JP6273690B2 - Photosensitive resin composition and photosensitive film using the same - Google Patents

Description

  The present invention relates to a photosensitive resin composition and a photosensitive film using the same.

  Conventionally, as a method of selectively cutting an object to be processed such as glass or ceramics, after providing a patterned photosensitive resin composition layer (hereinafter also referred to as a photosensitive layer) as a mask material on the object to be processed, A sand blasting method for selectively cutting a non-mask portion by spraying an abrasive is known.

  As the photosensitive resin composition used as the mask material for the sandblast treatment, for example, a dry film resist in which a photosensitive layer is provided on a support such as a polyester film is used. As the photosensitive layer, a photosensitive resin composition containing an alkali-soluble resin, urethane (meth) acrylate, and a photopolymerization initiator has been applied. As the alkali-soluble resin in the photosensitive resin composition, a cellulose derivative or a carboxy group-containing acrylic resin is used (for example, see Patent Document 1 or 2).

  In order to increase the sandblast resistance (hereinafter sometimes simply referred to as “blast resistance”) of such a photosensitive resin composition, it is necessary to lower the elastic modulus of the cured film. Increasing the amount of (meth) acrylate as much as possible has been performed. However, when the blending amount of urethane (meth) acrylate is increased, the tackiness of the photosensitive layer is increased at the stage before curing, so that the photosensitive layer is hardly peeled off from the support. As a result, it was difficult to transfer the photosensitive layer to the object to be processed.

  For this reason, in order to make it easy to transfer the photosensitive layer to the processing target while maintaining blast resistance, for example, water-soluble resin layer containing polyvinyl alcohol or partially saponified polyvinyl acetate, polyvinyl alcohol or partially saponified polyvinyl acetate with ethylene A water-soluble resin layer added with glycol, propylene glycol, polyethylene glycol or the like is provided as a release layer, and a release layer containing an alkali-soluble cellulose derivative is provided (for example, see Patent Document 3 or 4). By this method, the support can be easily peeled from the photosensitive layer.

Japanese Patent No. 3449572 Japanese Patent No. 3846958 JP-A-6-161098 JP 2012-27357 A

  However, the conventional photosensitive resin composition has a problem that the adhesiveness with the rib paste pattern-formed by the sandblast treatment is not sufficient, and the sandblast resistance is low. For this reason, the sandblast resistance at the time of high sandblasting pressure effective for shortening the processing time and increasing the processing thickness is not sufficient. In particular, in the manufacturing process of a plasma display panel (PDP), a finer pattern has been demanded as the pixel pitch is reduced. Further, in order to improve the adhesion of the photosensitive film, shorten the processing time, and increase the processing thickness, it is required to improve the sandblast resistance at a high sandblast pressure.

  Therefore, this invention solves the said subject and provides the photosensitive resin composition and photosensitive film excellent in the sandblast tolerance after hardening.

The present invention is as follows.
[1] A photosensitive resin composition in which a cured product obtained by a curing treatment has an elastic modulus of 200 MPa or less by a tensile test based on JIS K 7161 (1994).
[2] The photosensitive resin composition according to [1], comprising (A) a binder polymer containing a structural unit having a carboxy group, (B) a photopolymerizable compound, and (C) a photopolymerization initiator.
[3] (A) Binder polymer containing structural unit having carboxy group, (B) 2,2-bis (4-((meth) acryloxypolyethoxy) having 20 to 50 structural units of ethyleneoxy group The photosensitive resin composition according to [1] or [2], comprising a photopolymerizable compound containing phenyl) propane, and (C) a photopolymerization initiator.
[4] The photosensitive resin composition according to [3], wherein the photopolymerizable compound further contains urethane (meth) acrylate.
[5] The photosensitive resin composition according to [4], wherein the urethane (meth) acrylate has a weight average molecular weight of 10,000 or more and 100,000 or less.
[6] Photosensitive having a support and a photosensitive resin composition layer that is a coating film of the photosensitive resin composition according to any one of [1] to [5] disposed on the support. the film.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition and photosensitive film excellent in the sandblast tolerance after hardening can be provided.

It is a schematic cross section which shows one Embodiment of the photosensitive film of this invention. It is an electron micrograph which shows the cross section after the process of the sample for sandblast evaluation obtained using the photosensitive film concerning the Example of this invention (150 times).

The photosensitive resin composition of the present invention is a photosensitive resin composition in which a cured product of the photosensitive resin composition obtained by curing treatment has an elastic modulus of 200 MPa or less by a tensile test in accordance with JIS K 7161 (1994). It is.
As a result of intensive studies, the present inventors conducted a tensile test based on JIS K 7161 (1994) on the cured product obtained after curing the photosensitive resin composition. As a result, the photosensitive material having an elastic modulus of 200 MPa or less. It was found that the photosensitive resin composition can provide a photosensitive film excellent in resistance to sandblasting after curing. The present invention is based on this finding.

Although the details of the relationship between the elastic modulus of the cured product of the photosensitive resin composition and the sandblast resistance are unclear, the elastic modulus of the cured product of the photosensitive resin composition is 200 MPa or less as the elastic modulus by the tensile test described above. If so, it is presumed that the impact during sandblasting is appropriately absorbed by the resin, and as a result, both sandblast resistance and resolution are increased. However, the present invention is not limited to this assumption.
For this reason, the photosensitive resin composition of the present invention is suitable for application to PDP rib processing or glass cutting using a sandblasting method.

In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. .
In addition, in this specification, “to” indicates a range including numerical values described before and after that as a minimum value and a maximum value, respectively.
Furthermore, in this specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. means.
In this specification, (meth) acrylic acid means at least one of acrylic acid and methacrylic acid, and (meth) acrylate means at least one of acrylate (acrylic acid ester) and the corresponding methacrylate (methacrylic acid ester). To do.
The present invention will be described below.

