JP5760711B2 - Photosensitive resin composition, photosensitive element, method for producing resist pattern, and method for producing printed wiring board - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method for producing a resist pattern, and a method for producing a printed wiring board.

  Conventionally, in the field of printed wiring board production, as a resist material used for etching treatment, plating treatment, and the like, a photosensitive resin composition and a photosensitive element obtained using a support and a protective film are widely used. .

  A printed wiring board is obtained by laminating a photosensitive element on a circuit forming substrate and exposing it in a pattern. Then, the unexposed area is removed with a developing solution to form a resist pattern, and etching or plating is performed using the resist pattern as a mask. It is manufactured by a method in which a cured portion is peeled off from a substrate after processing to form a circuit.

  As a developing solution for removing the resist in the unexposed area, an alkali developing type using sodium carbonate or the like is mainly used from the viewpoint of environment and safety. The developer can be used as long as it has a certain ability to dissolve the photosensitive resin composition layer, and the photosensitive resin composition is dissolved or dispersed in the developer during development.

  Here, when the through hole provided on the circuit forming substrate is covered with a resist film, the photosensitive resin composition to be used includes a resist film that covers the through hole by a developer or water spray pressure. Is required to have a tenting property that does not break, that is, a tent reliability.

  As a photosensitive resin composition excellent in tent reliability, a photosensitive resin composition containing a bifunctional monomer or a trifunctional monomer having a urethane bond has been proposed (see, for example, Patent Documents 1 and 2). A photosensitive resin composition using a polycaprolactone-modified isocyanuric ring monomer is also disclosed (see, for example, Patent Document 3).

Japanese Patent Laid-Open No. 10-142789 JP 2001-117224 A WO2007 / 049519 pamphlet

  However, in the photosensitive resin composition containing the bifunctional monomer having a urethane bond described in Patent Documents 1 and 2, sufficient tent reliability may not be obtained, and further, the photosensitive resin composition containing a trifunctional monomer having a urethane bond. In some cases, the cured resin composition is hard and brittle. Moreover, in the photosensitive resin composition of patent document 3, the further improvement was calculated | required by the point of resolution.

  The present invention has been made in view of such circumstances, and is excellent in resolution, photosensitive resin composition excellent in mechanical strength of a cured film and flexible, that is, excellent in tent reliability. It is an object of the present invention to provide a resin composition, a photosensitive element using the same, a method for producing a resist pattern, and a method for producing a printed wiring board.

  The first aspect of the present invention comprises (A) component: binder polymer, (B) component: a polymerizable compound having at least one ethylenically unsaturated bond, and (C) component: photopolymerization initiator. It is a photosensitive resin composition containing and the compound (B) containing a compound represented by the following general formula (I).

(Wherein R ¹ represents a divalent organic group, and R ² represents a group represented by the following general formula (II))

(Wherein R ³ represents a hydrogen atom or a methyl group, X represents an alkylene group, and n represents an integer of 10 to 25)

  When the photosensitive resin composition contains the compound represented by the general formula (I), tent reliability and resolution can be improved.

Moreover, the 2nd aspect of this invention is a photosensitive element which has a support body and the photosensitive resin layer which is a coating film of the said photosensitive resin composition formed on the said support body.

The third aspect of the present invention is a photosensitive resin layer forming step of forming a photosensitive resin layer that is a coating film of the photosensitive resin composition on a circuit forming substrate, and at least one of the photosensitive resin layers. Production of a resist pattern comprising: an exposure step of irradiating a portion of actinic light to photocure an exposed portion; and a development step of removing the uncured portion of the photosensitive resin layer from the circuit forming substrate by development. Is the method.

Furthermore, a fourth aspect of the present invention is a printed wiring board manufacturing method including a step of forming a conductor pattern by etching or plating a circuit forming substrate on which a resist pattern is formed by the above resist pattern manufacturing method. is there.

  According to the present invention, a photosensitive resin composition having excellent resolution and excellent mechanical strength and flexibility of a cured film, that is, a photosensitive resin composition having excellent tent reliability, and the same are used. A photosensitive element, a resist pattern manufacturing method, and a printed wiring board manufacturing method can be provided.

It is a schematic plan view which shows the board | substrate for hole breakage number measurement in the Example of this invention. FIG. 2 is an enlarged view of a triple hole in a region indicated by A in FIG. 1.

  Hereinafter, the present invention will be described in detail. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, (meth) acrylate means acrylate and corresponding methacrylate, (meth) acryloyl group means acryloyl group and The corresponding methacryloyl group is meant.

  In addition, in this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. It is. In the present specification, a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. Further, when referring to the amount of each component in the composition in the present specification, when there are a plurality of substances corresponding to each component in the composition, the plurality of the components present in the composition unless otherwise specified. It means the total amount of substance.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention comprises (A) component: a binder polymer, (B) component: a polymerizable compound having at least one ethylenically unsaturated bond, and (C) component: a photopolymerization initiator. A photosensitive resin composition to be contained, wherein the component (B) is a compound represented by the following general formula (I), or a compound represented by the following general formula (III) and the following general formula (IV) It is the photosensitive resin composition containing the reaction product of the urethanation reaction of the compound represented by these.

