JP2014170041A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which can achieve high adhesiveness and short peeling time.SOLUTION: A photosensitive resin composition is formed of the following components (a) to (d): (a) 20-70 mass% of alkali-soluble polymer; (b) 5-30 mass% of an addition polymerizable monomer having at least one polymerizable ethylenic unsaturated bond in a molecule; (c) 0.01-30 mass% of a photopolymerization initiator; and (d) 20-40 mass% of an additive which is a compound that is not involved in a radical polymerization other than the (a) to (c) components. The addition polymerizable monomer contains a polyfunctional monomer having at least three polymerizable ethylenic unsaturated bonds in the molecule.

Description

  The present invention relates to a photosensitive resin composition.

  Conventionally, a printed wiring board is generally manufactured by a photolithography method. The photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed, and an exposed portion of the photosensitive resin composition is polymerized and cured (in the case of a negative type) or solubilized in a developer (positive). Mold) and unexposed areas (in the case of negative molds) or exposed areas (in the case of positive molds) are removed with a developer to form a resist pattern on the substrate, and etching or plating is performed to form a conductor pattern. After forming, the resist pattern is peeled off from the substrate to form a conductor pattern on the substrate.

  In the photolithography method, usually, when a photosensitive resin composition is applied onto a substrate, the photosensitive resin composition solution is applied to the substrate and dried, or a support or a photosensitive resin composition is used. Any method of laminating a photosensitive resin laminate (hereinafter also referred to as “dry film resist”) in which a layer (hereinafter also referred to as “photosensitive resin layer”) and, if necessary, a protective layer are sequentially laminated, on a substrate. Is used. In the production of printed wiring boards, the latter dry film resist is often used.

  A method for producing a printed wiring board using the dry film resist will be briefly described below.

  First, when the dry film resist has a protective layer such as a polyethylene film, it is peeled off from the photosensitive resin layer. Next, the photosensitive resin layer and the support are laminated on a substrate such as a copper clad laminate using a laminator so that the substrate, the photosensitive resin layer, and the support are in this order. Next, the exposed portion is polymerized and cured by exposing the photosensitive resin layer to ultraviolet rays or the like containing i rays (365 nm) emitted from an ultrahigh pressure mercury lamp through a photomask having a wiring pattern. Next, the support made of polyethylene terephthalate or the like is peeled off.

  Next, a non-exposed portion of the photosensitive resin layer is dissolved or dispersed and removed by a developing solution such as an aqueous solution having weak alkalinity to form a resist pattern on the substrate. Next, a known etching process or pattern plating process is performed using the formed resist pattern as a protective mask. In the method of removing a metal portion by etching, a metal in the hole is prevented from being etched by covering a through hole (through hole) of the substrate or a via hole for interlayer connection with a cured resist film. This construction method is called a tenting method. For the etching step, for example, cupric chloride, ferric chloride or a copper ammonia complex solution is used.

  Finally, the resist pattern is peeled from the substrate with an alkaline aqueous solution such as sodium hydroxide to produce a substrate having a conductor pattern, that is, a printed wiring board. In the method of pattern plating, copper plating is performed on the same copper surface, and if necessary, after further plating of solder, nickel, tin, etc., the resist pattern is peeled off from the substrate in the same manner. The copper surface such as the copper clad laminate that appears is etched.

  Therefore, the dry film resist is an important element for responding to the increase in the density and demand of printed wiring boards. Various dry film resists have been proposed as such dry film resists (see Patent Document 1).

JP-A-2005-92102

However, it has been difficult to achieve both high adhesion and short peeling time at a high level with the conventional technology.
That is, if the adhesion of the dry film is insufficient during the production of printed wiring boards, etc., the chemical solution will enter under the resist during the etching and plating process, and the intended pattern may not be obtained, or the finished line There may be rattling. Further, when it takes a long time to remove the dry film resist, it is necessary to reduce the line speed accordingly, and the productivity is adversely affected. If the resist does not completely peel from the substrate and remains, it becomes a foreign substance in a later process, which adversely affects the yield.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the photosensitive resin composition which can achieve high adhesiveness and short peeling time.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following technical means.
That is, the present invention is as follows.

｛式中、Ｒ¹は水素原子又は炭素数が１〜８である一価の有機基を表し、Ｒ²、Ｒ³及びＲ⁴はそれぞれ独立に水素原子又はメチル基を表し、Ａ¹は炭素数２〜６のアルキレン基を表し、ｎ¹、ｎ²及びｎ³はｎ¹＋ｎ²＋ｎ³＝３〜６０を満たす０以上の整数であり、ｎ⁴は０又は１であり、但し式中複数存在するＡ¹はそれぞれ同一でも異なっていてもよく、−（Ｏ−Ａ¹）−の繰り返し構造はランダムであってもブロックであってもよい。｝で表される化合物である、上記［１］に記載の感光性樹脂組成物。
［３］ 該ｎ¹、ｎ²及びｎ³が、ｎ¹＋ｎ²＋ｎ³＝６〜６０を満たす０以上の整数である、上記［２］に記載の感光性樹脂組成物。
［４］ 該一般式［Ｉ］で表される化合物の、該付加重合性モノマー中に占める割合が、１０〜８０質量％である、上記［２］又は［３］に記載の感光性樹脂組成物。
［５］ 該添加剤が、
下記一般式［ＩＩ］：
Ｒ⁵−Ｏ−（Ａ²−Ｏ）_ｎ５−Ｒ⁶ ［ＩＩ］
｛式中、Ｒ⁵及びＲ⁶は、それぞれ独立に水素原子又は炭素数が１〜３０である一価の有機基であり、Ａ²は、アルキレン基であり、ｎ⁵は、１以上４００以下の整数であり、−（Ａ²−Ｏ）−の繰り返し構造は、同一であっても異なっていてもよく、そして−（Ａ²−Ｏ）−の繰り返し構造が異なる場合には、ランダムであってもブロックであってもよい。｝で表される化合物、
下記一般式［ＩＩＩ］：

｛式中、Ｒ^７，Ｒ^８，Ｒ^９及びＲ^１０はそれぞれ独立に水素原子又は炭素数１〜３０のアルキル基、又は脂肪酸アシル基を表し、ｎ⁶、ｎ⁷、ｎ⁸及びｎ⁹はそれぞれ独立に０以上の整数であり、但しｎ⁶＋ｎ⁷＋ｎ⁸＋ｎ⁹は０〜４０であり、Ａ³は−ＣＨ（ＣＨ₃）ＣＨ₂−、−ＣＨ₂ＣＨ（ＣＨ₃）−又は−ＣＨ₂ＣＨ₂−を表し、−（Ａ³−Ｏ）−の繰り返し構造は、ランダムであっても、ブロックであってもよい。｝で表される化合物、及び
下記一般式［ＩＶ］：

