JP7056662B2 - Polymers, resin compositions, resin films, methods for manufacturing patterned resin films, and electronic components - Google Patents

Description

The present invention relates to a polymer, a resin composition, a resin film, a method for producing a patterned resin film, and an electronic component.

Various photosensitive compositions have been conventionally proposed as photoresist materials using polyarylene ether having excellent mechanical strength (see, for example, Patent Documents 1 and 2).

Patent Document 1 discloses a positive photosensitive resin composition containing a polyphenylene oxide (A) having a phenolic hydroxyl group and a compound (B) that generates an acid by light.

Patent Document 2 contains a polymer (a) obtained by double-adding a polyhydric phenol compound and a vinyl ether compound, and an acid generator (b) that generates an acid by irradiation with radiation. The composition is disclosed.

Japanese Unexamined Patent Publication No. 2000-275842 Japanese Unexamined Patent Publication No. 2005-266549

In recent years, in the field of manufacturing semiconductor integrated circuits and the like, further advancement of mounting technology has been required in order to realize large capacity and high integration, and high heat resistance with excellent reflow resistance and the like has been required. There is.

The subject of the present invention is a resin composition capable of forming a resin film having excellent heat resistance, a polymer useful as a component contained in the resin composition, a resin film having excellent heat resistance, and a method for producing a patterned resin film. And to provide an electronic component having the resin film.

The present inventors have conducted diligent studies to solve the above problems. As a result, they have found that the above problems can be solved by using a polymer having the following specific structure, and have completed the present invention.

The present invention is, for example, the following [1] to [22].

[1] (A) A structural unit having a partial structure represented by the following formula (i) in the same or different molecule (hereinafter also referred to as “structural unit (i)”) and the following formula (ii-1). A polymer containing a structural unit having a partial structure represented by, and one or more hydroxyl group-containing structural units (hereinafter, also referred to as "structural unit (ii)") selected from structural units having a phenolic hydroxyl group, and ( E) A resin composition containing a solvent.

［式（ｉ）中、Ｒ¹およびＲ²は、各々独立に、水素原子、炭素数１～２０の炭化水素基、前記炭素数１～２０の炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ₂－、－ＳＯ₃－、－ＯＳＯ₂ＮＲ－、－ＮＲＳＯ₂－、－ＮＲＣＯ－、－ＮＲ－および－ＣＯＮＲ－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基を示し、Ｒ¹およびＲ²は、相互に結合してＯＲ¹およびＯＲ²が結合するホウ素原子と共に環員数３～２０の環状構造を形成してもよい。前記Ｒは、水素原子または炭素数１～２０の炭化水素基であり、＊は結合手を示す。］

[In formula (i), R ¹ and R ² are independently each of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms. In between, it is selected from -O-, -COO-, -OCO-, -OSO _{2-, -SO 3-, -OSO 2 NR- ,} -NRSO _2- , -NRCO-, -NR- and -CONR-. Indicates a group having at least one type, or a group in which a part of a hydrogen atom in these groups is substituted, and R ¹ and R ² have a number of rings together with a boron atom to which OR ¹ and OR ² are bonded to each other. 3 to 20 annular structures may be formed. The R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * indicates a bond. ]

［式（ii-1）中、Ｒ³およびＲ⁴は、各々独立に、水素原子、炭素数１～２０の炭化水素基、または電子求引性基であり、但し、上記Ｒ³およびＲ⁴のうち、少なくともいずれかは電子求引性基であり、＊は結合手を示す。］
［２］重合体（Ａ）が、下記式（iii）で表される部分構造を有する構造単位（以下「構造単位（iii）」ともいう）をさらに含む、上記［１］に記載の樹脂組成物。

[In formula (ii-1), R ³ and R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an electron-withdrawing group, except that R ³ and R ⁴ are described above. Of these, at least one is an electron-withdrawing group, and * indicates a bond. ]
[2] The resin composition according to the above [1], wherein the polymer (A) further contains a structural unit having a partial structure represented by the following formula (iii) (hereinafter, also referred to as “structural unit (iii)”). thing.

［式（iii）中、Ｒ⁵は、炭素数１～２０の有機基であり；Ｒ⁶は、水素原子または炭素数１～２０の炭化水素基であり、ｎは０～３の整数であり、＊は結合手を示す。］
［３］重合体（Ａ）が、下記式（iv）で表される部分構造を有する構造単位（以下「構造単位（iv）」ともいう）をさらに含む、上記［１］～［２］のいずれかに記載の樹脂組成物。

[In formula (iii), R ⁵ is an organic group having 1 to 20 carbon atoms; R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 0 to 3. , * Indicates a bond. ]
[3] Of the above [1] to [2], the polymer (A) further contains a structural unit having a partial structure represented by the following formula (iv) (hereinafter, also referred to as “structural unit (iv)”). The resin composition according to any one.

［式（iv）中、Ｒ⁷およびＲ⁸は、各々独立に、水素原子、炭素数１～２０の炭化水素基、前記炭素数１～２０の炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ₂－、－ＳＯ₃－、－ＯＳＯ₂ＮＲ¹⁰⁵－、－ＮＲ¹⁰⁵ＳＯ₂－、－ＮＲ¹⁰⁵ＣＯ－、－ＮＲ¹⁰⁵－および－ＣＯＮＲ¹⁰⁵－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基を示し、Ｒ⁷およびＲ⁸は、相互に結合してＯＲ⁷およびＯＲ⁸が結合するリン原子と共に環員数３～２０の環状構造を形成してもよく、前記Ｒ¹⁰⁵は、水素原子または炭素数１～２０の炭化水素基であり、＊は結合手を示す。］
［４］重合体（Ａ）が、エポキシ基を有する構造単位（以下「構造単位（ｖ）」ともいう）をさらに含む、上記［１］～［３］のいずれかに記載の樹脂組成物。

[In formula (iv), R ⁷ and R ⁸ each independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms. In the meantime, -O-, -COO-, -OCO-, -OSO _2- , -SO _3- , -OSO ₂ NR 105-, -NR ¹⁰⁵ SO _2- , -NR ^{105 CO-} , -NR ^105- and Indicates a group having at least one selected from -CONR ^105- , or a group in which some of the hydrogen atoms in these groups are substituted, and R ⁷ and R ⁸ are bonded to each other to form OR ⁷ and OR ⁸ . A cyclic structure having 3 to 20 ring members may be formed together with the phosphorus atom to be bonded. R ¹⁰⁵ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * indicates a bond. ]
[4] The resin composition according to any one of the above [1] to [3], wherein the polymer (A) further contains a structural unit having an epoxy group (hereinafter, also referred to as "structural unit (v)").

[5] The resin composition according to any one of the above [1] to [4], wherein the hydroxyl group-containing structural unit is a structural unit having a partial structure represented by the above formula (ii-1).

[6] The structural unit having a phenolic hydroxyl group is any of the above [1] to [5], which is a structural unit derived from a phenolic hydroxyl group-containing unsaturated compound that is cyclized by heating to eliminate the phenolic hydroxyl group. The resin composition described.

[7] The resin composition according to any one of the above [1] to [6], wherein the structural unit having the partial structure represented by the above formula (i) is represented by the following formula (1).

［式（１）中、Ｒ¹およびＲ²は、それぞれ式（ｉ）中の同一記号と同義であり；Ｒ¹¹は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、または炭素数１～１０のフッ素化炭化水素基であり；Ｌ¹は、単結合、酸素原子、硫黄原子、または－Ｃ（＝Ｏ）－Ｘ¹－で表される基であり、Ｘ¹は、酸素原子、硫黄原子またはＮＨ基であり；Ｒ¹²は、炭素数１～２０の（ａ＋１）価の炭化水素基、前記炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ₂－、－ＳＯ₃－、－ＯＳＯ₂ＮＲ¹⁰¹－、－ＮＲ¹⁰¹ＳＯ₂－、－ＮＲ¹⁰¹ＣＯ－、－ＮＲ¹⁰¹－および－ＣＯＮＲ¹⁰¹－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基であり、前記Ｒ¹⁰¹は、水素原子または炭素数１～２０の炭化水素基であり；ａは１～３の整数である。］
［８］上記式（ii-1）で表される部分構造を有する構造単位が下記式（２）で表される、上記［１］～［７］のいずれかに記載の樹脂組成物。

[In formula (1), R ¹ and R ² are synonymous with the same symbol in formula (i), respectively; R ¹¹ is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or carbon. The number 1 to 10 fluorinated hydrocarbon groups; L ¹ is a single bond, an oxygen atom, a sulfur atom, or a group represented by -C (= O) -X ^1- , and X ¹ is oxygen. An atom, a sulfur atom or an NH group; R ¹² is a (a + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, -O-,-between at least one carbon-carbon bond in the hydrocarbon group. COO-, -OCO-, -OSO _2- , -SO _3- , -OSO ₂ NR ^101- , -NR ¹⁰¹ SO _2- , -NR ¹⁰¹ CO-, -NR ¹⁰¹ -and -CONR ¹⁰¹ -at least selected A group having one kind, or a group in which a part of hydrogen atoms in these groups is substituted, the R ¹⁰¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; a is 1 to 3 It is an integer. ]
[8] The resin composition according to any one of the above [1] to [7], wherein the structural unit having a partial structure represented by the above formula (ii-1) is represented by the following formula (2).

［式（２）中、Ｒ³およびＲ⁴は、それぞれ式（ii-1）中の同一記号と同義であり；Ｒ¹³は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、または炭素数１～１０のフッ素化炭化水素基であり；Ｌ²は、単結合、酸素原子、硫黄原子、または－Ｃ（＝Ｏ）－Ｘ²－で表される基であり、Ｘ²は、酸素原子、硫黄原子またはＮＨ基であり；Ｒ¹⁴は、炭素数１～２０の（ｂ＋１）価の炭化水素基、前記炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ₂－、－ＳＯ₃－、－ＯＳＯ₂ＮＲ¹⁰²－、－ＮＲ¹⁰²ＳＯ₂－、－ＮＲ¹⁰²ＣＯ－、－ＮＲ¹⁰²－および－ＣＯＮＲ¹⁰²－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基であり、前記Ｒ¹⁰²は、水素原子または炭素数１～２０の炭化水素基であり；ｂは１～３の整数である。］
［９］上記式（iii）で表される部分構造を有する構造単位が下記式（３）で表される、上記［２］に記載の樹脂組成物。

[In formula (2), R ³ and R ⁴ are synonymous with the same symbols in formula (ii-1), respectively; R ¹³ is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, Alternatively, it is a fluorinated hydrocarbon group having 1 to 10 carbon atoms; L ² is a single bond, an oxygen atom, a sulfur atom, or a group represented by -C (= O) -X ^2- , and X ² is. , Oxygen atom, sulfur atom or NH group; R ¹⁴ is a (b + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, -O- between at least one carbon-carbon bond in the hydrocarbon group. , -COO-, -OCO-, -OSO _2- , -SO _3- , -OSO ₂ NR 102-, -NR ¹⁰² SO _2- , -NR ^{102 CO-} , -NR ^102- and -CONR ^102- A group having at least one of these groups, or a group in which a part of hydrogen atoms in these groups is substituted, wherein R ¹⁰² is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; b is 1 to 1 to 20. It is an integer of 3. ]
[9] The resin composition according to the above [2], wherein the structural unit having the partial structure represented by the above formula (iii) is represented by the following formula (3).

