WO2012029785A1 - Photosensitive composition, and photosensitive film, permanent pattern, permanent pattern formation method and printed substrate - Google Patents

Abstract

A photosensitive composition comprising an inorganic filler having a partial structure represented by -L₁-NH-R₂ (wherein L₁ represents an alkylene group having 1-12 carbon atoms; and R₂ represents an organic group having 1-12 carbon atoms) on the surface thereof, a binder, a photopolymerization initiator and a polymerizable compound, wherein the content of the inorganic filler relative to the total solid content of the photosensitive composition is 30 mass% or more; and a photosensitive film, a permanent pattern, a permanent pattern formation method and a printed substrate, each of which uses the photosensitive composition.

Description

Photosensitive composition, photosensitive film, permanent pattern, method for forming permanent pattern, and printed circuit board

The present invention relates to a photosensitive composition suitably used for a solder resist and the like, a photosensitive film using the photosensitive composition, a high-definition permanent pattern (protective film, interlayer insulating film, solder resist, etc.), permanent With regard to the pattern formation method and the printed circuit board, in particular, a permanent pattern that is used for a wiring board and an electronic component module and has excellent thermal fatigue resistance against thermal history and temperature cycle test (TCT) during mounting, and its efficient formation method, Furthermore, the present invention relates to a printed board on which a permanent pattern is formed by the forming method.

In recent years, as represented by mobile communication devices, electronic devices are required to have high performance, high functionality, high quality, and high reliability as well as small size, thinness, and weight reduction. In addition, electronic component modules mounted on such electronic devices are required to be small in size and high in density. In response to such demands, in recent years, a wiring conductor has been formed by thin film formation using a low resistance metal such as copper or gold on the surface of an insulating substrate made of glass fiber and epoxy resin that can be reduced in weight and density A so-called printed circuit board on which a layer is formed 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 film to form an insulating layer. An opening is formed, and then the surface of the insulating layer is chemically roughened and a copper film is deposited using an electroless copper plating method and an electrolytic copper plating method, thereby forming a conductor layer in the opening and insulating. The wiring conductor layer is formed on the surface of the 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 deposited 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. Is formed. This solder resist layer is generally composed of an alkali-soluble photocrosslinkable resin having good adhesion to the wiring conductor layer and the insulating layer, and a flexible resin, and has a coefficient of thermal expansion determined by the heat 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.

Furthermore, this 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 moisture in the air is gradually absorbed, and this moisture may reduce the insulation resistance of the solder resist layer to 10 ⁸ Ω or less. Therefore, there is a problem that the wiring conductor layers are short-circuited, and further, this moisture corrodes the wiring conductor layers, and as a result, the electrical reliability of the wiring board is deteriorated. Further, in a semiconductor package substrate such as BGA (ball grid array) or CSP (chip size package), cream solder is printed in advance on a necessary portion, the whole is heated with infrared rays, and the solder is reflowed and fixed. In this process, the temperature reached inside and outside of the package is remarkably high at 220 ° C to 240 ° C, so that the coating film is cracked or peeled off from the substrate or the sealing material by thermal shock. There was a problem of deterioration in heat resistance, and this improvement was demanded.

In order to solve such problems, it has been proposed to add an elastomer to the solder resist (see Patent Document 1). As this elastomer, a polyester-based elastomer having a hydroxyl group is used as an example, and a wide variety of other elastomers are exemplified. It is said that the content of the elastomer needs to be 2 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin containing acidic ethylenically unsaturated groups.
However, it is certain that these elastomers can improve crack resistance (thermal shock resistance), but on the other hand, developability of unexposed portions of the solder resist is not sufficient.

Therefore, in order to improve developability, it is possible to add a carboxyl group-containing polyurethane and an elastomer obtained by reacting an epoxy group and an ethylenically unsaturated group in the molecule to the solder resist. It has been proposed (see Patent Document 2).
However, in order to improve thermal shock resistance (TCT), electrical insulation (HAST), and solder heat resistance, increasing the filling amount of an inorganic filler such as barium sulfate will increase the viscosity of the coating solution and improve the coating suitability. The problem still arises that it is not sufficient and screen printing cannot be performed. Moreover, depending on the case, the inorganic filler dispersion liquid before preparing a coating liquid may excessively thicken, and the problem that an inorganic filler cannot be disperse | distributed may arise.

In order to solve the problem that the inorganic filler cannot be dispersed, an insulating resin composition containing a thermosetting resin, an inorganic filler, and a polymer dispersant has been proposed (see Patent Document 3).
However, polymerization of the insulating resin composition is not initiated by light, and the insulating resin composition prevents the aggregation of the inorganic filler when the insulating resin composition is dried. The melt viscosity of the formed insulating film cannot be controlled, and since the inorganic filler has a large particle size, the insulating resin composition does not easily pass light. There was a problem that photocuring took time.

In addition, an insulating resin composition including a binder and a filler treated with a silane coupling agent has been proposed (see Patent Document 4).
However, the filling amount of the filler in the photosensitive composition is as low as 10% by mass to 13% by mass, and when the filling amount is high, the inorganic filler cannot be dispersed, and the particle size of the inorganic filler is small. Due to the large size, the insulating resin composition does not easily pass light, and there is a problem that it takes time to photocure the insulating resin composition.

Furthermore, a photosensitive film having a melt viscosity of 100,000 poise or less has been proposed (see Patent Document 5).
However, the filling amount of the inorganic filler in the photosensitive composition is as low as 7% by mass to 8% by mass, and when the filling amount is further increased, it is difficult to disperse the inorganic filler.

Japanese Patent Laid-Open No. 11-240930 JP 2007-2030 A JP 2006-188622 A JP 2003-234439 A JP 2001-303011 A

The present invention addresses the above-described problems and achieves the following objects. That is, the present invention can obtain a high-performance cured film excellent in embedding property, thermal shock resistance (TCT), electrical insulation (HAST), solder heat resistance, and resolution, and in a photosensitive film. It aims at providing the photosensitive composition which can improve the dispersibility of an inorganic filler, a photosensitive film, a permanent pattern, a permanent pattern formation method, and a printed circuit board.
Furthermore, the present invention can provide a high-performance cured film that has excellent embedding properties, thermal shock resistance (TCT), electrical insulation (HAST), solder heat resistance, and resolution, and high light transmittance. And it aims at providing the photosensitive composition which can improve the dispersibility of the inorganic filler in a photosensitive film, and a photosensitive film, a permanent pattern, a permanent pattern formation method, and a printed circuit board.

Means for solving the above problems are as follows. That is,
<1> A photosensitive composition containing at least one inorganic filler, a binder, a photopolymerization initiator, and a polymerizable compound,
The content of the inorganic filler in the total solid content of the photosensitive composition is 30% by mass or more,
The surface of the inorganic filler is a photosensitive composition having a partial structure represented by the following general formula (A).

-L ₁ -NH-R ₂ ... general formula (A)

In general formula (A), R ₂ represents an organic group having 1 to 12 carbon atoms, and L ₁ represents an alkylene group having 1 to 12 carbon atoms.
<2> The photosensitive composition according to <1>, wherein the inorganic filler has an average particle size (d50) of less than 0.3 μm.
<3> The photosensitive composition according to <1> or <2>, wherein the particle surface of the inorganic filler has a partial structure represented by the following general formula (B).

—Si (OR ₁ ) ₂ —L ₁ —NH—R ₂ ... Formula (B)

In general formula (B), R ₁ represents a methyl group or an ethyl group, R ₂ represents an organic group having 1 to 12 carbon atoms, and L ₁ represents an alkylene group having 1 to 12 carbon atoms. Here, the two R _{1 s} may be the same or different.
<4> The photosensitive composition according to any one of <1> to <3>, wherein the inorganic filler is treated with a silane coupling agent represented by the following general formula (C).

In the general formula (C), R represents a methyl group or an ethyl group, and n represents an integer of 1 to 5. Here, the three Rs may be the same or different.
<5> The photosensitive composition according to any one of <1> to <4>, wherein the inorganic filler is silica.
<6> The binder is an acid group- and ethylenically unsaturated group-containing resin and is at least one resin selected from a polyurethane resin, an epoxy resin, and a polyamide or a polyimide resin. <1> to <5> It is a photosensitive composition of any one of these.
<7> The photosensitive composition according to any one of <1> to <6>, wherein the binder is a polyurethane resin containing an acid group and an ethylenically unsaturated group.
<8> The binder has a mass average molecular weight of 2,000 to 60,000, an acid value of 20 mgKOH / g to 120 mgKOH / g, and an ethylenically unsaturated group equivalent of 0.05 mmol / g to 3.0 mmol. The photosensitive composition according to any one of <1> to <7>, which is a polyurethane resin containing an acid group and ethylenically unsaturated group of / g.
<9> The binder is an acid group and ethylenically unsaturated group-containing polyurethane resin, and the side chain contains at least one of functional groups represented by the following general formulas (1) to (3) <1> to <8> The photosensitive composition according to any one of <1> to <8>.

In the general formula (1), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group, and X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —. Here, R ¹² represents a hydrogen atom or a monovalent organic group.

In 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 the ^{R 12} of the general formula (1).

In general formula (3), R ⁹ to R ¹¹ each independently represents a hydrogen atom or a monovalent organic group. Z represents an oxygen atom, a sulfur atom, —N (R ¹³ ) —, or an optionally substituted phenylene group. Here, R ¹³ represents an alkyl group which may have a substituent.
<10> Any one of <1> to <9>, wherein the binder is a polyurethane resin containing an acid group and an ethylenically unsaturated group and has a partial structure represented by the following general formula (UG) It is a photosensitive composition as described in above.

In general formula (UG), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom or —N (R ¹² ) — is represented. Here, R ¹² represents a hydrogen atom or a monovalent organic group.
<11> The binder is an acid group and ethylenically unsaturated group-containing polyurethane resin, and is a reaction product of a diisocyanate compound and at least two diol compounds, and among the at least two diol compounds At least one is a diol compound having (1) an ethylenically unsaturated group, at least one of the hydroxyl groups being a secondary alcohol, and at least one other is (2) a diol compound having a carboxyl group. <1> to the photosensitive composition according to any one of <10>.
<12> The diol compound according to <11>, wherein the diol compound having the ethylenically unsaturated group (1) and at least one of the hydroxyl groups is a secondary alcohol is a compound represented by the following general formula (G): It is a photosensitive composition.

In general formula (G), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom or —N (R ¹² ) — is represented. Here, R ¹² represents a hydrogen atom or a monovalent organic group.
<13> The photosensitive composition according to any one of <1> to <12>, further containing a thermoplastic elastomer.
<14> 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 <13>. It is a photosensitive composition as described in above.
<15> having a photosensitive layer on the support,
A photosensitive film comprising the photosensitive composition according to any one of <1> to <14>.
<16> having a photosensitive layer made of a photosensitive composition on a support,
The photosensitive layer comprises an inorganic filler;
The particle surface of the inorganic filler has a partial structure represented by the following general formula (A),
The content of the inorganic filler in the total solid content of the photosensitive composition is 30% by mass or more,
The melt viscosity of the photosensitive layer at 30 ° C. is 1 × 10 ⁵ Pa · s or more, and the melt viscosity of the photosensitive layer at 70 ° C. is such that the average particle size of the inorganic filler is less than 0.3 μm. In this case, the photosensitive film is 5 × 10 ³ Pa · s or less, and when the average particle size of the inorganic filler is 0.3 μm or more, the photosensitive film is 2 × 10 ³ Pa · s or less.

-L ₁ -NH-R ₂ ... general formula (A)

In general formula (A), R ₂ represents an organic group having 1 to 12 carbon atoms, and L ₁ represents an alkylene group having 1 to 12 carbon atoms.
<17> The photosensitive film according to <16>, wherein the inorganic filler has an average particle size (d50) of less than 0.3 μm.
<18> The photosensitive film according to <16> or <17>, wherein the photosensitive layer contains at least one binder, a photopolymerization initiator, and a polymerizable compound together with the inorganic filler.
<19> The photosensitive film according to any one of <16> to <18>, wherein the content of the inorganic filler in the total solid content of the photosensitive composition is 50% by mass or more.
<20> The photosensitive film according to any one of <16> to <19>, wherein the particle surface of the inorganic filler has a partial structure represented by the following general formula (B).