In General Formula (I) and General Formula (II), R ¹ represents a divalent organic group, and R ² represents a group represented by General Formula (II). R ³ represents a hydrogen atom or a methyl group, X represents an alkylene group, and n represents an integer of 10 to 25.

In the general formula (III) and the general formula ^{(IV), R} 3, X and n are respectively the same as ^R 3, X and n in the general formula (II), ^{R 1} is the general formula (I) Synonymous with R ^{1 in the} middle.
By including the specific compound as a polymerizable compound, a photosensitive resin composition having excellent tent reliability and resolution can be configured. Therefore, the said photosensitive resin composition can be used suitably for manufacture of the multilayer printed wiring board which has a fine circuit layer, and can be used suitably especially for an object for tenting.

[(B) component: polymerizable compound having at least one ethylenically unsaturated bond]
The photosensitive resin composition of the present invention is represented by the compound represented by the general formula (I), the compound represented by the general formula (III), and the general formula (IV) as the component (B). The reaction product of the urethanation reaction with the compound to be produced is contained as an essential component.

In the general formula (I) and general formula (IV), R ¹ represents a divalent organic group.
The divalent organic group represented by R ¹ is not particularly limited as long as it contains a carbon atom and can link an isocyanurate ring and an amide group. For example, a C1-C10 alkylene group and a C6-C10 arylene group can be mentioned. Note that the alkylene group having 1 to 10 carbon atoms may be linear or branched. Moreover, three R < ¹ > in general formula (I) and general formula (IV) may be same or different, respectively.

  Specific examples of the alkylene group having 1 to 10 carbon atoms include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, neopentylene group, hexylene group, heptylene group, octylene group, Examples include 2-ethyl-hexylene group, nonylene group, and decylene group. A phenylene group etc. are mentioned as a C6-C10 arylene group.

In the present invention, R ¹ is preferably an alkylene group having 2 to 10 carbon atoms, and more preferably an alkylene group having 3 to 8 carbon atoms, from the viewpoints of tent reliability and resolution.

Three R ² in the general formula (I) may be the same or different.

  In the general formula (II) and general formula (III), X represents an alkylene group. Although there is no restriction | limiting in particular as carbon number of an alkylene group, From a viewpoint of tent reliability and resolution, it is preferable that it is a C2-C7 alkylene group, and it is a C2-C4 alkylene group. More preferred.

Specific examples of the alkylene group for X include an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. The alkylene group may be linear or branched. Further, ten or more Xs in the general formula (II) may be the same or different, but are preferably the same.
Furthermore, although n represents the integer of 10-25, it is preferable that it is 15-25 from a viewpoint of tent reliability and intensity | strength.

  The compound represented by the general formula (I) can be produced, for example, by a urethanization reaction between a compound represented by the following general formula (III) and a compound represented by the following general formula (IV). . The reaction condition is not particularly limited as long as it is a normal reaction condition for generating a urethane bond, and the reaction may be appropriately performed using a catalyst or the like.

R ^3, X and n are each and ^R 3, X and n in the general formula (II) synonymous, preferable embodiments thereof are also the same. And R ¹ is the general formula (I) in the same meaning as R ^1, preferred embodiment is also the same.

The compound represented by the general formula (I) is produced by the addition reaction of three molecules of the compound represented by the general formula (III) with the three isocyanate groups of the compound represented by the general formula (IV). It is a compound.
In addition to the compound represented by the general formula (I), the reaction product of the compound represented by the general formula (III) and the compound represented by the general formula (IV) includes one molecule of the general formula ( The compound represented by IV) may contain a compound produced by addition reaction of one or two compounds represented by the general formula (III). Moreover, reaction products other than these may be included.
The content rate of the compound represented by the general formula (I) contained in the reaction product of the compound represented by the general formula (III) and the compound represented by the general formula (IV) is not particularly limited. From the viewpoint of tent reliability and strength, it is preferably 15% by mass or more, and more preferably 25% by mass or more.

  In the photosensitive resin composition, the compound represented by the general formula (I), or the reaction product of the compound represented by the general formula (III) and the compound represented by the general formula (IV). There is no particular limitation on the rate. From the viewpoint of tent reliability, mechanical strength of the cured film, and flexibility, it is preferably 1% by mass to 25% by mass in the photosensitive resin composition, and more preferably 5% by mass to 20% by mass.

The photosensitive resin composition includes, as component (B), a compound represented by the general formula (I), a compound represented by the general formula (III), and a compound represented by the general formula (IV). As a reaction product, R ¹ is an alkylene group having 1 to 10 carbon atoms, X is an alkylene group having 2 to 4 carbon atoms, and n is 10 to 25 mass%. As a reaction product of the compound represented by the general formula (I) or the compound represented by the general formula (III) and the compound represented by the general formula (IV), R ¹ It is more preferable that X is an alkylene group having 2 to 4 carbon atoms, and n is 15 to 25% by mass of a compound containing 5 to 20% by mass.

