KR20170007755A - Photosensitive resin composition, photosensitive element, method for forming resist pattern, and process for producing printed wiring board - Google Patents

Abstract

(C ₄ H ₈ O) _n -: n is a number of not less than 2, and the number of the repeating units is not less than 2, As a structural unit, and a polytetramethylene oxide compound which may be a part or all of at least one selected from the group consisting of the component (A), the component (B) and the component (C), and the photosensitive resin composition Is less than 120 mgKOH / g.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a photosensitive element, a method of forming a resist pattern, and a method of manufacturing a printed wiring board. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002]

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

Background Art [0002] Conventionally, in the field of production of printed wiring boards, photosensitive resin compositions, photosensitive resin layers obtained by using photosensitive resin compositions, and photosensitive elements having a support and a protective layer have been widely used as resist materials used for etching treatment or plating treatment.

The printed wiring board is formed by laminating the photosensitive element on a circuit formation substrate, exposing the photosensitive resin layer in a pattern shape, removing the unexposed portion with a developer to form a resist pattern, and performing an etching treatment or a plating treatment, And then removing the cured portion, which is an exposed portion, from the substrate and removing it.

As the developer, an alkaline developer such as an aqueous solution of sodium carbonate and an aqueous solution of sodium hydrogencarbonate is the mainstream from the viewpoint of environmental safety and safety. The unexposed portions of the photosensitive resin layer are removed from the substrate by development with these developers and spray pressure of water washing. Therefore, it is required that the photosensitive resin composition is capable of forming a cured film (resist pattern) having excellent tent reliability (tentability), which is not broken by the spray pressure after development, development and washing.

In order to have excellent tent reliability, it is effective to enhance the flexibility of the cured film formed from the photosensitive resin composition. However, when the flexibility of the cured film is increased by using a conventional material having high hydrophilicity, there has been a problem that degradation in resolution due to decrease in alkali resistance of the cured film and etching collapse due to deterioration in etching resistance have occurred. For example, even when the photosensitive resin composition described in JP-A-61-228007 and JP-A-2013-83785 is used, the acid value of the photosensitive resin composition is not appropriate, the molecular weight of the photopolymerizable compound There has been room for improvement in the resolution, etching resistance, and tent reliability for reasons such as not being appropriate.

In recent years, there has been a strong demand for a laser direct imaging (LDI) method as a method of directly drawing a pattern made by CAD (Computer-aided design) with laser light without requiring a mask. However, from the viewpoint of throughput, since a resist material used for the LDI method which requires use at a lower exposure dose requires an alkali resistance and an etching resistance at a low exposure dose and a low curing degree, a material having a rigid skeleton is used. For this reason, a resist which is disadvantageous to tent reliability which requires the flexibility of a cured film, and which has high throughput, high resolution, etching resistance, and high tent reliability as a resist used in the LDI system has not been developed so far. For example, Japanese Patent Application Laid-Open No. 2006-234995, Japanese Laid-Open Patent Application No. 2007-122028, International Publication No. 2008/078483, Japanese Laid-Open Patent Publication No. 2009-69465, 103918, there was room for improvement in either of the resolution of the obtained resist, the reliability of the tent, and the etching resistance.

It is therefore an object of the present invention to provide a photosensitive resin composition which is capable of forming a resist pattern even at a low exposure dose and is excellent in tent reliability and etching resistance of a cured film to be formed. It is another object of the present invention to provide a photosensitive element using the photosensitive resin composition, a method of forming a resist pattern, and a method of manufacturing a printed wiring board.

Specific means for solving the above-mentioned problems include the following embodiments.

A photopolymerization initiator and a component (D): [- (C ₄ H ₈ O) _n -: n) ( ₁ ) 2 or more] as a structural unit and a polytetramethylene oxide compound which may be equivalent to at least one kind of at least one member selected from the group consisting of the component (A), the component (B) and the component (C) And the acid value of the nonvolatile fraction 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 1000 or more.

<3> The photosensitive resin composition according to <1> or <2>, wherein a part or the whole of the component (B) 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% by mass to 50% by mass.

<5> The photosensitive resin composition according to <3> or <4>, wherein the polytetramethylene oxide compound which is 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 polytetramethylene glycol dimethacrylate.

A photosensitive resin layer formed on the support using the photosensitive resin composition according to any one of <1> to <6>

.

&Lt; 8 &gt; A photosensitive resin composition comprising the steps of: forming a photosensitive resin layer on a substrate using the photosensitive resin composition described in any one of &lt; 1 &gt; to &lt; 6 & An exposure step of irradiating at least a part of the region of the photosensitive resin layer with an actinic ray to cure the region and a developing step of removing an unexposed portion other than the region of the photosensitive resin layer 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 described in <8>.

According to the present invention, a resist pattern can be formed even at a low exposure dose, and it is possible to provide a photosensitive resin composition excellent in tent reliability and etching resistance of a cured film to be formed. It is also possible to provide a photosensitive element using the photosensitive resin composition, a method of forming a resist pattern, and a method of manufacturing a printed wiring board.

1 is a cross-sectional view showing an embodiment of a photosensitive element of the present invention.
2 is a process diagram showing an example of a method of manufacturing a multilayer printed wiring board using the photosensitive element of the present invention.
3 is a top view of a substrate for measuring the number of hole breakages used for evaluating tent reliability

Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings as necessary. 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 redundant description is omitted. In addition, the dimensional ratios in the drawings are not limited to the ratios of the cities.

Refers to at least one of "acrylic acid" and "methacrylic acid", and "(meth) acrylate" means "acrylate" and the corresponding "methacrylate" (Meth) acryloyl group "means at least one of" acryloyl group "and" methacryloyl group ". "Poly (tetramethylene oxide)" means a structural unit represented by [- (C ₄ H ₈ O) _n -: n is 2 or more). The number of the structural unit indicates the degree to which the corresponding structural unit is added to the molecule. Therefore, although a single molecule is represented by an integer value, it represents a rational number which is an average value for a polymer of a plurality of kinds of molecules. The term "nonvolatile matter" means a component in a composition other than a volatile substance such as moisture and an organic solvent to be described later. Here, the volatile substance means a substance having a boiling point of 155 DEG C or lower at atmospheric pressure. The "total amount of components (A)" and "the total amount of components (B)" refer to the total amount of non-volatile components.

In this specification, the term " process "is included in this term, not only in the independent process but also in the case where the desired purpose of the process is achieved even if it can not be clearly distinguished from other processes. Or "~" indicates a range including numerical values before and after "~ " as a minimum value and a maximum value, respectively. The content of each component in the composition means the total amount of the plural substances present in the composition unless a plurality of substances corresponding to each component are present in the composition. In the numerical range described stepwise in this specification, the upper limit value or the lower limit value of the numerical range of any step may be replaced with the upper limit value or the lower limit value of the numerical range of another step. In the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the embodiment. The term "layer" includes the configuration of a part formed in a part in addition to the configuration of a shape formed on the whole surface when viewed as a plan view. The term "laminate" refers to stacking layers, wherein two or more layers may be bonded, or two or more layers may be removable.

<Photosensitive resin composition>

The photosensitive resin composition of the present embodiment is a photosensitive resin composition comprising a component (A): a binder polymer, a component (B): a photopolymerizable compound, a component (C): a photopolymerization initiator, and a component (D) ₄ H ₈ O) _n -: n is a number of at least 2] as a structural unit, and may be a part or all of at least one member selected from the group consisting of the component (A), the component (B) , And the acid value of the nonvolatile fraction of the photosensitive resin composition is less than 120 mgKOH / g. The photosensitive resin composition may further contain other components as necessary.