｛式中、Ａ⁴は、−ＣＨ（ＣＨ₃）ＣＨ₂−、−ＣＨ₂ＣＨ（ＣＨ₃）−又は−ＣＨ₂ＣＨ₂−を表し、ｎ¹⁰及びｎ¹¹は、それぞれ独立に０以上の整数であり、さらに好ましくは、ｎ¹⁰及びｎ¹¹は、各々独立に１〜３０の整数であり、ｎ¹⁰＋ｎ¹¹は１〜６０の整数であり、−（Ａ⁴−Ｏ）−の繰り返し構造は、同一であっても異なっていてもよく、そして−（Ａ⁴−Ｏ）−の繰り返し構造が異なる場合には、ランダムでもブロックでもよい。｝で表される化合物、よりなる群から選択される１種又は２種以上を含む、上記［１］〜［４］のいずれかに記載の感光性樹脂組成物。
［６］ 該一般式［ＩＩ］で表される化合物、該一般式［ＩＩＩ］で表される化合物、及び該一般式［ＩＶ］で表される化合物よりなる群から選択される１種又は２種以上の、該添加剤中に占める合計割合が、２０〜１００質量％である、上記［５］に記載の感光性樹脂組成物。
［７］ 以下の工程：
上記［１］〜［６］のいずれかに記載の感光性樹脂組成物から成る感光性樹脂層を支持体に積層するラミネート工程、
該感光性樹脂層を露光する露光工程、及び
該露光された感光性樹脂層を現像する現像工程、
を含む、レジストパターンの形成方法。
［８］ 以下の工程：
上記［１］〜［６］のいずれかに記載の感光性樹脂組成物から成る感光性樹脂層を基板に積層するラミネート工程、
該感光性樹脂層を露光する露光工程、
該露光された感光性樹脂層を現像して、レジストパターンが形成された基板を得る現像工程、
該レジストパターンが形成された基板をエッチング又はめっきする導体パターン形成工程、及び
該レジストパターンを剥離する剥離工程
を含む、配線板の製造方法。 [1] The following components (a) to (d):
(A) Alkali-soluble polymer: 20 to 70% by mass,
(B) addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule: 5 to 30% by mass;
(C) Photopolymerization initiator: 0.01 to 30% by mass, and (d) Additives: 20 to 40% by mass, which are compounds not involved in promotion of radical polymerization other than (a) to (c).
Consists of
A photosensitive resin composition, wherein the addition polymerizable monomer contains a polyfunctional monomer having at least three polymerizable ethylenically unsaturated bonds in the molecule.
[2] The polyfunctional monomer is represented by the following general formula [I]:

{Wherein, R ¹ represents a monovalent organic group hydrogen atom or a carbon number of 1~8, R ^2, R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, A ¹ is carbon represents an alkylene group having 2 to 6, n ^1, n ² and n ³ are 0 or an integer satisfying ^{n 1 + n 2 + n 3} = 3~60, n 4 is 0 or 1, provided that Shikichu A plurality of A ¹ may be the same or different, and the repeating structure of — (O—A ¹ ) — may be random or block. } The photosensitive resin composition as described in said [1] which is a compound represented by these.
[3] The photosensitive resin composition according to the above [2], wherein the n ¹ , n ² and n ³ are integers of 0 or more satisfying n ¹ + n ² + n ³ = 6 to 60.
[4] The photosensitive resin composition according to the above [2] or [3], wherein a proportion of the compound represented by the general formula [I] in the addition polymerizable monomer is 10 to 80% by mass. object.
[5] The additive is
The following general formula [II]:
_{^{R 5 -O- (A 2 -O)}} n5 -R 6 [II]
{Wherein R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, A ² is an alkylene group, and n ⁵ is 1 or more and 400 or less. The repeating structure of — (A ² —O) — may be the same or different, and when the repeating structure of — (A ² —O) — is different, it is random. Or a block. } A compound represented by
The following general formula [III]:

{Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or a fatty acid acyl group, and n ⁶ , n ⁷ , n ⁸ and n ⁹ are Each independently represents an integer of 0 or more, provided that n ⁶ + n ⁷ + n ⁸ + n ⁹ is 0 to 40, and A ³ is —CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) — or —. CH ₂ CH ₂ — is represented, and the repeating structure of — (A ³ —O) — may be random or block. }, And the following general formula [IV]:

{In the formula, A ⁴ represents -CH (CH ₃ ) CH _2- , -CH ₂ CH (CH ₃ )-or -CH ₂ CH _2- , and n ¹⁰ and n ¹¹ each independently represents 0 or more. N ¹⁰ and n ¹¹ are each independently an integer of 1 to 30, n ¹⁰ + n ¹¹ is an integer of 1 to 60, and — (A ⁴ —O) — is a repeating structure. May be the same or different, and may be random or block if the repeating structure of-(A ⁴ -O)-is different. }, The photosensitive resin composition in any one of said [1]-[4] containing 1 type, or 2 or more types selected from the group which consists of.
[6] One or two selected from the group consisting of the compound represented by the general formula [II], the compound represented by the general formula [III], and the compound represented by the general formula [IV] The photosensitive resin composition as described in [5] above, wherein a total ratio of the seeds or more in the additive is 20 to 100% by mass.
[7] The following steps:
A laminating step of laminating a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [6] on a support;
An exposure step of exposing the photosensitive resin layer; and a development step of developing the exposed photosensitive resin layer;
A method for forming a resist pattern, comprising:
[8] The following steps:
A laminating step of laminating a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [6] on a substrate;
An exposure step of exposing the photosensitive resin layer;
A development step of developing the exposed photosensitive resin layer to obtain a substrate on which a resist pattern is formed;
A method for manufacturing a wiring board, comprising: a conductor pattern forming step of etching or plating a substrate on which the resist pattern is formed; and a peeling step of peeling the resist pattern.

  According to this invention, the photosensitive resin composition which can achieve high adhesiveness and short peeling time is provided.

  Hereinafter, typical modes for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary. In the present disclosure, the mass% described regarding the amount of each component in the photosensitive resin composition is based on the total solid mass of the photosensitive resin composition unless otherwise specified.

The photosensitive resin composition of the present embodiment includes the following components (a) to (d):
(A) 20-70 mass% of alkali-soluble polymer,
(B) 5-30% by mass of an addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule (hereinafter also referred to as (b) addition polymerizable monomer),
(C) 0.01 to 30% by mass of a photopolymerization initiator, and (d) an additive which is a compound not involved in promotion of radical polymerization other than the above (a) to (c) (hereinafter referred to as (d) additive 20-40% by mass)
Including
The addition polymerizable monomer contains a polyfunctional monomer having at least three polymerizable ethylenically unsaturated bonds in the molecule (also simply referred to as a polyfunctional monomer in the present disclosure).
In the present embodiment, in addition to obtaining good peeling performance by using 20 to 40% by mass of (d) additive, good adhesion can be realized by using a polyfunctional monomer.

(A) Alkali-soluble polymer (a) The alkali-soluble polymer is typically a thermoplastic copolymer containing a carboxyl group-containing monomer as a copolymerization component.

  (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 or more from the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance to the developer, while maintaining the developability. To 500,000 or less is preferable. The lower limit of the weight average molecular weight of the more preferable (a) alkali-soluble polymer is 20,000, and the upper limit is 300,000. Moreover, (a) The molecular weight distribution (namely, weight average molecular weight / number average molecular weight) of the alkali-soluble polymer is preferably 1 to 6, more preferably 1 to 4, from the viewpoint of resolution.

