KR20110095404A - Photosensitive resin composition, and photosensitive element, resist pattern formation method and printed circuit board production method each utilizing same - Google Patents

Abstract

This invention is the photosensitive resin composition containing (A) binder polymer, (B) photopolymerizable compound, and (C) photoinitiator, (A) binder polymer is a structural unit based on (meth) acrylic acid, (meth) The photosensitive resin composition which has a structural unit based on the acrylic acid benzyl ester or the (meth) acrylic acid benzyl ester derivative, and the (B) photopolymerizable compound contains the compound represented by following General formula (1). In formula (1), R <^1> , R <^2> and R <^3> represent a hydrogen atom or a methyl group each independently, a, b and c respectively independently represent the integer of 1-48, and the total of a, b, and c is The number is 6-50.
However,

Description

PHOTOSENSITIVE RESIN COMPOSITION, AND PHOTOSENSITIVE ELEMENT, RESIST PATTERN FORMATION METHOD AND PRINTED CIRCUIT BOARD PRODUCTION METHOD EACH UTILIZING SAME}

This invention relates to the photosensitive resin composition, the photosensitive element using this, the formation method of a resist pattern, and the manufacturing method of a printed wiring board.

In the manufacturing field of a printed wiring board, as a resist material used for etching, plating, etc., the photosensitive resin composition and the photosensitive element (laminated body) are used widely.

A printed wiring board is manufactured as follows, for example. First, the photosensitive resin composition layer of the photosensitive element is laminated (laminated) on the circuit forming substrate. Next, actinic light is irradiated to the predetermined part of the photosensitive resin composition layer, the predetermined part is exposed, and it hardens. Then, after peeling off and removing a support film, the resist pattern which consists of hardened | cured material of the photosensitive resin composition on a board | substrate by removing (developing) parts (unexposed and uncured part) other than the predetermined part on a board | substrate. Is formed. An etching process or plating process is performed about the obtained resist pattern, and a circuit is formed on a board | substrate, and finally, a resist is peeled off and a printed wiring board is manufactured.

Here, an etching process is a method of peeling a resist after carrying out the etching removal of the conductor layer of the board | substrate for circuit formation which is not coat | covered with the resist pattern. On the other hand, the plating treatment is performed by plating the copper and solder on the conductor layer of the circuit forming substrate which is not covered with the resist pattern, and then removing the resist to soft-etch the metal surface coated with the resist. That's how.

As the method of exposure, the method of exposing through a photomask using a mercury lamp as a light source is used conventionally. Moreover, in recent years, the direct drawing exposure method which draws digital data of a pattern directly to the photosensitive resin composition layer called DLP (Digital_Light_Processing) or LDI (Laser_Direct_Imaging) is proposed (for example, Nonpatent literature 1). Reference). This direct drawing exposure method is introduced in the manufacture of a high-density package substrate because the alignment accuracy is better than the exposure method via a photomask and a high precision pattern is obtained.

However, in the above-described direct drawing exposure method, the use of monochromatic light such as a laser as a light source or the irradiation of light while scanning a substrate tends to require an exposure time as compared with the conventional exposure method. Therefore, in order to shorten an exposure time and to improve productive efficiency, it is necessary to improve the sensitivity of the photosensitive resin composition.

 On the other hand, with the recent increase in the density of printed wiring boards, the demand for photosensitive resin compositions for forming a resist pattern with higher resolution (removal accuracy of unexposed portions) and adhesion to substrates (development resistance of exposed portions) also increases. have. In particular, in package substrate preparation, a photosensitive resin composition capable of forming a resist pattern having a line width / space width (L / S) of 10/10 (unit: μm) or less is required.

In addition, in the high-density package substrate, since the width between circuits is narrow, it is also important that the resist shape (cross-sectional shape of the resist pattern) is excellent. If the cross-sectional shape of the resist is ladder type or inverted leg shape, or if the end edge of the resist is pulled out, the short circuit or disconnection may occur in the circuit formed by the subsequent etching process or plating process, which is not preferable. It is preferable that there is no end pull in the mold.

Moreover, what is excellent in the peeling characteristic (easiness at the time of peeling and removing hardened | cured material from a board | substrate) after hardening is calculated | required by the photosensitive resin composition. That is, the peeling time of a resist is shortened and the production efficiency of a peeling process improves. Moreover, by reducing the peeling piece size of a resist, reattachment of the peeling piece on a circuit board is prevented, and a production yield improves.

Here, Patent Literature 1 discloses a photosensitive resin composition using a specific binder polymer, a sensitizing dye, or the like as a photosensitive resin composition having good sensitivity that can also correspond to a direct drawing exposure method.

Patent document 2 discloses the photosensitive resin composition which introduce | transduced the polyfunctional acrylate compound and made many crosslinking points, in order to improve adhesiveness (development resistance) to a board | substrate.

Patent Literature 3 discloses a photosensitive resin composition using a polymerization inhibitor such as catechol and hydroquinone in order to improve contrast between the exposed portion and the unexposed portion.

Prior art literature

Patent Literature

Patent Document 1: Japanese Patent Publication No. 2005-122123

Patent Document 2: Japanese Patent Publication No. 2003-215799

Patent Document 3: Japanese Patent Publication No. 2000-162767

Non Patent Literature

Non Patent Literature 1: Electronics Packaging Technology, June 2002, pp. 74-79

The photosensitive resin composition is calculated | required to improve each characteristic like the sensitivity, resolution, adhesiveness, resist shape, and the peeling characteristic after hardening well.

However, although the photosensitive resin composition of patent document 1 is favorable in the point of a sensitivity and peeling characteristic, it is not necessarily enough from a point of resolution and adhesiveness.

While the photosensitive resin composition of patent document 2 has favorable adhesiveness, it is not enough from the point of peeling characteristic, and there exists a tendency for hardened | cured material to peel off from a board | substrate.

Although the photosensitive resin composition of patent document 3 is favorable in terms of resolution, adhesiveness, and imaging property, it is not enough in the point of a sensitivity, and requires a large exposure time when using the direct drawing exposure method.

As described above, the conventional photosensitive resin compositions did not sufficiently satisfactorily satisfy each characteristic required for the photosensitive resin composition for forming a resist pattern.

Therefore, an object of the present invention is to provide a photosensitive resin composition having good sensitivity, resolution, adhesion, resist shape, and peeling properties after curing, a photosensitive element, a method of forming a resist pattern, and a method of manufacturing a printed wiring board using the same. do.

In order to achieve the said objective, this invention is a photosensitive resin composition containing (A) binder polymer, (B) photopolymerizable compound, and (C) photoinitiator, (A) binder polymer is based on (meth) acrylic acid Photosensitive resin which has a structural unit and a structural unit based on (meth) acrylic-acid benzyl ester or (meth) acrylic-acid benzyl ester derivative, and (B) photopolymerizable compound contains the compound represented by following General formula (1) To provide a composition.

However,

In formula (1), R <^1> , R <^2> and R <^3> represent a hydrogen atom or a methyl group each independently, a, b and c respectively independently represent the integer of 1-48, and the total of a, b, and c is The number is 6-50.

That is, since the photosensitive resin composition of this invention has the said structure, all the sensitivity, resolution, adhesiveness, resist shape, and the peeling characteristic after hardening become favorable. MEANS TO SOLVE THE PROBLEM The present inventors can improve the resolution and the peeling characteristic after hardening by using the (A) binder polymer which has a specific structural unit, and (B) photopolymerizable compound containing the compound represented by the said general formula By using it, resolution, adhesiveness, and a resist shape can be improved, and it is speculated that the photosensitive resin composition which satisfy | fills all of the said characteristics was obtained by combining both. Moreover, it is thought that favorable sensitivity is obtained by combining (C) photoinitiator with these (A) binder polymer and (B) photopolymerizable compound.

In the photosensitive resin composition of this invention, the (B) photopolymerizable compound can further contain a bisphenol-A (meth) acrylate compound. Thereby, alkali developability, resolution, and the peeling characteristic after hardening of a photosensitive resin composition improve more.

