WO2019069835A1

WO2019069835A1 - Composition, cured product, and method for producing cured product

Info

Publication number: WO2019069835A1
Application number: PCT/JP2018/036598
Authority: WO
Inventors: 有希子金原; 光裕岡田; 哲千中屋敷
Original assignee: 株式会社Adeka
Priority date: 2017-10-04
Filing date: 2018-09-28
Publication date: 2019-04-11
Also published as: CN110869467A; JPWO2019069835A1; JP7236386B2; TWI794298B; TW201922889A; KR102629376B1; CN110869467B; KR20200061318A

Abstract

Provided is a composition that contains a compound A represented by general formula (A1), (A2), or (A3) and a compound B represented by general formula (B). The R9 in general formulas (A1), (A2), and (A3) and the R11 in general formula (B) preferably are each an alkyl group having 1 to 20 carbon atoms wherein the methylene group at the end on the oxygen atom side is substituted by -CO-O-. (Refer to the description for the symbols in the formulas.)

Description

Composition, cured product and method for producing cured product

The present invention relates to a composition.

In order to improve the durability such as light resistance and heat resistance of the curable composition, methods of stabilizing by adding an ultraviolet absorber, an antioxidant and the like are known (Patent Documents 1 to 3).

JP, 2011-048382, A US2016016919A1 JP, 2015-108649, A

However, even when the above-mentioned antioxidant is added, a cured product having sufficient durability may not be obtained.
With respect to such problems, the present inventors have found that the phenolic antioxidant has an action of trapping radicals which greatly affect the deterioration of the polymer, and in order to have such an action, the phenolic antioxidant It has been found that, when added into the polymerization system, it generally acts as a so-called polymerization inhibitor and may cause curing inhibition.
To address such problems, latent additives such as latent antioxidants and latent ultraviolet light absorbers are known which are inactivated in the polymerization system and which can be activated after curing.
However, even when a latent additive is used, there are cases where a cured product having sufficient durability can not be obtained, and it may be difficult to produce a cured product.

The present invention has been made in view of the above problems, and for example, it is a main object of the present invention to provide a composition capable of producing a cured product having durability and facilitating the production of the cured product. .

The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, the phenolic hydroxyl group is protected by a protecting group, and after removal of the protecting group, the compound exhibiting an antioxidant ability after removal of the protecting group and UV absorption after removal of the protecting group. It has been found that by using both of the compounds exhibiting an ability together, it is possible to obtain a cured product having excellent durability and to facilitate the production of the cured product, and the present invention has been completed.

That is, the present invention provides a composition comprising a compound A represented by the following general formula (A1), (A2) or (A3), and a compound B represented by the following general formula (B).

^{^{^{(Wherein, R 1, R 2, R}}} 1 ', R 2', R 1 " and ^{R 2"} are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, a carbon atom And an alkyl group of 1 to 40, an aryl group of 6 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or -O-R ⁹
At least one of R ¹ and R ² is -O-R ⁹ above;
At least one of R ¹ ′ and R ² ′ is —O—R ⁹ above,
At least one of R ^{1 ′} ′ and R ′ ′ ² is —O—R ⁹ above,
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ and R ¹⁴ are each independently a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms,
R ⁹ and R ¹¹ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl having 7 to 20 carbon atoms A group, a heterocycle-containing group having 2 to 20 carbon atoms or a trialkylsilyl group,
R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 40 carbon atoms,
The methylene group in the above alkyl group, aryl group, arylalkyl group, heterocyclic group and trialkylsilyl group is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO- , -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S- When substituted by -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, -SO ₂ -or a combination thereof There is
The alkyl group, the aryl group, the arylalkyl group, the heterocycle-containing group and the trialkylsilyl group may have a substituent,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
A plurality of R ^{3 's} , a plurality of R ^{4' s} , a plurality of R ^{5 's} , a plurality of R ^{6' s} and a plurality of R ⁷ 's and a plurality of R ¹⁴ ' s are combined to form a benzene ring or a naphthalene ring May be
The plurality of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ and R ¹⁴ may be identical to or different from each other,
m1 and m2 each independently represent an integer of 1 to 10,
m3 represents an integer of 1 to 3;
n represents an integer of 1 to 10,
a1 represents an integer of 0 to 4;
a2 represents an integer of 0 to 2;
a3 represents an integer of 0 to 4;
a4 represents an integer of 0 to 3;
a5 represents an integer of 0 to 3;
a6 represents an integer of 0 to 3-m3,
b1 represents an integer of 0 to 2;
X ^a1 represents a direct bond or an m1-valent atom or a bond group, X ^a2 represents a direct bond or an m-bivalent atom or a bond group, and X ^b represents a direct bond or an n-valent atom or a bond group . )

According to the present invention, since the compound A and the compound B each have a structure represented by the above general formula, ultraviolet light is released when R ⁹ and R ¹¹ protecting the phenolic hydroxyl group are eliminated. It shows absorption capacity and antioxidant capacity.
By using such a compound A and the compound B in combination, the composition can obtain a cured product having excellent durability.
Further, each of the compound A and the compound B, by the phenolic hydroxyl group is protected by R ⁹ and R ^11, can suppress the occurrence of curing inhibition. Therefore, the composition can be easily cured.
As such, the composition can produce a cured product having durability and can easily produce the cured product.

In the present invention, R ⁹ and R ¹¹ are preferably an alkyl group having 1 to 20 carbon atoms in which the terminal methylene group at the oxygen atom side is replaced by —CO—O—. This is because compound A and compound B facilitate elimination of R ⁹ and R ¹¹ .

In the present invention, the content of the compound A is preferably 1 part by mass to 99 parts by mass with respect to a total of 100 parts by mass of the compound A and the compound B. It is because the said composition has the outstanding durability because the said content is the above-mentioned range.

In the present invention, the composition preferably contains a polymerizable compound. It is because the said composition can exhibit the effect that manufacture of hardened | cured material is easy more effectively.

The present invention provides a cured product of the above composition.

According to the present invention, since the above-mentioned composition is used, the above-mentioned cured product is easy to manufacture and is excellent in durability.

The present invention provides a method for producing a cured product, which comprises the step of forming a cured product of the composition described above.

According to the present invention, for example, the production method of the cured product becomes easy by using the above-mentioned composition and having the above-mentioned steps. In addition, by carrying out the step of removing the protecting group R ⁹ contained in the compound A and the protecting group R ¹¹ contained in the compound B after the above steps, a cured product having durability can be easily obtained. Can.

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

A. Composition First, the composition of the present invention will be described.
The composition of the present invention is characterized by containing a compound A represented by the following general formula (A1), (A2) or (A3), and a compound B represented by the following general formula (B) It is a thing.

According to the present invention, the compound A can exhibit an ultraviolet absorbing ability by the elimination of R ⁹ protecting the phenolic hydroxyl group.
Further, the compounds B, by R ¹¹ protecting the phenolic hydroxyl group is eliminated, it is possible to indicate the antioxidant ability.
For this reason, for example, the said composition can manufacture the hardened | cured material etc. excellent in durability excellent in both light resistance and heat resistance.
Here, the reason why a cured product having excellent durability can be obtained by using Compound A and Compound B in combination is presumed as follows.

That is, the compound A absorbs less light irradiated for photocuring, as compared to a state in which the phenolic hydroxyl group is not protected by R ⁹ .
Moreover, Compound B, as compared to the state of the phenolic hydroxyl group by R ¹¹ is not protected, a lower scavenging radicals.
For this reason, Compound A and Compound B, by phenolic hydroxyl groups with R ⁹ and R ¹¹ each is protected, for example, the occurrence of curing inhibition of such photocurable composition can be suppressed.
However, when one of the compound A or the compound B is used in combination with, for example, a conventionally known antioxidant, ultraviolet absorber, etc., the above-mentioned function of inhibiting the inhibition of curing may not be sufficiently exhibited. .
For example, when the phenolic antioxidant is combined with the compound A, the curing inhibition occurs due to the action of trapping the radical by the phenolic antioxidant. As a result, the durability is lowered due to insufficient curing, and the compound A and the like after desorption of the phenolic antioxidant and R ⁹ easily bleed out.
On the other hand, when the ultraviolet light absorber is combined with the compound B, the light absorption by the ultraviolet light absorber also absorbs the light irradiated for the curing, and the curing inhibition occurs. As a result, along with the decrease in durability due to insufficient curing, the decrease in durability caused by the UV absorber, the compound B and the like after release of R ¹¹ easily bleed out occurs.
From such a thing, when the compound A and the compound B are used independently and combined with a conventionally well-known antioxidant etc., for example, the hardened | cured material excellent in durability may not be obtained.
On the other hand, in the present invention, since the compound A and the compound B are used in combination, it is possible to suppress the occurrence of curing inhibition as described above, and it becomes easy to sufficiently cure and bleed out is suppressed. The obtained cured product can exhibit excellent durability.

Further, the antioxidant and the ultraviolet light absorber having a phenolic hydroxyl group are easily aggregated in the composition under the influence of the phenolic hydroxyl group, and it is difficult to increase the addition amount to the composition, and the aggregation functions as well. Can not demonstrate enough.
On the other hand, the compound A and the compound B have excellent dispersion stability in the composition by having a structure in which the phenolic hydroxyl group is protected by R ⁹ and R ¹¹ respectively.
As a result, Compound A and Compound B are easy to disperse in the cured product, as well as easy to increase the amount added to the composition, as compared with the conventional antioxidant and UV absorber having phenolic hydroxyl group. Can fully demonstrate its function.
From this point of view as well, a compound A and a compound B can be used in combination to provide the antioxidant ability and the ultraviolet ray absorbing ability, whereby a cured product having excellent durability can be obtained.

Furthermore, as described above, the compound A and the compound B can suppress generation of curing inhibition of, for example, a photocurable composition and the like because the phenolic hydroxyl group is protected by R ⁹ and R ¹¹ .
From such a thing, manufacture of hardened | cured material becomes easy by the said composition.

In addition, when the phenolic ultraviolet absorber is combined with the compound B, the amount of light transmission is greatly reduced along the thickness direction of the composition, for example, the adhesion between the cured product and the substrate is reduced. There is also a problem that the cured product is likely to be peeled off from the substrate.
However, in the present invention, since Compound A and Compound B are used in combination, as described above, absorption of light irradiated during curing can be suppressed, and as a result, it is possible to obtain a cured product in which peeling from the substrate is suppressed. it can.

Furthermore, for example, when the composition contains, as a resin component, a component whose solubility in an alkali developer changes due to light irradiation, such as a photosensitive resin, for example, absorption of light irradiated for photosensitive expression Performance is low and light sensitivity can be stably expressed.
From such a thing, the said composition can be made into the photosensitive composition excellent in photosensitivity, durability, etc., for example.

The composition of the present invention comprises compound A and compound B.
Hereinafter, each component of the composition of the present invention will be described in detail.

1. Content of Compound A and Compound B The content of the compound A may be any one as long as the composition can produce a cured product having desired durability. For example, 100 parts by mass of the solid content of the composition The amount can be 0.001 parts by mass or more and 20 parts by mass or less, and is preferably 0.005 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 8 parts by mass It is preferable that it is the following, Especially, it is preferable that it is 1 to 6 mass parts especially. It is because the said composition which contains the compound A in such an amount is easy to manufacture the hardened | cured material which has durability, and manufacture of hardened | cured material becomes still easier. Moreover, it is because it is easy to disperse | distribute stably in a composition as it is the above-mentioned content.
In addition, in general, as the film thickness of the member to be used is thinner, the content of the ultraviolet absorber may be required to be increased. Therefore, even when the cured product of the above composition is used for a thin film member, the lower limit of the content of the above compound A is 100% of the solid content of the above composition from the viewpoint of exhibiting sufficient ultraviolet light absorbability. For example, the amount is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and preferably 5 parts by mass or more. By being the said minimum, it is because sufficient ultraviolet-ray absorptivity can be easily provided, even when it is a thin film member, for example.
In addition, solid content is what contains all the components other than a solvent.
Further, in the present description, the content is on a mass basis unless otherwise noted.
The content of the compound A varies depending on the content of the solvent and the like, and can be, for example, 0.001 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition. It is because it is easy to disperse | distribute stably in a composition by being said content.

The content of the compound A may be any as long as the composition can produce a cured product having desired durability, and, for example, 1 part by mass with respect to a total of 100 parts by mass of the compound A and the compound B The amount can be set to 99 parts by mass or less, preferably 15 parts by mass to 85 parts by mass, and particularly preferably 20 parts by mass to 80 parts by mass. It is because the said composition which contains the compound A in such an amount is easy to manufacture the hardened | cured material which has durability, and manufacture of hardened | cured material becomes still easier.

As content of the said compound B, a composition should just be what can manufacture the hardened | cured material which has desired durability, for example, 0.001 as a content with respect to solid content of 100 mass parts of the said composition The content can be in the range of not less than 20 parts by mass, preferably not less than 0.005 parts by mass and not more than 10 parts by mass, and particularly preferably 0.1 parts by mass to 8 parts by mass, Especially, it is preferable that it is 1 to 6 parts by mass. The composition containing the compound B in such an amount is easy to manufacture a cured product having durability, and it is easier to produce a cured product.
The content of the compound B varies depending on the content of the solvent and the like, and can be, for example, 0.001 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition. It is because it is easy to disperse | distribute stably in a composition by being said content. Moreover, it is because the said composition which contains the compound B in such an amount is easy to manufacture the hardened | cured material which has durability, and manufacture of hardened | cured material becomes still easier.

The total content of the compound A and the compound B may be any as long as the composition can produce a cured product having a desired durability, for example, with respect to 100 parts by mass of the solid content of the composition, It can be 0.01 parts by weight or more and 20 parts by weight or less, and more preferably 0.05 parts by weight or more and 15 parts by weight or less, and particularly preferably 0.1 parts by weight or more and 10 parts by weight or less Are particularly preferable, and in particular, 1 part by mass or more and 8 parts by mass or less are preferable. It is because the said composition containing the compound A and the compound B in such an amount is easy to manufacture the hardened | cured material which has durability, and manufacture of hardened | cured material becomes still easier.
In addition, even when the cured product of the above composition is used for a thin film member, the lower limit of the content of the above compound A and compound B is the solid content of the composition from the viewpoint of exhibiting sufficient ultraviolet absorbing ability. The amount is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and particularly preferably 4 parts by mass or more with respect to 100 parts by mass of each component. By being the said minimum, it is because sufficient ultraviolet-ray absorptivity can be easily provided, for example, also when it is a thin film member.
Although the total content of the compound A and the compound B varies depending on the content of the solvent and the like, for example, it may be 0.001 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition. it can. It is because it is easy to disperse | distribute stably in a composition by being said content. It is because the said composition containing the compound A and the compound B in such an amount is easy to manufacture the hardened | cured material which has durability, and manufacture of hardened | cured material becomes still easier.

2. Compound A
The compound A is represented by the above-mentioned general formula (A1), (A2) or (A3).
The compound A may have a structure in which a phenolic hydroxyl group is protected by a protecting group R ⁹ and may have an ultraviolet absorbing ability after the removal of the protecting group R ⁹ .
Having ultraviolet absorptivity can be, for example, capable of absorbing light in a wavelength range of 250 nm to 450 nm.
More specifically, having ultraviolet absorbing ability can be such that the maximum absorption wavelength is 250 nm or more and 400 nm or less in a wavelength range of 250 nm or more and 600 nm or less, and in particular, is 260 nm or more and 390 nm or less Are preferable, and in particular, those which are 280 nm or more and 380 nm or less are preferable. It is because the said composition becomes easy to manufacture the hardened | cured material which has durability.
In addition, as a measuring method of the maximum absorption wavelength below, what was melt | dissolved so that it may become a density | concentration of 0.01 g / L in a solvent, for example, chloroform, can be used, for example.
For the maximum absorption wavelength, for example, a sample for evaluation is filled in a quartz cell (optical path length 10 mm, thickness 1.25 mm), and the absorbance is measured using an absorptiometer (for example, U-3900 (manufactured by Hitachi High-Tech Science) Can be obtained by measuring

The compound A can have a maximum absorption wavelength on the short wavelength side in a wavelength range of 250 nm to 600 nm as compared with that after removal of the protective group R ⁹ .
The difference of the maximum absorption wavelength of the compound A from that after removal of the protecting group R ⁹ can be 1 nm or more, preferably 1 nm to 100 nm, and particularly preferably 1 nm to 50 nm. Is preferred. It is because the said compound A becomes a thing excellent in the hardening inhibitory inhibitory effect because the difference of the largest absorption wavelength is the said range.

The compound A can be such that the protecting group R ⁹ is released by heating.
The temperature at which the protective group R ⁹ contained in the compound A is eliminated may be, for example, 100 ° C. or more and 300 ° C. or less, and in particular, preferably 120 ° C. or more and 250 ° C. or less, 150 ° C. or more It is preferable that it is 230 degrees C or less. It is because the said composition becomes easy to manufacture of the hardened | cured material which has durability because it is the said detachment temperature.
The desorption temperature can be measured using STA (differential thermal thermal simultaneous measurement device), and can be the start temperature of the first weight loss.
The measurement conditions of the start temperature of the first weight loss can be, for example, 10 mg of the compound A in a measurement container to set a measurement temperature range: 30 ° C. to 350 ° C., and a temperature rising rate: 10 ° C./min.
As a differential thermal thermal simultaneous measurement device, STA7000 (manufactured by Hitachi High-Tech Science Co., Ltd.) can be used.

Above all, the compound A is preferably a compound represented by the above general formula (A1) or (A3). Such a composition is because it is easy to produce a cured product having durability.

Said ^{^{^{R 1, R 2, R 1}}} ', R 2', R 1 ", R 2", R 3, R 4, R 5, R 6, R 7 and ^{R 8} and ^{R 9} (hereinafter, these are collectively The alkyl group having 1 to 40 carbon atoms which is used for R ¹ etc. may be methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl , Iso-amyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, Iso-octyl, tert-octyl, adamantyl and the like can be mentioned.
Examples of the alkyl group having 1 to 20 carbon atoms used for R ⁹ include those having a predetermined number of carbon atoms among the alkyl groups having 1 to 40 carbon atoms used for the above R ^{1 and the} like. it can.
Examples of the aryl group having 6 to 20 carbon atoms used for the above R ^{1 and the} like include phenyl, naphthyl, anthracenyl and the like.
Examples of the arylalkyl group having 7 to 20 carbon atoms used for the above R ^{1 and the} like include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl and the like.
Examples of the heterocycle-containing group having 2 to 20 carbon atoms used for R ^{1 and the} like described above include, for example, pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl 2, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinone-1-yl, 2-piperidone-1-yl, 2, 4-dioxyimidazolidin-3-yl, 2,4-dioxazolidin-3-yl and the like can be mentioned.
Examples of the alkenyl group having 2 to 20 carbon atoms used for R ⁹ include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl and the like.
Examples of trialkylsilyl groups used for R ⁹ include trimethylsilane, triethylsilane, ethyldimethylsilane and the like.
Examples of the alkyl group having 1 to 8 carbon atoms used for R ′ include those exemplified as the alkyl group used for R ^{1 and the} like, which can satisfy the predetermined number of carbon atoms.
In addition, each group such as the above-mentioned alkyl group, aryl group, arylalkyl group, heterocycle-containing group, alkenyl group and trialkylsilyl group may have a substituent, and in particular, unless otherwise specified. Or have no substituent or have a substituent.
As a substituent which substitutes hydrogen atoms, such as such an alkyl group, an aryl group, an arylalkyl group, a heterocyclic containing group, an alkenyl group, and a trialkylsilyl group, ethylenic properties, such as vinyl, an allyl, an acryl, methacryl, are mentioned, for example Unsaturated groups; halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, Acyl groups such as oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl; acyloxy groups such as acetyloxy and benzoyloxy; amino, ethyl Mino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, Phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbo Substituted amino groups such as lamino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, etc .; sulfonamide group, sulfonyl group, carboxyl group, cyano group, A sulfo group, a hydroxyl group, a nitro group, a mercapto group, an imide group, a carbamoyl group, a sulfonamide group, a phosphonic acid group, a phosphoric acid group or a carboxyl group, a sulfo group, a phosphonic acid group, a salt of a phosphoric acid group etc. can be mentioned. .

