WO2019069960A1 - Composé, absorbeur latent de lumière ultraviolette, composition, produit durci, et procédé de production de produit durci - Google Patents

Composé, absorbeur latent de lumière ultraviolette, composition, produit durci, et procédé de production de produit durci Download PDF

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WO2019069960A1
WO2019069960A1 PCT/JP2018/036958 JP2018036958W WO2019069960A1 WO 2019069960 A1 WO2019069960 A1 WO 2019069960A1 JP 2018036958 W JP2018036958 W JP 2018036958W WO 2019069960 A1 WO2019069960 A1 WO 2019069960A1
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group
carbon atoms
compound
composition
integer
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Japanese (ja)
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有希子 金原
光裕 岡田
哲千 中屋敷
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株式会社Adeka
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Priority to JP2019546747A priority Critical patent/JP7393205B2/ja
Priority to KR1020197036459A priority patent/KR20200064029A/ko
Priority to CN201880046837.6A priority patent/CN111094256A/zh
Publication of WO2019069960A1 publication Critical patent/WO2019069960A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to a compound which is less likely to inhibit curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
  • Patent Documents 1 to 3 In order to improve the ultraviolet ray absorbing ability and heat resistance of the curable composition, methods of stabilizing by adding an ultraviolet light absorber and an antioxidant to the curable composition are known (Patent Documents 1 to 3) .
  • latent additives which can be activated after curing are inactivated in the above-mentioned light absorbing action in the polymerization system.
  • activation of the latent additive that can be activated after curing may require heating or the like, but may require easier activation.
  • the present invention has been made in view of the above problems, and has as its main object to provide a compound which is less in inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
  • the present inventors used a photoleaving group as a protecting group to protect the phenolic hydroxyl group contained in the ultraviolet absorber with the photoleaving group. It has been found that the adjustment of the time to develop the ultraviolet light absorbing ability is easy and the above-mentioned problems can be solved, and the present invention has been completed.
  • the present invention provides a compound represented by the following general formula (I-1).
  • A represents an atomic group capable of absorbing ultraviolet light
  • B represents a photoleaving group
  • k represents an integer of 1 to 10
  • the present invention also provides a latent UV absorber comprising the compound represented by the above general formula (I-1).
  • the present invention also provides a composition comprising the compound represented by the above general formula (I-1).
  • the present invention also provides a cured product of a composition comprising a compound represented by the above general formula (I-1) and a polymerizable compound.
  • a composition containing the compound represented by the general formula (I-1) and a polymerizable compound is cured to form a cured product, and the cured product is irradiated with light. And a step of removing the photoleaving group contained in the compound represented by the general formula (I-1).
  • the present invention also relates to a compound represented by the following general formula (I-2) (hereinafter sometimes referred to as “compound I-2”) and a leaving substance derived from a photoleaving group (hereinafter referred to as “compound And B) (hereinafter, may be referred to as “second composition”).
  • compound I-2 a compound represented by the following general formula (I-2)
  • compound And B a leaving substance derived from a photoleaving group
  • A represents an atomic group having an ultraviolet absorbing ability
  • k represents an integer of 1 to 10.
  • the present invention relates to a compound and a UV absorber using the same, a composition, a cured product thereof, a method for producing a cured product, and a second composition. These will be described in detail below.
  • the compound of the present invention is represented by the following general formula (I-1) (hereinafter, the compound of the present invention is also referred to as compound I-1).
  • A is an atomic group having an ultraviolet absorbing ability
  • B is a photoleaving group
  • k is an integer of 1 to 10
  • the atomic group A has an ultraviolet absorbing ability.
  • the compound I-1 of the present invention has a low ultraviolet absorbing ability before the elimination of the photoleaving group B, but exhibits an excellent ultraviolet absorbing ability based on the atomic group A after the elimination of the photoleaving group B. Therefore, when the compound I-1 before elimination of the photoleaving group B is added, for example, into the polymerization system, the compound I-1 has a low ability to absorb ultraviolet light, so absorption of light irradiated for polymerization is caused. Performance is low and it is difficult to inhibit the curing of the polymerization system.
  • the compound I-1 of the present invention when the compound I-1 of the present invention is irradiated with light, the photoleaving group is released and exhibits excellent ultraviolet absorbing ability. Therefore, by irradiating the cured product containing compound I-1 with light, the cured product can be easily imparted with ultraviolet absorbing ability.
  • the compound I-1 has the advantage of being less likely to cause damage to the cured product and its peripheral members such as the base material, since the compound I-1 does not need to be heat-treated to develop its ultraviolet absorbing ability. For the above reasons, the compound I-1 has, for example, little inhibition of curing, and can easily impart ultraviolet light absorbing ability and the like to a cured product.
  • the compound I-1 of the present invention has a low ability to absorb light irradiated for the development of photosensitivity before desorption of the photoleaving group B. Therefore, when the compound I-1 is added to a photosensitive composition whose solubility in an alkali developer changes by light irradiation, it is possible to stably exhibit photosensitivity.
  • the compound I-1 can easily impart ultraviolet light absorbing ability and the like to the photosensitive composition by carrying out light irradiation capable of releasing the light leaving group. As described above, the compound I-1 has less inhibition of expression of photosensitivity with respect to the photosensitive composition, and can easily impart ultraviolet light absorbing ability and the like to the photosensitive composition.
  • the compound I-1 of the present invention can easily adjust, for example, the dispersion or dissolution stability in the composition by having a photoleaving group B.
  • the compound I-1 can impart excellent dispersibility in the composition by selecting the photoleaving group B such that the affinity with other components contained in the composition is improved. Therefore, the compound I-1 can impart excellent ultraviolet light absorbing ability to the composition, and can also impart excellent dispersion stability during storage before use.
  • the compound I-1 of the present invention has a photoleaving group B.
  • the photoleaving group in the present invention can be a group which can be eliminated from compound I-1 by being irradiated with light of a specific wavelength.
  • the photoleaving group B is eliminated from compound I-1, and an atomic group having a hydroxyl group and an ultraviolet light absorbing ability, represented by the following general formula (I-2) A compound having A is formed.
  • A represents an atomic group capable of absorbing ultraviolet light
  • k represents an integer of 1 to 10
  • the wavelength of the light from which the photoleaving group B leaves the compound I-1 is, for example, the wavelength range of ultraviolet light or visible light. Specifically, the wavelength of 365 nm can be included, more specifically, the light of wavelength of 250 nm or more and 450 nm or less can be included, and preferably, the light of wavelength of 280 nm or more and 380 nm or less can be included. Can.
  • Integrated light quantity of the light irradiated to detach the light leaving group B from above Compound I-1 for example, be a 1000 mJ / cm 2 or more 10000 mJ / cm 2 or less, 1000 mJ / cm 2 or more 5000mJ / Cm 2 or less is preferable, and 2000 mJ / cm 2 or more and 4000 mJ / cm 2 or less is more preferable.
  • the integrated light quantity of the light irradiated for curing the composition containing the polymerizable compound etc. can be usually less than 1000 mJ / cm 2 . Therefore, when the integrated light amount is in the above-mentioned range, for example, application to a photocurable composition becomes easy.
  • the elimination of the photoleaving group B may be any one capable of imparting a desired ultraviolet absorbing ability, and for example, the elimination rate of the photoleaving group can be 50% or more, Especially, it is preferable that it becomes 80% or more. It is because application to a photocurable composition becomes easy.
  • the compound I-1 may have an integrated light quantity that suppresses photodetachment as long as a desired curing inhibition suppressing effect can be obtained, and can be less than 1000 mJ / cm 2 . It is because application to a photocurable composition becomes easy. Further, to suppress photodetachment may be any as long as a desired curing inhibition inhibitory effect can be obtained.
  • the desorption rate of the photoleaving group B can be less than 50%. Especially, it is preferable that it becomes 20% or less. It is because application to a photocurable composition becomes easy.
  • the integrated light quantity can be measured by preparing a 0.01% by mass acetonitrile solution of compound I-1 and using the same method as the method of measuring the desorption rate described in the examples.
  • the photoleaving group B satisfying the above requirements is represented by the following general formulas (B-1), (B-2), (B-3), (B-4), (B-5) And groups represented by (B-6), (B-7) and (B-8).
  • the following general formulas (B-1-a), (B-2-a), (B-3-a), (B-4), (B-5), (B-6), (B) -7-a), (B-7-b) and (B-8-a) are preferable, and a group represented by the following general formula (B-1-a) Is preferred.
  • the compound I-1 can be easily released and the cured product can be easily imparted with ultraviolet light absorbing ability and the like.
  • groups represented by the following general formulas (B-9) and (B-10) can also be mentioned.
  • R 11 , R 13 , R 16 , R 18 , R 19 , R 20 , R 23 , R 26 and R 28 each independently represent a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group
  • R 12, R 14, R 17 , R 21, R 22, R 24, R 25, R 27, R 29 and R 30 each independently represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl A 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-
  • each of R 31 and R 40 independently 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, an aryl group having 6 to 20 carbon atoms, carbon Represents an arylalkyl group having 7 to 20 atoms or a heterocycle-containing group having 2 to 20 carbon atoms
  • R 32 , R 33 , R 41 , R 42 , R 43 and R 44 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, 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,
  • alkyl group having 1 to 40 carbon atoms represented by (C) there are methyl group, ethyl group, propyl group, iso-propyl group, butyl group, sec-butyl group, tert-butyl group, iso-butyl group.
  • amyl group iso-amyl group, tert-amyl group, cyclopentyl group, hexyl group, 2-hexyl group, 3-hexyl group, cyclohexyl group, 4-methylcyclohexyl group, heptyl group, 2 Heptyl, 3-heptyl group, iso- heptyl, tert- heptyl, 1-octyl group, iso- octyl group, and a tert- octyl group and adamantyl group.
  • Examples of the aryl group having 6 to 20 carbon atoms represented by R 11 and the like include a phenyl group, a naphthyl group and an anthracenyl group.
  • Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R 11 and the like include a benzyl group, a fluorenyl group, an indenyl group and a 9-fluorenylmethyl group.
  • heterocycle-containing group having 2 to 20 carbon atoms represented by R 11 and the like described above examples include, for example, pyridyl group, pyrimidyl group, pyridazyl group, piperidyl group, pyranyl group, pyrazolyl group, triazyl group, pyrrolyl group, quinolyl group , Isoquinolyl group, imidazolyl group, benzimidazolyl group, triazolyl group, furyl group, furanyl group, benzofuranyl group, thienyl group, thiophenyl group, benzothiophenyl group, thiadiazolyl group, thiazolyl group, benzothiazolyl group, oxazolyl group, benzoxazolyl group , Isothiazolyl group, isoxazolyl group, indolyl group, 2-pyrrolidinone-1-yl group, 2-piperidone-1-yl group, 2,4-di
  • Examples of the alkyl group having 1 to 8 carbon atoms represented by R ′ include those exemplified for the alkyl group represented by R 11 and the like, and those having 1 to 8 carbon atoms.
  • the alkyl group, the aryl group, the arylalkyl group and the heterocyclic group may have a substituent.
  • the compounds I-1 of the present invention include those having no substituent and those having a substituent, unless otherwise specified.
  • Examples of the substituent which may substitute a hydrogen atom such as an alkyl group, an aryl group, an arylalkyl group and a heterocycle-containing group include, for example, ethylenic unsaturated groups such as a vinyl group, an allyl group, an acryl group and a methacryl group; Halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl group, 2-chloroacetyl group, propionyl group, octanoyl group, acryloyl group, methacryloyl group, phenylcarbonyl (benzoyl) group, phthaloyl group, 4-trifluoromethylbenzoyl group
  • acyl groups such as pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadec
  • the number of carbon atoms of the group defines the number of carbon atoms of the group after the substitution.
  • 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
  • the number of carbon atoms of the group defines the number of carbon atoms of the group after the replacement.
  • 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.
  • “—CO—O—C 39 H 79 ” corresponds to “an alkyl group having 40 carbon atoms in which the terminal methylene group is replaced by —CO—O—”.
  • the combination which substitutes the said methylene group can be made into the combination on the conditions which oxygen atom does not adjoin.
  • the terminal methylene group on the proximal side may be replaced by -O- to form an alkoxy group.
  • an alkoxy group for example, an alkoxy group having 1 to 10 carbon atoms can be mentioned.
  • Each of R 11 , R 13 , R 16 , R 18 , R 19 , R 20 , R 23 , R 26 and R 28 is preferably a group other than a hydroxyl group, and is a halogen atom, a cyano group, a nitro group or a carboxyl group It is preferably 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, a heterocyclic group having 2 to 20 carbon atoms, or the like.
  • the photoleaving group B is easily released from the compound I-1, and the synthesis of the compound I-1 becomes easy.
  • R 11 and R 23 are particularly preferably an alkoxy group having 1 to 10 carbon atoms such as a nitro group or a methoxy group, an alkyl group having 1 to 40 carbon atoms such as a methyl group, a halogen atom or the like. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
  • R 11 is preferably an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a halogen atom, and an alkoxy group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms It is more preferably an alkyl group or a halogen atom, still more preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom, and it is an alkoxy group having 1 to 3 carbon atoms, a chlorine atom or a bromine atom Particularly preferred. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
  • the R 13 , R 18 , R 19 , R 20 , R 26 and R 28 are preferably an alkyl group having 1 to 40 carbon atoms. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
  • R 16 it is preferable that two adjacent R 16 's combine with each other to form a benzene ring. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
  • R 31 and R 40 each is preferably a group other than a hydroxyl group, and is a halogen atom, a cyano group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, the number of carbon atoms
  • the arylalkyl group is preferably 7 to 20, or a heterocycle-containing group having 2 to 20 carbon atoms.
  • R 31 is preferably an alkyl group having 1 to 40 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 5 carbon atoms. Particularly preferred is an alkyl group having 1 to 3 carbon atoms.
  • -O- replacing the methylene group is such that the alkyl group and the arylalkyl group are interrupted respectively In other words, it may be substituted by a methylene group other than the ends of the alkyl group and the arylalkyl group.
  • R 12 is preferably a hydrogen atom, a carboxyl group, or an alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
  • R 14 , R 17 , R 21 , R 24 , R 25 , R 27 , R 29 and R 30 are preferably a hydrogen atom or an alkyl group having 1 to 40 carbon atoms, and a hydrogen atom Being particularly preferred. This is because the photoleaving group B is easily released from the compound I-1 and the synthesis of the compound I-1 is facilitated.
  • R 15 and R 22 are preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
  • Each of R 32 and R 33 independently is preferably a hydrogen atom, a carboxyl group or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, and a hydrogen atom Is particularly preferred. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
  • R 41 to R 44 are preferably each independently a hydrogen atom, a carboxyl group or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, and it is a hydrogen atom Is particularly preferred. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
  • the above b 1, b 2, b 3, b 6, b 7, b 8 and b 9 can be each independently an integer of 0 to 4 but preferably an integer of 0 to 3 from the viewpoint of easiness of synthesis, It is more preferably an integer of 0 to 2, still more preferably 0 to 1, and particularly preferably 0. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
  • the above b 4 and b 5 can be each independently an integer of 0 to 5, but from the viewpoint of easiness of synthesis, it is preferably an integer of 0 to 3 and more preferably an integer of 0 to 2 Preferably, it is 0 to 1, more preferably 0.
  • the above c1 can be an integer of 0 to 5, but from the viewpoint of easiness of synthesis, it is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and 0 to 1 It is more preferable that it is an integer of, and it is particularly preferable that it is 1. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
  • the above c 2 can be an integer of 0 to 4, but from the viewpoint of easiness of synthesis, it is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and 0 to 1 More preferably, it is an integer of 0, and particularly preferably 0. This is because a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product can be provided.
  • the type of photoleaving group B contained in compound I-1 of the present invention may be one type per compound I-1, and may be two or more types. From the viewpoint of facilitating the synthesis of the compound I-1, it is preferable to use one type, since curing inhibition is small, ultraviolet absorptivity and the like can be easily given to the cured product, and the compound I-1 can be easily synthesized.
  • the content number k of the photoleaving group is an integer of 1 to 10, the curing inhibition is small, and the cured product can be easily imparted with ultraviolet light absorbing ability and the like, and from the viewpoint of easiness of synthesis, It is preferably an integer of 1 to 5, more preferably an integer of 1 to 4, and particularly preferably an integer of 1 to 3.
  • Atomic group A having ultraviolet absorbing ability The atomic group A is an atomic group having an ultraviolet absorbing ability.
  • the compound I-1 of the present invention is irradiated with light of a specific wavelength, whereby the photoleaving group B is eliminated to produce a compound I-2 having a hydroxyl group. And, when the atomic group A has an ultraviolet absorbing ability, the compound I-2 exhibits an ultraviolet absorbing ability.
  • the phrase "having ultraviolet absorbing ability" means, for example, a compound having ultraviolet absorbing ability, specifically, compound I-1 after elimination of photoleaving group B, ie, compound I-2, having a wavelength of 250 nm or more It can be capable of absorbing light in the range of 450 nm or less.
  • the atomic group having ultraviolet absorbing ability can be a group of atoms having at least one group having ultraviolet absorbing ability or at least one group having ultraviolet absorbing ability. More specifically, the compound I-1 after elimination of the photoleaving group B, that is, the compound I-2, has a maximum absorption wavelength within the wavelength range of 250 nm to 600 nm.
  • It is preferably capable of absorbing light having a wavelength of 250 nm to 400 nm and capable of absorbing light having a maximum absorption wavelength of 260 nm to 390 nm, and particularly preferably absorbing a light having a maximum absorption wavelength of 280 nm to 380 nm. .
  • the maximum absorption wavelength of the compound I-1 after removal of the photoleaving group B, ie, the compound I-2 can be measured, for example, by the following measurement method.
  • a compound I-1 after elimination of the photoleaving group B that is, a compound I-2 dissolved in a solvent (acetonitrile) to a concentration of 0.01% by mass
  • a solvent acetonitrile
  • the evaluation sample is filled in a quartz cell (optical path length 10 mm, thickness 1.25 mm), and obtained by measuring the absorbance using an absorptiometer (for example, U-3900 (manufactured by Hitachi High-Tech Science Co., Ltd.)) Can.
  • the compound I-1 of the present invention is a compound I-1 (compound I-2) after the elimination of the photoleaving group B and the maximum absorption wavelength of the compound I-1 before the elimination of the photoleaving group B.
  • the maximum absorption wavelength of compound I-1 before elimination of photoleaving group B is shorter than the maximum absorption wavelength of compound I-2 in the range of 250 nm to 600 nm when the maximum absorption wavelength of Is preferred. It is because application to a photocurable composition becomes easy.
  • the difference in the maximum absorption wavelength of the compound I-1 with the compound I-2 after elimination of the photoleaving group B is preferably 1 nm or more, and more preferably 1 nm to 100 nm. It is particularly preferable to be 1 nm or more and 50 nm or less. It is because application to a photocurable composition becomes easy.
  • Such atomic group A can be the same as the atomic group generally used for a UV absorber having a phenolic hydroxyl group. That is, the compound I-2 is generally used as a UV absorber having a phenolic hydroxyl group.
  • the compound I-2 2-hydroxybenzophenones, 2- (2'-hydroxyphenyl) benzotriazoles, benzoates and triaryltriazines described in JP-A-2017-008221, etc.
  • benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers described in JP-A-2002-97224 can be used.
  • Examples of the atomic group A include a phenol structure in which a phenolic hydroxyl group is protected by a photoleaving group B, that is, one containing a benzene ring to which the B-O- is directly bonded.
  • a photoleaving group B that is, one containing a benzene ring to which the B-O- is directly bonded.
