JP4761909B2 - Photosensitive resin composition and laminate - Google Patents

Description

The present invention relates to a photosensitive resin composition that can be developed with an alkaline aqueous solution, a photosensitive resin laminate in which the photosensitive resin composition is laminated on a support, and a resist pattern on a substrate using the photosensitive resin laminate. The present invention relates to a method for forming the resist pattern and an application of the resist pattern. More specifically, the manufacture of printed wiring boards, the manufacture of flexible printed wiring boards, the manufacture of lead frames for IC chip mounting (hereinafter referred to as lead frames), metal foil precision processing such as metal mask manufacturing, BGA (ball grid array) Manufacture of semiconductor packages such as CSP (chip size package), manufacture of tape substrates represented by TAB (Tape Automated Bonding) and COF (Chip On Film: a semiconductor IC mounted on a film-like fine wiring board), semiconductor A photosensitive tree that provides a resist pattern suitable as a protective mask member when manufacturing a bump, manufacturing a member such as an ITO electrode, an address electrode, or an electromagnetic wave shield in the field of flat panel displays, and processing a substrate by sandblasting. It relates to a composition.

  Conventionally, printed wiring boards are manufactured by a photolithography method. The photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed to polymerize and cure the exposed portion of the photosensitive resin composition, and an unexposed portion is removed with a developer to form a resist on the substrate. A method of forming a conductor pattern on a substrate by forming a pattern, forming a conductor pattern by etching or plating, and then peeling and removing the resist pattern from the substrate.

  In the photolithography method described above, in applying the photosensitive resin composition onto the substrate, a method of applying a photoresist solution to the substrate and drying, or a support, a layer made of the photosensitive resin composition (hereinafter, “ Any of the methods of laminating a photosensitive resin laminate (hereinafter referred to as “dry film resist”) in which a protective resin layer is sequentially laminated on a substrate is used. In the production of printed wiring boards, the latter dry film resist is often used.

A method for producing a printed wiring board using the dry film resist will be briefly described below.
First, when the dry film resist has a protective layer such as a polyethylene film, it is peeled off from the photosensitive resin layer. Next, the photosensitive resin layer and the support are laminated on a substrate such as a copper-clad laminate using a laminator so that the substrate, the photosensitive resin layer, and the support are in this order. Next, the exposed portion is polymerized and cured by exposing the photosensitive resin layer with ultraviolet rays such as i rays (365 nm) emitted from an ultrahigh pressure mercury lamp through a photomask having a wiring pattern. Next, the support made of polyethylene terephthalate or the like is peeled off. Next, a non-exposed portion of the photosensitive resin layer is dissolved or dispersed and removed by a developing solution such as an aqueous solution having weak alkalinity to form a resist pattern on the substrate.

There are roughly two methods for creating a metal conductor pattern using a resist pattern on a substrate. There are a method for removing a metal portion not covered with a resist by etching and a method for attaching a metal by plating. is there. In particular, the former method is frequently used recently because of the simplicity of the process.
In the method of removing the metal portion by etching, the metal in the hole is prevented from being etched by covering the through hole (through hole) of the substrate and the via hole for interlayer connection with a cured resist film. This construction method is called a tenting method. The dry film resist used in the tenting method is required to have a high strength of the cured resist film because the cured resist film (referred to as a tenting film) that covers the holes during development or etching is required not to be damaged. I came.

  On the other hand, in the printed wiring board manufacturing technology, maskless exposure that does not require a photomask such as direct drawing by a laser has been spreading rapidly in recent years. As a light source for maskless exposure, light having a wavelength of 350 to 410 nm, particularly i-line or h-line (405 nm) is often used. Therefore, it is important to be able to form a highly sensitive resist pattern for light sources in these wavelength ranges. In the case of direct drawing exposure, the exposure time is longer than the batch exposure of the substrate, but if the resist sensitivity is high, the exposure time can be shortened as much as possible.

  In a photosensitive resin composition for a dry film resist, benzophenone, Michler's ketone, and derivatives thereof that have been conventionally used as photopolymerization initiators have localized absorption regions near a wavelength of 360 nm. Therefore, the dry film resist using the photopolymerization initiator has sufficient sensitivity to i-line, but the sensitivity decreases as the wavelength of the exposure light source approaches the visible region, and for light sources of 400 nm or more. It is difficult to obtain sufficient resolution and adhesion.

Further, another photopolymerization initiator, thioxanthone and derivatives thereof, can be combined with high sensitivity to an exposure light source having a wavelength of around 380 nm by selecting an appropriate sensitizer. However, in many cases, sufficient resolution cannot be obtained in the formed resist pattern even when the combination is used, and the sensitivity is also lowered for an exposure light source having a wavelength of 400 nm or more.
In recent years, semiconductor lasers near 405 nm have been widely used as light sources for direct-drawing exposure machines, and the exposure time has become shorter as the output increases, but a dry film that can provide sufficient tenting film strength in a short time There was no resist. Patent Document 1 discloses a photosensitive resin laminate containing a bisphenol-type monomer in which 22 to 48 units of an alkylene oxide chain are bonded, and exhibits good tenting properties by ultraviolet laser exposure of 357 ± 10 nm. However, further improvements have been sought in 405 ± 10 nm semiconductor lasers.

Patent Document 2 discloses a photosensitive resin composition using a pyrazoline compound, but there is no disclosure regarding the effect of tenting properties.
For these reasons, a photosensitive resin composition that exhibits good compatibility as a photosensitive resin composition for dry film resists and that is particularly excellent in sensitivity to a light source of 405 ± 10 nm, resolution, and tenting properties is desired. It was rare.

Japanese Patent Laid-Open No. 2002-323761 JP-A-2005-215142

  The present invention relates to a photosensitive resin composition that is excellent in sensitivity and resolution with respect to an exposure light source having a wavelength of 405 ± 10 nm, that has good tenting properties, and that can be developed with an alkaline aqueous solution, and photosensitivity using the photosensitive resin composition. It aims at providing the resin laminated body, the method of forming a resist pattern on a board | substrate using this photosensitive resin laminated body, and the use of this resist pattern.

The above object can be achieved by the following configuration of the present invention.
That is, the present invention is as follows.
(1) (a) Thermoplastic copolymer containing an α, β-unsaturated carboxyl group-containing monomer as a copolymerization component, having an acid equivalent of 100 to 600, and a weight average molecular weight of 5,000 to 500,000: 20 -90 mass%, (b) addition polymerizable monomer having at least one terminal ethylenically unsaturated group: 5-75 mass%, (c) photopolymerization initiator: 0.01-30 mass%, (d) A pyrazoline compound represented by the general formula (I): 0.001 to 10% by mass, and (b) an addition polymerizable monomer having a structure represented by the following general formula (II) as an addition polymerizable monomer A photosensitive resin composition.