The photosensitive resin composition contains a compound having polytetramethylene oxide as a structural unit (hereinafter also referred to as a polytetramethylene oxide compound) as the component (D), and the acid value of the nonvolatile content of the photosensitive resin composition is less than 120 mgKOH / g, A resist pattern can be formed even at a low exposure dose and a photosensitive resin composition having excellent tent reliability and etching resistance of the cured film to be formed can be obtained. Regarding the reason, the present inventors speculate 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, a suitable flexibility is imparted to the resist pattern to be formed. Therefore, it is considered that stress concentration hardly occurs in the resist pattern and tent reliability is improved. In addition, the structural unit of the polytetramethylene oxide contained in the polytetramethylene oxide compound may be said to have a high hydrophobicity. Therefore, by using a photosensitive resin composition containing a polytetramethylene oxide compound, it is considered that the resist pattern to be formed is improved in acid resistance and excellent in etching resistance.

Further, it is considered that the photosensitive resin composition is excellent in developer resistance because the acid value of the non-volatile component of the photosensitive resin composition is less than 120 mgKOH / g, and the tent reliability and etching resistance of the cured film to be formed are excellent. In addition, there is a tendency to form a resist pattern excellent in resolution and adhesion.

The acid value of the nonvolatile content of the photosensitive resin composition can be measured by the following method. First, 1 g of the photosensitive resin composition is precisely weighed, and 30 g of acetone is added to the photosensitive resin composition to uniformly dissolve the photosensitive resin composition. Then, an appropriate amount of phenolphthalein as an indicator is added to the solution of the photosensitive resin composition, and the resultant is appropriately adjusted with a 0.1N KOH aqueous solution. From the titration result, the acid value is calculated by the following formula (1): Vf represents the appropriate amount (mL) of phenolphthalein, Wp represents the weight (g) of the solution of the photosensitive resin composition as the component , And I represents the ratio (mass%) of the nonvolatile content of the solution of the photosensitive resin composition as the component (A)).

Acid value (mgKOH / g) = 10 x Vf x 56.1 / (Wp x 1) (1)

From the viewpoint of further improving the tent reliability and etching resistance of the resist pattern, the acid value of the nonvolatile content of the photosensitive resin composition is preferably 110 mgKOH / g or less, more preferably 100 mgKOH / g or less. From the viewpoint of developability of the resist pattern, it is preferably 40 mgKOH / g or more. From the viewpoint of the peeling time, it is more preferably 80 mgKOH / g or more, and still more 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 binder polymer as the component (A). The structure of the binder polymer is not particularly limited and can be selected from commonly used ones. The binder polymer may be used singly or in combination of two or more kinds. Examples of the binder polymer include a binder polymer including the following structural unit (A1), structural unit (A2), structural unit (A3), and the like.

Structural unit (A1)

It is preferable that at least one kind of the binder polymer includes a structural unit (A1) derived from at least one kind selected from the group consisting of styrene, styrene derivatives, benzyl (meth) acrylate and benzyl (meth) . This makes it possible to improve the adhesion of the binder polymer to the cured product while maintaining the flexibility of the binder polymer (A).

The content of the structural unit (A1) in the binder polymer is preferably 10% by mass to 60% by mass in the total amount of the component (A), more preferably in the range of 13% by mass More preferably 40% by mass to 40% by mass, and still more preferably 15% by mass to 25% by mass. When the content of the structural unit (A1) is 10 mass% or more, the adhesion of the cured film tends to be improved. When the content of the structural unit (A1) is 60 mass% or less, it is possible to suppress the increase of the peeling- Is likely to be improved.

Specific examples of the styrene derivatives include polymerizable styrene derivatives substituted in the? -Position or aromatic ring such as? -Methylstyrene, vinyltoluene, p-chlorostyrene and the like.

Specific examples of benzyl (meth) acrylate derivatives include 4-methylbenzyl (meth) acrylate, 4-ethylbenzyl (meth) acrylate, 4-tert- butylbenzyl (meth) acrylate, 4-methoxybenzyl Acrylate, 4-ethoxybenzyl (meth) acrylate, 4-hydroxybenzyl (meth) acrylate and 4-chlorobenzyl (meth) acrylate.

Structural unit (A2)

At least one of the binder polymers preferably contains a structural unit (A2) derived from alkyl (meth) acrylate from the viewpoint of tent reliability of the cured film. The alkyl group in the alkyl (meth) acrylate may be either straight-chain 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 more preferably 8 to 14 carbon atoms. Examples of the alkyl (meth) acrylate include a compound 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 a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, An undecyl group, a dodecyl group, and a structural isomer thereof. 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 substituents and the substitution position are not particularly limited.

From the viewpoint of further improving the tent 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 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, n- butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, undecyl (meth) acrylate, and dodecyl (meth) acrylate. These may be used alone or in combination of two or more.

When 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 1% by mass to 70% by mass from the viewpoint of adhesion, More preferably 30% by mass to 65% by mass, and still more preferably 45% by mass to 60% by mass. When the content of the structural unit (A2) is 1 mass% or more, the tent reliability of the cured film is further improved. When the content is 80 mass% or less, the resolution and adhesion of the cured film are further improved.

Structural unit (A3)

At least one of the binder polymers preferably contains a structural unit (A3) derived from a polymerizable monomer having a carboxy group from the viewpoint of alkali developability. The binder polymer containing the structural unit (A3) can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxy group and other polymerizable monomers.

Examples of the polymerizable monomer having a carboxy group include (meth) acrylic acid; (meth) acrylic acid derivatives such as? -bromoacrylic acid,? -croton acrylic acid,? -furyl (meth) acrylic acid and? -styryl (meth) acrylic acid; Maleic acid; Maleic acid derivatives such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; Fumaric acid, cinnamic acid,? -Cyano cinnamic acid, itaconic acid, crotonic acid, and propiolic acid. From the viewpoint of improving the sensitivity, (meth) acrylic acid is preferable, and methacrylic acid is more preferable.

When the binder polymer contains the structural unit (A3), the content ratio of the structural unit (A3) in the total amount of the component (A) is preferably from 12% by mass to 50% by mass from the viewpoint of balance between alkali development and developer resistance More preferably 15% by mass to 35% by mass, and still more preferably 15% by mass to 30% by mass from the viewpoint of better alkali developability.

· Other structural units

The binder polymer may contain other structural units besides the structural units (A1) to (A3). As the polymerizable monomer constituting the other structural unit, for example, 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 may be used alone or in combination of two or more.

The content of 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, and still more preferably 5% by mass or less from the viewpoints of adhesiveness, (For example, not more than 0.5% by mass). That is, the total content of the structural units (A1), (A2) and (A3) in the total amount of the component (A) is preferably 90 mass% or more, more preferably 95 mass% or more, (For example, 99.5 mass% or more) is more preferable.

· All properties of the binder polymer

The binder polymer can be obtained by polymerizing a monomer corresponding to each structural unit constituting the binder polymer. As the polymerization method, radical polymerization can be exemplified. When the binder polymer is a copolymer obtained by polymerizing two or more kinds of monomers, the respective structural units in the copolymer may be randomly contained in the copolymer as in the so-called random copolymer, May be a copolymer containing a structural unit formed continuously. Each structure unit may be a single species or plural species.

