JP5793924B2 - Photosensitive resin composition, photosensitive element, method for producing resist pattern, and method for producing printed wiring board - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element, a method for producing a resist pattern, a method for producing a printed wiring board, and printed wiring.

  Conventionally, in the field of printed wiring board production, as a resist material used for etching treatment or plating treatment, a photosensitive resin composition and a photosensitive element obtained using a support and a protective film are widely used. .

  The printed wiring board is obtained by laminating the photosensitive element on a circuit forming substrate and exposing it in a pattern, and then removing the unexposed portion with a developer to form a resist pattern, and using the mask as an etching treatment or After the plating process is performed to form a circuit, the cured portion is manufactured by a method of peeling off from the substrate.

  In the above exposure, conventionally, a mask exposure method in which actinic rays are irradiated through a mask film having a pattern is used. As a light source for actinic light, a light source that effectively emits ultraviolet rays, such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, and a xenon lamp, is used.

  In recent years, as an alternative to the mask exposure method, a direct drawing method in which actinic rays are directly irradiated in an image form using digital data without using a mask film has been put into practical use. As a light source used for the direct drawing method, a YAG laser, a semiconductor laser, etc. are used from the viewpoint of safety and handleability, and recently, a technology using a long-life, high-power gallium nitride blue laser, etc. Proposed.

  Further, along with higher definition and higher density in printed wiring boards, a direct drawing method called a DLP (Digital Light Processing) exposure method capable of forming a fine pattern has been introduced. In general, in the DLP exposure method, active light having a wavelength of 390 to 430 nm using a blue-violet semiconductor laser as a light source is used. In addition, an exposure method using a polygon multi-beam having a wavelength of 355 nm using a YAG laser as a light source, which is compatible with a small amount and a wide variety of products on a general-purpose printed wiring board, is also used.

  From the viewpoint of improving productivity, it is necessary to shorten the exposure time. However, in the exposure process in the direct drawing method, in addition to using a monochromatic light such as a laser as a light source and irradiating a light beam while scanning the substrate, a long exposure time is required as compared with an exposure method using a conventional photomask. Tend.

  As a method for shortening the exposure time, there is a method for increasing the sensitivity of the photosensitive resin composition. However, by simply increasing the sensitivity of the photosensitive resin composition, the surface curing of the resist pattern formed on the substrate proceeds, the light absorption at the bottom of the resist is hindered, and the bottom curability may be lowered. Due to the lowering of the bottom curability described above, the resist shape formed on the substrate may become an inverted trapezoid, or the adhesion and resolution may be reduced. Also in the developing process, since the bottom curability is not sufficient, the developer resistance inherent in the resist may be reduced.

  As the developer, an alkaline developer such as a sodium carbonate aqueous solution or a sodium hydrogen carbonate aqueous solution is mainly used from the viewpoint of environmental performance and safety. The unexposed portion of the photosensitive resin layer is removed from the substrate by the development with these developers and the spray pressure of water washing. Therefore, the photosensitive resin composition is required to have excellent tent reliability (tenting property) that is not damaged by the development or water spray pressure after exposure. However, when the bottom curability is not sufficient as described above, the tent reliability tends to decrease.

  Furthermore, the photosensitive resin composition is required to have excellent peel characteristics after curing. If the resist peeling property is poor, the peeling time becomes long and the production efficiency of the peeling process is lowered. Further, in a high-density package substrate, a peeling residue is generated between plating lines in a peeling process after fine wire plating, resulting in a decrease in production yield.

  Under the above circumstances, a number of photosensitive resin compositions have been disclosed so far (see, for example, Patent Documents 1 and 2).

Japanese Patent No. 3406526 JP 2010-217287 A

  However, as described above, it has been difficult to satisfy various characteristics such as tent reliability and peelability while maintaining high sensitivity. For example, the photosensitive resin composition of Patent Document 1 is good in terms of resolution, adhesion, and imaging properties, but is not sufficient in terms of sensitivity, and requires a lot of exposure time when using a direct drawing method. In addition, the photosensitive resin composition of Patent Document 2 has high sensitivity and good resist shape and excellent peelability in the direct drawing method, but there is room for improvement in terms of tent reliability.

  Therefore, an object of the present invention is to provide a photosensitive resin composition having particularly high sensitivity, excellent tent reliability, and good peelability when exposed by a direct drawing method. Moreover, it aims at providing the photosensitive element using the said photosensitive resin composition, the manufacturing method of a resist pattern, the manufacturing method of a printed wiring board, and printed wiring.

  As a result of intensive studies to solve the above-mentioned problems, the present invention uses a compound having a specific chemical structure as a photopolymerization initiator, so that when exposed by a direct drawing method, it has high sensitivity and excellent tent reliability. The present invention has been completed by finding that it is possible to provide a photosensitive resin composition having good releasability and further good releasability.

That is, the photosensitive resin composition contains (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, and the (C) photopolymerization initiator is represented by the following general formula (I). in including a compound represented. By using the compound represented by the following general formula (I) as the photopolymerization initiator (C), the photosensitive resin composition of the present invention has high sensitivity and good peeling when exposed by a direct drawing method. And excellent tent reliability.

In the formula, R ¹ represents an organic group containing a cycloalkyl group having 3 to 20 carbon atoms, R ² and R ³ each independently represent an alkyl group or an aryl group, and R ⁴ represents an alkyl group.

In the photosensitive resin composition of the present invention, the (B) photopolymerizable compound preferably contains a monofunctional photopolymerizable compound, and the monofunctional photopolymerizable compound is represented by the following general formula (II). It is more preferable from a peelable viewpoint to contain the compound which is.

Wherein, ^{R 5} represents a hydrogen atom or a methyl group, ^{R 6} represents a hydrocarbon group having 1 to 10 carbon atoms, m is an integer of 0 to 20.