—Si (OR ₁ ) ₂ —L ₁ —NH—R ₂ ... Formula (B)

In general formula (B), R ₁ represents a methyl group or an ethyl group, R ₂ represents an organic group having 1 to 12 carbon atoms, and L ₁ represents an alkylene group having 1 to 12 carbon atoms. Here, the two R _{1 s} may be the same or different.
<21> The photosensitive film according to any one of <16> to <20>, wherein the inorganic filler is treated with a silane coupling agent represented by the following general formula (C).

In the general formula (C), R represents a methyl group or an ethyl group, and n represents an integer of 1 to 5. Here, the three Rs may be the same or different.
<22> The photosensitive film according to any one of <16> to <21>, wherein the inorganic filler is silica.
<23> The binder is an acid group- and ethylenically unsaturated group-containing resin and is at least one resin selected from polyurethane resin, epoxy resin, polyamide, or polyimide resin. <18> to <22> It is a photosensitive film of any one of these.
<24> The photosensitive film according to any one of <18> to <23>, wherein the binder is a polyurethane resin containing an acid group and an ethylenically unsaturated group.
<25> The binder has a mass average molecular weight of 2,000 to 60,000, an acid value of 20 mgKOH / g to 120 mgKOH / g, and an ethylenically unsaturated group equivalent of 0.05 mmol / g to 3.0 mmol. The photosensitive film according to any one of <18> to <24>, which is a polyurethane resin containing an acid group and ethylenically unsaturated group of / g.
<26> The binder is a polyurethane resin containing an acid group and an ethylenically unsaturated group, and the side chain contains at least one of functional groups represented by the following general formulas (1) to (3) The photosensitive film according to any one of <18> to <25>.

In the general formula (1), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group, and X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —. Here, R ¹² represents a hydrogen atom or a monovalent organic group.

In 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 the ^{R 12} of the general formula (1).

In general formula (3), R ⁹ to R ¹¹ each independently represents a hydrogen atom or a monovalent organic group.
Z represents an oxygen atom, a sulfur atom, —N (R ¹³ ) —, or an optionally substituted phenylene group. Here, R ¹³ represents an alkyl group which may have a substituent.
<27> The binder according to any one of <18> to <26>, wherein the binder is a polyurethane resin containing an acid group and an ethylenically unsaturated group and has a partial structure represented by the following general formula (UG): It is the photosensitive film of description.

In general formula (UG), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom or —N (R ¹² ) — is represented. Here, R ¹² represents a hydrogen atom or a monovalent organic group.
<28> The binder is an acid group and ethylenically unsaturated group-containing polyurethane resin, and is a reaction product of a diisocyanate compound and at least two diol compounds, and among the at least two diol compounds At least one is a diol compound having (1) an ethylenically unsaturated group, at least one of the hydroxyl groups being a secondary alcohol, and at least one other is (2) a diol compound having a carboxyl group. <18>-<27> The photosensitive film described in any one of the above.
<29> The diol compound according to <28>, wherein the diol compound having an ethylenically unsaturated group (1) and at least one of the hydroxyl groups is a secondary alcohol is a compound represented by the following general formula (G): It is a photosensitive film.

In general formula (G), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom or —N (R ¹² ) — is represented. Here, R ¹² represents a hydrogen atom or a monovalent organic group.
<30> The photosensitive film according to any one of <16> to <29>, further containing a thermoplastic elastomer.
<31> 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 <30>. It is the photosensitive film of description.
<32> The photosensitive composition according to any one of <1> to <14> is applied to a surface of a substrate, dried to form a laminate by forming a laminate, and then exposed. , Developing a permanent pattern.
<33> A permanent pattern formed by the method for forming a permanent pattern according to <32>.
<34> A printed board comprising a permanent pattern formed by the method for forming a permanent pattern according to <32>.

According to the present invention, a high-performance cured film having excellent embedding property, thermal shock resistance (TCT), electrical insulation (HAST), solder heat resistance, resolution, and high light transmittance can be obtained. The photosensitive composition which can improve the dispersibility of the inorganic filler in a photosensitive film, and a photosensitive film, a permanent pattern, a permanent pattern formation method, and a printed circuit board can be provided.

The above and other features and advantages of the present invention will become more apparent from the following description.

FIG. 1 is an explanatory view showing the layer structure of the photosensitive film.

(Photosensitive composition)
The photosensitive composition of the present invention contains at least one inorganic filler, and particularly preferably contains a binder, a photopolymerization initiator, and a polymerizable compound, and includes a thermal crosslinking agent, an organic solvent, and a thermoplastic elastomer. , A thermosetting accelerator, a colorant, an adhesion promoter, a thermal polymerization inhibitor, and other components as necessary.
In addition, in this specification, solid content in a photosensitive composition means content (solid content) of the designated solid substance in the total solid of a photosensitive composition.

<Inorganic filler>
The inorganic filler (inorganic filler) used in the present invention has a partial structure in which the surface of the filler particles is represented by the following general formula (A). In addition, having on the surface of the particle is preferably chemically bonded to the surface of the filler particle, and a group partially containing the general formula (A) (the group is a monovalent to trivalent group as a whole). Any of these may be chemically bonded to a group (for example, a hydroxyl group) present on the particle surface of the filler.

-L ₁ -NH-R ₂ ... general formula (A)

In general formula (A), R ₂ represents an organic group having 1 to 12 carbon atoms, and L ₁ represents an alkylene group having 1 to 12 carbon atoms.

The partial structure represented by the general formula (A) has a partial structure represented by the following general formula (B) on the surface of the filler particle (preferably bonded to a group on the particle surface). preferable.

—Si (OR ₁ ) ₂ —L ₁ —NH—R ₂ ... Formula (B)

In general formula (B), R ₁ represents a methyl group or an ethyl group, R ₂ represents an organic group having 1 to 12 carbon atoms, and L ₁ represents an alkylene group having 1 to 12 carbon atoms. Here, the two R _{1 s} may be the same or different.
The inorganic filler having the partial structure represented by the general formula (A) or (B) on the particle surface of the filler is treated with a silane coupling agent represented by the following general formula (BA). It can be obtained by reacting with a group present on the particle surface.

(R ₁ O) ₃ Si—L ₁ —NH—R ₂ ... General formula (BA)

In the general formula (BA), R ₁ represents a methyl group or an ethyl group, R ₂ represents an organic group having 1 to 12 carbon atoms, and L ₁ represents an alkylene group having 1 to 12 carbon atoms. Here, the three R _{1 s} may be the same or different.
Of the silane coupling agents represented by the general formula (BA), a silane coupling agent represented by the following general formula (C) is preferable.

In the general formula (C), R represents a methyl group or an ethyl group, and n represents an integer of 1 to 5. Here, the three Rs may be the same or different.
Examples of the silane coupling agent represented by the general formula (C) include a compound (KBM-573) represented by the following structural formula.

The silane coupling agent represented by the general formula (BA) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 100 parts by mass of the inorganic filler. Those having a surface treatment of 0.1 to 5 parts by mass are preferred.

Whether or not the surface of the inorganic filler has a partial structural formula represented by the general formula (A) or (B) is determined using, for example, ESCA (PHI1800, manufactured by ULVAC-PHI). It can be measured by elemental analysis of the surface.

In the present invention, the inorganic filler is preferably a filler having an acidic particle surface. The inorganic filler having an acidic particle surface is not particularly limited and may be appropriately selected depending on the intended purpose. For example, inorganic fillers (silica, talc, etc.) containing silicon atoms as constituent atoms, barium atoms Inorganic fillers (such as barium sulfate) containing as a constituent atom are preferred, and inorganic fillers containing a silicon atom as a constituent atom are preferred.
The inorganic filler contains a silicon atom as a constituent atom, thereby improving the heat resistance of the cured film of the photosensitive composition, and a binder resin, particularly preferably an acid group and ethylenically unsaturated group-containing polyurethane resin described later. And the viscosity of the photosensitive composition can be maintained in a suitable range, and suitable coating suitability can be obtained.

In the present invention, the inorganic filler containing silicon atoms as constituent atoms is preferably silica (silica particles). Examples of silica include gas phase method silica, crystalline silica, and fused silica.

The average particle size (d50) of the inorganic filler used in the present invention is preferably 3.0 μm or less (preferably 10 nm to 3.0 μm), more preferably 2.5 μm or less (preferably 70 nm to 2.5 μm).
In particular, it is preferable in the present invention that the average particle size of the inorganic filler is less than 0.3 μm because the light transmittance is excellent. In the case of such fine particles, it is preferably 10 nm or more and less than 0.3 μm, more preferably 10 nm to 250 nm, and even more preferably 70 nm to 150 nm.
When the average particle size exceeds 3.0 μm, smoothness may not be maintained.
On the other hand, if the average particle diameter (d50) is within the above preferred range, it is advantageous from the viewpoint of coating viscosity, smoothness of the cured film and heat resistance.

The average particle size (d50) of the inorganic filler is defined as a particle size having 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 can be a dynamic light scattering method, and the size distribution analysis method can be measured as a cumulant method and / or a histogram method. it can.

The content of the inorganic filler in the total solid content of the photosensitive composition is 30% by mass or more (preferably 30% by mass to 80% by mass, more preferably 30% by mass to 75% by mass) in the present invention. However, it is preferably 35% by mass or more (preferably 35% by mass to 80% by mass, more preferably 35% by mass to 75% by mass), more preferably 40% by mass or more (preferably 40% by mass to 80% by mass, More preferably, it is 40% by mass to 75% by mass), still more preferably 50% by mass (preferably 50% by mass to 80% by mass, more preferably 50% by mass to 75% by mass).
When the solid content is less than 30% by mass, TCT resistance may be deteriorated, and when it exceeds 80% by mass, the viscosity of the film may increase. On the other hand, if the solid content is within the above-mentioned preferable range, it is advantageous in terms of resolution.

<Binder>
There is no restriction | limiting in particular as a binder, According to the objective, it can select suitably, For example, an acid group and ethylenically unsaturated group containing resin are preferable. Such resins include polyurethane resins, epoxy resins, polyamides or polyimide resins.
Here, the ethylenically unsaturated group is a group having an ethylene bond that is consumed in the measurement of bromine value and iodine value, and is not a group showing aromaticity such as benzene. The ethylenically unsaturated group is preferably a vinyl group which may have a substituent.
In the present invention, the epoxy resin is not a resin having an epoxy group but a resin reacted with an epoxy group of the epoxy resin, and will be described in detail later.
Of these acid group and ethylenically unsaturated group-containing resins, the above polyurethane resins and epoxy resins are preferable, and polyurethane resins are particularly preferable.
In addition, examples of the acid group include a carboxyl group, a sulfo group, and a phospho group. In the present invention, a carboxyl group is particularly preferable.

-Acid group and ethylenically unsaturated group-containing polyurethane resin-
The acid group and ethylenically unsaturated group-containing polyurethane resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, those having an ethylenically unsaturated bond in the side chain are preferred.
Here, the side chain is a chain that is linked from the chain of atoms constituting the main chain of the polyurethane resin by substitution with an atom that forms a branch or main chain, and has an ethylenically unsaturated bond in the side chain. Includes an ethylenically unsaturated group in such a side chain, or an atom constituting the main chain is directly substituted with an ethylenically unsaturated group. For example, a polyurethane resin obtained only by the reaction of a diol of HOCH ₂ CH═CHCH ₂ OH and OCN (CH ₂ ) ₆ NCO contains an ethylenically unsaturated bond in the main chain. In addition, the part by which the polymer terminal was sealed by the ethylenically unsaturated group containing compound is not a side chain.

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

--- Polyurethane resin (i)-
The polyurethane resin (i) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one of functional groups represented by the following general formulas (1) to (3) may be present on the side chain. One having one.

In general formula (1), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group.
Here, examples of the monovalent organic group include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group. , Amino group, alkylamino group, arylamino group, acylamino group, sulfonamido group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, carbamoyl group, sulfamoyl Group, hydroxyl group, mercapto group, cyano group, nitro group, carboxyl group, sulfo group, ureido group, urethane group and the like, and these groups may be further substituted with these substituents. In addition, the group similar to the above is mentioned also in each subsequent group and the monovalent organic group or substituent in each general formula.

