxyl group-containing diol compound having a COOH group and two OH groups via either a C atom or an N atom, and is appropriately selected according to the purpose. Examples thereof include compounds represented by the following general formulas (2-2) to (2-4), specifically, described in paragraph [0047] of JP-A-2007-2030. More specifically, 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-hydroxyphenyl) acetic acid, 2,2-bis (hydroxymethyl) Acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethyl glycine, N, N-bis (2-hydroxyethyl) -3-carboxy - such as propionamide, and the like. These may be used alone or in combination of two or more.
However, the general formula (2-2), _{R 2} is a hydrogen atom, a substituent (e.g., cyano group, Two Toro group, a halogen atom (-F, -Cl, -Br, -I ), - CONH 2 , —COOR ₆ , —OR ₆ , —NHCONHR ₆ , —NHCOOR ₆ , —NHCOR ₆ , —OCONHR ₆ , —CONHR ₆ (where R ₆ is an alkyl group having 1 to 10 carbon atoms, 7 to 15 carbon atoms) Each of which represents an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group. Among these, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and an aryl group having 6 to 15 carbon atoms are preferable.
However, in said general formula (2-2)-(2-4), R < ₃ >, R < ₄ > and R < ₅ > may be same or different, respectively, a single bond, a substituent (for example, alkyl group, An aralkyl group, an aryl group, an alkoxy group, or a halogeno group is preferred) and may represent a divalent aliphatic or aromatic hydrocarbon. Among these, an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable. Further, if necessary, any of other functional groups that do not react with the isocyanate group in the R ₃ , R ₄ and R ₅ , for example, any of carbonyl group, ester group, urethane group, amide group, ureido group, and ether group You may have. In addition, you may form a ring by 2 or 3 of said R < ₂ >, R < ₃ >, R < ₄ > and R < ₅ >. Ar represents a trivalent aromatic hydrocarbon which may have a substituent, and an aromatic group having 6 to 15 carbon atoms is preferable.

-Carboxyl group-free diol compound-
The carboxyl group-free diol compound is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include a carboxyl group-free high molecular weight diol compound and a carboxyl group-free low molecular weight diol compound. Specific examples include polyether diol compounds, polyester diol compounds, polycarbonate diol compounds, and diol compounds having a substituent that does not react with isocyanate groups. These may be used alone or in combination of two or more.

  The copolymerization amount of the carboxyl group-free diol is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 95 mol% or less, preferably 80 mol% or less in the carboxyl group-free low molecular weight diol. Is more preferable, and 50 mol% or less is particularly preferable. When the copolymerization amount exceeds 95 mol%, a urethane resin having good developability may not be obtained.

Examples of the carboxyl group-free high molecular weight diol compound include compounds represented by the following general formulas (3-1) to (3-5) having a weight average molecular weight of 800 to 3,000, and the like. Specifically, the compounds described in paragraphs [0022] to [0046] of JP-A-2007-2030 are exemplified.
Examples of the carboxyl group-free low molecular weight diol compound include compounds represented by the following general formulas (3-1) to (3-5) having a weight average molecular weight of 500 or less, specifically, And compounds described in paragraph [0048] of JP-A-2007-2030. Further, the carboxyl group-free low molecular weight diol compound can be added in the range as long as the alkali solubility is not lowered.
However, in said general formula (3-1)-(3-3), R < ₇ >, R < ₈ >, R < ₉ >, R < ₁₀ > and R < ₁₁ > may be the same respectively, may be different, and are bivalent. Represents an aliphatic or aromatic hydrocarbon. R ₇ , R ₉ , R ₁₀ and R ₁₁ are each preferably an alkylene group having 2 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, and an alkylene or carbon 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 , R ₈ , R ₉ , R ₁₀ and R ₁₁ , other functional groups that do not react with isocyanate groups, such as ether groups, carbonyl groups, ester groups, cyano groups, olefin groups, urethane groups , An amide group, a ureido group, or a halogen atom.
However, the general formula (3-4), R ₁₂ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a cyano group or a halogen atom. A hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl having 7 to 15 carbon atoms, a cyano group, or a halogen atom is preferable, and a hydrogen atom or one carbon atom is preferable. More preferred are ˜6 alkyl and aryl groups having 6 to 10 carbon atoms. R ₁₂ may have other functional groups that do not react with isocyanate groups, such as alkoxy groups, carbonyl groups, olefin groups, ester groups, or halogen atoms.
In the general formula (3-5), R ₁₃ represents an aryl group or a cyano group, preferably 6 to 10 aryl groups, or a cyano group carbon.
However, in said general formula (3-4), m represents the integer of 2-4.
In the general formula _{(3-1) ~ (3-5),} n 1, n 2, n 3, n 4 and _{n 5} are, each represent an integer of 2 or more, preferably an integer of 2 to 100. In the general formula (3-5), n ₆ represents 0 or an integer of 2 or more, and preferably 0 or an integer of 2 to 100.

The polyether diol compound is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of improving compatibility with other components in the photosensitive composition and improving storage stability. Examples thereof include compounds described in paragraphs [0068] to [0076] of JP-A-2005-250438.
The polyester diol compound is not particularly limited and can be appropriately selected according to the purpose.From the viewpoint of improving the compatibility with other components in the photosensitive composition and improving the storage stability, For example, in No. 2005-250438, paragraphs [0077] to [0079] and paragraphs [0083] to [0085], No. 1-No. 8 and no. 13-No. 18 and the like.
The polycarbonate diol compound is not particularly limited and can be appropriately selected depending on the purpose.From the viewpoint of improving the compatibility with other components in the photosensitive composition and improving the storage stability, For example, in No. 2005-250438, paragraphs [0080] to [0081] and paragraph [0084] No. 9-No. 12 listed compounds.
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.

There is no restriction | limiting in particular as said carboxyl group non-containing diol compound, Although it can select suitably according to the objective, The compound represented by following Structural formula (3-1)-(3-5) is preferable.

-Compound having epoxy group and ethylenically unsaturated group-
The compound having an epoxy group and an ethylenically unsaturated group is not particularly limited as long as it is a compound having an epoxy group and an ethylenically unsaturated group in the molecule through a —COO— bond. Examples thereof include compounds represented by the following general formulas (4-1) to (4-16). These may be used alone or in combination of two or more. Among these, from the viewpoint of sensitivity, a compound represented by the following general formula (4-1) and a compound represented by the following general formula (4-2) are preferable.
In the general formula _{(4-1) ~ (4-16),} R 14 represents a hydrogen atom or a methyl _{group, R 15} represents an alkylene group having 1 to 10 carbon _{atoms, R 16} is a carbon The hydrocarbon group of number 1-10 is represented. p represents 0 or an integer of 1 to 10.

<Method for synthesizing ethylenically unsaturated group-containing polyurethane resin>
The method for synthesizing the ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected according to the purpose. For example, the diisocyanate compound, the diol compound having the ethylenically unsaturated group, and the Examples include a method of synthesizing other copolymerization components by adding a known catalyst having an activity corresponding to each reactivity in an aprotic solvent and heating. When an isocyanate group remains at the end of the polymer, it can be synthesized by treatment with alcohols or amines so that the isocyanate group does not remain most tangentially.

