JP2019101049A - Photosensitive resin composition and method for producing circuit board - Google Patents

Abstract

To provide a photosensitive resin composition having excellent adhesiveness, and a method for producing a circuit board using the same.SOLUTION: A photosensitive resin composition contains a resin having a constitutional unit represented by general formula (a1), a compound having a methylol group or an alkoxyalkyl group, an aliphatic compound having two or more functional groups, which are one or more selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxy group, and a photosensitive acid generator.SELECTED DRAWING: None

Description

  The present disclosure relates to a photosensitive resin composition and a method of manufacturing a circuit board using the same.

  In the production of semiconductor elements or printed wiring boards, for example, a negative photosensitive resin composition is used to form a fine pattern. In this method, a photosensitive layer (coating film) is formed on a substrate (a wafer in the case of a semiconductor element, a substrate in the case of a printed wiring board) by coating of a photosensitive resin composition or the like, The exposed portion is cured by irradiating the light. Furthermore, a resin pattern which is a cured film of the photosensitive resin composition is formed on the substrate by selectively removing the unexposed area using a developer. Therefore, the photosensitive resin composition is required to be excellent in sensitivity to an actinic ray, capable of forming a fine pattern (resolution), and the like. For example, Patent Document 1 proposes a photosensitive resin composition which is excellent in resolution and heat resistance.

International Publication No. 2015/046522

  By the way, as for the photosensitive resin composition used for the above-mentioned use, in order to control exfoliation from a substrate, it is desirable for adhesiveness to a substrate to be good. However, as a result of examination by the present inventors, it was found that the photosensitive resin composition described in Patent Document 1 has room for improvement in adhesion to a substrate.

  An object of this indication is to provide the manufacturing method of the photosensitive resin composition which is excellent in adhesiveness, and the circuit board using the same.

［式（ａ１）中、Ｚ^１は、芳香族炭化水素環を示し、Ｒ^Ａ１、Ｒ^Ａ２は一価の置換基を示し、Ｒ^Ａ３は水素原子又は炭化水素基を示す。ｐは１以上の整数を示し、ｑ及びｒは０以上の整数を示す。複数存在するＺ^１、Ｒ^Ａ１、Ｒ^Ａ２、ｐ、ｑ及びｒはそれぞれ同一でも異なっていてもよい。］
［２］（Ａ）成分が、下記一般式（ａ２）で表される構成単位を更に有する樹脂である［１］に記載の感光性樹脂組成物。

［式（ａ２）中、Ｒ^Ａ４はメチル基又はヒドロキシ基を示し、ｓは０〜２の整数である。］
［３］一般式（ａ１）中のＺ^１がベンゼン環又はナフタレン環である、［１］又は［２］に記載の感光性樹脂組成物。
［４］一般式（ａ１）中のｐが１であり、ｑ及びｒが０である、［１］〜［３］のいずれかに記載の感光性樹脂組成物。
［５］（Ａ）成分が、一般式（ａ１）で表される構成単位を１０〜５０質量％有する、［１］〜［４］のいずれかに記載の感光性樹脂組成物。
［６］（Ｅ）成分：Ｓｉ−Ｏ結合を有する化合物を更に含有する、［１］〜［５］のいずれかに記載の感光性樹脂組成物。
［７］（Ｅ）成分がシランカップリング剤である、［６］に記載の感光性樹脂組成物。
［８］（ａ）［１］〜［７］のいずれかに記載の感光性樹脂組成物を基板上に塗布し、当該感光性樹脂組成物を乾燥して感光層を形成する工程と、
（ｂ）当該感光層を所定のパターンで露光し、現像し、更に加熱処理することで、樹脂パターンを得る工程と、
（ｃ）上記基板の露出部及び上記樹脂パターンの露出部をめっき処理することで、導体層を形成する工程と、
（ｄ）当該導体層の一部を除去して導体パターンを形成する工程と、
を備える回路基板の製造方法。 In view of the above circumstances, the present disclosure provides the invention described below.
[1] Component (A): a resin having a structural unit represented by the following general formula (a1),
Component (B): a compound having a methylol group or an alkoxyalkyl group,
Component (C): an aliphatic compound having two or more functional groups selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group, and
Component (D): A photosensitive resin composition containing a photosensitive acid generator.

[In Formula (a1), Z ¹ represents an aromatic hydrocarbon ring, R ^A1 and R ^A2 represent a monovalent substituent, and R ^A3 represents a hydrogen atom or a hydrocarbon group. p is an integer of 1 or more, and q and r are integers of 0 or more. Plural Z ¹ , R ^A1 , R ^A2 , p, q and r may be the same or different. ]
[2] The photosensitive resin composition according to [1], wherein the component (A) is a resin further having a structural unit represented by the following general formula (a2).

[In Formula (a2), R ^A4 represents a methyl group or a hydroxy group, and s is an integer of 0 to 2. ]
[3] ^{Z 1} in the general formula (a1) is a benzene ring or a naphthalene ring, [1] or a photosensitive resin composition according to [2].
[4] The photosensitive resin composition according to any one of [1] to [3], wherein p in the general formula (a1) is 1 and q and r are 0.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein the component (A) has 10 to 50% by mass of the constituent unit represented by the general formula (a1).
[6] Component (E): The photosensitive resin composition according to any one of [1] to [5], which further contains a compound having a Si-O bond.
[7] The photosensitive resin composition according to [6], wherein the component (E) is a silane coupling agent.
[8] (a) A step of applying the photosensitive resin composition according to any one of [1] to [7] onto a substrate, drying the photosensitive resin composition to form a photosensitive layer,
(B) a step of obtaining a resin pattern by exposing the photosensitive layer in a predetermined pattern, developing it, and further heat treating it;
(C) forming a conductor layer by plating the exposed portion of the substrate and the exposed portion of the resin pattern;
(D) removing a portion of the conductor layer to form a conductor pattern;
A method of manufacturing a circuit board comprising:

  According to the present disclosure, it is possible to provide a photosensitive resin composition having excellent adhesiveness and a method for producing a circuit board using the same.

It is a schematic cross section which shows the manufacturing method of the circuit board which concerns on one Embodiment of this indication.

  Hereinafter, one embodiment of the present disclosure will be specifically described, but the present disclosure is not limited thereto. In the following embodiments, it is needless to say that the constituent elements (including element steps and the like) are not necessarily essential unless particularly clearly stated and considered to be obviously essential in principle. . This should be interpreted similarly as to numerical values and ranges, and not to unduly limit the present disclosure.

  In addition, in the present specification, the terms “layer” and “film” are, in addition to the structure of the shape formed on the entire surface when observed as a plan view, the structure of the shape formed in a part Is included. The term "step" is not only an independent step but is included in the term if the intended purpose of the step is achieved, even if it can not be distinguished clearly from other steps. "EO-modified" means that it is a compound having a (poly) oxyethylene group, and "PO-modified" means that it is a compound having a (poly) oxypropylene group. Here, “(poly) oxyethylene group” means at least one of an oxyethylene group and a polyoxyethylene group in which two or more ethylene groups are linked by an ether bond. The “(poly) oxypropylene group” means at least one of an oxypropylene group and a polyoxypropylene group in which two or more propylene groups are linked by an ether bond. The term "Si-O bond" indicates a bond between a silicon atom and an oxygen atom, and may be part of a siloxane bond (Si-O-Si bond). The numerical range shown using "-" shows the range which includes the numerical value described before and after "-" as minimum value and the maximum value, respectively. The upper limit or lower limit of the numerical range of one step may be replaced with the upper limit or lower limit of the numerical range of another step in the numerical range which is described stepwise in this specification. In addition, in the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the example. “A or B” may contain either A or B, and may contain both. The materials exemplified below can be used singly or in combination of two or more unless otherwise specified. The content of each component in the composition means, when there is a plurality of substances corresponding to each component in the composition, the total amount of the plurality of substances present in the composition unless otherwise specified.

