TW201544904A - Photosensitive resin composition, photosensitive element, method of forming resist pattern and method of producing printed circuit board - Google Patents

Abstract

A photosensitive resin composition that comprises component (A): a binder polymer, component (B): a photopolymerizable compound, component (C): a photopolymerization initiator and component (D): a polytetramethylene oxide compound that has [(C4H8O)n-: n is a number of 2 or greater] as a structural unit, wherein an acid value of non-volatile components of the photosensitive resin composition is less than 120 mgKOH/g.

Description

Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing printed wiring board

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

In the field of the production of printed wiring boards, the resist material used in the etching treatment or the plating treatment, the photosensitive resin composition, and the photosensitive resin layer and the support obtained by using the photosensitive resin composition, The photosensitive element of the protective layer is widely used.

The printed wiring board is produced by laminating the photosensitive element on a circuit-forming substrate, exposing the photosensitive resin layer to a pattern, and removing the unexposed portion by a developing solution to form a resist. After the etching process or the plating treatment is performed to form a circuit on the substrate, the cured portion as the exposed portion is peeled off from the substrate and removed.

As the developer, an alkali developer such as a sodium carbonate aqueous solution or a sodium hydrogencarbonate aqueous solution is in the mainstream in terms of environmental and safety. The unexposed portion of the photosensitive resin layer is removed from the substrate by development of the developing solution and ejection pressure of the 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 ejection pressure of development and washing after exposure, and has excellent tenting reliability (covering) 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, when the flexibility of the cured film is improved by using a conventional material having high hydrophilicity, there is a problem that the resolution due to a decrease in alkali resistance of the cured film is lowered and the etching is deepened due to a decrease in etching resistance. For example, there is still room for improvement in analyticity, etch resistance, and cap hole reliability for the following reasons: the sensitization described in JP-A-61-228007 and JP-A-2013-83785 In the case of the resin composition, the acid value of the photosensitive resin composition is also inappropriate; the molecular weight of the photopolymerizable compound is not appropriate.

Further, recently, as a method of directly drawing a pattern created by computer-aided design (CAD) using laser light, it is strongly desired to correspond to laser direct imaging (LDI). )the way. However, from the viewpoint of throughput, the resist material used in the LDI method required to be used at a lower exposure amount requires low exposure amount and alkali resistance and etching resistance at low hardening degree. Therefore, the material of the rigid skeleton is used. Therefore, it is disadvantageous in terms of the reliability of the cap hole required for the flexibility of the cured film, and the resist used in the LDI method has not yet been developed to have high throughput, high resolution, etching resistance, and high capping. Reliable resist. For example, Japanese Patent Laid-Open No. Hei. 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 photosensitive resin composition described, there is room for improvement in the resolution of the obtained resist, the reliability of the cap hole, and the etching resistance.

[Problems to be solved by the invention]

Accordingly, an object of the present invention is to provide a photosensitive resin composition which can form a resist pattern even at a low exposure amount, and which is excellent in cap hole reliability and etching resistance of the formed cured film. Further, an object of the present invention is to provide a photosensitive element using the photosensitive resin composition, a method of forming a resist pattern, and a method of producing a printed wiring board. [Means for solving the problem]

The specific means for solving the above problems include the following embodiments. <1> A photosensitive resin composition comprising: (A) component: a binder polymer; (B) component: a photopolymerizable compound; (C) component: a photopolymerization initiator; and (D) component: The polytetramethylene 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 being selected from the group consisting of (A) component, (B) component, and C) A part or all of at least one of the groups consisting of the components; and the acid value of the nonvolatile matter of the photosensitive resin composition is less than 120 mgKOH/g.

The photosensitive resin composition as described in <1>, wherein the polytetramethylene oxide compound has a weight average molecular weight of 1,000 or more.

The photosensitive resin composition as described in <1>, wherein a part or all of the (B) component is a polytetramethylene oxide compound.

The photosensitive resin composition as described in <3>, 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 <3>, wherein the polytetramethylene oxide compound which is a part or all of the component (B) is polytetramethylene glycol (Meth) acrylate.

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

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

(8) A method of 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 as described in <7> a photosensitive element forming a photosensitive resin layer on a substrate; an exposure step of irradiating at least a portion of the photosensitive resin layer with actinic rays to harden the region; and a developing step of applying the photosensitive resin layer Unexposed portions outside of the region are removed from the substrate.

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

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

Hereinafter, embodiments for carrying out the invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments. In the drawings, the same elements are denoted by the same reference numerals, and the repeated description is omitted. In addition, the dimensional ratio of the drawings is not limited to the illustrated ratio.

In the present specification, the term "(meth)acrylic acid" means at least one of "acrylic acid" and "methacrylic acid", and the term "(meth)acrylate" means "acrylate" and the corresponding "methyl group". At least one of "acrylate" means "(meth)acryloyl group" means at least one of "acryloyl group" and "methacryloyl group". The term "polytetramethylene oxide" means 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, an integer value is represented for a single molecule, but as an aggregate of a plurality of molecules, a rational number as an average value is represented. The term "non-volatile matter" means a component in a composition other than a substance such as water or a volatile substance such as an organic solvent to be described later. Here, the substance to be volatilized means a substance having a boiling point of 155 ° C or less at atmospheric pressure. "Total amount of (A) component" and "Total amount of component (B)" mean the total amount of only non-volatile matter.

The term "step" in the present specification is used not only to include independent steps, but also to distinguish between other steps, and to achieve the desired purpose of the steps, it is also included in the term. In addition, the numerical range represented by "~" indicates the range including the numerical values described before and after "~" as the minimum value and the maximum value. Further, when a plurality of substances corresponding to the respective components are present in the composition, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless otherwise specified. Further, in the numerical range described step by step in the present specification, the upper limit value or the lower limit value of the numerical range of a certain stage may be replaced with the upper limit value or the lower limit value of the numerical range of the other stage. Further, in the numerical ranges described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples. The term "layer" includes a configuration of a shape formed on the entire surface when viewed as a plan view, and a configuration of a shape formed on a part. The term "layered" 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 the present embodiment contains: (A) component: a binder polymer; (B) component: a photopolymerizable compound; (C) component: a photopolymerization initiator; (D) component: a polytetramethylene oxide [-(C ₄ H ₈ O) _n -: n is a number of 2 or more] as a structural unit and may correspond to a component selected from (A) component and (B) component. And a part or all of the compound of at least one of the group consisting of the component (C); and the acid value of the nonvolatile matter of the photosensitive resin composition is less than 120 mgKOH/g. The photosensitive resin composition may further contain other components as needed.