  In the photosensitive resin composition of the present invention, the photopolymerizable compound (B) preferably contains a compound represented by the following general formula (III).

In the formula, R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and n represents an integer of 0 to 50.

  In the photosensitive resin composition of the present invention, the content of the compound represented by the general formula (I) is 100 parts by mass with respect to the total amount of the (A) binder polymer and the (B) photopolymerizable compound. From 0.01 to 0.5 parts by mass, it is preferable from the viewpoint of high sensitivity and further tent advantage.

  Moreover, this invention relates to the photosensitive element provided with a support film and the photosensitive resin layer formed using the said photosensitive resin composition formed on this support film.

  The present invention also includes a laminating step of laminating a photosensitive resin layer formed using the photosensitive resin composition on a substrate, and irradiating the photosensitive resin layer with actinic rays in an image form by a direct drawing method. Then, an exposure process for curing the exposed portion and an unexposed portion of the photosensitive resin layer are removed from the substrate to form a resist pattern composed of a cured product of the photosensitive resin composition on the substrate. And a developing process.

  Moreover, this invention relates to the manufacturing method of a printed wiring board including performing the etching process or the plating process of the board | substrate with which the resist pattern was formed by the said method.

  Moreover, this invention relates to the printed wiring board manufactured by the said method.

  According to the present invention, it is possible to provide a photosensitive resin composition having excellent sensitivity and having good peelability and excellent tent reliability when exposed by a direct drawing method. In addition, by providing a photosensitive element using the photosensitive resin composition, a method for producing a resist pattern, and a method for producing a printed wiring board, it is possible to produce a printed wiring board having a high-definition circuit pattern. Become.

It is an end view which shows one Embodiment of the photosensitive element of this invention. It is a top view of the hole tearing number measuring substrate used for evaluation of tent reliability.

  Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to the following embodiments. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

  In this specification, “(meth) acrylic acid” means “acrylic acid” and its corresponding “methacrylic acid”, and “(meth) acrylate” means “acrylate” and its corresponding “methacrylate”. , “(Meth) acryloyl group” means “acryloyl group” and the corresponding “methacryloyl group”.

Further, in the present invention, the term “process” is not limited to an independent process, and is included in this term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
Furthermore, the numerical range indicated using “to” in this specification indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment includes (A) a binder polymer (hereinafter also referred to as “(A) component”), (B) a photopolymerizable compound (hereinafter also referred to as “(B) component”). And (C) a photopolymerization initiator (hereinafter also referred to as “component (C)”), wherein the component (C) contains a compound represented by the following general formula (I). It is.

[(C) component: photopolymerization initiator]
(C) The photoinitiator which is a component contains the compound represented by the following general formula (I).

In the general formula (I), R ¹ represents an organic group containing a cycloalkyl group having 3 to 20 carbon atoms, R ² and R ³ each independently represents an alkyl group or an aryl group, and R ⁴ represents Indicates an alkyl group.

Since sensitivity and tent reliability are further improved, R ¹ is preferably an organic group containing a cycloalkyl group having 3 to 10 carbon atoms, and is an organic group containing a cycloalkyl group having 5 to 8 carbon atoms. Is more preferable.

The organic group containing a cycloalkyl group having 3 to 20 carbon atoms represented by R ¹ may have a cycloalkyl group via a divalent hydrocarbon group, and as the divalent hydrocarbon group, Is preferably an alkylene group, more preferably an alkylene group having 2 to 5 carbon atoms, and still more preferably an ethylene group.

The organic group containing a cycloalkyl group having 3 to 20 carbon atoms represented by R ¹ is preferably a cycloalkylalkylene group, and more preferably a cyclopentylethylene group.

In the general formula (I), since the sensitivity is further improved, R ² is an alkyl group or an aryl group, preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms, More preferably, it is a methyl group.

In the general formula (I), since sensitivity is further improved, R ³ is preferably an alkyl group or an aryl group, more preferably an alkyl group, and an alkyl group having 1 to 10 carbon atoms. Is more preferable, and an ethyl group is still more preferable.

In the general formula (I), since sensitivity is further improved, R ⁴ is an alkyl group, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group.

In the general formula (I), the substitution position of R ⁴ may be any of the ortho position, meta position, and para position, and the ortho position is preferable from the viewpoint of improving sensitivity.

As the compound represented by the above general formula (I), R ¹ is a cycloalkylethylene group, R ² is a methyl group, R ³ is an ethyl group, and R ⁴ is a methyl group (for example, Changzhou Strong Co., Ltd.) Sample name TR-PBG-304).

  The content of the compound represented by the general formula (I) is 0.01 to 0.5 mass with respect to 100 mass parts of the total amount of the component (A) and the component (B) from the viewpoint of sensitivity and tent advantage. Part, preferably 0.01 to 0.4 part by weight, more preferably 0.05 to 0.35 part by weight, and 0.05 to 0.3 part by weight. More preferably. When the content is 0.01 parts by mass or more, sufficient sensitivity is obtained, and when the content is 0.5 parts by mass or less, the resist shape is suppressed from being an inverted trapezoid, and sufficient adhesion and resolution are obtained.

In addition to the compound represented by the general formula (I), other component (C) (photopolymerization initiator) may be included.
Examples of the component (C) (photopolymerization initiator) other than the compound represented by the general formula (I) include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N , N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and 2- Aromatic ketones such as methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benz Anthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3- Quinones such as phenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone; benzoin methyl Benzoin ether compounds such as ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin, and ethyl benzoin; benzyl derivatives such as benzyl dimethyl ketal; 9,10-dimethoxyanthracene, 9,10-diethoxy Substituted anthracenes such as anthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dipentoxyanthracene; 2- (o-chlorophenyl) -4 , 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimers such as 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer and 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer Examples include a coumarin compound, an oxazole compound, and a pyrazoline compound. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid. These can be used alone or in combination of two or more.