（式中Ａは、それぞれ独立に、アリール基、複素環基からなる群から選ばれる置換基を表し、Ｂ及びＣは、それぞれ独立に、アリール基、複素環基、炭素数３以上の直鎖または分枝鎖のアルキル基、及びＮＲ₂（Ｒは水素原子、またはアルキル基）からなる群から選ばれる置換基を表す。ａは１〜２の整数，ｂ及びｃの夫々は０〜２の整数であるが、ａ＋ｂ＋ｃの値は１以上である。）

(In the formula, A independently represents a substituent selected from the group consisting of an aryl group and a heterocyclic group, and B and C each independently represent an aryl group, a heterocyclic group, and a straight chain having 3 or more carbon atoms. Or a branched alkyl group and a substituent selected from the group consisting of NR ₂ (R is a hydrogen atom or an alkyl group), a is an integer of 1 to 2, and b and c are each 0 to 2. (It is an integer, but the value of a + b + c is 1 or more.)

（式中、Ｒ_１及びＲ_２は、ＨまたはＣＨ_３であり、これらは同一であっても相違してもよい。また、ＤおよびＥは、一方が炭素数２個のアルキレン基であり、もう一方が炭素数３〜４個のアルキレン基であり、−（Ｄ−Ｏ）−及び−（Ｅ−Ｏ）−の繰り返し単位は、ブロック構造でもランダム構造でもよい。ｍ１、ｍ２、ｎ１、及びｎ２は、０または正の整数であり、これらの合計は、３１〜４８である。）

(In the formula, R ₁ and R ₂ are H or CH ₃ , which may be the same or different. One of D and E is an alkylene group having 2 carbon atoms, The other is an alkylene group having 3 to 4 carbon atoms, and the repeating unit of — (D—O) — and — (E—O) — may have a block structure or a random structure, m1, m2, n1, and n2 is 0 or a positive integer, and the sum of these is 31 to 48.)

（式中、Ｒは水素、アルキル基、アリール基、ピリジル基、又はアルコシキル基である。） (2) (c) The photopolymerization initiator contains a hexaarylbiimidazole and / or an acridine compound represented by the following general formula (III), and the photosensitive resin composition according to (1) .

(In the formula, R is hydrogen, an alkyl group, an aryl group, a pyridyl group, or an alkoxy group.)

(3) The photosensitive resin composition according to (1) or (2), further comprising an N-aryl amino acid represented by the following general formula (IV) or an ester compound thereof.
R ₁ —NHCH ₂ COO—R ₂ (IV)
(In the formula, R ₁ is an aryl group, and R ₂ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)
(4) A photosensitive resin laminate obtained by laminating the photosensitive resin composition according to any one of (1) to (3) on a support.
(5) A resist pattern forming method including a laminating step, an exposing step, and a developing step of forming a photosensitive resin layer on the substrate using the photosensitive resin laminate according to (4).
(6) The resist pattern forming method as described in (5), wherein in the exposure step, exposure is performed by direct drawing.

(7) A method for producing a printed wiring board, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method according to any one of (4) to (6).
(8) A lead frame manufacturing method including a step of etching a substrate on which a resist pattern is formed by the method according to any one of (4) to (6).
(9) A method for manufacturing a semiconductor package, including a step of etching or plating a substrate on which a resist pattern is formed by the method according to any one of (4) to (6).
(10) A method for producing a substrate having a concavo-convex pattern including a step of processing a substrate on which a resist pattern is formed by the method according to any one of (4) to (6) by sandblasting.

  The photosensitive resin composition of the present invention is highly sensitive to an exposure light source having a wavelength of 405 ± 10 nm. In addition, the photosensitive resin laminate of the present invention is excellent in sensitivity at the time of exposure and resolution of the resist pattern after development, and has good tenting properties. The resist pattern forming method of the present invention provides a resist pattern excellent in sensitivity, resolution, and adhesion, and is suitably used for printed wiring board manufacturing, lead frame manufacturing, semiconductor package manufacturing, and flat display manufacturing. can do.

Hereinafter, the present invention will be specifically described.
<Photosensitive resin composition>
The photosensitive resin composition of the present invention includes (a) an α, β-unsaturated carboxyl group-containing monomer as a copolymerization component, has an acid equivalent of 100 to 600, and a weight average molecular weight of 5,000 to 500,000. Thermoplastic copolymer: 20 to 90% by mass, (b) Addition polymerizable monomer having at least one terminal ethylenically unsaturated group: 5 to 75% by mass, (c) Photopolymerization initiator: 0.01 to 30 % By mass, (d) pyrazoline compound represented by the following general formula (I): 0.001 to 0.001
It contains 10% by mass, and (b) an addition polymerizable monomer having a structure represented by the following general formula (II) is contained as an addition polymerizable monomer.

（式中Ａ、Ｂ及びＣは、それぞれ独立に、アリール基、複素環基、炭素数３以上の直鎖または分枝鎖のアルキル基、ＮＲ_２（Ｒは水素原子、またはアルキル基）からなる群から選ばれる置換基を表す。ａ， ｂ及びｃの夫々は０〜２の整数であるが、ａ＋ｂ＋ｃの値は１以上である。）

(In the formula, A, B and C are each independently an aryl group, a heterocyclic group, a linear or branched alkyl group having 3 or more carbon atoms, or NR ₂ (R is a hydrogen atom or an alkyl group). Represents a substituent selected from the group, each of a, b and c is an integer of 0 to 2, but the value of a + b + c is 1 or more.)

（式中、Ｒ_１及びＲ_２は、ＨまたはＣＨ_３であり、これらは同一であっても相違してもよい。また、ＤおよびＥは、一方が炭素数２個のアルキレン基であり、もう一方が炭素数３〜４個のアルキレン基であり、−（Ｄ−Ｏ）−及び−（Ｅ−Ｏ）−の繰り返し単位は、ブロック構造でもランダム構造でもよい。ｍ１、ｍ２、ｎ１、及びｎ２は、０または正の整数であり、これらの合計は、３２〜４８である。）

(In the formula, R ₁ and R ₂ are H or CH ₃ , which may be the same or different. One of D and E is an alkylene group having 2 carbon atoms, The other is an alkylene group having 3 to 4 carbon atoms, and the repeating unit of — (D—O) — and — (E—O) — may have a block structure or a random structure, m1, m2, n1, and n2 is 0 or a positive integer, and the sum of these is 32-48.)

