JP2012078462A - Photosensitive resin composition, photosensitive solder resist composition and photosensitive solder resist film, and permanent pattern and method for forming the same and print circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of obtaining a high-performance cured film having excellent pattern forming properties, crack resistance, heat resistance, electrical insulating properties, developability and mechanical properties, a photosensitive solder resist composition using the photosensitive resin composition and a photosensitive solder resist film using the photosensitive solder resist composition, and a permanent pattern, an efficient method for forming the same and a print circuit board in which a permanent pattern is formed by the forming method.SOLUTION: The photosensitive resin composition contains a polyurethane resin, a thermal crosslinking agent and an imide resin having an urethane bond.

Description

  The present invention is a photosensitive resin composition suitably used for a solder resist, a photosensitive solder resist composition using the photosensitive resin composition, and a photosensitive solder resist film using the photosensitive solder resist composition, In addition, the present invention relates to a high-definition permanent pattern (protective film, interlayer insulating film, solder resist, etc.), a method for forming the same, and a printed circuit board.

  In recent years, electronic devices have been required to have high performance, high functionality, high quality, and high reliability as well as small size, thinness, and light weight as represented by mobile communication devices. Electronic component modules mounted on devices are also required to be small and high in density. In response to such demands, in recent years, the surface of an insulating substrate made of a glass fiber and an epoxy resin that can be made lighter and densified from a ceramic wiring substrate made of ceramics such as an aluminum oxide sintered body. In addition, a so-called printed circuit board in which a wiring conductor layer is formed by a thin film forming method using copper, gold or the like which is a low resistance metal has been used for an electronic component module. In addition, this printed board is also changing to a build-up wiring board capable of higher density wiring.

  For example, such a build-up wiring board is formed by laminating a film made of a thermosetting resin on an insulating board made of glass fiber and epoxy resin, and thermosetting the insulating layer to form an insulating layer. Then, the conductor layer is formed in the opening by chemically roughening the surface of the insulating layer and depositing a copper film using an electroless copper plating method and an electrolytic copper plating method. The wiring conductor layer is formed on the surface of the insulating layer, and the insulating layer and the wiring conductor layer are repeatedly formed.

Further, a solder resist layer having a thickness of 20 μm to 50 μm is provided on the surface of the wiring board in order to prevent oxidation and corrosion of the wiring conductor layer and to protect the insulating layer from heat when mounting electronic components on the wiring board. It is deposited. This solder resist layer is generally composed of an alkali-soluble photocrosslinkable resin that has good adhesion to the wiring conductor layer and the insulating layer, and a flexible resin, and has a coefficient of thermal expansion that is the same as that of the insulating layer and the wiring conductor layer. In order to match the expansion coefficient, the inorganic filler is contained in an amount of 5 to 75% by mass.
In addition, the wiring board has an opening formed in the solder resist layer on the wiring conductor layer by exposure and development, and an electronic component is electrically connected to the wiring conductor layer in the opening via a conductor bump made of solder or the like. Thus, an electronic component module such as a semiconductor device is obtained.
In general, a solder resist layer used in such an electronic component module has an insulation resistance of 10 ¹¹ Ω to 10 ¹³ Ω in a dry state.

However, this solder resist layer generally contains a hydroxyl group or a carboxyl group in order for the alkali-soluble photocrosslinkable resin to be contained to develop developability when an opening is formed in the solder resist layer by exposure and development. The water absorption rate is high and the moisture in the air is gradually absorbed, and this moisture reduces the insulation resistance of the solder resist layer to 10 ⁸ Ω or less, causing short circuit between the wiring conductor layers. As a result, the conductor layer is corroded, and as a result, the electrical reliability of the wiring board is deteriorated.

  Also, in semiconductor package substrates such as BGA (ball grid array) and CSP (chip size package), cream solder is printed in advance on necessary parts, the whole is heated with infrared rays, and the solder is reflowed and fixed. The external temperature reached is extremely high at 220 ° C to 240 ° C, so that the coating film is cracked or peeled off from the substrate or the gunning material by thermal shock, so-called reflow resistance (solder heat resistance) There was a problem of decline, and this improvement was demanded.

In order to solve such a problem, an imide resin having a carboxyl group, a linear hydrocarbon structure having a number average molecular weight of 700 to 4,500, a urethane bond, an imide ring, an isocyanurate ring and a cyclic aliphatic structure, and an epoxy A thermosetting imide resin composition containing a resin has been proposed (see Patent Document 1). This thermosetting imide resin composition is excellent in heat resistance, has a low dielectric constant and dielectric loss tangent, and has good mechanical properties such as tensile strength and tensile elongation.
However, the resin composition has a problem in that pattern formation is not sufficient and cracks are generated.

  Therefore, at present, there is a demand for providing a photosensitive resin composition that is not only excellent in heat resistance, dielectric properties, and mechanical properties, but also excellent in pattern formability and crack resistance.

Japanese Patent No. 4217952

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention provides a photosensitive resin composition capable of obtaining a high-performance cured film excellent in pattern formability, crack resistance, heat resistance, electrical insulation, developability, and mechanical properties, and the photosensitive resin composition. Photosensitive solder resist composition using the product, photosensitive solder resist film using the photosensitive solder resist composition, and permanent pattern, efficient formation method thereof, and print having a permanent pattern formed by the formation method An object is to provide a substrate.

Means for solving the problems are as follows. That is,
<1> A photosensitive resin composition comprising a polyurethane resin, a thermal crosslinking agent, and an imide resin having a urethane bond.
<2> The photosensitive resin composition according to <1>, wherein the polyurethane resin has a vinyl group and an acid group.
<3> The photosensitive resin according to any one of <1> to <2>, wherein the polyurethane resin has at least one of functional groups represented by the following general formulas (1) to (3) in a side chain. It is a composition.
In the general formula (1), R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent organic group, X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —, R ¹² represents a hydrogen atom or a monovalent organic group.
In the general formula (2), R ^{4 to} R ⁸ each independently represents a hydrogen atom or a monovalent organic group, and Y represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Wherein ^{R 12} has the same meaning as that of the ^{R 12} of the general formula (1).
In the general formula (3), R ^{9 to} R ¹¹ each independently represent a hydrogen atom or a monovalent organic group, and Z represents an oxygen atom, a sulfur atom, —N (R ¹³ ) —, or a substituent. The phenylene group which may have is represented. R ¹³ represents an alkyl group which may have a substituent.
<4> The photosensitive resin composition according to <3>, wherein the polyurethane resin has a functional group represented by the general formula (1) in a side chain.
<5> The polyurethane resin is a reaction product of a diisocyanate compound and a diol compound, and the diol compound has (i) at least one diol compound having a vinyl group and at least one being a secondary alcohol; (Ii) The photosensitive resin composition according to any one of <1> to <4>, containing at least one diol compound having a carboxyl group.
<6> The photosensitive resin composition according to <5>, wherein the diol compound having a vinyl group is a compound represented by the following general formula (G).
In the general formula (G), R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —, wherein R ¹² represents a hydrogen atom or a monovalent organic group.
<7> The imide resin having a urethane bond has a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and the following general formula (III) To (V). The photosensitive resin composition according to any one of <1> to <6>, which has any one or more of the terminal structures represented by (V).
In the general formulas (I) and (II), R ₁ represents an organic group having a cycloaliphatic structure having 6 to 13 carbon atoms. In the general formula (II), R ₂ represents a number average molecular weight. Represents a 700 to 4,500 linear hydrocarbon structure.
<8> The imide resin having a urethane bond has an acid value of 20 to 250, a number average molecular weight of the linear hydrocarbon structure portion of 700 to 4,500, and a content of the linear hydrocarbon structure portion of 20% by mass. -40% by mass, the concentration of the isocyanurate ring is 0.3 mmol / g to 1.2 mmol / g, the number average molecular weight is 2,000 to 30,000, and the weight average molecular weight is 3,000 to 100,000. The photosensitive resin composition according to <7>, which is 000.
<9> The photosensitive resin composition according to any one of <1> to <8>, wherein a mass ratio of the polyurethane resin and the imide resin having a urethane bond (polyurethane resin / imide resin) is 1 to 19. It is.
<10> The photosensitive resin composition according to any one of <1> to <9>, further including a polymerizable compound and a photopolymerization initiator.
<11> The photosensitive resin composition according to <1> to <10>, further including a thermoplastic elastomer.
<12> The above-mentioned <11, wherein the thermoplastic elastomer is at least one elastomer selected from a styrene elastomer, an olefin elastomer, a urethane elastomer, a polyester elastomer, a polyamide elastomer, an acrylic elastomer, and a silicone elastomer. > Photosensitive resin composition.
<13> A photosensitive solder resist composition comprising the photosensitive resin composition according to any one of <1> to <12>.
<14> A photosensitive solder resist film comprising a support and a photosensitive layer obtained by laminating the photosensitive solder resist composition according to <13> on the support.
<15> The photosensitive solder resist composition according to <14> is applied to a surface of a substrate, dried to form a laminate by forming a photosensitive layer, and then exposed and developed. This is a permanent pattern forming method.
<16> A permanent pattern formed by the method for forming a permanent pattern according to <15>.
<17> A printed circuit board wherein a permanent pattern is formed by the method for forming a permanent pattern according to <15>.

  According to the present invention, the conventional problems can be solved and the object can be achieved, and the heat resistance, pattern formation, crack resistance, heat resistance, electrical insulation, developability, and mechanical properties are excellent. Photosensitive resin composition capable of obtaining high performance cured film, photosensitive solder resist composition using the photosensitive resin composition, photosensitive solder resist film using the photosensitive solder resist composition, and A permanent pattern, an efficient formation method thereof, and a printed circuit board on which the permanent pattern is formed by the formation method can be provided.

FIG. 1 is an explanatory view showing an example of a layer structure of a photosensitive solder resist film.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention contains at least a polyurethane resin, a thermal crosslinking agent, and an imide resin, and preferably further includes a polymerizable compound, a photopolymerization initiator, a thermoplastic elastomer, and a thermosetting accelerator. Further, it contains an adhesion promoter, a thermal polymerization inhibitor, an inorganic filler, a colorant, an organic solvent, and the like, and further contains other components as necessary.

<Polyurethane resin>
The polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose, but has a structure derived from polyisocyanate and polyisocyanate, from the viewpoint of alkali developability and toughness of a cured film. It is preferable to use an acid-modified vinyl group-containing polyurethane resin.

<< Acid-modified vinyl group-containing polyurethane resin >>
The acid-modified vinyl group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (i) a polyurethane resin having an ethylenically unsaturated bond in the side chain, (ii) a carboxyl group Examples thereof include a polyurethane resin obtained by reacting a containing polyurethane with a compound having an epoxy group and a vinyl group in the molecule.

-(I) Polyurethane resin having an ethylenically unsaturated bond in the side chain-
The polyurethane resin having an ethylenically unsaturated bond in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose. What has at least 1 among the functional groups represented is mentioned.

In the general formula (1), R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent organic group.
Examples of R ^1, is not particularly limited and may be appropriately selected depending on the purpose, for example, a hydrogen atom, an alkyl group which may have a substituent. Among these, a hydrogen atom and a methyl group are preferable in terms of high radical reactivity.
The R ² and R ³ are not particularly limited and may be appropriately selected depending on the purpose. For example, each of R ² and R ³ is independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group. Group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryl which may have a substituent An oxy group, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent Etc. Among these, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.

In the general formula (1), X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —, and R ¹² represents a hydrogen atom or a monovalent organic group. R ¹² is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an alkyl group which may have a substituent. Among these, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.

  Here, the substituent that can be introduced is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogen atom. Amino group, alkylamino group, arylamino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, amide group, alkylsulfonyl group, arylsulfonyl group and the like.

In the general formula (2), R ^{4 to} R ⁸ each independently represents a hydrogen atom or a monovalent organic group. The R ^{4 to} R ⁸ are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, Nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent An alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like Can be mentioned. Among these, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.

Examples of the substituent that can be introduced include the same as those in the general formula (1). Y represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Wherein ^{R 12} has the same meaning as ^{R 12} in the general formula (1), and preferred examples are also the same.

In the general formula (3), R ^{9 to} R ¹¹ each independently represent a hydrogen atom or a monovalent organic group.
Examples of R ^9, is not particularly limited and may be appropriately selected depending on the purpose, for example, an alkyl group which may have a hydrogen atom or a substituent. Among these, a hydrogen atom and a methyl group are preferable in terms of high radical reactivity.
R ¹⁰ and R ¹¹ are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, Nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent An alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like Can be mentioned. Among these, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable because of high radical reactivity.

Here, examples of the substituent that can be introduced include those similar to those in the general formula (1). Moreover, in the said General formula (3), Z represents the phenylene group which may have an oxygen atom, a sulfur atom, -N (R < ¹³ >)-, or a substituent. R ¹³ is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an alkyl group which may have a substituent. Among these, a methyl group, an ethyl group, and an isopropyl group are preferable in terms of high radical reactivity.

