JP2008304527A - Photosensitive resin composition, photosensitive element using same, resist pattern forming method, and method for manufacturing printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in improvement of sensitivity, resolution and resist stripping property, a photosensitive element using the same, a resist pattern forming method and a method for manufacturing a printed wiring board. <P>SOLUTION: The photosensitive resin composition comprises: (A) a styrene-methacrylic acid-methacrylic ester terpolymerized binder polymer; a photopolymerizable compound containing (B-1) vinyl acetate and/or vinyl propionate as one of the constituents and further containing (B-2) a bisphenol A-(meth)acrylate bifunctional monomer; and (C) a photopolymerization initiator. The photosensitive element using the same, the resist pattern forming method and the method for manufacturing a printed wiring board are also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  In the field of manufacturing printed wiring boards, as a resist material used for etching and plating, a photosensitive resin composition and a layer containing this photosensitive resin composition (hereinafter referred to as “photosensitive resin composition layer”) are used. Photosensitive elements (laminates) formed on a support film and having a structure in which a protective film is disposed on a photosensitive resin composition layer are widely used.

Conventionally, a printed wiring board is manufactured by the following procedure, for example, using the photosensitive element.
First, the photosensitive resin composition layer of the photosensitive element is laminated on a circuit forming substrate such as a copper clad laminate.

  At this time, the surface opposite to the surface of the photosensitive resin composition layer in contact with the support film (hereinafter referred to as the “lower surface” of the photosensitive resin composition layer) (hereinafter referred to as the “upper surface of the photosensitive resin composition layer”). ") Is in close contact with the surface of the circuit forming substrate on which the circuit is formed.

Therefore, when the protective film is arrange | positioned on the upper surface of the photosensitive resin composition layer, this lamination operation is performed while peeling off the protective film.
Lamination is performed by thermocompression bonding the photosensitive resin composition layer to the underlying circuit-forming substrate (normal pressure laminating method).

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

Here, the etching treatment is a method of removing the cured resist after etching away the metal surface of the circuit forming substrate not covered with the cured resist formed after development.
On the other hand, the plating treatment is that the metal surface of the circuit forming substrate that is not covered with the cured resist formed after development is plated with copper and solder, and then the cured resist is removed and covered with this resist. This is a method of etching a metal surface.

  It is important that the photosensitive resin composition used for this is excellent in sensitivity, resolution, and resist release characteristics. If the photosensitive resin composition can provide a resist pattern having excellent resist peeling characteristics, it is possible to sufficiently reduce short circuits and disconnections between circuits.

  In addition, if the photosensitive resin composition can form a resist with excellent peeling characteristics, the resist patterning efficiency can be improved by shortening the resist peeling time, and the size of the resist peeling pieces can be increased. By reducing the size, the resist is not peeled off and the yield of circuit formation is improved.

  A photosensitive resin composition having excellent sensitivity, resolution, and resist release characteristics using a specific binder polymer, a photopolymerization initiator, and the like has been proposed in response to such demands (see, for example, Patent Documents 1 and 2). ).

However, the photosensitive resin compositions described in Patent Documents 1 and 2 have a problem that the resolution and resist stripping characteristics are not yet sufficient.
JP 2006-234959 A JP 2005-122123 A

  It is an object of the present invention to provide a photosensitive resin composition excellent in improvement in sensitivity, resolution and resist peeling characteristics, a photosensitive element using the same, a method for forming a resist pattern, and a method for producing a printed wiring board. Is.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies focusing on the composition of the photopolymerizable monomer. As a result, (B-1) a photosensitive resin composition that is sufficiently effective in improving resist stripping properties by using a photopolymerizable compound containing one or both of vinyl acetate and vinyl propionate as one of the components. It was found that can be obtained.

  Furthermore, (B-2) it was found that a photosensitive resin composition excellent in sensitivity and resolution can be obtained by adding a bisphenol A-based (meth) acrylate bifunctional monomer represented by the following formula (IV), and completed the present invention. It came to do.

（式中、Ｒ^１及びＲ^２は各々独立に水素原子又はメチル基を示し、ｐ、ｑ、ｓ及びｔは、ｐ＋ｑ＋ｓ＋ｔ＝４〜４０となるように選ばれる正の整数である。）

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and p, q, s, and t are positive integers selected such that p + q + s + t = 4 to 40).

The present invention is represented by [1] (A) a divalent group represented by the following general formula (I), a divalent group represented by the following general formula (II), and the following general formula (III). A binder polymer having a divalent group,
(B-1) One or both of vinyl acetate and vinyl propionate are contained as one of the components, and (B-2) a bisphenol A (meth) acrylate bifunctional monomer represented by the following formula (V) (Wherein R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and p, q, s and t are positive integers selected so that p + q + s + t = 4 to 40). It relates to a photosensitive resin composition comprising a photopolymerizable compound and (C) a photopolymerization initiator.

［一般式（Ｉ）、（ＩＩ）及び（ＩＩＩ）中、Ｒ^１、Ｒ^３、Ｒ^４及びＲ^５はそれぞれ独立に水素原子、メチル基又は炭素数２〜４のアルキル基を示し、Ｒ^２はそれぞれ独立に炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、ＯＨ基又はハロゲン原子を示し、ｍはそれぞれ独立に０〜５の整数を示す。］

[Formula (I), shows the (II) and (III) ^{in, R 1, R 3, R} 4 and ^{R 5} independently represent hydrogen atom, a methyl group or an alkyl group having 2 to 4 carbon atoms, ^{R 2} Each independently represents 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, and each m independently represents an integer of 0 to 5. ]

  Further, the present invention provides: [2] The (A) binder polymer has 5 to 60 parts by mass of the divalent group represented by the general formula (I) with respect to 100 parts by mass in total, and the general formula The above [1], which has 15 to 45 parts by mass of the divalent group represented by (II) and 10 to less than 60 parts by mass of the divalent group represented by the general formula (III). It relates to the described photosensitive resin composition.

  In addition, the present invention provides [3] (A) the binder polymer having 5 to 60 parts by mass of the divalent group represented by the general formula (I) with respect to 100 parts by mass in total, the general formula 15 to 45 parts by mass of the divalent group represented by (II), 5 to 60 parts by mass of the divalent group represented by the general formula (III) and 2 represented by the following general formula (V) It is related with the photosensitive resin composition of the said [1] or [2] description which has 5-60 mass parts of a valence.

［Ｒ^６及びＲ^７はそれぞれ独立に炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、ＯＨ基、又はハロゲン原子を示し、ｎはそれぞれ独立に０〜５の整数を示す。］

[R ⁶ and R ⁷ each independently represents 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, and n represents an integer of 0 to 5 independently. ]

The present invention also relates to [4] the photosensitive resin composition according to any one of the above [1] to [3], wherein the (C) photopolymerization initiator has a hexaarylbiimidazole compound.
The present invention also relates to a photosensitive resin composition comprising [5] the photosensitive resin composition according to any one of [1] to [4] above and further containing an amine compound.
Moreover, this invention is equipped with the photosensitive resin composition layer containing the photosensitive resin composition in any one of said [1]-[5] formed on the [6] support film and the said support film. Relates to the photosensitive element.