In the present invention, when the hydrogen atom in the group is substituted by a substituent, the number of carbon atoms of the group defines the number of carbon atoms of the group after the substitution. For example, when the hydrogen atom of the alkyl group having 1 to 40 carbon atoms is substituted, the term "C1 to 40 carbon atoms" refers to the number of carbon atoms after the hydrogen atom has been substituted, and the hydrogen atom is substituted Does not refer to the number of carbon atoms before the

^{^{^{R 1, R 2, R 1}}} ', R 2', alkyl group represented by ^{R 1} "and ^{R 2",} aryl group, arylalkyl group, heterocyclic ring-containing ^{^{^{group, R 3, R 4, R}}} 5, R ⁶ , alkyl groups represented by R ⁷ and R ⁸ , aryl groups, arylalkyl groups and heterocycle-containing groups, and alkyl groups represented by R ⁹ , alkenyl groups, aryl groups, arylalkyl groups, heterocycle-containing groups Group in each of the groups and trialkylsilyl groups is a carbon-carbon double bond, -O-, -S-, -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-, -NR'-,> P = O, -S-S-, -SO ₂ -or a combination thereof It may have been replaced. However, the number of carbon atoms of each group after replacement is 1 or more.
For example, the alkoxy group in which the methylene group at the end of the alkyl group is replaced by -O- includes methyloxy, ethyloxy, iso-propyloxy, butyloxy, sec-butyloxy, tert-butyloxy, iso-butyloxy, amyloxy, iso-amyloxy, tert-amyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy, tert- Heptyloxy, 1-octyloxy, iso-octyloxy, tert-octyloxy and the like.

In the present invention, when the methylene group in the group is replaced by the above divalent group, the number of carbon atoms of the group defines the number of carbon atoms of the group after the replacement. For example, in the present specification, when a methylene group in an alkyl group having 1 to 40 carbon atoms is replaced by the above divalent group, the “1 to 40 carbon atoms” means a group after a methylene group is replaced. It does not refer to the number of carbon atoms before the methylene group is replaced. Therefore, "an alkyl group having 1 to 20 carbon atoms in which the terminal methylene group is replaced by -CO-O-" is -CO-O-R ²⁰⁰ (where R ²⁰⁰ is an alkyl group having 1 to 19 carbon atoms) It corresponds to). In addition, “an alkyl group having 1 to 20 carbon atoms in which the terminal methylene group is replaced by —O—” corresponds to —O—R ²⁰¹ (R ²⁰¹ is an alkyl group having 1 to 20 carbon atoms) It is

At least one of R ¹ and R ² is -O-R ⁹ above.
It is preferable that ^{one of the} above R ¹ and R ² is the above-described —O—R ⁹ from the viewpoint of easy synthesis and further facilitates the production of a cured product having durability.
It said ^{R 1} and ^{R 2,} from the viewpoint of the larger the change in ultraviolet absorbing ability, it is preferable both ^{R 1} and ^{R 2} are ^{-O-R 9.}
In the above R ¹ and R ² , when only one is —O—R ⁹ , the other is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, the number of carbon atoms It is preferably an arylalkyl group of 7 to 20 or a heterocyclic group having 2 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 40 carbon atoms, and particularly preferably a hydrogen atom, The alkyl group is preferably an alkyl group of 1 to 5 carbon atoms, and particularly preferably a hydrogen atom or an unsubstituted alkyl group of 1 to 5 carbon atoms. It is because the said compound A will become a thing with a large change of ultraviolet-ray absorptivity by the other of said R < ¹ > and R < ² > being said group. Moreover, it is because the said compound A can suppress generation | occurrence | production of hardening inhibition. All matters set forth for R ¹ and ^{R 2} above may apply to ^{R 1} 'and ^{R 2',} also holds true for the ^{R 1} "and ^{R 2".}

R ⁹ is preferably an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 20 carbon atoms, particularly preferably It is preferable that it is an alkyl group having 1 to 8 carbon atoms. It is because the said compound A will become a thing with a large change of ultraviolet-ray absorptivity. Moreover, it is because the said composition becomes easy to manufacture of the hardened | cured material which has durability.
R ⁹ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or 2 carbon atoms In the case of a heterocycle-containing group of -20, those in which the terminal methylene group on the oxygen atom side is replaced by -CO-O-, that is, -CO-O- is bonded to the terminal on the oxygen atom side Is preferable.
More specifically, R ⁹ is an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms in which the terminal methylene group on the oxygen atom side is replaced by —CO—O— Is preferred.
An alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms in which the terminal methylene group at the oxygen atom side is replaced by —CO—O— is “* —CO—O—R It is a group represented by ³⁰⁰ ". In the formulas in “,” * represents a bond with an oxygen atom, and R ³⁰⁰ represents an alkyl group having 1 to 19 carbon atoms or an alkenyl group having 2 to 19 carbon atoms.
As R ⁹ , among the groups represented by “* —CO—O—R ³⁰⁰ ”, the terminal methylene group on the oxygen atom side is replaced by —CO—O— and it has 1 to 20 carbon atoms It is preferably an alkyl group, particularly preferably an alkyl group having 1 to 8 carbon atoms in which the terminal methylene group on the oxygen atom side is replaced by -CO-O-, and above all, especially on the oxygen atom side Preferably, the terminal methylene group of is substituted by —CO—O— and is an alkyl group having 1 to 8 carbon atoms which has no substituent, among which —CO—O—C ₄ H ₉ It is preferable that it is a group represented, and it is particularly preferable that it is a -CO-O-tert-butyl group. This is because, for example, R ⁹ can be easily eliminated by heating to generate a phenolic hydroxyl group. Moreover, as a result, the composition described above facilitates the production of a cured product having durability.
In addition, as what has the alkyl group by which the methylene group of the terminal of the oxygen atom side is substituted by -CO-O-, the compound etc. which are represented by general formula (A1-1) mentioned later are mentioned, for example it can.

R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 each} represents a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, 6 to 20 carbon atoms Or an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, preferably a halogen atom or an alkyl group having 1 to 40 carbon atoms, and the substituent Alkyl groups having 1 to 40 carbon atoms which do not have an alkyl group, alkyl groups having 1 to 40 carbon atoms having an ethylenically unsaturated group as a substituent, and carbons in which the methylene group at the end is replaced by -O- An alkyl group having 1 to 40 atoms (an alkoxy group having 1 to 40 carbon atoms), an alkyl group having 1 to 40 carbon atoms in which a methylene group is replaced by -O-CO-, or a methylene group at an end is- Replaced by O- Preferably, it is an alkyl group having 1 to 40 carbon atoms (an alkoxy group having 1 to 40 carbon atoms) in which the methylene group in the chain is replaced by —O—CO—, and has a substituent An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms having no substituent, an alkoxy having 1 to 20 carbon atoms having at least an ethylenically unsaturated group as a substituent Group, an alkyl group having 1 to 20 carbon atoms which has no substituent in which a methylene group is replaced by -O-CO-, or a substituent in which a methylene group in the chain is replaced by -O-CO- It is preferably an alkoxy group having 1 to 20 carbon atoms which is not contained, and in particular, an alkyl group having 1 to 10 carbon atoms not having a substituent, or 1 to 10 carbon atoms having no substituent. 10 alkoxy groups, As the group, an alkoxy group having 1 to 10 carbon atoms having at least an ethylenically unsaturated group, an alkyl group having 1 to 10 carbon atoms having no substituent in which a methylene group is replaced by —O—CO— It is preferable that the methylene group in the chain is an alkoxy group having 1 to 10 carbon atoms which does not have a substituent substituted with —O—CO—.
Above R ³ is preferably a halogen atom.
Above all, R ⁴ is preferably an alkoxy group having 1 to 10 carbon atoms which has no substituent.
As R ⁴ , an alkyl group having 1 to 20 carbon atoms which does not have a substituent can also be preferably used, and among them, an alkyl group having 3 to 15 carbon atoms having no substituent is preferable. Is preferable, and an alkyl group having 5 to 12 carbon atoms which does not have a substituent is preferable.
As R ⁵ and R ⁶ , an alkyl group having 1 to 10 carbon atoms which does not have a substituent can also be preferably used, and among them, an alkyl group having 1 to 5 carbon atoms having no substituent is particularly preferable. Is preferred.
R ⁷ is preferably a C 1 to C 10 alkoxy group having at least an ethylenically unsaturated group as a C 1 to C 10 alkyl group having no substituent or a substituent. It is preferable that it is an alkyl group having 1 to 5 carbon atoms which does not have a substituent, or an alkoxy group having 2 to 6 carbon atoms which has at least an ethylenically unsaturated group as a substituent.
R ⁷ represents an alkoxy group having 1 to 15 carbon atoms having no substituent can be preferably used. It is possible inter alia, an alkoxy group having 2 to 8 carbon atoms having no substituent Is preferred.
In addition, as what has a C1-C10 alkoxy group which does not have a substituent, the compound etc. which are represented by general formula (A3-1) mentioned later can be mentioned, for example.
Examples of the substituent having at least an ethylenically unsaturated group and having an alkoxy group having 1 to 10 carbon atoms include, for example, compounds represented by General Formula (A3-2) described later, and the like. .
When R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the groups described above, the composition can easily produce a cured product having durability.
Also, the bonding position of R ⁴ may be any position that can be bonded, but for example, it is preferable that it is para to the bonding position of —O—R ⁹ .
Further, the bonding position of R ⁵ may be any position that can be bonded, but for example, the meta position is preferable with respect to the bonding position of —O—R ⁹ .
Further, the bonding position of R ⁶ may be any position that can be bonded, but for example, the meta position is preferable with respect to the bonding position of —O—R ⁹ .
Further, the bonding position of R ⁷ may be any position that can be bonded, but may be, for example, an ortho position or a meta position with respect to the bonding position of —O—R ⁹ .

Although the above a1 and a3 are integers of 0 to 4, the production of a cured product having durability is facilitated, and from the viewpoint of easiness of synthesis, they are each independently an integer of 0 to 3 Among these, an integer of 0 to 2 is preferable, and in particular, 0 to 1 is preferable.
The a 2 is an integer of 0 to 2, but is preferably 1 to 2 from the viewpoint of solubility. It is because the said composition becomes easy to manufacture of the hardened | cured material which has durability.
The above a4 and a5 are integers of 0 to 3, but they are preferably integers of 0 to 2 from the viewpoint of easiness of synthesis because they facilitate the production of a cured product having durability. It is preferably 1 or 2.
Although the above a 6 is an integer of 0 to 3 m 3, it is preferable that it is an integer of 0 to 1, and it is 0, from the viewpoint of easiness of production of a cured product having durability and ease of synthesis. Is preferred.
The above m1 is an integer of 1 to 10, but is preferably 2 or more from the viewpoint of obtaining a cured product excellent in durability, and in particular, is preferably an integer of 2 to 6, In particular, an integer of 2 to 4 is preferable.
Although m 2 is an integer of 1 to 10, it is preferably an integer of 1 to 5 and particularly preferably an integer of 1 to 2 from the viewpoint of obtaining a cured product excellent in durability. preferable.
The above m3 is an integer of 1 to 3, but from the viewpoint of obtaining a cured product excellent in durability, it is preferably 2 or more, and more preferably 3 in particular.

The compounds A represented by the above general formulas (A1) and (A2) are each an m monovalent or m divalent (hereinafter referred to as m valence) represented by X ^a1 and X ^a2 (hereinafter sometimes referred to as X). Or a direct bond, or a specific atom or group or a direct bond, may have a structure in which m1 or m2 (hereinafter sometimes referred to as m) specific groups are bonded. The m specific groups are identical to or different from one another.

The above X represents an m-valent atom or a bonding group or a direct bond.
Specifically as the above atom or bonding group X, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a group represented by the following (II-a) or (II-b),> C = O,> NR ⁵³ , -OR ⁵³ , -SR ⁵³ , -NR ⁵³ R ⁵⁴ or an aliphatic hydrocarbon group having 1 to 120 carbon atoms having the same number of valences as m, an aromatic ring having 6 to 35 carbon atoms And R ⁵³ and R ^{54 each} represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, or an aromatic having 6 to 35 carbon atoms. And a ring-containing hydrocarbon group or a heterocyclic ring-containing group having 2 to 35 carbon atoms, wherein the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group and the heterocyclic ring-containing group are —O—, —S— and —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 -, - NR '} -, - S-S -, - SO 2 -, might be replaced by nitrogen atoms, or combinations thereof, aromatic or heterocyclic ring-containing in the aromatic ring-containing hydrocarbon radical The heterocycle in the group may be fused to another ring.
However, in the case where the bonding group X is a nitrogen atom, a phosphorus atom or a bonding group represented by the following (II-a) or (II-b), m is 3 and the bonding group X is an oxygen atom or a sulfur atom, In the case of C = O, —NH—CO—, —CO—NH— or> NR ⁵³ , m is 2 and when the linking group X is —OR ⁵³ , —SR ⁵³ or —NR ⁵³ R ⁵⁴ , m is And the linking group X may form a ring together with the benzene ring.

(* Indicates that it is a bond to an adjacent group in the * part.)

As the aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same valence as m used for the bonding group X, as m is monovalent, for example, methyl, ethyl, propyl, isopropyl, cyclopropyl and the like , Butyl, sec-butyl, tert-butyl, isobutyl, amyl, iso-amyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3 Alkyl groups such as heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl and the like; methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, Tert-Butyloxy, isobutylo S, amyloxy, isoamyloxy, tertiary amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy, Alkoxy groups such as decyloxy and the like; methylthio, ethylthio, propylthio, isopropylthio, butylthio, sec-butylthio, tert-butylthio, isobutylthio, amylthio, isoamylthio, tert-amylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, tert-heptylthio, Alkylthio groups such as n-octylthio, isooctylthio, tertiary octylthio, 2-ethylhexylthio and the like; vinyl, 1-methylethenyl, 2-methylethenyl 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl And alkenyl groups such as tricocenyl, and groups in which these groups are substituted by a substituent described later, and the like.
m is bivalent; alkylene such as methylene, ethylene, propylene, butylene and butyldiyl; the methylene chain of the above alkylene is replaced by -O-, -S-, -CO-O- or -O-CO- Residues of diols such as ethanediol, propanediol, butanediol, pentanediol, hexanediol, etc. Residues of dithiols such as ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, hexanedithiol and these groups will be described later Groups substituted by substituents, etc.,
As m is trivalent, for example, alkylpyridines such as propyridine and 1,1,3-butyridine and the like, and groups in which these groups are substituted by a substituent described later can be mentioned.
As a C6-C35 aromatic ring containing hydrocarbon group which has valence of the same number as m, m is monovalent and arylalkylalkyl such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl etc. Groups; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthyloxy; arylthio groups such as phenylthio and naphthylthio; and groups in which these groups are substituted by a substituent described later, etc.
and arylene and arylene groups such as phenylene and naphthylene; and residues of bifunctional phenols such as catechol and bisphenol as m is a divalent group; 2,4,8,10-tetraoxaspiro [5,5] undecane etc. and groups thereof Groups substituted by a substituent described later, and
Examples of trivalent m include phenyl-1,3,5-trimethylene and a group in which these groups are substituted by a substituent described later.
As a C2-C35 heterocycle-containing group having the same number of valences as m, pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, as m is a monovalent group. Imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinone-1-yl, 2-piperidone -1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxazolidin-3-yl, benzotriazolyl and the like, and groups in which these groups are substituted by the substituents described below Raising It is,
Groups in which m is a divalent ring and which have a pyridine ring, pyrimidine ring, piperidine ring, piperidine ring, piperazine ring, triazine ring, furan ring, thiophene ring, indole ring and the like, and groups in which these groups are substituted by substituents Listed
Examples of the group in which m is trivalent include a group having an isocyanuric ring, a group having a triazine ring, and a group in which these groups are substituted by a substituent described later.
Examples of the aliphatic hydrocarbon group R ⁵³ and the carbon atoms 1 to 35 for use in R ^54, an aliphatic hydrocarbon group or an aliphatic hydrocarbon group having a carbon number of 1 to 120 for use in the linking group X is later Among the groups substituted by the substituent to be substituted, those having a predetermined number of carbon atoms can be mentioned,
The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or the heterocyclic ring-containing group having 2 to 35 carbon atoms, which is used for R ⁵³ and R ^54, includes 6 to 35 carbon atoms used for the bonding group X Examples thereof include an aromatic ring-containing hydrocarbon group, a heterocyclic ring-containing group having 2 to 35 carbon atoms, or a group in which these groups are substituted by a substituent described later.
Each group such as the above-mentioned aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group-containing group may have a substituent, and unless otherwise noted, has a substituent. It is absent or has a substituent.
The substituent such as the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group and the heterocyclic group-containing group has the same content as the substituent that substitutes a hydrogen atom such as an alkyl group used for R ¹ etc. be able to.

When m is 2 as the bonding group X, a group represented by the following general formula (1) can be used.
When m is 3, the linking group X can be a group represented by the following general formula (2).
When m is 4 as the linking group X, a group represented by the following general formula (3) can be used.
When m is 5 as the bonding group X, a group represented by the following general formula (4) can be used.
When m is 6, the linking group X can be a group represented by the following general formula (5).

