KR20110112473A - Photosensitⅳe resin composition, photosensitⅳe element, method for resist pattern formation, and method for manufacturing printed wiring board - Google Patents

Abstract

[식(Ⅰ)~(Ⅳ) 중, R¹, R³, R⁵ 및 R⁶은 각각 독립적으로 수소원자 또는 메틸기를 나타내고, R² 및 R⁴는 각각 독립적으로 탄소수 1~3의 알킬기, 탄소수 1~3의 알콕시기, OH기 또는 할로겐원자를 나타내고, R⁷은 탄소수 1~6의 알킬기를 나타낸다.]The photosensitive resin composition of this invention contains the binder polymer (A) which has a bivalent group represented by following General formula (I)-(IV), (B) photopolymerizable compound, and (C) photoinitiator.

[In formula (I)-(IV), R <^1> , R <^3> , R <^5> and R <^6> represent a hydrogen atom or a methyl group each independently, R <^2> and R <^4> respectively independently represents a C1-C3 alkyl group and carbon number An alkoxy group, an OH group or a halogen atom of 1 to 3 is represented, and R ⁷ represents an alkyl group of 1 to 6 carbon atoms.]

Description

Method for forming photosensitive resin composition, photosensitive element, resist pattern and manufacturing method of printed wiring board {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE ELEMENT, METHOD FOR RESIST PATTERN FORMATION, AND METHOD FOR MANUFACTURING PRINTED WIRING BOARD}

This invention relates to the photosensitive resin composition, the photosensitive element, 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 layer containing this photosensitive resin composition (henceforth a "photosensitive resin composition layer") are formed on a support film, The photosensitive element (laminate) which has a structure which arrange | positioned the protective film on the photosensitive resin composition layer is used widely.

Conventionally, the printed wiring board is manufactured using the said photosensitive element, for example in the following procedures. That is, first, the photosensitive resin composition layer of the photosensitive element is laminated on a circuit forming substrate such as a copper sheet laminate. At this time, the surface (hereinafter, referred to as the "lower surface" of the photosensitive resin composition layer) on the side opposite to the surface in contact with the supporting film of the photosensitive resin composition layer (hereinafter, "top surface" of the photosensitive resin composition layer) Is in close contact with the surface on which the circuit for forming the circuit is formed. Therefore, when arrange | positioning a protective film on the upper surface of the photosensitive resin composition layer, the operation of this lamination is performed, removing a protective film. In addition, lamination is performed by heat-pressing a photosensitive resin composition layer to the board | substrate for base circuit formation (atmospheric pressure laminating method).

Next, the photosensitive resin composition layer is pattern-exposed through a mask film or the like. At this time, a support film is peeled off at the timing of either before exposure or after exposure. Thereafter, the unexposed portion of the photosensitive resin composition layer is dissolved or dispersed and removed with a developer. Subsequently, an etching process or plating process is performed to form a pattern, and finally, the hardened part is peeled off.

Here, an etching process is a method of peeling a hardening resist after carrying out the etching removal of the metal surface of the board | substrate for circuit formation not coat | covered with the hardening resist formed after image development. On the other hand, the plating treatment is a metal which is coated with the resist by removing the cured resist after performing a plating treatment such as copper and solder on the metal surface of the circuit forming substrate which is not covered by the cured resist formed after development. It is a method of etching a surface.

By the way, as a method of pattern exposure mentioned above, the method of exposing through a photomask using a mercury lamp as a light source conventionally is used. In recent years, as a new exposure technique, a direct drawing exposure method has been proposed in which digital data of a pattern called DLP (Digital Light Processing) is directly drawn on the photosensitive resin composition layer. This direct drawing exposure method is introduced for fabrication of high-density package substrates because the positional arrangement accuracy is better than that of the exposure method via a photomask and a fine pattern is obtained.

In pattern exposure, it is necessary to shorten exposure time as much as possible in order to improve the throughput of production. In the direct drawing exposure method described above, when a composition having the same sensitivity as that of the photosensitive resin composition used in the exposure method via a conventional photomask is used, a large exposure time is generally required. Therefore, it is necessary to raise the illuminance on the exposure apparatus side, or to raise the sensitivity of the photosensitive resin composition.

Moreover, it is important that the photosensitive resin composition is excellent also in the resolution and the peeling characteristic of a resist in addition to the sensitivity mentioned above. If the photosensitive resin composition can provide the resist pattern which is excellent in resolution, it becomes possible to fully reduce the short circuit and disconnection between circuits. In addition, if the photosensitive resin composition can form a resist having excellent peeling characteristics, the resist stripping time is shortened by shortening the peeling time of the resist, and the resist peeling is reduced by reducing the size of the peeling piece of the resist. There are few residues, and the yield of circuit formation improves. In response to these demands, photosensitive resin compositions having excellent sensitivity, resolution, and resist stripping characteristics using specific binder polymers, photopolymerization initiators, and the like have been proposed (see, for example, Patent Documents 1 and 2).

Patent Document 1: Japanese Patent Laid-Open No. 2006-234995

Patent Document 2: Japanese Patent Laid-Open No. 2005-122123

However, the photosensitive resin compositions described in Patent Documents 1 and 2 did not yet have sufficient resolution and resist stripping characteristics.

Then, an object of this invention is to provide the photosensitive resin composition, the photosensitive element, the formation method of a resist pattern, and the manufacturing method of a printed wiring board which are fully effective in the improvement of the resolution and resist peeling characteristic.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors earnestly examined about the composition of the binder polymer. As a result, by using the binder polymer of a specific structure, it discovered that the photosensitive resin composition which is fully effective in the improvement of the resolution and the resist peeling characteristic was obtained, and came to complete this invention.

That is, this invention is (A) the divalent group represented by the following general formula (I), the divalent group represented by the following general formula (II), the divalent group represented by the following general formula (III), and the following general It is a photosensitive resin composition containing the binder polymer which has a bivalent group represented by Formula (IV), (B) photopolymerizable compound, and (C) photoinitiator.

[Formula 1]

[Formula 2]

(3)

[Formula 4]

In formulas (I), (II), (III) and (IV), R ¹ , R ³ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a methyl group, and R ² And R ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an OH group, or a halogen atom, R ⁷ represents an alkyl group having 1 to 6 carbon atoms, and m or n each independently When the integer of 0-5 is shown and m or n is 2-5, some R <^2> or R <^4> may mutually be same or different.

The present inventors think that the photosensitive resin composition of this invention fully acquires the effect of the above-mentioned resolution and the resist peeling characteristic by using the binder polymer of the specific structure like the said (A) component. Moreover, the photosensitive resin composition of this invention has the outstanding sensitivity by containing said (A)-(C) component.

In the photosensitive resin composition of the present invention, the (A) binder polymer is represented by 10 to 60 parts by weight and a general formula (II) of a divalent group represented by the general formula (I) to 100 parts by weight of the total amount. 10-60 weight part of divalent groups, 20-50 weight part of divalent groups represented by general formula (III), and 1 weight part or more and less than 15 weight part of divalent groups represented by general formula (IV). This further improves the resolution and resist stripping characteristics of the photosensitive resin composition.

Moreover, in the photosensitive resin composition of this invention, it is preferable that (C) photoinitiator has a hexaaryl biimidazole compound. Thereby, the sensitivity of the photosensitive resin composition and the adhesiveness of a resist improve.

