WO2023176680A1 - 組成物及び硬化物 - Google Patents

組成物及び硬化物 Download PDF

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Publication number
WO2023176680A1
WO2023176680A1 PCT/JP2023/009027 JP2023009027W WO2023176680A1 WO 2023176680 A1 WO2023176680 A1 WO 2023176680A1 JP 2023009027 W JP2023009027 W JP 2023009027W WO 2023176680 A1 WO2023176680 A1 WO 2023176680A1
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group
mass
parts
carbon atoms
composition
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PCT/JP2023/009027
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English (en)
French (fr)
Japanese (ja)
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尭大 井上
涼平 佐藤
萩乃 森田
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株式会社Adeka
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a composition and a cured product thereof.
  • Patent Document 1 describes the use of a light shielding filter to adjust illuminance in an exposure apparatus for lithography such as a semiconductor integrated circuit.
  • Patent Document 2 describes the use of a gray colored layer that weakens light intensity at a certain rate as a light shielding filter used in an antireflection film.
  • Patent Document 3 proposes a composition containing a cationically polymerizable compound, a black pigment, a photoacid generator, and a solvent as a material for forming a black matrix used in color filters for liquid crystal displays and video cameras.
  • the light-shielding filters used in Patent Documents 1 and 2 are made of metal thin films or metal meshes, and are difficult to form on uneven surfaces or on large-area light-shielding objects. There may be restrictions.
  • the cured product obtained by curing the composition of Patent Document 3 still has unsatisfactory heat and humidity resistance and weather resistance.
  • the present inventors have conducted intensive studies on the causes of the above-mentioned problems, and have found that by using a composition containing a specific cationic polymerizable compound and a specific antioxidant, the present inventors have improved heat-and-moisture resistance and weather resistance. It has been found that a cured product with excellent properties can be formed.
  • the present disclosure provides a composition comprising a cationically polymerizable component and an antioxidant, wherein the cationically polymerizable component is selected from an alicyclic epoxy compound, an aliphatic epoxy compound, an aromatic epoxy compound, and an oxetane compound.
  • the present invention provides a composition including at least one type of sulfur-based antioxidant, wherein the antioxidant includes a sulfur-based antioxidant.
  • the above composition can form a cured product with excellent heat and humidity resistance and weather resistance.
  • the alicyclic epoxy compound has a chemical formula selected from the following general formulas (1-1), (1-2), (1-3), (1-4), and (1-5). It is preferable that at least one of the compounds represented by the above is included. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent a hydrogen atom, a halogen atom, a carbon atom, Represents an alkyl group having 1 to 20 atoms or an alkoxy group having 1 to 20 carbon atoms.
  • R 11 , 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 and R 26 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 and R 68 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • R 71 , R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 and R 88 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms
  • X represents a single bond, an alkylene group having 1 to 4 carbon atoms, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or a group in which two or more of these are linked.
  • the content of the alicyclic epoxy compound is preferably 0.5 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the cationically polymerizable component. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the aliphatic epoxy compound includes a polyfunctional aliphatic epoxy compound. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the aliphatic epoxy compound is preferably 5 parts by mass or more and 70 parts by mass or less based on 100 parts by mass of the cationically polymerizable component. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the oxetane compound is preferably 0.5 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the cationically polymerizable component. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the sulfur-based antioxidant is preferably a compound represented by the following general formula (2-1). This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • A represents a carbon atom or a sulfur atom
  • X 2 is a single bond, an alkylene group having 1 to 4 carbon atoms, a phenylene group having 6 to 18 carbon atoms, a carbonyl group, an ether bond, a thioether bond, an ester bond, a carbonate group, an amide group, or more than one of these represents a linked group
  • R B1 represents an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
  • m1 represents 2
  • X 2 represents a group containing a thioether bond in its structure.
  • the content of the sulfur-based antioxidant is preferably 10 parts by mass or more and 90 parts by mass or less based on 100 parts by mass of the antioxidant. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the composition further includes a black coloring material. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the composition further includes a photoacid generator. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the present disclosure provides a cured product of the above composition.
  • the present disclosure relates to a composition and a cured product using the same.
  • the composition and cured product of the present disclosure will be explained in detail.
