JP5965129B2 - Photobase generator and photosensitive resin composition containing the same - Google Patents

Description

  The present invention relates to a photobase generator that generates a base by light irradiation and optionally heating, and a photosensitive resin composition containing the photobase generator, and more specifically, a photobase generator that has good solubility in various solvents, And a photosensitive resin composition containing the same.

  Resin photocuring technology has advantages not found in conventional thermosetting technology, such as being capable of curing at low temperature and in a short time, as well as fine processing by photopatterning. Widely used in the material field. Resin photocuring techniques are roughly classified into three types: radical type, cationic type, and anionic type.

  Conventionally, the radical type is the mainstream, but the (meth) acrylic acid polymer used as the radical type has problems such as poor heat resistance and adhesiveness in addition to the problem of large cure shrinkage. Examples of the epoxy-acrylate-based photosensitive resin composition improved in these weak points include those described in Patent Document 1 and Patent Document 2. However, in terms of heat resistance and cure shrinkage, these photosensitive resin compositions are not yet sufficient.

  As the cation type, a photoacid generator is used, and a number of compounds have been developed. Examples of such photoacid generators include those described in Patent Document 3 and Patent Document 4. However, since any photoacid generator generates strong protonic acid when irradiated with light, corrosion of metals becomes a problem and it is considered difficult to put it to practical use in the field of electronic materials.

  As an anionic type expected to solve these problems, a photobase generator is used. Examples of such photobase generators include those described in Patent Document 5. However, this photobase generator has poor photosensitivity compared to radical type and cation type, and carbon dioxide gas coexists when base is generated, so that bubbles remain in the cured product and the strength of the cured product is reduced. It is a disadvantage that it is seen and disadvantageous when forming a fine pattern.

  A photosensitive resin composition comprising a photocyclization type photobase generator having a high photosensitivity and generating an amine compound without decarboxylation, and a base-reactive resin as a photobase generator that eliminates the above disadvantages Examples using this are described in Patent Document 6 and Patent Document 7. Since the photobase generator is excellent in high-temperature resistance, it is possible to form a pattern without generating a base in an unexposed portion by heating.

  On the other hand, a photocurable resin composition in which a photobase generator, a thiol group-containing curing agent, and an epoxy resin are combined can be used as a photosensitive resin composition that can be cured at a relatively low temperature. As such a photosensitive resin composition, for example, those described in Patent Document 8 are known.

JP-A-6-324490 Japanese Patent Publication No. 1-54390 JP-A-5-11441 Japanese Patent Laid-Open No. 11-15159 Japanese Patent Application Laid-Open No. 11-237741 JP 2009-80452 A JP 2010-106233 A Japanese Patent Laid-Open No. 2003-212856

  A photosensitive resin composition using a photobase generator can be produced by a simple process of mixing a photobase generator with an existing polymer precursor. However, as shown in Comparative Examples described later, the photobase generators described in Patent Document 6 and Patent Document 7 have low solubility in organic solvents, and a polymer precursor to be combined when a resin composition is used. There may be a case where a sufficient amount cannot be contained in the photosensitive resin composition due to reasons such as low affinity. In such a case, as a result, there was a problem that it did not function sufficiently as a photobase generator. Furthermore, since the photosensitive resin composition described in Patent Document 7 is not an alkali development type, there is a problem that an environmental load is applied.

  In view of the above circumstances, the object of the present invention is to provide a photobase generator excellent in affinity with various organic solvents and a polymer precursor (for example, a compound having an epoxy group) to be combined at the time of production of the photosensitive resin composition, and A photosensitive resin composition having a photopatterning property, which can provide a large solubility contrast (that is, a high residual film ratio) between an exposed portion and an unexposed portion regardless of the type of polymer precursor, and is capable of alkali development. It is to provide.

  As a result of intensive studies to achieve the above object, the present inventors have found that a photobase generator having a specific structure is excellent in affinity with various organic solvents and polymer precursors to be combined. The present inventors have found that a photosensitive resin composition capable of obtaining a large solubility contrast between an exposed part and an unexposed part can be provided regardless of the type of molecular precursor, and the present invention has been completed. That is, the present invention is as follows.

｛式中、
Ｒ¹、Ｒ²、Ｒ³及びＲ⁴はそれぞれ独立に：水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、若しくはアンモニオ基；又は、置換基を含んでもよい炭素数１〜２０の脂肪族炭化水素基、置換基を含んでもよい炭素数６〜２２の芳香族炭化水素基、置換基を含んでもよい炭素数１〜２０のアルコキシ基、置換基を含んでもよいアリールオキシ基、若しくはこれらの２つ以上が連結された基；であり、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴のうち２つ以上が結合して環状構造を形成していてもよく、
Ｒ⁵及びＲ⁶はそれぞれ独立に：水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、若しくはホスホナト基；又は、置換基を含んでもよい炭素数１〜２０の脂肪族炭化水素基、置換基を含んでもよい炭素数６〜２２の芳香族炭化水素基、置換基を含んでもよい炭素数１〜２０のアルコキシ基、置換基を含んでもよいアリールオキシ基、若しくはこれらの２つ以上が連結された基；であり、そして、
Ｚは下記一般式（２）又は（３）：

（式中、
Ｒ⁷、Ｒ⁸、Ｒ⁹及びＲ¹⁰はそれぞれ独立に：水素原子；又は、置換基を含んでもよい炭素数４〜１０の脂肪族炭化水素基、置換基を含んでもよい炭素数４〜１０のアルコキシ基、若しくはこれらの２つ以上が連結された基；であり、但し、Ｒ⁷及びＲ⁸の少なくとも１つ並びにＲ⁹及びＲ¹⁰の少なくとも１つは、置換基を含んでもよい炭素数４〜１０の脂肪族炭化水素基、置換基を含んでもよい炭素数４〜１０のアルコキシ基、若しくはこれらの２つ以上が連結された基であり、そして、
Ｒ¹¹及びＲ¹²はそれぞれ独立に、置換基を含んでもよい炭素数１〜６の脂肪族炭化水素基である。）
で表される部分構造である。｝
で表される、光塩基発生剤。
［２］ 該一般式（１）において、Ｚが該一般式（２）で表される部分構造である、上記［１］に記載の光塩基発生剤。
［３］ 該一般式（１）において、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶が水素である、上記［１］又は［２］に記載の光塩基発生剤。
［４］ メチルエチルケトン、プロピレングリコールモノメチルエーテルアセテート、酢酸エチル、ガンマブチロラクトン、及びメタノールからなる群から選択される少なくとも１つの溶媒に対する２５℃での溶解性が、溶液中の光塩基発生剤濃度で１質量％以上である、上記［１］〜［３］のいずれかに記載の光塩基発生剤。
［５］ エポキシ基を有する化合物（ａ）、
上記［１］〜［４］のいずれかに記載の光塩基発生剤を含む光塩基発生剤（ｂ）、
チオール基を有する硬化剤（ｃ）、並びに
カルボキシル基及び無水カルボキシル基の少なくとも一方を有する化合物（ｄ）、
を含有する、感光性樹脂組成物。
［６］ 該エポキシ基を有する化合物（ａ）が、ノボラック型エポキシ樹脂又はノボラック型エポキシ樹脂変性物である、上記［５］に記載の感光性樹脂組成物。
［７］ 該チオール基を有する硬化剤（ｃ）が、チオールカルボン酸エステル化物である、上記［５］又は［６］に記載の感光性樹脂組成物。
［８］ 該エポキシ基を有する化合物（ａ）、並びに該カルボキシル基及び無水カルボキシル基の少なくとも一方を有する化合物（ｄ）が、いずれも下記一般式（４）：

｛式中、
Ｒ^a、Ｒ^b、Ｒ^c、Ｒ^d及びＲ^eはそれぞれ独立に：飽和若しくは二重結合を１つ有する脂肪族炭化水素基；芳香族炭化水素基；鎖状脂肪族飽和炭化水素基と芳香族炭化水素基とが連結された基；又はこれらの基から選択される２つ以上が直接若しくは少なくとも酸素原子を介して連結された基；であり、置換基を含んでも無置換であってもよく、そして、
ｎ₁、ｎ₂及びｎ₃は１以上の整数である。｝
で表される化合物である、上記［５］〜［７］のいずれかに記載の感光性樹脂組成物。
［９］ 以下の（１）〜（３）の工程：
（１）エポキシ基を有する化合物（ａ）、上記［１］〜［４］のいずれかに記載の光塩基発生剤を含む光塩基発生剤（ｂ）、チオール基を有する硬化剤（ｃ）、並びにカルボキシル基及び無水カルボキシル基の少なくとも一方を有する化合物（ｄ）を含有する感光性樹脂組成物を、基材に塗布して膜を形成する工程、
（２）該膜に光照射することにより、該膜中に塩基を発生させ、該膜を硬化させる工程、並びに、
（３）該膜の硬化していない部分を、アルカリ現像液により該基材から除去することにより、該基材上にパターンを形成する工程、
を含む、パターン形成された基材の製造方法。
［１０］ 上記［９］に記載の製造方法により得られる基材を備える、電子部品。 [1] The following general formula (1):