Moreover, it is preferable that the photosensitive resin composition of this invention contains (D) dark dye further. Thereby, when exposing with the light which has a peak in a specific wavelength range, it can make maximum absorption near the specific wavelength range, and the sensitivity of the photosensitive resin composition becomes high.

Moreover, it is preferable that the photosensitive resin composition of this invention contains (E) amine compound further. As a result, the sensitivity of the photosensitive resin composition is further increased.

Moreover, this invention is a photosensitive element provided with a support film and the photosensitive resin composition layer containing the said photosensitive resin composition formed on the said support film. According to this support film, since the photosensitive resin composition layer containing the said photosensitive resin composition is provided, even if it forms a resist pattern by the direct drawing exposure method, it can implement at sufficient resolution. Moreover, it is also effective enough to improve the peeling characteristic of a resist.

Moreover, this invention is the lamination process of laminating | stacking the photosensitive resin composition layer containing the said photosensitive resin composition on the circuit formation board | substrate, and the exposure process which irradiates actinic light to the predetermined part of the photosensitive resin composition layer, and photocures an exposure part. And a developing step of removing a portion other than the exposed portion of the photosensitive resin composition layer from the circuit forming substrate on which the photosensitive resin composition layer is laminated. According to this resist pattern forming method, since the resist pattern is formed using the photosensitive resin composition layer containing the photosensitive resin composition, a resist pattern having a sufficient resolution can be formed even by a direct drawing exposure method with a short exposure time. have. Moreover, it is also effective enough to improve the peeling characteristic of a resist.

Moreover, this invention is the manufacturing method of the printed wiring board which has the process of forming a conductive pattern by etching or plating the circuit formation substrate in which the resist pattern was formed by the said resist pattern formation method. According to the manufacturing method of this printed wiring board, since the circuit formation board | substrate with which the resist pattern was formed by the said resist pattern formation method is used, a high density wiring can be formed and the disconnection and a short circuit are fully suppressed. Can be prepared.

According to the present invention, it is possible to provide a photosensitive resin composition, a photosensitive element, a method of forming a resist pattern, and a method of manufacturing a printed wiring board, which are sufficiently effective in improving resolution and resist stripping characteristics.

1
It is a schematic cross section which shows one preferable embodiment of the photosensitive element of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described in detail. In addition, in this invention, (meth) acrylic acid represents acrylic acid or methacrylic acid, (meth) acrylate means an acrylate or a corresponding methacrylate, and a (meth) acryloyl group is an acryloyl group or It means a methacryloyl group.

The photosensitive resin composition of this invention is (A) the bivalent group represented by the said General formula (I) (henceforth a "structural unit"), the divalent group represented by the said General formula (II), and the said general The binder polymer, (B) photopolymerizable compound, and (C) photoinitiator which have a bivalent group represented by Formula (III) and a bivalent group represented by the said General formula (IV) are contained.

First, the binder polymer which is (A) component is demonstrated.

(A) A binder polymer represents R <^1> a hydrogen atom or a methyl group in said general formula (I), R <^2> represents a C1-C3 alkyl group, a C1-C3 alkoxy group, an OH group, or a halogen atom and m represents the integer of 0-5. Styrene or a styrene derivative is mentioned as a polymerizable monomer which gives the structural unit represented by general formula (I). In addition, in this invention, a "styrene derivative" means what the hydrogen atom in styrene substituted by the substituent (organic groups, such as alkyl groups, halogen atoms, etc.). As a styrene derivative, (alpha) -methylstyrene etc. are mentioned, for example.

In addition, in said general formula (II), R <^3> represents a hydrogen atom or a methyl group, R <^4> represents a C1-C3 alkyl group, a C1-C3 alkoxy group, an OH group, or a halogen atom, m is 0- The integer of 5 is shown. As a polymerizable monomer which gives the structural unit represented by general formula (II), (meth) acrylic-acid benzyl or a (meth) acrylic-acid benzyl derivative is mentioned. As (meth) acrylic-acid benzyl derivative, (meth) acrylic-acid 4-methylbenzyl etc. are mentioned, for example.

In addition, in said general formula (III), R <^5> represents a hydrogen atom or a methyl group. (Meth) acrylic acid is mentioned as a polymerizable monomer which gives the structural unit represented by general formula (III).

In addition, in said general formula (IV), R <^6> represents a hydrogen atom or a methyl group each independently, R <^7> represents a C1-C6 alkyl group, and m or n respectively independently represents the integer of C5-C5 . From a viewpoint that the peeling time can be shortened and the resolution can be improved, R ⁷ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 carbon atoms (methyl group). (Meth) acrylic-acid alkylester is mentioned as a polymerizable monomer which gives the structural unit represented by general formula (IV).

As (meth) acrylic-acid alkylester, the compound etc. which are represented by following General formula (V) are mentioned, for example.

CH ₂ = C (R ⁸ ) -COOR ⁹ (V)

Here, in said general formula (V), R <^8> represents a hydrogen atom or a methyl group, and R <^9> represents a C1-C6 alkyl group. Moreover, as a C1-C6 alkyl group represented by R <^9> , a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and these structural isomers are mentioned, for example. As a polymerizable monomer represented by the said General formula (V), (meth) acrylic-acid methyl ester, (meth) acrylic-acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic-acid butyl ester, (meth) acrylic acid, for example Pentyl ester, (meth) acrylic acid hexyl ester, etc. are mentioned. These polymerizable monomers are used individually or in combination of 2 or more types.

In the binder polymer which is (A) component, it is preferable that the content rate of the structural unit represented by the said General formula (I) is 10-60 weight part with respect to 100 weight part of total amounts of (A) component, and it is 15- It is more preferable that it is 55 weight part, It is more preferable that it is 20-50 weight part, It is especially preferable that it is 20-40 weight part. Thereby, the adhesiveness with respect to the board | substrate for circuit formation of the photosensitive resin composition layer containing a photosensitive resin composition, and resist peeling characteristic can all be made favorable.

Moreover, it is preferable that it is 10-60 weight part with respect to 100 weight part of total amounts of (A) component, and, as for the content rate of the structural unit represented by the said General formula (II), it is more preferable that it is 15-55 weight part, 20 It is more preferable that it is -50 weight part, and it is especially preferable that it is 25-45 weight part. Thereby, the adhesiveness with respect to the board | substrate for circuit formation of the photosensitive resin composition layer containing a photosensitive resin composition, and resist peeling characteristic can all be made favorable.

Moreover, it is preferable that it is 10-60 weight part with respect to 100 weight part of total amounts of (A) component, and, as for the content rate of the structural unit represented by the said General formula (III), it is more preferable that it is 15-50 weight part, 20 It is more preferable that it is -40 weight part, and it is especially preferable that it is 25-35 weight part. Thereby, both resist peeling characteristic and developability can be made favorable.

Moreover, it is preferable that it is 1 weight part or more and less than 15 weight part with respect to 100 weight part of total amounts of (A) component, and, as for the content rate of the structural unit represented by the said General formula (IV), it is more preferable that it is 2-13 weight part. It is more preferable that it is 4-12 weight part, and it is especially preferable that it is 5-10 weight part. Thereby, the adhesiveness with respect to the board | substrate for circuit formation of the photosensitive resin composition layer containing a photosensitive resin composition, and resist peeling characteristic can all be made favorable.