In addition, the (B) photopolymerizable compound may further include a compound having one ethylenically unsaturated bond. Thereby, alkali developability, resist shape, and the peeling characteristic after hardening of the photosensitive resin composition improve further.

In addition, the (B) photopolymerizable compound may further include a polyalkylene glycol di (meth) acrylate compound having a (poly) oxyethylene chain and a (poly) oxypropylene chain. This improves the flexibility of the cured product (cured film) of the photosensitive resin composition.

In the photosensitive resin composition of this invention, (C) photoinitiator can contain 2,4,5-triaryl imidazole dimer. Thereby, the sensitivity and adhesiveness of the photosensitive resin composition further improve.

From the viewpoint of further improving the sensitivity of the photosensitive resin composition, the photosensitive resin composition of the present invention may further contain (D) a sensitizing dye.

In addition, from the viewpoint of further improving the sensitivity of the photosensitive resin composition, the photosensitive resin composition of the present invention may further contain an (E) amine compound.

In the photosensitive resin composition of this invention, the said (A) binder polymer may further have a structural unit based on styrene or a styrene derivative. Thereby, the resolution and adhesiveness of the photosensitive resin composition can be improved more.

Moreover, the (A) binder polymer may further have a structural unit based on the (meth) acrylic-acid alkylester. Thereby, alkali developability and peeling characteristic can be improved.

It is preferable that the weight average molecular weights of (A) binder polymer are 10000-100000. Thereby, alkali developability, development time, and developing solution resistance (adhesiveness) of the photosensitive resin composition can be improved more balanced.

Moreover, it is preferable that the acid value of (A) binder polymer is 100-250 mgKOH / g from a viewpoint of alkali developability and adhesiveness (development resistance).

This invention also provides the photosensitive element provided with the support film and the photosensitive resin composition layer which consists of the said photosensitive resin composition formed on the support film. By using the photosensitive element of this invention, the resist pattern which is excellent in all the resolution, adhesiveness, resist shape, and the peeling characteristic after hardening can be efficiently formed efficiently with good sensitivity.

The present invention also provides a lamination step of laminating a photosensitive resin composition layer made of the photosensitive resin composition on a substrate, an exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with the active light to expose the predetermined portion, and curing it; By removing the part other than the predetermined part of the photosensitive resin composition layer from a board | substrate, the formation method of the resist pattern which has a image development process of forming the resist pattern which consists of hardened | cured material of the photosensitive resin composition on a board | substrate is provided. Thereby, the resist pattern which is excellent in all the resolution, adhesiveness, resist shape, and the peeling characteristic after hardening can be efficiently formed efficiently with sensitivity.

It is preferable that the wavelength of the said actinic light is 390-420 nm. Thereby, the resist pattern with better resolution, adhesiveness, and resist shape can be efficiently formed more sensitively.

Moreover, this invention provides the manufacturing method of the printed wiring board containing the process of etching or plating the board | substrate with which the resist pattern was formed by the said resist pattern formation method. According to this manufacturing method, a printed wiring board having a high density package substrate and a densified wiring such as silicon chip rewiring can be manufactured with high accuracy and efficiency.

DETAILED DESCRIPTION OF THE INVENTION

EMBODIMENT OF THE INVENTION Hereinafter, the best form for implementing this invention is demonstrated in detail. However, this invention is not limited to the following embodiment. In addition, in this specification, (meth) acrylic acid means acrylic acid or methacrylic acid, (meth) acrylate means an acrylate or methacrylate, and a (meth) acryloyl group is an acryloyl group Or a methacryloyl group. In addition, a (poly) oxyethylene chain means an oxyethylene group or a polyoxyethylene chain, and a (poly) oxypropylene chain means an oxypropylene group or a polyoxypropylene chain.

<Photosensitive resin composition>

The photosensitive resin composition of this invention is (A) binder polymer (henceforth "(A) component"), (B) photopolymerizable compound (henceforth "(B) component"), and (C) photoinitiator (Hereinafter also referred to as "(C) component").

Hereinafter, each component which comprises the photosensitive resin composition of this invention is demonstrated in detail.

[(A) component: binder polymer]

The binder polymer which is (A) component has a structural unit based on (meth) acrylic acid, and a structural unit based on (meth) acrylic-acid benzyl ester or the (meth) acrylic-acid benzyl ester derivative. Such a binder polymer can be manufactured by radically polymerizing (meth) acrylic acid and (meth) acrylic acid benzyl ester or (meth) acrylic acid benzyl ester derivative, for example. Moreover, you may copolymerize another polymerizable monomer as needed.

As a (meth) acrylic-acid benzyl ester derivative, what has a substituent in the benzyl position and / or a phenyl group of (meth) acrylic-acid benzyl ester is mentioned, for example.

Content of the structural unit based on the (meth) acrylic-acid benzyl ester or the (meth) acrylic-acid benzyl ester derivative in (A) component is 5 with respect to 100 weight part of (A) component total weight from a viewpoint of resolution and the peelability after hardening. It is preferable that it is -65 weight part, It is more preferable that it is 10-55 weight part, It is still more preferable that it is 20-45 weight part. In order to improve the resolution further, 5 weight part or more is preferable, as for content of the said structural unit, 10 weight part or more is more preferable, and 20 weight part or more is more preferable. From a viewpoint of further improving peelability after hardening, 65 weight part or less is preferable, as for content of the said structural unit, 55 weight part or less is more preferable, and 45 weight part or less is still more preferable.

As other polymerizable monomers other than the (meth) acrylic acid, the (meth) acrylic-acid benzyl ester, or the (meth) acrylic-acid benzyl ester derivative, for example, in (alpha) position or aromatic rings, such as styrene, vinyltoluene, and (alpha) -methylstyrene, Substituted polymerizable styrene derivatives; acrylamides such as diacetone acrylamide; esters of vinyl alcohols such as vinyl-n-butyl ether; (meth) acrylic acid alkyl esters, (meth) acrylic acid cycloalkyl esters, and (meth) acrylic acids Furfuryl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid isobornyl ester, (meth) acrylic acid adamantyl ester, (meth) acrylic acid dicyclopentanyl ester, (meth) acrylic acid dimethylaminoethyl ester, (Meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoro (Meth) acrylic acid esters such as methyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate; α-bromo (meth) acrylic acid, α-cro (meth) acrylic acid, β (Meth) acrylic acid derivatives such as furyl (meth) acrylic acid and β-styryl (meth) acrylic acid; maleic acid derivatives such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate and monoisopropyl maleate Organic acid derivatives such as fumaric acid, cinnamic acid, α-cyano cinnamic acid, itaconic acid, crotonic acid, propiolic acid, and acrylonitrile. These can be used individually or in combination of 2 or more types arbitrarily.

The binder polymer (A) may further include a structural unit based on styrene or its derivative from the viewpoint of improving the resolution, adhesiveness and peeling properties in a balanced manner. (A) When binder polymer has a structural unit based on styrene or its derivatives, the content is 5-65 weight part with respect to 100 weight part of total weight of (A) component from a viewpoint of resolution, adhesiveness, and peeling characteristics. It is desirable to disclaim. Further, from the viewpoint of further improving resolution and adhesion, the content is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, still more preferably 15 parts by weight or more, particularly preferably 20 parts by weight or more. , 30 parts by weight or more is extremely preferable. Moreover, in the point which improves peelability more, 65 weight part or less is preferable, 60 weight part or less is more preferable, 55 weight part or more is more preferable, 50 weight part or less is especially preferable.

(A) It is preferable that a binder polymer further contains the structural unit based on the (meth) acrylic-acid alkylester from a viewpoint of improving alkali developability and peeling characteristics. (A) When a binder polymer contains the structural unit based on the (meth) acrylic-acid alkylester, from an alkali developability and a peeling characteristic, the content is with respect to 100 weight part of total weight of (A) component, It is preferable that it is 1-50 weight part, It is more preferable that it is 2-30 weight part, It is still more preferable that it is 3-20 weight part. Moreover, in the point which improves peelability more, 1 weight part or more is preferable, as for the said content, 2 weight part or more is more preferable, and 3 weight part or more is more preferable. Moreover, from the point which improves the resolution and adhesiveness after alkali image development, 50 weight part or less is preferable, 30 weight part or less is more preferable, 20 weight part or less is more preferable.

