JPWO2020111022A1 - Ethylene unsaturated resin composition and photosensitive resin composition - Google Patents

Abstract

Provided is a resin composition having a small amount of residual polymerization inhibitor, transparency, heat-resistant yellowing, and high fine particle dispersibility including a coloring material. The ethylenically unsaturated resin composition of the present invention contains an ethylenically unsaturated resin (A), a carbon cluster (c), and a solvent (B), and the carbon cluster (c) is in the form of fullerenes and soot. It is at least one of the substances, and its content is 0.00001 to 10 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated resin (A).

Description

The present invention relates to ethylenically unsaturated resin compositions and photosensitive resin compositions.
The present application claims priority based on Japanese Patent Application No. 2018-222730 filed in Japan on November 28, 2018, the contents of which are incorporated herein by reference.

Acrylic resins are used in various fields due to their excellent transparency, weather resistance, and well-balanced mechanical properties. Recently, it has been disclosed that by using a photosensitive resin composition composed of a resin having an ethylenically unsaturated group introduced therein, a black column spacer or the like as a member for a display is formed through coating, exposure, developing steps and the like. (Patent Document 1). As a method for introducing an ethylenically unsaturated group into a resin, a method of reacting a resin containing an epoxy group with an ethylenically unsaturated compound containing a carboxy group in the presence of a polymerization inhibitor and a catalyst is disclosed.

International Publication No. 2017/204079

In recent years, in order to improve the performance required for displays, the performance of highly heat-resistant yellowing and high pigment dispersibility has been regarded as important for acrylic resins. Therefore, it is desired to reduce the amount of the banning agent and the residual catalyst in excess of the amount of the polymerization banning agent required for storage.

The present invention has been made to solve the above problems, and the ethylenically unsaturated resin composition can be obtained by efficiently synthesizing even if a small amount of carbon clusters are used. That is, an object of the present invention is to submit an ethylenically unsaturated resin composition containing a small amount of carbon clusters, further, high heat-resistant yellowing, high fine particle dispersibility including a coloring material, and an excellent pattern shape. An object of the present invention is to provide a photosensitive resin composition from which a resist can be obtained.

That is, the present invention is shown by the following [1] to [13].
[1] Ethylene unsaturated resin (A) and
Carbon cluster (c) and
Contains solvent (B)
The carbon cluster (c) is at least one of fullerenes and soot-like substances, and the content thereof is 0.00001 to 10 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated resin (A). An ethylenically unsaturated resin composition characterized by being present.
[2] In the ethylenically unsaturated resin (A), a carboxy group-containing ethylenically unsaturated compound (m-2) is ring-opened and added to the epoxy group of the epoxy group-containing copolymer (P1), and further, the above. An ethylenically unsaturated resin (A1) formed by adding a polybasic acid anhydride (d) to a hydroxy group generated by opening an epoxy group.
The epoxy group-containing copolymer (P1) is
A structural unit derived from an epoxy group-containing (meth) acrylate (m-1) and a polymerizable monomer (m-3) having a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms, and the following chemical formula (1). At least one selected from the group consisting of structural units derived from the polymerizable monomer (m-4) represented by
The ethylenically unsaturated resin composition according to [1], which is a copolymer containing.

(X and X'in the formula (1) each independently represent a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms which may be linear or branched, and R1 and R2 are independent of each other. It is a hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom carboxy group or a substituent, and may have a cyclic structure connecting R1 and R2.)
[3] The ethylenically unsaturated resin (A) is a hydroxy group formed by ring-opening addition of a carboxy group-containing copolymer (P2) to an epoxy group of an epoxy group-containing ethylenically unsaturated compound (m-1). It is an unsaturated group-containing ethylenically unsaturated resin (A2) having an unsaturated group.
The carboxy group-containing copolymer (P2) is
Constituent units derived from the carboxy group-containing ethylenically unsaturated compound (m-2) and
It is composed of a structural unit derived from a polymerizable monomer (m-3) having a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms and a structural unit derived from a polymerizable monomer (m-4) represented by the following chemical formula (1). At least one selected from the group and
The ethylenically unsaturated resin composition according to [1], which is a copolymer containing.

(X and X'in the formula (1) each independently represent a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms which may be linear or branched, and R1 and R2 are independent of each other. It is a hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom carboxy group or a substituent, and may have a cyclic structure connecting R1 and R2.)
[4] In the ethylenically unsaturated resin (A), a carboxy group-containing ethylenically unsaturated compound (m-2) is ring-opened and added to the epoxy group of the epoxy resin (P3), and the epoxy group is further opened. It is an ethylenically unsaturated resin (A3) formed by adding a polybasic acid anhydride (d) to a hydroxy group generated by ringing.
The epoxy resin (P3) is
At least one selected from the group consisting of a novolak type epoxy resin (P3-1), a bisphenol type epoxy resin (P3-2), and a bifunctional epoxy resin having a biphenyl skeleton (P3-3) [1]. The ethylenically unsaturated resin composition according to the above.
[5] The ethylenically unsaturated resin (A) has a hydroxy group formed by ring-opening addition of a carboxy group-containing resin (P4) to an epoxy group of an epoxy group-containing ethylenically unsaturated compound (m-1). Ethylene unsaturated resin (A4)
The carboxy group-containing resin (P4) is a resin having a carboxy group formed by reacting an epoxy resin (P3) with a polyfunctional carboxylic acid (e).
The epoxy resin (P3) is
At least one selected from the group consisting of a novolak type epoxy resin (P3-1), a bisphenol type epoxy resin (P3-2), and a bifunctional epoxy resin having a biphenyl skeleton (P3-3) [1]. The ethylenically unsaturated resin composition according to the above.
[6] The ethylenically unsaturated resin (A) is
The ethylenically unsaturated resin (A5), which is obtained by adding a polybasic acid anhydride (d) to the hydroxy group of the ethylenically unsaturated resin (A2) according to [3], or the ethylenically according to [5]. The ethylenically unsaturated resin composition according to [1], which is an ethylenically unsaturated resin (A6) in which a polybasic acid anhydride (d) is added to a hydroxy group of an unsaturated resin (A4).
[7] The ethylenically unsaturated resin composition according to any one of [1] to [6], wherein the carbon cluster (c) is an unsubstituted fullerene.
[8] The ethylenically unsaturated resin composition according to any one of [1] to [7], which does not substantially contain a polymerization inhibitor other than the carbon cluster (c).
[9] The ethylenically unsaturated resin composition according to any one of [1] to [8], which further contains a reactive diluent (D).
[10] A photosensitive resin composition containing the ethylenically unsaturated resin composition according to any one of [1] to [9] and a photopolymerization initiator (E).
[11] Further containing a colorant (F),
The photosensitive resin composition according to [10], wherein the colorant (F) is at least one selected from the group consisting of dyes and pigments.
[12] The photosensitive resin composition according to [10] or [11], which is substantially free of a polymerization inhibitor other than the carbon cluster (c).
[13] A resist using the photosensitive resin composition according to any one of [10] to [12].

According to the present invention, an ethylenically unsaturated resin composition containing a small amount of carbon clusters, having high transparency, high heat-resistant yellowing, and high fine particle dispersibility including a coloring material, and a photosensitive resin composition using the same. Provided.

The present invention will be described in detail below.
[Ethylene unsaturated resin composition]
The ethylenically unsaturated resin composition of the present invention contains an ethylenically unsaturated resin (A), a carbon cluster (c), and a solvent (B). The carbon cluster (c) is at least one of fullerenes and soot-like substances. The content of the carbon cluster (c) is 0.00001 to 10 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated resin (A). It is preferable that the carbon cluster (c) is an unsubstituted fullerene. Further, the ethylenically unsaturated resin composition of the present invention may be substantially free of a polymerization inhibitor other than the carbon cluster (c). “Substantially free” means that the polymerization inhibitor other than the carbon cluster (c) is preferably 0.05 part by mass or less, more preferably 0, based on 100 parts by mass of the ethylenically unsaturated resin (A). It means that it includes less than 0.01 parts by mass.

The resin composition of the present invention may further contain a reactive diluent (D).

[Carbon cluster (c)]
By containing the carbon cluster (c), the ethylenically unsaturated resin composition of the present invention prevents gelation due to the polymerization of the double bond of the ethylenically unsaturated resin (A) and enhances storage stability. Can be done. Further, by using the carbon cluster (c) in the photosensitive resin composition containing the photopolymerization initiator (E) described later, heat-resistant yellowing and fine particle dispersibility including a coloring material are not adversely affected. A photosensitive resin composition is obtained, which is excellent in the above-mentioned properties and can obtain a resist having an excellent pattern shape.

The carbon cluster (c) is a group or fine particles formed by agglutination of several to several hundred atoms or molecules. The maximum diameter of the carbon cluster (c) is preferably 300 nm or less, and more preferably 100 nm or less. In the carbon cluster (c), the primary particles may be aggregated, but the size of the primary particles affects the dispersion of the carbon clusters (c), so the maximum diameter here is the maximum diameter of the primary particles. Is.
The carbon cluster (c) of the present invention is a fullerene or a soot-like substance.

As the fullerene used in the present invention, those having about 60 to 120 carbon atoms such as 60, 70, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96 are known. There is. In the present invention, the number of carbon atoms is not particularly limited, but 60 (C60) carbon atoms and 70 (C70) carbon atoms are preferable in terms of easy availability and excellent dispersibility. Further, fullerenes containing different atoms such as scandium (Sc), lanthanum (La), cerium (Ce), titanium (Ti) and nitrogen (N) can also be used. Moreover, oxides of the fullerene oxide fullerene each other was added _{(C60) 2} O or fullerene adduct between (C60-C60, C70-C60 , C70-C70 , etc.) and the like can be used.

The soot-like substance used in the present invention is preferably soot produced as a by-product during the production of fullerenes. It is contained in crude fullerenes produced in the manufacturing process of fullerenes. After solvent extraction and removal of fullerenes from crude fullerenes, the residue contains more of its soot-like material. This soot-like carbon substance contains an amorphous carbon molecule having a structure in which a 5-membered ring and a 6-membered ring are bonded like a fullerene and is not closed.
Examples of the method for producing fullerene producing a soot-like substance as a by-product include a resistance heating method, an arc discharge method, a microwave method, a high frequency heating method, a CVD method, a thermal plasma method, a combustion method, a laser method, and a thermal decomposition method. Both are manufactured in an environment with a pressure of 800 hPa or less. For example, in the case of the gas combustion method, the soot-like carbon substance can be obtained by firing a hydrocarbon raw material and an oxygen-containing gas in a reduced pressure environment. As the hydrocarbon raw material, for example, aromatic hydrocarbons such as toluene and benzene can be used. The depressurization condition is preferably 3 to 800 hPa, and the heating condition is preferably 1600 ° C. to 2000 ° C.

When the hydrocarbon raw material and the oxygen-containing gas are fired in the above-mentioned reduced pressure environment, hydrogen is released from the hydrocarbon raw material. Here, the mixing ratio of the hydrocarbon raw material and the oxygen-containing gas is preferably 2.5 to 3.5 in an equivalent ratio, and the amount of the hydrocarbon raw material is preferably increased. As a result, the reaction can be incomplete combustion. When the reaction is completely burned, carbon in the hydrocarbon raw material is combined with oxygen and discharged as carbon monoxide or carbon dioxide, which may make it difficult for the carbons to bond with each other. In the equivalent ratio, the ratio of the amount of the hydrocarbon raw material to be completely burned and the amount of oxygen is set to 1.

The hydrocarbon raw material from which hydrogen has been released is unstable and easily aggregates with the surrounding carbons. At this time, some of them react and chemically bond. The carbon compounds obtained in this process include soot-like substances and other carbon compounds.
The soot-like substance contains amorphous carbon molecules such as fullerenes, which cannot reach a predetermined spherical molecular structure, although the molecules are bonded to each other and a plurality of carbons are bonded to each other. Such an amorphous carbon molecule has the same structure as the partial structure of fullerene, and has an intermediate produced in the manufacturing process of fullerene, a structure in which a part of spherical fullerene is missing, or a structure in which the shell is not closed. Examples include carbon molecules. The amorphous carbon molecules may form a cluster structure in which a plurality of these carbon molecules are gathered. The cluster structure includes a nested structure in which carbon molecules having a large non-closed structure enclose carbon molecules having a small non-closed structure.

The carbon cluster (c) may have a substituent as long as the effects such as dispersibility and radical trapping ability are not impaired. Examples of the substituent include inden, malonic acid, methyl phenylbutyrate, etc., and examples of the fullerene derivative include ICBA (indenbis adduct), ICMA (inden adduct), PCBM (phenyl-C61-methyl butyrate, etc.), and the like. SAM (1-methyl-1H-pyrrolobenzoic acid adduct) and the like can be exemplified.