Moreover, when the content rate of the structural unit represented by the said General formula (I) and the structural unit represented by the said General formula (II) in the binder polymer which is (A) component is less than 10 weight part, respectively, There exists a tendency to become inferior, and when it exceeds 60 weight part, respectively, a peeling piece becomes large and there exists a tendency for peeling time to become long. Moreover, when the content rate of the structural unit represented by the said General formula (III) is less than 10 weight part, alkali solubility is inferior, peeling piece becomes large, peeling time tends to be long, and when it exceeds 60 weight part, There is a tendency for the sex to decrease. Moreover, when the content rate of the structural unit represented by the said General formula (IV) is less than 1 weight part, there exists a tendency for peelability to fall, and when it is 15 weight part or more, resolution tends to fall.

When preparing the photosensitive resin composition using this binder polymer, one type of binder polymer may be used independently, and two or more types of binder polymers may be used in combination arbitrarily. As a binder polymer in the case of using in combination of 2 or more types, for example, two or more types of binder polymers which consist of a different copolymerization component (a different repeat unit is included as a structural component), two or more types of binder polymers of a different 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.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the (A) binder polymer can be measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene). According to this measuring method, it is preferable that Mw of a binder polymer is 5000-150000, It is more preferable that it is 10000-100000, It is especially preferable that it is 20000-50000. If Mw is less than 5000, the developing solution resistance tends to be lowered, and if it exceeds 150000, the developing time tends to be long.

Moreover, 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. When dispersion degree exceeds 3.0, there exists a tendency for adhesiveness and resolution to fall.

As the binder polymer (A), for example, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin or the like can be used in combination. In addition, these resin is used individually or in combination of 2 or more types.

The binder polymer of this invention can be manufactured, for example by radically polymerizing a polymerizable monomer according to a conventional method.

The binder polymer (A) described above may include structural units other than the structural units represented by the general formulas (I) to (IV). It is most preferable that the above-mentioned (A) binder polymer has only the structural units represented by the said general formula (I)-(IV), but it does not impair the objective of this invention, You may have about 1-10 weight part with respect to the total amount of (A) component. In this case, as a polymerizable monomer which gives structural units other than the structural unit represented by the said General Formula (I)-(IV), for example, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester, 2-hydroxyethyl, 2-hydroxypropyl, 3 -Esters of vinyl alcohols such as acrylamides such as hydroxypropyl, 4-hydroxybutyl and diacetone acrylamide, acrylonitrile and vinyl-n-butyl ether, (meth) acrylic acid tetrahydrofurfuryl ester, and (meth Dimethyl dimethylaminoethyl acrylate, diethylaminoethyl ester (meth) acrylate, glycidyl ester (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3- Tetrafluoro Lofil (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, male And maleic acid monoesters such as acid anhydride, monomethyl maleate, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyano cinnamic acid, itaconic acid, crotonic acid and propiolic acid. These monomers are used individually or in combination of 2 or more types.

It is preferable that the (A) binder polymer in this invention consists of 1 type, or 2 or more types of the polymer which has a carboxyl group from a developable viewpoint at the time of performing alkali image development using alkaline solution. Such a binder polymer (A) can be manufactured by radically polymerizing the polymerizable monomer which has a carboxyl group other than (meth) acrylic acid, and the other polymerizable monomer by a conventional method, for example.

It is preferable that the acid value of (A) binder polymer is 80-250 mgKOH / g, It is more preferable that it is 100-220 mgKOH / g, It is especially preferable that it is 150-210 mgKOH / g. If the acid value is less than 80 mgKOH / g, the developing time tends to be long, and if it exceeds 250 mgKOH / g, the developing solution resistance of the photocured resist tends to decrease. In addition, when performing solvent image development as a image development process, it is preferable to prepare the polymerizable monomer which has a carboxyl group in small quantities.

In addition, the (A) binder polymer may have a characteristic group which has photosensitivity in the molecule as needed.

As a compounding quantity of the binder polymer of (A) component, it is preferable that it is 30-70 weight part with respect to 100 weight part of total amounts of (A) component and (B) component, It is more preferable that it is 35-65 weight part, 40-60 Particularly preferred is parts by weight. If this blending amount is less than 30 parts by weight, a good shape tends not to be obtained, and if it exceeds 70 parts by weight, a good sensitivity and resolution tend not to be obtained. The binder polymer which is (A) component is used individually by 1 type or in combination of 2 or more types.

Next, the photopolymerizable compound which is (B) component is demonstrated.

As a photopolymerizable compound which is (B) component, For example, (alpha), (beta) to the compound obtained by making (alpha), (beta)-unsaturated carboxylic acid react with a polyhydric alcohol, a bisphenol-A di (meth) acrylate compound, and a glycidyl group containing compound Urethane monomers, such as a compound obtained by making a unsaturated carboxylic acid react, the (meth) acrylate compound which has a urethane bond in a molecule | numerator, nonylphenoxy polyethyleneoxyacrylate (it is also called "nonylphenoxy polyethyleneglycol acrylate"), and phthalic acid type A compound, (meth) acrylic-acid alkylester, etc. are mentioned. These compounds are used individually or in combination of 2 or more types.

As a compound obtained by making (alpha), (beta)-unsaturated carboxylic acid react with the said 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, PO modified trimetholpropane tree ( Meta) acrylate, EO, PO modified trimetholpropane tri (meth) acrylate, tetrametholmethane tri (meth) acrylate, tetrametholmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acryl Elate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. These compounds are used individually or in combination of 2 or more types. Here, "EO" represents ethylene oxide and shows that the EO modified compound has a block structure of an ethylene oxide group. In addition, "PO" represents a propylene oxide and shows that the PO modified compound has a block structure of a propylene oxide group.

As said bisphenol A type | system | group di (meth) acrylate compound, 2, 2-bis (4- ((meth) acryloxy polyethoxy) phenyl) propane, 2, 2-bis (4- ((meth) ) Acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxy Polypropoxy) phenyl) propane etc. are mentioned. As said 2, 2-bis (4- ((meth) acryloxy polyethoxy) phenyl) propane, 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) acrylic Oxyheptaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynanoethoxy) 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) acrylic Oxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexadecae Methoxy) phenyl) propane and the like.

2, 2-bis (4- (methacryloxy pentaethoxy) phenyl) propane is BPE-500 (made by Shin-Nakamura Chemical Co., Ltd.) or FA-321M (made by Hitachi Chemical Co., Ltd., brand name) ), And 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (manufactured by Shinnakamura Chemical Co., Ltd., trade name). Do. It is preferable that it is 4-20, and, as for the number of the ethylene oxide groups in 1 molecule of 2, 2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, it is more preferable that it is 8-15. These compounds are used individually or in combination of 2 or more types.

As a (meth) acrylate compound which has a urethane bond in a molecule | numerator, for example, the (meth) acrylic monomer and diisocyanate compound which have an OH group in (beta) position (isophorone diisocyanate, 2, 6-toluene diisocyanate, 2, 4) Addition reaction 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. As EO modified urethane di (meth) acrylate, UA-11 (made by Shin-Nakamura Chemical Co., Ltd., brand name) is mentioned, for example. Moreover, as said EO, PO modified urethane di (meth) acrylate, UA-13 (made by Shin-Nakamura Chemical Co., Ltd., brand name) is mentioned, for example. These compounds are used individually or in combination of 2 or more types.