The weight average molecular weight and molecular weight distribution in the present disclosure are weight average molecular weight and molecular weight distribution measured by gel permeation chromatography (GPC) using a calibration curve of polystyrene (for example, Shodex STANDARD SM-105 manufactured by Showa Denko KK). Means. The weight average molecular weight and molecular weight distribution can be measured using, for example, gel permeation chromatography manufactured by JASCO Corporation under the following conditions:
Differential refractometer: RI-1530
Pump: PU-1580
Degasser: DG-980-50
Column oven: CO-1560
Column: KF-8025, KF-806M × 2, KF-807 in order
Eluent: THF

  (A) The alkali-soluble polymer is preferably obtained by copolymerizing a copolymer component composed of one or more first monomers described later and one or more second monomers described later. .

  The first monomer is a monomer containing a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable from the viewpoint of resolution. Here, (meth) acryl indicates acryl or methacryl. The same applies hereinafter.

  The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate, etc. And esters of vinyl alcohol; (meth) acrylonitrile, styrene, polymerizable styrene derivatives, and the like. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are preferable from the viewpoint of handleability, and styrene is particularly preferable from the viewpoint of resolution.

  (A) The alkali-soluble polymer is prepared by mixing the above first and second monomers and diluting with a solvent such as acetone, methyl ethyl ketone, or isopropanol, into a radical polymerization initiator such as benzoyl peroxide. Alternatively, it is preferable to carry out the synthesis by adding an appropriate amount of azoisobutyronitrile and stirring with heating. In some cases, the synthesis is performed while a part of the monomer mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As a synthesis means, in addition to the above solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

  Particularly preferable (a) alkali-soluble polymer has a copolymerization ratio of the first monomer and the second monomer of 100% by mass in total of the first monomer and the second monomer. Among them, the first monomer is 10 to 60% by mass, and the second monomer is 40 to 90% by mass, more preferably the first monomer is 15 to 35% by mass, And the second monomer is 65 to 85% by mass. The copolymerization ratio is preferable from the viewpoint of easily adjusting the alkali solubility and the molecular weight within a desired range.

  (A) As a more specific example of the alkali-soluble polymer, a polymer containing methyl methacrylate, methacrylic acid and styrene as a copolymer component, methyl methacrylate, methacrylic acid and n-butyl acrylate as a copolymer component And a polymer containing benzyl methacrylate, methyl methacrylate and 2-ethylhexyl acrylate as a copolymerization component.

  In this embodiment, the content of (a) the alkali-soluble polymer in the photosensitive resin composition (that is, the amount relative to the total solid content of the photosensitive resin composition) is 20% by mass to 70% by mass. The lower limit is 25% by mass, the preferred upper limit is 65% by mass, the more preferred lower limit is 40% by mass, and the more preferred upper limit is 60% by mass. This content is 20% by mass or more from the viewpoint of maintaining alkali developability, and on the other hand, it is 70% by mass or less from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist. .

(B) Addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule The addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule is an ethylenically unsaturated group. It has addition polymerizability by having. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group from the viewpoint of reactivity.
In this embodiment, (b) the addition polymerizable monomer contains a polyfunctional monomer having at least three polymerizable ethylenically unsaturated bonds in the molecule. According to this embodiment, the photosensitive resin composition which can form the cured film excellent in the adhesiveness to a board | substrate can be provided by the effect | action which complicates the crosslinked structure which a polyfunctional monomer has. The cured film formed from the photosensitive resin composition of the present embodiment is, for example, a substrate formed of a material such as copper, stainless steel (SUS), glass, indium tin oxide (ITO), particularly for a printed wiring board. Good adhesion to a metal plate or a metal film insulating plate as a substrate.

｛式中、Ｒ¹は水素原子又は炭素数が１〜８である一価の有機基を表し、Ｒ²、Ｒ³及びＲ⁴はそれぞれ独立に水素原子又はメチル基を表し、Ａ¹は炭素数２〜６のアルキレン基を表し、ｎ¹、ｎ²及びｎ³はｎ¹＋ｎ²＋ｎ³＝３〜６０を満たす０以上の整数であり、ｎ⁴は０又は１であり、但し式中複数存在するＡ¹はそれぞれ同一でも異なっていてもよく、−（Ｏ−Ａ¹）−の繰り返し構造はランダムであってもブロックであってもよい。｝
で表される化合物であることが好ましい。 As the polyfunctional monomer, from the viewpoint of chemical resistance, adhesion, and tenting property of the resist, the following general formula [I]:

{Wherein, R ¹ represents a monovalent organic group hydrogen atom or a carbon number of 1~8, R ^2, R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, A ¹ is carbon represents an alkylene group having 2 to 6, n ^1, n ² and n ³ are 0 or an integer satisfying ^{n 1 + n 2 + n 3} = 3~60, n 4 is 0 or 1, provided that Shikichu A plurality of A ¹ may be the same or different, and the repeating structure of — (O—A ¹ ) — may be random or block. }
It is preferable that it is a compound represented by these.

In the compound represented by the general formula [I], A ¹ is —CH (CH ₃ ) CH ₂ — and / or —CH ₂ CH (CH ₃ ) — from the viewpoints of peeling performance and developer dispersibility. And / or —CH ₂ CH ₂ —. In the case where different alkylene groups are mixed, the repeating structure is preferably a block from the viewpoint of resolution.

In the compound represented by the general formula [I], n ¹ + n ² + n ³ is preferably 3 or more from the viewpoints of flexibility and tenting properties of the cured film, and from the viewpoint of adhesion of the cured film to the substrate. More preferably, it is 6 or more. Moreover, it is preferable that it is 60 or less from a chemical-resistant viewpoint, and it is more preferable that it is 15 or less.

  Specific examples of the unsaturated compound represented by the general formula [I] include triacrylate obtained by adding an average of 3 units of ethylene oxide to trimethylolpropane, and an average of 3 units of propylene oxide to trimethylolpropane. Added triacrylate, triacrylate obtained by adding an average of 6 units of ethylene oxide to trimethylolpropane, triacrylate obtained by adding an average of 9 units of ethylene oxide to trimethylolpropane, glycerol triacrylate, trimethylolpropane acrylate Preferred examples thereof include triacrylate.

  Other specific examples of the polyfunctional monomer include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and pentaerythritol with an average of 4 moles of ethylene oxide. Examples thereof include tetraacrylate of added glycol and polyfunctional (meth) acrylate of isocyanuric acid ester compound.

  The proportion of the compound represented by the general formula [I] in the (b) addition polymerizable monomer is preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoint of adhesion of the cured resist. is there. The ratio is preferably 100% by mass from the viewpoint of adhesion. On the other hand, it is preferably 80% by mass or less, more preferably 60% by mass or less, from the viewpoint of obtaining good effects from other compounds that can be used as the (b) addition polymerizable monomer.

  Content of the polyfunctional monomer in the photosensitive resin composition becomes like this. Preferably it is 1-30 mass%, More preferably, it is 3-20 mass%, More preferably, it is 5-15 mass%. The content is 1% by mass or more from the viewpoint of obtaining good adhesion, and 30% by mass or less from the viewpoint of peeling performance.

The component (b) may contain other monomers in addition to the polyfunctional monomer.
From the viewpoint of high resolution, edge fuse properties, and tenting properties, it is preferable to use at least one bisphenol A (meth) acrylate compound as the component (b). The bisphenol A-based (meth) acrylate compound here means a carbon-carbon unsaturated double bond derived from a (meth) acryloyl group or a (meth) acryloyl group and -C ₆ H ₄ -C (CH derived from bisphenol A _{3) 2} -C ₆ H ₄ - is a compound having a group.