(Photosensitive resin composition)
The photosensitive resin composition according to the present embodiment includes (A) component: a resin having a structural unit represented by the following general formula (a1), (B) component: a compound having a methylol group or an alkoxyalkyl group, (C) Component: Aliphatic compound having two or more functional groups selected from acryloyloxy group, methacryloyloxy group, glycidyloxy group and hydroxyl group, and (D) component: Photosensitive acid generator Do. The photosensitive resin composition of the present embodiment may further contain a component (E): a compound having a Si-O bond, and the like. Each component will be described below.

<(A) component>
The photosensitive resin composition of the present embodiment contains, as the component (A), a resin having a structural unit represented by the following general formula (a1).

In formula (a1), Z ¹ represents an aromatic hydrocarbon ring, R ^A1 and R ^A2 represent a monovalent substituent, and R ^A3 represents a hydrogen atom or a hydrocarbon group. p is an integer of 1 or more, and q and r are integers of 0 or more.

In the formula (a1), the aromatic hydrocarbon ring represented by the ring Z ¹ may be, for example, a benzene ring, a fused polycyclic aromatic hydrocarbon and the like. The fused polycyclic aromatic hydrocarbon ring is, for example, a fused bicyclic hydrocarbon having 8 to 20 carbon atoms such as indene and naphthalene, preferably 10 to 16 carbons, and preferably fused tricyclic hydrocarbon such as anthracene and phenanthrene. Hydrogen, a fused tetracyclic hydrocarbon and the like can be mentioned. Z ¹ is preferably a benzene ring or a naphthalene ring.

In the formula (a1), the substitution number p of the hydroxy group is an integer of 1 or more, and may be, for example, 1 to 4, preferably 1 to 3, more preferably 1 or 2, and 1 Is more preferred. p may be the same or different from each other in different rings Z ¹ .

In formula (a1), R ^A1 is, for example, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydrocarbon group such as an aralkyl group, or alkoxy Groups, cycloalkoxy groups, aryloxy groups, aralkyloxy groups, alkylthio groups, acyl groups, alkoxycarbonyl groups, halogen atoms, nitro groups, cyano groups, substituted amino groups and the like. R ^A1 is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, or an aryl group having 6 to 10 carbon atoms such as a phenyl group, and is a methyl group, an ethyl group, a propyl group, a butyl group or a phenyl group Is more preferred.

If it is the same q is 2 or more in the ring Z ^1, R ^A1 may be the same or different, in the two rings Z ¹ R ^A1 may be the same or different from each other. q may be, for example, 0-8, and may be 0-4 or 0-3. q may be the same or different from each other in different rings Z ¹ . It is preferable that q is 0.

The position of substitution of a hydroxy group in ring Z ¹ is not particularly limited. For example, when Z ¹ is a benzene ring, the hydroxy group is a 2-position (ortho position) or 3-position (meta) to the position where the benzene ring is bound to fluorene. Or 4) (para), preferably 4 (para).

In Formula (a1), examples of R ^A2 include a hydrocarbon group such as a cyano group, a halogen atom, an alkyl group or an aryl group, and the like. As an alkyl group, C1-C12 alkyl groups, such as a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, t-butyl group, are mentioned, for example. If R ^A2 is ^{more, R A2} may be the same or different from each other. r is an integer of 0 or more, preferably 0 or 1, and more preferably 0. The two r's may be the same or different.

In formula (a1), R ^A3 is a hydrogen atom or a hydrocarbon group. As a hydrocarbon group, C1-C6 alkyl groups, such as a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, s-butyl group, t-butyl group, etc. are mentioned, for example.

The component (A) is preferably a resin further having a structural unit represented by the following general formula (a2).

In formula (a2), R ^A4 represents a methyl group or a hydroxy group, and s is an integer of 0-2. When s is 2, a plurality of R ^A4 may be the same or different.

In formula (a2), s is preferably 1, and R ^A4 is preferably a methyl group. The substitution position of R ^A4 is not particularly limited, when R ^A4 is a methyl group, is preferably in the meta or para position to the hydroxy group attached to the benzene ring. The component (A) preferably contains a constituent unit in which the methyl group R ^A4 in the formula (a2) is in the meta position and a constituent unit in the para position. In the formula (a2), the ratio of the constituent unit in which the methyl group is in the meta position to the constituent unit in the para position with respect to the hydroxy group bonded to the benzene ring may be, for example, 100: 0 to 0: 100, 100 It is preferably from 0: 0 to 60:40, more preferably from 90:10 to 70:30.

  The proportion of the constituent unit represented by the above general formula (a1) in the component (A) may be, for example, 10 to 50% by mass, preferably 15 to 40% by mass, and 20 to 30% by mass. It is more preferable that In the component (A), the compositional ratio of the structural unit represented by the general formula (a1) is the structural unit represented by the general formula (a1) and the structural unit represented by the general formula (a2) For example, it may be 4 to 20 mol%, preferably 6 to 16 mol%, and more preferably 8 to 12 mol% with respect to the total amount of

  The component (A) is preferably a resin soluble in an aqueous alkali solution. The component (A) preferably has a weight average molecular weight of 100,000 or less, and from 1,000 to 80,000, from the viewpoint of further improving the resolution, adhesiveness, developability, thermal shock resistance, heat resistance, etc. of the resulting cured film. Some are more preferable, 2000 to 50000 is further preferable, 2000 to 35000 is further more preferable, and 5000 to 20000 is particularly preferable. The weight-average amount means a value measured by gel permeation chromatography and converted based on a standard polystyrene calibration curve.

  As the component (A), commercially available products can be used. For example, FR-CR-001, FR-CR-002, FR-CR-003, FR-CR-004, FR of Gunei Chemical Industry Co., Ltd. -CR-005, FR-CR-006, FR-CR-007, etc. can be used.

  In the photosensitive resin composition of the present embodiment, the content of the component (A) is 30 to 90 parts by mass with respect to 100 parts by mass of the total amount (excluding the solvent) of the photosensitive resin composition. Preferably, it is 40 to 80 parts by mass. When the content of the component (A) is in this range, the film formed using the resulting photosensitive resin composition tends to be further excellent in the developability with an aqueous alkaline solution.

<(B) component>
The photosensitive resin composition of the present embodiment contains, as the component (B), a compound having a methylol group or an alkoxyalkyl group. The component (B) is preferably a compound further having at least one selected from the group consisting of an aromatic ring, a heterocycle and an alicyclic ring. Here, the aromatic ring means a hydrocarbon group having aromaticity (for example, a hydrocarbon group having 6 to 10 carbon atoms), and examples thereof include a benzene ring and a naphthalene ring. The heterocycle means a cyclic group having at least one hetero atom such as nitrogen atom, oxygen atom and sulfur atom (eg, a cyclic group having 3 to 10 carbon atoms), for example, a pyridine ring, an imidazole ring, A pyrrolidinone ring, an oxazolidinone ring, an imidazolidinone ring and a pyrimidinone ring can be mentioned. Moreover, an alicyclic ring means a cyclic hydrocarbon group having no aromaticity (eg, a cyclic hydrocarbon group having 3 to 10 carbon atoms), and examples thereof include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and the like A cyclohexane ring is mentioned. The alkoxyalkyl group means a group in which an alkyl group is bonded to an alkyl group via an oxygen atom. The two alkyl groups may be different from each other, for example, an alkyl group having 1 to 10 carbon atoms.