<Elastic modulus of cured product>
The photosensitive resin composition in the present invention is a photosensitive resin composition in which a cured product of the photosensitive resin composition obtained by the curing treatment has an elastic modulus of 200 MPa or less by a tensile test based on JIS K 7161 (1994). is there. When the elastic modulus of the cured product of the photosensitive resin composition in the tensile test is greater than 200 MPa, wear during sandblasting tends to be severe, and sufficient sandblast resistance is difficult to obtain.

  The elastic modulus of the cured product of the photosensitive resin composition is a sandblast resistance point of 200 MPa or less, preferably 180 MPa or less, more preferably 150 MPa or less, and further preferably 120 MPa or less. preferable. Although there is no restriction | limiting in particular about the lower limit of the elasticity modulus of the hardened | cured material of the photosensitive resin composition, generally 50 MPa or more is preferable and 80 MPa or more is more preferable at the point of the flaw prevention of a cured film.

The elastic modulus of the cured product of the photosensitive resin composition is a value obtained by a tensile test based on JIS K 7161 (1994). Hereinafter, unless otherwise specified, the elastic modulus obtained by this tensile test is simply referred to as “elastic modulus” in the present specification.
The hardened | cured material used for a measurement is used for the hardening process by the hardening conditions based on the composition of the photosensitive resin composition, and was hardened. The curing conditions for the curing treatment are selected according to the type of polymerizable compound contained in the photosensitive resin composition. The composition of the photosensitive resin composition and the curing (exposure) conditions will be described later.
When using the obtained hardened | cured material for a measurement, the cured film with a film thickness of 30 micrometers is cut | disconnected to the size of 10 mm x 50 mm, and it is set as a test piece. In addition, when the obtained hardened | cured material has a support film, a protective film, etc., it prepares as a test piece of the state which peeled off both the support film and the protective film.

  The elastic modulus was measured on a sample obtained by curing the photosensitive resin composition using a rheometer (manufactured by Rheotech Co., Ltd.) at a temperature of 23 ° C., a length between chucks of 50 mm, and a tensile speed of 20 mm / min. Measure the elastic modulus. Five similar samples are prepared, the elastic modulus is measured under the same conditions as described above, and the average value is taken as the elastic modulus. Other detailed conditions and the elastic modulus calculation method are performed in accordance with JIS K 7161 (1994).

<Photosensitive resin composition>
The photosensitive resin composition in the present invention is not particularly limited as long as the elastic modulus of the cured product of the photosensitive resin composition is 200 MPa or less. Examples of such a photosensitive resin composition include (A) a binder polymer containing a structural unit having a carboxy group, (B) at least one photopolymerizable compound, and (C) in terms of sandblast resistance and resolution improvement. The photosensitive resin composition which contains a photoinitiator and contains arbitrary other components as needed can be mentioned.

(A) Binder polymer containing a structural unit having a carboxy group The binder polymer containing a structural unit having a carboxy group is, for example, a polymerizable monomer having a carboxy group, or a polymerizable monomer having a carboxy group and others. The polymerizable monomer can be produced by radical polymerization. Examples of the polymerizable monomer having a carboxy group include acrylic acid and methacrylic acid. These polymer monomers having a carboxy group can be used singly or in combination of two or more.

  Examples of other polymerizable monomers include polymerizable monomers having a vinyl group. Examples of the polymerizable monomer having a vinyl group include (meth) acrylic acid alkyl esters such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, ethyl acrylate, and methyl acrylate, and styrene. , Α-methylstyrene, vinyltoluene, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, acrylonitrile, methacrylonitrile, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, styrene / maleic acid copolymer A combined half ester may be mentioned. These polymerizable monomers having a vinyl group can be used alone or in combination of two or more.

  The binder polymer containing a structural unit having a carboxy group may be a copolymer of (meth) acrylic acid and a polymerizable monomer having a vinyl group in terms of both alkali developability and pattern formability. Preferably, it is a copolymer of (meth) acrylic acid and at least one (meth) acrylic acid alkyl ester. As a copolymer of (meth) acrylic acid and (meth) acrylic acid alkyl ester, methacrylic acid / methyl methacrylate / butyl acrylate, methacrylic acid / methacrylic acid are compatible with alkali developability and pattern-forming property. Preferable examples include methyl / ethyl acrylate, methacrylic acid / methyl methacrylate / ethyl acrylate / styrene, and the like.

  The weight average molecular weight of the binder polymer containing the structural unit having a carboxy group is preferably 20,000 to 300,000. When the weight average molecular weight of the binder polymer containing the structural unit having a carboxy group is 20,000 or more, the film formability tends to be further improved, and when it is 300,000 or less, the developability tends to be further improved. .

The weight average molecular weight of the binder polymer is converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is approximated by a cubic equation using a standard polystyrene 5 sample set (PStQuick MP-H, PStQuick B [trade name, manufactured by Tosoh Corp.]). The GPC conditions are shown below.
Device Pump: L-2130 [manufactured by Hitachi High-Technologies Corporation]
Detector: L-2490 type RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-2350 [manufactured by Hitachi High-Technologies Corporation]
Column: Gelpack GL-R440 + Gelpack GL-R450 + Gelpack GL-R400M (three in total) (trade name, manufactured by Hitachi Chemical Co., Ltd.)
Column size: 10.7 mmI. D x 300mm
Eluent: Tetrahydrofuran Sample concentration: 10 mg / 2 mL
Injection volume: 200 μL
Flow rate: 2.05 mL / min Measurement temperature: 25 ° C

The acid value of the binder polymer containing the structural unit having a carboxy group is preferably 50 mgKOH / g to 200 mgKOH / g, and particularly preferably 60 mgKOH / g to 180 mgKOH / g. When the acid value of the binder polymer is 50 mgKOH / g or more, the developability tends to be improved, while when it is 200 mgKOH / g or less, the pattern tends to be easily formed.
Here, the acid value can be measured as follows. That is, first, about 1 g of a resin solution whose acid value is to be measured is precisely weighed, and then 30 g of acetone is added to this resin solution to dissolve it uniformly. Next, an appropriate amount of an indicator, phenolphthalein, is added to the solution, and titration is performed using a 0.1 N (mol / liter) aqueous KOH solution. And an acid value is computed by following Formula.
A = 10 × Vf × 56.1 / (Wp × I)
In the formula, A represents the acid value (mgKOH / g), Vf represents the titration amount (mL) of a 0.1N KOH aqueous solution, Wp represents the mass (g) of the measured resin solution, and I was measured. The ratio (mass%) of the non volatile matter in a resin solution is shown.
Moreover, it is preferable that this (B) component is soluble or swellable in aqueous alkali solution.