(A) Thermoplastic copolymer In the photosensitive resin composition of the present invention, the (a) thermoplastic copolymer contains an α, β-unsaturated carboxyl group-containing monomer as a copolymer component, and has an acid equivalent. And having a weight average molecular weight of 5,000 to 500,000.
The carboxyl group in the thermoplastic copolymer is necessary for the photosensitive resin composition to have developability and releasability with respect to a developer and a release solution made of an alkaline aqueous solution. The acid equivalent is 100
-600 is preferable, More preferably, it is 300-450. It is 100 or more from the viewpoint of securing compatibility with other components in the solvent or the composition, particularly (b) addition polymerizable monomer described later, and 600 or less from the viewpoint of maintaining developability and peelability. It is. Here, an acid equivalent means the mass (gram) of the thermoplastic copolymer which has a 1 equivalent carboxyl group in it. The acid equivalent is measured by potentiometric titration with a 0.1 mol / L NaOH aqueous solution using a Hiranuma Reporting Titrator (COM-555).

  The weight average molecular weight is preferably 5000 to 500,000. It is 5000 or more from the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance to the developer, and is 500,000 or less from the viewpoint of maintaining developability. More preferably, the weight average molecular weight is 20000 to 100,000. The weight average molecular weight in this case is a weight average molecular weight measured by gel permeation chromatography (GPC) using a polystyrene calibration curve. The weight average molecular weight can be measured using gel permeation chromatography manufactured by JASCO Corporation under the following conditions.

Differential refractometer: RI-1530
Pump: PU-1580
Degasser: DG-9-80-50
Column oven: CO-1560
Column: KF-8025, KF-806M × 2, KF-807 in order
Eluent: THF

The thermoplastic copolymer is a copolymer composed of at least one of the first monomers described later, or at least one of the first monomers and the second monomer described later. A copolymer comprising at least one of the above is preferable.
The first monomer is a monomer containing an α, β-unsaturated carboxyl group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable.

  The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, esters of vinyl alcohol such as vinyl acetate, (meth) acrylonitrile , Styrene, and polymerizable styrene derivatives. Of these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are particularly preferable.

The amount of the thermoplastic polymer contained in the photosensitive resin composition of the present invention is in the range of 20 to 90% by mass, and preferably in the range of 25 to 70% by mass. This amount is preferably 20% by mass or more from the viewpoint of maintaining alkali developability, and is preferably 90% by mass or less from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist.
(B) Addition polymerizable monomer (b) The addition polymerizable monomer having at least one terminal ethylenically unsaturated group used in the photosensitive resin composition of the present invention includes the following general compounds from the viewpoint of resolution and adhesion. Formula (II
It is desirable to contain the compound shown by this.

（式中、Ｒ_１及びＲ_２は、ＨまたはＣＨ_３であり、これらは同一であっても相違してもよい。また、ＤおよびＥは、炭素数が２〜４個のアルキレン基であり、それぞれ同一であっても異なっていてもよく、異なっている場合、−（Ｄ−Ｏ）−及び−（Ｅ−Ｏ）−の繰り返し単位は、ブロック構造でもランダム構造でもよい。ｍ１、ｍ２、ｎ１、及びｎ２は、０又は正の整数であり、これらの合計は、３１〜４８である。）

(In the formula, R ₁ and R ₂ are H or CH ₃ , which may be the same or different. D and E are alkylene groups having 2 to 4 carbon atoms. , Each may be the same or different, and in the case where they are different, the repeating unit of-(DO)-and-(EO)-may be a block structure or a random structure. n1 and n2 are 0 or a positive integer, and the sum of these is 31 to 48.)

  Examples of the compound represented by the general formula (II) include 2,2-bis {(4-acryloxypolyethoxy) phenyl} propane or 2,2-bis {(4-methacryloxypolyethoxy) phenyl} propane. Can be given. The polyethoxy group possessed by the compound includes hexadecaethoxy group, heptadecaethoxy group, octadecaethoxy group, nonadecaethoxy group, eicosaethoxy group, henicosaethoxy group, docosaethoxy group, tricosaethoxy group, and tetracosaethoxy group. A compound that is any group selected from the group consisting of: Further, 2,2-bis {(4-acryloxypolyalkyleneoxy) phenyl} propane or 2,2-bis {(4-methacryloxypolyalkyleneoxy) phenyl} propane can be used. Examples of the polyalkyleneoxy group possessed by the compound include a mixture of an ethoxy group and a propyloxy group, an adduct having a block structure or a random structure having a pentadecaethoxy group and a dipropyloxy group, and a pentadecaethoxy group. And an adduct of a block structure or a random structure of a tetrapropyloxy group are preferred. Among these, 2,2-bis {(4-methacryloxydipropyloxypentadecaethoxy) phenyl} propane is most preferable.

The amount of the compound represented by the general formula (II) contained in the photosensitive resin composition of the present invention is preferably 5 to 75% by mass, more preferably 5% in the photosensitive resin composition. -40 mass%. This amount is preferably 5% by mass or more from the viewpoint of developing tenting properties, and is preferably 40% by mass or less from the viewpoint of suppressing cold flow and delayed peeling of the cured resist.
It is a preferred embodiment of the present invention that the addition polymerizable monomer having the structure of the general formula (II) is contained in an amount of 10 to 90% by mass based on the total amount of the addition polymerizable monomer (b). 10 mass% or more is preferable from the viewpoint of expressing tenting properties, and 90 mass% or less is preferable from the viewpoint of reducing the particle size of the release resist.

As the (b) addition polymerizable monomer used in the photosensitive resin composition of the present invention, a known compound having at least one terminal ethylenically unsaturated group can be used in addition to the above compound.
For example, 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethylene glycol acrylate, a reaction product of a half ester compound of phthalic anhydride and 2-hydroxypropyl acrylate and propylene oxide (Nippon Shokubai Chemical Co., Ltd., trade name OE-A 200), 4-normal octylphenoxypentapropylene glycol acrylate, 2,2-bis [{4- (meth) acryloxypolyethoxy} phenyl] propane, 1,6-hexane Diol (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Polyoxyalkylene glycol di (meth) acrylate such as polyoxyethylene polyoxypropylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol penta Urethane groups such as (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4-methacryloxypentaethoxyphenyl) propane, urethanized product of hexamethylene diisocyanate and nonapropylene glycol monomethacrylate And polyfunctional (meth) acrylates containing isocyanuric acid ester compounds. These may be used alone or in combination of two or more.
The amount of the (b) addition polymerizable monomer contained in the photosensitive resin composition of the present invention is in the range of 5 to 75% by mass, and more preferably in the range of 15 to 70% by mass. This amount is preferably 5% by mass or more from the viewpoint of suppressing poor curing and development time delay, and is preferably 75% by mass or less from the viewpoint of suppressing cold flow and delayed peeling of the cured resist.