［式（３）中、Ｒ⁵、Ｒ⁶およびｎは、それぞれ式（iii）中の同一記号と同義であり；Ｒ¹⁵は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、または炭素数１～１０のフッ素化炭化水素基であり；Ｌ³は、単結合、酸素原子、硫黄原子、または－Ｃ（＝Ｏ）－Ｘ³－で表される基であり、Ｘ³は、酸素原子、硫黄原子またはＮＨ基であり；Ｒ¹⁶は、炭素数１～２０の（ｃ＋１）価の炭化水素基、前記炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ₂－、－ＳＯ₃－、－ＯＳＯ₂ＮＲ¹⁰⁴－、－ＮＲ¹⁰⁴ＳＯ₂－、－ＮＲ¹⁰⁴ＣＯ－、－ＮＲ¹⁰⁴－および－ＣＯＮＲ¹⁰⁴－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基であり、前記Ｒ¹⁰⁴は、水素原子または炭素数１～２０の炭化水素基であり；ｃは１～３の整数である。］
［１０］重合体（Ａ）が、上記式（ｉ）で表される部分構造を有する構造単位を、全構造単位中、５～６０モル％含む、上記［１］～［９］のいずれかに記載の樹脂組成物。

[In formula (3), R ⁵ , R ⁶ and n are synonymous with the same symbols in formula (iii), respectively; R ¹⁵ is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, Alternatively, it is a fluorinated hydrocarbon group having 1 to 10 carbon atoms; L ³ is a single bond, an oxygen atom, a sulfur atom, or a group represented by -C (= O) -X ^3- , and X ³ is. , Oxygen atom, sulfur atom or NH group; R ¹⁶ is a (c + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, -O- between at least one carbon-carbon bond in the hydrocarbon group. , -COO-, -OCO-, -OSO _2- , -SO _3- , -OSO ₂ NR 104-, -NR ¹⁰⁴ SO _2- , -NR ^{104 CO-} , -NR ^104- and -CONR ^104- A group having at least one of these groups, or a group in which a part of hydrogen atoms in these groups is substituted, wherein R ¹⁰⁴ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; and c is 1 to 1 to 20. It is an integer of 3. ]
[10] Any of the above [1] to [9], wherein the polymer (A) contains 5 to 60 mol% of the structural units having the partial structure represented by the above formula (i) in the total structural units. The resin composition according to.

[11] The polymer (A) contains all of one or more hydroxyl group-containing structural units selected from the structural unit having a partial structure represented by the above formula (ii-1) and the structural unit having a phenolic hydroxyl group. The resin composition according to any one of the above [1] to [10], which comprises 5 to 90 mol% in the structural unit.

[12] The above-mentioned [2] or [9], wherein the polymer (A) contains 5 to 50 mol% of the structural units having a partial structure represented by the above formula (iii) in the total structural units. Resin composition.

[13] The resin composition according to the above [4], wherein the polymer (A) contains 5 to 45 mol% of the structural units having the epoxy group in the total structural units.

[14] The resin composition according to any one of the above [1] to [13], further containing a photosensitive acid generator (B) or a photopolymerization initiator (D).

[15] The resin composition according to any one of the above [1] to [14], which further contains a cross-linking agent (C).

[16] Selected from a structural unit having a partial structure represented by the above formula (i), a structural unit having a partial structure represented by the above formula (ii-1), and a structural unit having a phenolic hydroxyl group. A polymer containing one or more hydroxyl group-containing structural units.

[17] The polymer according to the above [16], further comprising a structural unit having a partial structure represented by the above formula (iii).

[18] The polymer according to any one of the above [16] to [17], further comprising a structural unit having a partial structure represented by the above formula (iv).

[19] The polymer according to any one of [16] to [18] above, further comprising a structural unit having an epoxy group.

[20] A resin film obtained by curing the resin composition according to any one of the above [1] to [15].

[21] The step of applying the resin composition according to the above [14] on a support to form a coating film, the step of selectively exposing the coating film to obtain a selective exposure film, and the above-mentioned using an alkaline developer. A method for producing a patterned resin film, comprising a step of developing a selective exposure film to obtain a patterned coating film and a step of curing the patterned coating film to obtain a patterned resin film.

[22] An electronic component having the resin film according to the above [20].

According to the present invention, it is possible to provide a resin composition capable of forming a resin film having excellent heat resistance. Further, according to the present invention, it is possible to provide a polymer useful as a component contained in the resin composition, a resin film having excellent heat resistance, a method for producing a patterned resin film, and an electronic component having the resin film. can.

Hereinafter, embodiments for carrying out the present invention will be described with reference to preferred embodiments.

Unless otherwise specified, each component exemplified in the present specification, for example, each component in the resin composition, may be used alone or in combination of two or more.

In the present specification, each term is defined as follows.

The "hydrocarbon group" includes a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. The "hydrocarbon group" may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

The "chain hydrocarbon group" means a hydrocarbon group composed only of a chain structure without containing a cyclic structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group.

The "alicyclic hydrocarbon group" means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a cyclic structure and not containing an aromatic ring structure, and is a monocyclic alicyclic hydrocarbon group and many. Includes both alicyclic hydrocarbon groups of the ring. However, the "alicyclic hydrocarbon group" does not have to be composed only of the alicyclic hydrocarbon structure, and may include a chain structure as a part thereof.

The "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a cyclic structure. However, the "aromatic hydrocarbon group" does not have to be composed only of an aromatic ring structure, and may include a chain hydrocarbon structure and / or an alicyclic hydrocarbon structure as a part thereof. ..

The "patterned resin film" means a patterned resin film. The term "resin film" is used to include a patterned resin film.

[Resin composition]
The resin composition of the present invention contains the polymer (A) and the solvent (E) described below. Hereinafter, the polymer (A) of the present invention, which is suitably used as a component contained in the resin composition, will also be described.

The resin composition of the present invention may further contain a photosensitive acid generator (B) or a photopolymerization initiator (D). The resin composition of the present invention containing the above (B) or (D) is also referred to as a "photosensitive composition". In the present specification, the terms photosensitive and photopolymerization are used to mean radiation-sensitive and radiation-sensitive polymerization corresponding to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays.

<Polymer (A)>
The polymer (A) is a structural unit having a partial structure represented by the following formula (i) and a structural unit having a partial structure represented by the following formula (ii-1) in the same or different molecules. And one or more hydroxyl group-containing structural units selected from structural units having phenolic hydroxyl groups.

上記式の説明は後述する。

The above formula will be described later.

The polymer (A) may be made of, for example, one kind of polymer or two or more kinds of polymers. In the case of two or more polymers (blended product), if it can be confirmed by, for example, NMR analysis that the entire blended product has the structural unit (i) and the structural unit (ii), the structure is contained in the blended product. Polymers that do not have the unit (i) or (ii) may be included. The term "in the same or different molecule" (where the molecule means a polymer molecule) is used in this sense. The blend is, for example, a mixture of a polymer containing the structural unit (i) and a polymer containing the structural unit (ii). The polymer (A) preferably contains a structural unit (i) and a structural unit (ii) in the same molecule.

<< Structural unit (i) >>
The polymer (A) contains one or more structural units (i). The structural unit (i) contributes to the storage stability and coatability of the resin composition, the alkali solubility of the polymer (A), the mechanical strength and heat resistance of the resin film.

By imparting alkali solubility to the polymer (A), the coating film after exposure can be developed with an alkaline developer in the method for producing a patterned resin film of the present invention.

式（ｉ）中の記号の意味は以下のとおりである。

The meanings of the symbols in the formula (i) are as follows.

R ¹ and R ² are independently each of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and -O-, between at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms. A group having at least one selected from -COO-, -OCO-, -OSO _{2-, -SO 3-, -OSO 2 NR- ,} -NRSO _2- , -NRCO-, -NR- and -CONR- (hereinafter referred to as "COO-". "Substituted hydrocarbon group 1"), or a group in which some of the hydrogen atoms in these groups are substituted (hereinafter also referred to as "substituted hydrocarbon group 2"), and R ¹ and R ² are mutually. A cyclic structure having 3 to 20 ring members may be formed together with the boron atom to which OR ¹ and OR ² are bonded. The R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * indicates a bond.

Examples of the hydrocarbon groups having 1 to 20 carbon atoms listed in R ¹ , R ² and R include chain hydrocarbon groups having 1 to 20 carbon atoms and alicyclic hydrocarbon groups having 3 to 20 carbon atoms. preferable. In this way, the hydrocarbon groups having 1 to 20 carbon atoms listed in R ¹ , R ² and R are combined with a chain hydrocarbon group having 1 to 20 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. By doing so, it is possible to obtain a polymer having excellent heat resistance and solubility in a solvent and an alkaline developing solution and having a low dielectric constant.

Examples of the chain hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an i-butyl group, a sec-butyl group, a t-butyl group and an n-. Chain-saturated hydrocarbon groups such as butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and n-decyl group; chain unsaturated such as ethenyl group, propynyl group and ethynyl group. Hydrocarbon groups can be mentioned. Of these, chain saturated hydrocarbon groups are more preferred.

Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include an alicyclic saturated hydrocarbon group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and an adamantyl group; a cyclobutenyl group and a cyclopentenyl group. Examples thereof include alicyclic unsaturated hydrocarbon groups such as groups. Of these, alicyclic saturated hydrocarbon groups are preferable.

Examples of the substituted hydrocarbon group 1 include an alkyl ester alkyl group such as a methyl ester methyl group, an ethyl ester methyl group, and a propyl ester methyl group, and an alkyl ether such as a methyl ether methyl group, an ethyl ether methyl group, and a propyl ether methyl group. Alkyl groups can be mentioned.

Examples of the substituent that substitutes a part of the hydrogen atom in the substituted hydrocarbon group 2 include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) and an alkyl halide group.

R ¹ and R ² may be bonded to each other to form a cyclic structure having 3 to 20 ring members, preferably 3 to 15 ring members, together with the boron atom to which OR ¹ and OR ² are bonded. Examples of the partial structure represented by the formula (i) forming the annular structure include the partial structures represented by the following formulas (10) and (11).

上記式（１０）および（１１）中、Ｒ^rは、炭素数２～２０の２価の炭化水素基、前記炭素数２～２０の２価の炭化水素基中の少なくとも１つの炭素－炭素結合間にＮＲ¹⁰⁰基を有する基（前記Ｒ¹⁰⁰は、水素原子または炭素数１～２０の炭化水素基である）、または前記炭素数２～２０の２価の炭化水素基中の水素原子の一部が、ハロゲン原子、アルコキシ基およびアルコキシカルボニル基から選ばれる少なくとも１種で置換された基であり、前記ＮＲ¹⁰⁰基はホウ素原子の空軌道に配位結合していてもよい。＊は結合手を示す。Ｒ^rにおける前記２価の炭化水素基は、好ましくは２価の鎖状飽和炭化水素基または脂環式飽和炭化水素基であり、より好ましくは炭素数２～１０の２価の鎖状飽和炭化水素基または炭素数４～１０の２価の脂環式飽和炭化水素基である。Ｒ¹⁰⁰における前記炭素数１～２０の炭化水素基は、前述した置換炭化水素基１中のＲにおける炭化水素基と同様である。

In the above formulas (10) and (11), R ^r is a divalent hydrocarbon group having 2 to 20 carbon atoms and at least one carbon-carbon bond in the divalent hydrocarbon group having 2 to 20 carbon atoms. One of the hydrogen atoms in the group having an NR ¹⁰⁰ group in between (the R ¹⁰⁰ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) or the divalent hydrocarbon group having 2 to 20 carbon atoms. The moiety is a group substituted with at least one selected from a halogen atom, an alkoxy group and an alkoxycarbonyl group, and the NR ¹⁰⁰ group may be coordinated to an empty orbital of a boron atom. * Indicates a bond. The divalent hydrocarbon group in R ^r is preferably a divalent chain saturated hydrocarbon group or an alicyclic saturated hydrocarbon group, and more preferably a divalent chain saturated hydrocarbon having 2 to 10 carbon atoms. It is a hydrogen group or a divalent alicyclic saturated hydrocarbon group having 4 to 10 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms in R ¹⁰⁰ is the same as the hydrocarbon group in R in the substituted hydrocarbon group 1 described above.