  When the binder polymer includes a structural unit having a carboxy group, the content of the structural unit having a carboxy group (polymerizable monomer having a carboxy group in the total mass of the polymerizable monomer used for producing the binder polymer) Is preferably 10% by mass to 80% by mass, more preferably 15% by mass to 70% by mass, and 15% by mass from the viewpoint of the balance between alkali developability and alkali resistance. More preferably, it is -50 mass%. When the content of the structural unit having a carboxy group is 10% by mass or more, good alkali developability is obtained, and the development time tends to be shortened. Moreover, when it is 80 mass% or less, there exists a tendency for developing solution tolerance to improve and also adhesiveness to improve.

As the binder polymer containing a structural unit having a carboxy group, the following are more preferable from the viewpoint of sandblast resistance:
(1) Methacrylic acid / Methyl methacrylate / Butyl acrylate (mass ratio: 17/62/21, weight average molecular weight: 110,000, acid value 111 mgKOH / g),
(2) Methacrylic acid / Methyl methacrylate / Ethyl acrylate (Mass ratio: 18/52/30, Weight average molecular weight: 80,000, Acid value 114 mgKOH / g)
(3) Methacrylic acid / methyl methacrylate / ethyl acrylate / styrene (mass ratio: 26/34/20/20, weight average molecular weight: 65,000, acid value 170 mgKOH / g).
Among these, the binder polymer (1) is more preferable from the viewpoint of sandblast resistance and resolution.

(B) Photopolymerizable compound Although there is no restriction | limiting in particular as a polymeric compound if the elasticity modulus of the hardened | cured material of the photosensitive resin composition can be in the range mentioned above, From a viewpoint of sandblast resistance and resolution Therefore, it is preferable to include a bisphenol A (meth) acrylate compound.

  The bisphenol A (meth) acrylate compound is preferably a bisphenol A (meth) acrylate compound having an alkyleneoxy structural unit from the viewpoint of sandblast resistance after curing. The alkyleneoxy structural unit in the bisphenol A-based (meth) acrylate compound having an alkyleneoxy structural unit is preferably an alkyleneoxy structural unit having 5 or more carbon atoms in view of flexibility, and an alkyleneoxy having 10 or more carbon atoms. More preferably, it is a structural unit. Examples of the bisphenol A-based (meth) acrylate compound having an alkyleneoxy structural unit include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-(( (Meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) ) Phenyl) propane. Among these, 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane is preferable, for example, 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentaethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane may be mentioned.

  Among them, from the viewpoint of resistance to sandblasting, 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl represented by the following general formula (4b) and having 20 to 50 structural units of ethyleneoxy structural units ) It is preferable to contain propane.

In the general formula (4b), R ⁴¹ and R ⁴² each independently represent a hydrogen atom or a methyl group. (XO) _m1 and (XO) _m2 each represent a (poly) ethyleneoxy structural unit. m ₁ and _{m 2} is the number of structural units of the respective structural units, 0 to 40 independently, the sum of _{m 1} and _{m 2 (m} 1 + _{m 2)} is from 20 to 50. If the sum of m ₁ and m ₂ is 20 or more, the elastic modulus tends to be lowered to improve the sandblast resistance, and if it is 50 or less, the developability tends to be good. Here, the number of structural units indicates the number of ethyleneoxy structural units added in the molecule. Therefore, an integer value is shown for a single molecule, but a rational number that is an average value is shown as an aggregate of a plurality of types of molecules.

  Examples of the compound represented by the general formula (4b) include 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl). Propane, 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis ( Examples thereof include bisphenol A-based (meth) acrylate compounds such as 4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane. 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) is commercially available as BPE-1300NH (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.).

The compound of the general formula (4b) is 10% by mass to 70% by mass based on the total solid content of the photosensitive resin composition (total mass of nonvolatile components contained in the photosensitive resin composition). Is preferable, and it is more preferable that it is 20 mass%-60 mass%. When the compound of the general formula (4b) is 10% by mass or more, good photosensitivity tends to be obtained, and when it is 50% by mass or less, good film formability tends to be obtained.
The content of the compound of the general formula (4b) in the photopolymerizable compound (B) is preferably 5% by mass to 90% by mass, and more preferably 10% by mass to 80% by mass. 20% by mass to 70% by mass is more preferable, 40% by mass to 70% by mass is particularly preferable, and 50% by mass to 70% by mass is extremely preferable. When the compound of the general formula (4b) is 5% by mass or more, good photosensitivity tends to be obtained, and when it is 90% by mass or less, good film formability tends to be obtained.

  From the viewpoint of further reducing the elastic modulus of the cured product of the photosensitive resin composition, in addition to the compound represented by the formula (4b), at least one polymerizable compound having an ethylenically unsaturated bond as a photopolymerizable compound, Furthermore, it is more preferable to include.

  Examples of the polymerizable compound having an ethylenically unsaturated bond include urethane (meth) acrylate, and urethane (meth) acrylate is preferable.

