JP2023046035A - Photosensitive resin composition - Google Patents

Abstract

Kind Code: A1 A photosensitive resin composition is provided which is capable of forming an insulating layer having a small resolution limit and excellent adhesion to a GaAs substrate.
A photosensitive resin composition for forming an insulating layer on a GaAs substrate, comprising: (A) an alkali-soluble resin having a hydroxyl group; (B) a melamine resin containing one or more alkoxymethyl groups; A photosensitive resin composition comprising (C) a photoacid generator and (D) a silane coupling agent containing a trimethoxysilyl group.
[Selection figure] None

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin composition, and a photosensitive film, circuit board and semiconductor device using the same.

A circuit board such as a wafer level package usually comprises an insulating layer on a substrate such as a wafer. This insulating layer may be formed using a photosensitive resin composition (Patent Documents 1 and 2).

JP 2018-155938 A JP 2018-173573 A

Openings such as holes and trenches may be formed in the insulating layer by exposing and developing the photosensitive resin composition. Due to the progress of finer wiring in recent years, the opening is required to be small. Therefore, the photosensitive resin composition is required to have a small limiting resolution. The term "resolution limit" refers to the limit of the size of openings that can be formed in a photosensitive resin composition by exposure and development, and the smaller the better.

On the other hand, there are cases where a circuit board using a GaAs substrate (gallium arsenide substrate) as a base material capable of operating at a higher speed than a silicon substrate is used. Adhesion to the GaAs substrate is also required for the insulating layer formed on the GaAs substrate using the photosensitive resin composition. However, the current situation is that there is not necessarily a satisfactory photosensitive resin composition that can form an insulating layer with a small marginal resolution and excellent adhesion to a GaAs substrate. Development of resin compositions is desired.

The present invention has been invented in view of the above problems, and provides a photosensitive resin composition capable of forming an insulating layer having a small resolution limit and excellent adhesion to a GaAs substrate; A photosensitive film provided with a photosensitive resin composition layer containing a material; a circuit board provided with an insulating layer containing a cured product of the photosensitive resin composition and a method for producing the same; and a semiconductor device provided with the circuit board ; is intended to provide

The inventors have made extensive studies to solve the above problems. As a result, the present inventors have found (A) an alkali-soluble resin having a hydroxyl group, (B) a melamine resin containing one or more alkoxymethyl groups, (C) a photoacid generator, and (D) a trimethoxysilyl group. The inventors have found that a photosensitive resin composition containing a combination of a silane coupling agent containing
That is, the present invention includes the following.

（式（Ａ－１）中、
Ｒ^３は、下記式（ａ）で表される２価の基、下記式（ｂ）で表される２価の基、下記式（ｃ）で表される２価の基、又はこれらの組み合わせからなる２価の基を表し、
Ｘ^３及びＸ^４は、それぞれ独立に、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、ハロゲン原子、又は置換基を有していてもよい１価の複素環基を表し、
ｎ３及びｎ４は、それぞれ独立に、０～４の整数を表す。

式（ａ）中、Ｒ^１１及びＲ^１２は、それぞれ独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよい１価の複素環基、アミノ基、カルボニル基、カルボキシル基、又はこれらの組み合わせからなる基を表し、Ｒ^１１及びＲ^１２は互いに結合して環を形成していてもよい。＊は結合手を表す。
式（ｂ）中、Ｘ^１１は、それぞれ独立に、置換基を有していてもよいアルキル基を表す。ｐ１は、０～４の整数を表す。＊は結合手を表す。
式（ｃ）中、Ｘ^１２及びＸ^１３は、それぞれ独立に、置換基を有していてもよいアルキル基を表す。ｐ２及びｐ３は、それぞれ独立に、０～４の整数を表す。＊は結合手を表す。）
〔６〕 （Ａ）成分が、下記式（Ａ－２）で表される構造を含有する化合物を含む、〔１〕～〔５〕のいずれか一項に記載の感光性樹脂組成物。

（式（Ａ－２）中、
Ｒ^１は、それぞれ独立に、下記式（ａ）で表される２価の基を表し、
Ｘ^１は、それぞれ独立に、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、ハロゲン原子、又は置換基を有していてもよい１価の複素環基を表し、
ｎ１は、０～４の整数を表し、
ｍ１は、１～２００の整数を表す。＊は結合手を表す。

式（ａ）中、Ｒ^１１及びＲ^１２は、それぞれ独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよい１価の複素環基、アミノ基、カルボニル基、カルボキシル基、又はこれらの組み合わせからなる基を表し、Ｒ^１１及びＲ^１２は互いに結合して環を形成していてもよい。＊は結合手を表す。）
〔７〕 支持体と、該支持体上に設けられた、〔１〕～〔６〕のいずれか一項に記載の感光性樹脂組成物を含む感光性樹脂組成物層と、を備える感光性フィルム。
〔８〕 〔１〕～〔６〕のいずれか一項に記載の感光性樹脂組成物の硬化物を含む絶縁層を備える、回路基板。
〔９〕 ＧａＡｓ基板と、該ＧａＡｓ基板上に形成された前記絶縁層と、を備える、〔８〕に記載の回路基板。
〔１０〕 〔８〕又は〔９〕に記載の回路基板を備える、半導体装置。
〔１１〕 （Ｉ）ＧａＡｓ基板上に、請求項１～６のいずれか一項に記載の感光性樹脂組成物を含む感光性樹脂組成物層を形成する工程、
（ＩＩ）感光性樹脂組成物層に露光する工程、及び、
（ＩＩＩ）感光性樹脂組成物層を現像する工程、
をこの順に含む、回路基板の製造方法。 [1] A photosensitive resin composition for forming an insulating layer on a GaAs substrate,
(A) an alkali-soluble resin having a hydroxyl group;
(B) a melamine resin containing one or more alkoxymethyl groups;
(C) a photoacid generator, and (D) a silane coupling agent containing a trimethoxysilyl group,
A photosensitive resin composition comprising:
[2] The photosensitive resin composition of [1], wherein component (D) contains 11.5% by mass or more of Si atoms in the molecule.
[3] The photosensitive resin composition of [1] or [2], which contains (E) an organic filler.
[4] The photosensitive resin composition according to [3], wherein the amount of (E) the organic filler is 7% by mass or more and 30% by mass or less when the non-volatile component of the photosensitive resin composition is 100% by mass. thing.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein component (A) contains a compound having a structure represented by formula (A-1) below.

(In formula (A-1),
R ³ is a divalent group represented by the following formula (a), a divalent group represented by the following formula (b), a divalent group represented by the following formula (c), or a combination thereof represents a divalent group consisting of
X ³ and X ⁴ are each independently an optionally substituted alkyl group, an optionally substituted aryl group, a halogen atom, or an optionally substituted monovalent represents a heterocyclic group of
n3 and n4 each independently represent an integer of 0 to 4;

In formula (a), R ¹¹ and R ¹² each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted may be a monovalent heterocyclic group, an amino group, a carbonyl group, a carboxyl group, or a group consisting of a combination thereof, and R ¹¹ and R ¹² may combine with each other to form a ring. * represents a bond.
In formula (b), each X ¹¹ independently represents an optionally substituted alkyl group. p1 represents an integer from 0 to 4; * represents a bond.
In formula (c), X ¹² and X ¹³ each independently represent an optionally substituted alkyl group. p2 and p3 each independently represent an integer of 0 to 4; * represents a bond. )
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the component (A) contains a compound containing a structure represented by the following formula (A-2).

(In formula (A-2),
R ¹ each independently represents a divalent group represented by the following formula (a),
X ¹ is each independently an optionally substituted alkyl group, an optionally substituted aryl group, a halogen atom, or an optionally substituted monovalent heterocyclic ring represents the group,
n1 represents an integer from 0 to 4,
m1 represents an integer from 1 to 200; * represents a bond.

In formula (a), R ¹¹ and R ¹² each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted may be a monovalent heterocyclic group, an amino group, a carbonyl group, a carboxyl group, or a group consisting of a combination thereof, and R ¹¹ and R ¹² may combine with each other to form a ring. * represents a bond. )
[7] A photosensitive material comprising a support and a photosensitive resin composition layer containing the photosensitive resin composition according to any one of [1] to [6] provided on the support the film.
[8] A circuit board comprising an insulating layer containing a cured product of the photosensitive resin composition according to any one of [1] to [6].
[9] The circuit board according to [8], comprising a GaAs substrate and the insulating layer formed on the GaAs substrate.
[10] A semiconductor device comprising the circuit board according to [8] or [9].
[11] (I) forming a photosensitive resin composition layer containing the photosensitive resin composition according to any one of claims 1 to 6 on a GaAs substrate;
(II) a step of exposing the photosensitive resin composition layer, and
(III) a step of developing the photosensitive resin composition layer;
A method of manufacturing a circuit board, comprising in that order:

According to the present invention, a photosensitive resin composition capable of forming an insulating layer having a small limiting resolution and excellent adhesion to a GaAs substrate; A circuit board provided with an insulating layer containing a cured product of the photosensitive resin composition, a method for producing the same, and a semiconductor device provided with the circuit board.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims and their equivalents.

[1. Outline of photosensitive resin composition]
A photosensitive resin composition according to one embodiment of the present invention is a composition for forming an insulating layer on a GaAs substrate. This photosensitive resin composition comprises (A) an alkali-soluble resin having a hydroxyl group, (B) a melamine resin containing one or more alkoxymethyl groups, (C) a photoacid generator, and (D) a trimethoxysilyl group. in combination with a silane coupling agent containing In the following description, "(A) an alkali-soluble resin having a hydroxyl group" may be referred to as "(A) an alkali-soluble resin". Also, "(B) a melamine resin containing one or more alkoxymethyl groups" may be referred to as "(B) a melamine resin". Furthermore, (D) a silane coupling agent containing a trimethoxysilyl group may be referred to as "(D) a silane coupling agent".

This photosensitive resin composition can have a small limiting resolution. Moreover, according to this photosensitive resin composition, an insulating layer having excellent adhesion to a GaAs substrate can be formed.

The photosensitive resin composition may further contain optional components in combination with components (A) to (D). Preferred optional components include, for example, (E) organic fillers.

[2. (A) Alkali-soluble resin having a hydroxyl group]
The photosensitive resin composition contains (A) an alkali-soluble resin having a hydroxyl group as the (A) component. Since the hydroxyl group of the alkali-soluble resin (A) can undergo a cross-linking reaction with the melamine resin (B), a latent image can be formed on the photosensitive resin composition layer by exposure. Further, since the (A) alkali-soluble resin can be dissolved in an alkaline developer, the latent image can be developed. (A) The alkali-soluble resin may be used alone or in combination of two or more.