  In addition, the component (B) in the present invention is represented by the compound represented by the general formula (I), which is an essential component, or the compound represented by the general formula (III) and the general formula (IV). A polymerizable compound having at least one ethylenically unsaturated bond other than the reaction product of the compound (hereinafter, also referred to as “other polymerizable compound”) may be included.

  Examples of other polymerizable compounds include compounds obtained by condensation reaction of α, β-unsaturated carboxylic acids with polyhydric alcohols, and α, β-unsaturated carboxylic acids added to glycidyl group-containing compounds. Examples include compounds, alkyl esters of (meth) acrylic acid, phthalic acid esters of (meth) acrylic acid derivatives, (meth) acrylate compounds having a urethane bond, and bisphenol A-based (meth) acrylate compounds.

  Examples of the compound obtained by condensation reaction of α, β-unsaturated carboxylic acid with the polyhydric alcohol include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethyleneoxy groups and propyleneoxy groups. Polypropylene glycol di (meth) acrylate which is 2 to 14, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethyleneoxy groups and 2 to 14 propyleneoxy groups, trimethylolpropane di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethyleneoxytri (meth) acrylate, trimethylolpropanediethyleneoxytri (meth) acrylate, trimethylolpropane triethyleneoxytri (meth) acrylate Chlorate, trimethylolpropane tetraethyleneoxytri (meth) acrylate, trimethylolpropanepentaethyleneoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate and dipentaerythritol hexa (meth) acrylate.

  Examples of the compound obtained by adding an α, β-unsaturated carboxylic acid to the glycidyl group-containing compound include bisphenol A dioxyethylene di (meth) acrylate, bisphenol A trioxyethylene di (meth) acrylate, and bisphenol A. List bisphenol A polyoxyethylene di (meth) acrylate such as decaoxyethylene di (meth) acrylate, (meth) acrylate adduct of trimethylolpropane triglycidyl ether and (meth) acrylate adduct of bisphenol A diglycidyl ether Can do.

  Examples of the alkyl ester of (meth) acrylic acid include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic acid 2-ethylhexyl ester.

  Examples of the phthalic acid ester of the (meth) acrylic acid derivative include γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′-(meth) acryloyloxy. Examples include ethyl-o-phthalate and β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate.

Examples of the (meth) acrylate compound having a urethane bond include a (meth) acrylic acid derivative having an OH group at the β-position, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexa. Examples include addition reaction products with diisocyanate compounds such as methylene diisocyanate, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate and EO, PO-modified urethane di (meth) acrylate, and the like. .
Note that EO represents ethylene oxide, and the EO-modified compound has an ethyleneoxy group block structure. PO represents propylene oxide, and the PO-modified compound has a propyleneoxy group block structure. Examples of the EO-modified urethane di (meth) acrylate include the product name UA-11 manufactured by Shin-Nakamura Chemical Co., Ltd. Examples of EO and PO-modified urethane di (meth) acrylates include Shin-Nakamura Chemical Co., Ltd. and product name UA-13.

  Examples of the bisphenol A-based (meth) acrylate compound include 2,2-bis (4-((meth) acryloxypolyethyleneoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropyleneoxy). And phenyl) propane and 2,2-bis (4-((meth) acryloxypolyethyleneoxypolypropyleneoxy) phenyl) propane. These can be used alone or in combination of two or more.

  Among these, from the viewpoint of chemical resistance, it is preferable to include at least one of a bisphenol A-based (meth) acrylate compound and a phthalic acid ester of a (meth) acrylic acid derivative, and it is more preferable to include both.

  Although there is no restriction | limiting in particular as content rate of the said other polymeric compound, From a viewpoint of a tent reliability and resolution, it is 50 mass%-90 mass% in 100 mass% of total amounts of the said (B) component. It is preferable that it is 60 mass%-80 mass%.

  In addition, the content of the polymerizable compound (B) having at least one ethylenically unsaturated bond is 20% by mass to 60% by mass in 100% by mass of the total amount of the component (A) and the component (B). It is preferable that the content be 30% by mass to 55% by mass. When this content is 20% by mass or more, the photosensitivity tends to be high, and when it is 60% by mass or less, the flexibility of the cured film tends to be further improved.

[(A) component: binder polymer]
Component (A) that can be used in the present invention: Examples of the binder polymer include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. From the viewpoint of alkali developability, an acrylic resin is preferable. These can be used alone or in combination of two or more.

The (A) binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives substituted at the α-position or aromatic ring such as styrene, vinyl toluene and α-methylstyrene, acrylamide such as diacetone acrylamide, acrylonitrile and vinyl. -Esters of vinyl alcohol such as n-butyl ether, (meth) acrylic acid alkyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meta ) Acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid , Α Bromoacrylic acid, α-chloroacrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, etc. Mention may be made of maleic acid monoesters, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid and propiolic acid. These can be used alone or in combination of two or more.
Examples of the (meth) acrylic acid alkyl ester include the following general formula (V):

^{_{H 2 C = C (R 6}} ) -COOR 7 (V)

[In the formula (V), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents an alkyl group having 1 to 12 carbon atoms], the alkyl group of these compounds is a hydroxyl group, an epoxy group, And compounds substituted with a halogen group.
Examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁷ in the general formula (V) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Nonyl group, decyl group, undecyl group, dodecyl group and structural isomers thereof can be mentioned.