The method for introducing an ethylenically unsaturated group into the polymer side chain in the ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method of introducing a polyurethane resin by synthesizing a diol compound containing a saturated group.
The ethylenically unsaturated group is preferably introduced into the polymer side chain rather than the polymer end from the viewpoint that the introduction amount can be easily controlled and the introduction amount can be increased, and the crosslinking reaction efficiency is improved.

  The method for introducing an ethylenically unsaturated group into the polymer terminal in the ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the alcohols or amines described above For example, a method of introducing a residual isocyanate group at the polymer end by reacting with an alcohol or amine having an ethylenically unsaturated group, etc., may be mentioned.

  The method for introducing an ethylenically unsaturated group into the polymer main chain in the ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. And a method of introducing it by synthesizing a polyurethane resin using a diol compound having a polymerizable unsaturated group. The diol compound having an ethylenically unsaturated group in the main chain direction is not particularly limited and may be appropriately selected depending on the intended purpose. For example, cis-2-butene-1,4-diol, trans-2- Examples include butene-1,4-diol and polybutadiene diol.

There is no restriction | limiting in particular as a weight average molecular weight of the said ethylenically unsaturated group containing polyurethane resin, Although it can select suitably according to the objective, 5,000-60,000 are preferable and 5,000-50,000 are preferable. Is more preferable, and 5,000 to 30,000 is particularly preferable. When the weight average molecular weight is less than 5,000, a sufficiently low elastic modulus at a high temperature of the cured film may not be obtained, and when it exceeds 60,000, coating suitability and developability may deteriorate. is there.
In addition, the said weight average molecular weight uses a high-speed GPC apparatus (the Toyo Soda Co., Ltd. make, HLC-802A), made 0.5 mass% THF solution into a sample solution, and a column is 1 TSKgel HZM-M. The sample can be injected with 200 μL, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or UV detector (detection wavelength 254 nm). And a weight average molecular weight can be calculated | required from the molecular weight distribution curve calibrated with the standard polystyrene.

There is no restriction | limiting in particular as an acid value of the said ethylenically unsaturated group containing polyurethane resin, Although it can select suitably according to the objective, 20 mgKOH / g-120 mgKOH / g is preferable, 30 mgKOH / g-110 mgKOH / g is More preferred is 35 mg KOH / g to 100 mg KOH / g. If the acid value is less than 20 mgKOH / g, the developability may be insufficient, and if it exceeds 120 mgKOH / g, the development speed may be too high, and the development control may be difficult.
In addition, the said acid value can be measured based on JISK0070, for example. When the sample does not dissolve, dioxane or tetrahydrofuran can be used as a solvent.

There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said ethylenically unsaturated group containing polyurethane resin, Although it can select suitably according to the objective, 5 mass%-80 mass% are preferable. 30 mass% to 60 mass% is more preferable.
If the content is 5% by mass or more, it is advantageous in terms of good developability and exposure sensitivity, and if it is 80% by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong. Is advantageous.

<Polymerizable compound>
There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, The compound which has one or more ethylenically unsaturated groups is preferable. Examples of the ethylenically unsaturated group include (meth) acryloyl group, (meth) acrylamide group, vinylphenyl group, vinyl ester group, vinyl ether group, allyl group, allyl ether group, and allyl ester group.

  The compound having one or more ethylenically unsaturated groups is not particularly limited and may be appropriately selected depending on the purpose. For example, at least one selected from monomers having the ethylenically unsaturated groups Compound etc. are mentioned. These may be used alone or in combination of two or more. Among these, at least one compound selected from monomers having a (meth) acryloyl group is preferable.

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 acrylate such as acrylate, monofunctional methacrylate; 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, dihydrodicyclopentadienyl diacrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, (Meth) acrylated after addition reaction of ethylene oxide, propylene oxide, etc. to polyfunctional alcohols such as tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol Acrylates: Urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, etc. Polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, etc .; Epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid; And polyfunctional acrylates and methacrylates. These may be used alone or in combination of two or more.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.

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

<Photopolymerization initiator>
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected depending on the purpose. Examples thereof include neutral photopolymerization initiators. However, a photopolymerization initiator having photosensitivity to visible light from the ultraviolet region is preferable, and may be an activator that generates some kind of action with a photoexcited sensitizer and generates an active radical. Depending on the type, an initiator that initiates cationic polymerization may be used, and if necessary, other photopolymerization initiators may be included. These may be used alone or in combination of two or more.
The photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. However, it has a molecular extinction coefficient of at least about 50 within a wavelength range of about 300 nm to 800 nm (preferably, 330 nm to 500 nm). What contains at least 1 type of component which has is preferable.

  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, thiols, and the like. Compounds, and the like. Among these, (bis) acylphosphine oxide or its esters, acetophenone compounds, benzophenone compounds, benzoin from the viewpoints of sensitivity of the photosensitive layer, storage stability, adhesion between the photosensitive layer and the printed wiring board forming substrate, etc. Ether compounds, ketal derivative compounds, thioxanthone compounds, and oxime derivatives are preferred.

  The (bis) acylphosphine oxide is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2,6-dichlorobenzoylphenylphosphine oxide, 2,6-dimethyloxybenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 Examples thereof include 4-trimethyl-pentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

  The acetophenone compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, acetophenone, methoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxy Examples include cyclohexyl phenyl ketone, 4-diphenoxydichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one.

  The benzophenone compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, benzophenone, 4-phenylbenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 3,3′- Examples thereof include dimethyl-4-methoxybenzophenone and diphenoxybenzophenone.

  The benzoin ether compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include benzoin ethyl ether and benzoin propyl ether.

  There is no restriction | limiting in particular as said ketal derivative compound, According to the objective, it can select suitably, For example, benzyl dimethyl ketal etc. are mentioned.

  The thioxanthone compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, Examples include isopropylthioxanthone.

There is no restriction | limiting in particular as said oxime derivative, According to the objective, it can select suitably, For example, the derivative etc. which are represented with the following general formula (A) are mentioned.

However, in the general formula (A), R ¹ represents any ^one of a hydrogen atom, an optionally substituted acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group. , R ² each independently represents a substituent. m represents an integer of 0 to 4, and in the case of 2 or more, they may be connected to each other to form a ring. A represents any of 4, 5, 6, and 7-membered rings. A is preferably either a 5- or 6-membered ring.

In addition, about the said oxime compound, the matter as described in Unexamined-Japanese-Patent No. 2008-249857, Unexamined-Japanese-Patent No. 2008-242372, Unexamined-Japanese-Patent No. 2008-122546, Unexamined-Japanese-Patent No. 2008-122545, etc. is applicable. .
The oxime compound used in the present invention can be identified by measuring ¹ H-NMR spectrum and UV-vis absorption spectrum.