{Where
R ¹ , R ² , R ³ and R ⁴ are each independently: hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino Group, phosphinyl group, phosphono group, phosphonato group, amino group, or ammonio group; or an aliphatic hydrocarbon group having 1 to 20 carbon atoms that may contain a substituent, and 6 to 22 carbon atoms that may contain a substituent An aromatic hydrocarbon group, an alkoxy group having 1 to 20 carbon atoms which may contain a substituent, an aryloxy group which may contain a substituent, or a group in which two or more thereof are linked; and R ¹ , R ² , two or more of R ³ and R ⁴ may be bonded to form a cyclic structure;
R ⁵ and R ⁶ are each independently: hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group Or a phosphonato group; or an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 22 carbon atoms, or a substituent. An alkoxy group having 1 to 20 carbon atoms, an aryloxy group which may include a substituent, or a group in which two or more thereof are linked; and
Z is the following general formula (2) or (3):

(Where
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently: a hydrogen atom; or an aliphatic hydrocarbon group having 4 to 10 carbon atoms which may contain a substituent, and 4 to 10 carbon atoms which may contain a substituent. Or a group in which two or more of these are linked; provided that at least one of R ⁷ and R ⁸ and at least one of R ⁹ and R ¹⁰ may contain a substituent. A 4 to 10 aliphatic hydrocarbon group, an alkoxy group having 4 to 10 carbon atoms which may contain a substituent, or a group in which two or more of these are linked; and
R ¹¹ and R ¹² are each independently a C 1-6 aliphatic hydrocarbon group which may contain a substituent. )
Is a partial structure represented by }
A photobase generator represented by
[2] The photobase generator according to [1] above, wherein, in the general formula (1), Z is a partial structure represented by the general formula (2).
[3] The photobase generator according to the above [1] or [2], wherein, in the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen.
[4] The solubility at 25 ° C. in at least one solvent selected from the group consisting of methyl ethyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate, gamma butyrolactone, and methanol is 1 mass in terms of the concentration of the photobase generator in the solution. % Of the photobase generator according to any one of the above [1] to [3].
[5] Compound (a) having an epoxy group,
A photobase generator (b) comprising the photobase generator according to any one of [1] to [4] above,
A curing agent (c) having a thiol group, and a compound (d) having at least one of a carboxyl group and an anhydrous carboxyl group,
The photosensitive resin composition containing this.
[6] The photosensitive resin composition according to the above [5], wherein the compound (a) having an epoxy group is a novolac epoxy resin or a modified novolac epoxy resin.
[7] The photosensitive resin composition according to the above [5] or [6], wherein the curing agent (c) having a thiol group is a thiol carboxylate esterified product.
[8] The compound (a) having the epoxy group and the compound (d) having at least one of the carboxyl group and the anhydrous carboxyl group are both represented by the following general formula (4):

{Where
R ^a , R ^b , R ^c , R ^d and R ^e are each independently: an aliphatic hydrocarbon group having one saturated or double bond; an aromatic hydrocarbon group; a chain aliphatic saturated hydrocarbon group and an aromatic A group in which a hydrocarbon group is linked; or a group in which two or more selected from these groups are linked directly or through at least an oxygen atom; Well and
n ₁ , n ₂ and n ₃ are integers of 1 or more. }
The photosensitive resin composition in any one of said [5]-[7] which is a compound represented by these.
[9] The following steps (1) to (3):
(1) A compound (a) having an epoxy group, a photobase generator (b) containing the photobase generator according to any one of [1] to [4], a curing agent (c) having a thiol group, And a step of applying a photosensitive resin composition containing a compound (d) having at least one of a carboxyl group and an anhydrous carboxyl group to a substrate to form a film,
(2) A step of generating a base in the film by irradiating the film with light and curing the film; and
(3) A step of forming a pattern on the substrate by removing an uncured portion of the film from the substrate with an alkaline developer.
A process for producing a patterned substrate comprising:
[10] An electronic component comprising a substrate obtained by the production method according to [9].

  According to the present invention, a photobase generator excellent in affinity with various organic solvents and a polymer precursor to be combined, and a large solubility contrast between an exposed portion and an unexposed portion regardless of the type of the polymer precursor. The obtained photosensitive resin composition can be provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as this embodiment) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

｛式中、
Ｒ¹、Ｒ²、Ｒ³及びＲ⁴はそれぞれ独立に：水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、若しくはアンモニオ基；又は、置換基を含んでもよい炭素数１〜２０の脂肪族炭化水素基、置換基を含んでもよい炭素数６〜２２の芳香族炭化水素基、置換基を含んでもよい炭素数１〜２０のアルコキシ基、置換基を含んでもよいアリールオキシ基、若しくはこれらの２つ以上が連結された基（例えば、アラルキル基、アルキルアリール基、アルコキシアルキル基、アリールオキシアルキル基等）；であり、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴のうち２つ以上が結合して環状構造を形成していてもよく、
Ｒ⁵及びＲ⁶はそれぞれ独立に：水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、若しくはホスホナト基；又は、置換基を含んでもよい炭素数１〜２０の脂肪族炭化水素基、置換基を含んでもよい炭素数６〜２２の芳香族炭化水素基、置換基を含んでもよい炭素数１〜２０のアルコキシ基、置換基を含んでもよいアリールオキシ基、若しくはこれらの２つ以上が連結された基（例えば、アラルキル基、アルキルアリール基、アルコキシアルキル基、アリールオキシアルキル基等）；であり、そして、
Ｚは下記一般式（２）又は（３）：

（式中、
Ｒ⁷、Ｒ⁸、Ｒ⁹及びＲ¹⁰はそれぞれ独立に：水素原子；又は、置換基を含んでもよい炭素数４〜１０の脂肪族炭化水素基、置換基を含んでもよい炭素数４〜１０のアルコキシ基、若しくはこれらの２つ以上が連結された基；であり、但し、Ｒ⁷及びＲ⁸の少なくとも１つ並びにＲ⁹及びＲ¹⁰の少なくとも１つは、置換基を含んでもよい炭素数４〜１０の脂肪族炭化水素基、置換基を含んでもよい炭素数４〜１０のアルコキシ基、若しくはこれらの２つ以上が連結された基（例えば、アルコキシアルキル基等）であり、そして、
Ｒ¹¹及びＲ¹²はそれぞれ独立に、置換基を含んでもよい炭素数１〜６の脂肪族炭化水素基である。）
で表される部分構造である。｝
で表される光塩基発生剤を提供する。上記光塩基発生剤は、光の照射、又は光の照射と加熱とにより塩基を発生することができる。 [Photobase generator]
One embodiment of the present invention is the following general formula (1):

{Where
R ¹ , R ² , R ³ and R ⁴ are each independently: hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino Group, phosphinyl group, phosphono group, phosphonato group, amino group, or ammonio group; or an aliphatic hydrocarbon group having 1 to 20 carbon atoms that may contain a substituent, and 6 to 22 carbon atoms that may contain a substituent An aromatic hydrocarbon group, an alkoxy group having 1 to 20 carbon atoms that may contain a substituent, an aryloxy group that may contain a substituent, or a group in which two or more of these are linked (for example, an aralkyl group, an alkylaryl group, an alkoxyalkyl group, an aryloxyalkyl group or the like); a is, the R ^1, R ^2, R ³ and two or more ring structure by bonding with one of R ⁴ It may not make,
R ⁵ and R ⁶ are each independently: hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group Or a phosphonato group; or an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 22 carbon atoms, or a substituent. An alkoxy group having 1 to 20 carbon atoms, an aryloxy group which may contain a substituent, or a group in which two or more thereof are linked (for example, an aralkyl group, an alkylaryl group, an alkoxyalkyl group, an aryloxyalkyl group, etc.) And, and
Z is the following general formula (2) or (3):

(Where
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently: a hydrogen atom; or an aliphatic hydrocarbon group having 4 to 10 carbon atoms which may contain a substituent, and 4 to 10 carbon atoms which may contain a substituent. Or a group in which two or more of these are linked; provided that at least one of R ⁷ and R ⁸ and at least one of R ⁹ and R ¹⁰ may contain a substituent. A 4 to 10 aliphatic hydrocarbon group, an alkoxy group having 4 to 10 carbon atoms that may contain a substituent, or a group in which two or more of these are linked (for example, an alkoxyalkyl group); and
R ¹¹ and R ¹² are each independently a C 1-6 aliphatic hydrocarbon group which may contain a substituent. )
Is a partial structure represented by }
The photobase generator represented by these is provided. The photobase generator can generate a base by light irradiation or light irradiation and heating.