  The total content of component (C) is preferably 0.01 to 20 parts by mass, and 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of components (A) and (B). It is more preferable, and it is especially preferable that it is 0.2-5 mass parts. When the content of the component (C) is within this range, the sensitivity and the internal photocurability of the photosensitive resin composition become better.

[(A) component: binder polymer]
The binder polymer as the component (A) is not particularly limited as long as it is soluble in an alkaline aqueous solution and can form a film. For example, acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy Resin, alkyd resin, and phenol resin. Of these, acrylic resins are preferred from the standpoint of alkali developability. These can be used alone or in combination of two or more.

The component (A) can be produced, for example, by radical polymerization of a polymerizable monomer (monomer). Examples of the polymerizable monomer include styrene; a polymerizable styrene derivative substituted at the α-position or aromatic ring such as α-methylstyrene or vinyltoluene; acrylamide such as diacetone acrylamide; acrylonitrile; vinyl. -Ethers of vinyl alcohol such as n-butyl ether; (meth) acrylic acid alkyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meta ) (Meth) acrylic such as diethylaminoethyl acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate Acid esters; (Meth) acrylic acid, (meth) acrylic acid derivatives such as α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid; maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, maleic acid derivatives such as maleic acid monoisopropyl; full circle acid, cinnamic acid, alpha-cyanocinnamic acid, itaconic acid, crotonic acid, such as propiolic acid Organic acid derivatives are mentioned. These can be used alone or in combination of two or more.

  As said (meth) acrylic-acid alkylester, the compound represented by the following general formula (IV) is mentioned.

^{_{H 2 C = C (R 9}} ) -COOR 10 (IV)

In the general formula (IV), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents an alkyl group having 1 to 12 carbon atoms.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ¹⁰ in the general formula (IV) include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, Nonyl group, decyl group, undecyl group, dodecyl group and structural isomers thereof can be mentioned.

  Examples of the compound represented by the general formula (IV) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (meth) ) Acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) ) Acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester. These can be used alone or in combination of two or more.

  Moreover, as said (meth) acrylic-acid alkylester, the compound by which the alkyl group was substituted by the hydroxyl group, the epoxy group, or the halogen group in the compound represented by the said general formula (IV) is mentioned.

  The component (A) preferably contains a carboxyl group from the viewpoint of alkali developability. The component (A) containing a carboxyl group can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer. As the polymerizable monomer having a carboxyl group, (meth) acrylic acid is preferable, and methacrylic acid is more preferable.

  Component (A) carboxyl group content (ratio of polymerizable monomer having carboxyl group to total polymerizable monomer used) is the component (A) from the viewpoint of the balance between alkali developability and developer resistance. It is preferable that it is 12-50 mass% on the basis of the total mass of. In the point which is excellent in alkali developability, 15-35 mass% is preferable and 15-30 mass% is more preferable.

  The component (A) preferably contains styrene or a styrene derivative as a polymerizable monomer from the viewpoint of adhesion and release characteristics. The content of the above styrene or styrene derivative as a copolymerization component (ratio of styrene or styrene derivative to the total polymerizable monomer used) is (A ) 0.1 to 40% by mass based on the total mass of the components, preferably 1 to 30% by mass, more preferably 3 to 27% by mass. When the content is 0.1% by mass or more, the adhesion tends to be improved. When the content is 40% by mass or less, the peeling piece can be prevented from becoming large and the peeling time can be prevented from becoming long.

  These components (A) (binder polymer) can be used alone or in combination of two or more. Examples of the binder polymer used in combination of two or more types include, for example, two or more types of binder polymers composed of different copolymerization components, two or more types of binder polymers having different weight average molecular weights, and two or more types of binders having different dispersities. Examples thereof include polymers.

  The weight average molecular weight of the component (A) is preferably 20,000 to 100,000, more preferably 30,000 to 70,000, from the viewpoint of the balance between developer resistance and alkali developability. More preferably, it is 40,000-65,000. In addition, the weight average molecular weight in this specification is a value measured by a gel permeation chromatography method and converted by a calibration curve prepared using standard polystyrene, and the measurement conditions are the same as in the examples.

  The acid value of the binder polymer as the component (A) is preferably 120 to 200 mgKOH / g, and more preferably 150 to 170 mgKOH / g.

  The content of the component (A) is preferably 30 to 80 parts by mass, more preferably 40 to 75 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B), and 50 It is more preferable to set it to -70 mass parts. When the content of the component (A) is within this range, the coating property of the photosensitive resin composition and the strength of the photocured product become better.

[(B) component: photopolymerizable compound]
The photosensitive resin composition of this embodiment contains the photopolymerizable compound which is (B) component. The photopolymerizable compound as the component (B) includes a polymerizable compound having at least one ethylenically unsaturated bond, and includes a monofunctional photopolymerizable compound from the viewpoint of excellent peelability and tent reliability. preferable.

  Moreover, it is preferable that the photosensitive resin composition of this embodiment contains the compound represented by the following general formula (II) as said monofunctional photopolymerizable compound. Thereby, the photosensitive resin composition of this embodiment will have the outstanding peelability, when exposed by the direct drawing method.

Wherein, ^{R 5} represents a hydrogen atom or a methyl group, ^{R 6} represents a hydrocarbon group having 1 to 10 carbon atoms, m is an integer of 0 to 20.

In the general formula (II), R ⁵ is preferably a hydrogen atom.