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, and even more preferably from 40,000 to 100,000 from the viewpoint of balance between developing resistance and alkali developability. The weight average molecular weight in the present specification is a value measured by the gel permeation chromatography method under the same measurement conditions as those described in the examples and converted by 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.

The binder polymer contained in component (A) may be used singly or in combination of two or more. Examples of combinations of two or more kinds of binder polymers include two or more kinds of binder polymers different in kind and ratio of copolymerization components, two or more kinds of binder polymers having different weight average molecular weights, and combinations of two or more kinds of binder polymers having different degrees of dispersion. . The dispersion degree 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) preferably contains a binder polymer containing at least any one of the structural units (A1), (A2) and (A3) and a binder polymer containing at least one of the structural units (A1), Or a combination with a binder polymer. 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 epoxy resin, an amide resin, an amide epoxy resin, an alkyd resin, and a phenol resin may be used in combination with an acrylic resin (excluding the structural unit (A1) (A2) . Among them, an acrylic resin is preferable from the viewpoint of alkali developability. These may be used alone or in combination of two or more.

When the component (A) contains another binder polymer not containing any one of the structural units (A1), (A2) or (A3), the content of the structural unit (A1) in the total amount of the component (A) By mass to 60% by mass, more preferably from 13% by mass to 40% by mass, still 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 mass% or less, and more preferably 5 mass% or less. It is more preferable that the other binder polymer is substantially not contained (for example, 0.5 mass% or less), and it is particularly preferable that no other binder polymer is contained at all.

The content of the component (A) in the photosensitive resin composition is preferably 30 parts by mass to 70 parts by mass, more preferably 40 parts by mass to 65 parts by mass, in 100 parts by mass of the total of the components (A) and (B) , More preferably from 50 parts by mass to 60 parts by mass. When the content of the component (A) is within this range, the film properties 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 kind of photopolymerizable compound as the component (B). The photopolymerizable compound as the component (B) is not particularly limited, and can be appropriately selected from commonly used photopolymerizable compounds. As the photopolymerizable compound, a compound having a photopolymerizable unsaturated double bond can be mentioned. Examples of the photopolymerizable unsaturated double bond include a double bond contained in the (meth) acryloyl 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; Polyfunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Bisphenol A based (meth) acrylates such as 2,2-bis (4 - ((meth) acryloxypolyethyleneoxy) phenyl) propane and 2,2- Methacrylate compounds; (meth) acryloyloxyethylene-o-phthalate,? -hydroxyethyl-? '- (meth) acryloyloxyethylene-o- Phthalic acid derivatives such as hydroxypropyl -? '- (meth) acryloyloxyethylene-o-phthalate; Alkyl (meth) acrylates; And the like.

Among them, from the viewpoint of adhesion and resolution, the photopolymerizable compound preferably includes at least one member selected from the group consisting of a bisphenol A (meth) acrylate compound and a polyalkylene glycol poly (meth) acrylate (Meth) acrylate, at least one of bisphenol A-based (meth) acrylate compounds and at least one of polyalkylene glycol poly (meth) acrylate, (Oxypropyleneoxy) phenyl) propane and at least one of polyethylene glycol poly (meth) acrylate are preferably used in combination.

Examples of the 2,2-bis (4 - ((meth) acryloxypolyethyleneoxy) phenyl) propane include 2,2-bis (4- (meth) acryloxydiethyleneoxy) Bis (4 - ((meth) acryloxypentaethyleneoxy) phenyl) propane, and 2,2-bis (4 - ((meth) acryloxypentadecaethyleneoxy) phenyl) propane.

The 2,2-bis (4- (methacryloxypentaethyleneoxy) phenyl) propane is commercially available as BPE-500 (manufactured by Shin Nakamura Kagaku Kogyo K.K.), and 2,2-bis (4- (methacryloxypentadecethyleneoxy) phenyl) propane is commercially available as BPE-1300 (product name of Shin-Nakamura Kagaku Kogyo K.K.). These may be used singly or in combination of two or more.

When a plurality of photopolymerizable compounds as the component (B) are used in combination, the content of the compound having two or more photopolymerizable unsaturated double bonds in the total amount of the component (B) is preferably 75% by mass or more. And the content of the compound having two or more photopolymerizable unsaturated double bonds in the total amount of the component (B) in the molecule is 75 mass% or more, the tent reliability, resolution and adhesion of the cured film tend to be further improved.

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

[Component (C): photopolymerization initiator]

The photosensitive resin composition contains at least one photopolymerization initiator as the component (C). The photopolymerization initiator is not particularly limited and can be appropriately selected from photopolymerization initiators usually used. Among them, the component (C) preferably contains an acridine compound having one or two acridinyl groups in one molecule. That is, the component (C) is an acridine compound having two acridinyl groups (hereinafter also referred to as "(C1) compound") and an acridine compound having one acridinyl group (hereinafter referred to as " Quot; compound "). The term &quot; compound &quot;

As the compound (C1), for example, an acridine compound represented by the following general formula (II) can be mentioned.

In the formula (II), R ³ represents an alkylene group having 2 to 20 carbon atoms, an oxydialkylene group having 2 to 20 carbon atoms, or a thioalkylene group having 2 to 20 carbon atoms. From the viewpoint of more surely obtaining the effect of the photosensitive resin composition, 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 general formula (II) include 1,2-di (9-acridinyl) ethane, 1,3-di (9-acridinyl) propane, (9-acridinyl) pentane, 1,6-di (9-acridinyl) hexane, 1,7-di (9-acridinyl) octane, 1,9-di (9-acridinyl) decane, 1,10- Dodecane, 1,14-di (9-acridinyl) tetradecane, 1,16-di (9-acridinyl) hexa Di (9-acridinyl) alkanes such as decane, 1,18-di (9-acridinyl) octadecane, and 1,20-di (9-acridinyl) eicosane; 1,3-di (9-acridinyl) -2-oxapropane; Di (9-acridinyl) oxaalkane such as 1,5-di (9-acridinyl) -3-oxapentane; 1,3-di (9-acridinyl) -2-thiopropane; Di (9-acridinyl) thioalkanes such as 1,5-di (9-acridinyl) -3-thiapentane; And the like. These may be used alone or in combination of two or more.

N-1717 "(trade name, product of ADEKA, manufactured by Kabushiki Kaisha) as a compound (C1) wherein R ³ in the formula (II) is a heptylene group, from the viewpoint of improving the photosensitivity and resolution, ).

When the photosensitive resin composition contains the (C1) compound as the photopolymerization initiator, the content of the compound (C1) is preferably from 100 parts by mass to 100 parts by mass in total of the component (A) and the component (B) from the viewpoints of sensitivity, More preferably 0.1 part by mass to 1.4 parts by mass, and most preferably 0.3 part by mass to 1.4 parts by mass, for example, 0.1 part by mass to 10 parts by mass, 0.5 part by mass to 5 parts by mass, or 1 part by mass to 3 parts by mass, More preferably from 0.4 part by mass to 0.7 part by mass, particularly preferably from 0.5 part by mass to 0.6 part by mass. When the content of the compound (C1) is at least 0.1 part by mass, better sensitivity, resolution or adhesion tends to be obtained. When the amount is 1.4 parts by mass or less, a better resist shape tends to be obtained.

As the compound (C2), for example, an acridine compound represented by the following general formula (III) can be mentioned.