As nonylphenoxy polyethylene oxyacrylate, nonylphenoxy tetra ethylene oxyacrylate, nonyl phenoxy pentaethylene oxy acrylate, nonyl phenoxy hexa ethylene oxy acrylate, nonyl phenoxy hepta ethylene oxy acrylate, nonyl, for example. Phenoxy octaethylene oxyacrylate, nonyl phenoxy nona ethylene oxy acrylate, nonyl phenoxy deca ethylene oxy acrylate, nonyl phenoxy undeca ethylene oxy acrylate. As nonyl phenoxy octaethylene oxyacrylate, M-114 (made by Dong-A Synthetic Co., Ltd., brand name) is mentioned, for example. These compounds are used individually or in combination of 2 or more types.

Examples of the phthalic acid compound include β-chloro-β-hydroxypropyl-β '-(meth) acryloyloxyethyl-o-phthalate and β-hydroxyalkyl-β'-(meth) acryl. Iloxyalkyl-o-phthalate etc. are mentioned. These compounds are used individually or in combination of 2 or more types.

In addition, the component (B) of the present invention contains a polyalkylene glycol di (meth) acrylate having both an ethylene glycol chain and a propylene glycol chain in a molecule from the viewpoint of improving the flexibility of the cured film. desirable. The (meth) acrylate is not particularly limited as long as it has both an ethylene glycol chain and a propylene glycol chain (n-propylene glycol chain or isopropylene glycol chain) as the alkylene glycol chain in the molecule. Moreover, this (meth) acrylate is a C4-C6 alkylene glycol chain which is n-butylene glycol chain, isobutylene glycol chain, n-pentylene glycol chain, hexylene glycol chain, these structural isomers, etc. You may have more.

In the case where there are a plurality of ethylene glycol chains and propylene glycol chains, a plurality of ethylene glycol chains and propylene glycol chains may be present continuously in block form or randomly. In the isopropylene glycol 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.

Among these (B) components, the polyalkylene glycol di (meth) acrylate which has at least 1 polymerizable ethylenically unsaturated bond and has both an ethylene glycol chain and a propylene glycol chain in a molecule | numerator is the following general Formula (VI):

[Chemical Formula 5]

A compound represented by the following general formula (VII):

[Formula 6]

Compound represented by the following, and the following general formula (i):

[Formula 7]

The compound etc. which are represented by are mentioned. Here, in formula (VI), formula (VII), and formula (VII), R <^10> , R <^11> , R <^12> , R <^13> , R <^14> and R <^15> are respectively independently a hydrogen atom or a C1-C3 alkyl group. EO represents an ethylene glycol chain, PO represents a propylene glycol chain, and m ¹ to m ⁴ and n ¹ to n ⁴ each independently represent an integer of 1 to 30. These compounds are used individually or in combination of 2 or more types.

As a C1-C3 alkyl group in the said General Formula (VI)-(i), a methyl group, an ethyl group, n-propyl group, i-propyl group is mentioned, for example.

In addition, the total number (m ¹ + m ² , m ³ and m ⁴ ) of the repeating number of ethylene glycol chains in the general formulas (VI) to ( ⁱⁱⁱ ) is an integer of 1 to 30, and an integer of 1 to 10. It is preferable, it is more preferable that it is an integer of 4-9, and it is especially preferable that it is an integer of 5-8. If the number of repetitions exceeds 30, the tent reliability and resist shape tend to be deteriorated.

The total number (n ¹ , n ² + n ³ and n ⁴ ) of the repeating number of the propylene glycol chains in the general formulas (VI) to ( ⁱⁱⁱ ) is an integer of 1 to 30, and an integer of 5 to 20. It is preferable, it is more preferable that it is an integer of 8-16, and it is especially preferable that it is an integer of 10-14. When this number of repetitions exceeds 30, the resolution deteriorates and sludge tends to occur.

The formula Specific examples of the compounds represented by (Ⅵ), for example, R ¹⁰ = R ¹¹ = vinyl compound methyl ^{group, m 1 + m 2 = 4} ( mean value), n ¹ = 12 (average value) (Hitachi Mars Industrial Co., Ltd. brand name: FA-023M) etc. are mentioned. Moreover, as a specific example of a compound represented by the said general formula (i), For example, a vinyl compound whose R < ¹² > R <^13> = methyl group, m < ³ > (6) (average value), n <^2> + n < ³ > (12) (average value) Hitachi Chemical Co., Ltd. make, brand name: FA-024M) etc. are mentioned. Further, the above-mentioned formula (Ⅷ) Specific examples of the compounds represented by, for example, R ¹⁴ = R ¹⁵ = hydrogen atom, m ⁴ = 1 (mean value), n ⁴ = 9 (average value) of the vinyl compounds (Shin-Nakamura Chemical industry company make, sample name: NK ester HEMA-9P), etc. are mentioned. These compounds are used individually or in combination of 2 or more types.

As a compounding quantity of the photopolymerizable compound of (B) component, it is preferable that it is 30-70 weight part with respect to 100 weight part of total amounts of (A) component and (B) component, It is more preferable that it is 35-65 weight part, 40-60 Particularly preferred is parts by weight. When this compounding quantity is less than 30 weight part, there exists a tendency for favorable sensitivity and resolution not to be obtained, and when it exceeds 70 weight part, there exists a tendency for a favorable shape to not be obtained.

The photopolymerizable compound which is (B) component is used individually by 1 type or in combination of 2 or more types. It is preferable that this photopolymerizable compound contains the bisphenol-A (meth) acrylate compound or the (meth) acrylate compound which has a urethane bond in a molecule | numerator from a viewpoint of improving plating resistance and adhesiveness. Moreover, it is preferable to contain a bisphenol-A (meth) acrylate compound from a viewpoint of improving a sensitivity and a resolution.

Moreover, it is preferable that the photopolymerizable compound which is (B) component contains the photopolymerizable unsaturated compound which has one polymerizable ethylenically unsaturated bond in a molecule | numerator from a viewpoint of reducing the size of the peeling piece of a resist, and shortening peeling time. It is more preferable to use a photopolymerizable unsaturated compound having one polymerizable ethylenically unsaturated bond in a molecule and a photopolymerizable unsaturated compound having two or more polymerizable ethylenically unsaturated bonds in a molecule. In this case, for example, as the photopolymerizable unsaturated compound having one polymerizable ethylenically unsaturated bond in the molecule, phenoxy polyethyleneoxy (meth) acrylate, phenoxy polyethyleneoxy-polypropyleneoxy (meth) acrylate, octyl Phenoxyhexaethyleneoxy (meth) acrylate, octylphenoxyheptaethyleneoxy (meth) acrylate, octylphenoxyoctaethyleneoxy (meth) acrylate, octylphenoxy nonaethyleneoxy (meth) acrylate, octylphenoxy Decaethyleneoxy (meth) acrylate, nonylphenoxypolyethyleneoxy (meth) acrylate, nonylphenoxypolyethyleneoxy-polypropyleneoxy (meth) acrylate, the phthalic acid derivative which has a (meth) acryl group, etc. are mentioned. Moreover, as a photopolymerizable unsaturated compound which has two or more polymerizable ethylenically unsaturated bonds in a molecule | numerator, 1, 6- hexanediol di (meth) acrylate, 1, 4- cyclohexanediol di (meth) acrylate, an ethylene group Polyethylene glycol di (meth) acrylate with the number of 2-14, Polypropylene glycol di (meth) acrylate with the number of propylene groups 2-14, The polyethylene polypropylene glycol di of said general formula (VI)-(v) (Meth) acrylate, bisphenol-A di (meth) acrylate, di (meth) acrylate which has a urethane bond in a molecule | numerator, bis (acryloxyethyl) hydroxyethyl isocyanurate, bisphenol A diglycidyl ether Di (meth) acrylate, the (meth) acrylic acid addition product of phthalic acid glycidyl ester, etc. are mentioned.