  The present invention also provides [7] the photosensitive resin composition according to any one of [1] to [5] above or the photosensitive element according to [6] above on a circuit forming substrate. A lamination step of laminating a photosensitive resin composition layer containing a product, an exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray to photocure an exposed portion, and the photosensitive resin composition layer The present invention relates to a resist pattern forming method comprising a developing step of removing a portion other than the exposed portion of the photosensitive resin composition layer from a laminated circuit forming substrate.

  Furthermore, the present invention provides [8] Production of a printed wiring board having a step of forming a conductor pattern by etching or plating a circuit forming substrate on which a resist pattern is formed by the method for forming a resist pattern according to [7]. Regarding the method.

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

  Hereinafter, the best mode for carrying out the invention will be described in detail. In the present invention, (meth) acrylic acid means acrylic acid or methacrylic acid, (meth) acrylate means acrylate or a corresponding methacrylate, and (meth) acryloyl group means acryloyl group or methacryloyl group. means.

The photosensitive resin composition according to the present invention comprises (A) a divalent group represented by the above general formula (I), a divalent group represented by the above general formula (II), and the above general formula (III). A binder polymer having a divalent group represented by:
(B-1) One or both of vinyl acetate and vinyl propionate are contained as one of the components, and (B-2) a bisphenol A (meth) acrylate bifunctional monomer represented by the above formula (IV) (Wherein R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and p, q, s and t are positive integers selected so that p + q + s + t = 4 to 40). And (C) a photopolymerization initiator.

  In the present invention, (B-1) a photosensitive resin that is sufficiently effective in improving resist stripping characteristics by using a photopolymerizable compound containing one or both of vinyl acetate and vinyl propionate as one of the components. A composition is obtained, and (B-2) a photosensitive resin composition excellent in sensitivity and resolution is obtained by adding a bisphenol A-based (meth) acrylate bifunctional monomer represented by the above formula (IV). Conceivable.

  Since the photosensitive resin composition according to the present invention contains either or both of (B-1) vinyl acetate and vinyl propionate, it forms a photocrosslink and becomes insoluble during development (sodium carbonate). The present inventors consider that the structure of the portion where the film is peeled is replaced with a hydroxyl group as shown in the following formula with respect to sodium hydroxide so that the hydrophilicity is increased and the peelability is improved. ing.

  Since a similar reaction occurs when polyvinyl acetate (weight average molecular weight 10,000 to 200,000: in terms of polystyrene) is added to the binder polymer having a specific structure such as the component (A) used in the present invention, the resist Although the present inventors have already found that the release property is improved, since the compatibility of polyvinyl acetate with an acrylic polymer such as the component (A) is not sufficient, it can be used for improving the release property. The amount of polyvinyl acetate that can be produced is limited, and it is necessary to improve the peelability.

  In the photosensitive resin composition according to the present invention, (A) the binder polymer has 5 to 60 parts by mass of the divalent group represented by the above general formula (I) with respect to 100 parts by mass in total. 15 to 45 parts by mass of the divalent group represented by the general formula (II), 5 to 60 parts by mass of the divalent group represented by the general formula (III) and the general formula (V). It is preferable to have 5 to 60 parts by mass of divalent. Thereby, the resolution and resist stripping property of the photosensitive resin composition can be further improved.

Next, the binder polymer as the component (A) will be described.
(A) In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an OH group, or the like. Represents a halogen atom, and m represents an integer of 0 to 5;

  Examples of the polymerizable monomer that gives the structural unit represented by the general formula (I) include styrene and styrene derivatives. In the present invention, the “styrene derivative” refers to a compound in which a hydrogen atom in styrene is substituted with a substituent (an organic group such as an alkyl group or a halogen atom). Examples of the styrene derivative include α-methylstyrene.

In the general formula (II), R ³ 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 (II).

Further, in the general formula (III), ^{R 4} is each independently represent a hydrogen atom or a methyl group, ^{R 5} represents an alkyl group having 1 to 6 carbon atoms, ^{R 5} is an alkyl group having 1 to 4 carbon atoms An alkyl group having 1 carbon atom (methyl group) is more preferable. Examples of the polymerizable monomer that gives the structural unit represented by the general formula (III) include (meth) acrylic acid alkyl esters.

Furthermore, in the general formula (V), ^{R 6} represents a hydrogen atom or a methyl group, ^{R 7} represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, OH group or a halogen atom, m shows the integer of 0-5.

  Examples of the polymerizable monomer that gives the structural unit represented by the general formula (V) include benzyl (meth) acrylate or benzyl (meth) acrylate. Examples of the benzyl (meth) acrylate derivative include 4-methylbenzyl (meth) acrylate.

  Examples of the (meth) acrylic acid alkyl ester represented by the general formula (III) include compounds represented by the following general formula (VII).

(In the formula, R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ represents an alkyl group having 1 to 6 carbon atoms.)

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁹ in the general formula (VII) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and structural isomers thereof. It is done.

  Examples of the polymerizable monomer represented by the general formula (VII) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, and (meth) acrylic acid butyl. Examples include esters, (meth) acrylic acid pentyl esters, and (meth) acrylic acid hexyl esters. These polymerizable monomers are used alone or in combination of two or more.

  In the binder polymer as the component (A), the content of the structural unit represented by the general formula (I) is preferably 5 to 60 parts by mass with respect to 100 parts by mass of the total amount of the component (A). The amount is more preferably 15 to 55 parts by mass, and further preferably 20 to 50 parts by mass. Thereby, both the adhesiveness with respect to the circuit formation board | substrate of a photosensitive resin composition layer containing the photosensitive resin composition, and a resist peeling characteristic can be made favorable.

  Moreover, it is preferable that the content rate of the structural unit represented by the said general formula (II) is 15-45 mass parts with respect to 100 mass parts of total amounts of (A) component, and is 20-40 mass parts. More preferably, the amount is 25 to 35 parts by mass. Thereby, both resist stripping characteristics and developability can be improved.

  Moreover, it is preferable that the content rate of the structural unit represented by the said general formula (III) is 5-60 mass parts with respect to 100 mass parts of total amounts of (A) component, and is 5-50 mass parts. It is more preferable, and it is further more preferable that it is 5-40 mass parts. Thereby, both the adhesiveness with respect to the circuit formation board | substrate of a photosensitive resin composition layer containing the photosensitive resin composition, and a resist peeling characteristic can be made favorable.

