JP2012177777A - Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern formation method and printed substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition allowing all of flame retardance, prevention of bleed-out of flame retardant components and fracture resistance; and a photosensitive film and the like using the photosensitive composition.SOLUTION: A photosensitive composition contains a flame retardant, a resin having an urethane structure and a photoinitiator, where the above flame retardant is at least any of a cyclotriphosphazene compound, an aromatic phosphonate compound and a compound represented by the following general formula (A) and has at least one kind of hydrogen bonding group from an amide group, an urea group and an urethane group. (In the general formula (A), at least one of Rto Ris a monovalent organic group having at least any of an amide group, an urea group and an urethane group. m represents 0 or 1.)

Description

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

  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 film is laminated on a substrate such as a copper-clad laminate on which a permanent pattern is formed to form a laminate, and the photosensitive layer in the laminate is formed. There is known a method of forming a permanent pattern by performing exposure on the substrate, developing the photosensitive layer after the exposure to form a pattern, and then performing a curing process or the like.

  In the photosensitive composition that can be used for the solder resist, it is one of important issues to improve the flame resistance while improving the flame retardancy, and various studies have been made.

For example, (A) a soluble polyimide having solubility in tetrahydrofuran, and (B) a compound having a 10% weight loss temperature of 300 ° C. or more and 500 ° C. or less and containing a phosphorus atom and a nitrogen atom in one molecule And (C) a photosensitive resin composition containing a (meth) acrylic compound, wherein (B) is a cyclic phosphazene compound substituted with an organic group or a hydrogen atom (see Patent Document 1). .
Moreover, the photosensitive flame retardant composition containing the component which has an ethylenically unsaturated double bond and a carboxyl group, and a specific flame retardant is proposed (refer patent document 2).

  However, these proposed techniques have a problem that the flame retardant component bleeds out from the cured film.

  Moreover, the photosensitive resin composition containing the cyclophosphazene compound which has a specific functional group in a benzene ring is proposed (refer patent document 3).

  However, although the proposed technique can prevent bleed out due to the flame retardant component and has good folding resistance, it has a problem that it cannot sufficiently meet the demand for flame retardancy demanded in recent years.

  Therefore, a photosensitive composition having all of flame retardancy, prevention of bleeding out of the flame retardant component, and folding resistance, and a photosensitive film, a photosensitive laminate, and the photosensitive composition using the photosensitive composition, At present, there is a demand for providing a permanent pattern forming method and a printed circuit board.

Japanese Patent No. 4006677 JP 2010-250032 A JP 2009-98456 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention is a photosensitive composition having all of flame retardancy, prevention of bleed-out of the flame retardant component, and folding resistance, and a photosensitive film, a photosensitive laminate, and the like using the photosensitive composition. An object is to provide a method for forming a permanent pattern and a printed circuit board.

Means for solving the problems are as follows. That is,
<1> Contains a flame retardant, a resin having a urethane structure, and a photopolymerization initiator,
The flame retardant is at least one of a cyclotriphosphazene compound, an aromatic phosphonate compound, and a compound represented by the following general formula (A), and at least one of an amide group, a urea group, and a urethane group It is a photosensitive composition characterized by having a hydrogen bonding group.
In the general formula ^{(A), R} 1 ~R ¹³ are each independently hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, and , An amide group, a urea group, and a monovalent organic group having at least one of a urethane group. Note that at least one of R ^{1 to} R ¹³ is a monovalent organic group having at least one of an amide group, a urea group, and a urethane group. m represents 0 or 1.
<2> The photosensitive composition according to <1>, wherein the cyclotriphosphazene compound is a compound represented by the following general formula (B).
However, Ar < ¹ > -Ar < ⁶ > is group represented by the following general formula (B-1) in the said general formula (B).
In the general formula ^{(B-1), R 14} ~R 18 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms And having at least one of an alkoxy group having 1 to 10 carbon atoms, an alkylyloxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, an amide group, a urea group, and a urethane group; It represents one of monovalent organic groups having no (meth) acrylate group. Note that at least one of R ^{14 to} R ¹⁸ is a monovalent organic group having at least one of an amide group, a urea group, and a urethane group and having no (meth) acrylate group.
<3> The photosensitive composition according to <1>, wherein the aromatic phosphonate compound is at least one of a compound represented by the following general formula (C) and a compound represented by the following general formula (D). It is.
In the general formula ^{(C), R} 19 ~R ³³ are each independently hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, carbon A monovalent organic having at least any one of an alkoxy group having 1 to 10 carbon atoms, an alkyloxyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, and an amide group, a urea group, and a urethane group Represents any of the groups. Note that at least one of R ^{19 to} R ³³ is a monovalent organic group having at least one of an amide group, a urea group, and a urethane group.
In the general formula ^{(D), R} 34 ~R ⁵³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, carbon A monovalent organic having at least any one of an alkoxy group having 1 to 10 carbon atoms, an alkyloxyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, and an amide group, a urea group, and a urethane group Represents any of the groups. Note that at least one of R ^{34 to} R ⁵³ is a monovalent organic group having at least one of an amide group, a urea group, and a urethane group. R ^a and R ^b each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
<4> A photosensitive film comprising a photosensitive layer containing the photosensitive composition according to any one of <1> to <3> on a support.
<5> A photosensitive laminate comprising a photosensitive layer containing the photosensitive composition according to any one of <1> to <3> on a substrate.
<6> A method for forming a permanent pattern, comprising at least exposing a photosensitive layer formed of the photosensitive composition according to any one of <1> to <3>.
<7> A printed circuit board wherein a permanent pattern is formed by the method for forming a permanent pattern according to <6>.

  According to the present invention, the above-mentioned problems can be solved and the object can be achieved, and a photosensitive composition having all of flame retardancy, prevention of bleed-out of flame retardant components, and folding resistance, and A photosensitive film, a photosensitive laminate, a method for forming a permanent pattern, and a printed board using the photosensitive composition can be provided.

(Photosensitive composition)
The photosensitive composition of the present invention contains at least a flame retardant, a resin having a urethane structure, and a photopolymerization initiator, preferably contains a polymerizable compound and a thermal cross-linking agent, and, if necessary, other Contains the ingredients.

<Flame Retardant>
The flame retardant is at least one of a cyclotriphosphazene compound, an aromatic phosphonate compound, and a compound represented by the following general formula (A), and includes at least one of an amide group, a urea group, and a urethane group. Has a hydrogen bonding group.
In the general formula ^{(A), R} 1 ~R ¹³ are each independently hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, and , An amide group, a urea group, and a monovalent organic group having at least one of a urethane group. Note that at least one of R ^{1 to} R ¹³ is a monovalent organic group having at least one of an amide group, a urea group, and a urethane group. m represents 0 or 1.

The aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ¹ to R ¹³ in the general formula (A), is not particularly limited and may be appropriately selected depending on the intended purpose, of 1 to 6 carbon atoms An aliphatic hydrocarbon group is preferable, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable. As said C1-C10 aliphatic hydrocarbon group, a methyl group, an ethyl group, n-propyl group, n-butyl group, t-butyl group, n-hexyl group etc. are mentioned, for example.
The aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ¹³ of formula (A), is not particularly limited and may be appropriately selected depending on the purpose, a phenyl group, a naphthyl group preferable.

Amide group in R ¹ to R ¹³ of formula (A), the monovalent organic group having at least one urea group and urethane group, is not particularly limited, may be appropriately selected according to the purpose However, from the viewpoint of excellent flame retardancy, a monovalent organic group having 1 to 20 carbon atoms is preferable, a monovalent organic group having 2 to 15 carbon atoms is more preferable, and a monovalent organic group having 2 to 10 carbon atoms is preferable. The group is particularly preferred.