As (meth) acrylic-acid alkylester, the compound represented by following General formula (2) is mentioned. In formula (2), R <^4> represents a hydrogen atom or a methyl group, and R <^5> represents a C1-C12 alkyl group.

[Figure 2]

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁵ in General Formula (2) include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecylenate Real groups, dodecyl groups, and structural isomers thereof are mentioned. From the viewpoint of further improving the peeling characteristics, the alkyl group is preferably one having 4 or less carbon atoms.

As a compound represented by the said General formula (2), (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid pentyl ester, for example , (Meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid Undecyl ester and (meth) acrylic acid dodecyl ester are mentioned. These can be used individually or in combination of 2 or more types arbitrarily.

The weight average molecular weight (Mw) of the (A) binder polymer is preferably 10000 to 100,000 when measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene). Moreover, from the point which makes developing solution resistance (adhesiveness) of the hardened | cured material of the photosensitive resin composition favorable, 10000 or more are preferable, as for Mw of a binder polymer, 20000 or more are more preferable, and 25000 or more are more preferable. Moreover, since it is excellent in alkali developability, 100000 or less are preferable, as for Mw of a binder polymer, 80000 or less are more preferable, and 70000 or less are still more preferable.

It is preferable that the acid value of (A) binder polymer is 100-250 mgKOH / g. In addition, from the viewpoint of improving alkali developability, the acid value of the binder polymer is preferably 100 mgKOH / g or more, more preferably 120 mgKOH / g or more, still more preferably 140 gKOH / g or more, particularly preferably 150 mgKOH / g or more. . In addition, the acid value of the binder polymer is preferably 250 mgKOH / g or less, more preferably 230 mgKOH / g, still more preferably 220 mgKOH / g, and particularly preferably 210 mgKOH / g from the viewpoint of excellent developer resistance (adhesiveness). In addition, when performing solvent image development, it is preferable to prepare the polymeric monomer (monomer) which has carboxyl groups, such as (meth) acrylic acid, in small quantities.

It is preferable that it is 1.0-3.0, and, as for the dispersion degree (Mw / Mn) of (A) binder polymer, it is more preferable that it is 1.0-2.0. In the point which is excellent in adhesiveness and resolution, 3.0 or less are preferable and 2.0 or less are more preferable.

(A) The binder polymer may have the characteristic group which has photosensitivity with respect to the light which has a wavelength in the range of 350-440 nm in the molecule | numerator as needed.

(A) The binder polymer can be used individually by 1 type of binder polymer, and can also be used combining two or more types of binder polymers arbitrarily. As a binder polymer at the time of using in combination of 2 or more types, For example, two or more types of binder polymers which consist of another copolymerization component (it contains another monomer unit as a copolymerization component), and two or more types of binder polymers of another weight average molecular weight And two or more kinds of binder polymers having different degrees of dispersion. Moreover, the polymer which has the multi-mode molecular weight distribution of Unexamined-Japanese-Patent No. 11-327137 can also be used.

It is preferable to make content of (A) component (binder polymer) into 30-70 weight part with respect to 100 weight part of total amounts of (A) component and (B) component. In the point which provides film property, 30 weight part or more is preferable, 35 weight part or more is more preferable, and 40 weight part or more is more preferable. Moreover, since it is excellent in a sensitivity and resolution, 70 weight part or less is preferable, 65 weight part or less is more preferable, and 60 weight part or less is still more preferable.

[(B) component: Photopolymerizable compound]

The photopolymerizable compound which is (B) component contains the compound represented by following General formula (1).

[Tue 3]

In said general formula (1), R <^1> , R <^2> and R <^3> represent a hydrogen atom or a methyl group each independently. Further, the oxyethylene group "- (OC ₂ H ₄₎ -" repeat number of a, b and c of the, independently represent an integer of 1-48, respectively. However, the total number (a + b + c) is 6-50, and from a viewpoint of further improving resolution, adhesiveness, and a resist shape, it is preferable that it is 9-45, It is more preferable that it is 12-39, It is 15-36 More preferred.

As the compound represented by the above general formula (1), for ^{example, TMPT21E (R 1 = R 2} = R 3 = methyl, a + b + c = 21 ), TMPT30E (R 1 = R 2 = R 3 = methyl, a + b + c = 30 (Trade name, product made by Hitachi Chemical Co., Ltd.) is available.

Content of the compound represented by General formula (1) is 5-50 weight part with respect to 100 weight part of total weight of (B) component from a viewpoint of improving the resolution, adhesiveness, resist shape, and the peeling characteristic after hardening well. It is more preferable, and it is still more preferable that it is 10-40 weight part.

(B) A photopolymerizable compound contains a bisphenol-A (meth) acrylate compound with the compound represented by the said General formula (1) from a viewpoint of improving alkali developability, resolution, and the peeling characteristic after hardening. It is desirable to.

As a bisphenol-A (meth) acrylate compound, for example, 2, 2-bis (4- ((meth) acryloxy polyethoxy) phenyl) propane, 2, 2-bis (4- ((meth) acryl) Oxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolyprop Foxy) phenyl) propane is mentioned. Especially, 2, 2-bis (4- ((meth) acryloxy polyethoxy) phenyl) propane is preferable from a viewpoint of further improving resolution and peeling characteristics.

As 2, 2-bis (4- ((meth) acryloxy polyethoxy) phenyl) propane, it is 2, 2-bis (4- ((meth) acryloxy diethoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxypentaethoxy) phenyl) propane, 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) acryloxyundecethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4 -((Meth) acryloxy Tradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexadecaethoxy ) Phenyl) propane. Especially, it is preferable that it is 4-20, and, as for the number of the oxyethylene groups in 1 molecule of 2, 2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, it is more preferable that it is 8-15. .

Among these, 2, 2-bis (4- (methacryloxy pentaethoxy) phenyl) propane is BPE-500 (made by Shin-Nakamura Chemical Co., Ltd., brand name) or FA-321M (Hitachi Chemical Co., Ltd.) Commercially available). 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name). These can be used individually or in combination of 2 or more types arbitrarily.

As 2, 2-bis (4- ((meth) acryloxy polypropoxy) phenyl) propane, for example, 2, 2-bis (4- ((meth) acryloxy dipropoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4 -((Meth) acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic Oxyheptapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonapropoxy) Phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) propane, 2, 2-bis (4-((meth) acryloxydodecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxyhexadecapropoxy) phenyl) propane.

As 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, for example, 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) Phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) Phenyl) propane.

It is preferable that it is 20-80 weight part with respect to 100 weight part of total weight of (B) component, and, as for content when (B) component contains a bisphenol-A (meth) acrylate compound, it is more preferable that it is 30-70 weight part desirable.

In addition, the (B) component is a polyalkylene glycol di (which has a (poly) oxyethylene chain and a (poly) oxypropylene chain) in a molecule | numerator from a viewpoint of improving the flexibility of the hardened | cured material (cured film) of the photosensitive resin composition. It is preferable to further contain meth) acrylate.

As polyalkylene glycol di (meth) acrylate, it is a (poly) oxyalkylene chain in a molecule | numerator, and a (poly) oxyethylene chain and a (poly) oxypropylene chain ((poly) oxy-n-propylene) chain or (poly) Oxyisopropylene chain). In addition, the polyalkylene glycol di (meth) acrylate is, moreover, (poly) oxy-n-butylene chain, (poly) oxy isobutylene chain, (poly) oxy-n-pentylene chain, (poly) oxyhexylene You may have a (poly) oxyalkylene chain of about 4-6 carbon atoms which is a chain and these structural isomers.

In the molecule | numerator of polyalkylene glycol di (meth) acrylate, a (poly) oxyethylene chain and a (poly) oxypropylene chain may respectively exist in block form continuously or may exist randomly. In addition, in the (poly) oxyisopropylene chain, the secondary carbon of the propylene group may be bonded to the oxygen atom, and the primary carbon may be bonded to the oxygen atom.

As polyalkylene glycol di (meth) acrylate, especially the compound represented by following General formula (3), (4) or (5) is preferable. These can be used individually or in combination of 2 or more types.