  Moreover, it is preferable that the content rate of the structural unit represented by the said general formula (V) is 5-60 mass parts with respect to 100 mass parts of total amounts of (A) component, and is 15-55 mass parts. More preferably, the amount is 20 to 50 parts by mass. Thereby, the adhesiveness with respect to the board | substrate for circuit formation of the photosensitive resin composition layer containing the photosensitive resin composition, resolution, and a resist peeling characteristic can be made favorable.

  Moreover, in the binder polymer which is the component (A), the resolution tends to be inferior when the content ratio of the structural units represented by the general formulas (I), (III) and (IV) is less than 5 parts by mass, respectively. Yes, when the amount exceeds 60 parts by mass, the peeling piece tends to be large and the peeling time tends to be long.

  In addition, when the content ratio of the structural unit represented by the general formula (II) is less than 15 parts by mass, the alkali solubility is inferior, the peeling piece tends to be large, and the peeling time tends to be long. If it exceeds, the resolution tends to decrease.

  When preparing the photosensitive resin composition using the above binder polymer, one kind of binder polymer may be used alone, or two or more kinds of binder polymers may be used in any combination.

As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymerization components (including different repeating units as constituent components), two or more types of binders having different weight average molecular weights Examples thereof include polymers and two or more types of binder polymers having different degrees of dispersion.
In addition, a polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used.

  (A) The weight average molecular weight (Mw) and number average molecular weight (Mn) of a binder polymer can be measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene). According to this measurement method, the Mw of the binder polymer is preferably 5000 to 150,000, more preferably 10,000 to 100,000, and still more preferably 20,000 to 50,000. When Mw is less than 5000, the developer resistance tends to decrease, and when it exceeds 150,000, the development time tends to be long, and the resolution tends to decrease.

  Moreover, (A) The dispersion degree (Mw / Mn) of the binder polymer is preferably 1.0 to 3.0, and more preferably 1.0 to 2.0. When the degree of dispersion exceeds 3.0, the adhesion and resolution tend to decrease.

In the present invention, the binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer by a conventional method.
The above-mentioned (A) binder polymer may contain structural units other than the structural units represented by the general formulas (I) to (III) and (V).

  The above-mentioned (A) binder polymer preferably has only the structural units represented by the above general formulas (I) to (III) and (V), but to the extent that the object of the present invention is not impaired. The other structural unit may have about 1 to 10 parts by mass with respect to the total amount of component (A).

In this case, examples of the polymerizable monomer that gives structural units other than the structural units represented by the general formulas (I) to (III) and (V) include (meth) acrylic acid heptyl ester, (meth) Octyl acrylate ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester, 2- Acrylamide such as hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, diacetone acrylamide, esters of vinyl alcohol such as acrylonitrile, vinyl-n-butyl ether, (meth) acrylic acid tetrahydrofurfuryl ester, Dimethy (meth) acrylate Aminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (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, maleic anhydride , Maleic acid monoesters such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like.
These monomers are used alone or in combination of two or more.

  In the present invention, the (A) binder polymer is preferably composed of one or more kinds of polymers having a carboxyl group from the viewpoint of developability when alkali development is performed using an alkaline solution. Such (A) binder polymer is produced, for example, by radical polymerization of a polymerizable monomer having (meth) acrylic acid or other carboxyl group and another polymerizable monomer by a conventional method. be able to.

  (A) The acid value of the binder polymer is preferably 80 to 250 mgKOH / g, more preferably 100 to 220 mgKOH / g, and still more preferably 150 to 210 mgKOH / g. When the acid value is less than 80 mgKOH / g, the development time tends to be long, and when it exceeds 250 mgKOH / g, the developer resistance of the photocured resist tends to be lowered. Moreover, when performing solvent image development as a image development process, it is preferable to prepare the polymerizable monomer which has a carboxyl group in a small quantity.

  Moreover, (A) binder polymer may have the characteristic group which has photosensitivity in the molecule | numerator as needed.

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

Next, the essential component of the photopolymerizable compound as the component (B) contains (B-1) one or both of vinyl acetate and vinyl propionate as one of the components, and (B-2) Bisphenol A-based (meth) acrylate bifunctional monomer represented by the following formula (IV) (wherein R ¹ and R ² each independently represent a hydrogen atom or a methyl group, p, q, s and t are p + q + s + t) = A positive integer selected to be 4 to 40).

上記（Ｂ−２）成分ビスフェノールＡ系ジ（メタ）アクリレート化合物としては、例えば、２，２−ビス［４−〔（メタ）アクリロキシポリエトキシ〕フェニル］プロパン、２，２−ビス［４−（メタ）アクリロキシポリプロポキシ〕フェニル］プロパン、２，２−ビス［４−〔（メタ）アクリロキシポリブトキシ〕フェニル］プロパン、２，２−ビス［４−〔（メタ）アクリロキシポリエトキシポリプロポキシ〕フェニル］プロパン等が挙げられる。

Examples of the component (B-2) component bisphenol A di (meth) acrylate compound include 2,2-bis [4-[(meth) acryloxypolyethoxy] phenyl] propane, 2,2-bis [4- (Meth) acryloxypolypropoxy] phenyl] propane, 2,2-bis [4-[(meth) acryloxypolybutoxy] phenyl] propane, 2,2-bis [4-[(meth) acryloxypolyethoxypoly Propoxy] phenyl] propane and the like.

  Examples of the 2,2-bis [4-[(meth) acryloxypolyethoxy] phenyl] propane include 2,2-bis [4-[(meth) acryloxydiethoxy] phenyl] propane, 2,2 -Bis [4-[(meth) acryloxytriethoxy] phenyl] propane, 2,2-bis [4-[(meth) acryloxytetraethoxy] phenyl] propane, 2,2-bis [4-[(meta ) Acryloxypentaethoxy] phenyl] propane, 2,2-bis [4-[(meth) acryloxyhexaethoxy] phenyl] propane, 2,2-bis [4-[(meth) acryloxyheptaethoxy] phenyl] Propane, 2,2-bis [4-[(meth) acryloxyoctaethoxy] phenyl] propane, 2,2-bis [4-[(meth) acryloxy nanoe Xyl] phenyl] propane, 2,2-bis [4-[(meth) acryloxydecaethoxy] phenyl] propane, 2,2-bis [4-[(meth) acryloxyundecaethoxy] phenyl] propane, 2 , 2-bis [4-[(meth) acryloxydodecaethoxy] phenyl] propane, 2,2-bis [4-[(meth) acryloxytridecaethoxy] phenyl] propane, 2,2-bis [4- [(Meth) acryloxytetradecaethoxy] phenyl] propane, 2,2-bis [4-[(meth) acryloxypentadecaethoxy] phenyl] propane, 2,2-bis [4-[(meth) acryloxy Hexadecaethoxy] phenyl] propane and the like.