In the general formula (II), R ⁶ is preferably an alkyl group having 1 to 10 carbon atoms or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 5 to 10 carbon atoms. More preferably, it is a group. Specific examples include a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group, and a nonyl group is preferable.

  In the compound represented by the general formula (II), m is preferably an integer of 1 to 20, more preferably an integer of 2 to 10, more preferably 3 to 5 because adhesion is further improved. More preferably, it is an integer.

In the compound represented by the general formula (II), R ⁵ is preferably a hydrogen atom, R ⁶ is a nonyl group, and m is preferably an integer of 3 to 5.

  Examples of the compound represented by the general formula (II) include nonylphenoxytetraethylene glycol (meth) acrylate and nonylphenoxyoctaethylene glycol (meth) acrylate.

  In the photosensitive resin composition of the present invention, the component (B) preferably contains a compound represented by the following general formula (III). Thereby, the photosensitive resin composition of this embodiment will have the outstanding tent reliability, when exposed by the direct drawing method. Here, “tent reliability” means a property (tenting property) that is not damaged by the spray pressure of development or water washing after exposure. Is used to measure the deformed tent tear rate (%).

In the formula, R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and n represents an integer of 0 to 50.

  Examples of the compound represented by the general formula (III) include di (meth) acrylic anhydride (n = 0) and (poly) ethylene glycol di (meth) acrylate (n = 1 to 50). (Poly) ethylene glycol di (meth) acrylate is obtained by reacting (poly) ethylene glycol with (meth) acrylic acid. Examples of commercially available compounds represented by the above general formula (III) include polyethylene glycol dimethacrylates such as 9G, 14G, and 23G (all are trade names, manufactured by Shin-Nakamura Chemical Co., Ltd.). .

  The content of the compound represented by the general formula (III) is preferably 1 to 30% by mass on the basis of the total mass of the component (B) in terms of excellent balance between sensitivity and resolution.

The photosensitive resin composition of this embodiment can contain (B) components other than the compound represented by the said general formula (II) and (III). These components (B) are not particularly limited as long as they have an ethylenically unsaturated bond and can be photocrosslinked, and examples thereof include the following compounds (B1) to (B5). These can be used alone or in combination of two or more.
(B1) Bisphenol A di (meth) acrylate compound (B2) Compound obtained by reacting polyhydric alcohol with α, β-unsaturated carboxylic acid
(Excluding compounds represented by the above general formula (III))
(B3) Compound obtained by reacting glycidyl group-containing compound with α, β-unsaturated carboxylic acid (B4) Urethane monomer such as (meth) acrylate compound having urethane bond

  Especially, it is preferable that (B) component contains the bisphenol A type | system | group di (meth) acrylate compound (B1) at the point which is excellent in a sensitivity and the resolution. Examples of (B1) include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, And 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane.

  When the component (B) includes the bisphenol A-based di (meth) acrylate compound (B1), the content of the bisphenol A-based di (meth) acrylate compound (B1) is 20 to 20 based on the total mass of the component (B). It is preferable that it is 80 mass%, and it is more preferable that it is 30-70 mass%.

  Examples of the compound (B2) obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include polypropylene glycol di (meth) acrylate having 2 to 14 oxypropylene groups, and trimethylolpropane. Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate (one having a total number of repeating oxyethylene groups of 1 to 5), 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, dipentaerythritol Hexa (meth) acrylate may be mentioned. Here, “EO-modified” means a compound (polyoxyethylenated compound) having a block structure of a (poly) oxyethylene chain, and “PO-modified” means (poly) oxypropylene. This means a compound having a chain block structure (compound converted to polyoxypropylene), and “EO / PO modified” has a block structure of (poly) oxyethylene chain and (poly) oxypropylene chain. It means that the compound is a compound (polyoxyethylenated and polyoxypropylenated compound). These can be used alone or in combination of two or more.

  Examples of the urethane monomer (B4) include a (meth) acryl monomer having a hydroxyl group at the β-position and isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Addition reaction products with a diisocyanate compound, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate and the like can be mentioned. Examples of the EO-modified urethane di (meth) acrylate include Shin-Nakamura Chemical Co., Ltd., trade name UA-11, and the like. Examples of the EO, PO-modified urethane di (meth) acrylate include Shin-Nakamura Chemical Co., Ltd., trade name UA-13, and the like. Examples of tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate include, for example, trade name UA-21 manufactured by Shin-Nakamura Chemical Co., Ltd. When using UA-21, it is preferable that it is 5-25 mass% on the basis of the total mass of (B) component at the point which improves a tent reliability more, and it is more preferable that it is 7-15 mass%. . These can be used alone or in combination of two or more.

  It is preferable that content of (B) component (photopolymerizable compound) shall be 20-70 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. In terms of improving sensitivity and resolution, the content of the component (B) is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, and further preferably 30 parts by mass or more. The content of the component (B) is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 55 parts by mass or less, and further preferably 50 parts by mass in terms of imparting film properties and excellent resist shape after curing. Part or less is more preferable.

[Other ingredients]
Furthermore, the photosensitive resin composition of the present embodiment may contain, as necessary, dyes such as malachite green, Victoria pure blue, brilliant green, and methyl violet; leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, Photo-coloring agents such as o-chloroaniline and tribromomethylsulfone; thermal color-preventing agents; plasticizers such as p-toluenesulfonamide; pigments; fillers; antifoaming agents; flame retardants; An exfoliation accelerator; an antioxidant; a fragrance; an imaging agent; These can be used alone or in combination of two or more.

  The photosensitive resin composition of this embodiment can be dissolved in an organic solvent and used as a solution (coating solution) having a solid content of about 30 to 60% by mass. Examples of the organic solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof.