  Examples of the monomer represented by the general formula (V) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (Meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, Examples include (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, and (meth) acrylic acid dodecyl ester. These can be used alone or in combination of two or more.

Moreover, it is preferable that the binder polymer which is (A) component in this invention contains a carboxy group from a viewpoint of alkali developability. The binder polymer containing a carboxy group can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxy group and another polymerizable monomer.
Examples of the polymerizable monomer having a carboxy group include acrylic acid and methacrylic acid, and methacrylic acid is preferable.

The content of the structural unit derived from the polymerizable monomer having a carboxyl group in the (A) binder polymer (ratio of the polymerizable monomer having a carboxyl group to the total polymerizable monomer used) is determined by alkali development. From the standpoint of balance between property and alkali resistance, it is preferably 12% by mass to 50% by mass, more preferably 12% by mass to 40% by mass, and further preferably 15% by mass to 30% by mass. 15 mass% to 25 mass% is particularly preferable.
There exists a tendency for alkali developability to improve because this content rate is 12 mass% or more. Moreover, there exists a tendency which is excellent in alkali tolerance because it is 50 mass% or less.

Furthermore, it is preferable that the binder polymer which is (A) component in this invention contains the structural unit derived from styrene or a styrene derivative from a flexible viewpoint.
Although there is no restriction | limiting in particular as a content rate of the structural unit derived from the said styrene or a styrene derivative, From a viewpoint of making adhesiveness and a peeling characteristic favorable, 0.1 mass%-30 mass% are included in a binder polymer. Is preferably included, more preferably 1% by mass to 28% by mass, and particularly preferably 1.5% by mass to 27% by mass.
There exists a tendency for adhesiveness to improve because this content rate is 0.1 mass% or more. Moreover, by being 30 mass% or less, it can suppress that a peeling piece becomes large and can suppress that peeling time becomes long.

  These binder polymers are used individually by 1 type or in combination of 2 or more types. As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, two or more types of binder polymers having different degrees of dispersion are used. Examples thereof include a binder polymer.

The weight average molecular weight of the (A) binder polymer is preferably 20,000 to 300,000, more preferably 30,000 to 150,000, from the viewpoint of the balance between mechanical strength and alkali developability. More preferably, it is 40,000-110,000.
When the weight average molecular weight is 20,000 or more, the developer resistance tends to be further improved. Moreover, it can suppress that developing time becomes long because it is 300,000 or less.
In addition, the weight average molecular weight in this invention is the value measured by the gel permeation chromatography method, and converted with the analytical curve created using standard polystyrene.

The content of the (A) binder polymer is preferably 30% by mass to 80% by mass, and 50% by mass to 70% by mass with respect to 100% by mass of the total amount of the component (A) and the component (B). More preferably.
(A) The softness | flexibility of a cured film improves more because content of a component is 30 mass% or more. Moreover, there exists a tendency which shows a more favorable photosensitivity because it is 80 mass% or less.

[(C) component: photopolymerization initiator]
Examples of the photopolymerization initiator as component (C) include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone. 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2 Aromatic ketones such as morpholino-propanone-1; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone 2,3-diphenylanthraquinone, 1-chloroan Quinones such as laquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone; benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin ether compounds such as phenyl ether, benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; benzyl derivatives such as benzyldimethyl ketal; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o -Chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5- Diphenylimidazole dimer, 2 2,4,5-triarylimidazole dimers such as-(p-methoxyphenyl) -4,5-diphenylimidazole dimer; 9-phenylacridine, 1,7-bis (9,9'-acridinyl) Examples include acridine derivatives such as heptane; N-phenylglycine, N-phenylglycine derivatives; coumarin compounds; oxazole compounds.
These are used individually by 1 type or in combination of 2 or more types.

Moreover, the substituents of the aryl groups of two 2,4,5-triarylimidazoles in the 2,4,5-triarylimidazole dimer may be the same and symmetric compounds with each other, Differently asymmetric compounds may be used.
Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid.

  The photosensitive resin composition preferably contains at least one 2,4,5-triarylimidazole dimer as a photopolymerization initiator from the viewpoint of adhesion and sensitivity, and 2,4,5- More preferably, it contains at least one triarylimidazole dimer and at least one aromatic ketone.

The content of the (C) photopolymerization initiator is preferably 0.01% by mass to 20% by mass, and 0.2% by mass with respect to 100% by mass of the total amount of the component (A) and the component (B). It is more preferable that it is% -5 mass%.
When this content is 0.01% by mass or more, the photosensitivity tends to be better, and when it is 20% by mass or less, absorption on the surface of the photosensitive resin layer is increased during exposure. The internal photocuring tends to be better.

[Other ingredients]
Moreover, the said photosensitive resin composition can further contain another component as needed. Other components include sensitizing dyes such as coumarin and pyrazoline, dyes such as malachite green, photochromic agents such as tribromophenyl sulfone and leuco crystal violet, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, Examples thereof include pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion promoters, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, and thermal crosslinking agents.
As content of another component, it can contain about 0.01 mass%-20 mass%, respectively with respect to 100 mass% of total amounts of (A) component and (B) component. These are used alone or in combination of two or more.

