TWI671594B - Photosensitive resin composition, photosensitive element, method of forming resist pattern and method of producing printed circuit board - Google Patents

Abstract

The present invention provides a photosensitive resin composition comprising: (A) a component: a binder polymer; (B) a component: a photopolymerizable compound; (C) a component: a photopolymerization initiator; and (D) a component: The polytetramethylene oxide compound has [-(C ₄ H ₈ O) _n- : n is a number of 2 or more] as a structural unit, and may be equivalently selected from the group consisting of (A) component, (B) component, and ( C) A part or all of at least one of the group consisting of the components; and the non-volatile acid value of the photosensitive resin composition is less than 120 mgKOH / g.

Description

Forming method of photosensitive resin composition, photosensitive element, resist pattern, and manufacturing method of printed wiring board

The present invention relates to a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a printed wiring board.

Previously, in the field of manufacturing printed wiring boards, as a resist material used in an etching process or a plating process, a photosensitive resin composition and a photosensitive resin layer including a photosensitive resin composition, a support, and The photosensitive element of a protective layer is widely used.

A printed wiring board is manufactured by laminating the photosensitive element on a circuit-forming substrate, exposing the photosensitive resin layer to a pattern, and removing unexposed portions with a developing solution to form a resist. After the pattern is formed on the substrate by performing an etching process or a plating process, the hardened portion as an exposed portion is peeled off from the substrate and removed.

As the developing solution, in terms of environmental and safety knowledge, alkali developing solutions such as an aqueous sodium carbonate solution and an aqueous sodium hydrogen carbonate solution have become mainstream. The unexposed portion of the photosensitive resin layer is removed from the substrate by the development of these developing solutions and the spray pressure of water washing. Therefore, the photosensitive resin composition is required to be able to form a cured film (resist pattern) which is not damaged by the development and water jetting pressure after exposure, and has excellent tenting reliability (cap). Porosity).

In order to have excellent cap hole reliability, it is effective to improve the flexibility of the cured film formed of the photosensitive resin composition. However, if a conventional high-hydrophilic material is used to improve the flexibility of the cured film, there are problems in that the resolution of the cured film is reduced due to the decrease in alkali resistance, and the etching is deepened due to the decrease in etching resistance. For example, there is still room for improvement in resolution, etching resistance, and cover hole reliability for the following reasons: Photosensitivity described in Japanese Patent Laid-Open No. 61-228007 and Japanese Patent Laid-Open No. 2013-83785 In the case of the photosensitive resin composition, the acid value of the photosensitive resin composition is also inappropriate; and the molecular weight of the photopolymerizable compound is inappropriate.

Furthermore, recently, as a method of directly drawing a pattern created by computer-aided design (CAD) without using a mask, but using laser light, it is strongly expected to correspond to laser direct imaging (LDI). )the way. However, from the viewpoint of throughput, the resist material used in the LDI method which requires a smaller exposure amount requires a low exposure amount and alkali resistance and etching resistance at a low hardening degree. , So use a rigid frame material. Therefore, it is disadvantageous in terms of the reliability of the cap hole required for the flexibility of the cured film. As a resist used in the LDI method, no high-throughput, high-resolution, etching resistance, and high cap hole have been developed so far. Reliable resist. For example, in Japanese Patent Laid-Open No. 2006-234995, Japanese Patent Laid-Open No. 2007-122028, International Publication No. 2008/078483, Japanese Patent Laid-Open No. 2009-69465, and International Publication No. 2010/103918 In the case of the described photosensitive resin composition, there is room for improvement in any of the obtained resist, the resolution, the hole cover reliability, and the etching resistance.

[Problems to be Solved by the Invention]

Therefore, an object of the present invention is to provide a photosensitive resin composition capable of forming a resist pattern even at a low exposure amount, and having excellent cover hole reliability and etching resistance of the formed cured film. Another object of the present invention is to provide a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and a method for manufacturing a printed wiring board. [Means for solving problems]

Specific means for solving the problems include the following embodiments. <1> A photosensitive resin composition comprising: (A) a component: a binder polymer; (B) a component: a photopolymerizable compound; (C) a component: a photopolymerization initiator; and (D) a component: The polytetramethylene oxide compound has [-(C ₄ H ₈ O) _n- : n is a number of 2 or more] as a structural unit, and may be equivalently selected from the group consisting of (A) component, (B) component, and ( C) A part or all of at least one of the group consisting of the components; and the non-volatile acid value of the photosensitive resin composition is less than 120 mgKOH / g.

<2> The photosensitive resin composition according to <1>, wherein the polytetramethylene oxide compound has a weight average molecular weight of 1,000 or more.

<3> The photosensitive resin composition according to <1> or <2>, wherein a part or all of the (B) component is a polytetramethylene oxide compound.

<4> The photosensitive resin composition according to <3>, wherein the content of the polytetramethylene oxide compound in the total amount of the component (B) is 20% to 50% by mass.

<5> The photosensitive resin composition according to <3> or <4>, wherein the polytetramethylene oxide compound as a part or all of the component (B) is polytetramethylene glycol di (Meth) acrylate.

<6> The photosensitive resin composition according to <5>, wherein the polytetramethylene glycol di (meth) acrylate is a polytetramethylene glycol dimethacrylate.

<7> A photosensitive element comprising: a support; and a photosensitive resin layer formed on the support using the photosensitive resin composition according to any one of <1> to <6>.

<8> A method for forming a resist pattern, comprising: a photosensitive resin layer forming step, using the photosensitive resin composition according to any one of <1> to <6>, or according to <7> A photosensitive element, forming a photosensitive resin layer on the substrate; an exposure step, irradiating at least a part of the photosensitive resin layer with actinic rays to harden the area; and a developing step, the photosensitive resin layer Unexposed portions outside the region are removed from the substrate.

<9> A method for manufacturing a printed wiring board, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method according to <8>. [Effect of the invention]

According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a resist pattern even at a low exposure amount, and having excellent cap hole reliability and etching resistance of the formed cured film. Moreover, this invention can provide the photosensitive element using the said photosensitive resin composition, the formation method of a resist pattern, and the manufacturing method of a printed wiring board.

Hereinafter, the mode for implementing this invention is demonstrated in detail with reference to drawings as needed. However, the present invention is not limited to the following embodiments. In the drawings, the same elements are denoted by the same symbols, and redundant descriptions are omitted. The dimensional ratios of the drawings are not limited to the ratios shown in the drawings.

The "(meth) acrylic acid" in this specification means at least one of "acrylic acid" and "methacrylic acid", and the "(meth) acrylate" means "acrylate" and the corresponding "methacrylate" At least one of "acrylate" and "(meth) acryl" refers to at least one of "acryl" and "methacryl". The "polytetramethylene oxide" refers to a structural unit represented by [-(C ₄ H ₈ O) _n- : n is a number of 2 or more]. The number of structural units indicates how much the corresponding structural unit is added to the molecule. Therefore, although it represents an integer value for a single molecule, it represents a rational number as an average value as an aggregate of a plurality of molecules. The "non-volatile matter" refers to a component in a composition other than a volatile substance such as moisture and an organic solvent described later. Here, the volatile substance means a substance having a boiling point of 155 ° C. or lower at atmospheric pressure. "Total amount of (A) component" and "total amount of (B) component" refer to the total amount of nonvolatile matter only.

The term "step" as used in this specification includes not only independent steps, but even cases that cannot be clearly distinguished from other steps, as long as the desired purpose of the steps is achieved, they are included in the term. In addition, the numerical range shown using "~" means the range which contains the numerical value described before and after "~" as the minimum and maximum value, respectively. Furthermore, when there are a plurality of substances corresponding to each component in the composition, the content of each component in the composition refers to the total amount of the plurality of substances present in the composition unless otherwise specified. In addition, in the numerical range described stepwise in this specification, the upper limit value or lower limit value of a numerical range at a certain stage may be replaced with the upper limit value or lower limit value of a numerical range at another stage. In addition, in the numerical range described in this specification, the upper limit value or lower limit value of the numerical range may be replaced with the value shown in the examples. The term "layer" includes not only a configuration of a shape formed on the entire surface when viewed as a plan view, but also a configuration of a shape formed on a part. The term "lamination" means that layers are stacked, and two or more layers may be combined, or two or more layers may be desorbed.

<Photosensitive resin composition> The photosensitive resin composition of this embodiment contains: (A) component: a binder polymer; (B) component: a photopolymerizable compound; (C) component: a photopolymerization initiator; and (D) component: It has polytetramethylene oxide [-(C ₄ H ₈ O) _n- : n is a number of 2 or more] as a structural unit and may be equivalently selected from the components (A) and (B) And (C) a compound that is a part or all of at least one of the group consisting of components; and the non-volatile acid value of the photosensitive resin composition is less than 120 mgKOH / g. The photosensitive resin composition may further include other components as necessary.