R ¹ is preferably a hydrogen atom or an alkyl group which may have a substituent. Among these, a hydrogen atom and a methyl group are more preferable in terms of high radical reactivity. R ² and R ³ have a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group that may have a substituent, or a substituent. An aryl group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an aryl which may have a substituent An amino group, an alkylsulfonyl group which may have a substituent, and an arylsulfonyl group which may have a substituent are preferable. Among these, a hydrogen atom, a carboxyl group, and an alkoxycarbonyl group are preferable because of high radical reactivity. An alkyl group which may have a substituent and an aryl group which may have a substituent are more preferable.
X represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. Here, R ¹² represents a hydrogen atom or a monovalent organic group. Here, R ¹² is preferably an alkyl group which may have a substituent, and among them, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable in view of high radical reactivity.

Here, examples of the substituent in the group which may have a substituent include the groups described as the monovalent organic group in R ¹ to R ³ , and include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. An alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylamino group, an arylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an amide group, an alkylsulfonyl group, and an arylsulfonyl group. .

In the general formula (2), R ⁴ to R ⁸ each independently represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group for R ⁴ to R ⁸ include the groups described above for the monovalent organic group for R ¹ to R ³ . R ⁴ to R ⁸ have a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group that may have a substituent, or a substituent. An aryl group that may have a substituent, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent. An arylamino group, an alkylsulfonyl group which may have a substituent, and an arylsulfonyl group which may have a substituent are preferable. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, An alkyl group which may have a substituent and an aryl group which may have a substituent are more preferable.

Here, examples of the substituent in the group which may have a substituent include the groups described as the monovalent organic group in R ¹ to R ³ . Y represents an oxygen atom, a sulfur atom, or —N (R ¹² ) —. ^{Here, R 12} has the same meaning as ^{R 12} in general formula (1), and their preferable ranges are also the same and specific examples.

In general formula (3), R ⁹ to R ¹¹ each independently represents a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group for R ⁹ to R ¹¹ include the groups described above for the monovalent organic group for R ¹ to R ³ . R ⁹ is preferably a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom or a methyl group is more preferable in terms of high radical reactivity. R ¹⁰ and R ¹¹ are a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group that may have a substituent, or a substituent. An aryl group that may have, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent A preferable arylamino group, an optionally substituted alkylsulfonyl group, and an optionally substituted arylsulfonyl group are preferred. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group are preferred because of high radical reactivity. An alkyl group which may have a substituent and an aryl group which may have a substituent are more preferable.

Here, examples of the substituent in the group which may have a substituent include the groups described as the monovalent organic group in R ¹ to R ³ . Z represents an oxygen atom, a sulfur atom, —N (R ¹³ ) —, or an optionally substituted phenylene group. Here, R ¹³ is preferably an alkyl group which may have a substituent, and among them, a methyl group, an ethyl group, and an isopropyl group are more preferable in terms of high radical reactivity.

The polyurethane resin (i) is represented by a reaction product of at least one diisocyanate compound represented by the following general formula (4) and at least one diol compound represented by the general formula (5). A polyurethane resin having a structural unit as a basic skeleton.

OCN-X ⁰ -NCO General formula (4)
HO—Y ⁰ —OH Formula (5)

In the general formulas (4) and (5), X ⁰ and Y ⁰ each independently represent a divalent organic residue.

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

The diisocyanate compound represented by the general formula (4) is not particularly limited and can be appropriately selected depending on the purpose. For example, a triisocyanate compound and a monofunctional alcohol having an unsaturated group Or the product etc. which are obtained by carrying out addition reaction with 1 equivalent of monofunctional amine compounds are mentioned.
The triisocyanate compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraphs “0034” to “0035” of JP-A-2005-250438. 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, paragraphs of JP-A-2005-250438 And compounds described in “0037” to “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 (i) is a copolymer of diisocyanate compounds other than the diisocyanate compound containing the unsaturated group from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. It can also be made.

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

OCN-L ¹ -NCO General formula (6)

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

The diisocyanate compound represented by the general formula (6) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 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 diisocyanate; isophorone diisocyanate, 4,4 -Alicyclic diisocyanate compounds such as methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; 1 mol of 1,3-butylene glycol and tolylene diisocyanate And a diisocyanate compound that is a reaction product of a diol such as an adduct with 2 mol and a diisocyanate.

The diol compound represented by the general formula (5) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyether diol compounds, polyester diol compounds, and polycarbonate diol compounds.

Here, as a method for introducing an ethylenically unsaturated group into the side chain of the polyurethane resin, in addition to the above-described method, a diol compound containing an ethylenically unsaturated group in the side chain is used as a raw material for polyurethane resin production. The method used is also preferred. The diol compound containing an ethylenically unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the purpose. For example, a commercially available product such as trimethylolpropane monoallyl ether may be used. Or a compound such as a halogenated diol compound, a triol compound, or an aminodiol compound and a compound containing an unsaturated group, such as a carboxylic acid, an acid chloride, an isocyanate, an alcohol, an amine, a thiol, or a halogenated alkyl compound. It may be a compound easily produced by a reaction. There is no restriction | limiting in particular as a diol compound containing an ethylenically unsaturated group in the said side chain, According to the objective, it can select suitably.

In the present invention, a diisocyanate compound (preferably a compound represented by the general formula (4) or (6)) and a diol compound having an ethylenically unsaturated group and at least one hydroxyl group of which is a secondary alcohol ( Preferably, it is a reaction product with a diol compound having an ethylenically unsaturated group, at least one hydroxyl group being a secondary alcohol, and the other hydroxyl group being a primary alcohol, and more preferably A reactive product of a diisocyanate compound and two diol compounds, wherein one diol compound is a diol compound having an ethylenically unsaturated group and the other one is a diol compound having a carboxyl group. A reactive organism.
Examples of the diol compound containing an ethylenically unsaturated group in the side chain described above include compounds described in paragraphs “0057” to “0060” of JP-A-2005-250438, and the following general formula (G): Examples thereof include compounds described in paragraphs “0064” to “0066” of JP-A-2005-250438. Among these, compounds described in paragraphs “0064” to “0066” of JP-A-2005-250438 represented by the following general formula (G) are preferable.

In 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, X represents an oxygen atom, a sulfur atom, or — N (R ¹² ) — is represented. Here, R ¹² represents a hydrogen atom or a monovalent organic group.
Incidentally, ^R 1 ~ ^{R 3} and X in the general formula (G), said a general formula (1) the same meaning as ^R 1 ~ ^{R 3} and X in 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.

Here, the polyurethane resin derived from the diol compound represented by the general formula (G) has a partial structure represented by the following general formula (UG).

In general formula (UG), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom or —N (R ¹² ) — is represented. Here, R ¹² represents a hydrogen atom or a monovalent organic group. ^R 1 ^{~ R} 3, A and X in the general formula (UG) is the general formula (G) in the same meaning as ^R 1 ^{~ R} 3, A and X, and the preferred range is also the same.

The polyurethane resin having an ethylenically unsaturated bond in the side chain is, for example, ethylenic in the side chain from the viewpoint of improving compatibility with other components in the polymerizable composition and improving storage stability. A diol compound other than a diol compound containing an unsaturated group can be copolymerized.
The diol compound other than the diol compound containing an ethylenically unsaturated group in the side chain is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyether diol compound, a polyester diol compound, a polycarbonate diol Compounds and the like. These are diol compounds that do not contain an ethylenically unsaturated group or a carboxyl group as described below in the side chain.

A diol compound other than a diol compound containing an ethylenically unsaturated group in the side chain is preferably represented by the following general formula (U) and, when incorporated as a polyurethane resin, is represented by the following general formula (U1). Built in partial structure.

In the general formulas (U) and (U1), L ^U1 represents a divalent linking group containing no ethylenically unsaturated group and carboxyl group in the side chain.

L ^U1 includes, for example, an alkylene group, an arylene group, and a divalent heterocyclic group, and the alkylene group includes —O—, —OCOO—, a phenylene group, and a carbon-carbon double bond in the chain of the alkylene group. , A carbon-carbon triple bond, —OCO—Z ¹ —COO— (Z ¹ represents an alkylene group, an alkenylene group, or an arylene group).
L ^U1 in the general formulas (U) and (U1) is preferably — (CH ₂ CH ₂ O) n ^U1 CH ₂ CH ₂ —, — [CH ₂ CH (CH ₃ ) O] n ^U1 —CH ₂ CH (CH ₃ ) —, — (CH ₂ CH ₂ CH ₂ O) n ^U1 —CH ₂ CH ₂ CH ₂ —, — [(CH ₂ ) n ^{U 2} —OC (═O) — (CH ₂ ) n ^{U 3} — C (═O) O] n ^U4 —O (CH ₂ ) n ^U2 — or — [(CH ₂ ) n ^U5 —OC (═O) O] n ^U6 — (CH ₂ ) n ^U7 —. Here, n ^U1 to n ^U7 each independently represents a number of 1 or more.
The diol compounds other than the diol compound containing an ethylenically unsaturated group in the side chain are also preferably diol compounds represented by the following general formulas (III-1) to (III-5).

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

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

The polycarbonate diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the paragraphs “0080” to “0081” and paragraph “0084” of JP-A-2005-250438, 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 The described compounds and the like can be mentioned.

Furthermore, in the synthesis of the polyurethane resin having an ethylenically unsaturated bond in the side chain, a diol compound having a carboxyl group can be used in combination with the diol compound described above. Examples of the diol compound having a carboxyl group include those represented by the following general formulas (17) to (19).

In the general formulas (17) to (19), R ¹⁵ represents a hydrogen atom, a substituent (for example, a cyano group, a nitro group, a halogen atom such as —F, —Cl, —Br, —I, etc.), —CONH ₂ , —COOR ¹⁶ , —OR ¹⁶ , —NHCONHR ¹⁶ , —NHCOOR ¹⁶ , —NHCOR ¹⁶ , —OCONHR ¹⁶ (wherein R ¹⁶ is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms) And any other group that may have an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, and the like. 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 (17) to (19), L ⁹ , L ¹⁰ and L ¹¹ may be the same or different from each other, and may be a single bond, a substituent (for example, an alkyl group, an aralkyl group, an aryl group). Group, an alkoxy group, and a halogen atom are preferable.) As long as it represents a divalent aliphatic or aromatic hydrocarbon group which may have a group, there is no particular limitation, and it may be appropriately selected according to the purpose. However, an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable. If necessary, the L ⁹ to L ¹¹ may have another functional group that does not react with an isocyanate group, for example, a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, or an ether group. In addition, you may form a ring by two or three of said R < ¹⁵ >, L < ⁹ >, L < ¹⁰ >, L < ¹¹ >.
In the general formula (18), 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.

The diol compound having a carboxyl group represented by the general formulas (17) to (19) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 3,5-dihydroxybenzoic acid, 2 , 2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4- 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.

It is preferable because the presence of such a carboxyl group can impart properties such as hydrogen bonding and alkali solubility to the polyurethane resin.

Moreover, in the synthesis | combination of the polyurethane resin which has an ethylenically unsaturated bond in a side chain, the compound which ring-opened tetracarboxylic dianhydride with the diol compound other than the diol compound mentioned above can also be used together.
The compound obtained by ring-opening the tetracarboxylic dianhydride with a diol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, JP-A-2005-250438, paragraph “0095” to And 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 corresponding to each reactivity and heating. Is done. The molar ratio (M _a : M _b ) of the diisocyanate and diol compound used in the synthesis is not particularly limited and can be appropriately selected according to the purpose, and is 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 resin having an ethylenically unsaturated bond in the side chain, or between the photosensitive composition and the polyurethane resin having an ethylenically unsaturated bond in the side chain, by having an unsaturated group at the polymer terminal and main chain Crosslinking reactivity is improved, and the strength of the photocured product is increased. Here, as an unsaturated group, it is especially preferable to have an ethylenically unsaturated group from the ease of a crosslinking reaction.

Examples of the method for introducing an ethylenically unsaturated group at the polymer terminal include the following methods. That is, in the step of synthesizing a polyurethane resin having an ethylenically unsaturated bond in the side chain as described above, in the step of treating with a residual isocyanate group at the polymer terminal and an alcohol or an amine, it has an ethylenically unsaturated group. Alcohols or amines may be used. Specific examples of such a compound include the same compounds as those exemplified above as the monofunctional alcohol or monofunctional amine compound having an ethylenically unsaturated group.
The ethylenically unsaturated group is preferably introduced into the polymer side chain rather than the polymer end from the viewpoint that the introduction amount can be easily controlled and the introduction amount can be increased, and the crosslinking reaction efficiency is improved. .
The ethylenically unsaturated bond group to be introduced is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of forming a crosslinked cured film, a methacryloyl group, an acryloyl group, and a styryl group are preferable, and methacryloyl Group and acryloyl group are more preferable, and methacryloyl group is particularly preferable in terms of both the formability of the crosslinked cured film and the raw storage stability.
The amount of methacryloyl group introduced is not particularly limited and may be appropriately selected depending on the intended purpose. The ethylenically unsaturated group equivalent is preferably 0.05 mmol / g to 3.0 mmol / g, 0.5 mmol / g to 2.7 mmol / g is more preferable, 0.75 mmol / g to 2.4 mmol / g is more preferable, and 1.20 mmol / g to 2.4 mmol / g is particularly preferable.