  There is no restriction | limiting in particular as content in the said photosensitive composition solid content of the said photoinitiator, Although it can select suitably according to the objective, 0.1 mass%-30 mass% are preferable, 0 0.5 mass% to 20 mass% is more preferable, and 0.5 mass% to 15 mass% is particularly preferable.

<Thermal crosslinking agent>
The thermal crosslinking agent is not particularly limited as long as it is a compound containing at least one of an epoxy compound, an oxetane compound, a compound obtained by reacting an isocyanate compound with a blocking agent, and a melamine derivative. In order to improve the film strength after curing of the photosensitive layer formed by use, it can be appropriately selected according to a range that does not adversely affect developability and the like. In addition, the epoxy compound, the oxetane compound, a compound obtained by reacting the isocyanate compound with a blocking agent, and other known thermal crosslinking agents other than the melamine derivative may be contained, and these may be used alone. You may use, and may use 2 or more types together.
Among these, an epoxy compound, a melamine derivative, and an oxetane compound are preferable, an epoxy compound and an oxetane compound are more preferable, and an epoxy compound is particularly preferable in terms of raw storage and adhesion.

<< Epoxy compound >>
There is no restriction | limiting in particular as said epoxy compound, According to the objective, it can select suitably, For example, the epoxy compound which has an at least 2 oxirane group in 1 molecule, the epoxy compound which has an alkyl group in (beta) position, etc. are mentioned. Specific examples include epoxy compounds having an oxirane group described in JP-A-2007-47729.
Examples of the epoxy compound having at least two oxirane groups in one molecule include a bixylenol type or biphenol type epoxy resin (“YX4000, manufactured by Japan Epoxy Resin Co., Ltd.”) or a mixture thereof, an isocyanurate skeleton, and the like. Heterocyclic epoxy resins (“TEPIC, manufactured by Nissan Chemical Industries, Ltd.”, “Araldite PT810, manufactured by Ciba Specialty Chemicals”, etc.), bisphenol A type epoxy resins, novolac type epoxy resins, bisphenol F type epoxy resins (“ Epototo, manufactured by Toto Kasei Co., Ltd.), hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low odor) Epoxy resin, highly halogenated epoxy resin, brominated phenol novolac type epoxy resin, etc.), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, di Cyclopentadiene type epoxy resins (“HP-7200, HP-7200H, manufactured by Dainippon Ink & Chemicals, Inc.”), glycidylamine type epoxy resins (diaminodiphenylmethane type epoxy resin, diglycidylaniline, triglycidylaminophenol, etc.), Glyidyl ester type epoxy resin (phthalic acid diglycidyl ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Toin type epoxy resin, cycloaliphatic epoxy resin (3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT -300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries Ltd., etc.), imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type epoxy resin , Glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin (naphthol aralkyl epoxy resin, naphthol novolac epoxy resin, tetrafunctional naphthalene epoxy resin, commercially available product "ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.", "HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc."), phenol compounds and divinylbenzene, A reaction product of a polyphenol compound obtained by addition reaction with a diolefin compound such as dicyclopentadiene and epichlorohydrin, a ring-opening polymerization product of 4-vinylcyclohexene-1-oxide with peracetic acid or the like, linear Epoxy resin having phosphorus-containing structure, epoxy resin having cyclic phosphorus-containing structure, α-methylstilbene type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl type liquid crystal epoxy resin, azomethine phenyl type liquid crystal epoxy resin, binaphthyl type Liquid crystal epoxy resin, azine type Epoxy resin, glycidyl methacrylate copolymer epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation”), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene Type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, and the like.
As the epoxy compound having an alkyl group at the β-position, for example, all of two or more epoxy groups contained in one molecule may be β-alkyl-substituted glycidyl groups, and at least one epoxy group is β- -Alkyl substituted glycidyl group may be sufficient and the compound containing (beta) -alkyl substituted glycidyl group is preferable.

<< Oxetane compound >>
There is no restriction | limiting in particular as said oxetane compound, According to the objective, it can select suitably, For example, the oxetane compound etc. which have at least 2 oxetanyl group in 1 molecule are mentioned.
Examples of the oxetane compound having at least two oxetanyl groups in one molecule include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (OXT-121: manufactured by Toagosei Co., Ltd.). Bis (3-ethyl-3-oxetanylmethyl) ether (OXT-221: manufactured by Toagosei Co., Ltd.), bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3 -Oxetanylmethoxy) methyl] ether, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3 -Oxetanyl) methyl methacrylate or oligomers or copolymers thereof, etc. In addition to cetanes, compounds having an oxetane group, novolac resins, poly (p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcinarenes, resins having hydroxyl groups such as silsesquioxane, and the like, and In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

<< Compound obtained by reacting isocyanate compound with blocking agent >>
There is no restriction | limiting in particular as a compound obtained by making a blocking agent react with the said isocyanate compound, According to the objective, it can select suitably, For example, a blocking agent is added to the isocyanate group of a polyisocyanate compound, polyisocyanate, or its derivative (s). Examples include compounds obtained by reaction (block isocyanate compounds).
As the polyisocyanate compound, for example, a polyisocyanate compound described in JP-A-5-9407 can be used, and the polyisocyanate compound is aliphatic, cycloaliphatic or aromatic containing at least two isocyanate groups. It may be derived from a group-substituted aliphatic compound. Specifically, bifunctional isocyanate (for example, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene). Diisocyanate, bis (4-isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc.), the bifunctional isocyanate, trimethylolpropane, pentalithol tol Polyfunctional alcohols such as glycerin; alkylene oxide adducts of the polyfunctional alcohols and adducts of the bifunctional isocyanates; hexamethylene diisocyanate, hexamethylene-1,6-di Such as isocyanate or cyclic trimer of such derivatives thereof.
Examples of the blocking agent include alcohols (eg, isopropanol, tert-butanol, etc.), lactams (eg, ε-caprolactam, etc.), phenols (eg, phenol, cresol, p-tert-butylphenol, p-sec). -Butylphenol, p-sec-amylphenol, p-octylphenol, p-nonylphenol, etc.), heterocyclic hydroxyl compounds (eg, 3-hydroxypyridine, 8-hydroxyquinoline, etc.), active methylene compounds (eg, dialkyl malonate, Methyl ethyl ketoxime, acetylacetone, alkyl acetoacetate oxime, acetoxime, cyclohexanone oxime, etc.) and the like. Or the like can be used one polymerizable double bond and at least one compound having any one of the blocked isocyanate groups. In addition, as the blocked isocyanate dissociation catalyst, a commonly used catalyst can be used to promote dissociation of the blocked isocyanate, and examples thereof include zinc octylate, dibutyltin acetate, dibutyltin dilaurate, and the like. As an organic metal salt of Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) can be used.
As a commercial item of the said block isocyanate compound, Desmodur BL-3175 (made by Sumika Bayer Urethane Co., Ltd.) etc. are mentioned.