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 not volatile. The acid value of the fraction is less than 120 mgKOH/g, and a photosensitive resin composition which can form a resist pattern even at a low exposure amount and has a lid hole reliability and etching resistance of the formed cured film can be formed. The inventors of the present invention presume the following.

The polytetramethylene oxide compound has a highly flexible polytetramethylene oxide as a structural unit. Therefore, moderate flexibility is imparted to the formed resist pattern by using a photosensitive resin composition containing a polytetramethylene oxide compound. Therefore, it is considered that stress concentration is less likely to occur inside the resist pattern, and the reliability of the cap hole is improved. Further, the structural unit of the polytetramethylene oxide possessed by 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 resist pattern formed is improved in acid resistance and excellent in etching resistance.

Further, it is considered that the acid value of the nonvolatile matter of the photosensitive resin composition is less than 120 mgKOH/g, and the photosensitive resin composition having excellent developer resistance is formed, and the reliability and corrosion resistance of the formed cured film are improved. Excellent in engraving. Further, there is a tendency that a resist pattern excellent in resolution and adhesion can be formed.

The acid value of the nonvolatile matter of the photosensitive resin composition can be measured by the following method. First, after accurately measuring 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 0.1 N aqueous KOH solution. Then, based on the titration result, the acid value is calculated from the following formula (1) (wherein Vf represents a titer (mL) of phenolphthalein, and Wp represents a weight of a solution of the photosensitive resin composition as the component (A) (g I represents the ratio (% by mass) of the nonvolatile content of the solution of the photosensitive resin composition as the component (A). Acid value (mgKOH/g) = 10 × Vf × 56.1 / (Wp × I) (1)

The acid value of the nonvolatile content of the photosensitive resin composition is preferably 110 mgKOH/g or less, and more preferably 100 mgKOH/, from the viewpoint of further improving the reliability of the cap hole of the resist pattern and the etching resistance. g below. Further, from the viewpoint of developability of the resist pattern, it is preferably 40 mgKOH/g or more. Further, from the viewpoint of the peeling time, it is more preferably 80 mgKOH/g or more, and particularly preferably 90 mgKOH/g or more. Hereinafter, each component will be described in detail.

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

Structural unit (A1) At least one of the binder polymers preferably comprises a group selected from the group consisting of styrene, styrene derivatives, benzyl (meth) acrylate and benzyl (meth) acrylate derivatives. A structural unit (A1) derived from at least one of them. Thereby, not only the flexibility of the (A) binder polymer but also the adhesion at the time of forming a cured product can be maintained.

In view of the good adhesion between the cured film and the peeling property, the content of the structural unit (A1) in the binder polymer is preferably 10% by mass in the total amount of the component (A). 60% by mass, more preferably 13% by mass to 40% by mass, even more preferably 15% by mass to 25% by mass. When the content of the structural unit (A1) is 10% by mass or more, the adhesion of the cured film tends to be improved. When the content is 60% by mass or less, the release sheet can be prevented from becoming large, and the peeling time can be suppressed from becoming long. The tendency of the cover hole to be improved.

Specific examples of the styrene derivative include a polymerizable styrene derivative substituted with an α-position or an aromatic ring such as α-methylstyrene, vinyltoluene or p-chlorostyrene. 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) In terms of the reliability of the cover hole of the cured film, at least one of the binder polymers preferably 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 alkyl group preferably has 1 to 20 carbon atoms, more preferably 5 to 20 carbon atoms, and particularly preferably 8 to 14 carbon atoms. The alkyl (meth)acrylate may, for example, be a compound represented by the following formula (I).

CH ₂ =C(R ³ )-COOR ⁴ (I)

In the 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 formula (I) 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, and a decyl group. Mercapto, undecyl, dodecyl and structural isomers of such alkyl groups. The alkyl group having 1 to 20 carbon atoms represented by R ⁴ may be unsubstituted or may have a substituent. The substituent may, for example, be a hydroxyl group, an epoxy group, a halogen group or the like. When the alkyl group having 1 to 20 carbon atoms represented by R ⁴ has a substituent, the number of substituents and the position of substitution are not particularly limited.

The alkyl group represented by R ⁴ in the formula (I) is more preferably a carbon number of 5 to 20, and particularly preferably a carbon number of 8 to 14 from the viewpoint of further improving the reliability of the lid hole of the cured film.

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

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

Structural unit (A3) In terms of alkali developability, at least one of the binder polymers preferably contains a structural unit (A3) derived from a polymerizable monomer having a carboxyl group. The binder polymer containing the structural unit (A3) can be produced, for example, by radically polymerizing a polymerizable monomer having a carboxyl group with another polymerizable unit.

Examples of the polymerizable monovalent body 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 (A). Acrylic acid derivative; maleic acid; maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monoisopropyl ester, etc. maleic acid derivative; Alkenoic acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like. As for the improvement of the sensitivity, (meth)acrylic acid is preferable, and methacrylic acid is more preferable.

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 preferably in terms of the balance between the alkali developability and the developer resistance. It is more preferably 15% by mass to 35% by mass, and particularly preferably 15% by mass to 30% by mass, in terms of more excellent alkali developability, in the range of 12% by mass to 50% by mass.

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

The content of the other structural unit in the total amount of the component (A) is preferably 10% by mass or less, and more preferably 5% by mass or less, from the viewpoint of the adhesion, the characterization, and the developability of the cured film. It is preferably not contained (for example, 0.5% by mass or less). In other words, the total content of the structural unit (A1), the structural unit (A2), and the structural unit (A3) in the total amount of the component (A) is preferably 90% by mass or more, more preferably 95% by mass or more. It is preferably 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. The polymerization method can be exemplified by radical polymerization. In the case where the binder polymer is a copolymer obtained by polymerizing two or more kinds of monoliths, each structural unit in the copolymer may be randomly contained in the copolymer as a so-called random copolymer. It may also be a copolymer of structural units which are formed by continuously including the same kinds of single-quantity as a block copolymer. Moreover, each structural unit may be of a single type or a plurality of types.

In view of the balance between development resistance and alkali developability, the weight average molecular weight of the binder polymer is preferably from 20,000 to 300,000, more preferably from 30,000 to 200,000, still more preferably from 40,000 to 100,000. The weight average molecular weight in the present specification is a value obtained by conversion by a gel permeation chromatography method under the same measurement conditions as those described in the examples, and based on a standard curve prepared using standard polystyrene.