  • an atomic group containing a benzene ring and a benzotriazole ring to which B-O- is directly bonded an atomic group containing a benzophenone ring to which B-O- is directly bonded
  • benzene to which B-O- is directly bonded Mention may be made of atomic groups comprising a ring and a triazine ring.
  • At least one group of a benzotriazole group, a benzophenone group and a triazine group includes a structure directly bonded to a benzene ring contained in the above-mentioned phenol structure, and among them, a benzotriazole group, a benzophenone group and triazine group It is preferable that the bonding position of at least one group of the group to the benzene ring is ortho to the bonding position of B-O-. It is because it is easy to set it as a compound which has few hardening inhibition and can give an ultraviolet absorptivity etc. easily with respect to hardened
  • Examples of the compound I-1 of the present invention include those represented by the following general formulas (A-1), (A-2) and (A-3).
  • 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 the above -O-B
  • At least one of R 1 and R 2 is the above-mentioned -O-B
  • R 3 , R 4 , R 5 , R 6 , 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, the number of carbon atoms
  • n and m2 each independently represent an integer of 1 to 10, n represents an integer of 1 to 3; 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-n, X 1 and X 2 each represent an m1 monovalent or m2 divalent linking group.
  • Examples of the arylalkyl group having 7 to 20 carbons, a heterocycle-containing group having 2 to 20 carbons, and the alkyl group having 1 to 8 carbons represented by R ′ include the above-mentioned “1. And those exemplified as R 11 etc. and R ′ described in the above section can be mentioned.
  • At least one of R 1 and R 2 is -O-B. From the viewpoint of easiness of synthesis, it is preferable that one of the R 1 and R 2 be the above-described —O—B. From the viewpoint of making the change of the ultraviolet ray absorbing ability large, in the above R 1 and R 2 , it is preferable that both R 1 and R 2 be the above-described —O—B.
  • R 1 and R 2 each represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, a carbon atom, when only one is the above —O—B It is preferably an arylalkyl group having 7 to 20 atoms or a heterocyclic group having 2 to 20 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 40 carbon atoms.
  • the compound I-1 has a large change in the ultraviolet light absorbing ability.
  • the compound I-1 has a reduced inhibition of curing.
  • the above-mentioned alkyl group and arylalkyl group for example, those in which a methylene group is interrupted by -O-, -CO- or the like can be preferably used.
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are preferably a cyano group, a hydroxyl group, an alkyl group having 1 to 40 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms More preferably a cyano group, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group having 7 to 10 carbon atoms, and more preferably an alkyl group having 3 to 20 carbon atoms.
  • the alkyl group is preferably an alkyl group having 3 to 10 carbon atoms. This is because the synthesis of the compound I-1 of the present invention is facilitated, and the compound I-1 exerts an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
  • R 4 is preferably an alkyl group having a branched structure of 3 to 15 carbon atoms, An alkyl group having a branched structure of 5 to 12 is more preferable, an alkyl group having a branched structure of 6 to 11 carbon atoms is still more preferable, and an alkyl having a branched structure of 7 to 10 carbon atoms Particularly preferred is a group.
  • the bonding site in the benzene ring of R 4 may be bonded to any bondable position, but is preferably para to the bonding site of —O—B. This is because the compound I-1 exerts an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
  • R 5 and R 6 each have 1 to 10 carbon atoms in which the methylene group at the benzene ring side terminal is replaced by -O- 20 alkyl groups, that is, alkoxy groups having 1 to 20 carbon atoms are preferable, and alkoxy groups having 3 to 15 carbon atoms are particularly preferable, and alkoxy groups having 5 to 12 carbon atoms are preferable. Being particularly preferred.
  • the bonding site in the benzene ring of R 5 and R 6 may be bonded to any bondable position, but is preferably in the meta position with respect to the bonding site of —O—B. . This is because the compound I-1 exerts an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
  • R 7 is an alkyl having 1 to 20 carbon atoms in which the methylene group at the terminal of the benzene ring is replaced by -O- Group, that is, an alkoxy group having 1 to 20 carbon atoms is preferable, and in particular, a methylene chain other than the benzene ring side terminal is substituted by -O- or -O-CO-, having 3 to carbon atoms 20 alkoxy groups are preferable, and particularly, an alkoxy group having 3 to 15 carbon atoms in which a methylene chain other than the benzene ring side terminal is replaced by -O- or -O-CO- is particularly preferable, in particular And an alkoxy group having 6 to 15 carbon atoms in which a methylene chain other than the benzene ring side end is replaced by -O- or -O-CO-, and in particular, a methylene chain other than
  • the bonding site in the benzene ring of R 7 may be bonded to any bondable position, but is preferably in the meta position with respect to the bonding site of —O—B. This is because the compound I-1 exerts an excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
  • R8 is preferably an aryl group having 6 to 20 carbon atoms from the viewpoint of being able to exhibit excellent ultraviolet absorbing ability after elimination of the photoleaving group B, and in particular, it is possible to use 6 to 12 carbon atoms.
  • the aryl group is preferably an aryl group, and particularly preferably a phenyl group which may have a substituent.
  • any of those in which a methylene group is not interrupted, and those in which it is interrupted by -O-, -CO- or the like can be preferably used.
  • m1 and m2 represent an integer of 1 to 10.
  • m1 and m2 are preferably each independently an integer of 1 to 6, more preferably an integer of 1 to 4, and an integer of 1 to 3 It is particularly preferable, and in particular, an integer of 1 to 2 is particularly preferable. This is because the synthesis of the compound I-1 is facilitated, and the compound I-1 exhibits an excellent ultraviolet absorbing ability after the elimination of the photoleaving group B. Further, from the viewpoint of the compound I-1 exerting an excellent ultraviolet absorbing ability after elimination of the photoleaving group B, m2 is preferably an integer of 1.
  • the above n represents an integer of 1 to 3.
  • the above n is preferably an integer of 2 to 3, and particularly preferably 3, from the viewpoint that the compound I-1 has a large change in the ultraviolet light absorbing ability.
  • the compound n is preferably an integer of 1 to 2, and particularly preferably 1.
  • the above a1 and a3 each independently represent an integer of 0 to 4. From the viewpoint of easiness of synthesis, the above a1 and a3 are preferably each independently an integer of 0 to 3, more preferably an integer of 0 to 2, and an integer of 0 to 1 Particularly preferred. This is because the compound I-1 can be made to be a compound that exhibits excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
  • the above a2 represents an integer of an integer of 0 to 2. From the viewpoint of solubility, the a2 is preferably an integer of 1 to 2. Further, from the viewpoint of exhibiting excellent ultraviolet absorbing ability after the compound I-1 exhibits the elimination of the photoleaving group B, the a2 is preferably 1.
  • the above a4 and a5 each independently represent an integer of 0 to 3. From the viewpoint of easiness of synthesis, the above a4 and a5 are preferably an integer of 0 to 2, particularly preferably an integer of 1 to 2, and particularly preferably 1. This is because the compound I-1 can be made to be a compound that exhibits excellent ultraviolet absorbing ability after elimination of the photoleaving group B.
  • the above a6 represents an integer of 0 to 3-n.
  • the above a6 is preferably an integer of 0 to 1, and is 0, from the viewpoint that compound I-1 exerts an excellent ultraviolet absorptivity after removal of photoleaving group B and easiness of synthesis. Is preferred.
  • the compounds I-1 represented by the above general formulas (A-1) and (A-2) are each represented by X 1 and X 2 (hereinafter sometimes referred to as X) an m monovalent or m divalent
  • X an m monovalent or m divalent
  • m an m monovalent or m divalent
  • m an m monovalent or m divalent
  • m m1 or m2 (hereinafter sometimes referred to as m) specific groups are bonded to a specific atom or group which may be referred to as m-valent).
  • the m specific groups may be identical to one another or may be different.
  • the above X represents an m-valent bonding group.
  • the bonding group X is a direct bond, 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 OO,> 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 having 6 to 35 carbon atoms
  • R 53 and R 54 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, or the number of carbon atoms.
  • an aromatic hydrocarbon group having 6 to 35 carbon atoms or a heterocyclic group having 2 to 35 carbon atoms wherein the aliphatic hydrocarbon group, the aromatic ring containing hydrocarbon group and the heterocyclic group are -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 -, - NH- CO-O -, - NR '-, - S-S -, - SO 2 -, nitrogen atom or may have been interrupted in these combinations, the aromatic or heterocyclic
  • the ring may be fused to another ring.
  • the aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X, is, for example, a methyl group, an ethyl group or a propyl group, as m is a monovalent group.
  • the aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m which is represented by the above linking group X, is a methylene group, an ethylene group, a propylene group, a butylene group as the one where m is divalent And alkylene groups such as butyldiyl group; those in which the methylene chain of the above alkylene group is replaced with -O-, -S-, -CO-O-, -O-CO-; ethanediol, propanediol, butanediol, Residues of diol groups such as pentanediol and hexanediol; Residues of dithiol groups such as ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, hexanedithiol and the like, and groups in which these groups are substitute
  • the aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same number of valences as m, which is represented by the above linking group X, is, for example, a propyridine group and 1,1, Alkylidine groups such as 3-butylidine propyridine group; and groups in which these groups are substituted by a substituent described later.
  • the aromatic ring-containing hydrocarbon group having a carbon number of 6 to 35 and having the same number of valences as m, which is represented by the above linking group X, is, for example, a benzyl group, a phenethyl group or diphenylmethyl when m is monovalent
  • Arylalkyl groups such as triphenylmethyl group, styryl group and cinnamyl group; aryl groups such as phenyl group and naphthyl group; aryloxy groups such as phenoxy group and naphthyloxy group; arylthio groups such as phenylthio group and naphthylthio group:
  • the group etc. by which these groups were substituted by the substituent mentioned later are mentioned.
  • the aromatic ring-containing hydrocarbon group having a carbon number of 6 to 35 and having the same number of valences as m, which is represented by the bonding group X, is an arylene group such as a phenylene group and a naphthylene group when m is divalent.
  • arylene group such as a phenylene group and a naphthylene group when m is divalent.