<< Melamine derivative >>
The melamine derivative is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methylol melamine, alkylated methylol melamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl or the like). Can be mentioned. Among these, alkylated methylol melamine is preferable and hexamethylated methylol melamine is more preferable in that it has good storage stability and is effective in improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

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

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, fillers, thermal polymerization inhibitors, thermosetting accelerators, plasticizers, colorants (color pigments or dyes), groups Adhesion promoters on the surface of the material are preferably mentioned, and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling promoters, antioxidants, perfumes, surfaces You may use together a tension adjuster, a chain transfer agent, etc.). By appropriately containing these components, properties such as the stability, photographic properties, and film properties of the intended photosensitive film can be adjusted.

Examples of the filler include fillers described in paragraphs [0098] to [0099] of JP-A-2008-250074.
Examples of the thermal polymerization inhibitor include thermal polymerization inhibitors described in paragraphs [0101] to [0102] of JP-A-2008-250074.
Examples of the thermosetting accelerator include the thermosetting accelerator described in paragraph [0093] of JP-A-2008-250074.
Examples of the plasticizer include the plasticizers described in paragraphs [0103] to [0104] of JP-A-2008-250074.
Examples of the colorant include the colorants described in paragraphs [0105] to [0106] of JP-A-2008-250074.
Examples of the adhesion promoter include adhesion promoters described in paragraphs [0107] to [0109] of JP-A-2008-250074.

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

<Support>
The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, a support that can peel off the photosensitive layer and has good light transmittance is preferable, and the surface is smooth. A support having good properties is more preferred.

  The support is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably made of synthetic resin and transparent, specifically, polyethylene terephthalate, polyethylene naphthalate, polypropylene, Polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, Examples thereof include various plastic films such as polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose film, and nylon film. These may be used alone or in combination of two or more. Among these, polyethylene terephthalate is particularly preferable.

  There is no restriction | limiting in particular as thickness of the said support body, Although it can select suitably according to the objective, 2 micrometers-150 micrometers are preferable, 5 micrometers-100 micrometers are more preferable, 8 micrometers-50 micrometers are especially preferable.

  There is no restriction | limiting in particular as a shape of the said support body, Although it can select suitably according to the objective, A long shape is preferable. There is no restriction | limiting in particular as the length at the time of making the said support body elongate, According to the objective, it can select suitably, For example, the support body of the length of 10m-20,000m etc. are mentioned.

<Photosensitive layer>
If the said photosensitive layer is a layer which consists of the said photosensitive composition, 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.

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

  The method for forming the photosensitive layer is not particularly limited and may be appropriately selected depending on the purpose. For example, the photosensitive composition is dissolved or emulsified or dispersed in water or a solvent on the support. And a method of preparing a photosensitive composition solution, applying the solution directly and drying it, and then laminating it.

  There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, For example, methanol, ethanol, normal-propanol, isopropanol, normal-butanol, secondary butanol, normal-hexanol etc. Alcohols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, etc .; ethyl acetate, butyl acetate, acetic acid-normal-amyl, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, methoxypropyl Esters such as acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, Halogenated hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, etc. Can be mentioned. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

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

  There is no restriction | limiting in particular as said photosensitive film, Although it can select suitably according to the objective, It winds around a cylindrical core, and it is preferable that it is stored by winding in the elongate roll shape. . There is no restriction | limiting in particular as a length at the time of making the said photosensitive film elongate, For example, it can select suitably from the range of 10m-20,000m. Further, slitting may be performed so that the user can easily use, and a long body of 100 m to 1,000 m may be formed into a roll shape. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. From the viewpoint of protecting the end face and preventing edge fusion during storage, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the end face, and use a low moisture-permeable material for packaging. It is 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 is preferably used, and a thermoplastic resin layer, a barrier layer, a release layer, an adhesive layer, a light absorption layer are exemplified. A layer such as a surface protective layer may be formed. The said photosensitive film may have these layers individually by 1 type, and may have 2 or more types.

-Protective film-
There is no restriction | limiting in particular as said protective film, According to the objective, it can select suitably, For example, what is used for the said support body, a paper, a polyethylene film, a polypropylene film etc. are mentioned, Among these, polyethylene A film and a polypropylene film are preferable, and can be formed on the photosensitive layer.

  There is no restriction | limiting in particular as thickness of the said protective film, Although it can select suitably according to the objective, For example, 5 micrometers-100 micrometers are preferable, 8 micrometers-50 micrometers are more preferable, 10 micrometers-30 micrometers are especially preferable.

  Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. It is done.

  There is no restriction | limiting in particular as a static friction coefficient of the said support body and the said protective film, Although it can select suitably according to the objective, 0.3-1.4 are preferable and 0.5-1.2 are more. preferable. 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. This is advantageous.

Interlayer adhesion can be adjusted by surface-treating at least one of the support and the protective film.
As the surface treatment of the support, it may be performed in order to increase the adhesive force with the photosensitive layer and can be appropriately selected according to the purpose. Examples include flame treatment, ultraviolet irradiation treatment, high-frequency irradiation treatment, glow discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.
Examples of the surface treatment of the protective film include a treatment of forming an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol on the surface of the protective film. Examples of the method for forming the undercoat layer include a method in which the polymer coating solution is applied to the surface of the protective film and then dried at 30 ° C. to 150 ° C. for 1 to 30 minutes. There is no restriction | limiting in particular as temperature at the time of the said drying, Although it can select suitably according to the objective, 50 to 120 degreeC is preferable.

(Photosensitive laminate)
The photosensitive laminate includes at least a substrate and a photosensitive layer provided on the substrate, and further includes other layers as necessary.

<Substrate>
The substrate is not particularly limited and may be appropriately selected depending on the intended purpose as long as it becomes a substrate to be processed on which the photosensitive layer is formed or a transfer target to which at least the photosensitive layer of the photosensitive film is transferred. For example, it can be arbitrarily selected from those having high surface smoothness to those having an uneven surface.
There is no restriction | limiting in particular as a shape of the said base | substrate, Although it can select suitably according to the objective, A plate shape is preferable, Specifically, the board | substrate (printed circuit board) for well-known printed wiring board manufacture, a glass plate (Soda glass plate, etc.), synthetic resin film, paper, metal plate and the like.

<Photosensitive layer>
There is no restriction | limiting in particular as said photosensitive layer, According to the objective, it can select suitably, For example, the layer similar to the above-mentioned photosensitive layer etc. are mentioned.

<Method for producing photosensitive laminate>
There is no restriction | limiting in particular as a manufacturing method of the said photosensitive laminated body, According to the objective, it can select suitably, For example, at least any one of a heating and pressurizing at least the photosensitive layer in the photosensitive film of this invention. There is a method of transferring and laminating while performing.
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 temperature of the said heating, Although it can select suitably according to the objective, 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, Although it can select suitably according to the objective, 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 and pressurization, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator Co., Ltd. make, VP-II, Nichigo Morton stock) A product made by company, VP130) and the like are preferable.