(C) Photopolymerization initiator The photosensitive resin composition of the present invention contains (c) a photopolymerization initiator as an essential component. The amount of the (c) photopolymerization initiator contained in the photosensitive resin composition of the present invention is in the range of 0.01 to 30% by mass, and more preferably 0.05 to 10% by mass. From the viewpoint of obtaining sufficient sensitivity, 0.01% by mass or more is preferable, and from the viewpoint of sufficiently transmitting light to the bottom surface of the resist and obtaining good high resolution and adhesiveness, 30% by mass or less is preferable. .
Particularly, (c) hexaarylbiimidazole and / or an acridine compound represented by the following general formula (III) is preferable as a photopolymerization initiator, and further, an N-aryl amino acid represented by the following general formula (IV): Or it is preferable to contain the ester compound. Most preferably, the highest sensitivity is achieved by the combined use of hexaarylbiimidazole and N-aryl amino acids or the combined use of acridine compounds and N-aryl amino acids.

（式中、Ｒは水素またはアルキル基、アリール基、ピリジル基、アルコシキル基である。）

(In the formula, R is hydrogen or an alkyl group, an aryl group, a pyridyl group or an alkoxyl group.)

R ₁ —NHCH ₂ COO—R ₂ (IV)
(In the formula, R ₁ is an aryl group, and R ₂ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)
Examples of hexaarylbiimidazole include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbiimidazole, 2,4,5-tris- (o-chlorophenyl) ) -Diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -biimidazole, 2,2′-bis- (2-fluorophenyl) -4,4 ′ , 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3-difluoromethylphenyl) -4,4 ′, 5,5′-teto Kiss- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,4-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,5-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,6- Difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,4-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,5-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3 -Methoxyphenyl) -biimidazole, 2,2'-bis- 2,3,6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,4,5-trifluorophenyl) ) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,4,6-trifluorophenyl) -4,4 ′, 5 5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetrakis- (3 -Methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole And 2,2'-bis- (2,3,4,5,6-pentaph Orofeniru) -4,4 ', 5,5'-tetrakis - (3-methoxyphenyl) - biimidazole. In particular, 2- (o-chlorophenyl) -4,5-diphenylbiimidazole is a photopolymerization initiator having a high effect on the resolution and the strength of the cured film, and is preferably used.
These may be used alone or in combination of two or more.

  Examples of acridine compounds include 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9-ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- (4-tert-butylphenyl) acridine, 9- (4-methoxy) Phenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine, 9- (4-bromo Phenyl) acridine, 9- (3-methylphenyl) acridine, 9 (3-tert-butylphenyl) acridine, 9- (3-acetylphenyl) acridine, 9- (3-dimethylaminophenyl) acridine, 9- (3-diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, Examples include 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridyl) acridine, and the like. In particular, 9-phenylacridine is a photopolymerization initiator having a high effect in terms of sensitivity, and is preferably used.

It is also possible to use a photopolymerization initiator other than the above in combination. Examples of such a photopolymerization initiator include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloro. Quinones such as anthraquinone, 1,4-naphthoquinone, 9-, 10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone, benzophenone , Michler's ketone [4,4′-bis (dimethylamino) benzophenone], and aromatic ketones such as 4,4′-bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethyl Benzoin ethers such as benzoin, benzyl dimethyl ketal, benzyl diethyl ketal, combinations of thioxanthones and alkylaminobenzoic acid, combinations of pyrthioxanthone and ethyl dimethylaminobenzoate, and 1-phenyl-1,2-propanedione-2- Examples include oxime esters such as O-benzoin oxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime. Examples of the combination of the above thioxanthones and alkylaminobenzoic acid include, for example, a combination of ethylthioxanthone and ethyl dimethylaminobenzoate, a combination of 2-chlorothioxanthone and ethyl dimethylaminobenzoate, and isopropylthioxanthone and dimethylaminobenzoic acid. A combination with ethyl acid is mentioned.

  Examples of N-aryl amino acids or ester compounds thereof include N-phenylglycine, methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl of N-phenylglycine Ester, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, N-phenyl Examples include pentyl ester of glycine and octyl ester of N-phenylglycine. In particular, N-phenylglycine has a high sensitizing effect and is preferably used in combination with a photopolymerization initiator.

  Preferred examples of the photopolymerization initiator added to the photosensitive resin composition of the present invention other than hexaarylbiimidazole, acridine compound and N-arylamino acid include thioxanthones such as diethylthioxanthone and chlorothioxanthone, dimethylaminobenzoic acid Mention may be made of dialkylaminobenzoates such as ethyl, benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, and combinations thereof. Among these, Michler's ketone or 4,4′-bis (diethylamino) benzophenone is particularly preferable.

（式中Ａ、Ｂ及びＣは、それぞれ独立に、アリール基、複素環基、炭素数３以上の直鎖または分枝鎖のアルキル基、及びＮＲ_２（Ｒは水素原子、またはアルキル基）からなる群から選ばれる置換基を表す。ａ， ｂ及びｃの夫々は０〜２の整数であるが、ａ＋ｂ＋ｃの値は１以上である。） (D) Pyrazoline compound The photosensitive resin composition of the present invention comprises a pyrazoline compound represented by the following general formula (I) as an essential component as the (d) pyrazoline compound.

Wherein A, B and C are each independently an aryl group, a heterocyclic group, a linear or branched alkyl group having 3 or more carbon atoms, and NR ₂ (R is a hydrogen atom or an alkyl group). And each of a, b and c is an integer of 0 to 2, but the value of a + b + c is 1 or more.

  Examples of the pyrazoline compound represented by the general formula (I) include 1- (4-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-tert-butyl). -Styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1,5-bis- (4-tert-butyl-phenyl) -3- (4-tert-butyl-styryl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-ethoxy-phenyl) -pyrazoline, Phenyl-3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1,5-bis- (4-tert Octyl-phenyl) -3- (4-tert-octyl-styryl) -pyrazoline, 1- (4-dodecyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-dodecyl- Styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-dodecyl-stynyl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- ( 4-tert-octyl-phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- ( 4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-ter -Butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) ) -Pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4-tert-octyl-phenyl) ) -3- (4-Dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (2,4-dibutyl-phenyl) -3- (4-dodecyl-styryl) -5- (4 -Dodecyl-phenyl) -pyrazoline, 1-phenyl-3- (3,5-di-tert-butyl-styryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoli ,