Preferred examples of (A) the alkali-soluble resin include compounds having a structure represented by the following formula (A-1). Therefore, (A) the alkali-soluble resin preferably contains a compound having a structure represented by the following formula (A-1). A compound having a structure represented by formula (A-1) is hereinafter sometimes referred to as "(A-1) component".

（式（Ａ－１）中、Ｒ^３は、下記式（ａ）で表される２価の基、下記式（ｂ）で表される２価の基、下記式（ｃ）で表される２価の基、又はこれらの組み合わせからなる２価の基を表し、Ｘ^３及びＸ^４は、それぞれ独立に、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、ハロゲン原子、又は置換基を有していてもよい１価の複素環基を表し、ｎ３及びｎ４は、それぞれ独立に、０～４の整数を表す。）

(In formula (A-1), R ³ is a divalent group represented by formula (a) below, a divalent group represented by formula (b) below, or a divalent group represented by formula (c) below. represents a divalent group or a divalent group consisting of a combination thereof, X ³ and X ⁴ are each independently an alkyl group optionally having a substituent, optionally having a substituent represents an aryl group, a halogen atom, or an optionally substituted monovalent heterocyclic group, and n3 and n4 each independently represents an integer of 0 to 4.)

(In formula (a), R ¹¹ and R ¹² each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or a substituted represents an optionally monovalent heterocyclic group, an amino group, a carbonyl group, a carboxyl group, or a group consisting of a combination thereof, wherein R ¹¹ and R ¹² may combine to form a ring.* represents a bond.
In formula (b), each X ¹¹ independently represents an optionally substituted alkyl group. p1 represents an integer from 0 to 4; * represents a bond.
In formula (c), X ¹² and X ¹³ each independently represent an optionally substituted alkyl group. p2 and p3 each independently represent an integer of 0 to 4; * represents a bond. )

In formula (A-1), X ³ and X ⁴ each independently represent an optionally substituted alkyl group, an optionally substituted aryl group, a halogen atom, or a substituent. represents a monovalent heterocyclic group which may be possessed; Among them, X ³ and X ⁴ are preferably an optionally substituted alkyl group, an optionally substituted aryl group, and a halogen atom, which may have a substituent. An alkyl group and an optionally substituted aryl group are more preferred, and an optionally substituted alkyl group is even more preferred.

Alkyl groups may be straight chain, branched chain, or cyclic alkyl groups. Moreover, the cyclic alkyl group may be monocyclic or polycyclic. As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is even more preferable. Examples of alkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, s-butyl group, t-butyl group, 2-methylpropyl group, 3-heptyl group and the like. Among them, a methyl group is particularly preferred.

As the aryl group, an aryl group having 6 to 30 carbon atoms is preferable, an aryl group having 6 to 20 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is even more preferable. Examples of aryl groups include phenyl groups and naphthyl groups.

A halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.

The monovalent heterocyclic group is preferably a monovalent heterocyclic group having 3 to 21 carbon atoms, more preferably a monovalent heterocyclic group having 3 to 15 carbon atoms, and 1 having 3 to 9 carbon atoms. More preferred are valent heterocyclic groups. Monovalent heterocyclic groups also include monovalent aromatic heterocyclic groups (heteroaryl groups). Examples of monovalent heterocyclic groups include thienyl, pyrrolyl, furanyl, furyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, triazinyl, pyrrolidyl, piperidyl, quinolyl, and isoquinolyl groups. is mentioned. Among them, a pyrrolidyl group is preferred. A monovalent heterocyclic group refers to a group obtained by removing one hydrogen atom from a heterocyclic ring of a heterocyclic compound.

The alkyl group, aryl group and monovalent heterocyclic group represented by X ³ and X ⁴ may have a substituent. Substituents include, for example, a halogen atom, —OH, —O—C _1-6 alkyl group, —N(C _1-6 alkyl group) ₂ , C _1-6 alkyl group, C _6-10 aryl group, — NH ₂ , —NH(C _1-6 alkyl group), —CN, —C(O)O—C _1-6 alkyl group, —C(O)H, —NO ₂ and the like.

In this specification, the expression "optionally substituted" means, unless otherwise specified, unsubstituted or usually having 1 to 5 (preferably 1, 2 or 3) substituents means that there is In addition, when having a plurality of substituents, those substituents may be the same or different from each other. In this specification, the term “C _p−q ” (where p and q are positive integers and satisfies p<q) means that the number of carbon atoms of the organic group described immediately after this term is Represents p to q. For example, the expression "C _1-6 alkyl group" indicates an alkyl group having from 1 to 6 carbon atoms.

In formula (A-1), n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 3, more preferably 0 or 1, particularly preferably 1. .

In formula (A-1), R ³ is a divalent group represented by formula (a), a divalent group represented by formula (b), and a divalent group represented by formula (c). , or a divalent group consisting of a combination thereof.

In formula (a), R ¹¹ and R ¹² each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted may be a monovalent heterocyclic group, an amino group, a carbonyl group, a carboxyl group, or a group consisting of a combination thereof, and R ¹¹ and R ¹² may combine with each other to form a ring. Among them, R ¹¹ and R ¹² are each independently preferably a hydrogen atom or an alkyl group.

The optionally substituted alkyl group, optionally substituted aryl group, and optionally substituted monovalent heterocyclic group represented by R ¹¹ and R ¹² are , an optionally substituted alkyl group represented by X ³ and X ⁴ in formula (A-1), an optionally substituted aryl group, and an optionally substituted It can be the same as a good monovalent heterocyclic group.

Examples of the group consisting of a combination of these include, for example, a group consisting of a combination of an alkyl group and a carbonyl group, a group consisting of a combination of an aryl group and a carbonyl group, a group consisting of a combination of an alkyl group, an amino group and a carbonyl group, Examples thereof include a group consisting of a combination of an aryl group, an amino group and a carbonyl group.

R ¹¹ and R ¹² may combine with each other to form a ring. The ring structures that R ¹¹ and R ¹² may form include spiro rings and condensed rings. In this case, R ¹¹ and R ¹² are a group forming a cyclopentane ring, a group forming a cyclohexane ring, a group forming a 2,2-dimethyl-4-methylcyclohexane ring, a group forming a fluorene ring, and a pyrrolidine ring. or a group forming a γ-lactam ring.

Specific examples of the divalent group represented by formula (a) include the following groups. In the formula, "*" represents a bond.

X ¹¹ , X ¹² and X ¹³ in formulas (b) to (c) each independently represent an optionally substituted alkyl group. X ¹¹ to X ¹³ are the same as the optionally substituted alkyl groups represented by X ³ and X ⁴ in formula (A-1).

p1, p2, and p3 in formulas (b) to (c) each independently represent an integer of 0 to 4, preferably an integer of 0 to 3, more preferably 0 or 1 .

Specific examples of the divalent group represented by formula (b) include the following groups. In the formula, "*" represents a bond.

Specific examples of the divalent group represented by formula (c) include the following groups. In the formula, "*" represents a bond.

The divalent group represented by the combination represented by R ³ is a divalent group comprising a combination of a divalent group represented by the formula (b) and a divalent group represented by the formula (c), A divalent group consisting of a combination of a divalent group represented by (a) and a divalent group represented by formula (b), and a divalent group represented by formula (a) and the formula and a divalent group formed in combination with the divalent group represented by (c). Specific examples of these groups include the following groups. In the formula, "*" represents a bond.

The bonds in formulas (a) to (c) are bonded to either the ortho-position, the meta-position, or the para-position with respect to the OH group of the phenol moiety in formula (A-1). It is preferably bound at either the meta-position or the para-position, and more preferably at the para-position.

Specific examples of the component (A-1) include the following compounds.

A commercially available product may be used as the component (A-1). Specific examples of the commercially available component (A-1) include Honshu Chemical Co., Ltd. "BisE" and "BisP-HTG"; Mitsui Chemicals Fine Co., Ltd. "BisA", "BisF", and "BisP-M"; "BisP-AP", "BisP-MIBK", "BisP-B", "Bis-Z", "BisP-CP", "o,o'-BPF", "BisP-IOTD", "BisP-IBTD" ”, “BisP-DED”, “BisP-BA”; manufactured by Honshu Chemical Co., Ltd. “Bis-C”, “Bis26X-A”, “BisOPP-A”, “BisOTBP-A”, “BisOCHP-A”, “BisOFP -A", "BisOC-Z", "BisOC-FL", "BisOC-CP", "BisOCHP-Z", "Methylenebis P-CR", "TM-BPF", "BisOC-F", "Bis3M6B- IBTD", "BisOC-IST", "BisP-IST", "BisP-PRM", "BisP-LV" and the like.

Component (A-1) may be used singly or in combination of two or more.

The molecular weight of component (A-1) is preferably 150 or more, more preferably 160 or more, still more preferably 170 or more, and preferably 1000 or less, more preferably 800 or less, and still more preferably 500 or less.

The amount of component (A-1) is preferably 6% by mass or more, more preferably 8% by mass or more, and still more preferably 10% by mass or more when the non-volatile component of the photosensitive resin composition is 100% by mass. , preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. When the amount of component (A-1) is within the above range, both the resolution limit and the adhesion to the GaAs substrate can be effectively improved.

The amount of component (A-1) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more when the resin component of the photosensitive resin composition is 100% by mass. , preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less. The resin component of the photosensitive resin composition refers to a non-volatile component of the photosensitive resin composition excluding (E) fillers such as organic fillers and inorganic fillers. When the amount of component (A-1) is within the above range, both the resolution limit and the adhesion to the GaAs substrate can be effectively improved.

The amount of component (A-1) is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more when the total amount of the alkali-soluble resin (A) is 100% by mass, It is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. When the amount of component (A-1) is within the above range, both the resolution limit and the adhesion to the GaAs substrate can be effectively improved.

(A) Another preferable example of the alkali-soluble resin is a compound containing a structure represented by the following formula (A-2). Therefore, (A) the alkali-soluble resin preferably contains a compound containing a structure represented by the following formula (A-2). A compound containing a structure represented by formula (A-2) is hereinafter sometimes referred to as "(A-2) component".

(In formula (A-2), each R ¹ independently represents a divalent group represented by formula (a); each X ¹ independently represents an optionally substituted alkyl group, an aryl group optionally having substituents, a halogen atom, or a monovalent heterocyclic group optionally having substituents; n1 represents an integer of 0 to 4; represents an integer from 1 to 200. * represents a bond.)

In formula (A-2), each X ¹ is independently an optionally substituted alkyl group, an optionally substituted aryl group, a halogen atom, or a substituted represents a monovalent heterocyclic group which may be Each X ¹ can be independently the same as X ³ and X ⁴ in formula (A-1).