  Since the photosensitive film and the photosensitive laminate of the present invention have a uniform film thickness and an extremely low occurrence rate of surface defects such as pinholes and repellencies, they have excellent insulating properties and high-definition permanent patterns (protective films) , Interlayer insulating film, solder resist pattern, etc.) can be formed efficiently. Therefore, it can be widely used for forming a high-definition permanent pattern in the field of electronic materials, and can be suitably used particularly 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 said exposure process is a process of exposing with respect to the photosensitive layer in the photosensitive laminated body of this invention. The photosensitive laminate of the present invention is as described above.

  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.

  The exposure target is not particularly limited as long as it is a photosensitive layer in the photosensitive laminate, and can be appropriately selected according to the purpose. For example, as described above, a photosensitive film is formed on a substrate. It is preferably performed on a photosensitive laminate formed by laminating while performing at least one of heating and pressurization.

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

-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 unexposed part, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  The developer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include weak alkaline aqueous solutions, aqueous developers, organic solvents, etc. Among these, weak alkaline aqueous solutions are preferable. . Examples of the basic component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.

There is no restriction | limiting in particular as pH of the weak alkaline aqueous solution which is the said developing solution, Although it can select suitably according to the objective, 8-12 are preferable and 9-11 are more preferable.
There is no restriction | limiting in particular as said weak alkaline aqueous solution, According to the objective, it can select suitably, For example, 0.1 mass%-5 mass% sodium carbonate aqueous solution, 0.1 mass%-5 mass% Examples thereof include an aqueous potassium carbonate solution.

  There is no restriction | limiting in particular as temperature of the said developing solution, Although it can select suitably according to the developability of the said photosensitive layer, About 25 to 40 degreeC is preferable.

  The developer is a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.), to accelerate development. You may use together with organic solvents (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

-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.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the photosensitive laminate on which the permanent pattern is formed after the development. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Examples of the entire surface heat treatment method include a method of heating the entire surface of the photosensitive laminate on which the permanent pattern is formed after the development. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
The heating temperature in the entire surface heating is preferably 120 ° C to 250 ° C, more preferably 120 ° C to 200 ° C. When the heating temperature is 120 ° C. or higher, the film strength is improved by heat treatment, and when the heating temperature is 250 ° C. or lower, the resin in the photosensitive composition is decomposed to prevent the film quality from being weak and brittle.
The heating time in the entire surface heating is preferably 10 minutes to 120 minutes, more preferably 15 minutes to 60 minutes.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are 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 the printed wiring board by the permanent pattern forming method. Further, 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 wiring 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. And a semiconductor, components, etc. are mounted in the part which soldered. At this time, the permanent pattern by the hardened layer functions as a protective film, an insulating film (interlayer insulating film), and 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 said other 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 of the present invention will be described below, but the present invention is not limited to these examples.

(Synthesis Example 1)
<Synthesis of ethylenically unsaturated group-containing polyurethane resin U1>
In a 500 mL three-necked round bottom flask equipped with a condenser and a stirrer, 4.57 g (0.06 mol) of propylene glycol (PG), 19.31 g of 2,2-bis (hydroxymethyl) propionic acid (DMPA) (0.144 mol) and 23.06 g (0.144 mol) of glycerol monomethacrylate (GLM) were dissolved in cyclohexanone. To this, 60.06 g (0.240 mol) of 4,4′-diphenylmethane diisocyanate (MDI), 10.09 g (0.06 mol) of hexamethylene diisocyanate (HMDI), 2,6-di-t-butylhydroxytoluene (BHT) 0.18 g, 0.35 g of a trade name: Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) was added as a catalyst, and the mixture was heated and stirred at 75 ° C. for 5 hours. Then, it diluted with cyclohexanone, diluted, and stirred for 30 minutes, and 260.22 g of ethylenically unsaturated group containing polyurethane resin U1 solution (solid content 45 mass%) was obtained.
The obtained ethylenically unsaturated group-containing polyurethane resin U1 solution had a solid content acid value of 69 mgKOH / g, and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) was 7,000. Yes, the ethylenically unsaturated group equivalent was 1.23 mmol / g. The mass composition ratio of the aromatic group converted from the composition was 34% by mass.
The acid value was measured according to JIS K0070. However, when the sample did not dissolve, dioxane or tetrahydrofuran was used as a solvent.
The said weight average molecular weight was measured using the high-speed GPC apparatus (The Toyo Soda Co., Ltd. make, HLC-802A). That is, a 0.5 mass% THF solution was used as a sample solution, 62 columns of TSKgelGMH were used, 200 μL of a sample was injected, eluted with the THF solution, and measured with a refractive index detector at 25 ° C. Next, the weight average molecular weight was determined from the molecular weight distribution curve calibrated with standard polystyrene.
The said ethylenically unsaturated group equivalent was calculated | required by measuring a bromine number based on JISK2605.
The structural formulas of the compounds used are shown in Table 1-1. Table 3 shows the solid content acid value, weight average molecular weight, ethylenically unsaturated group equivalent, and mass composition ratio of the aromatic group of the obtained ethylenically unsaturated group-containing polyurethane resin.

(Synthesis Examples 2-9)
<Synthesis of ethylenically unsaturated group-containing polyurethane resin (U2 to U9)>
In the same manner as in Synthesis Example 1, using the diisocyanate compounds shown in Table 1-1 and Table 1-2 below and compounds having a polyfunctional alcohol group, an ethylenically unsaturated group-containing polyurethane resin (U2 to U9) Was synthesized.
In addition, Table 3 shows the solid content acid value, weight average molecular weight, ethylenically unsaturated group equivalent, and mass composition ratio of the aromatic group of the obtained ethylenically unsaturated group-containing polyurethane resin.

(Comparative Synthesis Examples 1 to 5)
<Synthesis of ethylenically unsaturated group-containing polyurethane resin (U10 to U14)>
In the same manner as in Synthesis Example 1, an ethylenically unsaturated group-containing polyurethane resin (U10 to U14) was synthesized using the diisocyanate compound shown in Table 2 below and a compound having a polyfunctional alcohol group.
In addition, Table 3 shows the solid content acid value, weight average molecular weight, ethylenically unsaturated group equivalent, and mass composition ratio of the aromatic group of the obtained ethylenically unsaturated group-containing polyurethane resin.

(Comparative Synthesis Example 6)
<Synthesis of ethylenically unsaturated group-containing polyurethane resin (U15)>
In a three-necked round-bottom flask equipped with a condenser and a stirrer, 52.56 g (0.360 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) was dissolved in 189 mL of propylene glycol monomethyl ether monoacetate. . To this, 75.08 g (0.300 mol) of 4,4′-diphenylmethane diisocyanate (MDI), 0.46 g of 2,6-di-t-butylhydroxytoluene, Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) 0 .46 g was added and stirred at 75 ° C. for 5 hours. Thereafter, 27.29 g (0.192 mol) of glycidyl methacrylate (GMA) and catalyst triphenylphosphine were further added to the solid content of 5,000 ppm, and the mixture was stirred at 110 ° C. for 5 hours, and then to room temperature. After cooling, 344 g of a polyurethane resin U15 solution (solid content: 45% by mass) was obtained.
The obtained polyurethane resin U15 solution has a solid content acid value of 61 mgKOH / g, a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) of 7500, and a photopolymerizable group equivalent ( Vinyl group equivalent) was 1.24 mmol / g. The composition mass ratio of the aromatic group converted from the composition was 32 mass%.
The structural formulas of the compounds used are shown in Table 2. Table 3 shows the solid content acid value, weight average molecular weight, ethylenically unsaturated group equivalent, and mass composition ratio of the aromatic group of the obtained ethylenically unsaturated group-containing polyurethane resin.