[Figure 4]

In said formula (3), (4), and (5), R represents a hydrogen atom or a methyl group each independently, EO represents an oxyethylene group, PO represents an oxypropylene group. m <_1> , m <_2> , m <_3> and m <_4> show the repeating number of the structural unit which consists of an oxyethylene group, n <_1> , n <_2> , n <_3> and n <_4> show the repeating number of the structural unit which consists of an oxypropylene group, The total number of repeating oxyethylene groups m ₁ + m ₂ , m ₃ and m ₄ (average) each independently represent an integer of 1 to 30, and the total number of repeating oxypropylene groups n ₁ , n ₂ + n ₃ and n ₄ (Average value) represents the integer of 1-30 each independently.

In the compound represented by the above general formula (3), (4) or (5), the repeating total number m ₁ + m ₂ , m ₃ and m ₄ of the oxyethylene group are integers of 1 to 30, among which 1 The integer of -10 is preferable, the integer of 4-9 is more preferable, and the integer of 5-8 is still more preferable. From the point which is excellent in resolution, adhesiveness, and resist shape, 30 or less are preferable, 10 or less are more preferable, 9 or less are more preferable, 8 or less are especially preferable.

In addition, oxy, and total number of repeats n _1, n an integer of ₂ + n ₃ and n ₄ is 1 to 30, the propylene group, particularly an integer from 5 to 20 preferably, and more preferably from 8 to 16 integer, and 10 The integer of -14 is more preferable. From the point which is excellent in the resolution improvement and the reduction of sludge, 30 or less are preferable, 20 or less are more preferable, 16 or less are more preferable, and 14 or less are especially preferable.

As the compound represented by formula (3), R = methyl _{group, m 1 + m 2 = 6} ( average value), n ₁ = 12 (average value) in the vinyl compound (manufactured by section is hidachi addition Kogyo, trade name: "FA-023M ") Etc. are mentioned. As the compound represented by the general formula (4), R = methyl group, m ₃ = 6 (average _{value), n 2 + n 3 =} 12 ( average value) in the vinyl compound (manufactured by section is hidachi addition Kogyo, trade name: "FA-024M ") Etc. are mentioned. As the compound represented by the general formula (5), R = a hydrogen atom, m ₄ = 1 (mean value), n ₄ = 9 (average value) in the vinyl compound (produced by Shin-Nakamura Kagaku Kogyo Co., Ltd., trade name: "NK Ester HEMA-9P ") Etc. are mentioned. These can be used individually or in combination of 2 or more types.

When (B) component contains polyalkylene glycol di (meth) acrylate which has a (poly) oxyethylene chain and a (poly) oxypropylene chain in a molecule | numerator, 100 weight part of total weights of (B) photopolymerizable compound It is preferable that it is 5-50 weight part with respect to it, and it is more preferable that it is 10-40 weight part.

As (B) component, the photopolymerizable compound of that excepting the above may be included. As a photopolymerizable compound of that excepting the above, if it has at least 1 ethylenically unsaturated bond in a molecule | numerator, there will be no restriction | limiting in particular, For example, the compound obtained by making (alpha), (beta)-unsaturated carboxylic acid react with a polyhydric alcohol, a urethane bond in a molecule | numerator It is obtained by making (alpha), (beta)-unsaturated carboxylic acid react with urethane monomers, such as a (meth) acrylate compound, nonylphenoxy polyethyleneoxyacrylate, a phthalic acid type compound, the (meth) acrylic-acid alkylester, and glycidyl-group containing compound which have The compound can be mentioned. These can be used individually or in combination of 2 or more types.

As a compound obtained by making (alpha), (beta)-unsaturated carboxylic acid react with a polyhydric alcohol, the polyethyleneglycol di (meth) acrylate whose number of ethylene groups is 2-14, for example, the polypropylene glycol whose number of propylene groups is 2-14 Di (meth) acrylate, trimetholpropanedi (meth) acrylate, trimetholpropane tri (meth) acrylate, EO-modified trimetholpropane tri (meth) acrylate (total repeat number of oxyethylene groups 1 5), PO-modified trimetholpropane tri (meth) acrylate, EO, PO-modified trimetholpropane tri (meth) acrylate, tetrametholmethane tri (meth) acrylate, tetramethylol methane tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are mentioned. These can be used individually or in combination of 2 or more types. "EO modified" means a compound (polyoxyethylenated compound) having a block structure of the (poly) oxyethylene chain, and "PO modified" means a compound having a block structure of the (poly) oxypropylene chain ( Means a polyoxypropylene compound, and "EO-EO modification" means a compound having a block structure of a (poly) oxyethylene chain and a (poly) oxypropylene chain (polyoxyethylenated and polyoxypropyleneated) Compound).

As a (meth) acrylate compound which has a urethane bond in a molecule | numerator, for example, the (meth) acryl monomer and diisocyanate compound (isophorone diisocyanate, 2, 6-toluene diisocyanate, 2,4 which have an OH group in a β-position) Addition reactant with -toluene diisocyanate, 1,6-hexamethylene diisocyanate, etc.), tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO And PO-modified urethane di (meth) acrylates. Examples of EO-modified urethane di (meth) acrylate include UA-11 (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name). Moreover, UA-13 (made by Shin-Nakamura Chemical Co., Ltd., brand name) is mentioned as EO and PO modified urethane di (meth) acrylate. These are used individually or in combination of 2 or more types.

Moreover, the photopolymerizable compound which has one ethylenically unsaturated bond in a molecule | numerator as (B) component can further be included. As a photopolymerizable compound which has one ethylenically unsaturated bond in a molecule | numerator, the above-mentioned nonylphenoxy polyethyleneoxy acrylate, a phthalic acid type compound, (meth) acrylic-acid alkylester, etc. are mentioned. Among them, nonylphenoxypolyethyleneoxyacrylate or phthalic acid-based compound is preferable from the viewpoint of improving the resolution, adhesion, resist shape, and peeling characteristics after curing in a good balance.

As nonyl phenoxy ethylene oxyacrylate, nonyl phenoxy triethylene oxy acrylate, nonyl phenoxy tetra ethylene oxy acrylate, nonyl phenoxy penta ethylene oxy acrylate, nonyl phenoxy hexa ethylene oxy acrylate, nonyl, for example. Phenoxyheptaethylene oxyacrylate, nonyl phenoxy octaethylene oxy acrylate, nonyl phenoxy nona ethylene oxy acrylate, nonyl phenoxy decaethylene oxy acrylate, nonyl phenoxy undeca ethylene oxy acrylate. These can be used individually or in combination of 2 or more types arbitrarily.

As the phthalic acid compound, for example, γ-chloro-β-hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth) acryloyl Oxyethyl-o-phthalate and β-hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate are mentioned. Especially, (gamma) -chloro- (beta) -hydroxypropyl (beta) '-(meth) acryloyloxyethyl o-phthalate is preferable. γ-chloro-β-hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate is commercially available as FA-MECH (manufactured by Hitachi Chemical Co., Ltd., trade name). These can be used individually or in combination of 2 or more types.

As the (meth) acrylic acid alkyl ester, the compound represented by the general formula (2) described above can be used.

When (B) component contains the photopolymerizable compound which has one ethylenically unsaturated bond in a molecule | numerator, the content is a viewpoint which improves the resolution, adhesiveness, resist shape, and the peeling characteristic after hardening well, (B It is preferable that it is 1-30 weight part with respect to 100 weight part of total weight of a component, It is more preferable that it is 3-25 weight part, It is still more preferable that it is 5-20 weight part.

It is preferable that content of (B) component (photopolymerizable compound) shall be 30-70 weight part with respect to 100 weight part of total amounts of (A) component and (B) component. In view of improving the sensitivity and resolution, the content of the component (B) is preferably 30 parts by weight or more, more preferably 35 parts by weight or more, and even more preferably 40 parts by weight or more. From the point which gives a film property and the point which is excellent in the resist shape after hardening, 70 weight part or less is preferable, as for content of (B) component, 65 weight part or less is more preferable, and 60 weight part or less is still more preferable.