  The aliphatic hydrocarbon group is saturated or unsaturated, and is a chain (linear or branched), alicyclic, or a combination thereof. The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group may contain a substituent as long as it does not affect the reaction. Examples of the substituent include halogen, hydroxyl group, mercapto group, sulfide group, amino group, cyano group, isocyano group, cyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, ester group, carbamoyl group, and thiocarbamoyl group. Nitro group, nitroso group, carboxyl group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group and the like.

  An aromatic hydrocarbon group is a hydrocarbon group having a conjugated cyclic structure. Examples of the aromatic hydrocarbon group having 6 to 22 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, and a biphenyl group. These aromatic hydrocarbon groups may contain a substituent as long as they do not affect the reaction. Examples of the substituent include halogen, hydroxyl group, mercapto group, sulfide group, amino group, cyano group, isocyano group, cyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, ester group, carbamoyl group, and thiocarbamoyl group. Nitro group, nitroso group, carboxyl group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group and the like.

  An alkoxy group is an oxy group to which an alkyl group is bonded, and may have a linear structure or a branched structure. Examples of the alkoxy group having 1 to 10 carbon atoms are methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group and the like. Furthermore, these alkoxy groups may contain a substituent as long as they do not affect the reaction. Examples of the substituent are the same as those described for the aliphatic hydrocarbon group.

  The aryloxy group may contain a substituent as long as it does not affect the reaction, and these substituents are the same as those described for the aromatic hydrocarbon group having 6 to 22 carbon atoms. Can be mentioned.

In the present embodiment, as R ¹ , R ² , R ³ and R ⁴ , from the viewpoint of solubility in various organic solvents, a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, Preferred are an alkoxy group having 20 carbon atoms, an aromatic hydrocarbon group having 6 to 22 carbon atoms, an aryloxy group, and a group in which two or more of these are connected. Among them, a hydrogen atom and a saturated aliphatic carbon atom having 1 to 18 carbon atoms A hydrogen group, an alkoxy group having 1 to 18 carbon atoms, a phenyl group, an aryloxy group, and a group in which two or more of these are connected are preferable.

In the present embodiment, R ⁵ and R ⁶ are preferably hydrogen atoms from the viewpoint of base generation efficiency of the photobase generator.

In the present embodiment, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are preferably hydrogen atoms from the viewpoint of physical properties of the cured product.

  In the present embodiment, Z is preferably a partial structure represented by the general formula (2) from the viewpoint of solubility in various organic solvents.

In the present embodiment, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are carbons which may contain a saturated aliphatic hydrocarbon group having 4 to 10 carbon atoms and a substituent from the viewpoint of solubility in various organic solvents. An alkoxy group of 4 to 10 and a group in which two or more of these are connected are preferable, and a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a butoxy group, a pentoxy group, a hexyloxy group, a heptyloxy group, An octyloxy group is more preferred. When R ⁷ , R ⁸ , R ^9, and R ¹⁰ have such a structure, the affinity between the various organic solvents and the epoxy group-containing compound and the photobase generator is increased, and light is absorbed in the photosensitive resin composition. A sufficient amount of a base generator can be contained.

In the present embodiment, R ¹¹ and R ¹² are preferably methylene, ethylene, propene, butylene, oxymethylene, oxyethylene, oxypropene, and oxybutylene from the viewpoint of the efficiency of the photobase generator.

  The method for producing the photobase generator represented by the general formula (1) in the present embodiment is not particularly limited, and can be produced by a known method. For example, cinnamic acid having each substituent and And an amine having each substituent can be produced by reacting in a mixed solvent of dehydrated tetrahydrofuran-dichloromethane in the presence of a condensing agent such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride. it can. In addition, the cinnamic acid which has each substituent, and the amine which has each substituent may use what was manufactured by the well-known method, and may use a commercial item.

  In the present embodiment, the photobase generator has a solubility in a solution at 25 ° C. in at least one solvent selected from the group consisting of methyl ethyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate, gamma butyrolactone, and methanol. The photobase generator concentration is preferably 1% by mass or more. In this case, the photobase generator has excellent solvent solubility. The solubility is more preferably 1.5% by mass or more, and further preferably 2% by mass or more.

[Photosensitive resin composition]
Another embodiment of the present invention is a photobase generator (b) (b) comprising a compound (a) having an epoxy group (also referred to as component (a)) and the photobase generator according to one embodiment of the present invention described above. Component)), a compound having a thiol group (c) (also referred to as (c) component), and a compound (d) having at least one of a carboxyl group and an anhydrous carboxyl group (also referred to as (d) component). A functional resin composition is provided.

((A) component)
There is no restriction | limiting in particular in the kind as compound (a) which has an epoxy group which can be used for the photosensitive resin composition of this Embodiment, For example, an epoxy resin and an epoxy resin modified material are mentioned.

  As the epoxy resin, known ones can be used, for example, glycidyl ether of dihydric phenol, polyglycidyl ether of polyhydric phenol having 3 to 6 or more hydroxy groups, aliphatic dihydric alcohol. Glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, aliphatic skeleton or alicyclic skeleton such as diglycidyl ether, polyglycidyl ether of aliphatic polyhydric alcohol having 3 to 6 or more hydroxy groups Glycidyl ester of polycarboxylic acid having, glycidyl amine of aromatic amine having active hydrogen atom, glycidyl amine of alicyclic amine having active hydrogen atom, glycidyl amine of heterocyclic amine having active hydrogen atom, chain Alicyclic epoxides, alicyclic epoxides, etc. It is.

  Examples of the glycidyl ethers of the dihydric phenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, and catechin diether. Glycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4′-dihydroxyphenyl diglycidyl ether, tetramethylbiphenyl diglycidyl ether, 9 , 9'-bis (4-hydroxyphenyl) fluorenediglycidyl ether, and bisphenol Diglycidyl ethers obtained from the reaction of Le A2 moles and 3 moles of epichlorohydrin and the like.

  Examples of polyglycidyl ethers of polyhydric phenols having 3 to 6 or more hydroxy groups include pyrogallol triglycidyl ether, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, di Naphthyltriglycidyl ether, tetrakis (4-hydroxyphenyl) ethanetetraglycidyl ether, p-glycidylphenyldimethyltolylbisphenol A glycidyl ether, trismethyl-tert-butyl-butylhydroxymethane triglycidyl ether, 4,4′-oxybis (1, 4-phenylethyl) tetracresol glycidyl ether, 4,4′-oxybis (1,4-phenylethyl) phenylglycidyl ether, biphenyl (Dihydroxynaphthalene) tetraglycidyl ether, glycidyl ether of phenol or cresol novolac resin, glycidyl ether of limonene phenol novolak resin, polyglycidyl ether of polyphenol obtained by condensation reaction of phenol and glioxal, glutaraldehyde or formaldehyde, and resorcin Examples thereof include polyglycidyl ethers of polyphenols obtained by a condensation reaction with acetone. The average number of epoxy groups is 2 to 10 and the softening point is preferably room temperature or higher from the viewpoint of the tackiness of the coating film. The average number of epoxy groups can be determined by dividing the average molecular weight determined by gel permeation chromatography (GPC) by the epoxy equivalent determined in accordance with JIS K7236. The softening point can be determined according to the ring and ball method and JIS K7234.

  Examples of the diglycidyl ether of the aliphatic dihydric alcohol include, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and polyethylene glycol diglycidyl ether. , Polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and diglycidyl ether of an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A.

  Examples of the polyglycidyl ether of the aliphatic polyhydric alcohol having 3 to 6 or more hydroxy groups include, for example, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether. And polyglycerol polyglycidyl ether.