Example 1
<Preparation of photosensitive composition coating solution>
The following components were mixed to prepare a photosensitive composition coating solution.
Specifically, the following components were mixed and dispersed for 1.5 hours in a bead mill (Eiger Mill M-50, manufactured by Eiger Japan, media; zirconia beads having a diameter of 1 mm, filling rate 75% by volume), and photosensitive. A composition coating solution was prepared.
-Composition of photosensitive composition solution-
-Solution of ethylenically unsaturated group-containing polyurethane resin U1 of Synthesis Example 1 32.3 parts by mass (solid content 45% by mass)
-Color pigment (HELIOGEN BLUE D7086) 0.021 parts by mass (BASF)
Coloring pigment (Pariotolol D0960) 0.006 parts by mass (BASF)
・ Dispersant (Solsperse 24000GR) 0.22 parts by mass (manufactured by Loop Resor)
-Polymerizable compound (dihydrodicyclopentadienyl diacrylate) 5.3 parts by mass (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.)
・ 0.6 parts by mass of photopolymerization initiator (IRG907, manufactured by Ciba Specialty Chemicals Co., Ltd.)
Sensitizer (DETX-S, Nippon Kayaku Co., Ltd.) 0.005 parts by mass Reaction aid (EAB-F, Hodogaya Chemical Co., Ltd.) 0.019 parts by mass Curing agent (melamine, Wako Jun) 0.16 parts by mass of thermal crosslinker (epoxy compound) 2.9 parts by mass (Epototo YDF-170, manufactured by Tohto Kasei Co., Ltd.)
Filler (SO-C2, manufactured by Admatex) 16.0 parts by mass Ion trap agent (IXE-6107, manufactured by Toagosei Co., Ltd.) 0.82 parts by mass Application aid (30% by mass methyl ethyl ketone solution) 2 parts by mass (Megafac F-780F, manufactured by Dainippon Ink & Chemicals, Inc.)
Elastomer (Esper 1612, manufactured by Hitachi Chemical Co., Ltd.) 2.7 parts by mass Solvent (cyclohexanone) 38.7 parts by mass

<Manufacture of photosensitive film>
The photosensitive composition solution was applied on 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. On the photosensitive layer, as a protective layer, a polypropylene film having a thickness of 20 μm (manufactured by Oji Specialty Paper Co., Ltd., Alphan E-200) was laminated to produce a photosensitive film.

<Production of photosensitive laminate>
The substrate was prepared by subjecting the surface of a copper-clad laminate (no through-hole, copper thickness 12 μm) on which wiring had been formed to a chemical polishing treatment. A vacuum laminator (manufactured by Nichigo Morton Co., Ltd., VP130) was peeled off on the copper-clad laminate so that the photosensitive layer of the photosensitive film was in contact with the copper-clad laminate. Thus, a photosensitive laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order was manufactured. The pressure bonding conditions were a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressing time of 10 seconds.

<Formation of permanent pattern>
-Exposure process-
From the polyethylene terephthalate film (support) side to the photosensitive layer in the manufactured photosensitive laminate, using an exposure machine for circuit board EXM-1172 (manufactured by Oak Manufacturing Co., Ltd.) through a photomask at 40 mJ / cm ² It was exposed to cure some areas 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 pattern.

-Curing process-
The entire surface of the photosensitive laminate on which the pattern was formed was subjected to a heat treatment at 150 ° C. for 1 hour to cure the surface of the pattern, increase the film strength, and form a permanent pattern.

(Examples 2-9)
In Example 1, the ethylenically unsaturated group-containing polyurethane resin U1 solution of Synthesis Example 1 was replaced with the solution of the ethylenically unsaturated group-containing polyurethane resins U2 to U9 of Synthesis Examples 2 to 9 (solid content 45 as shown in Table 4). A photosensitive composition solution was prepared in the same manner as in Example 1 except that the composition was changed to (mass%), and a photosensitive film, a photosensitive laminate, and a permanent pattern were produced using these photosensitive compositions. did.

(Example 10)
In Example 1, the thermal crosslinking agent was replaced from the epoxy compound (YDF-170, manufactured by Toto Kasei Co., Ltd.) to the oxetane compound (OXT-121, manufactured by Toagosei Co., Ltd.) so that the solid content was the same amount. In the same manner as in Example 1, photosensitive composition solutions were prepared, and a photosensitive film, a photosensitive laminate, and a permanent pattern were produced using these photosensitive compositions.

(Example 11)
In Example 1, the thermal crosslinking agent was changed from an epoxy compound (YDF-170, manufactured by Tohto Kasei Co., Ltd.) to a blocked isocyanate compound (a compound obtained by reacting an isocyanate compound with a blocking agent; Desmodur BL-3175, Sumika Bayer) Urethane Co., Ltd.) was replaced so that the solid content was the same amount, and the curing composition was changed from melamine to Neostan U-600 (Nitto Kasei Co., Ltd.). Each product solution was prepared, and a photosensitive film, a photosensitive laminate, and a permanent pattern were produced using these photosensitive compositions.

(Example 12)
In Example 1, except that the curing agent was replaced from melamine (manufactured by Wako Pure Chemical Industries, Ltd.) to DICY-7 (manufactured by Yuka Shell Epoxy Co., Ltd.) so that the solid content was the same amount, Example 1 In the same manner as above, a photosensitive composition solution was prepared, and a photosensitive film, a photosensitive laminate, and a permanent pattern were produced using the photosensitive composition.

(Comparative Examples 1-6)
In Example 1, the ethylenically unsaturated group-containing polyurethane resin U1 solution of Synthesis Example 1 was replaced with the ethylenically unsaturated group-containing polyurethane resin U10 to U15 solution of Comparative Example Synthesis Examples 1 to 6 as shown in Table 4 (solid content). A photosensitive composition solution was prepared in the same manner as in Example 1 except that the composition was changed to 45% by mass, and a photosensitive film, a photosensitive laminate, and a permanent pattern were formed using these photosensitive compositions. Manufactured.

(Comparative Example 7)
In Comparative Example 1, the thermal crosslinking agent was changed from an epoxy compound (YDF-170, manufactured by Tohto Kasei Co., Ltd.) to an oxazoline derivative (1,3-bis (4,5-dihydro-2-oxazolyl) benzene, manufactured by Tokyo Chemical Industry Co., Ltd. ), A photosensitive composition solution was prepared in the same manner as in Example 1 except that the curing agent was changed from melamine to n-octyl bromide, and a photosensitive film and a laminate were prepared using the photosensitive composition. And permanent patterns were produced.