In formula (A-2), each R ¹ independently represents a divalent group represented by formula (a). The divalent group represented by formula (a) is as described above.

The bond in formula (a) is preferably attached to either the ortho-position, the meta-position, or the para-position with respect to the OH group of the phenol moiety in formula (A-2), and the meta-position and para-positions, and more preferably both meta- and para-positions. When the bond in formula (a) is mixed with those bonded at the meta-position and para-position with respect to the OH group of the phenolic site in formula (A-2), in formula (a) Let m be the mass of the one in which the bond of is bonded to the meta position, and let p be the mass of the one in which the bond in formula (a) is bonded to the para position. At this time, the mixing ratio (m:p) is preferably 1:0.1 to 1:10, more preferably 1:0.1 to 1:5, even more preferably 1:0.1 to 1:2. , 1:0.5 to 1:1 are particularly preferred.

In formula (A-2), n1 represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably 0 or 1, and particularly preferably 1.

In formula (A-2), m1 represents an integer of 1 to 200, preferably an integer of 1 to 150, more preferably an integer of 1 to 100, and an integer of 1 to 50. is more preferred.

Specific examples of the component (A-2) include resins represented by the following formula (1). In the specific example, meta-position and para-position are mixed at a ratio of 60% and 40%, respectively, with respect to the OH group of the phenol site. In the following formula (1), n represents an integer of 1-200.

A commercially available product may be used as the component (A-2). Specific examples of the commercially available component (A-2) include "TR4020G" (resin represented by formula (1)) manufactured by Asahi Organic Chemicals Co., Ltd.; "TR4050G", "TR4080G" and "TR5020G" manufactured by Asahi Organic Chemicals. , "TR5050G", "TR6020G", "TR6050G", "TR6080G", "OC4500", "TRM30B20G", "TRM30B35G", "EP16F30G", "EP16F50G", "TR4000B", "EP0090G", "EP3010A", " PAPS-PN2", "PAPS-PN4", "AYPN-3.5" AV light series; Sumitomo Bakelite photoresist resin series; -30-40P", "PR-100L", "PR-100H", "PR-50", "PR-55", "PR-56-1", "PR-56-2", "WR-101" ”, “WR-102”, “WR-103”, “WR-104” and other phenolite series; ”, “LF-400”, “LF-500”; base resin series for photoresist manufactured by Meiwa Kasei Co., Ltd.;

Component (A-2) may be used alone or in combination of two or more.

Component (A-2) can be obtained, for example, by polycondensation of phenol or its derivative with aldehyde and/or ketone. Polycondensation can be carried out in the presence of a catalyst such as an acid or base. Therefore, the terminal of component (A-2) can be an optionally substituted hydroxyphenyl group or an aldehyde group, and both terminals are preferably optionally substituted hydroxyphenyl groups. .

The weight average molecular weight of component (A-2) is preferably 500 or more, more preferably 700 or more, still more preferably 1000 or more, and preferably 150,000 or less, more preferably 100,000 or less, and still more preferably 50,000 or less. The weight average molecular weight can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The amount of component (A-2) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more when the non-volatile component of the photosensitive resin composition is 100% by mass. , preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less. When the amount of component (A-2) is within the above range, both the resolution limit and the adhesion to the GaAs substrate can be effectively improved.

The amount of component (A-2) is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more when the resin component of the photosensitive resin composition is 100% by mass. , preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. When the amount of component (A-2) is within the above range, both the resolution limit and the adhesion to the GaAs substrate can be effectively improved.

The amount of component (A-2) is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more when the total alkali-soluble resin (A) is taken as 100% by mass. The upper limit is usually 100% by mass or less, and may be 90% by mass or less, 80% by mass or less, or 70% by mass or less. When the amount of component (A-2) is within the above range, both the resolution limit and the adhesion to the GaAs substrate can be effectively improved.

(A) When the mass of component (A-1) relative to 100% by mass of the total alkali-soluble resin is Wa1, and the mass of component (A-2) relative to the total 100% by mass of (A) alkali-soluble resin is Wa2, The mass ratio Wa1/Wa2 is preferably 0.1 or more, more preferably 0.2 or more, more preferably 0.3 or more, preferably 0.9 or less, more preferably 0.8 or less, and still more preferably 0.7 or less.

(A) The amount of the alkali-soluble resin is preferably 30% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass or more when the non-volatile component of the photosensitive resin composition is 100% by mass. , preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. (A) When the amount of the alkali-soluble resin is within the above range, both the resolution limit and the adhesion to the GaAs substrate can be effectively improved.

(A) The amount of the alkali-soluble resin is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more when the resin component of the photosensitive resin composition is 100% by mass. , preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. (A) When the amount of the alkali-soluble resin is within the above range, both the resolution limit and the adhesion to the GaAs substrate can be effectively improved.

[3. (B) Melamine resin containing one or more alkoxymethyl groups]
The photosensitive resin composition contains (B) a melamine resin containing one or more alkoxymethyl groups as component (B). Since the alkoxymethyl group contained in the melamine resin (B) can react with and bond with the hydroxyl group of the alkali-soluble resin (A), the photosensitive resin composition layer becomes insoluble in a developer or hardened by exposure. An insulating layer can be formed.

(B) The alkoxymethyl group contained in the melamine resin is represented by the following formula (B-1). In formula (B-1), "*" represents a bond.

In formula (B-1), R ²¹ represents an optionally substituted alkyl group. Alkyl groups may be straight chain, branched chain, or cyclic alkyl groups. Moreover, the cyclic alkyl group may be monocyclic or polycyclic. As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is even more preferable. Examples of alkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, s-butyl group, t-butyl group, and the like. is mentioned. Among them, a methyl group and a butyl group are preferable, and a methyl group is more preferable.

The alkyl group represented by R ²¹ may have a substituent.

The alkoxymethyl group is preferably contained in an alkoxymethylamino group represented by the following formula (B-1'). Therefore, (B) the melamine resin preferably contains an alkoxymethylamino group represented by formula (B-1'). In the formula, "*" represents a bond.

In formula (B-1′), R ²² is the same as R ²¹ in formula (B-1). R represents a hydrogen atom or an alkoxymethyl group.

The (B) melamine resin contained in the photosensitive resin composition according to the present embodiment usually contains one or more alkoxymethyl groups per molecule. (B) The number of alkoxymethyl groups per molecule of the melamine resin is preferably 2 or more from the viewpoint of obtaining a photosensitive resin composition with more excellent photosensitivity.

As the melamine resin (B), a melamine resin having a structure represented by the following formula (B-2) is preferable.

(In formula (B-2), X ²¹ , X ²² , X ²³ and X ²⁴ each independently represent a hydrogen atom or an alkoxymethyl group; R ⁵⁰ has a hydrogen atom, an amino group, or a substituent; an optionally substituted alkyl group, an optionally substituted aryl group, or an alkoxymethylamino group represented by formula (B-1′), provided that R ⁵⁰ is a hydrogen atom and a substituent is When an optionally substituted alkyl group or an optionally substituted aryl group is represented, at least one of X ²¹ , X ²² , X ²³ and X ²⁴ is an alkoxymethyl group. )

In formula (B-2), X ²¹ , X ²² , X ²³ and X ²⁴ each independently represent a hydrogen atom or an alkoxymethyl group. The alkoxymethyl group represented by X ²¹ to X ²⁴ can be the same as the group represented by formula (B-1). When R ⁵⁰ represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, at least one, preferably two or more of X ²¹ to X ²⁴ are , is an alkoxymethyl group. Preferably, when R ⁵⁰ represents a hydrogen atom, an amino group, an optionally substituted alkyl group, or an optionally substituted aryl group, at least one of X ²¹ to X ²⁴ , Preferably two or more are alkoxymethyl groups. More preferably, three or more of X ²¹ to X ²⁴ are alkoxymethyl groups, and particularly preferably four or more of X ²¹ to X ²⁴ are alkoxymethyl groups.

In formula (B-2), R ⁵⁰ is a hydrogen atom, an amino group, an optionally substituted alkyl group, an optionally substituted aryl group, or formula (B-1′) represents an alkoxymethylamino group represented by R ⁵⁰ is preferably an optionally substituted aryl group or an alkoxymethylamino group represented by the formula (B-1′), and an alkoxymethylamino group represented by the formula (B-1′) groups are more preferred. The optionally substituted alkyl group and optionally substituted aryl group represented by R ⁵⁰ have substituents represented by X ³ and X ⁴ in formula (A-1). It can be the same as the alkyl group which may be optionally substituted and the aryl group which may be substituted.

The melamine resin having a structure represented by formula (B-2) is preferably a melamine resin having a structure represented by formula (B-2').

(In formula (B-2′), X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ²⁹ and X ³⁰ each independently represent a hydrogen atom or an alkoxymethyl group, provided that X ²⁵ and X ²⁶ , X ²⁷ , X ²⁸ , X ²⁹ and X ³⁰ is an alkoxymethyl group.)

In formula (B-2′), X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ²⁹ and X ³⁰ each independently represent a hydrogen atom or an alkoxymethyl group. The alkoxymethyl group represented by X ²⁵ to X ³⁰ can be the same as the group represented by formula (B-1). At least one, preferably two or more of X ²⁵ to X ³⁰ are alkoxymethyl groups. It is more preferable that three or more of X ²⁵ to X ³⁰ are alkoxymethyl groups, more preferably four or more of X ²⁵ to X ³⁰ are alkoxymethyl groups, and all of X ²⁵ to X ³⁰ are alkoxymethyl groups. is particularly preferred.

(B) Specific examples of the melamine resin include the following melamine resins.

(B) Melamine resin may use a commercial item. Commercially available products include, for example, "MW-390", "MW-100LM" and "MX-750LM" manufactured by Sanwa Chemical Co., Ltd.; "Cymel-300", "Cymel-370" and "Cymel 327” and the like.

(B) The melamine resin may be used alone or in combination of two or more.

(B) The amount of the melamine resin is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more when the non-volatile component of the photosensitive resin composition is 100% by mass, It is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. (B) When the amount of the melamine resin is within the above range, both the resolution limit and the adhesion to the GaAs substrate can be effectively improved.

(B) The amount of melamine resin is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more when the resin component of the photosensitive resin composition is 100% by mass, It is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. (B) When the amount of the melamine resin is within the above range, both the resolution limit and the adhesion to the GaAs substrate can be effectively improved.