(In the above general formula (1), Y ¹ represents a single bond, —CR ⁵⁵ R ⁵⁶ —, —NR ⁵⁷ —, divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, 6 to 35 carbon atoms Or an aromatic ring-containing hydrocarbon group or a heterocyclic ring-containing group having 2 to 35 carbon atoms, or any substituent represented by the following (1-1) to (1-3): The methylene group in the aliphatic hydrocarbon group of 1 to 35, the aromatic ring-containing hydrocarbon group of 6 to 35 carbon atoms, and the heterocyclic ring-containing group of 2 to 35 carbon atoms is -O-, -S-,- CO-, -CO-O-, -O-CO- or -NH- or a combination of these groups may be substituted,
R ⁵⁵ and R ^{56 each} represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
Z ¹ and Z ² are each independently a direct bond, -O-, -S-,> CO, -CO-O-, -O-CO-, -SO _2- , -SS-, -SO-, Represents> NR ⁵⁸ or> PR ⁵⁸ ,
R ⁵⁷ and R ^{58 each} represents 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 heterocycle containing group having 2 to 35 carbon atoms ,
The * means that at the * part, it bonds to an adjacent group. )

(Wherein, R ⁵⁹ represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms, and R ⁶⁰ represents an alkyl group having 1 to 10 carbon atoms) And an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the above alkyl group, alkoxy group and alkenyl group may have a substituent, and c1 is 0 It is an integer of ~ 5, and * means that it bonds to an adjacent group at the * part.)

(* Indicates that it is a bond to an adjacent group in the * part.)

(In the above formula, R ⁶¹ and R ⁶² each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or the like An arylthio group of 6 to 20, an arylalkenyl group of 6 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms, a heterocycle-containing group of 2 to 20 carbon atoms, or a halogen atom; The methylene group in the arylalkyl group may be replaced by an unsaturated bond, -O- or -S-,
R ⁶¹ may form a ring between adjacent R ^{61 's} ,
c2 represents a number from 0 to 4;
c3 represents a number from 0 to 8,
c4 represents a number from 0 to 4;
c5 represents a number from 0 to 4;
The sum of the numbers of c4 and c5 is 2 to 4,
The * means that at the * part, it bonds to an adjacent group. )

(In the above general formula (2), Y ¹¹ is a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, or 6 to 35 carbon atoms Represents an aromatic ring-containing hydrocarbon group or a heterocyclic ring-containing group having 2 to 35 carbon atoms,
Z ¹ , Z ² and Z ³ are each independently a direct bond, -O-, -S-,> CO, -CO-O-, -O-CO-, -SO _2- , -SS-,- SO—,> NR ⁶² , PR ⁶² , 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 ring-containing group having 2 to 35 carbon atoms ,
R ⁶² represents 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 heterocycle containing group having 2 to 35 carbon atoms,
The methylene group in each of the above aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups having 6 to 35 carbon atoms and heterocyclic ring containing groups having 2 to 35 carbon atoms has a carbon-carbon double bond, -O-, It may be replaced by -CO-, -O-CO-, -CO-O- or -SO _2- . * Represents a part of *, which means to bond to an adjacent group. )

(In the above general formula (3), Y ¹² represents a carbon atom or a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or 2 carbon atoms Represents a heterocyclic ring-containing group of-35, and in the aliphatic hydrocarbon group having 1 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and the heterocyclic ring-containing group having 2 to 35 carbon atoms The methylene group of may be replaced by -CO-O-, -O-, -O-CO-, -NH-CO-, -NH- or -CO-NH-, and Z ¹ to Z ⁴ may be And each independently a group in the same range as the groups represented by Z ¹ to Z ³ in the above general formula (2) * represents a part *, which means to bond to an adjacent group)

(In the above general formula (4), Y ¹³ is a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 30 carbon atoms, or 2 to 30 carbon atoms Represents a hetero ring-containing group, and is an aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and a methylene group in the heterocyclic ring containing group having 2 to 35 carbon atoms ^May be replaced by -CO-O-, -O-, -O-CO-, -NH-CO-, -NH- or -CO-NH-, and Z ¹ to Z ⁵ are each independently In the above general formula (2), it is a group in the same range as the groups represented by Z ¹ to Z ^3. * indicates that * part is to be bonded to an adjacent group.)

(In the above general formula (5), Y ¹⁴ is a single bond, a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or 2 carbon atoms Represents a heterocycle-containing group of -35, wherein the aliphatic hydrocarbon group having 2 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or the heterocycle-containing group having 2 to 35 carbon atoms In which the methylene group may be replaced by -CO-O-, -O-, -O-CO-, -NH-CO-, -NH- or -CO-NH-, and Z ¹ to Z ⁶ is And each independently a group in the same range as the groups represented by Z ¹ to Z ³ in the above general formula (2) * represents a part *, which means to bond to an adjacent group)

The divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms used for Y ¹ in the group represented by the above general formula (1) is methane, ethane, propane, iso-propane, butane, sec-butane Tert-butane, iso-butane, hexane, 2-methylhexane, 3-methylhexane, heptane, 2-methylheptane, 3-methylheptane, iso-heptane, tert-heptane, 1-methyloctane, iso-octane, tert-octane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, 2,4-dimethylcyclobutane, 4-methylcyclohexane and the like, and divalent groups substituted with Z ¹ and Z ² can be mentioned. The group is -O-, -S-, -CO-, -CO-O-, -O-CO-, -NH- or Might be replaced by a group composed of a combination of these,
Examples of the divalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms include divalent groups in which groups such as phenylene, naphthylene and biphenyl are substituted with Z ¹ and Z ² , and the like
Examples of divalent heterocyclic groups having 2 to 35 carbon atoms include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chromane, xanthene, thiophene, thiolane and the like. Divalent groups substituted with ¹ and Z ² can be mentioned.
These groups may be further substituted by a halogen atom, a cyano group, a nitro group or an alkoxy group having 1 to 8 carbon atoms.
Each group such as the above-mentioned aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group-containing group may have a substituent, and unless otherwise noted, has a substituent. There are no unsubstituted or substituted ones.
The substituent such as the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group and the heterocyclic group-containing group has the same content as the substituent that substitutes a hydrogen atom such as an alkyl group used for R ¹ etc. be able to.

The alkyl group having 1 to 8 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the arylalkyl group having 7 to 20 carbon atoms which are used for R ⁵⁵ and R ⁵⁶ in the group represented by the above general formula (1) Among the contents exemplified as R ^{1 and the} like described above, those having a predetermined number of carbon atoms can be mentioned.

An aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and a carbon atom number used for R ⁵⁷ and R ⁵⁸ in the group represented by the above general formula (1) The heterocycle-containing group of 2 to 35 can be the same as the contents exemplified as R ⁵³ and R ⁵⁴ described above.

The cycloalkyl group having 3 to 10 carbon atoms used for R ⁵⁹ in the group represented by the above general formula (1-1) includes cyclopropyl, cyclobutyl, cyclopentyl, cyclobutyl, cyclooctyl and the like, and groups thereof Is a C 1 -C 10 alkyl group or a group substituted with a C 1 -C 10 alkoxy group,
Examples of the alkyl group having 1 to 10 carbon atoms and the alkoxy group having 1 to 10 carbon atoms which are used for R ⁶⁰ include those having a predetermined number of carbon atoms among the contents exemplified as the above R ^{1 and the} like,
As the alkenyl group having 2 to 10 carbon atoms, among those exemplified as the above R ^{1 and the} like, those having a predetermined number of carbon atoms can be mentioned.
The phenyl group, the alkyl group, the alkoxy group and the alkenyl group in the general formula (1-1) may have a substituent. Such a substituent may have the same contents as the substituent that substitutes a hydrogen atom such as an alkyl group used for R ¹ and the like.
The alkyl group, alkoxy group and alkenyl group in the above R ⁶⁰ may be, for example, those substituted with a halogen atom, and the position of substitution is not limited.

As the alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the arylalkyl group having 7 to 20 carbon atoms, which are used for the group represented by the above general formula (1-3), Among the contents exemplified as the above R ¹ etc., those satisfying a predetermined number of carbon atoms are mentioned,
Examples of the aryloxy group having 6 to 20 carbon atoms include phenyloxy, naphthyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy, 4-vinylphenyldioxy, 3-iso-propylphenyl Oxy, 4-iso-propylphenyloxy, 4-butylphenyloxy, 4-tert-butylphenyloxy, 4-hexylphenyloxy, 4-cyclohexylphenyloxy, 4-octylphenyloxy, 4- (2-ethylhexyl) Phenyloxy, 2,3-dimethylphenyloxy, 2,4-dimethylphenyloxy, 2,5-dimethylphenyloxy, 2.6-dimethylphenyloxy, 3.4-dimethylphenyloxy, 3.5-dimethylphenyloxy , 2,4-di tert-bu Rephenyloxy, 2,5-di-tert-butylphenyloxy, 2,6-di-tert-butylphenyloxy, 2.4-di-tert-pentylphenyloxy, 2,5-tert-amylphenyloxy, 4-cyclo Groups such as hexylphenyloxy, 2,4,5-trimethylphenyloxy, ferrocenyloxy and the like, and groups in which these groups are substituted with a halogen atom;
As the arylthio group having 6 to 20 carbon atoms, a group in which an oxygen atom of an aryloxy group having 6 to 20 carbon atoms which may be substituted with the above-mentioned halogen atom is substituted with a sulfur atom, etc.
As the arylalkenyl group having 8 to 20 carbon atoms, an oxygen atom of the aryloxy group having 6 to 20 carbon atoms which may be substituted by the above-mentioned halogen atom can be vinyl, allyl, 1-propenyl, isopropenyl, 2 And groups substituted with an alkenyl group such as butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl and the like.
Examples of the heterocycle-containing group having 2 to 20 carbon atoms include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, hexahydrotriazine, furan, tetrahydrofuran, chromane, xanthene, thiophene, thiofuran and the like, and groups thereof Are groups substituted with a halogen atom.
In addition, each group such as the above aryloxy group, arylthio group, arylalkenyl group, heterocyclic group and the like may have a substituent, and unless otherwise noted, has a substituent. There are no unsubstituted or substituted ones.
Examples of the substituent that substitutes a hydrogen atom such as an aryloxy group, an arylthio group, an arylalkenyl group, and a heterocycle-containing group are the same as the substituents that substitute a hydrogen atom such as an alkyl group used for R ¹ and the like. It can be content.

The trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms used for Y ¹¹ in the group represented by the general formula (2) is exemplified in the description of the bonding group X in the general formula (1) Examples thereof include trivalent groups in which an aliphatic hydrocarbon group having 1 to 120 carbon atoms is substituted by Z ¹ , Z ² and Z ³ , and methylene groups in these groups are —O—, —S— , -CO-, -CO-O-, -O-CO-, -SO _2- , -NH- or a combination thereof may be substituted,
As the trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms exemplified in the description of the bonding group X in the general formula (1) is ^And trivalent groups substituted with ¹ , Z ² and Z ³ ;
Examples of the trivalent heterocyclic group having 2 to 35 carbon atoms include the heterocyclic group having 2 to 35 carbon atoms exemplified in the description of the bonding group X in the above general formula (1) includes Z ¹ and Z ² and include trivalent group substituted by Z ^3.

Aliphatic hydrocarbon group having 1 to 35 carbon atoms, aromatic ring-containing carbon having 6 to 35 carbon atoms, which is used for Z ¹ , Z ² and Z ³ and R ⁶² in the group represented by the above general formula (2) The hydrogen group and the heterocycle-containing group having 2 to 35 carbon atoms can be the same as the contents exemplified as R ⁵³ and R ⁵⁴ described above.

The tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms used for Y ¹² in the group represented by the general formula (3) is exemplified in the description of the bonding group X in the general formula (1) Examples thereof include tetravalent groups in which an aliphatic hydrocarbon group having 1 to 120 carbon atoms is substituted with Z ¹ , Z ² , Z ³ and Z ⁴ , and a methylene group in the aliphatic hydrocarbon group is O-, -S-, -CO-, -COO-, -OCO-, -NH- or a combination of these groups may be substituted,
As the tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms exemplified in the description of the bonding group X in the general formula (1) is ^And tetravalent groups substituted with ¹ , Z ² , Z ³ and Z ⁴ ,
As the tetravalent heterocyclic group having 2 to 35 carbon atoms, the heterocyclic group having 2 to 35 carbon atoms exemplified in the description of the bonding group X in the general formula (1) is exemplified by Z ¹ and Z ² , Z ³ and Z ⁴ substituted tetravalent groups.

The pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms used for Y ¹³ in the group represented by the general formula (4) is exemplified in the description of the bonding group X in the general formula (1) And a pentavalent group in which the aliphatic hydrocarbon group having 1 to 120 carbon atoms is substituted with Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ , and a methylene group in the aliphatic hydrocarbon group. May be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -SO _2- , -NH- or a combination of these,
As the pentavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms exemplified in the description of the bonding group X in the general formula (1) is Z ^And pentavalent groups substituted with ¹ , Z ² , Z ³ , Z ⁴ and Z 5, and
As the pentavalent heterocyclic group having 2 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms exemplified in the description of the bonding group X in the general formula (1) is Z ¹ , The pentavalent group substituted by Z < ² >, Z < ³ >, Z < ⁴ > and Z <5> is mentioned.

The hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms used for Y ¹⁴ in the above general formula (5) includes 1 to 8 carbon atoms exemplified in the description of the bonding group X in the above general formula (1) And a hexavalent group in which the aliphatic hydrocarbon group of 120 is substituted by Z ¹ , Z ² , Z ³ , Z ⁴ , Z 5 and Z ⁶ , and the methylene group in the aliphatic hydrocarbon group is O-, -S-, -CO-, -COO-, -OCO-, -SO _2- , -NH- or a combination of these groups may be substituted,
As the hexavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms exemplified in the description of the bonding group X in the general formula (1) is ^A hexavalent group substituted by ¹ , Z ² , Z ³ , Z ⁴ , Z 5 and Z ⁶ ,
As the hexavalent heterocyclic group having 2 to 35 carbon atoms, the heterocyclic group having 2 to 35 carbon atoms exemplified in the description of the bonding group X in the general formula (1) is exemplified by Z ¹ and Z ² And Z ³ , Z ⁴ , Z ⁵ and Z ⁶ substituted hexavalent groups.

When m is 2 as the bonding group X, an aliphatic hydrocarbon group having 1 to 120 carbon atoms can be preferably used, and in particular, an alkylene group having 1 to 10 carbon atoms or a residue of a diol is preferable. It is preferably an alkylene group having 1 to 5 carbon atoms such as a methylene group having 1 carbon atom, and particularly preferably an alkylene group having 1 to 3 carbon atoms. This is because the production of a cured product having durability is easy and the production of compound A is easy.

In the present invention, when (1) m is 2, the above-mentioned X is preferably a substituent represented by the following general formula (101) or (102) or a group selected from the following group 1. The above X is a group selected from the following group 2 when (2) m is 3, and a group selected from the following group 3 when (3) m is 4, and (4) m is 5 It is preferable that it is a group selected from the following group 4 and (5) a group selected from the following group 5 when m is 6. It is because manufacture of the hardened | cured material which has durability is easy, and also acquisition and manufacture of a raw material are easy.

( ^Wherein , each of Y ¹¹¹ and Y ¹¹⁵ independently represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent,
Y ¹¹² and ^{Y 114} each independently, -O -, - CO -, - CO-O -, - O-CO -, - NR 13 -, - CO-NR 13 - or ^-NR 13 -CO- in Represents a group to be represented,
R ¹³ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent,
Y ¹¹³ ^{^{is, -CR 14 R 15 -, -}} NR 16 -, a divalent a group which may have a substituent aliphatic hydrocarbon group having a carbon number of 1 to 35, have a substituent R 6 represents an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may be substituted or a substituent represented by the following general formula (103):
R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
R ¹⁶ is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, an aromatic ring having 6 to 35 carbon atoms which may have a substituent Represents a heterocyclic group having 2 to 35 carbon atoms which may have a hydrocarbon group or a substituent,
One or more of the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group, and the methylene group in the heterocycle-containing group used for Y ¹¹¹ , Y ¹¹⁵ , R ¹³ , Y ¹¹³ and R ¹⁶ are —COO— , -O-, -OCO-, -NHCO-, -NH- or -CONH- in some cases,
* Represents a bonding point. )

(Wherein, each of Y ¹¹⁶ and Y ¹¹⁸ independently represents —NR ¹⁷ — or an aliphatic hydrocarbon group having 1 to 8 carbon atoms in which a methylene group may be replaced by an oxygen atom,
Y ¹¹⁷ is a direct bond, -O-, -S-, -SO _2- , -CR ¹⁸ R ¹⁹ -or the above (1-1), (1-2) or (1-3) Represents any substituent,
R ¹⁷ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent,
R ¹⁸ and R ¹⁹ each independently represent an alkyl group having 1 to 8 carbon atoms which may be substituted with a hydrogen atom or a halogen atom,
* Represents a bonding point. )

(Wherein, R ³¹ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, or 6 to 35 carbon atoms which may have a substituent) Or an aromatic ring-containing hydrocarbon group or a heterocyclic ring-containing group having 2 to 35 carbon atoms which may have a substituent,
* Represents a bonding point. )

(Wherein, Y ¹¹⁹ and Y ¹²⁰ each independently represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent,
* Represents a bonding point. )

(Wherein, R ³² is the same group as R ⁵⁷ in the above general formula (1), and when there are two or more in the group, it may be the same or different, and Z ¹¹ may be the above general formula (2 Group in the same range as the group represented by Z ¹ to Z ³ in
* Represents a bonding point. )

(Wherein, Z ¹⁰ , Z ¹¹ , Z ¹² , Z ¹³ and Z ¹⁴ each represent a group in the same range as the groups represented by Z ¹ to Z ³ in the general formula (2),
* Represents a bonding point. )

(In the above formula, Z ¹⁰ , Z ¹¹ , Z ¹² , Z ¹³ , Z ¹⁴ and Z ¹⁵ each represent a group in the same range as the groups represented by Z ¹ to Z ³ in the above general formula (2),
* Represents a bonding point. )

In addition, examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent used for Y ¹¹¹ , Y ¹¹⁵ , Y ¹¹⁶ , Y ¹¹⁸ , Y ¹¹⁹ and Y ¹²⁰ include Y ^{1 and the} like. Among the contents exemplified as the aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a divalent substituent used in the above, one having a predetermined number of carbon atoms can be mentioned.
In the above formula (101), Y ¹¹¹ and Y ¹¹⁵ may be the same or different.
Similarly, Y ¹¹⁶ and Y ¹¹⁸ in the above formula (102) and Y ¹¹⁹ and Y ¹²⁰ in the above formula (103) may be identical to or different from each other.
An aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a divalent substituent and an aromatic having 6 to 35 carbon atoms which may have a substituent, which may be used for Y ¹¹³ The ring-containing hydrocarbon group may have a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a divalent substituent used for Y ¹ or the like. The same content as the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms can be used.
Aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent used for R ¹³ , R ¹⁶ , R ¹⁷ and R ³¹ , and carbon atom number which may have a substituent The aromatic ring-containing hydrocarbon group having 6 to 35 and the heterocyclic ring-containing group having 2 to 35 carbon atoms which may have a substituent include substituents used for R ⁵³ and R ^{54 and the} like The aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent, and the substituent may be The content may be similar to that of a heterocyclic group having a carbon number of 2 to 35.
Examples of the alkyl group having 1 to 8 carbon atoms, the aryl group having 6 to 20 carbon atoms and the arylalkyl group having 7 to 20 carbon atoms used for R ¹⁴ , R ¹⁵ , R ¹⁸ and R ¹⁹ include R ^{1 and the} like The same contents as those satisfying the predetermined number of carbon atoms among the alkyl group having 1 to 40 carbon atoms, the aryl group having 6 to 20 carbon atoms and the arylalkyl group having 7 to 20 carbon atoms used for Can.
A plurality of ^{Z 11} each other included in each equation of the group 2 and group 3, ^{^Z} 10 ^~ ^Z ¹⁵ contained in the formula of ^Z 10 ^{~ 14} and the group 5 included in each equation of the group 4 , May be identical or different.