R ¹ and R ² are preferably hydrogen atoms from the viewpoint of heat resistance.

Examples of the structural unit (i) include a structural unit represented by the following formula (1).

式（１）中の記号の意味は以下のとおりである。

The meanings of the symbols in the formula (1) are as follows.

R ¹ and R ² are synonymous with the same symbol in formula (i), respectively.

R ¹¹ is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms. L ¹ is a single bond, an oxygen atom, a sulfur atom, or a group represented by −C (= O) −X ¹ −, and X ¹ is an oxygen atom, a sulfur atom, or an NH group. R ¹² is a (a + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and between at least one carbon-carbon bond in the hydrocarbon group, -O-, -COO-, -OCO-, -OSO ₂ -, -SO _3- , -OSO ₂ NR ^101- , -NR ¹⁰¹ SO _2- , -NR ¹⁰¹ CO-, -NR ^101- and -CONR ¹⁰¹ -A group having at least one selected from, or among these groups. R ¹⁰¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the substituent that replaces a part of the hydrogen atom include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) and an alkyl halide group. a is an integer of 1 to 3, preferably 1.

Examples of the hydrocarbon group having 1 to 10 carbon atoms in R ¹¹ include a chain hydrocarbon group having 1 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 10 carbon atoms. A group is preferable, and a methyl group and an ethyl group are more preferable.

Examples of the fluorinated hydrocarbon group having 1 to 10 carbon atoms in R ¹¹ include a fluorinated chain hydrocarbon group having 1 to 10 carbon atoms and a fluorinated alicyclic hydrocarbon group having 3 to 10 carbon atoms. Therefore, a fluorinated chain hydrocarbon group is preferable, and a trifluoromethyl group is more preferable.

As the above R ¹¹ , a hydrogen atom is preferable.

Examples of the (a + 1) -valent hydrocarbon group having 1 to 20 carbon atoms of R ¹² include a chain saturated hydrocarbon group such as a methylene group and an alkanediyl group such as an ethylene group, a cyclopentanediyl group, and a cyclohexanediyl. Examples thereof include a cycloalkandyl group such as a group, a norbornandyl group and a tetracyclododecandyl group, and an arylene group such as a phenylene group.

Examples of the structural unit (i) include structural units represented by the following formulas (12) to (22).

《構造単位（ii）》
重合体（Ａ）は、下記式（ii-1）で表される部分構造を有する構造単位（ii-1）、およびフェノール性水酸基を有する構造単位（ii-2）から選択される一以上の構造単位（ii）を含む。

<< Structural unit (ii) >>
The polymer (A) is one or more selected from a structural unit (ii-1) having a partial structure represented by the following formula (ii-1) and a structural unit (ii-2) having a phenolic hydroxyl group. Includes structural unit (ii).

First, the structural unit (ii-1) will be described.

The polymer (A) further contains a structural unit (ii-1) having a partial structure represented by the following formula (ii-1) in the same or different molecule as the molecule containing the structural unit (i). Can be done. Among these, the polymer (A) preferably contains the structural unit (i) and the structural unit (ii-1) in the same molecule.

式（ii-1）中の記号の意味は以下のとおりである。

The meanings of the symbols in equation (ii-1) are as follows.

R ³ and R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an electron-withdrawing group, except that at least one of R ³ and R ⁴ described above is an electron-withdrawing group. It is an attractive group, and an electron-withdrawing group is preferable, and * indicates a bond.

The hydrocarbon group having 1 to 20 carbon atoms is the same as the hydrocarbon group having 1 to 20 carbon atoms of R ¹ and R ² in the formula (i).

It is preferable that at least one of R ³ and R ⁴ is an electron-withdrawing group because the storage stability of the resin composition and the alkali solubility of the polymer (A) are improved. Examples of the electron-attracting group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano group; and fluorinated hydrocarbon group such as fluorinated alkyl group.

The above-mentioned fluorinated hydrocarbon group is a group in which a part or all of hydrogen atoms in the hydrocarbon group are substituted with fluorine atoms. As the fluorinated hydrocarbon group, a fluorinated hydrocarbon group having 1 to 20 carbon atoms is preferable, a fluorinated alkyl group having 1 to 20 carbon atoms is more preferable, and a fluorinated alkyl group having 1 to 10 carbon atoms is more preferable.

Among these, the electron-withdrawing group is preferably a fluorine atom, a cyano group or a fluorinated alkyl group, and more preferably a fluorine atom, a cyano group, a trifluoromethyl group or a hexafluoroisopropyl group.

The polymer (A) can contain one or more structural units (ii-1).

The structural unit (ii-1) contributes to the storage stability of the resin composition, the alkali solubility of the polymer (A), the hydrophobicity of the resin film, and the low dielectric constant.

Examples of the structural unit (ii-1) include a structural unit represented by the following formula (2).

式（２）中の記号の意味は以下のとおりである。

The meanings of the symbols in the formula (2) are as follows.

R ³ and R ⁴ are synonymous with the same symbol in equation (ii-1), respectively. R ¹³ is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms. L ² is a single bond, an oxygen atom, a sulfur atom, or a group represented by −C (= O) −X ² −, and X ² is an oxygen atom, a sulfur atom, or an NH group. R ¹⁴ is a (b + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and between at least one carbon-carbon bond in the hydrocarbon group, -O-, -COO-, -OCO-, -OSO ₂ -, -SO _3- , -OSO ₂ NR 102-, -NR ¹⁰² SO _2- , -NR ^{102 CO-, -NR 102-and-CONR 102 - A} group having at least one selected from, or among these groups. R ¹⁰² is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. b is an integer of 1 to 3, preferably 1. Specific examples, suitable examples and suitable reasons for R ¹³ and R ¹⁴ are the same as those for R ¹¹ and R ¹² in the formula (1), respectively.

Examples of the structural unit (ii-1) include structural units (23) to (28) represented by the following formulas.

上記式中のＲ¹³は、それぞれ式（２）中の同一記号と同義である。

R ¹³ in the above equation is synonymous with the same symbol in equation (2).

Next, the structural unit (ii-2) will be described.

The polymer (A) can further contain a structural unit (ii-2) having a phenolic hydroxyl group in the same or different molecule as the molecule containing the structural unit (i). Among these, the polymer (A) preferably contains the structural unit (i) and the structural unit (ii-2) in the same molecule.

The polymer (A) can contain one or more structural units (ii-2).

The structural unit (ii-2) contributes to the alkali solubility of the polymer (A), the storage stability and compatibility of the resin composition, the adhesion of the resin film, and the mechanical strength. Further, when the polymer (A) having the structural unit (ii-2) is used, a resin film having excellent solvent resistance and thermal meltability can be obtained.

Specific examples of the structural unit (ii-2) having a phenolic hydroxyl group include a structural unit derived from a phenolic hydroxyl group-containing unsaturated compound.

Examples of the phenolic hydroxyl group-containing unsaturated compound include 2-hydroxyphenyl (meth) acrylate, 2-hydroxyphenyl (meth) acrylamide, and the like, which are cyclized by heating to eliminate the phenolic hydroxyl group; 3-Hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 2,6-dimethyl-4-hydroxyphenyl (meth) acrylate, 3-hydroxyphenyl (meth) acrylamide, 4-hydroxyphenyl (meth) acrylamide , 2,6-Dimethyl-4-hydroxyphenyl (meth) acrylamide, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2,6-dimethyl-4-hydroxystyrene and other phenolic hydroxyl group-containing unsaturated Examples include compounds. Among these, the phenolic hydroxyl group disappears due to heating and the hygroscopicity disappears, so that a low-dielectric resin film can be obtained, and the copolymerization reactivity and the solvent resistance and dielectric properties of the resin film are exhibited. From the viewpoint, a phenolic hydroxyl group-containing unsaturated compound such as 2-hydroxyphenylacrylamide or 2-hydroxyphenylacrylate in which the phenolic hydroxyl group disappears by cyclization by heating is preferable.

<< Structural unit (iii) >>
The polymer (A) has a partial structure represented by the following formula (iii) in the same or different molecule as the molecule containing at least one structural unit selected from the structural units (i) and (ii). Structural units (iii) can be further included. Among these, the polymer (A) preferably contains a structural unit (i), a structural unit (ii), and a structural unit (iii) in the same molecule. The polymer (A) can contain one or more structural units (iii). The structural unit (iii) contributes to the alkali solubility of the polymer (A), the adhesion of the resin film, the mechanical strength and the heat resistance.

式（iii）中、Ｒ⁵は、炭素数１～２０の有機基（ただし、ＯＲ⁶に該当する基を除く）である。Ｒ⁶は、水素原子または炭素数１～２０の炭化水素基であり、ｎは０～３の整数であり、好ましくは０である。＊は結合手を示す。

In formula (iii), R ⁵ is an organic group having 1 to 20 carbon atoms (excluding the group corresponding to OR ⁶ ). R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 0 to 3, preferably 0. * Indicates a bond.

"Organic group" means a group containing at least one carbon atom.

Examples of the organic group having 1 to 20 carbon atoms in R ⁵ include a chain hydrocarbon group having 1 to 20 carbon atoms and an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Group; -O-, -COO-, -OCO-, -OSO _2- , -SO _3- , -OSO ₂ NR between at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms. A group having at least one selected from 103-, -NR ¹⁰³ SO _2- , -NR ^{103 CO-} , -NR ^103- and -CONR ^103- ; or a group in which a part of a hydrogen atom in these groups is substituted. Can be mentioned. Specific examples, preferred examples and suitable reasons for each group are the same as those of the hydrocarbon group having 1 to 20 carbon atoms, the substituted hydrocarbon group 1 and the substituted hydrocarbon group 2 described by R ¹ and R ² in the formula (i). Is.

The hydrocarbon group having 1 to 20 carbon atoms of R ⁶ includes a chain hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon having 6 to 20 carbon atoms. Hydrocarbon groups can be mentioned.

Specific examples, suitable examples and suitable reasons for the chain hydrocarbon group having 1 to 20 carbon atoms and the alicyclic hydrocarbon group having 3 to 20 carbon atoms of R ⁶ are R ¹ and R ² in the formula (i). It is the same as the chain hydrocarbon group and the alicyclic hydrocarbon group described as.

Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms of R ⁶ include an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group and an anthryl group; a benzyl group, a phenethyl group, a naphthylmethyl group and an ann. Examples thereof include an aralkyl group such as a tolylmethyl group.

Examples of the structural unit (iii) include a structural unit represented by the following formula (3).

式（３）中の記号の意味は以下のとおりである。

The meanings of the symbols in the formula (3) are as follows.