  The said coating liquid is apply | coated on surfaces, such as a support film mentioned later and a metal plate, and the photosensitive resin layer formed using the photosensitive resin composition of this embodiment can be formed by making it dry. . Examples of the metal plate include iron alloys such as copper, copper alloys, nickel, chromium, iron, and stainless steel, preferably copper, copper alloys, and iron alloys.

  The thickness of the photosensitive resin layer varies depending on the application, but is preferably about 1 to 100 μm in thickness after drying. The surface of the photosensitive resin layer opposite to the metal plate may be covered with a protective film. Examples of the protective film include polymer films such as polyethylene and polypropylene.

<Photosensitive element>
The photosensitive element of this invention has a support film and the photosensitive resin layer formed using the said photosensitive resin composition formed on this support film, The protective film provided as needed It is configured to have other layers such as.

  FIG. 1 shows an embodiment of the photosensitive element of the present invention. The photosensitive resin layer 4 can be formed on the support film 2 by applying the solution of the photosensitive resin composition onto the support film 2 and drying it. Next, the surface of the photosensitive resin layer 4 opposite to the supporting film 2 is covered with a protective film 6, thereby supporting the supporting film 2, the photosensitive resin layer 4 laminated on the supporting film 2, and the photosensitive film. The photosensitive element 10 of this embodiment provided with the protective film 6 laminated | stacked on the photosensitive resin layer 4 is obtained. Note that the protective film 6 is not necessarily provided.

As the support film 2, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used.
The thickness of the support film 2 (polymer film) is preferably 1 μm to 100 μm, more preferably 1 to 50 μm, and still more preferably 1 μm to 30 μm. When the thickness of the support is 1 μm or more, the support film can be prevented from being broken when the support film is peeled off. Moreover, the fall of the resolution is suppressed because it is 100 micrometers or less.

  The protective film 6 preferably has a lower adhesive force to the photosensitive resin layer 4 than the adhesive force of the support film 2 to the photosensitive resin layer 4 and is preferably a low fisheye film. Here, “fish eye” means that when a material is heat-melted, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidatively deteriorated materials, etc. are present in the film. It means what was taken in. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.

  Specifically, as the protective film 6, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used. Examples of commercially available products include polypropylene films such as Alfan MA-410 and E-200C manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., and polyethylene terephthalate films such as PS series such as PS-25 manufactured by Teijin Limited. The protective film 6 may be the same as the support film 2.

  The thickness of the protective film 6 is preferably 1 μm to 100 μm, more preferably 1 μm to 50 μm, and still more preferably 1 μm to 30 μm. When the thickness of the protective film is 1 μm or more, the protective film can be prevented from being broken when the photosensitive resin layer and the support film are laminated on the substrate while peeling off the protective film. When it is 100 μm or less, it is excellent in inexpensiveness.

  The photosensitive element of this embodiment can be manufactured as follows, for example. Preparing a coating solution prepared by dissolving at least (A) component: binder polymer, (B) component: polymerizable compound, and (C) photopolymerization initiator in the organic solvent; and supporting the coating solution. It can be manufactured by a manufacturing method including a step of coating on and forming a coating layer, and a step of drying the coating layer and forming a photosensitive resin layer.

  Application of the coating solution onto the support film 2 can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, or a bar coater.

  The drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. For example, it is preferable to carry out at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive resin layer is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.

  The thickness of the photosensitive resin layer 4 in the photosensitive element 10 can be appropriately selected depending on the intended use. The thickness after drying is preferably 1 μm to 200 μm, more preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm. More preferably. When the thickness is 1 μm or more, industrial coating becomes easy. When the thickness is 200 μm or less, the sensitivity and the photocurability of the resist bottom tend to be sufficiently obtained.

  The photosensitive element 10 may further include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.

The form of the obtained photosensitive element 10 is not particularly limited. For example, it may be in the form of a sheet, or may be in the form of a roll wound around a core. When winding in roll form, it is preferable to wind up so that the support film 2 may become an outer side. 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). From the viewpoint of end face protection, it is preferable to install an end face separator on the end face of the roll-shaped photosensitive element roll thus obtained, and it is preferable to install a moisture-proof end face separator from the standpoint of edge fusion resistance. As a packaging method, it is preferable to wrap and package in a black sheet with low moisture permeability.
The photosensitive element 10 can be used suitably for the manufacturing method of the resist pattern mentioned later, for example.

<Method for producing resist pattern>
A resist pattern can be formed using the photosensitive resin composition. The resist pattern manufacturing method of this embodiment includes (i) a laminating step of laminating a photosensitive resin layer formed using the photosensitive resin composition on a substrate, and (ii) the photosensitive resin layer. An exposure step of irradiating actinic rays in the form of an image by a direct drawing method to cure the exposed portion; and (iii) removing a non-exposed portion of the photosensitive resin layer from the substrate to form a photosensitive resin composition on the substrate. And a developing step of forming a resist pattern composed of a cured product.

(I) Lamination process First, the photosensitive resin layer formed using the photosensitive resin composition is laminated | stacked on a board | substrate. As the substrate, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used.

  For example, when the photosensitive element 10 has the protective film 6, the photosensitive resin layer 4 is laminated on the substrate after the protective film 6 is removed and then the photosensitive resin layer 4 of the photosensitive element 10. This is performed by pressure-bonding to the substrate while heating. Thereby, the laminated body provided with the board | substrate, the photosensitive resin layer 4, and the support film 2 in this order is obtained.

This lamination operation is preferably performed under reduced pressure from the viewpoint of adhesion and followability. It is preferable to heat the photosensitive resin layer and / or the substrate at the time of pressure bonding at a temperature of 70 ° C to 130 ° C. The pressure bonding is preferably performed at a pressure of about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). These conditions are appropriately selected as necessary. If the photosensitive resin layer is heated to 70 ° C. to 130 ° C., it is not necessary to pre-heat the substrate in advance, but the substrate can be pre-heated in order to further improve the stackability.

