JP6809873B2 - Laminate - Google Patents

Description

The present invention relates to a laminate, etc.

Traditionally, printed wiring boards have generally been manufactured by photolithography. In the photolithography method, first, a pattern exposure is performed on a photosensitive resin layer laminated on a substrate such as a copper-clad laminate or a flexible substrate. The exposed portion of the photosensitive resin layer is polymerized and cured (in the case of a negative type) or solubilized in a developing solution (in the case of a positive type). Next, the unexposed portion (in the case of the negative type) or the exposed portion (in the case of the positive type) is removed with a developing solution to form a resist pattern on the substrate. Further, after etching or plating to form a conductor pattern, the cured resist pattern (hereinafter, also referred to as “resist pattern”) is peeled off and removed from the substrate. By going through these steps, a conductor pattern is formed on the substrate.

In the photolithography method, a method of applying a solution of a photosensitive resin composition to a substrate and drying it, or a dry film resist (a photosensitive resin in which a photosensitive resin layer composed of a photosensitive resin composition is laminated on a support) is generally used. Any of the methods of laminating the photosensitive resin layer of the laminate) on the substrate is used. In particular, the latter is often used in the manufacture of printed wiring boards.

In recent years, with the miniaturization and weight reduction of electronic devices, the miniaturization and high density of printed wiring boards have progressed, and high-performance dry films capable of imparting functionality such as high resolution in the manufacturing method of printed wiring boards. Resist is required. In order to realize high resolution of a printed wiring board formed by using a dry film resist, for example, a photosensitive resin composition containing a benzotriazole derivative has been proposed (Patent Document 1).

In the photolithography method using a dry film resist, a substrate having various outer shapes (for example, flat surface, unevenness, non-plane surface, groove, preformed line / space, etc.) is also used. When laminating a dry film resist on a substrate in order to suppress inconvenient residual air or chemical substances between the substrate and the dry film resist in a laminate consisting of a substrate having an outer shape other than a flat surface and a dry film resist. A method of applying a liquid between the substrate and the dry film resist to fill the gap between the substrate and the dry film resist with the liquid (so-called "wet lamination process") has also been proposed (Patent Document 2).

International Publication No. 2006/016658 JP-A-2009-147295

In Patent Document 1, the photosensitive resin composition contains a benzotriazole derivative having a specific structure from the viewpoint of ensuring the adhesion of the photosensitive resin layer to the copper surface of the substrate and suppressing discoloration of the copper surface. Let me. However, the photosensitive resin layer made of the photosensitive resin composition described in Patent Document 1 has not been sufficiently examined for application to the wet lamination process, resulting in deterioration of resolution after the wet lamination process and short-circuit defects after the etching process. There was still room for improvement.

Patent Document 2 proposes a lamination liquid containing water and an interfacial energy modifier, and the lamination liquid is intended to fill the gap between the substrate and the dry film resist to be laminated together. As described in Patent Document 2, the wet lamination process improves the followability of the dry film resist by suppressing the inconvenient air residue between the substrate and the dry film resist, but the final solution of the wiring board. It has the fundamental problem of not contributing to image quality. Further, the wet lamination process described in Patent Document 2 still has room for improvement in terms of resolution deterioration after the wet lamination process and short circuit defects after the subsequent etching process.

Therefore, the problem to be solved by the present invention is a photosensitive resin composition capable of achieving both the ability of the resist material to follow the substrate and the ability to suppress short-circuit defects after the etching process, and a laminate provided on the base film. Is to provide.

｛式中、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子又はメチル基を表し、ＡはＣ_２Ｈ_４であり、ＢはＣ_３Ｈ_６であり、ｎ_１、ｎ_２、ｎ_３及びｎ_４は、ｎ_１＋ｎ_２＋ｎ_３＋ｎ_４＝２〜５０の関係を満たす整数であり、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、ブロックの場合、−（Ａ−Ｏ）−と−（Ｂ−Ｏ）−とのいずれがビスフェニル基側でもよい｝
で表されるアルキレンオキサイド変性ビスフェノールＡ型ジ（メタ）アクリレート化合物を含む、［１］〜［３］のいずれか１項に記載の積層体。
［５］
前記（Ｂ）エチレン性不飽和結合含有化合物は、
下記一般式（ＩＩＩ）：

｛式中、Ｒ_５、Ｒ_６及びＲ_７は、それぞれ独立に、水素原子又はメチル基を表し、Ｘは、炭素数２〜６のアルキレン基を表し、ｍ_２、ｍ_３及びｍ_４は、それぞれ独立に、０〜４０の整数であり、ｍ_２＋ｍ_３＋ｍ_４は、１〜４０であり、そしてｍ_２＋ｍ_３＋ｍ_４が２以上である場合には、複数のＸは、互いに同一であるか、又は異なっていてよい｝
で表されるトリ（メタ）アクリレート化合物；
下記一般式（ＩＶ）：

｛式中、Ｒ_８及びＲ_９は、それぞれ独立に、水素原子又はメチル基を表し、Ｙは、炭素数２〜６のアルキレン基を表し、Ｚは、２価の有機基を表し、ｓ及びｔは、それぞれ独立に、０〜４０の整数であり、かつｓ＋ｔ≧１である｝
で表されるウレタンジ（メタ）アクリレート化合物；及び
下記一般式（ＶＩ）：

｛式中、Ａは、Ｃ_２Ｈ_４を表し、Ｒ_６１は、水素原子又はメチル基を表し、Ｒ_６２は、水素原子、メチル基又はハロゲン化メチル基を表し、Ｒ_６３は、炭素数１〜６のアルキル基、ハロゲン原子又は水酸基を表し、ａは、１〜４の整数であり、ｋは０〜４の整数であり、そしてｋが２以上の整数である場合には、複数のＲ_６３は同一であっても異なっていてもよい｝
で表されるｏ−フタレート化合物；
から成る群から選択される少なくとも１つを含む、［１］〜［４］のいずれか１項に記載の積層体。
［６］
前記（Ｃ）光重合開始剤は、Ｎ−アリールアミノ酸又はそのエステル化合物を含む、［１］〜［５］のいずれか１項に記載の積層体。
［７］
前記（Ｃ）光重合開始剤は、Ｎ−フェニルグリシン又はそのエステル化合物を含む、［６］に記載の積層体。
［８］
前記（Ａ）アルカリ可溶性高分子は、前記（Ａ）アルカリ可溶性高分子を構成する単量体の全質量を基準として４０質量％以上のスチレンの構造単位を含む、［１］〜［７］のいずれか１項に記載の積層体。
［９］
ダイレクトイメージング露光用である、［１］〜［８］のいずれか１項に記載の積層体。
［１０］
［１］〜［９］のいずれか１項に記載の積層体の前記感光性樹脂組成物を支持体に積層するラミネート工程；
該感光性樹脂組成物を露光する露光工程；及び
該露光された感光性樹脂組成物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。
［１１］
［１］〜［９］のいずれか１項に記載の積層体の前記感光性樹脂組成物を基板に積層するラミネート工程；
該感光性樹脂組成物を露光する露光工程；
該露光された感光性樹脂組成物を現像して、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。 The present inventor has found that the above problems can be solved by the following technical means.
[1]
With the base film
A photosensitive resin layer containing a photosensitive resin composition provided on the base film and
It is a laminated body including
The photosensitive resin composition is
(A) Alkali-soluble polymer;
(B) Ethylene unsaturated bond-containing compound; and (C) Photopolymerization initiator;
Including
The base film can be peeled off from the photosensitive resin layer, and the photosensitive resin composition can be obtained by the following mathematical formula (1):
W _X- D _X ≤ 5 μm (1)
{Wherein, W _X has the photosensitive resin layer, in the presence of a liquid, the resist pattern obtained by exposure and development after lamination on a substrate having a groove width 100μm and depth 5 [mu] m, the 200μm width a resolution ([mu] m) which is defined as a space minimum width to resist lines, and D _X, in the resist pattern obtained by exposure and developing the photosensitive resin layer in the absence of liquid after lamination on the substrate , The resolution (μm) defined as the minimum space width for a resist line with a width of 200 μm}
A laminate characterized by satisfying the relationship represented by.
[2]
The photosensitive resin composition is
(D) Additives and
(E) Polymerization inhibitor and
Including
The additive (D) contains a benzotriazole compound that does not contain a carboxyl group and contains an amino group.
The laminate according to [1], wherein the (E) polymerization inhibitor contains an epoxy compound.
[3]
The laminate according to [1] or [2], wherein the (B) ethylenically unsaturated bond-containing compound contains an addition-polymerizable monomer having 20 mol or more of alkylene oxide units in the molecule.
[4]
As the (B) ethylenically unsaturated bond-containing compound, the following general formula (II):

{In the formula, R ₃ and R ₄ independently represent a hydrogen atom or a methyl group, where A is C ₂ H ₄ and B is C ₃ H ₆ , n ₁ , n ₂ , n ₃ and n ₄ is an integer satisfying the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 50, and the sequence of repeating units of − (A—O) − and − (BO) − is random. In the case of a block, either − (A—O) − or − (BO) − may be on the bisphenyl group side}.
The laminate according to any one of [1] to [3], which contains an alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by.
[5]
The (B) ethylenically unsaturated bond-containing compound is
The following general formula (III):

{In the formula, R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m ₂ , m ₃ and m ₄ represent. Independently, if m ₂ + m ₃ + m ₄ is an integer from 0 to 40, m ₂ + m ₃ + m ₄ is 1 to 40, and m ₂ + m ₃ + m ₄ is 2 or more, then the plurality of X's are identical to each other. May be present or different}
Tri (meth) acrylate compound represented by;
The following general formula (IV):

{In the formula, R ₈ and R ₉ independently represent a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, Z represents a divalent organic group, and s and t is an integer from 0 to 40 independently, and s + t ≧ 1}
Urethane di (meth) acrylate compound represented by; and the following general formula (VI):