  Among urethane (meth) acrylate compounds, the weight average molecular weight is preferably 10,000 or more, and more preferably 15,000 or more, from the viewpoint of reducing the elastic modulus of the cured product of the photosensitive resin composition. Although there is no restriction | limiting in particular about the upper limit of the weight average molecular weight of a urethane (meth) acrylate compound, It is preferable that it is 50000 or less from the point of coexistence of developability and a photosensitive characteristic. The weight average molecular weight of the urethane (meth) acrylate compound is converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is approximated by a cubic equation using a standard polystyrene 5 sample set (PStQuick MP-H, PStQuick B [trade name, manufactured by Tosoh Corp.]). The GPC conditions are the same as those described for the weight average molecular weight of the binder polymer.

  The urethane (meth) acrylate compound is preferably 10% by mass to 60% by mass, and more preferably 20% by mass to 50% by mass with respect to the total mass of the (B) photopolymerizable compound. When the urethane (meth) acrylate compound is 10% by mass or more, the sandblast resistance tends to be good, and when it is 60% by mass or less, the photosensitive characteristics tend to be good.

  The urethane (meth) acrylate compound refers to a reaction product of a compound having a terminal isocyanate group obtained by reacting a diol compound and a diisocyanate compound and a (meth) acrylate compound having a hydroxy group.

  Examples of the diol compound include polyesters and polyethers having a hydroxy group at the terminal. Examples of polyesters include, for example, polyesters obtained by ring-opening polymerization of lactones; polycarbonates; alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and dipropylene glycol; and maleic acid, fumaric acid, glutaric acid, Examples thereof include polyesters obtained by a condensation reaction with a dicarboxylic acid such as adipic acid.

  Specific examples of the lactones include δ-valerolactan, ε-caprolactone, β-propiolactone, α-methyl-β-propiolactone, β-methyl-β-propiolactone, α, α-dimethyl- β-propiolactone, β, β-dimethyl-β-propiolactone and the like can be mentioned.

  Specific examples of the polycarbonates include reaction products of diols such as bisphenol A, hydroquinone, and dihydroxycyclohexanone with carbonyl compounds such as diphenyl carbonate, phosgene, and succinic anhydride.

  Specific examples of the polyethers include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polypentamethylene glycol.

  Examples of the diisocyanate compound that reacts with the diol compound include dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, octane. Methylene diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate, 2,2,4-trimethylpentane-1,5-diisocyanate, nanomethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, isophorone Mention may be made of aliphatic or cycloaliphatic diisocyanate compounds such as diisocyanates. These aliphatic or alicyclic diisocyanate compounds can be used alone or in combination of two or more.

  Specific examples of the (meth) acrylate compound having a hydroxy group include hydroxymethyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, and 3-hydroxypropyl methacrylate. be able to. These (meth) acrylate compounds having a hydroxy group can be used singly or in combination of two or more.

  The urethane (meth) acrylate compound may be further reacted with a (meth) acrylic acid alkyl ester. Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic acid 2-ethylhexyl ester.

  The urethane (meth) acrylate compound preferably has a weight average molecular weight of 10,000 or more and has two ethylenically unsaturated groups from the viewpoint of further reducing the elastic modulus of the cured product of the photosensitive resin composition.

  The urethane (meth) acrylate compound may be synthesized by a conventional method, or a commercially available product may be obtained. Examples of the urethane (meth) acrylate compound that can be obtained include UF-8003M, UF-TCB-50, UF-TC4-55 (trade names, manufactured by Kyoeisha Chemical Co., Ltd.), and purple light UV-3000B (trade names, Japan). Synthetic Chemical Industry Co., Ltd.) and Hitaroid 9082-95 (trade name, manufactured by Hitachi Chemical Co., Ltd.). These are all urethane (meth) acrylate compounds having two ethylenically unsaturated groups.

  (B) The content of the photopolymerizable compound is preferably 30% by mass to 70% by mass and more preferably 40% by mass to 60% by mass based on the total solid content of the photosensitive resin composition. preferable. If the component (B) is 30% by mass or more, the pattern forming property tends to be good, and the blast resistance tends to be sufficient. If the component is 70% by mass or less, the photosensitive resin composition is less sticky. Tend to be.

(C) Photopolymerization initiator Examples of the photopolymerization initiator include anthraquinone derivatives such as 2-methylanthraquinone, benzophenone derivatives such as 3,3-dimethyl-4-methoxy-benzophenone, and 2,2-dimethoxy-2-phenyl. Acetophenone, acetophenone derivatives such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, benzoin alkyl ether derivatives such as benzoinpropyl ether, thioxanthone derivatives such as diethylthioxanthone, Michler's ketone, 2- (O-chlorophenyl) -4,5-diphenylimidazole dimer [2,2-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2-biimidazole], 9- Phenylacridine, dimethylbenzyl ketal, Examples include methylbenzoyldiphenylphosphine oxide, tribromomethylphenylsulfone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. It is done. These photopolymerization initiators can be used alone or in combination of two or more. Among these, as the photopolymerization initiator, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer [2,2-bis (2-chlorophenyl) -4,5,4 ′, 5 ′ -Tetraphenyl-1,2-biimidazole], 2,4,5-triarylimidazole dimer and the like are preferable from the viewpoint of sensitivity and resolution.

  (C) From the viewpoint of photosensitivity, the content of the photopolymerization initiator is preferably 0.1% by mass to 10% by mass based on the total solid content of the photosensitive resin composition, and is 0.2% by mass. It is more preferable that it is% -5 mass%.