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

The binder polymer contained in the component (A) may be used alone or in combination of two or more. Examples of the combination of two or more kinds of the 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 dispersity. A combination of two or more different binder polymers. Further, 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 containing at least one of the structural unit (A1), the structural unit (A2), or the structural unit (A3), and does not include the structural unit (A1) and 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 aqueous alkali solution and can form a film. For example, an acrylic resin (but not including a structural unit (A1), a structural unit (A2), and a structural unit (A3)), an epoxy resin, a guanamine resin, a guanamine epoxy resin, and an alkyd are mentioned. A resin and a phenol resin. Among them, from the viewpoint of alkali developability, an acrylic resin is preferred. These resins may be used alone or in combination of two or more.

In the case where the component (A) contains another binder polymer which does not contain any of the structural unit (A1), the structural unit (A2) or the structural unit (A3), the structure in the total amount of the component (A) The content of the unit (A1) is preferably from 10% by mass to 60% by mass, more preferably from 13% by mass to 40% by mass, even more preferably from 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 especially preferred that substantially no other binder polymer is included (for example, 0.5% by mass or less), and it is particularly preferable to completely exclude other binder polymers.

The content of the component (A) in the photosensitive resin composition is preferably from 30 parts by mass to 70 parts by mass, more preferably 40%, based on 100 parts by mass of the total of the components (A) and (B). The mass fraction is preferably 65 parts by mass, and more preferably 50 parts by mass to 60 parts by mass. When the content of the component (A) is within this range, the coating property of the photosensitive resin composition and the strength of the cured film tend to be better.

[Component (B): Photopolymerizable Compound] The photosensitive resin composition contains at least one of photopolymerizable compounds as the component (B). The photopolymerizable compound as the component (B) is not particularly limited, and can be appropriately selected from the photopolymerizable compounds which are usually used. The photopolymerizable compound may, for example, be a compound having an unsaturated double bond capable of photopolymerization. The unsaturated double bond which can be photopolymerized includes a double bond contained in a (meth) acrylonitrile group.

Specific examples of the photopolymerizable compound include polyalkylene glycols such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polyethylene polypropylene glycol di(meth)acrylate. (meth) acrylate; polyfunctional (meth) acrylate such as trimethylolpropane tri(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; , 2-bis(4-((meth)propenyloxy)oxy)phenyl)propane, 2,2-bis(4-((methyl)propenyloxy)oxypolyoxyloxy Bisphenol A (meth) acrylate compound such as phenyl)propane; γ-chloro-β-hydroxypropyl-β'-(meth) propylene oxime extended ethyl-o-phthalic acid Ester, β-hydroxyethyl-β'-(meth) propylene oxime extended ethyl-o-phthalate, β-hydroxypropyl-β'-(methyl) propylene oxime extended ethyl a phthalic acid derivative such as o-phthalate; an alkyl (meth) acrylate or the like.

Among these compounds, the photopolymerizable compound preferably contains a bisphenol A-based (meth) acrylate compound and a polyalkylene glycol poly (meth) acrylate from the viewpoint of adhesion and resolution. At least one of the constituent groups is more preferably a combination of at least one of a bisphenol A-based (meth) acrylate compound and a polyalkyl diol poly(meth) acrylate, and more preferably 2 At least one of 2-bis(4-((meth)acryloxyethoxy)oxy)phenyl)propane and at least one of polyethylene glycol poly(meth)acrylates are used in combination.

2,2-bis(4-((meth)acryloxycarbonyloxy)phenyl)propane, for example, 2,2-bis(4-((methyl) propylene oxy) Benzyl)phenyl)propane, 2,2-bis(4-((meth)propenyloxypentaethyloxy)phenyl)propane, 2,2-bis(4-((methyl) Propylene methoxy oxe pentaethyloxy)phenyl)propane and the like.

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

When a photopolymerizable compound as the component (B) is used in combination, the content of a compound having two or more photopolymerizable unsaturated double bonds in one molecule of the total amount of the component (B) The rate is preferably 75 mass% or more. The content of the compound having two or more photopolymerizable unsaturated double bonds in one molecule of the total amount of the component (B) is 75% by mass or more, and the cap hole reliability and resolution of the cured film are present. And the tendency to further improve the adhesion.

The content of the component (B) in the photosensitive resin composition is preferably from 20 parts by mass to 70 parts by mass per 100 parts by mass of the total of the components (A) and (B). In the total amount of the component (A) and the component (B), the content of the component (B) is preferably 20 parts by mass or more, from the viewpoint of further improving the reliability and the analytical property of the cap hole of the cured film. More preferably, it is 25 mass parts or more, More preferably, it is 30 mass parts or more. From the viewpoint of imparting good film properties to the photosensitive resin composition and improving the shape of the resist after curing, the total amount of the components (A) and (B) is 100 parts by mass, (B) The content of the component is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 55 parts by mass or less, and particularly preferably 50 parts by mass or less.

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

The (C1) compound is, for example, an acridine compound represented by the following formula (II).

[Chemical 1]

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

Examples of the compound represented by the above formula (II) include 1,2-bis(9-acridinyl)ethane, 1,3-bis(9-acridinyl)propane, and 1,4-di ( 9-Acridine)butane, 1,5-bis(9-acridinyl)pentane, 1,6-bis(9-acridinyl)hexane, 1,7-di(9-acridinyl) Heptane, 1,8-bis(9-acridinyl)octane, 1,9-bis(9-acridinyl)decane, 1,10-bis(9-acridinyl)decane, 1 ,11-bis(9-acridinyl)undecane, 1,12-bis(9-acridinyl)dodecane, 1,14-bis(9-acridinyl)tetradecane, 1,16 - bis(9-acridinyl)hexadecane, 1,18-bis(9-acridinyl)octadecane, 1,20-di(9-acridinyl)eicosane, etc. Pyridyl)alkane; 1,3-bis(9-acridinyl)-2-oxopropane; 1,5-bis(9-acridinyl)-3-oxapentane, etc. Oxahydroalkane; 1,3-bis(9-acridinyl)-2-thiahydropropane; 1,5-bis(9-acridinyl)-3-thiapentane, etc. Pyridyl) thioalkane and the like. These compounds may be used alone or in combination of two or more.

In view of the better understanding of light sensitivity and resolution, it is preferred to include an acridine compound in which R ³ in the formula (II) is a heptyl group (for example, manufactured by ADEKA Co., Ltd., product name) "N-1717") is a compound of (C1).

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

The (C2) compound is, for example, an acridine compound represented by the following formula (III).

[Chemical 2]

In the 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 of 0 to 5. When m is 2 or more, a plurality of R ^{4 's} may be the same or different.

Examples of the acridine compound represented by the above formula (III) include 9-phenyl acridine, 9-(p-methylphenyl) acridine, 9-(m-methylphenyl)acridine, and 9- (p-chlorophenyl) acridine, 9-(m-chlorophenyl)acridine, 9-aminoacridine, 9-dimethylaminoacridine, 9-diethylamino acridine and 9-pentyl Amino acridine. These compounds may be used alone or in combination of two or more.