The photosensitive resin composition contains a compound having a polytetramethylene oxide as a structural unit (hereinafter also referred to as a polytetramethylene oxide compound) as the component (D), and the photosensitive resin composition is non-volatile. An acid value of less than 120 mgKOH / g can form a photosensitive resin composition that can form a resist pattern even at a low exposure amount, and has a cap hole reliability and an etching resistance of the formed cured film. The reason for this is speculated by the present inventors as follows.

The polytetramethylene oxide compound has polytetramethylene oxide having high flexibility as a structural unit. Therefore, by using a photosensitive resin composition containing a polytetramethylene oxide compound, moderate flexibility is imparted to the formed resist pattern. Therefore, it is considered that stress concentration is hardly generated in the resist pattern, and the reliability of the cap hole is improved. The polytetramethylene oxide structural unit of the polytetramethylene oxide compound can be said to be highly hydrophobic. Therefore, it is considered that by using a photosensitive resin composition containing a polytetramethylene oxide compound, the acid resistance of the formed resist pattern is improved and the etching resistance is excellent.

Furthermore, it is considered that the photosensitive resin composition has a non-volatile acid value of less than 120 mgKOH / g, and thus becomes a photosensitive resin composition having excellent developer resistance, and the formed film has a hole cover reliability and corrosion resistance. Excellent etchability. In addition, there is a tendency that a resist pattern having excellent resolution and adhesion can be formed.

The nonvolatile acid value of the photosensitive resin composition can be measured by the following method. First, after accurately weighing 1 g of the photosensitive resin composition, 30 g of acetone was added to the photosensitive resin composition to uniformly dissolve the photosensitive resin composition. Then, an appropriate amount of phenolphthalein as an indicator was added to the solution of the photosensitive resin composition, and titration was performed using a 0.1N KOH aqueous solution. Then, based on the results of the titration, the acid value was calculated from the following formula (1) (where Vf represents the titer of phenolphthalein (mL), and Wp represents the weight (g) of the solution of the photosensitive resin composition as the component (A) ), I represents the nonvolatile matter ratio (mass%) of the solution of the photosensitive resin composition as the component (A)). Acid value (mgKOH / g) = 10 × Vf × 56.1 / (Wp × I) (1)

From the viewpoint of further improving the cover hole reliability and etching resistance of the resist pattern, the non-volatile acid value of the photosensitive resin composition is preferably 110 mgKOH / g or less, and more preferably 100 mgKOH / g or less. From the viewpoint of developability of the resist pattern, it is preferably 40 mgKOH / g or more. Furthermore, from a viewpoint of peeling time, 80 mgKOH / g or more is more preferable, and 90 mgKOH / g or more is more preferable. Hereinafter, each component is demonstrated in detail.

[(A) Component: Binder Polymer] The photosensitive resin composition contains at least one kind of a binder polymer as the (A) component. The structure of the adhesive polymer is not particularly limited, and can be selected from ordinary users. The binder polymer may be used singly or in combination of two or more kinds. Examples of the binder polymer include binder polymers including the following structural units (A1), structural units (A2), and structural units (A3).

Structural unit (A1) It is preferable that at least one of the binder polymer includes a group selected from the group consisting of styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative. At least one of the structural units (A1). Thereby, not only the flexibility of the adhesive polymer (A) can be maintained, but also the adhesiveness at the time of forming a cured product can be improved.

From the viewpoint of improving both the adhesiveness and the peeling characteristics of the cured film, the content rate of the structural unit (A1) in the adhesive polymer in the total amount of the component (A) is preferably 10% by mass to 60 mass%, more preferably 13 mass% to 40 mass%, and even more preferably 15 mass% to 25 mass%. When the content rate of the structural unit (A1) is 10% by mass or more, the adhesiveness of the cured film tends to be improved. When the content of the structural unit (A1) is 60% by mass or less, the release sheet can be suppressed from becoming larger and the peeling time can be prevented from increasing. Cover hole reliability tends to improve.

Specific examples of the styrene derivative include α-methylstyrene, vinyltoluene, and p-chlorostyrene, which are polymerizable styrene derivatives substituted in the α-position or an aromatic ring. Specific examples of the benzyl (meth) acrylate derivative include 4-methylbenzyl (meth) acrylate, 4-ethylbenzyl (meth) acrylate, and 4-tert-butyl (meth) acrylate Benzyl ester, 4-methoxybenzyl (meth) acrylate, 4-ethoxybenzyl (meth) acrylate, 4-hydroxybenzyl (meth) acrylate, 4-chlorobenzyl (meth) acrylate Wait.

Structural unit (A2) From the viewpoint of the reliability of the cover hole of the cured film, it is preferable that at least one of the adhesive polymer contains a structural unit (A2) derived from an alkyl (meth) acrylate. The alkyl group in the alkyl (meth) acrylate may be either linear or branched, and may be unsubstituted or may have a substituent. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 5 to 20 carbon atoms, and even more preferably 8 to 14 carbon atoms. Examples of the (meth) acrylic acid alkyl ester include compounds represented by the following general formula (I).

CH ₂ = C (R ³ ) -COOR ⁴ (I)

In the general formula (I), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group having 1 to 20 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁴ in the general formula (I) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, Decyl, undecyl, dodecyl and structural isomers of these alkyl groups. The alkyl group having 1 to 20 carbon atoms represented by R ⁴ may be unsubstituted or may have a substituent. Examples of the substituent include a hydroxyl group, an epoxy group, and a halogen group. When the alkyl group having 1 to 20 carbon atoms represented by R ⁴ has a substituent, the number of the substituents and the substitution position are not particularly limited.

From the viewpoint of further improving the cover hole reliability of the cured film, the alkyl group represented by R ⁴ in the general formula (I) is more preferably 5 to 20 carbon atoms, and even more preferably 8 to 14 carbon atoms.

Examples of the compound represented by the general formula (I) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) N-butyl acrylate, third butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, (meth) ) 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, and the like. These compounds may be used singly or in combination of two or more kinds.

When the adhesive polymer contains the structural unit (A2), the content rate of the structural unit (A2) in the total amount of the (A) component is preferably from the viewpoints of adhesion, resolvability, and developability. 1 mass% to 70 mass%, more preferably 30 mass% to 65 mass%, and even more preferably 45 mass% to 60 mass%. When the content rate of the structural unit (A2) is 1% by mass or more, the cover hole reliability of the cured film is further improved. When it is 80% by mass or less, the resolution and adhesion of the cured film are further improved. .

• Structural unit (A3) From the viewpoint of alkali developability, at least one of the binder polymers preferably includes a structural unit (A3) derived from a polymerizable monomer having a carboxyl group. The binder polymer containing a structural unit (A3) can be manufactured by radically polymerizing the polymerizable unit with a carboxyl group and another polymerizable unit, for example.

Examples of the polymerizable monomer having a carboxyl group include (meth) acrylic acid; α-bromoacrylic acid, α-chloroacrylic acid, β-furyl (meth) acrylic acid, and β-styryl (meth) acrylic acid (formaldehyde) Group) acrylic acid derivatives; maleic acid; maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monoisopropyl ester, and other maleic acid derivatives; fumaric acid Adipic acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, butenoic acid, propionic acid, and the like. From the viewpoint of improving sensitivity, (meth) acrylic acid is preferred, and methacrylic acid is more preferred.

In the case where the binder polymer contains the structural unit (A3), the content of the structural unit (A3) in the total amount of the component (A) is better from the viewpoint of the balance between alkali developability and developing solution resistance. It is 12% by mass to 50% by mass, and more preferably 15% by mass to 35% by mass, and even more preferably 15% by mass to 30% by mass in terms of more excellent alkali developability.

· Other structural units The adhesive polymer may contain structural units other than the structural units (A1) to (A3). Examples of polymerizable monomers constituting other structural units include acrylamide such as diacetone acrylamide; acrylonitrile; ethers of vinyl alcohols such as vinyl-n-butyl ether; and organic acid derivatives such as maleic anhydride . These polymerizable monomers may be used alone or in combination of two or more.

From the viewpoints of adhesiveness, resolvability, and developability of the cured film, the content of the other structural units in the total amount of the component (A) is preferably 10% by mass or less, more preferably 5% by mass or less, particularly It is preferably not substantially contained (for example, 0.5% by mass or less). That is, the total content of the structural unit (A1), the structural unit (A2), and the structural unit (A3) in the total amount of the (A) component is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly It is preferably substantially 100% by mass (for example, 99.5% by mass or more).

• Characteristics of the binder polymer The binder polymer is obtained by polymerizing a single body corresponding to each structural unit constituting the binder polymer. Examples of the polymerization method include radical polymerization. In the case where the binder polymer is a copolymer obtained by polymerizing two or more kinds of monomers, each structural unit in the copolymer may be randomly contained in the copolymer like a so-called random copolymer, It may also be a copolymer including a structural unit in which the same kind of monomer is continuously formed like a block copolymer. In addition, each structural unit may be a single type or a plurality of types.