The bonding position of the bonding group X to the benzene ring may be any bondable position within the benzene ring, for example, the ortho position or the meta position relative to the bonding position of -O-R ⁹ Is preferred. It is because manufacture of the hardened | cured material which has durability becomes easy.

The Xa1, when the m1 = 1, is preferably the same group as a hydrogen atom or an ^{R 4.}
The Xa2, when the m @ 2 = 1, is preferably the same group as a hydrogen atom or ^{R 6.}

Specific examples of the compound A include the compounds specifically described in WO 2014/021023, such as the compounds represented below.

Although the compound A may contain a phenolic hydroxyl group not protected by the protecting group R ⁹ , the number of phenolic hydroxyl groups contained in the compound A is preferably 2 or less, and 0 Is preferred. It is because the said compound A can suppress generation | occurrence | production of hardening inhibition.

The molecular weight of the compound A can be set according to the application of the compound A and the like.
The molecular weight can be, for example, 250 or more and 5000 or less, can be 300 or more and 2500 or less, and can be 350 or more and 1500 or less.
In addition, the said molecular weight can be represented by a weight average molecular weight (Mw), when the compound A is a polymer which contains a repeating structure as the structure.
The weight average molecular weight (Mw) can be determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC).
The weight average molecular weight Mw is, for example, HLC-8120 GPC manufactured by Tosoh Corp., and the elution solvent is N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide is added, and the polystyrene standard for calibration curve is Mw 377400 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (above, Easi PS-2 series manufactured by Polymer Laboratories) and Mw 1090000 (manufactured by Tosoh Corp.), and the measurement column is TSK-GEL ALPHA- It can be obtained by measurement as M × 2 (made by Tosoh Corp.).
Also, the measurement temperature can be 40 ° C., and the flow rate can be 1.0 mL / min.

Although the manufacturing method of the said compound A will not be specifically limited if it is a method which can obtain a desired structure, For example, it can be made into the method similar to the method as described in WO 2014/021023.

3. Compound B
The compound B is represented by the general formula (B).
Further, the compound B has a phenolic hydroxyl group is protected by a protecting group R ¹¹ structure, after elimination of the protective group R ^11, can be assumed to have antioxidant ability.
More specifically, having the ability to prevent oxidation means that it has a function of suppressing oxidation by heat, light and other energy of the substance after elimination of the above-mentioned protecting group R ¹¹ and has a radical scavenging action. be able to.

The compound B, as compared to after elimination of the protective group R ^11, those radicals scavenging is low.
The compound B, as compared to after elimination of the protective group R ^11, low radical scavenging action, residual film ratio before and after exposure of the photocurable composition (%) can be high.
The difference (%) in residual film ratio between the compound B and the compound after removal of the protective group R ¹¹ may be at least 0.1%, but may be 1.0% or more. And preferably 5.0% or more, and more preferably 10% or more. It is because manufacture of the hardened | cured material which has durability becomes easy.
The residual film ratio (%) is the film thickness after exposure and development with respect to the film thickness before exposure relative to the photocurable composition (film thickness after exposure and film thickness after exposure / film thickness before exposure × 100 (% Can be obtained from
The photocurable composition can include a radically polymerizable compound, a radical photopolymerization initiator, and a compound after elimination of the compound B or the protective group R ¹¹ , for example, as described in Examples to be described later. It can be made to be the same as the composition of Comparative Example 2 or Comparative Example 4 described in the section.
Further, as a method of measuring the residual film rate, for example, the method of “1. sensitivity evaluation 1” described in the embodiment described later can be used.

The compound B can be such that the protective group R ¹¹ is released by heating.
The temperature at which the protecting group R ¹¹ contained in the compound B is eliminated may be, for example, the same as the contents described in the section “2. Compound A”.

The alkyl group having 1 to 20 carbon atoms, the alkenyl group having 2 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, and the number of carbon atoms used for R ¹¹ Examples of the heterocycle-containing group or trialkylsilyl group of 2 to 20 include the same ones as described above as the group represented by R ⁹ in the section of “2. Compound A” above.
The alkyl group having 1 to 40 carbon atoms used for R ¹² , R ¹³ and R ¹⁴ , the aryl group having 6 to 20 carbon atoms represented by R ¹⁴ , the arylalkyl group having 7 to 20 carbon atoms, carbon The heterocycle-containing group having 2 to 20 atoms can be the same as the contents exemplified as R ^{1 and the} like in the section of “2. Compound A” above.
Examples of the alkyl group having 1 to 8 carbon atoms represented by R ′ in —NR′— which may replace a methylene group in each group represented as R ¹¹ , R ¹² , R ¹³ and R ¹⁴ include the above “ 2. In the section of Compound A, the same contents as exemplified as R ′ can be used.

The above R ¹¹ protects the phenolic hydroxyl group.
Such R ¹¹ can be the same as R ⁹ described in the section “2. Compound A” above.

R ¹² and R ¹³ are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms having no substituent. , in ^particular, it is preferred that either or both of ^{R 12} and ^{R 13} is a group represented by _-C 4 _{H 9,} among others in either or both of tert- butyl group ^{R 12} and ^{R 13} Is preferred. It is because manufacture of the hardened | cured material which has durability becomes easy.
At least one of R ¹² and R ¹³ is preferably an alkyl group having 1 to 40 carbon atoms, and in particular, both R ¹² and R ¹³ are an alkyl group having 1 to 40 carbon atoms. Is preferred. It is because manufacture of the hardened | cured material which has durability becomes easy.
Both of R ¹² and R ¹³ are preferably, for example, an alkyl group having 1 to 10 carbon atoms which does not have a substituent such as a tert-butyl group. It is because manufacture of the hardened | cured material which has durability becomes easy.

The R ¹⁴ is preferably an alkyl group having 1 to 40 carbon atoms. It is because manufacture of the hardened | cured material which has durability becomes easy.

The above n is an integer of 1 to 10, but is preferably an integer of 2 to 6 and more preferably an integer of 3 to 5 from the viewpoint of easiness of synthesis. It is because it becomes easy to obtain the hardened | cured material excellent in durability.

The above b1 is an integer of 0 to 2, but it is preferably 0 to 1 from the viewpoint of easiness of synthesis because it facilitates the production of a cured product having durability.

The compound B has a structure in which a specific n-valent atom represented by X ^b and n specific groups are bonded. The n specific groups are identical to or different from one another.

The bonding group X ^b represents an n-valent bonding group.
As such a linking group X ^b , the same contents as those of the linking group X described in the above “2. Compound A” can be used.
The bonding group X ^b is preferably a group represented by the above general formula (3), for example, when n is 4. It is because manufacture of the hardened | cured material which has durability becomes easy.
Y ¹² in the general formula (3) is preferably a carbon atom or a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, and more preferably a carbon atom. It is because manufacture of the hardened | cured material which has durability becomes easy.
Z ¹ to Z ⁴ in the above general formula (3) are -O-, -S-,> CO, -CO-O-, -O-CO-, -SO _2- , -SS-, -SO- > NR ⁶² , PR ⁶² and is preferably an aliphatic hydrocarbon group having 1 to 35 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 35 carbon atoms, and the methylene group is —COO— It is preferable that it is a C1-C40 aliphatic hydrocarbon group which is substituted by -O-, -OCO-, -NHCO-, -NH- or -CONH-, and the methylene at the terminal of Y ¹² side An aliphatic hydrocarbon group having 1 to 40 carbon atoms which does not have a substituent in which the group is replaced by -COO- or -OCO- can also be preferably used, and among them, a methylene group at the terminal of Y ¹² side Is substituted by -COO- or -OCO- A it is preferably to 1 to 10 carbon atoms is not aliphatic hydrocarbon group. This is because the production of a cured product having durability is easy, and furthermore, the production of compound B is easy.

In the present invention, when n is 2, the X ^b group is preferably a group represented by the above general formula (101).
In the above general formula (101), Y ¹¹¹ is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a substituent, and in particular, one or more unsubstituted carbon atoms may be substituted. It is preferable that it is an alkylene group of -3.
In the above general formula (101), Y ¹¹² is preferably -O- or -CO-O-, and Y ¹¹⁴ is preferably -O- or -O-CO-.
In the general formula (101), Y ¹¹³ is preferably a group represented by the general formula (103).
In the above general formula (103), Y ¹¹⁹ and Y ¹²⁰ are preferably aliphatic hydrocarbon groups having 1 to 5 carbon atoms which may have a substituent, and in particular, 2 or more carbon atoms It is preferably a linear or branched alkylene group of -5.
In the present invention, when n is 2, as the X ^b group, a group represented by the above general formula (102) can also be preferably used.
In the general formula ^{(102), Y 117} ^{is, -CR} 18 ^{R 19} - is preferably, among ^others, an aliphatic hydrocarbon group of ^{R 18} and ^{R 19} is a hydrogen atom or 1 to 4 carbon atoms It is preferable that R ¹⁸ be a hydrogen atom, and R ¹⁹ be an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
In the present invention, when n is 3, the group X ^b is preferably a group represented by (II-2), (II-3) or (II-6) in group 2.
In the general formulas (II-2), (II-3) and (II-6), Z ¹¹ is a direct bond or an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent And is preferably a direct bond or an unsubstituted C 1 -C 5 alkylene group.
In the general formulas (II-2), (II-3) and (II-6), a plurality of Z ¹¹ included in each formula may be the same or different.
Among them, in the present invention, at least one of three Z ^{11 in} the general formula (II-2) is a direct bond, and at least one is an unsubstituted alkylene group having 1 to 5 carbon atoms preferable. In general formulas (II-3) and (II-6), it is preferable that all of Z ^{11 be} unsubstituted alkyl groups having 1 to 5 carbon atoms.
In formulas (II-2) and (II-3), R ³² is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, Among them, a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent is preferable, and a hydrogen atom is particularly preferable.
In the present invention, when n is 4, it is preferable that the group X ^b be a group represented by (III-1) in group 3, instead of or in addition to the above-mentioned preferable group. In the general formula (III-1), Z ¹¹ may have a substituent, and the methylene group is a carbon-carbon double bond, -O-, -CO-, -O-CO-, -CO It is preferably an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may be substituted by -O- or -SO _2- , and the methylene group is substituted by -O-CO- or -CO-O-. Preferably, it is an alkylene group having 1 to 5 carbon atoms.
When the X ^b group is the above-mentioned group, the compound B can stably exhibit the antioxidant ability after the removal of the protecting group R ¹⁰² . Moreover, as a result, it is because manufacture of the hardened | cured material which has durability becomes easy.

The bonding position of the bonding group X ^{b to} the benzene ring may be any bondable position within the benzene ring, and for example, it is para to the bonding position of R ¹¹ -O-. Is preferred. By the coupling position is the position described above, the compound B is a leaving before and after the protective group R ^11, because becomes large changes in antioxidant capacity.

The above X ^b is preferably a hydrogen atom or a group similar to R ¹⁴ when n = 1.

Specific examples of the compound B include the compounds specifically described in WO 2014/021023, such as the compounds represented below.

The number, molecular weight, production method and the like of the phenolic hydroxyl group contained in the compound B can be the same as the contents described in the section of “2. Compound A”.

4. Resin Component The above composition can contain a resin component.
As such a resin component, the above-mentioned compounds A and B can be held, and it is suitably set according to the use etc. of a composition. And polymers having no polymerizable group, and the like, and among them, it is preferable to contain a polymerizable compound. It is because the said composition can exhibit the effect that manufacture of hardened | cured material is easy more effectively.
Specifically, the composition described above is able to more effectively exhibit the effect of facilitating the production of a cured product by containing the compound A having a small absorption of the irradiated light.
Moreover, it is because the said composition can be used as a photocurable composition, a thermosetting composition, etc., for example by including a polymeric compound as said resin component.

(1) Polymerizable Compound The above-mentioned polymerizable compound may be any one capable of forming a polymer, and usually has a polymerizable group.
Such polymerizable compounds differ depending on the type of polymerizable group, that is, the type of polymerization reaction, and examples thereof include radically polymerizable compounds, cationically polymerizable compounds, anionically polymerizable compounds, etc. However, it is preferable to include a radically polymerizable compound. It is because the said composition can exhibit the effect that manufacture of hardened | cured material is easy more effectively.
Specifically, the above composition is capable of more effectively exerting the effect that the production of a cured product is easy by containing the compound B in which the radical supplementing action is suppressed.

(A) Radically Polymerizable Compound The radically polymerizable compound may have one or more radically polymerizable group and may contain two or more radically polymerizable group.
The above-mentioned radical polymerizable compound is usually used together with a radical polymerization initiator.
As a radically polymerizable polymerizable group, ethylenic unsaturated double bond groups, such as a (meth) acryl group and a vinyl group, can be mentioned, for example.
In addition, (meth) acryl is used by the meaning containing an acryl and methacryl. Also, (meth) acrylate is used in the meaning including acrylate and methacrylate.

The radically polymerizable compound may be a compound having an acid value, or may be a compound having no acid value.
As a compound which has an acid value, the compound etc. which have a carboxyl group can be mentioned, for example.
By containing the compound which has an acid value as a radically polymerizable compound, the said composition reduces the solubility to the alkali developing solution of a light irradiation site | part, for example. Therefore, the composition can be used, for example, as a photosensitive composition whose solubility in a solvent such as an alkaline developer changes before and after light irradiation. More specifically, the above-mentioned composition can be used as a negative working composition by including a compound having an acid value.
As an alkali developing solution, what is generally used as alkali developing solutions, such as tetramethyl ammonium hydroxide (TMAH) aqueous solution and potassium hydroxide aqueous solution, can be used.

Among the above radical polymerizable compounds, for example, compounds having an ethylenically unsaturated double bond group and having an acid value include (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid , Fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetate, allyl acetate, cinnamic acid, sorbic acid, sorbic acid, mesaconic acid, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (phthalate) Mono (meth) acrylate, hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acryloyloxy ethyl ester], ω-carboxy polycaprolactone mono (meth) acrylate, and other polymers having a carboxy group and a hydroxyl group at both ends Meta) acrylate malate, dicyclopentadiene malate or one Unsaturated polybasic acids such as polyfunctional (meth) acrylates having a ruboxyl group and two or more (meth) acryloyl groups; phenol and / or cresol novolac epoxy resin, novolac epoxy resin having a biphenyl skeleton and a naphthalene skeleton, bisphenol Anovolak type epoxy compounds, novolac type epoxy compounds such as dicyclopentadiene novolac type epoxy compounds, polyphenylmethane type epoxy resins having a multifunctional epoxy group, epoxy resins such as epoxy compounds represented by the following general formula (III) An epoxy group of an epoxy resin such as a resin obtained by reacting an unsaturated monobasic acid with an epoxy group or an epoxy compound represented by the following general formula (III) is reacted with an unsaturated monobasic acid, and a polybasic acid anhydride is further Resin obtained by reaction, pentaerythritol Examples include polyfunctional acrylates having an acid value, which are reaction products of hydroxyl group-containing polyfunctional acrylates such as triacrylate and dipentaerythritol pentaacrylate and dibasic acid anhydrides such as succinic anhydride, phthalic anhydride and tetrahydrophthalic anhydride. Be

(Wherein, X ⁴¹ represents a direct bond, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O-, -S-, -SO _2- , -SS- Or —SO—, —CO—, —OCO— or a substituent represented by (1-1) to (1-3) above,
R ⁴¹ , R ⁴² , R ⁴⁴ and R ⁴⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or Represents a halogen atom,
d is an integer of 0 to 10; )

Examples of the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 8 carbon atoms, and the alkenyl group having 2 to 5 carbon atoms include those exemplified as R ^{1 and the} like in the section of “2. Compound A”. Among them, those having a predetermined number of carbon atoms can be mentioned.
Examples of the alkylidene group having 1 to 4 carbon atoms include methylidene, ethylidene, propylidene and butylidene.
Examples of the alicyclic hydrocarbon group include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl and the like.
The above-mentioned alkyl group, alkoxy group, alkenyl group, alkylidene group, alicyclic hydrocarbon group etc. may have a substituent, and unless otherwise noted, has a substituent. There are no unsubstituted or substituted ones.

The content of the compound having an acid value can be appropriately set according to the application of the composition, etc., but can be, for example, 30 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the resin component The content is preferably 35 parts by mass or more and 70 parts by mass or less, and particularly preferably 40 parts by mass or more and 60 parts by mass or less. When the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity.

Among the above radical polymerizable compounds, for example, as a compound having an ethylenically unsaturated double bond group and not having an acid value, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2- Hydroxypropyl, glycidyl (meth) acrylate, the following compound No. 1 A1 to No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate ( (Meth) acrylate isooctyl, (meth) acrylate isononyl, (meth) acrylate stearyl, (meth) acrylate lauryl, (meth) acrylate methoxyethyl, (meth) acrylate dimethylaminomethyl, (meth) acrylate dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meth ) Ethyl hexyl acrylate, (meth) acrylic acid Phenoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethane tri ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloyl ethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Polyhydric alcohol or ester of polyhydric phenol; Metal salt of unsaturated polybasic acid such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrofuran Phthalic anhydride-anhydrous Acid anhydride of unsaturated polybasic acid such as leic acid adduct, dodecenyl succinic anhydride, methyl hymic acid anhydride; (meth) acrylamide, methylene bis (meth) acrylamide, diethylene triamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyhydric amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanation Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylene Unsaturated aromatic compounds such as 2-phenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allylamine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; unsaturated imides such as maleimide, N-phenyl maleimide, N-cyclohexyl maleimide; And indenes such as 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl (meth) acrylate, poly-n- Macromonomers having a mono (meth) acryloyl group at the end of polymer molecular chain such as chill (meth) acrylate and polysiloxane; (meth) acrylonitrile, other vinyl such as ethylene, propylene, butylene, vinyl chloride and vinyl acetate Compounds, and macromonomers such as polymethyl methacrylate macromonomer and polystyrene macromonomer, monomethacrylate of tricyclodecane skeleton, N-phenylmaleimide, methacryloyloxymethyl-3-ethyl oxetane, etc., and (meth) acrylic acid Polymers and copolymers of (meth) acrylic acid obtained by reacting an isocyanate compound having an unsaturated bond such as Karenz MOI manufactured by Showa Denko KK and AOI with these, vinyl chloride, vinylidene chloride, divinyl succ Nath, Allyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl urethane compound of hydroxyl group-containing vinyl monomer and polyisocyanate compound, hydroxyl group-containing vinyl monomer And vinyl epoxy compounds of polyepoxy compounds, and reaction products of hydroxyl group-containing polyfunctional acrylates such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate with polyfunctional isocyanates such as tolylene diisocyanate and hexamethylene diisocyanate.
The number of radically polymerizable polymerizable groups contained in the compound having no acid value may be 1 or more, preferably 2 or more and 10 or less, and more preferably 3 or more and 8 or less.
The compound having no acid value may be a mixture of compounds having different numbers of polymerizable groups. This is because, for example, the adjustment of the curing speed and the hardness of the cured product becomes easy.
The compound having no acid value is, for example, a mixture of a compound having 3 polymerizable groups and a compound having 4 polymerizable groups, a compound having 5 polymerizable groups, and 6 polymerizable groups. And the like, and the like.