In formula (III), R ⁴ represents a halogen atom, an amino 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 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-chlorophenyl) acridine, 9-aminoacridine, 9-dimethylaminoacridine, Noacridine. These may be used alone or in combination of two or more.

When the photosensitive resin composition contains a (C2) compound as a photopolymerization initiator, the content of the (C2) compound is preferably 100 parts by mass or less per 100 parts by mass of the total amount of the component (A) and the component (B) from the viewpoints of sensitivity, 0.1 mass part to 10 mass part, 0.5 mass part to 5 mass part, or 1 mass part to 3 mass part, preferably 0.1 mass part to 1.4 mass part, and preferably 0.3 mass part to 1.4 mass part, More preferably 0.4 part by mass to 0.7 part by mass, and particularly preferably 0.5 part by mass to 0.6 part by mass. When the content of the compound (C2) is at least 0.1 part by mass, better sensitivity, resolution or adhesiveness tends to be obtained. When the amount is 1.4 parts by mass or less, a better resist shape tends to be obtained.

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

Examples of the photopolymerization initiators other than the compounds (C1) and (C2) include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Mihira ketone), N, , 4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Aromatic ketone compounds such as 1- [4- (methylthio) phenyl] -2-morpholinopropanone-1; Diethylanthraquinone, 2,3-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-di 2-methyl anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl 1,4-naphthoquinone, 2,3-dimethyl anthraquinone Quinone compounds; 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-di (methoxyphenyl) imidazole dimer, 2- (o- (O-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- , 2,4,5-triarylimidazole dimer such as 5-diphenylimidazole dimer; Benzyl derivatives such as benzyl dimethyl ketal; Substituted anthracene compounds such as 9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene and 9,10-diphenoxy anthracene; Coumarin compounds; Oxazole compounds; Pyrazoline compounds; Triarylamine compounds; And the like.

These photopolymerization initiators may be used singly or in combination of two or more. Further, a thioxanthone compound and a tertiary amine compound may be combined to form a photopolymerization initiator, such as a combination of diethylthioxanthone and dimethylaminobenzoic acid.

The 2,4,5-triarylimidazole dimer may be a compound wherein the substituents of the aryl groups of the two 2,4,5-triarylimidazole constituting the dimer are the same and are symmetrical , Or they may be different from each other and asymmetric.

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

The content of the component (C) is preferably 0.01 part by mass to 20 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B) from the viewpoints of sensitivity, More preferably 10 parts by mass to 10 parts by mass, and still more preferably 0.1 parts by mass to 5 parts by mass.

The photosensitive resin composition preferably contains at least one member selected from the group consisting of a (C1) compound and a (C2) compound as the component (C) from the viewpoints of sensitivity, ) And (B) is preferably 0.1 part by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, based on 100 parts by mass of the total amount 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 compounds may be used singly or in combination of two or more. The polytetramethylene oxide compound may correspond to a part or all of at least one kind 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 a single kind or a combination of two or more kinds having different structures (for example, n in the structure of - (C ₄ H ₈ O) _n - .

The structure of the polytetramethylene oxide in the polytetramethylene oxide compound is preferably a straight-chain structure, more preferably a structural unit represented by the following general formula (IV). By having such a structural unit, the flexibility of the resist pattern is further improved, and the tent reliability tends to be further improved.

In the formula (IV), n is a number of 2 or more. From the viewpoint of obtaining a cured film having more excellent tent reliability and peeling time, n is preferably 6 or more, more preferably 10 or more, and still more preferably 15 or more. The upper limit value of n is not particularly limited, but from the viewpoint of obtaining a cured film having more excellent developability, resolution and adhesion, the number is preferably 70 or less, more preferably 50 or less, and even more preferably 40 or less.

From the viewpoint of more excellent tent 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 still more preferably 2,000 or more. The weight average molecular weight of the polytetramethylene oxide compound is preferably 10,000 or less, more preferably 9000 or less, and even more preferably 8000 or less.

When 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 a structural unit derived from polytetramethylene oxide mono (meth) acrylate or a derivative thereof A polymer containing a structural unit derived from polytetramethylene oxide glycidyl ether or a derivative thereof, and 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-bis (4 - ((meth) acryloxypolytetramethylene (Meth) acrylate, poly (tetramethylene glycol) mono (meth) acrylate, polytetramethylene glycol di (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, polytetramethylene glycol and diisocyanate compound or triisocyanate compound Urethane reactant and the like.

When the polytetramethylene oxide compound is not significantly affected by any of the component (A), the component (B), and the component (C), specific examples of the polytetramethylene oxide compound include polytetramethylene glycol, esterified product of polytetramethylene glycol, Ethers and urethanes, and derivatives of esters, ethers and urethanes of polytetramethylene glycol.

The proportion of the polytetramethylene oxide structural units in one molecule of the polytetramethylene oxide compound is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. The polytetramethylene oxide compound may also 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, tent reliability and etching resistance, it is preferable that part or all of the component (B) is a polytetramethylene oxide compound.

As the polytetramethylene oxide compound corresponding to component (B), polytetramethylene glycol di (meth) acrylate, urethane reaction product of hydroxyethyl (meth) acrylate, polytetramethylene glycol and diisocyanate compound, and the like are preferable.

The content of the polytetramethylene oxide compound in the total amount of the component (B) is preferably from 20 mass% to 50 mass%, more preferably from 25 mass% to 45 mass%, and from 30 mass% to 40 mass% More preferable. When the content of the polytetramethylene oxide compound is 50 mass% or less, the peeling time, resolution, and adhesion of the cured film tend to be more excellent. Further, when the content of the polytetramethylene oxide compound is 20 mass% or more, tent reliability and etching resistance tend to be more excellent.

From the viewpoint that tent reliability is more excellent, the polytetramethylene oxide compound corresponding to component (B) is preferably polytetramethylene glycol di (meth) acrylate, more preferably polytetramethylene glycol dimethacrylate More preferably polytetramethylene glycol dimethacrylate having a weight average molecular weight of 1000 to 5000, and still more preferably a polytetramethylene glycol dimethacrylate compound having a weight average molecular weight of 1800 to 4000.

The content ratio of the structural unit of the polytetramethylene oxide with respect to the total amount of non-volatile components in the photosensitive resin composition is preferably 4% by mass or more, more preferably 6% by mass or more from the viewpoints of improvement in tent reliability and etching resistance, More preferably 10% by mass or more, and particularly preferably 14% by mass or more. From the viewpoint of improving the resolution, the content ratio of the structural unit of the polytetramethylene oxide to the total amount of the non-volatile components in the photosensitive resin composition is preferably 40% by mass or less, more preferably 30% by mass or less, By mass or less.

[Other components]

The photosensitive resin composition may contain, if necessary, dyes such as maracal green, Victoria pure blue, brilliant green, and methyl violet; Photochromic agents such as leuco crystal biotite, diphenylamine, benzylamine, triphenylamine, diethylaniline, and o-chloroaniline; Heat inhibitor; a plasticizer such as p-toluenesulfonamide; Pigments; Fillers; Defoamer; Flame retardant; An adhesion imparting agent; Leveling agents; Release promoter; Antioxidants; A polymerization inhibitor; Spices; An imaging agent; And other additives such as heat crosslinking agents.

When the photosensitive resin composition contains other additives, the content thereof may be appropriately selected depending on the purpose and the like. For example, about 0.01 to 20 parts by mass based on 100 parts by mass of the total amount of the component (A) and the component (B). These additives may be used singly or in combination of two or more kinds.