{In the formula, A represents C ₂ H ₄ , R ₆₁ represents a hydrogen atom or a methyl group, R ₆₂ represents a hydrogen atom, a methyl group or a methyl halide group, and R ₆₃ represents 1 carbon atoms. Represents an alkyl group, a halogen atom or a hydroxyl group of ~ 6, where a is an integer of 1-4, k is an integer of 0-4, and if k is an integer of 2 or more, a plurality of R's. ₆₃ may be the same or different}
O-phthalate compound represented by;
The laminate according to any one of [1] to [4], which comprises at least one selected from the group consisting of.
[6]
The laminate according to any one of [1] to [5], wherein the (C) photopolymerization initiator contains an N-aryl amino acid or an ester compound thereof.
[7]
The laminate according to [6], wherein the (C) photopolymerization initiator contains N-phenylglycine or an ester compound thereof.
[8]
[1] to [7], wherein the alkali-soluble polymer (A) contains 40% by mass or more of styrene structural units based on the total mass of the monomers constituting the alkali-soluble polymer (A). The laminate according to any one item.
[9]
The laminate according to any one of [1] to [8], which is used for direct imaging exposure.
[10]
Laminating step of laminating the photosensitive resin composition of the laminated body according to any one of [1] to [9] on a support;
An exposure step of exposing the photosensitive resin composition; and a developing step of developing the exposed photosensitive resin composition;
A method for forming a resist pattern including.
[11]
Laminating step of laminating the photosensitive resin composition of the laminate according to any one of [1] to [9] on a substrate;
An exposure step of exposing the photosensitive resin composition;
A developing step of developing the exposed photosensitive resin composition to obtain a substrate on which a resist pattern is formed;
A conductor pattern forming step of etching or plating a substrate on which the resist pattern is formed; and a peeling step of peeling off the resist pattern;
Manufacturing method of wiring board including.

According to the present invention, there is provided a photosensitive resin composition capable of achieving both the ability of a resist material to follow a substrate and the ability to suppress short-circuit defects after an etching process, and a laminate provided with the same on a base film. , The resolution of the printed wiring board formed by using the dry film resist can be improved.

Hereinafter, a mode for carrying out the present invention (hereinafter, abbreviated as “the present embodiment”) will be specifically described.
In addition, in this specification, the term "(meth) acrylic acid" means acrylic acid or methacrylic acid. The term "(meth) acryloyl group" means an acryloyl group or a methacryloyl group. The term "(meth) acrylate" means "acrylate" or "methacrylate".

<Photosensitive resin composition>
In this embodiment, the photosensitive resin composition comprises (A) an alkali-soluble polymer, (B) an ethylenically unsaturated bond-containing compound, and (C) a photopolymerization initiator. If desired, the photosensitive resin composition may further contain other components such as (D) additives and (E) polymerization inhibitors.

In the present embodiment, the photosensitive resin composition is based on the following mathematical formula (1):
W _X- D _X ≤ 5 μm (1)
{Wherein, W _X has a photosensitive resin layer made of a photosensitive resin composition, in the presence of a liquid, the resist obtained by exposure and development after lamination on a substrate having a groove width 100μm and depth 5μm resulting in a pattern, a resolution defined as a space minimum width to resist lines 200μm width ([mu] m), and D _X is the exposed and developed photosensitive resin layer in the absence of a liquid after laminated on a substrate The resolution (μm) defined as the minimum space width for a resist line having a width of 200 μm in the resist pattern to be used}.
Satisfy the relationship represented by.

W _X -D _X in Equation (1), a predetermined groove width (100 [mu] m) and groove depth on a substrate having a (5 [mu] m), a photosensitive resin layer made of a photosensitive resin composition according to the present embodiment, The resolution of the resist pattern obtained by exposure and development when laminated in the presence of liquid (so-called wet lamination) and the resist pattern obtained by exposure and development when laminated in the absence of liquid (so-called dry lamination). This is the difference from the resolution (hereinafter, also referred to as “wet-dry lamination resolution difference”).

When the wet-dry lamination resolution difference is 5 μm or less, short-circuit defects in the production process to which wet lamination is applied can be reduced. A general printed wiring board has scratches or irregularities that occur during handling, and irregularities from the inner layer. The liquid applied to wet lamination may stay on these irregularities. When the wet-dry lamination resolution difference is more than 5 μm, the resolution of the uneven portion deteriorates, leading to the occurrence of short circuit defects. According to the present invention, a stable wiring pattern can be obtained in the substrate regardless of the presence or absence of irregularities or scratches on the substrate.

Further, since wet lamination can improve the followability of the dry film resist, it is possible to secure sufficient followability even when the thickness of the resist layer is thin. If the resist layer can be thinned, the resolution after etching can be improved. Therefore, according to the present invention, it is possible to achieve both followability and fine wiring pattern in the wet lamination process.

The presence of metal ions in the base material is considered to be the cause of the wet-dry lamination resolution difference. Due to the presence of the liquid applied to the wet lamination, it is considered that metal ions of the substrate, for example, copper ions, migrate into the resist, especially in the portion where the liquid stays. It is believed that these metal ions promote the radical polymerization reaction and deteriorate the resolution during wet lamination. The composition of the photosensitive resin composition that suppresses the migration of copper ions is confirmed by a wet-dry lamination resolution difference of 5 μm or less. According to the present invention, it has been found that the degree of copper migration to the photosensitive resin composition correlates with the wet-dry resolution difference.

_W X -D _X in Equation (1), from the viewpoint of both trackability and short circuit inhibitory, less than 5 [mu] m, 4 [mu] m or less, 3 [mu] m or less, 2 [mu] m or less, it is also preferable 1μm or less, or 0 .mu.m.

The means for adjusting the wet-dry lamination resolution difference within the range of 5 μm or less is not particularly limited, and examples thereof include various adjustments of the composition of the photosensitive resin composition as described later for each component. ..

The wet-dry lamination resolution difference is determined by the method described in the examples.

Each component contained in the photosensitive resin composition according to the present embodiment will be described below.

(A) Alkali-soluble polymer (A) The alkali-soluble polymer is a polymer that is soluble in an alkaline substance. The alkali-soluble polymer (A) may be a single type copolymer, a mixture of a plurality of types of copolymers, and / or a mixture of a plurality of types of homopolymers.

In relation to alkali solubility, the acid equivalent of (A) the alkali-soluble polymer (if the component (A) contains a plurality of copolymers, the acid equivalent for the entire mixture) is determined by the photosensitive resin layer. It is preferably 100 or more from the viewpoint of development resistance, development resistance, resolution and adhesion of the resist pattern, and preferably 900 or less from the viewpoint of developability and peelability of the photosensitive resin layer. The acid equivalent of the alkali-soluble polymer (A) is more preferably 200 to 600, and even more preferably 250 to 500. The acid equivalent refers to the mass of a linear polymer having 1 equivalent of a carboxyl group therein.

In the present embodiment, from the viewpoint of improving the resolution of the resist pattern, the (A) alkali-soluble polymer is 40% by mass or more based on the total mass of the monomers constituting the (A) alkali-soluble polymer. It is preferable to contain the structural unit of styrene of. When the (A) alkali-soluble polymer contains a plurality of types of copolymers, (A) the blending ratio of each copolymer in the entire alkali-soluble polymer and the content of styrene structural units in each copolymer. It is preferable that the weighted average of the above is 40% by mass or more. The content of the structural unit of styrene in the (A) alkali-soluble polymer is preferably 90 from the viewpoint of developability and peelability, based on the total mass of the monomers constituting the (A) alkali-soluble polymer. It is mass% or less, more preferably 85 mass% or less, 80 mass% or less, 70 mass% or less, or 60 mass% or less.

The alkali-soluble polymer (A) is a homopolymer of the first monomer described later, a homopolymer of the second monomer described later, one or more of the first monomers and / or a second simple polymer. It may contain a copolymer obtained by copolymerizing a copolymerization component composed of one or more kinds of monomers.

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, maleic acid semi-ester and the like. Among these, (meth) acrylic acid is preferable from the viewpoint of alkali solubility.

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. , Tart-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate, etc. Vinyl alcohol esters; (meth) acrylonitrile; styrene, polymerizable styrene derivatives and the like.
Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, or tert-butyl (meth) acrylate is preferable from the viewpoint of improving the tent property of the resist pattern, and the tent property is preferable. From the viewpoint, n-butyl (meth) acrylate is more preferable, and from the viewpoint of resolution, styrene or a polymerizable styrene derivative is preferable.
Examples of the polymerizable styrene derivative include methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimmer and the like.

The alkali-soluble polymer (A) is prepared by mixing the above monomers and diluting with a solvent such as acetone, methyl ethyl ketone, methanol, ethanol, normal propyl alcohol, or isopropanol in a solution of a radical polymerization initiator, for example, excess. It is preferably synthesized by adding an appropriate amount of benzoyl oxide, azoisobutyronitrile and the like, and heating and stirring. In some cases, the alkali-soluble polymer (A) is synthesized while dropping a part of the mixture into the reaction solution. After completion of the reaction, a solvent may be further added to the product to adjust the concentration to a desired concentration. As the synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

The weight average molecular weight of the alkali-soluble polymer (A) (when the component (A) contains a plurality of copolymers, the weight average molecular weight of the entire mixture) is preferably 5,000 to 500,000. .. The weight average molecular weight of the alkali-soluble polymer (A) is preferably 5,000 or more from the viewpoint of maintaining a uniform thickness of the dry film resist and obtaining resistance to a developing solution, and improves the developability of the dry film resist. From the viewpoint of maintenance, it is preferably 500,000 or less. The weight average molecular weight of the alkali-soluble polymer (A) is more preferably 10,000 to 200,000, and even more preferably 20,000 to 100,000. The dispersity of the alkali-soluble polymer (A) is preferably 1.0 to 6.0.

In the present embodiment, the content of the alkali-soluble polymer (A) in the photosensitive resin composition is the same for each content component based on the total solid content of the photosensitive resin composition (hereinafter, unless otherwise specified). ), It is preferably in the range of 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and further preferably 40% by mass to 60% by mass. The content of the alkali-soluble polymer (A) is preferably 10% by mass or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer, and the resist pattern formed by exposure improves the performance as a resist material. From the viewpoint of sufficient exertion, it is preferably 90% by mass or less.

(B) Ethylene unsaturated bond-containing compound (B) The ethylenically unsaturated bond-containing compound is a compound having a polymerizable property by having an ethylenically unsaturated group in its structure. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group from the viewpoint of addition polymerization.