As a method for introducing an unsaturated group into the main chain, there is a method of using a diol compound having an unsaturated group in the main chain direction for the synthesis of a polyurethane resin. The diol compound having an unsaturated group in the main chain direction is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 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, 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 an ethylenically unsaturated group in the molecule--
The polyurethane resin here is a polyurethane resin (ii), comprising a diisocyanate and a carboxyl group-containing polyurethane having carboxylic acid group-containing diol as essential components, and a compound having an epoxy group and an ethylenically unsaturated group in the molecule. It is a polyurethane resin obtained by reaction. Depending on the purpose, as the diol component, a low molecular diol having a mass average molecular weight of 300 or less or a low molecular diol having a mass average molecular weight of 500 or more may be added as a copolymer component.
By using the polyurethane resin (ii), 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.
In addition, as the polyurethane resin (ii), a divalent aliphatic or aromatic hydrocarbon diisocyanate which may have a substituent, a COOH group and two OH groups through either a carbon atom or a nitrogen atom. A reaction product comprising a carboxylic acid-containing diol having a group as an essential component, and the obtained reaction product and an epoxy group and an ethylenically unsaturated group (preferably the above-mentioned general group) in the molecule through a —COO— bond It may be obtained by reacting with a compound having a group represented by the formulas (1) to (3).
The polyurethane resin (ii) is at least selected from diisocyanates represented by the following general formula (I) and carboxylic acid group-containing diols represented by the following general formulas (II-1) to (II-3): And at least one selected from polymer diols having a mass average molecular weight in the range of 800 to 3,000 represented by the following general formulas (III-1) to (III-5) according to the purpose: A reaction product with one kind, the obtained reaction product, and a compound having an epoxy group and an ethylenically unsaturated group in the molecule represented by the following general formulas (IV-1) to (IV-16) May be obtained by reacting with.

In general formula (I), R ₁ is a divalent aliphatic or aromatic hydrocarbon which may have a substituent (for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or a halogen atom is preferable). Represents. 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 (II-1), R ₂ represents a hydrogen atom, a substituent [for example, a cyano group, a nitro group, a halogen atom (—F, —Cl, —Br, —I), —CONH ₂ , —COOR ₆ , —OR ₆ , —NHCONHR ₆ , —NHCOOR ₆ , —NHCOR ₆ , —OCONHR ₆ , —CONHR ₆ (wherein R ₆ is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms) Each of which represents an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or an aryloxy group. Among these, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and an aryl group having 6 to 15 carbon atoms are preferable.
In general formulas (II-1) and (II-2), R ₃ , R ₄ and R ₅ 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 group, an alkoxy group, and a halogen atom are preferable). Among these, an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 15 carbon atoms are preferable, and an alkylene group having 1 to 8 carbon atoms is more preferable. Further, if necessary, R ₃ , R ₄ and R ₅ may have any other functional group that does not react with an isocyanate group, such as a carbonyl group, an ester group, a urethane group, an amide group, a ureido group, or an ether group. You may do it. _{Incidentally,} R _2, R 3, may form a ring two or three of _{R 4} and _{R 5.} Ar represents a trivalent aromatic hydrocarbon which may have a substituent, and is preferably an aromatic group having 6 to 15 carbon atoms.

In the general formulas (III-1) to (III-3), R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ may be the same or different, and may be different from each other. Or represents an aromatic hydrocarbon. R ₇ , R ₉ , R ₁₀ and R ₁₁ are each preferably an alkylene group having 2 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, and an alkylene or carbon having 2 to 10 carbon atoms Several to 10 arylene groups are more preferred. R ₈ represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms, 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 general formula (III-4), R ₁₂ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a cyano group or a halogen atom. A hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, a cyano group, or a halogen atom is preferable. An alkyl group having 6 to 6 carbon atoms and an aryl group having 6 to 10 carbon atoms are more preferable. R ₁₂ may 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 general formula (III-5), R ₁₃ represents an aryl group or a cyano group, preferably an aryl group or a cyano group having 6 to 10 carbon atoms.
In general formula (III-4), m represents a number of 2 to 4. In the general formulas (III-1) to (III-5), n ₁ , n ₂ , n ₃ , n ₄ and n ₅ each represents a number of 2 or more, and preferably a number of 2 to 100. In the general formula (III-5), n ₆ represents 0 or a number of 2 or more, and preferably 0 or a number of 2 to 100.

In the general formulas (IV-1) to (IV-16), R ₁₄ represents a hydrogen atom or a methyl group, R ₁₅ represents an alkylene group having 1 to 10 carbon atoms, and R ₁₆ represents 1 to carbon atoms. 10 hydrocarbon groups are represented. p represents 0 or a number from 1 to 10.

Further, the polyurethane resin (ii) may further be copolymerized with a low molecular weight diol containing no carboxylic acid group as the fifth component, and the low molecular weight diol may be any of the above general formulas (III-1) to (III). −5) and having a mass average molecular weight of 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 (ii), in particular, at least one selected from diisocyanates represented by the general formula (I) and carboxylic acid group-containing diols represented by the general formulas (II-1) to (II-3): And at least one selected from high molecular diol compounds having a mass average molecular weight of 800 to 3,000, represented by general formulas (III-1) to (III-5), depending on the purpose In addition, a reaction product with a low molecular weight diol containing no carboxylic acid group having a mass average molecular weight of 500 or less represented by general formulas (III-1) to (III-5) is further added to general formulas (IV-1) to (IV). IV-16), which is obtained by reacting a compound having one epoxy group and at least one (meth) acryl group in the molecule represented by any one of the molecules, and having an acid value of 20 mgKOH / g to 120 mgKO An alkali-soluble photocrosslinkable polyurethane resin that is H / g is preferred.

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

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

--Diisocyanate--
The diisocyanate compound represented by the general formula (I) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, compounds described in paragraph “0021” of JP-A-2007-2030, etc. Is mentioned.

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

--Carboxylic acid group-containing diol--
In addition, the diol compound having a carboxyl group represented by the general formulas (II-1) to (II-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.

--Low molecular weight diol containing no carboxylic acid groups--
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. It is done.
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.

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

-Content of polyurethane resin containing acid groups and ethylenically unsaturated groups-
The solid content in the photosensitive composition of the acid group and ethylenically unsaturated group-containing polyurethane resin (represented by the above-mentioned polyurethane resins (i) and (ii)) is not particularly limited, and depends on the purpose. Although it can be appropriately selected, it is preferably 5% by mass to 80% by mass, more preferably 20% by mass to 75% by mass, and particularly preferably 30% by mass to 70% by mass.
If the solid content is less than 5% by mass, the crack resistance may not be kept good, and if it exceeds 80% by mass, the heat resistance may fail. On the other hand, when the solid content is within the particularly preferable range, it is advantageous in terms of both good crack resistance and heat resistance.

--Mass average molecular weight of polyurethane resin containing acid groups and ethylenically unsaturated groups--
The mass average molecular weight of the acid group and ethylenically unsaturated group-containing polyurethane resin (represented by the aforementioned polyurethane resins (i) and (ii)) is not particularly limited and may be appropriately selected depending on the intended purpose. Is preferably 2,000 to 60,000, more preferably 2,000 to 50,000, still more preferably 2,000 to 30,000, particularly preferably 3,000 to 30,000, and 5,000 to 30 Is most preferred. When the mass 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. In particular, when the photosensitive composition of the present invention is used for a photosensitive solder resist, it has excellent dispersibility with inorganic fillers, excellent crack resistance and heat resistance, and developability of non-image areas with an alkaline developer. Excellent.
The mass average molecular weight is determined using, for example, a high-speed GPC apparatus (HLC-802A manufactured by Toyo Soda Co., Ltd.), a 0.5 mass% THF solution as a sample solution, and a column using one TSKgel HZM-M. 200 μL of the sample is injected, eluted with the THF solution, and measured at 25 ° C. with a refractive index detector or a UV detector (detection wavelength 254 nm). Next, the mass average molecular weight was determined from the molecular weight distribution curve calibrated with standard polystyrene.

-Acid value of polyurethane resin containing acid groups and ethylenically unsaturated groups-
The acid value (solid content acid value) of the acid group and ethylenically unsaturated group-containing polyurethane resin (represented by the above-mentioned polyurethane resins (i) and (ii)) is not particularly limited, and is appropriately determined depending on the purpose. Although it can be selected, 20 mg KOH / g to 120 mg KOH / g is preferable, 30 mg KOH / g to 110 mg KOH / g is more preferable, and 35 mg KOH / g to 100 mg KOH / g is particularly preferable. If the acid value is less than 20 mg KOH / g, the developability may be insufficient, and if it exceeds 120 mg KOH / g, the development speed may be too high, and development control may be difficult.
In addition, an acid value can be measured based on JISK0070, for example. However, if the sample does not dissolve, dioxane or tetrahydrofuran is used as the solvent.

--Equivalent ethylenically unsaturated group of polyurethane resin containing acid groups and ethylenically unsaturated groups--
The ethylenically unsaturated group equivalent of the acid group and ethylenically unsaturated group-containing polyurethane resin (represented by the aforementioned polyurethane resins (i) and (ii)) is not particularly limited and is appropriately selected depending on the purpose. However, 0.05 mmol / g to 3.0 mmol / g is preferable, 0.5 mmol / g to 2.7 mmol / g is more preferable, 0.75 mmol / g to 2.4 mmol / g is more preferable, 1 Particularly preferred is .20 mmol / g to 2.4 mmol / g. When the ethylenically unsaturated group equivalent is less than 0.05 mmol / g, the heat resistance of the cured film may be inferior, and when it exceeds 3.0 mmol / g, the crack resistance may be deteriorated.
The ethylenically unsaturated group equivalent can be determined, for example, by measuring the bromine number. A bromine number can be measured based on JISK2605, for example.
Here, the ethylenically unsaturated equivalent is typically a vinyl group equivalent, and the number of grams of bromine (Br ₂ ) added to 100 g of the resin to be measured obtained by the bromine number (gBr ₂ / 100 g) is converted to the number of moles of added bromine (Br ₂ ) per 1 g of resin.

-Epoxy resins containing acid groups and ethylenically unsaturated groups-
In terms of chemical structure, the epoxy resin containing acid groups and ethylenically unsaturated groups can be classified into 1) polyether series and 2) novolac type series.
Both the 1) polyether series and the 2) novolac type series are typically synthesized as follows.
First Synthesis Method (a) Epoxy compound having at least two epoxy groups in one molecule, (b) Compound having at least two hydroxyl groups and one carboxyl group in one molecule, and (c) ethylene (D) A polybasic acid anhydride is further reacted with the reaction product (I) with the monocarboxylic compound containing a polymerizable unsaturated group. Examples of the resin synthesized in this way include those described in Japanese Patent No. 2877659.
Second Synthesis Method (a) A reaction product (II) with an epoxy compound having at least two epoxy groups in one molecule and (c) an ethylenically unsaturated group-containing monocarboxylic compound, and (d) The polybasic acid anhydride is reacted. Examples of the resin synthesized in this way include resins described in Japanese Patent No. 4127010 (Japanese Patent Laid-Open No. 2004-133060) and International Publication No. 04/034147 pamphlet.

-Polyamide or polyimide resin-
The polyamide or polyimide resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include those described in JP 2010-6946 A.

<Polymerizable compound>
The polymerizable compound is not particularly limited and may be appropriately selected depending on the purpose, and is a compound having at least one radically polymerizable group (preferably an ethylenically unsaturated group) in the molecule. A monomer is preferable, and a compound having a boiling point of 100 ° C. or higher at normal pressure is more preferable. 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 Sa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate , Glycerin tri (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, trimethylolpropane, glycerin, bisphenol and other polyfunctional alcohols after addition reaction of ethylene oxide and propylene oxide to (meth) acrylate Urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, etc. Polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, etc .; reaction products of epoxy resin and (meth) acrylic acid Polyfunctional acrylates and methacrylates such as certain epoxy acrylates can be mentioned. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are more preferable.