There is no restriction | limiting in particular as said cyclotriphosphazene compound, Although it can select suitably according to the objective, The compound represented with the following general formula (B) is preferable.
However, Ar < ¹ > -Ar < ⁶ > is group represented by the following general formula (B-1) in the said general formula (B).
In the general formula ^{(B-1), R 14} ~R 18 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms And having at least one of an alkoxy group having 1 to 10 carbon atoms, an alkylyloxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, an amide group, a urea group, and a urethane group; It represents one of monovalent organic groups having no (meth) acrylate group. Note that at least one of R ^{14 to} R ¹⁸ is a monovalent organic group having at least one of an amide group, a urea group, and a urethane group and having no (meth) acrylate group.

Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms in ^R 14 ^{to R 18} in the general formula (B-1), is not particularly limited and may be appropriately selected depending on the intended purpose, 1 to carbon atoms 6 aliphatic hydrocarbon groups are preferable, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable. As said C1-C10 aliphatic hydrocarbon group, a methyl group, an ethyl group, n-propyl group, n-butyl group, t-butyl group, n-hexyl group etc. are mentioned, for example.
There is no restriction | limiting in particular as a C6-C10 aromatic hydrocarbon group in R < ¹⁴ > -R < ¹⁸ > of the said general formula (B-1), Although it can select suitably according to the objective, A phenyl group, a naphthyl Groups are preferred.
The alkoxy group having 1 to 10 carbon atoms in ^R 14 ^{to R 18} in the general formula (B-1), is not particularly limited and may be appropriately selected depending on the intended purpose, alkoxy of 1 to 6 carbon atoms Group is preferable, and an alkoxy group having 1 to 3 carbon atoms is more preferable. As said C1-C10 alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, n-butoxy group, n-hexyloxy group etc. are mentioned, for example.
The alkyloyl group having 1 to 10 carbon atoms in ^R 14 ^{to R 18} in the general formula (B-1), is not particularly limited and may be appropriately selected depending on the intended purpose, 1 to 6 carbon atoms Are preferred, and an alkyloyloxy group having 1 to 3 carbon atoms is more preferred. Examples of the alkyl group having 1 to 10 carbon atoms include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovaleryloxy group, and a pivaloyloxy group.
As the alkoxycarbonyl group having 1 to 10 carbon atoms in ^R 14 ^{to R 18} in general formula (B-1), is not particularly limited and may be appropriately selected depending on the intended purpose, of 1 to 6 carbon atoms An alkoxycarbonyl group is preferable, and an alkoxycarbonyl group having 1 to 3 carbon atoms is more preferable. Examples of the alkyloxy group having 1 to 10 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, and n-pentyl. An oxycarbonyl group etc. are mentioned.

As carbon number of monovalent organic group which has at least any one of the amide group, urea group, and urethane group in R < ¹⁴ > -R < ¹⁸ > of the said general formula (B-1), and does not have a (meth) acrylate group. The carbon number is not particularly limited and may be appropriately selected depending on the purpose. However, from the viewpoint of excellent flame retardancy, 1 to 20 carbon atoms are preferable, 2 to 15 carbon atoms are more preferable, and 2 to 10 carbon atoms are particularly preferable. preferable.
The (meth) acrylate group means an acryloyl group and a methacryloyl group.

There is no restriction | limiting in particular as said aromatic phosphonate compound, Although it can select suitably according to the objective, The compound represented by the following general formula (C) and the compound represented by the following general formula (D) It is preferably at least one of them.
In the general formula ^{(C), R} 19 ~R ³³ are each independently hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, carbon A monovalent organic having at least any one of an alkoxy group having 1 to 10 carbon atoms, an alkyloxyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, and an amide group, a urea group, and a urethane group Represents any of the groups. Note that at least one of R ^{19 to} R ³³ is a monovalent organic group having at least one of an amide group, a urea group, and a urethane group.
In the general formula ^{(D), R} 34 ~R ⁵³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, carbon A monovalent organic having at least any one of an alkoxy group having 1 to 10 carbon atoms, an alkyloxyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, and an amide group, a urea group, and a urethane group Represents any of the groups. Note that at least one of R ^{34 to} R ⁵³ is a monovalent organic group having at least one of an amide group, a urea group, and a urethane group. R ^a and R ^b each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.

R ^{19 to} R ³³ in the general formula (C), and R ^{34 to} R ⁵³ in the general formula (D), an aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms. The alkoxy group having 1 to 10 carbon atoms, the alkylyl group having 1 to 10 carbon atoms, and the alkoxycarbonyl group having 1 to 10 carbon atoms are not particularly limited and may be appropriately selected depending on the purpose. for example, it may be the same as those exemplified in the description of ^R 14 ^{to R 18} in the general formula (B-1). The preferred range is also the same.

As the monovalent organic group having at least one of an amide group, a urea group, and a urethane group in R ^{19 to} R ³³ of the general formula (C) and R ^{34 to} R ⁵³ of the general formula (D), There is no restriction | limiting in particular, Although it can select suitably according to the objective, From the point which is excellent in a flame retardance, a C1-C20 monovalent organic group is preferable, A C2-C15 monovalent organic group Is more preferable, and a monovalent organic group having 2 to 10 carbon atoms is particularly preferable.

The R ^a, and aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ^b, and aromatic hydrocarbon group having 6 to 10 carbon atoms in the general formula (D), is not particularly limited, depending on the purpose can be appropriately selected, for example, it may be the same as those exemplified in the description of R ¹⁴ to R ¹⁸ in the general formula (B-1). The preferred range is also the same.

Specific examples of the compound represented by the general formula (A) include the following compounds.

Specific examples of the compound represented by the general formula (B) include the following compounds.
However, at least one of Ar is an N-methylaminocarbonylphenyl group, and the other Ar is a methoxycarbonylphenyl group.

Specific examples of the compound represented by the general formula (C) include the following compounds.
However, one of R is the following group, and the other R is a tert-butylphenyl group.

Specific examples of the compound represented by the general formula (D) include the following compounds.
However, at least one of R is the following group, and the other R is a methylphenyl group.
However, at least one of R is an N-methylaminocarbonylphenyl group, and the other R is a methoxycarbonylphenyl group.

  There is no restriction | limiting in particular as content in the said photosensitive composition of the said flame retardant, Although it can select suitably according to the objective, 10 mass%-35 mass with respect to solid content of the said photosensitive composition % Is preferable, 15% by mass to 30% by mass is more preferable, and 20% by mass to 30% by mass is particularly preferable. When the content is less than 10% by mass, sufficient flame retardancy may not be maintained, and when it exceeds 35% by mass, folding resistance may be deteriorated. The more preferable range is advantageous in that high flame retardancy is maintained and folding resistance is excellent.

<Resin having urethane structure>
There is no restriction | limiting in particular as resin which has the said urethane structure, According to the objective, it can select suitably.
As the resin having a urethane structure, an ethylenically unsaturated group-containing polyurethane resin is preferable. Examples of the functional group containing an ethylenically unsaturated group include acryloyl group, methacryloyl group, vinylphenyl group, vinyl ether group, vinyl ester group, allyl group, allyl ether group, and allyl ester group.

-Ethylenically unsaturated group-containing polyurethane resin-
There is no restriction | limiting in particular as an ethylenically unsaturated group equivalent of the said ethylenically unsaturated group containing polyurethane resin, Although it can select suitably according to the objective, More than 1.5 mmol / g is preferable, 1.5 mmol / g More than ultra-3.0 mmol / g is more preferable. A sensitivity may fall that the said ethylenically unsaturated group equivalent is 1.5 mmol / g or less.
The functional group containing an ethylenically unsaturated group is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of sensitivity, an acryloyl group and a methacryloyl group are preferable, but the present invention is particularly limited thereto. It is not limited.
The said ethylenically unsaturated group equivalent can be calculated | required by measuring a bromine number, for example. The bromine number can be measured according to, for example, JIS K2605.