  • residues of bifunctional phenol groups such as catechol groups and bisphenol groups
  • 2,4,8,10-tetraoxaspiro [5,5] undecane groups and groups in which these groups are substituted by substituents described later Can be mentioned.
  • the aromatic ring-containing hydrocarbon group having a carbon number of 6 to 35 and having the same number of valences as m, which is represented by the above linking group X, is not particularly limited as m is trivalent: phenyl-1,3,5- A trimethylene group and a group in which this group is substituted by a substituent described later can be mentioned.
  • the heterocycle-containing group having 2 to 35 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X, is a pyridyl group, a pyrimidyl group, a pyridazyl group, a piperidyl group as the one in which m is monovalent , Pyranyl group, pyrazolyl group, triazyl group, pyrrolyl group, quinolyl group, isoquinolyl group, imidazolyl group, benzimidazolyl group, triazolyl group, furyl group, furanyl group, benzofuranyl group, thienyl group, thiophenyl group, benzothiophenyl group, thiadiazolyl group , Thiazolyl group, benzothiazolyl group, oxazolyl group, benzoxazolyl group, isothiazolyl group, isoxazolyl group, indolyl group
  • the heterocycle-containing group having 2 to 35 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X, is a pyridine ring, a pyrimidine ring, a piperidine ring, a piperazine ring as the m is divalent And a divalent group having a triazine ring, a furan ring, a thiophene ring, an indole ring and the like, and a group in which these groups are substituted by a substituent described later.
  • the hetero ring-containing group having 2 to 35 carbon atoms and having the same number of valences as m, which is represented by the aforementioned linking group X, is a trivalent group having an isocyanuric ring, a triazine ring, as m is trivalent. And groups in which these groups are substituted by the substituents described later.
  • the aliphatic hydrocarbon group represented by said X or this aliphatic hydrocarbon group is substituted by the substituent mentioned later Among the above groups, those having 1 to 35 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 represented by R 53 and R 54 has 6 to 35 carbon atoms represented by X above. 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 functional group such as the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group and the heterocyclic group-containing group may have a substituent.
  • the compounds I-1 of the present invention include those having no substituent and those having a substituent, unless otherwise specified.
  • Examples of the substituent such as an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, and a heterocycle-containing group include the same substituents as those for substituting a hydrogen atom such as an alkyl group used for R 11 and the like. It can be mentioned.
  • X may represent a group represented by the following general formula (1).
  • Y 1 represents a single bond, -CR 55 R 56 -, - NR 57 -, a divalent aliphatic hydrocarbon group having a carbon number of 1 to 35, divalent carbon atoms 6 to 35 aromatic ring-containing hydrocarbon group, divalent heterocyclic group having 2 to 35 carbon atoms, or any group represented by the following (1-1) to (1-3)
  • the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and the heterocyclic ring-containing group having 2 to 35 carbon atoms are -O-, -S-, -CO-, -COO- And -OCO- or -NH- or combinations thereof may be interrupted
  • R 55 and R 56 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
  • Z 1 and Z 2 are each independently represent a
  • R 59 represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent
  • R 60 represents an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, or a halogen atom
  • c1 represents an integer of 0 to 5
  • the * means that at the * part, it bonds to an adjacent group.
  • 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 in some cases, 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,
  • 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
  • Y 12 represents a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or Represents an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms;
  • -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH- may be interrupted, and Z 1 to Z 4 each independently represent the general formula (2) Represents a group in the same range as the group represented by Z 1 to Z 3 in
  • Y 13 represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a pentavalent aromatic ring-containing hydrocarbon group having 6 to 30 carbon atoms, or pentavalent carbon And an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms represented by the formula: -COO- And Z 1 to Z 5 may each independently be Z 1 to Z 1 in the above general formula (2), which may be interrupted by —O—, —OCO—, —NHCO—, —NH— or Represents the same group as the group represented by Z 3 )
  • Y 14 is a single bond, a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a hexavalent aromatic ring containing hydrocarbon group having 6 to 35 carbon atoms, or And an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, In some cases, it may be interrupted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and each of Z 1 to Z 6 is independently represented by the above general formula (7) Represents the same group as the groups represented by Z 1 to Z 3 )
  • Examples of the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 1 in the group represented by the above general formula (1) include 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 And 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 .
  • These groups may be interrupted by —O—, —S
  • Examples of the divalent heterocyclic group having 2 to 35 carbon atoms represented by Y 1 in the group represented by the above general formula (1) include pyridine, pyrazine, piperidine, piperazine, pyrimidine, pyridazine, triazine, and hexa Hydrotriazines, furans, tetrahydrofurans, chromans, xanthenes, thiophenes, thiolanes and the like include divalent groups substituted by Z 1 and Z 2 .
  • the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocycle-containing group represented by Y 1 in the group represented by the above general formula (1) have a halogen atom, a cyano group, a nitro group or one carbon atom It may be substituted with an alkoxy group of -8.
  • Each functional group such as the above aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic group-containing group may have a substituent, and unless otherwise specified, has a substituent. Not substituted or substituted.
  • Examples of the substituent such as an aliphatic hydrocarbon group, an aromatic ring-containing hydrocarbon group, and a heterocycle-containing group include the same substituents as those for substituting a hydrogen atom such as an alkyl group used for R 11 and the like. .
  • the alkyl group having 1 to 8 carbon atoms represented by R 55 and R 56 in the group represented by the above general formula (1) is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s- group Butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl Groups, 3-heptyl group, isoheptyl group, t-heptyl group, 1-octyl group, isooctyl group, t-octyl group and the like.
  • the aryl group having 6 to 20 carbon atoms represented by R 55 and R 56 in the group represented by the above general formula (1) includes a phenyl group, a naphthyl group, a 2-methylphenyl group and a 3-methylphenyl group , 4-methylphenyl group, 4-vinylphenyl group, 3-iso-propylphenyl group, 4-iso-propylphenyl group, 4-butylphenyl group, 4-iso-butylphenyl group, 4-tert-butylphenyl group , 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethyl Phenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-
  • the arylalkyl group having 7 to 20 carbon atoms represented by R 55 and R 56 in the group represented by the above general formula (1) includes a benzyl group, a phenethyl group, a 2-phenylpropan-2-yl group, And diphenylmethyl group, triphenylmethyl group, styryl, cinnamyl and the like.
  • Examples of the heterocycle-containing group of the formulas 2 to 35 may be the same as those exemplified as R 53 and R 54 .
  • the cycloalkyl group having 3 to 10 carbon atoms represented by R 59 in the group represented by the above general formula (1-1) is a cyclopropyl group, cyclobutyl group, cyclopentyl group, cycloheptyl group, cyclo Examples thereof include an octyl group and the like, and a group in which these groups are substituted with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
  • Examples of the alkyl group having 1 to 10 carbon atoms represented by R 60 in the group represented by the above general formula (1-1) include R 11 and the like in the above “1.
  • Photoleaving group B” Among the exemplified alkyl groups, those having 1 to 10 carbon atoms can be mentioned.
  • the alkoxy group having 1 to 10 carbon atoms represented by R 60 in the group represented by the above general formula (1-1) is exemplified by R 11 and the like in the above “1.
  • Photoleaving group B” Among the exemplified alkoxy groups, those having 1 to 10 carbon atoms can be mentioned.
  • alkenyl group having 2 to 10 carbon atoms represented by R 60 in the group represented by the above general formula (1-1) a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, 2- Examples include butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-octenyl and the like.
  • the alkyl group, alkoxy group and alkenyl group represented by R 60 may be substituted with a halogen atom, and the position of substitution is not limited.
  • an alkyl group having 1 to 10 carbon atoms represented by R 61 and R 62 an alkyl group having 6 to 20 carbon atoms, and 7 to carbon atoms
  • Examples of the arylalkyl group of 20 include those exemplified as R 11 and the like in the above-mentioned section “1.
  • Photoleaving group B those having a predetermined number of carbon atoms.
  • the arylalkenyl group having 8 to 20 carbon atoms represented by R 61 and R 62 in the group represented by the above general formula (1-3) is a carbon atom which may be substituted by the above halogen atom Groups in which the oxygen atom of the aryloxy group of formulas 6 to 20 is substituted with an alkenyl group such as vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl, etc. It can be mentioned.
  • the heterocyclic group containing 2 to 20 carbon atoms represented by R 61 and R 62 in the group represented by the above general formula (1-3) includes a pyridine group, a pyrazine group, a piperidine group, a piperazine group, A pyrimidine group, a pyridazine group, a triazine group, a hexahydro triazine group, a furan group, a tetrahydrofuran group, a chromane group, a xanthene group, a thiophene group and a thiofuran group, and groups in which these groups are substituted with a halogen atom are listed.
  • Each functional group in the group represented by the above general formula (1-3), such as aryloxy group, arylthio group, arylalkenyl group, heterocycle-containing group, represented by R 61 and R 62 has a substituent. And, unless otherwise specified, they are unsubstituted ones having no substituent or ones having a substituent.
  • the substituent that substitutes a hydrogen atom such as an aryloxy group, an arylthio group, an arylalkenyl group, and a heterocycle-containing group has the same content as the substituent that substitutes a hydrogen atom such as an alkyl group used for R 11 and the like. be able to.
  • Examples of the trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms represented by Y 11 in the group represented by the above general formula (2) include the fats exemplified in the explanation of X in the above general formula (1)
  • Group hydrocarbon group is substituted by Z 1 , Z 2 and Z 3 , and these groups include -O-, -S-, -CO-, -CO-O-,- O-CO-, -SO 2- , -NH- or a combination thereof may be substituted.
  • the trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 11 in the group represented by the general formula (2) is exemplified in the description of X in the general formula (1) Examples thereof include trivalent groups in which the aromatic ring-containing hydrocarbon group is substituted with Z 1 , Z 2 and Z 3 .