The content of the compound not having an acid value can be appropriately set according to the application etc. of the composition, but can be, for example, 10 parts by mass to 70 parts by mass with respect to 100 parts by mass of the resin component. And 30 parts by mass or more and 60 parts by mass or less, and more preferably 40 parts by mass or more and 50 parts by mass or less. When the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity.

The said radically polymerizable compound can be used individually or in mixture of 2 or more types. In addition, the radically polymerizable compound has an ethylenically unsaturated double bond group, and uses a compound having an acid value and a compound having an ethylenically unsaturated double bond group and not having an acid value in combination. Can.
When a radically polymerizable compound is used in mixture of 2 or more types, they may be copolymerized beforehand and it may be used as a copolymer.

(B) Cationic Polymerizable Compound and Anionic Polymerizable Compound The cationic polymerizable compound may be one having one or more cationically polymerizable groups.
The cationically polymerizable compound is usually used together with a cationic polymerization initiator.
Examples of the cationically polymerizable polymerizable group include cyclic ether groups such as an epoxy group and an oxetane group, and a vinyl ether group.
That is, as a cationically polymerizable compound, cyclic ether compounds, such as an epoxy compound and an oxetane compound, a vinyl ether compound, etc. are mentioned.

Examples of the above epoxy compounds include methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, C12 to 13 mixed alkyl glycidyl ether, phenyl 2-methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, glycidyl methacrylate, isopropyl glycidyl ether, allyl glycidyl ether, ethyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 4-n-butylphenyl Glycidyl ether, 4-phenylphenol glycidyl ether, cresyl glycidyl Ether, dibromocresyl glycidyl ether, decyl glycidyl ether, methoxy polyethylene glycol monoglycidyl ether, ethoxy polyethylene glycol monoglycidyl ether, butoxy polyethylene glycol monoglycidyl ether, phenoxy polyethylene glycol monoglycidyl ether, dibromophenyl glycidyl ether, 1,4-butane Diol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,1,2,2-tetrakis (glycidyloxyphenyl) ethane and pentaerythritol Glycidyl ether compounds such as tetraglycidyl ether; glycidyl acetate, Glycidyl esters such as sidyl stearate; 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, methylene bis (3,4-epoxycyclohexane), propane-2, 2-Diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, ethylene bis (3,4-epoxycyclohexane carboxylate), bis (3,4-epoxycyclohexyl) Methyl) adipate, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl 3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4 -Epoxycyclohexyl 6-Methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl 3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl , 4-Epoxy-5-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, dicyclopentadiene diepoxide, 3,4-epoxy-6- Examples thereof include epoxy cycloalkyl type compounds such as methyl cyclohexyl carboxylate, α-pinene oxide, styrene oxide, cyclohexene oxide and cyclopentene oxide, and N-glycidyl phthalimide.

Moreover, an epoxidized polyolefin can also be used as said epoxy compound. The epoxidized polyolefin is a polyolefin in which an epoxy group is introduced by modifying the polyolefin with an epoxy group-containing monomer. It can be produced by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and, if necessary, another monomer, by any of a copolymerization method and a graft method. Ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer and another monomer may be polymerized alone or in combination with other monomers. Also, the double bond of a non-conjugated polybutadiene having a hydroxyl group at the end can be obtained by epoxidation by the peracetic acid method, and one having a hydroxyl group in the molecule may be used. Moreover, a hydroxyl group can be urethane-ized with isocyanate, and a primary hydroxyl group-containing epoxy compound can be made to react here, and an epoxy group can be introduce | transduced.

Examples of ethylene or α-olefins of 3 to 20 carbon atoms include ethylene, propylene, butylene, isobutylene, 1,3-butadiene, 1,4-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3 -Butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and the like can be mentioned.

Examples of the epoxy group-containing monomer include glycidyl esters of α, β-unsaturated acids, vinyl benzyl glycidyl ether and allyl glycidyl ether. Specific examples of glycidyl esters of α, β-unsaturated acids include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylic acid, with glycidyl methacrylate being particularly preferred.

Examples of the other monomers include unsaturated aliphatic hydrocarbons such as vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, Fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, sorbic acid, mesaconic acid, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (metha] phthalic acid ) Acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. Mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) ) Acrylate malate, dicyclopentadiene · And unsaturated polybasic acids such as polyfunctional (meth) acrylates having one carboxyl group and two or more (meth) acryloyl groups; 2-hydroxyethyl (meth) acrylate, (meth) acrylate -2-Hydroxypropyl, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n (meth) acrylate -Octyl, isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, (meth ) Dimethylaminoethyl acrylate, aminopropyl (meth) acrylate, (meth) acrylic acid Dimethylaminopropyl, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) Tetrahydrofuryl acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylol ethane Li (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tri Unsaturated monobasic acids such as cyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate and polyester (meth) acrylate oligomers and esters of polyhydric alcohols or polyhydric phenols; (meth) acrylic acid Zinc, metal salts of unsaturated polybasic acids such as magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydroanhydride Phthalic acid, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride Adducts, acid anhydrides of unsaturated polybasic acids such as dodecenyl succinic anhydride and methyl hymic acid anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylene triamine tris (meth) acrylamide, xylylene bis (meth) acrylamide, Amides of unsaturated monobasic acids and polyvalent amines such as α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide, unsaturated aldehydes such as acrolein, (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, Shea Unsaturated nitriles such as allyl chloride; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfone Acids, unsaturated aromatic compounds such as 4-vinylbenzene sulfonic acid, vinyl benzyl methyl ether and vinyl naphthalene; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinyl amine, allylamine, N-vinyl pyrrolidone and vinyl piperidine Vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether and isobutyl vinyl ether; maleimide, N-phenyl maleate Unsaturated imides such as nmid and N-cyclohexyl maleimide; indens such as indene and 1-methyl indene; polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane Macromonomers having a mono (meth) acryloyl group at the terminal of: vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, Vinylcarbazole, vinylpyrrolidone, vinylpyridine, vinyl urethane compound of hydroxyl group-containing vinyl monomer and polyisocyanate compound, vinyl epoxy compound of hydroxyl group-containing vinyl monomer and polyepoxy compound Hydroxyl group-containing polyfunctional acrylate such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate; Reactant of polyfunctional isocyanate such as tolylene diisocyanate and hexamethylene diisocyanate; Hydroxyl group-containing polyfunctional such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate A multifunctional acrylate having an acid value which is a reaction product of an acrylate and a dibasic acid anhydride such as succinic anhydride, phthalic anhydride and tetrahydrophthalic anhydride can be mentioned.

A commercial item can also be used as said epoxidized polyolefin, For example, Epolide PB3600, Epolide PB4700 (made by Daicel); BF-1000, FC-3000 (made by ADEKA); Bond first 2C, bond first E, bond First CG 5001, Bond First CG 5004, Bond First 2 B, Bond First 7 B, Bond First 7 L, Bond First 7 M, Bond First VC 40 (Sumitomo Chemical Co., Ltd.); JP-100, JP-200 (Nippon Soda Co., Ltd.); Poly bd R And -45 HT, Poly bd R-15 HT (manufactured by Idemitsu Kosan Co., Ltd.) and Ricon 657 (manufactured by Arkema).

From the viewpoint of good heat resistance, it is more preferable to use a compound having a cardo skeleton as the above-mentioned epoxy compound.

Examples of the above-mentioned oxetane compounds include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, and 1,2-bis [(3-Ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, Triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1 , 6-Bis (3-ethyl-3-oxetanylmethoxy) hexane, 3-ethyl-3- (Phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane and 3- Ethyl 3- (chloromethyl) oxetane and the like can be mentioned.

Examples of the vinyl ether compounds include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, 2- Examples thereof include hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether and 1,6-cyclohexane dimethanol divinyl ether.

As the above-mentioned anionically polymerizable compound, those having one or more polymerizable groups capable of anionic polymerization may be used.
The above-mentioned anionically polymerizable compound is usually used together with an anionic polymerization initiator.
As said anionizable polymerizable group, an epoxy group, a lactone group, a (meth) acryl group etc. can be mentioned, for example.
That is, as the above-mentioned anion polymerization compound, an epoxy compound, a lactone compound, a compound which has a (meth) acryl group, etc. are mentioned.
Examples of the lactone compound include β-propiolactone and ε-caprolactone.
In addition, as an epoxy compound, the epoxy compound illustrated as said cationically polymerizable compound can be used. Moreover, as a compound which has a (meth) acryl group, what was illustrated as said radically polymerizable compound can be used.

The said cationically polymerizable compound and anionically polymerizable compound can be used individually or in mixture of 2 or more types, respectively.

(C) Molecular Weight of Polymerizable Compound The molecular weight of the above-mentioned polymerizable compound is appropriately set according to the use of the composition etc. be able to.
In addition, said molecular weight can be represented by a weight average molecular weight (Mw), when a polymeric compound is a polymer which contains a repeating structure as the structure.
The content of the polymerizable compound may be any amount as long as the composition can be used as a curable composition, but 1 part by mass or more in a total of 100 parts by mass of the compound A, the compound B and the polymerizable compound It can be 99 parts by mass or less, preferably 50 parts by mass or more and 99 parts by mass or less, and particularly preferably 80 parts by mass or more and 99 parts by mass or less. When the content is in the above-mentioned range, the composition is easy to use as a curable composition, and the effect of improving the durability such as light resistance and heat resistance of the curable composition is improved. It is because it can demonstrate more effectively.

(2) Polymer The above-mentioned polymer has no polymerizable group.
As such a polymer, any polymer having a repeating structure may be used, and a photosensitive resin having photosensitivity, a non-photosensitive resin having no photosensitivity, and the like can be mentioned.
The said composition can be used as a photosensitive composition, for example by including photosensitive resin as a resin component.

(A) Photosensitive resin The above-mentioned photosensitive resin has photosensitivity, and is used together with an acid generator, for example, dissolution of a chemical bond such as an ester group or acetal group by the action of an acid, etc. Mention may be made of positive resins which change in the direction in which the properties increase.
The composition described above contains a positive resin as a resin component, whereby the solubility of the light-irradiated portion in the alkali developer is increased.
Therefore, the composition can be used, for example, as a positive type composition, more specifically, as a photosensitive composition whose solubility in a solvent such as an alkaline developer changes before and after light irradiation.

As the positive resin, those obtained by partially replacing a high molecular weight polymer with an acid labile group having alkali solubility control ability can be used.
As the above-mentioned polymer, polyhydroxystyrene and derivatives thereof; polyacrylic acid and derivatives thereof; polymethacrylic acid and derivatives thereof; hydroxystyrene, acrylic acid, methacrylic acid and derivatives thereof and two or more formed Copolymer: two or more copolymers selected from hydroxystyrene, styrene and their derivatives, cycloolefin and its derivatives, maleic anhydride, and three or more copolymers selected from acrylic acid and its derivatives Combined; cycloolefin and derivatives thereof, maleimide, and three or more copolymers selected from acrylic acid and derivatives thereof; polynorbornene; at least one polymer selected from the group consisting of metathesis ring-opening polymers Etc. can be mentioned.
The acid labile group to be introduced into the above-mentioned polymer includes heteroalicyclic groups such as tertiary alkyl group, trialkylsilyl group, oxoalkyl group, aryl group substituted alkyl group, tetrahydropyran-2-yl group, etc. Tertiary alkylcarbonyl groups, tertiary alkylcarbonylalkyl groups, alkyloxycarbonyl groups and the like can be mentioned.

Detailed examples of the positive resin are the same as the contents described in, for example, JP-A-2003-192665, JP-A-2004-323704, claim 3, JP-A-10-10733, etc. Can.

A well-known acid generator can be used as an acid generator used with said positive resin. Specifically as said acid generator, the photocationic polymerization initiator mentioned later, a thermal cationic polymerization initiator, etc. can be mentioned.

(B) Non-Photosensitive Resin The above-mentioned non-photosensitive resin may be any one which does not have photosensitivity, for example, polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene -(Meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66 Nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, phenoxy resin, polyamide imide resin, polyamic acid resin, epoxy resin and the like.
As the non-photosensitive resin, for example, a polymer of the above-mentioned polymerizable compound can also be used.

(C) Molecular Weight of Polymer The weight average molecular weight (Mw) of the polymer is appropriately set according to the application etc. of the composition, but can be, for example, 1500 or more, and 1500 or more and 300000 or less It can be done.

(3) Resin component The content of the above-mentioned resin component is appropriately set according to the application etc. of the composition, for example, 1 to 99 parts by mass with respect to 100 parts by mass of solid content. The amount is preferably 20 parts by mass or more and 95 parts by mass or less, and more preferably 30 parts by mass or more and 90 parts by mass or less. It is because the said composition can hold | maintain the said compound B stably, for example, because the said content is the above-mentioned range.
The content of the resin component can be 1 part by mass or more and 99 parts by mass or less, and is 50 parts by mass or more and 99 parts by mass or less in 100 parts by mass of the compound A, the compound B and the resin component. Among them, 80 parts by mass or more and 99 parts by mass or less are preferable. It is because the said composition can hold | maintain the said compound A and the compound B stably, for example, because the said content is the above-mentioned range. Moreover, it is because the effect of improving durability, such as light resistance of a curable composition and heat resistance, can be exhibited more effectively.
The total content of the resin component, the compound A and the compound B can be 1 part by mass or more in 100 parts by mass of the composition, and in particular, 10 parts by mass or more and 99 parts by mass or less The amount is preferably 30 parts by mass or more and 95 parts by mass or less, and more preferably 50 parts by mass or more and 70 parts by mass or less. It is because the said composition becomes easy to manufacture of the hardened | cured material which has durability.

The type of the resin component may be only one type or a combination of two or more types.
The resin component may contain, for example, only one or both of the polymerizable compound and the polymer.
When the resin component contains both a polymerizable compound and a polymer, the content of the polymerizable compound can be appropriately set according to the application etc. of the composition, for example, the polymerizable compound and the polymer It can be 1 part by mass or more and 99 parts by mass or less with respect to 100 parts by mass.

5. Other Components The above composition may contain other components, as necessary, in addition to the compound A, the compound B and the resin component.
The above-mentioned other components can include a polymerization initiator, a colorant, a solvent, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound, an acid catalyst, a base catalyst and the like.

(1) Polymerization Initiator The above-mentioned polymerization initiator is contained as a curable component, and is usually used together with a polymerizable compound or the like.
The above-mentioned polymerization initiator may be any one capable of polymerizing a polymerizable compound, for example, a photopolymerization initiator capable of polymerizing a polymerizable compound by receiving light irradiation, and can polymerize a polymerizable compound by heating And thermal polymerization initiators.
The polymerization initiator is preferably a photopolymerization initiator from the viewpoint of effectively exerting the effect that the composition can be easily cured even when the composition contains the compound A and the compound B.

(A) Photopolymerization initiator The above-mentioned photopolymerization initiator may be any one capable of polymerizing the polymerizable compound by receiving light irradiation, for example, photo radical polymerization initiator, photo cationic polymerization initiator, photo anion A polymerization initiator etc. can be mentioned.

The photo radical polymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and conventionally known compounds can be used.
As said photo radical polymerization initiator, an acetophenone type compound, a benzyl type compound, a benzophenone series compound, a thioxanthone type compound, an oxime ester type compound etc. can be illustrated as a preferable thing, for example.

Examples of the above-mentioned acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl- 2-Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiary butyl dichloroacetophenone, p-tertiary butyl trichloroacetophenone, p-azidoben Salacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl ) -Butanone-1, b Zoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane -1- on and the like.

Examples of the above-mentioned benzyl compound include benzyl and the like.

Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide. Be

Examples of the thioxanthone compound include thioxanthone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone and the like.

As the above-mentioned oxime compound, particularly, a compound represented by the following general formula (IV) can be mentioned because the sensitivity and heat resistance are good.

(Wherein, R ⁷¹ and R ⁷² each independently represent a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms A group or a heterocycle-containing group having 2 to 20 carbon atoms,
R ⁷³ and R ⁷⁴ each independently represent a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, R ⁷⁵ , OR ⁷⁶ , SR ⁷⁷ , NR ⁷⁸ R ⁷⁹ , COR ⁸⁰ , SOR ⁸¹ , SO ₂ R ⁸² or It represents CONR ⁸³ ^{R ^84,} R ⁷³ and ^{R 74} are, may have bonded to each other to form a ring,
R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ are each independently an alkyl group having 1 to 20 carbon atoms and 6 to 6 carbon atoms 30 aryl groups, arylalkyl groups having 7 to 30 carbon atoms, or heterocycle-containing groups having 2 to 20 carbon atoms,
X ³ represents an oxygen atom, a sulfur atom, a selenium atom, CR ⁸⁵ R ⁸⁶ , CO, NR ⁸⁷ or PR ⁸⁸ ,
X ⁴ represents a single bond or CO;
R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms Represents
Each of the above alkyl groups or arylalkyl groups may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a heterocycle-containing group,
The methylene group in each of the above alkyl groups or arylalkyl groups may be replaced by -O-,
R ⁷³ and R ⁷⁴ may independently form a ring together with either of adjacent benzene rings,
e1 represents an integer of 0 to 4;
e2 represents an integer of 0 to 5; )

The carbon number of 1 used in R ⁷¹ , R ⁷² , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ in the above general formula (IV) Examples of the alkyl group of -20, the aryl group of 6 to 30 carbon atoms, the arylalkyl group of 7 to 30 carbon atoms, the heterocycle-containing group of 2 to 20 carbon atoms, and the substituents thereof include the above-mentioned "2. Among the contents exemplified as R ^{1 and the} like in the item of the compound A, those having a predetermined number of carbon atoms can be mentioned.

Examples of the oxime-based compound include: ethanone-1- [9-ethyl-6- (2-methylbenzoyl-9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl -6-Benzoyl-9H-carbazol-3-yl-octan-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethane- 1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethan-1-one oxime-O-benzoate, ethanone-1- [ 9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Non-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl -6- (2-Methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4 -(2,2-Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-) Carbazole-based ox having a carbazole structure such as methyl-4-tetrahydrofuranyl methoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) Muesuteru compounds.