  2,2-bis [4- (methacryloxypentaethoxy) phenyl] propane is BPD-500 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) or FA-321M (trade name, manufactured by Hitachi Chemical Co., Ltd.). 2,2-bis [4- (methacryloxypentadecaethoxy) phenyl] propane is commercially available as BPD-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). It is available.

  The number of ethylene oxide groups in one molecule of 2,2-bis [4-[(meth) acryloxypolyethoxy] phenyl] propane is preferably 4-20, and more preferably 8-15. These compounds are used alone or in combination of two or more.

  Examples of the photopolymerizable compound as component (B) include compounds obtained by reacting polyhydric alcohols with α, β-unsaturated carboxylic acids, bisphenol A di (meth) acrylate compounds, and glycidyl group-containing compounds. Compound obtained by reacting α, β-unsaturated carboxylic acid, urethane monomer such as (meth) acrylate compound having urethane bond in molecule, nonylphenoxypolyethyleneoxyacrylate (also referred to as “nonylphenoxypolyethyleneglycol acrylate”), Examples thereof include phthalic acid compounds and (meth) acrylic acid alkyl esters. These compounds are used alone or in combination of two or more.

  As the (meth) acrylate compound having a urethane bond in the molecule, for example, a (meth) acryl monomer having an OH group at the β-position and a diisocyanate compound (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate etc.) addition reaction product, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO modified urethane di (meth) acrylate, EO, PO modified urethane di (meth) acrylate, etc. Is mentioned.

Examples of the EO-modified urethane di (meth) acrylate include UA-11 [trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.].
Moreover, as said EO, PO modified urethane di (meth) acrylate, UA-13 [Shin-Nakamura Chemical Co., Ltd. make, brand name] is mentioned, for example. These compounds are used alone or in combination of two or more.

  Nonylphenoxypolyethyleneoxyacrylate includes, for example, nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethyleneoxyacrylate, nonylphenoxynonaethyleneoxy Examples include acrylate, nonylphenoxydecaethyleneoxyacrylate, and nonylphenoxyundecaethyleneoxyacrylate.

  Nonylphenoxyoctaethyleneoxyacrylate includes, for example, M-114 [trade name, manufactured by Toagosei Co., Ltd.]. These compounds are used alone or in combination of two or more.

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

  Furthermore, the component (B) of the present invention contains polyalkylene glycol di (meth) acrylate having both an ethylene glycol chain and a propylene glycol chain in the molecule from the viewpoint of improving the flexibility of the cured film. preferable.

  This (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 alkylene glycol chains in the molecule.

  In addition, this (meth) acrylate is further an n-butylene glycol chain, an isobutylene glycol chain, an n-pentylene glycol chain, a hexylene glycol chain, an alkylene glycol chain having about 4 to 6 carbon atoms such as a structural isomer thereof. You may have.

When there are a plurality of ethylene glycol chains and propylene glycol chains, the plurality of ethylene glycol chains and propylene glycol chains may be continuously present in blocks or randomly.
In the isopropylene glycol chain, the secondary carbon of the propylene group may be bonded to an oxygen atom, or the primary carbon may be bonded to an oxygen atom.

  Among these (B) components, polyalkylene glycol di (meth) acrylate having at least one polymerizable ethylenically unsaturated bond and having both an ethylene glycol chain and a propylene glycol chain in the molecule is, for example, Formula (VIII)

で表される化合物、下記一般式（ＩＸ）

A compound represented by the following general formula (IX)

で表される化合物及び下記一般式（Ｘ）

And the following general formula (X)

で表される化合物などが挙げられる。
（式（ＶＩＩＩ）、（ＩＸ）及び（Ｘ）中、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５はそれぞれ独立に水素原子又は炭素数１〜３のアルキル基を示し、ＥＯはエチレングリコール鎖を示し、ＰＯはプロピレングリコール鎖を示し、ｍ^１〜ｍ^４及びｎ^１〜ｎ^４はそれぞれ独立に１〜３０の整数を示す。）これらの化合物は、単独で又は２種類以上を組み合わせて用いられる。

The compound etc. which are represented by these are mentioned.
(In the formulas (VIII), (IX) and (X), R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, 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 may be used alone or in two kinds The above is used in combination.

  Examples of the alkyl group having 1 to 3 carbon atoms in the general formulas (VIII) to (X) include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group.

The total number (m ¹ + m ² , m ³ and m ⁴ ) of ethylene glycol chain repeats in the above general formulas (VIII) to (X) is an integer of 1 to 30, and an integer of 1 to 10 Is preferable, an integer of 4 to 9 is more preferable, and an integer of 5 to 8 is more preferable. If the number of repetitions exceeds 30, the tent reliability and the resist shape tend to deteriorate.

The repeating number total number of propylene glycol chain in the above general formula ^{(VIII) ~ (X) (} n 1, n 2 + n 3 and ^{n 4)} is an integer of 1 to 30, an integer of 5-20 Is preferable, an integer of 8 to 16 is more preferable, and an integer of 10 to 14 is more preferable. If the number of repetitions exceeds 30, the resolution deteriorates and sludge tends to be generated.

Specific examples of the compound represented by the general formula (VIII) include, for example, vinyl having R ¹⁰ = R ¹¹ = methyl group, m ¹ + m ² = 4 (average value), and n ¹ = 12 (average value). Compound [manufactured by Hitachi Chemical Co., Ltd., trade name: FA-023M] and the like.

Specific examples of the compound represented by the general formula (IX) include, for example, R ¹² = R ¹³ = methyl group, m ³ = 6 (average value), n ² + n ³ = 12 (average value) A certain vinyl compound [manufactured by Hitachi Chemical Co., Ltd., trade name: FA-024M] is exemplified.

Furthermore, specific examples of the compound represented by the general formula (X) include, for example, vinyl in which R ¹⁴ = R ¹⁵ = hydrogen atom, m ⁴ = 1 (average value), and n ⁴ = 9 (average value). Examples include compounds [manufactured by Shin-Nakamura Chemical Co., Ltd., sample name: NK ester HEMA-9P]. These compounds are used alone or in combination of two or more.

  Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 2 propylene groups. 14 polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate , EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Examples include erythritol hexa (meth) acrylate. These compounds are used alone or in combination of two or more.

Here, “EO” represents ethylene oxide, and an EO-modified compound represents one having a block structure of an ethylene oxide group.
“PO” represents propylene oxide, and a PO-modified compound has a propylene oxide group block structure.
In the component (B), a trifunctional photopolymerizable compound represented by the following general formula (XI) may be used.