In the ethylenically unsaturated group-containing polyurethane resin, the mass composition ratio of the aromatic group is preferably 30% by mass or more, and more preferably 40% by mass to 70% by mass. If the mass composition ratio is less than 30% by mass, the hardness may decrease.
Here, in the present invention, the term aromatic refers to an aromatic 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 an idiomatic concept.
In addition, when the said aromatic mass ratio contains the structural unit represented by the following general formula (I), X represents the ratio calculated by including in an aromatic.

There is no restriction | limiting in particular as said ethylenically unsaturated group containing polyurethane resin, Although it can select suitably according to the objective, For example, it is preferable that the group represented by the following general formula (I) is included.
However, in the general formula (I), X represents a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —CO—, or —O—. 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 represent a hydrogen atom or a monovalent organic group.
As the X, in view of developing property, _-CH 2 -, - O- are 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 is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, -OR ⁹ (wherein R ⁹ represents a monovalent organic group), an aryl group, an aryloxy group, an arylamino group, a diaryl Monovalent organic groups selected from amino groups and the like are preferred.
Examples of the halogen atom include fluorine, chlorine, bromine and the like.
As said R < ¹ >, R < ² >, R < ³ > and R < ⁴ >, a hydrogen atom, a C1-C20 alkyl group, and -OR < ⁹ > are preferable from a viewpoint of resolution, and a hydrogen atom is especially preferable.

The ethylenically unsaturated group-containing polyurethane resin contains an aromatic group represented by the following general formula (II), and the mass composition ratio of the aromatic group represented by the general formula (II) is 30% by mass. The above is preferable, and 40% by mass to 70% by mass is more preferable. If the mass composition ratio is less than 30% by mass, the hardness may decrease.
In the general formula (II), X represents a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —CO—, or —O—, CH ₂ — and —O— are preferable, and —CH ₂ — is more preferable.

The ethylenically unsaturated group-containing polyurethane resin contains a structural unit represented by a reaction product of a compound having an alcohol group which may be monofunctional or polyfunctional and 4,4′-diphenylmethane diisocyanate (MDI). It is preferable to be a polyurethane resin.
30 mass% or more is preferable and, as for the mass composition ratio of the said MDI in the said ethylenically unsaturated group containing polyurethane resin, 40 mass%-70 mass% are more preferable. If the mass composition ratio is less than 30% by mass, the hardness may decrease.

  There is no restriction | limiting in particular as said ethylenically unsaturated group containing polyurethane resin, According to the objective, it can select suitably, For example, (i) polyurethane resin which has an ethylenically unsaturated group in a side chain, (ii) carboxyl Examples thereof include a polyurethane resin obtained by reacting a group-containing polyurethane with a compound having an ethylenically unsaturated group.

-(I) Polyurethane resin having an ethylenically unsaturated group in the side chain--
The polyurethane resin having an ethylenically unsaturated group in the side chain of (i) is composed of at least one diisocyanate compound represented by the following general formula (i) and a diol compound represented by the following general formula (ii). It is a polyurethane resin having a structural unit represented by the reaction product of at least one kind as a basic skeleton.
OCN-X ⁰ -NCO ... General formula (i)
HO-Y ⁰ -OH ··· general formula (ii)
In the general formulas (i) and (ii), X ⁰ and Y ⁰ each independently represent a divalent organic group.

There is no restriction | limiting in particular as a diisocyanate compound represented by the said general formula (i), According to the objective, it can select suitably, 1 type may be used individually, or 2 or more types may be used together. Good. Examples thereof include a product obtained by addition reaction of a diisocyanate and a triisocyanate compound and one equivalent of a monofunctional alcohol having an ethylenically unsaturated group or a monofunctional amine compound.
The triisocyanate compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraphs [0034] to [0035] of JP-A-2005-250438. It is done.

The diisocyanate compound represented by the general formula (i) is not particularly limited and can be appropriately selected depending on the purpose. In the general formula (i), X ⁰ may have another functional group that does not react with the isocyanate group, for example, an ester, urethane, amide, or ureido group.
Examples of the diisocyanate compound represented by the general formula (i) include 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and p-xylylene diene. Aromatic diisocyanate compounds such as isocyanate, m-xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, 3,3′-dimethylbiphenyl-4,4′-diisocyanate; Aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer diisocyanate; isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) , An cycloaliphatic diisocyanate compound such as methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate A diisocyanate compound which is a reaction product of a diol and a 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 particularly preferable from the viewpoint of hardness.

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

  The polyurethane resin having an ethylenically unsaturated group in the side chain contains the ethylenically unsaturated group from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. It is also possible to copolymerize diisocyanate compounds other than the diisocyanate compound.

There is no restriction | limiting in particular as a diol compound represented by the said general formula (ii), According to the objective, it can select suitably, For example, it has a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, and a carboxyl group Commercially available compounds such as diol compounds and trimethylolpropane monoallyl ether, and compounds such as halogenated diol compounds, triol compounds, aminodiol compounds, and ethylenically unsaturated groups, carboxylic acids, acids It may be a compound that is easily produced by reaction with a compound such as chloride, isocyanate, alcohol, amine, thiol, or halogenated alkyl compound. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as a diol compound containing an ethylenically unsaturated group in a side chain, According to the objective, it can select suitably, For example, Paragraph [0057]-[0060] of Unexamined-Japanese-Patent No. 2005-250438. And the compounds described in paragraphs [0064] to [0066] of JP-A-2005-250438 represented by the following general formula (G). Among these, the compounds described in paragraphs [0064] to [0066] of JP-A-2005-250438 represented by the following general formula (G) are preferable.
However, in said general formula (G), R < ¹ > -R < ³ > represents a hydrogen atom or a monovalent organic group each independently, A represents a bivalent organic group, X is an oxygen atom, a sulfur atom, or -N ^{(R 12)} - represents the ^{R 12} represents a hydrogen atom, or a monovalent organic group.
Here, the monovalent organic group is not particularly limited and may be appropriately selected depending on the purpose. For example, an alkyl group, an alkenyl group, an aromatic which may be unsubstituted or substituted may be used. Group and the like.

Examples of the diol compound having a carboxyl group include those represented by the following formulas (X) to (Z).

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

As the diol compound having a carboxyl group represented by the formulas (X) to (Z),
There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 3, 5- dihydroxy benzoic acid, 2, 2-bis (hydroxymethyl) propionic acid, 2, 2-bis (2-hydroxyethyl) propion Acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4 -Hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) -3-carboxy-propionamide and the like. These may be used individually by 1 type and may use 2 or more types together.

  Since presence of such a carboxyl group can impart alkali solubility, it is preferable to include a diol having a carboxyl group. More specifically, the polyurethane resin having an ethylenically unsaturated group in the side chain is a resin further having a carboxyl group in the side chain, and more specifically, the ethylenically unsaturated group in the side chain is 0. 0.05 mmol / g to 3.00 mmol / g is preferable, 0.5 mmol / g to 3.00 mmol / g is more preferable, 1.5 mmol / g to 3.00 mmol / g is particularly preferable, and a carboxyl group is present in the side chain. The acid value is preferably 20 mgKOH / g to 120 mgKOH / g, more preferably 30 mgKOH / g to 110 mgKOH / g, and particularly preferably 35 mgKOH / g to 100 mgKOH / g.

  Here, there is no restriction | limiting in particular as a method of introduce | transducing an ethylenically unsaturated group into the side chain of the said polyurethane resin, According to the objective, it can select suitably. There is no restriction | limiting in particular as said diisocyanate compound, According to the objective, it can select suitably, A triisocyanate compound and the monofunctional alcohol which has an ethylenically unsaturated group, or 1 equivalent of monofunctional amine compounds are made to react. Examples of the diisocyanate compound that can be obtained by the method include compounds having an ethylenically unsaturated group in the side chain described in paragraphs [0042] to [0049] of JP-A-2005-250438.