｛式中、Ｒ¹¹及びＲ¹²はそれぞれ独立に水素原子又はメチル基を表し、Ａ⁵は炭素数２〜６のアルキレン基を表し、ｎ¹²及びｎ¹³はｎ¹²＋ｎ¹³＝２〜４０を満たす０以上の整数であり、但し式中複数存在するＡ⁵はそれぞれ同一でも異なっていてもよく、−（Ａ⁵−Ｏ）−の繰り返し構造はランダムであってもブロックであってもよい。｝
で表されるビスフェノールＡ系（メタ）アクリレート化合物を用いることが、解像性、及びテンティング性の観点から好ましい。 Among them, the following general formula [V]:

{Wherein R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, A ⁵ represents an alkylene group having 2 to 6 carbon atoms, and n ¹² and n ¹³ represent n ¹² + n ¹³ = 2 to 40. It is an integer of 0 or more that is satisfied, provided that a plurality of A ^{5 in the} formula may be the same or different, and the repeating structure of — (A ⁵ —O) — may be random or block. }
It is preferable to use a bisphenol A-based (meth) acrylate compound represented by the following from the viewpoints of resolution and tenting properties.

In the compound represented by the general formula [V], A ⁵ represents —CH (CH ₃ ) CH ₂ — and / or —CH ₂ CH (CH ₃ ) —, from the viewpoints of resolution and developer dispersibility. And / or —CH ₂ CH ₂ —, and when different alkylene groups are mixed, the repeating structure is preferably a block from the viewpoint of developer dispersibility.

In the compound represented by the general formula [V], n ¹² + n ¹³ is preferably 2 or more, and more preferably 4 or more, from the viewpoints of flexibility and tenting properties of the cured film. Moreover, it is preferable that it is 40 or less from a viewpoint of raw material handleability, and it is more preferable that it is 20 or less.

  Specific examples of the unsaturated compound represented by the general formula [V] include polyethylene glycol dimethacrylate obtained by adding an average of 2 units of ethylene oxide to both ends of bisphenol A, and an average of 5 units of both ends of bisphenol A, respectively. Polyethylene glycol dimethacrylate to which ethylene oxide is added, polyalkylene glycol dimethacrylate to which bisphenol A is added with an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide at both ends, and an average of 15 units at each end of bisphenol A Preferable examples include polyalkylene glycol dimethacrylate obtained by adding ethylene oxide and an average of 2 units of propylene oxide.

  The content of the unsaturated compound represented by the general formula [V] in the photosensitive resin composition is preferably 1% by mass or more, more preferably from the viewpoint of obtaining good resolution and tenting properties. From the viewpoint of being 5% by mass or more and advantageous for using a desired amount of the polyfunctional monomer, it is preferably 27% by mass or less, more preferably 25% by mass or less.

｛式中、Ｒ¹³及びＲ¹⁴はそれぞれ独立に水素原子又はメチル基を表し、Ａ⁶は炭素数２〜６のアルキレン基を表し、ｎ¹⁴は２〜４０を満たす整数であり、但し式中複数存在するＡ⁶はそれぞれ同一でも異なっていてもよく、−（Ａ⁶−Ｏ）−の繰り返し構造はランダムであってもブロックであってもよい。｝
で表される化合物を含むことは好ましい。 From the viewpoint of high resolution, cured film flexibility, and release piece solubility, as the component (b), the general formula [VI]:

{Wherein R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a methyl group, A ⁶ represents an alkylene group having 2 to ⁶ carbon atoms, and n ¹⁴ is an integer satisfying 2 to 40, provided that A plurality of A ⁶ may be the same or different, and the repeating structure of — (A ⁶ —O) — may be random or block. }
It is preferable to contain the compound represented by these.

In the compound represented by the general formula [VI], A ⁶ represents —CH (CH ₃ ) CH ₂ — and / or —CH ₂ CH (CH ₃ ) — from the viewpoints of peeling performance and developer dispersibility. And / or —CH ₂ CH ₂ —, and when different alkylene groups are present, the repeating structure is preferably a block from the viewpoint of resolution.

In the compound represented by the general formula [VI], n ¹⁴ is preferably 2 or more, and more preferably 4 or more, from the viewpoints of flexibility and tenting properties of the cured film. Moreover, it is preferable that it is 40 or less from a viewpoint of resolution and plating resistance, and it is more preferable that it is 30 or less.

Specific examples of the unsaturated compound represented by the general formula [VI] include diacrylates in which A ⁶ is an ethylene group and n ¹⁴ = 9, and dimethacrylates in which A ⁶ is a propylene group and n ¹⁴ is 7. Preferred examples include polyalkylene oxide dimethacrylate, wherein A ⁶ is a mixture of propylene group and ethylene group, and an average of 3 units of ethylene oxide is added to both ends of an average of 12 units of propylene oxide.

  The content of the unsaturated compound represented by the general formula [VI] in the photosensitive resin composition is preferably from the viewpoint of obtaining good high resolution, cured film flexibility, and peelable piece solubility. 1 mass% or more, more preferably 3 mass% or more, and preferably 27 mass% or less, more preferably 25 mass% or less from the viewpoint that it is advantageous for using a desired amount of polyfunctional monomer.

  As the component (b), in addition to the compounds represented by the above general formulas [I], [V] and [VI], for example, known compounds having at least one terminal ethylenically unsaturated group (hereinafter, (Sometimes referred to as “other monomers”) can be preferably used.

  Examples of other monomers include 2-hydroxy-3-phenoxypropyl acrylate, a reaction product of a half ester compound of phthalic anhydride and 2-hydroxypropyl acrylate, and propylene oxide, 1,6-hexanediol di (meth) acrylate. 1,4-cyclohexanediol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 4-nonylphenyl octaethylene glycol acrylate, 4 -Normal octyl phenoxy pentapropylene glycol acrylate etc. are mentioned. These may be used alone or in combination of two or more.

  The proportion of the compound represented by the general formula [V], the compound represented by the general formula [VI], and the other monomer in the (b) addition polymerizable monomer is prevented from curing failure, and From the viewpoint of chemical resistance of the cured resist, it is preferably 5% by mass or more, more preferably 10% by mass or more. On the other hand, it is preferably 90% by mass or less, and more preferably 70% by mass or less, from the viewpoint of suppressing the handleability of the dry film resist and suppressing the peeling delay of the cured resist.

  The content of the (b) addition polymerizable monomer in the photosensitive resin composition is 5 to 30% by mass, preferably 10 to 28% by mass, and more preferably 20 to 26% by mass. The content is 5% by mass or more from the viewpoint of chemical resistance of the cured resist, and 30% by mass or less from the viewpoint of peeling performance.

(C) Photopolymerization initiator (c) The photopolymerization initiator is a compound that polymerizes a monomer by light. (C) As the photopolymerization initiator, those usually used as photopolymerization initiators for photosensitive resins can be used as appropriate. From the viewpoint of resolution, hexaarylbisimidazole (hereinafter referred to as triarylimidazolyl dimer) is particularly suitable. Is also preferably used.