  By containing the component (B), when the photosensitive layer after resin pattern formation is heated and cured, the component (B) reacts with the component (A) to form a crosslinked structure, and the resin pattern becomes fragile. And deformation of the resin pattern can be prevented, and heat resistance can be improved. Further, specifically, a compound further having a phenolic hydroxyl group or a compound further having a hydroxymethylamino group can be preferably used, and the components (A) and (C) are not included. Component (B) can be used singly or in combination of two or more.

  As described later, by containing the component (D) in the photosensitive resin composition, an acid is generated by irradiation with an actinic ray or the like. By the catalytic action of the generated acid, a negative pattern is formed by reacting alkoxyalkyl groups in component (B) or alkoxyalkyl groups in component (B) with component (A) with dealcoholation. can do. Further, due to the catalytic action of the generated acid, the methylol groups in (B) component or the methylol group in (B) component and the (A) component react with dealcoholization to give a negative pattern. It can be formed.

  The compound having the above-mentioned phenolic hydroxyl group further has a phenolic hydroxyl group in addition to the methylol group or the alkoxyalkyl group, thereby developing not only the reaction with the component (C) or the component (A) but also the alkaline aqueous solution. It is possible to increase the dissolution rate of the unexposed area of the above to improve the sensitivity. The molecular weight of the compound having a phenolic hydroxyl group is preferably 94 to 2000 in terms of weight average molecular weight in consideration of improving the solubility in an alkaline aqueous solution, photosensitivity, mechanical properties, etc. in a well-balanced manner, and 108 to 2000 Is more preferably 108 to 1,500.

As the compound further having a phenolic hydroxyl group, conventionally known compounds can be used, but the compound represented by the following general formula (1) has the effect of promoting the dissolution of the unexposed area and curing of the photosensitive resin film It is preferable because it is excellent in the balance of the effect of preventing the melting of

In the general formula (1), Z represents a single bond or a divalent organic group, R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a monovalent organic group, and R ²⁶ and R ²⁷ each independently represent 1 A and b each independently represent an integer of 1 to 3; c and d each independently represent an integer of 0 to 3; Here, as the monovalent organic group, for example, an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl and propyl; and an alkenyl group having 2 to 10 carbon atoms, such as vinyl. An aryl group having 6 to 30 carbon atoms such as a phenyl group; and a group in which part or all of hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as a fluorine atom.

The compound represented by Formula (1) is preferably a compound represented by Formula (2).

In the general formula (2), X ₁ represents a single bond or a divalent organic group, R represents an alkyl group (e.g., an alkyl group having 1 to 10 carbon atoms).

  Moreover, you may use the compound represented by General formula (3) as a compound which has the said phenolic hydroxyl group.

一般式（３）中、Ｒはアルキル基（例えば、炭素原子数が１〜１０のアルキル基）を示す。

In general formula (3), R shows an alkyl group (for example, a C1-C10 alkyl group).

  In the general formula (1), a compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative. Further, as the divalent organic group represented by Z, an alkylene group having 1 to 10 carbon atoms such as methylene, ethylene and propylene; and an alkylidene having 2 to 10 carbon atoms such as ethylidene and the like An arylene group having 6 to 30 carbon atoms such as a phenylene group; a group in which part or all of hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as a fluorine atom; a sulfonyl group; a carbonyl group; Sulfide bond; amide bond and the like. Among these, Z is preferably a divalent organic group represented by the following general formula (4).

In the general formula (4), X ₂ represents a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylidene group (for example, an alkylidene group having 2 to 10 carbon atoms), The group which substituted one part or all part of the hydrogen atom by the halogen atom, a sulfonyl group, a carbonyl group, an ether bond, a sulfide bond, or an amide bond is shown. R ²⁸ represents a hydrogen atom, a hydroxyl group, an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms) or a haloalkyl group, and e represents an integer of 1 to 10. The plurality of R ²⁸ may be the same or different. Here, a haloalkyl group means an alkyl group substituted by a halogen atom.

  Examples of the compound further having a hydroxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) ( N-hydroxymethyl) urea etc. are mentioned. Moreover, you may use the nitrogen-containing compound etc. which alkyl-etherified all or one part of the hydroxymethylamino group of these compounds. Here, examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group, a butyl group or a mixture thereof, and may contain an oligomer component formed by partial self condensation. Specifically, hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, tetrakis (methoxymethyl) urea and the like can be mentioned.

  Specifically, the compound having a hydroxymethylamino group is preferably a compound represented by the general formula (5) or a compound represented by the general formula (6).

一般式（５）中、Ｒはアルキル基（例えば、炭素原子数が１〜１０のアルキル基）を示す。

In general formula (5), R shows an alkyl group (for example, a C1-C10 alkyl group).

一般式（６）中、Ｒはアルキル基（例えば、炭素原子数が１〜１０のアルキル基）を示す。

In general formula (6), R shows an alkyl group (for example, a C1-C10 alkyl group).

  The content of the component (B) is preferably 5 to 60 parts by mass, more preferably 10 to 45 parts by mass, and 10 to 35 parts by mass with respect to 100 parts by mass of the component (A). Is particularly preferred. When the content of the component (B) is 5 parts by mass or more, the reaction of the exposed portion is sufficient, so that the resolution is unlikely to be lowered, and the chemical resistance and the heat resistance tend to be good, 60 parts by mass If the following condition is satisfied, the photosensitive resin composition tends to be easily deposited on a desired support, and the resolution tends to be good. In the present specification, 100 parts by mass of the component (A) means that the solid content of the component (A) is 100 parts by mass.

<(C) component>
The functional group of the component (C) is preferably a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, more preferably a glycidyloxy group or an acryloyl group, and still more preferably an acryloyloxy group. Moreover, it is preferable that (C) component has three or more of the said functional groups. The upper limit of the number of functional groups is not particularly limited, and is, for example, 12. Specific examples of the component (C) include compounds represented by the general formulas (7) to (10).

In the general formulas (7) to (10), R ¹ , R ⁵ , R ¹⁶ and R ¹⁹ each represent a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group or a group represented by the general formula (11) ²¹ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, and R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ and R ²⁰ each represent a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, a group represented by the general formula (12) or a table of the general formula (13) shows a group each R ²² and R ²³ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, n and m are the integer of 1 to 10, respectively

  Examples of compounds having a glycidyloxy group include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl Ether, glycerin diglycidyl ether, dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, glycerin triglycidyl ether, Glycerol propoxylated Triglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, and the like diglycidyl 1,2-cyclohexane dicarboxylate. The compound which has these glycidyloxy groups can be used individually by 1 type or in mixture of 2 or more types.

  Among the compounds having a glycidyloxy group, trimethylolethane triglycidyl ether or trimethylolpropane triglycidyl ether is preferable in that it is excellent in sensitivity and resolution.

  Compounds having a glycidyloxy group are, for example, Epolight 40E, Epolight 100E, Epolight 70P, Epolight 200P, Epolight 1500 NP, Epolight 1600, Epolight 80 MF, Epolite 100 MF (all manufactured by Kyoeisha Chemical Co., Ltd., trade name), alkyl type epoxy resin ZX-1542 (Nippon Steel & Sumikin Chemical Co., Ltd., trade name), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L and Denacol EX-850L (all manufactured by Nagase Chemtech Inc., products Commercially available as

  The compound having a glycidyloxy group may be an aliphatic compound having three or more functional groups represented by the following general formula (c). By using the compound, the dissolution rate of the unexposed area at the time of development with an aqueous alkali solution can be increased, and the resolution can be improved.