In addition, a method of using a diol compound containing an ethylenically unsaturated group in the side chain as a raw material for producing a polyurethane resin can be mentioned. As the diol compound containing an ethylenically unsaturated group in the side chain, for example, a commercially available one such as trimethylolpropane monoallyl ether, a halogenated diol compound, a triol compound, an aminodiol compound, etc. The compound may be a compound that is easily produced by a reaction between a compound and a compound containing an ethylenically unsaturated group, such as a carboxylic acid, an acid chloride, an isocyanate, an alcohol, an amine, a thiol, or a halogenated alkyl compound. There is no restriction | limiting in particular as a diol compound containing an ethylenically unsaturated group in the said side chain, According to the objective, it can select suitably, For example, Paragraph [0057]-[0060 of Unexamined-Japanese-Patent No. 2005-250438. And the compounds described in paragraphs [0064] to [0066] of JP-A-2005-250438 represented by the general formula (G). Among these, the compounds described in paragraphs [0064] to [0066] of JP-A-2005-250438 represented by the general formula (G) are preferable.
Among these, from the viewpoint of sensitivity, a method using a diol compound containing an ethylenically unsaturated group in the side chain as a raw material for producing a polyurethane resin is preferable.

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

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

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

Moreover, in the synthesis | combination of the polyurethane resin which has an ethylenically unsaturated group in the said side chain, the diol compound which has a substituent which does not react with an isocyanate group other than the diol compound mentioned above can also be used together.
There is no restriction | limiting in particular as a diol compound which has a substituent which does not react with the said isocyanate group, According to the objective, it can select suitably, For example, Paragraph [0087]-[0088] of Unexamined-Japanese-Patent No. 2005-250438 And the described compounds.

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

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

  The amount introduced in the polyurethane resin having an ethylenically unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose. The ethylenically unsaturated group equivalent is 0.05 mmol / g. ˜3.00 mmol / g is preferable, 0.5 mmol / g to 3.00 mmol / g is more preferable, and 1.50 mmol / g to 3.00 mmol / g is particularly preferable.

  There is no restriction | limiting in particular as a weight average molecular weight of the polyurethane resin which has an ethylenically unsaturated group in the said side chain, Although it can select suitably according to the objective, 3,000-50,000 are preferable, developability From the viewpoint, 3,000 to 30,000 is more preferable.

  As the polyurethane resin having an ethylenically unsaturated group in the side chain, one having an ethylenically unsaturated group in the polymer terminal or main chain is also preferably used. By having an ethylenically unsaturated group at the polymer terminal and main chain, further, between the photosensitive composition and the polyurethane resin having an ethylenically unsaturated group, or between the polyurethane resins having an ethylenically unsaturated group in the side chain. Crosslinking reactivity is improved and the strength of the photocured product is increased.

Examples of the method for introducing an ethylenically unsaturated group at the polymer terminal include the following methods. That is, in the process of synthesizing a polyurethane resin having an ethylenically unsaturated group in the side chain as described above, in the step of treating with a residual isocyanate group at the polymer end and an alcohol or amine, the ethylenically unsaturated group is contained. Alcohols or amines may be used. Specific examples of such a compound include the same compounds as those exemplified above as the monofunctional alcohol or monofunctional amine compound having an ethylenically unsaturated 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 functional group containing an ethylenically unsaturated group to be introduced is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of forming a crosslinked cured film, a methacryloyl group, an acryloyl group, a vinylphenyl group The methacryloyl group and the acryloyl group are more preferable, and the methacryloyl group is particularly preferable in terms of both the formability of the crosslinked cured film and the raw storage stability.
The amount of methacryloyl group introduced is not particularly limited and may be appropriately selected depending on the intended purpose. The ethylenically unsaturated group equivalent is preferably 0.05 mmol / g to 3.00 mmol / g, 0.5 mmol / g to 3.00 mmol / g is more preferable, and 1.5 mmol / g to 3.00 mmol / g is particularly preferable.

  As a method for introducing an ethylenically unsaturated group into the main chain, there is a method in which a diol compound having an ethylenically unsaturated group in the main chain direction is used for the synthesis of the polyurethane resin. 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.

-(Ii) Polyurethane resin obtained by reacting a carboxyl group-containing polyurethane with a compound having an ethylenically unsaturated group--
The polyurethane resin (ii) is a polyurethane resin obtained by reacting a carboxyl group-containing polyurethane having a diisocyanate and a carboxylic acid group-containing diol as essential components with a compound having an ethylenically unsaturated group in the molecule. is there. Depending on the purpose, a low molecular diol having a weight average molecular weight of 300 or less or a high molecular diol having a weight average molecular weight of 500 or more may be added as a diol component as a copolymer component.
In addition, as the (ii) polyurethane resin, a diisocyanate of a divalent aliphatic and aromatic hydrocarbon which may have a substituent, a COOH group and two carbon atoms via one of a C atom and an N atom A reaction product comprising a carboxylic acid-containing diol having an OH group as an essential component, the reaction product obtained, and a compound having an epoxy group and an ethylenically unsaturated group in the molecule via a -COO- bond It may be obtained by reaction.
Moreover, as said (ii) polyurethane resin, at least selected from diisocyanate represented by the following general formula (1) and carboxylic acid group-containing diol represented by the following general formulas (2-1) to (2-3): And at least one selected from polymer diols having a weight average molecular weight in the range of 800 to 3,000 represented by the following general formulas (3-1) to (3-5) according to purposes: A reaction product obtained by reacting the obtained reaction product with a compound having an ethylenically unsaturated group in a molecule represented by the following general formulas (4-1) to (4-16). It may be obtained.
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 aromatic 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.
In the general formula (2-1), R ₂ represents a hydrogen atom, a substituent (for example, a cyano group, a ditro 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, aralkyl having 7 to 15 carbon atoms) Each group is included), which may have 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.
In the general formulas (2-1) and (2-2), R ₃ , R ₄ and R ₅ may be the same or different from each other, and may be a single bond or a substituent (for example, an alkyl group or an aralkyl group). , An aryl group, an alkoxy group, and a halogeno group are preferable). 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, in R ₃ , R ₄ and R ₅ , any other functional group that does not react with an isocyanate group, for example, a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, or an 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.

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.
In 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.
In the general formula (3-4), m represents an integer of 2 to 4.
In the general formulas (3-1) to (3-5), n ₁ , n ₂ , n ₃ , n ₄ and n ₅ each represents an integer of 2 or more, and an integer of 2 to 100 is preferable. In the general formula (3-5), _{n 6} is 0 or 2 or more an integer, 0 or an integer of 2 to 100 is preferred.

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.
As said compound which has an ethylenically unsaturated group, general formula (4-1) and (4-2) are preferable from a viewpoint of a sensitivity.

  The (ii) polyurethane resin may further be copolymerized with a carboxylic acid group-free low molecular weight diol as the fifth component. Examples of the low molecular weight diol include the general formulas (3-1) to ( 3-5) and having a weight average molecular weight of 500 or less. The carboxylic acid group-free low molecular weight diol can be added as long as the alkali solubility is not lowered.

  As the (ii) polyurethane resin, in particular, at least one selected from the diisocyanate represented by the general formula (1) and the carboxylic acid group-containing diol represented by the general formulas (2-1) to (2-3). A seed is an essential component, and at least one selected from polymer diols having a weight average molecular weight in the range of 800 to 3,000 represented by general formulas (3-1) to (3-5) according to the purpose. In addition to seeds and a reaction product with a low molecular weight diol having a weight average molecular weight of 500 or less and not containing carboxylic acid groups represented by general formulas (3-1) to (3-5), general formulas (4-1) to (4-1) (4-16) An acid value obtained by reacting a compound having one epoxy group and at least one (meth) acryl group in the molecule represented by any one of 20 mg KOH / g to 120 mg KOH / g Some alkali soluble A photocrosslinkable polyurethane resin is preferred.