R ⁵ , R ⁶ and n are synonymous with the same symbol in equation (iii), respectively. R ¹⁵ is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms. L ³ is a single bond, an oxygen atom, a sulfur atom, or a group represented by −C (= O) −X ³ −, and X ³ is an oxygen atom, a sulfur atom, or an NH group. R ¹⁶ is a (c + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and -O-, -COO-, -OCO-, -OSO ₂ between at least one carbon-carbon bond in the hydrocarbon group. -, -SO _3- , -OSO ₂ NR 104-, -NR ¹⁰⁴ SO _2- , -NR ^{104 CO-, -NR 104- and -CONR 104 - A} group having at least one selected from, or among these groups. It is a group in which a part of the hydrogen atom of the above is substituted, and the R ¹⁰⁴ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. c is an integer of 1 to 3, preferably 1. Specific examples, suitable examples and suitable reasons for each of the R ¹⁵ and R ¹⁶ groups are the same as those of R ¹¹ and R ¹² in the formula (1), respectively.

Examples of the structural unit (iii) include structural units (29) to (34) represented by the following formulas.

上記式中のＲ¹⁵は、それぞれ式（３）中の同一記号と同義である。

R ¹⁵ in the above equation is synonymous with the same symbol in equation (3).

《Structural unit (iv)》
The polymer (A) has a partial structure represented by the following formula (iv) in the same or different molecule as the molecule containing at least one structural unit selected from the structural units (i) and (ii). Structural units (iv) can be further included. Among these, the polymer (A) preferably contains a structural unit (i), a structural unit (ii), and a structural unit (iv) in the same molecule, and the polymer (A) contains the structural unit (iii). In this case, it is preferable to include the structural unit (i), the structural unit (ii), the structural unit (iii), and the structural unit (iv) in the same molecule. The polymer (A) can contain one or more structural units (iv). The structural unit (iv) contributes to the storage stability and compatibility of the resin composition, the adhesion of the resin film, the heat-resistant transparency and the anti-aging property.

式（iv）中の記号の意味は以下のとおりである。

The meanings of the symbols in equation (iv) are as follows.

R ⁷ and R ⁸ are independently each of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and -O-, between at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms. -COO-, -OCO-, -OSO _2- , -SO _3- , -OSO ₂ NR 105-, -NR ¹⁰⁵ SO _2- , -NR ^{105 CO-} , -NR ^105- and -CONR ^105- Represents a group having at least one, or a group in which some of the hydrogen atoms in these groups have been substituted, with R ⁷ and R ⁸ having ring members with a phosphorus atom to which OR ⁷ and OR ⁸ are bonded to each other. 3 to 20 annular structures may be formed. The R ¹⁰⁵ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Specific examples of each group of R ⁷ and R ⁸ are the same as those of R ¹ and R ² in the formula (i), respectively. * Indicates a bond.

R ⁷ and R ⁸ may be bonded to each other to form a cyclic structure having 3 to 20 ring members, preferably 3 to 15 ring members, together with the phosphorus atom to which OR ⁷ and OR ⁸ are bonded. Examples of the partial structure represented by the formula (iv) having the annular structure include the partial structures represented by the following formulas (35) to (36).

上記式（３５）および（３６）中、Ｒ^r1は、炭素数２～２０の２価の炭化水素基、または前記炭素数２～２０の２価の炭化水素基中の水素原子の一部が、ハロゲン原子、アルコキシ基およびアルコキシカルボニル基から選ばれる少なくとも１種で置換された基である。＊は結合手を示す。Ｒ^r1における前記２価の炭化水素基は、好ましくは２価の鎖状飽和炭化水素基または脂環式飽和炭化水素基であり、より好ましくは炭素数２～１０の２価の鎖状飽和炭化水素基または炭素数４～１０の２価の脂環式飽和炭化水素基である。

In the above formulas (35) and (36), R ^r1 is a divalent hydrocarbon group having 2 to 20 carbon atoms or a part of hydrogen atoms in the divalent hydrocarbon group having 2 to 20 carbon atoms. , A group substituted with at least one selected from a halogen atom, an alkoxy group and an alkoxycarbonyl group. * Indicates a bond. The divalent hydrocarbon group in R ^r1 is preferably a divalent chain saturated hydrocarbon group or an alicyclic saturated hydrocarbon group, and more preferably a divalent chain saturated hydrocarbon having 2 to 10 carbon atoms. It is a hydrogen group or a divalent alicyclic saturated hydrocarbon group having 4 to 10 carbon atoms.

From the viewpoint of heat resistance and storage stability, R ⁷ and R ⁸ are preferably hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, respectively, and hydrogen atoms or chain hydrocarbon groups having 1 to 20 carbon atoms. Is more preferable, and a hydrogen atom, a methyl group, an ethyl group, and an i-propyl group are even more preferable.

Examples of the structural unit (iv) include a structural unit represented by the following formula (4).

式（４）中の記号の意味は以下のとおりである。

The meanings of the symbols in the equation (4) are as follows.

R ⁷ and R ⁸ are synonymous with the same symbol in equation (iv), respectively. R ¹⁷ is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms. L ⁴ is a single bond, an oxygen atom, a sulfur atom, or a group represented by −C (= O) −X ⁴ −, and X ⁴ is an oxygen atom, a sulfur atom, or an NH group. R ¹⁸ is a (d + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and between at least one carbon-carbon bond in the hydrocarbon group, -O-, -COO-, -OCO-, -OSO ₂ -, -SO _3- , -OSO ₂ NR 106-, -NR ¹⁰⁶ SO _2- , -NR ^{106 CO-, -NR 106- and -CONR 106 - A} group having at least one selected from, or among these groups. It is a group in which a part of the hydrogen atom of the above is substituted, and the R ¹⁰⁶ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. d is an integer of 1 to 3, preferably 1. Specific examples, suitable examples and suitable reasons for each of the groups R ¹⁷ and R ¹⁸ are the same as those of R ¹¹ and R ¹² in the formula (1), respectively.

Examples of the structural unit (iv) include structural units represented by the following formulas (37) to (45).

上記式中のＲ¹⁷は、それぞれ式（４）中の同一記号と同義である。

R ¹⁷ in the above equation is synonymous with the same symbol in equation (4), respectively.

<< Structural unit (v) >>
The polymer (A) further comprises a structural unit (v) having an epoxy group in the same or different molecule as the molecule containing at least one structural unit selected from the structural units (i) and (ii). Can be done. Among these, the polymer (A) preferably contains the structural unit (i), the structural unit (ii), and the structural unit (v) in the same molecule, and the polymer (A) is the structural unit (iii) and /. Or, when (iv) is contained, it is preferable to include the structural unit (i), the structural unit (ii), the structural unit (iii), and / or (iv) and the structural unit (v) in the same molecule. The polymer (A) can contain one or more structural units (v). The structural unit (v) contributes to the storage stability of the resin composition, the adhesion of the resin film, and the mechanical strength.

Examples of the epoxy group include an oxylanyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure). Specific examples of the structural unit (v) having an epoxy group include structural units derived from an epoxy group-containing unsaturated compound such as an oxylanyl group-containing unsaturated compound and an oxetanyl group-containing unsaturated compound.

Examples of the oxyranyl group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, and glycidyl α-n-butyl acrylate. , Acrylic acid 3,4-epoxybutyl, methacrylic acid 3,4-epoxybutyl, acrylate 6,7-epoxyheptyl, methacrylic acid 6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, Examples thereof include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 3,4-epoxycyclohexylmethyl methacrylate.

Of these, glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylic acid, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, methacrylic acid 3, 4-Epoxycyclohexyl is preferable from the viewpoint of improving the copolymerization reactivity and the solvent resistance of the interlayer insulating film.

Examples of the oxetanyl group-containing unsaturated compound include, for example.
3- (Acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (Acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) )-2-Ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-acryloyloxyethyl) -2 -Pentafluoroethyl oxetane, 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) -2,2-difluorooxetane, 3- (2-acryloyloxyethyl) -2, Acrylic acid esters such as 2,4-trifluorooxetane, 3- (2-acryloyloxyethyl) -2,2,4,4-tetrafluorooxetane;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) )-2-Ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-methacryloyloxyethyl) -2 -Pentafluoroethyl oxetane, 3- (2-methacryloyloxyethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane, 3- (2-methacryloyloxyethyl) -2, Examples thereof include methacrylic acid esters such as 2,4-trifluorooxetane and 3- (2-methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane.

Of these, 3- (acryloyloxymethyl) -3-ethyloxetane and 3- (methacryloyloxymethyl) -3-ethyloxetane have copolymerization reactivity, compatibility of the resin composition, and solvent resistance of the resin film. It is desirable from the viewpoint of improvement.

<< Composition of polymer (A) >>
It is presumed that the resin composition can be cured by self-condensing the partial structure represented by the formula (i) in the polymer (A), which contributes to the improvement of heat resistance. It is presumed that the partial structure represented by the formula (ii-1) suppresses the self-condensation of the partial structure represented by the formula (i) during storage and contributes to the improvement of the storage stability of the resin composition. It is presumed that the structural unit (ii-2) contributes to the improvement of the alkali solubility of the polymer (A) and the improvement of the crosslinked physical properties such as the solvent resistance of the resin film. By self-condensing the partial structure represented by the formula (iii), the resin composition can be cured, which is presumed to contribute to the improvement of heat resistance. By self-condensing the partial structure represented by the formula (iv), the resin composition can be cured, which is presumed to contribute to the improvement of heat resistance.

In the polymer (A), the content ratio of the structural unit (i) is usually 5 to 60 mol%, preferably 5 to 40 mol%, and more preferably 5 to 20 mol%. When the content ratio of the structural unit (i) is within the above range, the storage stability and coatability of the resin composition, the alkali solubility of the polymer (A), the mechanical strength and heat resistance of the resin film tend to be improved. be.

In the polymer (A), the content ratio of the structural unit (ii) is usually 5 to 90 mol%.

When the polymer (A) contains the structural unit (ii-1), the content ratio of the structural unit (ii-1) is usually 5 to 90 mol%, preferably 10 to 80 mol%, and further. It is preferably 20 to 70 mol%. When the content ratio of the structural unit (ii-1) is within the above range, the storage stability of the resin composition, the alkali solubility of the polymer (A), the hydrophobicity of the resin film and the low dielectric constant tend to be improved. be.

When the polymer (A) contains the structural unit (ii-2), the content ratio of the structural unit (ii-2) is usually 5 to 70 mol%, preferably 10 to 40 mol%, and further. It is preferably 15 to 30 mol%. When the content ratio of the structural unit (ii-2) is within the above range, the compatibility of the resin composition, the alkali solubility of the polymer (A), and the low dielectric constant of the resin film tend to be improved.

When the polymer (A) contains the structural unit (iii), the content ratio of the structural unit (iii) is usually 5 to 50 mol%, preferably 5 to 40 mol%, and more preferably 5 to 5. It is 30 mol%. When the content ratio of the structural unit (iii) is within the above range, the alkali solubility of the polymer (A), the adhesion of the resin film, the mechanical strength and the heat resistance tend to be improved.

When the polymer (A) contains the structural unit (iv), the content ratio of the structural unit (iv) is usually 5 to 30 mol%, preferably 5 to 25 mol%, and more preferably 10 to 10. It is 20 mol%. When the content ratio of the structural unit (iv) is within the above range, the storage stability and compatibility of the resin composition, the adhesion of the resin film, the heat-resistant transparency and the anti-aging property tend to be improved.