  Examples of the glycidyl ester type epoxy resin include glycidyl esters of aromatic polycarboxylic acids such as phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, trimellitic acid triglycidyl ester, and the like. .

  Examples of the glycidyl ester of a polycarboxylic acid having an aliphatic skeleton or an alicyclic skeleton include, for example, an aromatic nucleus hydrogenated product of a glycidyl ester of an aromatic polycarboxylic acid, diglycidyl oxalate, diglycidyl oxalate, dimer acid. Examples thereof include glycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate, (co) polymer of glycidyl (meth) acrylate, and tricarbyl acid triglycidyl ester.

  Examples of the glycidylamines of the aromatic amines having an active hydrogen atom include N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′, N Examples include '-tetraglycidyldiaminodiphenylsulfone, N, N, N', N'-tetraglycidyldiethyldiphenylmethane, and N, N, O-triglycidylaminophenol.

  Examples of the alicyclic amine glycidylamine having an active hydrogen atom include hydrogenated N, N, N ′, N′-tetraglycidylxylylenediamine.

  Examples of the glycidylamines of the heterocyclic amines having an active hydrogen atom include trisglycidylmelamine.

  Examples of the chain aliphatic epoxide include epoxidized butadiene and epoxidized soybean oil.

  Examples of the alicyclic epoxide include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, and 3,4-epoxy. -6-methylcyclohexylmethyl-3 ', 4'-epoxy 6'-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3,4-epoxy-6-methyl) (Cyclohexylmethyl) butylamine.

  In the present embodiment, as the compound (a) having an epoxy group, one kind may be used alone, or two or more kinds may be used in combination. From the viewpoint of the performance and availability of the obtained cured product, the compound (a) having an epoxy group is preferably a glycidyl ether type epoxy resin or a glycidyl ester type epoxy resin, and more preferably a glycidyl ether type epoxy resin. On the other hand, when importance is attached to the tackiness of the photosensitive resin composition, the compound (a) having an epoxy group is preferably a novolak type epoxy resin or a modified novolak type epoxy resin, and the softening point temperature is room temperature or higher. A certain novolac type epoxy resin is still more preferable.

  The epoxy resin-modified product is not particularly limited as long as a part of the epoxy group of the epoxy resin is modified. The modified epoxy resin is, for example, in the first reaction, a hydroxyl group is formed by addition reaction of a carboxyl group and an epoxy group of a monocarboxylic acid in an amount corresponding to 10 to 70 mol% of the epoxy equivalent of the epoxy resin, What is obtained by half-esterifying the produced | generated or introduce | transduced hydroxy group and acid anhydride by 2nd reaction is mentioned. The monocarboxylic acid used here is not particularly limited, and examples thereof include acetic acid, propionic acid, butanoic acid, (meth) acrylic acid, cinnamic acid, cyanocinnamic acid, monomethylolpropane, dimethylolpropionic acid, and monomethylolbutane. An acid, dimethylol butanoic acid, etc. are mentioned. These monocarboxylic acids may be used alone or in combination of two or more.

  The solvent used in the first reaction is not particularly limited as long as it does not adversely affect the reaction. For example, a solvent having no hydroxyl group can be used. Specifically, ketones such as acetone, ethyl methyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene, and tetramethylbenzene; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, and dipropylene Glycol ethers such as diethyl ether; esters such as ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, Petroleum solvents such as solvent naphtha can be used.

  In the reaction, it is preferable to use a catalyst in order to accelerate the reaction. The catalyst is not particularly limited. For example, triethylamine, benzyldimethylamine, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine Methyltriphenyl stibine, chromium octoate, zirconium octoate and the like. As for the usage-amount of a catalyst, it is more preferable that it is 0.1-10 mass% of a reaction raw material mixture.

  The reaction conditions for the first reaction are not particularly limited, but the reaction temperature is usually 60 to 150 ° C. and the reaction time is 5 to 60 hours.

  The acid anhydride used in the second reaction is not particularly limited, and for example, one or two kinds from succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride and the like. These can be used in combination.

  Among the modified epoxy resins, a glycidyl ether type epoxy resin modified product or a glycidyl ester type epoxy resin modified product is preferable, and a glycidyl ether type epoxy resin modified product is more preferable. In consideration of the curing performance of the photosensitive resin composition, the physical properties and tackiness of the resulting cured product, a novolak-type epoxy resin-modified product is more preferable, and a novolak-type epoxy resin-modified product having a softening point temperature of room temperature or higher is even more preferable. preferable.

  The compound (a) having an epoxy group may be a compound further having at least one of a carboxyl group and an anhydrous carboxyl group. In this case, this compound serves as both the component (a) and the component (d) in the present embodiment.

((B) component)
The photosensitive resin composition of this Embodiment contains the photobase generator (b) containing the photobase generator which concerns on 1 aspect of this invention mentioned above. The photobase generator (b) may be composed of one or more photobase generators according to one aspect of the present invention, and contains one or more additional photobase generators. May be. The additional photobase generator is not particularly limited as long as it is a known one. For example, benzyl type photodeprotecting group type (for example, those described in J. Org. Chem., 55 (1990) 5919) Norrish Type II (e.g., as described in J. Chem. Soc., Perkin Trans. I, 1975, 1069), Norrish Type I (e.g., J. Am. Chem. Soc., 118 (1996) 12925). Described), amine imide types (for example, those described in J. Polym. Sci. Polym. Chem., 40 (2002) 4045), urethane oxime types (for example, J. Photopolym. Sci. Technol. 18). (2005) 141), Alki Oxime type (for example, those described in J. Photochem. Photobiol. A: Chem. 151 (2002) 27), “IRUGACURE907” manufactured by BASF, 2-aminotropone type (for example, pamphlet of International Publication No. 2008/072651) And the like). From the viewpoint of curing performance and the absence of symbiosis with carbon dioxide, it is preferable to use 2-aminotropone or a derivative thereof.

  Although the compounding quantity of a photobase generator (b) is not restrict | limited in particular, Usually, 0.001-100 mass parts with respect to 100 mass parts of compounds (a) which have an epoxy group, Preferably 0.005-80 mass parts, More preferably, it is 0.01-50 mass parts. The blending amount is preferably 0.001 part by mass or more from the viewpoint of obtaining a sufficiently practical curing rate, and preferably 100 parts by mass or less from the viewpoint of physical properties of the cured product. In the photobase generator (b), the content of the photobase generator according to one embodiment of the present invention described above is preferably 50 to 100% by mass.

(Component (c))
The photosensitive resin composition of this Embodiment contains the hardening | curing agent (c) which has a thiol group. By containing this, the photosensitive resin composition in which the photobase generator (b) coexists exhibits high curing performance. Conventionally, a cured product mainly composed of an epoxy resin is hard, brittle, and easily peelable. However, a cured product of a photosensitive resin composition containing a curing agent (c) having a thiol group. These physical properties are desirable in terms of elongation and the like. Therefore, such a photosensitive resin composition is suitable as an insulating material for printed wiring boards and semiconductors in the field of electronic materials.

  As the curing agent (c) having a thiol group, polythiol is preferable from the viewpoint of curing performance. The polythiol is not particularly limited as long as it is a known one, and examples thereof include alkylthiol compounds having 1 to 20 carbon atoms and 2 to 6 or more functional groups. Examples of such alkylthiol compounds include 1,4-butanedithiol and 1,8-octanedithiol. As a compound having a thiol group other than those, for example, a thiol obtained by reaction of polyoxide and hydrogen sulfide, a thiol carboxylic acid having 2 to 20 carbon atoms and having 2 to 3 or more functional groups (for example, Thiol acetic acid, thiol propionic acid, thiol butyric acid, thiol hexanoic acid, thiol octanoic acid, and thiol stearic acid) and esterified products (thiol carboxylic acid esterified products) of 2 to 30 carbon atoms and polyols having 2 to 6 functional groups. It is done. Among them, a thiol carboxylic acid ester is preferable from the viewpoint of the performance and availability of the cured product. Specifically, trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa Examples include kiss (3-mercaptopropionate), pentaerythritol tetrakisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthioglycolate, and the like.

  The range of (number of moles of thiol group in curing agent (c) having thiol group) ÷ (number of moles of photobase generator (b)) is 20.1 from the viewpoint of the curing rate of the photosensitive resin composition. Is preferably less than 6.7, more preferably less than 6.7. At the same time, the molar ratio of the thiol group to the total of epoxy groups contained in the compound (a) having an epoxy group and the compound (d) having at least one of a carboxyl group and an anhydrous carboxyl group described later is the physical property of the cured product. In view of the above, it is preferably in the range of 1.5 to 0.5, more preferably in the range of 1.2 to 0.8.