(Comparative Example 8)
In Example 1, the thermal crosslinking agent was changed from an epoxy compound (YDF-170, manufactured by Tohto Kasei Co., Ltd.) to an oxazoline derivative (1,3-bis (4,5-dihydro-2-oxazolyl) benzene, manufactured by Tokyo Chemical Industry Co., Ltd. ), A photosensitive composition solution was prepared in the same manner as in Example 1 except that the curing agent was changed from melamine to n-octyl bromide, and a photosensitive film and a laminate were prepared using the photosensitive composition. And permanent patterns were produced.

(Evaluation)
About each photosensitive composition solution, photosensitive film, photosensitive laminated body, and permanent pattern obtained in Examples 1-12 and Comparative Examples 1-8, surface hardness, folding resistance, insulation were as follows. , Solder heat resistance, thermal shock resistance, and plating resistance were evaluated. The results are shown in Table 4.

<Surface hardness>
The permanent pattern formed in Examples 1 to 12 and Comparative Examples 1 to 8 has the highest hardness without scratching the film when a load of 1 kg is applied using a pencil hardness tester according to the test method of JIS K-5400. The evaluation was made according to the following criteria. The results are shown in Table 4.
〔Evaluation criteria〕
◎: More than 4H and excellent surface hardness ○: 3H or more and 4H or less, surface hardness is slightly excellent ○: 2H or more and less than 3H, surface hardness is slightly inferior ×: Less than 2H, surface hardness is inferior

<Folding resistance>
Using the photosensitive films produced in Examples 1 to 12 and Comparative Examples 1 to 8, folding resistance was evaluated using the photosensitive laminates for evaluation obtained as described below.
First, a dry film resist was laminated on a substrate for flexible printed wiring boards (made by Nippon Steel Chemical Co., Ltd., trade name “ESPANEX MB” series) in which a copper foil with a thickness of 18 μm was laminated on a polyimide substrate (thickness 25 μm), and 200 mJ After exposure at / cm ² , development and etching were performed under the condition of 0.15 MPa / 90 s to produce a copper foil line pattern of L / S = 100/100 μm.
Next, the photosensitive layer produced on the obtained polyimide base material with a copper foil line pattern was laminated on the copper foil line pattern side, and the photosensitive laminated body for evaluation was obtained by exposing at 1,000 mJ / cm < ² >.
With the line pattern side of the obtained photosensitive laminate for evaluation being outside, the state of the folded part when it was folded 180 ° was observed visually and with a microscope (magnification: 200 times), and evaluated according to the following criteria. The results are shown in Table 4.
〔Evaluation criteria〕
○: No crack occurred △: Crack occurred only at the edge of the film ×: Crack occurred throughout the bent part

<Insulation>
Using the photosensitive composition solutions prepared in Examples 1-12 and Comparative Examples 1-8, the insulating properties of the evaluation substrates obtained as described below were evaluated.
First, the copper foil of the printed circuit board obtained by laminating a 12 μm thick copper foil on a glass epoxy base material is etched, the line width / space width is 50 μm / 50 μm, and the lines are not in contact with each other and are opposed to each other A comb electrode on the same surface was obtained. A photosensitive layer was formed on each comb-shaped electrode of this substrate by a conventional method using each photosensitive composition solution, and exposed at an optimum exposure amount (300 mJ / cm ^{2 to 1} J / cm ² ).
Next, after allowing to stand at room temperature for 1 hour, spray development was performed for 60 seconds with a 1% by mass aqueous sodium carbonate solution at 30 ° C., followed by heating (drying) at 80 ° C. for 10 minutes. Subsequently, the photosensitive layer was irradiated with ultraviolet rays with an energy amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by Oak Seisakusho. Further, the photosensitive layer was heat-treated at 150 ° C. for 60 minutes to obtain an evaluation substrate on which a solder resist was formed.
After connecting the polytetrafluoroethylene shield wires to the comb electrodes by Sn / Pb solder so that a voltage is applied between the comb electrodes of the evaluation substrate after heating, a voltage of 5 V is applied to the evaluation substrate. In the applied state, the substrate for evaluation was allowed to stand in a super accelerated high temperature high humidity life test (HAST) bath of 85% RH at 130 ° C. for 200 hours. The degree of occurrence of solder resist migration of the subsequent evaluation substrate was observed with a 100 × metal microscope. The results are shown in Table 4.
〔Evaluation criteria〕
A: The occurrence of migration cannot be confirmed, and the insulation is excellent. ○: The occurrence of migration is slightly confirmed on copper, but the insulation is good. ○: The occurrence of migration is confirmed, and the insulation is slightly inferior. : Migration is confirmed and the insulation is poor. ×: The electrodes are short-circuited and the insulation is poor.

<Solder heat resistance>
A rosin-based flux or a water-soluble flux was applied to each of the obtained substrates for evaluation, and immersed in a solder bath at 260 ° C. for 10 seconds. After repeating this for 6 cycles, the appearance of the coating film was visually observed and evaluated according to the following criteria. The results are shown in Table 4.
〔Evaluation criteria〕
○: There is no abnormality (peeling, swelling) in the appearance of the coating film, and there is no solder peeling.
Δ: Abnormality (peeling, blistering) in coating film appearance, or solder fluffing, but light to the extent ×: Abnormality (peeling, blistering) in coating film appearance, or solder flakinging Something heavy

<Cool thermal shock>
Using the photosensitive films produced in Examples 1 to 12 and Comparative Examples 1 to 8, test thermal shock resistance was evaluated as a reliability test item for the test plates obtained as described below.
First, each photosensitive film is pressure-bonded on a copper-clad laminate (glass epoxy substrate) from which the copper foil has been removed by etching (pressure-bonding conditions; pressure-bonding temperature 70 ° C., pressure-bonding pressure 0.2 MPa, pressure time 10 seconds). Laminated.
Next, from the polyethylene terephthalate film (support) side, using a circuit board exposure machine EXM-1172 (manufactured by Oak Manufacturing Co., Ltd.), exposure is performed at 40 mJ / cm ² through a photomask having a square pattern of 5 mm × 5 mm. A part of the photosensitive layer was cured.
And the development process and the hardening process were performed like the said image development process and the said hardening process process, and the test plate was obtained.
About these obtained test boards, the external appearance and resistance value change rate, such as a crack and peeling, were evaluated by the temperature cycle test (TCT). TCT used a vapor-phase cooling / heating tester, and the electronic component module was left in the vapor phase at temperatures of −55 ° C. and 125 ° C. for 30 minutes each. This was performed under the conditions of 1,000 cycles and 1,500 cycles as one cycle, and the thermal shock resistance was evaluated according to the following criteria. The results are shown in Table 4.
〔Evaluation criteria〕
○: No crack occurred △: Shallow crack occurred ×: Deep crack occurred