When the polymer (A) contains the structural unit (v), the content ratio of the structural unit (v) is usually 5 to 45 mol%. When the polymer (A) contains the structural unit (ii-1) and the structural unit (v), the content ratio of the structural unit (v) is usually 5 to 40 mol%, preferably 5 to 35 mol%. , More preferably 10 to 30 mol%, and when the polymer (A) contains the structural unit (ii-2) and the structural unit (v), the content ratio of the structural unit (v) is usually 5. It is ~ 45 mol%, preferably 10 ~ 45 mol%, more preferably 15 ~ 45 mol%. When the content ratio of the structural unit (v) is within the above range, the coatability and compatibility of the resin composition, the adhesion of the resin film, and the mechanical strength tend to be improved.

The content ratio of each structural unit of the polymer (A) is a value in all the structural units constituting the polymer (A), and can be measured by ¹³ C-NMR.

The weight average molecular weight (Mw) measured by the gel permeation chromatography method of the polymer (A) is the elastic modulus of the resin film obtained by curing the resin composition, crack resistance, and the resolution of the photosensitive composition. In terms of polystyrene, it is usually 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 5,000 to 50,000. The molecular weight distribution of the polymer (A) (Mw / Mn; Mn is a number average molecular weight) is usually 1.0 to 10.0, preferably 1.0 to 5.0, and more preferably 1.0 to 3. It is 0. Details of the method for measuring Mw and Mn are as described in Examples.

The polymer (A) may be used alone or in combination of two or more.

The content ratio of the polymer (A) is usually 30% by mass or more, preferably 40% by mass or more, more preferably 40% by mass, based on 100% by mass of the total of all the components excluding the solvent (E) from the resin composition of the present invention. It is preferably 50% by mass or more. When the content ratio of the polymer (A) is within the above range, a resin composition capable of forming a resin film having excellent heat resistance tends to be obtained.

The content ratio of the polymer (A) is usually 30 to 99% by mass, preferably 40 to 98% by mass, based on 100% by mass of the total of all the components excluding the solvent (E) from the photosensitive composition of the present invention. %, More preferably 50 to 95% by mass. When the content ratio of the polymer (A) is within the above range, a photosensitive composition having excellent heat resistance and capable of forming a patterned resin film having high resolution tends to be obtained.

<< Method for synthesizing polymer (A) >>
The polymer (A) can be synthesized, for example, by subjecting a predetermined monomer leading to each structural unit to polymerization such as radical polymerization in the presence of a polymerization initiator or a chain transfer agent in a polymerization solvent. .. For example, a monomer, a polymerization initiator and a polymerization solvent are charged in a reaction vessel, heated to a reaction temperature of about 40 to 120 ° C. under an inert gas atmosphere such as nitrogen gas, and reacted for 0.1 to 10 hours.

Examples of the polymerization initiator include azo compounds and peroxide compounds. The above-mentioned polymerization initiator may be used alone or in combination of two or more.

Examples of the polymerization solvent include, for example.
Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, diethylene glycol, propylene glycol;
Cyclic ethers such as tetrahydrofuran and dioxane;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Alkyl ethers of polyhydric alcohols such as ethers;
Alkyl ether acetates of polyhydric alcohols such as ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, diacetone alcohol;
Ethyl acetate, butyl acetate, methyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutane Examples thereof include esters such as methyl acid, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate.

Of these, cyclic ethers, alkyl ethers of polyhydric alcohols, alkyl ether acetates of polyhydric alcohols, ketones or esters are preferable.

The above-mentioned polymerization solvent may be used alone or in combination of two or more.

<Photosensitive acid generator (B)>
The resin composition of the present invention can contain a photosensitive acid generator (B), and by containing the photosensitive acid generator (B), it becomes a photosensitive composition.

The photosensitive acid generator (B) is a compound that generates an acid by light. By the treatment including the exposure treatment for the coating film formed from the photosensitive composition of the present invention, an acid is generated in the exposed portion based on the photosensitive acid generator (B), and the alkaline development of the exposed portion is based on the action of this acid. The solubility in the liquid changes.

The photosensitive composition may be either a negative type or a positive type. The type of the photosensitive acid generator (B) can be appropriately selected depending on the negative type composition or the positive type composition.

Examples of the photosensitive acid generator (B) include onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds, and compounds having a quinonediazide group. Hereinafter, the compound having a quinone diazide group is also referred to as "quinone diazide compound (b1)", and the other exemplified photosensitive acid generator is also referred to as "acid generator (b2)".

<< Kinondiazide compound (b1) >>
The quinone diazide compound (b1) is a compound in which a quinone diazide group is decomposed to form a carboxy group by light irradiation and contact treatment with water. The coating film formed from the composition containing the quinone diazide compound (b1) is a film that is sparingly soluble in an alkaline developer. A positive pattern is formed by utilizing the fact that the film changes from a poorly alkali-soluble state to an easily alkaline-soluble state by light irradiation and contact treatment with water.

Examples of the quinone diazide compound (b1) include a naphthoquinone diazide compound, specifically, a compound having one or more phenolic hydroxyl groups, 1,2-naphthoquinone diazide-4-sulfonic acid, and 1,2-naphtho. Examples thereof include ester compounds with quinonediazide-5-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid chloride or 1,2-naphthoquinonediazide-5-sulfonic acid chloride. Specific examples of the compound having one or more phenolic hydroxyl groups include the compounds described in paragraphs [0065] to [0070] of JP-A-2014-186300, which are described in the present specification. It is assumed that it is.

Examples of the quinone diazide compound (b1) include 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 2,3,4-trihydroxybenzophenone, 2,3,4'-tetrahydroxybenzophenone, 2 , 3,4,2', 4'-pentahydroxybenzophenone, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [ 1- (4-Hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene and 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1 -Methylethyl] phenyl] ethane (also known as 4,4'-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol) and 1, Estre with 2-naphthoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-5-sulfonic acid, 1,2-naphthoquinone diazide-4-sulfonic acid chloride or 1,2-naphthoquinone diazide-5-sulfonic acid chloride Examples include compounds.

The quinone diazide compound (b1) may be used alone or in combination of two or more.

When the quinone diazide compound (b1) is used as the photosensitive acid generator (B) in the photosensitive composition of the present invention, the content of the quinone diazide compound (b1) is preferably 100 parts by mass of the polymer (A). Is 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, still more preferably 5 to 30 parts by mass. When the content of the quinone diazide compound (b1) is at least the above lower limit value, the residual film ratio of the unexposed portion is improved, and an image faithful to the mask pattern can be easily obtained. When the content of the quinone diazide compound (b1) is not more than the above upper limit value, a resin film having an excellent pattern shape can be easily obtained, and foaming during film formation tends to be prevented.

<< Acid generator (b2) other than quinonediazide compound (b1) >>
The acid generator (b2) is a compound that forms an acid by light irradiation and is a compound other than the quinonediazide compound (b1). By irradiating the coating film formed from the composition containing the acid generator (b2) with light, the generated acid acts on the polymer (A), the cross-linking agent (C) described later, and the like to crosslink. The structure is formed and it becomes a film that is sparingly soluble in alkali. A negative pattern is formed by utilizing the fact that the film changes from a state of easy alkali dissolution to a state of poor alkali dissolution by light irradiation.

The acid generator (b2) is, for example, an onium salt compound such as an iodonium salt, a sulfonium salt, a phosphonium salt, a diazonium salt, a pyridinium salt; a halogen-containing compound such as a haloalkyl group-containing heterocyclic compound or a haloalkyl group-containing hydrocarbon compound; Sulfone compounds such as β-keto sulfone compounds, β-sulfonyl sulfone compounds and α-diazo compounds of these compounds; sulfonic acid compounds such as alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates, etc. Sulfoneimide compound; diazomethane compound. Specific examples of these compounds include the compounds described in paragraphs [0074] to [0079] of JP-A-2014-186300, which are described in the present specification.

Specific examples of the onium salt include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifuriolomethanesulfonate, and triphenyl. Sulfonium p-toluene sulfonate, triphenyl sulfonium hexafluoroantimonate, 4-t-butylphenyl diphenyl sulfonium trifluoromethane sulfonate, 4-t-butyl phenyl diphenyl sulfonium p-toluene sulfonate, 4,7-di-n-butoxy Examples thereof include naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, and 4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate.

The acid generator (b2) may be used alone or in combination of two or more.

When the acid generator (b2) is used as the photosensitive acid generator (B) in the resin composition of the present invention, the content of the acid generator (b2) is based on 100 parts by mass of the polymer (A). It is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 20 parts by mass, and further preferably 0.5 to 15 parts by mass. When the content of the acid generator (b2) is at least the above lower limit value, the exposed portion is sufficiently cured and the heat resistance is likely to be improved. When the content of the acid generator (b2) is not more than the upper limit value, it is easy to obtain a patterned resin film having high resolution without deteriorating the transparency to the exposure light.

<Crosslinking agent (C)>
The resin composition of the present invention may further contain a cross-linking agent (C) in order to improve the curability of the resin film. The cross-linking agent (C) is a compound having two or more polymerizable groups or reactive groups. The cross-linking agent (C) acts as a cross-linking component (curing component) that reacts with the polymer (A) or between the cross-linking agents. Examples of the polymerizable group or the reactive group include an ethylenically unsaturated group, an oxylanyl group, an oxetanyl group, an oxazolinyl group, an isocyanate group, an N-alkoxyalkylamino group, a methylol group and an alkylmethylol group.

Examples of the cross-linking agent (C) include a compound having two or more (meth) acryloyl groups, a compound having two or more N-alkoxyalkylamino groups, a methylol group-containing phenol compound, and an alkylmethylol group-containing phenol compound. Oxylan ring-containing compounds, oxetane ring-containing compounds, oxazoline ring-containing compounds, isocyanate group-containing compounds (including blocked compounds), aldehyde group-containing phenol compounds, and compounds having two or more (meth) acryloyl groups. , And compounds having two or more N-alkoxyalkylamino groups are preferred.

Examples of the compound having two or more (meth) acryloyl groups include polyfunctional (meth) acrylic acid esters such as bifunctional (meth) acrylic acid esters and trifunctional or more (meth) acrylic acid esters. ..

Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and 1,6-hexane. Examples thereof include diol di (meth) acrylate and 1,9-nonane diol di (meth) acrylate.

Examples of the trifunctional or higher functional (meth) acrylic acid ester include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and di. Pentaerythritol hexa (meth) acrylate, compound of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxy In addition to ethyl) phosphate, succinic acid-modified pentaerythritol tri (meth) acrylate, and succinic acid-modified dipentaerythritol penta (meth) acrylate, it has a linear alkylene group and an alicyclic structure, and has two or more isocyanate groups. Polyfunctional urethane (meth) obtained by reacting a compound having the above with a compound having one or more hydroxy groups in the molecule and having three, four or five (meth) acryloyloxy groups. Examples thereof include acrylate compounds.

Examples of the compound having two or more N-alkoxyalkylamino groups include compounds having two or more alkyl etherified amino groups (hereinafter, also referred to as “amino group-containing compound”), and the alkyl etherified amino. The group is, for example, a group represented by the following formula.

上記式中、Ｒ^C1はメチレン基またはアルキレン基であり、好ましくはメチレン基または炭素数２～１０のアルキレン基であり、Ｒ^C2はアルキル基であり、好ましくは炭素数１～１０のアルキル基である。

In the above formula, ^RC1 is a methylene group or an alkylene group, preferably a methylene group or an alkylene group having 2 to 10 carbon atoms, and ^RC2 is an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms. be.