  In the present invention, the blending amount of the (B) photopolymerizable compound is 20% by mass of the total amount of the (A) carboxy group-containing binder polymer, (B) the photopolymerizable compound and (C) the photopolymerization initiator. It is preferable to set it as -80 mass%, and it is more preferable to set it as 30 mass%-60 mass%. If this blending amount is 20% by mass or more, it tends to suppress a decrease in sensitivity, and if it is 80% by mass or less, resin seepage from the end face of the film roll is less likely to occur, and storage stability is improved. It tends to be better. Moreover, in order to make the elasticity modulus of the hardened | cured material of the photosensitive resin composition low enough, it is preferable to use 10 mass%-60 mass% as urethane (meth) acrylate among (B) photopolymerizable compounds.

  As a compounding quantity of the binder polymer which has (A) carboxy group in this invention, 20 mass of the total amount of the binder polymer which has (A) carboxy group, (B) photopolymerizable compound, and (C) photoinitiator. % To 80% by mass, and more preferably 30% to 60% by mass. If this blending amount is 20% by mass or more, the photocured product is not easily brittle, and when used as a photosensitive film, the coating property tends to be good, and if it is 80% by mass or less, the photosensitivity is high. Tend to be sufficient.

  In the present invention, the blending amount of (C) the photopolymerization initiator is 0.5 of the total amount of (A) a binder polymer having a carboxy group, (B) a photopolymerizable compound and (C) a photopolymerization initiator. It is preferable to set it as the mass%-10.0 mass%. If it is 0.5 mass% or more, photosensitivity tends to be sufficiently obtained, and if it is 10.0 mass% or less, the bottom curability of the resist tends to be good.

  The photosensitive resin composition of the present invention preferably contains the component (A), the component (B), and the component (C) as essential components and can be developed with an aqueous alkaline solution.

  Moreover, a various additive component can be added to the photosensitive resin composition of this invention as needed. Examples of additives that can be added include dyes such as malachite green, photochromic agents such as leuco crystal violet, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, phthalocyanine series such as phthalocyanine blue, azo series, etc. Organic pigments, inorganic pigments such as titanium dioxide, fillers composed of inorganic pigments such as silica, alumina, talc, calcium carbonate or barium sulfate, antifoaming agents, stabilizers, adhesion promoters, leveling agents, antioxidants, A fragrance | flavor and an imaging agent are mentioned. These additive components are each preferably contained in an amount of about 0.01% by mass to 20% by mass based on the total solid content of the photosensitive resin composition. Moreover, said additive component can be used individually by 1 type or in combination of 2 or more types, and also in each additive component, 1 type can be used individually or in combination of 2 or more types, respectively.

  Furthermore, the photosensitive resin composition may be mixed with a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof as necessary. It melt | dissolves and it can apply | coat as a solution of about 30 mass%-70 mass% solid content.

<Photosensitive film>
The photosensitive film of this invention has a support body and the photosensitive resin composition layer which is a coating film of the said photosensitive resin composition arrange | positioned on a support body. The photosensitive film may further include other layers such as a protective film provided as necessary.
The photosensitive film using the said photosensitive resin composition is demonstrated with reference to drawings.
FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the photosensitive film of the present invention. A photosensitive film 10 shown in FIG. 1 includes a support 12 and a photosensitive resin composition layer 14 provided on the support 12. The photosensitive resin composition layer 14 is a layer formed using the above-described photosensitive resin composition.

  The photosensitive resin composition layer 14 is a solution (hereinafter, also referred to as “coating liquid”) having a solid content of about 30% by mass to 70% by mass by dissolving the photosensitive resin composition of the present invention in the above solvent or mixed solvent. Then, it is preferable to form such a solution by applying the solution on the support 12.

  Although the thickness of the photosensitive resin composition layer 14 varies depending on the use, it is preferably 10 μm to 120 μm, more preferably 20 μm to 100 μm in thickness after drying after removing the solvent by heating and / or hot air blowing. preferable. If the thickness is within the above range, coating tends to be industrially easy. If the thickness is 10 μm or more, it tends to be easy to ensure sufficient blast resistance, and if it is 120 μm or less, the resolution tends not to be lowered.

  Examples of the support 12 included in the photosensitive film 10 include polymer films having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester. As a commercial item, Teijin G2-16 grade | etc., Is mentioned.

  The thickness of the support 12 is preferably 5 μm to 100 μm, and more preferably 10 μm to 30 μm. If this thickness is 5 μm or more, the support tends to be difficult to tear when the support is peeled off before development, and if it is 100 μm or less, the resolution tends not to decrease.

  Moreover, the photosensitive film 10 may coat | cover the surface F1 on the opposite side to the support body 12 on the photosensitive resin composition layer 14 with a protective film.

  As the protective film, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used. Commercially available products include polypropylene films such as Alfane MA-410 and E-200C manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., polyethylene films such as NF-13 manufactured by Tamapoli Co., and PS series such as PS-25 manufactured by Teijin Limited. And polyethylene terephthalate film. The protective film may be the same as the above support.

  The thickness of the protective film is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, still more preferably 5 μm to 30 μm, and particularly preferably 15 μm to 30 μm. When the thickness of the protective film is 1 μm or more, the protective film can be prevented from being broken when the protective film is peeled off. Moreover, productivity improves because the thickness of a protective film is 100 micrometers or less.

  The photosensitive film 10 formed by laminating two layers of the support 12 and the photosensitive resin composition layer 14 as described above, or three layers of the support 12, the photosensitive resin composition layer 14, and the protective film. The photosensitive film formed by laminating may be stored as it is, for example, or may be stored in a roll shape around a winding core with a protective film interposed. Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

  The photosensitive film 10 can be manufactured as follows, for example. (A) a binder polymer, (B) a polymerizable compound, and (C) a photopolymerization initiator are dissolved in a solvent to prepare a coating solution having a solid content of about 30% by mass to 70% by mass; Manufactured by a production method comprising the steps of coating the coating liquid on the support 12 to form a coating layer, and drying the coating layer to form the photosensitive resin composition layer 14 as a coating film. can do.