In the case where the photosensitive resin composition contains the (C2) compound as a photopolymerization initiator, the total of the components (A) and (B) in terms of sensitivity, resolution, and adhesion. The content of the (C2) compound may be, for example, 0.1 parts by mass to 10 parts by mass, 0.5 parts by mass to 5 parts by mass, or 1 part by mass to 3 parts by mass, preferably 0.1 part by mass to 1.4 parts by mass, based on 100 parts by mass, It is more preferably 0.3 parts by mass to 1.2 parts by mass, particularly preferably 0.4 parts by mass to 0.7 parts by mass, particularly preferably 0.5 parts by mass to 0.6 parts by mass. When the content of the (C2) compound is 0.1 part by mass or more, it is likely to have better sensitivity, resolution, or adhesion. When it is 1.4 parts by mass or less, there is a tendency to obtain a more favorable resist shape.

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

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- 1 aryl ketone compound; 2-ethyl hydrazine, phenanthrenequinone, 2-tert-butyl fluorene, octamethyl hydrazine, 1,2-benzopyrene, 2,3-benzo Bismuth, 2-phenylindole, 2,3-diphenylanthracene, 1-chloroindole, 2-methylindole, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl Anthraquinone compounds such as 1,4-naphthoquinone and 2,3-dimethylhydrazine; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin and 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- 2,4,5-triarylimidazole dimer such as diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer; benzyldimethyl shrinkage a benzyl derivative such as a ketone; 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10 a substituted hydrazine compound such as dipentyloxy hydrazine; a coumarin compound; an oxazole compound; a pyrazoline compound; a triarylamine compound. These photopolymerization initiators may be used alone or in combination of two or more. Further, a thioxanthone compound and a tertiary amine compound may be combined as a photopolymerization initiator in combination with diethyl thioxanthone and dimethylaminobenzoic acid.

Further, the 2,4,5-triarylimidazole dimer may be the same and symmetric compound of the substituents of the aryl groups of the two 2,4,5-triarylimidazoles constituting the dimer, or may be each other Different and asymmetric compounds.

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

The content of the component (C) is preferably from 0.01 part by mass to 20% by mass based on 100 parts by mass of the total of the components (A) and (B) from the viewpoint of the sensitivity, the adhesion, and the internal photocurability. It is more preferably 0.05 parts by mass to 10 parts by mass, particularly preferably 0.1 parts by mass to 5 parts by mass.

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

[Component (D): Polytetramethylene oxide compound] The photosensitive resin composition contains at least one of polytetramethylene oxide compounds as the component (D). The polytetramethylene oxide compound may be used alone or in combination of two or more. The polytetramethylene oxide compound may correspond to a part or all 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, a structural unit having n different from -(C ₄ H ₈ O) _n -) Combination of two or more.

The structure of the polytetramethylene oxide in the polytetramethylene oxide compound is preferably a linear chain, and more preferably a structural unit represented by the following formula (IV). By having such a structural unit, the flexibility of the resist pattern is further improved, and the reliability of the cap hole tends to be 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 lid hole reliability and peeling time, n is preferably a number of 6 or more, more preferably 10 or more, and particularly preferably 15 or more. The upper limit of n is not particularly limited, and from the viewpoint of obtaining a cured film having more excellent developability, analytical properties, and adhesion, it is preferably a number of 70 or less, more preferably 50 or less, and particularly preferably The number below 40.

The polytetramethylene oxide compound preferably has a weight average molecular weight of 1,000 or more, more preferably 1,500 or more, and particularly preferably 2,000 or more, from the viewpoint of more excellent cover hole reliability and peeling time. Further, the weight average molecular weight of the polytetramethylene oxide compound is preferably 10,000 or less, more preferably 9000 or less, and still 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 component (A) include polytetrazol A polymer of a structural unit derived from a methyl oxide mono(meth)acrylate or a derivative thereof, a polymer comprising a structural unit derived from a polytetramethylene oxide glycidyl ether or a derivative thereof, or the like.

When the polytetramethylene oxide compound corresponds to the photopolymerizable compound as the component (B), specific examples of the polytetramethylene oxide compound as the component (B) include 2,2-double. (4-((Methyl) propylene oxime polytetramethyleneoxy) phenyl) propane, polytetramethylene glycol di(meth) acrylate, polytetramethylene glycol mono (A) A urethane reactant, a hydroxyethyl (meth) acrylate and a polytetramethylene glycol, a diisocyanate compound or a urethane reactant of a triisocyanate compound.

In the case where the polytetramethylene oxide compound does not correspond to any of the component (A), the component (B) or the component (C), specific examples of the polytetramethylene oxide compound include poly Terpolymers, etherates and urethanes of tetramethylene glycol, polytetramethylene glycol, and esterified, etherified and urethane esters of polytetramethylene glycol derivative.

The polytetramethylene oxide compound is preferably 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 particularly preferably 90% by mass or more. . Further, the polytetramethylene oxide compound may have a polyalkylene oxide other than polytetramethylene oxide such as polyethylene oxide or polypropylene oxide as a structural unit.

From the viewpoint of further improving the resolution of the cured film, the reliability of the cap hole, and the etching resistance, it is preferred 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 a urethane reactant of a diisocyanate compound or the like.

The content of the polytetramethylene oxide compound in the total amount of the component (B) is preferably 20% by mass to 50% by mass, more preferably 25% by mass to 45% by mass, even more preferably 30% by mass to 40% by mass. quality%. When the content of the polytetramethylene oxide compound is 50% by mass or less, the peeling time, the resolution, and the 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, the cap hole reliability and the etching resistance tend to be more excellent.

From the viewpoint of being more excellent in the reliability of the cap hole, the polytetramethylene oxide compound corresponding to the component (B) is preferably polytetramethylene glycol di(meth)acrylate, more preferably Polytetramethylene glycol dimethacrylate, particularly preferably polytetramethylene glycol dimethacrylate having a weight average molecular weight of 1000 to 5000, and more preferably a polycondensation having a weight average molecular weight of 1800 to 4000 Tetramethylene glycol dimethacrylate compound.

In view of the improvement of the reliability of the cap hole and the improvement of the etching resistance, the content of the structural unit of the polytetramethylene oxide is preferably 4 mass with respect to the total amount of nonvolatile matter of the photosensitive resin composition. More preferably, it is 6% by mass or more, more preferably 10% by mass or more, and particularly preferably 14% by mass or more. In addition, the content of the structural unit of the polytetramethylene oxide is preferably 40% by mass or less, and more preferably the total amount of non-volatile 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 needed. ; leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethyl aniline, o-chloroaniline, etc. photochromic agent; thermochromic color preventive agent Plasticizer for p-toluenesulfonamide; pigment; filler; antifoaming agent; flame retardant; adhesion imparting agent; leveling agent; peeling accelerator; antioxidant; polymerization inhibitor; Other additives such as thermal crosslinking agents.