[(C) component: photoinitiator]

As (C) photoinitiator, if the thing with the wavelength of the optical wavelength of the exposure machine to be used and the wavelength required for the function expression of (C) photoinitiator is selected, a conventionally well-known thing can be used without a restriction | limiting in particular. (C) As a photoinitiator, for example, benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio Aromatic ketones such as phenyl] -2-morpholino-propanone-1; quinones such as alkylanthraquinone; benzoin ether compounds such as benzoin alkyl ether; benzoin compounds such as benzoin and alkyl benzoin; Benzyl derivatives such as benzyldimethyl ketal; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer 2,4,5-triaryl imidazole dimers such as these; acridine derivatives such as 9-phenylacridine and 1,7- (9,9'-acridinyl) heptane. These can be used individually or in combination of 2 or more types.

(C) It is preferable that a photoinitiator contains a 2,4,5-triaryl imidazole dimer from a viewpoint of improving a sensitivity and adhesiveness, and 2- (o-chlorophenyl) -4,5-di It is more preferable that phenylimidazole dimer is included. The 2,4,5-triarylimidazole dimer may be symmetrical or asymmetrical in structure.

It is preferable that content of (C) component (photoinitiator) is 0.1-10 weight part with respect to 100 weight part of total amounts of (A) component and (B) component. From the point which is excellent in a sensitivity, resolution, or adhesiveness, 0.1 weight part or more is preferable, as for content of (C) component, 1 weight part or more is more preferable, 2 weight part or more is more preferable, and 3 weight part or more Particularly preferred. Moreover, from the point which is excellent in the resist shape after hardening, 10 weight part or less is preferable, as for content of (C) component, 7 weight part or less is more preferable, 6 weight part or less is more preferable, and 5 weight part or less Particularly preferred.

[(D) component: sensitizing dye]

The photosensitive resin composition of this embodiment can further contain a sensitizing dye as (D) component. As (D) component, a conventionally well-known thing can be used without a restriction | limiting especially unless the effect of this invention is impaired. Specifically, (D) component as dialkylaminobenzophenone, pyrazoline, anthracene, coumarin, xanthone, oxazole, benzoxazole, thiazole, benzothiazole, triazole, stilbene, tria Binary, thiophenes, naphthalimides, and triarylamines are mentioned. These are used individually or in combination of 2 or more types.

When exposing the photosensitive resin composition layer using 390-420 nm actinic light especially, from a group which consists of pyrazoline, anthracene, coumarin, and triarylamine as (D) component from a viewpoint of a sensitivity and adhesiveness, It is preferable to include at least 1 sort (s) selected, and it is more preferable to contain pyrazoline, anthracene, or triarylamine especially.

When the photosensitive resin composition contains (D) component (sensitizing dye), it is preferable that the content shall be 0.01-10 weight part with respect to 100 weight part of total amounts of (A) component and (B) component. From the point which is excellent in a sensitivity and adhesiveness, 0.01 weight part or more is preferable, as for content of (D) component, 0.05 weight part or more is more preferable, 0.1 weight part or more is more preferable. Since the resist shape after hardening is excellent, 10 weight part or less is preferable, as for content of (D) component, 5 weight part or less is more preferable, and 3 weight part or less is further more preferable.

[(E) component: Amine compound]

The photosensitive resin composition of this embodiment can contain an amine compound as (E) component from a viewpoint of improving a sensitivity further. Examples of the (E) amine compound include bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, leucocrystal violet and the like. These can be used individually or in combination of 2 or more types.

When the photosensitive resin composition contains (E) component (amine type compound), it is preferable to make the content into 0.01-10 weight part with respect to 100 weight part of total amounts of (A) component and (B) component. From the point which is excellent in a sensitivity, 0.01 weight part or more is preferable, as for content of (E) component, 0.05 weight part or more is more preferable, 0.1 weight part or more is more preferable. In order to prevent an excess (E) amine compound from depositing as a foreign material after film formation, 10 weight part or less is preferable, as for content of (D) component, 5 weight part or less is more preferable, 2 weight part or less More preferred.

[Other Ingredients]

The photosensitive resin composition of this embodiment is a photopolymerizable compound (oxetane compound etc.) which has at least 1 cation-polymerizable cyclic ether group in a molecule | numerator, dye, such as a cationic polymerization initiator and marachite green, tribromophenyl as needed. Photochromic agents such as sulfones and leuco crystal violets, exothermic colorants, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion imparting agents, leveling agents, peeling accelerators, antioxidants, flavoring agents, imaging agents And a thermal crosslinking agent. These can be used individually or in combination of 2 or more types. It is preferable to make these content into about 0.01-20 weight part with respect to 100 weight part of total amounts of (A) component and (B) component, respectively.

<Solution of Photosensitive Resin Composition>

The photosensitive resin composition of this embodiment can be melt | dissolved in the organic solvent, and can be used as a solution (coating liquid) of about 30 to 60 weight% of solid content. As the organic solvent, for example, methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof Can be mentioned.

By apply | coating the said coating liquid on the surface, such as a metal plate, and drying, the photosensitive resin composition layer which consists of the photosensitive resin composition of this embodiment can be formed. As a metal plate, iron type alloys, such as copper, a copper type alloy, nickel, chromium, iron, stainless, Preferably copper, a copper type alloy, an iron type alloy is mentioned.

Although the thickness of the photosensitive resin composition layer changes with the uses, it is preferable that it is about 1-100 micrometers in the thickness after drying. You may coat | cover the surface on the opposite side to the metal plate of the photosensitive resin composition layer with a protective film. As a protective film, polymer films, such as polyethylene and a polypropylene, are mentioned.

<Photosensitive element>

The photosensitive element 1 of this invention is equipped with the photosensitive resin composition layer 3 formed on the support film 2 and the support film 2, as shown in FIG. 1, and, as needed, the photosensitive resin composition layer The protective film 4 is further provided on (3).

The photosensitive resin composition layer 3 which consists of the said photosensitive resin composition can be formed on the support film 2 by apply | coating the solution of the said photosensitive resin composition on the support film 2, and drying it. In this way, the photosensitive element 1 of this embodiment provided with the support film 2 and the photosensitive resin composition layer 3 formed on the support film 2 is obtained.

As a support film, the polymer film which has heat resistance and solvent resistance, such as polyester, such as polyethylene terephthalate, polypropylene, and polyethylene, can be used. When the thickness of a support film (polymer film) considers the influence on the intensity | strength and the resolution, it is preferable that it is 1-100 micrometers, It is more preferable that it is 5-50 micrometers, It is further more preferable that it is 5-30 micrometers. When this thickness is less than 1 micrometer, it exists in the tendency for a support film to tear easily when peeling a support film. Moreover, in order not to affect a resolution, 100 micrometers or less are preferable, 50 micrometers or less are more preferable, and 30 micrometers or less are more preferable.

The photosensitive element 1 may be equipped with the protective film 4 which coat | covers the surface on the opposite side to the support film 2 of the photosensitive resin composition layer 3 as needed.

As a protective film, it is preferable that the adhesive force with respect to the photosensitive resin composition layer is smaller than the adhesive force with respect to the photosensitive resin composition layer of a support film, and the film of a low fisheye is preferable. Herein, the term “fish eye” refers to the fact that foreign substances, undissolved products, oxidative degradation products, etc. of materials are taken into the film when the film is hot melted and kneaded, extruded, biaxially stretched, cast or the like. it means. That is, "low fish eye" means that there are few said foreign materials in a film.

As a protective film, the polymer film which has heat resistance and solvent resistance, such as polyester, such as polyethylene terephthalate, polypropylene, and polyethylene, etc. can be used specifically ,. Commercially available examples include polyethylene terephthalate films such as polypropylene films such as Alpan MA-410, E-200C manufactured by Oji Paper Co., Ltd., and PS-25 such as PS-25 manufactured by Teijin Corporation. In addition, a protective film may be the same as a support film.

It is preferable that the thickness of a protective film is 1-100 micrometers, It is more preferable that it is 5-50 micrometers, It is further more preferable that it is 5-30 micrometers, It is especially preferable that it is 15-30 micrometers. When this thickness is less than 1 micrometer, when laminating (laminating) the photosensitive resin composition layer and a protective film on a board | substrate, there exists a tendency for a protective film to tear easily, and when it exceeds 100 micrometers, it tends to become inadequate in a cheapness point. There is this.