  The application of the coating solution onto the support 12 can be performed by a known method such as a roll coater, comma coater, gravure coater, air knife coater, die coater, or bar coater.

  The drying of the coating layer is not particularly limited as long as at least a part of the solvent can be removed from the coating layer. For example, it is preferable to carry out at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of residual solvent in the photosensitive resin composition layer 14 is preferably 2% by mass or less from the viewpoint of preventing the diffusion of the solvent in the subsequent step.

<Resist pattern formation method>
The photosensitive film of this invention can be used suitably for the formation method of the resist pattern for sandblasting. Since the photosensitive film is excellent in sandblast resistance, a pattern having high sandblast resistance can be obtained by applying the photosensitive film to a method for forming a resist pattern for sandblasting. Below, the formation method of the resist pattern which can apply the photosensitive film of this invention is demonstrated.

  The resist pattern forming method using the above-described photosensitive film includes a removing step of removing the protective film from the above-described photosensitive film as necessary, the photosensitive film on the substrate, and the photosensitive film from the substrate side. A laminate step of laminating the photosensitive resin composition layer and the support in this order, and irradiating at least a part of the photosensitive resin composition layer with actinic rays, exposing the part of the area to a cured product. An exposure step of forming a region, and a development step of removing a region other than the cured product region of the photosensitive resin composition layer from the substrate to form a resist pattern by the cured product region on the substrate. Including. The resist pattern forming method may further include other steps as required.

  The removal step of removing the protective film as necessary may be performed by physically peeling the protective film from the surface of the photosensitive resin composition layer according to a conventional method.

  In the laminating step, the photosensitive film is laminated on the substrate. Examples of the substrate include glass, silicon, and ceramics. The substrate may be provided with, for example, an insulating layer, a conductor formed on the insulating layer, a rib paste layer, and the like.

  As a method of laminating the photosensitive film on the substrate in the laminating step, the photosensitive film is pressure-bonded (laminated) to the substrate while heating at least one of the photosensitive resin composition layer of the photosensitive film and the substrate. The method of laminating etc. is mentioned. When the photosensitive film has a protective film, the lamination step can be performed after removing the protective film. Thereby, the laminated body by which the board | substrate, the photosensitive resin composition layer of the photosensitive film, and the support body were laminated | stacked in this order is obtained.

  The heating temperature of the photosensitive resin composition layer is preferably 70 ° C to 130 ° C, and the pressure bonding pressure is preferably about 0.1 MPa to 1.0 MPa. These conditions are not particularly limited and can be appropriately selected as necessary. Further, if the photosensitive resin composition layer is heated to 70 ° C. to 130 ° C. as described above, it is not necessary to pre-heat the substrate in advance. Note that the stacking property can be further improved by pre-heating the substrate.

  In the exposure step, at least a part of the photosensitive resin composition layer is irradiated with actinic rays, and the region is exposed to form a cured product region (sometimes referred to as a “photocured portion”). A latent image is formed by photocuring the exposed portion irradiated with actinic rays.

  Examples of the method for forming the photocured portion (exposure method) include a method of irradiating actinic rays in an image form through a negative or positive mask pattern called an artwork (mask exposure method). Under the present circumstances, when the support body which exists on the photosensitive resin composition layer is transparent, an actinic ray can be irradiated as it is. When the support has light-shielding properties, the photosensitive resin composition layer is irradiated with actinic rays after removing the support.

  As the light source of actinic light, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or the like that can effectively emit ultraviolet rays can be used. Moreover, what can radiate | emit visible light effectively, such as a flood bulb for photography, a solar lamp, can also be used.

  The wavelength of the actinic ray (exposure wavelength) is preferably in the range of 340 nm to 430 nm, more preferably in the range of 350 nm to 420 nm, from the viewpoint of obtaining the effects of the present invention more reliably.

  In the development step, an uncured portion of the photosensitive resin composition layer is removed from the circuit forming substrate by a development treatment, so that a resist pattern, which is a cured product obtained by photocuring the photosensitive resin composition layer, is formed on the substrate. Formed. When the support film exists on the photosensitive resin composition layer, after removing the support, the unexposed portion is removed (development).

  As the development processing, wet development and dry development can be applied, and wet development is widely used. In the case of wet development, development is performed by a known method such as spraying, rocking dipping, brushing, or scrubbing using a developer corresponding to the photosensitive resin composition. You may develop by combining these 2 or more types of methods.

  The developer is appropriately selected according to the configuration of the photosensitive resin composition. Examples of the developer include an alkaline aqueous solution, an aqueous developer, an organic solvent developer, and the like. The developer is preferably an alkaline aqueous solution that is safe and stable and has good operability. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate; potassium phosphate, sodium phosphate, and the like. Alkali metal phosphates; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used.

  Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1% by mass to 5% by mass of sodium carbonate, a dilute solution of 0.1% by mass to 5% by mass of potassium carbonate, and 0.1% by mass to 5% by mass of sodium hydroxide. A dilute solution of 0.1 mass% to 5 mass% of sodium tetraborate is preferred. The pH of the alkaline aqueous solution is preferably in the range of 9-11. The temperature is adjusted in accordance with the alkali developability of the photosensitive resin composition layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed. As a developer such as an alkaline aqueous solution, a developer that is safer and more stable and has good operability is used. For example, a dilute solution of sodium carbonate at 20 ° C. to 50 ° C. (0.1% by mass to 5% by mass) Aqueous solution) or the like.

Above the resist pattern forming method, by performing after the removal of the unexposed portions, the order of 60 ° C. to 250 DEG ° C. heating or 0.2J ^/ cm ² ~10J ^/ cm 2 about the exposure as required, the resist pattern The method may further include a step of further curing.