From the viewpoint of the balance between the developer resistance and the alkali developability, the weight average molecular weight of the binder polymer is preferably 20,000 to 300,000, more preferably 30,000 to 200,000, and even more preferably 40,000 to 100,000. The weight average molecular weight in this specification is a value obtained by measuring by gel permeation chromatography under the same measurement conditions as those described in the examples, and converting it based on a calibration curve prepared using standard polystyrene.

The acid value of the binder polymer is preferably 60 mgKOH / g to 300 mgKOH / g, more preferably 120 mgKOH / g to 200 mgKOH / g, and even more preferably 150 mgKOH / g to 170 mgKOH / g.

(A) The binder polymer contained in a component may be used individually by 1 type, or may be used in combination of 2 or more type. Examples of the combination of two or more kinds of binder polymers include two or more kinds of binder polymers having different types and ratios of copolymerization components, two or more kinds of binder polymers having different weight average molecular weights, and a degree of dispersion. A combination of two or more different binder polymers. The degree of dispersion of the binder polymer is a value obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn).

The component (A) may be a binder polymer including at least any one of the structural unit (A1), the structural unit (A2), or the structural unit (A3), and the polymer without the structural unit (A1) or the structural unit (A2). ) Or a combination of other binder polymers of any of the structural units (A3). The other binder polymer is not particularly limited as long as it is soluble in an alkaline aqueous solution and can form a film. Examples include: acrylic resin (but not including structural unit (A1), structural unit (A2), structural unit (A3)), epoxy resin, ammonium resin, ammonium epoxy resin, alkyd Resin and phenol resin. Among these, an acrylic resin is preferable from the viewpoint of alkali developability. These resins can be used singly or in combination of two or more kinds.

In the case where the component (A) contains another binder polymer that does not include any one of the structural unit (A1), the structural unit (A2), or the structural unit (A3), the structure in the total amount of the (A) component The content rate of the unit (A1) is preferably 10% by mass to 60% by mass, more preferably 13% by mass to 40% by mass, and even more preferably 15% by mass to 25% by mass. When the component (A) contains another binder polymer, the content of the other binder polymer in the total amount of the component (A) is preferably 10% by mass or less, and more preferably 5% by mass or less. It is particularly preferred that it does not substantially contain other binder polymers (for example, 0.5% by mass or less), and it is particularly preferred that it does not contain other binder polymers at all.

The content of the (A) component in the photosensitive resin composition is preferably 30 to 70 parts by mass, and more preferably 40 to 100 parts by mass of the total amount of the (A) component and the (B) component. Part by mass to 65 parts by mass, particularly preferably 50 to 60 parts by mass. When content of (A) component exists in this range, there exists a tendency for the coating-film property of a photosensitive resin composition and the intensity | strength of a cured film to become more favorable.

[(B) Component: Photopolymerizable Compound] The photosensitive resin composition includes at least one kind of a photopolymerizable compound as the (B) component. The photopolymerizable compound as the (B) component is not particularly limited, and it can be appropriately selected from the commonly used photopolymerizable compounds and used. Examples of the photopolymerizable compound include compounds having an unsaturated double bond capable of photopolymerization. Examples of the unsaturated double bond that can be photopolymerized include the double bond contained in the (meth) acrylfluorenyl group.

Specific examples of the photopolymerizable compound include polyalkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polyethylene polypropylene glycol di (meth) acrylate. (Meth) acrylates; multifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; 2 , 2-bis (4-((meth) acryloxypolyvinyloxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyoxyloxypolyoxypropylene) Group) bisphenol A (meth) acrylate compounds such as phenyl) propane; γ-chloro-β-hydroxypropyl-β '-(meth) acryloxyethoxyethyl-o-phthalic acid Ester, β-hydroxyethyl-β '-(meth) acrylic acid oxyethyl-o-phthalate, β-hydroxypropyl-β'-(meth) acrylic acid oxyethyl -Phthalic acid derivatives such as phthalic acid esters; alkyl (meth) acrylates and the like.

Among these compounds, from the viewpoints of adhesion and resolvability, the photopolymerizable compound preferably contains a compound selected from the group consisting of bisphenol A-based (meth) acrylate compounds and polyalkylene glycol poly (meth) acrylates. It is more preferable to use at least one of the group consisting of at least one of a bisphenol A (meth) acrylate compound and at least one of a polyalkylene glycol poly (meth) acrylate, and it is particularly preferable to use 2 At least one kind of 2-bis (4-((meth) acryloxypolyvinyloxy) phenyl) propane and at least one kind of polyethylene glycol poly (meth) acrylate are used in combination.

Examples of 2,2-bis (4-((meth) acryloxypolyvinyloxy) phenyl) propane include 2,2-bis (4-((meth) acryloxyoxydiethylene) Yloxy) phenyl) propane, 2,2-bis (4-((meth) acrylfluorenylpentadethyloxy) phenyl) propane, 2,2-bis (4-((methyl ) Acrylic acid pentadecyl ethyloxy) phenyl) propane and the like.

2,2-Bis (4- (methacryloxypentylethyloxy) phenyl) propane is commercially available as BPE-500 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 2,2-bis (4- (methacryloxypentadecylethyloxy) phenyl) propane is commercially available as BPE-1300 (manufactured by Shin Nakamura Chemical Industry Co., Ltd., product name) . These compounds may be used alone or in combination of two or more.

When a plurality of photopolymerizable compounds are used as the component (B) in combination, a compound having two or more unsaturated double bonds capable of photopolymerization in one molecule in the total amount of the (B) component is contained. The ratio is preferably 75% by mass or more. Since the content of the compound having two or more unsaturated double bonds that can be photopolymerized in one molecule in the total amount of the (B) component is 75% by mass or more, there is reliability and resolvability of the cap hole of the cured film And the tendency to further improve the adhesion.

The content of the component (B) in the photosensitive resin composition is preferably set to 20 parts by mass to 70 parts by mass in 100 parts by mass of the total amount of the (A) component and the (B) component. From the viewpoint of further improving the cover hole reliability and resolution of the cured film, the content of the (B) component is preferably 20 parts by mass or more out of 100 parts by mass of the total amount of the (A) component and the (B) component. It is more preferably 25 parts by mass or more, and even more preferably 30 parts by mass or more. From the viewpoint of imparting a good film property to the photosensitive resin composition and a good shape of the cured resist, from 100 parts by mass of the total amount of (A) component and (B) component, (B The content of the component is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, particularly preferably 55 parts by mass or less, and particularly preferably 50 parts by mass or less.

[(C) Component: Photopolymerization Initiator] The photosensitive resin composition includes at least one kind of a photopolymerization initiator as (C) component. The photopolymerization initiator is not particularly limited, and can be appropriately selected and used from commonly used photopolymerization initiators. Among them, the component (C) is preferably an acridine compound having one or two acridine groups in one molecule. That is, the (C) component preferably contains an acridine compound (hereinafter also referred to as "(C1) compound") having one acridine group and one acridine group (hereinafter also referred to as " (C2) at least one of the compounds in the group consisting of the compound ").

Examples of the (C1) compound include an acridine compound represented by the following general formula (II).

[Chemical 1]

In formula (II), R ³ represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene group having 2 to 20 carbon atoms, or a thiodialkylene group having 2 to 20 carbon atoms. From the viewpoint of more surely obtaining the effect exhibited by the photosensitive resin composition, R ^{3 is} preferably an alkylene group having 2 to 20 carbon atoms, and more preferably an alkylene group having 4 to 14 carbon atoms.

Examples of the compound represented by the general formula (II) include 1,2-bis (9-acridyl) ethane, 1,3-bis (9-acridyl) propane, and 1,4-bis ( 9-acridyl) butane, 1,5-bis (9-acridyl) pentane, 1,6-bis (9-acridyl) hexane, 1,7-bis (9-acridyl) ) Heptane, 1,8-bis (9-acridyl) octane, 1,9-bis (9-acridyl) nonane, 1,10-bis (9-acridyl) decane, 1 , 11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane, 1,14-bis (9-acridinyl) tetradecane, 1,16 -Bis (9-acridyl) hexadecane, 1,18-bis (9-acridyl) octadecane, 1,20-bis (9-acridyl) eicosane, etc. Pyridyl) alkanes; 1,3-bis (9-acridyl) -2-oxapropane; 1,5-bis (9-acridyl) -3-oxapentane and other bis (9-acridyl) Dioxoalkane; 1,3-bis (9-acridyl) -2-thiopropane; 1,5-bis (9-acridyl) -3-thiopentane and other di (9-acryl) Pyridyl) thioalkane and the like. These compounds may be used alone or in combination of two or more.

From the viewpoint of making the photosensitivity and resolution better, it is preferable to include an acridine compound in which R ³ in formula (II) is a heptyl group (for example, manufactured by ADEKA Corporation, product name) "N-1717") as a (C1) compound.