In addition, from the viewpoint of improving the resolution, peeling time and exposure induction in a balanced manner, one kind of photopolymerizable unsaturated compound having one polymerizable ethylenically unsaturated bond in the molecule and two or more polymerizable ethylenically unsaturated bonds in the molecule are provided. It is especially preferable to use the photopolymerizable unsaturated compound which has a combination of two types. In this case, as a photopolymerizable unsaturated compound which has one polymerizable ethylenically unsaturated bond in a molecule | numerator, for example, phenoxy polyethyleneoxy (meth) acrylate, nonylphenoxy polyethyleneoxy (meth) acrylate, (meth) acryl Any one kind of phthalic acid derivative having a group can be used. Moreover, as a photopolymerizable unsaturated compound which has a 2 or more polymerizable ethylenically unsaturated bond in a molecule | numerator, For example, the polyethylene polypropylene glycol di (meth) acrylate of said general formula (VI)-(v), EO modification It is possible to use a combination of at least one compound selected from urethane di (meth) acrylate, EO and PO-modified urethane di (meth) acrylate, and a bisphenol A-based di (meth) acrylate compound.

Next, the photoinitiator which is (C) component is demonstrated.

The photoinitiator which is (C) component is 4,4'-bis (diethylamino) benzophenone, benzophenone, 2-benzyl-2- dimethylamino-1- (4-morpholinophenyl)-, for example. Aromatic ketones such as butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, quinones such as alkylanthraquinones, and benzoin such as benzoinalkyl ethers Benzoin compounds such as inether compounds, benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, and 2- (o- Chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) 2,4,5-triarylimidazole dimers, such as -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, And acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane.

In the above-mentioned 2,4,5-triarylimidazole dimer, the substituents of the aryl groups of the two 2,4,5-triarylimidazoles may be the same and give a symmetrical compound, and asymmetrically different. You may give a compound. In addition, it is preferable to use the hexaaryl biimidazole compound which is a 2,4,5-triaryl imidazole dimer from a viewpoint of adhesiveness and a sensitivity in a photoinitiator. These photoinitiators are used individually or in combination of 2 or more types.

Moreover, it is preferable that it is 0.1-10 weight part with respect to 100 weight part of total amounts of (A) component and (B) component, and, as for the compounding quantity of the photoinitiator which is (C) component, it is more preferable that it is 2-6 weight part, 3.5- It is especially preferable that it is 5 weight part. When this compounding quantity is less than 0.1 weight part, a favorable sensitivity and resolution tend to become difficult to be acquired, and when it exceeds 10 weight part, there exists a tendency which the desired good pattern resist pattern cannot be obtained. The photoinitiator which is (C) component is used individually by 1 type or in combination of 2 or more types.

The photosensitive resin composition of this invention is added to the above-mentioned (A)-(C) component, and it is preferable to contain (D) dark dye and / or (E) amine type compound.

The sensitizing dye which is (D) component in this invention can utilize the absorption wavelength of the actinic light used for exposure effectively, and the compound whose maximum absorption wavelength is 370-420 nm is preferable. In this invention, by using such a sensitizing dye, it becomes possible to have a sufficiently high sensitivity with respect to the exposure light of the direct drawing exposure method. When the maximum absorption wavelength of the sensitizing dye is less than 370 nm, the sensitivity to direct writing exposure light tends to decrease, and when it exceeds 420 nm, the stability tends to decrease even under a yellow light environment.

Examples of the sensitizing dyes include pyrazolines, anthracenes, coumarins, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stilbenes, triazines, thiophenes, and naphthales. And imides. It is preferable that a sensitizing dye contains anthracene from a viewpoint which can improve the resolution, adhesiveness, and a sensitivity. Moreover, it is preferable that the compounding quantity of a sensitizing dye is 0.01-10 weight part with respect to 100 weight part of total amounts of (A) component and (B) component, It is more preferable that it is 0.05-5 weight part, Especially it is 0.1-2 weight part desirable. If the amount is less than 0.01 part by weight, good sensitivity and resolution tend not to be obtained, and if it exceeds 10 parts by weight, there is a tendency that a resist pattern having a desired good shape cannot be obtained. The sensitizing dye which is (D) component is used individually by 1 type or in combination of 2 or more types.

As an amine compound which is (E) component, if it has an amino group in a molecule | numerator which can raise the sensitivity of the photosensitive resin composition, it will not specifically limit. As the specific example, bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, leuco crystal violet, etc. are mentioned, for example. It is preferable that the compounding quantity of an amine compound is 0.01-10 weight part with respect to 100 weight part of total amounts of (A) component and (B) component, It is more preferable that it is 0.05-5 weight part, It is especially preferable that it is 0.1-2 weight part Do. When this compounding quantity is less than 0.01 weight part, there exists a tendency for a favorable sensitivity not to be obtained, and when it exceeds 10 weight part, it exists in the tendency for (E) component to precipitate easily as a foreign material after film formation. The amine compound which is (E) component is used individually by 1 type or in combination of 2 or more types.

In the photosensitive resin composition of the present invention, if necessary, a photopolymerizable compound (such as an oxetane compound) having at least one cyclic ether group capable of cationic polymerization, a cationic polymerization initiator, dyes such as malachite green, tribromophenyl sulfone, Photochromic agents such as leucocrystal violet, exothermic color inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion imparting agents, leveling agents, peeling accelerators, antioxidants, flavoring agents, imaging agents, heat About 0.01-20 weight part of crosslinking agents etc. can be contained with respect to 100 weight part of total amounts of (A) component and (B) component, respectively. These are used individually or in combination of 2 or more types.

Further, the photosensitive resin composition of the present invention is a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether or the like You may melt | dissolve in a mixed solvent and make it the solution of about 30 to 60 weight% of solid content. This solution can be used as a coating liquid for forming the photosensitive resin composition layer of the photosensitive element.

In addition, the coating liquid is used for forming the photosensitive resin composition layer of the photosensitive element, and, for example, is coated with a liquid resist on the surface of a metal plate and dried to coat a protective film after drying. You may use it. As a material of a metal plate, iron-type alloys, such as copper, a copper-type alloy, nickel, chromium, iron, stainless, etc., Preferably copper, a copper-type alloy, an iron-type alloy etc. are mentioned.

Next, the photosensitive element of this invention is demonstrated. 1 is a schematic sectional view showing a preferred embodiment of the photosensitive element of the present invention. The photosensitive element 1 shown in FIG. 1 has the support film 2, the photosensitive resin composition layer 3 containing the said photosensitive resin composition formed on the support film 2, and the photosensitive resin composition layer 3 phase. It consists of the protective film 4 laminated | stacked on.