Examples of the amino group-containing compound include active methylol groups (CH ₂ OH) in nitrogen compounds such as (poly) methylolated melamine, (poly) methylolated glycol uryl, (poly) methylolated benzoguanamine, and (poly) methylolated urea. Examples thereof include compounds in which all or part (at least two) of the group) are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same or different from each other. Further, the methylol group which has not been alkyl etherified may be self-condensed within one molecule, or may be condensed between two molecules to form an oligomer component as a result. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycol uryl, tetrabutoxymethyl glycol uryl and the like can be used.

The cross-linking agent (C) may be used alone or in combination of two or more.

In the resin composition of the present invention, the content of the cross-linking agent (C) is usually 1 to 300 parts by mass, preferably 5 to 200 parts by mass, more preferably 10 parts by mass with respect to 100 parts by mass of the polymer (A). ~ 100 parts by mass. When the content of the cross-linking agent (C) is in the above range, a resin film having excellent resolution, stretchability and heat resistance tends to be formed.

<Photopolymerization Initiator (D)>
The resin composition of the present invention can contain a photopolymerization initiator (D). When a compound having an ethylenically unsaturated group, particularly a (meth) acryloyl group, is used as the cross-linking agent (C), by using the photopolymerization initiator (D), the resin composition of the present invention has a negative photosensitive composition. It becomes a thing.

The photopolymerization initiator (D) is a compound that generates an active species capable of initiating the polymerization of a polymerizable compound by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. By the exposure treatment on the coating film formed from the photosensitive composition, an active species capable of initiating polymerization is generated in the exposed portion based on the photopolymerization initiator (D), and two or more ethylenically non-reactive species are generated by this active species. The compound having a saturated group polymerizes, and the solubility of the exposed part in the alkaline developing solution changes.

Examples of the photopolymerization initiator (D) include thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O-acyloxime-based compounds, acylphosphine oxide-based compounds, onium salt-based compounds, and benzoin-based compounds. , Benzophenone-based compounds, α-diketone-based compounds, polynuclear quinone-based compounds, diazo-based compounds, and imidesulfonate-based compounds. Of these, at least one selected from thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O-acyloxime-based compounds and acylphosphine oxide-based compounds is preferable.

Specific examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethyl. Examples thereof include thioxanthone and 2,4-diisopropylthioxanthone.

Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholino). Phenyl) butane-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane-1-one can be mentioned.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,2'-bis ( 2,4-Dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-Tetraphenyl-1,2'-biimidazole can be mentioned.

Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5- (5- (5-). Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (fran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6 Examples thereof include triazine compounds having a halomethyl group such as -bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.

Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), etanone, 1- [9-ethyl-6. -(2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) ) Methoxybenzoyl} -9H-carbazole-3-yl]-, 1- (O-acetyloxime). As commercially available O-acyloxime compounds, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), OXE-03, OXE-04 (above, manufactured by BASF), etc. may be used. can.

Specific examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl-phosphine oxide, and bis (2). , 4,6-trimethylbenzoyl) -phenyl-phosphine oxide.

In the present invention, when a photopolymerization initiator other than the biimidazole-based compound such as an acetophenone-based compound is used, a sensitizer can also be used in combination. Examples of such a sensitizer include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Can be mentioned.

The photopolymerization initiator (D) may be used alone or in combination of two or more.

In the resin composition of the present invention, the content of the photopolymerization initiator (D) is preferably 0.01 to 120 parts by mass, more preferably 1 part by mass with respect to 100 parts by mass of the compound having an ethylenically unsaturated group. It is up to 100 parts by mass, more preferably 5 to 80 parts by mass. When the content of the photopolymerization initiator (D) is at least the above lower limit value, the exposed portion is sufficiently cured and the heat resistance is likely to be improved. When the content of the photopolymerization initiator (D) is not more than the upper limit value, it is easy to obtain a pattern having high resolution without deteriorating the transparency to the exposure light.

<Solvent (E)>
The resin composition of the present invention contains a solvent (E). By using the solvent (E), the handleability of the resin composition of the present invention can be improved, the viscosity can be adjusted, and the storage stability can be improved.

As the solvent (E), for example,
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether. Classes; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene. Propropylene glycol monoalkyl ether acetates such as glycol monobutyl ether acetate;
Cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butylcarbitol; lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n acetate -Adilide carboxylic acid esters such as butyl, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Other esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate;
Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, diethylene glycol, propylene glycol, tetrahydrofurfuryl alcohol;
Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone; lactones such as γ-butyrolactone Kind;
Aromatic hydrocarbons such as toluene and xylene;
Can be mentioned.

Among these, lactic acid esters, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, alcohols and lactones are preferable; ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, tetrahydrofurfuryl alcohol, Gamma-butyrolactone is more preferred.

The solvent (E) may be used alone or in combination of two or more.

In the resin composition of the present invention, the content of the solvent (E) is usually 40 to 900 parts by mass, preferably 60 to 60 parts by mass with respect to a total of 100 parts by mass of the components other than the solvent (E) in the composition. It is 400 parts by mass.

<Other additives (F)>
In addition, various additions such as an alkali-soluble polymer other than the polymer (A), an adhesion aid, crosslinked fine particles, a leveling agent, a surfactant, a sensitizer, an inorganic filler, and a quencher are added to the resin composition of the present invention. The agent can be contained within a range that does not impair the object and properties of the present invention.

<Preparation method of resin composition>
The resin composition of the present invention can be prepared by uniformly mixing each component. Further, in order to remove foreign substances, each component may be uniformly mixed, and then the obtained mixture may be filtered with a filter or the like. The resin composition is excellent in storage stability.

[Resin film]
Specifically, the resin film of the present invention is a resin film (cured film) obtained by curing the resin composition of the present invention. Since the polymer (A) contained in the resin composition of the present invention has excellent heat resistance, the resin film obtained by using the resin composition of the present invention also has excellent heat resistance.

Further, the resin film of the present invention has high mechanical strength, low coefficient of thermal expansion (linear expansion coefficient), low dielectric constant, excellent elongation physical properties, and is less likely to cause cracks even when subjected to impact.

Therefore, the resin film of the present invention is used as a surface protective film, an interlayer insulating film and a flattening film possessed by electronic components such as a circuit board (semiconductor element), a semiconductor package or a display element, and an insulating film for a high-density mounting substrate. It can be suitably used as a material, a photosensitive adhesive and a pressure sensitive adhesive.

The resin film of the present invention is produced, for example, by performing at least a step of applying the resin composition of the present invention on a support to form a coating film, and a step of curing the coating film to obtain a resin film. can do.

[Manufacturing method of patterned resin film]
In the method for producing a patterned resin film of the present invention, the resin composition of the present invention containing the photosensitive acid generator (B) or the photopolymerization initiator (D) is applied onto a support to form a coating film. A step (hereinafter also referred to as “coating step”), a step of selectively exposing the coating film to obtain a selective exposure film (hereinafter also referred to as “exposure step”), and a pattern of developing the selective exposure film with an alkaline developer. It has a step of obtaining a patterned coating film (hereinafter, also referred to as “development step”) and a step of curing the patterned coating film to obtain a patterned resin film (hereinafter, also referred to as “curing step”).

[1] Coating Step In the coating step, the resin composition of the present invention containing the photosensitive acid generator (B) or the photopolymerization initiator (D) is coated on the support and dried as necessary. The solvent (E) is removed. The drying conditions are, for example, using an oven or a hot plate, usually heating at 50 to 140 ° C. for 10 to 1000 seconds. In this way, a coating film is formed on the support. The film thickness of the coating film may be appropriately adjusted according to the film thickness of the finally obtained patterned resin film.

Examples of the support include silicon wafers, compound semiconductor wafers, wafers with metal thin films, glass substrates, quartz substrates, ceramic substrates, aluminum substrates, SUS substrates, substrates having semiconductor chips on the surface of these supports, and others. Examples include resin sheets. Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, and an inkjet method.

[2] Exposure Step In the exposure step, the coating film is selectively exposed by using, for example, a reticle, for example, a contact aligner, a stepper, or a scanner to obtain a selective exposure film. Examples of the exposure light include radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray, and light having a wavelength of 200 to 500 nm (eg, i-ray (365 nm)) is preferably used. The irradiation amount of the exposure light varies depending on the type of each component in the photosensitive composition, the mixing ratio, the thickness of the coating film, etc., but when i-line is used for the exposure light, the exposure amount is usually 100 to 1500 mJ / It is cm ² .

After that, the selective coating film can be heat-treated. Hereinafter, this process is also referred to as "PEB process". The PEB conditions vary depending on the type of each component in the resin composition, the mixing ratio, the thickness of the coating film, and the like, but are usually 70 to 150 ° C., preferably 80 to 120 ° C. for about 1 to 60 minutes. ..

[3] Development Step In the development step, for example, the selective exposure film is developed with an alkaline developer to form a patterned coating film on a support. Examples of the developing method include a shower developing method, a spray developing method, a dipping developing method, a paddle developing method and the like. The conditions of the developing method are usually about 1 to 10 minutes at 20 to 40 ° C.

As the alkaline developer, for example, alkaline compounds such as sodium hydroxide, potassium hydroxide, aqueous ammonia, tetramethylammonium hydroxyside, and choline are dissolved in water so as to have a concentration of 1 to 10% by mass. An aqueous solution can be mentioned. For example, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution in an appropriate amount. After developing the selective exposure film with an alkaline developer, it may be washed with water and dried.

[4] Curing Step After the developing step, the patterned coating film is cured by heating, for example. As the curing conditions, an oven or a hot plate is used, for example, heating at a temperature of 100 to 250 ° C. for about 1 minute to 10 hours.

[Electronic components]
The electronic component of the present invention has the resin film of the present invention. Examples of the electronic component include a circuit board (semiconductor element), a semiconductor package, or a display element.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "parts" is used to mean "parts by mass" in the following examples and the like.

1. 1. Measurement method of physical properties
Method for Measuring Average Molecular Weight (Mw, Mn) of Polymer (A) and Other Polymers The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by a gel permeation chromatography method under the following conditions.
-Column: Tosoh column TSK-M and TSK2500 are connected in series.-Solvent: N, N-dimethylformamide-Temperature: 40 ° C.
・ Detection method: Refractive index method ・ Standard material: Polystyrene
2. 2. Polymer synthesis
The compounds (M-1) to (M-8) used in the synthesis of the polymer are shown below.

［参考例１－１］（重合体（Ａ－１）の合成）
３００ｍＬの三口フラスコに化合物（Ｍ－１）５．９ｇ（５０モル％）および化合物（Ｍ－２）１０．８ｇ（５０モル％）をプロピレングリコールモノメチルエーテル４５ｇに溶解し、ラジカル重合開始剤としてアゾビスイソブチロニトリル０．９１８ｇ（全単量体に対して７モル％）を添加して単量体溶液を調製した。次いで１５分窒素バブリングを行った後、攪拌しながら８０℃に加熱した。溶液が７５℃となった時点を重合反応の開始時間として、重合反応を４時間実施した。重合反応終了後、重合溶液を水冷して３０℃以下に冷却し、メタノール６０ｇを加え、溶液と等量のノルマルヘキサンで５回液液抽出洗浄を行った。抽出洗浄後の重合体を含むメタノール溶液に等量のプロピレングリコールモノメチルエーテルを加えて、４０℃の水浴を備えたロータリーエバポレーターでメタノールを留去した上、さらに３０％程度まで濃縮し目的の重合体溶液と得た。重合体（Ａ－１）のＭｗは２１，０００であり、Ｍｗ／Ｍｎは２．１５であった。

[Reference Example 1-1] (Synthesis of polymer (A-1))
5.9 g (50 mol%) of compound (M-1) and 10.8 g (50 mol%) of compound (M-2) were dissolved in 45 g of propylene glycol monomethyl ether in a 300 mL three-necked flask, and azo was used as a radical polymerization initiator. A monomer solution was prepared by adding 0.918 g of bisisobutyronitrile (7 mol% with respect to all the monomers). Then, after performing nitrogen bubbling for 15 minutes, the mixture was heated to 80 ° C. with stirring. The polymerization reaction was carried out for 4 hours with the time when the solution reached 75 ° C. as the start time of the polymerization reaction. After completion of the polymerization reaction, the polymerization solution was cooled to 30 ° C. or lower with water, 60 g of methanol was added, and liquid-liquid extraction washing was performed 5 times with normal hexane in the same amount as the solution. An equal amount of propylene glycol monomethyl ether was added to a methanol solution containing the polymer after extraction and washing, methanol was distilled off with a rotary evaporator equipped with a water bath at 40 ° C., and the mixture was further concentrated to about 30% to obtain the target polymer. Obtained as a solution. The Mw of the polymer (A-1) was 21,000, and the Mw / Mn was 2.15.