As the oxime compound, for example, an indole oxime ester compound having an indole structure can also be used.
As an indole type oxime ester compound, the oxime ester compound etc. which are represented by the following general formula (V) described in international publication 2017/051680 can be mentioned, for example.

(Wherein, R ²⁰¹ and R ²⁰² each independently represent R ²¹¹ , OR ²¹¹ , COR ²¹¹ , SR ²¹¹ , CONR ²¹² R ²¹³ or CN,
R ²¹¹ , R ²¹² and R ²¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom Represents a heterocycle-containing group of 2 to 20,
The hydrogen atoms of the groups represented by R ²¹¹ , R ²¹² and R ²¹³ further include R ²²¹ , OR ²²¹ , COR ²²¹ , SR ²²¹ , NR ²²² R ²²³ , CONR ²²² R ²²³ , NR ²²² OR ²²³ , NCOR ²²² OCOR ²²³ , NR ²²² COR ²²¹ , OCOR ²²¹ , COOR ²²¹ , SCOR ²²¹ , OCSR ²²¹ , COSR ²²¹ , CSOR ²²¹ , and may be substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or COOR ²²¹ ,
R ²²¹ , R ²²² and R ²²³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom Represents a heterocycle-containing group of 2 to 20,
The hydrogen atom of the group represented by R ²²¹ , R ²²² and R ²²³ may be further substituted by a hydroxyl group, a nitro group, CN, a halogen atom, a hydroxyl group or a carboxyl group,
Methylene groups in the alkylene portion of the group represented by ^{^{^{^{R 211, R 212, R 213}}}} , R 221, R 222 and ^{R 223} is, -O -, - S -, - COO -, - OCO -, - OCOO-, ^{^{^{^{-CONR 224 -, - NR 224 -}}}} , - NR 224 CO -, - NR 224 COO -, - OCONR 224 -, - SCO -, - COS -, - OCS- or it may have been replaced by -SCOO- ,
R ²²⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocycle-containing group having 2 to 20 carbon atoms Represent
The alkyl part of the group represented by R ²¹¹ , R ²¹² , R ²¹³ , R ²²¹ , R ²²² , R ²²³ and R ²²⁴ may have branched side chains and may be cyclic alkyl,
R ²⁰³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocycle-containing group having 2 to 20 carbon atoms And the alkyl portion of the group represented by R ²⁰³ may have branched side chains and may be cyclic alkyl, and R ²⁰³ and R ²⁰⁷ and R ²⁰³ and R ²⁰⁸ together respectively. May form a ring,
The hydrogen atom of the group represented by R ²⁰³ is further R ²²¹ , OR ²²¹ , COR ²²¹ , SR ²²¹ , NR ²²² R ²²³ , CONR ²²² R ²²³ , NR ²²² OR ²²³ , NCOR ²²² OCOR ²²³ , NR ²²² COR ²²¹ , OCOR ²²¹ , COOR ²²¹ , SCOR ²²¹ , OCSR ²²¹ , COSR ²²¹ , CSOR ²²¹ , and may be substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or COOR ²²¹ ,
R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are each independently R ²¹¹ , OR ²¹¹ , SR ²¹¹ , COR ²¹⁴ , CONR ²¹⁵ R ²¹⁶ , NR ²¹² COR ²¹¹ , OCOR ²¹¹ , COOR ²¹⁴ , SCOR ²¹¹ , OCSR ²¹¹ , COSR ²¹⁴ , CSOR ²¹¹ , a hydroxyl group, CN or a halogen atom, and R ²⁰⁴ and R ²⁰⁵ , R ²⁰⁵ and R ^206, and R ²⁰⁶ and R ²⁰⁷ may together form a ring, respectively.
The hydrogen atoms of the groups represented by R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are further R ²²¹ , OR ²²¹ , COR ²²¹ , SR ²²¹ , NR ²²² R ²²³ , CONR ²²² R ²²³ , NR ²²² OR ²²³ , NCOR ²²² It may be substituted by OCOR ²²³ , NR ²²² COR ²²¹ , OCOR ²²¹ , COOR ²²¹ , SCOR ²²¹ , OCSR ²²¹ , COSR ²²¹ , CSOR ²²¹ , a hydroxyl group, a nitro group, CN, a halogen atom or COOR ²²¹ ,
R ²¹⁴ , R ²¹⁵ and R ^{216 each} represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
The alkyl part of the groups represented by R ²¹⁴ , R ²¹⁵ and R ²¹⁶ may have branched side chains and may be cyclic alkyl,
R ²⁰⁸ represents R ²¹¹ , OR ²¹¹ , SR ²¹¹ , COR ²¹¹ , CONR ²¹² R ²¹³ , NR ²¹² COR ²¹¹ , OCOR ²¹¹ , COOR ²¹¹ , SCOR ²¹¹ , OCSR ²¹¹ , COSR ²¹¹ , CSOR ²¹¹ , a hydroxyl group, CN or a halogen atom Represents
n1 represents 0 or 1; )

The number of carbon atoms used in R ²⁰³ , R ²¹¹ , R ²¹² , R ²¹³ , R ²¹⁴ , R ²¹⁵ , R ²¹⁶ , R ²²¹ , R ²²² , R ²²³ and R ²²⁴ in the above general formula (V) Examples of the alkyl group, the aryl group having 6 to 30 carbon atoms, the arylalkyl group having 7 to 30 carbon atoms, and the heterocycle-containing group having 2 to 20 carbon atoms include R ^{1 in} the section of “2. Among the contents exemplified as etc., those satisfying a predetermined number of carbon atoms are mentioned.

Other radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyl diphenyl phosphine oxide and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pill-1) -Yl)] Titanocene compounds such as titanium etc. may be mentioned.

Commercially available radical polymerization initiators include Adeka optomer N-1414, N-1717, N-1919, Adeka Arkles NCI-831, NCI-930 (manufactured by ADEKA Corporation), IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02, OXE 03, OXE 04, IRGACURE 784 (manufactured by BASF), TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-314 (manufactured by Tronly) and the like. Be

These radical photopolymerization initiators can be used alone or in combination of two or more depending on the desired performance.

The photocationic polymerization initiator is not particularly limited as long as it is a compound capable of releasing a substance that causes cationic polymerization to be initiated by light irradiation, and it is possible to use an existing compound, and preferably an energy ray. The compound is a double salt which is an onium salt that releases a Lewis acid upon irradiation with or a derivative thereof. Representative examples of such compounds include the following general formula:
[A1] ^{r +} [B1] ^r-
And salts of cations and anions represented by

The cation [A1] ^{r +} is preferably onium, and the structure thereof can be represented by, for example, the following general formula.
[(R ¹⁰¹ ) _{f 1} Q] ^{r +}

Furthermore, here, R ¹⁰¹ is an organic group having 1 to 60 carbon atoms and which may contain several atoms other than carbon atoms. f1 is an integer of 1 to 5; The f1 Rs ¹⁰¹ are independent of each other, and may be the same or different. Further, at least one of R ¹⁰¹ is preferably an organic group as described above having an aromatic ring. For example, when substituted by an alkyl group, alkoxy group, hydroxy group, hydroxyalkoxy group, halogen atom, benzyl group, thiophenoxy group, 4-benzoylphenylthio group, 2-chloro-4-benzoylphenylthio group, etc. A certain phenyl group is mentioned. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Also, when the valence of Q in the cation [A1] ^{r +} is q, it is necessary that the relationship r = f1-q holds (where N = N is treated as having a valence of 0).

The anion [B1] ^r- is preferably a halide complex, and its structure can be represented, for example, by the following general formula, [LX _f2 ] ^r- .

Furthermore, here, L is a metal or metalloid (Metalloid) which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like.
X _f2 is a halogen atom or a phenyl group which may be substituted by a halogen atom, an alkoxy group or the like. f2 is an integer of 3 to 7;
Also, when the valence of L in the anion [B1] ^r -is p, it is necessary that the relationship r = f2-p holds.

Specific examples of the anion [LX _f2 ] ^r- of the above general formula include tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate, tetrafluoroborate (BF ₄ ) ⁻ , Hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , hexafluoroarsenate (AsF ₆ ) ⁻ and hexachloroantimonate (SbCl ₆ ) ⁻ can be mentioned.

Further, the anion [B1] ^r- has the following general formula,
[LX _f2-1 (OH)] ^r-
The thing of the structure represented by can also be used preferably. L, X and f2 are the same as above. Other anions which can be used include perchlorate ion (ClO ₄ ) ⁻ ,
Trifluoromethyl sulfite (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , toluenesulfonate anion, trinitrobenzenesulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadeca There may be mentioned fluorooctane sulfonate, tetraaryl borate and tetrakis (pentafluorophenyl) borate.

In the present invention, among such onium salts, it is particularly effective and preferable to use an aromatic onium salt of the following (e) to (t). Among these, 1 type can be used individually or in mixture of 2 or more types.

(E) aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate and 4-methylphenyldiazonium hexafluorophosphate.

(F) Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate and tolycamyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt.

(G) Sulfonium salts represented by the following Group I or Group II: sulfonium salts such as hexafluoroantimony ion, tetrakis (pentafluorophenyl) borate ion and the like.

In addition, other preferable ones are (η5-2, 4-cyclopentadien-1-yl) [(1, 2, 3, 4, 5, 6 η)-(1-methylethyl) benzene] -iron- Iron-arene complexes such as hexafluorophosphate; aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum; mixtures with silanols such as triphenylsilanol : Etc. can also be mentioned.

A commercial item can also be used as said photocationic polymerization initiator, For example, IRUGACURE 261 (made by BASF Corporation), Adeka optomer SP-150, SP-151, SP-152, SP-170, SP-171, SP -172 (made by Adeka), UVE-1014 (made by General Electronics), CD-1012 (made by Sartmar), CI-2064, CI-2481 (made by Nippon Soda Co., Ltd.), Uvacure 1590, 1591 (Daicel UCB), CYRACURE UVI-6990 (manufactured by Union Carbide), BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103 and NDS-103 (manufactured by Midori Chemical Co., Ltd.), and the like.

Among these, aromatic iodonium salts, aromatic sulfonium salts and iron-arene complexes are preferably used from the viewpoint of practical use and light sensitivity.

As said photoanion polymerization initiator, what generate | occur | produces a base with light can be used, and what is well-known as a photoanion polymerization initiator can be used.
Examples of the photoanion polymerization initiator include acetophenone O-aroyloxime (acetophenone O-aroyloxime), nifedipine and the like.

(B) Thermal polymerization initiator As the above-mentioned thermal polymerization initiator, any one capable of polymerizing a polymerizable compound by heating may be used, and a radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator, etc. may be mentioned. Can.

As said thermal radical polymerization initiator, what generate | occur | produces a radical can be used by heating, and a well-known thing can be used as a thermal radical polymerization initiator.
As said thermal radical polymerization initiator, an azo compound, a peroxide, a persulfate, etc. can be illustrated as a preferable thing, for example.

Examples of the above azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1 ' And -azobis (1-acetoxy-1-phenylethane) and the like.

Examples of peroxides include benzoyl peroxide, di-t-butyl benzoyl peroxide, t-butyl peroxypivalate and di (4-t-butylcyclohexyl) peroxy dicarbonate.

Examples of the persulfate include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.

As said thermal cationic polymerization initiator, what generate | occur | produces cationic seed | species or a Lewis acid by heating can be used, and a well-known thing can be used as a thermal cationic polymerization initiator.
Specific examples of the thermal cationic polymerization initiator include salts such as sulfonium salts, thiophenium salts, thiolanium salts, benzyl ammonium, pyridinium salts and hydrazinium salts; and polyalkylpolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine. Alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophorone diamine; Aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenyl sulfone Glycidyl ethers such as the above polyamines and phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether Or a polyepoxy adduct modified product produced by reaction with various epoxy resins such as glycidyl esters of carboxylic acid according to a conventional method; the above organic polyamines and carboxylic acids such as phthalic acid, isophthalic acid and dimer acid Amidated modified products produced by reaction according to a conventional method; the above-mentioned polyamines and aldehydes such as formaldehyde and the like, having at least one aldehyded reactive site in the nucleus such as phenol, cresol, xylenol, tert-butylphenol and resorcin Mannich modified products produced by reacting phenols in a usual manner; polyvalent carboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid) , Dodecanedioic acid, 2 Methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer Aliphatic dicarboxylic acids such as acid and dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid; trimellitic acid, trimesic acid and castor oil fatty acid Etc .; acid anhydrides of tetracarboxylic acids such as pyromellitic acid etc.); dicyandiamide, imidazoles, carboxylic acid esters, sulfonic acid esters, amine imides and the like.
A commercial item can also be used as said thermal cationic polymerization initiator, For example, Adeka opton CP-77, Adeka opton CP-66 (made by ADEKA), CI-2639, CI-2624 (made by Nippon Soda Co., Ltd.), Sun Aid SI -60 L, San Aid SI-80 L, San Aid SI-100 L (manufactured by Sanshin Chemical Industry Co., Ltd.), and the like.

As said thermal anion polymerization initiator, what generate | occur | produces a base by heat can be used, and what is well-known as a thermal anion polymerization initiator can be used.
Specific examples of the anionic polymerization initiator include aliphatic amine compounds, aromatic amine compounds, secondary or tertiary amine compounds, imidazole compounds, polymercaptan compounds, and boron trifluoride-amine complex. , Dicyandiamide, organic acid hydrazide and the like can be used.

(C) Content of Polymerization Initiator The content of the polymerization initiator may be any as long as it can impart desired curability and photosensitivity. It can be in the range of not less than 30 parts by mass and preferably in the range of 0.5 parts by mass to 10 parts by mass. It is because a composition is excellent in curability etc. and is excellent also in dispersibility etc. by being said content.
The content of the polymerization initiator may be any as long as it can impart desired curability and photosensitivity. For example, it is 0.001 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable compound. The amount is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.1 parts by mass or more and 5 parts by mass or less. It is because a composition is excellent in curability etc. and is excellent also in dispersibility etc. by being said content.

(2) Coloring agent As said coloring agent, what is necessary is just to be able to provide desired coloring to hardened | cured material, and a dye or a pigment is mentioned.
As the dye, a compound having absorption at 380 to 1200 nm can be used, and for example, azo compound, anthraquinone compound, indigoid compound, triarylmethane compound, xanthene compound, alizarin compound, acridine compound, stilbene compound, thiazole compound, naphthol Compound, quinoline compound, nitro compound, indamine compound, oxazine compound, phthalocyanine compound, cyanine compound, diimmonium compound, cyanoethenyl compound, dicyanostyrene compound, rhodamine compound, perylene compound, polyene naphtholactam compound, coumarin compound, squalilium compound, squarylium compound, Spiropyran compounds, spirooxazine compounds, merocyanine compounds, oxonol compounds, styryl compounds, pi Lithium compounds, rhodanine compounds, oxazolone compounds, phthalimide compounds, cinnoline compounds, naphthoquinone compounds, azaanthraquinone compounds, porphyrin compounds, azaporphyrin compounds, pyromethene compounds, quinacridone compounds, diketopyrrolopyrrole compounds, indigo compounds, acridine compounds, azine compounds, Azomethine compounds, aniline compounds, quinacridone compounds, quinophthalone compounds, quinone imine compounds, iridium complex compounds, dyes such as europium complex compounds, and the like may be mentioned, and a plurality of these may be mixed and used.

As the pigment, an inorganic pigment or an organic pigment can be used. For example, nitroso compound, nitro compound, azo compound, diazo compound, xanthene compound, quinoline compound, anthraquinone compound, coumarin compound, phthalocyanine compound, isoindolinone compound, iso Indoline compounds, quinacridone compounds, anthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids; metal complex compounds of azo dyes, cyanine dyes; Lake pigment; carbon black obtained by furnace method, channel method, thermal method, or acetylene black, ketjen black or lamp black, etc. Carbon black: one prepared by coating the above carbon black with an epoxy resin and coated, one obtained by dispersing the carbon black in a solvent beforehand with a resin and adsorbing a resin of 20 to 200 mg / g, the above carbon black is acidic or alkaline Surface-treated, with an average particle diameter of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, CO in volatiles at 950 ° C., total oxygen amount calculated from CO ₂ is 9 mg per 100 m ² of surface area of carbon black Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon micro coil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, chromium oxide green, Miroli Blue, Baltic green, cobalt blue, manganese based, ferrocyanide, phosphate group blue, bitumen, ultramarine, cerulian blue, pyridinian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), Inorganic contents such as cadmium red, synthetic iron black, amber and organic pigments can be used. These pigments may be used alone or in combination of two or more.

Commercially available pigments can also be used as the above-mentioned inorganic pigment or organic pigment, and for example, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 22, 31, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; pigment oranges 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; pigment yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 154, 154, 154, 154, 154, 154, 166, 168, 175, 180, 185; pigment green 7, 10, 36; pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like.

As content of the said coloring agent, it can be referred to as 0.01 mass part or more and 50 mass parts or less with respect to 100 mass parts of solid content of a composition.

(3) Solvent The solvent may be any solvent as long as it can dissolve or disperse the above components. For example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2- Ketones such as heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, Ester solvents such as isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol solvents such as ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol and diacetone alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2 -Ether ester solvents such as acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, 1-t-butoxy-2-propanol, 3-methoxybutyl acetate, cyclohexanol acetate, etc. BTX solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; turpentine oil, D-limonene, Terpene-based hydrocarbon oils such as Nene; paraffin spirits such as Mineral Spirit, Swazor # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); Carbon tetrachloride, chloroform, trichloroethylene, methylene chloride Halogenated aliphatic hydrocarbon solvents such as 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, water and the like can be mentioned, and these solvents can be used as one or two or more mixed solvents.

The content of the solvent can be appropriately set according to the application etc. of the above composition, but preferably, the amount of components (solid content) other than the solvent in the above composition is preferably 1% by mass to 99% by mass The amount is as follows, and in particular, it is preferably 10% by mass to 90% by mass, and particularly preferably 30% by mass to 70% by mass. It is because the said composition becomes what was excellent in coating property etc. because the said content is the above-mentioned range.

(4) Chain Transfer Agent and Sensitizer As the chain transfer agent and the sensitizer, the sensitivity of the composition can be adjusted, and a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-Mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- 3- Mercapto compounds such as mercapto propionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, iodomethane such as 3-iodopropanesulfonic acid Alkylated compounds, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, tris hydroxyethyl tris thiopropionate, compound No. 1 below. C1, aliphatic polyfunctional thiol compounds, such as tri-mercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, manufactured by Showa Denko KK Karenz MT BD1, PE1, NR ^1, and the like.