<Plating resistance>
The plating resistance of the permanent pattern obtained as follows was evaluated.
The photosensitive laminated body manufactured in Examples 1-12 and Comparative Examples 1-8 except having used what carried out the chemical polishing process on the surface of a copper clad laminated board (no through-hole, copper thickness 12 micrometers) as a base | substrate. A photosensitive laminate produced in the same manner as above was used.
Using the circuit board exposure machine EXM-1172 (manufactured by Oak Manufacturing Co., Ltd.) on the surface of the photosensitive layer of the prepared photosensitive laminate, an independent wiring of 30 μm to 1,000 μm at an optimal exposure amount through a photomask. After forming a pattern and allowing to stand at room temperature for 10 minutes, the support is peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is applied to the entire surface of the photosensitive layer on the copper clad laminate. Spray development was performed at a spray pressure of 0.15 MPa for 2 to 3 times the shortest development time (or 40 to 60 seconds), and uncured regions were dissolved and removed. Thereafter, the entire surface was exposed at 200 mJ / cm ² with an ultrahigh pressure mercury lamp, and further subjected to heat treatment (post-bake) at 150 ° C. for 1 hour to form a permanent pattern. The results are shown in Table 4.
〔Evaluation criteria〕
○: No peeling at all Δ: No peeling at an image having a line width of less than 500 μm ×: peeling at an image having a line width of 500 μm or more

From the results of Table 4, in Examples 1 to 12, where the ethylenically unsaturated group equivalent is 1.2 mmol / g or more and 1.5 mmol / g or less, the unsaturated group equivalent is less than 1.2 mmol / g. It turned out that it is excellent in bending resistance and solder heat resistance compared with the comparative example 3 and the comparative examples 1 and 2 in which the said unsaturated group equivalent exceeds 1.5 mmol / g.
Moreover, Examples 1-12 whose mass composition ratio of the said aromatic group is 30 mass% or more compared with the comparative example 4 whose said mass composition ratio is less than 30 mass%, surface hardness, folding resistance, It was found to be excellent in insulation, solder heat resistance, and thermal shock resistance.
Moreover, Examples 1-12 in which the said ethylenically unsaturated group containing polyurethane resin contains the structural unit represented by the said general formula (I) are compared with the comparative examples 5 and 6 which do not contain the said structural unit, It was found to be excellent in folding resistance, insulation and solder heat resistance.
Moreover, Examples 1-12 in which the said thermal crosslinking agent contains at least any one of the compound obtained by making a blocking agent react with an epoxy compound, an oxetane compound, and an isocyanate compound are the comparative example 7 which does not contain the said thermal crosslinking agent, and Compared to 8, it was found to be excellent in folding resistance, insulation and plating resistance.

The photosensitive composition of the present invention not only improves surface hardness, thermal shock resistance, plating resistance, and insulation, but also has excellent folding resistance and solder heat resistance, so it can be suitably used for a solder resist. it can.
Since the photosensitive film of the present invention can efficiently form a high-definition permanent pattern, various patterns such as a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern, BGA (ball grid array), Suitable for semiconductor package formation such as CSP (chip size package) and TCP (tape carrier package), manufacturing of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, proofs, etc. In particular, it can be suitably used for forming a permanent pattern of a printed circuit board, forming a semiconductor package such as BGA (ball grid array), CSP (chip size package), and TCP (tape carrier package).
Since the pattern forming method of the present invention uses the photosensitive composition, it is used for forming semiconductor packages such as BGA (ball grid array), CSP (chip size package), and TCP (tape carrier package), a protective film, and an interlayer insulating film. And suitable for forming various patterns such as permanent patterns such as solder resist patterns, manufacturing of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, micromachines, and proofs. In particular, it can be suitably used for forming a permanent pattern of a printed circuit board, forming a semiconductor package such as BGA (ball grid array), CSP (chip size package), TCP (tape carrier package).

Claims (9)

It contains at least an ethylenically unsaturated group-containing polyurethane resin, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent,
The ethylenically unsaturated group equivalent of the ethylenically unsaturated group-containing polyurethane resin is 1.2 mmol / g or more and 1.5 mmol / g or less, and the mass composition ratio of the aromatic group is 30% by mass or more,
The thermal crosslinking agent comprises at least one of an epoxy compound, an oxetane compound, a compound obtained by reacting an isocyanate compound with a blocking agent, and a melamine derivative,
The said ethylenically unsaturated group containing polyurethane resin contains the structural unit represented by the following general formula (I), The photosensitive composition characterized by the above-mentioned.
However, in said general formula (I), R < ¹ >, R < ² > and R < ³ > may mutually be the same and may differ, respectively, and each represents a hydrogen atom or monovalent organic group, A is Represents a divalent organic residue, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, and R ¹² represents a hydrogen atom or a monovalent organic group. The ethylenically unsaturated group-containing polyurethane resin contains an aromatic group represented by the following general formula (1-1), and the mass composition ratio of the aromatic group represented by the general formula (1-1) is 30% by mass. It is the above, The photosensitive composition of Claim 1.
However, in the general formula (1-1), X represents a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —CO—, or —O—. To express. R ¹ , R ² , R ³ , and R ⁴ may be the same as or different from each other, and each represents a hydrogen atom, a monovalent organic group, a halogen atom, —OR ⁵ , —N ( R ⁶ ) (R ⁷ ) or —SR ⁸ , and R ⁵ , R ⁶ , R ⁷ , and R ⁸ each represent a hydrogen atom or a monovalent organic group. The ethylenically unsaturated group-containing polyurethane resin contains an aromatic group represented by the following general formula (1-2), and the mass composition ratio of the aromatic group represented by the general formula (1-2) is 30 masses. % Of the photosensitive composition according to claim 1.
However, in the general formula (1-2), X represents a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —CO—, or —O—. To express.   The ethylenically unsaturated group-containing polyurethane resin is a polyurethane resin containing a structural unit represented by a reaction product of a compound having a monofunctional or polyfunctional alcohol group and 4,4′-diphenylmethane diisocyanate (MDI). The photosensitive composition according to any one of claims 1 to 3. The ethylenically unsaturated group-containing polyurethane resin is a polyurethane resin containing a structural unit represented by a reaction product of a compound having a monofunctional or polyfunctional alcohol group and 4,4′-diphenylmethane diisocyanate (MDI). Yes,
The photosensitive composition according to any one of claims 1 to 4, wherein a mass composition ratio of the MDI in the ethylenically unsaturated group-containing polyurethane resin is 30% by mass or more.   A photosensitive film comprising a photosensitive layer containing the photosensitive composition according to claim 1 on a support.   A photosensitive laminate comprising a photosensitive layer containing the photosensitive composition according to claim 1 on a substrate.   A method for forming a permanent pattern, comprising at least exposing a photosensitive layer formed of the photosensitive composition according to claim 1.   A printed circuit board, wherein a permanent pattern is formed by the permanent pattern forming method according to claim 8.