  The urethane resin having an ethylenically unsaturated bond in the side chain includes at least one diisocyanate compound represented by the following general formula (4) and at least one diol compound represented by the following general formula (5): A polyurethane resin having a structural unit represented by the reaction product as a basic skeleton.

OCN-X ⁰ -NCO: General formula (4)
^HO-Y 0 -OH ··· the general formula (5)
In the general formula (4) and the general formula (5), X ⁰ and Y ⁰ each independently represent a divalent organic residue.

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

  There is no restriction | limiting in particular as a diisocyanate compound represented by the said General formula (4), According to the objective, it can select suitably, For example, the monofunctional alcohol or monofunctional alcohol which has a triisocyanate compound and an unsaturated group Examples thereof include diisocyanate compounds that can be obtained by addition reaction with 1 equivalent of an amine compound.

  The triisocyanate compound is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include compounds described in paragraphs “0034” to “0035” of JP-A-2005-250438. Is mentioned.

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

  Here, the method for introducing an unsaturated group into the side chain of the polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. A method using a diisocyanate compound containing is preferable. There is no restriction | limiting in particular as said diisocyanate compound, According to the objective, it can select suitably, By carrying out addition reaction of the monoisocyanate which has a triisocyanate compound, and a monofunctional amine compound or monofunctional amine compound. Examples of the diisocyanate compound that can be obtained include compounds having an unsaturated group in the side chain described in paragraphs “0042” to “0049” of JP-A-2005-250438.

  The polyurethane resin having an ethylenically unsaturated bond in the side chain contains the unsaturated group from the viewpoint of improving compatibility with other components in the photosensitive resin composition and improving storage stability. Diisocyanate compounds other than diisocyanate compounds can also be copolymerized.

The diisocyanate compound to be copolymerized is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a diisocyanate compound represented by the following general formula (6).
^OCN-L 1 -NCO ··· general formula (6)
In the general formula (6), L ¹ is a divalent aliphatic which may have a substituent (for example, any of an alkyl group, an aralkyl group, an aryl group, an alkoxy group, and a halogeno group is preferable). Or represents an aromatic hydrocarbon group. If necessary, L ¹ may have any other functional group that does not react with an isocyanate group, such as an ester group, a urethane group, an amide group, or a ureido group.

  There is no restriction | limiting in particular as a diisocyanate compound represented by the said General formula (6), According to the objective, it can select suitably, For example, the dimer of 2, 4- tolylene diisocyanate and 2, 4- tolylene diisocyanate 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethylbiphenyl-4,4 Aromatic diisocyanate compounds such as '-diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; isophorone diisocyanate, 4, 4' Alicyclic diisocyanate compounds such as methylene bis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; 1 mol of 1,3-butylene glycol and tolylene diisocyanate 2 Examples thereof include a diisocyanate compound which is a reaction product of a diol such as an adduct with a mole and a diisocyanate. These may be used alone or in combination of two or more.

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

  Here, as a method for introducing an unsaturated group into the side chain of the polyurethane resin, in addition to the above-described method, a method using a diol compound containing an unsaturated group in the side chain as a raw material for producing the polyurethane resin is also preferable. The diol compound containing an unsaturated group in the side chain may be, for example, a commercially available product such as trimethylolpropane monoallyl ether, and a compound such as a halogenated diol compound, a triol compound, or an aminodiol compound; Examples thereof include compounds that are easily produced by reaction with compounds such as carboxylic acids, acid chlorides, isocyanates, alcohols, amines, thiols, and halogenated alkyl compounds containing vinyl groups.

The diol compound containing an unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in paragraphs “0057” to “0060” of JP-A-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.
In the general formula (G), R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —, wherein R ¹² represents a hydrogen atom or a monovalent organic group.
Incidentally, ^R 1 to R ³ and X in the general formula (G) has the same meaning as ^R 1 to R ³ and X in the general formula (1), preferred embodiments versa.
By using the polyurethane resin derived from the diol compound represented by the general formula (G), the effect of suppressing the excessive molecular movement of the polymer main chain caused by the secondary alcohol having a large steric hindrance can be reduced. It is thought that improvement can be achieved.

The polyurethane resin having an ethylenically unsaturated bond in the side chain is not suitable for the side chain from the viewpoint of, for example, improving compatibility with other components in the photosensitive resin composition and improving storage stability. Diol compounds other than diol compounds containing saturated groups can be copolymerized.
The diol compound other than the diol compound containing an unsaturated group in the side chain is not particularly limited and may be appropriately selected according to the purpose. For example, a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, Etc.

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

  There is no restriction | limiting in particular as said polyester diol compound, According to the objective, it can select suitably, For example, Paragraph "0077"-"0079" of Unexamined-Japanese-Patent No. 2005-250438, Paragraph "0083"-"0085" No. 1-No. 8 and no. 13-No. 18 and the like.

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

Moreover, in the synthesis | combination of the polyurethane resin which has an ethylenically unsaturated bond 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.
The diol compound having a substituent that does not react with the isocyanate group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in paragraphs “0087” to “0088” of JP-A-2005-250438 And the compounds described.

  Furthermore, in the synthesis | combination of the polyurethane resin which has an ethylenically unsaturated bond in the said side chain, the diol compound which has a carboxyl group other than the diol compound mentioned above can also be used together. The diol compound having a carboxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds represented by the following general formulas (8) to (10).

In the general formulas (8) to (10), R ¹⁵ is a hydrogen atom, a hydrogen atom, a substituent (for example, a cyano group, a ditro group, a halogen atom (—F, —Cl, —Br, —I)). , —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 7 carbon atoms) Represents an aralkyl group of ˜15.), And the like may represent an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group that may have. Among these, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 15 carbon atoms are preferable.
In the general formulas (8) to (10), 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, an alkyl group, an aralkyl group, an aryl). A divalent aliphatic or aromatic hydrocarbon group optionally having a group, an alkoxy group, or a halogeno group. 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, the L ^{9 to} L ¹¹ may have other functional groups that do not react with the isocyanate group, such as a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, and an ether group. . In addition, you may form a ring by 2 or 3 of said R < ¹⁵ >, L < ⁷ >, L < ⁸ >, L < ⁹ >.
In the general formula (9), Ar is not particularly limited as long as it represents a trivalent aromatic hydrocarbon group which may have a substituent, and may be appropriately selected according to the purpose. An aromatic group having 6 to 15 carbon atoms is preferable.

  There is no restriction | limiting in particular as a diol compound which has a carboxyl group represented by the said General formula (8)-(10), 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) propionic 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.

The presence of such a carboxyl group is preferable in that the polyurethane resin can be provided with characteristics such as hydrogen bonding properties and alkali solubility. More specifically, the polyurethane resin having an ethylenically unsaturated bond group in the side chain is a resin having a carboxyl group in the side chain, and more specifically, the vinyl group in the side chain is 0.05 mmol. / G to 3.0 mmol / g, preferably 0.5 mmol / g to 2.7 mmol / g, more preferably 0.75 mmol / g to 2.4 mmol / g, In addition, the side chain preferably has a carboxyl group, and the acid value is preferably 20 mgKOH / g to 120 mgKOH / g, more preferably 30 mgKOH / g to 110 mgKOH / g, and 35 mgKOH / g to 100 mgKOH / g. g is particularly preferred.
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.

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

The polyurethane resin having an ethylenically unsaturated bond 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 depending on the 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.

  Further, as the polyurethane resin having an ethylenically unsaturated bond in the side chain, those having an unsaturated group in the polymer terminal and main chain are also preferably used. Polyurethane having an ethylenically unsaturated bond in the side chain, or between the photosensitive resin composition and the polyurethane resin having an ethylenically unsaturated bond in the side chain, by having an unsaturated group at the polymer terminal and main chain Crosslinking reactivity is improved between the resins, and the strength of the photocured product is increased. As a result, when a polyurethane resin having an ethylenically unsaturated bond in the side chain is used for a lithographic printing plate, a material having excellent toughness can be provided. Here, as an unsaturated group, it is especially preferable to have a carbon-carbon double bond from the viewpoint of easy occurrence of a crosslinking reaction.

As a method for introducing an unsaturated group into the polymer terminal, there are the following methods. That is, in the step of synthesizing the polyurethane resin having an ethylenically unsaturated bond in the side chain as described above, in the step of treating with the residual isocyanate group at the polymer end and the alcohol or amine, the alcohol having an unsaturated group. Alternatively, amines or the like may be used.
Specific examples of such a compound include the same compounds as those exemplified above as the monofunctional alcohol or monofunctional amine compound having an unsaturated group.
The unsaturated group is preferably introduced into the polymer side chain rather than the polymer terminal from the viewpoint that the introduction amount can be easily controlled and the introduction amount can be increased, and that the crosslinking reaction efficiency is improved.

The ethylenically unsaturated bond group to be introduced is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of forming a crosslinked cured film, a methacryloyl group, an acryloyl group, and a styryl group are preferable, and methacryloyl Group and acryloyl group are more preferable, and methacryloyl group is particularly preferable in terms of both the formability of the crosslinked cured film and the raw storage stability.
The amount of methacryloyl group introduced is not particularly limited and may be appropriately selected depending on the intended purpose. The vinyl group equivalent is preferably 0.05 mmol / g to 3.0 mmol / g, preferably 0.5 mmol. / G to 2.7 mmol / g is more preferable, and 0.75 mmol / g to 2.4 mmol / g is particularly preferable.

  As a method of introducing an unsaturated group into the main chain, there is a method of using a diol compound having an unsaturated group in the main chain direction for the synthesis of a polyurethane resin. There is no restriction | limiting in particular as a diol compound which has an unsaturated group in the said principal chain direction, According to the objective, it can select suitably, cis-2-butene-1, 4-diol, trans-2-butene-1 , 4-diol, polybutadiene diol, and the like.

  The polyurethane resin having an ethylenically unsaturated bond in the side chain can be used in combination with an alkali-soluble polymer containing a polyurethane resin having a structure different from that of the specific polyurethane resin. For example, the polyurethane resin having an ethylenically unsaturated bond in the side chain can be used in combination with a polyurethane resin containing an aromatic group in the main chain and / or side chain.

  Specific examples of the polyurethane resin (i) having an ethylenically unsaturated bond in the side chain include, for example, P-1 to P— shown in paragraphs “0293” to “0310” of JP-A-2005-250438. 31 polymers, and the like. Among these, the polymers of P-27 and P-28 shown in paragraphs “0308” and “0309” are preferable.

-(Ii) Polyurethane resin obtained by reacting a carboxyl group-containing polyurethane with a compound having an epoxy group and a vinyl group in the molecule-
The polyurethane resin 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 epoxy group and a vinyl group in the molecule. Depending on the purpose, a low molecular diol having a weight average molecular weight of 300 or less or a low molecular diol having a weight average molecular weight of 500 or more may be added as a copolymer component as a diol component.
By using the polyurethane resin, it is excellent in stable dispersibility with an inorganic filler, crack resistance and impact resistance, so that heat resistance, moist heat resistance, adhesion, mechanical properties, and electrical properties are improved.

  The polyurethane resin includes a divalent aliphatic or aromatic hydrocarbon diisocyanate which may have a substituent, a COOH group and two OH groups via any one of a C atom and an N atom. A reaction product comprising a carboxylic acid-containing diol as an essential component, which is obtained by reacting the obtained reaction product with a compound having an epoxy group and a vinyl group in the molecule via a —COO— bond It may be.

Moreover, as said polyurethane resin, at least 1 sort (s) chosen from the diisocyanate shown by the following general formula (11), and the carboxylic acid group containing diol shown by the following general formula (12-1)-(12-3), 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 (13-1) to (13-5) according to the purpose: A reaction product obtained by reacting the obtained reaction product with a compound having an epoxy group and a vinyl group in the molecule represented by the following general formulas (14-1) to (14-16) It may be.
However, in the general formula (11), 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 (12-1), 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 (12-1), (12-2) and (12-3), 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, an aralkyl group, an aryl group, an alkoxy group, and a halogeno group are preferable), and may represent a divalent aliphatic or aromatic hydrocarbon. Among these, an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable. Further, if necessary, 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 the general formulas (13-1) to (13-3), R ₇ , R ₈ , R ₉ , R _10, and R ₁₁ may be the same or different, and may be divalent. 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 (13-4), 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 (13-5), R ₁₃ represents an aryl group or a cyano group, and preferably an aryl group or a cyano group having 6 to 10 carbon atoms. In the general formula (13-4), m represents an integer of 2 to 4. In the general formulas (13-1) to (13-5), n ₁ , n ₂ , n ₃ , n ₄ and n ₅ each represent an integer of 2 or more, and an integer of 2 to 100 is preferable. In the general formula (13-5), n ₆ represents 0 or an integer of 2 or more, and 0 or an integer of 2 to 100 is preferable.

In the general formula _{(14-1) ~ (14-16),} 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.