1-phenyl-3- (2,6-di-tert-butyl-styryl) -5- (2,6-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2,5-di -Tert-butyl-styryl) -5- (2,5-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2,6-di-n-butyl-styryl) -5- (2 , 6-Di-
n-butyl-phenyl) -pyrazoline, 1- (3,4-di-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (3,5-di-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4-tert-butyl-phenyl) -3- (3,5-di-tert-butyl-phenyl) -5-phenyl-pyrazoline, 1- (3 5-di-tert-butyl-phenyl) -3- (3,5-di-tert-butyl-styryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-te t-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (4-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-tert- Butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (5-tert-octyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4- (5 -Tert-octyl-benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-thio) Sulfonyl) - pyrazoline,
1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazolin, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4 -Dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-stynyl) -5 (4-dodecyl-phenyl) -pyrazoline, 1- (4- (5-tert-octyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert -Butyl-phenyl) -pyrazolin, 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- ( 4-tert-butyl-phenyl) -pyrazoline, 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl- Phenyl) -pyrazoline, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline , 1- (4- (5-tert-octyl-benzooxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-thio) Nyl) -pyrazoline, 1- (4- (4,6-dibutyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1 -(4- (benzoxazol-2-yl) phenyl) -3- (3,5-di-tert-butylstyryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (2,6-di-tert-butyl-styryl) -5- (2,6-di-tert-butyl-phenyl) -pyrazoline,
1- (4- (benzoxazol-2-yl) phenyl) -3- (2,5-di-tert-butyl-styryl) -5- (2,5-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (2,6-di-n-butyl-styryl) -5- (2,6-di-n-butyl-phenyl) -pyrazoline, 1- (4- (4,6-di-tert-butyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (5,7-di-tert- Butyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (3,5 -Di-tert-bu Le - styryl) -5-phenyl - pyrazoline, 1- (4- (4,6-di -tert- butyl - benzoxazol-2-yl) phenyl) -3-
(3,5-di-tert-butyl-styryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5 (4-amino-phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-N-ethyl-phenyl) -pyrazoline, and 1-phenyl-3- (4- tert-butyl-styryl) -5- (4-N, N-diethyl-phenyl) -pyrazoline.

Among the pyrazoline compounds represented by the general formula (I), A, B and C are each independently an aryl group, a heterocyclic group, a linear or branched alkyl group having 3 or more carbon atoms, And a substituent selected from the group consisting of NR ₂ (R is a hydrogen atom or an alkyl group), and each of a, b and c is an integer of 0 to 2, but the value of a + b + c is 1 or more In the formula, a pyrazoline compound having a tert-butyl group in B or C, and both B and C is more preferable, and among them, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline is particularly preferred. In particular, for an exposure light source having a wavelength of 400 nm or more that is preferably used in maskless exposure, a pyrazoline compound having a benzoxazole group is preferable, and in particular, 1- (4- (benzoxazol-2-yl) phenyl) -3. -(4-tert-Butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline is preferred.

  The compound represented by the above general formula (I) is only required to be contained in the photosensitive resin composition of the present invention, and the total amount is 0.001 to 10% by mass, and a more preferable range. Is 0.005 to 5 mass%, and the most preferable range is 0.05 to 2 mass%. This amount is 0.001% by mass or more from the viewpoint of improving sensitivity and resolution, and is compatible and dispersible in an addition polymerizable monomer having a thermoplastic polymer and a terminal ethylenically unsaturated group. Is 10% by mass or less from the viewpoint of improving the resistance and exhibiting the effect as a dry film photoresist.

In addition, in the photosensitive resin composition of this invention, in addition to the pyrazoline compound shown by the said general formula (I), you may use other pyrazoline compounds together. Examples of such compounds include, for example, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-carboxy-phenyl) -pyrazoline, 1-phenyl-3- (4-tert- Butyl-styryl) -5- (4-mercapto-phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-hydroxy-phenyl) -pyrazoline, 1-phenyl-3 -(4-tert-butyl-styryl) -5- (4-ethylthio-phenyl) -pyrazoline and 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-ethoxycarbonyl-phenyl) -Pyrazoline.
In the photosensitive resin composition of the present invention, the (d) pyrazoline compound exhibits an effect as a sensitizer when used in combination with the above-described (c) photopolymerization initiator.

(E) Other components In the photosensitive resin composition of the present invention, in addition to the components described above, coloring substances such as dyes and pigments can be employed. As such a coloring substance, diphenylmethane dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, acridine dye and the like are used. For example, phthalocyanine green, auramine (CI41000), auramine G (CI41005), malachite green (CI42000), brilliant green (CI42040), astrazone blue G (CI42025), fuchsin (CI42510), fuchsin NB (CI42520), parafukunin (CI52500) ), Methyl violet (CI 42535), crystal violet (CI 42555), methyl green (CI 42585), astracyanin B (CI 42705), Victoria Blue B (CI 44045), Eisen Victoria Pure Blue BOH (CI 42595), Spirit Blue (CI 42775), para Magenta base (CI42500), Eisen basic cyanine 6GH (CI42 25), Astrazone Blue B (CI42140), Eisen Diamond Green GH (CI42040), Pyronin G (CI45005), Rhodamine B (CI45170), Rhodamine 3B (CI45175), Rhodamine 6GCP (CI45160), Acridine Orange NO (CI46003), Examples include phosphine (CI46045), leonin AL (CI46025), acriflavine (CI46000), acridine yellow G (CI46025), benzoflavin (CI46065), and the like.

Moreover, you may add a color former in the photosensitive resin composition of this invention so that a visible image can be given by exposure. Examples of such a coloring dye include a leuco dye or a combination of a fluorane dye and a halogen compound. Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, and chlorinated triazine compounds. .
The amount of the coloring substance and the color former is preferably 0.01 to 10% by mass in the photosensitive resin composition. It is preferably 0.01% by mass or more from the viewpoint of recognizing sufficient colorability (coloring property), 10% by mass or less from the viewpoint of maintaining the contrast between the exposed part and the unexposed part and maintaining storage stability.

Furthermore, in order to improve the thermal stability and storage stability of the photosensitive resin composition of the present invention, the photosensitive resin composition is selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles. It is preferable to contain at least one compound.
Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, 2,6-di-t-butyl-p-cresol, 2,2 'Methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), pentaerythrityltetrakis (3- (3,5-di-t-butyl-) 4-hydroxyphenyl) propionate (IRGANOX (registered trademark) 1010 manufactured by Ciba Geigy Japan), triethylene glycol-bis (3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate) (Ciba Geigy Japan) IRGANOX (registered trademark) 245), octadecyl-3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate (IRGANOX (registered trademark) 1076 manufactured by Ciba Geigy Japan), aluminum N-nitrosophenylhydroxylamine and the like. Aluminum N-nitrosophenylhydroxylamine is preferred from the viewpoints of thermal stability and storage stability.

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzo. Examples include triazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.
Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl). Examples include aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole.
The total amount of radical polymerization inhibitors, benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass. This amount is preferably 0.01% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and more preferably 3% by mass or less from the viewpoint of maintaining sensitivity.