(Ii) Exposure Step Next, exposure is performed by a direct drawing method. That is, a desired pattern is directly drawn on the photosensitive resin layer by irradiating the photosensitive resin layer 4 with an actinic ray such as a laser beam on the basis of digital data without using a mask film. At this time, when the support film 2 present on the photosensitive resin layer 4 is transmissive to actinic rays, actinic rays can be irradiated through the support film 2. When the support film 2 is light-shielding, the photosensitive resin layer is irradiated with actinic rays after the support film 2 is removed.

  Examples of the direct drawing method include a laser direct drawing exposure method and a DLP (Digital Light Processing) exposure method. As the active light source, a YAG laser, a semiconductor laser, a gallium nitride blue-violet laser or the like is preferable. Even those that effectively radiate ultraviolet rays such as carbon arc lamps, mercury vapor arc lamps, ultra-high pressure mercury lamps, high-pressure mercury lamps, xenon lamps, and those that effectively radiate visible light such as photographic flood bulbs and solar lamps Good. Although there is no restriction | limiting in particular in the light source in this invention, It is preferable at the point which improves the effect of this invention further to use the laser which has a wavelength of 355 nm vicinity as a light source.

(Iii) Development process Furthermore, the resist pattern comprised with the hardened | cured material of the photosensitive resin composition is formed on a board | substrate by removing the unexposed part of the photosensitive resin layer 4 from a board | substrate. When the support film 2 exists on the photosensitive resin layer 4, the support film 2 is removed, and then the unexposed portion is removed (development). Development methods include wet development and dry development, and wet development is widely used.

In the case of wet development, development is performed by a known development method using a developer corresponding to the photosensitive resin composition. As a developing method, dipping method, paddle method, a spray method, brushing, slapping, scratcher bi ring, it includes methods using reciprocal dipping, etc., from the viewpoint of improved resolution, high-pressure spray system is most suitable Yes. You may develop by combining these 2 or more types of methods.

  The configuration of the developer is appropriately selected according to the configuration of the photosensitive resin composition. For example, alkaline aqueous solution, aqueous developer, organic solvent developer and the like can be mentioned.

  The alkaline aqueous solution is safe and stable when used as a developer, and has good operability. 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, sodium phosphate, and the like. Alkali metal phosphates; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used.

  As alkaline aqueous solution, 0.1-5 mass% dilute solution of sodium carbonate, 0.1-5 mass% dilute solution of potassium carbonate, 0.1-5 mass% dilute solution of sodium hydroxide, 0.1-5 A dilute solution of mass% sodium tetraborate is preferred. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the alkali developability of the photosensitive resin layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.

  The aqueous developer is, for example, 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, borax, 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 aqueous developer is preferably as low as possible within a range where development is sufficiently performed, preferably 8 to 12, and more preferably 9 to 10.

  Examples of the organic solvent used in the aqueous developer 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. Etc. These are used alone or in combination of two or more. In general, the concentration of the organic solvent in the aqueous developer is preferably 2 to 90% by mass, and the temperature can be adjusted according to alkali developability. A small amount of a surfactant, an antifoaming agent or the like can be mixed in the aqueous developer.

  Examples of the organic solvent developer include organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. It is preferable to add water to these organic solvents in the range of 1 to 20% by mass in order to prevent ignition.

After removing the unexposed portion, the resist pattern may be further cured by heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm ² as necessary.

<Method for manufacturing printed wiring board>
A printed wiring board can be manufactured by etching or plating a substrate on which a resist pattern is formed by the above method. Etching or plating of the substrate is performed on the conductor layer of the substrate using the formed resist pattern as a mask.

  Etching solutions used in the etching process include cupric chloride solution, ferric chloride solution, alkaline etching solution, and hydrogen peroxide etching solution. It is preferable to use a diiron solution.

  Plating methods for plating treatment include 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 plating such as nickel sulfamate And gold plating such as hard gold plating and soft gold plating.

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

  Examples of the resist pattern peeling method include an immersion method and a spray method, which may be used alone or in combination. The printed wiring board on which the resist pattern is formed is not limited to a single-layer printed wiring board but may be a multilayer printed wiring board or may have a small-diameter through hole.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. Unless otherwise specified, “part” and “%” are based on mass.

[(A) component: binder polymer]
(Preparation of solution a)
A solution “a” was prepared by dissolving 2.0 g of azobisisobutyronitrile as a radical reaction initiator in a mixed solution of polymerizable monomers (copolymerization monomer, monomer) shown in Table 1. .
Further, 1.0 g of azobisisobutyronitrile was dissolved in 100 g of a mixed solution (mass ratio 6: 4) of 60 g of methyl cellosolve and 40 g of toluene to prepare “Solution b”.

(Radical polymerization reaction)
Into a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas introduction tube, 400 g of a mixed solution (mass ratio 3: 2) of 240 g of methyl cellosolve and 160 g of toluene was added. While the nitrogen gas was blown into the flask, the mixture was heated while stirring to raise the temperature to 80 ° C.

  The solution a was dropped into the mixed solution in the flask over 4 hours, and the solution in the flask was kept at 80 ° C. for 2 hours while stirring. Next, the solution b was added dropwise to the solution in the flask over 10 minutes, and then the solution in the flask was kept at 80 ° C. for 3 hours while stirring. Furthermore, the solution in the flask was heated to 90 ° C. over 30 minutes, kept at 90 ° C. for 2 hours, and then cooled to obtain a binder polymer solution as the component (A).