(5) Surfactant As the above-mentioned surfactant, those which can improve the dispersion stability, coatability and the like of the composition can be used, and fluorine such as perfluoroalkyl phosphate, perfluoroalkyl carboxylate and the like can be used. Surfactants, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates, cationic surfactants such as higher amine halides and quaternary ammonium salts, polyethylene glycol alkyl ether, polyethylene Nonionic surfactants such as glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides, surfactants such as amphoteric surfactants and silicone surfactants can be used, and these may be used in combination.

(6) Silane Coupling Agent The above silane coupling agent is a silane compound having a reactive group chemically bonded to an inorganic material such as glass and a reactive group chemically bonded to an organic material such as a synthetic resin, which is cured What can improve the adhesiveness etc. of a thing can be used. As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, KBE-9007, KBM-502, KBE-403, etc., silane coupling having an isocyanate group, methacryloyl group or epoxy group An agent is preferably used.

(7) Melamine Compound As the above-mentioned melamine compound, those which can improve the curability can be used. For example, (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, (poly) methylol urea, etc. of active methylol groups of the nitrogen compound (CH ₂ OH groups) of all or part (at least two) can be exemplified compounds alkyl etherified. Here, as an alkyl group which comprises an alkyl ether, a methyl group, an ethyl group, or a butyl group is mentioned, A mutually may be the same, It may differ. Moreover, the methylol group which is not alkyletherified may be self-condensing within one molecule, or may be condensed between two molecules to form an oligomer component as a result. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used. Among these, alkyletherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.

(8) Acid Catalyst and Base Catalyst The acid catalyst and the base catalyst are capable of promoting the elimination of the protective groups R ⁹ and R ¹¹ of the phenolic hydroxyl group contained in the compound A and the compound B.
The composition contains an acid catalyst and a base catalyst so that the protective groups R ⁹ and R ¹¹ can be removed at a lower temperature as compared with the case where the acid catalyst and the base catalyst are not contained.
As such an acid catalyst, inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid; Organic acids such as formic acid, acetic acid, oxalic acid, citric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and monoisopropyl phosphate Acids can be mentioned.
Examples of the base catalyst include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia; and amine compounds (organic bases) such as trimethylamine, triethylamine, monoethanolamine and diethanolamine.
The content of the acid catalyst and the base catalyst is appropriately set according to the type and the desired desorption temperature, etc., and 0.1 parts by weight with respect to a total of 100 parts by weight of the compound A and the compound B. It can be from 10 parts by mass to 10 parts by mass.

(9) Others The above-mentioned other components are, if necessary, further, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine, etc .; plasticizers; adhesion promoters; fillers; Agents; leveling agents; surface conditioners; antioxidants other than the above compound B such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants, etc .; ultraviolet absorbers other than the above compound A; dispersion Coagents may be included such as an anticoagulant, a catalyst, an effect accelerator, a crosslinker, and a thickener.

The total content of the additives can be 30 parts by mass or less in 100 parts by mass of the solid content of the composition.
The composition described above can provide a cured product having desired durability, and can contain a phenolic antioxidant and a UV absorber in addition to the compound A and the compound B, as long as the cured product can be easily produced. Although it may exist, it is preferable not to contain substantially.
Here, “not substantially contained” can be 1 part by mass or less in 100 parts by mass of the solid content of the composition, and in particular, it is preferably 0.01 part by mass or less, and 0.005 mass It is preferable that it is a part or less, It is preferable that it is 0.001 mass part or less, It is preferable that it is 0.0001 mass part or less.
The content of the above-mentioned phenolic antioxidant and ultraviolet absorber can be 1 part by mass or less with respect to a total of 100 parts by mass of the above compound A and compound B, and in particular, 0.01 parts by mass or less Is preferably 0.005 parts by mass or less, preferably 0.001 parts by mass or less, and preferably 0.0001 parts by mass or less. It is because it becomes possible to obtain a cured product excellent in durability.
Moreover, as said ultraviolet absorber, the ultraviolet absorber which has phenolic hydroxyl group can be mentioned. Examples of the ultraviolet absorber include 2-hydroxybenzophenones described in JP-A-2017-008221, 2- (2′-hydroxyphenyl) benzotriazoles, benzoates, triaryltriazines, and the like. The benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, etc. described in JP-A-97224 can be used.
As said phenolic antioxidant, it can be generally used as antioxidant which has phenolic hydroxyl group. Examples of the above-mentioned antioxidant include phenol based antioxidants described in JP-A-6-17998, JP-A-11-71355, JP-A-2002-97224, etc., JP-A-7-109380. The alkyl-substituted phenolic antioxidants described can be used.

6. Composition The viscosity of the composition may be, for example, 200 mPa · s or less, and 1 mPa · s or more and 200 mPa · s or less, from the viewpoint of having coatability. It is because the said composition is excellent in coatability.
The viscosity, JIS Z 8803: according to the 2011, rotational viscometer (e.g., Anton Paar, Physica ^MCR 3 01, etc.) using, refers to the measured values. In the present specification, in particular, processing without temperature designation and measurement may be performed at 25 ° C.

The method for producing the above composition may be any method as long as the above-mentioned components can be blended at a desired content, and may be a method in which the above-mentioned components are simultaneously added and mixed. It may be a method of mixing.

Applications of the above composition are thermosetting coatings, photocurable coatings or varnishes, thermosetting adhesives, photocurable adhesives, printed circuit boards, or color televisions such as color televisions, PC monitors, personal digital assistants, digital cameras, etc. Color filters for liquid crystal display panels for display, color filters for CCD image sensors, photo spacers, black column spacers, electrode materials for plasma display panels, touch panels, touch sensors, powder coatings, printing inks, printing plates, adhesives, for dental use Composition, resin for photolithography, gel coat, photoresist for electronics, electroplating resist, etching resist, both liquid and dry film, solder resist, for manufacturing color filters for various display applications or plasma display In the manufacturing process of panels, electroluminescent displays and LCDs Resists for forming structures, compositions for encapsulating electric and electronic parts, solder resists, magnetic recording materials, micromechanical parts, waveguides, optical switches, plating masks, etching masks, color test systems, glass Fiber cable coatings, stencils for screen printing, materials for producing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, microelectronics, bleaching materials, bleaching materials for image recording materials, microcapsules Decoloring materials for image recording materials using the same, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, photoresist materials used for forming a dielectric layer in sequential lamination of printed circuit boards, Various kinds of photoresist materials or protective films for 3D mounting It can be used for developing, and there is no particular limitation on the application.
Further, the above-mentioned application is not limited to the application requiring durability when used as a product, and for example, it can be suitably used also for a member which receives ultraviolet irradiation or the like in the manufacturing process.
As a member which receives ultraviolet irradiation etc. in a manufacturing process, in order to aim at surface modification of surface wettability improvement, adhesion improvement, etc., a member which receives irradiation, such as ultraviolet light, can be mentioned, for example.
Examples of the members required to have the above-mentioned wettability improvement and adhesion improvement include members laminated with other members. For example, various members such as a plasma display panel, an organic electroluminescence display, a liquid crystal display, etc. Image display, various sensors such as touch panels, color filters, photo spacers, brightness enhancement plates, light guide plates, light guide plates, TFT substrates, alignment films, liquid crystal layers, insulating films, acoustic elements such as speakers, members for constituting circuit boards etc. Examples of such a member include a surface modification in the manufacturing process of a lens, a keypad, a magnetic head for an HDD, and the like, and the prevention of deterioration of the member.
As members required to prevent surface modification and deterioration of members in the above-mentioned manufacturing process, members to be laminated with other members via an adhesive, members to be covered with other members by paints, etc. should also be mentioned. For example, components of various uses such as vehicles, transport devices such as interior and exterior members of aircraft, household appliances such as refrigerators and washing machines, and housing materials can also be mentioned.
In addition, after forming a pattern-like member on a base material, the base material may be irradiated with ultraviolet light or the like together with the base material for surface modification of the exposed base material. As said use, it can use preferably also for the member used with the member by which surface modification etc. are requested | required in such a manufacturing process. As the above-mentioned application, for example, a member used together with a member requiring surface cleaning or surface modification such as plastic film, glass, silicon wafer, various engineering plastics, optical lens, metal surface, plating, ceramic, mold etc. It can be mentioned.
From the viewpoint that the compound A and the compound B are excellent in the dispersion stability and the addition amount thereof is easy to be used as the above-mentioned application, for example, it is preferable to be used, for example, for manufacturing a thin film member. The thin film member can be, for example, a member having a film thickness of 100 μm or less, preferably 50 μm or less, and particularly preferably 20 μm or less.

B. Cured Product 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-mentioned composition.
More specifically, the cured product of the present invention is a cured product of a composition, and the above composition is characterized in that it contains a compound A, a compound B and a polymerizable compound.

According to the present invention, since the above-mentioned composition is used, the production is easy and the durability is excellent.

The cured product of the present invention uses the composition described above.
Hereinafter, the cured product of the present invention will be described in detail.

The composition contains the compound A, the compound B and the polymerizable compound.
In addition, the composition may include components other than the compound A, the compound B, and the polymerizable compound.
The composition can contain, for example, resin components other than the polymerizable compound, other components, and the like.
About the content of each component of such a composition, it can be made to be the same as the content as described in the said "A. composition" term.

The cured product may be a cured product of the above composition, and the compound A and the compound B contained in the cured product are desorbed even before removal of the protective groups (for example, R ⁹ and R ¹¹ ). Although it may be after separation, it is preferable after separation. It is because the said hardened | cured material will have the outstanding durability.
Incidentally, if it is after removal of the protecting group, the cured product typically has at least a compound A and a protecting group from a compound (e.g., R ⁹ and R ¹¹⁾ compound is eliminated. In the case where the protective group has been removed, the cured product may further contain the R ⁹ derived release and the R ¹¹ derived release.

The above-mentioned cured product usually contains a polymer of a polymerizable compound.
The residual ratio of the polymerizable compound contained in the cured product is appropriately set according to the application etc. of the cured product, and is, for example, 10 parts by mass or less with respect to 100 parts by mass of the cured product. It is preferable that it is below a mass part.
About such composition, since it can be made to be the same as the contents described in the section of the above-mentioned "A. composition", explanation here is omitted.

The cured product may be substantially free of a solvent.
As content of the solvent contained in the said hardened | cured material, it can be 1 mass part or less with respect to 100 mass parts of hardened | cured material, for example, can be 0.5 mass part or less.

The elastic modulus of the cured product is usually higher than that of the composition, and can be, for example, 10 ^-3 M or more, and can be 10 MPa or more. It is because the said hardened | cured material can hold | maintain the compound A, the compound B, etc. stably by being the said elasticity modulus.
About the upper limit of the above-mentioned elastic modulus, although it can set suitably according to the use etc. of hardened material, it can be made into 10 ⁶ MPa or less, for example.
Hereinafter, the elastic modulus refers to the compressive elastic modulus and can be measured at 23 ° C. in accordance with JIS K7181.
For the measurement sample, for example, a cube-shaped test piece having a side length of 6 mm can be prepared or cut out, and measurement can be performed at a test speed of 1 ± 0.2 mm / min according to JIS K7181.

About the planar view shape of the said hardened | cured material, it can set suitably according to the use etc. of the said hardened | cured material, For example, it can be set as pattern shapes, such as a dot form and a line form.
The thickness of the cured product can be appropriately set according to the application etc. of the cured product, and, for example, compound A and compound B are excellent in dispersion stability, and it is easy to increase the addition amount thereof From the viewpoint, for example, a thin film is preferable, for example, 0.1 μm or more and 100 μm or less, preferably 50 μm or less, particularly preferably 20 μm or less, and particularly 10 μm or less Is preferred.

About the use etc. of the said hardened | cured material, it can be made to be the same as that of the content as described in the term of the said "A. composition".

The method for producing the cured product is not particularly limited as long as the cured product of the composition can be formed into a desired shape.
As such a manufacturing method, for example, since it can be the same as the contents described in the section of “C. Manufacturing method of cured product” described later, the description here is omitted.

C. Method of Producing Cured Product Next, a method of 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 comprising the step of forming a cured product of the composition described above.
More specifically, the method for producing a cured product of the present invention is characterized by comprising a step of forming a cured product of a composition containing compound A, compound B and a polymerizable compound.

According to the present invention, for example, the production method of the cured product becomes easy by using the above-mentioned composition and having the above-mentioned steps. In addition, by carrying out the step of removing the protecting group R ⁹ contained in the compound A and the protecting group R ¹¹ contained in the compound B after the above steps, a cured product having durability can be easily obtained. It is because

The production method of the present invention includes the step of forming a cured product.
Hereinafter, each process of the manufacturing method of this invention is demonstrated in detail.

1. Step of forming a cured product The step of forming the cured product is a step of forming a cured product of the composition described above.
As a method of forming a cured product of such a composition, any method capable of forming a cured product of a desired shape may be used, and the method differs depending on the components contained in the composition.
In the method of forming the cured product, for example, when the composition contains a photopolymerization initiator as a polymerization initiator together with a polymerizable compound, the composition is irradiated with light to polymerize the polymerizable compounds with each other. Methods can be used.
The light irradiated to the composition may include light with a wavelength of 300 nm to 450 nm.
As a light source of the said light irradiation, an ultra-high pressure mercury, a mercury vapor arc, a carbon arc, a xenon arc etc. can be mentioned, for example.
Laser light may be used as the light to be irradiated. As the laser light, one containing light with a wavelength of 340 to 430 nm can be used.
As a light source of laser light, those emitting light in the visible to infrared region such as argon ion laser, helium neon laser, YAG laser, and semiconductor laser can also be used.
In addition, when using these lasers, the said composition can contain the sensitizing dye which absorbs the said area | region of visible to infrared.

In the method of forming the cured product, for example, when the composition contains a thermal polymerization initiator as a polymerization initiator together with a polymerizable compound, the composition is subjected to a heat treatment to polymerize the polymerizable compounds. Methods can be used.
The heating temperature may be such that the removal of the protective group from compound A and compound B can be suppressed.
The heating temperature may be, for example, 60 ° C. or more, preferably 100 ° C. or more and 300 ° C. or less.
In addition, heating temperature can be made into the temperature of the coating-film surface of a composition.
The heating time can be about 10 seconds to 3 hours.

The type of the method of forming the cured product may include only one type, or may include two or more types.

The composition contains the compound A, the compound B and the polymerizable compound.
In addition, the composition may include components other than the compound A, the compound B, and the polymerizable compound.
The composition can contain, for example, resin components other than the polymerizable compound, other components, and the like.
About the content of each component of such a composition, since it can be made to be the same as the content as described in the term of the said "A. composition", description here is abbreviate | omitted.

2. The above-mentioned production method can include, after the step of forming the cured product, the step of removing the protecting group R ⁹ contained in the compound A and the protecting group R ¹¹ contained in the compound B. .
By including such a step, a cured product having durability can be easily obtained.

As a method of removing the protecting group R ⁹ contained in the above compound A and the protecting group R ¹¹ contained in the above compound B in this step, any method capable of stably removing the above protecting group may be used, for example, It can be set as the method of heat-processing with respect to the said hardened | cured material.
The heating temperature for the cured product may be a temperature at which the protective group R ⁹ and the protective group R ¹¹ are eliminated, for example, a temperature higher than the desorption temperature of the protective group R ⁹ and the protective group R ¹¹ .
Further, when the composition contains an acid catalyst, a base catalyst and the like, the heating temperature can be equal to or less than the desorption temperature observed for the protective group R ⁹ and the protective group R ¹¹ alone.
The heating temperature can be, for example, 50 ° C. or more and 250 ° C. or less, preferably 60 ° C. or more and 200 ° C. or less, and particularly preferably 80 ° C. or more and 200 ° C. or less. It is because deterioration of a resin component etc., deterioration of the base material which supports hardened | cured material, etc. can be suppressed by being said heating temperature.
In addition, the temperature of the said hardened | cured material can be made into the temperature of the hardened | cured material surface.

3. Other Steps The above-mentioned production method may include other steps, as necessary, in addition to the step of forming a cured product and the step of removing.
As said other process, the process of apply | coating the said composition on a base material etc. can be mentioned, for example.
As a method of applying the composition, known methods such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, immersion and the like can be used.
The substrate can be appropriately set depending on the application of the cured product and the like, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, plastics and the like.
In addition, after the cured product is formed on a substrate, it may be used after being peeled off from the substrate or may be transferred from the substrate to another adherend.

4. Others The cured product produced according to the above-mentioned production method, the use and the like can be the same as the contents described in the section of "B. cured product".

The present invention is not limited to the above embodiment. The above embodiment is an exemplification, and it has substantially the same configuration as the technical idea described in the claims of the present invention, and any one having the same function and effect can be used. It is included in the technical scope of the invention.

Hereinafter, the present invention will be described in more detail by way of examples and the like, but the present invention is not limited to these examples.

[Production Example A1-1]
0.01 mol of a phenol compound, 0.05 mol of di-tert-butyl dicarbonate and 30 g of pyridine were mixed, 0.025 mol of 4-dimethylaminopyridine was added at room temperature under a nitrogen atmosphere, and the mixture was stirred at 60 ° C. for 3 hours. After cooling to room temperature, the reaction solution was poured into 150 g of ion exchanged water, and 200 g of chloroform was added to conduct oil-water separation. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and 100 g of methanol was added to the residue for crystallization. The obtained white powdery crystals were dried under reduced pressure at 60 ° C. for 3 hours to obtain the desired product (a compound represented by the following general formula (A1-1)). It was confirmed by ¹ H-NMR that the obtained white powdery crystals were the desired product. The results are shown in Tables 1 and 2 below. The phenol compound used was a compound in which two —COO-tert-butyl groups in the following A1-1 were substituted by hydrogen atoms.

[Production Examples A2-1, A3-1, A3-2, A3-3]
A compound of the following general formula (A2-1) was prepared in the same manner as in Production Example A1-1, except that phenol compounds corresponding to the following A2-1, A3-1, A3-2, and A3-3 were used as the phenol compound. Compounds (A3-1), (A3-2) and (A3-3) were synthesized. It was confirmed by ¹ H-NMR that the obtained white powdery crystals were the desired product. The results are shown in Table 1 below.

[Production Examples B-1 to B-3]
Compounds represented by the following general formulas B-1 to B-3 were produced in the same manner as in Production Example A1-1 except that phenol compounds corresponding to the following B-1 to B-3 were used as the phenol compound. Synthesized. It was confirmed by ¹ H-NMR that the obtained white powdery crystals were the desired product. The results are shown in Table 1 below.

Production Example 1
30.0 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 7.52 g of acrylic acid, 0.080 g of 2,6-di-t-butyl-p-cresol, tetrabutyl 0.183 g of ammonium chloride and 11.0 g of PGMEA were charged, and stirred at 90 ° C. for 1 hour, 105 ° C. for 1 hour and 120 ° C. for 17 hours. The reaction solution was cooled to room temperature, and 8.11 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride and 11.1 g of PGMEA were added and stirred at 100 ° C. for 5 hours. Furthermore, 12.0 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 0.080 g of 2,6-di-t-butyl-p-cresol and 0.600 g of PGMEA are added. After stirring at 90 ° C. for 90 minutes and at 120 ° C. for 5 hours, 24.0 g of PGMEA was added, and a resin no. 1 was obtained (Mw = 4900, Mn = 2250, acid value (solid content) 47 mg · KOH / g, solid content 45.0% by mass).