  These polymer compounds may be used alone or in combination of two or more. The content of the acid-modified ethylenically unsaturated group-containing polyurethane resin contained in the total solid content of the photosensitive composition is preferably 2% by mass to 30% by mass and more preferably 5% by mass to 25% by mass. preferable. When the content is less than 2% by mass, a sufficiently low elastic modulus at a high temperature of the cured film may not be obtained, and when it exceeds 30% by mass, the developability may deteriorate and the toughness of the cured film may decrease. .

  As a method for synthesizing the carboxyl group-containing polyurethane, the diisocyanate compound and the diol compound are synthesized by adding a known catalyst having an activity corresponding to the reactivity in an aprotic solvent and heating. The molar ratio of the diisocyanate and diol compound to be used is preferably 0.8: 1 to 1.2: 1. When an isocyanate group remains at the end of the polymer, the molar ratio of the diisocyanate and diol compound can be reduced by treatment with alcohols or amines. It is synthesized in such a way that no isocyanate groups remain entangled.

--- Diisocyanate ---
There is no restriction | limiting in particular as a diisocyanate compound shown by the said General formula (1), According to the objective, it can select suitably, For example, the compound described in paragraph [0021] of Unexamined-Japanese-Patent No. 2007-2030, Etc.

--- High molecular weight diol ---
The high molecular weight diol compound represented by the general formulas (3-1) to (3-5) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, as disclosed in JP-A-2007-2030 And compounds described in paragraphs [0022] to [0046].

--Carboxylic acid group-containing diol ---
Further, the diol compound having a carboxyl group represented by the general formulas (2-1) to (2-3) is not particularly limited and may be appropriately selected depending on the intended purpose. And the compounds described in paragraph [0047] of No. 2030 publication.

--- Low molecular weight diol containing no carboxylic acid group ---
The carboxylic acid group-free low molecular weight diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph [0048] of JP-A-2007-2030. Can be mentioned.
The copolymerization amount of the carboxylic acid group-free diol is preferably 95 mol% or less, more preferably 80% or less, and particularly preferably 50% or less in the low molecular weight diol. When the copolymerization amount exceeds 95 mol%, a urethane resin having good developability may not be obtained.

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 be deteriorated. .
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). Next, the weight average molecular weight was determined from the molecular weight distribution curve calibrated with 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. However, when the sample does not dissolve, dioxane or tetrahydrofuran is used as a solvent.
--Content of resin having urethane structure--
There is no restriction | limiting in particular as content in the said photosensitive composition of the resin which has the said urethane structure, Although it can select suitably according to the objective, 5 mass% with respect to solid content of the said photosensitive composition -80% by mass is preferable, 20% by mass to 75% by mass is more preferable, and 30% by mass to 70% by mass is particularly preferable.
If the content is less than 5% by mass, the crack resistance may not be kept good, and if it exceeds 80% by mass, the heat resistance may be lowered. On the other hand, when the content is 5% by mass or more, developability and exposure sensitivity are good, and when the content is 80% by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong.

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

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

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

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

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

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

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

  Examples of the functional group containing an ethylenically unsaturated group include acryloyl group, methacryloyl group, vinylphenyl group, vinyl ether group, vinyl ester 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 intended purpose. For example, at least one selected from monomers having a (meth) acryl group is Preferably mentioned.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin Poly (functional) alcohols such as tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc., which are subjected to addition reaction with ethylene oxide and propylene oxide, and converted to (meth) acrylate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50- Urethane acrylates described in JP-A-6034, JP-A-51-37193, etc .; JP-A-48-64183, JP-B-49-43191, JP-B-52-30 Polyester acrylates described in each publication of such 90 No.; and epoxy resin and (meth) polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  There is no restriction | limiting in particular as content in the said photosensitive composition of the said polymeric compound, Although it can select suitably according to the objective, 5 mass%-50 with respect to solid content of the said photosensitive composition % By mass is preferable, and 10% by mass to 40% by 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.

<Thermal crosslinking agent>
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive film, developability, etc. For example, an epoxy compound (for example, an epoxy compound having at least two oxirane groups in one molecule) and an oxetane compound having at least two oxetanyl groups in one molecule can be used. An epoxy compound having an oxirane group as described in Kai 2007-47729, an epoxy compound having an alkyl group at the β-position, an oxetane compound having an oxetanyl group, a polyisocyanate compound, a polyisocyanate, and an isocyanate group of a derivative thereof Examples thereof include compounds obtained by reacting a blocking agent.

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

  1 mass%-50 mass% are preferable, and, as for content in the said photosensitive composition solid content of the said thermal crosslinking agent, 3 mass%-30 mass% are more preferable. If the said content is 1 mass% or more, the film | membrane intensity | strength of a cured film will be improved, and if it is 50 mass% or less, developability and exposure sensitivity will become favorable.

  Examples of the epoxy compound include epoxy compounds described in paragraphs [0071] to [0074] of JP2010-256399A.

  Examples of the polyisocyanate compound include polyisocyanate compounds described in paragraphs [0075] to [0076] of JP 2010-256399 A.

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

<Other ingredients>
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a filler, a thermosetting accelerator, a thermal-polymerization inhibitor, a plasticizer, a coloring agent (coloring pigment or dye) etc. Furthermore, adhesion promoters to the substrate surface and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tensions) You may use together a regulator, 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.
The filler is described in detail, for example, in paragraphs [0098] to [0099] of JP-A-2008-250074.
The thermal polymerization inhibitor is described in detail, for example, in paragraphs [0101] to [0102] of JP-A-2008-250074.
The thermosetting accelerator is described in detail in paragraph [0093] of JP-A-2008-250074, for example.
The plasticizer is described in detail, for example, in paragraphs [0103] to [0104] of JP-A-2008-250074.
The colorant is described in detail, for example, in paragraphs [0105] to [0106] of JP-A-2008-250074.
The adhesion promoter is described in detail, for example, 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, it is preferable that the photosensitive layer is peelable and has good light transmittance, and further has a smooth surface. Is more preferable.

  The support is preferably made of synthetic resin and transparent, for example, 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, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films, such as ethylene, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular in the thickness of the said support body, Although it can select suitably according to the objective, For example, 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 in the length of the said elongate support body, For example, the thing of 10-20,000m length is mentioned.

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

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

  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; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, and the like ketones; ethyl acetate, butyl acetate, acetic acid-normal-amyl, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxy Esters such as propyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride Halogenated hydrocarbons such as monochlorobenzene; ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together. Moreover, you may add a well-known surfactant.

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

  There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 1 micrometer-100 micrometers are preferable, 2 micrometers-50 micrometers are more preferable, and 4 micrometers-40 micrometers are especially preferable.

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

<< Protective film >>
The photosensitive film may form a protective film on the photosensitive layer.
Examples of the protective film include those used for the support, paper, paper laminated with polyethylene, polypropylene, and the like. Among these, polyethylene film and polypropylene film are preferable.
There is no restriction | limiting in particular in the 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. . Moreover, interlayer adhesion can be adjusted by surface-treating at least one of the support and the protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

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

  For example, the photosensitive film is preferably wound around a cylindrical core, wound into a long roll, and stored. There is no restriction | limiting in particular in the length of the said elongate photosensitive film, 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 in the range of 100 m to 1,000 m may be formed into a roll. 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.

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

(Photosensitive laminate)
The photosensitive laminate of the present invention comprises at least a substrate and a photosensitive layer provided on the substrate, and is formed by laminating other layers appropriately selected according to the purpose.
The photosensitive layer is transferred from the photosensitive film produced by the manufacturing method described above, and has the same configuration as described above.