In the case where the photosensitive resin composition contains other additives, the content thereof can be appropriately selected depending on the purpose and the like. For example, it may be contained in an amount of from 0.01 part by mass to 20 parts by mass per 100 parts by mass of the total of the components (A) and (B). These additives may be used alone or in combination of two or more.

The photosensitive resin composition may further contain at least one of organic solvents. Examples of the organic solvent 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; and aromatic hydrocarbons such as toluene. Solvent; aprotic polar solvent 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 having a nonvolatile content of about 30% by mass to 60% by mass (hereinafter, a photosensitive resin composition containing an organic solvent is also referred to as a "coating liquid").

The photosensitive resin composition can be used for forming a photosensitive resin layer of a photosensitive element to be described later. That is, another embodiment of the present invention is the use of the photosensitive resin composition in a photosensitive element. Further, the photosensitive resin composition can be used in a method of forming a resist pattern to be described later and a method of 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 needed.

Fig. 1 shows an embodiment of a photosensitive element of the present invention. In the photosensitive element 10 shown in FIG. 1, a support 2, a photosensitive resin layer 4 formed using the photosensitive resin composition, and a protective layer 6 are laminated in this order. The photosensitive element 10 can be obtained, for example, in the following manner. A coating liquid as the photosensitive resin composition containing an organic solvent is applied onto the support 2 to form a coating layer, which is dried to form the photosensitive resin layer 4. Then, the surface of the photosensitive resin layer 4 on the opposite side to the support 2 is covered with the protective layer 6, thereby obtaining a photosensitive resin layer 4 including the support 2, formed on the support 2, and laminated on the photosensitive layer. The photosensitive element 10 of this embodiment of the protective layer 6 on the resin layer 4. The photosensitive element 10 may also not have the protective layer 6.

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

The thickness of the support 2 (polymer film) is preferably from 1 μm to 100 μm, more preferably from 1 μm to 50 μm, still more preferably from 1 μm to 30 μm. When the thickness of the support 2 is 1 μm or more, the support 2 can be prevented from being broken when the support 2 is peeled off from the photosensitive resin layer 4. Further, by the thickness of 100 μm or less, the decrease in resolution is suppressed.

The protective layer 6 is preferably a layer having a lower adhesive force to the photosensitive resin layer 4 than the support 2 to the photosensitive resin layer 4. Further, a film of low fisheye is preferred. Here, the term "fisheye" refers to a foreign matter, an undissolved substance, or an oxidatively degraded substance contained in a material when a film is produced by kneading, extrusion, biaxial stretching, casting, or the like by thermally melting a material. Wait for the person to enter the film. In other words, the term "low fisheye" means that the foreign matter or the like in the film is small.

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

The thickness of the protective layer 6 is preferably from 1 μm to 100 μm, more preferably from 1 μm to 50 μm, still more preferably from 1 μm to 30 μm. When the thickness of the protective layer 6 is 1 μm or more, the protective layer 6 is prevented from being broken when the photosensitive resin layer 4 and the support 2 are laminated on the substrate while the protective layer 6 is peeled off. When it is 100 μm or less, it tends to be excellent in workability and low cost.

Specifically, the photosensitive element of the present embodiment can be produced, for example, in the following manner. It can be produced by a manufacturing method including at least the following steps: preparing (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) photopolymerization initiator in the organic solvent a step of forming a coating liquid; a step of applying the coating liquid onto 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 can be applied to the support 2 by a known method using a roll coater, a notch 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 carried out at 70 ° C to 150 ° C for 5 minutes to 30 minutes. After drying, the amount of the residual organic solvent in the photosensitive resin layer obtained 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 depending on the application, and is preferably from 1 μm to 200 μm, more preferably from 5 μm to 100 μm, even more preferably from 10 μm to 50, in terms of thickness after drying. Mm. When the thickness after drying is 1 μm or more, industrial coating is easy, and when it is 200 μm or less, sufficient sensitivity and photocurability at the bottom of the resist tend to be obtained.

The photosensitive element 10 may further include an intermediate layer such as a buffer layer, an adhesive layer, a light absorbing layer, and a gas barrier layer. As the intermediate layer, the intermediate layer described in JP-A-2006-098982 or the like can be applied to the present invention.

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

The photosensitive element 10 can be suitably used, for example, in a method of forming a resist pattern described later.

<Method of Forming Resist Pattern> The photosensitive resin composition can be used to form a resist pattern on a substrate. The method for forming a resist pattern according to the present embodiment includes: (i) a photosensitive resin layer forming step of forming a photosensitive resin layer on the substrate using the photosensitive resin composition; and (ii) an exposure step, At least a portion of the photosensitive resin layer is irradiated with actinic rays to harden the region; and (iii) a developing step is performed to remove unexposed portions other than the region of the photosensitive resin layer from the substrate. The method of forming the resist pattern may also include other steps as needed.

(i) Photosensitive resin layer forming step First, a photosensitive resin layer is formed on a substrate by using a photosensitive resin composition. As the substrate, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used.

For example, when the photosensitive element 10 has the protective layer 6, the photosensitive resin layer is formed on the substrate, and after the protective layer 6 is removed, 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. Thereby, a laminate including the substrate, the photosensitive resin layer 4, and the support 2 in this order is obtained.

In view of the adhesion and followability of the photosensitive element 10, the lamination operation is preferably carried out under reduced pressure. The heating at the time of pressure bonding is preferably performed so that the temperature of the photosensitive resin layer 4 and the substrate becomes 70 to 130 °C. Further, it is preferably pressure-bonded under 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. Further, when the photosensitive resin layer 4 is heated to 70 ° C to 130 ° C, it is not necessary to preheat the substrate in advance, but by performing preheating of the substrate, the adhesion of the photosensitive element 10 can be further improved. Follow-up.

(ii) Exposure Step In the exposure step, at least a part of the photosensitive resin layer 4 formed on the substrate as described above is irradiated with actinic rays, and the exposed portion irradiated with the actinic rays is photocured to form Latent image. The method of irradiating the actinic ray includes, for example, a method of irradiating the actinic ray in an image shape by transmitting 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 actin 2 can be irradiated with the actinic rays. When the support 2 is impermeable to actinic rays, the support 2 is removed, and the actinic resin layer 4 is irradiated with actinic rays.