As the support film 2, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used. As a commercial thing, Polypropylene film, such as Arji MA-410 made by Oji Paper Co., Ltd., E-200C (above, brand name), Shin-Etsu Film Co., Ltd., and PS series made by Teijin Polyethylene terephthalate films, such as (for example, brand name: PS-25), etc. are mentioned, It is not limited to this.

Moreover, it is preferable that the support film 2 is 1-100 micrometers in thickness, and it is more preferable that it is 5-25 micrometers. When this thickness is less than 1 micrometer, there exists a tendency for a support film to tear easily at the time of peeling of the support film before image development, and when it exceeds 100 micrometers, there exists a tendency for the resolution to fall. In addition, you may use the support film 2 laminated | stacked on both surfaces of the photosensitive resin composition layer one as a support body of the photosensitive resin composition layer, and the other as a protective film of the photosensitive resin composition.

After the photosensitive resin composition layer 3 dissolves the said photosensitive resin composition in the above-mentioned solvent and turns it into the solution (coating liquid) of about 30 to 60 weight% of solid content, this solution is apply | coated on the support film 2 It is preferable to form by drying. Application | coating can be performed by the well-known method using a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, a bar coater, etc., for example. Drying can be performed at 70-150 degreeC and about 5 to 30 minutes. In addition, since the amount of the residual organic solvent in the photosensitive resin composition prevents the diffusion of the organic solvent in a later process, it is preferable to set it as 2 weight% or less.

Moreover, although the thickness of the photosensitive resin composition layer 3 changes with the use of the photosensitive element, it is preferable that it is 1-100 micrometers in thickness after drying, and it is more preferable that it is 1-50 micrometers. When this thickness is less than 1 micrometer, there exists a tendency for industrial coating difficulty, and when it exceeds 100 micrometers, the effect of this invention becomes small and there exists a tendency for adhesive force and resolution to fall.

Moreover, it is preferable that the transmittance | permeability with respect to the light of wavelength 405nm is 5 to 75%, as for the photosensitive resin composition layer 3, it is more preferable that it is 7 to 60%, and it is especially preferable that it is 10 to 40%. If the transmittance is less than 5%, the adhesion tends to be inferior, and if it exceeds 75%, the resolution tends to be inferior. The said transmittance | permeability can be measured with a UV spectrometer, As said UV spectrometer, the Hitachi Corporation make 228A type W beam spectrophotometer (brand name) etc. are mentioned.

As for the protective film 4, it is preferable that the adhesive force between the photosensitive resin composition layer 3 and the protective film 4 is smaller than the adhesive force between the photosensitive resin composition layer 3 and the support film 2, and also low-fish Children's films are preferred. In addition, with a "fish eye", when a material is heat-melted and a film is manufactured by kneading, extrusion, biaxial stretching, a casting method, etc., the foreign material, undissolved matter, oxidative deterioration, etc. of a material are taken in in a film.

As the protective film 4, the polymer film which has heat resistance and solvent resistance, such as polyethylene terephthalate, polypropylene, polyethylene, polyester, can be used, for example. As a commercial thing, Polypropylene film, such as Arji MA-410 made by Oji Paper Co., Ltd., E-200C (above, brand name), Shin-Etsu Film Co., Ltd., and PS series (made by Teijin Co., Ltd.) For example, although polyethylene terephthalate films, such as a brand name: PS-25), etc. are mentioned, it is not limited to this.

It is preferable that thickness of the protective film 4 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, there exists a tendency for a protective film to tear at the time of lamination, and when it exceeds 100 micrometers, there exists a tendency for a low cost.

Moreover, the photosensitive element 1 of this invention may further have intermediate | middle layers, such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer. In addition, the obtained photosensitive element 1 can be wound up and stored in a roll form on a sheet form or a core. Moreover, it is preferable at this time to wind up so that the support film 1 may become outermost. In the end face of the said roll-shaped photosensitive element roll, it is preferable to provide a cross section separator from a standpoint of end surface protection, and it is preferable to install a moisture proof cross section separator from a standpoint of inner edge fusion. Moreover, as a packing method, it is preferable to wrap in a black sheet with few moisture permeability, and to wrap. Examples of the core include plastics such as polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl chloride resins, and ABS resins (acrylonitrile-butadiene-styrene copolymers).

Next, the formation method of the resist pattern of this invention is demonstrated.

The method of forming a resist pattern of the present invention includes a lamination step of laminating a photosensitive resin composition layer containing the photosensitive resin composition on a circuit forming substrate, and irradiating active light to a predetermined portion of the photosensitive resin composition layer to expose the exposed portion. It includes at least a photocurable exposure step and a developing step of removing the photosensitive resin composition in portions other than the exposed portion from the circuit forming substrate. In addition, a "circuit formation board | substrate" means the board | substrate provided with the insulating layer and the conductor layer formed on the insulating layer. In addition, the circuit forming substrate may be multilayered, and wiring may be formed therein, or may have a small diameter through hole.

The following method is mentioned as a lamination | stacking method of the photosensitive resin composition layer on the circuit-forming board | substrate in a lamination process. First, a protective film is peeled off gradually from the photosensitive resin composition layer, and the part of the surface of the photosensitive resin composition layer which is gradually exposed at the same time is made to adhere to the surface which forms the circuit of the circuit formation substrate. The photosensitive resin composition layer is laminated by pressing the photosensitive resin composition layer onto the circuit forming substrate while heating the photosensitive resin composition layer. In addition, it is preferable to laminate | stack this operation | work under reduced pressure from the viewpoint of adhesiveness and followability improvement. It is preferable to heat the photosensitive resin composition layer and / or the board | substrate for circuit formation at 70-130 degreeC, and, as for the lamination | stacking of the photosensitive element, it is preferable to make a crimping pressure about 0.1-1.0 MPa (about 1-10 kgf / cm <2>). However, these conditions are not particularly limited. In addition, when the photosensitive resin composition layer is heated at 70 to 130 ° C as described above, it is not necessary to preheat the circuit forming substrate in advance, but in order to further improve the lamination property, the preheating treatment of the circuit forming substrate is performed. It may be.

As a method of forming the exposure part in an exposure process, the method (mask exposure method) which irradiates an actinic light on an image through the negative or positive mask pattern called artwork is mentioned. At this time, when the support film present on the photosensitive resin composition layer transmits active light, the active light can be irradiated through the support film. When the support film is light-shielding, the photosensitive resin composition is removed after removing the support film. Irradiate actinic light onto the layer. Moreover, you may employ | adopt the method of irradiating an active light image to an image by direct drawing exposure methods, such as a laser direct drawing exposure method and a DLP (Digital Light Processing) exposure method.

As a light source of active light, a well-known light source, for example, carbon arc lamp, mercury vapor arc lamp, high pressure mercury lamp, xenon lamp, gas laser such as argon laser, solid laser such as YAG laser, ultraviolet light such as semiconductor laser, visible light Effectively radiating and the like is used.

As a method of removing the portions other than the exposed portion in the developing step, first, when the supporting film is present on the photosensitive resin composition layer, the supporting film is removed, and thereafter, the furnace is developed by wet development, dry development, or the like. The method of removing and developing parts other than a light part is mentioned. As a result, a resist pattern is formed.