The solid content of the polymerizable compound in the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2% by mass to 50% by mass, and 3% by mass to 40% by mass. Is more preferable, and 4% by mass to 35% by mass is particularly preferable.
If the solid content is less than 2% by mass, pattern formation may not be possible, and if it exceeds 50% by mass, the crack resistance may be inferior. On the other hand, when the solid content is in the particularly preferable range, it is advantageous in that both good pattern formation and crack resistance can be achieved.

<Photopolymerization initiator>
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected according to the purpose. For example, it has 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 compounds described in JP-A-5-34920. Examples of the halogenated hydrocarbon compound having an oxadiazole skeleton include the compounds described in US Pat. No. 4,212,976.

The oxime derivative is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0085” of JP-A-2007-2030.

The ketone compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0087” of JP-A-2007-2030.

The photopolymerization initiator other than the above is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0086” of JP-A-2007-2030. It is done.

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 visible light, ultraviolet light laser, visible light laser or the like as a light irradiation means described later.
Sensitizers are excited by active energy rays and interact with other substances (eg, radical generators, acid generators, etc.) (eg, energy transfer, electron transfer, etc.). It is possible to generate useful groups.

The sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0089” of JP2007-2030A.

The combination of the photopolymerization initiator and the sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an electron transfer type initiation system described in JP-A 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. The combination of these is mentioned.

The solid content of the sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.05% by mass to 30% by mass with respect to all the components in the photosensitive composition. 0.1 mass% to 20 mass% is more preferable, and 0.2 mass% to 10 mass% is particularly preferable. When the solid content is less than 0.05% by mass, the sensitivity to active energy rays is reduced, the exposure process takes time, and the productivity may be reduced. Occasionally sensitizers may precipitate from the photosensitive layer.

A photoinitiator may be used individually by 1 type and may use 2 or more types together.
Particularly preferred examples of the photopolymerization initiator include halogenated hydrocarbons having the phosphine oxides, the α-aminoalkyl ketones, and the triazine skeleton, which are compatible 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 compound and an amine compound as a sensitizer described later.

The solid content of the photopolymerization initiator in the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5% by mass to 20% by mass, and preferably 0.5% by mass. % To 15% by mass is more preferable, and 1% to 10% by mass is particularly preferable.
When the solid content 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 solid content is in the above-mentioned particularly preferable range, it is advantageous in that a good pattern can be formed and the heat resistance is also improved.

<Thermal crosslinking agent>
There is no restriction | limiting in particular as a thermal crosslinking agent, According to the objective, it can select suitably, For example, an epoxy resin, a polyfunctional oxetane compound, etc. are mentioned.
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.

The epoxy resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paragraph “0095” of JP 2007-2030 A or paragraph “0130” of JP 2010-72340 A And the like.

The polyfunctional oxetane compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0096” of JP2007-2030A.

The solid content of the thermal crosslinking agent in the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass to 50% by mass, and 2% by mass to 40% by mass. Is more preferable, and 3% by mass to 30% by mass is particularly preferable.
When the solid content is less than 1% by mass, heat resistance may be inferior, and when it exceeds 50% by mass, developability and crack resistance may be inferior. On the other hand, if the solid content is in the above-mentioned 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. .

<< Other thermal crosslinking agents >>
Other thermal crosslinking agents can be added separately from the epoxy resin and polyfunctional oxetane compound. The other thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraphs “0098” to “0100” of JP-A-2007-2030. It is done.

<Thermoplastic elastomer>
There is no restriction | limiting in particular as a thermoplastic elastomer, According to the objective, it can select suitably, For example, a styrene-type elastomer, an olefin-type elastomer, a urethane-type elastomer, a polyester-type elastomer, a polyamide-type elastomer, an acrylic-type elastomer, and silicone Based elastomers and the like.
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.
The elastomer is as described in paragraphs “0197” to “0207” of JP-A-2007-199532.

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

The solid content of the thermosetting accelerator in the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.01% by mass to 20% by mass, 0.05 More preferred is from 15% by weight to 15% by weight, and particularly preferred is from 0.1% by weight to 10% by weight.
When the solid content 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 composition may deteriorate. is there. On the other hand, when the solid content is in the particularly preferred range, it is advantageous in that both the storage stability of the photosensitive composition and good physical properties of the cured film can be achieved.

<Colorant>
There is no restriction | limiting in particular as a 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.

The coloring pigment is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0106” of JP-A-2007-2030.

<Adhesion promoter>
The adhesion promoter is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0108” of JP-A-2007-2030.

The solid content of the adhesion promoter in the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.01% by mass to 20% by mass, and preferably 0.05% by mass. Is more preferably 15% by mass, and particularly preferably 0.1% by mass to 10% by mass.
If the solid content is less than 0.01% by mass, the toughness of the cured film may not be expressed, and if it exceeds 20% by mass, the preservability of the photosensitive composition may deteriorate. . On the other hand, when the solid content is in the particularly preferable range, it is advantageous in that both good storage stability and good cured film physical properties of the photosensitive composition can be achieved.

<Thermal polymerization inhibitor>
The thermal polymerization inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in paragraph “0113” of JP-A-2007-2030.

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

<Organic solvent>
The organic solvent is not particularly limited and may be appropriately selected depending on the purpose. For example, the organic solvent is described in paragraph “0043” of JP-A No. 11-240930 and paragraph “0121” of JP-A No. 2007-2030. Compounds and the like.

The content of the organic solvent in the photosensitive composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass to 80% by mass, and more preferably 2% by mass to 70% by mass. Preferably, 3% by mass to 60% by mass is particularly preferable.
When the content is less than 1% by mass, the composition has a high viscosity and it may be difficult to form a coating film. When the content exceeds 80% by mass, it may be difficult to control the desired film thickness. . On the other hand, when the content is within the above-mentioned particularly preferable range, it is advantageous from the viewpoint of coating film production suitability.

(Photosensitive film)
Although the photosensitive composition of this invention can be used also as a liquid resist by apply | coating and drying on the board | substrate with which conductor wiring was formed, it is especially useful for manufacture of the photosensitive film.
As shown in FIG. 1, the photosensitive film has at least a support 1 and a photosensitive layer 2, preferably a protective film 3, and, if necessary, a cushion layer and an oxygen barrier. It has other layers such as a layer (hereinafter abbreviated as a PC layer).
There is no restriction | limiting in particular as a form of a photosensitive film, According to the objective, it can select suitably, For example, the form which has a photosensitive layer and a protective film in this order on a support body, on a support body , A form having a PC layer, a photosensitive layer and a protective film in this order, a form having a cushion layer, a PC layer, a photosensitive layer and a protective film in this order on the support. The photosensitive layer may be a single layer or a plurality of layers.

The photosensitive layer is formed from a photosensitive composition.
The photosensitive composition is not particularly limited as long as it contains an inorganic filler, and can be appropriately selected according to the purpose. Examples thereof include the above-described photosensitive composition of the present invention.
The content of the inorganic filler in the total solid content of the photosensitive composition is 30% by mass or more (preferably 30% by mass to 80% by mass, more preferably 30% by mass to 75% by mass). As described above, preferably 35% by mass or more (preferably 35% by mass to 80% by mass, more preferably 35% by mass to 75% by mass), more preferably 40% by mass or more (preferably 40% by mass to 80% by mass). %, More preferably 40 mass% to 75 mass%), still more preferably 50 mass% (preferably 50 mass% to 80 mass%, more preferably 50 mass% to 75 mass%).

In the present invention, the melt viscosity at 30 ° C. of the photosensitive layer is particularly preferably 1 × 10 ⁵ Pa · s or more. If it is less than 1 × 10 ⁵ Pa · s, edge fusion may deteriorate.
The melt viscosity at 70 ° C. of the photosensitive layer is particularly preferably 5 × 10 ³ Pa · s or less, particularly 2 × 10 ³ Pa · s or less, when the average particle size of the inorganic filler is less than 0.3 μm. Is most preferred. If it exceeds 5 × 10 ³ Pa · s, a laminate failure may occur.
On the other hand, when the average particle size of the inorganic filler is 0.3 μm or more, 2 × 10 ³ Pa · s or less is particularly preferable, and 1.5 × 10 ³ Pa · s or less is particularly preferable, and 1.0 × 10 6 ³ Pa · s or less is more preferable. If it exceeds 2 × 10 ³ Pa · s, the embedding property may deteriorate.
If the melt viscosity at 70 ° C. of the photosensitive layer is in a more preferable range, it is advantageous in that sufficient improvement of lamination failure and sufficient embedding can be obtained.
The melt viscosity of the photosensitive layer should be measured using a melt viscosity measuring device such as a rheometer VAR-1000 type (Rheological Co., Ltd.) or Vibron DD-III type (Toyo Baldwin Co., Ltd.). Can do.
The details are as described in paragraphs “0115” to “0127” of Japanese Patent Application Laid-Open No. 2007-2030.

In addition, it is preferable that the viscosity of the coating liquid which consists of a photosensitive composition or the coating liquid which added the organic solvent to the photosensitive composition is 50 cp or less at 25 degreeC, and 30 cp or less is more preferable. The viscosity of the coating solution can be measured with an E-type viscometer, for example, trade name: VISCOMETER RE-80 manufactured by TOKI.
The photosensitive film of the present invention can be produced with a coating solution comprising the above photosensitive composition or a coating solution containing the photosensitive composition, which is preferable.

(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 as described in paragraphs “0128” to “0283” of Japanese Patent Application Laid-Open No. 2007-2030.

(Printed board)
The printed circuit board of the present invention has a permanent pattern formed on the substrate by the permanent pattern forming method. Furthermore, you may have another structure as needed.
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 permanent pattern are mentioned.

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

Binder resins 1 to 7 (Synthesis Examples 1 to 7) were synthesized as follows.

(Synthesis Example 1) Synthesis of Binder Resin 1 Cresol / Novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy equivalent 220) 2,200 parts by mass (10 equivalents), propylene glycol 134 parts by mass (1 mol) of monomethyl ether, 648.5 parts by mass (9 mol) of acrylic acid, 4.6 parts by mass of methylhydroquinone, 1131 parts by mass of carbitol acetate and 484.9 parts by mass of solvent naphtha were charged at 90 ° C. Heat and stir to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C., charged with 13.8 parts by mass of triphenylphosphine, heated to 100 ° C., reacted for about 32 hours, and a reaction product (hydroxyl group, 12 equivalents) having an acid value of 0.5 mgKOH / g. Got. Next, 364.7 parts by mass (2.4 mol) of tetrahydrophthalic anhydride, 137.5 parts by mass of carbitol acetate and 58.8 parts by mass of solvent naphtha were added to this, heated to 95 ° C., and reacted for about 6 hours. And cooled, diluted with carbitol acetate so that the solid content acid value is 40 mgKOH / g and the solid content concentration is 40%, and the ethylenically unsaturated group-containing polycarboxylic acid resin (binder resin 1) Got.

(Synthesis Example 2) Synthesis of Binder Resin 2 475 parts by mass of YDF2001 (manufactured by Toto Kasei Co., Ltd., bisphenol F type epoxy resin), 72 parts by mass of acrylic acid, 0.5 parts by mass of hydroquinone, and 120 parts by mass of carbitol acetate are charged. The reaction mixture was dissolved by heating to 90 ° C. and stirring. Next, the mixture was cooled to 60 ° C., charged with 2 parts by mass of benzyltrimethylammonium chloride, heated to 100 ° C., and reacted until the acid value reached 1 mgKOH / g. Next, 98 parts by weight of maleic anhydride and 85 parts by weight of carbitol acetate are added, heated to 80 ° C., reacted and cooled for about 6 hours, and diluted with carbitol acetate to a solid content concentration of 40% by weight. An acid-modified ethylenically unsaturated group-containing epoxy resin was obtained.