  Acetone was added to this binder polymer solution to prepare a non-volatile component (solid content) of 50% by mass. The weight average molecular weight of the binder polymer was 55000. The weight average molecular weight was measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve. The conditions for GPC are as follows.

-GPC conditions-
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.)
Column: The following three Gelpack GL-R420
Gelpack GL-R430
Gelpack GL-R440
(The above is a product name manufactured by Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran Measurement temperature: 25 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

[Solution of photosensitive resin composition]
By blending the component (B), the component (C), the additive and the solvent in the obtained binder polymer (component (A)) with the blending amount (g) shown in the following table, Examples 1 to 6 And the solution of the photosensitive resin composition of Comparative Examples 1-3 was prepared. In addition, the compounding quantity of (A) component shown in Table 2 is the mass (solid content) of a non-volatile component. In the table, “D-58” means that the solid content is 58 g.

The numerical value is the solid content of each component (unit: g)

The materials shown in Table 2 are as follows.
* 1: Copolymer of methacrylic acid / methyl methacrylate / styrene (25/50/25 (mass ratio)) prepared above, weight average molecular weight 55000, acid value 163 mg KOH / g, 50 mass% methyl sorb / toluene = 6 / 4 (mass ratio) solution

* 2: Bisphenol A polyoxyethylene dimethacrylate (product name, manufactured by Hitachi Chemical Co., Ltd.)
* 3: Nonylphenoxytetraethylene glycol acrylate (average number of oxyethylene groups is 4) (product name, manufactured by Hitachi Chemical Co., Ltd.)
* 4: Polyethylene glycol # 400 dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name, average value of the total number of oxyethylene groups is 9)

* 5: Compound represented by the following formula (IV) (sample name, manufactured by Changzhou Strong Co., Ltd.)

* 6: Compound represented by the following formula (V) (sample name (manufactured by Changzhou Strong Co., Ltd.))

* 7: Compound represented by the following formula (VI) (sample name (manufactured by Changzhou Strong Co., Ltd.))

* 8: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) (BASF Japan Ltd.)
* 9: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole

LCV: leuco crystal violet MKG: malachite green TLS: toluene
MAL: Methanol
ACS: Acetone

(Production of photosensitive element)
The solutions of the photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were uniformly coated on a 16 μm thick polyethylene terephthalate film (trade name “G2-16” manufactured by Teijin Limited). The photosensitive resin layer having a thickness of 38 μm after drying was formed by drying with a hot air convection dryer at 100 ° C. for 10 minutes. A protective film (manufactured by Tamapoly Co., Ltd., trade name “NF-13”) was laminated on the photosensitive resin layer by roll pressurization to form a polyethylene terephthalate film (supporting film) and the film thereon. The photosensitive element of Examples 1-6 and Comparative Examples 1-3 which consist of each photosensitive resin layer and the protective film formed on it was obtained.

(Laminated substrate)
1.6 mm thick copper-clad laminate (made by Hitachi Chemical Co., Ltd., trade name “MCL-E-67”) composed of glass epoxy material and copper foil (thickness 35 μm) formed on both sides thereof The copper surface was polished using a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, washed with water, and then dried with an air flow. After heating this copper clad laminated board (henceforth "a board | substrate") and heating up to 80 degreeC, the photosensitive element of Examples 1-6 or Comparative Examples 1-3 was made into the copper surface of the both sides of a board | substrate. Was laminated. Lamination is performed at a speed of 1.5 m / min so that the photosensitive resin layer of each photosensitive element adheres to each copper surface of the substrate while removing the protective film using a 110 ° C. heat roll. It was.

[Evaluation Test 1: Examples 1-6 and Comparative Examples 1-3]
(sensitivity)
The obtained multilayer substrate was allowed to cool, and when the temperature reached 23 ° C., a phototool having a step tablet was brought into close contact with the polyethylene terephthalate film (support film) on the surface of the multilayer substrate. As the step tablet, a 41-step step tablet having a density region of 0.00 to 2.00, a density step of 0.05, a tablet size of 20 mm × 187 mm, and each step size of 3 mm × 12 mm was used. . The photosensitive resin layer was exposed through a phototool having such a step tablet and a polyethylene terephthalate film. The exposure was performed with an exposure amount of 20 mJ / cm ² using an exposure machine (trade name “Paragon-9000m” manufactured by Nippon Orbotech Co., Ltd.) using a semiconductor-excited solid laser as a light source.

  After the exposure, the polyethylene terephthalate film was peeled off from the laminated substrate to expose the photosensitive resin layer. The exposed photosensitive resin layer was sprayed (development treatment) with a 1.0% by mass aqueous sodium carbonate solution at 30 ° C. for 50 seconds to remove unexposed portions. Thus, the cured film which consists of hardened | cured material of the photosensitive resin composition was formed in the copper surface of a laminated substrate. The sensitivity (photosensitivity) of the photosensitive resin compositions and photosensitive elements of Examples 1 to 6 and Comparative Examples 1 to 3 was evaluated by measuring the number of steps of the step tablet of the obtained cured film. The higher the number of steps of the step tablet, the higher the sensitivity. The results are shown in Table 3.

(Tent reliability)
As shown in FIG. 2, the above copper-clad laminate (trade name MCL-E-67 manufactured by Hitachi Chemical Co., Ltd.) has a diameter of 4 to 6 mm and 3 independent round holes 41 and 3 respectively. A triple hole 42 in which the round holes are connected and the interval between the round holes is gradually shortened was produced by a die cutting machine. The burr generated when the round hole 41 and the triple hole 42 were produced was removed using a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, and this was removed with the hole breakage number measuring substrate 40. did.
The obtained substrate for hole breakage number measurement 40 is heated to 80 ° C., and the protective film is peeled off from the photosensitive resin composition laminate obtained above so that the photosensitive resin layer faces the copper surface. The photosensitive elements of Examples 1 to 6 or Comparative Examples 1 to 3 were laminated under the conditions of 120 ° C. and 0.4 MPa.