  The polyurethane resin may further be copolymerized with a low molecular weight diol that does not contain a carboxylic acid group as a fifth component. Examples of the low molecular weight diol include those represented by the general formulas (13-1) to (13-5). The weight average molecular weight is 500 or less. The low molecular weight diol containing no carboxylic acid group can be added as long as the alkali solubility is not lowered and the elastic modulus of the cured film can be kept sufficiently low.

  As the polyurethane resin, in particular, a diisocyanate represented by the general formula (11) and at least one selected from carboxylic acid group-containing diols represented by the general formulas (12-1) to (12-3) are essential. As a component, depending on the purpose, 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 (13-1) to (13-5), In addition to the reaction product of the low molecular weight diol containing no carboxylic acid group having a weight average molecular weight of 500 or less represented by the formulas (13-1) to (13-5), the formulas (14-1) to (14-16) ), Which is obtained by reacting a compound having one epoxy group and at least one (meth) acrylic group in the molecule represented by any of the above formulas, and having an acid value of 20 mgKOH / g to 120 mgKOH / g Soluble photocrosslinking polyurethane resin is preferable.

  These polymer compounds may be used alone or in combination of two or more.

--Synthesis of polyurethane resin obtained by reacting carboxyl group-containing polyurethane with compound having epoxy group and vinyl group in molecule--
As a method for synthesizing the polyurethane resin, the diisocyanate compound and the diol compound are synthesized in an aprotic solvent by adding a known catalyst having an activity corresponding to each reactivity and heating. The molar ratio of the diisocyanate and diol compound to be used is preferably 0.8: 1 to 1.2: 1. When an isocyanate group remains at the end of the polymer, it can be treated with alcohols or amines to obtain 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 (11), 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 (13-1) to (13-5) 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 (12-1) to (12-3) 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.

--Carboxylic acid group-free low molecular weight diol--
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.

  Specific examples of the polyurethane resin obtained by reacting the above (ii) carboxyl group-containing polyurethane with a compound having an epoxy group and a vinyl group in the molecule include, for example, paragraphs “0314” to JP-A-2007-2030. Glycidyl acrylate as an epoxy group and vinyl group-containing compound in the polymers of U1 to U13, U1 to U4, and U6 to U11 shown in “0315” is converted into glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate (trade name: Cyclo Mer A400 (manufactured by Daicel Chemical Industries)), 3,4-epoxycyclohexylmethyl methacrylate (trade name: Cyclomer M400 (manufactured by Daicel Chemical Industries)), and the like.

  In addition to the said polyurethane resin, it is preferable to add other resin to the photosensitive resin composition of this invention in the quantity of 50 mass% or less with respect to the said polyurethane resin further as needed. Examples of the other resin include polyamide resin, epoxy resin, polyacetal resin, acrylic resin, methacrylic resin, polystyrene resin, and novolac type phenol resin.

  As content of the said resin, 5 mass parts-80 mass parts are preferable with respect to 100 mass parts of solid content of the said photosensitive resin composition, and 30 mass parts-70 mass parts are more preferable. When the content is 5 parts by mass or more, developability and exposure sensitivity are good, and when the content is 80 parts by mass or less, the adhesiveness of the photosensitive layer can be prevented from becoming too strong.

  Use of the polyurethane resin is advantageous in that it is excellent in pattern formability, crack resistance, developability, heat resistance, electrical insulation, and mechanical properties.

<< Weight average molecular weight of polyurethane resin >>
There is no restriction | limiting in particular as a weight average molecular weight of the said polyurethane resin, Although it can select suitably according to the objective, 2,000-60,000 are preferable, 3,000-50,000 are more preferable, 3, 000 to 30,000 is particularly preferred. When the weight average molecular weight is less than 2,000, 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. . On the other hand, when the photosensitive resin composition is used as a photosensitive solder resist when the weight average molecular weight is 2,000 to 60,000, it is excellent in crack resistance and heat resistance, and is a non-image part by an alkaline developer. Excellent developability.
The weight average molecular weight is, for example, a high-speed GPC device (HLC-802A manufactured by Toyo Soda Kogyo Co., Ltd.), a 0.5% by mass THF solution as a sample solution, and a column of one TSKgel HZM-M. 200 μL of sample is injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or UV detector (detection wavelength 254 nm).

<< Acid value of polyurethane resin >>
There is no restriction | limiting in particular as an acid value of the said 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 preferable, 35 mgKOH / g ˜100 mg KOH / g is particularly preferred. If the acid value is less than 20 mgKOH / g, the developability may be insufficient, and if it exceeds 120 mgKOH / g, the development rate may be too high, and 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.

<< Vinyl group equivalent of polyurethane resin >>
There is no restriction | limiting in particular as a vinyl group equivalent of the said polyurethane resin, Although it can select suitably according to the objective, 0.05 mmol / g-3 mmol / g are preferable, 0.5 mmol / g-2.7 mmol / g Is more preferable, and 0.75 mmol / g to 2.4 mmol / g is particularly preferable. When the vinyl group equivalent is less than 0.05 mmol / g, the heat resistance of the cured film may be inferior, and when it exceeds 3 mmol / g, the brittleness of the cured film may increase.
The vinyl group equivalent can be determined, for example, by measuring the bromine number. In addition, the said bromine number can be measured based on JISK2605, for example.

<< Content of polyurethane resin >>
There is no restriction | limiting in particular as content in the said photosensitive resin composition of the said polyurethane resin, Although it can select suitably according to the objective, 5 mass%-80 mass% are preferable, 20 mass%-75 mass% Is more preferable, and 30% by mass to 70% by mass is particularly preferable.
When the content is less than 5% by mass, the pattern formability, crack resistance, developability, and insulation may be deteriorated. When the content exceeds 80% by mass, the heat resistance may be broken. On the other hand, when the content is within the particularly preferable range, it is advantageous in terms of achieving both good crack resistance and heat resistance.

<Thermal crosslinking agent>
The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include epoxy resins, polyfunctional oxetane compounds, and paragraphs “0098” to “0100” of JP-A-2007-2030. And the compounds described. These may be used alone or in combination of two or more.
Among these, an epoxy resin compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxetanyl groups in one molecule are preferable.

  There is no restriction | limiting in particular as said epoxy resin, According to the objective, it can select suitably, For example, the compound etc. which were described in Paragraph "0095" of Unexamined-Japanese-Patent No. 2007-2030 etc. are mentioned.

  There is no restriction | limiting in particular as said polyfunctional oxetane compound, According to the objective, it can select suitably, For example, the compound etc. which were described in Unexamined-Japanese-Patent No. 2007-2030 paragraph "0096" etc. are mentioned.

  There is no restriction | limiting in particular as content in the said photosensitive resin composition of the said thermal crosslinking agent, Although it can select suitably according to the objective, 1 mass%-50 mass% are preferable, and 2 mass%-40 mass. % Is more preferable, and 3% by mass to 30% by mass is particularly preferable. When the content of the thermal crosslinking agent is less than 1% by mass, heat resistance may be deteriorated, and when it exceeds 50% by mass, developability and crack resistance may be deteriorated. On the other hand, when the content is within the particularly preferable range, a cured film can be produced with good sensitivity, and the formed cured film is advantageous in that both heat resistance and crack resistance can be achieved.

<Imide resin>
The imide resin contained in the photosensitive resin composition of the present invention is an imide resin having a urethane bond.
The imide resin is not particularly limited as long as it has a urethane bond, and can be appropriately selected according to the purpose. However, an imide resin further having an imide ring and an isocyanurate ring is preferable, and a general-purpose solvent ( For example, since it is excellent in solubility in aprotic polar organic solvents such as ketone solvents, ester solvents, ether solvents, etc., heat resistance and mechanical properties, a structural unit represented by the following general formula (I): An imide resin having a structural unit represented by the following general formula (II) and at least one of terminal structures represented by the following general formulas (III) to (V) is particularly preferable.
In the general formulas (I) and (II), R ₁ represents an organic group having a cyclic aliphatic structure having 6 to 13 carbon atoms, and R ₂ is a linear hydrocarbon having a number average molecular weight of 700 to 4,500. Represents the structure.

<< Method for producing imide resin >>
There is no restriction | limiting in particular as a manufacturing method of the said imide resin, According to the objective, it can select suitably, For example, it is a polyol compound which has a polyisocyanate compound (a1) and a linear hydrocarbon structure, Comprising: Prepolymer (A) having an isocyanate group at the terminal obtained by reacting with a polyol compound (a2) having a hydrocarbon structure portion having a number average molecular weight of 300 to 6,000, and a polycarboxylic acid having three or more carboxyl groups Examples thereof include a method of reacting an acid anhydride (B) in an organic solvent. As the manufacturing method, for example, the method described in Japanese Patent No. 4217952 can be used.

  Specific examples include a polyisocyanate having an isocyanurate ring derived from a diisocyanate having a cycloaliphatic structure having 6 to 13 carbon atoms and a polyol compound having a linear hydrocarbon structure, which is a linear hydrocarbon. Examples thereof include a method of reacting a prepolymer having an isocyanate group at the terminal obtained by reacting a polyol compound having a number average molecular weight of 700 to 4,500 with a structural portion and an acid anhydride of tricarboxylic acid in an organic solvent. .

-Prepolymer (A)-
--Polyisocyanate compound (a1)-
There is no restriction | limiting in particular as said polyisocyanate compound (a1), Although it can select suitably according to the objective, The compound which has a 2 or more isocyanate group in a molecule | numerator is preferable, for example, aromatic polyisocyanate, fat Group polyisocyanates (including cycloaliphatic polyisocyanates); examples thereof include nurate bodies, burette bodies, adduct bodies, and allohanate bodies of these polyisocyanates.
Specific examples of the aromatic polyisocyanate include, for example, compounds described in paragraph “0018” of Japanese Patent No. 4217952, and specific examples of the aliphatic polyisocyanate include, for example, those of Japanese Patent No. 4217952 Examples include the compounds described in paragraph “0019”.

  As the polyisocyanate compound (a1), an aliphatic polyisocyanate is obtained because an imide resin having good solubility in an organic solvent, compatibility with an epoxy resin or an organic solvent, and a low dielectric constant and dielectric loss tangent of a cured product can be obtained. Is preferred. In addition, an isocyanurate type polyisocyanate is preferable because an imide resin having good heat resistance of the cured product can be obtained.

  Furthermore, as the polyisocyanate compound (a1), an imide resin having good solubility in organic solvents and compatibility with epoxy resins and organic solvents, low dielectric constant and dielectric loss tangent of cured products, and good heat resistance is obtained. Therefore, the polyisocyanate compound (a11) having an isocyanurate ring derived from an aliphatic polyisocyanate is more preferable, and a polyisocyanate compound having an isocyanurate ring derived from a cyclic aliphatic polyisocyanate is more preferable. The polyisocyanate compound having an isocyanurate ring derived from the cycloaliphatic polyisocyanate preferably has 2 to 3 moles of a cyclic aliphatic structure with respect to 1 mole of the isocyanurate ring. What has 5 mol times-3 mol times is more preferable.

  The polyisocyanate compound (a11) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, one or more aliphatic diisocyanate compounds may be used as an isocyanurate such as a quaternary ammonium salt. Examples thereof include those obtained by isocyanurate formation in the presence or absence of an oxidization catalyst, and composed of a mixture of isocyanurates such as trimer, pentamer, and heptamer.

  Specific examples of the polyisocyanate compound (a11) include isocyanurate type polyisocyanate of isophorone diisocyanate, isocyanurate type polyisocyanate of hexamethylene diisocyanate, isocyanurate type polyisocyanate of hydrogenated xylene diisocyanate, isocyanurate type polyisocyanate of norbornane diisocyanate. An isocyanate etc. are mentioned.

  As the polyisocyanate compound (a11), an imide resin having good solubility in organic solvents and heat resistance of a cured product is obtained. Therefore, 30 isocyanurates of trimer are added to 100 parts by mass of the polyisocyanate compound (a1). Those containing at least 50 parts by mass are preferred, and those containing at least 50 parts by mass are particularly preferred.

  Moreover, as said polyisocyanate compound (a11), since the content rate of an isocyanate group is 10 mass%-30 mass%, since the imide resin with favorable organic solvent solubility and heat resistance of hardened | cured material is obtained. More preferred. Therefore, the polyisocyanate compound (a11) is a polyisocyanate compound having an isocyanurate ring derived from a cyclic aliphatic polyisocyanate, and the isocyanate group content is 10% by mass to 30% by mass. Is particularly preferred.

  The polyisocyanate having an isocyanurate ring may be used in combination with other polyisocyanates, but isocyanurate type polyisocyanates are preferably used alone.