When the photosensitive resin composition contains a (C1) compound as a photopolymerization initiator, in terms of sensitivity, resolvability, and adhesiveness, it is 100 with respect to the total amount of the (A) component and the (B) component The content of the (C1) compound may be, for example, 0.1 to 10 parts by mass, 0.5 to 5 parts by mass, or 1 to 3 parts by mass, more preferably 0.1 to 1.4 parts by mass, and particularly preferably It is 0.3 to 1.2 parts by mass, particularly preferably 0.4 to 0.7 parts by mass, and most preferably 0.5 to 0.6 parts by mass. When the content of the (C1) compound is 0.1 parts by mass or more, there is a tendency that a better sensitivity, resolution, or adhesion is obtained. When it is 1.4 parts by mass or less, there is a tendency that a more favorable resist shape is obtained.

Examples of the (C2) compound include an acridine compound represented by the following general formula (III).

[Chemical 2]

In formula (III), R ⁴ represents a halogen atom, an amine group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkylamino group having 1 to 6 carbon atoms. m represents an integer from 0 to 5. When m is 2 or more, a plurality of R ⁴ may be the same or different.

Examples of the acridine compound represented by the general formula (III) include 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine, 9- (P-chlorophenyl) acridine, 9- (m-chlorophenyl) acridine, 9-aminoacridine, 9-dimethylaminoacridine, 9-diethylaminoacridine, and 9-pentyl Aminoamine acridine. These compounds may be used alone or in combination of two or more.

In a case where the photosensitive resin composition includes a (C2) compound as a photopolymerization initiator, in terms of the sensitivity, resolvability, and adhesiveness, it is relative to the total of (A) component and (B) component The amount of the compound (C2) may be, for example, 0.1 to 10 parts by mass, 0.5 to 5 parts by mass, or 1 to 3 parts by mass, preferably 0.1 to 1.4 parts by mass, More preferably, it is 0.3 to 1.2 parts by mass, particularly preferably 0.4 to 0.7 parts by mass, and particularly preferably 0.5 to 0.6 parts by mass. When the content of the (C2) compound is 0.1 parts by mass or more, there is a tendency that a better sensitivity, resolution, or adhesion is obtained. When it is 1.4 parts by mass or less, there is a tendency that a more favorable resist shape is obtained.

The photosensitive resin composition may include, as the component (C), a photopolymerization initiator other than the compound (C1) and the compound (C2).

Examples of the photopolymerization initiator other than the (C1) compound and the (C2) compound include benzophenone and N, N'-tetramethyl-4,4'-diaminobenzophenone (Michlerone). ), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2- Dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinyl-acetone- Class 1 aromatic ketone compounds; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzo Anthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl Quinone compounds such as 1,4-naphthoquinone, 2,3-dimethylanthraquinone; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin, ethyl benzoin; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (methoxyphenyl) imidazole dimer, 2- ( (O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5- Diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, etc. 2,4,5-triarylimidazole dimer; benzyldimethyl condensation Benzyl derivatives such as ketones; 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10 -Substituted anthracene compounds such as dipentoxyanthracene; coumarin compounds; oxazole compounds; pyrazoline compounds; triarylamine compounds and the like. These photopolymerization initiators may be used alone or in combination of two or more. In addition, as a combination of diethylthioxanthone and dimethylaminobenzoic acid, a thioanthrone compound and a tertiary amine compound may be used as a photopolymerization initiator.

In addition, the 2,4,5-triarylimidazole dimer may be a compound in which the substituents of the aryl groups of two 2,4,5-triarylimidazoles constituting the dimer are the same and symmetrical, or may be each other. Different and asymmetric compounds.

When the photosensitive resin composition contains a photopolymerization initiator other than the (C1) compound and the (C2) compound as the (C) component, it is relative to (A) in terms of sensitivity and internal photocurability. The total amount of the component and the (B) component is 100 parts by mass. The content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, and even more preferably 0.2 part by mass. ~ 5 parts by mass.

From the viewpoints of sensitivity, adhesion, and internal photocurability, the content of the component (C) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total amount of the (A) component and the (B) component. Parts, more preferably 0.05 parts by mass to 10 parts by mass, and even more preferably 0.1 parts by mass to 5 parts by mass.

From the viewpoints of sensitivity, adhesion, and internal photocurability, the photosensitive resin composition preferably contains at least one selected from the group consisting of a (C1) compound and a (C2) compound as ( C) a component, and its content is 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, with respect to 100 parts by mass of the total amount of the (A) component and the (B) component.

[(D) Component: Polytetramethylene oxide compound] The photosensitive resin composition includes at least one type of a polytetramethylene oxide compound as the (D) component. The polytetramethylene oxide compound may be used singly or in combination of two or more kinds. The polytetramethylene oxide compound may correspond to a part or the whole of at least one selected from the group consisting of the component (A), the component (B), and the component (C). The polytetramethylene oxide compound contained in the photosensitive resin composition may be only one type or may have a different structure (for example, each has a different _{n in-} (C ₄ H ₈ O) _n- ). A combination of two or more.

The structure of the polytetramethylene oxide in the polytetramethylene oxide compound is preferably linear, and more preferably a structural unit represented by the following general formula (IV). By having such a structural unit, there is a tendency that the flexibility of the resist pattern is further improved, and the reliability of the cap hole is further improved.

[Chemical 3]

In the formula (IV), n is a number of 2 or more. From the viewpoint of obtaining a cured film having more excellent cap hole reliability and peeling time, n is preferably a number of 6 or more, more preferably a number of 10 or more, and even more preferably a number of 15 or more. The upper limit value of n is not particularly limited. In terms of obtaining a cured film having better developability, resolvability, and adhesion, the number is preferably 70 or less, more preferably 50 or less, and particularly preferably Numbers below 40.

From the viewpoint of more excellent cap hole reliability and peeling time, the weight average molecular weight of the polytetramethylene oxide compound is preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more. The weight average molecular weight of the polytetramethylene oxide compound is preferably 10,000 or less, more preferably 9,000 or less, and even more preferably 8,000 or less.

In the case where the polytetramethylene oxide compound corresponds to the binder polymer as the component (A), specific examples of the polytetramethylene oxide compound as the (A) component include polytetramethylene oxide compounds. A polymer of a structural unit derived from a methoxide mono (meth) acrylate or a derivative thereof, a polymer including a structural unit derived from a polytetramethylene oxide glycidyl ether or a derivative thereof, and the like.

In the case where the polytetramethylene oxide compound corresponds to the photopolymerizable compound as the (B) component, specific examples of the polytetramethylene oxide compound as the (B) component include 2,2-bis (4-((Meth) acryloxypolytetramethyleneoxy) phenyl) propane, polytetramethylene glycol di (meth) acrylate, polytetramethylene glycol mono (methyl (Meth) acrylate, urethane (meth) acrylate, and urethane reactants of polytetramethylene glycol and diisocyanate compounds or triisocyanate compounds.

In the case where the polytetramethylene oxide compound does not correspond to any of the (A) component, (B) component, or (C) component, specific examples of the polytetramethylene oxide compound include: poly Tetramethylene glycol, esterification, etherification and urethane of polytetramethylene glycol, and esterification, etherification and urethane of polytetramethylene glycol derivative.

The polytetramethylene oxide compound is preferably in one molecule, and the proportion of the polytetramethylene oxide structural unit is 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. . In addition, the polytetramethylene oxide compound may have a polyalkylene oxide other than polytetramethylene oxide such as polyethylene oxide and polypropylene oxide as a structural unit.

From the viewpoint of further improving the resolution of the cured film, the cover hole reliability, and the etching resistance, it is preferable that part or all of the component (B) is a polytetramethylene oxide compound. The polytetramethylene oxide compound corresponding to the component (B) is preferably: polytetramethylene glycol di (meth) acrylate, hydroxyethyl (meth) acrylate, and polytetramethylene glycol And urethane reactants of diisocyanate compounds.

The content of the polytetramethylene oxide compound in the total amount of the component (B) is preferably 20% to 50% by mass, more preferably 25% to 45% by mass, and even more preferably 30% to 40% by mass. quality%. When the content of the polytetramethylene oxide compound is 50% by mass or less, the peeling time, resolution, and adhesion of the cured film tend to be more excellent. In addition, when the content of the polytetramethylene oxide compound is 20% by mass or more, there is a tendency that capping reliability and etching resistance are more excellent.

From the viewpoint of being more excellent in cap hole reliability, the polytetramethylene oxide compound equivalent to the component (B) is preferably polytetramethylene glycol di (meth) acrylate, and more preferably The polytetramethylene glycol dimethacrylate is particularly preferably a polytetramethylene glycol dimethacrylate having a weight average molecular weight of 1,000 to 5000, and more preferably a polytetramethylene glycol dimethacrylate having a weight average molecular weight of 1800 to 4,000. Tetramethylene glycol dimethacrylate compound.

From the viewpoint of improvement in cap hole reliability and etching resistance, the content ratio of the structural unit of the polytetramethylene oxide is preferably 4 masses with respect to the total amount of the nonvolatile matter of the photosensitive resin composition. % Or more, more preferably 6% by mass or more, particularly preferably 10% by mass or more, and particularly preferably 14% by mass or more. In addition, from the viewpoint of improving the resolution, the content of the structural unit of the polytetramethylene oxide is preferably 40% by mass or less with respect to the total amount of the nonvolatile matter of the photosensitive resin composition. It is preferably 30% by mass or less, and particularly preferably 20% by mass or less.