［式（ｃ）中、Ｚは炭素数２〜４のアルキレン基を示し、ｎは１〜２０の整数を示す。］

[In formula (c), Z shows a C2-C4 alkylene group and n shows the integer of 1-20. ]

  Specific examples of the alkylene group having 2 to 4 carbon atoms include ethylene group, trimethylene group, tetramethylene group, propylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethylethylene group, 1 And 2-dimethylethylene or ethylethylene.

  The aliphatic compound having three or more functional groups represented by the general formula (c) is a functional group in which at least three of the hydroxyl groups in the trivalent or higher aliphatic polyhydric alcohol are represented by the general formula (c) And all of the hydroxyl groups may be substituted by the functional group represented by the above general formula (c). Examples of trivalent or higher aliphatic polyhydric alcohols include glycerin, diglycerin, triglycerin, tetraglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, sorbitan, sorbitol, 1,2,4-butanetriol, 1,2,6-hexanetriol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,1,1-tris (bishydroxymethyl) propane, 2,2-bis And hydroxymethyl) butanol-3, arabitol, ribitol, xylitol, mannitol, galactitol, allodulcit, sucrose and the like.

  The number of functional groups represented by the above general formula (c) is preferably 3 to 12, and more preferably 3 to 6.

  As an aliphatic compound which has three or more functional groups represented by the said General formula (c), for example, Nagase ChemteX Co., Ltd. product made from Nagase ChemteX Co., Ltd. Denacol EX-1310, Denacol EX-1410, Denacol EX A commercial product such as Denacol EX-610U manufactured by Nagase ChemteX Co., Ltd. and derived from sorbitol can be used.

  As a compound having an acryloyloxy group, EO modified dipentaerythritol hexaacrylate, PO modified dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, EO modified ditrimethylolpropane tetraacrylate, PO modified ditrimethylolpropane tetraacrylate, ditrimethylolpropane Tetraacrylate, EO modified pentaerythritol tetraacrylate, PO modified pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, EO modified pentaerythritol triacrylate, PO modified pentaerythritol triacrylate, pentaerythritol triacrylate, EO modified trimethylolpropane acrylate, PO modified Trimethylol B bread acrylate, trimethylolpropane acrylate, EO-modified glycerol tri acrylate, PO-modified glycerol triacrylate, glycerin triacrylate. These compounds having an acryloyloxy group can be used singly or in combination of two or more. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.

  As a compound having a methacryloyloxy group, EO modified dipentaerythritol hexamethacrylate, PO modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, EO modified ditrimethylolpropane tetramethacrylate, PO modified ditrimethylolpropane tetramethacrylate, ditrimethylolpropane Tetra methacrylate, EO modified pentaerythritol tetra methacrylate, PO modified pentaerythritol tetra methacrylate, pentaerythritol tetra methacrylate, EO modified pentaerythritol trimethacrylate, PO modified pentaerythritol trimethacrylate, pentaerythritol trimethacrylate, EO modified trimethylolpropane methacrylate DOO, PO-modified trimethylolpropane dimethacrylate, trimethylolpropane dimethacrylate, EO modified glycerol trimethacrylate, PO-modified glycerol trimethacrylate, glycerine trimethacrylate and the like. The compound which has these methacryloyloxy groups can be used individually by 1 type or in mixture of 2 or more types. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.

  Examples of the compound having a hydroxyl group include polyhydric alcohols such as dipentaerythritol, pentaerythritol and glycerin. The compound which has these hydroxyl groups can be used individually by 1 type or in mixture of 2 or more types.

  The content of the component (C) is preferably 20 to 70 parts by mass, more preferably 25 to 65 parts by mass, and 35 to 55 parts by mass with respect to 100 parts by mass of the component (A). Is particularly preferred. If the content of the component (C) is 20 parts by mass or more, crosslinking in the exposed area tends to be sufficient and tackiness tends to be sufficient, and if it is 70 parts by mass or less, the photosensitive resin composition is supported as desired It becomes easy to form a film on the body, and the resolution does not easily decrease.

<(D) component>
The photosensitive resin composition of the present embodiment contains a photosensitive acid generator. The photosensitive acid generator is a compound which generates an acid upon irradiation with an actinic ray or the like. By the catalytic effect of the acid generated from the photosensitive acid generator, the methylol groups or alkoxyalkyl groups in component (D), or the methylol group or alkoxyalkyl group in component (D) and the component (A) and However, the reaction with dealcoholization significantly reduces the solubility of the photosensitive resin composition in the developer, and a negative pattern can be formed.

  The component (D) is not particularly limited as long as it is a compound that generates an acid upon irradiation with an actinic ray or the like. As the component (D), onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfoneimide compounds, diazomethane compounds and the like can be mentioned. Among them, from the viewpoint of excellent availability, the component (D) is preferably at least one selected from the group consisting of an onium salt compound and a sulfoneimide compound. In particular, when a solvent is used, the component (D) is preferably an onium salt compound from the viewpoint of excellent solubility in the solvent.

  Examples of the onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts and the like. Specific examples of preferred onium salt compounds include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium heptadecafluorooctanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate , Diaryliodonium salts such as diphenyliodonium tris (pentafluoroethyl) trifluorophosphate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, and diphenyliodonium tris [(trifluoromethyl) sulfonyl] methanide; Such as sulfonium salt and the like. Among them, sulfonium salts are preferable from the viewpoint of further improving sensitivity and thermal stability, and triarylsulfonium salts are more preferable from the viewpoint of further improving thermal stability. The onium salt compounds can be used singly or in combination of two or more.

  Examples of the triarylsulfonium salt of the component (D) include a compound represented by the following general formula (d1), a compound represented by the following general formula (d2), a compound represented by the following general formula (d3), And at least one cation selected from the group consisting of compounds represented by the following general formula (d4), a tetraphenylborate skeleton, an alkylsulfonate skeleton having 1 to 20 carbon atoms, a phenylsulfonate skeleton, a 10-camphorsulfonate skeleton A sulfonium salt having an anion having at least one skeleton selected from the group consisting of a trisalkylsulfonyl methanide skeleton having 1 to 20 carbon atoms, a tetrafluoroborate skeleton, a hexafluoroantimonate skeleton and a hexafluorophosphate skeleton; It can be mentioned.

  The hydrogen atom of the phenyl group of the general formulas (d1), (d2), (d3) and (d4) is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, 2 to 12 carbon atoms At least one member selected from the group consisting of an alkylcarbonyl group of and an alkoxycarbonyl group having 2 to 12 carbon atoms, and in the case of a plurality of substituents, they may be identical or different from each other It is also good.

  The hydrogen atom of the phenyl group of the tetraphenyl borate skeleton is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, It may be substituted by at least one member selected from the group consisting of an alkylcarbonyl group having 2 to 12 carbon atoms and an alkoxycarbonyl group having 2 to 12 carbon atoms, and in the case of a plurality of substituents, they are identical to each other Or they may be different.

  The hydrogen atom of the alkyl sulfonate skeleton is at least one selected from the group consisting of fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, alkoxy group, alkyl carbonyl group, and alkoxy carbonyl group. It may be substituted, and when there are a plurality of substituents, they may be the same or different.

  The hydrogen atom of the phenyl group of the phenyl sulfonate skeleton is fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, carbon It may be substituted by at least one member selected from the group consisting of an alkylcarbonyl group of 2 to 12 and an alkoxycarbonyl group of 2 to 12 carbon atoms, and in the case of plural substituents, they are identical to each other May also be different.

  The hydrogen atom of the trisalkylsulfonyl methanide skeleton is at least selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, and an alkoxycarbonyl group. It may be substituted by one kind, and when there are a plurality of substituents, they may be the same or different.

  The fluorine atom of the hexafluorophosphate skeleton may be substituted with at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a perfluoroalkyl group having 1 to 12 carbon atoms, When there are a plurality of substituents, they may be the same or different.