  The said photosensitive resin composition can contain at least 1 sort (s) of the organic solvent as needed. As the organic solvent, a commonly used organic solvent is not particularly limited and can be used. Specific examples include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, and mixed solvents thereof.

For example, the above-mentioned (A) binder polymer, (B) polymerizable compound, and (C) photopolymerization initiator are dissolved in the organic solvent to obtain a solution having a solid content of about 30% by mass to 60% by mass (hereinafter, It can be used as a “coating liquid”.
In addition, solid content means the remaining component remove | excluding the volatile component from the said solution (photosensitive resin composition).

The said coating liquid can be used for formation of the photosensitive resin layer as follows, for example. A photosensitive resin layer derived from the photosensitive resin composition can be formed on the support by applying the coating solution on the surface of a support such as a support film or a metal plate described later and drying the support. .
Examples of the metal plate include iron-based alloys such as copper, copper-based alloys, nickel, chromium, iron, and stainless steel, preferably copper, copper-based alloys, and iron-based alloys.

  Although the thickness of the photosensitive resin layer to be formed varies depending on the application, the thickness after drying is preferably about 1 μm to 100 μm. You may coat | cover the surface (surface) on the opposite side to the surface which opposes the support body of the photosensitive resin layer with a protective film. Examples of the protective film include polyethylene and polymer films such as polypropylene.

<Photosensitive element>
The photosensitive element of the present invention has a support and a photosensitive resin layer that is a coating film of the photosensitive resin composition formed on the support, and a protective film provided as necessary The other layers are configured.

[Support]
As the support, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used.
The thickness of the support (hereinafter sometimes referred to as “support film”) is preferably 1 μm to 100 μm, more preferably 1 μm to 50 μm, and still more preferably 1 μm to 30 μm. When the thickness of the support is 1 μm or more, the support film can be prevented from being broken when the support film is peeled off. Moreover, the fall of the resolution is suppressed because it is 100 micrometers or less.

[Protective film]
The photosensitive element may further include a protective film that covers a surface (surface) opposite to the surface facing the support of the photosensitive resin layer, if necessary.

The protective film preferably has a lower adhesive force to the photosensitive resin layer than that of the support film to the photosensitive resin layer, and is preferably a low fisheye film.
Here, “fish eye” means that a material constituting a protective film is melted by heat, kneaded, extruded, biaxially stretched, a film is produced by a casting method, etc., and foreign materials, undissolved materials, oxidative deterioration of the material. This means that an object or the like is taken into the film. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.

  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 photosensitive resin layer and the support film are laminated on the substrate while peeling off the protective film. Moreover, productivity improves by being 100 micrometers or less.

[Production method]
The photosensitive element of this invention can be manufactured as follows, for example. (A) component: a binder polymer, (B) component: a polymerizable compound, and (C) a step of preparing a coating solution in which a photopolymerization initiator is dissolved in the organic solvent, and the coating solution on the support It can manufacture by the manufacturing method including the process of apply | coating to form a coating layer, and the process of drying the said coating layer and forming the photosensitive resin layer.

The details of the component (A): binder polymer, component (B): polymerizable compound, (C) photopolymerization initiator and organic solvent constituting the coating solution, and the details of the coating solution are as described above. Moreover, the said coating liquid may use a commercially available thing and may prepare it by a conventional method.
Application of the coating solution onto the support can be performed by a known method such as a roll coater, comma coater, gravure coater, air knife coater, die coater, bar coater, spray coater or the like.

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

  The thickness of the photosensitive resin layer in the photosensitive element can be appropriately selected depending on the application. The thickness of the photosensitive resin layer is preferably 1 μm to 200 μm, more preferably 5 μm to 100 μm, and particularly preferably 10 μm to 50 μm after drying. Industrial coating becomes easy and productivity improves because the thickness of the photosensitive resin layer is 1 micrometer or more. In the case of 200 μm or less, the effects of the present invention are sufficiently obtained, the photosensitivity is high, and the photocurability at the bottom of the resist tends to be excellent.

The photosensitive element of the present invention may further have an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, or a gas barrier layer, if necessary.
As these intermediate layers, for example, the intermediate layers described in JP-A-2006-089882 can be applied to the present invention.

The form of the photosensitive element of the present invention is not particularly limited. For example, it may be in the form of a sheet, or may be in the form of a roll wound around a core.
When it winds up in roll shape, it is preferable to wind up so that a support film may become an outer side.
Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS (acrylonitrile-butadiene-styrene copolymer).

  An end face separator is preferably installed on the end face of the roll-shaped photosensitive element thus obtained from the viewpoint of protecting the end face, and a moisture-proof end face separator is preferably installed from the viewpoint of edge fusion resistance. Moreover, as a packaging method, it is preferable to wrap and package in a black sheet with low moisture permeability.

  The photosensitive element of this invention can be used suitably for the manufacturing method of the resist pattern mentioned later, for example.