  • the number of carbon atoms in a group when a hydrogen atom in the group is substituted with a substituent, defines the number of carbon atoms in the group after the substitution.
  • 1 to 20 carbon atoms refers to the number of carbon atoms after the hydrogen atom is substituted, and the hydrogen atom is substituted. It does not refer to the previous number of carbon atoms.
  • the definition of the number of carbon atoms in a group in which a methylene group in a group having a predetermined number of carbon atoms is replaced with a divalent group shall be defined as the number of carbon atoms in the group after the substitution. do.
  • solid content of the composition refers to the content of all components in the composition excluding the solvent.
  • composition comprising a cationically polymerizable component and an antioxidant, wherein the cationically polymerizable component is selected from an alicyclic epoxy compound, an aliphatic epoxy compound, an oxetane compound, and an aromatic epoxy compound.
  • the antioxidant includes a sulfur-based antioxidant.
  • the composition of the present disclosure can form a cured product with excellent moist heat resistance and weather resistance.
  • heat and humidity resistance is a function that can maintain the light transmittance of a cured product after being exposed to a high humidity and high temperature environment. Specifically, when exposed to a high humidity and high temperature environment for a long period of time, It can be expressed by evaluating the transmittance of the cured product to light at 540 nm.
  • Weather resistance is durability against sunlight exposure, and specifically can be expressed by evaluating the transmittance of a cured product to 540 nm light after a weather resistance test using a xenon lamp.
  • the cationically polymerizable component is a compound that undergoes a polymerization or crosslinking reaction with an acid.
  • the cationically polymerizable component includes two or more cationically polymerizable compounds having a cationically polymerizable group.
  • Examples of the above-mentioned cationic polymerizable groups include epoxy groups, oxetanyl groups, cyclic lactone groups, cyclic acetal groups, cyclic thioether groups, cyclic ether groups such as spiro-orthoester groups, and vinyl ether groups.
  • examples of the cationically polymerizable compound include epoxy compounds, oxetane compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, cyclic ether compounds such as spiro-orthoester compounds, and vinyl ether compounds.
  • the epoxy compound is a compound having an epoxy group as a cationically polymerizable group.
  • a compound having both an epoxy group and an oxetanyl group corresponds to an epoxy compound.
  • the oxetane compound is a compound having an oxetanyl group as a cationic polymerizable group and not having an epoxy group.
  • the cationically polymerizable compounds other than the epoxy compound and the oxetane compound are compounds having neither an epoxy group nor an oxetanyl group.
  • the cationically polymerizable component includes an alicyclic epoxy compound and at least one selected from an aliphatic epoxy compound, an aromatic epoxy compound, and an oxetane compound. That is, the cationically polymerizable component contains an alicyclic epoxy compound as an essential component, and further contains at least one selected from aliphatic epoxy compounds, aromatic epoxy compounds, and oxetane compounds as an essential component.
  • the above-mentioned cationically polymerizable component contains only an alicyclic epoxy compound and an aliphatic epoxy compound among alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, and oxetane compounds, Often, it may contain only an alicyclic epoxy compound and an oxetane compound, it may contain only an alicyclic epoxy compound and an aromatic epoxy compound, and it may contain only an alicyclic epoxy compound and an aromatic epoxy compound.
  • the cationic polymerizable component contains at least one selected from an aliphatic epoxy compound and an oxetane compound together with an alicyclic epoxy compound. It is particularly preferable to contain an alicyclic epoxy compound, an aliphatic epoxy compound, and an oxetane compound. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the lower limit of the total content of the alicyclic epoxy compound, aliphatic epoxy compound, aromatic epoxy compound, and oxetane compound is preferably 50 parts by mass in 100 parts by mass of the cationically polymerizable component, and especially 60 parts by mass. It is preferably 70 parts by mass, particularly preferably 80 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the total of the alicyclic epoxy compound, the aliphatic epoxy compound, the aromatic epoxy compound, and the oxetane compound refers to the alicyclic epoxy compound, the aliphatic epoxy compound contained in the cationically polymerizable component. , refers to the total of aromatic epoxy compounds and oxetane compounds.
  • the cationically polymerizable component is an alicyclic epoxy compound among alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, and oxetane compounds.
