JP6063200B2 - Photosensitive resin composition - Google Patents

Description

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

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

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

A method for producing a printed wiring board using the dry film resist will be briefly described below.
First, when the dry film resist has a protective layer, for example, a polyethylene film, it is peeled off from the photosensitive resin layer. Next, a photosensitive resin layer and a support layer are laminated on a substrate such as a copper clad laminate using a laminator so that the substrate, the photosensitive resin layer, and the support layer are in this order. In addition, some laminating methods include a temporary attachment process. In this case, first, the temporary block is lowered to the substrate while the support and the photosensitive resin layer are adsorbed to the temporary block by vacuum suction, and the photosensitive resin layer is temporarily bonded to the substrate. Next, after the vacuum is released, the temporary block is lifted, and at the same time when the support and the photosensitive resin layer are separated from the temporary block, the laminate roll comes down and lamination begins. Next, the exposed portion is polymerized and cured by exposing the photosensitive resin layer to ultraviolet rays containing i-line (365 nm) emitted from an ultra-high pressure mercury lamp through a photomask having a wiring pattern. The support layer, such as polyethylene terephthalate, is then peeled off. Next, an unexposed portion of the photosensitive resin layer is dissolved or dispersed and removed with a developer, for example, an aqueous solution having weak alkalinity, to form a resist pattern on the substrate.

  The method for creating a metal conductor pattern using the resist pattern on the substrate thus formed can be roughly classified into two methods. The first method is a method in which after removing a copper surface such as a copper-clad laminate not covered with a resist pattern by etching, the resist pattern portion is removed with an alkaline aqueous solution stronger than the developer. In this case, for the simplicity of the process, a technique (tenting method) in which a through hole (through hole) is covered with a cured film and then etched is frequently used. The second method is to perform copper plating on the same copper surface, and if necessary, after further plating with solder, nickel, tin, etc. This is a method (plating method) for etching a copper surface such as a plate. For etching, an acidic etching solution such as cupric chloride, ferric chloride, copper ammonia complex solution, sulfuric acid / hydrogen peroxide aqueous solution or the like is used.

  Along with the recent miniaturization of wiring spacing on printed wiring boards, dry film resists are required to have high resolution and high adhesion in order to produce narrow pitch patterns with good yield. Often low molecular weight photopolymerizable monomers are often used to provide. However, when the protective layer is a general polyethylene film, if a large amount of low molecular weight monomer is used, the monomer in the photosensitive resin layer passes through the protective layer (hereinafter referred to as bleed out), and the protective layer is wound up. The problem of soiling the roll occurs. In many cases, the dry film resist is a roll product. In this case, since the protective layer and the support are in contact with each other, the monomer passing through the protective layer is transferred to the surface of the support and becomes sticky. A dry film resist having good bleed-out properties is required because the support is difficult to peel off from the attachment block and may cause a laminate failure.

  Furthermore, after development, a semi-cured resist called a soot (cured resist foot portion) (see FIG. 1) may be generated at the boundary between the cured resist and the substrate. This leads to a problem that the contact resolution becomes insufficient and the conductive pattern becomes unstable after the etching process.

  Recently, the importance of the plating method has been increasing from the viewpoint of producing a narrow pitch pattern with a high yield. However, when wiring is formed by plating using a resist pattern with a sash, the bottom of the plating line and the base are formed. Since the ground contact surface with the material is small, the contact is poor and the yield is deteriorated. For this reason, there is a demand for a dry film resist having a very small squeezed resist after development. Also, a dry film resist with a short development time is desired in order to increase productivity.

  Patent Document 1 discloses a photosensitive resin composition having a pentaerythritol skeleton tetra (meth) acrylate as an unsaturated compound in the photosensitive resin composition.

JP 2011-227309 A

  However, the resist shape, bleed-out property and development time are not mentioned. It is an object of the present invention to provide a photosensitive resin composition excellent in resist shape, minimum development time and bleed-out property, and a resist pattern forming method and a wiring board manufacturing method using the same.

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

｛式中、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立に水素原子又はメチル基であり、Ｒ_５は、それぞれ独立に、炭素数が３又は４であるアルキレン基であり、ｎ_１、ｎ_２、ｎ_３、ｎ_４、ｍ_１、ｍ_２、ｍ_３及びｍ_４は、それぞれ独立に０又は正の整数であり、ｎ_１＋ｎ_２＋ｎ_３＋ｎ_４＋ｍ_１＋ｍ_２＋ｍ_３＋ｍ_４は、８〜２０の整数であり、ｎ_１＋ｎ_２＋ｎ_３＋ｎ_４は、８〜２０の整数であり、ｍ_１＋ｍ_２＋ｍ_３＋ｍ_４は、０〜１２の整数であり、−（Ｃ_２Ｈ_４−Ｏ）−及び−（Ｒ_５Ｏ）−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交互であってもよく、そして−（Ｃ_２Ｈ_４−Ｏ）−及び−（Ｒ_５Ｏ）−の順序は、いずれが四級炭素側であってもよい。｝

｛式中、Ｘ_１〜Ｘ_８は、それぞれ独立に、水素原子又はハロゲン原子であり、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、Ｒ_８及びＲ_９は、それぞれ独立に、炭素数２〜６のアルキレン基を表し、ｎ_５及びｎ_６は、それぞれ独立に、０又は正の整数であり、そしてｎ_５＋ｎ_６は、２〜６である。｝

｛式中、Ｒ_１０は、水素原子又は（メタ）アクリロイル基を示し、１分子中に少なくとも４個以上の（メタ）アクリロイル基を含む。｝
で表される化合物のうち、（Ｉ）と（ＩＩ）又は（Ｉ）と（ＩＩＩ）を組み合わせて用いる感光性樹脂組成物。 [1] Based on the total solid content of the photosensitive resin composition, the following components:
(A) Alkali-soluble polymer: 10% by mass to 90% by mass,
(B) Compound having ethylenically unsaturated bond: 5% by mass to 70% by mass, and (C) Photopolymerization initiator: 0.01% by mass to 20% by mass,
And (B) the compound having an ethylenically unsaturated bond, the following general formulas (I) to (III):

{In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or a methyl group; R ₅ is each independently an alkylene group having 3 or 4 carbon atoms; ₁ , n ₂ , n ₃ , n ₄ , m ₁ , m ₂ , m ₃ and m ₄ are each independently 0 or a positive integer, and n ₁ + n ₂ + n ₃ + n ₄ + m ₁ + m ₂ + m ₃ + m ₄ is an integer of 8 to 20, n ₁ + n ₂ + n ₃ + n ₄ is an integer of 8 to 20, m ₁ + m ₂ + m ₃ + m ₄ is an integer of 0 to 12, and − (C The sequence of repeating units of ₂ H ₄ —O) — and — (R ₅ O) — may be random, block or alternating, and — (C ₂ H ₄ —O) —. and - (R 5 _O) - sequence of any may be a quaternary carbon side. }

{Wherein, X _{1 to} X ₈ each independently represents a hydrogen atom or a halogen atom, R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group, and R ₈ and R ₉ each represent Independently, it represents an alkylene group having 2 to 6 carbon atoms, n ₅ and n ₆ are each independently 0 or a positive integer, and n ₅ + n ₆ is 2 to 6. }

{In the formula, R ₁₀ represents a hydrogen atom or a (meth) acryloyl group, and contains at least 4 (meth) acryloyl groups in one molecule. }
The photosensitive resin composition which uses combining (I) and (II) or (I) and (III) among the compounds represented by these.