(B) The ethylenically unsaturated bond-containing compound is an addition polymerization having 20 mol or more, 21 mol or more, 25 mol or more, or 30 mol or more of alkylene oxide units in the molecule from the viewpoint of suppressing short-circuit defects after the etching process. It preferably contains a sex monomer. The upper limit of the amount of the alkylene oxide unit added to the molecule is not particularly limited, but from the viewpoint of the resist resolution after development, 60 mol or less is preferable, and 50 mol or less or 40 mol or less is more preferable.
Examples of the alkylene oxide include ethylene oxide and propylene oxide.

｛式中、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子又はメチル基を表し、かつｍ_１は、２〜４０を満たす数である。｝
で表されるエチレングリコールジ（メタ）アクリレート化合物；
（ｂ_２）下記一般式（ＩＩ）：

｛式中、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子又はメチル基を表し、ＡはＣ_２Ｈ_４であり、ＢはＣ_３Ｈ_６であり、ｎ_１、ｎ_２、ｎ_３及びｎ_４は、ｎ_１＋ｎ_２＋ｎ_３＋ｎ_４＝２〜５０の関係を満たす整数であり、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、ブロックの場合、−（Ａ−Ｏ）−と−（Ｂ−Ｏ）−とのいずれがビスフェニル基側でもよい。｝
で表されるアルキレンオキシド変性ビスフェノールＡ型ジ（メタ）アクリレート化合物；
（ｂ_３）下記一般式（ＩＩＩ）：

｛式中、Ｒ_５〜Ｒ_７は、それぞれ独立に、水素原子又はメチル基を表し、Ｘは、炭素数２〜６のアルキレン基を表し、ｍ_２、ｍ_３及びｍ_４は、それぞれ独立に、０〜４０の整数であり、ｍ_２＋ｍ_３＋ｍ_４は、１〜４０であり、そしてｍ_２＋ｍ_３＋ｍ_４が２以上である場合には、複数のＸは、互いに同一であるか、又は異なっていてよい｝
で表されるトリ（メタ）アクリレート化合物；
（ｂ_４）下記一般式（ＩＶ）：

｛式中、Ｒ_８及びＲ_９は、それぞれ独立に、水素原子又はメチル基を表し、Ｙは、炭素数２〜６のアルキレン基を表し、Ｚは、２価の有機基を表し、かつｓ及びｔは、それぞれ独立に、０〜４０の整数であり、かつｓ＋ｔ≧１である｝
で表されるウレタンジ（メタ）アクリレート化合物；
（ｂ_５）下記一般式（Ｖ）：

｛式中、Ｒは、それぞれ独立に、水素原子又はメチル基を表し、かつｎは、０〜３０の整数であり、かつ全てのｎの合計値が１以上である｝
で表されるヘキサ（メタ）アクリレート化合物；
（ｂ_６）下記一般式（ＶＩ）：

｛式中、Ａは、Ｃ_２Ｈ_４を表し、Ｒ_６１は、水素原子又はメチル基を表し、Ｒ_６２は、水素原子、メチル基又はハロゲン化メチル基を表し、Ｒ_６３は、炭素数１〜６のアルキル基、ハロゲン原子又は水酸基を表し、ａは、１〜４の整数であり、ｋは０〜４の整数であり、そしてｋが２以上の整数である場合には、複数のＲ_６３は同一であっても異なっていてもよい｝
で表されるｏ−フタレート化合物；及び
（ｂ_７）上記（ｂ_１）〜（ｂ_６）以外の付加重合性単量体；
から成る群から選択される少なくとも１つを含んでよい。 (B) The ethylenically unsaturated bond-containing compound is the following (b ₁ ) to (b ₇ ):
(B ₁ ) The following general formula (I):

{In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and m ₁ is a number satisfying 2 to 40. }
Ethylene glycol di (meth) acrylate compound represented by;
(B ₂ ) The following general formula (II):

{In the formula, R ₃ and R ₄ independently represent a hydrogen atom or a methyl group, where A is C ₂ H ₄ and B is C ₃ H ₆ , n ₁ , n ₂ , n ₃ and n ₄ is an integer satisfying the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 50, and the sequence of repeating units of − (A—O) − and − (BO) − is random. In the case of a block, either − (A—O) − or − (BO) − may be on the bisphenyl group side. }
An alkylene oxide-modified bisphenol type A di (meth) acrylate compound represented by
(B ₃ ) The following general formula (III):

{In the formula, R _{5 to} R ₇ independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m ₂ , m ₃ and m ₄ independently represent each. , 0 to 40, m ₂ + m ₃ + m ₄ is 1 to 40, and m ₂ + m ₃ + m ₄ is greater than or equal to 2, then the plurality of X's are identical to each other. Or may be different}
Tri (meth) acrylate compound represented by;
(B ₄ ) The following general formula (IV):

{In the formula, R ₈ and R ₉ independently represent a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, Z represents a divalent organic group, and s. And t are independently integers from 0 to 40, and s + t ≧ 1}
Urethane di (meth) acrylate compound represented by;
(B ₅ ) The following general formula (V):

{In the formula, R independently represents a hydrogen atom or a methyl group, n is an integer of 0 to 30, and the total value of all n is 1 or more}
Hexa (meth) acrylate compound represented by;
(B ₆ ) The following general formula (VI):

{In the formula, A represents C ₂ H ₄ , R ₆₁ represents a hydrogen atom or a methyl group, R ₆₂ represents a hydrogen atom, a methyl group or a methyl halide group, and R ₆₃ represents 1 carbon atoms. Represents an alkyl group, a halogen atom or a hydroxyl group of ~ 6, where a is an integer of 1-4, k is an integer of 0-4, and if k is an integer of 2 or more, a plurality of R's. ₆₃ may be the same or different}
O-phthalate compound represented by; and (b ₇ ) an addition-polymerizable monomer other than the above (b ₁ ) to (b ₆ );
It may contain at least one selected from the group consisting of.

The ethylenically unsaturated bond-containing compound (B) is an ethylene glycol di (meth) acrylate compound represented by (b ₁ ) general formula (I) from the viewpoint of adjusting the peeling time of the resist pattern and the size of the peeled piece. Is preferably included.

In the general formula (I), m ₁ is preferably 2 or more from the viewpoint of peeling time and peeling piece size, and preferably 20 or more from the viewpoint of suppressing short-circuit defects after the etching process, and has resolution. From the viewpoint of plating resistance and etching resistance, it is preferably 40 or less. m ₁ is more preferably 4 to 20, still more preferably 6 to 12. From the viewpoint of achieving both resolution and etching short defect suppression property, the (B) ethylenically unsaturated bond-containing compound is a compound satisfying m ₁ = 4 to 20 in the general formula (I), and in the general formula (I). It is preferable to simultaneously contain a compound satisfying m ₁ = 20 to 40.

Specific examples of the ethylene glycol di (meth) acrylate compound represented by the general formula (I) include tetraethylene glycol di (meth) acrylate having m ₁ = 4 and nonaethylene glycol di (meth) acrylate having m ₁ = 9. , M ₁ = 14 polyethylene glycol di (meth) acrylate, or m ₁ = 23 polyethylene glycol di (meth) acrylate is preferred.

The (B) ethylenically unsaturated bond-containing compound contains an alkylene oxide-modified bisphenol A-type di (meth) acrylate compound represented by (b ₂ ) general formula (II) in order to suppress short-circuit defects after the etching process. It is preferable to include it. B in the general formula (II) may be −CH ₂ CH ₂ CH ₂ − or −CH (CH ₃ ) CH ₂ −.

The hydrogen atom on the aromatic ring in the general formula (II) may be substituted with a heteroatom and / or a substituent.
Examples of the hetero atom include a halogen atom and the like, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a phenacyl group. , Amino group, alkylamino group with 1 to 10 carbon atoms, dialkylamino group with 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkyl mercapto group with 1 to 10 carbon atoms, aryl group, hydroxyl group , A hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group, an acyl group having 1 to 10 carbon atoms in the alkyl group, an alkoxy group having 1 to 20 carbon atoms, An alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, a group containing a heterocycle, or a group thereof. Examples thereof include an aryl group substituted with a substituent. These substituents may form a fused ring, or the hydrogen atom in these substituents may be substituted with a hetero atom such as a halogen atom. When the aromatic ring in the general formula (II) has a plurality of substituents, the plurality of substituents may be the same or different.

R ₃ and R ₄ in the general formula (II) may be independently hydrogen atoms or methyl groups, respectively, but from the viewpoint of ensuring contrast immediately after exposure of the photosensitive resin layer composed of the photosensitive resin composition. preferably one or both of R ₃ and R ₄ is a hydrogen atom, more preferably both of R ₃ and R ₄ are hydrogen atoms.

(B ₂ ) From the viewpoint of suppressing etching short defects, it is preferable that 20 mol or more of alkylene oxide is added to the alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II). .. More specifically, in the general formula (II), n ₁ , n ₂ , n ₃ and n ₄ preferably satisfy the relationship of n ₁ + n ₂ + n ₃ + n ₄ = _{4 to} 50, and more preferably n ₁ + n. The relationship of ₂ + n ₃ + n ₄ = 10 to 50 is satisfied, more preferably the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 20 to 50 is satisfied, and particularly preferably n ₁ + n ₂ + n ₃ + n ₄ = 30 to 50. Meet the relationship.

From the viewpoint of resolution, 40% by mass or more of the (B) ethylenically unsaturated bond-containing compound is preferably (b ₂ ) an alkylene oxide-modified bisphenol A type di (b ₂ ) represented by the general formula (II). A meta) acrylate compound, more preferably an alkylene oxide-modified bisphenol in which n ₁ , n ₂ , n ₃ and n ₄ in the general formula (II) satisfy the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 30 to 50. It is an A-type di (meth) acrylate compound. 50 wt% of the preferably (B) an ethylenically unsaturated bond-containing compound, more preferably 55 mass% or more, more preferably 60 wt%, and most preferably 80 wt%, _{(b 2)} the general formula (II ) Is an alkylene oxide-modified bisphenol A type di (meth) acrylate compound.