（式中、複数個のＸは各々独立に炭素数２〜６のアルキレン基を示し、３個のｊは各々独立に１〜３０の整数である。）上記一般式で表される光重合性化合物としては、ｊ＝７の場合、日立化成工業（株）製、サンプル名：ＴＭＰＴ−２１Ｅ がある。

(In the formula, a plurality of X's each independently represents an alkylene group having 2 to 6 carbon atoms, and three j's are each independently an integer of 1 to 30.) Photopolymerizability represented by the above general formula As a compound, when j = 7, there is a sample name: TMPT-21E manufactured by Hitachi Chemical Co., Ltd.

  (B) As a compounding quantity of the photopolymerizable compound of a component, it is preferable that it is 30-70 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and is 35-65 mass parts. It is more preferable, and it is still more preferable that it is 40-60 mass parts. If the amount is less than 30 parts by mass, good sensitivity and resolution tend not to be obtained, and if it exceeds 70 parts by mass, a good shape tends not to be obtained.

(B) The photopolymerizable compound which is a component is used individually by 1 type or in combination of 2 or more types.
This photopolymerizable compound preferably contains a bisphenol A (meth) acrylate compound or a (meth) acrylate compound having a urethane bond in the molecule from the viewpoint of improving plating resistance and adhesion. Moreover, it is preferable that a bisphenol A type (meth) acrylate compound is included from a viewpoint of improving a sensitivity and a resolution.

  The photopolymerizable compound (B) is a photopolymerization having one polymerizable ethylenically unsaturated bond in the molecule from the viewpoint of reducing the size of the resist strip and shortening the stripping time. The photopolymerizable unsaturated compound having one polymerizable ethylenically unsaturated bond in the molecule and two or more polymerizable ethylenically unsaturated bonds in the molecule are preferable. It is more preferable to use in combination with a photopolymerizable unsaturated compound.

  In this case, for example, as the photopolymerizable unsaturated compound having one polymerizable ethylenically unsaturated bond in the molecule, phenoxypolyethyleneoxy (meth) acrylate, phenoxypolyethyleneoxy-polypropyleneoxy (meth) acrylate, octylphenoxy Hexaethyleneoxy (meth) acrylate, octylphenoxyheptaethyleneoxy (meth) acrylate, octylphenoxyoctaethyleneoxy (meth) acrylate, octylphenoxynonaethyleneoxy (meth) acrylate, octylphenoxydecaethyleneoxy (meth) acrylate, nonylphenoxy Polyethyleneoxy (meth) acrylate, nonylphenoxypolyethyleneoxy-polypropyleneoxy (meth) acrylate, (meth) acrylic Phthalic acid derivative having a group.

  Examples of the photopolymerizable unsaturated compound having two or more polymerizable ethylenically unsaturated bonds in the molecule include 1,6-hexanediol di (meth) acrylate and 1,4-cyclohexanediol di (meth). Acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, polyethylene of the above general formulas (VIII) to (X) -Polypropylene glycol di (meth) acrylate, bisphenol A di (meth) acrylate, di (meth) acrylate having a urethane bond in the molecule, bis (acryloxyethyl) hydroxyethyl isocyanurate, bisphenol A diglycidyl ether di (meth) ) Acrylate, phthalate Glycidyl ester (meth) acrylate adducts.

  In addition, from the viewpoint of improving the resolution, stripping time and exposure tolerance in a balanced manner, one type of photopolymerizable unsaturated compound having one polymerizable ethylenically unsaturated bond in the molecule and two or more polymerizations in the molecule. It is particularly preferred to use a combination of two types of photopolymerizable unsaturated compounds having possible ethylenically unsaturated bonds.

  In this case, examples of the photopolymerizable unsaturated compound having one polymerizable ethylenically unsaturated bond in the molecule include phenoxypolyethyleneoxy (meth) acrylate, nonylphenoxypolyethyleneoxy (meth) acrylate, and (meth) acrylic. Any one of phthalic acid derivatives having a group can be used.

  Examples of the photopolymerizable unsaturated compound having two or more polymerizable ethylenically unsaturated bonds in the molecule include polyethylene / polypropylene glycol di (meth) acrylates of the above general formulas (VIII) to (X). EO-modified urethane di (meth) acrylate and at least one compound selected from EO and PO-modified urethane di (meth) acrylate, and a bisphenol A di (meth) acrylate compound can be used in combination.

Next, the photopolymerization initiator which is the component (C) will be described.
The photopolymerization initiator as the component (C) may be a hexaarylimidazole compound typified by 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, for example, 2- (o-bromo Phenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-bromophenyl) -4,5-di ( Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-ethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (2 , 6-dichlorophenyl) -4,5-dimer, 2- (2,6-difluorophenyl) -4,5-dimer, 2- (2,6-dichlorophenyl) -4,5-dimer Methoxyphenyl) imidazole dimer, 2- (2,6-difluorophenyl) -4,5-di (derivatives such methoxyphenyl) imidazole dimer and the like.

  In the 2,4,5-triarylimidazole dimer, the substituents of the aryl groups of the two 2,4,5-triarylimidazoles may be the same and give the target compound. Such compounds may be provided.

  In addition, from the viewpoint of adhesion and sensitivity, the photopolymerization initiator is a photosensitive resin composition sensitivity and resist adhesion by using a hexaarylbiimidazole compound that is a 2,4,5-triarylimidazole dimer. This is preferable because of improved properties. These photopolymerization initiators are used alone or in combination of two or more.

  In addition, the blending amount of the photopolymerization initiator that is the component (C) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B), and 2 to 6 More preferably, it is 3 parts by mass, and still more preferably 3-5 parts by mass. If the amount is less than 0.1 parts by mass, good sensitivity and resolution tend to be difficult to obtain, and if it exceeds 10 parts by mass, there is a tendency that a resist pattern having a desired shape cannot be obtained. (C) The photoinitiator which is a component is used individually by 1 type or in combination of 2 or more types.

  The photosensitive resin composition according to the present invention preferably contains (D) an amine compound in addition to the components (A) to (C) described above. (D) It is preferable to contain an amine compound since the sensitivity of the photosensitive resin composition is further improved.

  The amine compound as the component (D) is not particularly limited as long as it has an amino group in the molecule and can increase the sensitivity of the photosensitive resin composition. Specific examples thereof include N such as N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone) and N, N′-tetraethyl-4,4′-diaminobenzophenone (ethyl Michler ketone). , N′-tetraalkyl-4,4′-diaminobenzophenone, N-phenylglycine, N-phenylglycine derivatives, Coumarin 1 (a reagent from Kodak and Across) and the like as coumarin compounds having an alkylamino group, 7- Amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin (coumarin 1), 7-diethylamino-4-methylcoumarin), 7-methylamino-4-methylcoumarin, 7-ethylamino-4-methylcoumarin 4,6-dimethyl-7-ethylaminocoumarin 4,6 -Diethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-diethylaminocoumarin, 4,6-diethyl-7 -Coumarin derivatives such as dimethylaminocoumarin, 4,6-dimethyl-7-ethylaminocoumarin, 7-dimethylaminocyclopenta [c] coumarin, 7-aminocyclopenta [c] coumarin, and bis [ 4- (diethylamino) phenyl] methane, leucocrystal violet and the like.