--Polyisocyanate compound (a2)-
The polyol compound (a2) is preferably a polyol compound having a linear hydrocarbon structure portion having a number average molecular weight of 300 to 6,000. Among these, the organic solvent solubility and the phase with an epoxy resin or an organic solvent are preferable. A polyol having a number average molecular weight of 700 to 4,500 in a linear hydrocarbon structure portion because an imide resin having good solubility and mechanical properties, low dielectric constant and dielectric loss tangent of cured product, and excellent film-forming properties can be obtained. A compound is more preferable, and a polyol compound having a linear hydrocarbon structure part number average molecular weight of 800 to 4,200 is particularly preferable. When the number average molecular weight of the linear hydrocarbon structure portion is less than 300, the cured product may have a high dielectric constant and dielectric loss tangent, and the number average molecular weight of the linear hydrocarbon structure portion may be 6,000. If it exceeds, the polyol compound may have poor organic solvent solubility, compatibility with an epoxy resin or an organic solvent, and mechanical properties.

  Examples of the polyol compound (a2) include compounds having an average of 1.5 or more hydroxyl groups bonded to the terminal and / or side chain of the linear hydrocarbon structure in total per molecule. The linear hydrocarbon structure may be linear or branched. The linear hydrocarbon structure may be a saturated hydrocarbon chain or an unsaturated hydrocarbon chain, but a saturated hydrocarbon chain is more preferable from the viewpoint of changes in physical properties and stability during heating.

Examples of the polyol compound (a2) include polyol compounds having a polyolefin structure or a polydiene structure, wherein the polyol compound having a polyolefin structure or a polydiene structure has a number average molecular weight of 300 to 6,000 and hydrogenated products thereof. It is done.
Examples of the olefin include ethylene, propylene, butene, isobutylene, pentene, and methylpentene. Examples of the diene include pentadiene, hexadiene, pentadiene, isoprene, butadiene, propadiene, and dimethylbutadiene.

  Specific examples of the polyol compound (a2) include polyethylene polyol, polypropylene polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, etc., and the number of linear hydrocarbon structure portions. Examples include polyol compounds having an average molecular weight of 300 to 6,000. These may be used alone or in combination of two or more.

  The number of hydroxyl groups in the polyol compound (a2) is preferably from 1.5 to 3 on average because an imide resin that is difficult to gel, has good molecular growth, and has excellent mechanical properties can be obtained. Further, the number of hydroxyl groups is particularly preferably an average of 1.8 to 2.2.

  Examples of commercially available products of the polyol compound (a2) include liquid polybutadiene having hydroxyl groups at both ends, such as NISSO PB (G series) manufactured by Nippon Soda Co., Ltd., Poly-bd manufactured by Idemitsu Petrochemical Co., Ltd .; Hydrogenated polybutadiene having hydroxyl groups at both ends such as NISSO PB (GI series) manufactured by Mitsubishi Corporation, Polytail H manufactured by Mitsubishi Chemical Corporation, and Polytail HA; Hydroxyl groups at both ends such as Poly-iP manufactured by Idemitsu Petrochemical Co., Ltd. Examples include liquid C5 polymers having a hydroxyl group; Epole manufactured by Idemitsu Petrochemical Co., Ltd., hydrogenated polyisoprene having hydroxyl groups at both ends such as TH-1, TH-2, TH-3 manufactured by Kuraray Co., Ltd., and the like.

  Furthermore, as the polyol compound (a2), ester-modified polyol compounds and urethane-modified polyol compounds obtained by reacting various polybasic acids and polyisocyanates with the polyol compound having the linear hydrocarbon structure can also be used.

  As the polyol compound (a2), polybutadiene polyol and / or hydrogenated polybutadiene polyol are preferable, and hydrogenated polybutadiene polyol is particularly preferable.

In the imide resin, the linear hydrocarbon structure derived from the polyol compound (2a) is introduced between rigid skeletons having an imide bond.
There is no restriction | limiting in particular as a glass transition point of the said polyol compound (a2), Although it can select suitably according to the objective, -120 to 0 degreeC is preferable.

  In the production of the imide resin, the polyol compound (a2) may be used in combination with other hydroxyl group-containing compounds as long as the effects of the present invention are not impaired. At this time, the other hydroxyl group-containing compound is preferably used at 50% by mass or less based on the total hydroxyl group-containing compound.

  There is no restriction | limiting in particular as said other hydroxyl-containing compound, According to the objective, it can select suitably, A saturated polyol, unsaturated polyol, or alcohol may be sufficient, However A polyol is preferable. Examples of the other hydroxyl group-containing compounds include compounds described in paragraphs “0036” to “0037” of Japanese Patent No. 4217952.

-Acid anhydride (B) of polycarboxylic acid-
The acid anhydride (B) of the polycarboxylic acid having three or more carboxyl groups is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include tricarboxylic acid anhydrides and tetracarboxylic acids. And acid anhydrides.

  Examples of the acid anhydride of the tricarboxylic acid include trimellitic anhydride and naphthalene-1,2,4-tricarboxylic acid anhydride.

  The acid anhydride of the tetracarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraphs “0040” to “0041” of Japanese Patent No. 4217952. It is done.

  Specific examples of the imide resin include, for example, X-1 to X-8 shown in paragraphs “0069” to “0083” of Japanese Patent No. 4217952. Moreover, a commercial item can also be used for the said imide resin, for example, Unidic V8000 series (made by DIC Corporation) etc. are mentioned.

<< Molecular weight of imide resin >>
The molecular weight of the imide resin is not particularly limited and may be appropriately selected depending on the intended purpose. The number average molecular weight is 2,000 to 30,000 and the weight average molecular weight is 3,000 to 100,000. 000 imide resins are particularly preferred.
In the general formula (II), R ₂ preferably has a linear hydrocarbon structure having a number average molecular weight of 800 to 4,200.
The number average molecular weight and the weight average molecular weight of the imide resin can be determined by gel permeation chromatography (GPC) as the number average molecular weight and the weight average molecular weight in terms of polystyrene.

<< Acid value of imide resin >>
There is no restriction | limiting in particular as an acid value of the said imide resin, Although it can select suitably according to the objective, 20 mgKOH / g-250 mgKOH / g are preferable.
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.

<< Concentration of isocyanurate ring of imide resin >>
There is no restriction | limiting in particular as a density | concentration of the isocyanurate ring of the said imide resin, Although it can select suitably according to the objective, 0.3 mmol / g-1.2 mmol / g are preferable.
The concentration of the isocyanurate ring of the imide resin was determined by performing ¹³ C-NMR analysis (solvent: deuterated dimethyl sulfoxide (DMSO-d ₆ )), and the spectral intensity of carbon atoms caused by the isocyanurate ring at 149 ppm. From this, the concentration (mmol) of the isocyanurate ring per 1 g of the imide resin can be determined using a calibration curve. Moreover, the density | concentration of an imide ring can be similarly calculated | required from the spectral intensity of the carbon atom resulting from an imide ring in 169 ppm by < ¹³ > C-NMR analysis.

<< Content of linear hydrocarbon structure portion of imide resin >>
There is no restriction | limiting in particular as content rate of the linear hydrocarbon structure part of the said imide resin, Although it can select suitably according to the objective, 20 mass%-40 mass% are preferable.
The content of the linear hydrocarbon structure portion and the number average molecular weight in the imide resin are linear by decomposing urethane bonds by heat treatment of the imide resin in the presence of an organic amine, for example, in the presence of an organic amine. The hydrocarbon structure portion is separated from the imide resin, and the linear hydrocarbon structure portion is less polar than the imide structure portion. It can be obtained by extracting and measuring the amount of extraction and GPC analysis.
In addition, when manufacturing the said imide resin with the said manufacturing method, the content rate of the linear hydrocarbon structure part in the said imide resin can be calculated | required from the use weight ratio of the polyol compound (a2) in a synthetic raw material, The number average molecular weight of the linear hydrocarbon structure portion can be determined from the number average molecular weight of the polyol compound (a2).

<< Mole content of urethane group in imide resin >>
There is no restriction | limiting in particular as the molar content rate of the urethane group in the said imide resin, Although it can select suitably according to the objective, 5 to 50% is preferable and 10 to 45% is more preferable. If the content is less than 5%, sufficient heat resistance effect may not appear, and if it exceeds 50%, the film may be inferior in brittleness such as cracking when the composition is dried. .
The molar content of the urethane group can be measured by FT-IR (infrared spectroscopy).

<< Content of imide resin >>
There is no restriction | limiting in particular as content in the said photosensitive resin composition of the said imide resin, Although it can select suitably according to the objective, 2 mass%-40 mass% are preferable, and 5 mass%-30 mass% are preferable. Is more preferable, and 5% by mass to 25% by mass is particularly preferable. When the content of the imide resin is less than 2% by mass, heat resistance may be deteriorated. When it exceeds 40% by mass, the film is cracked when the photosensitive resin composition is dried. May be inferior.

<< Polyurethane resin / imide resin (mass ratio) >>
Further, the mass ratio of the polyurethane resin and the imide resin having a urethane bond (polyurethane resin / imide resin) is not particularly limited and may be appropriately selected depending on the intended purpose. 1-10 are more preferable and 2-5 are especially preferable. If the mass ratio is less than 1, developability may be deteriorated, and if it exceeds 19, pattern formability, crack resistance, developability, and insulation properties may be deteriorated.

<Polymerizable compound>
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. The compound has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. For example, at least one selected from monomers having a (meth) acryl group is preferable.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional 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 hex (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, Polyfunctional alcohols such as glycerin tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, and the like, and (meth) acrylated after addition reaction of ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-41708, Japanese Patent Publication Urethane acrylates described in publications such as JP 50-6034 and JP 51-37193; JP 48-64183, JP 49-4319 Polyester acrylates described in various publications such as JP, JP 30-30490, and polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. It is done. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are more preferable.

<< Content of polymerizable compound >>
There is no restriction | limiting in particular as content in the said photosensitive resin composition of the said polymeric compound, Although it can select suitably according to the objective, 2 mass%-50 mass% are preferable, and 3 mass%-40 mass are preferable. % Is more preferable, and 4% by mass to 35% by mass is particularly preferable. When the content of the polymerizable compound is less than 2% by mass, pattern formation may not be possible, and when it exceeds 50% by mass, crack resistance may be inferior. On the other hand, when the content of the polymerizable compound is within the particularly preferable range, it is advantageous in that pattern forming properties and crack resistance are improved.

<Photopolymerization initiator>
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected according to the purpose. For example, a halogenated hydrocarbon derivative (for example, a triazine skeleton) And those having an oxadiazole skeleton), phosphine oxide, hexaarylbiimidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, and the like.

  The halogenated hydrocarbon compound having a triazine skeleton is not particularly limited and may be appropriately selected depending on the intended purpose. For example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in British Patent No. 1388492, compounds described in Japanese Patent Laid-Open No. 53-133428, German Patent No. 3337024 Compounds, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, and JP-A-5-34920 Examples of the halogenated hydrocarbon compound having an oxadiazole skeleton include the compounds described in US Pat. No. 4,221,976.

  There is no restriction | limiting in particular as said oxime derivative, According to the objective, it can select suitably, For example, the compound etc. which were described in Paragraph "0085" of Unexamined-Japanese-Patent No. 2007-2030 etc. are mentioned.

  There is no restriction | limiting in particular as said ketone compound, According to the objective, it can select suitably, For example, the compound etc. which were described in Paragraph "0087" of Unexamined-Japanese-Patent No. 2007-2030 etc. are mentioned.

  Examples of photopolymerization initiators other than those described above include compounds described in paragraph “0086” of JP-A-2007-2030.

In addition to the photopolymerization initiator, a sensitizer can be added for the purpose of adjusting the exposure sensitivity and the photosensitive wavelength in exposure to the photosensitive layer described later.
The sensitizer can be appropriately selected by a visible light, an ultraviolet laser, a visible light laser or the like as a light irradiation means described later.
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of

  There is no restriction | limiting in particular as said sensitizer, According to the objective, it can select suitably, For example, the compound etc. which were described in Paragraph "0089" of Unexamined-Japanese-Patent No. 2007-2030 are mentioned.

  There is no restriction | limiting in particular as a combination of the said photoinitiator and the said sensitizer, According to the objective, it can select suitably, For example, the electron transfer type | mold start system of Unexamined-Japanese-Patent No. 2001-305734 [ (1) Electron donating initiator and sensitizing dye, (2) Electron accepting initiator and sensitizing dye, (3) Electron donating initiator, sensitizing dye and electron accepting initiator (ternary initiation system) ] Etc. are mentioned.

  There is no restriction | limiting in particular as content of the said sensitizer, Although it can select suitably according to the objective, 0.05 mass%-30 mass% are with respect to all the components in the said photosensitive resin composition. Preferably, 0.1% by mass to 20% by mass is more preferable, and 0.2% by mass to 10% by mass is particularly preferable. When the content of the sensitizer is less than 0.05% by mass, the sensitivity to active energy rays decreases, the exposure process takes time, and the productivity may decrease, exceeding 30% by mass. In some cases, the sensitizer may precipitate from the photosensitive layer during storage.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
Particularly preferable examples of the photopolymerization initiator include halogenated carbonization having the phosphine oxides, the α-aminoalkyl ketones, and the triazine skeleton, which can cope with laser light having a wavelength of 405 nm in the later-described exposure. Examples include a composite photoinitiator, a hexaarylbiimidazole compound, or titanocene, which is a combination of a hydrogen compound and an amine compound as a sensitizer described later.