｛式中、Ｙ_１〜Ｙ_８は、それぞれ独立に、水素原子又はハロゲン原子であり、Ｒ_１１及びＲ_１２は、それぞれ独立に水素原子又はメチル基を表し、Ｒ_１３及びＲ_１４は、それぞれ独立に炭素数２〜６のアルキレン基を表し、ｎ_７及びｎ_８は、それぞれ独立に、０又は正の整数であり、そしてｎ_７＋ｎ_８は、７〜４０である。｝
で表される化合物を含む、［１］記載の感光性樹脂組成物。 [2] The following general formula (IV);

{Wherein Y _{1 to} Y ₈ are each independently a hydrogen atom or a halogen atom, R ₁₁ and R ₁₂ each independently represent a hydrogen atom or a methyl group, and R ₁₃ and R ₁₄ are each independently Represents an alkylene group having 2 to 6 carbon atoms, n ₇ and n ₈ are each independently 0 or a positive integer, and n ₇ + n ₈ is 7 to 40. }
The photosensitive resin composition of [1] description including the compound represented by these.

[3] The (A) alkali-soluble polymer has an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000, and has an aromatic group in its side chain. 2]. The photosensitive resin composition of [2].

[4] In the general formula (I), n ₁ + n ₂ + n ₃ + n ₄ + m ₁ + m ₂ + m ₃ + m ₄ is an integer of 12 to 20, and any one of [1] to [3] The photosensitive resin composition of one term.

[5] _Y 1 to Y ₈ of _X 1 to X ₈ and Formula of the general formula (II) (IV) are all a hydrogen atom, according to any one of [2] to [4] Photosensitive resin composition.

[6] The following steps:
A laminating step of laminating a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [5] on a support;
An exposure step of exposing the photosensitive resin layer; and a development step of developing the exposed photosensitive resin layer;
A resist pattern forming method including:

[7] The following steps:
A laminating step of laminating a photosensitive resin layer comprising the photosensitive resin composition according to any one of [1] to [5] on a substrate;
An exposure step of exposing the photosensitive resin layer;
A development step of developing the exposed photosensitive resin layer to obtain a substrate on which a resist pattern is formed;
A method of manufacturing a wiring board, comprising: a conductor pattern forming step of etching or plating a substrate on which the resist pattern is formed; and a peeling step of peeling the resist pattern.

  According to the present invention, it is possible to provide a photosensitive resin composition excellent in resist shape, minimum development time and bleed-out property, and a resist pattern and a wiring board using the same.

It is a schematic explanatory drawing of the soot (cured resist foot part) of the boundary part of a cured resist and a board | substrate.

  Hereinafter, the best mode for carrying out the present invention (hereinafter abbreviated as “the present embodiment”) will be specifically described.

<Photosensitive resin composition>
In this embodiment, the photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. Moreover, in this embodiment, the photosensitive resin composition can form the photosensitive resin layer by applying to arbitrary supports. Hereinafter, each component contained in the photosensitive resin composition will be described.

(A) Alkali-soluble polymer (A) An alkali-soluble polymer is a polymer that can be dissolved in an alkaline solution. In this embodiment, (A) the alkali-soluble polymer preferably has a carboxyl group, more preferably has an acid equivalent of 100 to 600, and contains a carboxyl group-containing monomer as a copolymerization component. More preferably, it is a copolymer. Further, (A) the alkali-soluble polymer may be thermoplastic.

  (A) The acid equivalent of the alkali-soluble polymer is preferably 100 or more from the viewpoint of the development resistance of the photosensitive resin layer and the resolution and adhesion of the resist pattern, while the development of the photosensitive resin layer. Is preferably 600 or less from the viewpoints of releasability and releasability. The acid equivalent of (A) the alkali-soluble polymer is more preferably 200 to 500, and further preferably 250 to 450. In this specification, an acid equivalent means the mass (gram) of the polymer which has 1 equivalent of carboxyl groups in a molecule | numerator, Hiranuma Sangyo Co., Ltd. Hiranuma automatic titration apparatus (COM-555) is used, The acid equivalent was measured by potentiometric titration using a 0.1 mol / L aqueous sodium hydroxide solution.

  (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 or more from the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance to the developer. From the viewpoint of maintaining developability, it is preferably 500,000 or less. Moreover, (A) The weight average molecular weight (Mw) of the alkali-soluble polymer is more preferably 10,000 to 200,000, and further preferably 40,000 to 130,000. Furthermore, the dispersity (Mw / Mn) of (A) alkali-soluble polymer, which is the ratio of Mw to (A) number-average molecular weight (Mn) of alkali-soluble polymer, is 1.0 to 6.0. Preferably there is.

In this specification, a weight average molecular weight means the weight average molecular weight measured using the analytical curve of polystyrene (Showa Denko Co., Ltd. Shodex STANDARD SM-105) by gel permeation chromatography (GPC). The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured using gel permeation chromatography manufactured by JASCO Corporation under the following conditions.
Differential refractometer: RI-1530
Pump: PU-1580
Degasser: DG-980-50
Column oven: CO-1560
Column: KF-8025, KF-806M × 2, KF-807 in order
Eluent: THF

  (A) The alkali-soluble polymer is preferably obtained by polymerizing at least one of the first monomers described below. The (A) alkali-soluble polymer is more preferably obtained by copolymerizing at least one of the first monomers and at least one of the second monomers described below.

  The first monomer is a monomer containing a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable. In the present specification, “(meth) acryl” means acryl or methacryl, and “(meth) acrylate” means “acrylate” and “methacrylate”.

  The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate; vinyl acetate Esters of vinyl alcohol such as; and (meth) acrylonitrile, styrene, and polymerizable styrene derivatives such as methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl Ikikosan, dimer, styrene trimer), and the like. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene and benzyl (meth) acrylate are preferable.