  The compounding amount of the amine compound is preferably 0.01 to 10 parts by mass and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). Preferably, it is 0.1-2 mass parts. If the amount is less than 0.01 parts by mass, good sensitivity tends not to be obtained, and if it exceeds 10 parts by mass, the component (D) tends to precipitate as foreign matter after film formation. The amine compound which is (D) component is used individually by 1 type or in combination of 2 or more types.

  In the photosensitive resin composition according to the present invention, a photopolymerizable compound (such as an oxetane compound) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, malachite green, or the like, if necessary. Dyes, photochromic agents such as tribromophenylsulfone and leucocrystal violet, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion imparting Contains about 0.01 to 20 parts by mass of an agent, leveling agent, peeling accelerator, antioxidant, fragrance, imaging agent, thermal crosslinking agent, etc., with respect to 100 parts by mass of component (A) and component (B), respectively. can do. These may be used alone or in combination of two or more.

  The photosensitive resin composition according to the present invention is soluble in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. And it is good also as a solution about 30-60 mass% of solid content. This solution can be used as a coating solution for forming the photosensitive resin composition layer of the photosensitive element.

  In addition to using the coating solution to form the photosensitive resin composition layer of the photosensitive element, for example, the coating solution is applied as a liquid resist on the surface of a metal plate, dried, and then coated with a protective film. It may be used. Examples of the material of the metal plate include copper, copper alloys, iron alloys such as nickel, chromium, iron and stainless steel, preferably copper, copper alloys and iron alloys.

  Next, the photosensitive element of the present invention will be described. FIG. 1 is a schematic cross-sectional view of a photosensitive element according to an embodiment of the present invention. A photosensitive element 1 shown in FIG. 1 is laminated on a support film 2, a photosensitive resin composition layer 3 containing the photosensitive resin composition formed on the support film 2, and the photosensitive resin composition layer 3. It is comprised with the protective film 4 made. With such a configuration, it is possible to carry out with sufficient resolution, and there is a sufficient effect in improving the resist peeling characteristics.

  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. Examples of commercially available products include, for example, polypropylene films such as Alfane MA-410, D-200C (above, trade name) manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., and PS series manufactured by Teijin Limited (for example, Examples include, but are not limited to, polyethylene terephthalate films such as trade name: PS-25).

  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. If the thickness is less than 1 μm, the support film tends to be broken when the support film is peeled off before development, and if it exceeds 100 μm, the resolution tends to decrease. The support film 2 is used by laminating one side as a support for the photosensitive resin composition layer and the other as a protective film for the photosensitive resin composition layer on both sides of the photosensitive resin composition layer. Also good.

The photosensitive resin composition layer 3 is prepared by dissolving the photosensitive resin composition in a solvent as described above to obtain a solution (coating solution) having a solid content of about 30 to 60% by mass, and then applying this solution onto the support film 2. It is preferable to form it by applying to and drying.
The coating can be performed by a known method using, for example, a roll coater, comma coater, gravure coater, air knife coater, die coater, bar coater or the like.

Moreover, drying can be performed at 70-150 degreeC and about 5 to 30 minutes.
The amount of the residual organic solvent in the photosensitive resin composition is preferably 2% by mass or less from the viewpoint of preventing the organic solvent from diffusing in the subsequent step.

  Although the thickness of the photosensitive resin composition layer 3 changes with uses 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. If the thickness is less than 1 μm, it tends to be difficult to apply industrially, and if it exceeds 100 μm, the effect of the present invention is reduced, and the adhesive force and resolution tend to be reduced.

  The protective film 4 preferably has a smaller adhesive force between the photosensitive resin composition layer 3 and the protective film 4 than the adhesive force between the photosensitive resin composition layer 3 and the support film 2, and has a low fish eye. The film is preferred. "Fish eye" means that when a material is melted by heat, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidized degradation products, etc. It is taken in.

  As the protective film 4, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used. Examples of commercially available products include, for example, polypropylene films such as Alfane MA-410, D-200C (above, trade name) manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., and PS series manufactured by Teijin Limited (for example, Examples include, but are not limited to, polyethylene terephthalate films such as trade name: PS-25).

  The protective film 4 preferably has a thickness of 1 to 100 μm, more preferably 5 to 50 μm, further preferably 5 to 30 μm, and particularly preferably 15 to 30 μm. When the thickness is less than 1 μm, the protective film tends to be broken during lamination, and when it exceeds 100 μm, the cost tends to be inferior.

In addition, the photosensitive element 1 according to the present invention may further include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.
Moreover, the obtained photosensitive element 1 can be wound up and stored in a roll shape around a sheet shape or a core. In addition, it is preferable to wind up so that the support film 2 may become the outermost part in this case.

An end face separator is preferably installed on the end face of the roll-shaped photosensitive element roll from the viewpoint of end face protection, and a moisture-proof end face separator is preferably installed from the viewpoint of edge fusion resistance.
Moreover, as a packing method, it is preferable to wrap and package in a black sheet with low moisture permeability.

  Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

Next, a resist pattern forming method according to the present invention will be described.
The method for forming a resist pattern according to 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 active in a predetermined portion of the photosensitive resin composition layer. It includes at least an exposure step of irradiating light and photocuring the exposed portion, and a developing step of removing the photosensitive resin composition in a portion other than the exposed portion from the circuit forming substrate.

The “circuit forming substrate” refers to a substrate including an insulating layer and a conductor layer formed on the insulating layer. Further, the circuit forming substrate may be multilayered and may have wiring formed therein, and may have a small-diameter through hole.
According to the above resist pattern forming method, a resist pattern having a sufficient resolution can be formed, and at the same time, the resist peeling characteristics can be improved sufficiently.

The following method is mentioned as a lamination | stacking method of the photosensitive resin composition layer on the circuit formation board | substrate in a lamination process.
First, the protective film is gradually peeled from the photosensitive resin composition layer, and at the same time, the portion of the surface of the photosensitive resin composition layer that is gradually exposed is brought into close contact with the surface of the circuit forming substrate on which the circuit is formed. .

  And it laminates | stacks by crimping | bonding the photosensitive resin composition layer to the circuit formation board | substrate, heating the photosensitive resin composition layer. In addition, it is preferable to laminate | stack this operation | work under reduced pressure from the standpoint of adhesiveness and follow-up improvement.

In the lamination of the photosensitive element, the photosensitive resin composition layer and / or the circuit forming substrate is preferably heated to 70 to 130 ° C., and the pressure bonding pressure is about 0.1 to 1.0 MPa (1 to 10 kgf / cm). it is preferably about ^2), but not particularly limited to these conditions.