The photosensitive resin composition may further include at least one organic solvent. 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; Aromatic hydrocarbon solvents such as toluene; Non-protic polar solvents such as N, N-dimethylformamide; And the like. 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 may be appropriately selected depending on the purpose and the like. For example, a solution in which the nonvolatile content is 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 above photosensitive resin composition can be used for forming a photosensitive resin layer of a photosensitive element described later. That is, another embodiment of the present invention is the use of the photosensitive resin composition for the photosensitive element. The above-mentioned photosensitive resin composition can be used in a method of forming a resist pattern and a method of manufacturing a printed wiring board, which will be described later.

<Photosensitive element>

The photosensitive element of the present invention has a support and a photosensitive resin layer formed on the support using the photosensitive resin composition. The photosensitive element may have other layers such as a protective layer, if 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 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, as follows. A coating liquid as the photosensitive resin composition containing an organic solvent is coated on the support 2 to form a coating layer and the photosensitive resin layer 4 is formed by drying the coating layer. Subsequently, the surface of the photosensitive resin layer 4 opposite to the support 2 is covered with a protective layer 6 to form the photosensitive resin layer 4 formed on the support 2 and the photosensitive resin layer 4 The protective layer 6 laminated on the photosensitive element 10 of the present embodiment can be obtained. The photosensitive element 10 does not need to have 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, polyethylene and the like can be used.

The thickness of the support 2 (polymer film) is preferably 1 m to 100 m, more preferably 1 m to 50 m, and even more preferably 1 m to 30 m. When the thickness of the support 2 is 1 占 퐉 or more, breakage of the support 2 when the support 2 is peeled off from the photosensitive resin layer 4 can be suppressed. Or less than 100 占 퐉, whereby degradation of resolution is suppressed.

As the protective layer 6, it is preferable that the adhesive force to the photosensitive resin layer 4 is smaller than the adhesive force of the support body 2 to the photosensitive resin layer 4. [ Also, a low-cost fish eye film is preferable. Here, the "fish eye" refers to a film which is formed by heat melting a material, producing a film by kneading, extruding, biaxial stretching, casting or the like, a foreign substance contained in the material, . &Lt; / RTI &gt; That is, the term "low fish eye" means that there are few foreign matters 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. Examples of commercially available PS series include ARPAN MA-410, E-200C, a polypropylene film manufactured by Shin-Etsu Film Co., Ltd., and PS series such as PS-25 manufactured by Daikin Industries, Polyethylene terephthalate film, and the like. The protective layer 6 may be the same as the support 2.

The thickness of the protective layer 6 is preferably 1 m to 100 m, more preferably 1 m to 50 m, and even more preferably 1 m to 30 m. When the thickness of the protective layer 6 is 1 탆 or more, breakage of the protective layer 6 is prevented when the photosensitive resin layer 4 and the support 2 are laminated on the substrate while peeling off the protective layer 6 There is a tendency to be able to. When the thickness is 100 μm or less, handling and economics tend to be excellent.

Specifically, the photosensitive element of the present embodiment can be manufactured, for example, as follows. Preparing a coating liquid comprising at least a component (A): a binder polymer, (B) a component: a photopolymerizable compound, and (C) a photopolymerization initiator dissolved in the organic solvent, and applying the coating liquid onto the support (2) A step of forming a coating layer, and a step of drying the coating layer to form a photosensitive resin layer.

The application of the coating liquid onto the support 2 can be carried out by a known method using a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, a bar coater and the like.

The drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. For example, it 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 obtained photosensitive resin layer 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 may be appropriately selected depending on the application and is preferably 1 m to 200 m in thickness after drying, more preferably 5 m to 100 m, Is more preferable. When the thickness after drying is 1 占 퐉 or more, industrial coating becomes easy. When the thickness is 200 占 퐉 or less, the sensitivity and the photocurability of the resist bottom tends to be sufficiently obtained.

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

The shape of the obtained photosensitive element 10 is not particularly limited. For example, it may be in the form of a sheet, or it may be in the form of a roll wound around a core. In the case of winding in the form of a roll, it is preferable to wind the support 2 so as to be on the outer side. As the material of the core, a plastic such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, an ABS resin (acrylonitrile-butadiene-styrene copolymer) and the like can be mentioned. It is preferable that a cross-section separator is provided on the end face of the roll-shaped photosensitive element roll obtained from the viewpoint of the cross-sectional protection, and it is preferable to provide the cross-section of the moisture-proof cross section from the viewpoint of edge fusion. As a packaging method, it is preferable to wrap the package in a wrapped black sheet having low moisture permeability.

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

&Lt; Method of forming resist pattern &gt;

Using the photosensitive resin composition, a resist pattern can be formed on a substrate. The method for forming a resist pattern according to the present embodiment includes the steps of: (i) forming a photosensitive resin layer on a substrate using the photosensitive resin composition; (ii) forming a resist pattern on at least a part of the region of the photosensitive resin layer; (Iii) a developing step of removing the unexposed portions of the photosensitive resin layer other than the above region from the substrate. The method of forming the resist pattern may further include other steps as required.

(i) Photosensitive resin layer forming step

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

The formation of the photosensitive resin layer on the substrate can be performed by forming the photosensitive resin layer 10 on the photosensitive element 10 after removing the protective layer 6, for example, when the photosensitive element 10 has the protective layer 6 4) so as to be in contact with the substrate, and pressing (laminating) the photosensitive element 10 on the substrate while heating. Thereby, a laminate comprising the substrate, the photosensitive resin layer 4, and the support 2 in this order can be obtained.

The lamination is preferably performed under reduced pressure from the viewpoint of adhesion and followability of the photosensitive element 10. Heating at the time of pressing is preferably carried out such that the temperature of the photosensitive resin layer 4 and the substrate is 70 ° C to 130 ° C. Or compression is preferably carried out at a pressure of 0.1 MPa to 1.0 MPa (1 kgf / cm ^{2 to} 10 kgf / cm ² ). These conditions are suitably selected as needed. When the photosensitive resin layer 4 is heated to 70 to 130 占 폚, it is not necessary to preheat the substrate in advance, but the adhesion and followability of the photosensitive element 10 can be further improved by preheating the substrate have.

(ii) exposure step

In the exposure step, by irradiating actinic light to at least a part of the area of the photosensitive resin layer 4 formed on the substrate as described above, the exposed part irradiated with the actinic ray is photo-cured to form a latent image. As a method of irradiating an actinic ray, for example, there is a method of irradiating an actinic ray 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 the active ray, it is possible to irradiate the active ray through the support 2. When the support 2 is impermeable to the active ray, the photosensitive resin layer 4 is irradiated with an actinic ray after the support 2 is removed.

The light source of the active light ray is not particularly limited and may be a conventional known light source such as a carbon arc lamp, a mercury vapor arc, a gas laser such as an ultra high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp or an argon laser, a YAG laser Such as a solid laser, a semiconductor laser, and a gallium nitride blue-violet laser, can be used. The laser direct imaging exposure method may also be used.

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

(iii) development process

In the developing step, the uncured portions of the photosensitive resin layer 4 that are not exposed are removed from the substrate by development. Thus, a resist pattern as a cured product of the photosensitive resin layer 4 is formed on the substrate. When the support 2 is present on the exposed photosensitive resin layer 4, the support 2 is removed and then the uncured portion is removed (developed). In the developing method, a wet phenomenon and a dry phenomenon occur, and a wet phenomenon is widely used.