  After laminating, the hole breakage measuring substrate 40 is cooled, and when the temperature of the hole breakage measuring substrate 40 reaches 23 ° C., the laser is used as a light source for the polyethylene terephthalate film (support film) surface. Using an exposure machine, exposure was performed with an energy amount such that the number of remaining step steps after development of the Hitachi 41-step tablet was 17.0 (direct drawing method).

  After the exposure, the film was allowed to stand at room temperature for 15 minutes, and then the polyethylene terephthalate film was peeled off from the hole tearing number measurement substrate 40 and developed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 50 seconds. After development, the number of hole breaks in the triple holes was measured, the deformed tent tear rate was calculated, and the tent reliability (%) was evaluated. The smaller this value, the higher the tent reliability. The results are shown in Table 3.

(Peelability)
A pattern of 60 mm × 45 mm was drawn on the photosensitive resin layer of the laminated substrate by a direct drawing method using an exposure machine using the laser as a light source. The exposure was performed with an energy amount such that the number of remaining step steps after development of the Hitachi 41-step tablet was 17.0. After the exposure, the same development treatment as in the sensitivity evaluation was performed to obtain a test piece in which a cured film of 60 mm × 45 mm was formed on the substrate.

  The test piece was allowed to stand at room temperature for a whole day and night, then immersed (dip) in a 3 mass% sodium hydroxide aqueous solution (stripping solution) at 50 ° C., and stirred with a stirrer. The peelability was evaluated by measuring the time from the start of stirring until the cured film was completely peeled and removed from the substrate (peeling time (seconds)). The shorter the peeling time, the better the peelability. The results are shown in Table 3.

  The above results are summarized in Table 3.

  In any of Examples 1 to 6 using the photosensitive resin composition of the present invention, the sensitivity was higher than those of Comparative Examples 1 to 3. In particular, in Example 3, good results were obtained in sensitivity, tent reliability, and peelability. Moreover, when the peelability of Example 3 and Example 5 is compared, it can be seen that better peelability can be obtained by adding the photopolymerizable compound FA-314A. Regarding the comparative example, the photosensitivity to the direct drawing exposure method was insufficient, and the tent reliability was also inferior to that of the example.

2 Support film 4 Photosensitive resin layer 6 Protective film 10 Photosensitive element 40 Hole breakage measuring substrate 41 Round hole 42 3 holes

Claims (6)

(A) binder polymer contains a photopolymerizable compound (B) and (C) a photopolymerization initiator, wherein the (C) photopolymerization initiator, seeing containing a compound represented by the following formula (I),
The photopolymerizable compound (B) comprises a monofunctional photopolymerizable compound, the monofunctional photopolymerizable compound, including a compound represented by the following formula (II), a photosensitive resin composition.


[In the general formula (I), R ¹ represents an organic group containing a cycloalkyl group having 3 to 20 carbon atoms, R ² and R ³ each independently represents an alkyl group or an aryl group, and R ⁴ represents Represents an alkyl group. ]


[Wherein, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents a hydrocarbon group having 1 to 10 carbon atoms, and m represents an integer of 0 to 20. ] (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, wherein the (C) photopolymerization initiator includes a compound represented by the following general formula (I),
The photopolymerizable compound (B) is, including the compound represented by the following formula (III), sensitive photosensitive resin composition.


[In the general formula (I), R ¹ represents an organic group containing a cycloalkyl group having 3 to 20 carbon atoms, R ² and R ³ each independently represents an alkyl group or an aryl group, and R ⁴ represents Represents an alkyl group. ]


[Wherein, R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and n represents an integer of 0 to 50. ] (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, wherein the (C) photopolymerization initiator includes a compound represented by the following general formula (I),
The content of the compound represented by the general formula (I) is 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the total amount of the (A) binder polymer and (B) photopolymerizable compound. that sensitive photosensitive resin composition.


[In the general formula (I), R ¹ represents an organic group containing a cycloalkyl group having 3 to 20 carbon atoms, R ² and R ³ each independently represents an alkyl group or an aryl group, and R ⁴ represents Represents an alkyl group. ] A photosensitive element comprising: a support film; and a photosensitive resin layer formed using the photosensitive resin composition according to any one of claims 1 to 3 formed on the support film. . A laminating step of laminating a photosensitive resin layer formed using the photosensitive resin composition according to any one of claims 1 to 3 on a substrate;
An exposure step of irradiating the photosensitive resin layer with an actinic ray in an image shape by a direct drawing method and curing an exposed portion;
A development step of forming a resist pattern composed of a cured product of the photosensitive resin composition on the substrate by removing an unexposed portion of the photosensitive resin layer from the substrate. Manufacturing method. Photosensitivity containing (A) binder polymer, (B) photopolymerizable compound and (C) photopolymerization initiator, wherein (C) photopolymerization initiator contains a compound represented by the following general formula (I) A laminating step of laminating a photosensitive resin layer formed using a resin composition on a substrate;
An exposure step of irradiating the photosensitive resin layer with an actinic ray in an image shape by a direct drawing method and curing an exposed portion;
A development step of forming a resist pattern composed of a cured product of the photosensitive resin composition on the substrate by removing an unexposed portion of the photosensitive resin layer from the substrate. A method for producing a printed wiring board, comprising etching or plating a substrate on which a resist pattern has been formed by the production method.


[In the general formula (I), R ¹ represents an organic group containing a cycloalkyl group having 3 to 20 carbon atoms, R ² and R ³ each independently represents an alkyl group or an aryl group, and R ⁴ represents Represents an alkyl group. ]