  In particular, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer is a photopolymerization initiator having a high effect on resolution or the strength of a cured resist film, and is preferably used. These may be used alone or in combination with two or more different photopolymerization initiators. Triarylimidazolyl dimers (particularly 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer) can also be used in combination with the following acridine compounds, pyrazoline compounds and the like.

  In a preferred embodiment of the present invention, (c) an acridine compound or a pyrazoline compound is used as a photopolymerization initiator. As the acridine compound, 9-phenylacridine is particularly preferable from the viewpoint of sensitivity.

  Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -Pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline and the like are preferable.

  Other photopolymerization initiators include aromatic ketones, N-aryl-α-amino acid compounds, N-aryl amino acid ester compounds, halogen compounds, quinones, acetophenones, acylphosphine oxides, benzoin, benzoin. Examples include ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, and oxime esters.

  Examples of aromatic ketones include benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone, and 4-methoxy-4′-dimethylaminobenzophenone. Can be mentioned.

  Examples of N-aryl amino acids include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Among these, N-phenylglycine is particularly preferable.

  Moreover, you may contain the color former in the photosensitive resin composition so that a visible image can be given by exposure. Examples of such a coloring dye include a leuco dye or a combination of a fluorane dye and a halogen compound.

  For example, as leuco dyes, tris (4-dimethylamino-2-methylphenyl) methane [leucocrystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and fluorane dye Is mentioned. Among these, when leuco crystal violet is used, the contrast is good and preferable.

  When these coloring dyes are contained, the content in the photosensitive resin composition of the present invention is preferably 0.1 to 10% by mass based on the total solid content of the photosensitive resin composition.

  (C) Content of a photoinitiator is the range of 0.01-30 mass% on the basis of the total solid of the photosensitive resin composition, A more preferable minimum is 0.05 mass%, Furthermore, a preferable minimum Is 0.1% by mass, a more preferred upper limit is 15% by mass, and a more preferred upper limit is 10% by mass. (C) The content of the photopolymerization initiator is 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity at the time of photopolymerization by exposure, and the bottom surface of the photosensitive resin composition at the time of photopolymerization (that is, a portion far from the light source) From the viewpoint of sufficiently transmitting light up to) and obtaining good resolution and adhesion, it is 30% by mass or less.

(D) Additive The photosensitive resin composition of the present embodiment contains (d) 20 to 40% by mass of the additive. (D) The additive is a compound other than the components (a) to (c) described above and does not participate in the promotion of radical polymerization. That is, the additive (d) is a compound other than the components (a) to (c), and is intended to include all compounds other than the polymerizable compound and the compound known to those skilled in the art as a polymerization initiator. . Examples of the additive (d) include various plasticizers, surfactants, colorants, adhesion assistants, stabilizers, and the like. When the photosensitive resin composition contains the predetermined amount of the additive (d), for example, it is possible to control the flexibility adding action within a desired range. In this case, the cured film formed from the photosensitive resin composition of the present embodiment is, for example, a substrate formed of a material such as copper, stainless steel (SUS), glass, indium tin oxide (ITO), particularly a print. With respect to a metal plate or a metal film insulating plate, which is a substrate for a wiring board, it exhibits good peeling performance as well as good adhesion. In a preferred embodiment, (d) the additive is a plasticizer. In a preferred embodiment, the additive (d) is a group consisting of a compound represented by the following general formula [II], a compound represented by the following general formula [III], and a compound represented by the following general formula [IV]. 1 type or 2 types or more selected from are included.

(D) The additive is represented by the following general formula [II]:
R ⁵ —O— (A ² —O) _{n 5} —R ⁶ [II]
{Wherein R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, A ² is an alkylene group, and n ⁵ is 1 or more and 400 or less. The repeating structure of — (A ² —O) — may be the same or different, and when the repeating structure of — (A ² —O) — is different, it is random. Or a block. } Is preferable from the viewpoint of the flexibility of the cured film. At this time, R ⁵ and R ⁶ are each preferably a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or a fatty acyl group, more preferably a hydrogen atom or a lower alkyl group having 1 to 10 carbon atoms. . Examples of the lower alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a pentyl group. When both R ⁵ and R ⁶ are hydrogen atoms, the compound represented by the above general formula [II] is a diol, and either R ⁵ or R ⁶ is a hydrogen atom and the other is an alkyl group. In this case, the compound becomes a monoether form, and when R ⁵ and R ⁶ are both alkyl groups, the compound becomes a diether form. Among these, from the viewpoint of developer dispersibility, diols in which R ¹ and R ² are both hydrogen atoms are more preferable.

  (D) When the compound represented by the above general formula [II] is used as an additive, the amount of the compound in the photosensitive resin composition is preferably 0 from the viewpoint of obtaining a good effect by using the compound. 0.5 mass% or more, more preferably 3 mass% or more, and from the viewpoint of chemical resistance, it is preferably 15 mass% or less, more preferably 13 mass% or less.

In the compound represented by the general formula [II], A ² is an alkylene group. The number of carbon atoms of the alkylene group is preferably 2 or more from the viewpoint of handleability, and preferably 4 or less from the viewpoint of compatibility with other raw materials. Specifically, as the alkylene group, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) —, —CH ₂ CH ₂ — and the like can be mentioned, among which —CH (CH ₃ ) CH ₂ — or —CH ₂ CH (CH ₃ ) — is preferable.

The repeating units of — (A ² —O) — may be the same or different. When the repeating unit of — (A ² —O) — is different, the structure may be random or block. N ⁵ representing the number of repetitions is an integer of 1 or more and 400 or less. From the viewpoint of storage stability, n ⁵ is preferably 3 or more, more preferably 9 or more. Further, from the viewpoint of not impairing the handleability of other raw materials, n ⁵ is preferably 200 or less, and more preferably 100 or less.

｛式中、Ｒ^７，Ｒ^８，Ｒ^９及びＲ^１０はそれぞれ独立に水素原子又は炭素数１〜３０のアルキル基、又は脂肪酸アシル基を表し、ｎ⁶、ｎ⁷、ｎ⁸及びｎ⁹はそれぞれ独立に０以上の整数であり、但しｎ⁶＋ｎ⁷＋ｎ⁸＋ｎ⁹は０〜４０であり、Ａ³は−ＣＨ（ＣＨ₃）ＣＨ₂−、−ＣＨ₂ＣＨ（ＣＨ₃）−又は−ＣＨ₂ＣＨ₂−を表し、−（Ａ³−Ｏ）−の繰り返し構造は、ランダムであっても、ブロックであってもよい。｝で表されるソルビタン化合物を可塑剤として含むことは、現像液分散性の観点から好ましい。 (D) The additive is represented by the following general formula [III]:

{Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or a fatty acid acyl group, and n ⁶ , n ⁷ , n ⁸ and n ⁹ are Each independently represents an integer of 0 or more, provided that n ⁶ + n ⁷ + n ⁸ + n ⁹ is 0 to 40, and A ³ is —CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) — or —. CH ₂ CH ₂ — is represented, and the repeating structure of — (A ³ —O) — may be random or block. } Is preferable from the viewpoint of developer dispersibility.

  (D) When the compound represented by the above general formula [III] is used as an additive, the amount of the compound in the photosensitive resin composition is preferably 0 from the viewpoint of obtaining a good effect by using the compound. It is preferably 3% by mass or more, more preferably 1% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less from the viewpoint of developer foamability.