  In this embodiment, from the viewpoint of improving the resolution of the resist pattern, the (A) alkali-soluble polymer preferably has an aromatic group in the side chain of the structure.

  The (A) alkali-soluble polymer having an aromatic group in the side chain is prepared by using a compound having an aromatic group as the first monomer and / or the second monomer. be able to. Examples of the monomer having an aromatic group include benzyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, styrene, cinnamic acid, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxy). Styrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Among these, benzyl (meth) acrylate is preferable.

  In the present embodiment, (A) the alkali-soluble polymer is prepared by known polymerization method, preferably addition polymerization, more preferably radical polymerization of the first monomer and / or the second monomer. be able to.

  In the present embodiment, the content of the (A) alkali-soluble polymer in the photosensitive resin composition (based on the total solid content of the photosensitive resin composition. Hereinafter, the same applies to each component unless otherwise specified. Is preferably in the range of 10% by mass to 90% by mass, more preferably in the range of 20% by mass to 80% by mass, and still more preferably in the range of 30% by mass to 60% by mass. (A) The content of the alkali-soluble polymer is preferably 10% by mass or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer, while the resist pattern formed by exposure is used as a resist material. It is preferable that it is 90 mass% or less from a viewpoint of fully exhibiting the performance of this.

｛式中、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立に水素原子又はメチル基であり、Ｒ_５は、それぞれ独立に、炭素数が３又は４であるアルキレン基であり、ｎ_１、ｎ_２、ｎ_３、ｎ_４、ｍ_１、ｍ_２、ｍ_３及びｍ_４は、それぞれ独立に０又は正の整数であり、ｎ_１＋ｎ_２＋ｎ_３＋ｎ_４＋ｍ_１＋ｍ_２＋ｍ_３＋ｍ_４は、８〜２０の整数であり、好ましくは密着性の観点から１２〜２０の整数であり、ｎ_１＋ｎ_２＋ｎ_３＋ｎ_４は、８〜２０の整数であり、好ましくは１２〜２０の整数であり；ｍ_１＋ｍ_２＋ｍ_３＋ｍ_４は、０〜１２の整数であり、−（Ｃ_２Ｈ_４−Ｏ）−及び−（Ｒ_５Ｏ）−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交互であってもよく、そして−（Ｃ_２Ｈ_４−Ｏ）−及び−（Ｒ_５Ｏ）−の順序は、いずれが四級炭素側であってもよい。｝

｛式中、Ｘ_１〜Ｘ_８は、それぞれ独立に、水素原子又はハロゲン原子であり、好ましくはＸ_１〜Ｘ_８が全て水素原子であり、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、Ｒ_８及びＲ_９は、それぞれ独立に、炭素数２〜６のアルキレン基を表し、ｎ_５及びｎ_６は、それぞれ独立に、０又は正の整数であり、そしてｎ_５＋ｎ_６は、２〜６である。｝

｛式中、Ｒ_１０は、水素原子又は（メタ）アクリロイル基を示し、１分子中に少なくとも４個以上の（メタ）アクリロイル基を含む。｝
で表される化合物のうち、（Ｉ）と（ＩＩ）又は（Ｉ）と（ＩＩＩ）を組み合わせて用いることを必須とするが、（Ｉ）〜（ＩＩＩ）全てを含んでも構わない。 (B) Compound having an ethylenically unsaturated bond (B) A compound having an ethylenically unsaturated bond is a compound having polymerizability by having an ethylenically unsaturated group in its structure. In the present embodiment, the photosensitive resin composition has the following general formulas (I) to (III) as (B) compounds having an ethylenically unsaturated bond:

{In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or a methyl group; R ₅ is each independently an alkylene group having 3 or 4 carbon atoms; ₁ , n ₂ , n ₃ , n ₄ , m ₁ , m ₂ , m ₃ and m ₄ are each independently 0 or a positive integer, and n ₁ + n ₂ + n ₃ + n ₄ + m ₁ + m ₂ + m ₃ + m ₄ is an integer of 8 to 20, preferably an integer of 12 to 20 from the viewpoint of adhesion, and n ₁ + n ₂ + n ₃ + n ₄ is an integer of 8 to 20, preferably 12 to 20 M ₁ + m ₂ + m ₃ + m ₄ is an integer of 0 to 12, and the sequence of the repeating units of — (C ₂ H ₄ —O) — and — (R ₅ O) — was random. and it may be alternatively be also block, and _{- (C 2} H 4 -O) And - (R 5 _O) - sequence of any may be a quaternary carbon side. }

{Wherein, X _{1 to} X ₈ are each independently a hydrogen atom or a halogen atom, preferably X _{1 to} X ₈ are all hydrogen atoms, and R ₆ and R ₇ are each independently a hydrogen atom. Or a methyl group, R ₈ and R ₉ each independently represents an alkylene group having 2 to 6 carbon atoms, n ₅ and n ₆ are each independently 0 or a positive integer, and n ₅ + N ₆ is 2-6. }

{In the formula, R ₁₀ represents a hydrogen atom or a (meth) acryloyl group, and contains at least 4 (meth) acryloyl groups in one molecule. }
It is essential to use a combination of (I) and (II) or (I) and (III) among the compounds represented by formula (I), but all of (I) to (III) may be included.

In addition to the compound of (I), the present inventors further added a compound of (II) and / or a compound of (III) to the photosensitive resin composition, whereby resolution and adhesion are improved. The inventors have found that a photosensitive resin composition having an excellent balance of resist shape, minimum development time and bleed-out property can be obtained. Although not bound by theory, the molecular weight of the compound (I) is large, so that the bleed-out property is good, and n ₁ + n ₂ + n ₃ + n ₄ + m ₁ + m ₂ + m ₃ + m ₄ becomes 8 to 20 It is expected that the hydrophilicity will increase and the minimum development time will tend to be shorter. On the other hand, the compound of (II) has an aromatic ring, and n ₅ + n ₆ is as small as 2 to 6 and thus is considered to be highly hydrophobic, suppressing the expansion of the resist in the development step, and the resolution, It works advantageously in obtaining a pattern with good adhesion and resist shape. Therefore, when a combination of the compounds of (I) and (II) is used, a photosensitive resin composition having an excellent balance of resolution, adhesion, resist shape, minimum development time and bleed-out property can be obtained. Conceivable. In addition, the compound (III) has a large number of (meth) acryloyl groups relative to the molecular weight, and is considered to promote curing upon exposure. It is presumed that this is advantageous in obtaining a pattern with good resolution, adhesion and resist shape, and that better performance can be expressed by combining with the compound (I).