  The sulfonium salt used as the component (D) has, as a cation, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium, (2) from the viewpoint of being further excellent in sensitivity, resolution and insulating properties. -Methyl) phenyl [4- (4-biphenylylthio) phenyl] 4-biphenylylsulfonium, [4- (4-biphenylylthio) -3-methylphenyl] 4-biphenylylphenylsulfonium, (2-ethoxy) At least one selected from the group consisting of phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium and tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium It is preferably a compound.

  The sulfonium salt used as the component (D) is, as an anion, trifluoromethanesulfonate, nonafluorobutanesulfonate, hexafluoroantimonate, tris [(trifluoromethyl) sulfonyl] methanide, 10-camphorsulfonate, tris (pentafluoroethyl) The compound is preferably a compound having at least one selected from the group consisting of trifluorophosphate and tetrakis (pentafluorophenyl) borate.

  Specific examples of sulfonium salts include (2-ethoxy) phenyl [4- (4-biphenylylthio) -3-ethoxyphenyl] 4-biphenylylsulfonium nonafluorobutanesulfonate, [4- (4-biphenylylthio)] And phenyl] -4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tetrakis (pentafluorophenyl) borate and the like. The sulfonium salts can be used singly or in combination of two or more.

  Specific examples of sulfonimide compounds include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (p-toluenesulfonyloxy) -1,8- Naphthalimide, N- (10-camphorsulfonyloxy) -1,8-naphthalimide and the like can be mentioned. A sulfone imide compound can be used individually by 1 type or in mixture of 2 or more types.

  Component (D) can be used alone or in combination of two or more.

  The content of the component (D) is 0.1 to 100 parts by mass of the component (A) from the viewpoint of further improving the sensitivity, resolution, pattern shape, etc. of the photosensitive resin composition of the present embodiment 15 parts by mass, 0.3 to 10 parts by mass, 1 to 10 parts by mass, 3 to 10 parts by mass, 5 to 10 parts by mass, or 6 to 10 parts by mass.

<(E) component>
The photosensitive resin composition of the present embodiment may contain, as the component (E), a compound having a Si-O bond. The compound having a Si-O bond may be a compound having a siloxane bond. The component (E) is not particularly limited as long as it has a Si-O bond, and examples thereof include silica (silica filler) and silane compounds (silane coupling agent and the like). Component (E) can be used singly or in combination of two or more.

  When the photosensitive resin composition of the present embodiment contains the inorganic filler, the thermal expansion coefficient of the resin pattern can be reduced. When an inorganic filler is used as the component (E), the inorganic filler is preferably a silica such as fused spherical silica, fused and crushed silica, fumed silica, sol-gel silica and the like. The inorganic filler may have a Si-O bond by treating the inorganic filler with a silane compound. Among the inorganic fillers treated with a silane compound, as inorganic fillers other than silica, aluminum oxide, aluminum hydroxide, calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, magnesium hydroxide or talc, Inorganic fillers derived from mineral products such as mica may, for example, be mentioned.

  The average primary particle diameter of the inorganic filler is preferably 100 nm or less, more preferably 80 nm or less, and still more preferably 50 nm or less from the viewpoint of further excellent photosensitivity of the photosensitive layer. When the average primary particle diameter is 100 nm or less, the photosensitive resin composition is less likely to become cloudy, and light for exposure is likely to be transmitted through the photosensitive layer. As a result, since the unexposed area is easily removed, the resolution of the resin pattern tends to be difficult to reduce. The average primary particle diameter is a value obtained by converting from the BET specific surface area.

The thermal expansion coefficient of silica is preferably 5.0 × 10 ⁻⁶ / ° C. or less. From the viewpoint of easily obtaining a suitable particle diameter, the silica is preferably silica such as fused spherical silica, fumed silica, sol-gel silica, and more preferably fumed silica or sol-gel silica. The silica is preferably silica (nano silica) having an average primary particle diameter of 5 to 100 nm.

  When measuring the particle diameter of an inorganic filler, a well-known particle size distribution analyzer can be used. As a particle size distribution analyzer, a laser diffraction scattering type particle size distribution analyzer which obtains particle size distribution by calculation from the intensity distribution pattern of diffracted light and scattered light emitted from the particle group by irradiating the particle group with laser light; by dynamic light scattering method The particle size distribution meter etc. of the nanoparticle which ask for particle size distribution using frequency analysis are mentioned.

  When the photosensitive resin composition of the present embodiment contains a silane compound, the adhesion strength between the photosensitive layer after pattern formation and the substrate can be improved. When a silane compound is used as the component (E), the silane compound is not particularly limited as long as the silane compound has a Si-O bond. Examples of the silane compound include alkylsilanes, alkoxysilanes, vinylsilanes, epoxysilanes, aminosilanes, acrylsilanes, methacrylsilanes, mercaptosilanes, sulfide silanes, isocyanate silanes, sulfasilanes, styrylsilanes, alkylchlorosilanes and the like.

As a silane compound which is (E) component, the compound represented by following General formula (14) is preferable.
(R ¹⁰¹ O) _4-f -Si- (R ¹⁰² ) _f (14)

In the general formula (14), R ¹⁰¹ represents an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, or a propyl group, R ¹⁰² represents a monovalent organic group, and f represents Indicates an integer of 0 to 3. When f is 0, 1 or 2, the plurality of R ¹⁰¹ may be the same as or different from each other. When f is 2 or 3, the plurality of R ¹⁰² may be the same as or different from each other. From the viewpoint of further excellent resolution, R ¹⁰¹ is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms. When treating with a silane compound (such as a compound represented by the general formula (14)) to improve the dispersibility of the inorganic filler, f is preferably 0 to 2 from the viewpoint of further improving the dispersibility of the inorganic filler And 0 to 1 are more preferable.

  Specific examples of the silane compound which is the component (E) include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, and diisopropyl ester. Dimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane Phenyltrimethoxysilane, diphenyldimethoxysilane, triphenylsilanol, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3 Aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethylsilane Methoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3 -(Triethoxysilyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, 3-methacryloyloxyp Pirtrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- ( 1,3-Dimethylbutylidene) -3-aminopropyltriethoxysilane and the like. Component (E) is preferably a silane coupling agent, more preferably an epoxysilane having one or more glycidyloxy groups, and an epoxysilane having a trimethoxysilyl group or a triethoxysilyl group More preferable.

  The content of the component (E) is preferably 1.8 to 420 parts by mass, and more preferably 1.8 to 270 parts by mass with respect to 100 parts by mass of the component (A). The content of the component (E) may be 1 to 20 parts by mass, or 3 to 10 parts by mass with respect to 100 parts by mass of the component (A).

<(F) component>
The photosensitive resin composition of the present embodiment may further contain a solvent as the component (F) in order to improve the handleability of the photosensitive resin composition or to adjust the viscosity and storage stability. it can. The component (F) is preferably an organic solvent. The type of such organic solvent is not particularly limited as long as it can exhibit the above-mentioned performance, but, for example, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc. propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether Propylene glycol dialkyl ethers such as Propylene glycol monoalkyl ether acetates such as Cole monomethyl ether acetate, Propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, Propylene glycol monobutyl ether acetate, etc .; Cellosolve such as ethyl cellosolve and butyl cellosolve; Carbitol such as butyl carbitol; Methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate and other lactic acid esters; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, propionone Aliphatic carboxylic acid esters such as n-butyl acid and isobutyl propionate; methyl 3-methoxypropionate, 3-methoxy Other esters such as ethyl ropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; 2-butanone, 2-heptanone, 3 -Ketones such as heptanone, 4-heptanone and cyclohexanone; Amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like; Lactones such as γ-butyrolactone and the like. These organic solvents can be used singly or in combination of two or more.