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

<Method for producing photosensitive laminate>
Examples of the method for producing the photosensitive laminate include a method in which at least the photosensitive layer in the photosensitive film of the present invention is transferred and laminated while performing at least one of heating and pressing.

In the method for producing a photosensitive laminate, the photosensitive film of the present invention is laminated on the surface of the substrate while at least one of heating and pressing. 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 in the said heating temperature, According to the objective, it can select suitably, For example, 15 to 180 degreeC is preferable and 60 to 140 degreeC is more preferable.
There is no restriction | limiting in particular in the pressure of the said pressurization, According to the objective, it can select suitably, For example, 0.1 MPa-1.0 MPa are preferable, and 0.2 MPa-0.8 MPa are more preferable.

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

  The photosensitive film of the present invention and the photosensitive laminate can efficiently form a high-definition permanent pattern (such as a protective film, an interlayer insulating film, and a solder resist pattern). 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 such as a development step appropriately selected 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.

  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 laminate formed by laminating while performing at least one of heating and pressurization.

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

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

<< Development process >>
The development is performed by removing an unexposed portion of the photosensitive layer.
There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  There is no restriction | limiting in particular as said developing solution, According to the objective, it can select suitably, For example, alkaline aqueous solution, an aqueous developing solution, an organic solvent etc. are mentioned. Among these, a weak alkaline aqueous solution is 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 said weak alkaline aqueous solution, Although it can select suitably according to the objective, 8-12 are preferable and 9-11 are more preferable. As said weak alkaline aqueous solution, 0.1 mass%-5 mass% sodium carbonate aqueous solution or potassium carbonate aqueous solution etc. are mentioned, for example.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 ° C. to 40 ° C., for example.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development. Therefore, it may be used in combination with an organic solvent (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 treatment 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 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 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. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film, an insulating film (interlayer insulating film), or a solder resist, and prevents external impact and conduction between adjacent electrodes.

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

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not restrict | limited to these Examples at all.
In the following synthesis examples, “THF” means “tetrahydrofuran” and “DMF” means “N, N-dimethylformamide”.

(Synthesis Example 1)
<Synthesis of Compound a-1>
-Synthesis of M-1-
To a solution of 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (29.48 g, 136 mmol) in acetonitrile (350 mL) at room temperature under a nitrogen atmosphere was added 3-iodophenol (30.0 g, 136 mmol), tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ , 7.88 g, 6.82 mmol), and sodium acetate (NaOAc, 22.37 g, 273 mmol) were added, followed by 4 under a nitrogen atmosphere. Heated to reflux for hours. After cooling to room temperature, dilute aqueous hydrochloric acid solution was added, extracted with ethyl acetate, washed with saturated aqueous sodium chloride solution, and dried over sodium sulfate. The solvent was distilled off and the residue was purified by silica gel column chromatography (solvent: methylene chloride / methanol = 95/5 (vol / vol)) to obtain the following M-1 (35.3 g, 115 mmol).

-Synthesis of Compound a-1-
A mixture of n-butyl isocyanate (13.09 g, 132 mmol) and triethylamine (13.36 g, 132 mmol) was added dropwise at room temperature to a THF solution (80 mL) of M-1 (9.25 g, 30 mmol). After stirring at room temperature for 12 hours, the solvent was distilled off and the residue was purified by silica gel column chromatography (solvent: methylene chloride / methanol = 10/1 (vol / vol)) to give the following compound a-1 (11.0 g, 27 mmol). )

(Synthesis Example 2)
<Synthesis of Compound a-2>
-Synthesis of M-2-
A mixture of 2,6-diphenylphenol (25 g, 102 mmol) and zinc chloride (0.27 g, 1.98 mmol) was heated to 200 ° C. with stirring under a nitrogen stream to obtain phosphorus trichloride (17.4 g, 127 mmol). Was added dropwise over 1 hour, and phosphorus trichloride (2 g, 14.6 mmol) was added dropwise after another 30 minutes. After stirring at 200 ° C. under a nitrogen stream for 2 hours, the reaction product was cooled to room temperature, and excess phosphorus trichloride was distilled off under reduced pressure. The residue was distilled under reduced pressure (0.1 mmHg, 190 ° C.) to obtain M-2 (27 g, 86.9 mmol) shown below.

-Synthesis of M-3-
The obtained M-2 (27 g, 86.9 mmol) was dissolved in toluene (50 mL), and water (1.6 g, 88.8 mmol) was added dropwise at room temperature over 1 hour. After heating to reflux for 1 hour, the mixture was further heated to reflux for 2 hours while blowing nitrogen to remove residual hydrochloric acid gas. The reaction product was cooled to room temperature, and the resulting white precipitate was filtered off and dried in vacuo to obtain the following M-3 (24.1 g, 82.5 mmol).

-Synthesis of M-4-
Triethylamine (NEt ₃ , 13.14 g, 130 mmol) was added dropwise to a THF solution (180 mL) of 4-chloromethylbenzoyl chloride (18.9 g, 100 mmol) and aniline (9.31 g, 100 mmol) under ice cooling. . The mixture was stirred at room temperature for 5 hours, and the resulting reaction product was added to water, extracted with ethyl acetate, washed with a saturated aqueous sodium chloride solution, and dried by adding sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (solvent: hexane / ethyl acetate = 1/1 (vol / vol)) to obtain M-4 (20.9 g, 85 mmol) shown below.

-Synthesis of Compound a-2-
To a DMF solution (100 mL) of M-3 (7.31 g, 25 mmol), cesium carbonate (24.44 g, 75 mmol) and tetra n-butylammonium iodide (TBAI, 27.7 g, 75 mmol) were added with stirring. . After stirring at room temperature for 1 hour, M-4 (11.45 g, 75 mmol) was added to the reaction mixture and stirred at room temperature for 12 hours. The obtained reaction product was added to water and extracted with ethyl acetate. The obtained organic layer was separated, washed with a saturated aqueous sodium chloride solution, and dried by adding sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (solvent: hexane / ethyl acetate = 1/2 (vol / vol)) to obtain compound a-2 (7.15 g, 14.3 mmol).

(Synthesis Example 3)
<Synthesis of Compound b-1>
-Synthesis of M-5-
Methyl 3-hydroxybenzoate (40.04 g, 236 mmol) and cesium carbonate (171.49 g, 526.3 mmol) were added to THF (500 mL) and stirred at 0 ° C. while stirring at 0 ° C. hexachlorocyclotriphosphazene (15.0 g). , 43.1 mmol) in THF (50 mL) was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 3 hours. The obtained reaction product was added to water and extracted with ethyl acetate. The obtained organic layer was separated, washed with a saturated aqueous sodium chloride solution, and dried by adding sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (solvent: hexane / ethyl acetate = 5/1 (vol / vol)) to obtain M-5 (40.4 g, 38.8 mmol) shown below.

-Synthesis of Compound b-1-
To a THF solution (180 mL) of the obtained M-5 (30.2 g, 29 mmol), a 40% by mass methanol solution (180 mL) of methylamine was added at room temperature, and the mixture was stirred at room temperature for 15 hours. The obtained reaction product was added to water and extracted with ethyl acetate. The obtained organic layer was separated, washed with a saturated aqueous sodium chloride solution, and dried by adding sodium sulfate. The solvent was distilled off and the residue was purified by silica gel column chromatography (solvent: hexane / ethyl acetate = 1/2 (vol / vol)) to obtain the following compound b-1 (28.6 g).