In the case of the wet phenomenon, development is carried out by a known developing method using a developer corresponding to the photosensitive resin composition. Examples of the developing method include a dipping method, a paddle method, a spraying method, a brushing method, a slapping method, a scrubbing method, and a method using a sliding dipping method. From the viewpoint of resolution improvement, a high pressure spraying method is most suitable. Two or more of these methods may be combined for development.

The constitution of the developer is appropriately selected depending on the constitution of the photosensitive resin composition. Examples thereof include an alkaline aqueous solution and an organic solvent developer.

The alkaline aqueous solution, when used as a developer, is safe and stable, and has good operability. Examples of the base of the alkaline aqueous solution include alkaline hydroxides such as hydroxides of lithium, sodium or potassium, carbonates of lithium, sodium, potassium or ammonium, alkali carbonates such as bicarbonate, alkali metal phosphates such as potassium phosphate, sodium phosphate, sodium pyrophosphate, Alkali metal pyrophosphate such as potassium phosphate, sodium borate (sodium tetraborate), metasilicate sodium, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3 -Propanediol, 1,3-diamino-2-propanol, and morpholine.

The alkaline aqueous solution to be used for the development is preferably a lean solution of 0.1 mass% to 5 mass% sodium carbonate, a lean solution of 0.1 mass% to 5 mass% potassium carbonate, a lean solution of 0.1 mass% to 5 mass% sodium hydroxide, A dilute solution of 5% by mass sodium sodium borate and the like are preferable. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11. The temperature is controlled in accordance with the alkali developability of the photosensitive resin composition layer.

In the alkaline aqueous solution used for the development, a small amount of a surface active agent, a defoaming agent, and an organic solvent for promoting development may be added. Examples of the organic solvent to be added to the alkaline aqueous solution include acetone, ethyl acetate, alkoxyethanol having an alkoxy group of 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol monobutyl ether, and the like. These organic solvents may be used singly or in combination of two or more. When the alkaline aqueous solution contains an organic solvent, the content of the organic solvent is preferably 2% by mass to 90% by mass in the total amount of the alkaline aqueous solution. Further, the temperature can be adjusted in accordance with the alkali developability.

Examples of the organic solvent used in the organic solvent developer include organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methylisobutylketone, . It is preferable that water is added to these organic solvents in an amount of 1% by mass to 20% by mass for prevention of flammability to form an organic solvent developer.

The forming method of this embodiment of the resist pattern, after removing the uncured part of the development process, by carrying out the 60 ℃ heating or exposure of ^{0.2J / cm 2 ~10 J / cm} 2 of ~250 ℃ necessary , And further curing the resist pattern.

&Lt; Manufacturing method of printed wiring board &gt;

The method for manufacturing a printed wiring board of the present invention includes a step of etching or plating a substrate on which a resist pattern is formed by the above-described method of forming a resist pattern. Thus, a conductor pattern is formed. The manufacturing method of the printed wiring board may include other steps such as a resist removing step if necessary. The etching treatment or the plating treatment of the substrate is carried out with respect to the conductor layer or the like of the substrate, using the formed resist pattern as a mask.

In the etching treatment, the conductor layer in the region not covered with the resist is removed by etching using the resist pattern formed on the substrate as a mask to form a conductor pattern. The method of the etching treatment is appropriately selected according to the conductor layer to be removed. Examples of the etching solution include a cupric chloride solution, a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide etching solution. Of these, it is preferable to use a ferric chloride solution in that the etch factor is favorable.

On the other hand, in the plating process, using a resist pattern formed on a substrate as a mask, copper, solder or the like is plated on a conductor layer in a region not covered with a resist. After the plating treatment, the resist is removed, and the conductor layer in the region covered by the resist is further 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, copper pyrophosphate plating, solder plating such as high-speed solder plating, plating with a watt bath (nickel sulfate-nickel chloride plating), nickel plating with nickel sulfamate , 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 carried out, for example, by using an aqueous solution more strongly alkaline than the alkaline aqueous solution used in the above-described development step. As the strongly alkaline aqueous solution, for example, 1 mass% to 10 mass% aqueous sodium hydroxide solution and 1 mass% to 10 mass% potassium hydroxide aqueous solution can be used. Among them, 1 mass% to 10 mass% aqueous sodium hydroxide solution or potassium hydroxide aqueous solution is preferably used, and more preferably 1 mass% to 5 mass% aqueous sodium hydroxide solution or potassium hydroxide aqueous solution is used.

In the case where the resist pattern is removed after the plating process, a desired printed wiring board can be manufactured by further etching the conductor layer in the region covered with the resist by etching and forming the conductor pattern. The method of the etching treatment is appropriately selected according to the conductor layer to be removed. For example, the above-described etching solution can be applied.

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

2 is a diagram showing an example of a method for manufacturing a multilayer printed wiring board using the photosensitive element of the present embodiment. The multilayer printed wiring board 100A shown in Fig. 2 (f) has wiring patterns on its surface and inside. The multilayer printed wiring board 100A can be 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 its surface (see Fig. 2 (a)). The interlaminar insulating layer 103 can be formed by printing a thermosetting composition on a surface of a printed wiring board using a laminator even if the thermosetting composition is formed by printing using a screen printing machine or a roll coater It may be formed by pasting. Then, an opening 104 is formed by using a YAG laser or a carbon dioxide gas laser at a place where it is necessary to electrically connect to the outside, and a smear (residue) around the opening 104 is formed And is removed by a desmear process (see Fig. 2 (b)). Subsequently, a seed layer 105 is formed by electroless plating (see FIG. 2 (c)). A photosensitive resin layer 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, a wiring pattern 107 is formed by an electrolytic plating method, and the resist pattern 106 is removed by a removing liquid. Thereafter, the seed layer 105 is removed by etching (see Fig. 2 (e)). The above process is repeated to form the solder resist 108 on the outermost surface, whereby the multilayer printed wiring board 100A can be manufactured (see Fig. 2 (f)).

The photosensitive resin composition of the present embodiment can be suitably used for the production 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 described concretely with reference to Examples, but the present invention is not limited to these Examples. Also, unless otherwise noted, "parts" and "%" are on a mass basis.

[Component (A): binder polymer] [Synthesis method of binder polymer (P-1)] (Preparation of solution a-1)

2.0 g of azobisisobutyronitrile as a radical reaction initiator was dissolved in a mixture of the polymerizable monomers (copolymerizable monomers and monomers) shown in Table 1 to prepare "Solution a-1 ".

(Radical polymerization reaction)

A flask equipped with a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introducing tube was charged with 400 g of a mixed solution (weight ratio 3: 2) of 240 g of methyl cellosolve as an organic solvent and 160 g of toluene. While the nitrogen gas was blown into the flask, the mixed solution was heated with stirring to raise the temperature to 80 캜.

"Solution a-1" was added dropwise to the mixed solution in the flask over a period of 4 hours with constant dropping rate, and then the solution in the flask was stirred at 80 캜 for 2 hours. Subsequently, a solution obtained by further dissolving 1 g of azobisisobutyronitrile in 100 g of "solution a-1" was added dropwise to the solution in the flask over a period of 10 minutes with constant dropping rate, Lt; / RTI &gt; The solution in the flask was heated to 90 DEG C over 30 minutes, kept at 90 DEG C for 2 hours and cooled to obtain a solution of the binder polymer (P-1).

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

-GPC condition-

Pump: Hitachi L-6000 type (manufactured by Hitachi Seisakusho Co., Ltd.)