  • Examples of the trivalent heterocyclic group having 2 to 35 carbon atoms represented by Y 11 in the group represented by the above general formula (2) include the heterocycles exemplified in the description of X in the above general formula (1)
  • Examples include trivalent groups in which the containing group is substituted with Z 1 , Z 2 and Z 3 .
  • Examples of the hydrocarbon group or the heterocycle-containing group having 2 to 35 carbon atoms can include the same ones as those exemplified as R 53 and R 54 described above.
  • Examples of the aliphatic hydrocarbon group having 1 to 35 carbon atoms having a tetravalent carbon atom represented by Y 12 in the group represented by the general formula (3) include the fats exemplified in the description of X in the general formula (1)
  • Group hydrocarbon group is substituted by Z 1 , Z 2 , Z 3 and Z 4 and examples thereof include -O-, -S-, -CO-, -COO-, -OCO-,- It may be interrupted by NH-or a combination of these.
  • the tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 12 in the group represented by the above general formula (3) is exemplified in the description of X in the above general formula (1)
  • a tetravalent group in which the aromatic ring-containing hydrocarbon group is substituted with Z 1 , Z 2 , Z 3 and Z 4 can be mentioned.
  • Examples of the tetravalent heterocyclic group having 2 to 35 carbon atoms represented by Y 12 in the group represented by the general formula (3) include the heterocyclic rings exemplified in the description of X in the general formula (1). Examples include tetravalent groups in which the containing group is substituted by Z 1 , Z 2 , Z 3 and Z 4 .
  • Examples of the pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y 13 in the group represented by the above general formula (4) include the fats exemplified in the explanation of X in the above general formula (1)
  • Group hydrocarbon group is substituted by Z 1 , Z 2 , Z 3 , Z 4 and Z 5 and examples thereof include -O-, -S-, -CO-, -CO-O-, It may be replaced by a group of -O-CO-, -SO 2- , -NH- or a combination thereof.
  • the pentavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 13 in the group represented by the general formula (4) is exemplified in the description of X in the general formula (1)
  • a pentavalent group in which the aromatic ring-containing hydrocarbon group is substituted with Z 1 , Z 2 , Z 3 , Z 4 and Z 5 can be mentioned.
  • Examples of the pentavalent heterocyclic group having 2 to 35 carbon atoms represented by Y 13 in the group represented by the general formula (4) include the heterocycles exemplified in the description of X in the general formula (1) containing groups include pentavalent group substituted with Z 1, Z 2, Z 3 , Z 4 and Z 5.
  • Examples of the aliphatic hydrocarbon group having 2 to 35 carbon atoms which is represented by Y 14 in the general formula (5) include the aliphatic hydrocarbon groups exemplified in the description of X in the general formula (1). And a hexavalent group substituted by Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 , and the groups include -O-, -S-, -CO-, -COO-,- It may be interrupted by OCO-, -SO 2- , -NH- or a combination thereof.
  • Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms having a hexavalent carbon atom represented by Y 14 in the general formula (5) include the aromatic ring-containing hydrocarbons exemplified in the description of X in the general formula (1)
  • a hexavalent group in which a group is substituted by Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 can be mentioned.
  • Examples of the hexavalent heterocyclic group having 2 to 35 carbon atoms represented by Y 14 in the general formula (5) include the heterocyclic groups exemplified in the description of X in the general formula (1) as Z And hexavalent groups substituted with 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 .
  • the bonding group X is preferably an aliphatic hydrocarbon group having 1 to 120 carbon atoms, more preferably an alkylene group or a residue of a diol, and having 1 to 12 carbon atoms.
  • an alkylene group of 10 or a diol residue of 1 to 10 carbon atoms is preferable, and an alkylene group of 1 to 5 carbon atoms or a diol residue of 1 to 5 carbon atoms is particularly preferable.
  • an alkylene group having 1 to 3 carbon atoms is preferable. This is because the compound can be made to be a compound which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product, and furthermore, the production of the compound I-1 is easy.
  • the bonding position of the bonding group X to the benzene ring may be any position in the benzene ring that can be bonded, but for example, the ortho position or the meta position with respect to R 2 is preferable. It is because it can be set as a compound which has few hardening inhibition and can give an ultraviolet absorptivity etc. easily with respect to hardened
  • the above atomic group A may be one containing a phenolic hydroxyl group, that is, one in which the compound I-1 contains a phenolic hydroxyl group not protected by the photoleaving group B, but the number of phenolic hydroxyl groups is 2 The number is preferably not more than one, more preferably zero. This is because the compound I-1 has less inhibition of curing.
  • Compound The compound of the present invention may be any compound represented by the above general formula (I-1), but is represented by the above general formula (A-1), (A-2) or (A-3) It is preferably a compound, and as the photoleaving group B, one represented by the above general formula (B-1-a) is preferable. It is because synthesis is easy, and furthermore, photodetachment is easy. Moreover, it is because an ultraviolet absorptivity etc. can be easily provided with respect to hardened
  • the molecular weight of the compound I-1 can be set according to the use of the compound I-1.
  • the molecular weight of the compound I-1 is, for example, preferably 250 or more and 5000 or less, more preferably 300 or more and 2500 or less, and particularly preferably 350 or more and 1500 or less. It is because it can be set as a compound which has few hardening inhibition and can give an ultraviolet absorptivity etc. easily with respect to hardened
  • the molecular weight of the compound I-1 is represented by weight average molecular weight (Mw) when the compound I-1 is a polymer having a repeating structure as its 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.
  • the method for producing the compound I-1 is not particularly limited as long as it can obtain a desired structure, and, for example, JP-A-57-111375, JP-A-3-173843 and JP-A-6- It is obtained by reacting an alkyl halide compound with a phenolic compound produced by the method described in Japanese Patent Application Laid-Open No. 128195, Japanese Patent Application Laid-Open No. 7-206771, Japanese Patent Application Laid-Open No. 7-252191 or Japanese Patent Application Laid-Open No. Can.
  • the compound I-1 is inactive before light irradiation, and the light leaving group is eliminated by light irradiation to generate a compound I-2 having a phenolic hydroxyl group. Further, the compound I-2 exhibits ultraviolet absorbing ability.
  • the application of the compound I-1 is preferably an application that is required to exhibit an ultraviolet absorptivity by light irradiation. Can.
  • the latent ultraviolet light absorber of the present invention comprises the compound I-1 of the present invention.
  • the latent UV absorber of the present invention has less inhibition of curing and can easily impart ultraviolet absorptivity and the like to a cured product.
  • the content of the compound I-1 in the latent ultraviolet absorber of the present invention is not particularly limited, and can be appropriately set according to the application of the latent ultraviolet absorber and the like.
  • the latent ultraviolet absorber of the present invention comprises 100 parts by mass of the compound I-1 in 100 parts by mass of the latent ultraviolet absorber, that is, the latent ultraviolet absorber comprises only the compound I-1 It can be done.
  • the latent ultraviolet absorber of the present invention may contain other components.
  • the content of the compound I-1 may be, for example, more than 20 parts by mass and 99 parts by mass or less in 100 parts by mass of the latent ultraviolet absorber.
  • the latent ultraviolet absorber has a small amount of inhibition of curing, and can effectively exhibit the effect of easily imparting ultraviolet absorptivity and the like to a cured product.
  • the type of the compound I-1 contained in the latent ultraviolet absorber may be only one type or two or more types.
  • the number of types can be, for example, 2 or more and 5 or less.
  • the compound I-1 described above can be the same as the contents described in the section “A. Compound”, and thus the description thereof is omitted here.
  • the latent ultraviolet absorber preferably contains, as another component, a resin component such as a polymer having no polymerizable group. This is because the compound I-1 can be stably held.
  • the shape of the latent ultraviolet absorber may be powdery, and may be pelletized.
  • a method for producing the latent ultraviolet absorber for example, a method may be used in which the compound I-1 and the resin component are mixed using an extruder etc. it can.
  • composition of the present invention comprises the compound I-1.
  • composition of the present invention it is possible to provide, for example, a composition which has less inhibition of curing and which can provide an excellent cured product of ultraviolet absorption ability.
  • each component of the said composition is demonstrated.
  • the content of the compound I-1 in the composition of the present invention is not particularly limited as long as it is an amount capable of imparting a desired ultraviolet absorbing ability and the like to the composition.
  • the content of the compound I-1 in the composition of the present invention 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 solid content of the composition, and 0.005 parts by mass or more and 10 parts by mass It is preferable that it is less than part. It is because it is easy to set it as a composition which has few hardening inhibition and can easily give an ultraviolet absorptivity etc. easily with respect to hardened
  • solid content contains all the components other than a solvent.
  • the content is on a mass basis unless otherwise noted.
  • the content of the compound I-1 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. And 0.005 parts by mass or more and 10 parts by mass or less. It is because it is easy to set it as a composition which has few hardening inhibition and can easily give an ultraviolet absorptivity etc. easily with respect to hardened
  • the type of the compound I-1 contained in the composition may be only one type or two or more types.
  • the type can be, for example, two or more and five or less.
  • the compound I-1 described above can be the same as the contents described in the section “A. Compound”, and thus the description thereof is omitted here.
  • the above composition may contain other components other than the above compound I-1 depending on its use and the like.
  • the resin component is mentioned, for example. This is because, for example, when the composition of the present invention contains a resin component in addition to the compound I-1, curability and the like can be easily imparted to the above composition, for example.
  • the composition of this invention contains a polymerization initiator with the said resin component as another component. By containing the resin component and the polymerization initiator as other components, the composition of the present invention can easily impart curability and the like to the composition.
  • Resin component examples include those capable of holding the above-mentioned compound I-1, which may be appropriately set depending on the application etc. of the composition, for example, polymerizing having a polymerizable group The compound etc. and the polymer which does not have a polymeric group etc. can be mentioned.
  • a polymerizable compound as the resin component, the composition can be used, for example, as a photocurable composition or a thermosetting composition.