The light source of the actinic ray is not particularly limited, and a conventionally known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, an argon laser or the like may be used, and a yttrium aluminum garnet ( Yttrium aluminum garnet, YAG) Solid-state lasers such as lasers, semiconductor lasers, and gallium nitride-based blue-violet lasers emit light sources such as ultraviolet light and visible light. Alternatively, a direct exposure method using a laser can be used.

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

(iii) Developing step In the developing step, the unexposed unhardened portion of the photosensitive resin layer 4 is removed from the substrate by development. Thereby, a resist pattern of a cured product which is photocured as the photosensitive resin layer 4 is formed on the substrate. In the case where the support 2 is present on the photosensitive resin layer 4 after exposure, after the support 2 is removed, removal (development) of the unhardened portion is performed. There are wet development and dry development in the development method, and wet development is widely used.

In the case of wet development, development is carried out by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the development method include a method using a dipping method, a liquid coating method, a spraying method, a brushing, a slap, a scrub, a shaking, and the like, and from the viewpoint of improving the resolution, the high pressure injection method is preferable. It is also possible to combine two or more of these methods for development.

The configuration of the developer can be appropriately selected depending on the configuration of the photosensitive resin composition. For example, an alkaline aqueous solution, an organic solvent developing solution, etc. are mentioned.

When the alkaline aqueous solution is used as a developing solution, it is safe and stable, and has good workability. As the base of the alkaline aqueous solution, an alkali hydroxide such as a hydroxide of lithium, sodium or potassium; a carbonate such as lithium, sodium, potassium or ammonium carbonate or a hydrogencarbonate; an alkali metal phosphate such as potassium phosphate or sodium phosphate; Alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate, borax (sodium tetraborate), sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino 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% by mass to 5% by mass of sodium carbonate, a thin solution of 0.1% by mass to 5% by mass of potassium carbonate, and a thin solution of 0.1% by mass to 5% by mass of sodium hydroxide. A thin solution of 0.1% by mass to 5% by mass of sodium tetraborate. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11. Further, the temperature thereof can be adjusted in accordance with the alkali developability of the photosensitive resin composition layer.

A small amount of a surfactant, an antifoaming agent, an organic solvent for promoting development, and the like may be added to the alkaline aqueous solution used for development. The organic solvent to be added to the alkaline aqueous solution may, for example, be acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol or 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 of the organic solvent is preferably from 2% by mass to 90% by mass based on the total amount of the alkaline aqueous solution. Further, the temperature thereof can be adjusted in accordance with the alkali developability.

The organic solvent used in the organic solvent developer may, for example, be 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone or methyl isobutylene. Ketone, γ-butyrolactone and the like. In the organic solvent, in order to prevent ignition, it is preferred to add water in an amount of from 1% by mass to 20% by mass to prepare an organic solvent developing solution.

The method for forming a resist pattern according to the present embodiment may further include the step of, after removing the uncured portion in the developing step, heating at 60 ° C to 250 ° C or 0.2 J/cm ² to 10 J as necessary. Exposure of /cm ² whereby the resist pattern is further hardened.

<Manufacturing Method of Printed Wiring Board> The method of manufacturing a printed wiring board according to the present invention includes the step of etching or plating a substrate on which a resist pattern is formed by the method of forming the resist pattern. Thereby, a conductor pattern is formed. The method of manufacturing the printed wiring board may include other steps such as a resist removal step as needed. The formed resist pattern is used as a mask, and the substrate is subjected to an etching treatment or a plating treatment on the conductor layer or the like of the substrate.

In the etching process, the resist pattern formed on the substrate is used as a mask, and the conductor layer in the region not covered with the resist is removed by etching to form a conductor pattern. The etching treatment method can be appropriately selected depending on 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 liquids, a ferric chloride solution is preferably used in terms of an excellent etch factor.

On the other hand, in the plating treatment, the resist pattern formed on the substrate is used as a mask, and copper, solder, or the like is plated on the conductor layer in a region not covered with the resist. After the plating treatment, the resist is removed, and the conductor layer in the region covered with the resist is etched to form a conductor pattern. 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, and Watt bath (nickel sulfate-chlorine). Nickel plating, nickel plating such as nickel sulfamate, gold plating such as hard gold plating, soft gold plating, and the like.

After the etching treatment and the plating treatment, the resist pattern on the substrate is removed. The removal of the resist pattern can be performed, for example, using an aqueous solution which is more alkaline than the alkaline aqueous solution used in the development step. As the strongly alkaline aqueous solution, for example, a 1% by mass to 10% by mass aqueous sodium hydroxide solution, a 1% by mass to 10% by mass aqueous potassium hydroxide solution, or the like can be used. Among them, a 1% by mass to 10% by mass aqueous sodium hydroxide solution or a potassium hydroxide aqueous solution is preferably used, and a 1% by mass to 5% by mass aqueous sodium hydroxide solution or a potassium hydroxide aqueous solution is more preferably used.

When the resist pattern is removed after the plating treatment, the conductor layer in the region covered with the resist is etched by etching to form a conductor pattern, whereby a desired printed wiring board can be manufactured. The etching treatment method can be appropriately selected depending on the conductor layer to be removed. For example, the etching solution can be applied.

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

(a) to (f) of FIG. 2 are views showing an example of a method of 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 front surface and inside. The multilayer printed wiring board 100A is obtained by laminating a copper clad laminate, an interlayer insulating material, a metal foil, or the like, and 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 its surface (see FIG. 2(a)). The interlayer insulating layer 103 can be formed by printing a thermosetting composition using a screen printing machine or a roll coater, or a film containing a thermosetting composition can be prepared in advance, and the film can be attached to the printed wiring using a laminator. Formed on the surface of the substrate. Then, a YAG laser or a carbon dioxide laser is used to form the opening 104 at a portion that needs to be electrically connected to the outside, and the slag (residue) around the opening 104 is removed by the desmear treatment (refer to FIG. 2(b)). . Then, the seed layer 105 is formed by electroless plating (see FIG. 2(c)). The photosensitive element of the present 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 liquid. Then, the seed layer 105 is removed by etching (refer to FIG. 2(e)). By repeating the above steps, the solder resist 108 is formed on the outermost surface, whereby the multilayer printed wiring board 100A can be produced (see FIG. 2(f)).

The photosensitive resin composition of the present embodiment can be suitably used for producing a printed wiring board. That is, one of the preferred embodiments of the present invention is the use of the photosensitive resin composition in the production of a printed wiring board. [Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. In addition, "parts" and "%" are quality standards unless otherwise stated.

[(A) component: binder polymer] [Synthesis method of binder polymer (P-1)] (Preparation of solution a-1) Polymerizable single body (copolymerized monomer) shown in Table 1 In the mixed solution of the monomer and the monomer, 2.0 g of azobisisobutyronitrile as a radical reaction initiator was dissolved to prepare "solution a-1".