For example, in the case of wet development, a developer corresponding to photosensitive resin compositions such as an alkaline aqueous solution, an aqueous developer, an organic solvent developer, and the like are used, for example, a dip method, a battle method, a spray method, a shaking method, and brushing. And development by known methods such as scraping. As the developing method, a high pressure spray method is most suitable for improving resolution. Moreover, you may use together 2 or more types of image development methods as needed.

As a developing solution, the alkaline aqueous solution etc. which are safe and stable, and have good operability are used. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as hydroxides of lithium, sodium or potassium, alkali carbonates such as carbonates or bicarbonates of lithium, sodium, potassium or ammonium, alkali metal phosphates such as potassium phosphate and sodium phosphate, Alkali metal pyrophosphates, such as sodium pyrophosphate and potassium pyrophosphate, borax, etc. are used.

Moreover, as said alkaline aqueous solution used for image development, a lean solution of 0.1-5 weight% sodium carbonate, a lean solution of 0.1-5 weight% potassium carbonate, a lean solution of 0.1-5 weight% sodium hydroxide, 0.1-5 weight% tetraborate Preferred are lean solutions of sodium (borax). Moreover, it is preferable to make pH of this alkaline aqueous solution into the range of 9-11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. Moreover, you may add a surfactant, an antifoamer, a small amount of organic solvents for accelerating image development, etc. in alkaline aqueous solution.

As said aqueous developing solution, the developing solution which consists of water or alkali aqueous solution, and 1 or more types of organic solvent is mentioned. As the base of the alkaline aqueous solution, in addition to the substances already mentioned above, for example, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1, 3-propanediol, 1,3-diaminopropanol-2, morpholine, etc. are mentioned. It is preferable to make pH of a developing solution as small as possible in the range which can fully develop a resist, It is preferable to set it as pH8-12, and it is more preferable to set it as pH9-10.

As said organic solvent, 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, di Ethylene glycol monobutyl ether etc. are mentioned. These are used individually or in combination of 2 or more types. It is preferable that the density | concentration of the organic solvent is 2 to 90 weight% normally, and the temperature can be adjusted according to developability. Moreover, a small amount of surfactant, an antifoamer, etc. can also be added to an aqueous developing solution.

As the organic solvent developer using an organic solvent alone, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl iso Butyl ketone, (beta) -butyrolactone, etc. are mentioned. It is preferable that these organic solvent developing solutions add water in 1 to 20 weight% in order to prevent flammability.

As a process after image development, you may harden | cure a resist pattern further by performing heating of about 60-250 degreeC, or exposure of about 0.2-10J / cm <2> as needed.

Next, the manufacturing method of the printed wiring board of this invention is demonstrated.

The manufacturing method of the printed wiring board of this invention forms the conductor pattern by etching or plating the circuit formation board | substrate with which the resist pattern was formed by the formation method of the resist pattern of the said invention.

Etching and plating of the circuit forming substrate are performed on the conductor layer and the like of the circuit forming 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, a ferric chloride solution is used because of the good Hact factor. It is preferable. As the plating method in the case of plating, for example, copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-slow solder plating, watt bath (nickel sulfate-nickel chloride) plating, sulfamic acid And nickel plating such as nickel, gold plating such as hard gold plating, and soft gold plating.

After completion of etching or plating, the resist pattern can be peeled off with a strongly alkaline aqueous solution, for example, than the alkaline aqueous solution used for development. As this strongly alkaline aqueous solution, 1-10 weight% sodium hydroxide aqueous solution, 1-10 weight% potassium hydroxide aqueous solution, etc. are used, for example. As a peeling system, an immersion system, a spray system, etc. are mentioned, for example, You may use an immersion system, a spray system independently, and may use it together. The printed wiring board is obtained by the above.

As mentioned above, although preferred embodiment of this invention is described, this invention is not limited to the said embodiment.

Example

Hereinafter, although the preferable Example of this invention is demonstrated in detail, this invention is not limited to these Examples.

(Synthesis of Binder Polymer ((A) Component))

To a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas introduction tube, 450 g of a mixture of methyl cellosolve and toluene in a weight ratio of 3: 2 was added, stirred with suction of nitrogen gas, and heated to 80 ° C. . On the other hand, a solution (hereinafter referred to as "solution a") which mixed 150 g of methacrylic acid, 25 g of methyl methacrylate, 125 g of benzyl methacrylate, and 200 g of styrene and 9.0 g of azobisisobutyronitrile as a copolymerization monomer was prepared. The solution a was added dropwise to the mixture of methyl cellosolve and toluene having a weight ratio of 3: 2 prepared in advance over 4 hours, and then kept warm for 2 hours with stirring at 80 ° C. Furthermore, the solution which melt | dissolved 1.2 g of azobisisobutyronitrile was dripped at 100 g of the mixture of methyl cellosolve and toluene of a weight ratio 3: 2 over 10 minutes. After stirring the solution after dripping for 3 hours, stirring at 80 degreeC, it heated at 90 degreeC over 30 minutes. After heat-retaining at 90 degreeC for 2 hours, it cooled and obtained binder polymer (A-1).

The nonvolatile matter (solid content) of the binder polymer (A-1) was 47.8 wt%, and the weight average molecular weight was 30,000. In addition, the weight average molecular weight was measured by gel permeation chromatography method, and it derived by converting using the analytical curve of standard polystyrene. The conditions of GPC are shown below.

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

Column: Gelpack GL-R420 + Gelpack GL-R430 + Gelpack GL-R440 (3 in total) (above, manufactured by Hitachi Chemicals, Ltd., trade name)

Eluent: tetrahydrofuran

Measuring temperature: 40 ℃

Flow rate: 2.05 mL / min

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

Moreover, binder polymer (A-2)-(A-10) were synthesize | combined so that it may become a composition shown in following Table 1 by the method similar to the synthesis method of binder polymer (A-1) mentioned above.

TABLE 1

(Preparation of Photosensitive Resin Composition)

The said binder polymer (A-1)-(A-10) and the following materials were mix | blended in the weight ratio shown in Table 2, and the solution of the photosensitive resin composition of Examples 1-6 and Comparative Examples 1-5 was prepared. .

<Photopolymerizable compound ((B) component)>

B-1: 2, 2-bis (4- (methacryloxy pentaethoxy) phenyl) propane (made by Hitachi Chemical Co., Ltd., brand name: FA-321M)

B-2: The compound represented by the above general formula (VIII), wherein R ¹² and R ¹³ are methyl groups, m ³ = 6 (average value) and n ² + n ³ = 12 (average value), respectively (Hidachi Chemical Industries, Ltd.). Co., Ltd., brand name: FA-024M)

B-3: 4-normal nonyl phenoxy octaethylene oxyacrylate (made by Dong-A Synthetic Co., Ltd., brand name: M-114)

<Photoinitiator ((C) component)>

C-1: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole (made by Hampford, brand name: BCIM)

<Dense dye ((D) component)>

D-1: 9,10-dibutoxy anthracene (made by Kawasaki Kasei Kogyo Co., Ltd., brand name: DBA, wavelength [lambda [n] = 368 nm, 388 nm, 410 nm which shows absorption maximum)

<(E) Coloring Agent (Amine Compound)>

E-1: leuco crystal violet (made by Yamada Chemical Co., Ltd.)