Column: 3 total less

Gelpack GL-R420

Gelpack GL-R430

Gelpack GL-R440

  (All trade names, manufactured by Hitachi Chemical Co., Ltd.)

Eluent: Tetrahydrofuran

Measuring temperature: 25 ° C

Flow rate: 2.05 mL / min

Detector: Hitachi L-3300 type RI (Hitachi SEISAKUSHO Co., Ltd.)

[Synthesis method of binder polymer (P-2)] (Preparation of solution a-2)

1.0 g of azobisisobutyronitrile as a radical reaction initiator was dissolved in a mixture of the polymerizable monomers (copolymerizable monomers and monomers) shown in Table 1 to prepare "Solution a-2 ". Thereafter, a radical polymerization reaction was carried out in the same manner as in the case of 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)

2.0 g of azobisisobutyronitrile as a radical reaction initiator was dissolved in a mixture of the polymerizable monomers (copolymerizable monomers and monomers) shown in Table 1 to prepare "Solution a-3 ". Thereafter, a radical polymerization reaction was carried out in the same manner as in the case of 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]

By blending 8 g of acetone, 8 g of toluene and 8 g of methanol with the components (B), (C), (D) and other components in the binder polymer solution obtained above in the blend amount (g) shown in the following Table 2, Solutions of the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6 were prepared. The compounding amount of the binder polymer shown in Table 2 is the mass (nonvolatilization amount) of the nonvolatile component.

Details of the materials shown in Table 2 are as follows.

&Lt; Component (A): Binder polymer &gt;

P-1: Copolymer of the above-prepared binder polymer: methacrylic acid / benzyl methacrylate (24/76 by mass), methylcellulose having a weight average molecular weight of 55,000, an acid value of 157 mgKOH / g and a nonvolatile content of 50% Solvent / toluene = 6/4 (by weight) solution.

P-2: Copolymer of the above-prepared binder polymer: methacrylic acid / methyl methacrylate / 2-ethylhexyl acrylate (25/50/25 by mass ratio), weight average molecular weight of 100,000, acid value of 163 mgKOH / Methylcellosolve / toluene = 6/4 (mass ratio) solution having a volatile content of 50 mass%.

P-3: Copolymer of methacrylic acid / benzyl methacrylate (31/69 (mass ratio)), methylcellosolve / toluene 6/5 weight average molecular weight of 55,000, acid value of 202 mg KOH / g and nonvolatile content of 50% 4 (by weight) solution.

&Lt; Component (B): photopolymerizable compound &gt;

FA-321M: bisphenol A polyoxyethylene dimethacrylate (product name, manufactured by Hitachi Chemical Co., Ltd.), molecular weight 804;

FA-2200M: polyethylene glycol dimethacrylate (product name, product of Hitachi Chemical Co., Ltd.), molecular weight 2116;

FA-P2200M: polypropylene glycol dimethacrylate (product name, manufactured by Hitachi Chemical Co., Ltd.), molecular weight 2137;

UA-HCY-19: urethane reaction product of hexamethylene diisocyanate trimer and polyethylene oxide methacrylate (product name of Shin Nakamura Kagaku Kogyo Kabushiki Kaisha), molecular weight 2522.

FA-137M: trimethylolpropane polyethylene oxide trimethacrylate (product name, manufactured by Hitachi Chemical Co., Ltd.), molecular weight: 1259.

&Lt; Component (C): photopolymerization initiator &gt;

N-1717: 1,7-di (9-acridinyl) heptane (product of ADEKA, product name).

EAB: 4,4'-bis (diethylamino) benzophenone (product name, manufactured by Hodogaya Chemical Industry Co., Ltd.).

B-CIM: 2- (2-Chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-2H- 1H-imidazole (product name, manufactured by Hodogaya Chemical Industry Co., Ltd.).

&Lt; Component (D): polytetramethylene oxide compound &gt;

FA-PTG28M: Corresponds to polytetramethylene glycol dimethacrylate (product name, manufactured by Hitachi Chemical Co., Ltd.), molecular weight 2170, and component (B).

FA-PTG9M: corresponds to polytetramethylene glycol dimethacrylate (product name, manufactured by Hitachi Chemical Co., Ltd.), molecular weight 802, and component (B).

A-PTMG650: Polytetramethylene glycol diacrylate (product of Shin-Nakamura Kagaku Co., Ltd.). Molecular weight 774 corresponds to component (B).

PTMG-2000: Polytetramethylene glycol (product name, manufactured by Mitsubishi Chemical Corporation), molecular weight 2034;

&Lt; Other components &gt;

LCV: Loico crystal violet (product name, made by Yamada Kakuga)

MKG: Maracal green (product name, manufactured by Osaka Yuki Kagaku Kogyo Kabushiki Kaisha)

[Production of photosensitive element]

The photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6 were coated on a polyethylene terephthalate film (trade name: "G2-16") (trade name, available from Daikin Industries, Ltd.) And dried in a hot air convection type dryer at 100 ° C for 10 minutes to form a photosensitive resin layer having a thickness of 30 μm after drying. In this Example where a support, a photosensitive resin layer, and a protective layer were laminated in this order by laminating a polyethylene film (trade name "NF-13" 1 to 10 and Comparative Examples 1 to 6, respectively.

[Preparation of laminated substrate for evaluation]

Subsequently, the copper surface of a 1.6 mm thick copper clad laminate (trade name: MCL-E-67, manufactured by Hitachi Kasei K.K.) comprising a glass epoxy material and copper foils (35 μm in thickness) Was polished using a polishing machine having a brush equivalent to # 600 (manufactured by Sankei Kikai Co., Ltd.), washed with water, and then dried with air flow. After the copper clad laminate (hereinafter referred to as "substrate") was heated and heated to 80 ° C, the photosensitive elements related to Examples 1 to 10 and Comparative Examples 1 to 6 were laminated (laminated) To prepare evaluation laminate boards. The laminate was heated at a rate of 1.5 m / min by using a heat roll at 110 캜 so that the photosensitive resin layer of each photosensitive element adhered to each copper surface of the substrate while removing the protective layer. The heat roll pressure at the time of laminating was 0.4 MPa.

[Evaluation of Sensitivity]

The resultant laminated substrate for evaluation was allowed to cool to 23 占 폚. Subsequently, a phototool having a step tablet was closely attached to a support on the surface of the evaluation laminated substrate. As the step tablet, a 41 step tablet having a concentration range of 0.00 to 2.00, a concentration step of 0.05, a tablet size of 20 mm x 187 mm, and each step size of 3 mm x 12 mm was used. The photosensitive resin layer was exposed through a phototool having a step tablet and a polyethylene terephthalate film. The exposure was carried out at an exposure amount of 17 mJ / cm ² using an exposure machine (trade name: "Paragon-9000m", manufactured by Nihon Olbotech Co., Ltd.) using a semiconductor excitation solid laser as a light source.

After exposure, the support was peeled off from the evaluation laminate substrate to expose the photosensitive resin layer. The unexposed portion was removed by spraying (developing) a 1.0 mass% sodium carbonate aqueous solution at 30 캜 for 50 seconds on the exposed photosensitive resin layer. Thus, a cured film of a cured product of the photosensitive resin composition was formed on the copper surface of the evaluation laminated substrate. The sensitivity (photosensitivity) of the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6 and the photosensitive element obtained therefrom was evaluated by measuring the number of stages of the step tablet of the obtained cured film. The higher the number of stages of the step tablet, the higher the sensitivity. The results are shown in Table 2.