You may make the photosensitive resin composition of this invention contain additives, such as a plasticizer, as needed. Examples of such additives include phthalic acid ester compounds such as diethyl phthalate and diphenyl phthalate, sulfonamide compounds such as p-toluenesulfonamide, petroleum resin, rosin, polyethylene glycol, polypropylene glycol (Toa Gosei Chemical Industry). Carbodiol (registered trademark) D-2000), ethylene glycol-propylene glycol block copolymer, and compounds Adecanol (registered trademark) SDX-1569 in which ethylene oxide or propylene oxide is added to both ends of bisphenol A, adecanol ( (Registered trademark) SDX-1570, Adecanol (registered trademark) SDX-1571, Adecanol (registered trademark) SDX-479 (manufactured by Asahi Denka Co., Ltd.), New Paul (registered trademark) BP-23P, New Paul (registered trademark) BP-3P, New Paul (registered trademark) BP-5P, New Paul (registered trademark) BPE-20T, New Paul (registered trademark) BPE-60, New Paul (registered trademark) BPE-100, New Paul (registered trademark) BPE-180 (manufactured by Sanyo Chemical Co., Ltd.), UNIOR (registered trademark) DB-400, UNIOR (registered trademark) DAB-800, UNIOR (registered trademark) DA-350F, UNIOR (registered trademark) DA-400, UNIOR (registered trademark) DA-700 (manufactured by NOF Corporation), BA-P4U glycol, BA-P8 glycol (manufactured by Nippon Emulsifier Co., Ltd.), tributyl citrate, triethyl citrate, acetyl Triethyl citrate, acetyl tri-n-propyl citrate, tri-n-butyl acetyl citrate, etc. And the like.
The amount of the additive such as a plasticizer is preferably 5 to 50% by mass, more preferably 5 to 30% by mass in the photosensitive resin composition. 5 mass% or more is preferable from a viewpoint of suppressing the delay of image development time or providing a softness | flexibility to a cured film, and 50 mass% or less is preferable from a viewpoint of suppressing insufficient hardening and cold flow.

<Photosensitive resin composition preparation solution>
The photosensitive resin composition of the present invention may be a photosensitive resin composition preparation liquid to which a solvent is added. Suitable solvents include acetone, ketones typified by methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid is 500 to 4000 mPa · sec at 25 ° C.
<Photosensitive resin laminate>
The photosensitive resin laminate of the present invention comprises a photosensitive resin layer and a support that supports the layer. If necessary, the photosensitive resin laminate may have a protective layer on the surface opposite to the support of the photosensitive resin layer. good.

Next, a method for producing the photosensitive resin laminate of the present invention will be described.
For example, the photosensitive resin composition used for the photosensitive resin layer (B) is mixed with a solvent for dissolving them to form a uniform solution, and first applied onto the support (A) using a bar coater or a roll coater. Then, the photosensitive resin layer (B) made of the photosensitive resin composition is laminated on the support (A). Next, a photosensitive resin laminate can be produced by laminating the protective layer (C) on the photosensitive resin layer (B).

The support (A) in the present invention is preferably transparent so as to transmit active light, and preferably has a low haze value. When the haze value is high, scattering of the active light to be exposed increases, and the resolution and shape sharpness of the resist are lost. The haze value is preferably 3 or less, more preferably 1 or less, and even more preferably 0.6 or less. Moreover, a thing with a high total light transmittance is desirable. This is because as the total light transmittance is higher, the amount of active light to be exposed is less attenuated and the energy efficiency is higher. The total light transmittance is preferably 85% or more. Furthermore, the thing with few foreign materials adhering inside a film is desirable. Examples of the foreign material include a catalyst for synthesizing the resin of the film raw material, a lubricant for preventing blocking when the film is used as a roll, and dust mixed during film production. When there are many foreign substances, the defect of a cured resist, the abnormality of a resist shape, and the shakiness of a resist side surface will be caused. The number of foreign matters is 30 μm or more is 0 per 9 m 2 of film, 20 μm or more and less than 30 μm is 1 or less per 9 m 2 of film, and preferably 10 μm or more and less than 20 μm is 4 or less.
Examples of the support (A) include polyethylene terephthalate film, polyethylene naphthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethacrylic acid. Examples include a methyl copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film, and a polyethylene terephthalate film and a polyethylene naphthalate film are preferable.

Examples of suitable polyethylene terephthalate films include Toray Lumirror FB60 (trade name), Teijin AT301 (trade name) and G2 (trade name), Kolon FP (trade name), Mitsubishi Chemical Polyester R340G ( Product name) and R310 (product name).
10-30 micrometers is preferable and, as for the thickness of a support body (A), More preferably, it is 12-20 micrometers. The film thickness of the support (A) is preferably 10 μm or more from the viewpoint of handleability, and is preferably 30 μm or less from the viewpoint of resolution.
The physical strength of the support (A) is preferably high. This is because film breakage during the production of the dry film resist hardly occurs. The breaking strength is preferably 150 MPa or more (MD direction) and 240 MPa or more (TD direction) by a method according to JISC2151. The elongation at break is preferably 220% or less (MD direction) and 160% or less (TD direction) in accordance with JISC2151.

The thermal properties of the support (A) are preferably those with small heat shrinkage. This is because if the heat shrinkage is small, the film size is difficult to change during drying by heating during dry film resist production, or the production temperature can be increased by raising the drying temperature. The heat shrinkage rate is preferably 4% or less (MD direction) and 2.6% or less (TD direction) in accordance with ASTM D882.
The thickness of the photosensitive resin layer (B) of the present invention after drying is preferably 1 μm or more from the viewpoint of film forming coatability, and is preferably 150 μm or less from the viewpoint of resolution and adhesiveness, more preferably. 3-50 μm is used.

As thickness of the layer (C) of the protective film used as needed for the photosensitive resin laminated body of this invention, it is 15-50 micrometers normally, More preferably, 18-40 micrometers is required.
If the thickness of the protective layer (C) is less than 15 μm, it is difficult to produce due to the low strength. If the thickness of the protective layer (C) exceeds 50 μm, the cost is increased, which is economically disadvantageous.
The protective layer (C) preferably has few convex portions. The undissolved protrusions (called microgel) of the raw material generated in the polyethylene film are transferred to the photosensitive resin layer, and a depression is formed in the photosensitive resin layer. This portion becomes an air void, which is used in the etching process and the plating process. At this time, the etching solution or the plating solution enters the voids at the bottom of the resist, thereby causing defects such as circuit application, disconnection, and short-circuiting, thereby reducing the yield of the final product. The smaller the number of microgels, the better. The number of microgels of 50 μm or more is preferably 30 or less per 5 m 2 and more preferably 10 or less.