Specific examples of the compound represented by the general formula (I) include, for example, R ₁ , R ₂ , R ₃ and R ₄ are H, and n ₁ , n ₂ , n ₃ and n ₄ are positive integers. N ₁ + n ₂ + n ₃ + n ₄ is 15, and m ₁ + m ₂ + m ₃ + m ₄ is 0, and a commercially available compound (MCD-15E manufactured by Sartomer Japan Co., Ltd.) is mentioned. The compound represented by the above general formula (I) can also be obtained by an appropriate synthesis method. For example, a compound in which R ₁ , R ₂ , R ₃ and R ₄ are H, n ₁ + n ₂ + n ₃ + n ₄ is 18, and m ₁ + m ₂ + m ₃ + m ₄ is 8 is used as the pentaerythritol raw material. The product obtained by reacting 18 mol of ethylene oxide with 8 mol of propylene oxide can be obtained by esterification with acrylic acid in the presence of a suitable acid catalyst. These may be used alone or in combination of two or more.

Further, among the above general formula (I), m ₁ + m ₂ + m ₃ + m ₄ is 0, and n ₁ + n ₂ + n ₃ + n ₄ is 8 or more from the viewpoint of adhesion and 20 or less from the viewpoint of resolution. Those are preferred. Furthermore, in this embodiment, the present inventors converted a compound of the general formula (II) wherein m ₁ + m ₂ + m ₃ + m ₄ is 0 and n ₁ + n ₂ + n ₃ + n ₄ is 12 to 20 And / or it discovered that a further favorable characteristic was given to the photosensitive resin composition by using in combination with the compound of general formula (III).

The arrangement of the repeating units of — (C ₂ H ₄ —O) — and — (R ₅ O) — in the general formula (I) may be random, block, or alternating. The order of — (C ₂ H ₄ —O) — and — (R ₅ O) — may be either on the quaternary carbon side. Here, the quaternary carbon side refers to the position bonded to the methylene group bonded to the quaternary carbon at the center of the pentaerythritol skeleton of the general formula (I).

Moreover, X < ₁ > -X < ₈ > in the said general formula (II) is a hydrogen atom or a halogen atom each independently, Preferably X < ₁ > -X < ₈ > is all hydrogen atoms. Examples of the halogen atom include bromine, chlorine, fluorine and the like, and X _{1 to} X ₈ may be different halogen atoms.

In the general formula (II), R ₈ and R ₉ preferably have 2 or more carbon atoms from the viewpoint of bleed-out property and cured film flexibility, and preferably 6 or less carbon atoms from the viewpoint of developability. More preferably, it is C2-C4. Further, n ₅ + n ₆ is preferably 2 or more from the viewpoint of developability and cured film flexibility, and preferably 6 or less from the viewpoint of resolution. More preferably, it is 2-4.

  Specific examples of the compound represented by the general formula (II) include, for example, a compound in which bisphenol A is modified with alkylene oxide and having (meth) acryloyl groups at both ends. There are oxide modification, butylene oxide modification, pentylene oxide modification, hexylene oxide modification and the like. Examples of the ethylene oxide-modified bisphenol A having (meth) acryloyl groups at both ends include, for example, polyethylene glycol dimethacrylate (SR-manufactured by Sartomer) in which 1 mol of ethylene oxide is added to both ends of bisphenol A on average. 348, Miwon M-249, Eternal EM-3260), diglycolate of polyethylene glycol with an average of 2 moles of ethylene oxide added to both ends of bisphenol A (manufactured by Shin-Nakamura Chemical Co., Ltd.) NK ester BPE-200) and bisphenol A, and polyethylene glycol dimethacrylate having 3 moles of ethylene oxide added on average. These may be used alone or in combination of two or more. Among them, diglycolate of polyethylene glycol in which 1 mol of ethylene oxide is added to both ends of bisphenol A on average is preferable from the viewpoint of resolution.

  In the general formula (III), the number of (meth) acryloyl groups in one molecule is preferably 4 or more from the viewpoint of obtaining sufficient cured film strength, resist shape, and resolution. Specific examples of the general formula (III) include, for example, dipentaerythritol hexaacrylate (A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol methacrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol. Examples include tetra (meth) acrylate. These may be used alone or in combination of two or more. Dipentaerythritol hexaacrylate is preferred from the viewpoint of cured film strength, resolution, and resist shape.

｛式中、Ｙ_１〜Ｙ_８は、それぞれ独立に水素原子又はハロゲン原子であり、好ましくはＹ_１〜Ｙ_８が全て水素原子であり、Ｒ_１１及びＲ_１２は、それぞれ独立に水素原子又はメチル基を表し、Ｒ_１３及びＲ_１４は、それぞれ独立に炭素数２〜６のアルキレン基を表し、ｎ_７及びｎ_８は、それぞれ独立に、０又は正の整数であり、そしてｎ_７＋ｎ_８は、７〜４０である。｝
で表される化合物を含むことが密着性及びブリードアウト性の観点から好ましい。上記一般式（ＩＶ）において、ｎ_７＋ｎ_８は、ブリードアウト性及び密着性の観点から７以上、解像性の観点から４０以下が好ましい。Ｙ_１〜Ｙ_８については、上記一般式（ＩＩ）のＸ_１〜Ｘ_８について記載したのと同様にして選択される。 In this embodiment, the following general formula (IV):

{Wherein Y _{1 to} Y ₈ are each independently a hydrogen atom or a halogen atom, preferably Y ₁ to Y ₈ are all hydrogen atoms, and R ₁₁ and R ₁₂ are each independently a hydrogen atom or a methyl atom. R ₁₃ and R ₁₄ each independently represents an alkylene group having 2 to 6 carbon atoms, n ₇ and n ₈ are each independently 0 or a positive integer, and n ₇ + n ₈ is 7-40. }
It is preferable from a viewpoint of adhesiveness and bleed-out property to contain the compound represented by these. In the general formula (IV), n ₇ + n ₈ is preferably 7 or more from the viewpoint of bleed-out property and adhesion, and 40 or less from the viewpoint of resolution. Y _{1 to} Y ₈ are selected in the same manner as described for X _{1 to} X _{8 in} the general formula (II).

  Specific examples of the general formula (IV) include, for example, a compound in which bisphenol A is modified with alkylene oxide and has (meth) acryloyl groups at both ends. The alkylene oxide modification includes ethylene oxide modification, propylene oxide modification, butylene oxide. Modification, pentylene oxide modification, hexylene oxide modification and the like. Examples of the modified ethylene oxide include 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentaethoxy) phenyl) propane ( NK ester BPE-500) manufactured by Shin-Nakamura Chemical Co., Ltd., 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) Heptaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyun) Caethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane such as-((meth) acryloxyhexadecaethoxy) phenyl) propane and the like. These may be used alone or in combination of two or more. 2,2-bis (4-((meth) acryloxypentaethoxy) phenyl) propane is preferred from the viewpoint of excellent balance between bleed-out property, resolution and adhesion.