[Reference Examples 1-2 to 1-6, Examples 1-7, Reference Examples 1-8 to 1-10] (Synthesis of Polymers (A-2) to (A-10))
In Reference Examples 1-2 to 1-6, Examples 1-7, and Reference Examples 1-8 to 1-10, the same as Reference Example 1-1 except that the types and amounts of monomers shown in Table 2 were used. In the same manner, polymers (A-2) to (A-10) were obtained.

３．樹脂組成物の調製
［参考例２－１］
重合体（Ａ－１）１００部を溶媒（Ｅ－１）２５０部に２５℃で溶解させ、樹脂組成物（Ｊ－１）を調製した。得られた樹脂組成物を用いて、所定の評価を行った。

3. 3. Preparation of resin composition [ Reference Example 2-1]
A resin composition (J-1) was prepared by dissolving 100 parts of the polymer (A-1) in 250 parts of the solvent (E-1) at 25 ° C. A predetermined evaluation was performed using the obtained resin composition.

The solvent (E-1) is propylene glycol monomethyl ether.

[Reference Examples 2-2 to 2-6, Examples 2-7, Reference Examples 2-8 to 2-10, Comparative Example 2-1]
Reference Examples 2-2 to 2-6, Examples 2-7, and Reference Examples 2-8 to 2-10 are the same as those of Reference Example 2-1 except that the polymers of the types and amounts shown in Table 3 are used. The resin compositions (J-2) to (J-10) were prepared, and the obtained resin compositions were used for predetermined evaluation. Further, in Comparative Example 2-1 except that the amount of hydroxystyrene-styrene copolymer (product name: Styrene Marcalinker CST, manufactured by Maruzen Petrochemical Co., Ltd.) shown in Table 3 was used as the polymer (CA-1). Prepared a resin composition (CJ-1) in the same manner as in Reference Example 2-1 and performed a predetermined evaluation using the obtained resin composition.

4. The evaluation method of the evaluation resin composition is as follows.

4-1. The heat-resistant resin compositions (J-1) to (J-10) and (CJ-1) were heat-cured at 200 ° C. for 1 hour to obtain a resin film, and then nitrogen was obtained by thermogravimetric analysis (TGA). It was measured under an atmosphere at a heating rate of 10 ° C./min and evaluated at a 5% by mass thermogravimetric reduction temperature (Td5). The case where the 5 mass% thermogravimetric reduction temperature was 350 ° C. or higher was designated as "A", the case where the temperature was 300 ° C. or higher and lower than 350 ° C. was designated as "B", and the case where the temperature was lower than 300 ° C. was designated as "C".

4-2. Storage stability The viscosities of the resin compositions (J-1) to (J-10) and (CJ-1) after being stored at 5 ° C. for 1 month were measured. The viscosity was measured at 25 ° C. using an E-type viscometer (“VISCONIC ELD.R” manufactured by Toki Sangyo Co., Ltd.). "A" when the viscosity increase rate after storage at 5 ° C for 1 month is less than 5%, "B" when 5% or more and less than 10%, "C" when 10% or more and less than 15%, 15% The above case was designated as "D". "-" Means unmeasured.

4-3. The alkali-soluble resin compositions (J-1) to (J-10) and (CJ-1) are applied onto a silicon wafer so as to have a film thickness of 5 μm, and dried on a hot plate at 80 ° C. for 3 minutes. A coating film of the resin composition was obtained. Then, the coating film was immersed in an aqueous solution of tetramethylammonium hydroxyside having a concentration of 2.38% by mass at 23 ° C. for 120 seconds. The case where the coating film was completely dissolved was designated as "A", the case where a small amount of residue was found was designated as "B", and the case where the coating film remained undissolved was designated as "C".

4-4. Mechanical strength resin compositions (J-1) to (J-10) and (CJ-1) are uniformly applied onto a Teflon (registered trademark) sheet and dried in an oven at 80 ° C. for 10 minutes to form a resin composition. A coating film was formed. Next, the coating film was heat-treated in an oven at 200 ° C. for 1 hour, and then peeled off from the Teflon sheet to obtain a cured film (resin film) having a thickness of about 30 μm. The mechanical strength of the peeled cured film was measured with a tensile tester. At the time of measurement, the width of the sample was 5 mm, the distance between the chucks was 20 mm, the tensile speed was 5 mm / min, and the measurement temperature was about room temperature (20 to 25 ° C.). "A" is when the average of the measured values of 5 or more test pieces obtained from the cured film obtained under the same conditions is 70 MPa or more, "B" is when it is 50 MPa or more and less than 70 MPa, and "B" is when it is 30 MPa or more and less than 50 MPa. The case of "C" and less than 30 MPa was defined as "D".

4-5. Coefficient of linear expansion (average coefficient of linear expansion)
The coefficient of linear expansion of the cured film (resin film) obtained in the above-mentioned "4-4" was measured by a thermomechanical analyzer. The width of the sample was 3 mm, and the distance between the chucks was 10 mm. The load was 9.8 mN and the heating rate was 5 ° C./min. When the average coefficient of linear expansion at 100 to 150 ° C. is less than 100 ppm, it is called "A", when it is 100 ppm or more and less than 140 ppm, it is called "B", when it is 140 ppm or more and less than 180 ppm, it is called "C", and when it is 180 ppm or more, it is called "D". bottom.

4-6. The dielectric constant resin compositions (J-1) to (J-10) and (CJ-1) are applied onto a SUS substrate so as to have a film thickness of 5 μm, dried on a hot plate at 80 ° C. for 3 minutes, and then dried. It was heat-cured in an oven at 200 ° C. for 1 hour. The dielectric constant of the obtained cured film (resin film) at 1 MHz was measured, and when it was less than 4.0, it was "A", when it was 4.0 or more and less than 4.5, it was "B", and when it was 4.5 or more. The case was set to "C".

５．感光性組成物の調製
感光性組成物の調製に用いた各成分を以下に示す。

5. Preparation of Photosensitive Composition Each component used for preparation of the photosensitive composition is shown below.

Photosensitive acid generator (B-1): 4,4'-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide- Condensate of 5-sulfonic acid chloride Photosensitive acid generator (B-2): 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate cross-linking agent (C-1): with dipentaerythritol pentaacrylate Mixture with Dipentaerythritol Hexaacrylate Photoinitiator (D-1): 2,4,6-trimethylbenzoyl-diphenyl-phosphinoxide solvent (E-1): Propropylene glycol monomethyl ether solvent (E-2): Tetrahydrofurfuryl alcohol solvent (E-3): γ-butyrolactone surfactant (F-1): FTX-218 (manufactured by Neos Co., Ltd.)
[Reference Example 3-1]
The solvent (E-1) contains 100 parts of the polymer (A-1), 80 parts of the cross-linking agent (C-1), 30 parts of the photopolymerization initiator (D-1), and 0.1 part of the surfactant (F-1). ) Was dissolved in 490 parts at 25 ° C. to prepare a photosensitive composition (PR-1). A predetermined evaluation was performed using the obtained photosensitive composition.

[Reference Examples 3-2 to 3-6, Examples 3-7, Reference Examples 3-8 to 3-10, Comparative Example 3-1]
In Reference Examples 3-2 to 3-6, Examples 3-7, Reference Examples 3-8 to 3-10, and Comparative Example 3-1 except that the types and amounts of the compounding components were changed as shown in Table 4. Prepared photosensitive compositions (PR-2) to (PR-10) and (CPR-1) in the same manner as in Reference Example 3-1. A predetermined evaluation was performed using the obtained photosensitive composition.

6-1. Photolithography Evaluation The evaluation method for the photosensitive composition is as follows.

The photosensitive composition was spin-coated on a silicon wafer having a resolution and a residual film ratio of 6 inches, and then heated at 110 ° C. for 3 minutes using a hot plate to prepare a uniform coating film having a thickness of 10 μm. Next, using an aligner (manufactured by Sus Microtec, model "MA-150"), ultraviolet rays from a high-pressure mercury lamp were applied to the coating film via a pattern mask so that the exposure amount at a wavelength of 350 nm was 500 mJ / cm ² . Irradiated. Then, the coated film after exposure was immersed-developed at 23 ° C. for 120 seconds using a 2.38 mass% concentration tetramethylammonium hydroxyside aqueous solution. Next, the developed coating film was washed with ultrapure water for 30 seconds, air-dried with air, and then observed with a microscope (MHL110 manufactured by Olympus Corporation), and the pattern of the minimum pattern resolved was obtained. The dimensions were defined as resolution (unit: μm). In addition, the film thickness was measured using a stylus type film thickness meter P-16 manufactured by KLA-Tencor, and the residual film thickness (100% × (film thickness after development / film before development) was measured from the difference in film thickness before and after development. Thickness)) was calculated and evaluated according to the following evaluation criteria. In the case of Examples 3-2 to 3-6, after the exposure, the mixture was heated at 110 ° C. for 3 minutes using a hot plate.

A: Residual film rate 90% or more B: Residual film rate 80% or more and less than 90% C: Residual film rate less than 80%
6-2. Solvent resistance
The photosensitive compositions (PR-1) to (PR-10) and (CPR-1) were placed in a 1 mm thick metal frame placed on a Teflon sheet and treated in a vacuum oven at an internal temperature of 50 ° C. for 2 hours. Later, a heavy pressure of 0.5 ton was applied and pressed at 200 ° C. for 2 hours to peel off from the Teflon sheet to obtain a cured film having a thickness of about 0.5 mm. This cured film was cut into 1 cm squares for testing, weighed, and then immersed in 5 ml of NMP (N-methylpyrrolidone) at room temperature for 3 days to change the shape of the cured film (visual shape change, weight change). Was evaluated. The weight of the cured film after NMP immersion was measured after the cured film after NMP immersion was dried in a vacuum oven at an internal temperature of 80 ° C. for 3 days. Each weight of the cured film before and after NMP immersion was measured with a Sartorius precision balance BP311D. "A" when there is no visual change in shape and the weight loss is less than 3%, "B" when the weight loss is 3% or more and less than 10% regardless of the change in visual shape, 10% or more. Was defined as "C".

6-3. For the heat-meltable photosensitive compositions (PR-1) to (PR-10) and (CPR-1), two 1 cm square cured film test pieces obtained by the same method as in "6-2" above were stacked. A 5 cm square stainless steel substrate having a thickness of 1 mm was sandwiched between the upper and lower parts and pressed under a heavy pressure of 0.5 tons at 200 ° C. for 1 hour, and the change in shape was evaluated as thermal meltability. "M1" when the two cured film test pieces are melt-deformed and integrated, "m2" when the two cured film test pieces are melt-deformed but not integrated, and the cured film test piece The case where the film was not melted and deformed and was not integrated was defined as "m3".