｛式中、Ａ⁴は、−ＣＨ（ＣＨ₃）ＣＨ₂−、−ＣＨ₂ＣＨ（ＣＨ₃）−又は−ＣＨ₂ＣＨ₂−を表し、ｎ¹⁰及びｎ¹¹は、それぞれ独立に０以上の整数であり、さらに好ましくは、ｎ¹⁰及びｎ¹¹は、各々独立に１〜３０の整数であり、ｎ¹⁰＋ｎ¹¹は１〜６０の整数であり、−（Ａ⁴−Ｏ）−の繰り返し構造は、同一であっても異なっていてもよく、そして−（Ａ⁴−Ｏ）−の繰り返し構造が異なる場合には、ランダムでもブロックでもよい。｝
で表されるビスフェノールＡ（ＢｉｓＡ）化合物を可塑剤として含むことは、耐薬品性の観点から好ましい。 (D) The additive is represented by the following general formula [IV]:

{In the formula, A ⁴ represents -CH (CH ₃ ) CH _2- , -CH ₂ CH (CH ₃ )-or -CH ₂ CH _2- , and n ¹⁰ and n ¹¹ each independently represents 0 or more. N ¹⁰ and n ¹¹ are each independently an integer of 1 to 30, n ¹⁰ + n ¹¹ is an integer of 1 to 60, and — (A ⁴ —O) — is a repeating structure. May be the same or different, and may be random or block if the repeating structure of-(A ⁴ -O)-is different. }
It is preferable from a chemical-resistant viewpoint to contain the bisphenol A (BisA) compound represented by these as a plasticizer.

  (D) When the compound represented by the above general formula [IV] is used as an additive, the amount of the compound in the photosensitive resin composition is preferably 1 from the viewpoint of obtaining a good effect by using the compound. From the viewpoint of handleability, it is preferably 15% by mass or less, and more preferably 10% by mass or less.

  One or more selected from the group consisting of a compound represented by the above general formula [II], a compound represented by the above general formula [III], and a compound represented by the above general formula [IV] The total proportion of the component (d) in the additive is preferably 20% by mass or more, and more preferably 50% by mass or more, from the viewpoint of obtaining good peelability of the cured resist. The above ratio is preferably 100% by mass from the viewpoint of good release performance, but (d) from the viewpoint of obtaining the effect by using other components described later as an additive, for example, 95% by mass or less, Or it can be 90 mass% or less.

  The compound having an alkylene oxide repeating structure as described above is particularly preferably used for enhancing the peeling performance of the cured resist. (D) The amount of the compound having an alkylene oxide repeating structure as an additive is preferably 20 to 35% by mass based on the total solid content of the photosensitive resin composition, and preferably 22 to 30% by mass. It is more preferable. The lower limit is preferably 20% by mass from the viewpoint of particularly improving the peeling performance and the dispersion performance in the developer, and the upper limit is preferably 35% by mass from the viewpoint of maintaining the chemical resistance of the cured resist.

  In addition, (d) additives include, for example, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri Plasticizers such as -n-propyl and tri-n-butyl acetylcitrate can be used. In particular, it is preferable to use p-toluenesulfonic acid amide from the viewpoint of making the peeled piece fine.

  The photosensitive resin composition of the present embodiment can contain various additives as part of (d) the additive. Specific examples include coloring substances such as dyes and pigments. As such a coloring substance, as a base dye, for example, basic green 1 [CAS number (hereinafter the same): 633-03-4], malachite green oxalate [2437-29-8], brilliant green [633 -03-4], fuchsin [632-99-5], methyl violet [603-47-4], methyl violet 2B [8004-87-3], crystal violet [548-62-9], methyl green [82 -94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5], Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], Basic Yellow 2 [2465-27-2]. Among these, basic green 1, malachite green oxalate, and basic blue 7 are preferable, and basic green 1 and basic blue 7 are particularly preferable from the viewpoint of improving hue stability and exposure contrast.

  When it contains the said coloring substance, it is preferable that content of a coloring substance is 0.001-1 mass% on the basis of the total solid of the photosensitive resin composition. When the content of the coloring material is 0.001% by mass or more, the effect of improving the handleability is good, and when it is 1% by mass or less, the effect of maintaining the storage stability is good.

  Furthermore, in order to improve the thermal stability and storage stability of the photosensitive resin composition, at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles and carboxybenzotriazoles is added to the photosensitive resin composition. It is preferable to make it contain.

  Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2 Examples include '-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like.

  Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole and the like can be mentioned.

  Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, (N, N-dibutylamino) carboxybenzotriazole, N- ( N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) amino And ethylene carboxybenzotriazole.

  The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.001 to 3% by mass based on the total solid content of the photosensitive resin composition, and a more preferable lower limit is 0. 0.002% by mass, and a more preferable upper limit is 1% by mass. The total content is preferably 0.001% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and preferably 3% by mass or less from the viewpoint of maintaining sensitivity.

  As the additive (d) of the photosensitive resin composition according to the present embodiment, an antioxidant may be contained as necessary. Examples of the antioxidant include triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (monononylphenyl) phosphite, and bis (monononylphenyl) -dinonylphenyl phosphite. Fight etc. are mentioned.

  The content of the antioxidant in the photosensitive resin composition is preferably in the range of 0.01% by mass to 0.8% by mass, the more preferable lower limit is 0.02% by mass, and the more preferable upper limit is 0.00. 3% by mass. When this content is 0.01 mass% or more, the effect which is excellent in the hue stability of the photosensitive resin composition expresses favorably, and the sensitivity at the time of exposure of the photosensitive resin composition becomes favorable. On the other hand, when the content is 0.8% by mass or less, since color developability is suppressed, hue stability is improved and adhesion is also improved.

  These (d) additives may be used alone or in combination of two or more. Content of the (d) additive in the photosensitive resin composition of this embodiment is the range of 20-40 mass% on the basis of the total solid of the photosensitive resin composition, and a more preferable minimum is 22 mass. %, And a more preferable upper limit is 35% by mass. (D) The content of the additive is 20% by mass or more from the viewpoint of the peelability and handleability of the cured resist, and 40% by mass or less from the viewpoint of the developer dispersibility and resolution of the unexposed film. .

<Photosensitive resin composition preparation solution>
You may use the photosensitive resin composition of this embodiment as the photosensitive resin composition formulation liquid formed by adding a solvent to this. Suitable solvents include ketones represented by methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid is 500 to 4000 mPa · sec at 25 ° C.

<Photosensitive resin laminate>
Another aspect of the present invention provides a photosensitive resin laminate having a support and a photosensitive resin layer made of the above-described photosensitive resin composition according to the present invention laminated on the support. The photosensitive resin laminate of the present invention has a protective layer on the surface of the photosensitive resin layer opposite to the support-forming side, if necessary, in addition to the photosensitive resin layer and the support that supports the layer. May be.

  The support is preferably a transparent one that transmits light emitted from the exposure light source. Examples of such a support include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film. , A polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, those stretched as necessary can be used. The haze is preferably 5 or less. The thinner the film, the more advantageous in terms of image forming property and economic efficiency, but a film having a thickness of 10 to 30 μm is preferably used because the strength needs to be maintained.