Examples of the film used for the protective layer (C) include polyolefin films such as polyethylene films and polypropylene films, polyester films, and polyester films whose peelability is improved by silicone treatment or alkyd treatment. Among these, a polyethylene film is particularly preferable.
Examples of suitable polyethylene films include GF-18 (trade name), GF-83 (trade name), GF-85 (trade name), GF-818 (trade name), and GF-858 (product) manufactured by Tamapoli. Name).

  Further, an important characteristic of the protective layer (C) used for the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support and can be easily peeled with respect to the adhesion with the photosensitive resin layer. For example, a polyethylene film and a polypropylene film can be preferably used as the protective layer. Also, a film having excellent peelability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

<Resist pattern formation method>
A resist pattern using the photosensitive resin laminate of the present invention can be formed by a process including a laminating process, an exposing process, and a developing process. An example of a specific method is shown.
First, a laminating process is performed using a laminator. When the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated on the substrate surface with a laminator. In this case, the photosensitive resin layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces as necessary. The heating temperature at this time is generally 40 to 160 ° C. Moreover, the adhesiveness with respect to the board | substrate of the obtained resist pattern improves by performing this thermocompression bonding twice or more. At this time, for the crimping, a two-stage laminator having two rolls may be used, or it may be repeatedly crimped through the roll several times.

Next, an exposure process is performed using an exposure machine. If necessary, the support is peeled off and exposed to active light through a photomask. The exposure amount is determined from the light source illuminance and the exposure time. You may measure using a photometer.
In the exposure step, a maskless exposure method may be used. In maskless exposure, exposure is performed directly on a substrate by a drawing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350 to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, a developing process is performed using a developing device. After exposure, if a support is present on the photosensitive resin layer, this is excluded. Subsequently, the unexposed portion is developed and removed using a developer composed of an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ or the like is preferable. These are selected according to the characteristics of the photosensitive resin layer, but an aqueous Na ₂ CO ₃ solution having a concentration of 0.2 to 2% by mass is generally used. A surface active agent, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution. In addition, it is preferable to maintain the temperature of this developing solution in a development process at the constant temperature in the range of 20-40 degreeC.
Although a resist pattern is obtained by the above-mentioned process, a heating process at 100 to 300 ° C. can be further performed depending on the case. By carrying out this heating step, chemical resistance can be further improved. For heating, a heating furnace of a hot air, infrared ray, far infrared ray, or the like can be used.

<Method for manufacturing printed wiring board>
The method for producing a printed wiring board according to the present invention is performed by forming a resist pattern on a copper-clad laminate or a flexible substrate as a substrate by the above-described resist pattern forming method, and then performing the following steps.
First, a process of forming a conductor pattern on the copper surface of the substrate exposed by development using a known method such as an etching method or a plating method is performed.
Thereafter, the resist pattern is peeled off from the substrate with an aqueous solution having alkalinity stronger than that of the developer to obtain a desired printed wiring board. The alkaline aqueous solution for peeling (hereinafter also referred to as “peeling solution”) is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of 2 to 5% by mass is generally used. It is possible to add a small amount of a water-soluble solvent to the stripping solution. In addition, it is preferable that the temperature of this peeling liquid in a peeling process is the range of 40-70 degreeC.

<Lead frame manufacturing method>
The lead frame manufacturing method of the present invention is performed by performing the following steps after forming a resist pattern on a metal plate such as copper, copper alloy, or iron-based alloy as a substrate by the above-described resist pattern forming method.
First, a step of etching the substrate exposed by development to form a conductor pattern is performed. Then, the peeling process which peels a resist pattern with the method similar to the manufacturing method of the above-mentioned printed wiring board is performed, and a desired lead frame is obtained.

<Semiconductor package manufacturing method>
The semiconductor package manufacturing method according to the present invention is performed by forming a resist pattern by the above-described resist pattern forming method on a wafer on which a circuit as an LSI has been formed as a substrate, and then performing the following steps.
First, a step of forming a conductor pattern by performing columnar plating such as copper or solder on the opening exposed by development is performed. Thereafter, a peeling process for peeling the resist pattern by the same method as the above-described method for manufacturing a printed wiring board is performed, and further, a thin metal layer other than the columnar plating is removed by etching. A semiconductor package is obtained.

<Manufacturing method of substrate having concave / convex pattern>
The resist pattern can be used as a protective mask member when the substrate is processed by the sandblasting method by the resist pattern forming method described above.
Examples of the substrate include glass, silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and metal material. A resist pattern is formed on the substrate such as glass by the same method as the resist pattern forming method described above. After that, a blasting material is sprayed on the formed resist pattern to be cut to a desired depth, and a resist pattern portion remaining on the substrate is removed from the substrate with an alkali stripping solution or the like, and then on the substrate. It can be set as the base material which has a fine uneven | corrugated pattern. The blasting material used for the above-mentioned sandblasting process may be a known material, for example, fine particles of about 2 to 100 μm such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, stainless steel and the like.
The above-described method for producing a substrate having a concavo-convex pattern by the sandblasting method can be used for production of flat panel display partition walls, organic EL glass cap processing, silicon wafer drilling processing, ceramic pinning processing, and the like. it can. Moreover, it can utilize for manufacture of the electrode of a metal material layer chosen from the group which consists of a ferroelectric film and a noble metal, a noble metal alloy, a refractory metal, and a refractory metal compound.

Hereinafter, examples of embodiments of the present invention will be described in more detail by way of examples.
First, methods for producing samples for evaluation of Examples , Reference Examples and Comparative Examples will be described, and then an evaluation method and evaluation results for the obtained samples will be shown.
1. Production of Evaluation Sample The photosensitive resin laminates in Examples , Reference Examples and Comparative Examples were produced as follows.
<Preparation of photosensitive resin laminate>
A photosensitive resin composition and a solvent having the composition shown in Table 1 are well stirred and mixed to prepare a photosensitive resin composition preparation liquid, and a polyethylene terephthalate film R340G16 (trade name, 16 μm thickness, haze, manufactured by Mitsubishi Polyester Film Co., Ltd.) as a support. 0.5%, total light transmittance 90%, breaking strength 225 MPa (MD), 315 MPa (TD), breaking elongation 155% (MD), 105% (TD), heat shrinkage rate 2.2% (MD), 0.8% (TD)) was uniformly coated using a bar coater and dried in a dryer at 95 ° C. for 4 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 38 μm.
Next, on the surface on which the polyethylene terephthalate film of the photosensitive resin layer is not laminated, as a protective layer, a polyethylene film GF-818 (manufactured by Tamapoly Co., Ltd., trade name, 21 μm thickness, Ra = 0.065 μm, 50 μm or more of microgel) The number was 22/5 m ² or less) to obtain a good photosensitive resin laminate.
Table 2 shows the names of the material components in the photosensitive resin composition preparation liquid represented by abbreviations in Table 1 .