(B ₂ ) A preferable specific example of the alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by the general formula (II) is polyethylene glycol in which an average of 1 unit of ethylene oxide is added to both ends of bisphenol A. Di (meth) acrylate of polyethylene glycol with an average of 2 units of ethylene oxide added to both ends of di (meth) acrylate and bisphenol A, and di (meth) acrylate of polyethylene glycol with an average of 5 units of ethylene oxide added to both ends of bisphenol A. Di (meth) acrylate of polyethylene glycol with an average of 7 units of ethylene oxide added to both ends of meta) acrylate and bisphenol A, and an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide added to both ends of bisphenol A, respectively. Di (meth) acrylate of polyalkylene glycol, di (meth) acrylate of polyalkylene glycol with an average of 15 units of ethylene oxide added to both ends of bisphenol A, and an average of 2 units of ethylene oxide at both ends of bisphenol A. Examples thereof include di (meth) acrylate of polyalkylene glycol to which a unit of propylene oxide is added.

In the general formula (II), n ₁ , n ₂ , n ₃ and n ₄ preferably satisfy the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 10 from the viewpoint of resolution, and n ₁ + n ₂ + n. It is also particularly preferable to satisfy the relationship of ₃ + n ₄ = 2-4.

(B) The ethylenically unsaturated bond-containing compound is a compound satisfying n ₁ + n ₂ + n ₃ + n ₄ = 30 to 50 in the general formula (II) from the viewpoint of achieving both resolution and etching short defect suppression property. It is particularly preferable that the compounds satisfying n ₁ + n ₂ + n ₃ + n ₄ = 2 to 10 in the general formula (II) are simultaneously contained.

The ethylenically unsaturated bond-containing compound (B) preferably contains a tri (meth) acrylate compound represented by the general formula (III) (b ₃ ) from the viewpoint of resolution. X in the general formula (III) is an alkylene group having 2 to 6 carbon atoms, and is, for example, −CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ −, −CH (CH ₃ ) CH ₂ −, etc. Good.

(B ₃ ) The tri (meth) acrylate compound represented by the general formula (III) has a relatively long chain alkylene oxide moiety from the viewpoint of tentability, flexibility of the cured film, and short-circuit defect suppression after the etching process. It is preferable to have. More specifically, in the general formula (III), m ₂ + m ₃ + m ₄ is preferably 20 to 40.

(B ₃ ) A preferable specific example of the tri (meth) acrylate compound represented by the general formula (III) is ethylene oxide (EO) -modified trimethylolpropane tri (meth) acrylate (EO average addition mole number: 10 to 40). ), Propylene oxide (PO) -modified trimethylolpropane tri (meth) acrylate (PO average addition mole number: 10 to 40) and the like. In particular, ethylene oxide (EO) -modified trimethylolpropane tri (meth) acrylate (EO average number of moles added: 21) is preferable.

The ethylenically unsaturated bond-containing compound (B) preferably contains a urethane di (meth) acrylate compound represented by the general formula (IV) (b ₄ ) from the viewpoint of resolution.

In the general formula (IV), Z represents a divalent organic group, for example, an alkylene group having 1 to 10 carbon atoms, an alkylene oxide group having 2 to 10 carbon atoms, and a number of carbon atoms which may have a substituent. A divalent alicyclic group of 3 to 10 may be used.

In the general formula (IV), Y represents an alkylene group having 2 to 6 carbon atoms, and is, for example, −CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ −, −CH (CH ₃ ) CH ₂ −, and the like. Good.

From the viewpoint of further improving the tentability, the − (YO) _s − portion and the − (YO) _t − portion in the general formula (IV) are independently − (C ₂ H ₄ O). It is also preferable that it is substituted with − (C ₃ H ₆ O) ₉ −. From the viewpoint of suppressing short-circuit defects after the etching process, s + t = 20 to 40 is preferable.

(B ₄ ) Preferred specific examples of the urethane di (meth) acrylate compound represented by the general formula (IV) include a (meth) acrylic monomer having a hydroxyl group at the β-position, isophorone diisocyanate, 2,6-toluene diisocyanate, and 2, Addition reaction products with diisocyanate compounds such as 4-toluene diisocyanate and 1,6-hexamethylene diisocyanate, tris ((meth) acryloxitetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate and EO, PO Modified urethane di (meth) acrylate can be mentioned. EO represents ethylene oxide, and the EO-modified compound has a block structure of an ethylene oxide group. Further, PO represents propylene oxide, and the PO-modified compound has a block structure of a propylene oxide group. Examples of the EO-modified urethane di (meth) acrylate include, for example, Shin-Nakamura Chemical Industry Co., Ltd., trade name "UA-11" and the like. Examples of the EO and PO-modified urethane di (meth) acrylate include, for example, Shin-Nakamura Chemical Industry Co., Ltd., trade name "UA-13". These may be used alone or in combination of two or more.

The ethylenically unsaturated bond-containing compound (B) preferably contains a hexa (meth) acrylate compound represented by the general formula (V) (b ₅ ) from the viewpoint of resolution.

In order to further improve the resolution, it is preferable that the average value of all n is 6 or more, or n is 1 or more, respectively, in the general formula (V). The total value of n is not particularly limited, but the total value of n is preferably 20 to 30 from the viewpoint of suppressing short-circuit defects after the etching process.

(B ₅ ) Preferred specific examples of the hexa (meth) acrylate compound represented by the general formula (V) are dipentaerythritol hexa (meth) acrylate and dipentaerythritol with a total of 1 to 36 mols of ethylene at the six ends. Examples thereof include hexa (meth) acrylate to which oxide is added, and hexa (meth) acrylate to which a total of 1 to 10 mol of ε-caprolactone is added to the six ends of dipentaerythritol. In particular, hexa (meth) acrylate in which a total of 24 mol or more of ethylene oxide is added to the six ends of dipentaerythritol is preferable.

From the viewpoint of resolution, the ethylenically unsaturated bond-containing compound (B) preferably contains an o-phthalate compound represented by the general formula (VI) (b ₆ ).

Examples of the o-phthalate compound represented by the general formula (VI) include γ-chloro-β-hydroxypropyl-β'-(meth) acryloyloxyethyl-o-phthalate and β-hydroxyethyl-β'-(. Examples thereof include acryloyloxyethyl-o-phthalate and β-hydroxypropyl-β'-(meth) acryloyloxyethyl-o-phthalate. Among these, γ-chloro-β-hydroxypropyl-β'-(meth) acryloyloxyethyl-o-phthalate is preferable. These may be used alone or in combination of two or more.

The (B) ethylenically unsaturated bond-containing compound may contain an addition-polymerizable monomer other than the components (b ₁ ) to (b ₄ ) as the component (b ₇ ).

As the component (b ₇ ), a di (meth) acrylate other than the components (b ₁ ) and (b ₂ ), for example, a polyalkylene glycol such as polypropylene glycol di (meth) acrylate and polybutylene glycol di (meth) acrylate. Di (meth) acrylate can be mentioned. Examples of the polyalkylene glycol di (meth) acrylate include a dimethacrylate of a polyalkylene glycol in which an average of 12 mol of propylene oxide is added to a polypropylene glycol to which an average of 3 mol of ethylene oxide is added to both ends. Examples thereof include a dimethacrylate of a polyalkylene glycol in which an average of 15 mol of ethylene oxide is added to both ends of a polypropylene glycol to which an average of 18 mol of propylene oxide is added.

Further, as the component (b ₇ ), the following:
Tri (meth) acrylates other than the component (b ₃ ), for example, trimethylolpropane tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate. etc;
Tetra (meth) acrylates, such as ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, pentaerythritol (poly) alkoxytetra (meth) acrylate, etc .;
Penta (meth) acrylates, such as dipentaerythritol penta (meth) acrylates;
A compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid; and a compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid;
Can be mentioned.

In the present embodiment, the total content of all the (B) ethylenically unsaturated bond-containing compounds in the photosensitive resin composition is preferably 1% by mass from the viewpoint of resolution and short-circuit defect suppression after etching. It is in the range of ~ 70% by mass, more preferably 2% by mass to 60% by mass, further preferably 4% by mass to 50% by mass, and particularly preferably 20% by mass to 50% by mass.
From the viewpoint of suppressing short-circuit defects after the etching process, the (B) ethylenically unsaturated bond-containing compound preferably has 20 mol or more of alkylene oxide units in the molecule. The content of the ethylenically unsaturated bond-containing compound having 20 mol or more of alkylene oxide units in the molecule is preferably 5% by mass or more of the entire photosensitive resin composition from the viewpoint of suppressing short-circuit defects after the etching process. It is more preferably mass% or more, preferably 40 mass% or less from the viewpoint of post-development resolution, and more preferably 30 mass% or less or 20 mass% or less.

(C) Photopolymerization Initiator (C) Photopolymerization Initiator is a compound that polymerizes a monomer by light. The photosensitive resin composition contains a compound generally known in the art as a photopolymerization initiator.

The content of the (C) photopolymerization initiator in the photosensitive resin composition is preferably 0.01% by mass to 20% by mass, more preferably 0.05% by mass to 10% by mass, still more preferably 0.1. It is in the range of mass% to 7% by mass. The content of the photopolymerization initiator (C) is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and sufficiently transmits light to the bottom surface of the resist to obtain good high resolution. From the viewpoint of obtaining, it is preferably 20% by mass or less.

(C) Examples of the photopolymerization initiator include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoins or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, and oxime esters. , Aclynes and the like, and further include hexaarylbiimidazole, pyrazoline compounds, N-aryl amino acids or ester compounds thereof (for example, N-phenylglycine), organic halogen compounds and the like. These can be used alone or in combination of two or more.
Among these, acridines are particularly suitable for direct imaging exposure, and N-aryl amino acids or ester compounds thereof are preferable from the viewpoint of the sensitivity of the photosensitive resin layer and the resolution of the resist pattern.

Examples of acridines include acridine, 9-phenylacridine, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, and 1,8-bis (9-acridinyl) octane. Acridines such as 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, and 1,12-bis (9-acridinyl) dodecane. Derivatives can be mentioned. From the viewpoint of suitability for direct imaging exposure, the content of acridines in the photosensitive resin composition is preferably 0.1% by mass to 5% by mass, more preferably 0.3% by mass to 3% by mass, still more preferably. Is in the range of 0.5% by mass to 2% by mass.