(Component (d))
The compound (d) having at least one of a carboxyl group and an anhydrous carboxyl group that can be used in the photosensitive resin composition of the present embodiment is one having at least one of a carboxyl group and an anhydrous carboxyl group in the molecule. There is no particular limitation. The component (d) may be a compound further having an epoxy group. In this case, as described above, the compound serves as both the component (a) and the component (d) in the present embodiment.

  The type of the compound (d) having at least one of a carboxyl group and an anhydrous carboxyl group is not particularly limited. For example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, fumaric acid, sorbic acid, Examples thereof include ionomers and monocarboxylic acids obtained by copolymerizing a monomer component containing an unsaturated monomer containing a carboxy group in advance, such as cinnamic acid. Examples of the monocarboxylic acid include acetic acid, propionic acid, butanoic acid, (meth) acrylic acid, cinnamic acid, cyanocinnamic acid, monomethylolpropane, dimethylolpropionic acid, monomethylolbutanoic acid, dimethylolbutanoic acid and the like. It is done. Among these, preferred specific examples include polyacrylic acid, polymethacrylic acid, polyglutamic acid and the like, polyacrylic acid and polymethacrylic acid are more preferred, and polymethacrylic acid is still more preferred.

｛式中、
Ｒ^a、Ｒ^b、Ｒ^c、Ｒ^d及びＲ^eはそれぞれ独立に：飽和若しくは二重結合を１つ有する脂肪族炭化水素基；芳香族炭化水素基；鎖状脂肪族飽和炭化水素基と芳香族炭化水素基とが連結された基；又はこれらの基から選択される２つ以上が直接若しくは少なくとも酸素原子を介して連結された基；であり、置換基を含んでも無置換であってもよく、そして、
ｎ₁、ｎ₂及びｎ₃は１以上の整数である。｝
で表される化合物であることが好ましい。Ｒ^a及びＲ^bは３価の基であり、Ｒ^cは２〜４価の基であり、そしてＲ^d及びＲ^eは２価の基である。 From the viewpoint of the physical properties of the cured product, a compound having a structure of at least one of a carboxyl group and an anhydrous carboxyl group and an epoxy group in one molecule (that is, corresponds to component (a) and component (d) Are also preferred. As an example, the components (a) and (d) are both represented by the following general formula (4):

{Where
R ^a , R ^b , R ^c , R ^d and R ^e are each independently: an aliphatic hydrocarbon group having one saturated or double bond; an aromatic hydrocarbon group; a chain aliphatic saturated hydrocarbon group and an aromatic A group in which a hydrocarbon group is linked; or a group in which two or more selected from these groups are linked directly or through at least an oxygen atom; Well and
n ₁ , n ₂ and n ₃ are integers of 1 or more. }
It is preferable that it is a compound represented by these. R ^a and R ^b are trivalent groups, R ^c is a divalent to tetravalent group, and R ^d and R ^e are divalent groups.

Examples of the substituent in the case where R ^a , R ^b , R ^c , R ^d, and R ^e include a substituent include a halogen group, a carboxyl group, and a hydroxyl group. Examples of the halogen group include a fluoro group, a chloro group, a bromo group, and an iodo group. Among these, a fluoro group, a chloro group, and a bromo group are preferable from the viewpoint of physical properties of the cured product.

  The saturated aliphatic hydrocarbon group is a chain group, a cyclic group, or a group in which two or more of these are linked. Examples of the chain group include groups derived from alkanes such as methane, ethane, n-propane, isopropane, n-butane, isobutane, and tert-butane (that is, a hydrogen atom is extracted from the alkane). . Among these, a group derived from methane or ethane is preferable from the viewpoint of physical properties of the cured product. Examples of the cyclic group include groups derived from cycloalkanes such as cyclopropane, 2-methylcyclopropane, and cyclohexane. Among these, a group derived from cyclohexane is preferable from the viewpoint of physical properties of the cured product.

  The aliphatic hydrocarbon having one double bond is a chain group, a cyclic group, or a group in which two or more of these are linked. Examples of the chain group include ethylene, n-propene, isopropene, n-butene, isobutene, 2-methylpropene, 1-methyl-1-butene, 3-methyl-1-butene, and 1,1-dimethyl-2. -Groups derived from alkenes such as propene, 1-pentene and the like. Among these, a group derived from ethylene, n-propene, or isopropene is preferable from the viewpoint of physical properties of the cured product. Examples of the cyclic group include groups derived from cycloalkene such as cyclohexene, cyclopentene, norbornene and the like. Among these, a group derived from cyclohexene is preferable from the viewpoint of physical properties of the cured product.

  Examples of the aromatic hydrocarbon group include groups derived from benzene, naphthalene, anthracene, phenanthrene, tetracene, pyrene, and perylene. Among these, a group derived from benzene or naphthalene is preferable from the viewpoint of physical properties of the cured product.

Examples of the group in which the chain aliphatic saturated hydrocarbon group and the aromatic hydrocarbon group are linked are derived from toluene, phenylalkane, biphenylalkane, naphthylalkane and the like (that is, 2 from these alkane moieties). Group having a structure in which up to 4 hydrogen atoms are extracted). Among these, a group derived from phenyl-C ₁₆ alkane or biphenyl-C ₁₆ alkane is preferable, and a group derived from toluene is more preferable from the viewpoint of physical properties of the cured product.

  Examples of the linkage via at least an oxygen atom include linkage by a functional group such as an ether group, an ester group, and an alkyleneoxy group. Among these, an ether bond and an alkyleneoxy bond are preferable from the viewpoint of physical properties of the cured product.

n ₁ and n ₂ are integers of 1 or more, and represent the number of repeating units of R ^a and R ^b , respectively. n ₁ and n ₂ are preferably 1 to 50 and more preferably 2 to 20 from the viewpoint of physical properties of the cured product. n ₂ is preferably 1 to 20 and more preferably 1 to 5 from the viewpoint of alkali solubility.

n ₃ is an integer of 1 or more and defines the valence of R ^c . n ₃ is preferably 1 to 3, more preferably 1 to 2, from the viewpoints of alkali solubility and physical properties of the cured product.

  In this embodiment, as the component (d), the above-described compounds can be used alone or in combination of two or more.

  When the component (d) is used separately from the component (a), the weight average molecular weight of the component (d) is not particularly limited, but is 100 to 1,000,000 from the viewpoint of alkali solubility and physical properties of the cured product. Is preferred. Further, the ratio of the carboxyl group-containing unit contained in the molecule of the component (d) is not particularly limited as long as the solubility in the alkali developer is ensured, but the repeating unit in the molecular chain is not limited. Of these, 10 mol% or more is preferable, 15 mol% or more is more preferable, and 20 mol% or more is more preferable.

In this Embodiment, it is preferable that the usage-amount of the compound which has a carboxyl group as (d) component satisfy | fills the relationship of following formula (i) from an alkali developability viewpoint.
0.02 ≦ (total number of moles of carboxyl groups of component (a) and component (d)) ÷ (total number of moles of epoxy groups of component (a) and component (d)) ≦ 2 (i)

  For example, when using a compound which is both the component (a) and the component (d), the molar ratio of the carboxyl group to the epoxy group in the compound is preferably in the range of 0.02 to 2. From the viewpoint of alkali developability, the molar ratio is preferably 0.02 or more, more preferably 0.08 or more, and still more preferably 0.18 or more. The molar ratio is preferably 2 or less, more preferably 1.50 or less, and still more preferably 1.20 or less, from the viewpoint of the physical properties of the cured product. In addition, about an anhydrous carboxyl group, the said anhydrous carboxyl group 1 mol calculates as what has 2 mol of carboxyl groups.

  In addition to the components (a) to (d) described above, the photosensitive resin composition in the present embodiment includes an inorganic filler, a colorant, a polymerization inhibitor, a thickener, an antifoaming agent, a leveling agent, and adhesiveness. Additives, photoradical initiators, and other additives can be blended alone or in combination of two or more as required. When the additive is blended, the total amount is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of component (a).

  Examples of the inorganic filler include known ones such as barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, talc, clay, magnesium carbonate, aluminum oxide, aluminum hydroxide, and mica. It is used for the purpose of improving various physical properties such as adhesion between the cured product and the substrate and hardness of the cured product.