(Synthesis Example 3) Synthesis of Binder Resin 3 350 parts by mass of A1 component EXA-7376 (manufactured by Dainippon Ink & Chemicals), 70 parts by mass of acrylic acid as A2 component, 0.5 parts by mass of methylhydroquinone, carbitol 120 parts by mass of acetate was added, and the mixture was reacted by heating to 90 ° C. and stirring to completely dissolve the mixture. Next, the obtained solution was cooled to 60 ° C., 2 parts by mass of triphenylphosphine was added and heated to 100 ° C., and the reaction was continued until the acid value of the solution reached 1 mgKOH / g. To the solution after the reaction, 98 parts by mass of maleic anhydride as an A4 component and 85 parts by mass of carbitol acetate were added, heated to 80 ° C., reacted for about 6 hours, cooled, and the solid content was 40% by mass. A solution of component A was obtained by diluting with carbitol acetate.
The component A is a reaction product obtained by reacting (A1) glycidyl ether of bisphenol formaldehyde resin and (A2) an unsaturated carboxyl compound having an ethylenically unsaturated group and a carboxyl group (hereinafter referred to as “A3 component”). ) And (A4) acid anhydride, a resin having an ethylenically unsaturated group and a carboxyl group.

(Synthesis Example 4) Synthesis of Binder Resin 4 YDPF-1000 (manufactured by Tohto Kasei Co., Ltd.) 400 parts by mass, A2 component acrylic acid 72 parts by mass, methyl hydroquinone 0.5 parts by mass, carbitol acetate 120 parts by mass A portion was placed in a reaction vessel, reacted by heating to 90 ° C. and stirring, and the mixture was allowed to react while completely dissolved. Next, the obtained solution was cooled to 60 ° C., 2 parts by mass of triphenylphosphine was added and heated to 100 ° C., and the reaction was continued until the acid value of the solution reached 1 mgKOH / g. To the solution after the reaction, 100 parts by mass of tetrahydrophthalic anhydride, which is an A4 component, and 85 parts by mass of carbitol acetate are added, heated to 80 ° C., reacted for about 6 hours, and then cooled to a solid content of 40% by mass. As a result, the solution was diluted with carbitol acetate to obtain a solution of component A.
The component A is a reaction product obtained by reacting (A1) glycidyl ether of bisphenol formaldehyde resin and (A2) an unsaturated carboxyl compound having an ethylenically unsaturated group and a carboxyl group (hereinafter referred to as “A3 component”). ) And (A4) acid anhydride, a resin having an ethylenically unsaturated group and a carboxyl group.

(Synthesis Example 5) Synthesis of Binder Resin 5 In a flask equipped with a stirrer and a reflux condenser, 10 g of tetracarboxylic dianhydride (M1) having an amide bond (solid content 60% by mass, 0.01 mol), 2.87 g (0.007 mol) of 4,4 ′-[isopropylidenebis (p-phenyleneoxy)] dianiline (BAPP), 1.36 g (0.003 mol) of Jeffamine D400 (Mitsui Chemical Fine), dimethyl 2.82 g of acetamide was charged and stirred at room temperature for 8 hours to obtain a polyimide precursor (P2) having an amide bond as component (A). The obtained polyimide precursor had the repeating structure shown below, its mass average molecular weight was 30,000, and the solid content concentration was 40% by mass.

(Synthesis Example 6) Synthesis of Binder Resin 6 In a 500 mL three-neck round bottom flask equipped with a condenser and a stirrer, 32.00 g (0.216 mol) of 2,2-bis (hydroxymethyl) propionic acid (DMPA) Then, 9.00 g (0.009 mol) of polypropylene glycol (molecular weight 1,000) (PPG1000) was dissolved in 118 mL of propylene glycol monomethyl ether monoacetate. To this, 37.54 g (0.15 mol) of 4,4-diphenylmethane diisocyanate (MDI), 0.1 g of 2,6-di-t-butylhydroxytoluene, Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) 0 0.2 g was added and stirred at 75 ° C. for 5 hours, and then 9.61 g of methyl alcohol was added. Thereafter, 17.91 g (0.126) of glycidyl methacrylate (GMA) as an ethylenically unsaturated group-containing epoxy compound and 5,000 ppm of catalyst triphenylphosphine were further added, and the mixture was stirred at 110 ° C. for 5 hours. The solution was cooled to 214 g of a polymer solution.
The binder resin 6 (acid-modified ethylenically unsaturated group-containing polyurethane resin) obtained above has a solid content concentration of 40% by mass, a solid content acid value of 75 mgKOH / g, and gel permeation chromatography ( GPC) had a mass average molecular weight (polystyrene standard) of 12,000 and an ethylenically unsaturated group equivalent of 1.3 mmol / g.

(Synthesis Example 7) Synthesis of Binder Resin 7 Into a 500 mL three-necked round bottom flask equipped with a condenser and a stirrer was added 10.22 g (0.069 mol) of 2,2-bis (hydroxymethyl) butanoic acid (DMBA). ), 12.97 g (0.081 mol) of glycerol monomethacrylate (GLM) and 4.80 g (0.004 mol) of polypropylene glycol (molecular weight 1200) (PPG1200) were 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, and the trade name: Neostan U-600 (Nitto Kasei Co., Ltd.) 0.2 g) was added and heated and stirred at 75 ° C. for 5 hours. Thereafter, the mixture was diluted with 9.61 mL of methyl alcohol and stirred for 30 minutes to obtain 145 g of a polymer solution (solid content concentration: 40% by mass).
The obtained binder resin 7 has a solid content acid value of 65 mgKOH / g, a mass average molecular weight (polystyrene standard) measured by gel permeation chromatography (GPC) of 15,000, and an ethylenically unsaturated group. The equivalent weight was 1.26 mmol / g.

(Example 1 series)
Surface treated fillers 1 to 6 (Preparation Examples 1 to 6) were synthesized as follows.

(Preparation Example 1) Preparation of surface treatment filler 1 Silica particles (trade name: SO-C2, manufactured by Admatechs, average particle size (d50): 0.5 μm) with respect to 100 parts by mass are silane cups having the following structural formula A surface treatment filler 1 was prepared by adding 1 part by mass of a ring agent (trade name: KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) and performing silane coupling treatment.

Preparation Example 2 Preparation of Surface Treatment Filler 2 Silane coupling with respect to 182 parts by mass of filler (trade name: B-30, manufactured by Sakai Chemical Industry Co., Ltd., average particle size (d50): 0.3 μm, barium sulfate) A surface treatment filler 2 was prepared by adding 1 part by mass of an agent (trade name: KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) and performing a silane coupling treatment.

(Preparation Example 3) Preparation of Surface Treatment Filler 3 A silane cup having the following structural formula with respect to 100 parts by mass of silica particles (trade name: SO-C2, manufactured by Admatechs, average particle size (d50): 0.5 μm) A surface treatment filler 3 was prepared by adding 1 part by mass of a ring agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) and performing a silane coupling treatment.

(Preparation Example 4) Preparation of Surface Treatment Filler 4 Silane cups having the following structural formula with respect to 100 parts by mass of silica particles (trade name: SO-C2, manufactured by Admatechs, average particle size (d50): 0.5 μm) A surface treatment filler 4 was prepared by adding 1 part by mass of a ring agent (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) and performing a silane coupling treatment.

(Preparation Example 5) Preparation of Surface Treatment Filler 5 A silane cup having the following structural formula with respect to 100 parts by mass of silica particles (trade name: SO-C2, manufactured by Admatechs, average particle size (d50): 0.5 μm) A surface treatment filler 5 was prepared by adding 1 part by mass of a ring agent (trade name: KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.) and performing silane coupling treatment.

(Preparation Example 6) Preparation of Surface Treatment Filler 6 A silane cup having the following structural formula with respect to 100 parts by mass of silica particles (trade name: SO-C2, manufactured by Admatechs, average particle size (d50): 0.5 μm) A surface treatment filler 6 was prepared by adding 1 part by mass of a ring agent (trade name: HMDS-3, manufactured by Shin-Etsu Chemical Co., Ltd.) and performing a silane coupling treatment.

Example 1-1
<Preparation of photosensitive composition coating solution>
The following components were mixed to prepare a photosensitive composition coating solution.
The viscosity of the photosensitive composition coating solution was measured using an E-type viscometer (trade name: VISCOMETER RE-80, manufactured by TOKI).
――――――――――――――――――――――――――――――――――
Binder resin 1 synthesized in Synthesis Example 1 32.3 parts by mass Coloring pigment: HELIOGEN BLUE D7086 (manufactured by BASF)
0.021 parts by mass Coloring pigment: Pariotol Yellow D0960 (manufactured by BASF)
0.006 parts by mass Polymerizable compound: DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.) 5.3 parts by mass Initiator: Irgacure 907 (manufactured by BASF Corp.) 0.6 parts by mass Sensitizer: DETX-S (Nipponization) 0.005 parts by mass Reaction aid: EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) 0.019 parts by mass Curing agent: Melamine (trade name: Wako Pure Chemical Industries, Ltd.) 0.16 parts by mass Thermal crosslinking Agent: Epototo YDF-170 (manufactured by Toto Kasei Co., Ltd.)
2.9 parts by mass Inorganic filler: Surface treatment filler 1 16.0 parts by mass Ion trap agent: IXE-6107 (manufactured by Toagosei Co., Ltd.) 0.82 parts by mass Application aid: Megafac F-780F 0.2 parts by mass ( Dai Nippon Ink Co., Ltd .: 30% by mass methyl ethyl ketone solution)
Elastomer: Espel 1612 (manufactured by Hitachi Chemical Co., Ltd.)
2.7 parts by mass Cyclohexanone (solvent) 38.7 parts by mass

-Production of photosensitive film-
Using a polyethylene terephthalate film (PET) having a thickness of 25 μm as a support, the photosensitive composition coating solution was applied onto the support with a bar coater so that the thickness of the photosensitive layer after drying was about 30 μm. It was dried in a hot air circulation dryer at 80 ° C. for 30 minutes to produce a photosensitive film.

With respect to this photosensitive film, the melt viscosity of the photosensitive layer was measured using a rheometer VAR-1000 type (manufactured by Rheological Co., Ltd.) under the following conditions.
--Measurement conditions for melt viscosity--
Melt viscoelasticity was measured using a plate having a diameter of 20 mm at a strain of 0.005 and a frequency of 1 Hz. The temperature range was 25 ° C. to 85 ° C., and the measurement was performed at a rate of temperature increase of 5 ° C./min.

<Formation of permanent pattern>
-Preparation of laminate-
Next, the surface of a copper-clad laminate with no wiring formed (no through-hole, copper wiring thickness 12 μm printed wiring board) was prepared as a substrate by subjecting it to a chemical polishing treatment. The copper clad laminate is laminated on the copper clad laminate using a vacuum laminator (VP130, manufactured by Nichigo Morton Co., Ltd.) so that the photosensitive layer of the photosensitive film is in contact with the copper clad laminate. A laminate in which 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 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressing time of 10 seconds.

-Exposure process-
The photosensitive layer in the prepared laminate is exposed from the polyethylene terephthalate film (support) side through a photomask at 40 mJ / cm ² using a circuit board exposure machine EXM-1172 (manufactured by Oak Manufacturing Co., Ltd.). Then, a part 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. The developability and photosensitivity were evaluated using the obtained images.

-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.

The measurement and evaluation by the reliability test are as follows.
The measurement results including the coating solution viscosity of the photosensitive composition and the melt viscosity of the photosensitive layer are summarized in Table 1 below.

<Evaluation method>

-Evaluation of embeddability-
The embedded state of the photosensitive layer between the wiring patterns of L / S (line / space) = 50 μm / 50 μm was observed at a magnification of 50 to 200 times using an optical microscope and evaluated based on the following criteria.
〔Evaluation criteria〕
○: When the photosensitive film embeds a step between the pattern circuit and the base film, and there is no gap between the photosensitive film and the copper-clad laminate with circuit. Δ: The photosensitive film and the above When there is a gap between the copper-clad laminate with circuit or when air bubbles or the like are generated between the pattern circuit and the photosensitive laminate △ ^× : To the substrate because the melt viscosity is too low Bubbles do not enter when laminating, but when the photosensitive layer oozes between the substrate and the support ×: When the melt viscosity is too high to laminate

-Thermal shock resistance (crack resistance) (TCT)-
As a reliability test item, appearance such as cracks and peeling was evaluated by a temperature cycle test (TCT). TCT uses a gas-phase cold heat tester, and the electronic component module is left in the gas phase at −55 ° C. and 125 ° C. for 30 minutes each, and this is regarded as one cycle under the conditions of 1,000 cycles and 1,500 cycles. The thermal shock resistance was evaluated according to the following criteria.
〔Evaluation criteria〕
○: No crack occurred.
Δ: Shallow cracks occurred.
X: Deep cracks occurred.