  Further, an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support and can be easily peeled with respect to the adhesion with the photosensitive resin layer. For example, a polyethylene film and a polypropylene film can be preferably used as the protective layer. Further, for example, a film having excellent peelability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

  The thickness of the photosensitive resin layer in the photosensitive resin laminate of the present embodiment is preferably 5 to 100 μm, more preferably 7 to 60 μm. As the thickness is thinner, the resolution is improved, and as the thickness is increased, the film strength is improved. Therefore, the thickness can be appropriately selected according to the application.

  As a method for preparing the photosensitive resin laminate of the present invention by sequentially laminating the support, the photosensitive resin layer, and if necessary, the protective layer, a conventionally known method can be employed.

  For example, the photosensitive resin composition used for forming the photosensitive resin layer is made into the above-mentioned photosensitive resin composition preparation solution, and is first coated on a support using a bar coater or a roll coater and dried. Then, a photosensitive resin layer made of the photosensitive resin composition is laminated on the support. Then, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

<Resist pattern formation method>
The present invention includes a laminating step of laminating a photosensitive resin layer comprising the above-described photosensitive resin composition of the present invention on a support, an exposure step of exposing the photosensitive resin layer, and the exposed photosensitive resin layer. There is also provided a resist pattern forming method including a developing step of developing. An example of the resist pattern forming method of the present embodiment is shown below.

  First, in a laminating process, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated on the substrate surface with a laminator. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like. In this case, the photosensitive resin layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces as necessary. The heating temperature at this time is generally 40 to 160 ° C. Moreover, the adhesiveness with respect to the board | substrate of the resist pattern obtained by performing this thermocompression bonding twice or more improves. At this time, a two-stage laminator provided with two rolls may be used for pressure bonding, or a laminate of the substrate and the photosensitive resin layer may be repeatedly passed through the roll and pressure bonded.

  Next, in the exposure step, the photosensitive resin composition is exposed to active light using an exposure machine. If necessary, the exposure can be performed after peeling off the support. In the case of exposure through a photomask, the exposure amount is determined by the light source illuminance and the exposure time, and may be measured using a light meter.

  In the exposure step, a maskless exposure method may be used. In maskless exposure, exposure is performed directly on the substrate by a drawing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350 nm to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, in the development step, unexposed portions in the exposed photosensitive resin layer are removed with a developer using a developing device. After exposure, if a support is present on the photosensitive resin layer, this is excluded. Subsequently, the unexposed portion is developed and removed using a developer composed of an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, an aqueous solution such as Na ₂ CO ₃ or K ₂ CO ₃ is preferable. These are selected in accordance with the characteristics of the photosensitive resin layer, but an aqueous Na ₂ CO ₃ solution having a concentration of 0.2% by mass to 2% by mass is common. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed. In addition, it is preferable to maintain the temperature of the developing solution in a development process at a constant temperature in the range of 20 ° C to 40 ° C.

  Although a resist pattern is obtained by the above-mentioned process, depending on the case, the heating process of 100 to 300 degreeC can also be performed further. By carrying out this heating step, chemical resistance can be further improved. For heating, a heating furnace such as hot air, infrared rays, or far infrared rays can be used.

<Conductor pattern manufacturing method>
The present invention also includes a laminating step of laminating a photosensitive resin layer comprising a photosensitive resin composition on a substrate, an exposing step of exposing the photosensitive resin layer, developing the exposed photosensitive resin layer, and forming a resist pattern. A method for producing a wiring board is provided, which includes a developing step for obtaining a substrate on which the resist pattern is formed, a conductor pattern forming step for etching or plating the substrate on which the resist pattern is formed, and a peeling step for peeling the resist pattern. An example of this method is shown below.

  In the laminating step, a photosensitive resin layer is formed on a substrate that is a metal plate or a metal film insulating plate. Next, the photosensitive resin layer is exposed in an exposure step. Next, a resist pattern is formed by removing unexposed portions of the exposed photosensitive resin layer with a developer. That is, the steps up to the formation of the resist pattern can be performed in the same manner as described above with respect to the method for forming the resist pattern. Next, in the conductor pattern forming step, the substrate on which the resist pattern is formed is etched or plated. After forming the conductor pattern, a printed wiring board having a desired wiring pattern can be obtained by further performing a peeling step of peeling the resist pattern from the substrate with an aqueous solution having alkalinity stronger than that of the developer. In the production of a printed board, a copper-clad laminate or a flexible board is preferably used as the board. There is no particular limitation on the alkaline aqueous solution for stripping (hereinafter also referred to as “stripping solution”), but an aqueous solution of NaOH or KOH having a concentration of 2% by mass to 5% by mass is generally used. A small amount of a water-soluble solvent can be added to the stripping solution. The temperature of the stripping solution in the stripping step is preferably in the range of 40 ° C to 70 ° C.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

(Examples 1-7 and Comparative Examples 1-6)
First, a method for producing samples for evaluation of Examples and Comparative Examples will be described, and then an evaluation method and evaluation results for the obtained samples will be shown.

1. Production of Evaluation Samples Evaluation samples in Examples and Comparative Examples were produced as follows.
<Preparation of photosensitive resin laminate>
The raw material shown in the following Table 1 (however, the number of each component indicates the blending amount (part by mass) as a solid content) and the solvent were sufficiently stirred and mixed to prepare a photosensitive resin composition preparation. Further, a polyethylene terephthalate film having a thickness of 16 μm was prepared as a support. The photosensitive resin composition preparation liquid was uniformly applied to the surface of the polyethylene terephthalate film using a bar coater, and dried in a 95 ° C. dryer for 210 seconds to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 28 μm.
Next, a 19 μm thick polyethylene film was bonded as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate.

The details of the material components B-1 to P-5 in the photosensitive resin composition preparation liquid represented by the abbreviations in Table 1 are as follows.
B-1: Ternary copolymer (methacrylic acid 25% by mass, methyl methacrylate 50% by mass, styrene 25% by mass (weight average molecular weight 50,000, acid equivalent 344)
B-2: Ternary copolymer (methacrylic acid 25% by mass, methyl methacrylate 65% by mass, butyl acrylate 10% by mass (weight average molecular weight 110,000, acid equivalent 344)
B-3: Ternary copolymer (methacrylic acid 25% by mass, methyl methacrylate 65% by mass, butyl acrylate 10% by mass (weight average molecular weight 80,000, acid equivalent 344)

M-1: triacrylate obtained by adding an average of 9 moles of ethylene oxide to trimethylolpropane M-2: dimethacrylate M of polyethylene glycol obtained by adding an average of 5 moles of ethylene oxide to both ends of bisphenol A -3: Dimethacrylate M-4 of polyalkylene glycol obtained by adding an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of bisphenol A respectively. An average of 12 moles of propylene oxide was added. Polyalkylene glycol dimethacrylate M-5 having an average of 3 moles of ethylene oxide added to both ends of polypropylene glycol M-5: Triacrylate M-6 having an average of 3 moles of ethylene oxide added to trimethylolpropane: 4-nonylpheny Heptaethylene glycol dipropylene glycol acrylate

I-1: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer I-2: 4,4′-bis (diethylamino) benzophenone I-3: N-phenylglycine

D-1: Diamond Green D-2: Leuco Crystal Violet

P-1: Polypropylene glycol having a weight average molecular weight of 2000 P-2: Propylene glycol obtained by adding an average of 2.5 moles of propylene oxide on both sides of bisphenol A P-3: Polyoxyethylene sorbitan trioleate Company made, New Call 3-85)
P-4: p-toluenesulfonamide P-5: aluminum salt added with 3 moles of nitrosophenylhydroxylamine

2. Evaluation criteria
Peelability :
As a substrate for evaluation, a 1.2 mm-thick copper-clad laminate in which 35 μm-thick rolled copper foil was laminated was used, and the surface was wet buffol polished (manufactured by 3M Co., Ltd., Scotch Bright (registered trademark) HD # 600, 2 times. Through).