[Evaluation of adhesion and resolution]

An evaluation pattern having a line width / space width of n / 400 (unit: μm, n = 5 μm to 200 μm at intervals of 2.5 μm) was formed on the evaluation laminated substrate for evaluation of adhesion, And phototool data having an evaluation pattern of a space width of 400 / n (unit: μm, n = 5 μm to 200 μm and spacing of 2.5 μm) were respectively used. The exposure was carried out at an exposure amount of 17 mJ / cm ² using an exposure machine (trade name: "Paragon-9000m", manufactured by Nihon Olbotech Co., Ltd.) using a semiconductor excitation solid laser as a light source. Subsequently, development processing was carried out under the same conditions as the evaluation of the photosensitivity to remove the unexposed portion. The adhesion was evaluated by the minimum value (unit: mu m) of the width of the line area where the cured film remained by the developing treatment. The resolution was evaluated by the minimum value (unit: μm) of the width of the space between the line regions in which portions not photocured by the developing process can be removed neatly. The evaluation of adhesion and resolution are all good values as the numerical value is small. The results are shown in Table 2.

[Evaluation of peelability]

The evaluation laminate substrate was exposed using phototool data for forming a rectangular cured film of 45 mm x 65 mm for evaluation of peelability. The exposure was carried out at an exposure amount of 17 mJ / cm ² using an exposure machine (trade name: "Paragon-9000m", manufactured by Nihon Olbotech Co., Ltd.) using a semiconductor excitation solid laser as a light source. Subsequently, development processing was performed under the same conditions as those for evaluating the photosensitivity to remove the unexposed portions.

Thereafter, 300 ml of a 3.0 wt% NaOH aqueous solution (exfoliation solution) at 50 캜 was prepared in a 400-ml beaker. The substrate after development was immersed in the peeling liquid while agitating the peeling liquid at 200 rpm using an agitator having a length of 30 mm, and the time (unit: second) from when the cured film was released from the substrate was measured. Further, it is evaluated that the longer the time taken for the cured film to fall off the substrate, the shorter the peeling time and the better the peelability. The results are shown in Table 2.

[Etching Resistance]

The copper surface of a 1.6 mm thick copper-clad laminate (made by Hitachi Chemical Co., Ltd., trade name "MCL-E-67") consisting of a glass epoxy material and a copper foil (thickness 100 μm) And polished using a polishing machine having a brush (manufactured by Sankei Co., Ltd.), washed with water, and then dried with an air flow. After the copper clad laminate (hereinafter referred to as "substrate") was heated and heated to 80 ° C, the photosensitive elements related to Examples 1 to 10 and Comparative Examples 1 to 6 were laminated (laminated) , And evaluation laminated boards were produced. Thereafter, the steps up to the developing treatment were carried out in the same manner as the above-mentioned method of preparing the substrate for evaluation of adhesion and resolution.

Next, etching was performed at twice the shortest etching time. And then immersed in a 3.0 wt% aqueous solution of NaOH at 50 DEG C, and the copper pattern was observed after peeling off the resist. (A disappearance of a line region) of 5 占 퐉 or more when a difference between a resist pattern before peeling and an outline of the obtained copper pattern is observed on the upper surface of the substrate, and a case where the line is etched linearly according to the resist pattern before peeling &Quot; x "was used when the line-roughness (change in the width of the line area) was visible. When line roughness occurred but less than 5 占 퐉, it was determined to be?. The "shortest etching time" is a value obtained by measurement as follows. First, the above-mentioned copper clad laminate was cut into a size of 30 mm x 30 mm to obtain 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 占 폚 and the shortest time to visually confirm that the copper layer of the copper clad laminate had been removed was defined as the shortest etching time did.

[Tent Reliability]

The tent reliability was evaluated by making the substrate 40 for measuring the number of hole breakages shown in Fig. 3 as follows. Three independent circular holes 41 and three circular holes are connected to the copper laminated plate (product name "MCL-E-67", manufactured by Hitachi Chemical Co., Ltd.) with a hole diameter of 4 mm to 6 mm, Further, three continuous holes (42) in which the intervals of the circular holes are gradually shortened are produced by a perforator. The circular holes 41 and the three continuous holes 42 were removed by using a polishing machine having a brush having a brush equivalent to # 600 (made by Sanke Kikai Co., Ltd.) .

The resulting substrate for hole breakage number measurement was heated to 80 DEG C and the protective layer was peeled off from the photosensitive element related to Examples 1 to 10 and Comparative Examples 1 to 6 so that the photosensitive resin layer was peeled off from the hole- And the laminate was laminated under the conditions of 120 DEG C and 0.4 MPa, respectively, to produce laminate substrates for tent reliability evaluation.

After laminating, the laminate substrate for tent reliability evaluation was cooled to 23 deg. Subsequently, an exposure device (trade name: "Paragon-9000m &quot;, trade name, manufactured by Nihon Olvotech Co., Ltd.) having a semiconductor excitation solid laser as a light source was used to expose the photosensitive element from the support to an exposure amount of 17 mJ / cm ² .

After the exposure, the substrate was left for 15 minutes at room temperature. Subsequently, the support was peeled from the tent reliability evaluation laminate substrate and developed by spraying a 1 mass% sodium carbonate aqueous solution at 30 占 폚 for 50 seconds. After development, the number of hole breaks in three consecutive holes was measured, and the release tent destruction rate was calculated as the number of hole breaks with respect to the total number of three consecutive holes to evaluate the tent reliability (%). The higher this number, the higher the reliability of the tent. The results are shown in Table 2.

As shown in the above evaluation results, in the case of using the photosensitive element related to Examples 1 to 10 using the photosensitive resin composition of the present invention, as compared with the case where the photosensitive element related to Comparative Examples 1 to 6 was used, , Resolution, etching resistance, peelability and excellent tent reliability. With respect to the photosensitive element related to the comparative example, the photosensitivity was the same as that of the photosensitive element related to the embodiment, but was inferior to the etching resistance. In Comparative Examples 1, 3 and 6, tent reliability was poor, and Comparative Example 5 was inferior in peelability.

The disclosure of Japanese Patent Application No. 2014-099630 is hereby incorporated by reference in its entirety. All publications, patent applications, and technical specifications described in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, and technical specification were specifically and individually indicated to be incorporated by reference. do.

Claims (9)

(C ₄ H ₈ O) _n -: n is a number of not less than 2, and the number of the repeating units is not less than 2, As a structural unit, and a polytetramethylene oxide compound which may be a part or all of at least one selected from the group consisting of the component (A), the component (B) and the component (C), and the photosensitive resin composition Is less than 120 mgKOH / g. The method according to claim 1,
Wherein the polytetramethylene oxide compound has a weight average molecular weight of 1000 or more. The method according to claim 1 or 2,
Wherein part or all of the component (B) is a polytetramethylene oxide compound. The method of claim 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 method according to claim 3 or 4,
Wherein the polytetramethylene oxide compound which is part or all of the component (B) is polytetramethylene glycol di (meth) acrylate. The method of 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 photosensitive resin layer forming step of forming a photosensitive resin layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 6 or the photosensitive element according to claim 7;
An exposure step of irradiating at least a part of the area of the photosensitive resin layer with an actinic ray to cure the area,
And a developing step of removing unexposed portions other than the region of the photosensitive resin layer from the substrate. A method for manufacturing 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 claim 8.

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