<Method for producing resist pattern>
The method for producing a resist pattern of the present invention comprises (i) a photosensitive resin layer forming step of forming a photosensitive resin layer that is a coating film of the photosensitive resin composition on a circuit forming substrate, and (ii) the photosensitive resin. An exposure step of irradiating at least a part of the photosensitive resin layer with an actinic ray to photocure the exposed portion; and (iii) a development step of removing the uncured portion of the photosensitive resin layer from the circuit forming substrate by development. And includes other processes as necessary.

(I) Photosensitive resin layer forming step In the photosensitive resin layer forming step, a photosensitive resin which is a coating film of the above photosensitive resin composition on a circuit forming substrate (hereinafter sometimes abbreviated as "substrate"). A layer is formed. The circuit forming substrate usually includes an insulating layer and a conductor layer formed on the insulating layer. The surface of the circuit forming substrate that is in contact with the photosensitive resin layer is usually a metal surface, but the material is not particularly limited.

  As a method for forming the photosensitive resin layer on the substrate, for example, when the photosensitive element has a protective film, the photosensitive resin layer of the photosensitive element is necessary after removing the protective film. In accordance with this, it can be performed by pressure bonding to the circuit forming substrate while heating. Thereby, the laminated body provided with the board | substrate for circuit formation, the photosensitive resin layer, and a support body in this order is obtained.

This photosensitive resin layer forming step is preferably performed under reduced pressure from the viewpoint of adhesion and followability. Heating at the time of pressure bonding is preferably performed at a temperature of 70 ° C to 130 ° C. The crimping is preferably performed at a pressure of about ^{0.1MPa~1.0MPa (1kgf / cm 2 ~10kgf /} cm 2 approximately), is selected as necessary in these conditions.
Note that a pre-heat treatment of the circuit forming substrate can be performed as necessary. If the photosensitive resin layer is heated to 70 ° C. to 130 ° C., it is not essential to pre-heat the circuit forming substrate in advance, but the pre-heat treatment of the circuit forming substrate further improves the adhesion and followability. Can be made.

(Ii) Exposure step In the exposure step, at least part of the photosensitive resin layer formed on the circuit forming substrate is irradiated with actinic rays, so that the exposed portion irradiated with actinic rays is photocured, A latent image is formed.
Under the present circumstances, when the support body (support film) which exists on the photosensitive resin layer is transparent with respect to actinic light, it can irradiate actinic light through a support film. On the other hand, when the support film is impermeable to actinic rays, the photosensitive resin layer is irradiated with actinic rays after the support film is removed.

  Examples of the exposure method include a method of irradiating an actinic ray in an image form through a negative or positive mask pattern called an artwork (mask exposure method). Alternatively, a method of irradiating actinic rays in the form of an image by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be employed.

  Examples of active light sources include known light sources such as carbon arc lamps, mercury vapor arc lamps, ultrahigh pressure mercury lamps, high pressure mercury lamps, xenon lamps, argon lasers and other solid state lasers such as YAG lasers, semiconductor lasers, and gallium nitride. A laser that effectively emits ultraviolet rays such as a blue-violet laser is used. Moreover, you may use what radiates | emits visible light effectively, such as a flood bulb for photography, a solar lamp.

(Iii) Development step In the development step, the uncured portion of the photosensitive resin layer is removed from the circuit forming substrate by development, whereby a resist pattern made of a cured product obtained by photocuring the photosensitive resin layer is obtained. It is formed on a circuit forming substrate.
When the support film exists on the photosensitive resin layer, the support film is removed, and then the unexposed portions other than the exposed portions are removed (developed). Development methods include wet development and dry development.

In the case of wet development, development is performed by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the developing method include a method using a dipping method, a paddle method, a spray method, brushing, slapping, scrubbing , rocking immersion, and the like. From the viewpoint of improving resolution, the high pressure spray method is most suitable. You may develop by combining these 2 or more types of methods.

  The configuration of the developer is appropriately selected according to the configuration of the photosensitive resin composition. For example, alkaline aqueous solution, aqueous developer, organic solvent developer and the like can be mentioned.

  The alkaline aqueous solution is safe and stable when used as a developer, 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 alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate.

  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. Moreover, it is preferable to make pH of the alkaline aqueous solution used for image development into the range of 9-11, and the temperature is adjusted according to the developability of the photosensitive resin layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.

  The aqueous developer is, for example, a developer composed of water or an alkaline aqueous solution and one or more organic solvents. Here, as the base of the alkaline aqueous solution, in addition to the substances described above, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1, Examples include 3-propanediol, 1,3-diaminopropanol-2, morpholine and the like. The pH of the aqueous developer is preferably as low as possible within a range where development is sufficiently performed, preferably 8 to 12, and more preferably 9 to 10.

  Examples of the organic solvent used in the aqueous developer include 3-acetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol mono Examples include ethyl ether and diethylene glycol monobutyl ether. These are used individually by 1 type or in combination of 2 or more types. In general, the content of the organic solvent in the aqueous developer is preferably 2% by mass to 90% by mass. The temperature can be adjusted according to the developability of the photosensitive resin layer. A small amount of a surfactant, an antifoaming agent or the like can be mixed in the aqueous developer.