  In the present embodiment, the photosensitive resin composition includes (B) the compound having an ethylenically unsaturated bond, not only the compounds represented by the general formulas (I) to (IV), but also other compounds. May include. Examples of other compounds include polyalkylene glycol di (meth) acrylate, a photopolymerizable compound having one ethylenically unsaturated bond, a (meth) acrylate compound having a urethane bond, and α, β-unsaturated polyhydric alcohol. Examples include compounds other than the above general formula (III) obtained by reacting a saturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, phthalic acid compounds, and the like. These may be used alone or in combination of two or more.

  As polyalkylene glycol di (meth) acrylate, for example, nonaethylene glycol diacrylate, polyalkylene glycol having an average of 12 moles of propylene oxide added and an ethylene oxide added to both ends at an average of 3 moles at both ends, respectively. For example, dimethacrylate. From the viewpoints of adhesion and resolution, polyalkylene glycol dimethacrylate having an average of 3 moles of ethylene oxide added to both ends of polypropylene glycol with an average of 12 moles of propylene oxide added is (B). It is preferably contained in a compound having an ethylenically unsaturated bond. These may be used alone or in combination of two or more.

  Examples of the photopolymerizable compound having one ethylenically unsaturated bond include nonylphenoxypolyethyleneoxy (meth) acrylate, nonylphenoxypolypropyleneoxy (meth) acrylate, butylphenoxypolyethyleneoxy (meth) acrylate, butylphenoxypolypropyleneoxy ( And (meth) acrylate. These may be used alone or in combination of two or more.

  Examples of the (meth) acrylate compound having a urethane bond include hexamethylene diisocyanate, tolylene diisocyanate, or a diisocyanate compound (for example, 2,2,4-trimethylhexamethylene diisocyanate), a hydroxyl group in one molecule (meta ) Urethane compounds with compounds having an acrylic group (for example, 2-hydroxypropyl acrylate, oligopropylene glycol monomethacrylate). Specifically, it is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (manufactured by NOF Corporation, Blemmer PP1000). These may be used alone or in combination of two or more.

  Examples of compounds other than the general formula (III) obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Examples include EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, and PO-modified trimethylolpropane tri (meth) acrylate. These may be used alone or in combination of two or more.

  Examples of the compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4- (meth) acryloxy- 2-hydroxy-propyloxy) phenyl and the like.

  Examples of the phthalic acid compounds include γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloloxyalkyl-o—. A phthalate etc. are mentioned. These can be used alone or in combination of two or more.

  In addition, (B) tricyclodecane di (meth) acrylate, (2,2-bis {4- (methacryloxypentaethoxy) cyclohexyl} propane, or the like may be included as a compound having an ethylenically unsaturated bond.

  In this embodiment, content of the compound which has (B) ethylenically unsaturated bond in the photosensitive resin composition becomes like this. Preferably it is the range of 5 mass%-70 mass%, More preferably, it is 20 mass%-60 It is the range of mass%, More preferably, it is the range of 30 mass%-60 mass%. (B) The content of the compound having an ethylenically unsaturated bond is preferably 5% by mass or more from the viewpoint of suppressing the curing failure of the photosensitive resin layer and the delay of the development time. It is preferable that it is 70 mass% or less from a viewpoint of suppressing the peeling delay of a flow and hardened resist.

(C) Photopolymerization initiator (C) The photopolymerization initiator is a compound that polymerizes a monomer by light. The photosensitive resin composition contains what is generally known in this technical field as (C) photoinitiator. Content of the (C) photoinitiator with respect to the total solid of the photosensitive resin composition is the range of 0.01-20 mass%, and a more preferable range is 0.5-10 mass%. The amount is 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and is 20% by mass or less from the viewpoint of sufficiently transmitting light to the bottom surface of the resist and obtaining good high resolution.

  Such (c) photopolymerization initiators include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoates, Oxime esters, acridines (eg, 9-phenylacridine, bisacridinylheptane), hexaarylbiimidazole, pyrazoline derivatives, N-arylamino acids or ester compounds thereof (eg, N-phenylglycine), and halogens Compound etc. are mentioned. These can be used alone or in combination of two or more.

  Examples of aromatic ketones include benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone. Can do. 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. Furthermore, from the viewpoint of transmittance, the blending amount of aromatic ketones is preferably 0.01 to 0.5% by mass based on 100% by mass of the solid content of the photosensitive resin composition.

  Examples of hexaarylbiimidazole include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris- (o-chlorophenyl) ) -Diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 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′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2 , 6-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,4-trifluorophenyl) -4, 4 ', 5,5'-tetrakis- (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′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis -(2,4,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4,6-tri Fluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4', 5,5'- Tetrakis- (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 singly 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. Furthermore, from the viewpoint of sensitivity, the blending amount of hexaarylbiimidazole is preferably 0.5 to 5.0% by mass based on 100% by mass of the solid content of the photosensitive resin composition.

(D) Other component In this embodiment, it is preferable that the photosensitive resin composition contains additives, such as a dye, a plasticizer, antioxidant, a stabilizer, if desired.

  Examples of the dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green], fuchsin, phthalocyanine green, auramine base, paramadienta, crystal violet, Methyl orange, Nile blue 2B, Victoria blue, Malachite green (Hodogaya Chemical Co., Ltd., Eisen (registered trademark) MALACHITE GREEN), Basic Blue 20, Diamond Green (Hodogaya Chemical Co., Ltd., Eisen (registered trademark) DIAMOND GREEN GH) Etc. Among these, diamond green and leuco crystal violet are preferable from the viewpoint of improving colorability, hue stability and exposure contrast. These can be used alone or in combination of two or more.

  In the present embodiment, the content of the dye in the photosensitive resin composition is preferably in the range of 0.001% by mass to 3% by mass, more preferably in the range of 0.01% by mass to 2% by mass. More preferably, it is the range of 0.04 mass%-1 mass%. The content of the dye is preferably 0.001% by mass or more from the viewpoint of obtaining good colorability, while being 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. preferable.

  Examples of the plasticizer include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene monomethyl ether, Glycol esters such as oxypropylene monoethyl ether and polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, citric acid Triethyl acid, triethyl acetyl citrate, tri-n-propyl acetyl citrate, and tri-n-butyl acetyl citrate Propylene glycol respectively by adding propylene oxide to both sides of the bisphenol A, and ethylene glycol, respectively adding ethylene oxide to both sides of the bisphenol A and the like. These can be used alone or in combination of two or more.