<< Content of photopolymerization initiator >>
There is no restriction | limiting in particular as content in the said photosensitive resin composition of the said photoinitiator, Although it can select suitably according to the objective, 0.5 mass%-20 mass% are preferable, 0.5 More preferably, 15% by mass to 15% by mass is preferable, and 1% by mass to 10% by mass is particularly preferable. When the content of the photopolymerization initiator is less than 0.5% by mass, the exposed area tends to be eluted during development, and when it exceeds 20% by mass, the heat resistance may be lowered. On the other hand, when the content of the photopolymerization initiator is within the particularly preferable range, it is advantageous in that a good pattern can be formed and heat resistance is also improved.

<Thermoplastic elastomer>
Heat resistance, flexibility, and toughness can be imparted to the photosensitive resin composition by adding the elastomer to the photosensitive resin composition.

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

<< Styrenic elastomer >>
There is no restriction | limiting in particular as said styrene-type elastomer, According to the objective, it can select suitably, For example, a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butylene-styrene block copolymer And styrene-ethylene-propylene-styrene block copolymer.
In addition to styrene which is a component constituting the styrene elastomer, styrene derivatives such as α-methyl styrene, 3-methyl styrene, 4-propyl styrene and 4-cyclohexyl styrene can be used.

  Specific examples of the styrene-based elastomer include commercially available products such as TUFPRENE, SORPRENE T, ASAPRENE T, TUFTEC (manufactured by Asahi Kasei Co., Ltd.), Elastomer AR (manufactured by Aron Kasei Co., Ltd.), Kraton G, and Superflex. (Shell Japan), JSR-TR, TSR-SIS, Dynalon (Nippon Synthetic Rubber Co., Ltd.), Denka STR (Denki Kagaku Kogyo Co., Ltd.), Quintac (Zeon Japan), TPE-SB Series (manufactured by Sumitomo Chemical Co., Ltd.), Lavalon (manufactured by Mitsubishi Chemical Co., Ltd.), Septon, Hibler (manufactured by Kuraray Co., Ltd.), Sumiflex (manufactured by Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimer (manufactured by Riken Vinyl Industries, Ltd. Manufactured).

<< Olefin elastomer >>
There is no restriction | limiting in particular as said olefin type elastomer, According to the objective, it can select suitably, For example, C2-C20, such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene, etc. α-olefin copolymer, for example, ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), etc., and dicyclopentadiene, 1,4-hexadiene, Examples thereof include non-conjugated dienes having 2 to 20 carbon atoms such as cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, and isoprene, and α-olefin copolymers.
Moreover, the carboxy modified NBR which copolymerized methacrylic acid to the butadiene-acrylonitrile copolymer is mentioned. Specifically, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, propylene / α-olefin copolymer rubber, butene / α-olefin copolymer rubber, etc. Can be mentioned.

  Specifically, as the olefin-based elastomer, commercially available products include milastoma (manufactured by Mitsui Chemicals), EXACT (manufactured by Exxon Chemical), ENGAGE (manufactured by Dow Chemical), R-45HT (manufactured by Idemitsu Kosan Co., Ltd.), BAC-45 (manufactured by Osaka Organic Chemical Industries, Ltd.), PB3600 (manufactured by Daicel Chemical Industries, Ltd.), hydrogenated styrene-butadiene rubber (DYNABON HSBR, manufactured by Nippon Synthetic Rubber Co., Ltd.), butadiene-acrylonitrile copolymer (NBR series) Nippon Synthetic Rubber Co., Ltd.), or both-end carboxyl group-modified butadiene-acrylonitrile copolymers having a crosslinking point (XER series, Nippon Synthetic Rubber Co., Ltd.).

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

  The number average molecular weight of the polymer (long chain) diol is preferably 500 to 10,000, and in addition to ethylene glycol, short chain diols such as propylene glycol, 1,4-butanediol, and bisphenol A may be used. The number average molecular weight of the short-chain diol is preferably 48 to 500. Examples of commercially available urethane elastomers include PANDEX T-5205LL, T-5210, T-5265L, T-R01, T-2185, T-2983N (manufactured by DIC Corporation), and Syractran E790.

<< Polyester elastomer >>
There is no restriction | limiting in particular as said polyester-type elastomer, According to the objective, it can select suitably, For example, what is obtained by polycondensing dicarboxylic acid or its derivative (s) and a diol compound or its derivative (s) is mentioned.
Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which hydrogen atoms of these aromatic nuclei are substituted with a methyl group, an ethyl group, a phenyl group, and the like. Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These may be used alone or in combination of two or more.

  Examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol. And alicyclic diols and dihydric phenols represented by the following structural formulas.

However, in the structural formula, Y represents any one of an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, —O—, —S—, and —SO ₂ —. Represents a direct bond between benzene rings. R ¹ and R ² represent halogen or an alkyl group having 1 to 12 carbon atoms. l and m represent an integer of 0 to 4, and p is 0 or 1.

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

<< Polyamide elastomer >>
There is no restriction | limiting in particular as said polyamide-type elastomer, According to the objective, it can select suitably, For example, the polyether block amide type | mold and polyether ester which used polyamide for the hard phase, and used polyether and polyester for the soft phase. The polyamide is roughly classified into two types of block amide type, and polyamide-6, 11, 12 or the like is used as the polyamide, and polyoxyethylene, polyoxypropylene, polytetramethylene glycol or the like is used as the polyether. Specifically, as commercially available products, UBE polyamide elastomer (manufactured by Ube Industries Co., Ltd.), Daiamide (manufactured by Daicel Huls Co., Ltd.), PEBAX (manufactured by Toray Industries, Inc.), Grilon ELY (manufactured by MMS Japan Co., Ltd.), Nopamid ( Mitsubishi Chemical Co., Ltd.), Relax (DIC Co., Ltd.), TAPE-617 (Fuji Kasei Co., Ltd.) and the like.

<< Acrylic elastomer >>
The acrylic elastomer is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, and the like based on an acrylic ester. Examples of the crosslinking point monomer include glycidyl methacrylate and allyl glycidyl ether. Furthermore, acrylonitrile and ethylene can be copolymerized. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like. Specifically, LA polymer (made by Kuraray Co., Ltd.) etc. are mentioned as a commercial item.

<< Silicone-based elastomer >>
The silicone elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the silicone elastomer is mainly composed of organopolysiloxane, such as polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane. Etc. Specific examples of commercially available products include KE series, X-22-169B, X-22-164B, X-22-9002 (manufactured by Shin-Etsu Chemical Co., Ltd.), BY series, SF series (above, Toray Dow Corning Silicone Co., Ltd.) Company-made).

  In addition to the elastomer, a rubber-modified epoxy resin can be used. The rubber-modified epoxy resin includes, for example, a part or all of the epoxy groups of the bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac type epoxy resin or cresol novolac type epoxy resin. It is obtained by modifying with a terminal carboxylic acid-modified butadiene-acrylonitrile rubber, a terminal amino-modified silicone rubber or the like. Among these elastomers, in terms of shear adhesion, Pandex T series (manufactured by DIC Corporation), which is a carboxyl group-modified butadiene-acrylonitrile copolymer, a polyester-based elastomer having a hydroxyl group, and a soluble polyurethane elastomer, is available. preferable.

<< Elastomer content >>
As content in the said photosensitive resin composition of the said elastomer, 1 mass part-50 mass parts are preferable with respect to 100 mass parts of the said photosensitive resin compositions, 2 mass parts-20 mass parts are more preferable, 3 Part by mass to 10 parts by mass are particularly preferred. If the content is less than 1 part by mass, the crack resistance may not be inferior, and if it exceeds 50 parts by mass, the unexposed part tends not to be eluted with the developer. On the other hand, when the content is within the particularly preferable range, it is advantageous in terms of improving developability and crack resistance.

<Thermosetting accelerator>
There is no restriction | limiting in particular as said thermosetting accelerator, According to the objective, it can select suitably, For example, the compound described in Paragraph "0101" of Unexamined-Japanese-Patent No. 2007-2030 is mentioned.

<< Content of thermosetting accelerator >>
There is no restriction | limiting in particular as content in the said photosensitive resin composition of the said thermosetting accelerator, Although it can select suitably according to the objective, 0.01 mass%-20 mass% are preferable, 0.05 More preferably, 15% by mass to 15% by mass is preferable, and 0.1% by mass to 10% by mass is particularly preferable. When the content of the thermosetting accelerator is less than 0.01% by mass, the toughness of the cured film may not be expressed, and when it exceeds 20% by mass, the storage stability of the photosensitive resin composition is stabilized. Sexuality may worsen. On the other hand, when the content of the thermosetting accelerator is within the particularly preferable range, it is advantageous in that the storage stability and the cured film physical properties of the photosensitive resin composition are improved.

<Adhesion promoter>
There is no restriction | limiting in particular as said adhesion promoter, According to the objective, it can select suitably, For example, the compound described in Paragraph "0108" of Unexamined-Japanese-Patent No. 2007-2030 is mentioned.

<< Content of adhesion promoter >>
There is no restriction | limiting in particular as content in the said photosensitive resin composition of the said adhesion promoter, Although it can select suitably according to the objective, 0.01 mass%-20 mass% are preferable, 0.05 mass % To 15% by mass is more preferable, and 0.1% to 10% by mass is particularly preferable. When the content of the adhesion promoter is less than 0.01% by mass, it may not be possible to express the toughness of the cured film. May get worse. On the other hand, when the content is within the particularly preferable range, it is advantageous in that the storage stability and the cured film properties of the photosensitive resin composition are improved.

<Thermal polymerization inhibitor>
There is no restriction | limiting in particular as said adhesion promoter, According to the objective, it can select suitably, For example, the compound described in Paragraph "0113" of Unexamined-Japanese-Patent No. 2007-2030 is mentioned.

<Inorganic filler>
There is no restriction | limiting in particular as said inorganic filler, Although it can select suitably according to the objective, It is preferable to contain the silica particle whose average particle diameter (d50) is 0.2 micrometer-3.0 micrometers. When the inorganic filler contains silica particles, the heat resistance of the cured film is improved, the dispersibility with the polyurethane resin is improved, and the viscosity of the photosensitive resin composition can be maintained in a suitable range. , Suitable applicability is obtained.

There is no restriction | limiting in particular as a silica in the said silica particle, According to the objective, it can select suitably, For example, vapor phase method silica, crystalline silica, fused silica etc. are mentioned.
There is no restriction | limiting in particular as an average particle diameter (d50) of the said silica particle, Although it can select suitably according to the objective, 0.2 micrometer-3.0 micrometers are preferable, and 0.3 micrometer-2.5 micrometers are more preferable. 0.5 μm to 2.5 μm is particularly preferable.

When the average particle diameter (d50) of the silica particles is less than 0.2 μm, the coating viscosity may be high, and when it exceeds 3.0 μm, the smoothness may not be maintained. On the other hand, when the average particle diameter (d50) of the silica particles is within the particularly preferable range, it is advantageous in terms of coating viscosity, smoothness of a cured film and heat resistance.
The average particle size (d50) of the silica particles is defined as a particle size of an integrated value of 50% when expressed as an integrated (cumulative) mass percentage, and is defined as d50 (D ₅₀ ) or the like. Yes, for example, using a dynamic light scattering photometer (trade name DLS7000, manufactured by Otsuka Electronics Co., Ltd.), the measurement principle is a dynamic light scattering method, and the size distribution analysis method is a cumulant method and / or a histogram method. be able to.

<< Content of inorganic filler >>
There is no restriction | limiting in particular as content in the said photosensitive resin composition of the said silica particle, Although it can select suitably according to the objective, 1 mass%-50 mass% are preferable, and 3 mass%-50 mass% are preferable. Is more preferable, and 5% by mass to 45% by mass is particularly preferable. When the content of the silica particles is less than 1% by mass, the heat resistance may be inferior, and when it exceeds 50% by mass, the pattern formability may be inferior. On the other hand, when the content is within the particularly preferable range, it is advantageous in that the pattern formability and heat resistance are improved.

<Colorant>
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, The dye selected suitably from a coloring pigment and well-known dye can be used.
There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, the compound described in Paragraph "0106" of Unexamined-Japanese-Patent No. 2007-2030 is mentioned.
There is no restriction | limiting in particular as content in the said photosensitive resin composition of the said coloring agent, According to the objective, it can select suitably.

<Organic solvent>
The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0043” of JP-A No. 11-240930 and paragraphs of JP-A No. 2007-2030. And the compounds described in “0121”.

<< Content of organic solvent >>
There is no restriction | limiting in particular as content in the said photosensitive resin composition of the said organic solvent, Although it can select suitably according to the objective, 1 mass%-80 mass% are preferable, and 2 mass%-70 mass% are preferable. Is more preferable, and 3% by mass to 60% by mass is particularly preferable. When the content of the organic solvent is less than 1% by mass, the viscosity of the composition may be high and it may be difficult to form a coating film. When the content exceeds 80% by mass, it is difficult to control the desired film thickness. May be. On the other hand, when the content of the organic solvent is within the particularly preferable range, it is advantageous from the viewpoint of coating film production suitability.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include thixotropic agents such as benton, montmorillonite, aerosol, amide wax, silicone-based, fluorine-based, polymer-based, etc. Additives such as antifoaming agents and leveling agents can be used.