  The content of the component (F) is preferably 30 to 200 parts by mass, and more preferably 60 to 120 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition excluding the component (F). preferable.

  In addition, the photosensitive resin composition of this embodiment may contain other components other than the above-mentioned component. Examples of other components include coloring agents, adhesion assistants, leveling agents, inorganic fillers having no Si-O bond, inhibitors of reactions accompanying irradiation with actinic rays, adhesion assistants, and the like.

(Method of manufacturing circuit board)
FIG. 1 is a diagram illustrating a method of manufacturing a circuit board according to an embodiment of the present disclosure. The method for producing a circuit board according to the present embodiment comprises the steps of: (a) applying the photosensitive resin composition described above onto the substrate 1 and drying the photosensitive resin composition to form a photosensitive layer 2; b) exposing the photosensitive layer 2 in a predetermined pattern, developing it, and heating it to obtain a resin pattern 4; and (c) plating the exposed portion of the substrate 1 and the exposed portion of the resin pattern 4 And (d) removing a portion of the conductor layer 7 to form a conductor pattern 8 (circuit). That is, the method for manufacturing a circuit board according to the present embodiment is a method for manufacturing a circuit board provided on the substrate 1 with the resin pattern 4 formed using a predetermined pattern and the miniaturized conductor pattern 8. . Here, the resin pattern is a pattern of a resin obtained by curing the photosensitive layer on which a predetermined pattern is formed, and the resin in the resin pattern is partially or entirely cured.

  Each step will be described in detail below.

<(A) Process>
The step (a) is a step of applying the photosensitive resin composition described above onto the substrate 1 and drying the photosensitive resin composition to form a photosensitive layer 2 (see FIG. 1A). That is, the step (a) can be said to be a step of obtaining a substrate provided with the photosensitive layer 2 containing the photosensitive resin composition.

  As a method of apply | coating the photosensitive resin composition to a board | substrate, the dipping method, the spray method, the bar-coat method, the roll coat method, and the spin coat method are mentioned, for example. The thickness of the coating film can be appropriately controlled by adjusting the coating means, the solid content concentration and the viscosity of the photosensitive resin composition. The thickness of the photosensitive layer 2 varies depending on the application, but the thickness of the photosensitive layer 2 after drying is preferably 1 to 100 μm, more preferably 2 to 60 μm, and still more preferably 3 to 25 μm. And 4 to 8 μm are particularly preferable.

  As the substrate 1, for example, a resin-coated copper foil, a copper-clad laminate, a silicon wafer provided with a metal sputter film, or an alumina substrate can be used. The surface of the substrate 1 on which the photosensitive layer 2 is to be formed may be a cured resin layer formed using a photosensitive resin composition. In that case, the adhesion to the substrate tends to be improved.

<(B) Process>
The step (b) is a step of obtaining the resin pattern 4 by exposing the photosensitive layer 2 with a predetermined pattern, developing it, and further heat treatment (see FIGS. 1 (b) and (c)).

First, the photosensitive layer 2 is exposed in a predetermined pattern through a predetermined mask pattern. Examples of the actinic ray used for exposure include a ray using a g-line stepper as a light source; an ultraviolet ray using a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an i-line stepper or the like as a light source; The exposure dose is appropriately selected depending on the light source used, the thickness of the coating film, etc. For example, when a coating film having a thickness of 10 to 50 μm is irradiated with ultraviolet light using a high pressure mercury lamp, the exposure dose is 100 to 5000 mJ /. It may be about cm ² .

  Next, the photosensitive layer 2 after exposure is developed with an alkaline developer, and the photosensitive layer 2 on which a predetermined pattern is formed is obtained by dissolving and removing the area (unexposed area) other than the portion cured by exposure. (Refer to FIG. 1 (b)). The area removed here is the area (circuit groove 3) where the conductor pattern 8 is to be formed. Examples of the development method in this case include a shower development method, a spray development method, an immersion development method, and a paddle development method. The development conditions are usually at 20 to 40 ° C. for 1 to 10 minutes.

  As the alkaline developing solution, for example, an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide or choline is dissolved in water to a concentration of about 1 to 10% by mass, ammonia water, etc. Aqueous alkaline solution can be used. Among them, it is preferable to use a tetramethyl ammonium hydroxide aqueous solution from the viewpoint of excellent resolution of the resin pattern 4. An appropriate amount of, for example, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline aqueous solution. After development with an alkaline developer, the film is washed with water and dried.

  Next, the photosensitive layer 2 on which the predetermined pattern is formed is subjected to a heat treatment to obtain a resin pattern 4 (see FIG. 1C). By heat treatment, insulating film characteristics are developed. The conditions in particular of heat processing are not restrict | limited, It can adjust according to the use of hardened | cured material. For example, the heating temperature may be 50 to 250 ° C., and the heating time may be 30 minutes to 10 hours.

  The heat treatment may be performed in two steps for the purpose of sufficiently advancing the curing and preventing the deformation of the shape of the obtained resin pattern 4. When heat treatment is performed in two steps, for example, the heating temperature and heating time of the first step are 50 to 120 ° C. and 5 minutes to 2 hours, respectively, and the heating temperature and heating time of the second step are 80 to 200 ° C. and It can be 10 minutes to 10 hours.

  When heat-processing on the above-mentioned conditions, a heating installation in particular is not restrict | limited, For example, a common oven and an infrared oven can be used.

  In the method for manufacturing a circuit board according to the present embodiment, a heat treatment (post-exposure bake) may be performed after exposure and before development. Although the conditions for post-exposure baking vary depending on the content of the photosensitive resin composition, the thickness of the coating film, etc., it is usually preferable to heat at 70 to 150 ° C. for 1 to 60 minutes, and 1 to 60 at 80 to 120 ° C. It is more preferable to heat for a minute.

<(C) Process>
The step (c) is a step of forming the conductor layer 7 by plating the exposed portion of the substrate 1 and the exposed portion of the resin pattern 4 (see FIGS. 1D and 1E). The exposed portion of the substrate 1 is a region on the surface of the substrate 1 on which the resin pattern is formed, in which the resin pattern is not formed.

  The method of plating treatment is not particularly limited, and may be, for example, a method using electrolytic plating, electroless plating or sputtering.

  The thickness of the conductor layer 7 can be appropriately adjusted by the height of the wiring groove to be formed, but is preferably 1 to 35 μm, and more preferably 3 to 25 μm.

  The conductor layer 7 may be composed of a seed metal layer 5 and a plating layer 6 grown thereon. That is, the step (c) may include the step of forming the seed metal layer 5 on the exposed portion of the substrate 1 and the exposed portion of the resin pattern 4 (see FIG. 1D). When forming the seed metal layer 5, the plating layer 6 can be formed by plating on the formed seed metal layer 5 (see FIG. 1E).

  Although it does not specifically limit as the formation method of the seed metal layer 5, For example, electroless plating and sputtering are mentioned.

  When the seed metal layer 5 is formed by electroless plating, the metal constituting the seed metal layer 5 is, for example, gold, platinum, silver, copper, aluminum, cobalt, chromium, nickel, titanium, tungsten, iron, tin, indium And the like, or a solid solution (alloy) of two or more types of metals such as nickel-chromium alloy. Among these metals, chromium, nickel, titanium, nickel-chromium alloy, aluminum, zinc, copper and copper are preferable among them from the viewpoints of versatility of metal film formation, cost, ease of removal by etching, and the like. Nickel alloy, copper-titanium alloy, gold, silver or copper is preferred, chromium, nickel, titanium, nickel-chromium alloy, aluminum, zinc, gold, silver or copper is more preferred, titanium or copper Is particularly preferred. In addition, the seed metal layer 5 may be a single layer, or may be a multilayer structure in which two or more different metals are stacked.