<Dye>

Malachite Green (Osaka Organic Chemical Industry Co., Ltd. product)

<Solvent>

Acetone

toluene

Methanol

TABLE 2

(Production of Photosensitive Element)

The solution of each obtained photosensitive resin composition was apply | coated uniformly on the 16-micrometer-thick polyethylene terephthalate film used as a support film. Then, it dried using the hot air convection type dryer of 70 degreeC and 110 degreeC, and formed the photosensitive resin composition layer of 25 micrometers after drying. Then, the protective film was laminated | stacked on the photosensitive resin composition layer by roll pressurization, and the photosensitive element which concerns on each Example 1-6 and Comparative Examples 1-5 was obtained.

(Production of test piece)

Then, the copper surface of the copper-clad laminate (Hitachi Chemical Co., Ltd. make, brand name: MCL-E-67) which is the glass epoxy material which laminated | stacked copper foil (35 mm in thickness) on both surfaces, the grinding | polishing machine which has a brush of # 600 equivalency ( It polished using Sanke Co., Ltd., and washed with water, and dried in airflow, and obtained the copper clad laminated board (substrate). Thereafter, the copper-clad laminate was warmed to 80 ° C., and then each photosensitive resin composition layer was brought into close contact with the surface of the copper-clad laminate, while removing the protective film of each of the photosensitive elements on the copper-clad laminate. It laminated (laminated) under the pressure of 4 kgf / cm <2>, and produced the test piece.

(Characteristic evaluation)

<Light sensitivity>

When the copper sheet laminate in which each photosensitive element was laminated was cooled to 23 ° C, the support film had a concentration range of 0.00 to 2.00, a concentration step of 0.05, a tablet of 20 mm x 187 mm, and a size of each step of 3 mm x 12 mm. The phototool with the sweet step tablet was stuck. Exposure to the photosensitive resin composition layer through a phototool and a supporting film at an exposure dose of 50 mJ / cm 2 using a weaving machine DE-1AH (trade name) manufactured by Hitachivia Mechanics Co., Ltd. using a 405 nm blue violet laser diode as a light source ( Drawing). In addition, the illumination intensity was measured using the ultraviolet illuminometer (The Ushio Electric Co., Ltd. make, brand name: UIT-150) to which the 405 nm corresponding probe was applied.

Subsequently, the support film was peeled off, a 1 wt% sodium carbonate aqueous solution was sprayed at 30 ° C. for 24 seconds, and the unexposed portion of the photosensitive resin composition layer was removed and developed. Then, the photosensitivity of the photosensitive resin composition was evaluated by measuring the number of steps of the step tablet of the photocured film formed on the copper clad laminated board. Evaluation of photosensitivity is represented by the number of steps of a step tablet, and shows that the photosensitivity is high, so that the number of steps of this step tablet is high. The obtained results are shown in Table 4.

<Resolution>

The resolution was exposed using a phototool having a wiring pattern of line width / space width 6/6 to 30/30 (unit: mm) as a negative for resolution evaluation. Here, in the resist pattern formed by the development after exposure, the smallest value (unit: micrometer) of the space width between the line widths in the part from which the unexposed part was removed cleanly was an index of the resolution. The smaller the numerical value is, the better the evaluation of the resolution is. The obtained results are shown in Table 4.

<Resist shape>

The resist shape after image development was observed using the scanning electron microscope (brand name: Hitachi Scanning Electron Microscope S-500A). It is preferable that the resist shape is close to a rectangle.

Peelability

Peelability was evaluated by the following method. First, the photosensitive resin composition layer which concerns on each Example and the comparative example was formed on the copper clad laminated board, each photosensitive resin composition layer was exposed and developed, and the photocuring film of the size of 40 mm x 50 mm was produced. And peeling was performed using 3% sodium hydroxide aqueous solution. Peelability evaluation made the time at the time of completion | finish of peeling of a photocurable film from a copper clad laminated board on peeling time. Moreover, the size of the peeling piece after peeling completion was observed visually. In Table 3, it shows about the conditions of the peeling process, and the index of the size of a peeling piece. The obtained results are shown in Table 4.

[Table 3]

TABLE 4

*

<Evaluation result>

As shown in Table 4, each of Examples 1-6 had a high resolution of 10 micrometers, the peeling time was moderately short, the peeling piece size was also small, and the balance of resolution and peelability was taken. On the other hand, in Comparative Example 1, 2, 5, the resolution of the thing with favorable peelability was low. Moreover, in Comparative Examples 3 and 4, although it was a high resolution, peeling time was long and peeling piece size was large. As mentioned above, the effect of the photosensitive resin composition which concerns on this invention was confirmed.

According to the present invention, it is possible to provide a photosensitive resin composition, a photosensitive element, a method of forming a resist pattern, and a method of manufacturing a printed wiring board, which are sufficiently effective in improving resolution and resist stripping characteristics.

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

Claims (9)

(A) The divalent group represented by the following general formula (I), the divalent group represented by the following general formula (II), the divalent group represented by the following general formula (III), and the following general formula (IV) A binder polymer having a divalent group, which has a degree of dispersion of 1.0 to 2.0,
(B) a photopolymerizable compound, and
(C) photoinitiator,
Photosensitive resin composition containing.
[Formula 1]

(2)

(3)

[Chemical Formula 4]

[In Formula (I), Formula (II), Formula (III), and Formula (IV), R <^1> , R <^3> , R <^5> , and R <^6> respectively independently represent a hydrogen atom or a methyl group, and R <^7> is an alkyl group M and n are both 0] The said (A) binder polymer is 10-60 weight part and 2 represented by the said General formula (II) with respect to the total amount of 100 weight part of Claim 1, The bivalent group represented by the said General formula (I) of Claim 1 Photosensitive resin which has 10-60 weight part of valent groups, 20-50 weight part of divalent groups represented by the said General formula (III), and 1 weight part or more and less than 15 weight part of divalent groups represented by the said General formula (IV). Composition. The photosensitive resin composition of Claim 1 or 2 in which the said (B) photopolymerizable compound contains the polyalkylene glycol di (meth) acrylate which has both an ethylene glycol chain and a propylene glycol chain in a molecule | numerator. The photosensitive resin composition of Claim 1 or 2 in which the said (C) photoinitiator has a hexaaryl biimidazole compound. (D) The photosensitive resin composition of Claim 1 or 2 which further contains a dye. The photosensitive resin composition of Claim 1 or 2 which further contains the (E) amine type compound. A photosensitive element provided with a support film and the photosensitive resin composition layer containing the photosensitive resin composition of Claim 1 or 2 formed on this support film. A lamination step of laminating the photosensitive resin composition layer containing the photosensitive resin composition according to claim 1 or 2 on a circuit forming substrate, and irradiating active light to a predetermined portion of the photosensitive resin composition layer to photocuring the exposed portion. And a developing step of removing portions other than the exposed portion of the photosensitive resin composition layer from the circuit forming substrate on which the photosensitive resin composition layer is laminated. The manufacturing method of the printed wiring board which has the process of etching or plating the circuit formation substrate in which the resist pattern was formed by the formation method of the resist pattern of Claim 8, and forming a conductor pattern.

Images