  • Alicyclic epoxy compound is a compound having at least one alicyclic epoxy group in the molecule, that is, a compound having a cycloalkene oxide structure, and has multiple alicyclic epoxy groups in one molecule. It may have a formula epoxy group, or it may have an epoxy group other than an alicyclic epoxy group. Moreover, the above-mentioned alicyclic epoxy compounds may be used in combination of two or more types. A compound having an aromatic ring also falls under the category of an alicyclic epoxy compound if it has an alicyclic epoxy group.
  • a cycloalkene oxide structure is a cyclohexene oxide structure or a cyclopentene oxide structure obtained by epoxidizing a cyclohexene ring-containing compound or a cyclopentene ring-containing compound with an oxidizing agent. This is a structure in which parts are shared.
  • examples of compounds having one cycloalkene oxide structure include 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentadiene diepoxide, and epoxyhexahydro Examples include dioctyl phthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, and 1,2-epoxy-2-epoxyethylcyclohexane.
  • compounds having two cycloalkene oxide structures include compounds having a structure in which two cycloalkene oxide structures are condensed directly or via a cycloalkane structure, and compounds in which two cycloalkene oxide structures are connected by a linking group.
  • examples include compounds having the following.
  • Specific examples of compounds having a structure in which two cycloalkene oxide structures are condensed directly or via a cycloalkane structure include compounds represented by any of the following formulas (1-1) to (1-4).
  • Specific examples of compounds having a structure in which two cycloalkene oxide structures are connected by a linking group include compounds represented by the following formula (1-5).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent a hydrogen atom, a halogen atom, a carbon atom, Represents an alkyl group having 1 to 20 atoms or an alkoxy group having 1 to 20 carbon atoms.
  • R 11 , 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 and R 26 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 and R 68 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • R 71 , R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 and R 88 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms
  • X represents a single bond, an alkylene group having 1 to 4 carbon atoms, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or a group in which two or more of these are linked.
  • a group in which two or more of these are connected refers to a group in which two or more groups selected from alkylene groups, carbonyl groups, ether bonds, ester bonds, carbonate groups, and amide groups are not adjacent to each other other than the alkylene groups. It can be a group bonded like this. Furthermore, two or more groups of the same type may be combined, such as ester bond-alkylene group-ester bond-alkylene group.
  • Examples of the halogen atoms represented by R 51 to R 68 in 4) and R 71 to R 88 in the above formula (1-5) include fluorine, chlorine, bromine, and iodine.
  • Examples of the alkyl group having 1 to 20 carbon atoms represented by R 51 to R 68 in 4) and R 71 to R 88 in the above formula (1-5) include a methyl group, an ethyl group, and a propyl group.
  • Examples of the alkoxy group having 1 to 20 carbon atoms represented by R 51 to R 68 in 4) and R 71 to R 88 in the above formula (1-5) include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • Examples of the alkyl group include groups having a predetermined number of carbon atoms among the alkyl groups listed as the alkyl groups represented by R 1 to R 10 in formula (1-1) above. Specific examples include methylene group, methylmethine group, isopropylidene group, ethylene group, trimethylene group, and tetramethylene group.
  • X is a group in which a plurality of groups selected from an alkylene group, a carbonyl group, an ether bond, an ester bond, a carbonate group, and an amide group having 1 to 4 carbon atoms are connected
  • the total number of carbon atoms in can be 2 or more and 20 or less.
  • a single bond is one in which carbon atoms to which X is connected are directly bonded to each other.
  • Examples of compounds in which two cycloalkene oxide rings are bonded via such a single bond include a compound represented by the following formula (A1-4).
  • Examples of methods for producing the compounds represented by formulas (1-1) to (1-5) include the production method described in JP-A No. 2019-189844.
  • commercially available compounds include, for example, THI-DE (manufactured by ENEOS Corporation).
  • commercially available compounds include, for example, DE-102 (manufactured by ENEOS Corporation).
  • commercially available compounds include, for example, DE-103 (manufactured by ENEOS Corporation).
  • Examples of commercially available compounds represented by the above formula (1-5) include Celloxide 2021P and Celloxide 8000 (manufactured by Daicel Corporation).