(Free radical polymerization) In a flask equipped with a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introduction tube, 400 g of a mixture of 240 g of methyl cellosolve as an organic solvent and 160 g of toluene was charged (mass ratio was 3:2). Nitrogen gas was blown into the flask, and while the mixture was stirred, the mixture was heated to a temperature of 80 °C.

In the mixed liquid in the flask, the dropping rate was fixed, and after the "solution a-1" was added dropwise for 4 hours, the solution in the flask was stirred at 80 ° C for 2 hours. Then, 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 for 10 minutes, and then the inside of the flask was placed. The solution was stirred at 80 ° C for 3 hours. Further, the solution in the flask was heated to 90 ° C for 30 minutes, and the mixture was kept at 90 ° C for 2 hours, and then cooled to obtain a solution of the binder polymer (P-1).

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

-GPC condition - Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd.) Pipe column: The following three total Gelpack GL-R420 Gelpack GL-R430 Gelpack GL-R440 (The above is manufactured by Hitachi Chemical Co., Ltd., Name) Dissolved solution: Tetrahydrofuran Measurement temperature: 25 ° C Flow rate: 2.05 mL/min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

[Synthesis Method of Binder Polymer (P-2)] (Preparation of Solution a-2) In a mixed solution of a polymerizable monomer (copolymerized monomer or monomer) shown in Table 1, 1.0 was dissolved. g "Solvent a-2" was prepared as azobisisobutyronitrile as a radical reaction initiator. Then, radical polymerization was carried out in the same manner as in the binder polymer (P-1) to obtain a solution of the binder polymer (P-2). The binder polymer (P-2) had a weight average molecular weight of 100,000.

[Synthesis Method of Binder Polymer (P-3)] (Preparation of Solution a-3) In a mixed solution of a polymerizable monomer (copolymerized monomer or monomer) shown in Table 1, dissolution 2.0 g "Solvent a-3" was prepared as azobisisobutyronitrile as a radical reaction initiator. Then, radical polymerization was carried out in the same manner as in the binder polymer (P-1) to obtain a solution of the binder polymer (P-3). The binder polymer (P-3) had a weight average molecular weight of 55,000.

[Preparation of Photosensitive Resin Composition] In the solution of the obtained binder polymer, the components (B), (C), and (D) were blended in the amount (g) shown in Table 2 below. Further, a solution of the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6 was prepared by separately preparing 8 g of acetone, 8 g of toluene, and 8 g of methanol. Further, the amount of the binder polymer shown in Table 2 is the mass (non-volatile content) of the nonvolatile component.

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

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

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

<Component (B): Photopolymerizable Compound> FA-321M: bisphenol A polyoxyethylene ethyl dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name), molecular weight: 804. FA-2200M: Polyethylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name), molecular weight 2116. FA-P2200M: Polypropylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name), and having a molecular weight of 2,137. UA-HCY-19: a urethane reactant of hexamethylene diisocyanate trimer and polyethylene oxide methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name), molecular weight is 2522. FA-137M: Trimethylolpropane polyethylene oxide trimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name), molecular weight 1259.

<Component (C): Photopolymerization initiator> N-1717: 1,7-bis(9-acridinyl)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 2170, equivalent (B) ingredients. FA-PTG9M: polytetramethylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name), having a molecular weight of 802, which corresponds to the component (B). A-PTMG650: polytetramethylene glycol diacrylate (manufactured 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 a polyphenylene terephthalate having a thickness of 16 μm so as to have a uniform thickness. The ethylene formate film (manufactured by Teijin Co., Ltd., trade name "G2-16") (support) was dried by a hot air convection dryer at 100 ° C for 10 minutes to form a film thickness of 30 μm after drying. 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 roll pressing, whereby the layers were sequentially laminated. Photosensitive elements of Examples 1 to 10 and Comparative Examples 1 to 6 of a support, a photosensitive resin layer, and a protective layer.

[Production of laminated substrate for evaluation] Next, a 1.6 mm thick copper-clad laminate including a glass epoxy material and a copper foil (thickness: 35 μm) formed on both surfaces (manufactured by Hitachi Chemical Co., Ltd., trade name The copper surface of "MCL-E-67") was polished using a grinder (manufactured by Sanqi Co., Ltd.) having a brush equivalent to #600, and after washing with water, it was dried by air flow. After heating the copper-clad laminate (hereinafter referred to as "substrate") to a temperature of 80 ° C, the photosensitive elements of Examples 1 to 10 and Comparative Examples 1 to 6 were laminated (laminated) on the substrate. A laminated substrate for evaluation was fabricated on the copper surfaces on both sides. The photosensitive resin layer of each photosensitive element was adhered to the copper surface of the board|substrate, and the laminated surface was laminated at the speed of 1.5 m/min, using the heating roll of 110 degreeC. Further, the heating roll pressure at the time of 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 is adhered to the support on the surface of the laminated substrate for evaluation. The ladder plate is a 41-step ladder plate having a concentration region 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 was exposed through a light tool having such a ladder plate and a polyethylene terephthalate film. Exposure machine using a semiconductor-excited solid laser as a light source (manufactured by Orbotech Co., Ltd., trade name "Paragon-9000m"), exposed at an exposure of 17 mJ/cm ² .

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

[Evaluation of Adhesiveness and Analytical Property] The optical tool data having the line width/space width of n/400 (unit: μm, n = 5 μm to 200 μm) is used for each of the evaluation laminated substrates. The evaluation pattern for 2.5 μm interval is used as an evaluation evaluation for the adhesion evaluation and the evaluation pattern with a line width/space width of 400/n (unit: μm, n=5 μm to 200 μm, and 2.5 μm interval). use. Exposure machine using a semiconductor-excited solid laser as a light source (manufactured by Orbotech Co., Ltd., trade name "Paragon-9000m"), exposed at an exposure of 17 mJ/cm ² . Then, development processing was performed under the same conditions as the evaluation of the photosensitivity, and the unexposed portions were removed. The adhesion was evaluated based on the minimum value (unit: μm) of the width of the line region in which the cured film remained by the development treatment. The analytical property was evaluated based on the minimum value (unit: μm) of the width of the space between the line regions where the uncured portion was completely removed by the development treatment. The adhesion and the evaluation of the characterization were all values that were as small as possible. The results are shown in Table 2.