  Examples of the colorant include phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, and the like.

  Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, and fethiazine.

  Examples of the thickener include asbestos, olben, benton, montmorillonite and the like.

  Further, the photosensitive resin composition of the present embodiment may contain a known compound having a hydroxy group. Such a compound contributes to the acceleration of the curing reaction of the compound having an epoxy group.

Another aspect of the present invention is the following steps (1) to (3):
(1) Compound (a) having epoxy group, photobase generator (b) including photobase generator according to one embodiment of the present invention, curing agent (c) having thiol group, carboxyl group and anhydrous Applying a photosensitive resin composition containing a compound (d) having at least one of carboxyl groups to a substrate to form a film;
(2) A step of generating a base in the film by irradiating the film with light and curing the film; and
(3) A step of forming a pattern on the substrate by removing an uncured portion of the film from the substrate with an alkaline developer.
A method for producing a patterned substrate comprising:

  In this Embodiment, the patterned base material can be manufactured using the photosensitive resin composition mentioned above. According to the above method, basicity can be expressed without exposure to carbon dioxide gas or the like by exposure, so that a fine pattern can be easily and easily formed on a substrate.

  The substrate on which the photosensitive resin composition is applied is not particularly limited, and specific examples thereof include, for example, polyester-based substrates such as polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate, and condensation type polyimide. Polyimide base materials such as addition type polyimide, high temperature addition type polyimide, epoxy resin base materials such as BA type epoxy resin, BF type epoxy resin, phenoxy resin, phenol novolac resin, cresol novolac resin, phenol such as polyhydroxystyrene Resin base materials, polyolefin base materials such as polyethylene, polypropylene, polystyrene, polycycloolefin, etc., nylon 6,6, nylon 6, nylon 6, T, nylon 4,6, nylon 12, nylon 6,12, etc. In addition to base materials such as polyurethane, polycarbonate, polyacetal, polyphenylene ether, poly (meth) acrylate, acrylonitrile-butadiene-styrene copolymer, polyphenylene sulfide, polyether ether ketone, polyether imide Base materials such as polyethylene, polyethersulfone and polybenzoxazole, resin bases reinforced with glass fibers, etc., metal systems such as Cu, Ag, Au, Ni, Pd, Co, Rh, Fe, In and Sn Examples include base materials. The photosensitive resin composition of the present embodiment does not necessarily require a sintering process at a high temperature when formed as a film on a substrate. Therefore, the heat resistance of the substrate is not limited. Therefore, various resins as described above can be used as the base material.

  In the present embodiment, the form of the substrate is not particularly limited, and specific examples thereof include, for example, films, sheets, tapes, fine particles, laminates, three-dimensional molded products, and Cu, Ag, Au, Ni, Examples thereof include a printed wiring board, a film, a tape, and the like obtained by patterning a metal such as Pd, Co, Rh, Fe, In, and Sn.

  In the present embodiment, the method for applying the photosensitive resin composition to the substrate is not particularly limited, and specific examples thereof include, for example, an inkjet method, a spray method, a spin coating method, a roll coating method, and an electrostatic coating method. And publicly known methods such as curtain coating, flexographic printing, gravure printing, offset printing, gravure offset printing, and screen printing. Among these, the flexographic printing method and the gravure printing method are preferable. By applying the photosensitive resin composition to the substrate by these printing methods, a protective film having a thickness suitable for patterning can be formed with high positional accuracy.

  When the photosensitive resin composition of the present embodiment is applied to a substrate, the photosensitive resin composition of the present embodiment can be dissolved in an organic solvent to obtain a photosensitive resin composition solution. The organic solvent is not particularly limited. For example, ethers represented by diethyl ether, tetrahydrofuran, dioxane and the like; glycol monoethers represented by ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether and the like ( So-called cellosolves); ketones typified by methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone; typified by ethyl acetate, butyl acetate, n-propyl acetate, i-propyl acetate, propylene glycol monomethyl ether acetate, etc. Esters: alcohols such as methanol, ethanol, isopropanol, butanol, cyclohexanol, ethylene glycol, and glycerin Halogenated hydrocarbons represented by methylene chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, chlorobenzene; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl Amides represented by pyrrolidone and the like; Lactones represented by γ-butyrolactone; Sulfoxides represented by dimethyl sulfoxide; Chain or cyclic saturated hydrocarbons represented by hexane, cyclohexane and heptane; Other organic polarities And solvents. Furthermore, examples of the organic solvent include aromatic hydrocarbons represented by benzene, toluene, and xylene; and other organic nonpolar solvents. These organic solvents are used alone or in combination of two or more. Among these, amides, lactones, sulfoxides, esters, ketones, and alcohols are preferable because the solubility of the photobase generator tends to be good.

  The amount of the organic solvent added is appropriately selected so that, for example, when the photosensitive resin composition is applied onto a substrate and a coating film of the photosensitive resin composition is formed, the organic solvent is uniformly applied. However, it is preferably in the range of 0.1 to 200 parts by weight, more preferably in the range of 1 to 150 parts by weight, and most preferably from 10 parts by weight with respect to 100 parts by weight of the photosensitive resin composition. The range is 100 parts by mass.

The photosensitive resin composition of the present embodiment is cured by being subjected to only light irradiation, by being simultaneously subjected to light irradiation and heating, or by being heated after light irradiation. To do. In this embodiment mode, heating is not necessarily required, but it is preferable to heat appropriately depending on desired physical properties, pattern shape, and the like. The light irradiation is preferably performed using irradiation light in a wavelength region of 150 to 750 nm. More specifically, using a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp and / or a metal hydride lamp as a light source, light irradiation is performed at an irradiation dose of 0.01 to 100 J / cm ^2. Thus, the photosensitive resin composition can be efficiently cured. The light irradiation is preferably performed at a dose of 0.05 to 20 J / cm ² using irradiation light in a wavelength range of 300 to 500 nm. The atmosphere for light irradiation may be in air or in an inert gas, but is preferably in an inert gas, more preferably a nitrogen gas atmosphere.

  In addition, the heating temperature in the case of heating is not particularly limited as long as it is a temperature below the decomposition point of the photosensitive resin composition of the present embodiment, and is usually preferably 30 to 400 ° C, and preferably 50 to A temperature of 300 ° C. is more preferable. The heating time in the case of heating is preferably 1 second to 3 hours, and more preferably 30 seconds to 1 hour in order to perform curing more sufficiently. The atmosphere for heating may be in air or in an inert gas.

  In the present embodiment, a pattern can be formed by dissolving and removing an uncured portion of the film (that is, a portion that has not been insolubilized) from the base material with an alkali developer (pattern forming step).

  Examples of the alkali developer that can be used in the present embodiment include organic alkali compounds and inorganic alkali compounds. Since these can be used as an alkaline aqueous solution, they have the advantage of being environmentally friendly.

  Examples of the organic alkali compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, di-n- Examples include propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, and triethanolamine.

  Examples of inorganic alkali compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate, Examples thereof include lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, and ammonia.

  Further, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a storage stabilizer, a resin dissolution inhibitor, and the like can be added to the alkaline aqueous solution.

  Another aspect of the present invention provides an electronic component including a base material obtained by the manufacturing method according to one aspect of the present invention described above. The patterned substrate obtained by the above-mentioned method can form a fine pattern compared to a substrate patterned by, for example, screen printing, and compared with a substrate using a non-photosensitive insulating material. Therefore, the man-hours can be reduced and there is an advantage that it is simple. Such a base material can be suitably used as an electronic component such as a flexible wiring board or an IC tag antenna circuit board. More specifically, antenna circuits for RFID IC tags, printed wiring board circuits such as flexible, rigid, rigid flex, etc., fine wiring for electromagnetic shielding, semiconductor wiring, transistor wiring, capacitor wiring, resistor wiring Wiring and electrodes for batteries, wiring and electrodes for organic EL displays, wiring and electrodes for inorganic EL displays, wiring and electrodes for digital signage, wiring and electrodes for electronic paper, wiring and electrodes for liquid crystal displays, wiring and electrodes for plasma displays It can be applied to uses such as wiring and electrodes for surface emitting lighting such as organic EL.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. In addition, the chemical structure of the produced photobase generator was confirmed by 1H NMR measurement.