-Insulation (HAST)-
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 (40 mJ / cm ² ). Subsequently, after leaving still at room temperature for 1 hour, spray development was performed for 20 second in 1 mass% sodium carbonate aqueous solution of 30 degreeC. 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 a shield wire made of polytetrafluoroethylene to these comb electrodes by Sn / Pb solder so that a voltage is applied between the comb electrodes of the evaluation laminate after heating, 50 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 laminate for evaluation was observed with a 100-fold metal microscope.

〔Evaluation criteria〕
○: The occurrence of migration cannot be confirmed, and the insulation is excellent.
○ Δ: Migration is slightly observed on copper, but insulation is good.
(Triangle | delta): Generation | occurrence | production of migration is confirmed and it is somewhat inferior to insulation.
X: The electrodes are short-circuited and insulative.

-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 criteria.
〔Evaluation criteria〕
○: There is no abnormality (peeling, swelling) in the appearance of the coating film, and there is no solder peeling.
Δ: A slight abnormality (peeling, blistering) in the appearance of the coating film, or solder flaking but light to the extent.
X: There are many abnormalities (peeling, blisters) in the appearance of the coating film, or there is solder peeling but a heavy one.

-Evaluation of resolution-
The photosensitive laminate was allowed to stand at 55% RH for 10 minutes at room temperature (23 ° C.). A photomask having a round hole pattern with a diameter of 50 μm to 200 μm from the obtained polyethylene terephthalate film (support) of the photosensitive laminate using a circuit board exposure machine EXM-1172 (manufactured by Oak Manufacturing Co., Ltd.) The exposure was carried out at 40 mJ / cm ² .
The exposure amount at this time is the amount of light energy necessary for curing the photosensitive layer of the photosensitive film in the sensitivity evaluation. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate.
The entire surface of the photosensitive layer on the copper clad laminate is sprayed with a 1% by weight sodium carbonate aqueous solution at 30 ° C. as the developer at a spray pressure of 0.15 MPa for twice the shortest development time to dissolve the uncured region. Removed.
The surface of the copper-clad laminate with a cured resin pattern obtained in this way is observed with an optical microscope, there is no residue at the bottom of the round hole of the pattern, there are no abnormalities such as blistering / peeling of the pattern, and space The minimum round hole pattern width that can be formed was measured, and this was taken as the resolution and evaluated according to the following criteria. The smaller the numerical value, the better the resolution.

〔Evaluation criteria〕
A: A round hole having a diameter of 90 μm or less can be resolved, and the resolution is excellent.
(Circle) (triangle | delta): A round hole exceeding 90 micrometers in diameter and 120 micrometers or less can be resolved, and resolution is favorable.
Δ: A round hole having a diameter exceeding 120 μm and not more than 200 μm can be resolved, and the resolution is slightly inferior.
X: A round hole cannot be resolved and the resolution is inferior.

(Examples 1-2 to 1-7)
In Example 1-1, instead of the binder resin 1 synthesized in Synthesis Example 1, the binder resins 1-2 to 1-7 synthesized in Synthesis Examples 2 to 7 were used, and the photosensitive composition coating liquids of the respective formulations were used. As shown in Table 1 below, this was prepared in the same manner as in Example 1-1, the viscosity of the coating solution was measured, and a photosensitive film was prepared in the same manner as in Example 1-1 using the coating solution. Then, reliability was evaluated in the same manner as in Example 1-1. The obtained results are shown in Table 1 below.

(Example 1-8)
In Example 1-6, the surface treatment filler 2 was used in place of the surface treatment filler 1 as the inorganic filler, and the photosensitive composition coating solution was prepared as in Example 1-6 as shown in Table 2 below. In the same manner, the viscosity of the coating solution was measured, and a photosensitive film was prepared using the coating solution in the same manner as in Example 1-6. The reliability was evaluated in the same manner as in Example 1-6. went. The obtained results are shown in Table 2 below.

(Examples 1-9 to 1-11)
In Example 1-6, except that the photosensitive composition coating solution was changed to the composition ratio shown in Table 2 below, it was prepared in the same manner as in Example 1-6, and the viscosity of the coating solution was measured. Using the coating solution, a photosensitive film was produced in the same manner as in Example 1-6, and the reliability was evaluated in the same manner as in Example 1-6. The obtained results are shown in Table 2 below.

(Comparative Examples 1-1, 1-3 and 1-4)
In Example 1-6, SO-C2 (manufactured by Admatechs, silica) not surface-treated with a silane coupling agent was used as the inorganic filler, and as shown in Table 3 below, the same as in Example 1-6 And the viscosity of the coating solution was measured. Further, using the coating solution, a photosensitive film was prepared in the same manner as in Example 1-6, and reliability was evaluated in the same manner as in Example 1-6. It was. The obtained results are shown in Table 3 below.

(Comparative Example 1-2)
In Comparative Example 1-1, using the binder resin 1 synthesized in Synthesis Example 1 instead of the binder resin 6 synthesized in Synthesis Example 6, the photosensitive composition coating solution was compared as shown in Table 3 below. Prepared in the same manner as in Example 1-1, measured the viscosity of the coating solution, and further produced a photosensitive film in the same manner as in Comparative Example 1-1 using the coating solution. Reliability evaluation was performed. The obtained results are shown in Table 3 below.

(Comparative Examples 1-5 to 1-8)
In Comparative Example 1-1, the silane coupling agents 3 to 6 prepared in Preparation Examples 3 to 6 were used instead of SO-C2 (manufactured by Admatechs, silica) that was not surface-treated with the silane coupling agent. As shown in Table 3 below, a photosensitive composition coating solution was prepared in the same manner as in Comparative Example 1-1, and the viscosity of the coating solution was measured. A photosensitive film was prepared in the same manner as described above, and the reliability was evaluated in the same manner as in Comparative Example 1-1. The obtained results are shown in Table 3 below.

From the results shown in Tables 1 to 3, the photosensitive composition containing the inorganic filler having a partial structure represented by the general formula (A) on the surface of the inorganic filler has good dispersibility, applicability, and application. A photosensitive coating film having a planar shape can be obtained, and the formed photosensitive coating film has an embedding property, thermal shock resistance (TCT), electrical insulation (HAST), solder heat resistance, and resolution. An excellent cured film can be obtained, and can be suitably used for the production of printed wiring boards, high-density multilayer boards, semiconductor packages, and the like.
Further, when Examples 1-1 to 1-11 and Comparative Examples 1-1 to 1-8 were compared, there was no significant difference in coating solution viscosity, but there was a large difference in film melt viscosity. This is probably because in Comparative Examples 1-1 to 1-8, aggregation occurred during the drying of the coating solution.

(Example 2 series)
Surface treated fillers 7 to 12 (Preparation Examples 7 to 12) were synthesized as follows.

(Preparation Example 7) Preparation of Surface Treatment Filler 7 A silane coupling agent having the following structural formula with respect to 100 parts by mass of silica particles (trade name: NSS-4N, manufactured by Tokuyama Corporation, average particle diameter (d50): 90 nm) ( Surface treatment filler 7 was prepared by adding 1 part by mass of trade name: KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd., and performing silane coupling treatment.

(Preparation Example 8) Preparation of surface treatment filler 8 Filler (trade name: B-30, manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter (d50): prepared to 0.2 μm) 182 parts by mass of silane coupling agent 1 part by mass of (trade name: KBM-573) was added and silane coupling treatment was performed to prepare a surface treatment filler 8.
Note that B-30 (manufactured by Sakai Chemical Industry Co., Ltd., barium sulfate) having an average particle diameter (d50) of 0.3 μm was crushed and used so that the average particle diameter was 0.2 μm.
(Preparation Example 9) Preparation of Surface Treatment Filler 9 With respect to 100 parts by mass of silica particles (trade name: NSS-4N, manufactured by Tokuyama Corporation, average particle size (d50): 90 nm), a silane coupling agent having the following structural formula ( A surface treatment filler 9 was prepared by adding 1 part by mass of trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd., and performing silane coupling treatment.

(Preparation Example 10) Preparation of Surface Treatment Filler 10 A silane coupling agent having the following structural formula with respect to 100 parts by mass of silica particles (trade name: NSS-4N, manufactured by Tokuyama Corporation, average particle size (d50): 90 nm) ( 1 part by mass of trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and silane coupling treatment was performed to prepare a surface treatment filler 10.

(Preparation Example 11) Preparation of Surface Treatment Filler 11 A silane coupling agent having the following structural formula (100 parts by mass of silica particles (trade name: NSS-4N, manufactured by Tokuyama Corporation, average particle diameter (d50): 90 nm)) Surface treatment filler 11 was prepared by adding 1 part by mass of trade name: KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd., and performing silane coupling treatment.

(Preparation example 12) Preparation of surface treatment filler 12 Silica particles (trade name: NSS-4N, manufactured by Tokuyama Corporation, average particle size (d50): 90 nm) with respect to 100 parts by mass are silane coupling agents having the following structural formula ( A surface treatment filler 12 was prepared by adding 1 mass of trade name: HMDS-3, manufactured by Shin-Etsu Chemical Co., Ltd., and performing silane coupling treatment.

Example 2-1
In Example 1-1, a photosensitive composition coating solution was prepared in the same manner as in Example 1-1 except that the surface treatment filler 7 was used in place of the surface treatment filler 1 of the inorganic filler. Of a conductive film, preparation of a laminate, and formation of a permanent pattern. The added amount of the inorganic filler is 16.0 parts by mass as in Example 1-1.
The viscosity of the photosensitive composition coating solution and the melt viscosity of the photosensitive layer were measured in the same manner as in Example 1-1. The measurement by the reliability test was performed in the same manner as in Example 1-1 except that the light transmittance (HAZE) described below was added to Example 1-1. Each evaluation of crack property) (TCT), insulation property (HAST), solder heat resistance (reflow resistance), and resolution was performed.
These measurement results are summarized in Table 4 below.

-Evaluation of light transmission (HAZE)-
Evaluation of light transmission (HAZE) was conducted using Opto Design Inc. Using JCH-200S (trade name) manufactured by JCH-200S, the diffuse transmittance (Td) and total light transmittance (Tt) of the photosensitive film were measured, and a value of (Td / Tt) × 100 was obtained. evaluated. Here, it shows that transparency is so high that this value is low.

(Examples 2-2 to 2-7)
In Example 2-1, instead of the binder resin 1 synthesized in Synthesis Example 1, binder resins 2 to 7 synthesized in Synthesis Examples 2 to 7 were used. As shown in FIG. 4, it was prepared in the same manner as in Example 2-1, the viscosity of the coating solution was measured, and a photosensitive film was prepared in the same manner as in Example 2-1, using the coating solution. Reliability evaluation was performed in the same manner as in Example 2-1. These measurement results are summarized in Table 4 below.

(Example 2-8)
In Example 2-6, the surface treatment filler 8 was used in place of the surface treatment filler 7 as the inorganic filler, and the photosensitive composition coating solution was prepared as in Example 2-6 as shown in Table 5 below. In the same manner, the viscosity of the coating solution was measured, and a photosensitive film was prepared using the coating solution in the same manner as in Example 2-6. The reliability was evaluated in the same manner as in Example 2-6. went. These measurement results are summarized in Table 5 below.

(Examples 2-9 and 2-10)
In Example 2-6, the photosensitive composition coating solution was prepared in the same manner as in Example 2-6 except that the composition ratio was as shown in Table 5 below, and the viscosity of the coating solution was measured. Using the coating solution, a photosensitive film was produced in the same manner as in Example 2-6, and the reliability was evaluated in the same manner as in Example 2-6. These measurement results are summarized in Table 5 below.

(Comparative Examples 2-1, 2-3 and 2-4)
In Example 2-6, silica particles not treated with a silane coupling agent (average particle diameter (d50): 90 nm, NSS-4N, manufactured by Tokuyama Corporation) were used as inorganic fillers, as shown in Table 6 below. In addition, the viscosity of the coating solution was prepared in the same manner as in Example 2-6, and a photosensitive film was prepared in the same manner as in Example 2-6 using the coating solution. Reliability evaluation was performed in the same manner as in 6. The measurement results are summarized in Table 6 below.