  Further, if the photosensitive resin composition layer is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the circuit forming substrate in advance, but in order to further improve the laminating property, the circuit forming substrate is not necessary. It is also possible to perform a pre-heat treatment.

  Examples of the method for forming the exposed portion in the exposure step include a method of irradiating an image with active light through a negative or positive mask pattern called an artwork (mask exposure method). At this time, when the support film present on the photosensitive resin composition layer transmits actinic rays, the support film can be irradiated with actinic rays, and when the support film is light-shielding, the support film After removing the light, the photosensitive resin composition layer is irradiated with actinic rays.

  Alternatively, a method of irradiating actinic rays in an image form by a direct drawing exposure method such as a laser direct drawing exposure method or a B-1LP (B-1 digital Light ProcDssing) exposure method may be employed.

  As a light source of actinic light, known light sources such as carbon arc lamp, mercury vapor arc lamp, high pressure mercury lamp, xenon lamp, gas laser such as argon laser, solid state laser such as YAG laser, ultraviolet ray such as semiconductor laser, visible light, etc. That effectively radiate are used.

  As a method for removing portions other than the exposed portion in the development process, first, when a support film is present on the photosensitive resin composition layer, the support film is removed, and then wet development, dry development, etc. And a method of developing by removing portions other than the exposed portion. Thereby, a resist pattern is formed.

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

  As the developer, an alkaline aqueous solution which is safe and stable and has good operability is used. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide, alkali carbonates such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate, potassium phosphate, and phosphoric acid. Examples include alkali metal phosphates such as sodium, alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, and borax.

  The alkaline aqueous solution used for development includes a dilute solution of 0.1 to 5% by mass sodium carbonate, a dilute solution of 0.1 to 5% by mass potassium carbonate, and a dilute solution of 0.1 to 5% by mass sodium hydroxide. A dilute solution of 0.1 to 5% by mass sodium tetraborate (borax) is preferable.

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.
In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development may be added.

  Examples of the aqueous developer include a developer composed of water or an alkaline aqueous solution and one or more organic solvents. Here, as the base of the alkaline aqueous solution, in addition to the substances described above, for example, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1, 3-propanediol 1,3-diaminopropanol-2, morpholine and the like. The pH of the developer is preferably as low as possible within a range where the resist can be sufficiently developed, preferably pH 8-12, and more preferably pH 9-10.

  Examples of the organic solvent include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like. It is done. These may be used alone or in combination of two or more.

Moreover, it is preferable that the density | concentration of an organic solvent is 2 to 90 mass% normally, and the temperature can be adjusted according to developability.
In addition, a small amount of a surfactant, an antifoaming agent, or the like can be added to the aqueous developer.

  Examples of the organic solvent developer using an organic solvent alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. It is done. These organic solvent-based developers are preferably added with water in an amount of 1 to 20% by mass in order to prevent ignition.

As the treatment after development, the resist pattern may be further cured and used by heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm ² as necessary.

Next, the manufacturing method of the printed wiring board which becomes this invention is demonstrated.
The printed wiring board manufacturing method according to the present invention is a method for forming a conductor pattern by etching or plating a circuit forming substrate on which a resist pattern is formed, by the resist pattern forming method of the present invention.

  Etching and plating of the circuit forming substrate are performed on the conductor layer of the circuit forming substrate and the like using the formed resist pattern as a mask. Etching solutions used for etching include cupric chloride solution, ferric chloride solution, alkaline etching solution, hydrogen peroxide etching solution, etc., and among these, chloride chloride is used because of its good etch factor. It is preferable to use a diiron solution.

  Moreover, as a 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 throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel sulfamate, etc. Nickel plating, hard gold plating, and gold plating such as soft gold plating.

After completion of the etching or plating, the resist pattern can be peeled off with, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. As this strongly alkaline aqueous solution, for example, a 1 to 10% by mass sodium hydroxide aqueous solution, a 1 to 10% by mass potassium hydroxide aqueous solution and the like are used.

Examples of the peeling method include an immersion method and a spray method, and the immersion method and the spray method may be used alone or in combination. A printed wiring board can be obtained by such a method.
As mentioned above, although the best form for implementing this invention was demonstrated, this invention is not restrict | limited to these.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | 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 at a mass ratio of 3: 2 was added and stirred while blowing nitrogen gas. Heated to ° C.

  On the other hand, a solution (hereinafter referred to as “solution a”) prepared by mixing 150 g of methacrylic acid, 25 g of methyl methacrylate, 125 g of benzyl methacrylate, 200 g of styrene and 9.0 g of azobisisobutyronitrile as a comonomer was prepared. The solution a was added dropwise over 4 hours to a mixture of methyl cellosolve and toluene having a mass ratio of 3: 2 prepared in advance, and the mixture was kept warm at 80 ° C. for 2 hours.

  Furthermore, a solution in which 1.2 g of azobisisobutyronitrile was dissolved in 100 g of a mixture of methyl cellosolve and toluene having a mass ratio of 3: 2 was dropped over 10 minutes. The solution after dropping was kept at 80 ° C. for 3 hours with stirring, and then heated to 90 ° C. over 30 minutes. The mixture was kept at 90 ° C. for 2 hours and then cooled to obtain a binder polymer (a-1).

  The nonvolatile content (solid content) of the binder polymer (a-1) was 47.8% by mass, and the weight average molecular weight was 30,000. In addition, the weight average molecular weight was derived | led-out by measuring with the gel permeation chromatography method and converting using the analytical curve of a standard polystyrene.

  Moreover, binder polymers (a-2) to (a-4) were synthesized by the same method as the synthesis method of the binder polymer (a-1) described above so as to have the composition shown in Table 1 below.

(Adjustment of photosensitive resin composition)
<Binder polymer (A) component>
Table 2 shows binder polymers (a-1) to (a-4), photopolymerizable compounds (B-1) to (B-5), photopolymerization initiator (C-1), hydrogen donor, dye and solvent. The solutions of the photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were prepared at a mass ratio shown in FIG.