で表される塩基発生剤（１）を収率７６％で得た。
¹H NMR (400 MHz, CDCl₃, 22.5 ^oC) δ 8.51 (br, 1H, OH), 8.45 (d, J = 15.6 Hz, 1H, CH=CHCO), 7.42-7.08 (m, 12H, aromatic), 6.96-6.72 (m, 3H, aromatic and CH=CHCO), 4.74 (s, 2H, NCH), 4.61 (s, 2H, NCH). (Production Example 1: Synthesis of photobase generator (1))
In a 300 mL eggplant flask, 2.47 g of o-coumaric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 50 g of a mixed solvent of dehydrated tetrahydrofuran-dichloromethane (mass ratio 1: 1), and 1-ethyl-3- 2.80 g of (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred. After adding 2.47 g of dibenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.), the reaction solution was stirred for 4 hours while returning to room temperature. The reaction solution was concentrated using a rotary evaporator, dissolved in toluene, and washed successively with an aqueous sodium hydroxide solution, dilute hydrochloric acid, a saturated aqueous sodium bicarbonate solution, and brine. Anhydrous magnesium sulfate was added to the extract and allowed to stand for 1 hour, and the solid content was removed by filtration, followed by concentration with a rotary evaporator. The obtained solid was recrystallized in a hexane-ethyl acetate mixed solvent to obtain the following chemical formula (5):

The base generator (1) represented by the formula was obtained in a yield of 76%.
¹ H NMR (400 MHz, CDCl ₃ , 22.5 ^o C) δ 8.51 (br, 1H, OH), 8.45 (d, J = 15.6 Hz, 1H, CH = CHCO), 7.42-7.08 (m, 12H, aromatic) , 6.96-6.72 (m, 3H, aromatic and CH = CHCO), 4.74 (s, 2H, NCH), 4.61 (s, 2H, NCH).

で表される光塩基発生剤（２）を収率６３％で得た。
¹H NMR (400 MHz, CDCl₃, 22.5 ^oC) δ 10.00 (br, 1H, OH), 7.70 (d, J = 15.6 Hz, 1H, CH=CHCO), 7.57 (d, J = 7.8 Hz, 1H, aromatic), 7.17 (t, J = 7.3 Hz, 1H, aromatic), 7.09 (d, J = 15.6 Hz, 1H, CH=CHCO), 6.88 (d, J = 7.8 Hz, 1H, aromatic), 6.81 (t, J = 7.8 Hz, 1H, aromatic), 3.46-3.36 (m, 4H, NCH₂), 1.70-1.46 (m, 4H, NCH₂CH₂CH₂), 1.35 (dd, J = 14.1, 7.3 Hz, 4H, CH₂CH₂CH₃), 0.94 (t, J = 6.8 Hz, 6H, CH₃). (Production Example 2: Synthesis of photobase generator (2))
The following chemical formula (6) was obtained in the same manner as in Production Example 1 except that dibutylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of dibenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) in Production Example 1. ):

A photobase generator (2) represented by the formula:
¹ H NMR (400 MHz, CDCl ₃ , 22.5 ^o C) δ 10.00 (br, 1H, OH), 7.70 (d, J = 15.6 Hz, 1H, CH = CHCO), 7.57 (d, J = 7.8 Hz, 1H , aromatic), 7.17 (t, J = 7.3 Hz, 1H, aromatic), 7.09 (d, J = 15.6 Hz, 1H, CH = CHCO), 6.88 (d, J = 7.8 Hz, 1H, aromatic), 6.81 ( t, J = 7.8 Hz, 1H, aromatic), 3.46-3.36 (m, 4H, NCH ₂ ), 1.70-1.46 (m, 4H, NCH ₂ CH ₂ CH ₂ ), 1.35 (dd, J = 14.1, 7.3 Hz , 4H, CH ₂ CH ₂ CH ₃ ), 0.94 (t, J = 6.8 Hz, 6H, CH ₃ ).

で表される光塩基発生剤（３）を収率６９％で得た。
¹H NMR (400 MHz, CDCl₃, 22.5 ^oC) δ 8.24 (d, J = 15.6 Hz, 1H, CH=CHCO), 7.42 (d, J = 7.8 Hz, 1H, aromatic), 7.27-7.14 (m, 3H, aromatic and CH=CHCO), 6.92 (d, J = 7.8 Hz, 1H, aromatic), 6.85-6.81 (m, 2H, aromatic), 3.46-3.35 (m, 4H, NCH₂), 1.70-1.56 (m, 4H, NCH₂CH₂CH₂), 1.40-1.24 (m, 12H, CH₂CH₂CH₂CH₂CH₃), 0.89 (t, J = 6.8 Hz, 6H, CH₃). (Production Example 3: Synthesis of photobase generator (3))
Except for using dihexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of dibenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) in Production Example 1, the same chemical formula (7 ):

A photobase generator (3) represented by the formula:
¹ H NMR (400 MHz, CDCl ₃ , 22.5 ^o C) δ 8.24 (d, J = 15.6 Hz, 1H, CH = CHCO), 7.42 (d, J = 7.8 Hz, 1H, aromatic), 7.27-7.14 (m , 3H, aromatic and CH = CHCO), 6.92 (d, J = 7.8 Hz, 1H, aromatic), 6.85-6.81 (m, 2H, aromatic), 3.46-3.35 (m, 4H, NCH ₂ ), 1.70-1.56 (m, 4H, NCH ₂ CH ₂ CH ₂ ), 1.40-1.24 (m, 12H, CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ), 0.89 (t, J = 6.8 Hz, 6H, CH ₃ ).

で表される光塩基発生剤（４）を収率６８％で得た。
¹H NMR (400 MHz, CDCl₃, 22.5 ^oC) δ 8.07 (d, J = 15.6 Hz, 1H, CH=CHCO), 7.87 (br, 1H, OH), 7.43 (d, J = 7.8 Hz, 1H, aromatic), 7.25-7.15 (m, 2H, aromatic), 7.04 (d, J = 15.6 Hz, 1H, CH=CHCO), 6.89-6.84 (m, 2H, aromatic), 3.73-3.60 (m, 8H, CH₂OCH₂), 3.52-3.47 (m, 4H, NCH₂), 1.19 (t, J = 6.8 Hz, 6H, CH₃). (Production Example 4: Synthesis of photobase generator (4))
The same procedure as in Production Example 1 was conducted except that bis (2-ethoxyethyl) amine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of dibenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) in Production Example 1. The following chemical formula (8):

A photobase generator (4) represented by the formula:
¹ H NMR (400 MHz, CDCl ₃ , 22.5 ^o C) δ 8.07 (d, J = 15.6 Hz, 1H, CH = CHCO), 7.87 (br, 1H, OH), 7.43 (d, J = 7.8 Hz, 1H , aromatic), 7.25-7.15 (m, 2H, aromatic), 7.04 (d, J = 15.6 Hz, 1H, CH = CHCO), 6.89-6.84 (m, 2H, aromatic), 3.73-3.60 (m, 8H, CH ₂ OCH ₂ ), 3.52-3.47 (m, 4H, NCH ₂ ), 1.19 (t, J = 6.8 Hz, 6H, CH ₃ ).

で表される光塩基発生剤（５）を収率５８％で得た。
¹H NMR (400 MHz, CDCl₃, 22.5 ^oC) δ 8.52 (br, 1H, OH), 8.09 (d, J = 15.6 Hz, 1H, CH=CHCO), 7.40 (d, J = 7.8 Hz, 1H, aromatic), 7.31-7.11 (m, 6H, aromatic), 6.93-6.89 (m, 2H, aromatic and CH=CHCO), 6.83 (t, J = 7.3 Hz, 1H, aromatic), 4.73 (d, J = 11.7Hz, 1H, NCH), 4.08 (d, J = 11.7 Hz, 1H, NCH), 3.02, (t, J = 12.7 Hz, 1H, NCH), 2.63 (t, J = 12.7 Hz, 1H, NCH), 2.54 (t, J = 6.3 Hz, 2H, CH₂Ph), 1.86-1.56 (m, 4H, CH₂CHCH₂), 1.48-1.20 (m, 1H, CH₂CHCH₂). (Production Example 5: Synthesis of photobase generator (5))
The following chemical formula was obtained in the same manner as in Production Example 1 except that 4-benzylpiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of dibenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.) in Production Example 1. (9):

A photobase generator (5) represented by the formula:
¹ H NMR (400 MHz, CDCl ₃ , 22.5 ^o C) δ 8.52 (br, 1H, OH), 8.09 (d, J = 15.6 Hz, 1H, CH = CHCO), 7.40 (d, J = 7.8 Hz, 1H , aromatic), 7.31-7.11 (m, 6H, aromatic), 6.93-6.89 (m, 2H, aromatic and CH = CHCO), 6.83 (t, J = 7.3 Hz, 1H, aromatic), 4.73 (d, J = 11.7Hz, 1H, NCH), 4.08 (d, J = 11.7 Hz, 1H, NCH), 3.02, (t, J = 12.7 Hz, 1H, NCH), 2.63 (t, J = 12.7 Hz, 1H, NCH) , 2.54 (t, J = 6.3 Hz, 2H, CH ₂ Ph), 1.86-1.56 (m, 4H, CH ₂ CHCH ₂ ), 1.48-1.20 (m, 1H, CH ₂ CHCH ₂ ).