  When forming the seed metal layer 5 by electroless plating, an electroless plating solution is used. A known autocatalytic electroless plating solution can be used as the electroless plating solution, and metal species, reducing agent species, complexing agent species, hydrogen ion concentration, dissolved oxygen concentration contained in the electroless plating solution Etc. are not particularly limited. As electroless plating, for example, an electroless copper plating solution containing ammonium hypophosphite, hypophosphorous acid, ammonium borohydride, hydrazine, formalin, etc. as a reducing agent; electroless plating using sodium hypophosphite as a reducing agent Nickel-phosphorus plating solution; Electroless nickel-boron plating solution using dimethylaminoborane as reducing agent; Electroless palladium plating solution; Electroless palladium-phosphorous plating solution using sodium hypophosphite as reducing agent; Electroless gold plating Solution: Electroless silver plating solution; Electroless nickel-cobalt-phosphorus plating solution using sodium hypophosphite as a reducing agent can be used.

  Further, in the method of forming the seed metal layer 5 by electroless plating, for example, after the catalyst nucleus of silver, palladium, zinc, cobalt or the like is attached to the portion where the seed metal layer 5 is formed, the above-mentioned electroless plating It may be a method of forming a metal thin film on a catalyst core using a liquid.

  There is no particular limitation on the method of attaching the catalyst nucleus to the exposed portion of the substrate 1 and the exposed portion of the resin pattern 4. For example, a solution in which a metal compound, salt or complex of a metal serving as a catalyst core is dissolved in water or an organic solvent (for example, alcohol and chloroform) to a concentration of 0.001 to 10% by mass is prepared After immersing the substrate 1 on which the resin pattern 4 is formed in this solution, there is a method in which the metal in the solution is reduced to precipitate the metal. In addition, an acid, an alkali, a complexing agent, a reducing agent, etc. can be contained in the solution in the said method as needed.

  When forming the seed metal layer 5 by sputtering, as a metal which comprises the seed metal layer 5, the metal similar to the case where the seed metal layer 5 is formed by electroless plating can be used, for example.

  Although the metal which comprises the plating layer 6 is not specifically limited, It is preferable that it is copper. Examples of the method of forming the plating layer 6 on the seed metal layer 5 include a method of growing plating by wet plating such as electrolytic plating.

  When forming the seed metal layer 5, after forming the seed metal layer 5, before forming the plating layer 6, an antirust process can be performed to the seed metal layer 5 using an antirust agent.

  When the seed metal layer 5 is formed, the thickness of the seed metal layer 5 is not particularly limited, but is preferably 10 nm to 5000 nm, more preferably 20 nm to 2000 nm, and preferably 30 nm to 1000 nm. More preferably, it is particularly preferably 50 nm to 500 nm, and most preferably 50 nm to 300 nm. When the thickness is 10 nm or more, the plating layer 6 tends to be uniformly formed by electrolytic plating, and when the thickness is 5000 nm or less, the removal time of the seed metal layer by etching or polishing is appropriately shortened. The cost of removing the seed metal layer 5 can be reduced.

  After the formation of the conductor layer 7, the conductor layer 7 may be heated for the purpose of improving adhesion and the like. The heating temperature is usually 50 to 350 ° C, preferably 80 to 250 ° C. The heating may be performed under pressure. As a pressurizing method, for example, a method using physical pressurizing means such as a heat press machine or a pressure heating roll machine can be mentioned. The pressure applied is usually 0.1 to 20 MPa, preferably 0.5 to 10 MPa. Within this range, the adhesion between the seed metal layer 5 and the resin pattern 4 or the substrate 1 tends to be excellent.

<(D) Process>
The step (d) is a step of removing a part of the conductor layer 7 to form a conductor pattern 8 (see FIG. 1 (f)). As shown in FIG. 1E, the conductor layer 7 is formed on the entire surface of the exposed portion of the substrate 1 and the exposed portion of the resin pattern 4. That is, the plating (metal film) is formed also in the area other than the area (circuit groove 3) where the conductor pattern 8 is to be formed. Therefore, the step (d) can be said to be a step of removing the metal film formed in the region other than the circuit groove 3 in the conductor layer 7.

  The method of removing a part of the conductor layer 7 may be a known method for removing metal. For example, the method may be mechanical polishing and / or etching.

  When a part of the conductor layer 7 is removed by mechanical polishing, the method of mechanical polishing is preferably chemical mechanical polishing (hereinafter also referred to as "CMP"). As a method of removing a part of the conductor layer 7 by the CMP method, for example, a polishing cloth (polishing pad) is attached on a polishing platen, and the surface of the polishing cloth is dipped with a metal polishing agent. The surface is pressed against the surface of the polishing pad, and in the state where a predetermined pressure (hereinafter referred to as "polishing pressure") is applied to the surface of the conductor layer 7 from the back surface, the polishing table is turned, , And a portion of the conductor layer 7 may be removed.

  The metal polishing agent used for CMP may contain, for example, an oxidizing agent and solid abrasive grains (hereinafter simply referred to as “abrasive grains”), and, if necessary, a metal oxide dissolving agent, a protective film It may further contain a forming agent and the like. The basic mechanism of CMP using a polishing agent containing an oxidizing agent and abrasive grains is considered as follows. First, it is considered that the surface of the metal film to be polished is oxidized by the oxidizing agent to form an oxide layer, and the oxide layer is scraped off by the abrasive grains to polish the metal film. When polished by such a mechanism, the oxide layer on the surface of the metal film formed in the circuit groove 3 does not touch the polishing cloth so much, so the metal film formed in the circuit groove 3 has an effect of scraping off by the abrasive grains. It is difficult. Therefore, there is a tendency that as the polishing by CMP progresses, the metal film in the region other than the circuit groove 3 is removed and the polishing surface is flattened.

  The polishing agent is preferably a polishing agent that can be used at a polishing rate of 5000 to 3000 Å / min.

  In the case of removing a part of the conductor layer 7 by etching, the method of etching includes a sand blast method and a wet etching process. In the case of the sandblasting method, etching is performed by spraying cutting particles such as silica, alumina or the like onto the portion of the conductor layer 7 to be removed. In the case of a wet etching process, etching is performed using an etchant. As an etching solution, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, an ammonium persulfate aqueous solution and a hydrogen peroxide etching solution can be used.

  The thickness of the portion of the conductor layer 7 to be removed in the step (d), that is, the thickness of the metal film in the region other than the circuit groove 3 may be about 0.1 to 35 μm.

  In the circuit board manufactured by the above method, the semiconductor element is mounted at the corresponding portion, and the electrical connection can be secured. Moreover, the circuit board which has the conductor pattern 8 miniaturized can be obtained by said method.

  EXAMPLES The objects and advantages of the present disclosure will be described in detail by way of examples, but the present disclosure is not limited by these examples.

Example 1 and Comparative Example 1
<Preparation of Photosensitive Resin Composition>
Compound (B-1) having an alkoxyalkyl group, compound (C-1) having a glycidyloxy group, and photosensitivity with respect to 100 parts by mass of the resin component (A-1 to A-2) having a phenolic hydroxyl group The compound (E: 1), the compound (E-1) having a Si-O bond, and the solvent (F-1), each having the basic acid generator (D-1) and the solvent (F-1) in the compounding amounts (unit: mass part) The solution was pressure-filtered using a 1.0 μm-hole syringe filter (manufactured by GE Healthcare Japan Ltd., trade name: Resist 30 (1.0 μm PTFE)) to obtain a photosensitive resin composition. .