(Photosensitive solder resist composition)
The photosensitive solder resist composition of the present invention contains the photosensitive resin composition of the present invention.
According to the photosensitive solder resist composition of the present invention, a solder resist having excellent pattern formability, crack resistance, heat resistance, electrical insulation, developability, and mechanical properties can be obtained.
In the photosensitive solder resist composition of the present invention, a conventional alkali-soluble photocrosslinkable resin can be mixed and used together with the photosensitive resin composition.
The alkali-soluble photocrosslinkable resin is a resin that is soluble in a 1% aqueous sodium carbonate solution (pH = 10) containing an alkali-soluble group and a crosslinkable group involved in photopolymerization in the molecule.
The conventional alkali-soluble photocrosslinkable resin is not particularly limited and may be appropriately selected depending on the purpose. For example, it is described in paragraphs “0050” to “0070” of JP-A-2007-2030. Things.

(Photosensitive solder resist film)
The photosensitive solder resist composition of the present invention can be used as a liquid resist by coating and drying on a substrate on which a conductor wiring is formed, but is particularly useful for the production of a photosensitive solder resist film.
As shown in FIG. 1, the photosensitive solder resist film has at least a support 1 and a photosensitive layer 2, preferably a protective film 3, and, if necessary, a cushion layer. And other layers such as an oxygen blocking layer (hereinafter sometimes abbreviated as “PC layer”).
The form of the photosensitive film is not particularly limited and can be appropriately selected according to the purpose. For example, the photosensitive layer and the protective film are provided in this order on the support, The PC layer, the photosensitive layer, and the protective film are provided in this order on the support, and the cushion layer, the PC layer, the photosensitive layer, and the protective film are provided on the support. The form etc. which have in order are mentioned. The photosensitive layer may be a single layer or a plurality of layers.

<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 can be peeled off and that light transmittance is good, and that the surface is smooth. Is more preferable.

There is no restriction | limiting in particular as said support body, According to the objective, it can select suitably, For example, a transparent synthetic resin film is mentioned.
The transparent synthetic resin film is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meta) ) 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, Examples include various plastic films such as polytetrafluoroethylene, polytrifluoroethylene, cellulose-based films, and nylon films. These may be used alone or in combination of two or more. Among these, the transparent synthetic resin film is preferably polyethylene terephthalate.
The support is not particularly limited and may be appropriately selected depending on the intended purpose. For example, JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-173320 Examples include the support described in JP-A-5-72724.

There is no restriction | limiting in particular as thickness of the said support body, Although it can select suitably according to the objective, 4 micrometers-300 micrometers are preferable, and 5 micrometers-175 micrometers are more preferable.
There is no restriction | limiting in particular as a shape of the said support body, Although it can select suitably according to the objective, A long shape is preferable. There is no restriction | limiting in particular as the length of the said elongate support body, Although it can select suitably according to the objective, 10m-20,000m are preferable.

<Photosensitive layer>
The layer is formed by the photosensitive solder resist composition of the present invention.
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said photosensitive layer, Although it can select suitably according to the objective, Usually, it laminates | stacks on the said support body.

  There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, 3 micrometers-100 micrometers are preferable, and 5 micrometers-70 micrometers are more preferable.

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

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

  There is no restriction | limiting in particular as solid content concentration of the said photosensitive soldering resist composition solution, Although it can select suitably according to the objective, 10 mass%-90 mass% are preferable, and 15 mass%-50 mass% are More preferred.

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 are not particularly limited and can be appropriately selected according to the purpose. The conditions vary depending on each component, the type of solvent, the ratio of use, etc., but usually at a temperature of 60 ° C. to 110 ° C. for 30 seconds. ~ 15 minutes.

<Protective film>
The protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged.
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said protective film, Although it can select suitably according to the objective, Usually, it provides on the said photosensitive layer.
Examples of the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet. Among these, a polyethylene film and a polypropylene film are preferable.
There is no restriction | limiting in particular as thickness of the said protective film, Although it can select suitably according to the objective, 5 micrometers-100 micrometers are preferable, and 8 micrometers-30 micrometers are more preferable.

When the protective film is used, it is preferable that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
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, the relationship of the above adhesive forces can be satisfy | filled by surface-treating at least any one of a support body and a 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, as a static friction coefficient of the said support body and the said protective film, 0.3-1.4 are preferable and 0.5-1.2 are more preferable. When the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed, and when it exceeds 1.4, it is difficult to wind into a good roll. Sometimes.

The photosensitive solder resist film is not particularly limited and can be appropriately selected depending on the purpose. Is preferred.
There is no restriction | limiting in particular as length of the said elongate photosensitive soldering resist 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 is formed by applying the polymer coating solution on the surface of the protective film and then drying it at 30 to 150 ° C. (especially 50 to 120 ° C.) for 1 to 30 minutes. be able to.
In addition to the photosensitive layer, the support, and the protective film, a cushion layer, an oxygen blocking layer (PC layer), a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like may be included. .
The cushion layer is a layer that has no tackiness at room temperature and melts and flows when laminated under vacuum and heating conditions.
The PC layer is usually a film of about 1.5 μm formed mainly of polyvinyl alcohol.

The photosensitive solder resist film has a small surface tackiness, a good laminating property and handleability, and a photosensitive solder having excellent pattern forming properties, crack resistance, heat resistance, electrical insulation properties, developability, and mechanical properties. It has a photosensitive layer on which a resist composition is laminated. For this reason, it can be widely used for the formation of permanent patterns such as printed wiring boards, color filters, pillar materials, rib materials, spacers, partition walls and other display members, holograms, micromachines, proofs, etc. It can be suitably used for the forming method.
In particular, since the photosensitive solder resist film of the present invention has a uniform thickness, it is more accurately laminated on a substrate when a permanent pattern is formed.

(Permanent pattern and permanent pattern forming method)
The permanent pattern of the present invention is obtained by the permanent pattern forming method of the present invention.
The permanent pattern is preferably at least one of a protective film, an interlayer insulating film, and a solder resist pattern.
When the permanent pattern is a solder resist pattern, the dynamic elastic modulus at 220 ° C. is preferably 20 MPa to 100 MPa, more preferably 25 MPa to 80 MPa, and particularly preferably 30 MPa to 50 MPa. If the dynamic elastic modulus is less than 20 MPa, the heat resistance may be inferior, and if it exceeds 100 MPa, the thermal shock resistance may be inferior and cracks may occur in the cured film.

In the method for forming a permanent pattern of the present invention, as a first aspect, the photosensitive solder resist composition of the present invention is applied to the surface of a substrate, dried to form a photosensitive layer, and then exposed and developed.
Moreover, in the permanent pattern formation method of the present invention, as a second aspect, the photosensitive solder resist film of the present invention is laminated on the surface of the substrate under at least one of heating and pressurization, and then exposed. develop.
Hereinafter, the details of the permanent pattern of the present invention will be clarified through the description of the method for forming a permanent pattern of the present invention.

<Base material>
The substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a printed wiring board forming substrate such as a copper-clad laminate, a glass plate such as a soda glass plate, or a synthetic resin film , Paper, metal plate and the like.
Among these, a printed wiring board forming substrate on which wiring is already formed is preferable in that high-density mounting of a semiconductor or the like on a multilayer wiring board or a build-up wiring board is possible.

  The substrate is a laminate in which a photosensitive layer made of the photosensitive solder resist composition is formed on the substrate as the first aspect, or the photosensitive solder resist film as the second aspect. It is possible to use by forming a laminate in which the photosensitive layers are laminated so as to overlap each other. That is, by exposing the photosensitive layer in the laminated body to be described later, the exposed region can be cured, and a permanent pattern can be formed by development to be described later.

<Laminated body>
There is no restriction | limiting in particular as a formation method of the laminated body of a said 1st aspect, Although it can select suitably according to the objective, The said photosensitive soldering resist composition is apply | coated and dried on the said base material. The formed photosensitive layer is preferably laminated.
The method for coating and drying is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the photosensitive solder resist composition solution is spin coater, slit spin coater, roll coater, die coater, curtain. The method of apply | coating using a coater etc. is mentioned.

There is no restriction | limiting in particular as a formation method of the laminated body of the said 2nd aspect, Although it can select suitably according to the objective, At least any one of a heating and pressurization of the said photosensitive film on the said base material is carried out. A method of laminating while performing is preferable. 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 material.
There is no restriction | limiting in particular as the temperature of the said heating, Although it can select suitably according to the objective, 70 to 130 degreeC is preferable and 80 to 110 degreeC is more preferable.
There is no restriction | limiting in particular as said pressurization pressure, Although it can select suitably according to the objective, 0.01 MPa-1.0 MPa are preferable and 0.05 MPa-1.0 MPa are more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating and pressurization, According to the objective, it can select suitably, For example, heat press, a heat roll laminator (For example, Taisei Laminator Co., Ltd. make, VP- II), a vacuum laminator (for example, MVLP500 manufactured by Meiki Seisakusho Co., Ltd.) and the like can be mentioned as suitable devices.

<Exposure process>
The exposure step is a step of performing pattern exposure on the photosensitive layer.

  The subject of the exposure is not particularly limited as long as it is a material having a photosensitive layer, and can be appropriately selected according to the purpose. However, the photosensitive solder resist composition or the photosensitive solder resist is formed on a substrate. It is preferable to be performed on the laminate formed with a film.

  There is no restriction | limiting in particular as exposure to the said laminated body, According to the objective, it can select suitably, For example, you may expose the said photosensitive layer through the said support body, cushion layer, and PC layer, After peeling the support, the photosensitive layer may be exposed through the cushion layer and the PC layer. After peeling the support and cushion layer, the photosensitive layer is exposed through the PC layer. Alternatively, the photosensitive layer may be exposed after the support, the cushion layer and the PC layer are peeled off.

  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. Among these, digital exposure is preferable.

  The digital exposure is not particularly limited and can be appropriately selected depending on the purpose.For example, a control signal is generated based on pattern formation information to be formed, and light modulated in accordance with the control signal is generated. It is preferable to use.

  The digital exposure means is not particularly limited and may be appropriately selected depending on the purpose. For example, light irradiation means for irradiating light, light emitted from the light irradiation means based on pattern information to be formed And a light modulation means for modulating the light intensity.

<< light modulation means >>
The light modulation means is not particularly limited as long as it can modulate light, and can be appropriately selected according to the purpose, but preferably has n pixel portions.
The light modulation means having the n picture elements is not particularly limited and may be appropriately selected according to the purpose, but a spatial light modulation element is preferable.

The spatial light modulation element is not particularly limited and may be appropriately selected according to the purpose. For example, a spatial light modulation element of a digital micromirror device (DMD) or a MEMS (Micro Electro Mechanical Systems) type ( Examples thereof include SLM (Special Light Modulator), an optical element (PLZT element) that modulates transmitted light by an electro-optic effect, and a liquid crystal light shutter (FLC).
Among these, a digital micromirror device (DMD) is preferable.

The light modulation means preferably includes pattern signal generation means for generating a control signal based on pattern information to be formed. In this case, the light modulation unit modulates light according to the control signal generated by the pattern signal generation unit.
There is no restriction | limiting in particular as said control signal, According to the objective, it can select suitably, For example, a digital signal is mentioned.

<Development process>
The developing step is a step of forming a permanent pattern by exposing the photosensitive layer by the exposing step, curing the exposed region of the photosensitive layer, and then developing by removing the uncured region.

  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.

  The developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alkali metal or alkaline earth metal hydroxide or carbonate, hydrogen carbonate, aqueous ammonia, quaternary ammonium salt An aqueous solution of Among these, an aqueous sodium carbonate solution is preferable.

The developer may be used in combination with a surfactant, an antifoaming agent, an organic base, an organic solvent or the like for accelerating development.
The organic base is not particularly limited and may be appropriately selected depending on the intended purpose. For example, benzylamine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanol An amine etc. are mentioned.
The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohols, ketones, esters, ethers, amides, and lactones.
The developer may be an aqueous developer obtained by mixing water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

<Curing process>
The permanent pattern forming method of the present invention preferably further includes a curing treatment step.
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed permanent pattern after the development step is performed.

  There is no restriction | limiting in particular as said hardening process, According to the objective, it can select suitably, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned.

The method for the entire surface exposure treatment is not particularly limited and can be appropriately selected depending on the purpose. For example, a method for exposing the entire surface of the laminate on which the permanent pattern is formed after the development step. Etc. The entire surface exposure accelerates the curing of the resin in the photosensitive solder resist 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, According to the objective, it can select suitably, For example, UV exposure machines, such as a super-high pressure mercury lamp, etc. are mentioned.