The ratio of the mass of (A) alkali-soluble resin to the mass of (B) melamine resin contained in the photosensitive resin composition ((B) melamine resin/(A) alkali-soluble resin) is preferably 0.01 or more, It is more preferably 0.1 or more, particularly preferably 0.2 or more, preferably 0.5 or less, more preferably 0.4 or less, and particularly preferably 0.3 or less.

[4. (C) Photoacid Generator]
The photosensitive resin composition contains (C) a photoacid generator as the (C) component. The (C) photoacid generator generates an acid upon irradiation with actinic rays such as ultraviolet rays, and the generated acid can accelerate the reaction between the (A) alkali-soluble resin and the (B) melamine resin. Therefore, the solubility of the photosensitive resin composition in the developer can be effectively reduced by the exposure, so that the latent image formation by the exposure can proceed smoothly. (C) Photo-acid generator may be used individually by 1 type, and may be used in combination of 2 or more types.

As the photoacid generator (C), a compound that generates an acid upon exposure to actinic rays can be used. (C) Photoacid generators include, for example, halogen-containing compounds, onium salt compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds, and oxime ester compounds. Among them, halogen-containing compounds are preferred.

(C) Halogen-containing compounds suitable for use as the photoacid generator include, for example, haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Preferred specific examples of halogen-containing compounds include 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran -2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4 -methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine , 1,10-dibromo-n-decane, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, phenyl-bis(trichloromethyl)-s-triazine, 4-methoxyphenyl-bis(trichloro s-triazine derivatives such as methyl)-s-triazine, styryl-bis(trichloromethyl)-s-triazine and naphthyl-bis(trichloromethyl)-s-triazine. Commercially available halogen-containing compounds can be used, and examples of commercially available products include “TFE-triazine”, “TME-triazine”, “MP-triazine”, “MOP-triazine”, “dimethoxy” manufactured by Sanwa Chemical Co., Ltd. triazine” (halogen-containing compound-based photoacid generator having a triazine skeleton) and the like.

(C) Onium salt compounds that can be suitably used as photoacid generators include, for example, iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts and the like. Preferred specific examples of onium salt compounds include tris(4-methylphenyl)sulfonium trifluoromethanesulfonate, tris(4-methylphenyl)sulfonium hexafluorophosphonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-tert-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyl-diphenylsulfonium p-toluenesulfonate, 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate and the like. Commercially available onium salt compounds can be used, and examples of commercially available products include "TS-01" and "TS-91" manufactured by Sanwa Chemical Co., Ltd.; "CPI-110A" and "CPI-210S" manufactured by San-Apro. , "HS-1", "LW-S1", "IK-1", "CPI-310B"; Sanshin Chemical Industry Co., Ltd. "SI-110L", "SI-180L", "SI-100L" etc. mentioned.

Examples of diazoketone compounds that can be suitably used as the (C) photoacid generator include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, and diazonaphthoquinone compounds. Preferred specific examples of diazoketone compounds include 1,2-naphthoquinonediazide-4-sulfonic acid ester compounds of phenols.

Examples of sulfone compounds that can be suitably used as the (C) photoacid generator include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Preferred specific examples of sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis(phenacylsulfonyl)methane, and the like.

(C) Examples of sulfonic acid compounds suitable for use as a photoacid generator include alkylsulfonate esters, haloalkylsulfonate esters, arylsulfonate esters, and iminosulfonates. Preferred specific examples of the sulfonic acid compound include benzoin tosylate, pyrogalloltrifluoromethanesulfonate, o-nitrobenzyltrifluoromethanesulfonate, o-nitrobenzyl p-toluenesulfonate and the like.

(C) Specific examples of the sulfonimide compound that can be suitably used as the photoacid generator include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethyl sulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)naphthylimide, etc. mentioned.

(C) Specific examples of the diazomethane compound that can be suitably used as the photoacid generator include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, and the like. A commercially available diazomethane compound can be used.

(C) Specific examples of the oxime ester compound that can be suitably used as the photoacid generator include benzeneacetonitrile, 2-methyl-α-[2-[[(propylsulfonyl)oxy]imino]-3(2H)- thienylidene], benzeneacetonitrile, 2-methyl-α-[2-[[[(4-methylphenyl)sulfonyl]oxy]imino]-3(2H)-thienylidene] and the like. Examples of commercially available products include "PAG103", "PAG121", "PAG169", and "PAG203" manufactured by BASF.

(C) The amount of the photoacid generator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably It is 0.1% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

[5. (D) Silane coupling agent containing trimethoxysilyl group]
The photosensitive resin composition contains (D) a silane coupling agent containing a trimethoxysilyl group as the (D) component. When (D) a silane coupling agent containing a trimethoxysilyl group is used in combination with the components (A) to (C) described above, it is possible to improve both the limiting resolution and the adhesion to the GaAs substrate. be.

(D) The trimethoxysilyl group contained in the silane coupling agent is represented by the formula “(CH ₃ O) ₃ Si—”. (D) The number of trimethoxysilyl groups contained in one molecule of the silane coupling agent is usually one, but may be two or more. (D) The number of trimethoxysilyl groups per molecule of the silane coupling agent is preferably 1-3.

(D) Silane coupling agents typically contain an organic group in combination with a trimethoxysilyl group. This organic group does not have to be reactive. Examples of non-reactive organic groups include monovalent or divalent or higher saturated hydrocarbon groups (e.g., methyl group, ethyl group, propyl group, pentylene group, alkyl group such as octyl group; methylene group, ethylene propylene group, pentylene group, alkylene group such as octylene group), monovalent or divalent aromatic hydrocarbon group (e.g., aryl group such as phenyl group, naphthyl group; arylene group such as phenylene group, naphthylene group, etc.) ).

Further, the organic group may have reactivity. For example, an organic group may contain functional groups that can react with suitable organic compounds to form chemical bonds. Examples of such functional groups include vinyl groups, epoxy groups, styryl groups, acryloyl groups, methacryloyl groups, amino groups, ureido groups, isocyanate groups, isocyanurate groups, mercapto groups, acid anhydride groups, and the like. Among them, a vinyl group, an epoxy group, and an isocyanurate group are preferred. One type of these functional groups may be used alone, or two or more types may be used in combination.

The above functional group may be directly bonded to the silicon atom of the trimethoxysilyl group, or may be bonded via a suitable linking group. For example, the organic group may contain a linking group through which the functional group is attached to the silicon atom. Examples of the linking group include alkylene groups such as a methylene group, a propylene group and a hexylene group; alkyleneoxy groups such as a methyleneoxy group and an ethyleneoxy group; a methyleneoxymethylene group, a propyleneoxymethylene group and an octyleneoxymethylene group; an alkyleneoxyalkylene group of; and the like, but are not limited to these.

From the viewpoint of effectively enhancing the adhesion to the GaAs substrate, the mass ratio of Si atoms contained in the molecule of (D) the silane coupling agent is preferably within a specific range. Specifically, the mass ratio is preferably 11.5% by mass or more, more preferably 11.8% by mass or more.

(D) Silane coupling agents include, for example, alkoxysilane coupling agents such as 1,2-bis(trimethoxysilyl)ethane; vinyl groups such as vinyltrimethoxysilane and 7-octenyltrimethoxysilane; Silane coupling agent containing; epoxy group-containing silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane styryl group-containing silane coupling agents such as p-styryltrimethoxysilane; methacryloyl group-containing silane coupling agents such as 3-methacryloxypropyltrimethoxysilane and 8-methacryloxyoctyltrimethoxysilane; 3-acryloxy Acryloyl group-containing silane coupling agents such as propyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxy Amino group-containing silane coupling agents such as silane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, etc. ureido group-containing silane coupling agents such as 3-ureidopropyltrimethoxysilane; isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltrimethoxysilane; tris-(trimethoxysilylpropyl) isocyanurate, 1, isocyanurate group-containing silane coupling agents such as 3-diallyl-5-(3-(trimethoxysilyl)propyl)-1,3,5-triazinane-2,4,6-trione; 3-mercaptopropyltrimethoxy mercapto group-containing silane coupling agents such as silane, mercaptomethyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane, 4-mercaptobutyltrimethoxysilane; acid anhydrides such as 3-trimethoxysilylpropylsuccinic anhydride group-containing silane coupling agents; N-(3-trimethoxysilylpropyl)urea, and the like.

(D) As the silane coupling agent, a commercially available product may be used. (D) Examples of commercially available silane coupling agents include "KBM-1003" (vinyltrimethoxysilane), "KBM-1083" (7-octenyltrimethoxysilane) and "KBM" manufactured by Shin-Etsu Chemical Co., Ltd. -303” (2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane), “KBM-403” (3-glycidoxypropyltrimethoxysilane), “KBM-4803” (8-glycidoxyoctyltrimethoxysilane) methoxysilane), "KBM-1403" (p-styryltrimethoxysilane), "KBM-503" (3-methacryloxypropyltrimethoxysilane), "KBM-5803" (8-methacryloxyoctyltrimethoxysilane), "KBM-5103" (3-acryloxypropyltrimethoxysilane), "KBM-603" (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane), "KBM-903" (3-aminopropyl trimethoxysilane), "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane), "KBM-575" (N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride salt), “KBM-6803” (N-2-(aminoethyl)-8-aminooctyltrimethoxysilane), “KBM-9659” (tris-(trimethoxysilylpropyl) isocyanurate), “X-12- 1290" (1,3-diallyl-5-(3-(trimethoxysilyl)propyl)-1,3,5-triazinane-2,4,6-trione), "KBM-803" (3-mercaptopropyltrione) methoxysilane), "X-12-967C" (3-trimethoxysilylpropylsuccinic anhydride); "Sila Ace S810" (3-mercaptopropyltrimethoxysilane) manufactured by Chisso; "SIM6473.5C" manufactured by Azmax ” (mercaptomethyltrimethoxysilane), “SIU9058.0” (N-(3-trimethoxysilylpropyl) urea);

(D) The silane coupling agent may be used alone or in combination of two or more.

(D) The amount of the silane coupling agent is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably 1.5% by mass when the non-volatile component of the photosensitive resin composition is 100% by mass. % by mass or more, preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 15% by mass or less. (D) When the amount of the silane coupling agent is within the above range, both the resolution limit and the adhesion to the GaAs substrate can be effectively improved.

(D) The amount of the silane coupling agent is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably 1.5% by mass when the resin component of the photosensitive resin composition is 100% by mass. % by mass or more, preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 15% by mass or less. (D) When the amount of the silane coupling agent is within the above range, both the resolution limit and the adhesion to the GaAs substrate can be effectively improved.