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 done. These can be used alone or in combination of two or more. Among these, 4,4'-bis (diethylamino) benzophenone is preferable from the viewpoint of adhesion. Further, from the viewpoint of transmittance, the content of aromatic ketones in the photosensitive resin composition is preferably 0.01% by mass to 0.5% by mass, more preferably 0.02% by mass to 0.3. It is in the range of mass%.

Examples of hexaarylbiimidazole are 2- (o-chlorophenyl) -4,5-diphenylbimidazole, 2,2', 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl). -4', 5'-diphenylbimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbimidazole, 2,4,5-tris- (o-chlorophenyl) ) -Diphenylbimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -bimidazole, 2,2'-bis- (2-fluorophenyl) -4,4' , 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4', 5,5'-tetrakis- (3- Methoxyphenyl) -biimidazole, 2,2'-bis- (2,4-difluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'- Bis- (2,5-difluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,6-difluorophenyl) -4 , 4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4-trifluorophenyl) -4,4', 5,5'- Tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl)- Biimidazole, 2,2'-bis- (2,3,6-trifluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis -(2,4,5-trifluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4,5-tri Fluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-Tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4', 5,5'- Tetrax- (3-methoxyphenyl) -biimidazole , And 2,2'-bis- (2,3,4,5,6-pentafluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole and the like. , These can be used alone or in combination of two or more. From the viewpoint of high sensitivity, resolution and adhesion, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferable.

In the present embodiment, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.05% by mass to 7% by mass from the viewpoint of improving the peeling property and / or sensitivity of the photosensitive resin layer. %, More preferably 0.1% by mass to 6% by mass, still more preferably in the range of 1% by mass to 4% by mass.

Examples of the N-aryl amino acid include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Of these, N-phenylglycine is particularly preferable from the viewpoint of the sensitivity of the photosensitive resin layer or the resolution of the resist pattern.
Examples of the ester compound of N-aryl amino acid include N-phenylglycine ethyl ester. N-Phenylglycine ethyl ester is particularly preferable from the viewpoint of the sensitivity of the photosensitive resin layer or the resolution of the resist pattern.

The content of the N-aryl amino acid or its ester compound in the photosensitive resin composition is 0.05 mass by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of improving the peeling property and / or the sensitivity. It is preferably% to 5% by mass, and more preferably 0.1 to 2% by mass.

Examples of the organic halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, and tris ( Examples include 2,3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, and triazine chlorinated compounds. In particular, tribromomethylphenyl sulfone is preferably used. The content of the organic halogen compound in the photosensitive resin composition is 0.05% by mass to 5% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of improving the peeling property and / or the sensitivity. It is preferably 0.1% by mass to 3% by mass, and more preferably 0.1% by mass to 3% by mass.

Other photosensitizers include, for example, 2-ethylanthraquinone, octaethyl anthraquinone, 1,2-benz anthraquinone, 2,3-benz anthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone. , 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and quinones such as 3-chloro-2-methylanthraquinone, benzoin, benzoin Benzoin ethers such as ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin, benzyl dimethyl ketal, benzyl diethyl ketal, and 1-phenyl-1,2-propanedione-2-O-benzoin oxime, and 1-phenyl. Examples thereof include oxime esters such as -1,2-propanedione-2- (O-ethoxycarbonyl) oxime. The content of the photosensitizer in the photosensitive resin composition is 0.05% by mass to 5% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of improving the peeling property and / or the sensitivity. It is preferably%, and more preferably 0.1% by mass to 3% by mass.

Further, in the present embodiment, it is also preferable that the photosensitive resin composition contains a pyrazoline compound as a photosensitizer. Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazolin and 1- (4- (benzoxazole-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 and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline are preferred.

(D) Additive In the present embodiment, the photosensitive resin composition does not contain (i) a carboxyl group as an additive and contains an amino group from the viewpoint of suppressing short-circuit defects after etching. It preferably contains a triazole compound (hereinafter abbreviated as "(i) compound") and (ii) an epoxy compound as a polymerization inhibitor (E).

The presence of metal ions in the base material is considered to be the cause of the wet-dry lamination resolution difference. Due to the presence of the liquid applied to the wet lamination, it is considered that metal ions of the substrate, for example, copper ions, migrate into the resist, especially in the portion where the liquid stays. It is believed that these metal ions promote the radical polymerization reaction and deteriorate the resolution during wet lamination. It is considered that the (i) compound and / or the (ii) epoxy compound has an effect of reducing the wet-dry lamination resolution difference by capturing this metal ion and suppressing an unnecessary reaction.

The compound (i) preferably has an amino group in the molecule from the viewpoint of improving the short-circuit defect suppression property after etching. The amino group and benzotriazole skeleton can enhance the ability to capture the metal ions migrated by the retention of the liquid applied to the wet lamination and improve the short circuit defect after etching. The compound (i) preferably does not contain a carboxyl group in the molecule from the viewpoint of improving the short-circuit defect suppression property after etching. It is considered that the carboxyl group generates hydrogen ions by the retention of the liquid applied to the wet lamination, and it is considered that the hydrogen ions are involved in the radical polymerization reaction and exacerbate the short circuit defect after etching.

Examples of the compound (i) include 1- (N, N-bis (2-ethylhexyl) aminomethyl) benzotriazole, 1- (N, N-bis (2-ethylhexyl) aminomethyl) methylbenzotriazole, 2, 2'-(((Methyl-1-H-benzotriazole-1-yl) methyl) imino) bisethanol, 2,2'-(((1-H-benzotriazole-1-yl) methyl) imino) bis Ethanol, 1- (2-ethylhexylamino) -benzotriazole, 1- (2-di-n-octylaminomethyl) -benzotriazole, 1-hydroxy-benzotriazole, 1- [bis (2-hydroxyethyl) aminomethyl ] -5-Methyl-1H-benzotriazole and the like.

In the present embodiment, the content of the compound (i) in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 2% by mass, and further preferably 0. It is in the range of 0.05% by mass to 1% by mass. The content of the compound (i) is preferably 0.001% by mass or more from the viewpoint of suppressing short-circuit defects after etching, and from the viewpoint of maintaining the sensitivity of the photosensitive resin layer and maintaining the resolution. It is preferably 3% by mass or less.

(Ii) The epoxy compound is a compound having an epoxy group. Examples of the (ii) epoxy compound include an alkylene oxide compound and the like. The alkylene oxide compound preferably contains at least two glycidyl groups in the molecule. The epoxy compound inhibits the polymerization reaction by the migrated metal ions due to the retention of the liquid applied to the wet lamination, and improves the short-circuit defect after etching.

｛式中、Ｘ_７は、酸素原子、又は式−Ｏ−Ｘ_８−Ｏ−（式中、Ｘ_８は、炭素数１〜１００の直鎖若しくは分岐のアルキレン基、炭素数３〜１０の脂環式アルキレン基、及び炭素数５〜２０のアリーレン基から成る群から選ばれる少なくとも１つの炭化水素基を含有する２価の基であり、かつ該炭化水素基は、ハロゲン原子、酸素原子及び窒素原子から成る群から選ばれる少なくとも１つの原子で置換されていてもよい）で表される基であり；Ｒ_７８及びＲ_７９は、それぞれ独立に、炭素数１〜１００の直鎖若しくは分岐のアルキレン基、炭素数３〜１０の脂環式アルキレン基、及び炭素数５〜２０のアリーレン基から成る群から選ばれる少なくとも１つの炭化水素基を含有する２価の基であり、かつ該炭化水素基は、ハロゲン原子、酸素原子及び窒素原子から成る群から選ばれる少なくとも１つの原子で置換されていてもよく、かつＲ_７８及びＲ_７９がともに存在する場合には、Ｒ_７８及びＲ_７９は、同一でも異なっていてもよく、Ｒ_７８及びＲ_７９が異なる場合には、−（Ｒ_７８−Ｏ）−及び−（Ｒ_７９−Ｏ）−の繰り返し単位の配列は、ブロックでもランダムでもよく；そしてｌ及びｍは、それぞれ独立に、０〜５０の整数であり、かつｌ＋ｍは０〜５０の整数である｝
で表される化合物が挙げられる。 Examples of the alkylene oxide compound include the following general formula (VII):

{In the formula, X ₇ is an oxygen atom, or formula-O-X _8- O- (in the formula, X ₈ is a linear or branched alkylene group having 1 to 100 carbon atoms, and a fat having 3 to 10 carbon atoms. It is a divalent group containing at least one hydrocarbon group selected from the group consisting of a cyclic alkylene group and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group is a halogen atom, an oxygen atom and a nitrogen. It is a group represented by (may be substituted with at least one atom selected from the group consisting of atoms); R ₇₈ and R ₇₉ are independently linear or branched alkylenes having 1 to 100 carbon atoms, respectively. A divalent group containing at least one hydrocarbon group selected from the group consisting of a group, an alicyclic alkylene group having 3 to 10 carbon atoms, and an arylene group having 5 to 20 carbon atoms, and the hydrocarbon group. May be substituted with at least one atom selected from the group consisting of halogen atoms, oxygen atoms and nitrogen atoms, and if both R ₇₈ and R ₇₉ are present, then R ₇₈ and R ₇₉ are the same. However, if R ₇₈ and R ₇₉ are different, the sequence of repeating units of-(R _78- O)-and-(R _79- O)-may be block or random; and l And m are independently integers from 0 to 50, and l + m is an integer from 0 to 50}.
Examples thereof include compounds represented by.

From the viewpoint of resolution, X ₇ in the general formula (VII) includes an oxygen atom, a divalent group obtained by removing hydrogen from the hydroxyl group of bisphenol A (hereinafter, also referred to as a bisphenol A type group), and a hydroxyl group of hydrogenated bisphenol A. A divalent group obtained by removing hydrogen from the group (hereinafter, also referred to as a hydrogenated bisphenol A type group) is preferable, and a bisphenol A type group and a hydrogenated bisphenol A type group are more preferable.