The entire surface heat treatment method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, after the development step, the entire surface on the laminate on which the permanent pattern is formed is heated. Etc. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
There is no restriction | limiting in particular as heating temperature in the said whole surface heating, Although it can select suitably according to the objective, 120 to 250 degreeC is preferable and 120 to 200 degreeC is more preferable. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the photosensitive solder resist composition is decomposed and the film quality is weak. May become brittle.
There is no restriction | limiting in particular as heating time in the said whole surface heating, Although it can select suitably according to the objective, 10 minutes-120 minutes are preferable, and 15 minutes-60 minutes are more preferable.
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, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

When the substrate is a printed wiring board such as a multilayer wiring board, the permanent pattern of the present invention can be formed on the printed wiring board, and further soldered as follows.
That is, the development step forms a hardened layer that is the permanent pattern, 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 or an insulating film (interlayer insulating film), and prevents external impact and conduction between adjacent electrodes.

  In the permanent pattern forming method of the present invention, it is preferable to form at least one of a protective film and an interlayer insulating film. When the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, the wiring can be protected from external impact and bending, particularly when the interlayer insulating film is the interlayer insulating film. Is useful for high-density mounting of semiconductors and components on, for example, multilayer wiring boards and build-up wiring boards.

The permanent pattern forming method of the present invention can be widely used for forming various patterns because the pattern can be formed at a high speed, and can be particularly suitably used for forming a wiring pattern.
Further, the permanent pattern formed by the permanent pattern forming method of the present invention has excellent surface hardness, insulation, heat resistance, moisture resistance, etc., and is suitably used as a protective film, interlayer insulation film, solder resist pattern, etc. can do.

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

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

  Polyurethane resins (U-1) to (U-3) (Synthesis Examples 1 to 3) were synthesized as follows.

(Synthesis Example 1: Synthesis of polyurethane resin (U-1))
A 500 mL three-necked round bottom flask equipped with a condenser and a stirrer was charged with 10.86 g (0.081 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and 16.82 g of glycerol monomethacrylate (GLM). (0.105 mol) was dissolved in 79 mL of propylene glycol monomethyl ether monoacetate. To this, 37.54 g (0.15 mol) of 4,4-diphenylmethane diisocyanate (MDI), 0.1 g of 2,6-di-t-butylhydroxytoluene, as a catalyst, trade name: Neostan U-600 (Nitto Kasei) 0.2 g) was added and stirred at 75 ° C. for 5 hours. Thereafter, it was diluted with 9.61 mL of methyl alcohol and stirred for 30 minutes to obtain 145 g of a polymer solution. The synthesized polyurethane resin is represented by (U-1) in the following table.
The polyurethane resin (U-1) obtained above has a solid content acid value of 70 mgKOH / g, and a weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) is 8,000. The vinyl group equivalent was 1.5 mmol / g.

  The acid value was measured according to JIS K0070. However, when the sample did not dissolve, dioxane or tetrahydrofuran was used as a solvent.

  The weight average molecular weight was measured using a high-speed GPC apparatus (HLC-802A manufactured by Toyo Soda Industry Co., Ltd.). That is, a 0.5 mass% THF solution was used as a sample solution, 62 columns of TSKgelGMH were used, 200 μL of a sample was injected, eluted with the THF solution, and measured with a refractive index detector at 25 ° C. Next, the weight average molecular weight was determined from the molecular weight distribution curve calibrated with standard polystyrene.

  The said vinyl group equivalent was calculated | required by measuring a bromine number based on JISK2605.

(Synthesis Example 2: Synthesis of polyurethane resin (U-2))
In Synthesis Example 1, 37.54 g (0.15 mol) of 4,4-diphenylmethane diisocyanate (MDI) was mixed with 30.03 g (0.12 mol) of 4,4-diphenylmethane diisocyanate (MDI) and hexamethylene diisocyanate ( In place of the combination with 5.05 g (0.03 mol) of HMDI), 10.86 g (0.081 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and 16.82 g of glycerol monomethacrylate (GLM) (0.105 mol) is combined with 10.22 g (0.069 mol) of 2,2-bis (hydroxymethyl) butanoic acid (DMBA) and 12.97 g (0.081 mol) of glycerol monomethacrylate (GLM). And 4.80 g of polypropylene glycol (molecular weight 400) (PPG400) Instead of the combination of 0.012 moles), except for changing the addition amount of propylene glycol monomethyl ether monoacetate from 79mL to 77 mL, in the same manner as in Synthesis Example 1, was synthesized polyurethane resin (U-2).
When the acid value, weight average molecular weight, and vinyl group equivalent of the polyurethane resin (U-2) obtained above were measured by the same method as in Synthesis Example 1, the solid content acid value was 65 mgKOH / g, The weight average molecular weight (polystyrene standard) measured by an association chromatography (GPC) was 15,000, and the vinyl group equivalent was 1.26 mmol / g.

(Synthesis Example 3: Synthesis of polyurethane resin (U-3))
In Synthesis Example 1, 37.54 g (0.15 mol) of 4,4-diphenylmethane diisocyanate (MDI) was mixed with 30.03 g (0.12 mol) of 4,4-diphenylmethane diisocyanate (MDI) and hexamethylene diisocyanate ( In place of the combination with 5.05 g (0.03 mol) of HMDI), 10.86 g (0.081 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and 16.82 g of glycerol monomethacrylate (GLM) (0.105 mol) is combined with 7.24 g (0.054 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) and 10.09 g (0.063 mol) of glycerol monomethacrylate (GLM). ) And polypropylene glycol (molecular weight 400) (PPG400) 15.60. A polyurethane resin (U-3) was synthesized in the same manner as in Synthesis Example 1 except that the amount of propylene glycol monomethyl ether monoacetate was changed from 79 mL to 83 mL instead of the combination with (0.039 mol). .
When the acid value, weight average molecular weight, and vinyl group equivalent of the polyurethane resin (U-3) obtained above were measured by the same method as in Synthesis Example 1, the solid content acid value was 45 mgKOH / g, The weight average molecular weight (polystyrene standard) measured by an association chromatography (GPC) was 20,000, and the vinyl group equivalent was 0.9 mmol / g.

Example 1
<Preparation of photosensitive solder resist film 1>
-Preparation of photosensitive solder resist composition coating solution 1-
The following components were mixed to prepare a photosensitive solder resist composition coating solution 1.
[Composition of photosensitive resin composition]
Polyurethane resin (U-1) synthesized in Synthesis Example 1 (solid content: 45 mass%) 32.3 mass parts imide resin: V-8001BM 9.3 mass parts (solid content: 40 mass%, urethane group molar content : 12%, manufactured by DIC Corporation)
Polymerizable compound: DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.) 5.3 parts by mass Initiator: IRG907 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.9 parts by mass sensitizer: DETX (manufactured by Nippon Kayaku Co., Ltd.) 0 0.02 parts by mass sensitizer: EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) 0.06 parts by mass Curing agent: DICY-7 (manufactured by Yuka Shell Epoxy Co., Ltd.) 2.6 parts by mass Thermal cross-linking agent: Epototo YDF- 170 (manufactured by Tohto Kasei Co., Ltd.) 7.5 parts by mass Polyamide-based thermoplastic elastomer: TAPE-617 1.8 parts by mass (manufactured by Fuji Kasei Kogyo Co., Ltd.)
Pigment dispersion: 38.0 parts by mass Other: 0.13 parts by mass of Megafac F-780F (manufactured by Dainippon Ink Co., Ltd .: 30% by mass methyl ethyl ketone solution)
Cyclohexanone (solvent) 8.0 parts by mass

The pigment dispersion is prepared and prepared as follows. That is, after the following composition was mixed in advance, a motor mill M-250 (manufactured by Eiger) was used by using zirconia beads having a diameter of 1.0 mm and dispersing at a peripheral speed of 9 m / s for 3 hours.
[Composition of pigment dispersion]
Silica: (Admatex, SO-C2, average particle size 0.5 μm) 4.9 parts by mass Polyurethane resin (U-1) synthesized in Synthesis Example 1 (solid content: 45% by mass) 2.4 parts by mass phthalocyanine Blue 0.021 parts by mass Anthraquinone yellow pigment (PY24) 0.006 parts by mass Cyclohexanone 30.7 parts by mass

-Production of photosensitive solder resist film 1-
As shown in FIG. 1, a polyethylene terephthalate film (PET) having a thickness of 25 μm is used as a support 1, and the photosensitive solder resist composition coating solution 1 is dried on the support 1 by a bar coater. 2 was applied to a thickness of about 30 μm and dried in a hot air circulating drier at 80 ° C. for 30 minutes to prepare a photosensitive solder resist film 1.

<Formation of permanent pattern>
-Preparation of laminate-
The substrate was prepared by subjecting a surface of a copper-clad laminate (no through-hole, printed wiring board with a copper thickness of 12 μm) to which a wiring had been formed, subjected to a chemical polishing treatment. The copper-clad laminate is laminated using a vacuum laminator (MVLP500, manufactured by Meiki Seisakusho Co., Ltd.) so that the photosensitive layer of the photosensitive solder resist film 1 is in contact with the copper-clad laminate. A laminate in which a tension laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order was prepared.
The pressure bonding conditions were a pressure bonding temperature of 90 ° C., a pressure bonding pressure of 0.4 MPa, and a laminating speed of 1 m / min.
The developability of the obtained laminate was evaluated by the following evaluation method.

-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.
About the obtained test board, pattern formation property (permanent pattern surface shape), thermal shock resistance (crack resistance), heat resistance, and insulation were evaluated by the following evaluation methods.

<Evaluation method>
-Permanent pattern surface shape-
The permanent pattern surface (50 μm × 50 μm) formed in the development step was photographed with a scanning electron microscope (SEM), and the shape of the formed permanent pattern surface was evaluated according to the following evaluation criteria. The results are shown in Table 2.
[Evaluation criteria]
○: There is no defect or there are 1 to 5 defects, and the shape of the formed permanent pattern is not affected. ○ Δ: There are 6 to 10 defects, but the shape of the formed permanent pattern. Δ: There are 11 to 20 defects, and the defects may cause shape abnormality on the end face of the permanent pattern. ×: There are 21 or more defects, and the defects are on the end face of the permanent pattern. What causes shape abnormalities

-Thermal shock resistance (crack resistance)-
A solder resist layer is formed on a printed circuit board obtained by laminating a copper foil having a thickness of 12 μm on a glass epoxy base material on the photosensitive laminate, and a HMW-201GX type exposure made by Oak Manufacturing Co., Ltd. through a 2 mm square photomask. The exposure was performed with an optimum exposure dose (300 mJ / cm ^{2 to 1} J / cm ² ) that can form a 2 mm square pattern. Next, after standing at room temperature for 1 hour, spray development was performed for 60 seconds with a 1% by mass aqueous sodium carbonate solution at 30 ° C., followed by heating (drying) at 80 ° C. for 10 minutes. Subsequently, the photosensitive layer was irradiated with ultraviolet rays with an energy amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by Oak Seisakusho. Further, the photosensitive layer was heat-treated at 150 ° C. for 60 minutes to obtain an evaluation substrate on which a solder resist having a 2 mm square opening was formed.
The obtained substrate was exposed to an atmosphere of −65 ° C. for 15 minutes, then exposed to an atmosphere of 150 ° C. for 15 minutes, and then repeatedly exposed to the air of −65 ° C. 1,000 times. The crack and peeling degree on the solder resist of the evaluation substrate through the thermal cycle were observed with an optical microscope. The results are shown in Table 2 below.
[Evaluation criteria]
○: Solder resist is not cracked and peeled and is excellent in toughness ○ △: Solder resist is slightly cracked but has good toughness △: Solder resist is slightly cracked and peeled, tough Slightly inferior ×: Solder resist has obvious cracks and peeling, and has poor toughness

-Developability-
An unexposed photosensitive layer having a thickness of 10 μm on a substrate is spray-developed at 30 ° C. using a 1% by mass aqueous sodium carbonate solution and evaluated according to the following evaluation criteria based on whether it can be removed in 10 to 60 seconds. did. The results are shown in Table 2.
[Evaluation criteria]
○: Removed in 5 seconds or more but less than 40 seconds, no development residue ○ △: Removed in 40 or more but less than 50 seconds Δ: Removed in 50 or more but less than 60 seconds ×: Development residue still present after 60 seconds

-Solder heat resistance (Reflow resistance)-
A rosin-based flux or a water-soluble flux was applied to the test piece and immersed in a solder bath at 260 ° C. for 10 seconds. After repeating this for 6 cycles, the appearance of the coating film was visually observed and evaluated according to the following evaluation criteria. The results are shown in Table 2.
[Evaluation criteria]
○: There is no abnormality (peeling or blistering) in the coating film appearance, and there is no solder flaking. ○ △: There is a slight swelling in the coating film appearance, but there is no blistering or solder flaking. There is swelling and there is some solder peeling ×: There is peeling or swelling on the coating film appearance and there is solder peeling