<Board surface preparation>
The substrate for sensitivity and resolution evaluation was a 1.6 mm thick copper clad laminate on which 35 μm rolled copper foil was laminated, and the surface was wet buffol polished (manufactured by 3M, Scotch Bright (registered trademark) HD # 600, 2 times).
<Laminate>
While peeling the polyethylene film of the photosensitive resin laminate, it was laminated at a roll temperature of 105 ° C. with a hot roll laminator (Asahi Kasei Electronics Co., Ltd., AL-70) on a copper clad laminate that had been leveled and preheated to 60 ° C. . The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

<Exposure>
Exposure with a direct drawing type exposure device (Hitachi Via Mechanics Co., Ltd., DI exposure machine DE-1AH, light source: GaN blue-violet diode, main wavelength 407 ± 3 nm) with an exposure amount that the number of step tablet steps is 7 by the following sensitivity evaluation did.
<Development>
After the polyethylene terephthalate film was peeled off, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed for a predetermined time to dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, the minimum time required for completely dissolving the photosensitive resin layer in the unexposed portion was defined as the minimum development time.

2. Evaluation Method (1) Sensitivity Evaluation A substrate for sensitivity and resolution evaluation that had passed 15 minutes after lamination was exposed using a 21-step tablet manufactured by Stofer whose brightness has changed from transparent to black in 21 levels. After the exposure, the film was developed with a development time twice as long as the minimum development time, and the exposure amount at which the number of step tablet stages where the resist film remained completely was 7 was ranked as the optimum exposure amount as follows.
A: The optimum exposure amount is 50 mJ / cm ² or less.
○: The optimum exposure dose exceeds ^{50mJ / cm 2, 100mJ / cm} 2 or less.
X: The optimum exposure amount exceeds 100 mJ / cm ² .

(2) Resolution Evaluation A substrate for sensitivity and resolution evaluation 15 minutes after lamination was exposed at an optimum exposure amount through a line pattern mask having a ratio of 1: 1 between the exposed area and the unexposed area. Development was performed with a development time twice as long as the minimum development time, and the minimum mask line width in which a cured resist line was normally formed was defined as a resolution value.
A: The resolution value is 40 μm or less.
○: The resolution value exceeds 40 μm and is 50 μm or less.
X: The value of resolution exceeds 50 μm.

(3) Tenting evaluation A photosensitive resin laminate was laminated on both sides of a 1.6 mm thick copper-clad laminate with a 6 mm diameter hole, exposed at the optimum exposure, and a minimum development time of 2 Developed with double development time. And the number of hole tears was measured and the tear rate was computed by the following numerical formula.
Tent film tear rate (%) = [number of hole tears (pieces) / total number of holes (pieces)] × 100
Based on the tent film tear rate (%), ranking was performed as follows.
○: Less than 1% △: 1% or more and less than 3% ×: 3% or more Evaluation Results Table 1 shows the evaluation results of the examples , reference examples, and comparative examples.

  The present invention relates to the manufacture of printed wiring boards, the manufacture of lead frames for IC chip mounting, the manufacture of metal foils such as the manufacture of metal masks, the manufacture of packages such as BGA or CSP, the manufacture of tape substrates such as COF and TAB, the production of semiconductor bumps It can be used for manufacturing, manufacturing of partition walls of flat panel displays such as ITO electrodes, address electrodes and electromagnetic wave shields, and a method of manufacturing a substrate having an uneven pattern by sandblasting.

Claims (10)

(A) Thermoplastic copolymer containing an α, β-unsaturated carboxyl group-containing monomer as a copolymerization component, having an acid equivalent of 100 to 600, and a weight average molecular weight of 5,000 to 500,000: 20 to 90 mass %, (B) addition polymerizable monomer having at least one terminal ethylenically unsaturated group: 5 to 75% by mass, (c) photopolymerization initiator: 0.01 to 30% by mass, (d) the following general formula ( Pyrazoline compound represented by I): 0.001 to 10% by mass, and (b) an addition polymerizable monomer having a structure represented by the following general formula (II) as an addition polymerizable monomer Resin composition.

(In the formula, A independently represents a substituent selected from the group consisting of an aryl group and a heterocyclic group, and B and C each independently represent an aryl group, a heterocyclic group, and a straight chain having 3 or more carbon atoms. Or a branched alkyl group and a substituent selected from the group consisting of NR ₂ (R is a hydrogen atom or an alkyl group), a is an integer of 1 to 2, and b and c are each 0 to 2. (It is an integer, but the value of a + b + c is 1 or more.)

(Wherein R ₁ and R ₂ are H or CH ₃ , which may be the same or different. One of D and E is an alkylene group having 2 carbon atoms, The other is an alkylene group having 3 to 4 carbon atoms, and the repeating unit of — (D—O) — and — (E—O) — may have a block structure or a random structure, m1, m2, n1, and n2 is 0 or a positive integer, and the sum of these is 31 to 48.) (C) The photoinitiator contains the hexaarylbiimidazole and / or the acridine compound represented by the following general formula (III), The photosensitive resin composition of Claim 1 characterized by the above-mentioned.

(In the formula, R is hydrogen, an alkyl group, an aryl group, a pyridyl group, or an alkoxy group.) The photosensitive resin composition according to claim 1 or 2, further comprising an N-aryl amino acid represented by the following general formula (IV) or an ester compound thereof.
R ₁ —NHCH ₂ COO—R ₂ (IV)
(In the formula, R ₁ is an aryl group, and R ₂ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)   The photosensitive resin laminated body formed by laminating | stacking the photosensitive resin composition in any one of Claims 1-3 on a support body.   A resist pattern forming method comprising a laminating step, an exposing step, and a developing step of forming a photosensitive resin layer on the substrate using the photosensitive resin laminate according to claim 4.   6. The resist pattern forming method according to claim 5, wherein in the exposure step, direct drawing is performed for exposure. The manufacturing method of a printed wiring board including the process of etching or plating the board | substrate which formed the resist pattern by the method in any one of Claims 4-6.   A method for manufacturing a lead frame, comprising a step of etching a substrate on which a resist pattern has been formed by the method according to claim 4.   A method for manufacturing a semiconductor package, comprising a step of etching or plating a substrate on which a resist pattern has been formed by the method according to claim 4.   The manufacturing method of the base material which has an uneven | corrugated pattern including the process of processing the board | substrate which formed the resist pattern by the method in any one of Claims 4-6 by sandblasting.