  • the polymerizable compound varies depending on the type of the polymerizable group, that is, the type of the polymerization reaction, and may be, for example, a radical polymerizable compound, a cationic polymerizable compound, an anionic polymerizable compound, etc. it can. It is preferable that the said polymeric compound contains a radically polymerizable compound from a viewpoint of demonstrating the effect that hardening inhibition decreases effectively.
  • 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.
  • 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.
  • (meth) acryl is used by the meaning containing an acryl and methacryl.
  • (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.
  • a compound which has an acid value the compound etc. which have a carboxyl group can be mentioned, for example.
  • 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.
  • 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.
  • TMAH tetramethyl ammonium hydroxide
  • the radically polymerizable compound has, for example, an ethylenically unsaturated double bond group, and as a compound having an acid value, (meth) acrylic acid, ⁇ -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 1) Mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends such as acryloyloxyethyl] and ⁇ -carboxypolycaprolactone mono (meth) acrylate; hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth)
  • 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 represented by R 41 , R 42 , R 44 and R 44 include the above-mentioned “A Among those exemplified as R 11 and the like in the item of “compound”, those satisfying a predetermined number of carbon atoms can be mentioned.
  • Examples of the C 1-4 alkylidene group represented by X 41 include methylidene group, ethylidene group, propylidene group and butylidene group.
  • Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by X 41 include a cyclopropylene group, a cyclopentylene group, a cyclohexylene group and a cycloheptylene group.
  • the above-mentioned alkyl group, alkoxy group, alkenyl group, alkylidene group and alicyclic hydrocarbon group may have a substituent, and unless otherwise specified, it is an unsubstituted group having no substituent. Or a substituent.
  • Examples of the substituent that substitutes a hydrogen atom of the alkyl group, alkoxy group, alkenyl group, alkylidene group and alicyclic hydrocarbon group are the same as the substituent that substitutes a hydrogen atom such as an alkyl group used for R 11 and the like. It can be content.
  • the above-mentioned radically polymerizable compound has, for example, an ethylenically unsaturated double bond group, and as a compound having no acid value, 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate Propyl, 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, butoxyethoxye
  • the said radically polymerizable compound can be used individually or in mixture of 2 or more types.
  • 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.
  • 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.
  • the content of the radically polymerizable compound can be appropriately set according to the application etc.
  • the composition can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, and 10 parts It is preferable that it is a part or more and 90 mass parts or less, Especially, it is preferable that it is 40 mass parts or more and 80 mass parts or less.
  • the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity. Moreover, it is because there can be provided a composition which has less inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
  • the content of the polymerizable compound may be any one as long as the composition can be used as a curable composition, but 1 part by mass or more to 99 parts in total of 100 parts by mass of the compound I-1 and the polymerizable compound. It can be made into parts by mass or less, preferably 50 parts by mass or more and 99 parts by mass or less, and more preferably 80 parts by mass or more and 99 parts by mass or less, and 90 parts by mass or more and 98 parts by mass or less Is preferred. When the content is in the above-mentioned range, the composition can provide a composition which has less inhibition of curing and can easily impart ultraviolet light absorbing ability and the like to a cured product.
  • the content of the compound I-1 and the radically polymerizable compound can be appropriately set according to the application of the composition and the like, and for example, 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition.
  • the amount is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less.
  • the composition can be used as a negative composition excellent in sensitivity.
  • a composition which has less inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
  • 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.
  • 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
  • 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 ⁇ -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 ⁇ -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.
  • 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.
  • 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
  • ethylene or ⁇ -olefins of 3 to 20 carbon atoms examples 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 ⁇ , ⁇ -unsaturated acids, vinyl benzyl glycidyl ether and allyl glycidyl ether.
  • Specific examples of glycidyl esters of ⁇ , ⁇ -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, ⁇ -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], ⁇ -carboxypolycaprolactone mono (meth) acrylate, etc.
  • unsaturated aliphatic hydrocarbons such as vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluoroethylene
  • a commercial item can also be used as said epoxidized polyolefin,
  • Epolide PB3600, Epolide PB4700 made by Daicel
  • BF-1000, FC-3000 made by ADEKA
  • Bond first 2C bond first E
  • JP-100, JP-200 (Nippon Soda Co., Ltd.)
  • Poly bd R And -45 HT Poly bd R-15 HT
  • Ricon 657 manufactured by Arkema
  • oxetane compounds examples 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-oxet
  • vinyl ether compounds examples 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.
  • 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.
  • an 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 ⁇ -propiolactone and ⁇ -caprolactone.
  • an epoxy compound the epoxy compound illustrated as said cationically polymerizable compound can be used.
  • 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.
  • (B) Polymer Having No Polymerizable Group As a resin that can be used for the composition of the present invention, as described above, a polymer having no polymerizable group can be used.
  • the weight average molecular weight (Mw) of the polymer having no polymerizable group 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 can do.
  • Mw weight average molecular weight of the polymer having no polymerizable group
  • the composition of the present invention can be used as a photosensitive composition, for example, by including a photosensitive resin as a resin component.
  • Photosensitive resin has photosensitivity, and is used together with an acid generator, for example, it dissolves in a developer such as cleavage of chemical bond such as ester group or acetal group by action of acid 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.
  • polystyrene and derivatives thereof 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.
  • 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.
  • 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.
  • positive resin 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.
  • the photocationic polymerization initiator mentioned later, a thermal cationic polymerization initiator, etc. can be mentioned.
  • Non-Photosensitive resin may be any one not having 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.
  • the non-photosensitive resin for example, a polymer of the above-mentioned polymerizable compound can also be used.
  • (C) Resin component The content of the above resin component in the composition of the present invention can be appropriately determined according to the application etc. of the composition, and for example, 1 part by mass in 100 parts by mass of the solid content of the composition
  • the content is preferably 99 parts by mass or less, more preferably 20 parts by mass or more and 95 parts by mass or less, and particularly preferably 30 parts by mass or more and 90 parts by mass or less. It is because the said composition can hold
  • the content of the resin component can be appropriately set according to the application etc.
  • the composition can be, for example, 1 part by mass or more and 99 parts by mass or less, and 10 parts by mass or more in 100 parts by mass of the composition.
  • the content is preferably 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less.
  • the composition can be used as a negative composition excellent in sensitivity.
  • the content of the above resin component varies depending on the application etc.
  • the composition can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass in total of the compound I-1 and the resin component.
  • the content is preferably 50 parts by mass or more and 99 parts by mass or less, and more preferably 80 parts by mass or more and 99 parts by mass or less, and preferably 90 parts by mass or more and 98 parts by mass or less. It is because the said composition can provide the composition which can easily provide an ultraviolet absorptivity etc. easily with respect to hardened
  • the composition is 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition. It is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 40 parts by mass or more and 80 parts by mass or less.
  • the content is in the above-mentioned range, for example, the composition can be used as a negative composition excellent in sensitivity. Moreover, it is because there can be provided a composition which has less inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
  • the type of the resin component contained in the composition of the present invention 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.
  • the content of the polymerizable compound can be appropriately set according to the application of the composition, etc. It can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the polymerizable compound and the polymer.
  • 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 above-mentioned polymerization initiator is preferably a photopolymerization initiator from the viewpoint of effectively exerting the effect that the above-mentioned compound I-1 functions as an ultraviolet absorber.
  • 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.
  • 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.
  • 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-N-phenyl
  • benzyl compound examples include benzyl and the like.
  • benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide.
  • thioxanthone compound examples include thioxanthone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone and the like.
  • 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
  • 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, sometimes are 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
  • 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),
  • an indole oxime ester compound having an indole structure can also be used.
  • 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.
  • 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
  • the hydrogen atoms of the groups represented by R 211 , R 212 and R 213 are 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
  • the hydrogen atom of the group represented by R 203 further includes 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 , It may be substituted by 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 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 , CO
  • the hydrogen atoms of the groups represented by R 204 , R 205 , R 206 and R 207 are further selected from 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 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 group represented by R 214 , R 215 and R 216 may be branched side chain or cyclic alkyl; R 208 represents R 211
  • 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 the items of the above-mentioned “1. Among the contents exemplified as R 11 and the like, those having a predetermined number of carbon atoms can be mentioned.
  • 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.
  • 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
  • photo radical polymerization initiators may be used alone or in combination of two or more depending on the desired performance.
  • the content of the photo radical polymerization initiator may be any as long as it can impart desired curability and photosensitivity. For example, 0.001 parts by mass or more and 20 parts by mass with respect to 100 parts by mass of the polymerizable compound The amount may be as follows, preferably 0.1 to 30 parts by mass, and more preferably 0.5 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 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 +
  • 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;
  • Each of e R 58 is independent of each other and may be the same or different.
  • at least one of R 101 is preferably an organic group as described above having an aromatic ring. For example, even when substituted by an alkyl group, an alkoxy group, a hydroxy group, a hydroxyalkoxy group, a halogen atom, a benzyl group, a thiophenoxy group, a 4-benzoylphenylthio group, a 2-chloro-4-benzoylphenylthio group, etc. A certain phenyl group is mentioned.
  • 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- .
  • 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.
  • anion [LX f2 ] r- of the above general formula examples 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.
  • the anion [B1] r- has the following general formula, [LX f2-1 (OH)] r-
  • L, X and f2 are the same as above.
  • Other anions that can be used include perchlorate ion (ClO 4 ) ⁇ , trifluoromethyl sulfite ion (CF 3 SO 3 ) ⁇ , fluorosulfonate ion (FSO 3 ) ⁇ , toluene sulfonate anion And trinitrobenzenesulfonic acid anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraaryl borate and tetrakis (pentafluorophenyl) borate.
  • 1 type can be used individually or in mixture of 2 or more types.
  • aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate and 4-methylphenyldiazonium hexafluorophosphate.
  • Diaryls such as diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate and tolycamyliodonium tetrakis (pentafluorophenyl) borate Iodonium salt.
  • Sulfonium salts represented by the following Group I or Group II: sulfonium salts such as hexafluoroantimony ion, tetrakis (pentafluorophenyl) borate ion and the like.