Application | coating of the solution of the photosensitive resin composition on the support film can be performed by well-known methods, such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, and a bar coater.

It is preferable to perform drying of the said solution at 70-150 degreeC for about 5 to 30 minutes. After drying, it is preferable to make the amount of the residual organic solvent in the photosensitive resin composition layer into 2 weight part or less from a viewpoint of preventing the diffusion of the organic solvent in a later process.

Although the thickness of the photosensitive resin composition layer in a photosensitive element changes with a use, it is preferable that it is 1-100 micrometers in the thickness after drying, It is more preferable that it is 1-50 micrometers, It is more preferable that it is 5-40 micrometers. . When this thickness is less than 1 micrometer, there exists a tendency for industrial coating to become difficult, and when it exceeds 100 micrometers, there exists a tendency for adhesiveness and resolution to become difficult to be fully acquired.

It is preferable that the transmittance | permeability with respect to the ultraviolet-ray of the said photosensitive resin composition layer is 5-75% with respect to the ultraviolet-ray of wavelength 405nm. In terms of excellent adhesion, the transmittance is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more. In the point which is excellent in resolution, 75% or less is preferable, 65% or less is more preferable, and 55% or less is more preferable.

The transmittance can be measured by a UV spectrometer. As a UV spectrometer, the Hitachi Corporation make 228 A-type W-beam spectrophotometer is mentioned.

The photosensitive element may further have intermediate | middle layers, such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.

The obtained photosensitive element can be wound up in a sheet form or winding up to roll shape, and can be stored. When winding up in roll shape, it is preferable to wind up so that a support film may become an outer side. Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). It is preferable to provide a cross-sectional separator in the cross section of the roll-shaped photosensitive element roll obtained in this way, and to provide a moisture proof cross-section separator from the standpoint of inner edge fusion. As a packing method, it is preferable to wrap and wrap in the black sheet | seat with small moisture permeability.

<Formation method of resist pattern>

The resist pattern can be formed using the photosensitive resin composition of this invention. The method of forming a resist pattern according to the present embodiment includes (i) a lamination step of laminating a photosensitive resin composition layer made of the photosensitive resin composition on a substrate, and (ii) actinic light on a predetermined portion of the photosensitive resin composition layer. The resist which consists of hardened | cured material of the photosensitive resin composition on a board | substrate by irradiating and exposing the predetermined part and hardening | curing, and removing (iii) parts other than the predetermined part of the photosensitive resin composition layer from a board | substrate. It has a developing process of forming a pattern.

(i) lamination process

First, the photosensitive resin composition layer which consists of a photosensitive resin composition is laminated | stacked on a board | substrate. As a board | substrate, the board | substrate (circuit formation board | substrate) provided with the insulating layer and the conductor layer formed on this insulating layer can be used.

Lamination | stacking on the board | substrate of a photosensitive resin composition layer is performed by crimping | bonding to the said board | substrate, heating a photosensitive resin composition layer of a photosensitive element, for example after removing the protective film of the said photosensitive element. Thereby, the laminated body which consists of a board | substrate, the photosensitive resin composition layer, and a support film, and these laminated | stacked in order is obtained.

It is preferable to perform this lamination | stacking operation under reduced pressure from the standpoint of adhesiveness and followability. It is preferable to perform heating of the photosensitive resin composition layer and / or board | substrate at the time of crimping | compression-bonding, and it is preferable to crimp | bond at the pressure of about 0.1-1.0 MPa (about 1-10 kgf / cm <2>), There is no restriction | limiting in particular in these conditions. In addition, when the photosensitive resin composition layer is heated to 70-130 degreeC, it is not necessary to preheat-process a board | substrate previously, In order to further improve lamination property, you may perform a preheating process of a board | substrate.

(ii) exposure process

Next, actinic light is irradiated to the predetermined part of the photosensitive resin composition layer on a board | substrate, the predetermined part is exposed, and it hardens. At this time, when the support film existing on the photosensitive resin composition layer is transparent to actinic light, actinic light can be irradiated through the support film, but when the support film is light-shielding, the photosensitive resin composition is removed after removing the support film. Irradiate actinic light onto the layer.

As an exposure method, the method (mask exposure method) which irradiates an actinic light on an image through the negative or positive mask pattern called artwork is mentioned. Moreover, you may employ | adopt the method which irradiates an actinic light on an image by the direct drawing exposure method, such as the LDI (Laser Direct Direct Imaging) exposure method or the DLP (Digital Light Processing Processing) exposure method.

As a light source of active light, a well-known light source can be used, For example, a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, a xenon lamp, a gas laser, such as an argon laser, a solid laser, such as a YAG laser, a semiconductor laser, etc. Effectively emitting ultraviolet rays, visible light, and the like.

As a wavelength (exposure wavelength) of an actinic light, it is preferable to carry out in the range of 350-420 nm from a viewpoint which acquires the effect of this invention more reliably, and it is more preferable to carry out in the range of 390-420 nm.

(iii) developing process

Moreover, the resist pattern which consists of hardened | cured material of the photosensitive resin composition is formed on a board | substrate by removing parts other than the predetermined part of the photosensitive resin composition layer from a board | substrate. When a support film exists on the photosensitive resin composition layer, after removing a support film, parts (unexposed part) other than the said predetermined part (exposed part) are removed (developed). There are wet development and dry development in the developing method, but wet development is widely used.

In the case of wet development, development is carried out by a known development method using a developer corresponding to the photosensitive resin composition. As the developing method, a method using a dip method, a battle method, a spray method, brushing, slapping, scraping, oscillation dipping and the like can be cited. In view of improving resolution, a high pressure spray method is most suitable. You may develop in combination of these 2 or more types of methods.

As a developing solution, alkaline aqueous solution, an aqueous developing solution, an organic solvent developing solution, etc. are mentioned.

When used as a developing solution, alkaline aqueous solution is safe and stable, and its operativity is favorable. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxide; alkali carbonates such as carbonate or bicarbonate of lithium, sodium, potassium or ammonium; alkali metal phosphates such as potassium phosphate and sodium phosphate; sodium pyrophosphate and fatigue Alkali metal pyrophosphates, such as potassium phosphate, are used.

As the alkaline aqueous solution, a lean solution of 0.1 to 5% by weight sodium carbonate, a lean solution of 0.1 to 5% by weight potassium carbonate, a lean solution of 0.1 to 5% by weight sodium hydroxide, and a lean solution of 0.1 to 5% by weight sodium tetraborate are preferred. . It is preferable to make pH of alkaline aqueous solution into the range of 9-11, and the temperature is adjusted according to the alkali developability of the photosensitive resin composition layer. In alkaline aqueous solution, you may mix surface active agent, an antifoamer, a small amount of organic solvents for promoting image development, etc ..

An aqueous developing solution is a developing solution which consists of water or alkaline aqueous solution, and 1 or more types of organic solvents, for example. Here, as the base of the alkaline aqueous solution, in addition to the substances mentioned above, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl- 1,3-propanediol, 1,3-diaminopropanol-2, and morpholine are mentioned. It is preferable to make pH of an aqueous developing solution as small as possible in the range in which image development is fully performed, It is preferable to set it as pH8-12, and it is more preferable to set it as pH9-10.

As an organic solvent used for an aqueous developing solution, acetone, ethyl acetate, the alkoxy ethanol which has a C1-C4 alkoxy group, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether And diethylene glycol monobutyl ether. These are used individually or in combination of 2 or more types. It is preferable to make the density | concentration of the organic solvent in an aqueous developing solution normally 2 to 90 weight%, and the temperature can be adjusted according to alkali developability. In the aqueous developer, a small amount of a surfactant, an antifoaming agent, or the like may be mixed.

As the organic solvent developer, organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone Can be mentioned. It is preferable to add water to these organic solvents in 1 to 20weight% of a range in order to prevent flammability.

After removing an unexposed part, a resist pattern can also be hardened further by performing about 60-250 degreeC heating or exposure of about 0.2-10 J / cm <2> as needed.