As a preferable example of the alkylene oxide compound, when X ₇ in the general formula (VII) is an oxygen atom, ethylene glycol diglycidyl ether (for example, Epolite 40E manufactured by Kyoeisha Chemical Co., Ltd.) and diethylene glycol diglycidyl ether (for example, Kyoeisha Chemical Co., Ltd.) Epolite 100E), triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether (for example, Epolite 200E manufactured by Kyoeisha Chemical Co., Ltd.), pentaethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, heptaethylene glycol di Glycidyl ether, octaethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether (for example, Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), decaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether (for example, Epolite 70P manufactured by Kyoeisha Chemical Co., Ltd.) ), Dipropylene glycol diglycidyl ether, Tripropylene glycol diglycidyl ether (for example, Epolite 200P manufactured by Kyoeisha Chemical Co., Ltd.), Tetrapropylene glycol diglycidyl ether, Pentapropylene glycol diglycidyl ether, Hexapropylene glycol diglycidyl ether, Heptapropylene Glycol diglycidyl ether (for example, Epolite 400P manufactured by Kyoeisha Chemical Co., Ltd.), neopentyl glycol diglycidyl ether (for example, Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl ether (for example, Kyoeisha Chemical Co., Ltd.) Epolite 1600), hydrogenated bisphenol A diglycidyl ether (for example, Epolite 4000 manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be mentioned. Of these, hydrogenated bisphenol A diglycidyl ether is preferable.

When X ₇ in the general formula (VII) is a bisphenol A type group, a preferable example of the alkylene oxide compound is bisphenol A-propylene oxide 2 mol adduct diglycidyl ether (for example, Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.). ), Bisphenol A-propylene oxide 4 mol adduct Diglycidyl ether, Bisphenol A-propylene oxide 6 mol adduct Diglycidyl ether, Bisphenol A-propylene oxide 8 mol adduct Diglycidyl ether, Bisphenol A-propylene oxide 10 mol adduct Diglycidyl ether, bisphenol A-ethylene oxide 2 mol adduct Diglycidyl ether, bisphenol A-ethylene oxide 4 mol adduct Diglycidyl ether, bisphenol A-ethylene oxide 6 mol adduct Diglycidyl ether, bisphenol A-ethylene oxide 8 mol adduct Diglycidyl Examples thereof include ether, bisphenol A-ethylene oxide 10 mol adduct diglycidyl ether and the like. Of these, diglycidyl ether, which is an adduct of 2 mol of bisphenol A-propylene oxide, is preferable.

When X ₇ in the general formula (VII) is a hydrogenated bisphenol A type group, preferred examples of the alkylene oxide compound are hydrogenated bisphenol A-ethylene oxide 2 mol adduct diglycidyl ether and hydrogenated bisphenol A-ethylene oxide. 4 mol adduct diglycidyl ether, hydrogenated bisphenol A-ethylene oxide 6 mol adduct diglycidyl ether, hydrogenated bisphenol A-ethylene oxide 8 mol adduct diglycidyl ether, hydrogenated bisphenol A-ethylene oxide 10 mol adduct diglycidyl ether, Hydrogenated bisphenol A-propylene oxide 2 mol additive diglycidyl ether, hydrogenated bisphenol A-propylene oxide 4 mol additive diglycidyl ether, hydrogenated bisphenol A-propylene oxide 6 mol additive diglycidyl ether, hydrogenated bisphenol A- Examples thereof include diglycidyl ether with 8 mol of propylene oxide and diglycidyl ether with 10 mol of hydrogenated bisphenol A-propylene oxide.

The content of the epoxy compound in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 2% by mass, and further preferably 0.05% by mass to 1. It is in the range of 5% by mass. The content of the epoxy compound is preferably 0.001% by mass or more from the viewpoint of suppressing short-circuit defects after etching, and is preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. preferable.

If desired, the photosensitive resin composition may also contain additives such as stabilizers, discoloring agents, dyes, plasticizers, and antioxidants.
From the viewpoint of suppressing etching short-circuit defects of the photosensitive resin composition and the thermal stability or storage stability, the photosensitive resin composition may contain an additive other than the compound (i) as a stabilizer.
As the additive other than the compound (i), a compound having a tetrazole skeleton, an imidazole skeleton, a triazole skeleton, a thiazole skeleton and the like are preferable. It is more preferable that these compounds contain a mercapto group.
Examples of the compound include:
Imidazoles, such as 2-mercapto-1-methylimidazole, 2-mercaptobenzimidazole, 2-mercapto-5-methyl-benzimidazole, 5-chloro-2-mercaptobenzimidazole, 5-methoxy-2-mercaptobenzimidazole. ;
Thiazoles such as 2-mercaptobenzothiazole, 6-amino-2-mercaptobenzothiazole, 2-mercapto-5-methoxybenzothiazole, 5-chloro-2-mercaptobenzothiazole;
Tetrazoles such as 1-methyl-5-mercapto-1H-tetrazole, 1-phenyl-5-mercapto-1H-tetrazole, 1-methyl-5-amino-tetrazole, 5-amino-1H-tetrazole, 5-benzyl -1H-tetrazole, 5-methyltetrazole, 1-methyl-1H-tetrazole, 5-methylthio-1H-tetrazole, 5-phenyltetrazole, 5-ethylthio-1H-tetrazole, 5-benzylthio-1H-tetrazole;
Triazoles with uncondensed aromatic rings, such as 1,2,4-triazole, 1,2,3-triazole, 3-mercapto-1,2,4-triazole, 1,3,4-triazole-3 -Ol, 3-mercapto-4-methyl-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 3-amino-1,2,4-triazole;
Benzotriazoles such as 1,2,3-benzotriazole, 5-chloro-1,2,3-benzotriazole, carboxybenzotriazole;
Benzoxazoles, such as 2-mercaptobenzoxazole;
And so on.

From the viewpoint of suppressing etching short-circuit defects of the photosensitive resin composition and suppressing thermal stability or storage stability, the photosensitive resin composition contains (ii) a polymerization inhibitor (E) other than the epoxy compound as a stabilizer. Is preferable.

(Ii) Examples of the polymerization inhibitor other than the epoxy compound include a compound having a phenolic hydroxyl group and an amine-based polymerization inhibitor. Among these, a compound having a phenolic hydroxyl group is preferable from the viewpoint of suppressing short-circuit defects after etching.

Examples of the compound having a phenolic hydroxyl group include p-methoxyphenol, hydroquinone, pyrogallol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, and 2,2'-methylenebis (4-methyl-). 6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethyleneglycol-bis (3) -3-t-Butyl-5-methyl-4-hydroxyphenylpropionate) and the like.

Examples of the amine-based polymerization inhibitor include naphthylamine, diphenylnitrosamine, and nitrosophenylhydroxyamine aluminum salt.

In the present embodiment, the total content of all the stabilizers in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 2% by mass, still more preferably. Is in the range of 0.05% by mass to 1.5% by mass. The total content of the stabilizer is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. It is preferably 3% by mass or less.

Examples of the discoloring agent include leuco dyes and fluorane dyes. The use of a discoloring agent is preferable in terms of visibility due to the color development of the exposed portion. Further, when an inspection machine or the like reads an alignment marker for exposure, it is advantageous that the contrast between the exposed portion and the unexposed portion is large because the position can be easily recognized.

Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet] and bis (4-dimethylaminophenyl) phenylmethane [leuco malachite green]. In particular, from the viewpoint of improving the contrast, it is preferable to use leuco crystal violet as the leuco dye. The content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass. This content is preferably 0.1% by mass or more from the viewpoint of the contrast between the exposed portion and the unexposed portion, and preferably 10% by mass or less from the viewpoint of maintaining storage stability.

Examples of the base dye include Basic Green 1 [CAS number (hereinafter, the same): 633-03-4] (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), malachite green oxalate [2437. -29-8] (for example, Aizen Malachite Green, trade name, manufactured by Hodogaya Chemical Co., Ltd.), Brilliant Green [633-03-4], Fuxin [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] (For example, Aizen Victoria Pure Blue BOH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), Rhodamin B [81-88-9], Rhodamin 6G [989-38-8], Basic Yellow 2 [2465-272-2] ] Etc. can be mentioned. Of these, Basic Green 1, Malachite Green Oxalate, and Basic Blue 7 are preferable, and Basic Green 1 is particularly preferable from the viewpoint of improving hue stability and exposure contrast.

In the present embodiment, the content of the base dye in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 2% by mass, still more preferably 0.01. It is in the range of mass% to 1% by mass. The content of the dye is preferably 0.001% by mass or more from the viewpoint of obtaining good colorability, and preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

Examples of the plasticizer include toluene sulfonic acid amides such as o-toluene sulfonic acid amide and p-toluene sulfonic acid amide; polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, and polyoxypropylene. Glycol esters such as monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether; phthalates such as diethyl phthalate Tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, and tri-n-butyl acetyl citrate; propylene glycol and bisphenol A with propylene oxide added to both sides of bisphenol A, respectively. Examples thereof include ethylene glycol to which ethylene oxide is added on both sides.

In the present embodiment, the content of the plasticizer in the photosensitive resin composition is preferably in the range of 0.1% by mass to 5% by mass, more preferably 1% by mass to 4% by mass.

The additives described above can be used alone or in combination of two or more.

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

<Photosensitive resin laminate>
The laminate according to the present embodiment (hereinafter, also referred to as “photosensitive resin laminate”) includes a base film and a photosensitive resin layer containing the above-mentioned photosensitive resin composition provided on the base film. If desired, the photosensitive resin laminate may have a protective layer on the side opposite to the base film side of the photosensitive resin layer.

The base film can be peeled off from the photosensitive resin layer. The base film is not particularly limited, but preferably transmits light emitted from an exposure light source. Examples of such a base film include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, and polymethylmethacrylate copolymer film. Examples thereof include polystyrene films, polyacrylonitrile films, styrene copolymer films, polyamide films, and cellulose derivative films. These films may be stretched if necessary. The haze of the film is preferably 0.01% to 5.0%, more preferably 0.01% to 2.5%, still more preferably 0.01% to 1.0%. The thinner the film, the more advantageous in terms of image formation and economy, but the thickness of the film is preferably 10 μm to 30 μm because it is necessary to maintain the strength.