(Synthesis Example 4)
<Synthesis of compound c-1>
A methanol solution (250 mL) added with methyl 3-hydroxybenzoate (20.0 g, 0.131 mol) and methylamine (0.6 mol) was sealed in a pressure vessel and heated at 155 ° C. for 12 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (solvent: methylene chloride / methanol = 10/1 (vol / vol)) to give 3-hydroxy-N-methylbenzamide (13 .5 g, 89.3 mmol).
A THF solution (50 mL) in which the obtained 3-hydroxy-N-methylbenzamide (4.84 g, 32 mmol) and diphenyl chlorophosphate (8.06 g, 30 mmol) were dissolved was cooled to 0 ° C., and triethylamine (4. 55 g, 45 mmol) was added dropwise. The mixture was warmed to room temperature and stirred for 6 hours. The obtained reaction product was added to water and extracted with ethyl acetate. The obtained organic layer was separated, washed with a saturated aqueous sodium chloride solution, and dried by adding sodium sulfate. The solvent was distilled off and the residue was purified by silica gel column chromatography (solvent: methylene chloride / methanol = 20/1 (vol / vol)) to obtain the following compound c-1 (9.58 g, 25.0 mmol).

(Synthesis Example 5)
<Synthesis of Compound c-2>
A solution of 4-methylphenol (10.9 g, 100 mmol) in N, N-dimethylformamide (50 mL) and methyl isocyanate (6.00 g, 105 mmol) in acetonitrile (10 mL) was added dropwise at an internal temperature of 10 ° C. to 20 ° C. did. The mixture was stirred at an internal temperature of 25 ° C. to 35 ° C. for 12 hours, concentrated under reduced pressure, water (100 mL) was added, and the mixture was stirred at room temperature. The obtained precipitate was collected by filtration, washed with cold water, recrystallized from a mixed solvent of water and methanol, and N- (4-hydroxyphenyl) -N′-methylurea (8.60 g, 51.8 mmol) was added. Obtained.
Obtained N- (4-hydroxyphenyl) -N′-methylurea (5.32 g, 32 mmol), 4-t-butylphenol (4.80 g, 32 mmol), and phenyl dichlorophosphate (6.33 g, 30 mmol). The dissolved THF solution (50 mL) was cooled to 0 ° C. and triethylamine (9.10 g, 90 mmol) was added dropwise. The mixture was warmed to room temperature and stirred for 6 hours. The obtained reaction product was added to water and extracted with ethyl acetate. The obtained organic layer was separated, washed with a saturated aqueous sodium chloride solution, and dried by adding sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (solvent: methylene chloride / methanol = 10/1 (vol / vol)) to obtain the following compound c-2 (11.18 g).

(Synthesis Example 6)
<Synthesis of Compound d-1>
Magnesium chloride (1.8 g, 18.9 mmol) was added to bisphenol A (114 g, 0.5 mol) and phosphoryl chloride (460 g, 3.0 mol), and the mixture was heated and stirred at 100 ° C. for 4 hours. After cooling to room temperature, excess phosphoryl chloride was removed under reduced pressure to obtain the following M-6 (crude, 220 g).
A THF solution (150 mL) in which the obtained M-6 (13.86 g, 30 mmol), m-cresol (6.92 g, 64 mmol), and 4-acetamidophenol (9.67 g, 64 mmol) were dissolved was heated to 0 ° C. Upon cooling, triethylamine (NEt ₃ , 18.2 g, 180 mmol) was added dropwise. The mixture was warmed to room temperature and stirred for 6 hours. The obtained reaction product was added to water and extracted with ethyl acetate. The obtained organic layer was separated, washed with a saturated aqueous sodium chloride solution, and dried by adding sodium sulfate. The solvent was distilled off and the residue was purified by silica gel column chromatography (solvent: methylene chloride / methanol = 8/1 (vol / vol)) to obtain the following compound d-1 (19.5 g).

(Synthesis Example 7)
<Synthesis of Compound d-2>
Dissolve M-6 (13.86 g, 30 mmol) obtained in Synthesis Example 6, methyl 4-hydroxybenzoate (9.77 g, 64 mmol), and 4-hydroxy-N-methylbenzamide (9.68 g, 64 mmol). The THF solution (150 mL) was cooled to 0 ° C. and triethylamine (18.2 g, 180 mmol) was added dropwise. The mixture was warmed to room temperature and stirred for 6 hours. The obtained reaction product was added to water and extracted with ethyl acetate. The obtained organic layer was separated, washed with a saturated aqueous sodium chloride solution, and dried by adding sodium sulfate. The solvent was distilled off and the residue was purified by silica gel column chromatography (solvent: methylene chloride / methanol = 10/1 (vol / vol)) to obtain the following compound d-2 (20.7 g).

(Synthesis Example 8)
<Synthesis of ethylenically unsaturated group-containing polyurethane resin>
In a 500 mL three-necked round bottom flask equipped with a condenser and a stirrer, 2.41 g (0.018 mol) of malic acid, 5.23 g of 2,2-bis (hydroxymethyl) propionic acid (DMPA) (0 0.039 mol) and 17.78 g (0.111 mol) of glycerol monomethacrylate were dissolved in 74 mL of cyclohexanone. To this, 30.03 g (0.12 mol) of 4,4-diphenylmethane diisocyanate (MDI), 5.05 g (0.03 mol) of hexamethylene diisocyanate (HMDI), 2,6-di-t-butylhydroxytoluene 0 0.1 g and 0.2 g of Neostan U-600 (manufactured by Nitto Kasei Co., Ltd., inorganic bismuth) were added as a catalyst, and the mixture was heated and stirred at 75 ° C. for 5 hours. Thereafter, the mixture was diluted with 9.61 mL of methyl alcohol and stirred for 30 minutes to obtain 165 g of an ethylenically unsaturated group-containing polyurethane resin solution (solid content: 45 mass%) represented by the following formula.
The obtained ethylenically unsaturated group-containing polyurethane resin solution has a solid content acid value of 68 mgKOH / g, and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) is 6,500. The ethylenically unsaturated group equivalent was 1.83 mmol / g.
The acid value was measured according to JIS K0070. However, when the ethylenically unsaturated group-containing polyurethane resin did not dissolve, dioxane or tetrahydrofuran was used as a solvent.
The weight average molecular weight is determined by using a high-speed GPC device (HLC-802A manufactured by Toyo Soda Industry Co., Ltd.), a 0.5% by mass THF solution as a sample solution, and a column using one TSKgel HZM-M, A 200 μL sample was injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or a UV detector (detection wavelength: 254 nm).
The said ethylenically unsaturated group equivalent was calculated | required by measuring a bromine number based on JISK2605.

However, in said formula, a4 is 49.7 mass%, b4 is 8.3 mass%, c4 is 8.6 mass%, d4 is 29.4 mass%, and e4 is 4.0 mass%.
Example 1
-Composition of photosensitive composition solution-
-Solution of the ethylenically unsaturated group-containing polyurethane resin of Synthesis Example 8 (adjusted to a solid content of 40% by mass) ... 110.38 parts by mass-Compound a-1 ... 25 parts by mass-Coloring pigment: HELIOGEN BLUE D7086 (BASF Co., Ltd.) ... 0.07 parts by mass Coloring pigment: Pariotol Yellow D0960 (BASF Co., Ltd.) ... 0.02 parts by mass Polymerizable compound: DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.) -18.07 parts by mass-Initiator: IRG907 (manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 1.97 parts by mass-Sensitizer: DETX-S (manufactured by Nippon Kayaku Co., Ltd.) ... 0.02 parts by mass Part / reaction aid: EAB-F (made by Hodogaya Chemical Co., Ltd.) 0.07 parts by mass Curing agent: Melamine (made by Wako Pure Chemical Industries, Ltd.) 0.54 parts by weight, thermal crosslinking Agent: Epototo YDF-170 (manufactured by Nippon Steel Chemical Co., Ltd.) ... 9.85 parts by mass coating aid: Mega-Fac F-780F (manufactured by Dainippon Ink & Chemicals, Inc., 3 mass% methyl ethyl ketone solution) -0.23 parts by mass-Cyclohexanone (solvent) ... 33.78 parts by mass

-Production of photosensitive film-
A photosensitive composition solution having the above composition 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 38 μm on the support. Formed. 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.