Claims (11)

(A) In the same or different molecules
The structural unit represented by the following formula (1) and
The structural unit represented by the following formula (2) and
The structural unit represented by the following formula (3) and
The structural unit represented by the following formula (4) and
A resin composition containing a polymer containing a structural unit having an epoxy group, and (E) a solvent.

[In the formula (1), R ¹ and R ² are independently each of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms. In between, it is selected from -O-, -COO-, -OCO-, -OSO _{2-, -SO 3-, -OSO 2} NR- _{, -NRSO} 2- , _-NRCO- , -NR- and -CONR-. A group having at least one kind, or a group in which a part of a hydrogen atom in these groups is substituted is shown, and R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹ and R ² are. , May be bonded to each other to form a cyclic structure with 3 to 20 ring members with the boron atom to which OR ¹ and OR ² are bonded; R ¹¹ is a hydrogen atom, a fluorine atom, and a hydrocarbon having 1 to 10 carbon atoms. A group, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms; L ¹ is a single bond, an oxygen atom, a sulfur atom, or a group represented by -C (= O) -X ^1- , and X ¹ is an oxygen atom, a sulfur atom or an NH group; R ¹² is a (a + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and-between at least one carbon-carbon bond in the hydrocarbon group. O-, -COO-, -OCO-, -OSO _2- , -SO _3- , -OSO ₂ NR ^101- , -NR ¹⁰¹ SO _2- , -NR ¹⁰¹ CO- , -NR ^101- and -CONR ^101- A group having at least one selected from the above, or a group in which a part of hydrogen atoms in these groups is substituted, wherein R ¹⁰¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; a is. It is an integer of 1 to 3. ]

[In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an electron-attracting group, except that among the above R ³ and R ⁴ . , At least one of which is an electron-attracting group; R ¹³ is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms; L ² Is a single bond, an oxygen atom, a sulfur atom, or a group represented by -C (= O) -X ^2- ; X ² is an oxygen atom, a sulfur atom or an NH group; R ¹⁴ is a carbon. (B + 1) -valent hydrocarbon groups of number 1 to 20, -O-, -COO-, -OCO-, -OSO _2- , -SO ₃ between at least one carbon-carbon bond in the hydrocarbon group. -, -OSO ₂ NR ^102- , -NR ¹⁰² SO _2- , -NR ¹⁰² CO- , -NR ^102- and -CONR ¹⁰² -A group having at least one selected from, or one of the hydrogen atoms in these groups. The moiety is substituted group, R ¹⁰² is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; b is an integer of 1 to 3. ]

[In formula (3), R ⁵ is an organic group having 1 to 20 carbon atoms; R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 0 to 3. R ¹⁵ is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms; L ³ is a single bond, an oxygen atom, a sulfur atom, or -C (= O) -X ^3- is a group represented by-where X ³ is an oxygen atom, a sulfur atom or an NH group; R ¹⁶ is a (c + 1) -valent hydrocarbon having 1 to 20 carbon atoms. -O-, -COO-, -OCO-, -OSO _2- , -SO _3- , -OSO ₂ NR ^104- , -NR ¹⁰⁴ between at least one carbon-carbon bond in the group, said hydrocarbon group. A group having at least one selected from SO _2- , -NR ¹⁰⁴ CO- , -NR ^104- and -CONR 104- ^, or a group in which a part of a hydrogen atom in these groups is substituted, and the above-mentioned R ¹⁰⁴ . Is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; c is an integer of 1 to 3. ]

[In the formula (4), R ⁷ and R ⁸ are independently each of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms. In the meantime, -O-, -COO-, -OCO-, -OSO _2- , -SO _3- , -OSO ₂ NR 105- , -NR ¹⁰⁵ SO _2- , -NR ^{105 CO-} , -NR ^105- and A group having at least one selected from -CONR 105- ^, or a group in which a part of a hydrogen atom in these groups is substituted is shown, and R ¹⁰⁵ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Yes, R ⁷ and R ⁸ may be bonded together to form a cyclic structure with 3 to 20 ring members with the phosphorus atom to which OR ⁷ and OR ⁸ are bonded; R ¹⁷ is a hydrogen atom, a fluorine atom, It is a hydrocarbon group having 1 to 10 carbon atoms or a fluorinated hydrocarbon group having 1 to 10 carbon atoms; L ⁴ is a single bond, an oxygen atom, a sulfur atom, or -C (= O) -X ^4- . The group represented; X ⁴ is an oxygen atom, a sulfur atom or an NH group; R ¹⁸ is a (d + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, at least one of the above hydrocarbon groups. Between carbon-carbon bonds, -O-, -COO-, -OCO-, -OSO _2- , -SO _3- , -OSO ₂ NR ^106- , -NR ¹⁰⁶ SO _2- , -NR ¹⁰⁶ CO-,- A group having at least one selected from NR ^106- and -CONR 106- ^, or a group in which a part of hydrogen atoms in these groups is substituted, and the R ¹⁰⁶ is a hydrogen atom or a group having 1 to 20 carbon atoms. It is a hydrocarbon group; d is an integer of 1 to 3. ] The resin composition according to claim 1, wherein the polymer (A) contains 5 to 60 mol% of the structural units represented by the above formula (1) in the total structural units. The resin composition according to claim 1 or 2, wherein the polymer (A) contains 5 to 90 mol% of the structural units represented by the above formula (2) in the total structural units. The resin composition according to any one of claims 1 to 3 , wherein the polymer (A) contains 5 to 50 mol% of the structural units represented by the above formula (3) in the total structural units. The resin composition according to any one of claims 1 to 4 , wherein the polymer (A) contains 5 to 45 mol% of the structural unit having an epoxy group in the total structural unit. The resin composition according to any one of claims 1 to 5 , further comprising a photosensitive acid generator (B) or a photopolymerization initiator (D). The resin composition according to any one of claims 1 to 6 , further comprising a cross-linking agent (C). The structural unit represented by the following formula (1) and
The structural unit represented by the following formula (2) and
The structural unit represented by the following formula (3) and
The structural unit represented by the following formula (4) and
A polymer containing a structural unit having an epoxy group.

[In the formula (1), R ¹ and R ² are independently each of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms. In between, it is selected from -O-, -COO-, -OCO-, -OSO _{2-, -SO 3-, -OSO 2} NR- _{, -NRSO} 2- , _-NRCO- , -NR- and -CONR-. A group having at least one kind, or a group in which a part of a hydrogen atom in these groups is substituted is shown, and R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹ and R ² are. , May be bonded to each other to form a cyclic structure with 3 to 20 ring members with the boron atom to which OR ¹ and OR ² are bonded; R ¹¹ is a hydrogen atom, a fluorine atom, and a hydrocarbon having 1 to 10 carbon atoms. A group, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms; L ¹ is a single bond, an oxygen atom, a sulfur atom, or a group represented by -C (= O) -X ^1- , and X ¹ is an oxygen atom, a sulfur atom or an NH group; R ¹² is a (a + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and-between at least one carbon-carbon bond in the hydrocarbon group. O-, -COO-, -OCO-, -OSO _2- , -SO _3- , -OSO ₂ NR ^101- , -NR ¹⁰¹ SO _2- , -NR ¹⁰¹ CO- , -NR ^101- and -CONR ^101- A group having at least one selected from the above, or a group in which a part of hydrogen atoms in these groups is substituted, wherein R ¹⁰¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; a is. It is an integer of 1 to 3. ]

[In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an electron-attracting group, except that among the above R ³ and R ⁴ . , At least one of which is an electron-attracting group; R ¹³ is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms; L ² Is a single bond, an oxygen atom, a sulfur atom, or a group represented by -C (= O) -X ^2- ; X ² is an oxygen atom, a sulfur atom or an NH group; R ¹⁴ is a carbon. (B + 1) -valent hydrocarbon groups of number 1 to 20, -O-, -COO-, -OCO-, -OSO _2- , -SO ₃ between at least one carbon-carbon bond in the hydrocarbon group. -, -OSO ₂ NR ^102- , -NR ¹⁰² SO _2- , -NR ¹⁰² CO- , -NR ^102- and -CONR ¹⁰² -A group having at least one selected from, or one of the hydrogen atoms in these groups. The moiety is substituted group, R ¹⁰² is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; b is an integer of 1 to 3. ]

[In formula (3), R ⁵ is an organic group having 1 to 20 carbon atoms; R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 0 to 3. R ¹⁵ is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms; L ³ is a single bond, an oxygen atom, a sulfur atom, or -C (= O) -X ^3- is a group represented by-where X ³ is an oxygen atom, a sulfur atom or an NH group; R ¹⁶ is a (c + 1) -valent hydrocarbon having 1 to 20 carbon atoms. -O-, -COO-, -OCO-, -OSO _2- , -SO _3- , -OSO ₂ NR ^104- , -NR ¹⁰⁴ between at least one carbon-carbon bond in the group, said hydrocarbon group. A group having at least one selected from SO _2- , -NR ¹⁰⁴ CO- , -NR ^104- and -CONR 104- ^, or a group in which a part of a hydrogen atom in these groups is substituted, and the above-mentioned R ¹⁰⁴ . Is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; c is an integer of 1 to 3. ]

[In the formula (4), R ⁷ and R ⁸ are independently each of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms. In the meantime, -O-, -COO-, -OCO-, -OSO _2- , -SO _3- , -OSO ₂ NR 105- , -NR ¹⁰⁵ SO _2- , -NR ^{105 CO-} , -NR ^105- and A group having at least one selected from -CONR 105- ^, or a group in which a part of a hydrogen atom in these groups is substituted is shown, and R ¹⁰⁵ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Yes, R ⁷ and R ⁸ may be bonded together to form a cyclic structure with 3 to 20 ring members with the phosphorus atom to which OR ⁷ and OR ⁸ are bonded; R ¹⁷ is a hydrogen atom, a fluorine atom, It is a hydrocarbon group having 1 to 10 carbon atoms or a fluorinated hydrocarbon group having 1 to 10 carbon atoms; L ⁴ is a single bond, an oxygen atom, a sulfur atom, or -C (= O) -X ^4- . The group represented; X ⁴ is an oxygen atom, a sulfur atom or an NH group; R ¹⁸ is a (d + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, at least one of the above hydrocarbon groups. Between carbon-carbon bonds, -O-, -COO-, -OCO-, -OSO _2- , -SO _3- , -OSO ₂ NR ^106- , -NR ¹⁰⁶ SO _2- , -NR ¹⁰⁶ CO-,- A group having at least one selected from NR ^106- and -CONR 106- ^, or a group in which a part of hydrogen atoms in these groups is substituted, and the R ¹⁰⁶ is a hydrogen atom or a group having 1 to 20 carbon atoms. It is a hydrocarbon group; d is an integer of 1 to 3. ] A resin film obtained by curing the resin composition according to any one of claims 1 to 7 . A step of applying the resin composition according to claim 6 on a support to form a coating film, a step of selectively exposing the coating film to obtain a selective exposure film, and a step of selectively exposing the selective exposure film with an alkaline developer. A method for producing a patterned resin film, which comprises a step of developing and obtaining a patterned coating film and a step of curing the patterned coating film to obtain a patterned resin film. The electronic component having the resin film according to claim 9 .