Further, an important property of the protective layer used in the photosensitive resin laminate is that the protective layer has a smaller adhesion to the photosensitive resin layer than the base film and can be easily peeled off. As the protective layer, for example, a polyethylene film, a polypropylene film, or the like is preferable. For example, a film having excellent peelability described in JP-A-59-202457 can be used. The film thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.

In the present embodiment, the thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 5 μm to 100 μm, more preferably 7 μm to 60 μm. The smaller the thickness of the photosensitive resin layer, the better the resolution of the resist pattern, while the larger the thickness, the stronger the cured film, so that it can be selected according to the application.

A known method may be used as a method for producing a photosensitive resin laminate by sequentially laminating a base film, a photosensitive resin layer, and, if desired, a protective layer. As described above, by adjusting the wet-dry lamination resolution difference of the photosensitive resin composition according to the present embodiment to 5 μm or less, it is possible to achieve both followability and short-circuit defect suppression property, and thus the photosensitive resin. The composition can be used for both wet lamination and dry lamination.

For example, the above-mentioned photosensitive resin composition formulation is prepared, then applied on a base film using a bar coater or a roll coater, dried, and the photosensitive resin composed of the photosensitive resin composition formulation is applied on the base film. Laminate the layers. Further, if desired, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

<Resist pattern formation method>
The method for forming the resist pattern includes a laminating step of laminating a photosensitive resin layer containing the above-mentioned photosensitive resin composition on a support, an exposure step of exposing the photosensitive resin layer, and developing the exposed photosensitive resin layer. The developing steps to be performed are preferably included in this order. An example of a specific method for forming a resist pattern in the present embodiment is shown below.

First, in the laminating step, a photosensitive resin layer is formed on the 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-bonded to the substrate surface with a laminator and laminated. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO) and the like.

In the present embodiment, the photosensitive resin layer may be laminated on only one side of the substrate surface, or may be laminated on both sides if necessary. The heating temperature at the time of laminating is generally 40 ° C to 160 ° C. Further, by performing the heat bonding at the time of laminating twice or more, the adhesion of the obtained resist pattern to the substrate can be improved. At the time of heat crimping, a two-stage laminator provided with two rolls may be used, or the laminate of the substrate and the photosensitive resin layer may be repeatedly crimped several times through the rolls. In the case of wet lamination, prior to lamination, the liquid is applied to the surface of the substrate by contacting a sponge roll impregnated with the liquid with the substrate, spraying the liquid directly on the substrate, or immersing the substrate in the liquid. ..

Next, in the exposure step, the photosensitive resin composite layer is exposed to active light using an exposure machine. Exposure can be performed after the support has been peeled off, if desired. When exposing through a photomask, the amount of exposure is determined by the illuminance of the light source and the exposure time, and may be measured using a photometer. In the exposure step, direct imaging exposure may be performed. In direct imaging exposure, a photomask is not used and the exposure is performed directly on the substrate by a drawing device. As the light source, a semiconductor laser having a wavelength of 350 nm to 410 nm or an ultrahigh pressure mercury lamp is used. When the drawing pattern is controlled by a computer, the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, in the developing step, the unexposed portion or the exposed portion of the photosensitive resin layer after exposure is removed with a developing solution using a developing device. If there is a base film or support on the photosensitive resin layer after exposure, this is excluded. Subsequently, the unexposed portion or the exposed portion is developed and removed using a developing solution composed of an alkaline aqueous solution to obtain a resist image.

As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ , K ₂ CO _3, or the like is preferable. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin layer, but a Na ₂ CO ₃ aqueous solution having a concentration of 0.2% by mass to 2% by mass is generally used. A surface active agent, a defoaming agent, a small amount of an organic solvent for accelerating development, or the like may be mixed in the alkaline aqueous solution. The temperature of the developer in the developing step is preferably kept constant within the range of 20 ° C. to 40 ° C.

A resist pattern can be obtained by the above steps, but if desired, a heating step can be further performed at 100 ° C. to 300 ° C. By carrying out this heating step, the chemical resistance of the resist pattern can be improved. In the heating step, a heating furnace of a type using hot air, infrared rays, or far infrared rays can be used.

The photosensitive resin composition of the present embodiment can be suitably used for forming a circuit of a printed circuit board. Generally, a subtractive process and a semi-additive process (SAP) are used as a circuit forming method for a printed circuit board.

The subtractive process is a method of forming a circuit by removing only non-circuit parts by etching from a conductor arranged on the entire surface of a substrate.
SAP is a method in which a resist is formed on a non-circuit portion on a conductor seed layer arranged on the entire surface of a substrate, and then only the circuit portion is formed by plating.

<Manufacturing method of conductor pattern>
The method for producing the conductor pattern includes a laminating step of laminating a photosensitive resin layer made of the above-mentioned photosensitive resin composition on a substrate such as a metal plate and a metal film insulating plate, an exposure step of exposing the photosensitive resin layer, and exposure. A development step of obtaining a substrate on which a resist pattern is formed by removing an unexposed portion or an exposed portion of the photosensitive resin layer with a developing solution, and a conductor pattern forming step of etching or plating a substrate on which a resist pattern is formed. , Preferably in this order.

In the present embodiment, the method for manufacturing a conductor pattern is performed by using a metal plate or a metal film insulating plate as a substrate, forming a resist pattern by the above-mentioned resist pattern forming method, and then passing through a conductor pattern forming step. In the conductor pattern forming step, a conductor pattern is formed on a substrate surface (for example, a copper surface) exposed by development by using a known etching method or plating method.

Furthermore, the present invention is suitably applied to, for example, the following applications.

<Manufacturing method of wiring board>
A wiring board having a desired wiring pattern (for example, by further performing a peeling step of peeling the resist pattern from the substrate with an aqueous solution having a stronger alkalinity than the developer after producing the conductor pattern by the method for producing the conductor pattern (for example). Printed wiring board) can be obtained.

The alkaline aqueous solution for peeling (hereinafter, also referred to as “stripping liquid”) is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of 2% by mass to 5% by mass, or an organic amine-based stripping solution is used. Commonly used. A small amount of water-soluble solvent may be added to the stripping solution. Examples of the water-soluble solvent include alcohol and the like. The temperature of the stripping liquid in the stripping step is preferably in the range of 40 ° C. to 70 ° C.

<Manufacturing of lead frame>
A lead frame can be manufactured by forming a resist pattern by a resist pattern forming method using a metal plate such as copper, a copper alloy, or an iron-based alloy as a substrate, and then performing the following steps. First, a step of etching the substrate exposed by development to form a conductor pattern is performed. After that, a desired lead frame can be obtained by performing a peeling step of peeling the resist pattern by the same method as the method for manufacturing a wiring board.

<Manufacturing of base material with uneven pattern>
The resist pattern formed by the resist pattern forming method can be used as a protective mask member when the substrate is processed by the sandblasting method. In this case, examples of the substrate include glass, silicon wafers, amorphous silicon, polycrystalline silicon, ceramics, sapphire, and metal materials. A resist pattern is formed on these substrates by a method similar to the resist pattern forming method. After that, a sandblasting step of spraying a blasting material onto the formed resist pattern to cut it to a desired depth and a stripping step of removing the resist pattern portion remaining on the substrate from the substrate with an alkaline stripping solution or the like are performed. , A base material having a fine uneven pattern on a substrate can be manufactured.

In the sandblasting step, a known blasting material may be used, but for example, fine particles having a particle size of 2 μm to 100 μm including SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, stainless steel and the like are generally used. To.

<Manufacturing of semiconductor packages>
A semiconductor package can be manufactured by using a wafer for which a large-scale integrated circuit (LSI) has been formed as a substrate, forming a resist pattern on the wafer by a resist pattern forming method, and then performing the following steps. .. First, a step of forming a conductor pattern is performed by subjecting the openings exposed by development to columnar plating such as copper or solder. After that, a peeling step of peeling the resist pattern is performed by the same method as the manufacturing method of the wiring board, and further, a step of removing the thin metal layer of the portion other than the columnar plating by etching is performed to obtain a desired semiconductor package. Obtainable.

In the present embodiment, the photosensitive resin composition is used for manufacturing a printed wiring board; manufacturing a lead frame for mounting an IC chip; precision processing of a metal foil such as manufacturing a metal mask; a ball grid array (BGA), and a chip size package. (CSP) and other packages; Chip-on-film (COF), Tape Automated Bonding (TAB) and other tape substrates; Semiconductor bumps; and ITO electrodes, address electrodes, electromagnetic shields and other flat panels It can be used in the manufacture of partition walls for displays.
Unless otherwise specified, the values of the above-mentioned parameters are measured according to the measurement method in the examples described later.

The measurement of the physical property values of the polymer and the monomer, and the method of preparing the evaluation sample of Examples and Comparative Examples will be described. Next, the evaluation method for the obtained sample and the evaluation result thereof are shown.

(1) Measurement or calculation of physical property values <Measurement of weight average molecular weight or number average molecular weight of polymer>
The weight average molecular weight or number average molecular weight of the polymer is determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex® manufactured by Showa Denko Corporation) (registered trademark). KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, moving layer solvent: tetrahydrofuran, polystyrene standard sample (using calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko Corporation) Obtained as polystyrene conversion.
Further, the degree of dispersion of the polymer was calculated as the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).

<Acid equivalent>
As used herein, the acid equivalent means the mass (gram) of a polymer having one equivalent of a carboxyl group in the molecule. The acid equivalent was measured by a potentiometric titration method using a 0.1 mol / L sodium hydroxide aqueous solution using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.

(2) Method for preparing evaluation samples The evaluation samples in Examples 1 to 17 and Comparative Examples 1 to 7 were prepared as follows.

<Preparation of photosensitive resin laminate>
The components shown in Table 1 or 2 below (however, the numbers of each component indicate the blending amount (parts by mass) as solid content) and the solvent were sufficiently stirred and mixed to obtain a photosensitive resin composition preparation solution. .. The names of the components represented by abbreviations in Tables 1 and 2 are shown in Table 3 below. A 16 μm thick polyethylene terephthalate film (manufactured by Mitsubishi Plastics Co., Ltd., R310-16B) was used as a support film, and this mixture was uniformly applied to the surface of the polyethylene terephthalate film using a bar coater and in a dryer at 95 ° C. It was dried for 2 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer was 20 μm.