-Lamination on substrate-
The substrate was prepared by subjecting a surface of a copper clad laminate (no through hole, copper thickness: 12 μm) to chemical polishing. A vacuum laminator (manufactured by Nichigo Morton Co., Ltd., VP130) was used on the copper-clad laminate while peeling off the protective film from the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper-clad laminate. Thus, a laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order was prepared.
The pressure bonding conditions were as follows: a vacuuming time of 40 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure time of 10 seconds.
About the obtained laminated body, the resist pattern was formed with the method shown below.

-Exposure process-
A predetermined pattern can be obtained with a laser beam of 405 nm from the polyethylene terephthalate film (support) side using a pattern forming apparatus by blue-violet laser exposure having a predetermined pattern with respect to the photosensitive layer in the prepared laminate. In this way, an energy amount of 40 mJ / cm ² was irradiated for exposure, and a partial region of the photosensitive layer was cured.

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

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

<Evaluation>
The following evaluation was performed. The results are shown in Table 1.

-Flame resistance-
Flame retardancy was performed by a method similar to UL (Underwriter Laboratories Inc.) flame resistance test standard UL-94. A specific method is shown below.
A flexible printed wiring board substrate (trade name “ESPANEX MB” series, manufactured by Nippon Steel Chemical Co., Ltd.) in which a copper foil with a thickness of 18 μm is laminated on a polyimide base material is etched to remove the copper foil, whereby a polyimide with a thickness of 12.5 μm is obtained. A substrate was obtained.
The photosensitive composition solution was applied to one side of the polyimide substrate and dried to form a photosensitive layer having a thickness of 38 μm on the polyimide substrate.
Using a circuit board exposure machine EXM-1172 (manufactured by Oak Manufacturing Co., Ltd.), the entire surface of the photosensitive layer is exposed at 100 mJ / cm ² , followed by heat treatment (post baking) at 150 ° C. for 1 hour to form a cured layer. After being obtained, a sample for flame retardancy test was obtained by cutting into a size of 1.3 cm × 12.5 cm.
The obtained sample for flame retardancy test was hung with a clamp, a 20 mm flame was indirectly flamed for 3 seconds, and the flame extinguishing time (t1) was measured. Subsequently, after indirect flame of 20 mm again for 3 seconds, the flame extinction time (t2) was measured. The total time of t1 and t2 was defined as “burning time”.
The burning time was evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
◎: Sample with combustion time of 5 seconds or less ○: Sample with combustion time exceeding 5 seconds and 10 seconds or less ×: Sample with combustion time exceeding 10 seconds NOT: Sample that burns out completely

<Bleed out>
The surface layer (permanent pattern) of the test plate on which the permanent pattern was formed was left at 40 ° C. for one week, was observed with a microscope (magnification: 200 times), and evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
○: The surface is not whitened and no crystal is precipitated.
X: The surface is whitened or crystals are precipitated.

<Folding resistance>
A dry film resist is 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 of 18 μm thickness is laminated on a polyimide substrate (thickness 25 μm), and 200 mJ / cm After exposure at ² , the film was developed and etched under the condition of 0.15 MPa / 90 s to produce a copper foil line pattern of L / S = 100/100 μm.
Thus, 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 exposed at 1,000 mJ / cm ² to obtain a laminate for evaluation.
The state of the folded part when the line pattern side of the obtained evaluation laminate was folded 180 ° was observed visually and with a microscope (magnification: 200 times), and evaluated according to the following criteria.
〔Evaluation criteria〕
○: No crack occurred △: Crack occurred only at the edge of the film ×: Crack occurred throughout the bent part

(Examples 2-14, Comparative Examples 1-6)
In Example 1, the type of flame retardant, and the content of the flame retardant (the content (mass%) of the flame retardant with respect to the solid content of the photosensitive composition) of the type of flame retardant listed in Table 1 and the flame retardant A photosensitive composition solution, a photosensitive film, and a test plate were prepared in the same manner as in Example 1 except that the content (the content (mass%) of the flame retardant with respect to the solid content of the photosensitive composition) was changed. .
Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 7)
In the same manner as in Example 1, except that the ethylenically unsaturated group-containing polyurethane resin was replaced with an epoxy resin (ZAR-2036H, manufactured by Nippon Kayaku Co., Ltd., acid-modified bisphenol A type epoxy acrylate). Composition solution, photosensitive film, and test plate were prepared.
Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

In Table 1, the flame retardant content is the content (% by mass) of the flame retardant with respect to the solid content of the photosensitive composition. The polyurethane resin represents the ethylenically unsaturated group-containing polyurethane resin obtained in Synthesis Example 8. Comparative compounds 1 to 6 are the following compounds, respectively. In addition, the comparative compound 5 was synthesize | combined according to the method as described in Unexamined-Japanese-Patent No. 2010-250032. Comparative compound 6 was synthesized according to the method described in JP2009-98456A.

The photosensitive composition of the present invention can be suitably used as a solder resist material because it has all of flame retardancy, prevention of bleeding out of the flame retardant component, and folding resistance.
The photosensitive film, photosensitive laminate, permanent pattern forming method, and printed circuit board of the present invention have all of flame retardancy, prevention of bleed-out of flame retardant components, and folding resistance, and therefore flame retardancy is required. It can be suitably used for printed circuit boards to be printed, particularly flexible printed circuit boards.

Claims (7)

Contains a flame retardant, a resin having a urethane structure, and a photopolymerization initiator,
The flame retardant is at least one of a cyclotriphosphazene compound, an aromatic phosphonate compound, and a compound represented by the following general formula (A), and at least one of an amide group, a urea group, and a urethane group A photosensitive composition having a hydrogen bonding group.
In the general formula ^{(A), R} 1 ~R ¹³ are each independently hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, and , An amide group, a urea group, and a monovalent organic group having at least one of a urethane group. Note that at least one of R ^{1 to} R ¹³ is a monovalent organic group having at least one of an amide group, a urea group, and a urethane group. m represents 0 or 1. The photosensitive composition according to claim 1, wherein the cyclotriphosphazene compound is a compound represented by the following general formula (B).
However, Ar < ¹ > -Ar < ⁶ > is group represented by the following general formula (B-1) in the said general formula (B).
In the general formula ^{(B-1), R 14} ~R 18 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms And having at least one of an alkoxy group having 1 to 10 carbon atoms, an alkylyloxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, an amide group, a urea group, and a urethane group; It represents one of monovalent organic groups having no (meth) acrylate group. Note that at least one of R ^{14 to} R ¹⁸ is a monovalent organic group having at least one of an amide group, a urea group, and a urethane group and having no (meth) acrylate group. The photosensitive composition according to claim 1, wherein the aromatic phosphonate compound is at least one of a compound represented by the following general formula (C) and a compound represented by the following general formula (D).
In the general formula ^{(C), R} 19 ~R ³³ are each independently hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, carbon A monovalent organic having at least any one of an alkoxy group having 1 to 10 carbon atoms, an alkyloxyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, and an amide group, a urea group, and a urethane group Represents any of the groups. Note that at least one of R ^{19 to} R ³³ is a monovalent organic group having at least one of an amide group, a urea group, and a urethane group.
In the general formula ^{(D), R} 34 ~R ⁵³ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, carbon A monovalent organic having at least any one of an alkoxy group having 1 to 10 carbon atoms, an alkyloxyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, and an amide group, a urea group, and a urethane group Represents any of the groups. Note that at least one of R ^{34 to} R ⁵³ is a monovalent organic group having at least one of an amide group, a urea group, and a urethane group. R ^a and R ^b each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.   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 6.