<Photopolymerizable Compound [Component (B)]>
B-1: Vinyl acetate (Wako Pure Chemical Industries)
B-2: 2,2-bis [4- (methacryloxypentaethoxy) phenyl] propane [manufactured by Hitachi Chemical Co., Ltd., trade name: FA-321M]
B-3: A compound represented by the above general formula (IX), wherein R ¹² and R ¹³ are each a methyl group, m ³ = 6 (average value), n ² + n ³ = 12 (average value) Vinyl compound [manufactured by Hitachi Chemical Co., Ltd., trade name: FA-024M]
B-4: 4-normalnonylphenoxyoctaethyleneoxyacrylate [manufactured by Toagosei Co., Ltd., trade name: M-114]
B-5: 21EO modified trimethylolpropane triacrylate [manufactured by Hitachi Chemical Co., Ltd., developed product name: TMPT-21E]

<Photopolymerization initiator [(C) component]>
C-1: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole [B-CIM, manufactured by Hodogaya Chemical Co., Ltd.]
<(D) Hydrogen donor (amine compound)>
D-1: Diethylaminobenzophenone [EAB, manufactured by Hodogaya Chemical Co., Ltd.]
D-2: Coumarin 1 [Coumarin 1, manufactured by Acros Corporation]

<Dye>
Malachite green (Osaka Organic Chemical Industry Co., Ltd.)
<Solvent>
Acetone Toluene Methanol

(Production of photosensitive element)
Next, the obtained photosensitive resin composition solutions (Examples 1 to 3 and Comparative Examples 1 and 2) were uniformly distributed on a 16 μm-thick polyethylene terephthalate film (trade name G2-16, manufactured by Teijin Limited). After coating and drying with a hot air convection dryer at 100 ° C. for 10 minutes, a photosensitive element was obtained by covering with a polyethylene protective film [trade name NF-15, manufactured by Tamapoly Co., Ltd.]. In addition, the film thickness of the photosensitive resin composition layer after drying was 25 μm.

  On the other hand, the copper surface of a copper-clad laminate (made by Hitachi Chemical Co., Ltd., trade name MCL-E-61), which is a glass epoxy material laminated with copper foil (thickness 35 μm) on both sides, is a brush equivalent to # 600 Polishing was carried out using a polishing machine (manufactured by Sankei Co., Ltd.), washed with water, and dried with an air stream. And the obtained copper-clad laminated board was heated at 80 degreeC, and the photosensitive resin composition layer was laminated | stacked on the copper surface, peeling the protective film of a photosensitive element, and the laminated body was obtained. The lamination was performed at a speed of 1.5 m / min with a heat roll at 110 ° C.

Next, on the obtained laminate, a stove 21 step tablet is placed as a negative, and an exposure machine (manufactured by Oak Co.) EXM-1201 having a high pressure mercury lamp lamp is used. The exposure was performed at 60, 120 mJ / cm ² .

  Subsequently, the polyethylene terephthalate film was peeled off, sprayed with a 1 wt% sodium carbonate aqueous solution at 30 ° C. for 40 seconds to remove the unexposed portion, and then the number of steps of the step tablet of the photocured film formed on the copper-clad laminate Was measured, and the amount of exposure required to leave the seven steps of the 21-step tablet of the stopher was calculated from the logarithmic regression calculation to obtain the photosensitivity.

  The photosensitivity of each photosensitive resin composition was evaluated, and the results are shown in Tables 3 and 4. The photosensitivity is indicated by the exposure amount, and the lower this value, the higher the photosensitivity. In addition, a photo tool having a 21-step tablet of Stower and a photo tool having a wiring pattern with a line width / space width of 8/8 to 30/30 (unit: μm) as a negative for resolution evaluation are brought into close contact with each other. 2 Exposure was performed with an energy amount such that the number of steps remaining after development of the 1-step tablet was 7.0.

  Then, the resolution is obtained from the smallest value of the space width between the line widths in which the unexposed part can be removed cleanly by the development processing, and the results are shown in Tables 3 and 4. The smaller the numerical value, the better the resolution.

  Further, a test piece irradiated with an exposure amount (7.0 steps / 21) corresponding to each sensitivity was developed with a 1% by weight aqueous sodium carbonate solution. After leaving for one day and night, the test piece was immersed in a 3% by weight sodium hydroxide aqueous solution maintained at 45 ° C., and the time when the photocured film (resist) began to peel (peeling time (seconds)) was measured. The results are shown in Tables 3 and 4. A shorter peeling time is preferable.

  As shown in Tables 3 and 4, according to the present invention, it has excellent resolution and excellent characteristics in terms of photosensitivity, and the peeling time from the substrate after curing is also compared with that of the comparative example. It is clear that it is short.

It is a schematic cross section of the photosensitive element which becomes the Example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photosensitive element 2 Support film 3 Photosensitive resin composition layer 4 Protective film

Claims (8)

(A) A binder having a divalent group represented by the following general formula (I), a divalent group represented by the following general formula (II), and a divalent group represented by the following general formula (III) polymer,
(B-1) One or both of vinyl acetate and vinyl propionate are contained as one of the components, and (B-2) a bisphenol A (meth) acrylate bifunctional monomer represented by the following formula (IV) (Wherein R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and p, q, s and t are positive integers selected so that p + q + s + t = 4 to 40). A photosensitive resin composition comprising a photopolymerizable compound and (C) a photopolymerization initiator.

[Formula (I), shows the (II) and (III) ^{in, R 1, R 3, R} 4 and ^{R 5} independently represent hydrogen atom, a methyl group or an alkyl group having 2 to 4 carbon atoms, ^{R 2} Each independently represents 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, and each m independently represents an integer of 0 to 5. ]   The divalent group represented by the general formula (II) is 5 to 60 parts by mass of the divalent group represented by the general formula (I) with respect to 100 parts by mass of the (A) binder polymer. The photosensitive resin composition according to claim 1, which has 15 to 45 parts by weight of the above group and 10 parts by weight or more and less than 60 parts by weight of the divalent group represented by the general formula (III). The divalent group represented by the general formula (II) is 5 to 60 parts by mass of the divalent group represented by the general formula (I) with respect to 100 parts by mass of the (A) binder polymer. 15 to 45 parts by mass of the group, 5 to 60 parts by mass of the divalent group represented by the general formula (III) and 5 to 60 parts by mass of the divalent group represented by the following general formula (V) The photosensitive resin composition of Claim 1 or 2.

[R ⁶ and R ⁷ 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, and n represents an integer of 0 to 5 independently. ]   The photosensitive resin composition according to claim 1, wherein the (C) photopolymerization initiator has a hexaarylbiimidazole compound.   The photosensitive resin composition formed by containing the amine compound further in the photosensitive resin composition in any one of Claims 1-4.   The photosensitive element provided with the photosensitive resin composition layer containing the photosensitive resin composition in any one of Claims 1-5 formed on the supporting film and the said supporting film.   A photosensitive resin composition layer containing the photosensitive resin composition according to claim 1 or the photosensitive resin composition according to claim 6 on a circuit-forming substrate. Laminating step for laminating, exposure step for irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays to photo-curing an exposed portion, and circuit-forming substrate on which the photosensitive resin composition layer is laminated. A method for forming a resist pattern, comprising: a developing step of removing a portion other than the exposed portion of the resin composition layer.   A method for manufacturing a printed wiring board, comprising: forming a conductor pattern by etching or plating a circuit forming substrate on which a resist pattern is formed by the method for forming a resist pattern according to claim 7.

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