[Other ingredients] The photosensitive resin composition may further include dyes such as malachite green, victoria pure blue, brilliant green, and methyl violet as required. ; Photochromic agent such as leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, or o-chloroaniline; thermochromic agent Plasticizers such as p-toluenesulfonamide; pigments; fillers; defoamers; flame retardants; adhesion-imparting agents; leveling agents; peeling promoters; antioxidants; polymerization inhibitors; perfumes; imaging agents; Thermal cross-linking agents and other additives.

When the said photosensitive resin composition contains other additives, the content can be suitably selected according to the objective etc. For example, it may contain about 0.01 mass parts-about 20 mass parts with respect to 100 mass parts of the total amount of (A) component and (B) component, respectively. These additives may be used alone or in combination of two or more.

The photosensitive resin composition may further include at least one organic solvent. Examples of organic solvents include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl cellosolve, ethyl cellosolve and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene Solvents; aprotic polar solvents such as N, N-dimethylformamide. These organic solvents may be used alone or in combination of two or more. The content of the organic solvent contained in the photosensitive resin composition can be appropriately selected depending on the purpose and the like. For example, it can be used as a solution whose non-volatile content is about 30% to 60% by mass (hereinafter, a photosensitive resin composition containing an organic solvent is also referred to as a "coating liquid").

The said photosensitive resin composition can be used for forming the photosensitive resin layer of the photosensitive element mentioned later. That is, another embodiment of the present invention is the use of the photosensitive resin composition in a photosensitive element. The photosensitive resin composition can be used in a method for forming a resist pattern to be described later and a method for producing a printed wiring board.

<Photosensitive Element> The photosensitive element of the present invention includes a support and a photosensitive resin layer formed on the support using the photosensitive resin composition. The photosensitive element may include other layers such as a protective layer as necessary.

FIG. 1 shows an embodiment of the photosensitive element of the present invention. In the photosensitive element 10 shown in FIG. 1, a support 2, a photosensitive resin layer 4, and a protective layer 6 formed using the photosensitive resin composition are laminated in this order. The photosensitive element 10 can be obtained as follows, for example. The photosensitive resin layer 4 is formed by applying a coating solution of the photosensitive resin composition containing an organic solvent on the support 2 to form a coating layer, and drying the coating layer. Then, the surface of the photosensitive resin layer 4 on the side opposite to the support 2 is covered with a protective layer 6 to obtain a support 2, a photosensitive resin layer 4 formed on the support 2, and a photosensitive layer The photosensitive element 10 according to this embodiment of the protective layer 6 on the flexible resin layer 4. The photosensitive element 10 may not include the protective layer 6.

As the support 2, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used.

The thickness of the support 2 (polymer film) is preferably 1 μm to 100 μm, more preferably 1 μm to 50 μm, and even more preferably 1 μm to 30 μm. When the thickness of the support 2 is 1 μm or more, the support 2 can be suppressed from being broken when the support 2 is peeled from the photosensitive resin layer 4. In addition, when the thickness is 100 μm or less, a decrease in resolution is suppressed.

The protective layer 6 is preferably a layer having a smaller adhesive force to the photosensitive resin layer 4 than the adhesive force of the support 2 to the photosensitive resin layer 4. In addition, a low fisheye film is preferred. Here, the "fisheye" refers to a foreign substance, an undissolved substance, and an oxidative degradation substance contained in a material when the material is thermally melted and a film is produced by kneading, extrusion, biaxial stretching, casting, or the like. Wait to enter the membrane. That is, the term "low fisheye" means that there are few foreign matter or the like in the film.

Specifically, as the protective layer 6, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used. Commercially available films include: Alphan MA-410, E-200C manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., PS series such as PS-25 manufactured by Teijin Co., Ltd. And other polyethylene terephthalate films. The protective layer 6 may be the same layer as the support 2.

The thickness of the protective layer 6 is preferably 1 μm to 100 μm, more preferably 1 μm to 50 μm, and even more preferably 1 μm to 30 μm. When the thickness of the protective layer 6 is 1 μm or more, there is a tendency that when the photosensitive resin layer 4 and the support 2 are laminated on the substrate while the protective layer 6 is peeled off, the protective layer 6 can be prevented from cracking. If it is 100 μm or less, it tends to be excellent in operability and inexpensiveness.

Specifically, the photosensitive element of this embodiment can be manufactured as follows, for example. It can be manufactured by a manufacturing method including at least the following steps: preparing to dissolve (A) component: a binder polymer, (B) component: a photopolymerizable compound, and (C) a photopolymerization initiator in the organic solvent A step of forming a coating solution; a step of applying the coating solution on the support 2 to form a coating layer; and a step of drying the coating layer to form a photosensitive resin layer.

The coating liquid may be applied onto the support 2 by a known method using a roll coater, a notch wheel coater, a gravure coater, an air knife coater, a die coater, a bar coater, or the like. Come on.

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 is preferably performed at 70 ° C to 150 ° C for 5 minutes to 30 minutes. The amount of the residual organic solvent in the obtained photosensitive resin layer after drying is preferably 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step.

The thickness of the photosensitive resin layer 4 in the photosensitive element 10 can be appropriately selected according to the application. The thickness after drying is preferably 1 μm to 200 μm, more preferably 5 μm to 100 μm, and even more preferably 10 μm to 50. μm. When the thickness after drying is 1 μm or more, industrial coating becomes easy. When the thickness is 200 μm or less, sufficient sensitivity and photocurability of the resist bottom tend to be obtained.

The photosensitive element 10 may further include an intermediate layer such as a buffer layer, an adhesive layer, a light absorption layer, and a gas barrier layer. As these intermediate layers, the intermediate layers described in Japanese Patent Laid-Open No. 2006-098982 and the like can also be applied to the present invention.

The form of the obtained photosensitive element 10 is not particularly limited. For example, it may be a sheet shape, or it may be a shape wound into a roll shape on a winding core. In the case where the roll is wound in a roll shape, it is preferably wound so that the support body 2 becomes the outer side. Examples of the material of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). On the end surface of the roll-shaped photosensitive element roller obtained in the manner described above, it is preferable to provide an end surface separation film in terms of the end surface protection knowledge, and in terms of resistance to edge fusion, it is preferable to provide a moisture-proof end surface Separation membrane. As a packing method, it is preferable to wrap with a black sheet with small moisture permeability.

The photosensitive element 10 can be used suitably for the formation method of the resist pattern mentioned later, for example.

<Method for Forming a Resist Pattern> A resist pattern can be formed on a substrate using the photosensitive resin composition. The method for forming a resist pattern according to this embodiment includes: (i) a photosensitive resin layer forming step, using the photosensitive resin composition, to form a photosensitive resin layer on a substrate; (ii) an exposure step, for the At least a part of the photosensitive resin layer is irradiated with actinic radiation to harden the area; and (iii) a developing step of removing unexposed portions outside the area of the photosensitive resin layer from the substrate. The method for forming a resist pattern may further include other steps as required.

(I) Step of forming photosensitive resin layer First, a photosensitive resin layer is formed on a substrate using a photosensitive resin composition. As the substrate, a substrate (a substrate for circuit formation) including an insulating layer and a conductor layer formed on the insulating layer can be used.

For example, when the photosensitive element 10 has a protective layer 6, the photosensitive resin layer is formed on the substrate by removing the protective layer 6, and then the photosensitive resin layer 4 of the photosensitive element 10 is placed in contact with the substrate. The photosensitive element 10 is pressure-bonded (laminated) to the substrate while being heated while being heated. Thereby, a laminated body including the substrate, the photosensitive resin layer 4 and the support 2 in this order was obtained.

From the viewpoint of the adhesiveness and followability of the photosensitive element 10, the lamination operation is preferably performed under reduced pressure. Heating at the time of compression bonding is preferably performed so that the temperature of the photosensitive resin layer 4 and the substrate becomes 70 ° C to 130 ° C. In addition, it is preferable to perform compression bonding at a pressure of 0.1 MPa to 1.0 MPa (1 kgf / cm ² to 10 kgf / cm ² ). These conditions can be appropriately selected as needed. In addition, if the photosensitive resin layer 4 is heated to 70 ° C. to 130 ° C., it is not necessary to perform pre-heat treatment on the substrate, but by performing pre-heat treatment on the substrate, it is possible to further improve the adhesion and Followability.

(Ii) Exposure step In the exposure step, at least a part of the area of the photosensitive resin layer 4 formed on the substrate is irradiated with actinic rays, and the exposed portion irradiated with the actinic rays is photocured to form Latent image. The method of irradiating actinic rays is, for example, a method of irradiating actinic rays in an image form through a negative or positive mask pattern. At this time, when the support 2 existing on the photosensitive resin layer 4 is transparent to actinic rays, the actinic rays can be irradiated through the support 2. When the support 2 is impermeable to actinic rays, the photosensitive resin layer 4 is irradiated with actinic rays after the support 2 is removed.