  In this embodiment, content of the plasticizer in the photosensitive resin composition becomes like this. Preferably it is 0.1 mass%-50 mass%, More preferably, it is 1 mass%-20 mass%. The content of the plasticizer is preferably 0.1% by mass or more from the viewpoint of suppressing the delay in the development time of the photosensitive resin layer and imparting flexibility to the cured film, while the cured film is insufficiently cured. And it is preferable that it is 50 mass% or less from a viewpoint of suppressing a cold flow.

  Examples of the antioxidant include triphenyl phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., trade name: TPP), tris (2,4-di-tert-butylphenyl) phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd.). , Product name 2112), tris (monononylphenyl) phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., product name: 1178), bis (monononylphenyl) -dinonylphenyl phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., product) Name: 329K). These can be used alone or in combination of two or more.

  In this embodiment, content of antioxidant in the photosensitive resin composition becomes like this. Preferably it is the range of 0.01 mass%-0.8 mass%, More preferably, it is 0.01 mass%-0.00. The range is 3% by mass. The content of the antioxidant is preferably 0.01% by mass or more from the viewpoint of favorably developing the hue stability of the resist pattern and improving the sensitivity of the photosensitive resin layer. From the viewpoints of exhibiting good hue stability and improving adhesion while suppressing the color developability, it is preferably 0.8% by mass or less.

  The stabilizer is preferably used from the viewpoint of improving the thermal stability and / or storage stability of the photosensitive resin composition. Examples of the stabilizer include at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, and alkylene oxide compounds having a glycidyl group. These can be used alone or in combination of two or more.

  Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis. (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4) -Hydroxyphenyl) propionate], nitrosophenylhydroxyamine aluminum salt (for example, aluminum salt added with 3 mol of nitrosophenylhydroxylamine), diphenylnitrosamine and the like. Among these, an aluminum salt added with 3 moles of triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] or nitrosophenylhydroxylamine is preferable. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

  Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole, 1- (2-di-n- And a 1: 1 mixture of butylaminomethyl) -5-carboxylbenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxylbenzotriazole. Among these, a 1: 1 mixture of 1- (2-di-n-butylaminomethyl) -5-carboxylbenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxylbenzotriazole is preferable. . Moreover, these can be used individually by 1 type or in combination of 2 or more types.

  Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole. These can be used alone or in combination of two or more.

  Examples of the alkylene oxide compound having a glycidyl group include neopentyl glycol diglycidyl ether (for example, Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (for example, Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), Bisphenol A-propylene oxide 2 mol adduct diglycidyl ether (for example, Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl ether (for example, Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.), etc. . These can be used alone or in combination of two or more.

  In this embodiment, the total content of the radical polymerization inhibitor, benzotriazoles, carboxybenzotriazoles, and alkylene oxide compounds having a glycidyl group in the photosensitive resin composition is preferably 0.001% by mass to 3%. It is the range of mass%, More preferably, it is the range of 0.05-1 mass%. This total content is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, while, on the other hand, from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. It is preferable that it is 3 mass% or less.

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

<Photosensitive resin laminate>
In this embodiment, the photosensitive resin laminated body which has a support body and the photosensitive resin layer which consists of the said photosensitive resin composition laminated | stacked on this support body can be provided. If desired, the photosensitive resin laminate may have a protective layer on the side opposite to the support side of the photosensitive resin layer.

  The support is preferably a transparent one that transmits light emitted from the exposure light source. Examples of such a support include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film. , A polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, those stretched as necessary can be used. The haze is preferably 0.01% to 5.0%, more preferably 0.01% to 2.5%, and still more preferably 0.01% to 1.0%. The thinner the film, the more advantageous in terms of image forming property and economic efficiency, but a film having a thickness of 10 to 30 μm is preferably used because the strength needs to be maintained.

  In addition, an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is smaller than the support in terms of adhesion to the photosensitive resin layer and can be easily peeled off. As a protective layer, a polyethylene film, a polypropylene film, etc. are preferable, for example. Further, for example, a film having excellent peelability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.

  In this embodiment, the thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 5 μm to 100 μm, and more preferably 7 μm to 60 μm. The smaller the thickness of the photosensitive resin layer is, the more the resolution of the resist pattern is improved. On the other hand, the larger the thickness is, the more the strength of the cured film is improved.

  A conventionally known method can be employed as a method for producing a photosensitive resin laminate by sequentially laminating a support, a photosensitive resin layer, and if necessary, a protective layer.

  For example, the photosensitive resin composition preparation liquid is prepared, then coated on a support using a bar coater or roll coater and dried, and the photosensitive resin composition containing the photosensitive resin composition preparation liquid is formed on the support. A resin layer is laminated. Furthermore, if desired, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

<Resist pattern formation method>
The present invention includes a lamination step of laminating the photosensitive resin layer on a support, an exposure step of exposing the photosensitive resin layer, and a development step of developing the exposed photosensitive resin layer (preferably in order). A resist pattern forming method is also provided. An example of a specific method for forming a resist pattern in the present embodiment is shown below.

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

  Next, in the exposure step, the photosensitive resin assembly layer is exposed to active light using an exposure machine. The exposure can be performed after peeling the support, if desired. In the case of exposing through a photomask, the exposure amount is determined by the light source illuminance and the exposure time, and may be measured using a light meter. In the exposure process, a maskless exposure method may be used. In maskless exposure, exposure is performed directly on the substrate by a drawing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350 nm to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.

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

  Although a resist pattern is obtained by the above steps, in some cases, a heating step of 100 ° C. to 300 ° C. can be further performed. By performing this heating step, the chemical resistance of the resist pattern can be improved. A heating furnace of a hot air, infrared ray, far infrared ray, or the like can be used for the heating step.

<Conductor pattern manufacturing method>
The present invention includes a laminating step of laminating the photosensitive resin layer on a substrate such as a metal plate or a metal film insulating plate, an exposure step of exposing the photosensitive resin layer, an unexposed portion of the exposed photosensitive resin layer, or Conductor pattern including (preferably in sequence) a development step of obtaining a substrate on which a resist pattern is formed by removing the exposed portion with a developer, and a conductor pattern formation step of etching or plating the substrate on which the resist pattern is formed A manufacturing method is also provided. In this embodiment, the conductor pattern manufacturing method is performed by using a metal plate or a metal film insulating plate as a substrate, forming a resist pattern by the above-described resist pattern forming method, and then performing 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 using a known etching method or plating method.