[Examples 1 to 20 and Comparative Examples 1 to 28]
Compound A, ultraviolet light absorber, compound B, antioxidant, polymerizable compound having an acid value, polymerizable compound having no acid value, photopolymerization initiator, silane coupling according to the composition described in Tables 2 to 5 below The agent and the solvent were blended to obtain a composition.
Moreover, the following materials were used for each component.
In addition, the compounding quantity in a table | surface represents the mass part of each component.

(Compound A)
A-1: Compound A-2 represented by the above-mentioned general formula (A1-1): Compound A-3 represented by the above-mentioned general formula (A2-1): represented by the above-mentioned general formula (A3-1) Compound A-4: Compound A-5 represented by the above general formula (A3-2): compound represented by the above general formula (A3-3)

(UV absorber)
A′-1: UV Absorber LA-29 manufactured by ADEKA
A′-2: UV Absorber LA-31 manufactured by ADEKA
A'-3: UV Absorber LA-F70 manufactured by ADEKA

(Compound B)
B-1: Compound B-2 represented by Formula (B-1): Compound B-3 represented by Formula (B-2): Formula (B-3) Compound

(Antioxidant)
B '-1: Antioxidant AO-60 manufactured by ADEKA

(A polymerizable compound having an acid value)
C-1: Radically polymerizable compound (Lipoxy SPC-1000 manufactured by Showa Denko 29% by mass PGMEA solution)
C-2: Resin No. 1 produced in Production Example 1 1

(A polymerizable compound having no acid value)
D-1: Radically polymerizable compound (Aronix M-450 (a mixture of pentaerythritol tri and tetraacrylates 3 to 4 manufactured by Toagosei Co., Ltd.))
D-2: Radically polymerizable compound (Kayarad DPHA (a mixture of dipentaerythritol penta and hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.)
D-3: Cationic polymerizable compound (NK Oligo EA-1020 (bisphenol A epoxy acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.)
D-4: Radically polymerizable compound (Art resin UN-3320 (urethane acrylate) manufactured by Rootskami Kogyo Co., Ltd.)
D-5: Cationic polymerizable compound (EP-4100E (bisphenol A epoxy resin) manufactured by ADEKA Co., Ltd.)
D-6: Cationic polymerizable compound (Celloxide 2021 P (alicyclic epoxy compound) manufactured by Daicel Corporation)

(Photopolymerization initiator)
E-1: Compound represented by the following formula (E1) (oxime ester photo radical polymerization initiator)
E-2: Compound represented by the following formula (E2) (oxime ester photo radical polymerization initiator)
E-3: Irgacure TPO manufactured by BASF (phosphine oxide radical polymerization initiator)
E-4: SP-171 (sulfonium salt photo cationic polymerization initiator) manufactured by ADEKA Corporation

(Silane coupling agent)
F-1: Shine Chemical Industry Co., Ltd. silane coupling agent KBE-403

(solvent)
G-1: PGMEA

Evaluation of the said Example and comparative example was performed in accordance with the following method. However, in the compositions of Comparative Examples 10, 11, 18, and 19, the following evaluation could not be performed because solids were precipitated at the time of preparation.

1. Sensitivity evaluation 1
Among the compositions prepared in the respective Examples and Comparative Examples, Examples 1 to 12, 17 to 20, and Comparative Examples 1 to 9, 12 to 17, 20, 25 to 28 containing a polymerizable compound having an acid value The following line width sensitivity and residual film sensitivity were evaluated as the sensitivity evaluation of the composition. The results are shown in Tables 2-5.
First, the compositions of Examples 1 to 12, 17 to 20 and Comparative Examples 1 to 9, 12 to 17, 20, and 25 to 28 were spin-coated on a glass substrate (500 rpm, 2 seconds, 900 rpm, 5 The coated film was formed to have a thickness of 10 μm after drying (pre-baking). Next, the coated film is prebaked at 90 ° C. for 90 seconds using a hot plate, and exposed (40 mJ / cm ² ) through a mask (opening line width 20 μm) using a high pressure mercury lamp as a light source And a cured product was obtained. Then, after developing using a 2.5 mass% sodium carbonate aqueous solution as a developing solution, it was thoroughly washed with water, and post baked at 230 ° C. for 30 minutes using an oven to fix the pattern.
The line width of the obtained pattern was measured by an electron microscope, and the line width sensitivity was evaluated based on the following criteria.
The film thickness of the obtained pattern was measured with an electron microscope, and the residual film sensitivity was evaluated by the following method.
(Line width sensitivity)
:: line width of cured product / 20 μm is 1.0 or more.
X: The line width of the cured product / 20 μm is less than 1.0.
(Remaining film sensitivity)
Film thickness after post-baking / film thickness after pre-baking × 100 (%) was calculated.
When the line width sensitivity is “〇” and the residual film sensitivity is 70% or more, the composition is inhibited from occurrence of curing inhibition and shows that the composition is sufficiently cured.

2. Sensitivity evaluation 2
Of the compositions prepared in the respective Examples and Comparative Examples, evaluation using the step tablet was conducted as the sensitivity evaluation of the compositions of Examples 13 to 16 and Comparative Examples 21 to 24 not containing a polymerizable compound having an acid value. Did.
Specifically, the above composition was applied to a PET film with a bar coater to a thickness of about 3 μm. Next, after prebaking at 80 ° C. for 30 minutes, exposure was performed (20 mW / cm ² ) using an ultra-high pressure mercury lamp (UL 750) as a light source. The exposure was performed so that the exposure light amount was 400 mJ. Under the present circumstances, the negative film made so that light transmittance might be decreased in steps in order to measure a photosensitivity (The optical density 0.05 is made into the 1st step, The optical density is 0.15 at a time for every step. An increasing step tablet was used. Then, development was carried out by washing for 10 seconds in an environment of 25 ° C. using isopropanol (IPA). It was then dried at 80 ° C. for 30 minutes. Next, the photosensitivity was evaluated by measuring the number of steps of the step tablet of the cured product formed on the PET film. The results are shown in Table 4 below.
The higher the number of steps of the step tablet, the higher the light sensitivity. In addition, when the number of steps of the step tablet is 10 or more, the composition is inhibited from occurrence of inhibition of curing and shows that the composition is sufficiently cured.

3. A sample for evaluation was obtained in the same manner as in "1. Sensitivity evaluation 1" except that heat resistance development processing and washing with water were not performed. Then, using an oven, a heat resistance test was performed in which the evaluation sample was heat-treated at 200 ° C. for 2 hours.
The difference in transmittance (%) at a wavelength of 430 nm before and after the heat resistance test of the sample for evaluation ((transmittance (% before heat resistance test-transmittance (%) before heat resistance test) was measured, and The heat resistance was evaluated on the basis of the standard, and the results are shown in Tables 2 to 5.
Good: The transmittance difference (%) is less than 1% with respect to the transmittance before the heat resistance test.
X: The difference in transmittance (%) is 1% or more with respect to the transmittance before the heat resistance test.
In addition, a hardened | cured material shows that it is excellent in heat resistance in heat resistance evaluation being "O".

4. Light Resistance A sample for evaluation was obtained in the same manner as in “1. Sensitivity evaluation 1” except that development processing and washing with water were not performed. A 96-hour light resistance test was performed on the sample for evaluation using a Suga Test Instruments xenon light resistance tester Table Sun XT-1500L. The difference in transmittance (%) at a wavelength of 430 nm before and after the light resistance test of the sample for evaluation ((transmittance (%) before light resistance test-transmittance (%) after light resistance test) was measured. The light resistance was evaluated on the basis of the standard, and the results are shown in Tables 2 to 5.
Good: The transmittance difference (%) is less than 3% with respect to the transmittance before the light resistance test.
X: The difference in transmittance (%) is 3% or more with respect to the transmittance before the light resistance test.
In addition, a hardened | cured material shows that it is excellent in light resistance in light resistance evaluation being "O".

[Summary]
From Tables 2 to 5, it was confirmed that the compositions of the examples were able to be sufficiently cured because the occurrence of inhibition of curing was suppressed even when the compounds A and B were contained. From this result, it was confirmed that the compositions of the examples are easy to produce a cured product.
Further, it was confirmed that the compositions of the examples were good results in both heat resistance and light resistance, and were excellent in durability.

Preparation Example 2 Preparation of Blue Pigment Dispersion As a dispersant, DISPERBYK-161 (8.4 parts by mass; manufactured by BIC Chemie Japan) and pigment blue 15: 6 (14 parts by mass) as a coloring agent were mixed with PGMEA (77.6). A blue pigment dispersion (solid content concentration: 22.4 mass%, pigment concentration in solid content: 62.5 mass%, solvent PGMEA) was produced by dispersing the pigment using a bead mill.

Example 21, Comparative Examples 29 to 33
Compound A, UV absorber, compound B, antioxidant, polymerizable compound having an acid value, polymerizable compound having no acid value, a photopolymerization initiator, a silane coupling agent, according to the composition described in Table 6 below A solvent and a colorant were blended to obtain a composition. The compounding amounts in the table represent parts by mass of each component.
The components other than C-3 and H-1 represent the same components as those used in Examples 1 to 20 and Comparative Examples 1 to 28 and the like.

C-3: SPC-3000 (made by Showa Denko, solid content 42.7% by mass, PGMEA solution)
H-1: Blue pigment dispersion (blue pigment dispersion prepared in the above-mentioned Preparation Example 2, solid content concentration 22.4 mass%, pigment concentration in solid content 62.5 mass%, solvent PGMEA)

[Evaluation]
The following evaluation was performed about the composition obtained by the Example and the comparative example. The results are shown in Table 6 below.

1. Sensitivity evaluation (line width sensitivity)
The compositions of Examples and Comparative Examples were spin-coated on a glass substrate, prebaked at 90 ° C. for 120 seconds using a hot plate, and cooled at 23 ° C. for 60 seconds. Spin-coating conditions were adjusted so that it might become the thickness of the coating film which becomes the chromaticity coordinate (x, y) = (0.135, 0.098) after post-baking. Then, it exposed through a photomask (mask opening 30 micrometers) using the ultrahigh pressure mercury lamp (exposure gap 300 micrometers, exposure amount 40 mJ / cm < ² >). After developing using a 0.04 mass% KOH aqueous solution as a developing solution, it was thoroughly washed with water, and postbaked at 230 ° C. for 20 minutes using a clean oven to fix the pattern. The obtained pattern was observed with an electron microscope, and the line width of the portion corresponding to the mask opening was measured and evaluated according to the following criteria. The results are shown in Table 6 below.
A line width 35 μm or more B less than 35 μm 30 μm or more C line width less than 30 μm It can be judged that the larger the line width, the better the sensitivity.

2. The compositions of Examples and Comparative Examples were spin-coated on a heat resistant glass substrate, prebaked at 90 ° C. for 120 seconds using a hot plate, and then cooled at 23 ° C. for 60 seconds. Spin-coating conditions were adjusted so that it might become the thickness of the coating film which becomes the chromaticity coordinate (x, y) = (0.135, 0.098) after post-baking.
Thereafter, after exposure at 150 mJ / cm ² using an extra-high pressure mercury lamp, post-baking was performed at 230 ° C. for 20 minutes using a clean oven to prepare an evaluation sample. The obtained sample was heated at 250 ° C. for 1 hour using a clean oven, and the Y value was determined from the transmittance at 380 to 780 nm before and after heating according to JIS Z8701. From the obtained Y value, retention (%) = Y value after heat resistance test / Y value before heat resistance test × 100 was calculated, and heat resistance evaluation was performed based on the following criteria. The results are shown in Table 6 below.
Good: The retention rate (%) is 99% or more.
X: The retention rate (%) is less than 99%.
In addition, a hardened | cured material shows that it is excellent in heat resistance in heat resistance evaluation being "O".

3. Light Resistance The compositions of Examples and Comparative Examples were spin-coated on a glass substrate, prebaked at 90 ° C. for 120 seconds using a hot plate, and cooled at 23 ° C. for 60 seconds. Spin-coating conditions were adjusted so that it might become the thickness of the coating film which becomes the chromaticity coordinate (x, y) = (0.135, 0.098) after post-baking. Thereafter, after exposure at 150 mJ / cm ² using an extra-high pressure mercury lamp, post-baking was performed at 230 ° C. for 20 minutes using a clean oven to prepare an evaluation sample. A 200 hour light resistance test was performed on the sample for evaluation using a Suga Test Instruments Xenon Light Resistance Tester Table Sun XT-1500L.
The difference in transmittance (%) at a wavelength of 430 nm before and after the light resistance test of the sample for evaluation ((transmittance (%) before light resistance test-transmittance (%) after light resistance test) was measured. The light resistance was evaluated based on the criteria, and the results are shown in Table 6 below.
Good: The transmittance difference (%) is less than 2% with respect to the transmittance before the light resistance test.
X: The difference in transmittance (%) is 2% or more with respect to the transmittance before the light resistance test.
In addition, a hardened | cured material shows that it is excellent in light resistance in light resistance evaluation being "O".

The present invention has the effect of being able to produce a cured product having durability and capable of providing a composition that is easy to produce a cured product.

Claims

A compound A represented by the following general formula (A1), (A2) or (A3),
The composition containing the compound B represented by following General formula (B).

(Wherein, R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl having 6 to 20 carbon atoms A group, an arylalkyl group having 7 to 20 carbon atoms, a heterocycle-containing group having 2 to 20 carbon atoms, or -O-R 9 ,
At least one of R 1 and R 2 is -O-R 9 above;
R 3 and R 4 each independently represent a halogen atom, cyano group, hydroxyl group, nitro group, carboxyl group, alkyl group having 1 to 40 carbon atoms, aryl group having 6 to 20 carbon atoms, or 7 to carbon atoms 20 arylalkyl groups or heterocyclic groups containing 2 to 20 carbon atoms,
R 9 represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or 2 to 6 carbon atoms 20 a heterocyclic group or a trialkylsilyl group, wherein the alkyl group, the aryl group, the arylalkyl group, the heterocyclic group and the methylene group in the trialkylsilyl group have a carbon-carbon double bond, -O- , -S-, -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-, -NR'-,> P = O, -S-S- , -SO 2 -or a combination of these may be substituted,
The alkyl group, the aryl group, the arylalkyl group, the heterocycle-containing group and the trialkylsilyl group may have a substituent,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
The plurality of R 3 s and the plurality of R 4 s may be bonded to each other to form a benzene ring or a naphthalene ring,
The plurality of R 3 and the plurality of R 4 may be the same as or different from each other,
m1 represents an integer of 1 to 10,
a1 represents an integer of 0 to 4;
a2 represents an integer of 0 to 2;
X a1 represents a direct bond or an m monovalent atom or a bonding group. )

(Wherein, R 1 ′ and R 2 ′ are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, 6 to 20 carbon atoms And an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or -O-R 9 ,
At least one of R 1 ′ and R 2 ′ is the above-described —O—R 9 ,
R 5 and R 6 each independently represent a halogen atom, cyano group, hydroxyl group, nitro group, carboxyl group, alkyl group having 1 to 40 carbon atoms, aryl group having 6 to 20 carbon atoms, or 7 to carbon atoms 20 arylalkyl groups or heterocyclic groups containing 2 to 20 carbon atoms,
R 9 has the same meaning as in formula (A1),
The methylene group in the alkyl group, aryl group, arylalkyl group, heterocyclic group and trialkylsilyl group is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO- , -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S- When substituted by -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, -SO 2 -or a combination thereof There is
The alkyl group, the aryl group, the arylalkyl group, the heterocycle-containing group and the trialkylsilyl group may have a substituent,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
The plurality of R 5 s and the plurality of R 6 s may be bonded to each other to form a benzene ring or a naphthalene ring,
Several R < 5 > and several R < 6 > may be same or different, respectively,
m2 represents an integer of 1 to 10,
a3 represents an integer of 0 to 4;
a4 represents an integer of 0 to 3;
X a2 represents a direct bond or an m-bivalent atom or a bonding group. )

(Wherein, R 1 ′ ′ and R 2 ′ ′ each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, or 6 to 20 carbon atoms And an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or -O-R 9 ,
At least one of R 1 ′ ′ and R 2 ′ ′ is the above-described —O—R 9 ,
R 7 and R 8 each independently represent a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms 20 arylalkyl groups or heterocyclic groups containing 2 to 20 carbon atoms,
R 9 has the same meaning as in formula (A1),
The methylene group in the alkyl group, aryl group, arylalkyl group, heterocyclic group and trialkylsilyl group is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO- , -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S- When substituted by -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, -SO 2 -or a combination thereof There is
The alkyl group, the aryl group, the arylalkyl group, the heterocycle-containing group and the trialkylsilyl group may have a substituent,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
Several R 7 may be combined to form a benzene ring or a naphthalene ring,
The plurality of R 7 and the plurality of R 8 may be identical to or different from each other,
m3 represents an integer of 1 to 3;
a5 represents an integer of 0 to 3;
a6 represents an integer of 0 to 3-m3. )

(Wherein, R 11 represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, carbon Represents a heterocyclic group having 2 to 20 atoms or a trialkylsilyl group,
R 12 and R 13 each independently represent a hydrogen atom or an alkyl group having 1 to 40 carbon atoms,
R 14 is a halogen atom, cyano group, hydroxyl group, nitro group, carboxyl group, alkyl group having 1 to 40 carbon atoms, aryl group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, or carbon Represents a heterocycle-containing group having 2 to 20 atoms,
The methylene group in the alkyl group, aryl group, arylalkyl group, heterocyclic group and trialkylsilyl group is a carbon-carbon double bond, -O-, -S-, -CO-, -O-CO- , -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S- When substituted by -CO-NH-, -NH-CO-, -NH-CO-O-, -NR'-,> P = O, -S-S-, -SO 2 -or a combination thereof There is
The alkyl group, the aryl group, the arylalkyl group, the heterocycle-containing group and the trialkylsilyl group may have a substituent,
R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
Several R 14 may be combined to form a benzene ring or a naphthalene ring,
Several R 14 may be the same or different.
n represents an integer of 1 to 10,
b1 represents an integer of 0 to 2;
X b represents a direct bond or an n-valent atom or a bonding group. )
The composition according to claim 1, wherein each of R 9 and R 11 is an alkyl group having 1 to 20 carbon atoms in which the terminal methylene group at the oxygen atom side is replaced by -CO-O-.
The composition according to claim 1 or 2, wherein a content of the compound A is 1 part by mass or more and 99 parts by mass or less with respect to a total of 100 parts by mass of the compound A and the compound B.
The composition according to any one of claims 1 to 3, comprising a polymerizable compound.
A cured product of the composition according to claim 4.
The manufacturing method of hardened | cured material which has the process of forming hardened | cured material of the composition of Claim 4.