There are no particular restrictions on the source of actinic rays. Existing known light sources can be used, such as: carbon arc lamps, mercury vapor arc lamps, ultra-high pressure mercury lamps, high-pressure mercury lamps, xenon lamps, argon lasers and other gas lasers, yttrium aluminum garnet ( yttrium aluminum garnet (YAG) lasers and other solid-state lasers, semiconductor lasers, and gallium nitride-based blue-violet lasers are effective light sources that emit ultraviolet and visible light. Alternatively, direct laser exposure can be used.

The photosensitive resin composition of this embodiment can be suitably used for the direct drawing exposure method. That is, one of the preferred embodiments of the present invention is the application of the photosensitive resin composition in a direct drawing exposure method.

(Iii) Development step In the development step, the unexposed uncured portion of the photosensitive resin layer 4 is removed from the substrate by development. Thereby, a resist pattern as a cured product obtained by photocuring the photosensitive resin layer 4 is formed on the substrate. When the support 2 is present on the photosensitive resin layer 4 after exposure, the support 2 is removed, and then the uncured portion is removed (developed). The development method includes wet development and dry development, and wet development is widely used.

In the case of wet development, development is performed by a known development method using a developing solution corresponding to the photosensitive resin composition. Examples of the development method include a method using a dipping method, a liquid coating method, a spray method, brushing, slap, scrubbing, and shaking dipping. From the viewpoint of improving the resolution, a high-pressure spray method is most preferred. It is also possible to develop by combining two or more of these methods.

The configuration of the developing solution can be appropriately selected according to the configuration of the photosensitive resin composition. Examples thereof include an alkaline aqueous solution and an organic solvent developer.

When the alkaline aqueous solution is used as a developing solution, it is safe and stable, and the operability is good. The alkali of the alkaline aqueous solution can be used: alkali hydroxides such as lithium, sodium or potassium hydroxide; carbonates such as lithium, sodium, potassium or ammonium carbonate, bicarbonate; alkali metal phosphates such as potassium phosphate, sodium phosphate ; Alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, borax (sodium tetraborate), sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, ethylenediamine, 2-amino groups 2-hydroxymethyl-1,3-propanediol, 1,3-diamino-2-propanol, morpholine and the like.

The alkaline aqueous solution used for development is preferably a thin solution of 0.1 to 5% by mass of sodium carbonate, a thin solution of 0.1 to 5% by mass of potassium carbonate, and a thin solution of 0.1 to 5% by mass of sodium hydroxide. , 0.1% to 5% by mass of a dilute solution of sodium tetraborate. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11. The temperature can be adjusted in accordance with the alkali developability of the photosensitive resin composition layer.

A small amount of a surfactant, a defoaming agent, an organic solvent for promoting development, etc. may be added to the alkaline aqueous solution used in the development. Examples of the organic solvent added to the alkaline aqueous solution include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, and diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like. These organic solvents may be used alone or in combination of two or more. When the alkaline aqueous solution contains an organic solvent, the content rate of the organic solvent is preferably 2 to 90% by mass based on the total amount of the alkaline aqueous solution. The temperature can be adjusted according to the alkali developability.

Examples of the organic solvent used in the organic solvent developer include: 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamidine, cyclohexanone, methyl isobutyl Ketone, γ-butyrolactone, etc. Among these organic solvents, in order to prevent ignition, it is preferable to prepare an organic solvent developing solution by adding water in a range of 1 to 20% by mass.

The method for forming a resist pattern in this embodiment may further include the following steps: after removing the unhardened part in the developing step, heating at 60 ° C to 250 ° C or 0.2 J / cm ² to 10 J as necessary / cm ² exposure, thereby further hardening the resist pattern.

<The manufacturing method of a printed wiring board> The manufacturing method of the printed wiring board of this invention includes the process of etching or plating the board | substrate with which the resist pattern was formed by the said resist pattern formation method. Thereby, a conductor pattern is formed. The manufacturing method of a printed wiring board may include other steps, such as a resist removal step, as needed. Using the formed resist pattern as a mask, the conductor layer of the substrate is subjected to an etching process or a plating process.

In the etching process, a resist pattern formed on a substrate is used as a mask, and a conductor layer in a region not covered by the resist is removed by etching to form a conductor pattern. The etching method can be appropriately selected according to the conductor layer to be removed. Examples of the etching solution include a copper chloride solution, a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide etching solution. Among these etching solutions, a ferric chloride solution is preferably used in terms of good etch factor.

On the other hand, in the plating process, a resist pattern formed on a substrate is used as a mask, and copper, solder, or the like is plated on a conductor layer in a region not covered with the resist. After the plating process, the resist is removed, and the conductive layer in the area covered with the resist is etched to form a conductive pattern. The method of the plating treatment may be an electrolytic plating treatment or an electroless plating treatment. Examples of the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, Watt bath (nickel sulfate-chlorine Nickel plating), nickel sulfonate and other nickel plating, hard gold plating, soft gold plating and other 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 using, for example, an aqueous solution that is more alkaline than the alkaline aqueous solution used in the developing step. Examples of the strongly alkaline aqueous solution include a 1% to 10% by mass sodium hydroxide aqueous solution, and a 1% to 10% by mass potassium hydroxide aqueous solution. Among them, it is preferable to use a 1% to 10% by mass sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution, and it is more preferable to use a 1% to 5% by mass sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution.

When the resist pattern is removed after the plating process is performed, the conductive layer in the area covered by the resist is further etched by an etching process to form a conductive pattern, whereby a desired printed wiring board can be manufactured. The etching method can be appropriately selected according to the conductor layer to be removed. For example, the etchant can be applied.

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

FIGS. 2 (a) to 2 (f) are diagrams showing an example of a method for manufacturing a multilayer printed wiring board using the photosensitive element of the embodiment. The multilayer printed wiring board 100A shown in FIG. 2 (f) has a wiring pattern on the surface and inside. The multilayer printed wiring board 100A is obtained by laminating a copper-clad laminate, an interlayer insulating material, a metal foil, and the like, and appropriately forming a wiring pattern by an etching method, a semi-additive method, or the like.

First, an interlayer insulating layer 103 is formed on both surfaces of a copper-clad laminate 101 having a wiring pattern 102 on the surface (see FIG. 2 (a)). The interlayer insulating layer 103 may be formed by printing a thermosetting composition using a screen printing machine or a roll coater, or a film containing the thermosetting composition may be prepared in advance, and the film may be attached to a printed wiring using a laminator. Formed on the surface of the substrate. Next, the opening 104 is formed using a YAG laser or a carbon dioxide laser at a portion that needs to be electrically connected to the outside, and the slag (residue) around the opening 104 is removed by a sizing treatment (see FIG. 2 (b)) . Next, the seed layer 105 is formed by an electroless plating method (see FIG. 2 (c)). The photosensitive element of this embodiment is laminated on the seed layer 105 to form a photosensitive resin layer, and a predetermined portion is exposed and developed to form a resist pattern 106 (see FIG. 2 (d)). Then, the wiring pattern 107 is formed by an electrolytic plating method, and the resist pattern 106 is removed by a stripping solution. Then, the seed layer 105 is removed by etching (see FIG. 2 (e)). By repeating the above steps, a solder resist 108 is formed on the outermost surface, whereby a multilayer printed wiring board 100A can be produced (see FIG. 2 (f)).

The photosensitive resin composition of this embodiment can be used suitably for manufacture of a printed wiring board. That is, one of the preferred embodiments of the present invention is the application of the photosensitive resin composition to the production of a printed wiring board. [Example]

Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, "parts" and "%" are quality standards.

[(A) Component: Binder polymer] [Synthesis method of the binder polymer (P-1)] (Preparation of solution a-1) Polymerizable monomers (copolymerized monomers) shown in Table 1 , Monomer), 2.0 g of azobisisobutyronitrile as a radical reaction initiator was dissolved to prepare "solution a-1".

(Radical Polymerization Reaction) In a flask equipped with a reflux cooler, a thermometer, a dropping funnel, and a nitrogen introduction tube, 400 g of a mixed solution of 240 g of methyl cellulose as an organic solvent and 160 g of toluene (mass ratio is 3: 2). Nitrogen was blown into the flask, and the mixture was heated to 80 ° C. while being stirred.

In the mixed solution in the flask, the dropping rate was fixed, and after adding "solution a-1" dropwise over 4 hours, the solution in the flask was stirred at 80 ° C for 2 hours. Next, in the solution in the flask, the dropping acceleration was fixed, and a solution in which 1 g of azobisisobutyronitrile was further dissolved in 100 g of "solution a-1" was added dropwise over 10 minutes, and then the inside of the flask was dropped. The solution was stirred at 80 ° C for 3 hours. Furthermore, the solution in the flask was heated to 90 ° C. for 30 minutes, and was held at 90 ° C. for 2 hours, and then cooled to obtain a solution of a binder polymer (P-1).