The abbreviations in Table 1 are as follows.
A-1: Novolak resin having a cardophenol-modified site (manufactured by Gunei Chemical Industry Co., Ltd., trade name: FR-CR-006, weight average molecular weight: 15100)
A'-1: cresol novolak resin (Asahi Organic Material Co., Ltd., trade name: TR4020G, weight average molecular weight: 13,000)
B-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicalac MX-270)
C-1: trimethylolpropane triglycidyl ether (manufactured by Nagase ChemteX Co., Ltd., trade name: EX-321L)
D-1: Triarylsulfonium salt (San-Apro Co., Ltd., trade name: CPI-310B, anion: tetrakis (pentafluorophenyl) borate)
E-1: 3-glycidoxypropyl trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-403)
F-1: Propylene glycol monomethyl ether acetate (manufactured by Wako Pure Chemical Industries, Ltd., trade name: acetic acid 2-methoxy-1-methylethyl)

<Evaluation of resolution>
The photosensitive resin composition was spin-coated on a 6-inch silicon wafer, and heated on a hot plate at 120 ° C. for 3 minutes to form a coating having a thickness of 5 μm. Using the i-line stepper (FPA-3000iW, manufactured by Canon Inc.), reduction coating exposure was performed on the produced coating film through an i-line (365 nm) through a mask. As a mask, a mask having a pattern in which the width of the exposed portion and the unexposed portion is 1: 1 is used in an interval of 2 μm: 2 μm to 30 μm: 30 μm. The exposure amount is in the range of 100~1100mJ / cm ^2, was subjected to the reduction projection exposure while changing by 100 mJ / cm ^2.

  The exposed coating was then heated at 85 ° C. for 4 minutes (post exposure bake). While using a 2.38 mass% tetramethylammonium hydroxide aqueous solution (manufactured by Tama Chemical Co., Ltd., trade name: TMAH 2.38%) as a developing solution, a developing machine (manufactured by Takizawa Sangyo Co., Ltd., trade name: AD-1200) Spray a developer at 23 ° C onto the photosensitive layer (coating film) in a time equivalent to four times the shortest development time (the shortest time for the unexposed area to be removed) (pump discharge pressure [developer]: 0 .16 MPa) to remove the unexposed area. Next, the developer is sprayed with purified water at 23 ° C. (manufactured by Wako Pure Chemical Industries, Ltd., trade name: purified water) as a rinse liquid for 60 seconds (pump discharge pressure [rinse liquid]: 0.12 to 0.14 MPa) Washed away. Then, by drying, a resin pattern was formed. Next, the resin pattern was cured by heat treatment at 180 ° C. for 60 minutes using a solvent drying safety specification thermostat (manufactured by Kushimoto Chemical Co., Ltd., trade name: HG220). The formed resin pattern was observed under magnification of 1000 times using a metallurgical microscope. The smallest value of the space width was evaluated as the minimum resolution among the patterns formed so that the space portion (unexposed portion) was removed cleanly and the line portion (exposed portion) did not meander or chip. The evaluation results are shown in Table 1.

<Evaluation of adhesion>
The above photosensitive resin composition is spin-coated on a copper-clad laminate (trade name: MCL-E-679, manufactured by Hitachi Chemical Co., Ltd.), heated at 120 ° C. for 3 minutes on a hot plate, and the thickness is 9 A coating of ̃11 μm was prepared. Equal-magnification projection exposure was performed on the entire surface of the photosensitive layer with an i-line (365 nm) using a projection exposure apparatus (manufactured by Ushio Inc., trade name: UX-2240SM-XJ-0). The exposure dose was 1000 mJ / cm ² . Next, the exposed coating film is heated at 85 ° C. for 4 minutes (post-exposure bake), and then heated at 180 ° C. for 60 minutes in a solvent drying safety specification thermostat (manufactured by Kushimoto Chemical Co., Ltd., trade name: HG220) It was processed to obtain a cured film.

With respect to the cured film on the obtained copper-clad laminate, a cross cut test of 100 squares was carried out with reference to JIS standard (JIS K 5600-5-6) to evaluate the adhesion between the cured film and copper. . On the test surface, using a cutter knife and a cutter guide, 11 parallel vertical and horizontal parallel lines were drawn at intervals of 1 mm, and a grid-like cut was made so that 100 squares could be formed in 1 cm ² . Next, strongly press-bond a tape (made by Sekisui Chemical Co., Ltd., trade name: Sekisui Cellotape (registered trademark) No. 252) to the cross-cut portion, and quickly pull the end of the tape at an angle of 60 ° within 0.5 seconds. After peeling, the condition of the grid was observed, and the adhesion was evaluated according to the following criteria. The evaluation results are shown in Table 1.
A: A part of the entire area is not peeled off.
B: Of the entire area, partial peeling has occurred.

  As is clear from Table 1, Example 1 using a resin having a cardophenol-modified site is extremely excellent in adhesion between a cured film and copper, as compared to Comparative Example 1 using a cresol novolac resin. , It turned out that it is excellent in reliability.

  The photosensitive resin composition of the present disclosure can be applied as a material used for a surface protective film or an interlayer insulating film of a semiconductor element. Moreover, it can apply as a material used for the soldering resist of a wiring board material, or an interlayer insulation film. In particular, since the photosensitive resin composition of the present disclosure is excellent in both resolution and adhesiveness, it is suitably used for a highly integrated package substrate and the like which are thinned and densified.

  DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2 ... Photosensitive layer, 3 ... Circuit groove, 4 ... Resin pattern, 5 ... Seed metal layer, 6 ... Plating layer, 7 ... Conductor layer, 8 ... Conductor pattern.

Claims (8)

Component (A): a resin having a structural unit represented by the following general formula (a1)
Component (B): a compound having a methylol group or an alkoxyalkyl group,
Component (C): an aliphatic compound having two or more functional groups selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group, and
Component (D): A photosensitive resin composition containing a photosensitive acid generator.

[In Formula (a1), Z ¹ represents an aromatic hydrocarbon ring, R ^A1 and R ^A2 represent a monovalent substituent, and R ^A3 represents a hydrogen atom or a hydrocarbon group. p is an integer of 1 or more, and q and r are integers of 0 or more. Plural Z ¹ , R ^A1 , R ^A2 , p, q and r may be the same or different. ] The photosensitive resin composition according to claim 1, wherein the component (A) is a resin further having a structural unit represented by the following general formula (a2).

[In Formula (a2), R ^A4 represents a methyl group or a hydroxy group, and s is an integer of 0 to 2. ] Z ¹ in the general formula (a1) is a benzene ring or a naphthalene ring, a photosensitive resin composition according to claim 1 or 2.   The photosensitive resin composition according to any one of claims 1 to 3, wherein p in the general formula (a1) is 1 and q and r are 0.   The photosensitive resin composition as described in any one of Claims 1-4 in which (A) component has 10-50 mass% of structural units represented by General formula (a1).   Component (E): The photosensitive resin composition according to any one of claims 1 to 5, further comprising a compound having a Si-O bond.   The photosensitive resin composition according to claim 6, wherein the component (E) is a silane coupling agent. (A) applying the photosensitive resin composition according to any one of claims 1 to 7 onto a substrate and drying the photosensitive resin composition to form a photosensitive layer;
(B) a step of obtaining a resin pattern by exposing the photosensitive layer in a predetermined pattern, developing it, and further heat treating it;
(C) forming a conductor layer by plating the exposed portion of the substrate and the exposed portion of the resin pattern;
(D) removing a portion of the conductor layer to form a conductor pattern;
A method of manufacturing a circuit board comprising:

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