(D) The ratio of the weight _WD of the silane coupling agent to the total weight WA + WB of ( _A ) _{the weight WA of the alkali-soluble resin and (B) the weight WB of the melamine resin (WD / ( WA + WB} )) is preferably 0.01 or more, more preferably 0.015 or more, still more preferably 0.02 or more, preferably 0.5 or less, more preferably 0.3 or less, particularly preferably 0.2 It is below.

[6. (E) Organic filler]
The photosensitive resin composition may further contain a filler as an optional component in combination with the components (A) to (D) described above. The filler is usually incompatible with the resin component and can exist as particles in the photosensitive resin composition and its cured product. The photosensitive resin composition preferably contains (E) an organic filler as this filler.

(E) Organic fillers are generally flexible because they are made of organic materials. Therefore, when (E) the organic filler is used, the stress can be dispersed in the insulating layer, and the crack resistance and insulating properties of the insulating layer can be improved. (E) Organic fillers include, for example, urethane particles, rubber particles, polyamide particles, and silicone particles.

As the urethane particles, commercially available products may be used, for example, "MM-101SW", "MM-101SWA", "MM-101SM", "MM-101SMA", "MM-110SMA" manufactured by Negami Kogyo Co., Ltd.; Examples include the RKB series manufactured by Resinus Kasei Co., Ltd., and the like.

As the rubber particles, resin particles that are made insoluble and infusible in an organic solvent by chemically cross-linking a resin exhibiting rubber elasticity can be used. Examples of rubber particles include acrylonitrile-butadiene rubber particles, butadiene rubber particles, acrylic rubber particles, and methyl methacrylate-butadiene-styrene copolymer particles. As the rubber particles, commercially available products may be used, for example, "EXL-2655" manufactured by Dow Chemical Japan; AC4030", "AC3364", "IM101"; Kureha Chemical Co., Ltd. "Paraloid EXL2655", "EXL2602"; Kaneka Corporation "B-11A", "B513", "B22", "B-521", " B-561", "B-564", "FM-21", "FM-40", "FM-50", "M-701", "M-711", "M-732", "M- 300", "FM-40", "M-570", "M-210"; and RKB series manufactured by Resinus Chemicals.

As the polyamide particles, resin particles having amide bonds can be used. Examples of polyamide particles include particles of aliphatic polyamide such as nylon, particles of aromatic polyamide such as Kevlar, and polyamideimide particles. As the polyamide particles, commercially available products may be used, such as "VESTOSINT 2070" manufactured by Daisel Huls; "SP500" manufactured by Toray Industries, Inc.;

(E) Organic fillers may be used singly or in combination of two or more.

(E) The average particle size of the organic filler is preferably 0.005 µm or more, more preferably 0.01 µm or more, still more preferably 0.05 µm or more, preferably 5 µm or less, more preferably 2 µm or less, and even more preferably is 1 μm or less, particularly preferably 0.5 μm or less. The average particle size of the organic filler can be measured using dynamic light scattering. Specifically, the average particle size of the organic filler can be determined by uniformly dispersing the organic filler in an appropriate organic solvent using ultrasonic waves, and using a concentrated particle size analyzer (for example, "FPAR-1000" manufactured by Otsuka Electronics Co., Ltd.). The particle size distribution of the organic filler is created by using a mass standard, and the median diameter is used as the average particle diameter.

(E) The amount of the organic filler may be 0% by mass, or may be more than 0% by mass, but is preferably 3% by mass or more, when the nonvolatile component of the photosensitive resin composition is 100% by mass. It is preferably 5% by mass or more, more preferably 7% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less. (E) When the amount of the organic filler is within the above range, both the limiting resolution and the adhesion to the GaAs substrate can be effectively improved.

[7. (F) optional additive]
The photosensitive resin composition may contain (F) an optional additive as an optional non-volatile component in combination with the non-volatile components such as components (A) to (E) described above. Examples of (F) additives as component (F) include thermoplastic resins; inorganic fillers such as silica particles and alumina particles; phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, Colorants such as carbon black and naphthalene black; Polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol and pyrogallol; Thickeners such as bentone and montmorillonite; Foaming agents; flame retardants such as epoxy resins, antimony compounds, phosphorus compounds, aromatic condensed phosphates, and halogen-containing condensed phosphates; thermosetting resins such as phenolic curing agents and cyanate ester curing agents; mentioned. (F) Additives may be used singly or in combination of two or more.

[8. (G) Solvent]
The photosensitive resin composition may contain (G) a solvent as a volatile component in combination with the above non-volatile components such as components (A) to (F). The viscosity of the photosensitive resin composition can be adjusted by using the (G) solvent as the (G) component. (G) Solvents include, for example, organic solvents.

Examples of (G) solvents include ketone solvents such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbon solvents such as toluene, xylene and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ether solvents such as ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; ester solvents such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate and ethyl diglycol acetate; octane , decane and other aliphatic hydrocarbon solvents; and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. A solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

The amount of the (G) solvent may be 0% by mass, may be more than 0% by mass, and is preferably 5% by mass or more when the entire photosensitive resin composition including the (G) solvent is taken as 100% by mass. , more preferably 10% by mass or more, still more preferably 15% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. The content of the (G) solvent in the photosensitive resin composition layer of the photosensitive film is preferably 0.5 mass when the entire photosensitive resin composition including the (G) solvent is taken as 100 mass%. % or more, more preferably 1 mass % or more, still more preferably 2 mass % or more, preferably 30 mass % or less, more preferably 20 mass % or less, still more preferably 15 mass % or less.

[9. Method for producing a photosensitive resin composition]
The method for producing the photosensitive resin composition is not particularly limited. The photosensitive resin composition can be produced, for example, by mixing components (A) to (D) and, if necessary, components (E) to (G). At the time of mixing, if necessary, kneading may be performed using a kneading device such as a triple roll, ball mill, bead mill, or sand mill, or stirring may be performed using a stirring device such as a super mixer or planetary mixer. There is no restriction on the order of mixing each component. Moreover, you may cool or heat in the process of mixing each component.

[10. Properties and uses of the photosensitive resin composition]
The photosensitive resin composition according to the present embodiment can have a small limit resolution. Therefore, by using the photosensitive resin composition, an insulating layer having small-sized openings can be formed. In one example, a photosensitive resin composition layer having a dry thickness of 20 μm is formed from a photosensitive resin composition, and an insulating layer having via holes is formed from the photosensitive resin composition layer by the method described in Examples. In this case, the minimum opening diameter of via holes that can be properly formed in the insulating layer can be reduced. Specifically, the opening diameter can be preferably 25 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less.

The photosensitive resin composition according to the present embodiment can obtain a cured product that can adhere to a GaAs substrate with high adhesion. Therefore, by using the photosensitive resin composition, it is possible to form an insulating layer that can adhere to a GaAs substrate with high adhesion. In one example, a photosensitive resin composition layer is formed on a GaAs substrate by the method described in the Examples and cured to form an insulating layer. When a cross-cut tape peel test is performed on this insulating layer in accordance with JIS K5600-5-6: 1999 (ISO2409: 1992), preferably the classification in Table 1 of JIS K5600-5-6: 1999 8.3 A result of "0" to "2" can be obtained, more preferably a result of classification "0" to "1" can be obtained, and a result of classification "0" is particularly preferable. In the above classification, the smaller the numerical value, the better the adhesion. Specifically, a classification of "0" represents perfectly smooth edges of the cut and no delamination on any grid mesh. Classification "1" also indicates that there is minor peeling of the coating at the intersection of the cuts, but no significantly more than 5% of the cross-cuts are affected. In addition, category "2" indicates that the coating has delaminated along the edges of the cuts and/or at the intersections, but clearly more than 5% but not more than 15% of the crosscuts are affected. It means nothing.

Generally, the photosensitive resin composition according to the present embodiment can obtain a cured product that can adhere to a conductor layer such as a copper foil with high adhesion. Therefore, by using the photosensitive resin composition, it is possible to form an insulating layer that can adhere to the conductor layer with high adhesion. In one example, a photosensitive resin composition layer is formed on a copper foil by the method described in the Examples and cured to form an insulating layer. In this case, the load (peeling strength) required to peel off the copper foil from the insulating layer can be 0.4 kgf or more per 10 mm of width.

The use of the above-described photosensitive resin composition is not particularly limited, and examples include photosensitive films, insulating resin sheets such as prepreg; layer-forming materials for circuit boards (laminate applications, multilayer printed wiring board applications, etc.); solder resists , buffer coat film, underfill material, die bonding material, semiconductor sealing material, hole-filling resin, parts-embedding resin, etc. In particular, from the viewpoint of utilizing the advantage of being able to form an insulating layer that can adhere to a GaAs substrate with high adhesion, the photosensitive resin composition is used as a material for forming an insulating layer on a GaAs substrate. is preferable, and it is more preferable to use it as a material for an insulating layer of a circuit board having a GaAs substrate.

Examples of circuit boards comprising a GaAs substrate include semiconductor chip packages comprising a GaAs substrate, such as multi-chip packages, package-on-packages, wafer-level packages, panel-level packages, and system-in-packages; package substrates comprising the aforementioned semiconductor chip packages. printed wiring boards including GaAs substrates, such as rigid substrates, flexible substrates, single-layer substrates, thin substrates, and component-embedded substrates; Among these, the photosensitive resin composition is suitable for wafer level packages comprising GaAs wafers. The wafer level package includes, for example, a fan-in type wafer level package and a fan-out type wafer level package, and any of them may be applied.

In the circuit board, the insulating layer formed from the photosensitive resin composition may be an insulating layer for forming a wiring layer on the insulating layer. Moreover, the insulating layer formed from the photosensitive resin composition may be an interlayer insulating layer. Furthermore, the insulating layer formed from the photosensitive resin composition may be a solder resist. Moreover, the insulating layer formed from the photosensitive resin composition may be a buffer coat film. The insulating layer formed from the photosensitive resin composition described above can usually adhere to both the GaAs substrate and the conductor layer with high adhesion. It is preferable to use

[11. Photosensitive film]
A photosensitive film according to one embodiment of the present invention comprises a support and a photosensitive resin composition layer formed on the support. Since the photosensitive resin composition layer is formed of the photosensitive resin composition, it contains the photosensitive resin composition and usually contains only the photosensitive resin composition.

Examples of the support include polyethylene terephthalate film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, triacetyl acetate film and the like, and polyethylene terephthalate film is particularly preferred.

Commercially available supports include, for example, product names “Alphan MA-410” and “E-200C” manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and product name “PS-25” manufactured by Teijin Limited. and polyethylene terephthalate films such as PS series. In order to facilitate peeling of the support, the surface of the support may be coated with a release agent such as a silicone coating agent. Examples of the support whose surface is treated with a release agent include "AL-5" manufactured by Lintec Corporation. The thickness of the support is preferably in the range of 5 μm to 100 μm, more preferably in the range of 10 μm to 50 μm.