Acetone was added to the solution of the binder polymer (P-1) to prepare a non-volatile content (non-volatile content) of 50% by mass. The weight average molecular weight of the binder polymer (P-1) was 55,000. The weight-average molecular weight was measured by gel permeation chromatography (GPC), and was derived by conversion using a standard polystyrene calibration curve. The conditions of GPC are as follows.

-GPC conditions-Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd.) String: 3 Gelpack GL-R420 Gelpack GL-R430 Gelpack GL-R440 (the above are manufactured by Hitachi Chemical Co., Ltd. Name) Eluent: Tetrahydrofuran Measurement temperature: 25 ° C Flow rate: 2.05 mL / min Detector: Hitachi L-3300 RI (manufactured by Hitachi, Ltd.)

[Synthesis method of the binder polymer (P-2)] (Preparation of solution a-2) In a mixed solution of polymerizable monomers (copolymerized monomers and monomers) shown in Table 1, 1.0 was dissolved. g Azobisisobutyronitrile as a radical reaction initiator to prepare "solution a-2". Then, a radical polymerization reaction was performed in the same manner as the binder polymer (P-1) to obtain a solution of the binder polymer (P-2). The weight average molecular weight of the binder polymer (P-2) was 100,000.

[Synthesis method of binder polymer (P-3)] (Preparation of solution a-3) In a mixed solution of polymerizable monomers (copolymerized monomers and monomers) shown in Table 1, 2.0 was dissolved g Azobisisobutyronitrile as a radical reaction initiator to prepare "solution a-3". Then, a radical polymerization reaction was performed in the same manner as the binder polymer (P-1) to obtain a solution of the binder polymer (P-3). The weight average molecular weight of the binder polymer (P-3) was 55,000.

[Preparation of photosensitive resin composition] In the solution of the obtained adhesive polymer, the components (B), (C), and (D) were blended at the blending amounts (g) shown in Table 2 below. And other components, and 8 g of acetone, 8 g of toluene, and 8 g of methanol, to prepare solutions of the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6, respectively. In addition, the compounding quantity of the binder polymer shown in Table 2 is the mass (non-volatile content) of a non-volatile component.

The details shown in Table 2 are as follows. <(A) Ingredient: Binder polymer> P-1: Binder polymer prepared as described above: methacrylic acid / benzyl methacrylate (24/76 (mass ratio)) copolymer, weight average molecular weight Methyl cellosolve solution of 55,000, acid value of 157 mgKOH / g, and nonvolatile content of 50% by mass / toluene = 6/4 (mass ratio).

· P-2: The prepared binder polymer: a copolymer of methacrylic acid / methyl methacrylate / 2-ethylhexyl acrylate (25/50/25 (mass ratio)), the weight average molecular weight is A solution of 100,000 methyl acid cellosolve / toluene = 6/4 (mass ratio) with an acid value of 163 mgKOH / g and a non-volatile content of 50% by mass.

P-3: Copolymer of methacrylic acid / benzyl methacrylate (31/69 (mass ratio)), a weight average molecular weight of 55,000, an acid value of 202 mgKOH / g, and a non-volatile content of 50% by weight of formazan Base cellosolve / toluene = 6/4 (mass ratio) solution.

<(B) component: Photopolymerizable compound> FA-321M: Bisphenol A polyoxyethylene dimethacrylate (made by Hitachi Chemical Co., Ltd., product name), and molecular weight is 804. · FA-2200M: polyethylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name), with a molecular weight of 2116. · FA-P2200M: Polypropylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name), with a molecular weight of 2137. · UA-HCY-19: Carbamate reactant of hexamethylene diisocyanate terpolymer and polyethylene oxide methacrylate (made by Shin Nakamura Chemical Industry Co., Ltd., product name) 2522. · FA-137M: Trimethylolpropane polyethylene oxide trimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name), with a molecular weight of 1259.

<(C) component: Photopolymerization initiator> N-1717: 1,7-bis (9-acridyl) heptane (manufactured by ADEKA Co., Ltd., product name). EAB: 4,4'-bis (diethylamino) benzophenone (manufactured by Hodogaya Chemical Industry Co., Ltd., product name). B-CIM: 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-2H-imidazol-2-yl] -4,5-di Phenyl-1H-imidazole (manufactured by Hodogaya Chemical Industry Co., Ltd., product name).

<(D) component: Polytetramethylene oxide compound>-FA-PTG28M: Polytetramethylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name), molecular weight is 2170, which is equivalent to (B) Ingredients. FA-PTG9M: Polytetramethylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name), with a molecular weight of 802, which is equivalent to component (B). A-PTMG650: polytetramethylene glycol diacrylate (made by Shin Nakamura Chemical Co., Ltd., product name). The molecular weight is 774, which corresponds to the component (B). PTMG-2000: Polytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, product name), molecular weight 2034.

＜ Other ingredients ＞ · LCV: leuco crystal violet (manufactured by Yamada Chemical Co., Ltd., product name) · MKG: malachite green (manufactured by Osaka Organic Chemical Industry Co., Ltd., product name)

[Production of Photosensitive Element] The photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6 were each applied to polyparaphenylene terephthalate having a thickness of 16 μm so that the thickness became uniform. Ethylene formate film (manufactured by Teijin Co., Ltd., trade name "G2-16") (support) was dried with a hot air convection dryer at 100 ° C for 10 minutes to form a dried film with a thickness of 30 μm. Photosensitive resin layer. On the photosensitive resin layer, a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name "NF-13") (protective layer) was laminated by roller pressing to obtain successively laminated layers. The photosensitive elements of Examples 1 to 10 and Comparative Examples 1 to 6 of the support, the photosensitive resin layer, and the protective layer.

[Production of laminated substrate for evaluation] Next, a 1.6 mm thick copper-clad laminated board (made by Hitachi Chemical Co., Ltd., including Hitachi Chemical Co., Ltd.) including a glass epoxy material and copper foils (thickness: 35 μm) formed on both sides thereof was manufactured. "MCL-E-67") was used to polish the copper surface using a grinder (manufactured by Sanki Co., Ltd.) with a brush equivalent to # 600, and after washing with water, it was dried with an air stream. After heating this copper clad laminated board (hereinafter referred to as "substrate") to 80 ° C, the photosensitive elements of Examples 1 to 10 and Comparative Examples 1 to 6 were laminated (laminated) on the substrate. Laminated substrates for evaluation were produced on the copper surfaces on both sides. Using a 110 ° C. heating roller, while removing the protective layer, the photosensitive resin layer of each photosensitive element was brought into close contact with each copper surface of the substrate, and laminated at a speed of 1.5 m / min. The heating roll pressure during lamination was set to 0.4 Mpa.

[Evaluation of sensitivity] The obtained laminated substrate for evaluation was left to cool to 23 ° C. Then, a photo tool having a step tablet was closely adhered to the support on the surface of the evaluation laminated substrate. The ladder plate is a 41-step ladder plate with a concentration range of 0.00 to 2.00, a concentration step of 0.05, a plate size of 20 mm × 187 mm, and a step size of 3 mm × 12 mm. The photosensitive resin layer is exposed through a light tool having such a ladder plate and a polyethylene terephthalate film. Using an exposure machine using a semiconductor-excited solid laser as a light source (manufactured by Orbotech Co., Ltd., trade name "Paragon-9000m"), exposure was performed at an exposure of 17 mJ / cm ² .

After the exposure, the support was peeled from the multilayer substrate for evaluation to expose the photosensitive resin layer. The exposed photosensitive resin layer was sprayed (developed) with a 1.0 mass% sodium carbonate aqueous solution at 30 ° C. for 50 seconds, thereby removing unexposed portions. In this manner, a cured film containing a cured product of a photosensitive resin composition was formed on the copper surface of the multilayer substrate for evaluation. The sensitivity (photosensitivity) of the photosensitive resin composition of Examples 1 to 10 and Comparative Examples 1 to 6 and the photosensitive element obtained by measuring the number of steps of the obtained stepped plate of the cured film was measured. ) For evaluation. The higher the number of steps of the ladder plate, the higher the sensitivity. The results are shown in Table 2.

[Evaluation of Adhesiveness and Analyzability] The following optical tool materials were used on the evaluation multilayer substrate, respectively, which had a line width / space width of n / 400 (unit: μm, n = 5 μm to 200 μm, and 2.5 μm interval) for evaluation of adhesion, and line / space width of 400 / n (unit: μm, n = 5 μm to 200 μm and 2.5 μm interval) evaluation pattern for analytical evaluation use. Using an exposure machine using a semiconductor-excited solid laser as a light source (manufactured by Orbotech Co., Ltd., trade name "Paragon-9000m"), exposure was performed at an exposure of 17 mJ / cm ² . Then, the development process was performed on the same conditions as the evaluation of the said light sensitivity, and the unexposed part was removed. The adhesiveness was evaluated based on the minimum value (unit: μm) of the width of the line region where the cured film remained by the development process. The resolution was evaluated based on the minimum value (unit: μm) of the width of the space between the line regions that can completely remove the non-light-cured portion by the development process. Both the adhesion and the evaluation of the evaluation were good values as the numerical value was smaller. The results are shown in Table 2.