(Comparative Example 2-2)
In Comparative Example 2-1, the binder composition 1 synthesized in Synthesis Example 1 was used in place of the binder resin 6 synthesized in Synthesis Example 6, and the photosensitive composition coating solution was compared as shown in Table 6 below. Prepared in the same manner as in Example 2-1, measured the viscosity of the coating solution, and further produced a photosensitive film in the same manner as in Comparative Example 2-1, using the coating solution, as in Comparative Example 2-1. Reliability evaluation was performed. The measurement results are summarized in Table 6 below.

(Comparative Examples 2-5 to 2-8)
In Comparative Example 2-1, instead of silica particles that were not surface-treated with a silane coupling agent (trade name: NSS-4N, manufactured by Tokuyama Corporation, average particle size (d50): 90 nm), Preparation Examples 9 to 12 Using the prepared surface treatment fillers 9 to 12, a photosensitive composition coating solution was prepared in the same manner as in Comparative Example 2-1, as shown in Table 6 below, and the viscosity of the coating solution was measured. Using the coating solution, a photosensitive film was produced in the same manner as in Comparative Example 2-1, and the reliability was evaluated in the same manner as in Comparative Example 2-1. The measurement results are summarized in Table 6 below.

(Comparative Example 2-9)
In Example 2-1, a composition coating solution having the composition of Example 2 in Table 1 of paragraph “0045” in JP-A-2003-234439 was prepared, the viscosity of the coating solution was measured, and the coating was further performed. Using the solution, as shown in Table 7 below, a photosensitive film was produced in the same manner as in Example 2-1, and the reliability was evaluated in the same manner as in Example 2-1. These measurement results are summarized in Table 7 below.

From the results shown in Tables 4 to 7, the photosensitive composition containing the inorganic filler having the partial structure represented by the general formula (A) on the surface of the inorganic filler has good dispersibility, coating suitability, coating A photosensitive coating film having a planar shape can be obtained, and the formed photosensitive coating film has an embedding property, thermal shock resistance (TCT), electrical insulation (HAST), solder heat resistance, and resolution. A cured film that is excellent and has high light transmittance can be obtained, and can be suitably used for the production of printed wiring boards, high-density multilayer boards, semiconductor packages, and the like.
Further, when Examples 2-1 to 2-10 and Comparative Examples 2-1 to 2-9 were compared, there was no significant difference in coating solution viscosity, but there was a large difference in film melt viscosity. This is probably because in Comparative Examples 2-1 to 2-9, aggregation occurred during the drying of the coating solution.
Here, the light transmittance (HAZE) of the photosensitive film produced in Example 1-1 was separately evaluated, and Examples 2-1 to 2-10 were much superior to Example 1-1. It was confirmed.

The photosensitive composition of this invention can be used suitably for a soldering resist.
The photosensitive film of the present invention is used for forming various patterns such as protective films, interlayer insulating films, and permanent patterns such as solder resist patterns, manufacturing of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, holograms, etc. It can be suitably used for the manufacture of micromachines and proofs, 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 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, and proofs, and can be particularly suitably used for the formation of permanent patterns on printed boards.

While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

This application claims priority based on Japanese Patent Application Nos. 2010-193617 and 2010-193627 filed in Japan on August 31, 2010, which are incorporated herein by reference. Incorporated as part of the description.

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

Claims (34)

A photosensitive composition containing at least one inorganic filler, a binder, a photopolymerization initiator, and a polymerizable compound,
The content of the inorganic filler in the total solid content of the photosensitive composition is 30% by mass or more,
The photosensitive composition characterized by the particle | grain surface of this inorganic filler having the partial structure represented by the following general formula (A).
-L ₁ -NH-R ₂ ... general formula (A)
In general formula (A), R ₂ represents an organic group having 1 to 12 carbon atoms, and L ₁ represents an alkylene group having 1 to 12 carbon atoms. The photosensitive composition according to claim 1, wherein the inorganic filler has an average particle size (d50) of less than 0.3 μm. 3. The photosensitive composition according to claim 1, wherein the particle surface of the inorganic filler has a partial structure represented by the following general formula (B).
—Si (OR ₁ ) ₂ —L ₁ —NH—R ₂ ... Formula (B)
In general formula (B), R ₁ represents a methyl group or an ethyl group, R ₂ represents an organic group having 1 to 12 carbon atoms, and L ₁ represents an alkylene group having 1 to 12 carbon atoms. Here, the two R _{1 s} may be the same or different. The photosensitive composition according to any one of claims 1 to 3, wherein the inorganic filler is treated with a silane coupling agent represented by the following general formula (C).

In the general formula (C), R represents a methyl group or an ethyl group, and n represents an integer of 1 to 5. Here, the three Rs may be the same or different. The photosensitive composition according to any one of claims 1 to 4, wherein the inorganic filler is silica. The binder is an acid group- and ethylenically unsaturated group-containing resin and is at least one resin selected from polyurethane resin, epoxy resin, polyamide or polyimide resin. The photosensitive composition of any one of these. The photosensitive composition according to any one of claims 1 to 6, wherein the binder is an acid group and ethylenically unsaturated group-containing polyurethane resin. The binder has a weight average molecular weight of 2,000 to 60,000, an acid value of 20 mgKOH / g to 120 mgKOH / g, and an ethylenically unsaturated group equivalent of 0.05 mmol / g to 3.0 mmol / g. 8. The photosensitive composition according to claim 1, which is a polyurethane resin containing an acid group and an ethylenically unsaturated group. The binder is an acid group and ethylenically unsaturated group-containing polyurethane resin, and the side chain contains at least one of functional groups represented by the following general formulas (1) to (3). The photosensitive composition according to any one of claims 1 to 8.

In the general formula (1), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group, and X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —. Here, R ¹² represents a hydrogen atom or a monovalent organic group.

In 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 the ^{R 12} of the general formula (1).

In general formula (3), R ⁹ to R ¹¹ each independently represents a hydrogen atom or a monovalent organic group. Z represents an oxygen atom, a sulfur atom, —N (R ¹³ ) —, or an optionally substituted phenylene group. Here, R ¹³ represents an alkyl group which may have a substituent. The binder according to any one of claims 1 to 9, wherein the binder is a polyurethane resin containing an acid group and an ethylenically unsaturated group, and has a partial structure represented by the following general formula (UG). The photosensitive composition as described in any one of.

In general formula (UG), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom or —N (R ¹² ) — is represented. Here, R ¹² represents a hydrogen atom or a monovalent organic group. The binder is an acid group and ethylenically unsaturated group-containing polyurethane resin, and is a reaction product of a diisocyanate compound and at least two diol compounds, and at least one of the at least two diol compounds. Is a diol compound having (1) an ethylenically unsaturated group, at least one of the hydroxyl groups being a secondary alcohol, and at least one other is (2) a diol compound having a carboxyl group The photosensitive composition according to any one of claims 1 to 10. The diol compound having an ethylenically unsaturated group (1) and at least one hydroxyl group of which is a secondary alcohol is a compound represented by the following general formula (G): The photosensitive composition as described.

In general formula (G), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom or —N (R ¹² ) — is represented. Here, R ¹² represents a hydrogen atom or a monovalent organic group. The photosensitive composition according to any one of claims 1 to 12, further comprising a thermoplastic elastomer. 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. Item 14. The photosensitive composition according to item 13. Having a photosensitive layer on a support;
A photosensitive film, wherein the photosensitive layer comprises the photosensitive composition according to any one of claims 1 to 14. Having a photosensitive layer comprising a photosensitive composition on a support;
The photosensitive layer comprises an inorganic filler;
The particle surface of the inorganic filler has a partial structure represented by the following general formula (A),
The content of the inorganic filler in the total solid content of the photosensitive composition is 30% by mass or more,
The melt viscosity of the photosensitive layer at 30 ° C. is 1 × 10 ⁵ Pa · s or more, and the melt viscosity of the photosensitive layer at 70 ° C. is such that the average particle size of the inorganic filler is less than 0.3 μm. In this case, the photosensitive film is 5 × 10 ³ Pa · s or less, and when the average particle size of the inorganic filler is 0.3 μm or more, the photosensitive film is 2 × 10 ³ Pa · s or less.
-L ₁ -NH-R ₂ ... general formula (A)
In general formula (A), R ₂ represents an organic group having 1 to 12 carbon atoms, and L ₁ represents an alkylene group having 1 to 12 carbon atoms. The photosensitive film according to claim 16, wherein the inorganic filler has an average particle size (d50) of less than 0.3 μm. The photosensitive film according to claim 16 or 17, wherein the photosensitive layer contains at least one binder, a photopolymerization initiator, and a polymerizable compound together with the inorganic filler. The photosensitive film according to any one of claims 16 to 18, wherein the content of the inorganic filler in the total solid content of the photosensitive composition is 50% by mass or more. The photosensitive film according to any one of claims 16 to 19, wherein the particle surface of the inorganic filler has a partial structure represented by the following general formula (B).
—Si (OR ₁ ) ₂ —L ₁ —NH—R ₂ ... Formula (B)
In general formula (B), R ₁ represents a methyl group or an ethyl group, R ₂ represents an organic group having 1 to 12 carbon atoms, and L ₁ represents an alkylene group having 1 to 12 carbon atoms. Here, the two R _{1 s} may be the same or different. The photosensitive film according to any one of claims 16 to 20, wherein the inorganic filler is treated with a silane coupling agent represented by the following general formula (C).

In the general formula (C), R represents a methyl group or an ethyl group, and n represents an integer of 1 to 5. Here, the three Rs may be the same or different. The photosensitive film according to any one of claims 16 to 21, wherein the inorganic filler is silica. The binder is an acid group- and ethylenically unsaturated group-containing resin, and is at least one resin selected from polyurethane resin, epoxy resin, polyamide or polyimide resin. The photosensitive film of any one of these. The photosensitive film according to any one of claims 18 to 23, wherein the binder is a polyurethane resin containing an acid group and an ethylenically unsaturated group. The binder has a weight average molecular weight of 2,000 to 60,000, an acid value of 20 mgKOH / g to 120 mgKOH / g, and an ethylenically unsaturated group equivalent of 0.05 mmol / g to 3.0 mmol / g. The photosensitive film according to any one of claims 18 to 24, which is a polyurethane resin containing an acid group and an ethylenically unsaturated group. The binder is an acid group and ethylenically unsaturated group-containing polyurethane resin, and the side chain contains at least one of functional groups represented by the following general formulas (1) to (3). The photosensitive film according to any one of claims 18 to 25.

In the general formula (1), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group, and X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —. Here, R ¹² represents a hydrogen atom or a monovalent organic group.

In 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 the ^{R 12} of the general formula (1).

In general formula (3), R ⁹ to R ¹¹ each independently represents a hydrogen atom or a monovalent organic group. Z represents an oxygen atom, a sulfur atom, —N (R ¹³ ) —, or an optionally substituted phenylene group. Here, R ¹³ represents an alkyl group which may have a substituent. 27. The binder according to claim 18, wherein the binder is a polyurethane resin containing an acid group and an ethylenically unsaturated group and has a partial structure represented by the following general formula (UG). The photosensitive film of description.

In general formula (UG), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom or —N (R ¹² ) — is represented. Here, R ¹² represents a hydrogen atom or a monovalent organic group. The binder is an acid group and ethylenically unsaturated group-containing polyurethane resin, and is a reaction product of a diisocyanate compound and at least two diol compounds, and at least one of the at least two diol compounds. Is a diol compound having (1) an ethylenically unsaturated group, at least one of the hydroxyl groups being a secondary alcohol, and at least one other is (2) a diol compound having a carboxyl group The photosensitive film according to any one of claims 18 to 27. The diol compound having an ethylenically unsaturated group (1) and at least one hydroxyl group of which is a secondary alcohol is a compound represented by the following general formula (G): The photosensitive film as described.

In general formula (G), R ¹ to R ³ each independently represents a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom or —N (R ¹² ) — is represented. Here, R ¹² represents a hydrogen atom or a monovalent organic group. The photosensitive film according to any one of claims 16 to 29, further comprising a thermoplastic elastomer. 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. Item 31. The photosensitive film according to Item 30. The photosensitive composition according to any one of claims 1 to 14 is applied to the surface of a substrate, dried to form a laminate by laminating a photosensitive layer, and then exposing and developing. A permanent pattern forming method. A permanent pattern formed by the method for forming a permanent pattern according to claim 32. A printed circuit board comprising a permanent pattern formed by the permanent pattern forming method according to claim 32.

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