The thickness of the photosensitive resin composition layer is not particularly limited, and can be, for example, 1 μm or more and 100 μm or less. Among them, it is preferably 2 μm or more, more preferably 4 μm or more, and preferably 50 μm or less, more preferably 30 μm or less.

The photosensitive film may have a protective film that protects the photosensitive resin composition layer. Usually, the protective film is provided on the opposite side of the photosensitive resin composition layer to the support. As the protective film, for example, a film made of the same material as the support can be used. The adhesion between the protective film and the photosensitive resin composition layer is preferably smaller than the adhesion between the support and the photosensitive resin composition layer. The photosensitive film is usually used after peeling off the protective film.

A photosensitive film can be produced, for example, by coating a photosensitive resin composition on a support. From the viewpoint of smooth application, a varnish-like photosensitive resin composition containing a solvent may be prepared and the varnish-like photosensitive resin composition may be applied. When a photosensitive resin composition containing a solvent is applied, it may be dried after application, if necessary.

The photosensitive resin composition layer included in the photosensitive film may or may not contain a solvent, but the amount of the solvent is preferably small. The preferred range of the amount of solvent in the photosensitive resin composition layer is as described above.

[12. circuit board]
A circuit board according to one embodiment of the present invention includes an insulating layer containing a cured product of the photosensitive resin composition described above. This insulating layer preferably contains only a cured product of the photosensitive resin composition. Since the insulating layer can adhere to the GaAs substrate with high adhesion, it is preferably provided on the GaAs substrate. Therefore, the circuit board preferably includes a GaAs substrate and an insulating layer formed on the GaAs substrate. In this circuit board, the GaAs substrate and the insulating layer are usually in contact with each other. Moreover, from the viewpoint of utilizing the advantage of the limited resolution being small, it is preferable that the insulating layer has openings formed by exposure and development.

The photosensitive resin composition described above can be used as a negative photosensitive resin composition. Therefore, for example, the circuit board is
(I) forming a photosensitive resin composition layer on a GaAs substrate;
(II) a step of exposing the photosensitive resin composition layer, and
(III) a step of developing the photosensitive resin composition layer;
can be manufactured by a manufacturing method including in this order.

Moreover, the manufacturing method described above may further include an optional step. The manufacturing method may include, for example, step (IV) of heating the photosensitive resin composition layer between step (II) and step (III). Moreover, the manufacturing method may include, for example, a step (V) of further exposing the photosensitive resin composition layer after the step (III). Furthermore, the manufacturing method may include, for example, a step (VI) of heat-treating the photosensitive resin composition layer after the step (III). Moreover, the manufacturing method may include a step (VII) of forming a conductor layer on the insulating layer. This manufacturing method will be described in detail below.

[12.1. Step (I)]
The method for manufacturing a circuit board according to this embodiment includes step (I) of forming a photosensitive resin composition layer on a GaAs substrate. Since the photosensitive resin composition layer is formed of the photosensitive resin composition, it contains the photosensitive resin composition and usually contains only the photosensitive resin composition.

A substrate containing gallium arsenide is used as the GaAs substrate. A gallium arsenide wafer can be used as the GaAs substrate. A wafer is usually prepared as a disc, but the shape of the wafer is not limited to a disc. The wafer may also include a conductor layer, which may be patterned.

There is no particular limitation on the method of forming the photosensitive resin composition layer. For example, a photosensitive resin composition layer may be formed by coating a photosensitive resin composition on a GaAs substrate. From the viewpoint of smooth application, a varnish-like photosensitive resin composition containing a solvent may be prepared and the varnish-like photosensitive resin composition may be applied.

Examples of coating methods include gravure coating, micro gravure coating, reverse coating, kiss reverse coating, die coating, slot die, lip coating, comma coating, blade coating, roll coating, and knife coating. Method, curtain coating method, chamber gravure coating method, slot orifice method, spin coating method, slit coating method, spray coating method, dip coating method, hot melt coating method, bar coating method, applicator method, air knife coating method, curtain flow coating method, offset printing method, brush coating method, screen printing method, and the like.

The photosensitive resin composition may be applied once or may be applied in multiple times. Also, different coating methods may be combined for implementation. In order to avoid contamination with foreign matter, it is preferable to carry out the coating in an environment such as a clean room where foreign matter is less generated.

After applying the photosensitive resin composition, the photosensitive resin composition layer may be dried, if necessary. Drying can be performed using a drying device such as a hot air oven or a far-infrared oven. It is preferable to appropriately set the drying conditions according to the composition of the photosensitive resin composition. Specifically, the drying temperature is preferably 50°C or higher, more preferably 70°C or higher, particularly preferably 80°C or higher, preferably 150°C or lower, more preferably 130°C or lower, and particularly preferably 120°C. It is below. The drying time is preferably 30 seconds or longer, more preferably 60 seconds or longer, particularly preferably 120 seconds or longer, and preferably 60 minutes or shorter, more preferably 20 minutes or shorter, and particularly preferably 5 minutes or shorter.

For example, a photosensitive film may be used to form the photosensitive resin composition layer. As a specific example, a photosensitive resin composition layer of a photosensitive film can be laminated on a GaAs substrate to form a photosensitive resin composition layer on the GaAs substrate. Lamination is usually performed by pressing the photosensitive resin composition layer of the photosensitive film onto the GaAs substrate while heating. This lamination is preferably carried out under reduced pressure by a vacuum lamination method. Moreover, before lamination, a preheating treatment for heating the photosensitive film and the GaAs substrate may be performed, if necessary.

The lamination conditions are, for example, a pressure bonding temperature (laminating temperature) of 70° C. to 140° C. and a pressure bonding pressure of 1 kgf/cm ² to 11 kgf/cm ² (9.8×10 ⁴ N/m ² to 107.9×10 ⁴ N/ m ² ) and a crimping time of 5 seconds to 300 seconds. Moreover, lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. The lamination may be performed in batch mode or continuously using rolls.

A vacuum lamination method can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nikko Materials, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a roll-type dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. be able to.

When the photosensitive resin composition layer is formed using a photosensitive film, the support is usually peeled off at an appropriate time before step (III).

[12.2. Step (II)]
The method for manufacturing a circuit board according to the present embodiment includes step (II) of exposing the photosensitive resin composition layer after step (I). In this step (II), the photosensitive resin composition layer is usually irradiated with actinic rays to form a latent image on the photosensitive resin composition layer. Specifically, in step (II), a specific portion of the photosensitive resin composition layer is selectively irradiated with actinic rays. Therefore, the photosensitive resin composition layer has an exposed portion irradiated with actinic rays and a non-exposed portion not irradiated with actinic rays. A latent image corresponding to the opening is formed by the non-exposed portion.

As the actinic ray, it is preferable to use an appropriate ray according to the composition of the photosensitive resin composition. The wavelength of actinic rays is usually 190 nm to 1000 nm, preferably 240 nm to 550 nm, but rays of other wavelengths may be used. Specific examples of active light sources include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferred.

It is preferable to set the irradiation amount of actinic rays so that a desired opening can be formed after development. In one example, the range of specific irradiation dose is preferably 10 mJ/cm ² or more, more preferably 50 mJ/cm ² or more, particularly preferably 200 mJ/cm ² or more, and preferably 10,000 mJ/cm ² or less. It is more preferably 8,000 mJ/cm ² or less, particularly preferably 1,000 mJ/cm ² or less.

Irradiation with actinic rays is usually performed using a mask. Specifically, the photosensitive resin composition layer is irradiated with actinic rays through a mask having a light-transmitting portion and a light-shielding portion. Actinic rays pass through the light-transmitting portion and enter the exposed portion, but cannot pass through the light-shielding portion and therefore cannot enter the non-exposed portion. Therefore, the photosensitive resin composition layer can be provided with an exposed portion and a non-exposed portion corresponding to the light-transmitting portion and the light-shielding portion. The mask may be brought into close contact with the photosensitive resin composition layer (contact exposure method), or may be exposed using parallel rays without close contact (non-contact exposure method).

In general, the light shielding portion of the mask is formed to have a planar shape corresponding to the opening to be formed in the insulating layer. A "planar shape" represents a shape viewed from the thickness direction unless otherwise specified. Further, the light shielding portion having a planar shape corresponding to the opening of the insulating layer may be hereinafter referred to as "mask pattern". In one example, a via pattern such as a round hole pattern may be employed as the mask pattern. The via diameter (opening diameter) is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. Although the lower limit is not particularly limited, it can be 0.1 μm or more, 0.5 μm or more, or the like.

When a support is present on the photosensitive resin composition layer, the exposure may be performed through the support, or the exposure may be performed after the support is peeled off.

[12.3. Step (IV)]
The method for manufacturing a circuit board according to the present embodiment may include step (IV) of heating the photosensitive resin composition layer after step (II) and before step (III). Heating in step (IV) can accelerate the cross-linking reaction between (A) the alkali-soluble resin and (B) the melamine resin, so that the solubility of the exposed area in the developer can be rapidly reduced. can.

The heating temperature in step (IV) may be a hot plate or an oven. The heating temperature can be, for example, 40° C. or higher and 115° C. or lower. Also, the heating time can be, for example, 30 seconds or more and 60 minutes or less.
In particular, when heating is performed with a hot plate, the heating temperature is preferably 50° C. or higher, more preferably 60° C. or higher, particularly preferably 70° C. or higher, and preferably 115° C. or lower, more preferably 110° C. or lower. , particularly preferably 105° C. or less. The heating time is preferably 30 seconds or longer, more preferably 60 seconds or longer, particularly preferably 120 seconds or longer, and preferably 30 minutes or shorter, more preferably 20 minutes or shorter, and particularly preferably 10 minutes or shorter.
When heating is performed in an oven, the heating temperature is preferably 40° C. or higher, more preferably 50° C. or higher, and preferably 100° C. or lower, more preferably 90° C. or lower. The heating time is preferably 3 minutes or longer, more preferably 10 minutes or longer, particularly preferably 15 minutes or longer, and preferably 60 minutes or shorter, more preferably 50 minutes or shorter, and particularly preferably 40 minutes or shorter.

[12.4. Step (III)]
The method for manufacturing a circuit board according to the present embodiment includes step (III) of developing the photosensitive resin composition layer after step (II). Development can remove the unexposed areas that were not exposed in step (II) to form openings. Development is usually carried out by a wet development method in which the photosensitive resin composition layer is brought into contact with a developer. Examples of the developer include an alkaline aqueous solution, an aqueous developer, an organic solvent, and the like.