The amount of the carbon cluster (c) added is 0.00001 to 10 parts by mass, preferably 0.0001 to 5 parts by mass, based on 100 parts by mass of the ethylenically unsaturated resin (A). It is more preferably 005 to 1 part by mass. When it is 0.00001 parts by mass or more, it is possible to prevent the double bond of the ethylenically unsaturated resin (A) from polymerizing and gelling the composition. If it is 10 parts by mass or less, the curability is not adversely affected even when it is photocured as a photosensitive resin composition described later.
If the carbon cluster (c) is finally contained in the ethylenically unsaturated resin composition, the effect of the present invention can be obtained. Further, if the carbon cluster (c) is added from the stage of synthesizing the ethylenically unsaturated resin (A), the carbon cluster (c) can be more efficiently dispersed in the ethylenically unsaturated resin composition.
The amount of the carbon cluster (c) added in the synthesis of the ethylenically unsaturated resin (A) is preferably 0.0001 to 0.1 parts by mass with respect to 100 parts by mass in total of the polymer and the monomer as materials, and is 0. .005 to 0.05 parts by mass is more preferable.
When the amount of carbon clusters (c) added during the reaction is 0.1 parts by mass or less, the reaction is not hindered even when the ethylenically unsaturated resin (A) is radically cured. When the amount is 0.0001 parts by mass or more, radicals generated during the reaction for obtaining the ethylenically unsaturated resin (A) can be sufficiently trapped to prevent gelation of the ethylenically unsaturated resin (A).

Since the amount of carbon cluster (c) used is small, it is preferable to use unsubstituted fullerene for carbon cluster (c) because of its availability, and there is no mixture of C60, C70 and other higher-order fullerenes. It is more preferable to use a substituted fullerene.

As the carbon cluster (c), for example, nanom mix ST (composed of about 60% of C60, about 25% of C70, and other higher-order fullerenes) manufactured by Frontier Carbon Co., Ltd., which is a fullerene mixture, can be used.

[Polymerization inhibitors other than carbon cluster (c)]
Polymerization inhibitors other than the carbon cluster (c) are usually added to prevent gelation due to the polymerization of the double bond introduced into the ethylenically unsaturated resin (A), except for the carbon cluster (c) according to the present invention. The type of the polymerization inhibitor is not particularly limited, and specific examples thereof include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, and dibutyl hydroxytoluene.

[Ethylene unsaturated resin (A)]
The ethylenically unsaturated resin (A) of the present invention is not particularly limited as long as it is a resin containing an ethylenically unsaturated group, but preferably an epoxy group-containing compound (a) and a carboxy group-containing compound (b) are reacted. The resin is obtained by subjecting the mixture to an ethylenically unsaturated group, and at least one of the epoxy group-containing compound (a) and the carboxy group-containing compound (b) contains an ethylenically unsaturated group. For example, it can be obtained by reacting a resin containing an epoxy group and an unsaturated compound containing a carboxy group as a polymerization inhibitor in the presence of a carbon cluster (c) and a catalyst. Alternatively, for example, a method in which an unsaturated compound containing an epoxy group and a resin containing a carboxy group are reacted in the presence of a carbon cluster (c) and a catalyst as a polymerization inhibitor can also be obtained.

The epoxy group-containing compound (a) according to the present invention is not particularly limited as long as it is a compound having an epoxy group. Preferably, the epoxy group-containing copolymer (P1) in the first embodiment described later, the epoxy group-containing ethylenically unsaturated compound (m-1) in the second embodiment and the fourth embodiment described later, and the third described later. Epoxy resin (P3) in the embodiment can be mentioned.
The carboxy group-containing compound (b) according to the present invention is not particularly limited as long as it is a compound having a carboxy group. Preferably, the carboxy group-containing ethylenically unsaturated compound (m-2) in the first and third embodiments described later, the carboxy group-containing copolymer (P2) in the second embodiment described later, and the fourth embodiment described later. Examples thereof include a carboxy group-containing resin (P4) in the embodiment.

When the amount of the carbon cluster (c) used is 0.00001 to 10 parts by mass with respect to 100 parts by mass of the total of the epoxy group-containing compound and the carboxy group-containing compound, for example, the finally obtained ethylenically unsaturated The resin composition contains 0.00001 to 10 parts by mass of carbon clusters (c) with respect to 100 parts by mass of the ethylenically unsaturated resin (A).

[First Embodiment]
[Ethylene unsaturated resin (A1)]
The ethylenically unsaturated resin (A1) of the present embodiment has an epoxy group of an epoxy group-containing copolymer (P1) which is an epoxy group-containing compound (a) and a carboxy group-containing ethylene which is a carboxy group-containing compound (b). The ethylenically unsaturated compound (m-2) is ring-opened and added, and if necessary, the polybasic acid anhydride (d) is added to the hydroxy group generated by the ring-opening of the epoxy group. It is a resin having a saturated group. The epoxy group-containing copolymer (P1) is a polymerizable monomer having a structural unit derived from an epoxy group-containing ethylenically unsaturated compound (m-1) and a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms (P1). It is a copolymer containing at least one selected from the group consisting of a structural unit derived from m-3) and a structural unit derived from the polymerizable monomer (m-4) represented by the above chemical formula (1). The ethylenically unsaturated resin (A1) can further contain a structural unit derived from an aromatic ring-containing polymerizable monomer (m-5) and the like.

The ethylenically unsaturated resin (A1) according to this embodiment contains a structural unit derived from the addition reaction of the carboxy group-containing ethylenically unsaturated compound (m-2), so that a double bond having excellent photosensitivity can be introduced. At the same time, a hydroxy group having excellent alkali developability can be obtained by opening the ring of the epoxy group. Further, if a carboxylic acid is introduced by adding a polybasic acid anhydride (d) to the obtained hydroxy group, the alkali developability can be enhanced. With this structural unit, sufficient hardness of the cured product is exhibited and high solvent resistance is exhibited.
Further, by not reacting the entire amount of the epoxy group with the carboxy group-containing ethylenically unsaturated compound (m-2) and leaving a part thereof, it is possible to simultaneously develop the curability by heat.

[Epoxy group-containing copolymer (P1)]
The monomer (M1) forming the epoxy group-containing copolymer (P1) according to the ethylenically unsaturated resin (A1) of the present embodiment (hereinafter, may be simply referred to as “copolymer (P1)”) is , A polymerizable monomer (m-3) having an epoxy group-containing ethylenically unsaturated compound (m-1) and a bridging ring-type hydrocarbon group having 10 to 20 carbon atoms, and the polymerizable property represented by the above chemical formula (1). Contains at least one selected from the group consisting of monomers (m-4). The monomer (M1) can further contain an aromatic ring-containing polymerizable monomer (m-5), another polymerizable monomer (m-6), and the like. By further having the aromatic ring-containing polymerizable monomer (m-5), an epoxy group-containing copolymer (P1) having more excellent colorant dispersibility can be obtained.

[Epoxy group-containing ethylenically unsaturated compound (m-1)]
The epoxy group-containing ethylenically unsaturated compound (m-1) (hereinafter, may be simply referred to as "monomer (m-1)") does not have a carboxy group, and has an epoxy group and an ethylenically unsaturated group. The monomer is not particularly limited as long as it has. Specific examples include glycidyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, and lactone adducts thereof (for example,). , Cyclomer® A200, M100) manufactured by Daicel Chemical Industry Co., Ltd., mono (meth) acrylic acid ester of 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, dicyclopentenyl ( Examples thereof include an epoxidized product of meta) acrylate and an epoxidized product of dicyclopentenyloxyethyl (meth) acrylate. These epoxy group-containing ethylenically unsaturated compounds (m-1) may be used alone or in combination of two or more. In particular, glycidyl (meth) acrylate is preferable from the viewpoint of easy availability and good reactivity.

The structural unit derived from the epoxy group-containing ethylenically unsaturated compound (m-1) and the carboxy group-containing ethylenically unsaturated compound (m-2) described later provide a photosensitive group exhibiting photocurability. It is an essential origin configuration in the ethylenically unsaturated resin (A1) of one form of the invention.
By introducing a photosensitive group that exhibits photocurability, the cured film exhibits sufficient hardness and high solvent resistance.

[Polymerizable monomer (m-3)]
The polymerizable monomer (m-3) (hereinafter, may be simply referred to as “monomer (m-3)”) has a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms. Here, the bridging cyclic hydrocarbon means a substance having a structure represented by the following formula (2) or (3) represented by adamantan and norbornane, and the bridging cyclic hydrocarbon group is a group. , Refers to a group corresponding to the remaining part of the structure except for a part of hydrogen. Further, the polymerizable monomer (m-3) does not contain the polymerizable monomer (m-4) described later.

(In the formula (2), A and B each represent a linear or branched alkylene group (including a cyclic formula), and R3 represents a hydrogen atom or a methyl group. A and B are the same but different. It may be, and the branches of A and B may be connected to form a ring.)

(In the formula (3), A', B', and D represent a linear or branched alkylene group (including a cyclic formula), respectively, and R4 represents a hydrogen atom or a methyl group. A', B', D May be the same or different, and the branches of A', B', and D may be connected to form a ring.
)

As the monomer (m-3), a (meth) acrylate having a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms is preferable, and it has an adamantyl (meth) acrylate or a structure represented by the following formula (4) ( Meta) acrylate is more preferred.

(In formula (4), R5 to R7 represent hydrogen atoms or methyl groups, respectively. R8 and R9 may be hydrogen atoms or methyl groups, or may be linked to each other to form a saturated or unsaturated ring. The ring is preferably a 5- or 6-membered ring. * Represents a bond linked to a (meth) acryloyloxy group.)

Examples of the above (m-3) include dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate and the like. These can be used alone or in combination of two or more.

[Polymerizable monomer (m-4)]
The polymerizable monomer (m-4) (hereinafter, may be simply referred to as “monomer (m-4)”) is a monomer represented by the following general formula (1).

(X and X'in the formula (1) each independently represent a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms which may be linear or branched, and R1 and R2 are independent of each other. It is a hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent, and may have a cyclic structure connecting R1 and R2.)

The monomer (m-4) is not particularly limited as long as it has a chemical structure represented by the general formula (1). In the general formula (1), examples of X and X'representing a linear or branched hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. Groups, isobutyl groups, t-butyl groups and the like can be mentioned. Further, examples of the substituent in the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent shown by R1 and R2 include an alkoxy group and an aryl group. Examples of R1 and R2 are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group and 2-ethylhexyl group. Linear or branched alkyl groups such as cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group and the like. Cyclic groups; alkyl groups substituted with alkoxy groups such as 1-methoxyethyl group and 1-ethoxyethyl group; alkyl groups substituted with aryl groups such as phenylaralkyl groups and the like can be mentioned.

Examples of the monomer (m-4) having a chemical structure represented by the general formula (1) are norbornene (bicyclo [2.2.1] hept-2-ene) and 5-methylbicyclo [2.2.1]. ] Hept-2-ene, 5-ethylbicyclo [2.2.1] Hept-2-ene, tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} ] Dodeca-3-ene, dicyclopentadiene, tricyclo [5.2.1.0 ^2,6 ] deca-8-ene, tricyclo [5.2.1.0 ^2,6 ] deca-3 -En, tricyclo [4.4.0.1 ^2,5 ] undeca-3-ene, tricyclo [6.2.1.0 ^1,8 ] undeca-9-en, tricyclo [6.2.1.0] ^1,8 ] Undeca-4-ene, tetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} . 0 ^1,6 ] Dodeca-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} . 0 ^1,6 ] Dodeca-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . ^{17 and 12} ] Dodeca-3-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . ^{17 and 10} . 0 ^1,6 ] Dodeca-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-4-ene, pentacyclo [7.4.0.1 ^{2,5. 19 and 12} . ^{08, 13} ] Pentadeca-3-en and the like can be mentioned. These can be used alone or in combination of two or more.

By using the above-mentioned monomer (m-3) and / or the above-mentioned monomer (m-4), it contributes to smooth coating property, high heat-resistant decomposition property and high heat-resistant yellowing of the cured film. Either one of the monomer (m-3) and the monomer (m-4) may be used, or both may be used.

[Aromatic ring-containing polymerizable monomer (m-5)]
The aromatic ring-containing polymerizable monomer (m-5) (hereinafter, may be simply referred to as “monomer (m-5)”) is a monomer having no carboxy group or epoxy group and having an aromatic ring. For example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p. Aromatic vinyl compounds such as −methoxystyrene, p-nitrostyrene, p-cyanostyrene, p-acetylaminostyrene; benzyl (meth) acrylate, rosin (meth) acrylate, phenyl (meth) acrylate, cumyl (meth) acrylate, Phenoxyethyl (meth) acrylate, phenoxy-polyethylene glycol (meth) acrylate (trade name: light acrylate P-200A, manufactured by Kyoei Chemical Co., Ltd.), nonylphenoxypolyethylene glycol mono (meth) acrylate, o-phenoxybenzyl (meth) acrylate, m-Phenyloxybenzyl (meth) acrylate, p-phenoxybenzyl (meth) acrylate, 4-phenoxyphenyl (meth) acrylate, biphenyloxyethyl (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate, naphthalene (meth) Examples thereof include acrylate and anthracene (meth) acrylate. Among these, from the viewpoint of elastic recovery rate, the ethylenically unsaturated resin (A1) used in the present invention is at least selected from the group consisting of benzyl (meth) clearate, styrene, biphenyl skeleton, naphthalene skeleton and anthracene skeleton. It is more preferable to introduce a structural unit having one kind.

[Other polymerizable monomers (m-6)]
The epoxy group-containing copolymer (P1) according to this embodiment is a polymerizable monomer (m-6) other than the monomers (m-1) to (m-5) (hereinafter, simply "monomer (m-)". 6) ”may be copolymerized. Other polymerizable monomers (m-6) are other than those shown in the monomers (m-1), (m-3), (m-4), (m-5), and the monomers (m-2) described later. Is a copolymerizable monomer. This monomer (m-6) is generally a radically polymerizable compound having an ethylenically unsaturated group. For example, examples of this monomer (m-6) include (meth) acrylic acid esters, (meth) acrylic acid amides, maleimides, unsaturated dicarboxylic acid diesters, and dienes such as butadiene. Specific examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylic rate, and sec. -Butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylic rate, pentyl (meth) acrylate, neopentyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, hexyl ( Meta) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, Rosin (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, Includes naphthalene (meth) acrylate, anthracene (meth) acrylate and the like. Specific examples of the (meth) acrylic acid amide include (meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, and (meth) acrylic acid N, N-. It contains dipropylamide, (meth) acrylic acid N, N-di-iso-propylamide, (meth) acrylic acid anthracenylamide and the like. Specific examples of maleimides include vinyl compounds such as (meth) acrylate anilide, (meth) acryloylnitrile, achlorine, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, and vinyl acetate; N- Includes cyclohexylmaleimide, N-laurylmaleimide and the like. Specific examples of unsaturated dicarboxylic acid diesters include diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconic acid and the like. These can be used alone or in combination of two or more, if necessary.

[Ratio of each monomer-derived structure of the epoxy group-containing copolymer (P1)]
In the copolymer (P1) according to the present invention, the monomer (M1) contains a monomer (m-1), and if necessary, for example, a monomer (m-3), a monomer (m-4), or the like. , When a monomer (m-5) is contained, the value of the molar ratio of each polymerizable monomer added for the copolymerization reaction is used as the ratio of each monomer-derived structure. The blending ratio (molar ratio) of each monomer is not particularly limited, but the blending ratio of the monomer (m-1) is preferably 9 to 70 mol%, more preferably 13 to 65 mol%. When the compounding ratio of the monomer (m-1) is 9 mol% or more, sufficient curability can be exhibited when the photosensitive resin composition is prepared. When the compounding ratio of the monomer (m-1) is 70 mol% or less, the compounding ratio of the monomer (m-3) and / or the monomer (m-4) becomes sufficiently large, and the desired thermal decomposability and refractive index can be obtained. An ethylenically unsaturated resin (A1) having is obtained.

When the monomer (m-3) and / or the monomer (m-4) is used, the blending ratio thereof is 0 mol with respect to 100 mol% of the total amount of the monomer (M1) of the epoxy group-containing copolymer (P1). It is preferably more than% to 40 mol%, more preferably more than 0 mol% to 30 mol%. When the blending ratio is more than 0 mol% or more, desired heat-decomposability, heat-resistant yellowing, and good solubility in a solvent can be obtained.
When the monomer (m-5) is used, the blending ratio thereof is more than 0 mol% to 50 mol% with respect to 100 mol% of the total amount of the monomer (M1) of the epoxy group-containing copolymer (P1). Is preferable, and more preferably more than 0 mol% to 40 mol%.
When the monomer (m-6) is used, the blending ratio shall be more than 0 mol% to 10 mol% with respect to the total amount of the monomer (M1) of the epoxy group-containing copolymer (P1) of 100 mol%. Is preferable, and more preferably more than 0 mol% to 5 mol%.

[Copolymerization reaction (method for producing epoxy group-containing copolymer (P1))]
The epoxy group-containing copolymer (P1) according to the present invention can be produced by using a copolymerization reaction of a monomer (M1). The copolymerization reaction carried out in the present invention can be carried out according to a radical polymerization method known in the art. For example, after dissolving the monomer used for copolymerization in a solvent, a polymerization initiator is added to the solution, and the temperature is 50 to 140 ° C., more preferably 60 to 130 ° C. for 1 to 20 hours, more preferably 1 to 12 hours. You just have to react. Further, the monomer used for the copolymerization and the polymerization initiator may be reacted with the solvent adjusted to 50 to 140 ° C. while dropping.

The solvent that can be used in this copolymerization reaction is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
As the copolymerization reaction solvent, the solvent for addition reaction described later can be used.

The amount of the solvent used in this copolymerization reaction is not particularly limited, but is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass when the total amount of the monomers used in the copolymerization is 100 parts by mass. In particular, by setting the amount of the solvent used to 1000 parts by mass or less, the decrease in the molecular weight of the copolymer (P1) due to the chain transfer action is suppressed, and the viscosity of the copolymer (P1) is controlled within an appropriate range. be able to. Further, by using 30 parts by mass or more of the solvent, it is possible to prevent an abnormal polymerization reaction, stably carry out the polymerization reaction, and prevent coloring and gelation of the copolymer (P1). You can also do it.

The polymerization initiator that can be used in this copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound is used. Can be done. Specifically, azobisisobutyronitrile, azobisisovaleronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), azobis (2-methylpropionic acid) dimethyl, benzoyl peroxide, dicumyl. Peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, t-hexylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2- Ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate and the like can be mentioned.
These can be used alone or in combination of two or more, and it is desirable to select a radical polymerization initiator having an appropriate half-life according to the polymerization temperature.

The amount of the polymerization initiator used in this copolymerization reaction is not particularly limited, but is generally 0.5 to 20 parts by mass, preferably 1.0 to 100 parts by mass when the total number of monomers used in the copolymerization is 100 parts by mass. It is 10 parts by mass.

[Carboxy group-containing ethylenically unsaturated compound (m-2)]
The carboxy group-containing ethylenically unsaturated compound (m-2) (hereinafter, may be simply referred to as “monomer (m-2)”) does not have an epoxy group and reacts with an epoxy group among acid groups. The monomer is not particularly limited as long as it has a good carboxy group and an ethylenically unsaturated group. For example, unsaturated monobasic acid or unsaturated dibasic acid monoester can be mentioned. As unsaturated monobasic acid, (meth) acrylic acid, itaconic acid, crotonic acid, cinnamic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) Acryloyloxyethyl Hexahydrophthalic Acid, α-Bromo (meth) Acrylic Acid, β-Frill (Meta) Acrylic Acid, Crotonic Acid, Propiole Acid, Katsura Acid, α-Cyano Keizai Acid, Monomethyl Maleate, Monoethyl Maleate, Malein Examples thereof include unsaturated carboxylic acids such as monoisopropyl acid, monomethyl fumarate, and monoethyl itacone. Examples of the unsaturated dibasic acid monoester include monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, and monoethyl itaconic acid. These carboxy group-containing ethylenically unsaturated compounds (m-2) may be used alone or in combination of two or more. Among these, (meth) acrylic acid is preferable from the viewpoint of availability and reactivity.

The reaction ratio of the carboxy group-containing ethylenically unsaturated compound (m-2) is preferably 10 to 70 mol% when the total of the monomers (M1) of the epoxy group-containing copolymer (P1) is 100 mol%. , More preferably 15-65 mol%. When the blending ratio of the carboxy group-containing ethylenically unsaturated compound (m-2) is 10 mol% or more, sufficient curability can be exhibited when the photosensitive resin composition is prepared. When it is 70 mol% or less, the ethylenically unsaturated resin (A1) having a desired thermostable decomposition property can be obtained by sufficiently securing the blending ratio of the monomer (M1). The ratio of adding the carboxy group-containing ethylenically unsaturated compound (m-2) to the number of moles of the epoxy group of the epoxy group-containing copolymer (P1) is preferably 90 to 100%. , More preferably 95-100%. When the addition ratio of the carboxy group-containing ethylenically unsaturated compound (m-2) is 90% or more, sufficient curability can be exhibited when the photosensitive resin composition is prepared.

[Polybasic acid anhydride (d)]
The polybasic acid anhydride (d) is not particularly limited as long as it has an acid anhydride structure having good reactivity with a hydroxy group, but a polybasic acid anhydride (d) having a ring structure in which no by-product is generated after the reaction is preferable. be. Specifically, 1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride , Methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, succinic anhydride, octenyl succinic anhydride and the like.

The reaction ratio of the polybasic acid anhydride (d) is preferably 10 to 70 mol%, more preferably 15 when the total of the monomers (M1) of the epoxy group-containing copolymer (P1) is 100 mol%. ~ 65 mol%. It is preferably 20 to 100 mol%, more preferably 30 to 90 mol%, based on the number of moles to which the carboxy group-containing ethylenically unsaturated compound (m-2) is added.

[Manufacturing method of ethylenically unsaturated resin (A1)]
The ethylenically unsaturated resin (A1) according to the present embodiment is, for example, a carboxy group-containing ethylenically unsaturated compound (m-) after adding a polymerization inhibitor and a catalyst to a solution of an epoxy group-containing copolymer (P1). 2) is added and the epoxy group is subjected to a ring-opening addition reaction under the conditions of 50 to 150 ° C., preferably 80 to 130 ° C., and then the polybasic acid anhydride (d) is added as necessary to carry out the addition reaction. It can be manufactured by letting it. It is preferable to use the carbon cluster (c) as the polymerization inhibitor.

When reacting the carboxy group-containing ethylenically unsaturated compound (m-2), there is no particular problem even if the solvent used in the above copolymerization reaction is contained, so the solvent is removed after the copolymerization reaction is completed. The reaction can be carried out without doing anything. Here, the polymerization inhibitor is added to prevent gelation due to the polymerization of the introduced double bond.

[catalyst]
Examples of the catalyst used in the present embodiment include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chromium chelate compounds. .. These catalysts may be used alone or in combination of two or more.
The amount of the catalyst used in the present embodiment is not particularly limited, but generally 0.01 to 5 parts by mass when the resin precursor (epoxy group-containing copolymer (P1)) is 100 parts by mass. It is a part, preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 part by mass.

[Solvent used during addition reaction]
The solvent used in this embodiment is not particularly limited, and known solvents can be appropriately used. As the solvent, an ether compound, a ketone compound, an ester compound, an aromatic hydrocarbon compound, and a carboxylic acid amide compound can be used. Examples of the ether compound include (poly) alkylene glycol monoalkyl ether; (poly) alkylene glycol monoalkyl ether acetate; other ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran. Specific examples of (poly) alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, and triethylene. Glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono- Includes n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and the like. Specific examples of the (poly) alkylene glycol monoalkyl ether acetate include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Specific examples of the ketone compound include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like. Specific examples of ester compounds include methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3 -Methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, propion N-butyl acid, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate Etc. are included. Specific examples of aromatic hydrocarbon compounds include toluene, xylene and the like. Specific examples of the carboxylic acid amide compound include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like. These solvents may be used alone or in combination of two or more.

Among the above solvents, glycol ether solvents are preferable. That is, it is preferable to use (poly) alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether and (poly) alkylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate as the solvent.

The amount of the solvent used for producing the resin of the present embodiment is not particularly limited, but when the resin precursor is 100 parts by mass, it is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass. It is a mass part. When the amount of the above solvent used is 1000 parts by mass or less, the viscosity of the resin can be controlled in an appropriate range, which is preferable. On the other hand, when the amount of the solvent used is 30 parts by mass or more, seizure can be prevented during the reaction and the synthesis reaction can be stably carried out, which is preferable. Further, when the amount of the above solvent used is 30 parts by mass or more, coloring or gelation of the resin can be prevented.

[Second Embodiment]
[Ethylene unsaturated resin (A2)]
The ethylenically unsaturated resin (A2) according to this embodiment is a carboxy group-containing compound (b) in addition to the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1) which is the epoxy group-containing compound (a). It is a resin containing a hydroxy group and an ethylenically unsaturated group formed by ring-opening addition of a certain carboxy group-containing copolymer (P2). The carboxy group-containing copolymer (P2) contains at least a structural unit derived from the carboxy group-containing ethylenically unsaturated compound (m-2), and if necessary, a crosslinked cyclic hydrocarbon having 10 to 20 carbon atoms. A structural unit derived from a polymerizable monomer (m-3) having a group, a structural unit derived from the polymerizable monomer (m-4) represented by the above general formula (1), and an aromatic ring-containing polymerizable monomer (m-5). ) Is a copolymer containing a constituent unit derived from the above.

The ethylenically unsaturated resin (A2) according to this embodiment contains a structural unit derived from the addition reaction of the epoxy group-containing ethylenically unsaturated compound (m-1), so that a double bond having excellent photosensitivity can be introduced. At the same time, a hydroxy group can be obtained by opening the ring of the epoxy group. As a result, curability by light or heat can be exhibited, and alkali developability can be exhibited. With this structural unit, sufficient hardness of the cured product is exhibited and high solvent resistance is exhibited. Further, the carboxylic acid can be introduced at the same time by leaving a part of the carboxy group of the carboxy group-containing copolymer (P2) without reacting with the epoxy group of the monomer (m-1).

As the epoxy group-containing ethylenically unsaturated compound (m-1) according to the present embodiment, the one according to the first embodiment can be used.

The addition ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) to the number of moles of carboxy contained in the carboxy group-containing copolymer (P2) is preferably 90 to 100 mol%, more preferably. Is 95-100 mol%. When the addition ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is 90 mol% or more, sufficient curability can be exhibited when the photosensitive resin composition is prepared.
The reaction ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is preferably 10 when the total of all the monomers (M2) used in the epoxy group-containing copolymer (P2) is 100 mol%. It is ~ 70 mol%, more preferably 15-65 mol%. When the compounding ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is 10 mol% or more, sufficient curability can be exhibited when the photosensitive resin composition is prepared.

[Carboxy group-containing copolymer (P2)]
The total monomer (M2) of the carboxy group-containing copolymer (P2) according to the ethylenically unsaturated resin (A2) of the present embodiment (hereinafter, may be simply referred to as “copolymer (P2)”) is A polymerizable monomer (m-3) containing at least a carboxy group-containing ethylenically unsaturated compound (m-2) and, if necessary, a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms. , The polymerizable monomer (m-4) represented by the above chemical formula (1), the aromatic ring-containing polymerizable monomer (m-5), other polymerizable monomer (m-6), and the like can be contained.

Carboxy group-containing ethylenically unsaturated compound (m-2), polymerizable monomer (m-3), polymerizable monomer (m-4), aromatic ring-containing polymerizable monomer (m-5), and others according to this embodiment. The polymerizable monomer (m-6) of the above is the same as that described in the first embodiment, and the description thereof will be omitted.

[Ratio of each monomer-derived structure of the carboxy group-containing copolymer (P2)]
In the copolymer (P2) according to the present invention, all the monomers (M2) contain a carboxy group-containing ethylenically unsaturated compound (m-2), and if necessary, further bridge with 10 to 20 carbon atoms. A polymerizable monomer having a ring-type hydrocarbon group (m-3), a polymerizable monomer represented by the general formula (1) (m-4), an aromatic ring-containing polymerizable monomer (m-5), and the like can be used. When it is contained, the value of the molar ratio of each polymerizable monomer added for the copolymerization reaction is used as the ratio of the structure derived from each monomer. The blending ratio (molar ratio) of each monomer is not particularly limited, but when the total of all the monomers (M2) is 100 mol%, the blending ratio of the monomer (m-2) is preferably 9 to 70 mol%. , More preferably 13-65 mol%. When the compounding ratio of the monomer (m-2) is 9 mol% or more, sufficient curability can be exhibited when the photosensitive resin composition is prepared. When the compounding ratio of the monomer (m-2) is 70 mol% or less, the compounding ratio of the monomer (m-3), the monomer (a-4), and the monomer (m-5) becomes sufficiently large, which is desired. An ethylenically unsaturated resin (A2) having heat-decomposability can be obtained.

When the monomer (m-3) and / or the monomer (m-4) is used, the blending ratio thereof is the total with respect to the total amount of 100 mol% of all the monomers (M2) of the carboxy group-containing copolymer (P2). It is preferably more than 0 mol% to 40 mol%, more preferably more than 0 mol% to 30 mol%. When the blending ratio is 1 mol% or more, desired heat-decomposability, heat-resistant yellowing, and good solubility in a solvent can be obtained.

When the monomer (m-5) is used, the blending ratio may be more than 0 mol% to 50 mol% with respect to 100 mol% of the total amount of the carboxy group-containing ethylenically unsaturated compound (m-2). It is preferably more than 0 mol% to 40 mol%, more preferably.
When the monomer (m-6) is used, the blending ratio shall be more than 0 mol% to 10 mol% with respect to the total amount of the monomer (M2) of the epoxy group-containing copolymer (P2) of 100 mol%. Is preferable, and more preferably more than 0 mol% to 5 mol%.

[Copolymerization reaction (method for producing a carboxy group-containing copolymer (P2))]
The carboxy group-containing copolymer (P2) according to the present invention can be produced by using a copolymerization reaction in the same manner as the copolymer (P1) according to the first embodiment.

[Manufacturing method of ethylenically unsaturated resin (A2)]
The method for producing an ethylenically unsaturated resin (A2) is to react an epoxy group-containing ethylenically unsaturated compound (m-1) with a carboxy group-containing copolymer (P2) in the presence of a polymerization inhibitor and a catalyst to produce ethylene. It is a method for producing a sex unsaturated resin (A2), and it is preferable that the polymerization inhibitor is the above-mentioned carbon cluster (c).

As an example of this embodiment, the ethylenically unsaturated resin (A2) according to this embodiment is prepared after adding a carbon cluster (c) as a polymerization inhibitor to the above-mentioned solution of the carboxy group-containing copolymer (P2). , Epoxide group-containing ethylenically unsaturated compound (m-1) is added, and the epoxy group of the first embodiment is reacted under the same conditions as the ring-opening addition reaction to produce the product. The carbon cluster (c) and the solvent used are the same as in the first embodiment.

[Third Embodiment]

[Ethylene unsaturated resin (A3)]
The ethylenically unsaturated resin (A3) used in this embodiment is an epoxy group-containing compound (b) carboxy group-containing ethylenically unsaturated compound with an epoxy group of the epoxy resin (P3) which is an epoxy group-containing compound (a). A carboxy group and an ethylenically unsaturated compound, in which the polybasic acid anhydride (d) is further added to the hydroxy group formed by opening the ring of the epoxy group, preferably to the ring-opened addition of (m-2). It is a resin containing a saturated group. The epoxy resin (P3) can be selected from the group consisting of a novolak type epoxy resin (P3-1), a bisphenol type epoxy resin (P3-2), and a bifunctional epoxy resin having a biphenyl skeleton (P3-3). preferable.
That is, as the ethylenically unsaturated resin (A3) used in this embodiment, a novolak type epoxy resin (P3-1) to which a carboxy group-containing ethylenically unsaturated compound (m-2) is added is required. An ethylenically unsaturated resin (A3-1) to which a polybasic acid anhydride (d) is further added, or a dibasic acid and a carboxy group-containing ethylenically unsaturated compound (m) to a bisphenol type epoxy resin (P3-2). An ethylenically unsaturated resin (A3-2) in which a polybasic acid anhydride (d) is further added as needed to the substance to which -2) is added, or a bifunctional epoxy resin (P3-3) having a biphenyl skeleton. ) To which a carboxy group-containing ethylenically unsaturated compound (m-2) is added, and if necessary, an ethylenically unsaturated resin (A3-3) to which a polybasic acid anhydride (d) is further added. Can be mentioned.
As the carboxy group-containing ethylenically unsaturated compound (m-2), carbon cluster (c), catalyst, solvent used, etc. used in this embodiment, those of the first embodiment can be used.

[Ethylene unsaturated resin (A3-1)]
The ethylenically unsaturated resin (A3-1) is required after adding a carboxy group-containing ethylenically unsaturated compound (m-2) to the novolak type epoxy resin (P3-1) in order to introduce a double bond. It can be produced by adding a polybasic acid anhydride (d) to introduce a carboxy group according to the above.

Examples of the novolak type epoxy resin (P3-1) include cresol novolac type epoxy resin and phenol novolac type epoxy resin. These novolak type epoxy resins may be used alone or in combination of two or more.

[Ethylene unsaturated resin (A3-2)]
The ethylenically unsaturated resin (A3-2) is required after adding a carboxy group-containing ethylenically unsaturated compound (m-2) to the bisphenol type epoxy resin (P3-2) in order to introduce a double bond. It can be produced by adding a polybasic acid anhydride (d) to introduce a carboxy group according to the above.

Examples of the bisphenol type epoxy resin (P3-2) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. These bisphenol type epoxy resins may be used alone or in combination of two or more. Among these, bisphenol A type epoxy resin is preferable from the viewpoint of availability and reactivity.

[Ethylene unsaturated resin (A3-3)]
The ethylenically unsaturated resin (A3-3) is prepared by adding a carboxy group-containing ethylenically unsaturated compound (m-2) to a bifunctional epoxy resin (P3-3) having a biphenyl skeleton in order to introduce a double bond. After that, it can be produced by adding a polybasic acid anhydride (d) to introduce a carboxy group as needed.
The bifunctional epoxy resin (P3-3) having a biphenyl skeleton is not particularly limited as long as it has a biphenyl skeleton in the molecule and has two epoxy groups. Examples of the biphenyl skeleton include those represented by the following formula (5).

In the above formula (5), R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and E and E'independently represent an organic group having an epoxy group.

Specific examples of the bifunctional epoxy resin having a biphenyl skeleton include YX4000 manufactured by Mitsubishi Chemical Corporation (R'is CH ₃ in the following formula (6)) and YX4000K (R'in the following formula (6)). CH _3), in YX4000H (formula (6), R 'is CH _3), in YL6121HA (formula (6), R' and compound compound is H and R 'is CH ₃ (Mixture of) and the like.

If necessary, a saturated monobasic acid may be added to the epoxy group of the ethylenically unsaturated resin (A3) together with the carboxy group-containing ethylenically unsaturated compound (m-2). The saturated monobasic acid is not particularly limited, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, lauric acid, tridecylic acid, palmitic acid, and stearic acid. The saturated monobasic acid may be used alone or in combination of two or more. Among these, acetic acid and propionic acid are preferable from the viewpoint of boiling point and reactivity. Flexibility is improved by using an ethylenically unsaturated resin (A3) to which a saturated monobasic acid is added together with a carboxy group-containing ethylenically unsaturated compound (m-2).

As the polybasic acid anhydride (d), the polybasic acid anhydride (d) described in the first embodiment can be used.

The ethylenically unsaturated resin (A) used in the present invention is an ethylenically unsaturated compound containing an epoxy group in a carboxy group derived from the polybasic acid anhydride (d) in the ethylenically unsaturated resin (A3) of the present embodiment. m-1) may be further added. As the epoxy group-containing ethylenically unsaturated compound, the epoxy group-containing ethylenically unsaturated compound (m-1) described in the first embodiment can be used.

The reaction conditions for obtaining the ethylenically unsaturated resin (A3) or the epoxy resin (P3) used in the present invention may be appropriately set according to a conventional method.
In the addition reaction of the carboxy group-containing ethylenically unsaturated compound (m-2) and the saturated monobasic acid used as needed, for example, each raw material, a polymerization inhibitor and an addition reaction catalyst are added to a solvent, preferably. The reaction may be carried out in an atmosphere having an oxygen gas concentration of 2 to 10% by volume, more preferably an oxygen gas concentration of 5 to 7% by volume, preferably 100 to 140 ° C., more preferably 110 to 130 ° C. for 2 to 12 hours.
The addition reaction of the epoxy group-containing ethylenically unsaturated compound is preferably carried out in an atmosphere having an oxygen gas concentration of 2 to 10% by volume, more preferably an oxygen gas concentration of 5 to 7% by volume, preferably 100 to 140 ° C., more preferably 110. It may be carried out at ~ 130 ° C. for 2 to 10 hours.

The preferable constituent unit ratio of the ethylenically unsaturated resin (A3) used in the present invention is as follows. In the ethylenically unsaturated resin (A3), the structural unit derived from the epoxy resin (P3) is 40 to 70% by mass, and the structural unit derived from the carboxy group-containing ethylenically unsaturated compound (m-2) is 5 to 35% by mass. %, The constituent unit derived from the polybasic acid anhydride (d) is 10 to 40% by mass. When a saturated monobasic acid is used, the constituent unit derived from the saturated monobasic acid is more than 0 mol% to 20% by mass. When the epoxy group-containing ethylenically unsaturated compound (m-1) is used, the structural unit derived from the epoxy group-containing ethylenically unsaturated compound (m-1) is more than 0 mol% to 10% by mass.
Further, in setting a preferable structural unit ratio of the ethylenically unsaturated resin (A3) used in the present invention, a carboxy group-containing ethylenically unsaturated compound (carboxyl group-containing ethylenically unsaturated compound) to an epoxy group contained in the structural unit derived from the epoxy resin (P3). It is preferable that the total addition rate of the constituent units derived from m-2) and the saturated monobasic acid used as needed is 90 to 100% in total with respect to the epoxy group, and the carboxy group-containing ethylenically unsaturated compound. The addition rate of the structural unit derived from the polybasic acid anhydride to the hydroxy group generated by the addition of the structural unit derived from (m-2) and the saturated monobasic acid used as needed is 5 to 80%. It is preferably 10 to 70%, and more preferably 10 to 70%. Further, the addition rate of the structural unit derived from the epoxy group-containing ethylenically unsaturated compound (m-1) to the carboxy group generated by the addition of the structural unit derived from the polybasic acid anhydride (d) is 10 to 50%. Is preferable.

[Manufacturing method of ethylenically unsaturated resin (A3)]
The method for producing an ethylenically unsaturated resin (A3) is an ethylenically unsaturated resin in which an epoxy resin (P3) and a carboxy group-containing ethylenically unsaturated compound (m-2) are reacted in the presence of a polymerization inhibitor and a catalyst. It is a method for producing (A3), and it is preferable that the polymerization inhibitor is the carbon cluster (c) described above.

[Fourth Embodiment]

[Ethylene unsaturated resin (A4)]
The ethylenically unsaturated resin (A4) according to this embodiment is a carboxy group-containing compound (b) in addition to the epoxy group of the epoxy group-containing ethylenically unsaturated compound (m-1) which is the epoxy group-containing compound (a). It is an ethylenically unsaturated resin having a hydroxy group formed by ring-opening addition of a certain carboxy group-containing resin (P4).

As the epoxy group-containing ethylenically unsaturated compound (m-1) used in the present embodiment, the one of the first embodiment can be used.
The amount of the epoxy group-containing ethylenically unsaturated compound (m-1) added is preferably more than 0 parts by mass to 10 parts by mass with respect to 100 parts by mass of the carboxy group-containing resin (P4). When the addition amount of the epoxy group-containing ethylenically unsaturated compound (m-1) exceeds 0 parts by mass, the sensitivity can be increased, which is preferable. On the other hand, when the addition amount of the epoxy group-containing ethylenically unsaturated compound (m-1) is 10 parts by mass or less, the elastic recovery rate and developability can be maintained, which is preferable.
The molar ratio of the added epoxy group-containing ethylenically unsaturated compound (m-1) to the structural unit derived from the carboxy group-containing resin (P4) in the ethylenically unsaturated resin (A4) is 0.05 to 0.3. Is preferable.

[Carboxy group-containing resin (P4)]
The carboxy group-containing resin (P4) used in this embodiment is a resin having a carboxy group formed by reacting an epoxy resin (P3) with a polyfunctional carboxylic acid (e).
As the epoxy resin (P3), the epoxy resin (P3) used in the third embodiment can be used.

[Polyfunctional carboxylic acid (e)]
The polyfunctional carboxylic acid (e) is not particularly limited. It may be either a saturated or unsaturated polyfunctional carboxylic acid. Specific examples thereof include adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, tartaric acid, glutamate, and sebacic acid. The dibasic acid may be used alone or in combination of two or more. Among these, adipic acid and itaconic acid are preferable from the viewpoint of reactivity.

[Ratio of structural units of carboxy group-containing resin (P4)]
The carboxy group-containing resin (P4) preferably contains 30 to 80% by mass of a structural unit derived from the epoxy resin (P3) and 20 to 70% by mass of a structural unit derived from the polyfunctional carboxylic acid (e). Here, the molar ratio of the structural unit derived from the polyfunctional carboxylic acid (e) to the structural unit derived from the epoxy resin (P3) in the carboxy group-containing resin (P4) is 0.1 to 0.8. It is preferably 0.15 to 0.7, and more preferably 0.15 to 0.7.

[Manufacturing method of carboxy group-containing resin (P4)]
The carboxy group-containing resin (P4) used in this embodiment can be produced, for example, by subjecting an epoxy resin (P3) and a polyfunctional carboxylic acid (e) to an addition reaction in the presence of an addition catalyst.
The conditions of the addition reaction for obtaining the carboxy group-containing resin (P4) used in this embodiment may be appropriately set according to a conventional method. The addition reaction is carried out, for example, by adding each raw material and an addition catalyst to a solvent, preferably in an atmosphere having an oxygen gas concentration of 2 to 10% by volume, more preferably an oxygen gas concentration of 5 to 7% by volume, preferably 50 to 150 ° C. , More preferably, it may be carried out at 60 to 140 ° C. for 1 to 12 hours.

The solvent that can be used in the above-mentioned addition reaction is not particularly limited, and known solvents can be appropriately used. For example, the solvent used for the addition reaction of the first embodiment can be used.
The polycondensation catalyst that can be used in the above-mentioned addition reaction is not particularly limited, and known polycondensation catalysts can be appropriately used. For example, the catalyst used for the addition reaction of the first embodiment can be used.

[Manufacturing method of ethylenically unsaturated resin (A4)]
In the method for producing an ethylenically unsaturated resin (A4), an epoxy group-containing ethylenically unsaturated compound (m-1) and a carboxy group-containing resin (P4) are reacted in the presence of a polymerization inhibitor and a catalyst to cause an ethylenically unsaturated resin (A4). It is a method for producing a saturated resin (A4), and it is preferable that the polymerization inhibitor is a carbon cluster (c). The carboxy group-containing resin (P4) is a resin having a carboxy group formed by reacting an epoxy resin (P3) with a polyfunctional carboxylic acid (e).

As an example of this embodiment, the ethylenically unsaturated resin (A4) according to this embodiment is prepared after adding a carbon cluster (c) and a catalyst as a polymerization inhibitor to the above-mentioned solution of the carboxy group-containing resin (P4). , Epoxide group-containing ethylenically unsaturated compound (m-1) can be added and reacted under the same conditions as the ring-opening addition reaction of the epoxy group of the first embodiment. The carbon cluster (c) and the solvent used are the same as in the first embodiment.

[Fifth Embodiment]
[Ethylene unsaturated resin (A5)]
The ethylenically unsaturated resin (A5) of the present embodiment is an ethylene unsaturated obtained by further adding a polybasic acid anhydride (d) to the hydroxy group of the ethylenically unsaturated resin (A2) of the second embodiment. It is a resin containing a saturated group. The hydroxy group is a hydroxy group formed by ring-opening addition of a carboxy group-containing copolymer (P2) to an epoxy group of an epoxy group-containing ethylenically unsaturated compound (m-1).

The ethylenically unsaturated resin (A5) of the present embodiment is photosensitive because it contains structural units derived from the addition reaction of the epoxy group-containing ethylenically unsaturated compound (m-1) and the polybasic acid anhydride (d). At the same time as introducing an excellent double bond, a hydroxy group having excellent alkali developability can be obtained by opening the ring of the epoxy group. With this structural unit, sufficient hardness of the cured product is exhibited and high solvent resistance is exhibited. Furthermore, by introducing an acidic group or a hydroxy group as an alkaline developable group, the affinity of the copolymer with the alkaline developer is enhanced, a high-definition curing pattern can be formed, and strict dimensional accuracy is realized. do.
Further, the carboxylic acid can be introduced at the same time by leaving a part of the carboxy group of the carboxy group-containing copolymer (P2) without reacting with the epoxy group. Further, a polybasic acid anhydride can be added to the obtained hydroxyl group to increase the amount of carboxylic acid introduced.

The reaction ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is the same as the reaction ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) of the ethylenically unsaturated resin (A2) of the second embodiment. Is.

The ratio of the polybasic acid anhydride (d) to the number of moles of the epoxy group-containing ethylenically unsaturated compound (m-1) in the ethylenically unsaturated resin (A2) is preferably 10 to 90 mol%. , More preferably 30-70 mol%. When the ratio of the polybasic acid anhydride (d) is 10 mol% or more, further curability can be exhibited when the photosensitive resin composition is prepared. When it is 90 mol% or less, the unreacted product of the polybasic acid anhydride (d) does not remain, and a desired ethylenically unsaturated resin (A5) can be obtained.
The reaction ratio of the polybasic acid anhydride (d) is the monomer (m-1), the monomer (m-2) constituting the carboxy group-containing copolymer (P2), and any monomer (m-3). And / or when the total of the monomer (m-4), the arbitrary monomer (m-5) and the like is 100 mol%, it is preferably 5 to 65 mol%, more preferably 5 to 50 mol%. When the compounding ratio of the polybasic acid anhydride (d) is 5 mol% or more, further curability can be exhibited when the photosensitive resin composition is prepared. When the blending ratio of the polybasic acid anhydride (d) is 65 mol% or less, a copolymer having a desired refractive index can be obtained.

[Manufacturing method of ethylenically unsaturated resin (A5)]
The ethylenically unsaturated resin (A5) is prepared under the conditions of 50 to 150 ° C., preferably 80 to 130 ° C. by adding a polybasic acid anhydride (d) after producing the ethylenically unsaturated resin (A2). It can be produced by reacting a hydroxy group with a polybasic acid anhydride (d).

When the polybasic acid anhydride (d) is reacted, there is no particular problem even if the solvent used for producing the ethylenically unsaturated resin (A2) is contained, so that the ethylenically unsaturated resin (A2) is used. After the reaction for obtaining is completed, the reaction can be carried out without removing the solvent.

[Sixth Embodiment]
[Ethylene unsaturated resin (A6)]
The ethylenically unsaturated resin (A6) of the present embodiment is an ethylene unsaturated obtained by further adding a polybasic acid anhydride (d) to the hydroxy group of the ethylenically unsaturated resin (A4) of the fourth embodiment. It is a resin containing a saturated group. The hydroxy group is a hydroxy group formed by ring-opening addition of a carboxy group-containing resin (P4) to an epoxy group of an epoxy group-containing ethylenically unsaturated compound (m-1).

The ethylenically unsaturated resin (A6) of the present embodiment is photosensitive because it contains structural units derived from the addition reaction of the epoxy group-containing ethylenically unsaturated compound (m-1) and the polybasic acid anhydride (d). At the same time as introducing an excellent double bond, a hydroxy group having excellent alkali developability can be obtained by opening the ring of the epoxy group. With this structural unit, sufficient hardness of the cured product is exhibited and high solvent resistance is exhibited. Furthermore, by introducing an acidic group or a hydroxy group as an alkaline developable group, the affinity of the copolymer with the alkaline developer is enhanced, a high-definition curing pattern can be formed, and strict dimensional accuracy is realized. do.
Further, the carboxylic acid can be introduced at the same time by leaving a part of the carboxy group of the carboxy group-containing resin (P4) without reacting with the epoxy group. Further, a polybasic acid anhydride can be added to the obtained hydroxyl group to increase the amount of carboxylic acid introduced.

The reaction ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) is the same as the reaction ratio of the epoxy group-containing ethylenically unsaturated compound (m-1) of the ethylenically unsaturated resin (A4) of the fourth embodiment. Is.

The ratio of the polybasic acid anhydride (d) to the number of moles of the epoxy group-containing ethylenically unsaturated compound (m-1) is preferably 10 to 90 mol%, more preferably 30 to 70 mol%. Is.
When the ratio of the polybasic acid anhydride (d) is 10% mol or more, further curability can be exhibited when the photosensitive resin composition is prepared. When it is 90 mol% or less, the unreacted product of the polybasic acid anhydride (d) does not remain, and the desired ethylenically unsaturated resin (A6) can be obtained.
The reaction ratio of the polybasic acid anhydride (d) is preferably more than 0% by mass to 10% by mass with respect to the ethylenically unsaturated resin (A6). When the amount of the polybasic acid anhydride (d) added is more than 0% by mass, the sensitivity can be increased, which is preferable. On the other hand, when the amount of the polybasic acid anhydride (d) added is 10% by mass or less, the elastic recovery rate and developability can be maintained, which is preferable.

[Manufacturing method of ethylenically unsaturated resin (A6)]
The ethylenically unsaturated resin (A6) is prepared under the conditions of 50 to 150 ° C., preferably 80 to 130 ° C. by adding a polybasic acid anhydride (d) after producing the ethylenically unsaturated resin (A4). It can be produced by reacting a hydroxy group with a polybasic acid anhydride (d).

When the polybasic acid anhydride (d) is reacted, there is no particular problem even if the solvent used for producing the ethylenically unsaturated resin (A4) is contained, so that the ethylenically unsaturated resin (A4) is used. After the reaction for obtaining is completed, the reaction can be carried out without removing the solvent.

[Characteristics of ethylenically unsaturated resin (A)]
The molecular weight of the ethylenically unsaturated resin (A) obtained in the first to sixth embodiments of the present invention (polystyrene-equivalent weight average molecular weight by gel permeation chromatography (GPC)) is preferably 1000 to 50,000. It is preferably 3000 to 40,000. When this molecular weight is 1000 or more, the solvent resistance and heat decomposition resistance of the cured film can be sufficiently ensured. On the other hand, when the molecular weight is 50,000 or less, the molecular weight and the viscosity can be controlled in an appropriate range, which is practical. Further, from the viewpoint of elastic recovery rate, the weight average molecular weight is preferably 3000 to 30000.

The acid value (JIS K6901 5.3) of the ethylenically unsaturated resin (A) is usually 20 to 300 KOH mg / g, preferably 30 to 200 KOH mg / g. When the acid value is 20 KOH mg / g or more, the developability is good, which is preferable. On the other hand, when the acid value is 300 KOHmg / g or less, the exposed portion (photocurable portion) is less likely to dissolve in the alkaline developer, which is preferable. Further, from the viewpoint of elastic recovery rate, the acid value of the ethylenically unsaturated resin (A) is preferably 30 to 200 KOHmg / g.

The hydroxyl group equivalent of the ethylenically unsaturated resin (A) is usually 200 to 4000 g / mol, preferably 200 to 2500 g / mol. By setting the hydroxyl group equivalent to 4000 g / mol or less, more preferably 2500 g / mol or less, the water repellency of the alkaline developer can be suppressed and good developability can be realized. On the other hand, if the hydroxyl group equivalent is less than 200 g / mol, the amount of other substituents required for the present invention is reduced, and the desired curability, heat-decomposability, heat-resistant yellowing, and refractive index may not be obtained. ..
The hydroxyl group equivalent in the present specification is the mass of the ethylenically unsaturated resin (A) per number of moles of hydroxy groups, and is a theoretical value calculated from the amount of raw materials charged with the reaction rate of 100%.

The unsaturated group equivalent of the ethylenically unsaturated resin (A) is not limited as long as it produces the desired effect of the present invention, but is usually 100 to 4000 g / mol, preferably 200 to 2000 g / mol. More preferably, it is 300 to 500 g / mol. When the unsaturated group equivalent is 100 g / mol or more, it is preferable because it is effective in improving the physical characteristics of the coating film and the alkali developability. On the other hand, when the unsaturated group equivalent is 4000 g / mol or less, it is preferable because it is effective in further increasing the sensitivity. Further, when the unsaturated group equivalent is 100 g / mol or more, it is effective for further enhancing the heat-resistant decomposition property and the heat-resistant yellowing. From the viewpoint of elastic recovery rate, the unsaturated group equivalent of the ethylenically unsaturated resin (A) is preferably 200 to 2000 g / mol.
In the present specification, the unsaturated group equivalent is a theoretical value calculated from the charged amount when it is assumed that the raw materials used for introducing the unsaturated group have completely reacted.

The epoxy equivalent of the ethylenically unsaturated resin (A) used in the present invention is not limited as long as the desired effect of the present invention is obtained, but is usually 100 to 4000 g / mol, preferably 200 to 2000 g / mol. More preferably, it is 300 to 500 g / mol. When the epoxy equivalent is 100 g / mol or more, it is effective and preferable in improving the physical characteristics of the coating film and the storage stability. On the contrary, when the epoxy equivalent is 4000 g / mol or less, it is effective in further enhancing the solvent resistance.
The epoxy equivalent is the mass of the polymer per mole of the epoxy group of the polymer. This value can be determined by dividing the mass of the polymer by the amount of epoxy groups in the polymer (g / mol). In the present specification, the "epoxy equivalent" is a theoretical value calculated as a reaction rate of 100% from the amount of the raw material used for introducing the epoxy group and the amount of the carboxy group-containing compound (b) to be subjected to an addition reaction. ..

[Solvent (B)]
The solvent (B) of the ethylenically unsaturated resin composition is not particularly limited as long as it is a solvent that does not react with the ethylenically unsaturated resin (A). As the solvent (B), the same solvent as that used when producing the ethylenically unsaturated resin (A) can be used, and the solvent contained after the reaction can be used as it is, or can be further added. can. Further, when other components are added, they may coexist there. Specific examples of the solvent (B) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol. Examples thereof include monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, and diethylene glycol ethyl ether acetate. These can be used alone or in combination of two or more. Among these, glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate used in producing the ethylenically unsaturated resin (A) are preferable.

The blending amount of the solvent (B) in the resin composition of the present embodiment is generally 30 to 1000 parts by mass, preferably 50 to 50 parts by mass, assuming that the total amount of the components excluding the solvent (B) in the composition is 100 parts by mass. It is 800 parts by mass, more preferably 100 to 700 parts by mass. If the blending amount is within this range, the resin composition has an appropriate viscosity.

[Reactive Diluent (D)]
The reactive diluent (D) is not particularly limited, but one containing an ethylenically unsaturated double bond, preferably a vinyl group and a (meth) acryloyloxy group is preferable. Specific examples include aromatic vinyl-based monomers such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallylphthalate, and diallylbenzenephosphonate; polycarboxylic acids such as vinyl acetate and vinyl adipate. Monomers: Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropandi (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Examples thereof include (meth) acrylic monomers such as dipentaerythritol hexa (meth) acrylate and tri (meth) acrylate of tris (hydroxyethyl) isocyanurate; triallyl cyanurate and the like. These can be used alone or in combination of two or more.

The amount of the reactive diluent (D) to be blended in the resin composition of the present embodiment is generally 10 to 90 parts by mass, preferably 10 to 90 parts by mass, assuming that the total amount of the components excluding the solvent (B) in the composition is 100 parts by mass. Is 20 to 80 parts by mass, more preferably 25 to 70 parts by mass. If the blending amount is within this range, the resin composition has an appropriate viscosity, and the photosensitive resin composition using the resin composition has an appropriate photocurability.

[Photosensitive resin composition]
Photosensitive Resin Composition of the Present Invention The present invention comprises an ethylenically unsaturated resin (A), a carbon cluster (c), a solvent (B), a reactive diluent (D), and a photopolymerization initiator (E). including. Photosensitive resin composition of the present invention The present invention may further contain a colorant (F).
Further, the photosensitive resin composition of the present invention may be substantially free of a polymerization inhibitor other than the carbon cluster (c). “Substantially free” means 0.010 parts by mass or less, preferably 0.05 parts by mass, of a polymerization inhibitor other than the carbon cluster (c) with respect to 100 parts by mass of the ethylenically unsaturated resin (A). It means to include less than one copy.

The blending amount of the solvent (B) in the photosensitive resin composition of the present embodiment is generally 30 to 1000 parts by mass, preferably 30 parts by mass, assuming that the total amount of the components excluding the solvent (B) in the composition is 100 parts by mass. It is 50 to 800 parts by mass, more preferably 100 to 700 parts by mass. If the blending amount is within this range, the photosensitive resin composition has an appropriate viscosity.

The blending amount of the reactive diluent (D) in the photosensitive resin composition of the present embodiment is generally 10 to 90% by mass, assuming that the total amount of the components excluding the solvent (B) in the composition is 100% by mass. , It is preferably 20 to 80% by mass, and more preferably 25 to 70% by mass. If the blending amount is within this range, the photosensitive resin composition has an appropriate viscosity, and the photosensitive resin composition has an appropriate photocurability.

[Photopolymerization Initiator (E)]
The photopolymerization initiator (E) is not particularly limited, and specific examples thereof include benzoin such as benzoin, benzoin methyl ether, and benzoin ethyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1 , 1-Dichloroacetophenone, 4- (1-t-butyldioxy-1-methylethyl) acetophenone and other acetophenones; 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and other anthraquinones. Classes; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone; quettals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4- (1-t-butyldioxy-1-). Benzophenones such as methylethyl) benzophenone, 3,3', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -1-one; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1; acylphosphine oxides; and xanthons and the like. These can be used alone or in combination of two or more.

The blending amount of the photopolymerization initiator (E) in the photosensitive resin composition of the present embodiment is generally 0.1 when the total of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass. It is ~ 30 parts by mass, preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass. If the blending amount is within this range, a photosensitive resin composition having appropriate photocurability can be obtained.

[Colorant (F)]
The colorant (F) is not particularly limited as long as it dissolves or disperses in the solvent (B), and known dyes or pigments can be used. When a dye is used as the colorant (F), a brighter coloring pattern can be obtained as compared with the case where a pigment is used, and good alkali developability is exhibited. On the other hand, when a pigment is used as the colorant (F), the heat resistance of the coloring pattern is higher than when a dye is used. Dyes and pigments may be used in combination depending on the required performance and the target pixel color.

"dye"
The dyes include acid dyes having acidic groups such as carboxy groups and acidic dyes from the viewpoints of solubility in solvent (B) and alkaline developing solution, interaction with other components in the photosensitive resin composition, heat resistance, and the like. It is preferable to use a salt of the dye with a nitrogen compound, a sulfonamide of an acid dye, or the like. Specific examples of such dyes include acid alizarin violet N; acid black1, 2, 24, 48; acid blue1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90. , 92, 112, 113, 120, 129, 147; acid chrome violet K; acid fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52 , 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid chrome 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42 , 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food chrome 3 and derivatives thereof and the like.
Among these, azo-based, xanthene-based, anthraquinone-based or phthalocyanine-based acid dyes are preferable. These dyes can be used alone or in combination of two or more, depending on the color of the target pixel.

"Pigment"
Specific examples of pigments include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; C.I. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments; C.I. I. Pigment Green 7, 36, 58 and other green pigments; C.I. I. Pigment Brown 23, 25 and other brown pigments; C.I. I. Pigment Blacks 1 and 7, carbon black, titanium black, black pigments such as iron oxide and the like can be mentioned. These pigments can be used alone or in combination of two or more, depending on the color of the target pixel.

When the colorant (F) is blended in the photosensitive resin composition of the present embodiment, the blending amount is generally 5 when the total of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass. It is ~ 80 parts by mass, preferably 5 to 70 parts by mass, and more preferably 10 to 60 parts by mass.

When a pigment is used as the colorant (F), a known dispersant may be added to the photosensitive resin composition from the viewpoint of improving the dispersibility of the pigment. As the dispersant, it is preferable to use a polymer dispersant having excellent dispersion stability over time. Examples of polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified esters. Examples include system dispersants. Commercially available such polymer dispersants under trade names such as EFKA (manufactured by EFKA), Disperbyk (manufactured by Big Chemie), Disparon (manufactured by Kusumoto Kasei Co., Ltd.), and SOLSPERSE (manufactured by Zeneca). You may use what has been done. The blending amount of the dispersant in the photosensitive resin composition of the present embodiment may be appropriately set according to the type of pigment or the like used.

[Composition of ethylenically unsaturated resin composition]
The blending amount of the ethylenically unsaturated resin (A), the carbon cluster (c), and the solvent (B) in the resin composition of the present embodiment is the sum of the components excluding the solvent (B) in the resin composition. With 100 parts by mass, the ethylenically unsaturated resin (A) is preferably 50 to 99.9 parts by mass; the carbon cluster (c) is preferably 0.00001 to 10 parts by mass; the solvent ( B) is preferably 30 to 1000 parts by mass, more preferably 50 to 800 parts by mass, and even more preferably 100 to 700 parts by mass.

When the resin composition of the present embodiment contains the reactive diluent (D), the blending amount of the ethylenically unsaturated resin (A), the carbon cluster (c), the solvent (B), and the reactive diluent (D). Is 100 parts by mass of the components excluding the solvent (B) in the resin composition, 10 to 90 parts by mass of the ethylenically unsaturated resin (A), and 0.00001 to 10 parts by mass of the carbon cluster (c). Parts, solvent (B) is 30 to 1000 parts by mass, reactive diluent (D) is 10 to 90 parts by mass, preferably ethylenically unsaturated resin (A) is 20 to 80 parts by mass, carbon clusters ( c) is 0.0001 to 0.10 parts by mass, the solvent (B) is 50 to 800 parts by mass, and the reactive diluent (D) is 20 to 80 parts by mass, more preferably an ethylenically unsaturated resin ( A) is 30 to 75 parts by mass, carbon cluster (c) is 0.0005 to 0.05 parts by mass, solvent (B) is 100 to 700 parts by mass, and reactive diluent (D) is 25 to 70 parts by mass. be.
[Composition of photosensitive resin composition]

Amount of the ethylenically unsaturated resin (A), carbon cluster (c), solvent (B), reactive diluent (D), and photopolymerization initiator (E) of the photosensitive resin composition of the present embodiment. When the total of the components excluding the solvent (B) in the photosensitive resin composition is 100 parts by mass, preferably, the ethylenically unsaturated resin (A) is 5 to 80 parts by mass and the carbon cluster (c) is 0. The solvent (B) is 30 to 1000 parts by mass, the reactive diluent (D) is 10 to 90 parts by mass, and the photopolymerization initiator (E) is 0.1 to 30 parts by mass. More preferably, the ethylenically unsaturated resin (A) is 8 to 70 parts by mass, the carbon cluster (c) is 0.0001 to 5 parts by mass, the solvent (B) is 50 to 800 parts by mass, and the reactive diluent (D). ) Is 20 to 80 parts by mass, the photopolymerization initiator (E) is 0.5 to 20 parts by mass, and more preferably, the ethylenically unsaturated resin (A) is 10 to 60 parts by mass, and the carbon cluster (c). Is 0.005 to 1 part by mass, the solvent (B) is 100 to 700 parts by mass, the reactive diluent (D) is 25 to 70 parts by mass, and the photopolymerization initiator (E) is 1 to 15 parts by mass.

When the photosensitive resin composition of the present embodiment contains a colorant (F), an ethylenically unsaturated resin (A), a carbon cluster (c), a solvent (B), a reactive diluent (D), and photopolymerization. Generally, the amount of the initiator (E) and the colorant (F) blended is 5 for the ethylenically unsaturated resin (A), where 100 parts by mass is the total of the components excluding the solvent (B) in the photosensitive resin composition. ~ 80 parts by mass, carbon cluster (c) 0.00001 to 10 parts by mass, solvent (B) 30 to 1000 parts by mass, reactive diluent (D) 10 to 89 parts by mass, photopolymerization initiator (E) ) Is 0.1 to 30 parts by mass, the colorant (F) is 5 to 80 parts by mass, preferably the ethylenically unsaturated resin (A) is 8 to 70 parts by mass, and the carbon cluster (c) is 0. 0001 to 0.10 parts by mass, solvent (B) 50 to 800 parts by mass, reactive diluent (D) 20 to 80 parts by mass, photopolymerization initiator (E) 0.5 to 20 parts by mass, coloring The agent (F) is 5 to 70 parts by mass, more preferably the ethylenically unsaturated resin (A) is 10 to 60 parts by mass, the carbon cluster (c) is 0.0005 to 0.5 parts by mass, and the solvent ( B) is 100 to 700 parts by mass, the reactive diluent (D) is 25 to 70 parts by mass, the photopolymerization initiator (E) is 1 to 15 parts by mass, and the colorant (F) is 10 to 60 parts by mass. ..

In addition to the above components, the photosensitive resin composition of the present embodiment has known additives such as known coupling agents, leveling agents, and thermal polymerization inhibitors, and known additives in order to impart predetermined properties. Colorants, fillers, dispersants and the like may be blended. The blending amount of these additives is not particularly limited as long as it does not impair the effects of the present invention.

[Manufacturing method of photosensitive resin composition]
The photosensitive resin composition of the present embodiment can be produced by mixing each of the above components using a known mixing device. In the photosensitive resin composition of the present embodiment, a resin composition containing an ethylenically unsaturated resin (A) and a solvent (B) is first prepared, and then a reactive diluent (D) and photopolymerization are started. It is also possible to mix and produce the agent (E). The resin composition can be used for preparing the photosensitive resin composition of the present embodiment, and can also be used for other purposes.

[Resin cured film]
Since the photosensitive resin composition of the present embodiment contains the resin of the present embodiment, a cured film having excellent developability, good colorant dispersibility and solvent resistance, and a high elastic recovery rate can be obtained. Be done.
Therefore, the photosensitive resin composition of the present embodiment is suitable as a material for a black matrix, a color filter, and a black column spacer.
Further, the photosensitive resin composition of the present embodiment has good colorant dispersibility, and even if it sufficiently contains a black colorant, general properties such as developability can be sufficiently satisfied, and the subject can be covered. A resin cured film having good adhesion to the formed surface can be formed. Therefore, according to the photosensitive resin composition of the present embodiment, it is possible to form a black pattern having good adhesion to the surface to be formed and having sufficient light-shielding properties.

[Manufacturing method of resin cured film]
The cured resin film of the present embodiment can be produced, for example, by the method shown below.
First, the photosensitive resin composition is applied onto the surface to be formed of the cured resin film to form a resin layer (coating film). Next, the resin layer is exposed through a mask having a predetermined pattern, and the exposed portion is photocured. Next, the unexposed portion of the resin layer is developed with a developing solution to obtain a cured resin film having a predetermined pattern. Then, if necessary, post-baking (heat treatment) of the cured resin film is performed.
When exposing the resin layer, a halftone mask having a predetermined pattern may be used. In this case, the unexposed portion and the semi-exposed portion are developed with a developing solution to obtain a resin cured film having a predetermined pattern.

The method for applying the photosensitive resin composition is not particularly limited, and examples thereof include a screen printing method, a roll coating method, a curtain coating method, a spray coating method, and a spin coating method.
After applying the photosensitive resin composition, the solvent (B) contained in the resin layer is volatilized by heating using a heating means such as a circulation oven, an infrared heater, or a hot plate, if necessary. May be good. The heating conditions after coating are not particularly limited, and may be appropriately set according to the composition of the photosensitive resin composition. For example, the heating temperature after coating can be 50 ° C. to 120 ° C., and the heating time can be 30 seconds to 30 minutes.

The method for exposing the resin layer is not particularly limited, and examples thereof include a method of irradiating active energy rays such as ultraviolet rays and excimer laser light.
The energy dose to be applied to the resin layer may be appropriately set according to the composition of the photosensitive resin composition. For example, the energy dose to irradiate the resin layer ^{can be 30 to 2000 mJ / cm 2} , but is not limited to this range.
The light source used for exposure is not particularly limited, but a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be arbitrarily selected and used.

As the developing solution used for development, it is preferable to use an alkaline developing solution because excellent developability can be obtained. Examples of the alkaline developing solution include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide and the like; aqueous solutions of amine compounds such as ethylamine, diethylamine and dimethylethanolamine; tetramethylammonium and 3-methyl. -4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfon Amidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and aqueous solutions of p-phenylenediamine compounds such as sulfates, hydrochlorides or p-toluenesulfonates thereof Can be mentioned.
The developing solution may contain an antifoaming agent, a surfactant and the like, if necessary.

After developing with a developing solution, it is preferable to wash the cured resin film having a predetermined pattern with water and dry it.
Further, after developing with a developing solution, it is preferable to perform post-baking (heat treatment) of a resin cured film having a predetermined pattern. By performing post-baking, the curing of the resin cured film can be further promoted. The post-baking conditions are not particularly limited and can be arbitrarily selected, and may be appropriately set according to the composition of the photosensitive resin composition. For example, the heating temperature of the post bake can be 130 ° C. to 250 ° C. The heating time of the post-bake is preferably 10 minutes to 4 hours, more preferably 20 minutes to 2 hours.

[Image display device]
The image display device of the present embodiment includes the resin cured film of the present embodiment. Specific examples of the image display device include a liquid crystal display device, an organic EL display device, and the like.
As the image display device, for example, it is preferable that one or more members selected from a black matrix, a color filter, and a black column spacer are formed of the cured resin film of the present embodiment.

The material of the base material forming the surface to be formed of the resin cured film is not particularly limited, but is, for example, on the surface of glass, silicon, polycarbonate, polyester, polyamide, polyamideimide, polyimide, aluminum, printed wiring board, or the like. Examples thereof include a substrate on which a wiring pattern is formed, an array substrate, and the like.

The manufacturing method of the image display device of the present embodiment may include a step of forming the resin-cured film of the present embodiment by the manufacturing method described above, and the members other than the members formed of the resin-cured film may be included. It can be manufactured according to a conventional method.

The cured resin film obtained by curing the photosensitive resin composition of the present embodiment has excellent developability, good colorant dispersibility and solvent resistance, and a high elastic recovery rate. Therefore, it is suitable as a material for a black matrix, a color filter, and a black column spacer provided in an image display device.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples. In this embodiment, parts and percentages are all based on mass unless otherwise specified.
[Example 1]
137.5 g of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, and the mixture was stirred while substituting with nitrogen, and the temperature was raised to 120 ° C. Then, in a monomer mixture consisting of 141.7 g (1.00 mol) of glycidyl methacrylate, 4.7 g (0.02 mol) of tricyclodecanyl methacrylate, and 5.0 g (0.05 mol) of styrene, 13. 3 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nichiyu Co., Ltd., Perbutyl® O) was added thereto, and the mixture was added dropwise to the flask over 2 hours from the dropping funnel. After completion of the dropping, the copolymerization reaction was carried out by further stirring at 120 ° C. for 2 hours to generate an epoxy group-containing copolymer (P1) solution. There, 6.0 g of a trimethylbenzene solution containing 72.0 g of acrylic acid as a monomer (m-2) and 3% by mass of fullerene (manomu (registered trademark) mix ST, manufactured by Frontier Carbon Co., Ltd.) as a polymerization inhibitor was added, and a tri was used as a catalyst. 0.67 g (0.3 parts by mass) of phenylphosphine was charged, and the mixture was heated at 110 ° C. for 10 hours while blowing low oxygen air infused with nitrogen gas so that the oxygen concentration was 4 to 7% by volume.
Then, after confirming that the acid value was 1.0 KOH mg / g or less, 15.6 g of tetrahydrophthalic anhydride was charged as the polybasic acid anhydride (d) and reacted at 110 ° C. for 2 hours to have a solid content concentration of 50. An ethylenically unsaturated resin composition (solid acid value 32.4 KOHmg / g, weight average molecular weight 9400), which is a solution containing a mass% ethylenically unsaturated resin (A1), was obtained. The solid content means a residual amount of heating when the ethylenically unsaturated resin (A1) solution is heated at 130 ° C. for 2 hours, and the ethylenically unsaturated resin (A1) is the main component.
The addition reaction rate of acrylic acid to the epoxy group was calculated by measuring the acid value (monomer residual rate) in the reaction solution and found to be 99.1%.

[Examples 2 to 4 and Comparative Examples 1 to 3]
In Examples 2 and 3, the amount of the fullerene solution added was changed, and in Example 4, instead of the fullerene solution, a solution (concentration 0) of an inden adduct of fullerene (manom (registered trademark) spectra NPQ3000 manufactured by Frontier Carbon Co., Ltd.) was used. It is a solution containing an ethylenically unsaturated resin in the same manner as in Example 1 except that BHT (di-t-butylhydroxytoluene) is used instead of the fullerene solution in the comparative example. The composition was obtained. The results are shown in Table 1.
[Example 5]
In Example 5, an ethylenically unsaturated resin solution was obtained in the same manner as in Example 1 except that the polymerization inhibitor was changed to 0.02% by mass of a soot-like substance. As the soot-like substance, the one obtained by the following method was used. Toluene and pure oxygen gas were supplied to the reaction tube at a ratio of 3: 1 and mixed, and heated at 67 hPa and 180 ° C. to obtain soot. Then, it was washed twice with toluene to obtain a soot-like substance. The results are shown in Table 1.

[Example 6]
185.6 g of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, and the mixture was stirred while replacing nitrogen, and the temperature was raised to 120 ° C.
Then, in a monomer mixture consisting of 58.5 g (0.68 mol) of methacrylic acid, 33.7 g (0.15 mol) of tricyclodecanyl methacrylate, and 3.0 g (0.02 mol) of benzyl methacrylate, 2 .9 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nichiyu Co., Ltd., perbutyl® O) was added dropwise to the flask over 2 hours from the dropping funnel. .. After completion of the dropping, the copolymerization reaction was carried out by further stirring at 120 ° C. for 2 hours to generate a carboxy group-containing copolymer (P2) solution. 3.5 g of a trimethylbenzene solution containing 35 g of glycidyl methacrylate as a monomer (m-1) and 3% by mass of fullerene (manom (registered trademark) mix ST, manufactured by Frontier Carbon Co., Ltd.) as a polymerization inhibitor, and triphenylphosphine as a catalyst. 0.39 g (0.3 parts by mass) was charged and heated at 110 ° C. for 10 hours while blowing low oxygen air infused with nitrogen gas so that the oxygen concentration was 4% to 7%.
Then, after confirming that the acid value is 72.0 KOH mg / g or less, the ethylenically unsaturated resin composition (solid) is a solution containing the ethylenically unsaturated resin (A2) having a solid content concentration of 28.6% by mass. A fractionated acid value of 196.8 KOH mg / g and a weight average molecular weight of 18500) were obtained.
The reaction rate between the acid and the epoxy was calculated by measuring the acid value in the reaction solution and found to be 97.8%.

[Examples 7 to 10 and Comparative Examples 4 to 6]
In Examples 6 to 8, the amount of the fullerene solution added was changed, in Example 9, the polymerization inhibitor was changed to an inden adduct of fullerene, and in Example 10, the polymerization inhibitor was changed to a soot-like substance. In Comparative Example, an ethylenically unsaturated resin composition was obtained in the same manner as in Example 1 except that BHT was used instead of the fullerene solution. The results are shown in Table 2.

[Example 11]
224.1 g of cresol novolac epoxy N-695 (epoxy equivalent 215) manufactured by DIC Corporation, which is an epoxy resin (P3), and PGMEA94. The temperature is raised to 120 ° C. while blowing low oxygen air infused with nitrogen gas so that 5 g is added and the oxygen concentration becomes 4 to 7% by volume. After that, it was confirmed that the acid value was 42.0 KOH mg / g or less, and 75.1 g (1.04 mol) of acrylic acid was added as a monomer (m-2) to fullerene (manom (registered trademark) mix ST manufactured by Frontier Carbon Co., Ltd.). 8 g of a trimethylbenzene solution containing 3% by mass and 0.9 g of triphenylphosphine dissolved therein are added dropwise over 10 minutes. After that, the reaction was continued until the acid value became 1 or less, 33.4 g of succinic anhydride was charged as the polybasic acid anhydride (d), and the reaction was carried out at 110 ° C. for 1 hour to obtain an ethylenic property having a solid content concentration of 38.5% by weight. An ethylenically unsaturated resin composition (solid acid value 60.8 KOHmg / g, weight average molecular weight 5900), which is a solution containing an unsaturated resin (A3-1), was obtained.
The reaction rate was calculated to be 99.1% by measuring the acid value (monomer residual rate) in the reaction solution.

[Examples 12 to 15 and Comparative Examples 7 to 9]
In Examples 12 to 13, the amount of the fullerene solution added was changed, in Example 14, the polymerization inhibitor was changed to an inden adduct of fullerene, and in Example 15, the polymerization inhibitor was changed to a soot-like substance. In the comparative example, an ethylenically unsaturated resin composition was obtained in the same manner as in Example 9 except that BHT was used instead of the fullerene solution. The results are shown in Table 3.

[Example 16]
In a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, 64.3 g (0.30 mol) of 1,2,4-cyclohexanetricarboxylic acid as polyfunctional carboxylic acid (e) and epoxy resin. While blowing low oxygen air infused with nitrogen gas so that the oxygen concentration becomes 4 to 7% by adding 67.1 g of AER-2603 (epoxy equivalent 188) manufactured by Asahi Kasei Co., Ltd., 0.54 g of triphenylphosphine, and 88.1 g of PGMEA. The temperature is raised to 120 ° C. After that, the reaction was carried out until the acid value became 138 KOH mg / g or less to obtain a carboxy group-containing resin (P4), and then 50.7 g of glycidyl methacrylate as a monomer (m-1) was added to fullerene (manufactured by Frontier Carbon Co., Ltd., nanom (registered trademark)). Mix ST) Addition of 4.9 g of a solution for trimethylbenzene containing 3% by mass is added dropwise over 10 minutes. After confirming that the acid value was 40 KOH mg / g or less, 17.9 g of succinic anhydride was added as the polybasic acid anhydride (d) and reacted at 110 ° C. for 1 hour to obtain a solid content concentration of 48.5% by weight. An ethylenically unsaturated resin composition (solid acid value 107.8 KOHmg / g, weight average molecular weight 6100), which is a solution containing the ethylenically unsaturated resin (A6), was obtained.
The reaction rate was calculated to be 95.4% by measuring the acid value (monomer residual rate) in the reaction solution.

[Examples 17 to 20 and Comparative Examples 10 to 12]
In Examples 17 to 18, the amount of the fullerene solution added was changed, in Example 19, the polymerization inhibitor was changed to an inden adduct of fullerene, and in Example 20, the polymerization inhibitor was changed to a soot-like substance. In Comparative Example, an ethylenically unsaturated resin composition was obtained in the same manner as in Example 13 except that BHT was used instead of the fullerene solution. The results are shown in Table 4.

The acid value and molecular weight of the ethylenically unsaturated resin contained in the synthesized ethylenically unsaturated resin composition were measured by the following methods.
[Measurement method of acid value]
Measurements were made according to JIS K6901 5.3.2 using a mixed indicator of bromothymol blue and phenol let. It means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the ethylenically unsaturated resin (A) which is a solid content.
As for the solid content, the heating residue when the sample was heated at 130 ° C. for 2 hours was measured.

[Measurement method of weight average molecular weight (Mw)]
It was measured under the following conditions using gel permeation chromatography (GPC) and converted to standard polystyrene.
Column: Showdex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko KK)
Column temperature: 40 ° C
Sample: 0.2% tetrahydrofuran solution of copolymer Developing solvent: Tetrahydrofuran Detector: Differential refractometer (SHODEX (registered trademark) RI-71S) (manufactured by Showa Denko KK)
Flow rate: 1 mL / min

As shown in Tables 1 to 4, synthesis is possible even if the amount of fullerene as a inhibitor is reduced in the examples, but in the comparative example, if the amount of BHT is reduced, the cross-linking of the double bond cannot be suppressed and gelation occurs. It will happen.

[Examples 21 to 52, Comparative Examples 13 to 20]
Using the resins of Examples 1 to 20 and Comparative Examples 1, 4, 7 and 10, respectively, a photosensitive resin composition having the formulations shown in Tables 5 to 8 was prepared. In addition, the compounding amount of the resin in the table was described by the value of the solid content, and the solvent contained in the synthesis of the resin was described by adding it to the item of "solvent" in the table.

[Evaluation of OD value]
The photosensitive resin compositions of Examples 21 to 36 and Comparative Examples 13 to 16 were used on a glass substrate, and a coating film was prepared with a spin coater so as to have a film thickness of 1.5 μm. The solvent in the coating film was volatilized by heating the prepared coating film at 90 ° C. for 3 minutes. Next, the entire surface of the coating film was exposed (exposure amount 200 mJ / cm2) using a multi-light ML-251D / B manufactured by Ushio, Inc. and an irradiation optical unit PM25C-100, and photocured. The OD value of the film cured after 30 minutes at 230 ° C. was measured using an OD value meter 361T manufactured by X-rite. The results are shown in Table 9. The larger the OD value, the better the black matrix because it does not allow light to pass through.

[Evaluation of resist pattern shape]
A coating film having a thickness of 2.5 μm is prepared by the same method as the evaluation of the OD value, and the coating film is covered with a mask of a line & space pattern having a line width of 20 μm and irradiated with Multilight ML-251D / B manufactured by Ushio, Inc. It was exposed (exposure amount 50 mJ / cm2) using an optical unit PM25C-100 and photocured. After irradiation, the mixture was developed with a 0.2 mass% potassium hydroxide aqueous solution for 120 seconds and further post-baked at 230 ° C. for 30 minutes to obtain a desired pattern. The ratio of the area at a height of 5% from the bottom to the top of the pattern is T / B, and the results are shown in Table 9. The closer the T / B is to 1, the closer it is to the desired pattern shape.

[Evaluation of heat-resistant yellowing]
The photosensitive resin compositions of Examples 37 to 52 and Comparative Examples 17 to 20 were used on a glass substrate, respectively, to prepare a composition shown in Table 6, and the film thickness was 2.5 μm with a spin coater. The coating film was prepared as described above. The solvent in the coating film was volatilized by heating the prepared coating film at 90 ° C. for 3 minutes. Next, the entire surface of the coating film was exposed (exposure amount 50 mJ / cm2) using a multi-light ML-251D / B manufactured by Ushio, Inc. and an irradiation optical unit PM25C-100, and photocured. After irradiation, the film cured after 30 minutes at 230 ° C. was measured for the absorbance at the maximum absorption wavelength of the resin-cured film using a UV spectrum meter UV-1650PC manufactured by SIMAZU.
The results are shown in Table 10. The smaller ΔEab, the less yellowing is good.

[Evaluation of transparency]
A coating film was prepared in the same manner as in the evaluation of heat-resistant yellowing, and the transmittance from a wavelength of 380 nm to 780 nm was measured. The average value of the transmittance of each wavelength was defined as the average transmittance (%).
The results of Examples 37 to 44 and Comparative Examples 17 and 18 are shown in Table 11. The results of Examples 45 to 52 and Comparative Examples 19 and 20 are shown in Table 12.

As shown in Tables 9 to 10, it can be seen that the photosensitive resin containing the carbon cluster (c) has excellent dispersibility of the colorant, and a cured product having excellent pattern shape and heat-resistant yellowing can be obtained. Further, as shown in Tables 11 and 12, it can be seen that the photosensitive resin using the ethylenically unsaturated resin synthesized by using the carbon cluster (c) has improved transparency.

Claims (13)

Ethylene unsaturated resin (A) and
Carbon cluster (c) and
Contains solvent (B)
The carbon cluster (c) is at least one of fullerenes and soot-like substances, and the content thereof is 0.00001 to 10 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated resin (A). An ethylenically unsaturated resin composition characterized by being present. In the ethylenically unsaturated resin (A), a carboxy group-containing ethylenically unsaturated compound (m-2) is ring-opened and added to the epoxy group of the epoxy group-containing polymer (P1), and the epoxy group is further added. An ethylenically unsaturated resin (A1) formed by adding a polybasic acid anhydride (d) to a hydroxy group generated by ring opening.
The epoxy group-containing copolymer (P1) is
A structural unit derived from an epoxy group-containing (meth) acrylate (m-1) and a polymerizable monomer (m-3) having a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms, and the following chemical formula (1). At least one selected from the group consisting of structural units derived from the polymerizable monomer (m-4) represented by
The ethylenically unsaturated resin composition according to claim 1, which is a copolymer containing.

(X and X'in the formula (1) each independently represent a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms which may be linear or branched, and R1 and R2 are independent of each other. It is a hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom carboxy group or a substituent, and may have a cyclic structure connecting R1 and R2.) The ethylenically unsaturated resin (A) has a hydroxy group formed by ring-opening addition of a carboxy group-containing copolymer (P2) to an epoxy group of an epoxy group-containing ethylenically unsaturated compound (m-1). It is a saturated group-containing ethylenically unsaturated resin (A2).
The carboxy group-containing copolymer (P2) is
Constituent units derived from the carboxy group-containing ethylenically unsaturated compound (m-2) and
It is composed of a structural unit derived from a polymerizable monomer (m-3) having a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms and a structural unit derived from a polymerizable monomer (m-4) represented by the following chemical formula (1). At least one selected from the group and
Is a copolymer containing
The ethylenically unsaturated resin composition according to claim 1.

(X and X'in the formula (1) each independently represent a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms which may be linear or branched, and R1 and R2 are independent of each other. It is a hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom carboxy group or a substituent, and may have a cyclic structure connecting R1 and R2.) In the ethylenically unsaturated resin (A), a carboxy group-containing ethylenically unsaturated compound (m-2) is ring-opened and added to the epoxy group of the epoxy resin (P3), and the epoxy group is further ring-opened. An ethylenically unsaturated resin (A3) formed by adding a polybasic acid anhydride (d) to the generated hydroxy group.
The epoxy resin (P3) is
Claim 1 is at least one selected from the group consisting of a novolak type epoxy resin (P3-1), a bisphenol type epoxy resin (P3-2), and a bifunctional epoxy resin having a biphenyl skeleton (P3-3). The ethylenically unsaturated resin composition according to the above. The ethylenically unsaturated resin (A) is an ethylenically unsaturated compound having a hydroxy group formed by ring-opening addition of a carboxy group-containing resin (P4) to an epoxy group of an epoxy group-containing ethylenically unsaturated compound (m-1). Saturated resin (A4)
The carboxy group-containing resin (P4) is a resin having a carboxy group formed by reacting an epoxy resin (P3) with a polyfunctional carboxylic acid (e).
The epoxy resin (P3) is
At least one selected from the group consisting of a novolak type epoxy resin (P3-1), a bisphenol type epoxy resin (P3-2), and a bifunctional epoxy resin having a biphenyl skeleton (P3-3).
The ethylenically unsaturated resin composition according to claim 1. The ethylenically unsaturated resin (A) is
The ethylenically unsaturated resin (A5) obtained by adding a polybasic acid anhydride (d) to the hydroxy group of the ethylenically unsaturated resin (A2) according to claim 3, or the ethylenically according to claim 5. The ethylenically unsaturated resin composition according to claim 1, which is an ethylenically unsaturated resin (A6) in which a polybasic acid anhydride (d) is added to a hydroxy group of an unsaturated resin (A4). The ethylenically unsaturated resin composition according to any one of claims 1 to 6, wherein the carbon cluster (c) is an unsubstituted fullerene. The ethylenically unsaturated resin composition according to any one of claims 1 to 7, which does not substantially contain a polymerization inhibitor other than the carbon cluster (c). The ethylenically unsaturated resin composition according to any one of claims 1 to 8, further containing a reactive diluent (D). The ethylenically unsaturated resin composition according to any one of claims 1 to 9,
A photosensitive resin composition containing a photopolymerization initiator (E). Further contains a colorant (F),
The photosensitive resin composition according to claim 10, wherein the colorant (F) is at least one selected from the group consisting of dyes and pigments. The photosensitive resin composition according to claim 10 or 11, which does not substantially contain a polymerization inhibitor other than the carbon cluster (c). A resist using the photosensitive resin composition according to any one of claims 10 to 12.