Next, a 19 μm-thick polyethylene film (manufactured by Tamapoli Co., Ltd., GF-818) was attached as a protective layer on the surface of the photosensitive resin composition layer on the side where the polyethylene terephthalate film was not laminated to be a photosensitive resin. A laminate was obtained.

<Board surface preparation>
Jet scrub polishing of a 0.4 mm thick copper-clad laminate with 35 μm rolled copper foil laminated using a grinding material (Sacrund R (registered trademark # 220) manufactured by Nippon Carlit Co., Ltd.) at a spray pressure of 0.2 MPa. By doing so, an evaluation substrate was produced. Further, using a dry film resist having a thickness of 25 μm, grooves having a width of 100 μm and a depth of 5 μm were formed on the evaluation substrate surface by an etching method so as to be parallel and perpendicular to the processing direction of the evaluation substrate.

<Dry lamination>
While peeling off the polyethylene film of the photosensitive resin laminate, the photosensitive resin laminate was rolled on an evaluation substrate preheated to 50 ° C by a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation) at a roll temperature of 105 ° C. A test piece was obtained by laminating. The air pressure was 0.35 MPa and the laminating speed was 2.0 m / min.

<Wet lamination>
Ion-exchanged water was prepared as the lamination liquid. The evaluation substrate having the grooves formed was immersed in ion-exchanged water, and the surface of the substrate was coated with ion-exchanged water. The polyethylene film of the photosensitive resin laminate was peeled off, and the photosensitive resin laminate was rolled on an evaluation substrate immersed in ion-exchanged water at a roll temperature of 105 ° C. using a hot roll laminator (AL-700, manufactured by Asahi Kasei Corporation). A test piece was obtained by laminating. The air pressure was 0.35 MPa and the laminating speed was 2.0 m / min.

<Exposure>
Using a direct drawing type exposure device (manufactured by Nippon Orbotech Co., Ltd., Paragon Ultra-100, main wavelength 355 nm), exposure was performed with various exposure amounts using a stofer 21-step step tablet as a mask. At this time, the exposure was performed so that the exposure pattern was perpendicular to the groove of the evaluation substrate. The resolution value was exposed using a drawing pattern obtained in 1 μm increments.

<Development>
After peeling the polyethylene terephthalate film from the photosensitive resin laminate, use a developing device manufactured by Fuji Kiko Co., Ltd. with a full cone type nozzle at a developing spray pressure of 0.15 MPa and 1 mass% Na ₂ CO at 30 ° C. _{The three} aqueous solutions were sprayed for a predetermined time to develop, and the unexposed portion of the photosensitive resin layer was dissolved and removed. At this time, the shortest time required for the photosensitive resin layer in the unexposed portion to completely dissolve was measured as the minimum development time, and development was performed in twice the minimum development time to prepare a resist pattern. At that time, the washing step was performed with a flat type nozzle at a washing spray pressure of 0.15 MPa for the same time as the developing step.

(3) Sample evaluation method <Dry evaluation resolution (after development)>
For the cured resist pattern obtained by the exposure and development after the dry lamination, the value of the resolution defined as the minimum space width for the resist line having a width of 200 μm was obtained as the dry lamination resolution. The exposure step was performed with an exposure amount such that the number of residual film limit stages after development was six.
In the cured resist pattern, there is no residual resist on the substrate surface of the unexposed portion and the substrate surface is exposed, there are no protrusions of resist components such as threads drawn from the cured resist, and the linearity of the line is also good. , The minimum space width that was normally formed without adhesion between the cured resists was evaluated.

<Wet lamination resolution (after development)>
A wet lamination resolution (after development) was obtained in the same manner as in the method for determining the dry lamination resolution (after development) except that the wet lamination was performed instead of the dry lamination.

<Wet-dry lamination resolution difference>
The wet-dry lamination resolution difference was calculated by subtracting the dry lamination resolution (after development) from the wet lamination resolution (after development), and evaluated according to the following criteria.
◯ (Good): The wet-dry lamination resolution difference is 5 μm or less.
X (defective): Wet-dry lamination resolution difference exceeds 5 μm.

<Sensitivity (required exposure)>
After the dry lamination, during the exposure and development steps, the exposure amount at which the number of residual film limit stages after development was 6 was determined and evaluated according to the following criteria.
◯ (Good): The exposure amount is less than 20 mJ / cm ² .
Δ (allowable): The exposure amount is 20 mJ / cm ² or more.

<Resolution after etching>
Wet lamination resolution (after development) was adopted as the resolution after etching and evaluated according to the following criteria.
⊚ (significantly good): The resolution after etching is less than 17 μm.
◯ (Good): The resolution after etching is 17 μm or more and 20 μm or less.
Δ (allowable): The resolution after etching is more than 20 μm and less than 25 μm.
X (defective): The resolution after etching is 25 μm or more.

<Resolution (normal)>
The dry lamination resolution (after development) was adopted as the resolution (normal).

(4) Evaluation Results The evaluation results of Examples 1 to 17 and Comparative Examples 1 to 7 are shown in Tables 1, 2 or 3 below. In Tables 1 and 2, the abbreviation "long-chain RO monomer" represents a monomer having 20 mol or more of alkylene oxide units in the molecule.

Claims (11)

With the base film
A photosensitive resin layer containing a photosensitive resin composition provided on the base film and
It is a laminated body including
The photosensitive resin composition is
(A) Alkali-soluble polymer;
(B) Ethylene unsaturated bond-containing compound; and (C) Photopolymerization initiator;
Including
The base film can be peeled off from the photosensitive resin layer, and the photosensitive resin composition can be obtained by the following mathematical formula (1):
W _X- D _X ≤ 5 μm (1)
{Wherein, W _X has the photosensitive resin layer, in the presence of a liquid, the resist pattern obtained by exposure and development after lamination on a substrate having a groove width 100μm and depth 5 [mu] m, the 200μm width a resolution ([mu] m) which is defined as a space minimum width to resist lines, and D _X, in the resist pattern obtained by exposure and developing the photosensitive resin layer in the absence of liquid after lamination on the substrate , The resolution (μm) defined as the minimum space width for a resist line with a width of 200 μm}
A laminate characterized by satisfying the relationship represented by. The photosensitive resin composition is
(D) Additives and
(E) Polymerization inhibitor and
Including
The additive (D) contains a benzotriazole compound that does not contain a carboxyl group and contains an amino group.
The laminate according to claim 1, wherein the (E) polymerization inhibitor contains an epoxy compound. The laminate according to claim 1 or 2, wherein the (B) ethylenically unsaturated bond-containing compound contains an addition-polymerizable monomer having 20 mol or more of alkylene oxide units in the molecule. As the (B) ethylenically unsaturated bond-containing compound, the following general formula (II):

{In the formula, R ₃ and R ₄ independently represent a hydrogen atom or a methyl group, where A is C ₂ H ₄ and B is C ₃ H ₆ , n ₁ , n ₂ , n ₃ and n ₄ is an integer satisfying the relationship of n ₁ + n ₂ + n ₃ + n ₄ = 2 to 50, and the sequence of repeating units of − (A—O) − and − (BO) − is random. In the case of a block, either − (A—O) − or − (BO) − may be on the bisphenyl group side}.
The laminate according to any one of claims 1 to 3, which contains an alkylene oxide-modified bisphenol A type di (meth) acrylate compound represented by. The (B) ethylenically unsaturated bond-containing compound is
The following general formula (III):

{In the formula, R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group, X represents an alkylene group having 2 to 6 carbon atoms, and m ₂ , m ₃ and m ₄ represent. Independently, if m ₂ + m ₃ + m ₄ is an integer from 0 to 40, m ₂ + m ₃ + m ₄ is 1 to 40, and m ₂ + m ₃ + m ₄ is 2 or more, then the plurality of X's are identical to each other. May be present or different}
Tri (meth) acrylate compound represented by;
The following general formula (IV):

{In the formula, R ₈ and R ₉ independently represent a hydrogen atom or a methyl group, Y represents an alkylene group having 2 to 6 carbon atoms, Z represents a divalent organic group, and s and t is an integer from 0 to 40 independently, and s + t ≧ 1}
Urethane di (meth) acrylate compound represented by; and the following general formula (VI):

{In the formula, A represents C ₂ H ₄ , R ₆₁ represents a hydrogen atom or a methyl group, R ₆₂ represents a hydrogen atom, a methyl group or a methyl halide group, and R ₆₃ represents 1 carbon atoms. Represents an alkyl group, a halogen atom or a hydroxyl group of ~ 6, where a is an integer of 1-4, k is an integer of 0-4, and if k is an integer of 2 or more, a plurality of R's. ₆₃ may be the same or different}
O-phthalate compound represented by;
The laminate according to any one of claims 1 to 4, which comprises at least one selected from the group consisting of. The laminate according to any one of claims 1 to 5, wherein the (C) photopolymerization initiator contains an N-aryl amino acid or an ester compound thereof. The laminate according to claim 6, wherein the (C) photopolymerization initiator contains N-phenylglycine or an ester compound thereof. Any of claims 1 to 7, wherein the alkali-soluble polymer (A) contains 40% by mass or more of styrene structural units based on the total mass of the monomers constituting the alkali-soluble polymer (A). The laminate according to item 1. The laminate according to any one of claims 1 to 8, which is for direct imaging exposure. Laminating step of laminating the photosensitive resin composition of the laminated body according to any one of claims 1 to 9 on a support;
An exposure step of exposing the photosensitive resin composition; and a developing step of developing the exposed photosensitive resin composition;
A method for forming a resist pattern including. Laminating step of laminating the photosensitive resin composition of the laminate according to any one of claims 1 to 9 on a substrate;
An exposure step of exposing the photosensitive resin composition;
A developing step of developing the exposed photosensitive resin composition to obtain a substrate on which a resist pattern is formed;
A conductor pattern forming step of etching or plating a substrate on which the resist pattern is formed; and a peeling step of peeling off the resist pattern;
Manufacturing method of wiring board including.