Examples of alkaline aqueous solutions as developers include aqueous solutions of alkali metal compounds. Examples of alkali metal compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates and bicarbonates such as sodium carbonate and sodium bicarbonate; sodium phosphate; , alkali metal phosphates such as potassium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; Examples of the alkaline aqueous solution include aqueous solutions of organic bases containing no metal ions, such as tetraalkylammonium hydroxide. One type of alkaline aqueous solution may be used alone, or two or more types may be used in combination. Among them, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferable because it does not contain metal ions and has little effect on the semiconductor chip. The pH of the alkaline aqueous solution is preferably in the range of 8-14, for example. Further, the base concentration of the alkaline aqueous solution is preferably 0.1% by mass to 10% by mass.

Examples of the organic solvent as the 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 mono butyl ether and the like. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types. The concentration of the organic solvent is usually 2% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more, relative to the total amount of the developer. 100% by weight of the developer may be an organic solvent. Organic solvent-based developers that can be used alone include, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

If necessary, the developer may contain additives such as surfactants and antifoaming agents in order to improve the development action.

The development time is preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly specified, but is preferably 20° C. or higher, preferably 50° C. or lower, and more preferably 40° C. or lower.

The developing method includes, for example, a paddle method, a spray method, an immersion method, a brushing method, a slapping method, an ultrasonic method and the like.

After development using the developer, the photosensitive resin composition layer may be further rinsed. Rinsing is preferably done with a solvent different from the developer. For example, the same type of solvent as contained in the photosensitive resin composition may be used for rinsing. Rinsing time is preferably 5 seconds to 1 minute.

[12.5. Step (V)]
Although the photosensitive resin composition layer may be cured by the above-described process to obtain an insulating layer, from the viewpoint of further progressing the curing of the photosensitive resin composition layer to obtain an insulating layer having excellent mechanical strength, The method for manufacturing a circuit board according to the embodiment may include a step (V) of further exposing the photosensitive resin composition layer after step (III). In this step (V), the photosensitive resin composition layer is irradiated with actinic rays. As the actinic ray used for the exposure in the step (V), the same actinic ray used for the exposure in the step (II) can be used.

It is preferable to set the dose of actinic rays in step (V) so that desired openings can be formed after development. In one example, the range of specific irradiation dose is preferably 500 mJ/cm ² or more, more preferably 800 mJ/cm ² or more, particularly preferably 1000 mJ/cm ² or more, and preferably 10,000 mJ/cm ² or less. It is more preferably 8,000 mJ/cm ² or less, particularly preferably 6,000 mJ/cm ² or less.

[12.6. Step (VI)]
Although the photosensitive resin composition layer may be cured by the above-described process to obtain an insulating layer, from the viewpoint of further progressing the curing of the photosensitive resin composition layer to obtain an insulating layer having excellent mechanical strength, The method for manufacturing a circuit board according to the embodiment preferably includes step (VI) of heat-treating the photosensitive resin composition layer after step (III). When the method for manufacturing a circuit board includes step (V), step (VI) is preferably performed after step (V).

The heat treatment can be performed, for example, using a heating device such as a clean oven. The atmosphere during the heat treatment may be air or an inert gas atmosphere such as nitrogen. The heat treatment conditions may be selected according to the type and amount of the resin component in the photosensitive resin composition, preferably 150° C. to 250° C. for 20 minutes to 180 minutes, more preferably 160° C. ~230°C for 30 minutes to 120 minutes.

[12.7. Step (VII)]
The method for manufacturing a circuit board according to this embodiment may include a step (VII) of forming a conductor layer on the insulating layer. A conductor material used for the conductor layer is not particularly limited. For example, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor layer may be a single metal layer or an alloy layer. The alloy layer includes, for example, a layer formed from an alloy of two or more metals selected from the above group (eg, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoint of versatility, cost, and ease of patterning of conductor layer formation, single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred. A metal layer is more preferred.

The conductor layer may have a single layer structure, or may have a multi-layer structure including two or more single metal layers or alloy layers made of different kinds of metals or alloys. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

The thickness of the conductor layer is usually 3 μm to 35 μm, preferably 5 μm to 30 μm, depending on the design of the circuit board.

There are no restrictions on the method of forming the conductor layer. The conductor layer may be formed by, for example, a sputtering method. Also, the conductor layer may be formed by combining, for example, electroless plating and electrolytic plating. Furthermore, the conductor layer may be formed only by electroless plating by forming a plating resist having a pattern opposite to that of the conductor layer.

Among them, the conductor layer is preferably formed by a sputtering method. When the conductor layer is formed by sputtering, a conductor seed layer is usually formed on an insulating layer by sputtering, and then a conductor sputter layer is formed on the conductor seed layer by sputtering. Also, the surface of the insulating layer may be cleaned by reverse sputtering before forming the conductive seed layer by sputtering. Ar gas, O ₂ gas, and N ₂ gas are preferable as the gas used for reverse sputtering. Sputtering can be performed using various sputtering devices such as magnetron sputtering and mirrortron sputtering. Examples of metals forming the conductive seed layer include Cr, Ni, Ti, and nichrome. Cr and Ti are particularly preferred. The thickness of the conductive seed layer is preferably 5 nm or more, more preferably 10 nm or more, and preferably 1000 nm or less, more preferably 500 nm or less. Examples of the metal forming the conductor sputter layer include Cu, Pt, Au, Pd, and the like. Cu is particularly preferred. The thickness of the conductor sputtered layer is preferably 50 nm or more, more preferably 100 nm or more, and preferably 3000 nm or less, more preferably 1000 nm or less.

A copper plating layer may be further formed on the layer formed by sputtering by electrolytic copper plating. The thickness of the copper plating layer is preferably 5 μm or more, more preferably 8 μm or more, and preferably 75 μm or less, more preferably 35 μm or less.

The conductor layer may be patterned. As a pattern forming method, for example, a subtractive method, a semi-additive method, or the like can be used.

[12.8. optional process]
The method for manufacturing a circuit board according to the present embodiment may further include arbitrary steps in combination with the steps described above.
For example, the method of manufacturing the circuit board may include the step of drilling holes in the insulating layer. The hole to be formed may be a trench that does not penetrate the insulating layer, a via hole that penetrates only the insulating layer, or a through hole that penetrates the entire circuit board. Drilling can be performed, for example, by drilling, laser, plasma, or other methods.

Moreover, the method of manufacturing the circuit board may include a step of subjecting the insulating layer to a desmear treatment. When the insulating layer is perforated, resin residue (smear) may adhere to the formed holes. The desmear process removes this smear. Desmearing may be performed by dry desmearing, wet desmearing, or a combination thereof.

Further, the circuit board manufacturing method may include a step of dicing the manufactured circuit board.

The method for manufacturing the circuit board may repeat the above-described steps. For example, steps (I) to (VII) may be repeated to manufacture a multi-layer circuit board having insulating layers and conductor layers alternately formed on a GaAs substrate.

[13. semiconductor device]
The circuit board described above can be used in the manufacture of semiconductor devices. A semiconductor device includes a circuit board, and is used in, for example, electrical products (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.). A semiconductor device is mentioned.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, unless otherwise specified, the operations described below were performed in the atmosphere at normal temperature and normal pressure (23° C., 1 atm).

[Examples 1 to 17 and Comparative Examples 1 to 6]
Reagents ((A-1) component, (A-2) component, (B) component, (B') component, (C) component, (D) in the amounts (parts by mass) shown in Tables 1 and 2 below) Components (D') and (E)) and 2-butanone (MEK) were mixed to prepare a photosensitive resin composition.
In the table below, the abbreviations of reagents have the following meanings.

(A) Component:
(A-1) Component:
・ BisE: “BisE” manufactured by Honshu Chemical Co., Ltd.
・ BisA: "BisA" manufactured by Mitsui Chemicals Fine Co., Ltd.
・ BisP-HTG: "BisP-HTG" manufactured by Honshu Chemical Co., Ltd.
・ BisP-M: "BisP-M" manufactured by Mitsui Chemicals Fine Co., Ltd.

(A-2) Component:
- TR4020G: A cresol novolac resin "TR4020G" manufactured by Asahi Organic Chemicals.

(B) Component:
Cymel-300: "Cymel-300" manufactured by Daicel Allnex. A compound in which R represents a methyl group in the following formula (BX).
Cymel-370N: "Cymel-370N" manufactured by Daicel Allnex. A compound represented by the following formula (BX) in which R represents a methyl group or a hydrogen atom.
Cymel-327: "Cymel-327" manufactured by Daicel Allnex. A compound represented by the following formula (BX) in which R represents a methyl group and part of the groups —CH ₂ OR are replaced with hydrogen atoms. Therefore, —N(CH ₂ OR) ₂ bonded to the triazine ring is partially replaced with a group represented by the following formula (b-1). In formula (b-1), * represents a bond.

(B') Component:
・ MX-270: “Nikalac MX-270” manufactured by Sanwa Chemical Co., Ltd.
・TML-BPA: “TML-BPA” manufactured by Honshu Chemical Co., Ltd.

(C) Component:
· MP-triazine: "MP-triazine" manufactured by Sanwa Chemical Co., Ltd.

(D) Component:
・ KBM-403: “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.
・ KBM-9659: “KBM-9659” manufactured by Shin-Etsu Chemical Co., Ltd.
・ KBM-1003: “KBM-1003” manufactured by Shin-Etsu Chemical Co., Ltd.
・X-12-1290: “X-12-1290” manufactured by Shin-Etsu Chemical Co., Ltd.
・ KBM-4803: “KBM-4803” manufactured by Shin-Etsu Chemical Co., Ltd.
・ KBM-1083: “KBM-1083” manufactured by Shin-Etsu Chemical Co., Ltd.

(D') component:
・ KBE-1003: “KBE-1003” manufactured by Shin-Etsu Chemical Co., Ltd.
・ KBM-402: “KBM-402” manufactured by Shin-Etsu Chemical Co., Ltd.

(E) Component:
・MM-101SM: Urethane fine particles "MM-101SM" manufactured by Neagari Kogyo Co., Ltd. Average particle size 0.07-0.1 μm.

[Production of photosensitive film]
As a support, a polyethylene terephthalate film (“Lumirror T60” manufactured by Toray Industries, Inc., thickness 38 μm) whose surface was subjected to release treatment was prepared. The photosensitive resin composition prepared in each of Examples and Comparative Examples was uniformly applied on the support with a die coater so that the thickness of the photosensitive resin composition layer after drying was 20 μm, and After drying at 110° C. for 6 minutes, a photosensitive film was obtained. This photosensitive film had a support and a photosensitive resin composition layer formed on the support.