[Peelability Evaluation] On the laminated substrate for evaluation, a rectangular cured film of 45 mm × 65 mm was used as a light tool material for peelability evaluation. Exposure machine using a semiconductor-excited solid laser as a light source (manufactured by Orbotech Co., Ltd., trade name "Paragon-9000m"), exposed at an exposure of 17 mJ/cm ² . Then, development processing was performed under the same conditions as the evaluation of the photosensitivity, and the unexposed portions were removed. Then, 300 ml of a 50 ° C, 3.0% by mass aqueous NaOH solution (release liquid) was prepared in a beaker having a capacity of 400 ml. 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 released from the substrate was measured. Further, the earlier the time until the cured film was separated from the substrate, the shorter the peeling time, and the better the peeling property was evaluated. The results are shown in Table 2.

[Etase resistance] A 1.6 mm-thick copper-clad laminate containing a glass epoxy material and a copper foil (thickness: 100 μm) formed on both surfaces thereof (manufactured by Hitachi Chemical Co., Ltd., trade name "MCL-E- The copper surface of 67") was polished using a grinder (manufactured by Sanqi Co., Ltd.) having a brush equivalent to #600, and after washing with water, it was dried by air flow. After heating the copper-clad laminate (hereinafter referred to as "substrate") to a temperature of 80 ° C, the photosensitive elements of Examples 1 to 10 and Comparative Examples 1 to 6 were laminated (laminated) on the substrate. A laminated substrate for evaluation was fabricated on the copper surfaces on both sides. Then, in the same manner as the method of producing the adhesion and the analytical evaluation substrate, the steps up to the development process are performed. Then, etching is performed twice as long as the shortest etching time. The copper pattern was observed by immersing in a 3.0% by mass aqueous NaOH solution at 50 ° C, peeling off the resist. When the resist pattern is linearly etched along the resist pattern before peeling, it is "○", and when the difference between the resist pattern before peeling and the outline of the obtained copper pattern is observed from the upper surface of the substrate, The case where the line of 5 μm or more is missing (the disappearance of the line area) or the line is rough (the change of the width of the line area) is seen as "x". When the line is rough, the case where it is less than 5 μm is set to "△". In addition, the "shortest etching time" is a value measured as follows. First, the copper clad laminate was cut into a size of 30 mm × 30 mm as a test piece. The test piece was sprayed at a pressure of 0.15 MPa using a 5 mol/L copper chloride solution at 50 ° C, and the shortest time from which the copper layer of the copper clad laminate was removed was visually confirmed as the shortest etching time.

[Cover Hole Reliability] The hole crack number measuring substrate 40 shown in Fig. 3 was produced as follows, and the cover hole reliability was evaluated using the substrate 40. On a copper clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name "MCL-E-67"), three separate circular holes 41 having a diameter of 4 mm to 6 mm and a separate diameter are respectively produced by a stripper. A three-hole 42 in which three circular holes are connected and the intervals of the circular holes are gradually shortened. The burr generated when the round hole 41 and the triple hole 42 were produced was removed by using a grinder (manufactured by Sanke Co., Ltd.) having a brush equivalent to #600, and this was used as the hole crack number measuring substrate 40.

The substrate for measuring the number of fractures of the obtained pores was heated to 80° C., and the protective layers were peeled off from the photosensitive members of Examples 1 to 10 and Comparative Examples 1 to 6 to measure the number of cracks in the photosensitive resin layer and the number of holes. The copper surfaces of the substrate 40 were placed opposite to each other, and laminated under conditions of 120 ° C and 0.4 MPa to form a laminated substrate for evaluation of the reliability of the cap holes.

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

After the exposure, the mixture was allowed to stand at room temperature for 15 minutes, and then the support was peeled off from the laminated substrate for evaluation of the reliability of the cover hole, and a 1% by mass aqueous sodium carbonate solution at 30 ° C was sprayed for 50 seconds to carry out development. After the development, the number of cracks in the three-joined holes was measured, and the fracture rate of the deformed cover holes was calculated as the number of cracks in the total number of three-joined holes, and the reliability (%) of the cover holes 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, in the case of using the photosensitive elements of Examples 1 to 10 using the photosensitive resin composition of the present invention, the photosensitive elements of Comparative Examples 1 to 6 were used. In comparison, both showed good adhesion, resolution, etch resistance, peelability, and excellent cap hole reliability. In the photosensitive element of the comparative example, although the photosensitivity was equal to that of the photosensitive element of the example, the etching resistance was inferior. Further, in Comparative Example 1, Comparative Example 3, and Comparative Example 6, the lid hole reliability was poor, and Comparative Example 5 was inferior in peelability.

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 the specification are incorporated by reference to the same extent as the respective disclosures In this manual.

2‧‧‧Support
4‧‧‧Photosensitive resin layer
6‧‧‧Protective layer
10‧‧‧Photosensitive components
40‧‧‧Substrate for measuring the number of holes broken
41‧‧‧ round hole
42‧‧‧Three holes
100A‧‧‧Multilayer printed wiring board
101‧‧‧Copper laminate
102‧‧‧Wiring pattern
103‧‧‧Interlayer insulation
104‧‧‧ openings
105‧‧‧ seed layer
106‧‧‧resist pattern
107‧‧‧Wiring pattern
108‧‧‧Soldering agent

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

no

Claims (9)

A photosensitive resin composition comprising: (A) component: a binder polymer; (B) component: a photopolymerizable compound; (C) component: a photopolymerization initiator; and (D) component: polytetrazol The methyl oxide compound has a number of [-(C ₄ H ₈ O) _n -:n of 2 or more] as a structural unit, and may correspond to a component selected from the group consisting of (A) component, (B) component, and (C) component. A part or all of at least one of the constituent groups; and the acid value of the nonvolatile matter of the photosensitive resin composition is less than 120 mgKOH/g. The photosensitive resin composition according to claim 1, wherein the polytetramethylene oxide compound has a weight average molecular weight of 1,000 or more. The photosensitive resin composition according to Item 1 or 2, wherein a part or all of the component (B) is a polytetramethylene oxide compound. The photosensitive resin composition according to the third aspect of the invention, 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 according to claim 3, wherein the polytetramethylene oxide compound which is a part or all of the component (B) is polytetramethylene glycol (Meth) acrylate. The photosensitive resin composition according to claim 5, 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 according to any one of claims 1 to 6. A method of forming a resist pattern, comprising: a photosensitive resin layer forming step using the photosensitive resin composition according to any one of claims 1 to 6 or as claimed in claim 7 The photosensitive element according to the invention, wherein a photosensitive resin layer is formed on a substrate; and an exposure step of irradiating at least a part of the photosensitive resin layer with actinic rays to harden the region; and a developing step of sensitizing the photosensitive layer Unexposed portions other than the regions of the resin layer are removed from the substrate. A method of manufacturing a printed wiring board, comprising the step of etching or plating a substrate on which a resist pattern is formed by a method of forming a resist pattern according to claim 8 of the patent application.