<Sandblasting method>
The resist pattern obtained by the resist pattern forming method as a preferred embodiment using the photosensitive film of the present invention is preferably applied to a mask material for sandblasting. Since the photosensitive film is excellent in resistance to sandblasting, it is effective as a mask material for sandblasting. For this reason, the to-be-processed object which has a highly precise pattern is obtained by performing a sandblast process with respect to the resist pattern formed using the photosensitive film.

Various known materials are used as blasting materials for sandblasting. As the blast material, for example, fine particles of about ₂ μm to 100 μm such as glass beads, SiC, SiO ₂ , Al ₂ O ₃ , ZrO, etc. are used. These fine particles may be used alone or in combination of two or more.

  The pressure of blasting in the sandblasting treatment can be 0.1 MPa to 1.0 MPa, and preferably 0.15 MPa to 0.8 MPa in terms of both sandblast resistance and precision blasting properties.

  The sandblasting method can be applied to various purposes, and is particularly preferably applied to the manufacturing process of PDP. The workpiece to be sandblasted is not limited to this.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

(Examples 1-4, Comparative Examples 1-5)
First, each component shown in Table 1 was mixed by mixing the solid content (mass of non-volatile components) shown in Table 1 at a mixing ratio (mass basis, g unit) (however, methyl ethyl ketone is a mass basis as a liquid). The solution of the photosensitive resin composition of Examples 1-4 and Comparative Examples 1-5 was obtained. Details of each component in Table 1 are as follows. The weight average molecular weight of urethane acrylate is a catalog value. In the table, “-” means not blended.

(A) component:
40% by mass methyl cellosolve / toluene (mass ratio) of a copolymer of methacrylic acid / methyl methacrylate / butyl acrylate (mass ratio; 17/62/21, weight average molecular weight: 110,000, acid value 111 mgKOH / g) : 60/40) Solution (B) component (B) -1: 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane (made by Shin-Nakamura Chemical Co., Ltd., trade name “BPE-1300NH” )
(B) -2: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (manufactured by Hitachi Chemical Co., Ltd., trade name: “FA-321M”)
(B) -3: Urethane acrylate resin (UF-TC4-55 (weight average molecular weight: 30000) (manufactured by Kyoeisha Chemical Co., Ltd.)
(B) -4: Urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “purple light UV-3000B”)
(B) -5: Urethane acrylate (weight average molecular weight 4,500, manufactured by Kyoeisha Chemical Co., Ltd., trade name “UF-8001G-20M”)
(B) -6: Urethane acrylate (weight average molecular weight 6,400, manufactured by Seisha Chemical Co., Ltd., trade name “UF-8003”)
(B) -7: A compound (trade name “Hitaroid”) comprising a photopolymerizable compound obtained by reacting a polycarbonate compound having a hydroxy group at the terminal, an organic isocyanate and 2-hydroxyethyl acrylate, and having a weight average molecular weight of 4000. 9082-95 ", Hitachi Chemical Co., Ltd., 75 mass% methyl ethyl ketone solution).
(C):
2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole FP-600:
Phosphate ester flame retardant, manufactured by ADEKA Corporation, trade name “ADK STAB FP-600”)
(X-1): Diamond green (X-2): Leuco crystal violet (X-3): Methyl ethyl ketone

[Preparation of photosensitive film]
The photosensitive resin composition solutions of Examples 1 to 4 and Comparative Examples 1 to 5 are 16 μm-thick polyethylene terephthalate film (trade name “G2-16” manufactured by Teijin Limited, hereinafter referred to as “PET film”) as a support. ) To form a photosensitive resin composition layer by coating uniformly on each of them, and then dried at 100 ° C. for 10 minutes using a hot air convection dryer, Examples 1-4, Comparative Examples 1- 5 photosensitive film was obtained. The film thickness after drying of the photosensitive resin composition layer of each photosensitive film was 50 μm.

  Next, a 25 μm thick polyethylene film (trade name “NF-13”, manufactured by Tamapoly Co., Ltd.) is protected on the surface of each photosensitive film opposite to the side in contact with the support of the photosensitive resin composition layer. Each was laminated as a film to obtain a photosensitive film with a protective film.

[Preparation of evaluation laminate]
Next, on a SiO ₂ sputtered glass substrate heated at 80 ° C. for 10 minutes, using a manual laminator (manufactured by Hitachi Chemical Co., Ltd., trade name “HLM-3000”), a roll temperature of 110 ° C. and a laminating speed of 1.0 m / Minutes, under the conditions of roll pressure 0.4 MPa, while peeling the polyethylene film of the obtained photosensitive film with a protective film, the photosensitive resin composition layer was laminated with the glass substrate side, Obtained.

[Evaluation of light sensitivity]
On the obtained PET film of the laminate for evaluation, a photo tool having a stove 21-step tablet as a negative was brought into close contact, and an EXM-1201 type exposure machine manufactured by Oak Manufacturing Co., Ltd. was used to make 21 steps of stopher. The photosensitive resin composition layer was exposed through a phototool and a PET film with an energy amount such that the number of steps remaining after development of the step tablet was 8.0.

  Next, the PET film is peeled off to expose the photosensitive resin composition layer, and then developed by spraying a 1.0 mass% sodium carbonate aqueous solution for 40 seconds under the conditions of a liquid temperature of 30 ° C. and a spray pressure of 0.16 MPa. The unexposed part was removed. The above-mentioned energy amount at the time of exposure was used as a numerical value for evaluating photosensitivity. The lower this value, the higher the photosensitivity. The results are shown in Table 1.

[Resolution evaluation]
Evaluation on a PET film of a phototool having a stove 21-step tablet and a phototool having a wiring pattern having a line width / space width of 30/30 to 200/200 (unit: μm) as a negative for resolution evaluation A photosensitive resin through a photo tool and a PET film with an energy amount of 8.0 after development of the stove 21-step tablet using the above-described exposure machine, with the above-described exposure machine being used. The composition layer was exposed.