  Examples of the organic solvent developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. These organic solvents preferably add water in the range of 1% by mass to 20% by mass in order to prevent ignition.

In the present invention, the resist by after removal of unexposed portions, of ² ~10mJ / cm 2 of about 60 ° C. to 250 DEG ° C. of about heat treatment or 0.2 mJ ^/ cm as required exposure processing or the like performed in the development step The method may further include a step of further curing the pattern.

<Method for manufacturing printed wiring board>
The printed wiring board manufacturing method of the present invention includes a step of forming a conductor pattern by etching or plating a circuit forming substrate on which a resist pattern is formed by the above-described resist pattern manufacturing method. It includes other processes such as a removal process.

  In the etching process, using the resist pattern formed on the substrate as a mask, the conductor layer of the circuit forming substrate not covered with the resist is removed by etching to form a conductor pattern.

  The etching method is appropriately selected according to the conductor layer to be removed. For example, as an etching solution, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, and a hydrogen peroxide-based etching solution can be mentioned. It is desirable to use a ferric chloride solution from the viewpoint of good etch factor. .

On the other hand, in the plating process, copper, solder, or the like is plated on the conductor layer of the circuit forming substrate that is not covered with the resist, using the resist pattern formed on the substrate as a mask.
After the plating process, the cured resist is removed, and the conductor layer covered with the resist is etched to form a conductor pattern.

  The plating treatment method may be electrolytic plating treatment or electroless plating treatment. Examples of plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, nickel plating such as watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating, and hard gold. Examples thereof include gold plating such as plating and soft gold plating.

  After the etching process and the plating process, the resist pattern on the substrate is removed. The removal of the resist pattern can be performed, for example, with a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step. As this strongly alkaline aqueous solution, for example, a 1% by mass to 10% by mass sodium hydroxide aqueous solution, a 1% by mass to 10% by mass potassium hydroxide aqueous solution and the like are used. Especially, it is preferable to use 1 mass%-10 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, and it is more preferable to use 1 mass%-5 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.

  Examples of the resist pattern removal method include an immersion method and a spray method, and these may be used alone or in combination.

  When the resist pattern is removed after the plating treatment, a desired printed wiring board can be manufactured by further etching the conductor layer covered with the resist by the etching treatment to form a conductor pattern. The etching method is appropriately selected according to the conductor layer to be removed. For example, the above-described etching solution can be applied.

  The printed wiring board manufacturing method of the present invention can be applied not only to a single-layer printed wiring board but also to a multilayer printed wiring board, and also to a printed wiring board having a small-diameter through hole. .

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples without departing from the technical idea of the present invention. Unless otherwise specified, “part” and “%” are based on mass.

<Examples 1-4, Comparative Examples 1-2>
Each component which shows a kind and compounding quantity (unit: g) in Table 1 was mixed, and the solution of the photosensitive resin composition concerning Examples 1-4 and Comparative Examples 1-2 was obtained.

Abbreviations of each component in Table 1 are as follows.
[Component A]
(A-1): methacrylic acid / methyl methacrylate / butyl acrylate / styrene (25/50/20/5 (mass ratio), weight average molecular weight = 80,000, 50 mass% methyl cellosolve / toluene = 6 / 4 (mass ratio) solution (A-2): methacrylic acid / methyl methacrylate / ethyl acrylate (20/55/25 (mass ratio), weight average molecular weight = 80,000, 50 mass% methyl cellosolve / Toluene = 6/4 (mass ratio) solution

The weight average molecular weight was measured by a gel permeation chromatography (GPC) method and calculated by using a standard polystyrene calibration curve. The conditions of GPC and the acid value measurement procedure are shown below.
(GPC conditions)
Pump: Hitachi L-6000 type [manufactured by Hitachi, Ltd.]
Column: Gelpack GL-R420 + Gelpack GL-R430 + Gelpack GL-R440 (three in total) [above, manufactured by Hitachi Chemical Co., Ltd., product name]
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI [manufactured by Hitachi, Ltd., product name]

[B component]
BPE-500: 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) [manufactured by Shin-Nakamura Chemical Co., Ltd.]
FA-MECH: γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate [manufactured by Hitachi Chemical Co., Ltd.]
Sample A: a compound represented by the above general formula (I), in which R ¹ is —C ₆ H ₁₂ —, R ² is n = 10 in general formula (II), X is an ethylene group, and Compound in which R ³ is a methyl group Sample B: a compound represented by the general formula (I), wherein R ¹ is —C ₆ H ₁₂ —, and R ² is n = in the general formula (II) 15, a compound in which X is an ethylene group and R ³ is a methyl group. JTX0309: a compound represented by the following general formula (VI), wherein R ⁵¹ and R ⁵² are represented by the following general formula (VIIa) A compound in which R ⁵³ is a group represented by the following general formula (VIIb) (manufactured by Nippon Cytec Industries, Ltd., sample name: JTX0309)

  UA-21: Tris (methacryloyloxytetraethylene glycol isocyanate hexamethylene) isocyanurate [manufactured by Shin-Nakamura Chemical Co., Ltd.]