<Method of manufacturing a printed wiring board>

A printed wiring board can be manufactured by etching or plating the board | substrate with which the resist pattern was formed by the said method. Etching or plating of the substrate is performed on the conductor layer or the like of the substrate using the formed resist pattern as a mask.

Examples of the etching solution in the case of etching include a cupric chloride solution, a ferric chloride solution, an alkali etching solution and a hydrogen peroxide etching solution, and among them, it is preferable to use a ferric chloride solution in terms of good etch factor. Do.

As the plating method in the case of plating, copper plating such as copper sulfate plating, copper pyrophosphate plating, solder plating such as high slow solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, hard Gold plating, such as gold plating and soft gold plating, is mentioned.

After completion of etching or plating, the resist pattern can be peeled off by a strongly alkaline aqueous solution, for example, than the alkaline aqueous solution used for development. As this strongly alkaline aqueous solution, the 1-10 weight% sodium hydroxide aqueous solution and the 1-10 weight% potassium hydroxide aqueous solution are used, for example. Especially, it is preferable to use the 1-10 weight% sodium hydroxide aqueous solution or the potassium hydroxide aqueous solution, and it is more preferable to use the 1-5 weight% sodium hydroxide aqueous solution or the potassium hydroxide aqueous solution.

As a peeling method of a resist pattern, an immersion system, a spray system, etc. are mentioned, These may be used independently or may be used together. The printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board, may have a small diameter through hole, or may be a printed wiring board having a densified wiring such as a high density package substrate and a silicon chip rewiring.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition with favorable sensitivity, resolution, adhesiveness, resist shape, and the peeling characteristic after hardening, the formation method of the photosensitive element resist pattern using this, and the manufacturing method of a printed wiring board can be provided.

1: is a schematic cross section which shows suitable one Embodiment of the photosensitive element of this invention.

Example

Hereinafter, an Example is given and it demonstrates more concretely about this invention. However, the present invention is not limited to the following examples.

(A) binder polymer

(A-1)

Solution obtained by mixing 150 g of methacrylic acid as polymerizable monomer (monomer), 125 g of benzyl methacrylate, 25 g of methyl methacrylate, and 200 g of styrene (weight ratio 30/25/5/40) and 9.0 g of azobisisobutyronitrile Was made into "solution a".

The solution obtained by melt | dissolving 1.2 g of azobisisobutyronitrile in 100 g of mixed liquids (weight ratio 3: 2) of 60 g of methyl cellosolves and 40 g of toluene was made into "solution b."

To a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping lot, and a nitrogen gas introduction tube, 450 g of a mixed solution (weight ratio 3: 2) of 270 g of methyl cellosolve and 180 g of toluene was added thereto, followed by stirring while blowing nitrogen gas into the flask. It heated up to 80 degreeC.

The solution a was added dropwise to the mixed solution in the flask over 4 hours, and then the mixture was kept at 80 ° C for 2 hours with stirring. Subsequently, the solution b was added dropwise to the solution in the flask over 10 minutes, and the mixture was kept at 80 ° C for 3 hours while stirring the solution in the flask. Furthermore, the solution in the flask was hung for 30 minutes, heated to 90 ° C, kept at 90 ° C for 2 hours, and then cooled to obtain a solution of binder polymer (A-1).

The nonvolatile matter (solid content) of the binder polymer (A-1) was 47.8 wt%, the weight average molecular weight was 30000, and the acid value was 196 mgKOH / g. In addition, the weight average molecular weight was measured by the gel permeation chromatography method (GPC), and it derived by converting using the analytical curve of standard polystyrene. The conditions of GPC are shown below.

(GPC condition)

Pump: Hitachi @ L-6000 type (made by Hitachi, Ltd., brand name)

Column: Three in total

Gelpack GL-R420

Gelpack GL-R430

Gelpack GL-R440 (above, Hitachi Kase Kogyo Co., Ltd., brand name)

Eluent: Tetrahydrofuran

Measurement temperature: 40 degrees Celsius

Flow rate: 2.05mL / minute

Detector: Hitachi L-3300 type RI (made by Hitachi, Ltd., brand name)

(A-2)-(A-6)

Using the material shown in Table 1 as a polymerizable monomer (monomer) in the weight ratio shown in the same table, it is the same as obtaining the solution of binder polymer (A-1), and of binder polymer (A-2)-(A-6) Each solution was obtained.

[Preparation of Solution of Photosensitive Resin Composition]

The solution of the photosensitive resin composition of Examples 1-14 and Comparative Examples 1-2 was prepared by mixing the component shown in the following Tables 2 and 3 by the compounding quantity shown in the same table. In addition, the compounding quantity of (A) component shown in Table 2 and 3 is the weight (solid amount) of a non volatile matter.

About the detail of each component shown in the said Tables 2 and 3, it is as follows.

(B) photopolymerizable compound

TMPT21 (made by Hitachi Chemical Co., Ltd., brand name): EO modified trimetholol propane triacrylate (In general formula (1), it is R < ¹ > R <^2> = R < ³ > methyl group and a + b + c = 21 (average value). compound)

A-TMPT-3EO (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., brand name): EO-modified trimetholol propane triacrylate (3 repeat total number of oxyethylene group)

FA-321M (made by Hitachi Chemical Co., Ltd., brand name): 2, 2-bis (4- (methacryloxy pentaethoxy) phenyl) propane

BPE-100 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., brand name): EO-modified bisphenol A-based dimethacrylate (2.6 number of repeat total number of oxyethylene groups)

M-114 (made by Toa Synthetic Co., Ltd.): 4-normal nonyl phenoxy octaethylene glycol acrylate

FA-MECH (made by Hitachi Chemical Co., Ltd., brand name): (2-hydroxy-3-chloro) propyl-2-methacryloyloxyethyl phthalate

FA-024M (manufactured by Hitachi Chemical Co., Ltd., trade name): Compound represented by formula (4) wherein R is a methyl group, m ₃ = 6 (average), n ₂ + n ₃ = 12 (average)

(C) photopolymerization initiator

B-CIM (made by Hampford, brand name): 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenylbisimidazole

(D) sensitizing dye

DBA (product made in Kawasaki Kasei Kogyo Co., Ltd.): 9,10-dibutoxy anthracene

PYR-1 (manufactured by Nippon Chemical Co., Ltd., product name): 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) pyrazoline

J205 (made by Nippon Distillation Industry Co., Ltd., brand name): The triphenylamine derivative represented by following formula (9).

[Figure 5]

(E) Amine Compound

LCV (product made by Yamada Chemical Co., Ltd.): leuco crystal violet

(dyes)

MKG (product made in Osaka Yuki Chemical Industry Co., Ltd., brand name): Marachite green

[Photosensitive element]

The solution of the photosensitive resin composition of the said Example and a comparative example was apply | coated uniformly on the polyethylene terephthalate film (Teijin Co., Ltd. brand name "HTF-01") of thickness each 16 micrometers, respectively, and 70 degreeC and 110 degreeC hot air convection. It dried with the type | mold dryer, and formed the photosensitive resin composition layer whose film thickness after drying is 25 micrometers. A photosensitive element in which a protective film (manufactured by Tama Poly Co., Ltd., trade name "NF-15") is bonded on the photosensitive resin composition layer, and a polyethylene terephthalate film (support film), a photosensitive resin composition layer, and a protective film are laminated in this order. Got.

[Laminated Substrate]

A brush equivalent of 을 600 is made by using the copper surface of the copper clad laminated board (made by Hitachi Chemical Co., Ltd., brand name "MCL-E-67") which consists of a glass epoxy material and copper foil (35 micrometers in thickness) formed on both surfaces. The eggplant was polished using a polishing machine (manufactured by Sankei Co., Ltd.), and washed with water and dried by air flow. After heating this copper clad laminated board (henceforth "substrate"), and heating up at 80 degreeC, the photosensitive element which concerns on Examples 1-14 and Comparative Examples 1-2 is laminated on the copper surface of a board | substrate (lamination | stacking). )did. Lamination was performed on the conditions of the temperature of 120 degreeC, and lamination pressure of 4 kgf / cm <2>, making the photosensitive resin composition layer of each photosensitive element adhere to the copper surface of a board | substrate, removing a protective film. In this way, a laminated substrate having a photosensitive resin composition layer and a polyethylene terephthalate film laminated on a copper surface of the substrate was obtained.