[Peelability Evaluation] On the laminated substrate for evaluation, exposure was performed by using a cured film having a rectangular shape of 45 mm × 65 mm as an optical tool material for the evaluation of peelability. Using an exposure machine using a semiconductor-excited solid laser as a light source (manufactured by Orbotech Co., Ltd., trade name "Paragon-9000m"), exposure was performed at an exposure of 17 mJ / cm ² . Then, the development process was performed on the same conditions as the evaluation of the said light sensitivity, and the unexposed part was removed. Then, 300 ml of a 50 ° C, 3.0% by mass NaOH aqueous solution (peeling solution) was prepared in a 400 ml beaker. While the peeling liquid was stirred at 200 rpm using a stirrer having a length of 30 mm, the developed substrate was immersed in the peeling liquid, and the time (unit: second) until the cured film was detached from the substrate was measured. In addition, the earlier the time until the cured film is detached from the substrate, the shorter the peeling time, and the better the peelability was evaluated. The results are shown in Table 2.

[Etching resistance] For a 1.6 mm thick copper-clad laminate (made by Hitachi Chemical Co., Ltd.) including a glass epoxy material and copper foils (thickness: 100 μm) formed on both sides thereof (trade name "MCL-E- 67 ″), the copper surface was polished using a grinder (manufactured by Sanki Co., Ltd.) having a brush equivalent to # 600, and after washing with water, it was dried with an air stream. After heating this copper clad laminated board (hereinafter referred to as "substrate") to 80 ° C, the photosensitive elements of Examples 1 to 10 and Comparative Examples 1 to 6 were laminated (laminated) on the substrate. Laminated substrates for evaluation were produced on the copper surfaces on both sides. Then, the steps up to the development process are performed in the same manner as the method for producing the substrate for evaluation of adhesion and resolvability. Then, the etching is performed at twice the shortest etching time. The copper pattern was observed by immersing in a 3.0 mass% NaOH aqueous solution at 50 ° C, peeling off the resist. A case where the etching was performed linearly along the resist pattern before peeling was taken as “○”, and when a difference between the contour of the resist pattern before peeling and the obtained copper pattern was observed from the upper surface of the substrate, A case where a line of 5 μm or more is missing (the disappearance of the line area) or the line is rough (a change in the width of the line area) is regarded as “×”. The case where the line was rough but was less than 5 μm was set to “Δ”. The "minimum etching time" is a value measured in the following manner. First, the copper-clad laminated board was cut into a size of 30 mm × 30 mm as a test piece. A 5 mol / L copper chloride solution at 50 ° C was used to spray the test piece at a pressure of 0.15 MPa, and the shortest time that can be visually confirmed that the copper layer of the copper clad laminate was removed was taken as the shortest etching time.

[Capping Hole Reliability] A substrate 40 for measuring the number of hole cracks as shown in FIG. 3 was prepared as follows, and the covering hole reliability was evaluated using this substrate 40. On a copper-clad laminated board (manufactured by Hitachi Chemical Co., Ltd. under the trade name "MCL-E-67"), a demolding machine was used to make three independent circular holes 41 and 6 in diameter, respectively, and The three continuous holes 42 are connected with three circular holes and the interval between the circular holes is gradually shortened. A grinder (manufactured by Sankai Co., Ltd.) having a brush equivalent to # 600 was used to remove burrs generated when the circular holes 41 and the triple holes 42 were made, and this was used as the substrate 40 for measuring the number of hole breaks.

The obtained substrate for measuring the number of hole cracks was heated to 80 ° C, the protective layer was peeled from the photosensitive elements of Examples 1 to 10 and Comparative Examples 1 to 6, and the number of cracks of the photosensitive resin layer and the holes was measured. The copper substrates of the substrate 40 were arranged so as to face each other, and were laminated under the conditions of 120 ° C. and 0.4 MPa, respectively, and laminated substrates for reliability evaluation of the via hole were produced.

After lamination, the laminated substrate for lid hole reliability evaluation was left to cool to 23 ° C. Next, an exposure machine using a semiconductor-excited solid laser as a light source was used from above the support of the photosensitive element (manufactured by Orbotech Co., Ltd., trade name "Paragon-9000m") Exposure was performed at an exposure amount of 17 mJ / cm ² .

After exposure, it was left at room temperature for 15 minutes, and then the support was peeled from the laminated substrate for lid hole reliability evaluation, and a 1% by mass sodium carbonate aqueous solution at 30 ° C. was sprayed for 50 seconds to develop. After development, the number of hole breaks of the triple hole was measured, and the deformation cap hole breakage rate was calculated as the number of hole breaks with respect to the total number of triple holes, and the cover hole reliability (%) was evaluated. The higher the value, the higher the reliability of the cover hole. The results are shown in Table 2.

As shown in the above evaluation results, when the photosensitive elements of Examples 1 to 10 using the photosensitive resin composition of the present invention are used, and when the photosensitive elements of Comparative Examples 1 to 6 are used, In comparison, they all showed good adhesion, resolvability, etching resistance, peelability, and excellent cap hole reliability. The photosensitive element of the comparative example had the same light sensitivity as the photosensitive element of the example, but had poor etching resistance. Furthermore, the cap hole reliability of Comparative Example 1, Comparative Example 3, and Comparative Example 6 was poor, and the peelability of Comparative Example 5 was poor.

The disclosure of Japanese Patent Application No. 2014-099630 is incorporated herein by reference in its entirety. All documents, patent applications, and technical specifications described in this specification are incorporated by reference to the same extent as when each document, patent application, and technical specification is specifically and individually described to be incorporated by reference. In this manual.

2‧‧‧ support

4‧‧‧ photosensitive resin layer

6‧‧‧ protective layer

10‧‧‧ Photosensitive Element

40‧‧‧ substrate for measuring the number of hole breaks

41‧‧‧ round hole

42‧‧‧Three holes

100A‧‧‧Multilayer printed wiring board

101‧‧‧ Copper-clad laminate

102‧‧‧wiring pattern

103‧‧‧Interlayer insulation

104‧‧‧ opening

105‧‧‧seed layer

106‧‧‧ resist pattern

107‧‧‧wiring pattern

108‧‧‧solder resist

FIG. 1 is an end view showing an embodiment of a photosensitive element according to the present invention. FIGS. 2 (a) to 2 (f) are process diagrams showing an example of a method for manufacturing a multilayer printed wiring board using the photosensitive element of the present invention. FIG. 3 is a plan view of a substrate for measuring the number of hole cracks used in the evaluation of the reliability of a cap hole.

Claims (10)

A photosensitive resin composition comprising: (A) component: binder polymer; (B) component: photopolymerizable compound; (C) component: photopolymerization initiator; and (D) component: polytetrahyd A methyl oxide compound having [-(C ₄ H ₈ O) _n- : n is a number of 2 or more] as a structural unit, and may be equivalent to a component selected from the group consisting of (A) component, (B) component and (C) component Part or all of at least one of the group consisting of; and the acid value of the nonvolatile matter of the photosensitive resin composition is less than 120 mgKOH / g, and the component (D) is represented by the following general formula (IV) Structural units:

In the above formula (IV), n is a number of 2 or more. The photosensitive resin composition as described in item 1 of the patent application range, wherein the weight average molecular weight of the polytetramethylene oxide compound is 1,000 or more. The photosensitive resin composition as described in item 1 or 2 of the patent application, wherein part or all of the component (B) is a polytetramethylene oxide compound. The photosensitive resin composition as described in Item 3 of the patent application range, wherein the content of the polytetramethylene oxide compound in the total amount of the component (B) is 20% by mass to 50% by mass. The photosensitive resin composition as described in item 3 of the patent application scope, wherein the polytetramethylene oxide compound as a part or all of the component (B) is polytetramethylene glycol bis (methyl) Acrylate. The photosensitive resin composition as described in item 4 of the patent application scope, wherein the polytetramethylene oxide compound as part or all of the component (B) is polytetramethylene glycol bis (methyl) Acrylate. The photosensitive resin composition as described in item 5 of the patent application range, wherein the polytetramethylene glycol di (meth) acrylate is polytetramethylene glycol dimethacrylate. A photosensitive element comprising: a support; and a photosensitive resin layer formed on the support using the photosensitive resin composition as described in any one of patent application items 1 to 7. A method for forming a resist pattern, comprising: a photosensitive resin layer forming step using the photosensitive resin composition as described in any one of patent application items 1 to 7 or as claimed in patent application item 8 The photosensitive element described in the item, a photosensitive resin layer is formed on the substrate; an exposure step, irradiating at least a part of the photosensitive resin layer with actinic rays to harden the area; The unexposed portion outside the region of the sexual resin layer is removed from the substrate. A method for manufacturing a printed wiring board includes the steps of etching or plating a substrate on which a resist pattern is formed by the method for forming a resist pattern as described in item 9 of the patent application.