  • other preferable ones are ( ⁇ 5-2, 4-cyclopentadien-1-yl) [(1, 2, 3, 4, 5, 6 ⁇ )-(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.
  • aromatic iodonium salts, aromatic sulfonium salts and iron-arene complexes are preferably used from the viewpoint of practical use and light sensitivity.
  • photoanion polymerization initiator what generate
  • the photoanion polymerization initiator include acetophenone O-aroyloxime (acetophenone O-aroyloxime), nifedipine and the like.
  • 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.
  • thermal radical polymerization initiator what generate
  • a thermal radical polymerization initiator an azo compound, a peroxide, a persulfate, etc. can be illustrated as a preferable thing, for example.
  • azo compounds examples 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.
  • peroxides examples include benzoyl peroxide, di-t-butyl benzoyl peroxide, t-butyl peroxypivalate and di (4-t-butylcyclohexyl) peroxy dicarbonate.
  • persulfate examples include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.
  • thermal cationic polymerization initiator what generate
  • 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
  • a commercial item can also be used as said thermal cationic polymerization initiator,
  • 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.
  • thermal anion polymerization initiator what generate
  • 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.
  • the content of the polymerization initiator may be any as long as it can impart desired curability and the like, and for example, 0.1 parts by mass or more and 30 parts by mass in 100 parts by mass of solid content. It can be made into parts by mass or less and preferably 0.5 parts by mass or more and 10 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.
  • the content of the polymerization initiator may be any as long as it can impart desired curability and photosensitivity, and for example, 0.001 to 20 parts by mass with respect to 100 parts by mass of the polymerizable compound It is preferable that it is 0.1 mass part or more and 30 mass parts or less, and it is preferable that it is 0.5 mass part or more and 10 mass parts or less. It is because a composition is excellent in curability etc. and is excellent also in dispersibility etc. by being said content.
  • the other components may be, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butyl catechol or phenothiazine; plasticizer; adhesion promoter; filler; Foaming agents; leveling agents; surface conditioners; antioxidants such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants, etc .; UV absorbers other than the compounds represented by the above compound I-1; Dispersion aids; aggregation inhibitors; catalysts; effects accelerators; crosslinkers; additives such as thickeners etc. can be included.
  • a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butyl catechol or phenothiazine
  • plasticizer adhesion promoter
  • filler Filler
  • Foaming agents leveling agents
  • surface conditioners such as phenolic antioxidants, phosphite antioxidants, thioether
  • a dye or a pigment may be mentioned as long as it can impart a desired color to a composition or a cured product thereof or the like.
  • 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, s
  • an inorganic pigment or an organic pigment can be used.
  • 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
  • the coloring agent 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.
  • the content of the coloring agent can be 0.01 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition.
  • the solvent may be any solvent as long as it can dissolve or disperse the above-mentioned components.
  • 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-dimethyl
  • the content of the solvent varies depending on the application of the composition, etc., and can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the composition, and 10 parts by mass or more and 70 parts by mass It is preferable that it is less than part. It is because it is easy to make it excellent in coating property etc.
  • (C) 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.
  • a sulfur atom-containing compound is generally used.
  • 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.
  • (D) Surfactant As said surfactant, what can improve the dispersion stability of a composition, coating property, etc. can be used, Fluorine, such as perfluoro alkyl phosphate ester and perfluoro alkyl carboxylic acid salt 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.
  • Fluorine such as perfluoro alkyl phosphate ester and perfluoro alkyl carboxylic acid salt
  • Surfactants anionic surfactants such as higher fatty acid
  • 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, What can improve the adhesiveness etc. of a thing or its hardened
  • cured material can be used.
  • a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used.
  • (F) Melamine compound As the above-mentioned melamine compound, those which can improve the curability can be used, for example, (poly) methylolmelamine, (poly) methylolglycoluril, (poly) methylolbenzoguanamine, (poly) methylolurea and the like 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.
  • an alkyl group which comprises an alkyl ether a methyl group, an ethyl group, or a butyl group is mentioned, It may mutually be same or different.
  • 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.
  • hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used.
  • alkyletherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable.
  • 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 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.
  • thermosetting coatings 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
  • Resists for forming optical 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
  • the application is not limited to the application in which the durability to ultraviolet light is required at the time of use as a product etc.
  • it can be suitably used also for a member which receives ultraviolet irradiation or the like in the manufacturing process.
  • 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.
  • the members required to have the above-mentioned wettability improvement and adhesion improvement include members laminated with other members.
  • 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.
  • 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.
  • 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.
  • 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.
  • required in such a manufacturing process for example, members used together with members that require surface cleaning or surface modification such as plastic film, glass, silicon wafer, various engineering plastics, optical lenses, metal surfaces, plating, ceramics, dies etc. It can be mentioned.
  • the cured product of the present invention is a cured product of a composition containing the compound I-1 of the present invention and a polymerizable compound.
  • composition of the present invention uses the above-mentioned composition, it has a good ultraviolet absorbing ability and the like.
  • 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 I-1 and a polymerizable compound.
  • the composition may also contain components other than the compound I-1 and the polymerizable compound.
  • 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 term of "2. other components" of the above-mentioned "C. composition”.
  • the compound I-1 contained in the composition may be before or after elimination of the photoleaving group B in the cured product, but is preferably after elimination . It is because the said hardened
  • the above-mentioned cured product usually contains a polymer of a polymerizable compound.
  • the remaining amount of the polymerizable compound contained in the cured product is appropriately set according to the application of the cured product and the like, and is, for example, 10 parts by mass or less in 100 parts by mass of the cured product, and 1 part It is preferable that it is less than part.
  • the cured product may be substantially free of a solvent.
  • cured material it can be 1 mass part or less in 100 mass parts of hardened
  • 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. With the elastic modulus, the cured product can stably hold the compound I-1 and the like. 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.
  • 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.
  • the method for producing the above-mentioned cured product may be any method as long as the above-mentioned composition can be cured, for example, it may be the same as the method described in “F. Method for producing a cured product” described later. it can.
  • the second composition of the present invention comprises a compound represented by the following general formula (I-2) (hereinafter sometimes referred to as “compound I-2”) and a leaving substance derived from a photoleaving group (hereinafter referred to as “compound I-2”) , And may be referred to as "compound B '").
  • A represents an atomic group having an ultraviolet absorbing ability
  • k represents an integer of 1 to 10.
  • the second composition can be easily formed, for example, using the composition described above.
  • the second composition can easily impart ultraviolet absorbing ability and the like.
  • the second composition of the present invention comprises the compound I-2 and the compound B ′.
  • the second composition of the present invention will be described in detail.
  • Compound I-2 The compound I-2 exhibits ultraviolet absorbing ability.
  • the compound I-2 is a compound in which the B-O- in the compound I-1 is substituted with an -OH group.
  • the contents of such compound I-1 can be the same as the contents described in the section “A. Compound” above, so the description thereof is omitted here.
  • the content of the compound I-2 in the composition may be any as long as it can impart a desired ultraviolet absorbing ability and the like.
  • the total of the compound I-2 and the compound B ′ corresponds to the “C. It can be made the same as the content in the solid content of the above-mentioned compound I-1 described in the item of Article].
  • the compound B ′ is a leaving substance derived from a photoleaving group.
  • the photoleaving group may be any group capable of binding to the phenolic hydroxyl group as a protecting group, and the same as the contents described in “1.
  • Photoleaving group B” of the above “A. Compound”. be able to.
  • any compound can be used as long as it can be taken after the photoleaving group is eliminated from the phenolic hydroxyl group.
  • the photoleaving group B after leaving the phenolic hydroxyl group is usually highly reactive and can have various structures.
  • the photoleaving group B is preferably a compound represented by the general formulas (B-1-a), (B-2), (B-3), (B-4), (B-5), When it is represented by B-6), (B-7), etc., for example, the following general formulas (B-111-a), (B-112), (B-113), (B) -114), (B-115), (B-116), (B-117) and the like can be included.
  • R 11 contained in the compound B', R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22, R 23, R 24, R 25 , R 26 and R 27 and b 1, b 2, b 3, b 4, b 5, b 6, b 7 and b 8 are the same as the contents described in the section “A. I omit it.
  • the type of the compound B ′ may be only one type or a combination of two or more types.
  • the above-mentioned second composition comprises the compound I-2 and the compound B ′, and usually comprises other components.
  • other components include the contents described in the section "2.
  • the other components preferably include a resin component, and particularly preferably include a polymer having no polymerizable group such as a polymer of a polymerizable compound. This is because, for example, the second composition can effectively exert the effect of being able to easily impart the ultraviolet absorptivity and the like to a cured product and the like.
  • the number of kinds of resin components may be one, or two or more kinds may be used in combination.
  • the second composition contains a solvent, a polymerizable compound, etc., and may have a coating property, and the viscosity in that case is the same as the content described in the above-mentioned "C. composition”. It can be done.
  • the second composition is a cured product containing a polymer of a polymerizable compound
  • the elastic modulus of the second composition is the same as the content described in the section "D. cured product”. can do.
  • the method for producing a cured product of the present invention comprises the steps of curing the composition containing the compound I-1 and the polymerizable compound described above to form a cured product, and irradiating the cured product with light. And d) removing the photoleaving group B contained in the compound.
  • the above-mentioned production method can be easily cured and can easily impart ultraviolet absorbing ability and the like.
  • the production method of the present invention includes the steps of forming a cured product and removing it.
  • each process of the manufacturing method of this invention is demonstrated in detail.
  • Step of forming a cured product is a step of forming a cured product of the composition described above.
  • the curing method uses a method of irradiating the composition with light to polymerize the polymerizable compounds.
  • the light irradiated to the composition may include light with a wavelength of 300 nm to 450 nm.
  • 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.
  • the laser light one containing light with a wavelength of 340 to 430 nm can be used.
  • 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.
  • the said composition can contain the sensitizing dye which absorbs the said area
  • the total light quantity of the irradiated light is preferably one that can suppress the detachment of the photoleaving group B, and can be, for example, less than 1000 mJ / cm 2 and not more than 800 mJ / cm 2. And can be 500 mJ / cm 2 or less.