で表される比較光塩基発生剤（１）及び（２）を合成した。 (Comparative Production Examples 1 and 2: Synthesis of Comparative Photobase Generators (1) and (2))
As comparative photobase generators (1) and (2), the following chemical formulas (10) and (11) are described in accordance with the description in Patent Document 7 (Japanese Patent Laid-Open No. 2010-106233):

Comparative photobase generators (1) and (2) represented by

で表される化合物を得た。 (Production Example 6: Synthesis of modified epoxy resin)
Cresol-Novolac type epoxy resin (trade name “ECN1299” manufactured by Asahi Kasei Chemicals Corporation, epoxy equivalent 225 (g / eq), average number of epoxy groups 5.4, softening point 92 ° C.) 53 parts by mass, 2,2-bis 9.8 parts by mass of (hydroxymethyl) propionic acid, 37.2 parts by mass of 2- (2-butoxyethoxy) ethyl acetate, and 0.28 parts by mass of triphenylphosphine were dissolved and reacted at 100 ° C. for 16 hours in a nitrogen atmosphere I let you. After confirming that the residual amount of 2,2-bis (hydroxymethyl) propionic acid was 0 by KOH titration, 0.24 parts by mass of cumene hydroperoxide was added. Subsequently, 17.6 parts by mass of tetrahydrophthalic anhydride and 17.6 parts by mass of propylene glycol monomethyl ether acetate were added to the reaction product, and reacted at 100 ° C. for 6 hours in a nitrogen atmosphere to obtain the following chemical formula (12):

The compound represented by these was obtained.

(Examples 1 to 5 and Comparative Examples 1 and 2)
(Evaluation of solvent solubility of photobase generator)
The photobase generators (1) to (5) and the comparative photobase generators (1) and (2) were examined for solubility in various solvents. Specifically, first, a solution in which each photobase generator was dissolved in DMSO was prepared, and a calibration curve was prepared using HPLC (LC-10A manufactured by Shimadzu Corporation). Next, a photobase generator is added to various solvents until suspended, and after stirring for 4 hours at 25 ° C., filtration is performed using a 0.2 μm filter. The obtained filtrate is analyzed by HPLC, and a calibration curve is obtained. From this, the photobase generator concentration in the solution was calculated. Regarding the photobase generator, ◎ when the concentration is 1% by mass or more, ○ when the concentration is 0.2% by mass or more and less than 1% by mass, 0.1% by mass or more and less than 0.2% by mass. A case was evaluated as Δ, and a case where it was less than 0.1% by mass was evaluated as ×. The obtained results are shown in Table 1. As shown in Table 1, the comparative photobase generators (1) and (2) have poor solvent solubility, whereas the photobase generators (1) to (5) of the present invention are clearly superior solvents. It shows solubility.

(Examples 6 to 10 and Comparative Examples 3 and 4: Preparation of photosensitive resin composition and evaluation of alkali developing light patterning)
For the photobase generators (1) to (5) and the comparative photobase generators (1) and (2), preparation of the photosensitive resin composition and evaluation of photopatterning performance were performed. Specifically, 100 parts by mass of the modified epoxy resin synthesized in Production Example 6, 4.5 parts by mass of each photobase generator, dipentaerythritol hexa-3-mercaptopropionate (abbreviation DPMP, SC Organic Chemistry Co., Ltd.) )) 3.8 parts by mass, 40.9 parts by mass of propylene glycol monomethyl ether acetate were mixed to prepare a photosensitive resin composition. The case where the photobase generator is completely dissolved and the obtained photosensitive resin composition becomes a uniform solution, ○, the photobase generator is not completely dissolved and the photosensitive resin composition becomes a suspension. The case was evaluated as x, and the results obtained are shown in Table 2.

Next, filtration using a filter paper having a pore diameter of 1 μm was performed, and the obtained photosensitive resin composition was spin-coated on a silicon wafer using a spin coater, heated at 100 ° C. for 5 minutes, and then 10 μm thick. A coating film was obtained. Here, a full-wavelength exposure of 1000 mJ / cm ^{2 in} terms of i-line was performed using a high-pressure mercury lamp from above the photomask. Next, heating was performed under appropriate conditions (for example, 120 ° C. × 5 min) to cure the exposed portion, and then development was performed with a 2.38 mass% TMAH aqueous solution to remove the unexposed portion. Then, it heated at 200 degreeC for 1 hour, and the cured film by which the photo patterning was carried out was obtained. Table 2 shows the results of measuring the film thickness of the obtained cured film pattern and evaluating the remaining film ratio. The remaining film ratio was calculated from the following formula (ii).
Residual film ratio = (film thickness after curing) / (film thickness before exposure) × 100 (ii)

  As shown in Table 2, when the comparative photobase generators (1) and (2) are used, the photosensitive resin composition becomes a suspension, whereas the photobase generator (1) of the present invention. When ~ 5 was used, a uniform solution was obtained. From this result, it is clear that the photobase generator of the present invention is excellent not only in solvent solubility but also in affinity for compounds having an epoxy group. As a result, since a sufficient amount can be blended in the photosensitive resin composition, as shown in Table 2, a high residual film ratio is shown as compared with the case where a comparative base generator is used.

  The photobase generator and photosensitive resin composition of the present invention can be suitably used for insulating materials that require patterning in the field of electronic materials. Moreover, the patterned substrate obtained by using the photosensitive resin composition can be suitably used as a flexible wiring board, an IC tag antenna circuit board, and the like.

Claims (8)

The following general formula (1):

{Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen,
And
Z is the following general formula (2) :

(Wherein, R ⁷ and R ⁸ is a chain aliphatic hydrocarbon group having 4 to 10 carbon atoms.)
A photobase generator represented by The solubility at 25 ° C. in at least one solvent selected from the group consisting of methyl ethyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate, gamma butyrolactone, and methanol is 1% by mass or more in terms of the concentration of the photobase generator in the solution. The photobase generator according to claim 1. Compound (a) having an epoxy group,
A photobase generator (b) comprising the photobase generator according to claim 1 or 2 ,
A curing agent (c) having a thiol group, and a compound (d) having at least one of a carboxyl group and an anhydrous carboxyl group,
The photosensitive resin composition containing this. The photosensitive resin composition of Claim 3 whose compound (a) which has the said epoxy group is a novolak-type epoxy resin or a novolak-type epoxy resin modified material. The photosensitive resin composition of Claim 3 or 4 whose hardening | curing agent (c) which has the said thiol group is thiol carboxylic acid esterification thing. The compound (a) having the epoxy group and the compound (d) having at least one of the carboxyl group and the anhydrous carboxyl group are both represented by the following general formula (4):

{Where
R ^a , R ^b , R ^c , R ^d and R ^e are each independently: an aliphatic hydrocarbon group having one saturated or double bond; an aromatic hydrocarbon group; a chain aliphatic saturated hydrocarbon group and an aromatic A group in which a hydrocarbon group is linked; or a group in which two or more selected from these groups are linked directly or through at least an oxygen atom; Well and
n ₁ , n ₂ and n ₃ are integers of 1 or more. }
In a compound represented by, the photosensitive resin composition according to any one of claims 3-5. The following steps (1) to (3):
(1) A compound (a) having an epoxy group, a photobase generator (b) containing the photobase generator according to claim 1 or 2 , a curing agent (c) having a thiol group, and a carboxyl group and anhydrous carboxyl Applying a photosensitive resin composition containing a compound (d) having at least one of groups to a substrate to form a film;
(2) a step of generating a base in the film by irradiating the film with light and curing the film; and
(3) A step of forming a pattern on the base material by removing an uncured portion of the film from the base material with an alkaline developer.
A process for producing a patterned substrate comprising: A method of manufacturing an electronic component comprising a patterned substrate,
A method comprising obtaining the patterned substrate by the manufacturing method according to claim 7 .