[C component]
B-CIM: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer EAB: N, N′-tetraethyl-4,4′-diaminobenzophenone

[Other ingredients]
・ MKG: Malachite Green ・ LCV: Leuco Crystal Violet

  The photosensitive resin composition solution obtained above was uniformly applied as a support film onto a 16 μm thick polyethylene terephthalate film (trade name G2-16, manufactured by Teijin Limited), and dried at 100 ° C. with hot air convection. After drying for 10 minutes in a machine to form a photosensitive resin layer, a protective film made of polyethylene (trade name: NF-13, manufactured by Tamapoly Co., Ltd.) is applied on the photosensitive resin layer to protect the photosensitive resin layer. A resin composition laminate was obtained. The film thickness after drying of the photosensitive resin layer was 40 μm.

  Next, a 1.6 mm thick copper clad laminate (manufactured by Ein Co., Ltd.) provided with 35 μm thick copper foil on both sides, as shown in FIG. Three independent round holes 41 and three continuous holes 42 in which the three round holes are connected and the interval between the round holes is gradually shortened were produced by a die cutter for each of the four hole diameters. The burr generated when the round hole 41 and the triple hole 42 were produced was removed using a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, and this was removed with the hole breakage number measuring substrate 40. did.

  The obtained hole breaking number measurement substrate was heated to 80 ° C., the protective film was peeled off from the photosensitive resin composition laminate obtained above, and 120 so that the photosensitive resin layer faced the copper surface. Lamination was performed at 0.4 ° C. at 0 ° C. to obtain a laminate in which a photosensitive resin layer and a polyethylene terephthalate film were laminated on a hole tearing number measurement substrate. After lamination, the hole breakage measurement substrate is cooled, and when the hole breakage measurement substrate temperature reaches 23 ° C., the stove 21-step tablet is brought into close contact with the polyethylene terephthalate film surface, and the exposure has a high-pressure mercury lamp. Using the machine HMW-201B (manufactured by Oak Co., Ltd.), photo-curing was performed with an exposure amount at which 8.0 steps were photo-cured.

(Tent reliability)
After the exposure, the film was allowed to stand at room temperature for 15 minutes, and then the polyethylene terephthalate film was peeled off from the hole-breaking-number measuring substrate and developed by spraying a 1% by weight aqueous sodium carbonate solution at 30 ° C. for 60 seconds. After development, the number of hole breaks of the triple holes was measured, the deformed tent breakage rate was calculated, and the tent reliability was evaluated.
Next, for the cured film covering the round hole portion, a cylinder with an insertion diameter of 1.5 mm was used, and the strength and elongation until breakage were measured with a rheometer (manufactured by Rheotech Co., Ltd.). The greater the strength and elongation values, the better the tent reliability. These results are shown in Table 2.

(Resolution)
The resolution was evaluated as follows.
A photo tool having a stove 21-step tablet and a photo tool having a wiring pattern with a space width / line width of 30/400 to 200/400 (unit: μm) as a negative for resolution evaluation are brought into close contact with each other, and the 21 steps of the stove Exposure was performed with an energy amount such that the number of remaining steps after development in the step tablet was 8.0.
Here, the resolution was evaluated based on the smallest value (unit: μm) of the space width between the line widths where the portion not photocured by the development processing could be removed cleanly. In addition, the evaluation of resolution means that it is so favorable that a numerical value is small.

As is clear from Table 2, Examples 1 to 4 have low deformed tent tear rates and large strength and elongation values. On the other hand, Comparative Example 1 has a high deformed tent tear rate and small strength and elongation values. Comparative Examples 1 and 2 are inferior to Examples 1 to 4 in terms of resolution.
Therefore, according to the present invention, a photosensitive resin composition having excellent mechanical strength and flexibility of a cured film, that is, a photosensitive resin composition having excellent tent reliability, a photosensitive element using the photosensitive resin composition, and a resist pattern. It is possible to provide a manufacturing method and a manufacturing method of a printed wiring board.

40 Substrate for hole breakage measurement 41 Round hole 42 3 holes

Claims (4)

(A) component: binder polymer,
(B) component: a polymerizable compound having at least one ethylenically unsaturated bond;
(C) component: a photopolymerization initiator,
The photosensitive resin composition containing the compound in which the said (B) component contains the compound represented by the following general formula (I).


(Wherein R ¹ represents a divalent organic group, and R ² represents a group represented by the following general formula (II))


(Wherein R ³ represents a hydrogen atom or a methyl group, X represents an alkylene group, and n represents an integer of 10 to 25) A support;
A photosensitive resin layer is a coating film of the photosensitive resin composition of claim 1 which is formed on said support,
A photosensitive element. A photosensitive resin layer forming step of forming a photosensitive resin layer which is a coating film of the photosensitive resin composition according to claim 1 on a circuit forming substrate;
An exposure step of irradiating at least a part of the photosensitive resin layer with actinic rays and photocuring an exposed portion;
And a development step of removing the uncured portion of the photosensitive resin layer from the circuit forming substrate by development. A printed wiring board manufacturing method including a step of forming a conductor pattern by etching or plating a circuit forming substrate on which a resist pattern is formed by the method for manufacturing a resist pattern according to claim 3 .