  After surface preparation, the copper clad laminate is preheated to 60 ° C and laminated at a roll temperature of 105 ° C using a hot roll laminator (Asahi Kasei Co., Ltd., AL-700) while peeling the polyethylene film of the photosensitive resin laminate. did. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

The substrate for peelability evaluation after 15 minutes from lamination was exposed through a mask having a pattern of 6 cm × 5 cm. After developing with a developing time twice as long as the minimum developing time, it was immersed in an aqueous solution of caustic soda at 50 ° C. and 3 wt%, and the time for removing the resist film was measured and ranked as follows. The mask was placed on a polyethylene terephthalate film as a support, and an ultra-high pressure mercury lamp (OMW Seisakusho, HMW-201KB) was used. The exposure amount was 60 mJ / cm ² . At this time, the minimum development time was defined as the minimum time required for the photosensitive resin layer in the unexposed portion to be completely dissolved.
A: The peeling time is 20 seconds or less.
○: The peeling time exceeds 20 seconds and is 30 seconds or less.
X: Peeling time exceeds 30 seconds.

Adhesion :
As a substrate for evaluation, a 0.4 mm thick copper clad laminate in which rolled copper foils having a thickness of 18 μm were used, and the surface was subjected to jet scrub polishing (Ishii Notation Co., Ltd., abrasive grain A # 400, 0.2 MPa). It was flat.
Laminate at a roll temperature of 105 ° C using a hot roll laminator (ALA-700, manufactured by Asahi Kasei Co., Ltd.) while peeling the polyethylene film of the photosensitive resin laminate on a copper clad laminate placed at 23 ° C after leveling. did. The air pressure was 0.35 MPa, and the laminating speed was 2 m / min.

The peelable evaluation substrate that had passed 15 minutes after lamination was exposed through a mask having a dot pattern with a diameter of 100 μm. After developing with a development time twice as long as the minimum development time, the adhesion between the resist and the copper surface was observed using an SEM and ranked as follows. The mask was placed on a polyethylene terephthalate film as a support, and an ultra-high pressure mercury lamp (OMW Seisakusho, HMW-201KB) was used. The exposure amount was 60 mJ / cm ² . At this time, the minimum development time was defined as the minimum time required for the photosensitive resin layer in the unexposed portion to be completely dissolved. Observation was performed on four 100 μm dot patterns.
(Double-circle): A sushi float is not seen by the bottom of a dot pattern.
○: Some sedges are seen at the bottom of the dot pattern.
X: Susuki float is seen in the whole dot pattern, or a dot pattern cannot be formed.

3. Evaluation results The evaluation results of Examples and Comparative Examples are shown in Table 1 above.
As is clear from Table 1, in Examples 1 to 7, by adopting the configuration of the present invention, the adhesiveness and peelability were successfully improved.

  The present invention can be used, for example, in the manufacture of printed wiring boards.

Claims (8)

The following components (a) to (d);
(A) Alkali-soluble polymer: 20 to 70% by mass,
(B) addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule: 5 to 30% by mass;
(C) Photopolymerization initiator: 0.01 to 30% by mass, and (d) Additives: 20 to 40% by mass, which are compounds not involved in promotion of radical polymerization other than the above (a) to (c).
Consists of
The photosensitive resin composition in which the addition polymerizable monomer contains a polyfunctional monomer having at least three polymerizable ethylenically unsaturated bonds in the molecule. The polyfunctional monomer is represented by the following general formula [I]:

{Wherein, R ¹ represents a monovalent organic group hydrogen atom or a carbon number of 1~8, R ^2, R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, A ¹ is carbon represents an alkylene group having 2 to 6, n ^1, n ² and n ³ are 0 or an integer satisfying ^{n 1 + n 2 + n 3} = 3~60, n 4 is 0 or 1, provided that Shikichu A plurality of A ¹ may be the same or different, and the repeating structure of — (O—A ¹ ) — may be random or block. } The photosensitive resin composition of Claim 1 which is a compound represented by these. The photosensitive resin composition according to claim 2, wherein the n ¹ , n ^2, and n ³ are integers of 0 or more that satisfy n ¹ + n ² + n ³ = 6 to 60.   The photosensitive resin composition of Claim 2 or 3 whose ratio which the compound represented by the said general formula [I] occupies in the said addition polymerizable monomer is 10-80 mass%. The additive is
The following general formula [II]:
R ⁵ —O— (A ² —O) _{n 5} —R ⁶ [II]
{Wherein R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, A ² is an alkylene group, and n ⁵ is 1 or more and 400 or less. The repeating structure of — (A ² —O) — may be the same or different, and when the repeating structure of — (A ² —O) — is different, it is random. Or a block. } A compound represented by
The following general formula [III]:

{Wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or a fatty acid acyl group, and n ⁶ , n ⁷ , n ⁸ and n ⁹ are Each independently represents an integer of 0 or more, provided that n ⁶ + n ⁷ + n ⁸ + n ⁹ is 0 to 40, and A ³ is —CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) — or —. CH ₂ CH ₂ — is represented, and the repeating structure of — (A ³ —O) — may be random or block. }, And the following general formula [IV]:

{In the formula, A ⁴ represents -CH (CH ₃ ) CH _2- , -CH ₂ CH (CH ₃ )-or -CH ₂ CH _2- , and n ¹⁰ and n ¹¹ each independently represents 0 or more. N ¹⁰ and n ¹¹ are each independently an integer of 1 to 30, n ¹⁰ + n ¹¹ is an integer of 1 to 60, and — (A ⁴ —O) — is a repeating structure. May be the same or different, and may be random or block if the repeating structure of-(A ⁴ -O)-is different. } The photosensitive resin composition of any one of Claims 1-4 containing 1 type, or 2 or more types selected from the group which consists of a compound represented by these.   One or more selected from the group consisting of the compound represented by the general formula [II], the compound represented by the general formula [III], and the compound represented by the general formula [IV] The photosensitive resin composition of Claim 5 whose total ratio which occupies in the said additive is 20-100 mass%. The following steps:
A laminating step of laminating a photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 1 to 6 on a support;
An exposure step of exposing the photosensitive resin layer; and a development step of developing the exposed photosensitive resin layer;
A method for forming a resist pattern, comprising: The following steps:
A laminating step of laminating a photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 1 to 6 on a substrate;
An exposure step of exposing the photosensitive resin layer;
A development step of developing the exposed photosensitive resin layer to obtain a substrate on which a resist pattern is formed;
A method for manufacturing a wiring board, comprising: a conductor pattern forming step of etching or plating a substrate on which the resist pattern is formed; and a peeling step of peeling the resist pattern.