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

<Manufacturing method of wiring board>
After producing a conductor pattern according to the present invention, a wiring board having a desired wiring pattern (for example, a printed wiring board) is obtained by further performing a peeling step of peeling the resist pattern from the substrate with an aqueous solution having alkalinity stronger than the developer. ) Can be obtained. In the production of the wiring board, a copper-clad laminate or a flexible board is preferably used as the board. The alkaline aqueous solution for stripping (hereinafter also referred to as “stripping solution”) is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of 2% by mass to 5% by mass is generally used. . A small amount of a water-soluble solvent can be added to the stripping solution. Examples of the water-soluble solvent include alcohol. The temperature of the stripping solution in the stripping step is preferably in the range of 40 ° C to 70 ° C.

<Manufacture of lead frames>
A lead frame can be manufactured by forming a resist pattern by the above-mentioned 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. Then, a desired lead frame can be obtained by performing a peeling process in which the resist pattern is peeled by the same method as the method for manufacturing the wiring board.

<Manufacture of a substrate having an uneven pattern>
The resist pattern formed by the resist pattern forming method can be used as a protective mask member when processing a substrate by a sandblasting method. Examples of the substrate at this time include glass, a silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and a metal material. A resist pattern is formed on these substrates by the same method as the above resist pattern forming method. Thereafter, the substrate is subjected to a sandblasting process in which a blast material is sprayed from the formed resist pattern and cut to a desired depth, and a resist pattern portion remaining on the substrate is removed from the substrate with an alkali stripping solution or the like. The base material which has a fine uneven | corrugated pattern on it can be manufactured. As a blasting material used in the above-mentioned sandblasting process, known materials can be used. For example, fine particles having a particle size of about 2 μm to 100 μm, such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, stainless steel, etc. Is commonly used.

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

  In this embodiment, the photosensitive resin composition is used for the manufacture of printed wiring boards, the manufacture of lead frames for mounting IC chips, the manufacture of metal foils such as the manufacture of metal masks, ball grid arrays (BGA), or chip sizes, Manufacture of packages such as packages (CSP), manufacture of tape substrates such as chip-on-film (COF) or tape automated bonding (TAB), manufacture of semiconductor bumps, flat panels such as ITO electrodes or address electrodes, electromagnetic wave shields, etc. It can be used for manufacturing a partition of a display.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto. (Examples 1-9 and Comparative Examples 1-4)
First, a method for producing samples for evaluation of Examples and Comparative Examples will be described, and then an evaluation method and evaluation results for the obtained samples will be shown.

1. Preparation of Evaluation Samples Evaluation samples in Examples and Comparative Examples were prepared as follows.
<Preparation of photosensitive resin laminate>
A photosensitive resin composition mixed solution obtained by sufficiently stirring and mixing a photosensitive resin composition and a solvent having a composition shown in the following Table 1 (however, each component number indicates a blending amount (part by mass) as a solid content). The photosensitive resin composition was uniformly applied using a blade coater on the surface of a 16 μm-thick polyethylene terephthalate film (Toray Industries, Inc., FB40), which was a support film, and was placed in a dryer at 95 ° C. for 5 minutes. It dried and formed the uniform photosensitive resin layer on the support film. The thickness of the photosensitive resin layer was 25 μm. Then, a 19 μm-thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-818) was bonded as a protective film on the surface of the photosensitive resin layer to obtain a photosensitive resin laminate. Table 2 shows the names of the material components in the prepared photosensitive resin composition preparation.

<Board surface preparation>
The substrate for evaluation of resolution, adhesion, and resist shape is a 0.4 mm thick copper clad laminate on which 35 μm rolled copper foil is laminated with a spray pressure of 0.2 MPa as a grinding material (Nippon Carlit Co., Ltd., Sac Random R (registered trademark # 220)) was used for scrubbing with jet scrub.
<Laminate>
While peeling off the polyethylene film of the photosensitive resin laminate, the photosensitive resin laminate was applied to a copper-clad laminate that had been leveled and preheated to 60 ° C. with a hot roll laminator (Asahi Kasei Co., Ltd., AL-700). A test piece was obtained by laminating at a roll temperature of 105 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.
<Exposure>
It exposed with the exposure amount of 100 mJ / cm <2> with the parallel light exposure machine (Corporation | KK Oak Manufacturing Co., Ltd. product, HMW-801) using the chromium glass mask.
<Development>
After the polyethylene terephthalate film is peeled off, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed for a predetermined time using 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 developed to dissolve and remove the unexposed portions of the photosensitive resin layer. At this time, the minimum time required for completely dissolving the photosensitive resin layer in the unexposed portion 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 process was performed at the same time as the developing process at a washing spray pressure of 0.15 MPa with a flat type nozzle.

2. Evaluation method <Minimum development time>
At the time of development, the minimum development time was defined as the minimum time required for the photosensitive resin layer in the unexposed portion to be completely dissolved. The minimum development time was ranked as follows.
○: 23 seconds or less ×: More than 23 seconds.
<Resolution>
The evaluation board | substrate which passed 15 minutes after lamination was exposed through the chromium glass mask which has a line pattern of the ratio of 1: 1 of the width | variety of an exposed part and an unexposed part. Thereafter, development was performed in a time twice as long as the minimum development time, and the minimum mask width in which the cured resist line was normally formed was defined as a resolution value, and the resolution was ranked as follows. In addition, the minimum mask width | variety formed normally without the fall of a cured resist pattern or adhesion | attachment of cured resists was evaluated.
A: Resolution value is 10 μm or less;
○: The resolution value exceeds 10 μm and is 12 μm or less;
X: The value of resolution exceeds 12 μm.
<Adhesion>
The evaluation board | substrate which passed 15 minutes after lamination was exposed through the chromium glass mask which has the line pattern of the ratio of 1: 100 of the width | variety of an exposed part and an unexposed part. Thereafter, development was carried out in a time twice as long as the minimum development time, and the minimum mask width in which the cured resist line was normally formed was defined as the adhesion value, and was ranked as follows.
A: Adhesion value is 10 μm or less;
○: Adhesion value exceeds 10 μm and 12 μm or less;
X: Adhesion value exceeds 12 μm.
<Resist shape>
The evaluation substrate 15 minutes after the lamination was exposed through a chromium glass mask having a line pattern with a width ratio of 1: 1 between the exposed portion and the unexposed portion, and developed in a time twice as long as the minimum development time. Susees generated at the foot of the obtained 15 μm resist line were observed, and the resist shapes were ranked as follows. In addition, FIG. 1 is a schematic explanatory diagram of a sword (cured resist foot portion) at a boundary portion between the cured resist and the substrate. The length of the sword was measured as the distance along the substrate surface from the side wall surface of the cured resist pattern to the sword edge.
◎: No stake ○: Suseo <2 μm ×: Suseo 2 μm or more <Bleedout property>
The photosensitive resin laminate wound up in a roll is stored at 23 ° C under light-shielding conditions, and the time until stickiness occurs on the surface of the support film (excluding the outermost layer of the roll) due to bleed out is ranked as follows: The bleed-out property was evaluated.
A: Time until stickiness occurs on the surface of the support film is 3 months or more. O: Time until stickiness occurs on the surface of the support film is 1 month or more and less than 3 months. X: Time until stickiness occurs on the surface of the support film. Is less than one month Evaluation results The evaluation results of Examples 1 to 9 and Comparative Examples 1 to 4 are shown in Table 1.