[Evaluation of sensitivity]

When the obtained laminated substrate was left to cool and it became 23 degreeC, on the polyethylene terephthalate film of a laminated substrate, concentration area 0.00-2.00, density | concentration step 0.05, tablet size 20mm * 187mm, and size of each step are 3mm * 12mm. Photo tool having 41 steps of step tablets was stuck. A phototool and a polyethylene terephthalate film were used at an energy amount (exposure amount) of 70 mJ / cm 2 using a linear drawing exposure machine (manufactured by Hitachi Via Mechanics Co., Ltd., trade name "DE-1AH") having a blue-violet laser diode having a wavelength of 405 nm as a light source. It exposed through the photosensitive resin composition layer through it. In addition, the measurement of illuminance was performed using the ultraviolet illuminometer (The Ushio Electric Co., Ltd. make, brand name "UIT-150") to which the 405 nm corresponding probe was applied.

After exposure, the polyethylene terephthalate film was peeled from the laminated substrate, the photosensitive resin composition layer was exposed, and the unexposed part was removed by spraying a 1 weight% sodium carbonate aqueous solution at 30 degreeC for 24 second. In this way, the cured film which consists of hardened | cured material of the photosensitive resin composition was formed on the copper surface of a board | substrate. The sensitivity of the photosensitive resin composition was evaluated by measuring the remaining fraction of the step tablet obtained as a cured film. The sensitivity is expressed by the number of steps of the step tablet, and the higher the number of steps, the better the sensitivity. The results are shown in Tables 5 and 6.

[Evaluation of Resolution and Adhesion]

Remaining 41-stage step tablet using a drawing pattern having a line width L / space width S (hereinafter referred to as "L / S") of 5/5 to 30/30 (unit: µm) Exposure (drawing) was performed with respect to the photosensitive resin composition layer of the said laminated | multilayer board | substrate by the amount of energy of which the number of stages becomes 11 steps. After the exposure, the same development treatment as in the evaluation of the sensitivity was performed.

After development, the space portion (unexposed portion) is removed cleanly, and by the value of the smallest line width / space width among the resist patterns formed without causing the line portion (exposed portion) to meander or decay, Resolution and adhesiveness were evaluated. The smaller this value means, the better both resolution and adhesiveness are. The results are shown in Tables 5 and 6.

[Evaluation of Resist Shape]

In the said resolution and adhesiveness evaluation, the obtained resist shape (cross-sectional shape of a resist pattern) was observed using the Hitachi Scanning Electron Microscope S-500A. The results are shown in Tables 5 and 6. In the case where the resist shape is trapezoidal or inverted trapezoid, or there is a pull or crack at the edge of the resist, there is a tendency that short circuit or disconnection tends to occur in the circuit formed by the subsequent etching treatment or plating treatment. Therefore, it is desired that the resist shape is rectangular (rectangular), and there is no edge pulling or cracking of the resist.

In addition, a "crack" means that a crack or a crack generate | occur | produced in the line part (exposure part) of a resist pattern, or the dent and heat insulation generate | occur | produced in the line part with it.

[Evaluation of Peeling Characteristics]

Each photosensitive element was laminated on the said copper clad laminated board (substrate), and it exposed and developed on the conditions shown in Table 4, and produced the test piece (40 mm x 50 mm) in which the cured film was formed on the board | substrate. After leaving this test piece overnight at room temperature (25 degreeC), it peeled on the conditions shown in Table 4. The time from the start of stirring until the cured film is completely peeled off from the substrate was taken as the peeling time. Moreover, the size of the peeling piece after peeling was observed visually, and the following references | standards evaluated. The shorter the peeling time and the smaller the peeled piece size means the better the peeling characteristics. In addition, when the peeling piece size is a sheet form, the case of "L" and the case of 30-40 mm angle smaller than "M" and 30 mm angle is described as "S". The results are shown in Tables 5 and 6.

As is apparent from Tables 5 and 6, the photosensitive resin compositions of Examples 1 to 14 were all excellent in sensitivity, resolution, adhesiveness, resist shape, and peeling properties after curing. On the other hand, the comparative example which does not contain the comparative example 1 and the photopolymerizable compound represented by General formula (1) using the binder polymer which does not have a structural unit based on the (meth) acrylic-acid benzyl ester or the (meth) acrylic-acid benzyl ester derivative In the photosensitive resin composition of 2, any of resolution, adhesiveness, or a resist shape was inferior compared with the thing of an Example.

Industrial availability

The photosensitive resin composition of this invention is applied as a material which forms the resist pattern for manufacturing a printed wiring board. In particular, since the said photosensitive resin composition has all the favorable sensitivity, resolution, adhesiveness, resist shape, and the peeling characteristic after hardening, the printed wiring board which has densified wiring like a high density package board | substrate and a silicon chip rewiring is efficiently and efficiently. It is also suitably used for forming a resist pattern for manufacturing.

One… Photosensitive element, 2... Support film, 3... Photosensitive resin composition layer, 4... Protective film.

Claims (15)

As a photosensitive resin composition containing (A) binder polymer, (B) photopolymerizable compound, and (C) photoinitiator,
The (A) binder polymer has a structural unit based on (meth) acrylic acid, and a structural unit based on (meth) acrylic acid benzyl ester or (meth) acrylic acid benzyl ester derivative,
The photosensitive resin composition in which the said (B) photopolymerizable compound contains the compound represented by following General formula (1).
However,

[In Formula (1), R <^1> , R <^2> and R <^3> represent a hydrogen atom or a methyl group each independently, a, b, and c respectively independently represent the integer of 1-48, and a, b, and c of The total number is 6 ~ 50.] The photosensitive resin composition of Claim 1 in which the said (B) photopolymerizable compound contains a bisphenol-A (meth) acrylate compound further. The photosensitive resin composition of Claim 1 or 2 in which the said (B) photopolymerizable compound further contains the compound which has one ethylenically unsaturated bond. The polyalkylene glycol di (meth) acrylate compound according to any one of claims 1 to 3, wherein the photopolymerizable compound (B) has a (poly) oxyethylene chain and a (poly) oxypropylene chain. It further contains the photosensitive resin composition. The photosensitive resin composition of any one of Claims 1-4 in which the said (C) photoinitiator contains a 2,4,5-triaryl imidazole dimer. The photosensitive resin composition of any one of Claims 1-5 which further contain (D) sensitizing dye. The photosensitive resin composition of any one of Claims 1-6 which further contains (E) amine type compound. The photosensitive resin composition of any one of Claims 1-7 in which the said (A) binder polymer further has a structural unit based on styrene or a styrene derivative. The photosensitive resin composition of any one of Claims 1-8 in which the said (A) binder polymer further has a structural unit based on the (meth) acrylic-acid alkylester. The photosensitive resin composition of any one of Claims 1-9 whose weight average molecular weights of the said (A) binder polymer are 10000-100000. The photosensitive resin composition of any one of Claims 1-10 whose acid value of the said (A) binder polymer is 100-250 mgKOH / g. The photosensitive element provided with the support film and the photosensitive resin composition layer which consists of the photosensitive resin composition of any one of Claims 1-11 formed on this support film. A lamination step of laminating a photosensitive resin composition layer made of the photosensitive resin composition according to any one of claims 1 to 11 on a substrate;
An exposure step of irradiating active light to a predetermined portion of the photosensitive resin composition layer to expose the predetermined portion and to cure it;
The formation method of the resist pattern which has a image development process of forming the resist pattern which consists of hardened | cured material of the photosensitive resin composition on the said board | substrate by removing parts other than the said predetermined part of the said photosensitive resin composition layer from the said board | substrate. The formation method of the resist pattern of Claim 13 whose wavelength of the said actinic light is in the range of 390-420 nm. The manufacturing method of the printed wiring board containing the process of etching or plating the board | substrate with which the resist pattern was formed by the method of Claim 13 or 14.

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