−Insulation−
Etching was performed on the copper foil of a printed circuit board in which a 12 μm thick copper foil was laminated on a glass epoxy base material, the line width / space width was 50 μm / 50 μm, the lines were not in contact with each other, and the same facing each other A comb electrode on the surface was obtained. A solder resist layer was formed on the comb-shaped electrode of this substrate by a conventional method, and exposure was performed with an optimum exposure amount (300 mJ / cm ^{2 to 1} J / cm ² ). Next, after standing at room temperature for 1 hour, spray development was performed for 60 seconds with a 1% by mass aqueous sodium carbonate solution at 30 ° C., followed by heating (drying) at 80 ° C. for 10 minutes. Subsequently, the photosensitive layer was irradiated with ultraviolet rays with an energy amount of 1 J / cm ² using an ultraviolet irradiation device manufactured by Oak Manufacturing Co., Ltd. Further, the photosensitive layer was heat-treated at 150 ° C. for 60 minutes to obtain an evaluation substrate on which a solder resist was formed.
After connecting the polytetrafluoroethylene shield wires to the comb electrodes with Sn / Pb solder so that a voltage is applied between the comb electrodes of the evaluation laminate after heating, 5 V is applied to the evaluation laminate. With the voltage applied, the evaluation laminate was allowed to stand in a super accelerated high temperature and high humidity life test (HAST) bath at 130 ° C. and 85% RH for 200 hours. Thereafter, the degree of migration of the solder resist in the evaluation laminate was observed with a 100-fold metal microscope and evaluated according to the following evaluation criteria. The results are shown in Table 2.
[Evaluation criteria]
○: Occurrence of migration cannot be confirmed and insulation is excellent ○ △: Occurrence of migration is confirmed slightly on copper, but insulation is good △: Occurrence of migration is confirmed, and insulation is slightly inferior × : Short circuit between electrodes and poor insulation

(Example 2)
<Preparation of photosensitive solder resist film 2>
-Preparation of Photosensitive Solder Resist Composition Coating Solution 2-
In Example 1, the addition amount of the polyurethane resin (U-1) synthesized in Synthesis Example 1 was changed to 37.5 parts by mass to 27.5 parts by mass, and the addition amount of the imide resin was 9.3 parts by mass. A photosensitive solder resist composition coating solution 2 was prepared in the same manner as in Example 1 except that the content was changed to 14.1 parts by mass.

-Production of photosensitive solder resist film 2-
In Example 1, it replaced with the photosensitive soldering resist composition coating liquid 1, and produced the photosensitive soldering resist film 2 by the method similar to Example 1 except having used the photosensitive soldering resist composition coating liquid 2. did.

<Formation of permanent pattern>
In Example 1, a permanent pattern was formed by the same method as in Example 1 except that the photosensitive solder resist film 2 was used in place of the photosensitive solder resist film 1, and the same method as in Example 1 was used. Then, pattern formation, crack resistance, developability, heat resistance, and insulation were evaluated. The results are shown in Table 2.

(Example 3)
<Preparation of photosensitive solder resist film 3>
-Preparation of photosensitive solder resist composition coating solution 3-
In Example 1, the addition amount of the polyurethane resin (U-1) synthesized in Synthesis Example 1 was changed to 32.3 parts by mass to 36.7 parts by mass, and the addition amount of the imide resin was 9.3 parts by mass. A photosensitive solder resist composition coating solution 3 was prepared in the same manner as in Example 1 except that the content was changed to 4.9 parts by mass.

-Production of photosensitive solder resist film 3-
In Example 1, it replaced with the photosensitive soldering resist composition coating liquid 1, and produced the photosensitive soldering resist film 3 by the method similar to Example 1 except having used the photosensitive soldering resist composition coating liquid 3. did.

<Formation of permanent pattern>
In Example 1, a permanent pattern was formed by the same method as in Example 1 except that the photosensitive solder resist film 3 was used in place of the photosensitive solder resist film 1, and the same method as in Example 1 was used. Then, pattern formation, crack resistance, developability, heat resistance, and insulation were evaluated. The results are shown in Table 2.

Example 4
<Preparation of photosensitive solder resist film 4>
-Preparation of photosensitive solder resist composition coating solution 4-
In Example 1, in place of the polyurethane resin (U-1) synthesized in Synthesis Example 1, the polyurethane resin (U-2) synthesized in Synthesis Example 2 (solid content: 45% by mass) was used. A photosensitive solder resist composition coating solution 4 was prepared in the same manner as in Example 1.

-Production of photosensitive solder resist film 4-
In Example 1, a photosensitive solder resist composition film 4 was prepared in the same manner as in Example 1 except that the photosensitive solder resist composition coating liquid 4 was used instead of the photosensitive solder resist composition coating liquid 1. did.

<Formation of permanent pattern>
In Example 1, a permanent pattern was formed in the same manner as in Example 1 except that the photosensitive solder resist film 4 was used in place of the photosensitive solder resist film 1, and in the same manner as in Example 1. Then, pattern formation, crack resistance, developability, heat resistance, and insulation were evaluated. The results are shown in Table 2.

(Example 5)
<Preparation of photosensitive solder resist film 5>
-Preparation of photosensitive solder resist composition coating solution 5-
In Example 1, instead of the polyurethane resin (U-1) synthesized in Synthesis Example 1, the polyurethane resin (U-3) synthesized in Synthesis Example 3 (solid content: 45% by mass) was used. A photosensitive solder resist composition coating solution 5 was prepared in the same manner as in Example 1.

-Preparation of photosensitive solder resist film 5-
In Example 1, it replaced with the photosensitive soldering resist composition coating liquid 1, and produced the photosensitive soldering resist film 5 by the method similar to Example 1 except having used the photosensitive soldering resist composition coating liquid 5. did.

<Formation of permanent pattern>
In Example 1, a permanent pattern was formed by the same method as in Example 1 except that the photosensitive solder resist film 5 was used in place of the photosensitive solder resist film 1, and the same method as in Example 1 was used. Then, pattern formation, crack resistance, developability, heat resistance, and insulation were evaluated. The results are shown in Table 2.

(Example 6)
<Preparation of photosensitive solder resist film 7>
-Preparation of photosensitive solder resist composition coating solution 6-
In Example 1, a photosensitive solder resist composition coating solution 6 was prepared in the same manner as in Example 1 except that the polyamide-based thermoplastic elastomer was not added.

-Production of photosensitive solder resist film 6-
In Example 1, it replaced with the photosensitive soldering resist composition coating liquid 1, and produced the photosensitive soldering resist film 6 by the method similar to Example 1 except having used the photosensitive soldering resist composition coating liquid 6. did.

<Formation of permanent pattern>
In Example 1, a permanent pattern was formed in the same manner as in Example 1 except that the photosensitive solder resist film 6 was used instead of the photosensitive solder resist film 1, and in the same manner as in Example 1. Then, pattern formation, crack resistance, developability, heat resistance, and insulation were evaluated. The results are shown in Table 2.

(Comparative Example 1)
<Preparation of photosensitive solder resist film 7>
-Preparation of photosensitive solder resist composition coating solution 7-
In Example 1, a photosensitive solder resist composition coating solution 8 was prepared in the same manner as in Example 1 except that the polyurethane resin (U-1) was not added.

-Production of photosensitive solder resist film 7-
In Example 1, the photosensitive solder resist composition film 7 was prepared in the same manner as in Example 1 except that the photosensitive solder resist composition coating liquid 7 was used instead of the photosensitive solder resist composition coating liquid 1. did.

<Formation of permanent pattern>
In Example 1, a permanent pattern was formed in the same manner as in Example 1 except that the photosensitive solder resist film 7 was used instead of the photosensitive solder resist film 1, and in the same manner as in Example 1. Then, pattern formation, crack resistance, developability, heat resistance, and insulation were evaluated. The results are shown in Table 2.

(Comparative Example 2)
<Preparation of photosensitive solder resist film 8>
-Preparation of photosensitive solder resist composition coating solution 8-
In Example 1, a photosensitive solder resist composition coating solution 8 was prepared in the same manner as in Example 1 except that the thermal crosslinking agent was not added.

-Production of photosensitive solder resist film 8-
In Example 1, a photosensitive solder resist composition film 8 was produced in the same manner as in Example 1 except that the photosensitive solder resist composition coating liquid 8 was used instead of the photosensitive solder resist composition coating liquid 1. did.

<Formation of permanent pattern>
In Example 1, a permanent pattern was formed in the same manner as in Example 1 except that the photosensitive solder resist film 8 was used instead of the photosensitive solder resist film 1, and in the same manner as in Example 1. Then, pattern formation, crack resistance, developability, heat resistance, and insulation were evaluated. The results are shown in Table 2.

  Table 1 below shows values obtained by converting the addition amount of each component of the photosensitive solder resist compositions 1 to 8 in Examples 1 to 6 and Comparative Examples 1 to 2 into solid content. Table 2 below collectively shows the results of Examples 1 to 6 and Comparative Examples 1 and 2.

  From the results shown in Table 2, the photosensitive resin composition in which the polyurethane resin, the thermal crosslinking agent, and the imide resin having a urethane bond are combined has not only excellent heat resistance and dielectric properties, but also pattern formability and crack resistance. It was found to be excellent in performance.

The photosensitive resin composition of the present invention can obtain a high-performance cured film excellent in pattern formability, crack resistance, heat resistance, electrical insulation, developability, and mechanical properties, and is therefore suitable for a solder resist. Can be used.
The photosensitive solder resist film of the present invention is a liquid crystal structure member such as a protective film, an interlayer insulating film, various patterns such as permanent patterns such as a solder resist pattern, a color filter, a pillar material, a rib material, a spacer, and a partition wall. It can be suitably used for the production of holograms, micromachines, proofs, etc., and can be particularly suitably used for forming a permanent pattern on a printed circuit board.
Since the pattern forming method of the present invention uses the photosensitive resin composition, it is used for forming various patterns such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, a color filter, a pillar material, a rib material, a spacer. It can be suitably used for the production of liquid crystal structural members such as partition walls, the production of holograms, micromachines, proofs, and the like, and can be particularly suitably used for the formation of permanent patterns on printed boards.

DESCRIPTION OF SYMBOLS 1 Support body 2 Photosensitive layer 3 Protective film

Claims (14)

  A photosensitive resin composition comprising a polyurethane resin, a thermal crosslinking agent, and an imide resin having a urethane bond.   The resin composition according to claim 1, wherein the polyurethane resin has a vinyl group and an acid group. The photosensitive resin composition according to any one of claims 1 to 2, wherein the polyurethane resin has a functional group represented by the following general formula (1) in a side chain.
In the general formula (1), R ^{1 to} R ³ each independently represent a hydrogen atom or a monovalent organic group, X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —, R ¹² represents a hydrogen atom or a monovalent organic group.   The polyurethane resin is a reaction product of a diisocyanate compound and a diol compound, and the diol compound is (i) at least one diol compound having a vinyl group and at least one being a secondary alcohol, and (ii) The photosensitive resin composition in any one of Claim 1 to 3 containing at least 1 sort (s) of the diol compound which has a carboxyl group. The imide resin having a urethane bond has a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and from the following general formula (III) to (V The photosensitive resin composition in any one of Claim 1 to 4 which has any 1 or more types of the terminal structure represented by this.
In the general formulas (I) and (II), R ₁ represents an organic group having a cycloaliphatic structure having 6 to 13 carbon atoms. In the general formula (II), R ₂ represents a number average molecular weight. Represents a 700 to 4,500 linear hydrocarbon structure.
  The imide resin having a urethane bond has an acid value of 20 to 250, a number average molecular weight of the linear hydrocarbon structure part of 700 to 4,500, and a content of the linear hydrocarbon structure part of 20% by mass to 40% by mass. %, The concentration of the isocyanurate ring is from 0.3 mmol / g to 1.2 mmol / g, the number average molecular weight is from 2,000 to 30,000, and the weight average molecular weight is from 3,000 to 100,000. The photosensitive resin composition of Claim 5.   The photosensitive resin composition according to any one of claims 1 to 6, wherein a mass ratio of the polyurethane resin and the imide resin having a urethane bond (polyurethane resin / imide resin) is 1 to 19.   The resin composition according to any one of claims 1 to 7, further comprising a polymerizable compound and a photopolymerization initiator.   The photosensitive resin composition according to any one of claims 1 to 8, further comprising a thermoplastic elastomer.   A photosensitive solder resist composition comprising the photosensitive resin composition according to claim 1.   A photosensitive solder resist film comprising: a support; and a photosensitive layer obtained by laminating the photosensitive solder resist composition according to claim 10 on the support.   A photosensitive solder resist composition according to claim 10 is applied to the surface of a substrate, dried to form a laminate by laminating a photosensitive layer, and then exposed and developed to form a permanent pattern. Method.   It forms with the permanent pattern formation method of Claim 12, The permanent pattern characterized by the above-mentioned.   A printed circuit board, wherein a permanent pattern is formed by the permanent pattern forming method according to claim 12.