From the results shown in Table 1, it can be seen that Examples 1 to 9 are excellent in resolution, adhesion, resist shape, minimum development time, and bleed-out property by adopting the configuration of the present invention. Comparative Examples 1 to 3 do not include the compounds (B-1 and B-2) of the above general formula (I) as B) compounds having an ethylenically unsaturated bond, and Comparative Example 4 is B) ethylenic. Since the compound (B-3) of the above general formula (II) and the compound (B-4) of (III) are not included as the compound having an unsaturated bond, the resolution, adhesion, resist shape, and minimum development Time and bleed out characteristics do not satisfy all characteristics. From the comparison between Examples 1 and 6 and Examples 7, 8 and 9, n ₁ + n ₂ + n ₃ + n ₄ + m ₁ + m ₂ + m ₃ + m ₄ in the above general formula (I) is an integer of 12 to 20 N ₁ + n ₂ + n ₃ + n ₄ is an integer of 12 to 20, and m ₁ + m ₂ + m ₃ + m ₄ is solved by using the compound (B-2) which is an integer of 0 to 12. It can be seen that imageability and adhesion are improved. From the comparison between Example 5 and Examples 6 to 8, the resolution, adhesion and resist are obtained by using (A) alkali-soluble polymers (A-1 and A-2) having an aromatic group in the side chain. It can be seen that the shape is excellent. From the comparison between Examples 2 and 3 and Examples 4, 7, and 8, the resolution was obtained by including the compound (B-5) of the general formula (IV) as the compound (B) having an ethylenically unsaturated bond. It can be seen that it is excellent in the balance of property, adhesion, resist shape, and bleed-out property.

  The photosensitive resin composition described above is used for the manufacture of printed wiring boards, the manufacture of lead frames for mounting IC chips, the precision processing of metal foils such as the manufacture of metal masks, the manufacture of packages such as BGA or CSP, and the tapes such as COF or TAB. It can be used for the production of substrates, the production of semiconductor bumps, the production of partition walls for flat panel displays such as ITO electrodes or address electrodes, and electromagnetic wave shields.

1 Cured resist pattern 2 Substrate 3 Suso

Claims (7)

Based on the total solid content of the photosensitive resin composition, the following components:
(A) Alkali-soluble polymer: 10% by mass to 90% by mass,
(B) Compound having ethylenically unsaturated bond: 5% by mass to 70% by mass, and (C) Photopolymerization initiator: 0.01% by mass to 20% by mass,
And (B) the compound having an ethylenically unsaturated bond, the following general formulas (I) to (III):

{In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or a methyl group; R ₅ is each independently an alkylene group having 3 or 4 carbon atoms; ₁ , n ₂ , n ₃ , n ₄ , m ₁ , m ₂ , m ₃ and m ₄ are each independently 0 or a positive integer, and n ₁ + n ₂ + n ₃ + n ₄ + m ₁ + m ₂ + m ₃ + m ₄ is an integer of 8 to 20, n ₁ + n ₂ + n ₃ + n ₄ is an integer of 8 to 20, m ₁ + m ₂ + m ₃ + m ₄ is an integer of 0 to 12, and − (C The sequence of repeating units of ₂ H ₄ —O) — and — (R ₅ O) — may be random, block or alternating, and — (C ₂ H ₄ —O) —. and - (R 5 _O) - sequence of any may be a quaternary carbon side. }

{Wherein, X _{1 to} X ₈ are each independently a hydrogen atom or a halogen atom, R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group, and R ₈ and R ₉ are each independently Represents an alkylene group having 2 to 6 carbon atoms, n ₅ and n ₆ are each independently 0 or a positive integer, and n ₅ + n ₆ is 2 to 6. }

{In the formula, R ₁₀ represents a hydrogen atom or a (meth) acryloyl group, and contains at least 4 (meth) acryloyl groups in one molecule. }
Among a compound represented by, have use in combination (I) and (II) or (I) the (III), however, in the case of using a combination of (I) and the (II) (I) compound The photosensitive resin composition except for the case where is ethoxylated, proxiated pentaerythritol tetraacrylate (an average of 8 mol of ethylene oxide and an average of 8 mol of propylene oxide) . The following general formula (IV);

{Wherein Y _{1 to} Y ₈ are each independently a hydrogen atom or a halogen atom, R ₁₁ and R ₁₂ each independently represent a hydrogen atom or a methyl group, and R ₁₃ and R ₁₄ are each independently Represents an alkylene group having 2 to 6 carbon atoms, n ₇ and n ₈ are each independently 0 or a positive integer, and n ₇ + n ₈ is 7 to 40. }
The photosensitive resin composition of Claim 1 containing the compound represented by these.   The (A) alkali-soluble polymer has an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000, and has an aromatic group in its side chain. Photosensitive resin composition. In the said general formula (I), n < ₁ > + n < ₂ > + n < ₃ > + n < ₄ > + m < ₁ > + m < ₂ > + m < ₃ > + m < ₄ > is an integer of 12-20 as described in any one of Claims 1-3. Photosensitive resin composition. _Y 1 to Y ₈ of _X 1 to X ₈ and Formula of the general formula (II) (IV) are all a hydrogen atom, a photosensitive resin composition according to any one of claims 2 to 4 object. The following steps:
A laminating step of laminating a photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 1 to 5 on a support;
An exposure step of exposing the photosensitive resin layer; and a development step of developing the exposed photosensitive resin layer;
A resist pattern forming method including: The following steps:
A laminating step of laminating a photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 1 to 5 on a substrate;
An exposure step of exposing the photosensitive resin layer;
A development step of developing the exposed photosensitive resin layer to obtain a substrate on which a resist pattern is formed;
A method of manufacturing a wiring board, comprising: a conductor pattern forming step of etching or plating a substrate on which the resist pattern is formed; and a peeling step of peeling the resist pattern.

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