[Evaluation of limiting resolution]
A copper-clad laminate was prepared by plating a silicon wafer with copper to form a copper layer having a thickness of 5 μm and roughening the layer with a 1% hydrochloric acid aqueous solution for 60 seconds. A photosensitive film was placed on the copper-clad laminate so that the photosensitive resin composition layer was in contact with the surface of the copper layer, and laminated using a vacuum laminator (VP160, manufactured by Nikko Materials Co., Ltd.). The lamination conditions were vacuuming time of 30 seconds, compression temperature of 80° C., compression pressure of 0.7 MPa, and pressure time of 30 seconds. After standing at room temperature for 10 minutes, the support was peeled off to obtain an intermediate laminate comprising a copper-clad laminate and a photosensitive resin composition layer.

This intermediate laminate was subjected to heat treatment at 100° C. for 3 minutes. Thereafter, the photosensitive resin composition layer of the intermediate laminate was exposed to ultraviolet rays (wavelength: 365 nm, intensity: 40 mW/cm ² ) through a quartz glass mask. The optimum exposure amount was set in the range of 50 mJ/cm ² to 1000 mJ/cm ² . Here, the optimum value represents a value that can minimize the limit resolution. As the quartz glass mask, a mask having a plurality of mask patterns with different dimensions was used so that a plurality of round holes (via holes) having different design values of opening diameters could be drawn. After standing at room temperature for 5 minutes, heat treatment was performed at 100° C. for 3 minutes. A 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23° C. was sprayed as a developer over the entire surface of the photosensitive resin composition layer of the intermediate laminate at a spray pressure of 0.1 MPa for 1 minute to carry out spray development. rice field. After the spray development, ultraviolet irradiation of 1 J/cm ² was performed, and heat treatment was performed at 190° C. for 60 minutes to cure the photosensitive resin composition layer. Through the above operations, an insulating layer was formed on the copper-clad laminate from the cured product of the photosensitive resin composition.

The diameter of the bottom of the via hole formed in the insulating layer was measured by observation with a scanning electron microscope (SEM) (1000x magnification). When the diameter of the bottom of the via hole was in the range of 60% or more and 120% or less of the design value of the via hole, it was determined that the via hole was properly formed. Among the appropriately formed via holes, the via hole with the smallest design value was selected, and the design value of the selected via hole was obtained as the limiting resolution.

[Evaluation of GaAs adhesion]
A photosensitive film was placed on a 6-inch gallium arsenide wafer as a GaAs substrate so that the photosensitive resin composition layer was in contact with the gallium arsenide wafer. Lamination was performed using a vacuum laminator (VP160, manufactured by Nikko Materials Co., Ltd.) to obtain a laminate comprising a gallium arsenide wafer, a photosensitive resin composition layer, and a support in this order. The lamination conditions were vacuuming time of 30 seconds, compression temperature of 80° C., compression pressure of 0.7 MPa, and pressure time of 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or longer, and the entire surface of the photosensitive resin composition layer was exposed to ultraviolet light through the support. The exposure dose at this time was set to the optimum value described above. After allowing the laminate to stand at room temperature for 5 minutes, the support was peeled off. Next, heat treatment was performed at 100° C. for 10 minutes. Spray development was performed by spraying a 2.38% by mass aqueous tetramethylammonium hydroxide solution at 23° C. for 1 minute at a spray pressure of 0.1 MPa as a developer over the entire surface of the photosensitive resin composition layer. After the spray development, ultraviolet irradiation of 1 J/cm ² was performed, and heat treatment was performed at 190° C. for 60 minutes to cure the photosensitive resin composition layer. Through the above operations, a sample substrate including a gallium arsenide wafer and an insulating layer formed of a cured product of a photosensitive resin composition was obtained.

The insulating layer of the obtained sample substrate was subjected to a cross-cut tape peel test in accordance with JIS K5600-5-6:1999 (ISO2409:1992). Adhesion to the gallium arsenide wafer was evaluated according to the following evaluation criteria.
"A": Corresponds to Class 0 in Table 1 of JIS K5600-5-6:1999 8.3.
"B": Corresponds to Class 1 in Table 1 of JIS K5600-5-6:1999 8.3.
"C": Corresponds to Class 2 in Table 1 of JIS K5600-5-6:1999 8.3.
"D": Corresponds to Class 3 in Table 1 of JIS K5600-5-6:1999 8.3.
"E": Corresponds to Class 4 or Class 5 in Table 1 of JIS K5600-5-6:1999 8.3.

[Measurement of Cu adhesion]
A rolled copper foil (“BHY-22B-T” manufactured by JX Nippon Mining & Metals Co., Ltd., thickness 18 μm) washed and dried with 10% sulfuric acid was prepared. A photosensitive film was placed on the glossy surface of the rolled copper foil so that the photosensitive resin composition layer was in contact with the surface of the copper layer. Lamination was performed using a vacuum laminator (VP160, manufactured by Nikko Materials Co., Ltd.) to obtain a laminate comprising a rolled copper foil, a photosensitive resin composition layer, and a support in this order. The lamination conditions were vacuuming time of 30 seconds, compression temperature of 80° C., compression pressure of 0.7 MPa, and pressure time of 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or longer, and the entire surface of the photosensitive resin composition layer was exposed to ultraviolet light through the support. The exposure dose at this time was set to the optimum value described above. After allowing the laminate to stand at room temperature for 5 minutes, the support was peeled off. Next, heat treatment was performed at 100° C. for 10 minutes. Spray development was performed by spraying a 2.38% by mass aqueous tetramethylammonium hydroxide solution at 23° C. for 1 minute at a spray pressure of 0.1 MPa as a developer over the entire surface of the photosensitive resin composition layer. After the spray development, ultraviolet irradiation of 1 J/cm ² was performed, and heat treatment was performed at 190° C. for 60 minutes to cure the photosensitive resin composition layer. Through the above operations, a sample substrate including a rolled copper foil and an insulating layer formed of a cured product of a photosensitive resin composition was obtained.

The insulating layer side of the obtained sample substrate and the glass epoxy substrate are joined, and the peeling strength of the copper foil is measured using a tensile tester (manufactured by TSE, "AC-50C-SL ”). Specifically, a cut was made in the rolled copper foil of the sample substrate to surround a portion having a width of 10 mm and a length of 100 mm. The load when 35 mm was peeled off in the vertical direction was measured as the peel strength. Based on the measured peel strength, the adhesion to copper foil was evaluated according to the following criteria.
"◯": The peel strength is 0.4 kgf or more.
"X": The peel strength is less than 0.4 kgf.

[result]
The compositions and evaluation results of the photosensitive resin compositions of Examples and Comparative Examples described above are shown in the table below. In the table below, the numerical values in the columns of reagents represent parts by mass. In the table below, abbreviations have the following meanings.
(E) component concentration: ratio of (E) component to 100% by mass of non-volatile components in the photosensitive resin composition.
Si ratio: Mass ratio of Si atoms contained in the silane coupling agent.
Type of alkoxy group: The type of alkoxy group contained in the alkoxysilyl group of the silane coupling agent.
"M" in the column "type of alkoxy group": methoxy group.
"E: Ethoxy group" in the "Alkoxy group type" column.
GaAs adhesion: adhesion to a GaAs substrate.
Cu adhesion: Adhesion to copper foil.

Claims (11)

A photosensitive resin composition for forming an insulating layer on a GaAs substrate,
(A) an alkali-soluble resin having a hydroxyl group;
(B) a melamine resin containing one or more alkoxymethyl groups;
(C) a photoacid generator, and (D) a silane coupling agent containing a trimethoxysilyl group,
A photosensitive resin composition comprising: 2. The photosensitive resin composition according to claim 1, wherein component (D) contains 11.5% by mass or more of Si atoms in the molecule. 3. The photosensitive resin composition according to claim 1, comprising (E) an organic filler. 4. The photosensitive resin composition according to claim 3, wherein the amount of (E) the organic filler is 7% by mass or more and 30% by mass or less when the non-volatile component of the photosensitive resin composition is 100% by mass. The photosensitive resin composition according to any one of claims 1 to 4, wherein the component (A) contains a compound having a structure represented by the following formula (A-1).

(In formula (A-1),
R ³ is a divalent group represented by the following formula (a), a divalent group represented by the following formula (b), a divalent group represented by the following formula (c), or a combination thereof represents a divalent group consisting of
X ³ and X ⁴ are each independently an optionally substituted alkyl group, an optionally substituted aryl group, a halogen atom, or an optionally substituted monovalent represents a heterocyclic group of
n3 and n4 each independently represent an integer of 0 to 4;

In formula (a), R ¹¹ and R ¹² each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted may be a monovalent heterocyclic group, an amino group, a carbonyl group, a carboxyl group, or a group consisting of a combination thereof, and R ¹¹ and R ¹² may combine with each other to form a ring. * represents a bond.
In formula (b), each X ¹¹ independently represents an optionally substituted alkyl group. p1 represents an integer from 0 to 4; * represents a bond.
In formula (c), X ¹² and X ¹³ each independently represent an optionally substituted alkyl group. p2 and p3 each independently represent an integer of 0 to 4; * represents a bond. ) The photosensitive resin composition according to any one of claims 1 to 5, wherein the component (A) contains a compound containing a structure represented by the following formula (A-2).

(In formula (A-2),
R ¹ each independently represents a divalent group represented by the following formula (a),
X ¹ is each independently an optionally substituted alkyl group, an optionally substituted aryl group, a halogen atom, or an optionally substituted monovalent heterocyclic ring represents the group,
n1 represents an integer from 0 to 4,
m1 represents an integer from 1 to 200; * represents a bond.

In formula (a), R ¹¹ and R ¹² each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted may be a monovalent heterocyclic group, an amino group, a carbonyl group, a carboxyl group, or a group consisting of a combination thereof, and R ¹¹ and R ¹² may combine with each other to form a ring. * represents a bond. ) A photosensitive film comprising a support and a photosensitive resin composition layer containing the photosensitive resin composition according to any one of claims 1 to 6 provided on the support. A circuit board comprising an insulating layer comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 6. 9. The circuit board according to claim 8, comprising a GaAs substrate and said insulating layer formed on said GaAs substrate. A semiconductor device comprising the circuit board according to claim 8 . (I) forming a photosensitive resin composition layer containing the photosensitive resin composition according to any one of claims 1 to 6 on a GaAs substrate;
(II) a step of exposing the photosensitive resin composition layer, and
(III) a step of developing the photosensitive resin composition layer;
A method of manufacturing a circuit board, comprising in that order: