TW202311236A - Compound, composition, cured product, and method for producing cured product - Google Patents

Abstract

The present disclosure provides a compound represented by general formula (I). (I) (In the formula, Ara is a group obtained by removing n1 hydrogen atoms from a structure represented by general formula (A), and is bonded to R1 at a portion from which the hydrogen atoms have been removed, R1 is a group containing a COOH group, and n1 represents an integer of at least 1. When a plurality of R1's are present, the plurality of R1's may be the same as or different from each other.) (A) (In the formula, Ar1 and Ar2 each independently represent an aromatic group.).

Description

Compound, composition, cured product and method for producing the cured product

The present invention relates to a compound having carbonyl, carboxyl and aromatic rings.

The photosensitive composition is obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond. Since it can be polymerized and hardened by irradiating energy rays (light), it is used for photocurable inks, photosensitive Printing plates, various photoresists, etc.

As a photoinitiator used for the said photosensitive composition, the use of a benzophenone type compound is proposed by following patent document 1. prior art literature patent documents

Patent Document 1: US4861916B

[Problem to be solved by the invention]

Compounds used as photopolymerization initiators are required to have high heat resistance in order to avoid inconvenience such as outgassing due to decomposition during the production of cured products. However, when the conventional benzophenone-based compounds are used as photopolymerization initiators, they have poor heat resistance.

The present invention was made in view of the above problems, and its main purpose is to provide a compound which has excellent heat resistance and is suitable as a photopolymerization initiator. [Technical means to solve the problem]

The inventors of the present invention conducted earnest research in order to solve the above-mentioned problems. As a result, it was found that by having a structure in which aromatic groups such as a benzophenone structure are bonded through a carbonyl group, and further having a carboxyl group structure, it becomes excellent in heat resistance. , thus completing the present invention.

That is, the present invention provides a compound characterized by being represented by the following general formula (I) (hereinafter, may be referred to as compound I).

[chemical 1]

(Ar ¹及Ar ²分別獨立地表示芳香族基) (In the formula, Ar ^a is a base formed by removing n1 hydrogen atoms from the structure represented by the following general formula (A), and bonds with R ¹ at the part where the hydrogen atoms have been removed, and R ¹ is a group containing a COOH group base, n1 represents an integer of 1 or more. When there are plural ^R1s , they may be the same or different from each other) [Chem. 2]

(Ar ¹ and Ar ² each independently represent an aromatic group)

According to the present invention, since it has the above-mentioned specific structure and has a carboxyl group, the above-mentioned compound I has excellent sensitivity and heat resistance when used as a photopolymerization initiator, for example.

In the present invention, the above compound I is preferably represented by the following general formula (II-1) or (III-1). The reason is that the above compound I has excellent sensitivity and heat resistance when used as a photopolymerization initiator, for example.

[Chem 3]

[chemical 4]

(In the formula, X ^a and X ^b are divalent bonding groups, each independently representing >CR ¹⁴ R ¹⁵ , -O-, -S- or >NR ¹⁴ , R ¹⁴ and R ¹⁵ independently representing a hydrogen atom, An aliphatic hydrocarbon group with 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group with 6 to 35 carbon atoms, or a heterocyclic group with 2 to 35 carbon atoms, L ^a and L ^b are divalent bonding groups, each independently Indicates direct bond, -O-, -S-, >C=O, >NR ⁵³ , aliphatic hydrocarbon group with 1 to 120 carbon atoms, aromatic ring hydrocarbon group with 6 to 35 carbon atoms or 2 to 35 carbon atoms However, one or more methylene groups in the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group and the heterocyclic group may be substituted by -S-, -O-, carbon-carbon double bond , -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO- O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -O-CO-NH-, >NR', >P=O, -SS -, -SO ₂ or a combination thereof, R ⁵³ represents a hydrogen atom, an aliphatic hydrocarbon group with 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group with 6 to 35 carbon atoms, or a heterocyclic ring with 2 to 35 carbon atoms R' represents a hydrogen atom or an alkyl group with 1 to 8 carbon atoms, R ^a1 , R ^a2 , R ^b1 and R ^b2 each independently represent an aliphatic hydrocarbon group with 1 to 35 carbon atoms, or an alkyl group with 6 to 35 carbon atoms An aromatic ring-containing hydrocarbon group or a heterocyclic group containing 2 to 35 carbon atoms, a1, a2, b1 and b2 are each independently an integer of 0 to 4)

In the present invention, in formula (II-1) or (III-1), L ^a and L ^b are preferably selected from aliphatic hydrocarbon groups with 1 to 120 carbon atoms, and aromatic hydrocarbon groups with 6 to 35 carbon atoms. A cyclohydrocarbyl group and a heterocyclic group-containing group with 2 to 35 carbon atoms in which at least one methylene group is substituted with -S-, preferably selected from the above-mentioned aliphatic hydrocarbon group, the above-mentioned aromatic ring-containing group A group in which the methylene group at the end of the benzene ring side of the hydrocarbon group and the above-mentioned heterocyclic group-containing group is substituted with -S-. The reason is that the sensitivity of the above compound I is excellent.

The present invention provides a composition characterized by comprising the above compound I.

According to the composition of the present invention, by including the above-mentioned compound I, it exhibits excellent sensitivity, and the compound I is excellent in heat resistance, so when the cured product is produced, there is less outgassing due to decomposition products.

The present invention provides a cured product characterized in that it is a cured product of the above composition.

According to the present invention, by being a cured product of the composition comprising the above compound I, the cured product has less outgassing.

The present invention provides a method for producing a cured product, characterized by the step of irradiating the composition with light.

According to the production method of the cured product of the present invention, by using the composition containing the compound I, the production of the cured product is easy, and the outgassing of the cured product is less. [Effect of Invention]

According to the present invention, there can be provided a compound which has excellent heat resistance and is suitable as a photopolymerization initiator.

The present invention relates to a compound, a composition, its cured product and a method for producing the cured product. Hereinafter, the compound, the composition, the cured product, and the method for producing the cured product of the present invention will be described in detail.

A. Compound First, the compounds of the present invention will be described. Compound I of the present invention is represented by the following general formula (I).

[chemical 5]

(Ar ¹及Ar ²分別獨立地表示芳香族基) (In the formula, Ar ^a is a base formed by removing n1 hydrogen atoms from the structure represented by the following general formula (A), and bonds with R ¹ at the part where the hydrogen atoms have been removed, and R ¹ is a group containing a COOH group base, n1 represents an integer above 1) [Chemical 6]

(Ar ¹ and Ar ² each independently represent an aromatic group)

According to the present invention, since it has the above-mentioned specific structure and has a carboxyl group, the above-mentioned compound I has excellent sensitivity and heat resistance when used as a photopolymerization initiator, for example. Also, compound I can function as a hydrogen abstraction type photoradical polymerization initiator. Here, the reason why the said effect is exhibited by having the said specific structure is presumed as follows.

That is, the above-mentioned compound easily improves sensitivity by having the aromatic group Ar ^a as described above. For example, as an aromatic group, by increasing the number of aromatic rings, free radicals are easily generated even under long-wavelength light, and the sensitivity is excellent. Furthermore, by having a carboxyl group, intermolecular force is strengthened by a hydrogen bond, and as a result, it is excellent in heat resistance. In particular, carbonyl groups and hydroxyl groups, which are groups that can form hydrogen bonds, are densely present in carboxyl groups. Therefore, for example, even compared with the case where only hydroxyl groups are included, the hydrogen bonding ability is excellent, and it has excellent heat resistance. From the above, the compound has the above-mentioned specific structure, and when used as a photopolymerization initiator, for example, has excellent sensitivity and heat resistance as shown above.

In addition, the above-mentioned compounds are easily bonded to other compounds via the carboxyl group. Therefore, the above-mentioned compound can also improve heat resistance by bonding with other compounds, such as a resin component, for example. From this point of view, the above compounds also have excellent sensitivity and heat resistance.

Hereinafter, the compound of this invention is demonstrated in detail.

The above-mentioned compound I is represented by the above-mentioned general formula (I). As such a compound I, at least the aromatic group Ar ¹ may have R ¹ . Ar ^a is a group obtained by removing a total of n1 hydrogen atoms from either or both of Ar ¹ and Ar ² in the above general formula (A). That is to say, compound I is a compound in which a total of n1 hydrogen atoms in either or both of ^Ar1 and ^Ar2 in the general formula (A) are replaced by ^R1 . That is to say, in this specification, " ^Ara is a group obtained by removing n1 hydrogen atoms from the structure represented by the following general formula (A), and is bonded to ^R1 at the part where the hydrogen atoms are removed." , means that Ar ^a is a base having a total of n1 bonding bonds in either or both of Ar ¹ and Ar ² in the general formula (A), and the n1 bonding bonds are bonded to R ¹ Bond key. Ar ¹ and Ar ² in the general formula (A) can be set as a monovalent group in the state where n1 hydrogen atoms have not been removed. As compound I, specifically, it can be set as a compound in which only Ar in the aromatic groups Ar ¹ and Ar ² represented by the following general formula (I-1) has ^{R 1 (} hereinafter sometimes referred to as compound I -1), or a compound having R ¹ in both the aromatic group Ar ¹ and the aromatic group Ar ² represented by the following general formula (I-2) (hereinafter sometimes referred to as compound I-2). In the present invention, among them, in terms of the balance of sensitivity and heat resistance and the viewpoint of easy synthesis, compound I is preferably represented by the following general formula (I-1) where only the aromatic group Ar has ^{R 1} .

[chemical 7]

(In the formula, Ar ¹ and Ar ² each independently represent an aromatic group, R ¹ is a group including a COOH group, and n1 represents an integer of 1 or more. When there are multiple R ^1s , the multiple R ^1s may be identical to each other , can also be different)

[chemical 8]

(In the formula, Ar ¹ and Ar ² each independently represent an aromatic group, R ¹ and R ² each independently represent a group containing a COOH group, n1 and n2 each independently represent an integer greater than 1. When there are multiple R ¹ or In the case of R ² , there are multiple R ¹ or R ² which may be the same or different from each other)

As mentioned above, the above-mentioned compound I can be in the form of the compound represented by the above-mentioned general formula (I-1) (the first embodiment) or in the form of the compound represented by the above-mentioned general formula (I-2) Like (the 2nd embodiment). Hereinafter, Compound I will be described in the first embodiment and the second embodiment.

1. First Embodiment The first embodiment of the compound I of the sample invention is that the above-mentioned compound I is represented by the above-mentioned general formula (I-1). The above-mentioned aromatic group Ar ¹ is the one to which n1 R ^1s are bonded. In the above-mentioned compound I-1, the above-mentioned aromatic groups Ar ¹ and Ar ² (hereinafter, Ar ¹ and Ar ² may be collectively referred to as "Ar" in some cases) are aromatic groups. Such an aromatic group Ar may contain at least one aromatic ring. The aromatic group Ar may include an aromatic ring, and the >C=O bond of the formula (A) is bonded to an atom constituting the ring structure of the aromatic ring. As said aromatic ring, an aromatic hydrocarbon ring and an aromatic heterocyclic ring are mentioned, for example. The aromatic rings in the aromatic groups Ar ¹ and Ar ² may be the same or different, but they are preferably different in terms of heat resistance and sensitivity. In addition, the two bonding bonds >C=O in the formula (A) are preferably bonded to the carbon atoms constituting the ring structure of the aromatic ring in each of Ar ¹ and Ar ² .

環、聯三伸苯環、二氫苊環、螢蒽環、茀環等及該等之縮合環。 上述芳香族烴環亦可使用下述通式(a-1)所表示之結構。 As the above-mentioned aromatic hydrocarbon ring, all the atoms forming the ring structure may be carbon atoms, and may be a single ring or a condensed ring, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, Naphthacene ring, pyrene ring, benzopyrene ring,

ring, biphenylene ring, dihydroacenaphthene ring, fluoranthene ring, fenene ring, etc., and their condensed rings. The structure represented by the following general formula (a-1) can also be used for the said aromatic hydrocarbon ring.

[chemical 9]

(wherein, X ¹ is >C=O, Y ¹ is >CH ₂ or >C=O)

The above-mentioned aromatic heterocyclic ring may include atoms other than carbon atoms among the atoms forming the ring structure, and may be a single ring or a condensed ring. For example, furan ring, benzofuran ring, dibenzofuran ring, dibenzofuran ring, Furan ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, Thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridyl ring, Catalyst ring, pyrimidine ring, three 𠯤 ring, quinoline ring, isoquinoline ring, phenoline, quinoline, phenanthridine ring, benzimidazole ring, phetidine ring, quinazoline ring, quinazolinone ring , Azulene ring, etc. The structure represented by the following general formula (a-2) can also be used for the said aromatic heterocycle.

[chemical 10]

(wherein, X ² is >NH, >O, >S, >S=O or >C=O, Y ² is >CH ₂ , >NH, >O, >S, >S=O or >C= O, except when X ² is >C=O and Y ² is >CH ₂ or >C=O)

Regarding the above-mentioned aromatic group, in the aromatic ring in the group, the hydrogen atom in the aromatic ring is replaced by an aliphatic hydrocarbon group with 1 to 35 carbon atoms or a non-aromatic group with 2 to 35 carbon atoms including a heterocyclic ring. sex base. The aliphatic hydrocarbon group having 1 to 35 carbon atoms may, for example, be the same as those exemplified below as the aliphatic hydrocarbon group having 1 to 35 carbon atoms used in R ^a1 or the like. As the non-aromatic group having 2 to 35 carbon atoms including a heterocyclic ring, one of the following groups exemplified as the heterocyclic ring-containing group having 2 to 35 carbon atoms used in R ^a1 etc., which does not have The base of the aromatic ring. The methylene in these groups can be substituted by -S-, -O-, carbon-carbon double bond, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH -CO-O-, -O-CO-NH-, >NR', >P=O, -SS-, -SO ₂ , or combinations thereof (hereinafter also referred to as "-S-, etc."). In the following, when the above-mentioned aliphatic hydrocarbon group or the above-mentioned non-aromatic group containing a heterocycle is bonded to the aromatic ring in the aromatic group Ar, the case where the methylene group is substituted with -S-, etc. may also be included. They are collectively referred to as "non-aromatic bonding groups". R' is a hydrogen atom or an alkyl group represented by 1 to 8 carbon atoms. As the alkyl group represented by R', those described below as the alkyl group used in formula (III) satisfying the specified number of carbon atoms can be used.

The above-mentioned aromatic ring or non-aromatic bonding group may have a substituent, and unless otherwise specified, it is an unsubstituted one having no substituent or a substituent having a substituent. As such a substituent substituting a hydrogen atom in an aromatic ring or a non-aromatic bonding group, a group other than a carboxyl group can be used, for example, a vinyl group such as a vinyl group, an allyl group, an acrylic group, a methacrylic group, etc. Sexually unsaturated groups; Halogen atoms such as fluorine, chlorine, bromine, iodine; Acetyl, 2-chloroacetyl, propionyl, octyl, acryl, methacryl, phenylcarbonyl (benzoyl base), phthaloyl, 4-trifluoromethylbenzoyl, pivalyl, o-hydroxybenzoyl, oxalyl, stearyl, methoxycarbonyl, ethoxycarbonyl , tertiary butoxycarbonyl, n-octadecyloxycarbonyl, aminoformyl and other acyl groups; acetyloxy, benzoyloxy and other acyloxy groups; amino, ethylamino, dimethylamino , diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamine, dodecylamino, anilino, chlorophenylamino, toluidine, methoxyanilino, N- Methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino , Formamide group, pivalylamine group, laurylamino group, aminoformylamine group, N,N-dimethylaminocarbonylamine group, N,N-diethylaminocarbonylamino group, 𠰌 Linylcarbonylamino, Methoxycarbonylamino, Ethoxycarbonylamino, Tertiary Butoxycarbonylamino, n-Octadecyloxycarbonylamine, N-Methyl-Methoxycarbonylamino , phenoxycarbonylamine, sulfamoylamine, N,N-dimethylaminosulfonamide, methylsulfonamide, acesulfonamide, benzenesulfonylamide and other substituted amines group; sulfonamide group, sulfonyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imino group, aminoformyl group, sulfonamide group, phosphonic acid group, phosphoric acid group or sulfo group, phosphonic acid base, salt of phosphate group.

In the present invention, regarding the number of carbon atoms specified in a specific group, when a hydrogen atom in a specific group is substituted with a substituent, the number of carbon atoms in the substituent is included. For example, as the number of carbon atoms of an alkyl group having a substituent, the number of carbon atoms of a vinylhexyl group is counted as 8.

When the number of ring structures included in Ar is 2 or more, the above-mentioned aromatic group Ar is not limited to those containing condensed rings formed by condensing aromatic rings, and may also include such as biphenyl skeleton, benzophenone, etc. The skeleton is a structure in which aromatic rings are bonded by divalent bonding groups. The above-mentioned aromatic group Ar may have, for example, a structure in which two or more aromatic rings are bonded by a bonding group such as a single bond, -CO-, -S-, or a nitrogen atom. Furthermore, in the biphenyl skeleton, the above-mentioned bonding group is a single bond, and in the benzophenone skeleton, the above-mentioned bonding group is a carbonyl group (—CO—). Also, when the aromatic group has a structure in which the aromatic ring is directly bonded to nitrogen, the nitrogen atom can function as a trivalent group.

As the number of ring structures in the above-mentioned aromatic group Ar, as long as it is 1 or more, and compound I-1 having the desired sensitivity can be obtained, it is preferably 1 to 20, especially preferably 1 to 10, especially Preferably, it is from 1 to 5, especially preferably from 1 to 3. It is because the sensitivity and heat resistance of the said compound I are excellent when the said total number is the said range. Also, the reason is that the above-mentioned compound I becomes an easy synthesizer. Furthermore, as an example in which the number of the above ring structures is two, the aromatic group Ar includes a naphthalene ring, a biphenyl skeleton, a benzophenone skeleton, a benzofuran skeleton, a benzophenone skeleton, etc. as the aromatic ring. situation. As an example where the number of the above-mentioned ring structures is three, a case where the aromatic group Ar includes a phenanthrene ring, an anthracene ring, and a carbazole ring as an aromatic ring may be mentioned. In addition, as an example in which the number of the above-mentioned ring structures is four, an example in which the aromatic group Ar includes a naphthacene ring or the like as an aromatic ring may be mentioned. The number of ring structures mentioned here does not include the number of non-aromatic rings such as aliphatic rings. Also, the number of ring structures refers to the total number of ring structures included in one aromatic group Ar, for example, when the aromatic group Ar has a plurality of aromatic condensed ring structures, it is the total number of ring structures in each condensed ring .

Among them, the above-mentioned aromatic group Ar ¹ is preferably one containing an aromatic hydrocarbon ring. The above-mentioned aromatic group Ar ¹ preferably includes a condensed ring when the number of ring structures is 2 or more. The reason is that the above compound I-1 is excellent in sensitivity and heat resistance. As the aromatic hydrocarbon ring used in the above-mentioned aromatic group ^Ar1 , more specifically, it is preferably a benzene ring, a naphthalene ring, a benzophenone skeleton, etc., and among them, a benzene ring and a naphthalene ring are preferred, especially benzene ring. The reason is that the above compound I-1 is excellent in sensitivity and heat resistance. When the aromatic group Ar ¹ is a benzene ring, L ¹ can be bonded to the carbonyl group at any position of ortho, meta, or para, preferably the meta or para position, and most preferably the para position. The reason is that it has an excellent balance of heat resistance, sensitivity, and ease of synthesis.

As the number of ring structures in the above-mentioned aromatic group ^Ar2 , as long as it is 1 or more, and the compound I-1 with the desired sensitivity can be obtained, it is preferably 2 or more and 20 or less, and preferably 2 or more and 10 or less, More preferably, it is from 2 to 5, especially preferably from 2 to 3. It is because the sensitivity and heat resistance of the said compound I are excellent when the said number is the said range. Also, the reason is that the above-mentioned compound I-1 is easy to synthesize. The above-mentioned aromatic group Ar ² preferably includes a condensed ring when the number of ring structures is 2 or more. The reason is that the above compound I-1 is excellent in sensitivity and heat resistance. Also, the above-mentioned aromatic group Ar ² preferably includes an aromatic heterocyclic ring. The reason is that the above compound I-1 is excellent in sensitivity and heat resistance. Examples of the condensed ring containing three ring structures used in ^the above-mentioned aromatic group Ar and being an aromatic heterocycle include an aromatic ring represented by the above-mentioned (a-2), a dibenzothiophene ring, Dibenzofuran ring, carbazole ring, oxene ring, etc. Among them, oxene ring and carbazole ring are preferred, and carbazole ring is particularly preferred. The reason is that the above-mentioned compound I-1 is excellent in sensitivity and heat resistance, and the reason is that in particular, it is excellent in sensitivity. As the condensed ring containing two ring structures used in the above-mentioned aromatic group Ar ² and is an aromatic heterocyclic ring, for example, a benzofuran ring, an indole ring, a benzothiophene ring, a quinoline ring, Naphthalene ring and the like, among which benzofuran ring is preferred. The reason is that the above compound I-1 is excellent in sensitivity and heat resistance.

The above-mentioned R ¹ is a group containing a COOH group. The number of COOH groups contained in R ¹ may be 1 or more, for example, 1 to 10. From the viewpoint of easy synthesis, the above-mentioned number is preferably from 1 to 5, especially preferably from 1 to 3, especially preferably 1. Furthermore, the COOH group may form a salt such as an alkali metal salt such as COO ^- Na ⁺ , an ammonium salt such as COO ^- NH4 ⁺ , or the like.

When the number of COOH groups contained ⁱⁿ R ¹ is 1, the above R 1 may be, for example, a group represented by -L ¹ -COOH. In addition, the above-mentioned L ¹ is a divalent bonding group.

Such a bonding group L ¹ may, for example, be a direct bond, an oxygen atom, a sulfur atom, >C=O, >NR ⁵³ , an aliphatic hydrocarbon group having 1 to 120 carbon atoms, or an aromatic-containing hydrocarbon group having 6 to 35 carbon atoms. Cyclohydrocarbon groups or heterocyclic groups with 2 to 35 carbon atoms, etc. However, one or more methylene groups among these aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups and heterocyclic groups may be substituted by - S-etc. Examples of R ⁵³ above include a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms.

As the aliphatic hydrocarbon group having 1 to 120 carbon atoms used in L ¹ , an alkylene group is preferably mentioned. The alkylene group may, for example, be a methylene group, an ethylidene group, a propylidene group, a butylene group or a butyldiyl group. Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms used in ^L1 include: arylylene groups such as phenylene, naphthylene, and methylphenylene; difunctional groups such as catechol and bisphenol; Phenol residues, etc. As the heterocyclic group having 2 to 35 carbon atoms used in ^L1 , in addition to pyridine ring, pyrimidine ring, piperidine ring, piperidine ring, trioxetin ring, furan ring, thiophene ring, indole In addition to the ring group, a group having a 2,4,8,10-tetraoxaspiro[5,5]undecane ring, etc. may, for example, be mentioned. The heterocyclic group with 2 to 35 carbon atoms used in ^L1 may be a group obtained by removing two hydrogen atoms from the heterocyclic ring, or one or more hydrogen atoms in the heterocyclic ring may be substituted It is a base formed of aliphatic hydrocarbon groups such as alkyl groups. In the latter case, the bonding bond may exist in any one of the aliphatic hydrocarbon group and the heterocyclic ring. The aliphatic hydrocarbon group having 1 to 35 carbon atoms used for R ⁵ may, for example, be the same as those exemplified for the aliphatic hydrocarbon group having 1 to 35 carbon atoms used in R ^a1 and the like below. As the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and the heterocyclic ring-containing group having 2 to 35 carbon atoms used in ^R53 , carbon atoms used in R ^a1 etc. are exemplified below, respectively. The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and the heterocyclic ring-containing group having 2 to 35 carbon atoms are the same group. The functional groups such as aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups, and heterocyclic ring-containing groups used in the above L ¹ and R ⁵³ sometimes have substituents, and unless otherwise specified, they are unsubstituted (that is, unsubstituted ) or those with substituents. As a substituent for hydrogen atoms of such substituted aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups, and heterocyclic ring-containing groups, hydrogen atoms in the aromatic ring or non-aromatic bonding group contained in the above-mentioned substituted aromatic group Ar may be used. The substituents are the same.

The aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, and methylene group in the heterocyclic group used in the above-mentioned ^L1 are sometimes substituted with -S-, -O-, carbon-carbon double bond, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O -CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -O-CO-NH-, >NR', >P=O, -SS-, -SO ₂ Or a combination of these (hereinafter, also described as "-S-etc."). R' is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The aromatic ring or heterocyclic ring in the aromatic ring-containing hydrocarbon group and heterocyclic ring-containing group used in the above-mentioned L ¹ and R ⁵³ may also be condensed with other rings.

As long as the above-mentioned ^L1 can obtain the compound I-1 having the desired sensitivity and heat resistance, it is preferable that the methylene group in the group is sometimes substituted with -S-, etc., having 1 to 120 carbon atoms. Aliphatic hydrocarbon group, the methylene group in the group is sometimes substituted by -S- and other carbon atoms containing 6 to 35 aromatic ring hydrocarbon groups or the methylene group in the group is sometimes substituted by carbon atoms such as -S- A heterocyclic group with a number of 2 to 35, preferably the methylene group in the group is sometimes substituted by an aliphatic hydrocarbon group with 1 to 120 carbon atoms such as -S-, especially the methylene group in the group An aliphatic hydrocarbon group with 1 to 10 carbon atoms, such as -S-, is sometimes substituted, especially preferably when the methylene group in the group is sometimes substituted with an aliphatic hydrocarbon group with 1 to 5 carbon atoms, such as -S-. Hydrocarbyl. The reason is that the above-mentioned compound I-1 is excellent in sensitivity and heat resistance by having the above-mentioned structure. The methylene in the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, and heterocyclic ring-containing group used in the above ^L1 is preferably substituted with -S-, -O-, or -CO-, which is preferably substituted for -S-. The reason is that the above-mentioned compound I-1 is excellent in sensitivity and heat resistance by having the above-mentioned structure. Also, the methylene group substituted by a divalent substituent such as -S-, -O-, or -CO- in the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group used in the above-mentioned ^L1 is preferably It is a methylene group including an end on the side of the aromatic group Ar, that is, a divalent substituent such as -S-, -O-, or -CO- is preferably directly bonded to the aromatic group Ar. The reason is that the above-mentioned compound I-1 is excellent in sensitivity and heat resistance by having the above-mentioned structure. Also, the reason is that the above compound I-1 is easy to synthesize. The methylene group at the end of the Ar side of the aliphatic hydrocarbon group, aromatic ring hydrocarbon group and heterocyclic group-containing aromatic group used as ^L1 is substituted with -S-, -O-, -CO-. Preferably they are represented by * ¹ -SR ⁵⁴ -* ² , * ¹ -OR ⁵⁴ -* ² or * ¹ -CO-R ⁵⁴ -* ² , more preferably they are represented by * ¹ -SR ⁵⁴ -* ² . * ¹ is a bond to an atom constituting the ring structure of the aromatic ring of the aromatic group Ar, and * ² is a bond to COOH. As R ⁵⁴ , there may be mentioned the same groups as the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, or heterocyclic ring-containing group exemplified as L ¹ , preferably an aliphatic hydrocarbon group having 1 to 119 carbon atoms, and an aliphatic hydrocarbon group having 6 to 10 carbon atoms. 34 aromatic ring-containing hydrocarbon groups or heterocyclic ring-containing groups with 2 to 34 carbon atoms, more preferably aliphatic hydrocarbon groups with 1 to 119 carbon atoms, more preferably aliphatic hydrocarbon groups with 1 to 20 carbon atoms, and even more It is preferably an aliphatic hydrocarbon group having 1 to 9 carbon atoms, most preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Specific examples of the substituted methylene group include a methylene group at the end of the aromatic group Ar side, compounds represented by the following formula (I-1-5) and the like.

In the present invention, when the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group-containing methylene group are substituted with -S-, etc., the number of carbon atoms is counted as the number of carbon atoms after substitution. For example, when the methylene group in the ethyl group is substituted with a methoxy group of -O-, the number of carbon atoms is 1. Also, in the present invention, two or more methylene groups in the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group or heterocyclic group are substituted with "-S-, -O-, carbon-carbon double bond, -CO -, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -O-CO-NH-, >NR', >P=O, -SS-, or - In the case of SO ₂ ", it is preferable that the substituted divalent groups are not adjacent to each other.

The above-mentioned n1 represents the number of R ¹ bonded to the aromatic group Ar, is an integer of 1 or more, and can be appropriately set according to the type of the aromatic group Ar, etc. For example, when the aromatic group Ar is a monocyclic ring including only one benzene ring, n1 may be an integer of 1-5. For example, when the aromatic group Ar contains only one naphthalene ring or only one dibenzofuran ring, n1 can be set as an integer of 1 to 7, and when only one carbazole ring is included, n1 An integer of 1 to 8 may be used, and n1 may be an integer of 1 to 9 when only one oxene ring is included. The aforementioned n1 is preferably an integer of 1 to 2, and is preferably 1 from the viewpoint of compatibility with resin components and the like. The number of COOH groups contained in the compound I-1 needs only to be 1 or more, and is preferably an integer of 1 to 4 from the viewpoint of heat resistance. The reason is to be an easy synthesizer. From the viewpoint of compatibility with resin components, etc., the number of COOH groups contained in the above compound I-1 is preferably an integer of 1 to 5, preferably an integer of 1 to 2, more preferably 1 .

More specifically, the above-mentioned compound I-1 is preferably a compound represented by the following general formula (II-1) ((hereinafter, sometimes referred to as "compound II-1") or represented by formula (III-1) (hereinafter sometimes referred to as "compound III-1"). In addition, the above-mentioned compound II-1 is preferably a compound represented by the following general formula (II-2) (hereinafter, may be referred to as "compound II-2"). Furthermore, the above-mentioned compound III-1 is preferably a compound represented by the following general formula (III-2) (hereinafter sometimes referred to as "compound III-2)") or a compound represented by formula (III-3) ( Hereinafter, it may be referred to as "compound III-3"). The reason is that the above-mentioned compound III-2 is excellent in the balance of sensitivity and heat resistance, and the above-mentioned compound III-3 is excellent in sensitivity. The reason is that the compound I-1 has the above-mentioned structure, and the compound I-1 is excellent in sensitivity and heat resistance.

[chemical 11]

(In the formula, X ^a is a divalent bonding group, which means > CR ¹⁴ R ¹⁵ , -O-, -S- or > NR ¹⁴ , R ¹⁴ and R ¹⁵ independently represent a hydrogen atom, a carbon atom number of 1 to 35 an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group with 6 to 35 carbon atoms, or a heterocyclic ring-containing group with 2 to 35 carbon atoms, L ^a is a divalent bonding group, representing a direct bond, -O-, -S-, >C=O, >NR ⁵³ , an aliphatic hydrocarbon group with 1 to 120 carbon atoms, an aromatic ring-containing hydrocarbon group with 6 to 35 carbon atoms, or a heterocyclic ring-containing group with 2 to 35 carbon atoms, however, the aliphatic hydrocarbon group , One or more methylene groups in the aromatic ring-containing hydrocarbon group and the heterocyclic ring-containing group may be substituted with -S-, -O-, carbon-carbon double bond, -CO-, -O-CO-, - CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, - CO-NH-, -NH-CO-, -NH-CO-O-, -O-CO-NH-, >NR', >P=O, -SS-, -SO ₂ or a combination thereof, R ⁵³ represents a hydrogen atom, an aliphatic hydrocarbon group with 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group with 6 to 35 carbon atoms, or a heterocyclic group with 2 to 35 carbon atoms, R' is a hydrogen atom or a carbon atom with 1 An alkyl group of ∼8, R ^a1 and R ^a2 each independently represent an aliphatic hydrocarbon group with 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group with 6 to 35 carbon atoms, or a heterocyclic group with 2 to 35 carbon atoms, a1 and a2 are independently integers from 0 to 4)

[chemical 12]

(The symbols in the formula are the same as the above general formula (II-1))

[chemical 13]

(In the formula, X ^b is a divalent bonding group, each independently representing >CR ¹⁴ R ¹⁵ , -O-, -S- or >NR ¹⁴ , R ¹⁴ and R ¹⁵ independently representing a hydrogen atom, the number of carbon atoms An aliphatic hydrocarbon group with 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group with 6 to 35 carbon atoms, or a heterocyclic ring group with 2 to 35 carbon atoms, L ^b is a divalent bonding group, which means a direct bond, -O-, - S-, >C=O, >NR ⁵³ , an aliphatic hydrocarbon group with 1 to 120 carbon atoms, an aromatic ring-containing hydrocarbon group with 6 to 35 carbon atoms, or a heterocyclic group with 2 to 35 carbon atoms, however, the One or more methylene groups in the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group, and the heterocyclic ring-containing group may be substituted with -S-, -O-, carbon-carbon double bond, -CO-, -O-CO -, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S -, -CO-NH-, -NH-CO-, -NH-CO-O-, -O-CO-NH-, >NR', >P=O, -SS-, -SO ₂ or the like combination, R ⁵³ represents a hydrogen atom, an aliphatic hydrocarbon group with 1 to 35 carbon atoms, an aromatic ring hydrocarbon group with 6 to 35 carbon atoms, or a heterocyclic group with 2 to 35 carbon atoms, R' is a hydrogen atom or an alkane R ^b1 and R ^b2 independently represent an aliphatic hydrocarbon group with 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group with 6 to 35 carbon atoms, or a heterocyclic group with 2 to 35 carbon atoms, b1 and b2 respectively Independently an integer from 0 to 4)

[chemical 14]

(In the formula, X ^b2 is a divalent bonding group, which means >CR ¹⁴ R ¹⁵ , -O-, -S- or >NR ¹⁴ , R ¹⁴ , R ¹⁵ , L ^b , R ⁵³ , R ^b1 , R ^b2 , b1 and b2 are the same as the above general formula (III-1))

[chemical 15]

(In the formula, X ^b3 is a divalent bonding group, which means >CR ¹⁴ R ¹⁵ , -O-, -S- or >NR ^{14 , R 14 ,} R ¹⁵ , L ^b , R ⁵³ , R ^b1 , R ^b2 , b1 and b2 are the same as the above general formula (III-1))

Examples of the aliphatic hydrocarbon group having 1 to 35 carbon atoms used for R ^a1 , R ^a2 , R ^b1 , R ^b2 , R ¹⁴ , R ¹⁵ , and R ⁵³ include methyl, ethyl, and propyl. Base, isopropyl, cyclopropyl, butyl, second butyl, third butyl, isobutyl, pentyl, isopentyl, third pentyl, cyclopentyl, hexyl, 2-hexyl, 3 -hexyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, third heptyl, n-octyl, isooctyl, third octyl Alkyl, 2-ethylhexyl, nonyl, isononyl, decyl and other alkyl groups; methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, second butyl yloxy, tertiary butyloxy, isobutyloxy, pentyloxy, isopentyloxy, tertiary pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, iso Heptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy and other alkanes Oxygen; methylthio, ethylthio, propylthio, isopropylthio, butylthio, second butylthio, third butylthio, isobutylthio, pentylthio, isopentylthio, The third pentylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, the third heptylthio, n-octylthio, isooctylthio, the third octylthio, 2-ethyl Alkylthio such as hexylthio; vinyl, 1-methylvinyl, 2-methylvinyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl -3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl , Eicosenyl, Tritricenyl and other alkenyl groups. Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms used for R ^a1 , R ^a2 , R ^b1 , R ^b2 , R ¹⁴ , R ¹⁵ , and R ⁵³ include benzyl, phenethyl, Aralkyl groups such as diphenylmethyl, triphenylmethyl, styryl, and phenylallyl; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthyloxy; phenylthio, Arylthio groups such as naphthylthio, etc. Examples of the heterocyclic group having 2 to 35 carbon atoms used for R ^a1 , R ^a2 , R ^b1 , R ^b2 , R ¹⁴ , R ¹⁵ , and R ⁵³ above include pyridyl, pyrimidyl, Pyridine, piperidinyl, pyranyl, pyrazolyl, triazinyl, pyrrolyl, quinolinyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl (furyl), furan Furanyl, benzofuryl, thienyl, thiophenyl, benzothienyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzozizolyl, Isothiazolyl, isozazolyl, indolyl, 2-pyrrolidinone-1-yl, 2-piperidinon-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4 -Dioxyzoxazolidine-3-yl, benzotriazolyl, etc., or a group in which these are bonded to an aliphatic hydrocarbon group, etc. Each functional group such as the above-mentioned aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, and heterocyclic ring-containing group may have a substituent, and unless otherwise specified, it is unsubstituted or has a substituent without a substituent. As a substituent for hydrogen atoms of such substituted aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups, and heterocyclic ring-containing groups, hydrogen atoms in the aromatic ring or non-aromatic bonding group contained in the above-mentioned substituted aromatic group Ar may be used. The substituents are the same. The aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, and methylene group in the heterocyclic ring-containing group used in the above-mentioned R ^a1 , R ^a2 , R ^b1 , R ^b2 , R ¹⁴ , R ¹⁵ , and R ⁵³ are sometimes substituted by - S-, -O-, carbon-carbon double bond, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO- , -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -NH-CO-O- , -O-CO-NH-, >NR', >P=O, -SS-, -SO ₂ -, nitrogen atom or a combination thereof. R' is a hydrogen atom or an alkyl group represented by 1 to 8 carbon atoms. The aromatic ring or heterocyclic ring in the aromatic ring-containing hydrocarbon group and heterocyclic ring-containing group used for R ^a1 , R ^a2 , R ^b1 , R ^b2 , R ¹⁴ , R ¹⁵ and R ⁵³ may be condensed with other rings.

The above-mentioned X ^a represents >CR ¹⁴ R ¹⁵ , -O-, -S- or >NR ¹⁴ , preferably >CR ¹⁴ R ¹⁵ , >NR ¹⁴ , especially >NR ¹⁴ . The reason is that by having the above-mentioned structure, the above-mentioned compound I-1 is excellent in sensitivity and heat resistance, and the reason is that in particular, it is excellent in sensitivity.

The aforementioned X ^b , X ^b2 and X ^b3 represent >CR ¹⁴ R ¹⁵ , -O-, -S- or >NR ¹⁴ , preferably -O-. The reason is that the above-mentioned compound I-1 is excellent in the balance of sensitivity and heat resistance by having the above-mentioned structure. In addition, the aforementioned X ^b3 is preferably >NR ¹⁴ from the viewpoint of being excellent in sensitivity and heat resistance and being easy to synthesize. In this case, R ¹⁴ is preferably an aliphatic hydrocarbon group having 1 to 35 carbon atoms because it has excellent solubility in a solvent. R ¹⁴ is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms because of its excellent sensitivity, and is particularly preferably an alkyl group having 1 to 10 carbon atoms. The above-mentioned L ^a and L ^b may have the same content as the above-mentioned ^L1 , so the description here is omitted. All of the above-mentioned preferable configurations described with respect to the above-mentioned L ¹ correspond to L ^a and L ^b .

The above-mentioned R ¹⁴ is preferably an aliphatic hydrocarbon group having 1 to 35 carbon atoms, especially preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, particularly preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms. The reason is that the above-mentioned compound I-1 is excellent in sensitivity and heat resistance by having the above-mentioned structure. Among them, R ¹⁴ above is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms. The reason is that the above-mentioned compound I-1 becomes an easy synthesizer. In terms of sensitivity and heat resistance, R ¹⁴ is preferably an alkyl group. R ^a2 is preferably an aliphatic hydrocarbon group having 1 to 35 carbon atoms, especially preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, particularly preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms. The reason is that the above-mentioned compound I-1 is excellent in sensitivity and heat resistance by having the above-mentioned structure. In terms of sensitivity and heat resistance, R ^a2 is preferably an alkyl group. The above-mentioned R ¹⁵ , R ⁵³ , R ^a1 , R ^b1 , and R ^b2 are preferably each independently an aliphatic hydrocarbon group having 1 to 35 carbon atoms, among which an aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferred, especially Preferably, it is an aliphatic hydrocarbon group having 1 to 5 carbon atoms. The reason is that the above-mentioned compound I-1 is excellent in sensitivity and heat resistance by having the above-mentioned structure.

The above-mentioned a1 is an integer of 0-4, and is preferably an integer of 0-2 from the viewpoint of easy synthesis of the compound, and among them, is preferably an integer of 0-1, particularly preferably 0. The reason is that the above compound I-1 is excellent in sensitivity and heat resistance. The above-mentioned a2 is an integer of 0-4, and is preferably an integer of 0-2 from the viewpoint of easy synthesis of the compound, among which, an integer of 0-1 is preferable, and 1 is especially preferable. The reason is that the above compound I-1 is excellent in sensitivity and heat resistance. Said b1 is an integer of 0-4, and is preferably an integer of 0-2 from the viewpoint of easy synthesis of the compound, among them, an integer of 0-1 is preferable, and 0 is especially preferable. The reason is that the above compound I-1 is excellent in sensitivity and heat resistance. The above-mentioned b2 is an integer of 0-4, and is preferably an integer of 0-2 from the viewpoint of easy synthesis of the compound, and among them, is preferably an integer of 0-1, especially preferably 0. The reason is that the above compound I-1 is excellent in sensitivity and heat resistance.

As said compound I-1, specifically, the compound shown below is mentioned.

[chemical 16]

[chemical 17]

The molecular weight of the above compound I-1 can be set in accordance with the use of the compound I-1 and the like. The above-mentioned molecular weight may be, for example, 250 to 5,000, 300 to 2,500, or 350 to 1,500. The reason is that the above compound I is excellent in sensitivity and heat resistance. Also, the reason is that the above-mentioned compound I becomes easy to synthesize.

As the 10% weight reduction temperature of the above-mentioned compound I-1, as long as it can form a hardened product with little outgassing, for example, it can be set to 200°C or higher, preferably 250°C or higher, especially preferably 300°C or higher . The reason is that the above compound I-1 is excellent in heat resistance. Furthermore, as for the weight loss temperature, a differential thermal-thermogravimetric simultaneous measurement device (manufactured by Seiko Instruments Nanotechnology Co., Ltd., model: EXSTAR TG/DTA6200") can be used. For a sample of about 5 mg, nitrogen gas 200 mL/min , When the heating start temperature is 30°C, the heating end temperature is 500°C, and the sample is heated at a heating rate of 10°C/min, the thermal loss is measured. % weight reduction temperature.

The production method of the above compound I-1 is not particularly limited as long as the desired structure can be obtained, for example, it can be produced by the method of the following formula. For example, Compound I can be obtained by sequentially reacting an aromatic compound (Ar ² -H) with a carboxylic acid halide, a compound having a carboxyl group and a thiol group. The following example is an example, but by changing the types of aromatic compounds, carboxylic acid halides, and compounds having carboxyl groups and thiol groups, other compounds can be similarly produced.

. [chemical 18]

.

2. Second Embodiment The second embodiment of the compound I of the sample invention is that the above-mentioned compound I is represented by the above-mentioned general formula (I-2). Regarding the aromatic groups Ar ¹ , Ar ² , R ¹ and n1 contained in the above general formula (I-2) (hereinafter, sometimes referred to as compound I-2), except that R ¹ is included in Ar ¹ and Ar ² Except for the two aromatic groups, it can be the same as the above-mentioned compound I-1.

As said compound I-2, the compound shown below is mentioned specifically,.

[chemical 19]

The molecular weight, 10% weight reduction temperature, production method, and other matters of the above-mentioned compound I-2 are also the same as the above-mentioned compound I-1.

3. Other As the use of the above-mentioned compound I, for example, it can be used as a photopolymerization initiator component that generates radicals by light irradiation, and further can be used as a photopolymerization initiator component in a photocurable composition. As the application of the above-mentioned photocurable composition, for example, it can be used in the following various applications: photocurable paint or varnish, photocurable adhesive, printed circuit board, or color TV, PC (personal computer, personal computer) monitor, portable Color filters in liquid crystal display elements for color display in information terminals, digital cameras, etc., alignment films for aligning liquid crystal compositions, electrode materials for plasma display panels, powder coatings, printing inks, printing plates, adhesives , dental compositions, gel coats, photoresists for electronic engineering, plating resists, etch resists, both liquid and dry films, solder resists, color filters for various display applications Optical sheets or resists used to form structures in the manufacturing steps of plasma display panels, electroluminescence display devices, and LCD (liquid crystal display, liquid crystal display devices), compositions for encapsulating electrical and electronic components, magnetic Recording materials, micromechanical parts, waveguides, optical switches, masks for plating, masks for etching, color test systems, coatings for glass fiber cables, stencils for screen printing, materials for the manufacture of three-dimensional objects using stereolithography, Holographic recording materials, image recording materials, fine electronic circuits, decolorizing materials, decolorizing materials for image recording materials, decolorizing materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, Photoresist materials for UV (ultraviolet, ultraviolet) and visible light laser direct imaging systems, photoresist materials or protective films for the formation of dielectric layers in sequential build-up of printed circuit boards, etc., the combination of the above photocurable There is no particular limitation on the use of the object. In addition, the above-mentioned compound I can be used in a state where it is bonded to another compound via a carboxyl group. For example, the above-mentioned compound I can be used in a photocurable composition or the like as a photopolymerization initiator component or the like in a state of being bonded to other compounds such as a resin component, and can also be used in the above-mentioned uses and the like.

When the above-mentioned compound I is used as a photopolymerization initiator, the content of the above-mentioned compound I contained in the photopolymerization initiator may be any one that can impart desired photopolymerization curability to the composition, It can be set suitably according to the use etc. of a composition. As said content, it can be set as 100 mass parts in 100 mass parts of photoinitiators, ie, the said photoinitiator is the said compound I. Also, the above-mentioned content may be less than 100 parts by mass in 100 parts by mass of the photopolymerization initiator, that is, the photopolymerization initiator is a composition comprising the above-mentioned compound I and other components, for example, it can be set to more than 10 parts by mass And it is 99 mass parts or less, Preferably it is 50 mass parts or more and 95 mass parts or less. In addition, in this description, unless otherwise stated, content is a mass basis.

The type of the said compound I contained in the said photoinitiator may be only 1 type, and may be 2 or more types. The above-mentioned types may be, for example, two or more and five or less. In addition, as an example in which the above-mentioned photopolymerization initiator contains two or more kinds of the above-mentioned compound I, for example, one containing two or more kinds of compound I-1 as the above-mentioned compound I, one containing two or more kinds of compound I-2 One, one including both compound I-1 and compound I-2, etc.

As said other component, the polymeric compound described in following "B. Composition", the polymer which does not have a polymeric group, a solvent, other components etc. are mentioned, for example. Among them, it is preferable to contain a polymer that does not have the above-mentioned polymerizable group as the above-mentioned other components. In addition, the above-mentioned compound I may be in a bonded state with the above-mentioned other components.

The shape of the above-mentioned photopolymerization initiator may be powder or granular. In the case of pellets, as a method for producing the above-mentioned photopolymerization initiator, for example, a method of mixing the above-mentioned compound I and the polymer component using an extruder or the like, and then molding it into pellets can be used.

B. Composition Next, the composition of the present invention will be described. The composition of the present invention is characterized by comprising the above-mentioned compound I.

According to the present invention, the above-mentioned composition exhibits excellent sensitivity and becomes less outgassed by including the above-mentioned compound I.

The composition of the present invention comprises the above compound I. Hereinafter, each component contained in the composition of this invention is demonstrated in detail.

1. Compound I The content of the compound I is not particularly limited as long as it can impart desired curability and the like to the composition. As said content, for example, it can be 0.05-10 mass parts with respect to 100 mass parts of solid content of a composition, Preferably it is 0.1-5 mass parts. In addition, the solid content is what includes all components except a solvent.

The type of the above-mentioned compound I contained in the above-mentioned composition may be only one type, or may be two or more types. The above-mentioned types may be, for example, two or more and five or less.

In addition, since the above-mentioned compound I is the same as that described in the section of "A. Compound", the description here is omitted.

2. Resin composition The above-mentioned composition contains the above-mentioned compound I, but may contain a resin component. As the above-mentioned resin component, the above-mentioned compound I may be retained, and it is appropriately set according to the use of the composition, for example, a polymerizable compound, a polymer having no polymerizable group, and the like. By containing a polymerizable compound as the said resin component, the said composition can be used as a photocurable composition etc., for example.

(1) Polymeric compound By containing the said polymeric compound, the said composition can be used easily as a photocurable composition. As the above-mentioned polymerizable compound, as long as it can form a polymer, for example, a radical polymerizable compound having a radical polymerizable group can be used. As said radically polymerizable group, ethylenically unsaturated double bonds, such as a (meth)acryl group and a vinyl group, etc. are mentioned, for example. In addition, (meth)acrylic acid is used in the meaning including acrylic acid and methacrylic acid. In addition, (meth)acrylate is used in the meaning including acrylate and methacrylate.

The above-mentioned radically polymerizable compound may be a compound having an acid value, or may be a compound not having an acid value. As a radically polymerizable compound which has an acid value, the compound etc. which have a carboxyl group are mentioned, for example. The above-mentioned composition reduces the solubility of the light-irradiated part in an alkaline developing solution by including a compound having an acid value as a radically polymerizable compound. Therefore, the said composition can be used as the photosensitive composition whose solubility to solvents, such as an alkaline developing solution, changes before and after light irradiation, for example. More specifically, the above composition can be used as a negative tone composition by including a compound having an acid value. As an alkaline developing solution, what is generally used as an alkaline developing solution, such as a tetramethylammonium hydroxide (TMAH) aqueous solution and an aqueous potassium hydroxide solution, can be used.

Regarding the above-mentioned radically polymerizable compound, for example, a compound having an ethylenically unsaturated double bond group and having an acid value includes (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, and maleic acid. , methylmaleic acid, fumaric acid, bicycloheptenedicarboxylic acid, crotonic acid, methacrylic acid, vinyl acetate, allyl acetate, cinnamic acid, hexadienoic acid, methylfumaric acid, Mono[2-(meth)acryloxyethyl]succinate, mono[2-(meth)acryloxyethyl]phthalate, ω-carboxypolycaprolactone mono(form Mono(meth)acrylate, hydroxyethyl(meth)acrylate/maleate, hydroxypropyl(meth)acrylate/cis Butenoate, dicyclopentadiene/maleate or polyfunctional (meth)acrylate with one carboxyl group and two or more (meth)acryl groups; phenol and/or Cresol novolac epoxy resin, novolak epoxy resin having biphenyl skeleton or naphthalene skeleton, bisphenol A novolac epoxy compound, dicyclopentadiene novolac epoxy compound, etc. , polyphenylmethane type epoxy resin with multifunctional epoxy groups, and the epoxy groups of epoxy resins such as epoxy compounds represented by the following general formula (III) act on unsaturated monobasic acids, and then act on polybasic acid anhydrides to obtain Resins, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and other hydroxyl-containing polyfunctional acrylates and succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, etc. Multifunctional acrylates, etc.

As the above-mentioned unsaturated monobasic acid, a compound having one ethylenically unsaturated double bond group and one carboxyl group can be used, for example: acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, hexadienoic acid, methacrylic acid hydroxyl group Ethyl/Maleate, Hydroxyethyl Acrylate/Maleate, Hydroxypropyl Methacrylate/Maleate, Hydroxypropyl Acrylate/Maleate, Bicyclic Pentadiene/maleate, etc.

As the polybasic acid anhydride, carboxylic anhydride can be used, for example, biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphenyltetracarboxylic dianhydride, maleic anhydride, trimellitic anhydride Acid anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol dianhydrotrimellitate, glycerol trianhydrotrimellitate, hexahydrophthalic acid Diformic anhydride, Methyl tetrahydrophthalic anhydride, Resilicate anhydride, Methyl tetrahydrophthalic anhydride, Trialkyltetrahydrophthalic anhydride, Hexahydrophthalic anhydride, 5-(2,5- Dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl Succinic anhydride, methyl bicycloheptenedicarboxylic anhydride, etc.

[chemical 20]

(wherein, X ⁴¹ represents a direct bond, an alkylene group with 1 to 4 carbon atoms, an alicyclic hydrocarbon group with 3 to 20 carbon atoms, -O-, -S-, -SO ₂ -, -SS-, -SO-, -CO-, -OCO- or a substituent represented by any one of the following (1-1) to (1-3), R ⁴¹ , R ⁴² , R ⁴⁴ and R ⁴⁴ each independently represent hydrogen atom, alkyl group with 1 to 5 carbon atoms, alkoxy group with 1 to 8 carbon atoms, alkenyl group with 2 to 5 carbon atoms or halogen atom, d is an integer of 0 to 10)

[chem 21]

(In the above formula, ^R59 represents a hydrogen atom, a phenyl group sometimes having a substituent, or a cycloalkyl group with 3 to 10 carbon atoms, ^R60 represents an alkyl group with 1 to 10 carbon atoms, and an alkyl group with 1 to 10 carbon atoms. An alkoxy group with ~10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, or a halogen atom, c1 is an integer of 0 to 5, * means that the * part is bonded to the adjacent group)

[chem 22]

(* means bonding with the adjacent group at the * part)

[chem 23]

(In the above formula, R ⁶¹ and R ⁶² independently represent an alkyl group with 1 to 10 carbon atoms, an aryl group with 6 to 20 carbon atoms, an aryloxy group with 6 to 20 carbon atoms, an aryloxy group with 6 to 20 carbon atoms, and an alkyl group with 6 to 20 carbon atoms. Arylthio group with 20 carbon atoms, aralkenyl group with 6 to 20 carbon atoms, aralkyl group with 7 to 20 carbon atoms, heterocyclic group with 2 to 20 carbon atoms or halogen atom, the alkyl group and aralkyl group The methylene group in is sometimes substituted with an unsaturated bond, -O- or -S-, R ⁶¹ sometimes forms a ring with adjacent R ⁶¹ , c2 represents the number from 0 to 4, and c3 represents 0 The number of ~ 8, c4 represents the number of 0 ~ 4, c5 represents the number of 0 ~ 4, the total number of c4 and c5 is 2 ~ 4, * means that the * part is bonded to the adjacent group)

Examples of the alkylene group used in the general formula (III) include methylene, ethylene, propylene, butylene and the like. Examples of the alicyclic hydrocarbon group used in the general formula (III) include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and the like. As the alkyl group used in the above general formula (III), (1-1), (1-3), methyl, ethyl, propyl, isopropyl, butyl, second butyl, tertiary butyl, isobutyl, pentyl, isopentyl, tertiary pentyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2- Heptyl, 3-heptyl, isoheptyl, tertiary heptyl, 1-octyl, isooctyl, tertiary octyl, adamantyl, and the like can be used with specific numbers of carbon atoms among them. Examples of the halogen atom used in the above general formulas (III), (1-1), (1-3) and the like include fluorine, chlorine, bromine, iodine and the like. Examples of the alkoxy group used in the above general formulas (III) and (1-1) include: methyloxy, ethyloxy, isopropyloxy, butyloxy, second butyl Oxygen, tertiary butyloxy, isobutyloxy, pentyloxy, isopentyloxy, tertiary pentyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, Cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, isoheptyloxy, third heptyloxy, 1-octyl Oxygen, isooctyloxy, tertiary octyloxy, etc. Examples of the alkenyl group used in the above general formulas (III) and (1-1) include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3- Butadienyl, 2-pentenyl, 2-octenyl, etc.

As the cycloalkyl group used in the group represented by the above general formula (1-1), for example: cyclopropyl group, cyclobutyl group, cyclopentyl group, cycloheptyl group, cyclooctyl group, etc. A group substituted with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

、噻吩、硫呋喃等基及該等基經鹵素原子取代之基等。 作為上述R ⁶¹可藉由相鄰之R ⁶¹彼此而形成之環，例如可例舉：環戊烷環、環己烷環、環戊烯環、苯環、哌啶環、𠰌啉環、內酯環、內醯胺環等5～7員環。 Examples of the aryl group used in the general formula (1-3) include phenyl, naphthyl, anthracenyl and the like. Examples of the aralkyl group used in the general formula (1-3) include benzyl, fenyl, indenyl, 9-fenylmethyl and the like. Examples of the aryloxy group having 6 to 20 carbon atoms used in the group represented by the above general formula (1-3) include phenoxy, naphthyloxy, 2-methylphenoxy, 3- Methylphenoxy, 4-methylphenoxy, 4-vinylphenyldioxy, 3-isopropylphenoxy, 4-isopropylphenoxy, 4-butylphenoxy, 4-tert-butylphenoxy, 4-hexylphenoxy, 4-cyclohexylphenoxy, 4-octylphenoxy, 4-(2-ethylhexyl)phenoxy, 2,3- Dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2.6-dimethylphenoxy, 3.4-dimethylphenoxy, 3.5-di Methylphenoxy, 2,4-di-tert-butylphenoxy, 2,5-di-tert-butylphenoxy, 2,6-di-tert-butylphenoxy, 2.4- Di-tertiary pentylphenoxy, 2,5-tertiary pentylphenoxy, 4-cyclohexylphenoxy, 2,4,5-trimethylphenoxy, ferrocenyloxy, etc. groups and those groups substituted by halogen atoms. The arylthio group having 6 to 20 carbon atoms may, for example, be a group in which the oxygen atom of the aryloxy group having 6 to 20 carbon atoms substituted by the aforementioned halogen atom is sometimes substituted with a sulfur atom. Examples of the aralkenyl group having 8 to 20 carbon atoms include vinyl, allyl, and 1-propene in which the oxygen atom of an aryloxy group having 6 to 20 carbon atoms may also be substituted with the above-mentioned halogen atom. A group derived from alkenyl groups such as isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, and 2-octenyl. The heterocyclic group having 2 to 20 carbon atoms includes, for example, pyridine, pyridine, piperidine, piperidine, pyrimidine, pyridoxine, trisulfone, hexahydrotricarboxylate, furan, tetrahydrofuran, and chromane. Nom, 𠮿

, thiophene, thiofuran and other groups, and groups in which these groups are substituted with halogen atoms, etc. The above-mentioned R ⁶¹ may be a ring formed by adjacent R ⁶¹ , for example, a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a thioline ring, an internal Ester ring, lactamide ring and other 5-7 membered rings.

Furthermore, the alkyl group, aryl group, aralkyl group, alkoxy group, alkylene group, alicyclic hydrocarbon group, alkenyl group used in the above general formula (IV), (1-1), (1-3) , cycloalkyl, aryloxy, arylthio, arylalkenyl, and various functional groups containing heterocyclic groups may sometimes have substituents. Unless otherwise specified, they are unsubstituted without substituents or have substituents. As a substituent which substitutes the hydrogen atom of each substituent, the same content as the substituent which substitutes the hydrogen atom used for the aromatic group Ar etc. can be set.

It does not specifically limit as a radically polymerizable compound which has the said acid value, For example, the resin etc. which were described in Unexamined-Japanese-Patent No. 2004-264414 are mentioned.

Also, as the above-mentioned radically polymerizable compound having an acid value, a copolymer of acrylate, or a phenol and/or cresol novolak epoxy resin, a polyphenylmethane type epoxy resin having a multifunctional epoxy group, Resin obtained by reacting unsaturated monobasic acid to the epoxy group of epoxy compound such as epoxy acrylate resin, and then reacting with polybasic acid anhydride. The epoxy acrylate resin mentioned here is made by reacting (meth)acrylic acid to the above-mentioned epoxy compound. As an example, it can be exemplified: Ripoxy SPC-2000, Dicklight UE-777 manufactured by DIC Corporation, Japan U- U-Pica 4015 manufactured by Pica Corporation and the like. Moreover, it is preferable that the compound which has alkali developability which may have the said ethylenically unsaturated bond contains the unsaturated group of 0.2-1.0 equivalent. Among these, epoxy acrylate resins and polymers having carboxyl groups are preferred.

The above-mentioned polymer having a carboxyl group is not particularly limited as long as it has a structural unit having a carboxyl group (hereinafter referred to as "structural unit (U1)"). , epoxy group, vinyl group, vinyl ether group, mercapto group, and isocyanate group, etc. is "Structural Unit (U3)"). The above-mentioned polymer having a carboxyl group may have structural units other than the above-mentioned structural units (U1) to (U3) (hereinafter referred to as "structural unit (U4)").

The structural unit (U1) is preferably a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter referred to as "compound (u1)"). As said compound (u1), monocarboxylic acid, dicarboxylic acid, the anhydride of dicarboxylic acid, etc. are mentioned, for example. Examples of the monocarboxylic acid include: acrylic acid, methacrylic acid, crotonic acid, 2-acryloxyethylsuccinic acid, 2-methacryloxyethylsuccinic acid, 2-acryloxyethylsuccinic acid, Ethylhexahydrophthalic acid, 2-methacryloxyethylhexahydrophthalic acid, etc. As said dicarboxylic acid, maleic acid, fumaric acid, methylmaleic acid, etc. are mentioned, for example. As an anhydride of the said dicarboxylic acid, the anhydride of the said dicarboxylic acid etc. are mentioned.

Among these, acrylic acid, methacrylic acid, 2-acryloxyethylsuccinic acid, 2-methacrylic acid, and Acryloyloxyethylsuccinic acid or maleic anhydride. Furthermore, compound (u1) can be used individually or in mixture of 2 or more types.

As said structural unit (U2), the structural unit derived from the polymerizable unsaturated compound (henceforth "compound (u2)") which has an epoxy group or an oxetanyl group is preferable. The compound (u2) is preferably at least one selected from the group consisting of a polymerizable unsaturated compound having an epoxy group and a polymerizable unsaturated compound having an oxetanyl group.

Examples of the polymerizable unsaturated compound having an epoxy group include, for example, oxiranyl (cyclo)alkyl (meth)acrylate, α-alkylacrylate oxiranyl (cyclo)alkyl Glycidyl ether compound etc. which have an ester and a polymerizable unsaturated bond; As a polymerizable unsaturated compound which has an oxetanyl group, the (meth)acrylate which has an oxetanyl group etc. are mentioned, respectively, for example.

Regarding the above-mentioned compound (u2), as specific examples thereof, as the oxiranyl (cyclo)alkyl (meth)acrylate, for example, glycidyl (meth)acrylate, (meth)acrylate ) 2-methyl glycidyl acrylate, 4-hydroxybutyl glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate Ester, 6,7-epoxycyclohexyl (meth)acrylate, 6,7-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ] decyl ester etc.; As α-alkyl acrylate oxiranyl (cyclo) alkyl ester, for example can respectively exemplify: α-glycidyl ethacrylate, α-n-propyl glycidyl acrylate, α - Glycidyl n-butyl acrylate, 6,7-epoxyheptyl α-ethacrylate, 3,4-epoxycyclohexyl α-ethacrylate, etc.; as glycidyl ethers with polymerizable unsaturated bonds Compounds, for example, can be exemplified respectively: o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc.; , such as: 3-((meth)acryloxymethyl)oxetane, 3-((meth)acryloxymethyl)-3-ethyloxetane Alkane, 3-((meth)acryloxymethyl)-2-methyloxetane, 3-((meth)acryloxyethyl)-3-ethyloxetane alkane, 2-ethyl-3-((meth)acryloxyethyl)oxetane, 3-methyl-3-(meth)acryloxymethyloxetane, 3-Ethyl-3-(meth)acryloyloxymethyloxetane and the like.

Among these specific examples, in terms of polymerizability, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, methyl 3,4 ^- epoxycyclohexylmethyl acrylate, 3,4-epoxytricyclo[5.2.1.02.6]decyl methacrylate, 3,4-epoxytricyclo[ ^5.2.1.02.6 ]decyl acrylate , 3-methacryloxymethyl-3-ethyloxetane, 3-methyl-3-methacryloxymethyloxetane or 3-ethyl-3- Methacryloxymethyloxetane.

The above compound (u2) can be used individually or in mixture of 2 or more types.

As a structural unit which has a methacryl group or an acryl group as a crosslinkable group in the said structural unit (U2), the structural unit which has a (meth)acryloxy group can be used preferably. The above-mentioned structural unit having a (meth)acryloyloxy group can be obtained by reacting a carboxyl group in a polymer with a (meth)acrylate having an epoxy group. The reacted structural unit having a (meth)acryloyloxy group is preferably a structural unit represented by the following formula (U).

(式中，R ¹⁰⁰⁰及R ¹⁰⁰¹分別獨立為氫原子或甲基。u為1～6之整數。R ¹⁰⁰²為下述式(Uα)或下述式(Uβ)所表示之二價基，*表示鍵結鍵) [chem 24]

(In the formula, R ¹⁰⁰⁰ and R ¹⁰⁰¹ are independently a hydrogen atom or a methyl group. u is an integer from 1 to 6. ^{R 1002} is a divalent group represented by the following formula (Uα) or the following formula (Uβ),* means bond key)

(式(Uα)中，R ¹⁰⁰³為氫原子或甲基。上述式(Uα)及上述式(Uβ)中，*表示鍵結鍵) [chem 25]

(In the formula (Uα), R ¹⁰⁰³ is a hydrogen atom or a methyl group. In the above formula (Uα) and the above formula (Uβ), * represents a bond)

Regarding the structural unit represented by the above formula (U), for example, when reacting a copolymer having a carboxyl group with glycidyl methacrylate, 2-methyl glycidyl methacrylate and other compounds, the formula (U ) in R ¹⁰⁰² becomes formula (Uα). On the other hand, when reacting a copolymer having a carboxyl group with a compound such as 3,4-epoxycyclohexylmethyl methacrylate, R ¹⁰⁰² in formula (U) becomes formula (Uβ).

In the reaction of the carboxyl group in the above-mentioned polymer with an unsaturated compound such as (meth)acrylate having an epoxy group, in the presence of an appropriate catalyst if necessary, preferably in a polymer containing a polymerization inhibitor Add an unsaturated compound with an epoxy group into the solution, and stir for a specified time under heating. As said catalyst, tetrabutylammonium bromide etc. are mentioned, for example. As said polymerization inhibitor, p-methoxyphenol etc. are mentioned, for example. The reaction temperature is preferably from 70°C to 100°C. The reaction time is preferably 8 hours to 12 hours.

Among the structural unit ratios of the polymer having a carboxyl group, the content ratio of the structural unit having a (meth)acryloxy group as a crosslinkable group is preferably 10 mol% of the total structural units of the polymer having a carboxyl group ～70 mol%, more preferably 20 mol%～50 mol%.

When the ratio of the structural unit having a (meth)acryloyloxy group is within the above range, heat resistance and development defects during image development are reduced, and generation of image development residue can be suppressed.

As said structural unit (U3), the structural unit derived from the polymerizable unsaturated compound (henceforth "compound (u3)") which has a silyl group is preferable.

As the above-mentioned compound (u3), for example, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylethyldimethoxysilane, Silane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, etc.

The above-mentioned compound (u3) can be used individually or in mixture of 2 or more types.

The above-mentioned structural unit (U4) is a structural unit other than the above-mentioned (U1) to (U3), and is preferably derived from a polymerizable unsaturated compound (hereinafter referred to as "compound ( u4)") Structural unit. Examples of the compound (u4) include: alkyl (meth)acrylates, cycloalkyl (meth)acrylates, aryl (meth)acrylates, aralkyl (meth)acrylates, Dialkyl unsaturated dicarboxylates, (meth)acrylic esters with oxa-containing 5-membered rings or oxa-6-membered rings, vinyl aromatic compounds, conjugated diene compounds and other polymerizable unsaturated compounds . As specific examples of these, as the alkyl (meth)acrylate, for example, methyl acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylic acid n-butyl, second-butyl (meth)acrylate, third-butyl (meth)acrylate, etc.; as cycloalkyl (meth)acrylate, for example, respectively: cyclohexyl (meth)acrylate , 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate, 2-(tricyclo[5.2. 1.0 ^2,6 ]decane-8-yloxy)ethyl ester, iso(meth)acrylate, etc.; As aryl (meth)acrylate, for example, phenyl acrylate, etc. can be exemplified respectively; Aralkyl (meth)acrylate, for example, respectively: benzyl (meth)acrylate, etc.; As unsaturated dicarboxylic acid dialkyl ester, for example, respectively: diethyl maleate , diethyl fumarate, etc.; As (meth)acrylic acid esters having an oxa-containing 5-membered ring or an oxa-containing 6-membered ring, for example, (meth)acrylic tetrahydrofuran-2-yl Esters, tetrahydropyran-2-yl (meth)acrylate, 2-methyltetrahydropyran-2-yl (meth)acrylate, etc.; As vinyl aromatic compounds, for example, respectively, for example: Styrene, α-methylstyrene, etc.; Examples of conjugated diene compounds include, for example, 1,3-butadiene, isoprene, etc.; Examples of other polymerizable unsaturated compounds include, for example, Examples: 2-hydroxyethyl (meth)acrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, etc.

Among the compounds (u4) exemplified above, in terms of copolymerization reactivity, n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, methacrylic acid Tricyclo[5.2.1.0 ^2,6 ]decane-8-yl ester, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene, etc.

Compound (u4) can be used individually or in mixture of 2 or more types.

The preferred polymer having a carboxyl group in this embodiment can be synthesized by copolymerizing a mixture of polymerizable unsaturated compounds containing the compounds (u1) to (u4) shown above in the following ratios. Also, by reacting the carboxyl group in the structural unit derived from the compound (u1) in the obtained copolymer with the (meth)acrylate having an epoxy group, it is possible to have the structural unit.

Preferably used in the following ranges: Compound (u1): preferably 0.1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, further preferably 5 mol% to 15 mol%; Compound (u2): preferably 1 mol% to 95 mol%, more preferably 10 mol% to 60 mol%, further preferably 20 mol% to 30 mol%; Compound (u3): preferably less than 50 mol %, more preferably 1 mol % to 40 mol %, further preferably 10 mol % to 30 mol %; Compound (u4): preferably at most 80 mol %, more preferably 1 mol % to 60 mol %, further preferably 25 mol % to 50 mol %.

Regarding a polymerizable composition containing a polymer having a carboxyl group obtained by copolymerizing a mixture of polymerizable unsaturated compounds containing compound (u1) to compound (u4) within the above-mentioned range, it is not necessary to obtain a higher resolution. Good coatability is impaired, so even if it is a high-definition pattern, it is preferable to provide a cured film whose balance of characteristics can be adjusted to a high degree.

The weight average molecular weight (Mw) of the polymer having a carboxyl group is preferably from 2,000 to 100,000, more preferably from 5,000 to 50,000. By using a polymer having a carboxyl group having a Mw in this range, a higher resolution can be achieved without compromising good coatability, so even for a high-definition pattern, it is possible to provide hardening with a highly adjusted balance of characteristics membrane. The method for measuring the weight average molecular weight refers to the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC).

A polymer having a carboxyl group can be produced by polymerizing a mixture of the above-mentioned polymerizable unsaturated compounds, preferably in a suitable solvent, preferably in the presence of a radical polymerization initiator.

Examples of the solvent used in the above polymerization include: diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol Monomethyl ether, Ethylene glycol monobutyl ether acetate, Propylene glycol monomethyl ether acetate (PGMEA), Dipropylene glycol monomethyl ether acetate, 3-Methoxybutyl acetate, Cyclohexyl acetate, Benzyl alcohol , 3-methoxybutanol, etc. These solvents can be used individually or in mixture of 2 or more types.

The above-mentioned radical polymerization initiator is not particularly limited, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile ), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl- Azo compounds such as 2,2'-azobis(2-methylpropionate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators can be used individually or in mixture of 2 or more types.

Regarding the above-mentioned radically polymerizable compound, for example, as a compound having an ethylenically unsaturated double bond group and not having an acid value, there may be exemplified: (meth)acrylic acid-2-hydroxyethyl ester, (meth)acrylic acid-2 -Hydroxypropyl ester, glycidyl (meth)acrylate, the following compounds No.A1 to No.A4, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, Tertiary butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, (meth) Stearyl acrylate, lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, (methoxyethyl) base) aminopropyl acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, (meth)acrylic acid Butoxyethoxyethyl, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofuryl (meth)acrylate, vinyl (meth)acrylate, (meth) Allyl Acrylate, Benzyl (meth)acrylate, Ethylene Glycol Di(meth)acrylate, Diethylene Glycol Di(meth)acrylate, Triethylene Glycol Di(meth)acrylate, Polyethylene Glycol Di(meth)acrylate, Polyethylene Glycol Di(meth)acrylate Diol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tri Methylolethane tri(meth)acrylate, Trimethylolpropane tri(meth)acrylate, Dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, Pentaerythritol tetra(meth)acrylate base) acrylate, pentaerythritol tri(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, tris[(meth)acrylethyl]isocyanurate, polyester (methyl ) Esters of unsaturated monobasic acids such as acrylate oligomers and polyols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth)acrylate and magnesium (meth)acrylate; maleic anhydride, Yikon Acid anhydride, Methylmaleic anhydride, Methyltetrahydrophthalic anhydride, Tetrahydrophthalic anhydride, Trialkyltetrahydrophthalic anhydride, 5-(2,5-Dioxytetrahydrofuran base)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, formaldehyde Anhydrides of unsaturated polybasic acids such as biscycloheptenedicarboxylic anhydride; (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriaminetri(meth)acrylamide , xylylenedimethylbis(meth)acrylamide, α-chloroacrylamide, N-2-hydroxyethyl(meth)acrylamide and other unsaturated monobasic acids and amides of polyamines; acrolein, etc. Unsaturated aldehydes; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene dicyanide, allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4- Methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinyl Unsaturated aromatic compounds such as benzyl methyl ether and vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinylamine, allylamine, N-vinylpyrrolidone, vinylpiperidine Unsaturated amine compounds such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether and other vinyl ethers; maleimide, N-phenylmaleimide Unsaturated imines such as imine and N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; fats such as 1,3-butadiene, isoprene and chloroprene family of conjugated dienes; polystyrene, poly(methyl)acrylate, poly(meth)acrylate n-butyl, polysiloxane, etc. have mono(meth)acryl at the end of the polymer molecular chain Macromonomers based on macromonomers; (meth)acrylonitrile, ethylidene, propylidene, butyl, vinyl chloride, vinyl acetate and other vinyl compounds, and polymethylmethacrylate macromonomers, poly Macromonomers such as styrene macromonomer, monomethacrylate of tricyclodecane skeleton, N-phenylmaleimide, methacryloxymethyl-3-ethyloxetane Copolymers of alkanes, etc. and (meth)acrylic acid, and copolymers of (meth)acrylic acid obtained by reacting these with isocyanate compounds having unsaturated bonds such as Karenz MOI and AOI manufactured by Showa Denko Co., Ltd., or vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl sulfide, vinylimidazole, Vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl-containing vinyl monomers and vinyl urethane compounds of polyisocyanate compounds, hydroxyl-containing vinyl monomers and Reactants of polyepoxy compounds such as vinyl epoxy compounds, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and other hydroxyl-containing multifunctional acrylates and toluene diisocyanate and hexamethylene diisocyanate.

[Chem. 26] Compound No.A1

[Chem. 27] Compound No.A2

[Chem. 28] Compound No.A3

[Chem. 29] Compound No.A4

The above-mentioned radically polymerizable compound can be used individually or in mixture of 2 or more types. Moreover, the radically polymerizable compound can use combining the compound which has an ethylenically unsaturated double bond group and has an acid value, and the compound which has an ethylenically unsaturated double bond group and does not have an acid value. When using a radically polymerizable compound in mixture of 2 or more types, it can copolymerize these beforehand, and can use it as a copolymer.

The content of the above-mentioned polymerizable compound is not particularly limited as long as the hardened product with the desired strength can be obtained. For example, it can be set to 10 parts by mass or more and 99 parts by mass or less with respect to 100 parts by mass of the solid content of the composition, preferably It is not less than 50 parts by mass and not more than 99 parts by mass, more preferably not less than 80 parts by mass and not more than 99 parts by mass. The reason is that the above-mentioned composition can stably maintain the above-mentioned Compound I, for example, when the above-mentioned content is within the above-mentioned range.

(2) Polymers without polymerizable groups The above-mentioned composition may contain a polymer having no polymerizable group. The reason is that, for example, adjustment of photosensitivity etc. can be easily performed in the said composition by containing the said polymer.

As such a polymer, as long as it does not have a polymerizable group, for example, polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(methyl) Acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS (acrylonitrile- butadiene-styrene, acrylonitrile-butadiene-styrene) resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide , Saturated polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamide acid resin, epoxy resin, etc. As the above-mentioned polymer, for example, a polymer of the above-mentioned polymerizable compound can also be used.

The weight average molecular weight (Mw) of the said polymer is set suitably according to the use of a composition etc., For example, it can be 1,500 or more, and can be 1,500 or more and 300,000 or less. In addition, below, weight average molecular weight can be calculated|required as the standard polystyrene conversion value by gel permeation chromatography (GPC). Regarding the above-mentioned weight average molecular weight Mw, for example, GPC (LC-2000plus series) manufactured by JASCO Co., Ltd. can be used, the dissolution solvent is tetrahydrofuran, and the polystyrene standard for the calibration curve is Mw1, 110,000, 707,000, 397,000, 189,000, 98,900, 37,200, 13,700, 9,490, 5,430, 3,120, 1,010, 589 (TSKgel standard polystyrene manufactured by Tosoh Co., Ltd.), set the measuring column to KF-804, KF-803, KF-802 ( Showa Denko Co., Ltd.) was measured and obtained. In addition, the measurement temperature may be set to 40° C., and the flow rate may be set to 1.0 mL/min.

The above-mentioned polymer may have an acid value. The reason is that the polymer tends to impart alkali developability to the composition. The acid value of the above-mentioned polymer can be appropriately set according to the required alkali solubility, and can be set at 10 mgKOH/g to 200 mgKOH/g, preferably 30 mgKOH/g to 150 mgKOH/g. It is because the alkali developability of a composition is excellent by the said acid value being the said range. Here, the acid value represents the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of the solid content of the polymer, and it can be performed by the method described in JIS K 0070 measured value.

(3) Resin component The content of the above-mentioned resin component can be appropriately set according to the use of the composition, etc. For example, it can be set to 1 part by mass or more and 99 parts by mass or less, preferably 20 parts by mass or more, based on 100 parts by mass of the solid content of the composition. 99 mass parts or less, preferably 30 mass parts or more and 99 mass parts or less. The reason is that the above-mentioned composition can stably maintain the above-mentioned Compound I, for example, when the above-mentioned content is within the above-mentioned range.

3. Solvent The above-mentioned composition may contain a solvent for dispersing or dissolving the above-mentioned compound I and the like. As the above-mentioned solvent, as long as it can disperse or dissolve the components of the composition, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone , methyl isobutyl ketone, cyclohexanone, 2-heptanone and other ketones; ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, Dipropylene glycol dimethyl ether and other ether solvents; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, TEXANOL, etc. Ester solvents; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol, etc.; Alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate Ether ester solvents such as esters and ethoxy ether propionate; BTX solvents such as benzene, toluene, xylene, etc.; aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane, etc.; turpentine, D-limonene terpene-based hydrocarbon oils such as pinene; mineral spirits, paraffin-based solvents such as Swazol #310 (Cosmo Matsuyama Petroleum Company), Solvesso #100 (Exon Chemical Company); carbon tetrachloride, chloroform, trichloroethylene, di Halogenated aliphatic hydrocarbon solvents such as methyl chloride and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N ,N-dimethylformamide; N,N-dimethylacetamide; N-methylpyrrolidone; dimethylsulfoxide; Used in the form of solvent. Among them, from the viewpoint of good compatibility with compound I, polymers, etc., ketones, ether ester solvents, etc. are preferred, and propylene glycol-1-monomethyl ether-2-acetic acid is particularly preferred. Esters (hereinafter also referred to as "PGMEA" or "propylene glycol monomethyl ether acetate"), cyclohexanone, etc.

Content of the said solvent can be set suitably according to coatability etc., For example, it can set it as 10 mass parts or more and 90 mass parts or less with respect to 100 mass parts of compositions.

4. Other ingredients The above-mentioned composition may contain other components as needed in addition to the above-mentioned compound I and the resin component. Examples of the above-mentioned other components include colorants, inorganic compounds, dispersants for dispersing colorants, inorganic compounds, etc., chain transfer agents, sensitizers, surfactants, silane coupling agents, and melamine. As said other component, initiators, such as a photoradical polymerization initiator and a thermal radical polymerization initiator other than the said compound I, can also be mentioned. For such other components, known materials can be used, for example, those described in International Publication No. 2014/021023 can be used.

Examples of the above-mentioned other components include reaction accelerators that increase the radical initiation energy of the above-mentioned compound I. Such a reaction accelerator includes, for example, compounds containing at least one CH group at the α-position with respect to a heteroatom, such as organic amines, phosphines, alcohols, and thiols. More specifically, such a reaction accelerator may be the same as those described in Japanese Patent Application Laid-Open No. 62-502403 and the like. In the present invention, organic amines are preferred, especially primary, secondary and tertiary aliphatic, aromatic, aromatic-aliphatic or heterocyclic amine compounds, among which triethylamine can be used particularly preferably and other tertiary amines.

The content of the above-mentioned other components is appropriately selected according to the purpose of use, and is not particularly limited. For example, the total may be 50 parts by mass or less with respect to 100 parts by mass of the solid content of the composition.

5. Composition As a method for producing the above-mentioned composition, any known mixing method can be used as long as the above-mentioned components can be mixed so as to have a desired content. As a use of the said composition, it can be used as a photocurable composition hardened by light irradiation, for example. In addition, as a specific use, it may be the same as that described in the item of "A. Compound" above.

C. Hardened Next, the cured product of the present invention will be described. The cured product of the present invention is characterized in that it is a cured product of the above composition.

According to the present invention, since the above-mentioned composition is used, the above-mentioned cured product has less outgassing.

The cured product of the present invention uses the above-mentioned composition. Hereinafter, the cured product of the present invention will be described in detail. Furthermore, the above-mentioned composition may be the same as that described in the item of "B. Composition" above. The above-mentioned composition usually contains a resin component such as a polymerizable compound in order to form a cured product.

The above-mentioned cured product usually contains a polymer component. Such a polymer component may, for example, be a polymer of the polymerizable compound described in the section of "B. Composition", or a polymer, etc., and generally, it may be a polymer containing at least a polymerizable compound. The content of the polymer and the content of the polymer component of the above-mentioned polymerizable compound may be the same as the content of the polymerizable compound and the content of the resin component described in the item "B. Composition".

The storage elastic modulus of the above-mentioned cured product is usually higher than that of the above-mentioned composition, and can be appropriately set according to the use of the cured product and the like.

As said hardened|cured material, what does not contain a solvent substantially may be sufficient. The content of the solvent contained in the cured product is, for example, 1 part by mass or less, preferably 0.5 part by mass or less with respect to 100 parts by mass of the cured product. The reason is that when the said content is the said range, the said hardened|cured material is excellent in stability with time.

The plan view shape, thickness, and the like of the above-mentioned cured product can be appropriately set in accordance with the use and the like of the above-mentioned cured product.

The method for producing the cured product is not particularly limited as long as the cured product of the above composition can be formed into a desired shape. Such a production method is, for example, the same as that described in the following "D. Production method of cured product", so the description here is omitted.

Regarding the use and the like of the above-mentioned cured product, it may be the same as that described in the item "A. Compound" above.

D. Manufacturing method of hardened product Next, a method for producing the cured product of the present invention will be described. The method for producing a cured product of the present invention is characterized by the step of irradiating the composition with light.

According to the present invention, by using the composition containing the above-mentioned compound I, the production of the cured product is relatively easy, and the above-mentioned cured product has less outgassing.

The manufacturing method of the present invention includes the step of performing light irradiation. Hereinafter, each step of the production method of the present invention will be described in detail.

1. Steps of light irradiation This step is a step of irradiating the above composition with light. The light irradiated to the composition in this step may be any compound I can generate radicals, and may include, for example, light with a wavelength of 300 nm to 450 nm. The amount of light to be irradiated may be any one that can form a cured product with desired hardness, and it may be appropriately adjusted according to the thickness of the coating film of the composition and the like. As a light source for the above-mentioned light irradiation, for example, ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, etc. may be mentioned. As the light to be irradiated, laser light can be used. As the laser light, those including light with a wavelength of 340 nm to 430 nm can be used. As the light source of laser light, argon ion laser, helium-neon laser, YAG (yttrium aluminum garnet, yttrium aluminum garnet) laser, semiconductor laser, etc. that emit light from visible light to infrared region can also be used. Furthermore, in the case of using such lasers, the above composition may contain a sensitizing pigment that absorbs in the relevant region from visible light to infrared light.

The method of irradiating light may be a method of irradiating the entire coating film of the composition in plan view, or a method of irradiating a part of the coating film. When the object to be irradiated with light is a part of the coating film, the method of irradiating light can be, for example, a method of irradiating light through a mask or the like, a method of irradiating only the hardened portion of the composition, or the like.

Furthermore, the above-mentioned composition may be the same as that described in the item of "B. Composition" above. The above composition usually contains a polymerizable compound in order to form a cured product.

2. Other steps The above-mentioned production method includes a step of irradiating light, and may also include other steps as necessary. Examples of the above-mentioned other steps include: a step of forming a coating film of the above-mentioned composition before the step of irradiating light; a step of developing after the step of irradiating light; The step of removing the solvent carried out after the step of , the step of heating carried out after the above step of light irradiation, etc.

As the step of forming the above-mentioned coating film, any method can be used as long as it can obtain a coating film of the composition having a desired thickness, for example, a spin coater, a roll coater, a bar coater, or a die coater can be used. Machine, curtain coater, various printing, dipping and other known methods. The base material on which the coating film of the above composition is formed can be appropriately selected according to the application of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, plastics, and the like. In addition, after the above-mentioned cured product is formed on the base material, it can be peeled off from the base material and used, or it can be transferred from the base material to another base material and used.

As the image development method in the step of performing image development, any method can be used as long as it can remove the uncured composition. For example, a known image development method such as a method of removing with an alkaline developer can be used.

As the method of removing the solvent in the step of removing the solvent, any method can be used as long as the content of the solvent contained in the cured product can be adjusted to a desired amount, for example, a method of heating, that is, performing prebaking Step as a method to remove a step etc.

As the heating temperature in the step of heating (post-baking step) performed after the step of irradiating light, any temperature can be used as long as the mechanical strength of the cured product can be improved. Set appropriately.

3. Other Regarding the cured product produced by the above-mentioned production method, its use, etc., it may be the same as that described in the item "C. Hardened product" above.

The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are examples, and those having substantially the same configuration as the technical idea described in the claims of the present invention and having the same function and effect are included in the technical scope of the present invention. [Example]

Hereinafter, the present invention will be described in more detail with reference to production examples, examples, and comparative examples, but the present invention is not limited to these examples and the like.

[Example 1-1] As shown in the following reaction formula, add 0.15 mol of aromatic compound and 140 g of dichloroethane, and then add 0.16 mol of aluminum chloride and carboxylic acid amide halide (4 -fluoro-2-methylbenzoyl chloride) 0.15 mol. After warming up to room temperature, it was stirred for 1 hour. The reaction solution was poured into ice water for oil-water separation. The organic layer was washed with water, and the solvent was distilled off under reduced pressure to obtain (compound (1)). Next, 0.1 mol of the above compound (1), 100 g of dimethylformamide, 0.2 mol of mercaptopropionic acid, and 0.4 mol of potassium carbonate were added, followed by stirring at 110° C. for 48 hours. Then, after cooling to room temperature, 50 g of ion-exchanged water was added to the reaction liquid, the pH was adjusted to be acidic with hydrochloric acid, and 200 g of ethyl acetate was added to carry out oil-water separation. The organic layer was washed with water, dried under reduced pressure, and the residue was added to a silica gel column using chloroform/methanol=volume ratio 9/1 as a developing solvent to obtain a compound represented by the following formula (I-1-5) I. It was confirmed by ¹ H-NMR (Hydrogen-Nuclear Magnetic Resonance, hydrogen-nuclear magnetic resonance) and IR (infrared radiation, infrared radiation) that the obtained compound was the target object.

[chem 30]

[Example 1-2] As shown in the following reaction formula, add 0.1 mol of benzaldehyde having a hydroxyl group, 0.1 mol of 2-chloro-4'-fluoroacetophenone, 0.2 mol of potassium carbonate, and 78 g of acetone for 2 hours. Heat to reflux. After cooling, ion-exchanged water was added, and the precipitate was separated by filtration and dried under reduced pressure to obtain compound (2). Then, compound I-1 represented by the following formula (I-1-35) was obtained by subjecting compound (2) to the same treatment as in Example 1. It was confirmed by ¹ H-NMR that the obtained compound was the target object.

[chem 31]

[Example 1-3] As shown in the following reaction formula, the compound I-1 represented by the following formula (I-1-48) was obtained by performing the same treatment as in Example 1. In addition, it was confirmed by ¹ H-NMR that the obtained compound was the target object.

[chem 32]

[Table 1] H-NMR Chemical shift/ppm (multiplicity, number of protons) Compound I-1-5 DMSO-d6 8.55 (d, 1H), 8.21 (d, 1H), 7.83 (d, 1H), 7.68 (t, 2H), 7.51 (dt, 1H), 7.32 - 7.24 (m, 4H), 4.49 (q, 2H), 3.31 (d, 2H), 2.64 (d, 2H), 2.26 (s, 3H), 1.34 (t, 3H) Compound I-1-35 CDCI3 8.02 (d, 2H), 7.73 (d, 1H), 7.63 (d, 1H), 7.55 (s, 1H) 7.50 (t, 1H), 7.42 (d, 2H), 7.34 (t, 1H), 3.31 ( d, 2H), 2.80 (d, 2H)

[Table 2] IR Spectrum Absorption Spectrum/cm ^-1 Compound I-1-5 1697, 1632, 1589, 1547, 1412, 1300, 1271, 972, 901, 849, 744

[Examples 2-1 to 2-2, Comparative Example 2-1] Each component was mixed according to the composition of following Table 4, and the composition was prepared. In addition, the number represents a mass part.

(resin component) A-1: Kayarad DPHA (a polymeric compound having no acid value; manufactured by Nippon Kayaku Co., Ltd.) B-1: EA-1020 (polymerizable compound (epoxy acrylate) not having an acid value; manufactured by Nippon Kayaku Co., Ltd.)

(photopolymerization initiator) C-1: Compound I-1-5 (compound I-1, obtained in Example 1-1) C-2: Compound I-1-35 (compound I-1, obtained in Example 1-2) C'-1: Benzophenone (photopolymerization initiator, manufactured by Tokyo Chemical Industry Co., Ltd.)

(other) D-1: SH-29PA (leveling agent, manufactured by Toray Dow Corning Co., Ltd.) E-1: Methyl ethyl ketone (solvent)

[evaluate] 1. Heat resistance Take the compound of the example and the photopolymerization initiator of C'-1, using a differential thermal-thermogravimetric simultaneous measurement device (manufactured by Seiko Electronics Nanotechnology Co., Ltd., model: EXSTARTG/DTA6200"), about 5 mg, Measure the heat loss of the sample when the temperature rises at a heating rate of 10°C/min under a nitrogen atmosphere of 200 mL/min, at a heating start temperature of 30°C, at a heating end temperature of 500°C. The temperature at the time point at which the weight of the sample decreases by 10% relative to the time point at 30° C. is defined as the 10% weight loss temperature. The results are shown in Table 3 below. Furthermore, it can be used as a radical photopolymerization initiator whose 10% weight reduction temperature is 250° C. or higher and has excellent heat resistance.

[table 3] Heat resistance (℃) Compound I-1-5 289 Compound I-1-35 307 C'-1 159

2. Sensitivity The compositions of Examples and Comparative Examples were coated with a thickness of about 30 μm on an easy-bonding PET film (manufactured by Toyobo: product number COSMOSHINE A4300, 100 μm) using a #14 rod coater. Then, after pre-baking at 80° C. for 3 minutes, 3000 mJ/cm ² of ultraviolet light was irradiated using an ultra-high pressure mercury lamp. At this time, in order to be able to measure the light sensitivity, use a film made in such a way that the light transmittance gradually decreases (the optical density is 0.05 as the first stage, and the optical density of each stage is increased by 0.10). Then, it was developed by developing with propylene glycol-1-monomethyl ether-2-acetate (PGMEA). Then, it dried at 80 degreeC for 30 minutes. Then, the photosensitivity was evaluated by measuring the number of stages of the step exposure meter of the cured film formed on the simple PET film. The results are shown in Table 4 below. Furthermore, the higher the number of stages of the stage exposure meter, the higher the light sensitivity. In addition, it can be used as a radical photopolymerization initiator having 2 or more stages and having excellent sensitivity.

[Table 4] Example comparative example 2-1 2-2 2-1 resin composition A-1 50 50 50 B-1 50 50 50 polymerization initiator C-1 2 - - C-2 - 2 - C'-1 - - 2 other D-1 0.1 0.1 0.1 E-1 50 50 50 Sensitivity (number of segments) 15 19 6

According to Table 3 and Table 4, it can be confirmed that the compound I of the example has excellent sensitivity and heat resistance. Also, from such a situation, the compositions of the examples showed excellent sensitivity and were less outgassed.

Claims (6)

A compound represented by the following general formula (I), [Chem. 1]

(In the formula, Ar ^a is a base formed by removing n1 hydrogen atoms from the structure represented by the following general formula (A), and bonds with R ¹ at the part where the hydrogen atoms have been removed, and R ¹ is a group containing a COOH group base, n1 represents an integer greater than 1; when there are multiple ^R1s , the multiple ^R1s may be the same or different) [Chem. 2]

(In the formula, Ar ¹ and Ar ² each independently represent an aromatic group). The compound as claimed in item 1, wherein the above-mentioned compound is represented by the following general formula (II-1) or (III-1), [Chemical 3]

[chemical 4]

(In the formula, X ^a and X ^b are divalent bonding groups, each independently representing >CR ¹⁴ R ¹⁵ , -O-, -S- or >NR ¹⁴ , R ¹⁴ and R ¹⁵ independently representing a hydrogen atom, An aliphatic hydrocarbon group with 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group with 6 to 35 carbon atoms, or a heterocyclic group with 2 to 35 carbon atoms, L ^a and L ^b are divalent bonding groups, each independently Indicates direct bond, -O-, -S-, >C=O, >NR ⁵³ , aliphatic hydrocarbon group with 1 to 120 carbon atoms, aromatic ring hydrocarbon group with 6 to 35 carbon atoms, and 2 to 35 carbon atoms However, one or more methylene groups in the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group and the heterocyclic group may be substituted by -S-, -O-, carbon-carbon double bond , -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO- O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, -O-CO-NH-, >NR', >P=O, -SS -, -SO ₂ or a combination thereof, R ⁵³ represents a hydrogen atom, an aliphatic hydrocarbon group with 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group with 6 to 35 carbon atoms, or a heterocyclic ring with 2 to 35 carbon atoms R' represents a hydrogen atom or an alkyl group with 1 to 8 carbon atoms, R ^a1 , R ^a2 , R ^b1 and R ^b2 each independently represent an aliphatic hydrocarbon group with 1 to 35 carbon atoms, or an alkyl group with 6 to 35 carbon atoms aromatic ring-containing hydrocarbon group or heterocyclic ring-containing group with 2 to 35 carbon atoms, a1, a2, b1 and b2 are each independently an integer of 0 to 4). The compound of claim 2, wherein L ^a and L ^b are independently selected from aliphatic hydrocarbon groups with 1 to 120 carbon atoms, aromatic ring-containing hydrocarbon groups with 6 to 35 carbon atoms, and aliphatic hydrocarbon groups with 2 to 35 carbon atoms. A group in which one or more methylene groups in the heterocyclic group are substituted with -S-. A composition comprising the compound according to any one of claims 1-3. A cured product, which is a cured product of the composition as claimed in claim 4. A method for producing a cured product, comprising the step of irradiating the composition according to claim 4 with light.