  • the above curing method uses a method of subjecting the composition to a heat treatment to polymerize the polymerizable compounds.
  • the heating temperature may be any temperature as long as the composition can be cured stably, and can be 60 ° C. or more, preferably 100 ° C. or more and 300 ° C. or less.
  • 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 curing method may include only one type, or may include two or more types.
  • the composition used in this step contains the compound I-1 and a polymerizable compound.
  • the composition may include other components other than the compound I-1 and the polymerizable compound.
  • 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 item of "2. other components" of the above-mentioned “C. composition", explanation here is omitted. .
  • Step of leaving is a step of leaving the photoleaving group B contained in the compound I-1.
  • any method may be used as long as the cured product is irradiated with light.
  • the light irradiated to the cured product and the total light amount thereof are not particularly limited as long as the light leaving group B can be eliminated, but the light of “1. light of the above-mentioned“ A.
  • the same contents as those described in the section of "Leaving group B" can be adopted.
  • a light source of light irradiation although it is suitably selected according to the wavelength of the light irradiated, it shall be the same as the content as described in the term of said "1.
  • Process of forming hardened material for example. be able to.
  • the temperature of the cured product in this step can be appropriately set according to the heat resistance and the like of the cured product and the substrate supporting the cured product, but can be, for example, 200 ° C. or less, 0 ° C. or more, The temperature is preferably 150 ° C. or less, and more preferably 0 ° C. or more and 100 ° C. or less. It is because detachment
  • the temperature of the cured product is the temperature of the surface of the cured product.
  • the above-mentioned production method includes the step of forming a cured product and the step of desorbing, but may include other steps as required.
  • coating the said composition on a base material etc. can be mentioned, for example.
  • 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.
  • the cured product 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.
  • the present invention is not limited to the above embodiment.
  • the above embodiment is an exemplification, has substantially the same configuration as the technical idea described in the present invention, and exhibits the same operation and effect as that of the technical scope of the present invention. Is included in
  • Example 1 0.005 mol of the phenol compound (compound I-2) in scheme 1 below, 0.005 mol of potassium carbonate and 12 g of DMF are mixed, and 0.0075 mol of o-nitrobenzyl chloride is added dropwise at room temperature under a nitrogen atmosphere, and at 80 ° C. The mixture was stirred for 2 hours, and the following reaction gave compound I-1-2 corresponding to compound I-1.
  • Oil-water separation was performed by adding 50 g of ethyl acetate and 50 g of ion-exchanged water to the reaction solution. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and crystallization was performed with methanol. The obtained white solid was dried under reduced pressure at 45 ° C. for 2 hours to obtain the desired product (Compound I-1-2). It was confirmed by H-NMR and IR that the obtained white solid was the desired product.
  • Example 2 The following compounds I-1-3, I-1-40, I-1-32, I-1-35, I-1-28, in the same manner as in Example 1, except that o-nitrobenzyl chloride was changed Obtained I-1-34. Specifically, compounds I-1-3, I-1-40, I-1-32, I-1-35, I-1-28 and 1-34 of Examples 2-7 are prepared by the following method. Manufactured. In addition, it was confirmed by H-NMR that the white solid obtained in Examples 2 to 7 was the desired product. Example 2 The mixture was heated and stirred in chlorobenzene solvent at 90 ° C. for 4 hours using 1.1 equivalents of N-bromosuccinimide and 0.01 equivalents of AIBN with respect to 2-ethylnitrobenzene.
  • Example 4 Compound I-1-32 was obtained in the same manner as in Example 1 except that 4'-methoxyphenacyl bromide was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
  • Example 5 Compound I-1-35 was obtained in the same manner as in Example 1 except that 2-bromo-2-phenylacetophenone was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
  • Example 6 Compound I-1-28 was obtained in the same manner as in Example 1 except that 2-bromo-2'-nitroacetophenone was used instead of o-nitrobenzyl chloride.
  • Example 7 Compound I-1-34 was obtained in the same manner as in Example 1 except that 4-bromomethyl-7-methoxycoumarin was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
  • Example 8 The mixture was heated and stirred in chlorobenzene solvent at 90 ° C. for 4 hours using 1.1 equivalents of N-bromosuccinimide and 0.01 equivalents of AIBN based on 4-methoxy-2-nitrotoluene. After oil-water separation with ethyl acetate and washing with water, purification with a silica column gave the corresponding benzyl bromide compound.
  • Compound I-1-4 was obtained in the same manner as in Example 1 except that this benzyl bromide compound was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
  • Example 9 Compound I-1-41 was obtained in the same manner as in Example 8 except that 3-chloro-2-nitrotoluene was used instead of 4-methoxy-2-nitrotoluene. It was confirmed by H-NMR that the obtained white solid was the desired product.
  • Compound I-1-42 was obtained in the same manner as in Example 8 except that 3-methoxy-2-nitrotoluene was used instead of 4-methoxy-2-nitrotoluene. It was confirmed by H-NMR that the obtained white solid was the desired product.
  • Example 11 Compound I-1-43 was obtained in the same manner as in Example 8 except that 3-methoxy-2-nitro-6-bromotoluene was used instead of 4-methoxy-2-nitrotoluene. It was confirmed by H-NMR that the obtained white solid was the desired product.
  • Example 12 Compound I-1-44 was obtained in the same manner as in Example 1 except that 2-bromo-2′-methylacetophenone was used instead of o-nitrobenzyl chloride. It was confirmed by H-NMR that the obtained white solid was the desired product.
  • Example 13 An intermediate compound was obtained in the same manner as in Example 1 except that 4- (2-bromoacetyl) phenyl t-butyl carbonate was used instead of o-nitrobenzyl chloride.
  • Example 14 Dissolve 0.004 mol of a phenol compound (phenol compound in scheme 1) in 40 mL of pyridine, add 0.006 mol of NPPOC-Cl (2- (2-nitrophenyl) propyl chloroformate) dropwise, and stir for 6 hours at room temperature It stirred. 200 g of ethyl acetate and 50 g of ion-exchanged water were added to the reaction solution to conduct oil-water separation.
  • Table 5 The components shown in Table 5 below were mixed in the proportions shown in Table 5 to obtain the compositions of Examples 18 to 20 and Comparative Examples 1 and 2.
  • the symbols in Table 5 indicate the following compounds.
  • the numerical value in a table represents a mass part.
  • A-1 Polymerizable compound (NK Oligo EA-1020 (bisphenol A epoxy acrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • A-2 Radically polymerizable compound (Kayarad DPHA (a mixture of dipentaerythritol penta and hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.)
  • B-1 IRGACURE 907 manufactured by BASF (radical polymerization initiator)
  • C-1 Shine Chemical Industry Co., Ltd. silane coupling agent KBE-403
  • D-1 2-butanone
  • E-1 compound represented by the following formula (1) (ultraviolet absorber)
  • F-1 Compound I-1-3
  • F-2 Compound I-1-35
  • F-3 Compound I-1-47
  • compositions of Examples 18 to 20 and Comparative Examples 1 and 2 were each applied to a glass substrate by a spin coater, prebaked at 80 ° C. for 3 minutes, and then exposed using a super high pressure mercury lamp (UL 750) as a light source. (20 mW / cm 2 ). The exposure was performed so that the exposure light amount was 100 mJ / cm 2 . Thereafter, the sample was further irradiated with 3000 mJ / cm 2 to prepare a sample for light resistance evaluation. A 24-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 470 nm before and after the light resistance test of the sample for evaluation was measured.
  • the light resistance was evaluated on the basis of the standard.
  • Good The difference in transmittance (%) is less than 5% relative to the transmittance before the light resistance test.
  • X The difference in transmittance (%) is 5% or more with respect to the transmittance before the light resistance test. It shows that a cured
  • compositions of Examples 18 to 20 containing the compound I-1 have better light resistance as compared with the composition of Comparative Example 1 which does not contain a UV absorber. Further, the compositions of Examples 18 to 20 have better curability as compared with the composition of Comparative Example 2 containing a known ultraviolet absorber. From this, it can be seen that according to the present invention, a composition having less curing inhibition and having excellent light resistance can be obtained.
  • the compound of the present invention it is possible to provide a compound which is less in inhibition of curing and which can easily impart ultraviolet light absorbing ability and the like to a cured product.
  • the latent ultraviolet absorber of the present invention has little inhibition of curing and can easily impart ultraviolet absorptivity and the like to a cured product.
  • the composition of the present invention it is possible to provide a composition capable of obtaining a cured product having excellent curing performance and having excellent ultraviolet absorptivity.
  • cured material of this invention the hardened
  • a cured product having excellent ultraviolet absorptivity and the like can be produced without causing inhibition of curing.
  • the second composition of the present invention it is possible to provide a composition capable of obtaining a cured product having excellent ultraviolet absorption ability without causing inhibition of curing.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Polymerisation Methods In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un composé représenté par la formule générale (I-1). (Dans la formule, A représente un groupe d'atomes ayant une capacité d'absorption de lumière ultraviolette, B représente un groupe de photo-élimination, et k représente un nombre entier de 1 à 10). L'invention concerne également une composition contenant un composé représenté par la formule générale (I-2) et un produit d'élimination dérivé du groupe de photo-élimination. (Dans la formule, A représente le groupe d'atomes ayant une capacité d'absorption de lumière ultraviolette, et k représente un nombre entier de 1 à 10).
PCT/JP2018/036958 2017-10-05 2018-10-02 Composé, absorbeur latent de lumière ultraviolette, composition, produit durci, et procédé de production de produit durci WO2019069960A1 (fr)

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KR1020197036459A KR20200064029A (ko) 2017-10-05 2018-10-02 화합물, 잠재성 자외선 흡수제, 조성물, 경화물 및 경화물의 제조 방법
CN201880046837.6A CN111094256A (zh) 2017-10-05 2018-10-02 化合物、潜在性紫外线吸收剂、组合物、固化物及固化物的制造方法

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