  Next, the PET film is peeled off to expose the photosensitive resin composition layer, and then developed by spraying a 1.0 mass% sodium carbonate aqueous solution for 40 seconds under the conditions of a liquid temperature of 30 ° C. and a spray pressure of 0.16 MPa. The unexposed part was removed. Here, the resolution was evaluated based on the smallest value (unit: μm) of the space width between the line widths in which a rectangular resist shape was obtained by development processing. It shows that it is excellent in the resolution, so that this value is small. The results are shown in Table 1.

[Elastic modulus evaluation]
The above-prepared photosensitive film with a protective film was laminated twice on a copper-clad laminate (MCL-E679-12D (manufactured by Hitachi Chemical Co., Ltd.)) using a 110 ° C. heat roll while peeling off the protective film. Next, the photosensitive resin composition layer was exposed through a PET film at 150 mJ / cm ² using an EXM-1201 type exposure machine (manufactured by Oak Manufacturing Co., Ltd.) Then, after removing the PET film, 30 ° C. A predetermined cured film was produced by spraying with a 1.0% by weight sodium carbonate aqueous solution for 40 seconds, and the thickness of the cured film was 30 μm, and then the cured film was cut into a size that could be measured at 10 mm × 50 mm. Using a rheometer (manufactured by Rheotech Co., Ltd.), a tensile test was performed under the conditions of a temperature of 23 ° C., a length between chucks of 50 mm, and a tensile speed of 20 mm / min. Standards of other tensile tests were determined JIS K 7161 (1994) conforming to. Modulus from the initial slope of the S-S curve obtained at that time.

[Sandblast test]
A SiO ₂ glass substrate is heated at 80 ° C., and a photosensitive film with a protective film is peeled off on the surface of the SiO ₂ glass substrate. A sample for sandblast treatment test was obtained by laminating at a speed of 0.0 m / min and a roll pressure of 0.4 MPa.
A negative for sandblast evaluation of line width / space width = 300/300 (unit: μm) was placed on the PET film of the obtained sample, and 150 mJ / cm ² with an EXM-1201 type exposure machine manufactured by Oak Manufacturing Co., Ltd. The photosensitive resin composition layer was exposed through a PET film at an exposure amount of 1, and then left at room temperature for 30 minutes.
Next, the PET film was peeled off, and the sample after the exposure treatment in which the photosensitive resin composition layer was exposed was used at a liquid temperature of 30 ° C. and a spray pressure of 0.16 MPa using a 1.0 mass% sodium carbonate aqueous solution. Development was carried out by spraying for 40 seconds to remove the resin in the unexposed area.

Thereafter, using SiC (silicon carbide) # 800 as an abrasive, sandblasting was performed 5 times at a blast pressure of 0.15 MPa, a nozzle moving width: 300 mm, a nozzle moving speed: 8 m / min, and a conveyor speed: 15 mm / min. . The surface of the sample after the treatment was observed, the line width after the treatment was measured and compared with the line width before the treatment, and sandblast resistance was evaluated. The evaluation criteria are as follows.
A: No chipping or peeling is observed in the resist pattern after sandblasting. Alternatively, the line width change after sandblasting is less than 10% of the negative value. B: The resist pattern is chipped or peeled off after sandblasting. Alternatively, the line width change after sandblasting is 10% or more with respect to the negative value.

As shown in Table 1, it was found that the photosensitive films made of the photosensitive resin compositions of Examples 1 to 4 were excellent in sandblast resistance when the cured product had an elastic modulus of 200 MPa or less.
Further, FIG. 2 shows a cross section obtained by cutting the evaluation sample after sandblasting obtained using the photosensitive film of the example of the present invention along the thickness direction of the substrate in the evaluation sample at 150 times. It is an electron micrograph when observed with. Observation of the electron micrograph was performed at an acceleration voltage of 15 kV. In the embodiment of the present invention, since the resistance to sandblasting is high, as shown in FIG. 2, the rib paste layer 24 disposed on the substrate 20 and masked with the cured product 22 of the photosensitive film has no chipping and peeling. It can be seen that the pattern is formed accurately with little change in line width.

  In particular, a polymerizable compound containing 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane having an ethyleneoxy group having 20 to 50 structural units and a weight average molecular weight of 10,000 or more It was found that a photosensitive film including a combination with the urethane acrylate and having a photocured product having an elastic modulus of 200 MPa or less is excellent in sandblast resistance.

  In contrast, it was found that the photosensitive films of Comparative Examples 1 to 5 in which the elastic modulus of the cured product exceeded 200 MPa had low sandblast resistance.

  Therefore, according to the present invention, it is possible to provide a photosensitive film excellent in sandblast resistance after curing, and a photosensitive resin composition for obtaining such a photosensitive film.

  10 photosensitive film, 12 support, 14 photosensitive resin composition layer, 20 substrate, 22 cured product of photosensitive film, 24 rib paste layer

Claims (3)

About the photosensitive resin composition layer whose film thickness after drying is 50 micrometers, the hardened | cured material obtained by performing a hardening process on the conditions of exposure amount 150mJ / cm < ² > is a tension | tensile_strength based on JISK7161 (1994). According to the test, it has an elastic modulus of 200 MPa or less,
(A) Binder polymer containing structural unit having carboxy group, (B) 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane having 20-50 structural units of ethyleneoxy group And a photopolymerizable compound containing urethane (meth) acrylate , and (C) a photopolymerization initiator,
The content of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane having 20 to 50 structural units of the ethyleneoxy group in the photopolymerizable compound is 40% by mass to The photosensitive resin composition which is 90 mass%. The weight average molecular weight of the urethane (meth) acrylate is 10,000 to 100,000, the photosensitive resin composition of claim 1. The photosensitive film which has a support body and the photosensitive resin composition layer which is a coating film of the photosensitive resin composition of Claim 1 or Claim 2 arrange | positioned on the said support body.