  • the alicyclic epoxy compound has two or more cycloalkene oxide structures. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the number of functional groups in the alicyclic epoxy compound is preferably 2 or more and 5 or less, more preferably 2 or more and 3 or less, and particularly preferably 2. This is because the above composition can form a cured product with better moist heat resistance and weather resistance. Note that the number of functional groups of the alicyclic epoxy compound includes the number of epoxy groups other than the cycloalkene oxide structure.
  • the alicyclic epoxy compound preferably includes a compound having a structure in which two cycloalkene oxide structures are directly condensed, or a compound having a structure in which two cycloalkene oxide structures are connected by a linking group. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the alicyclic epoxy compound has a chemical formula selected from the above formulas (1-1), (1-2), (1-3), (1-4) and (1-5).
  • it contains at least one compound represented by the formula (1-1), (1-2), and (1-5).
  • R 1 to R 10 in the above formula (1-1), R 11 to R 26 in the above formula (1-2), R 31 to R 48 in the above formula (1-3), and the above formula (1- R 51 to R 68 in 4) and R 71 to R 88 in the above formula (1-5) are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • X in the above formula (1-5) may be a single bond, an alkylene group having 1 to 4 carbon atoms, an ester bond, or a group in which an alkylene group having 1 to 4 carbon atoms and an ester bond are connected.
  • it is a group in which a single bond or an alkylene group having 1 to 4 carbon atoms and an ester bond are connected, particularly a group in which a single bond or an alkylene group having 1 to 2 carbon atoms and an ester bond are connected. It is preferable that it is a group in which these are connected, and a single bond is particularly preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the molecular weight of the alicyclic epoxy compound is preferably 100 or more and 400 or less, more preferably 120 or more and 300 or less, and particularly preferably 150 or more and 250 or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the epoxy equivalent of the above alicyclic epoxy compound is 50 g/eq. More than 200g/eq. It is preferably less than 60g/eq. More than 150g/eq. It is more preferable that it is not more than 70 g/eq. More than 130g/eq. It is preferable that it is below. This is because, by having the above epoxy equivalent, the composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the alicyclic epoxy compound is 0.5 parts by mass or more in a total of 100 parts by mass of the alicyclic epoxy compound, aliphatic epoxy compound, aromatic epoxy compound, and oxetane compound. It is preferably 80 parts by mass or less, particularly preferably 1 part by mass or more and 50 parts by mass or less, particularly preferably 2 parts by mass or more and 30 parts by mass or less, especially 3 parts by mass. It is preferably 20 parts by mass or less, and even more preferably 5 parts by mass or more and 20 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the alicyclic epoxy compound is preferably 0.5 parts by mass or more and 80 parts by mass or less, particularly 1 part by mass or more and 50 parts by mass or less, in 100 parts by mass of the cationically polymerizable component. It is preferably 2 parts by mass or more and 30 parts by mass or less, particularly preferably 3 parts by mass or more and 20 parts by mass or less, and even more preferably 5 parts by mass or more and 20 parts by mass or less. It is preferable that there be. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the alicyclic epoxy compound is preferably 0.5 parts by mass or more and 80 parts by mass or less, particularly 1 part by mass or more and 50 parts by mass or less, based on 100 parts by mass of the solid content of the composition. It is preferably 2 parts by mass or more and 30 parts by mass or less, particularly preferably 3 parts by mass or more and 20 parts by mass or less, and even more preferably 5 parts by mass or more and 20 parts by mass. It is preferable that it is below. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the above-mentioned aliphatic epoxy compound represents a compound having an epoxy group having neither an alicyclic epoxy group nor an aromatic ring. Moreover, the above-mentioned aliphatic epoxy compounds may be used in combination of two or more types. Examples of the aliphatic epoxy compounds include polyfunctional epoxy compounds and monofunctional aliphatic epoxy compounds. In the present disclosure, it is preferable that the aliphatic epoxy compound includes a polyfunctional aliphatic epoxy compound. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • polyfunctional aliphatic epoxy compound is a compound that has at least two epoxy groups in its molecule and has neither an alicyclic epoxy group nor an aromatic ring. Moreover, the above-mentioned polyfunctional aliphatic epoxy compounds may be used in combination of two or more types.
  • Examples of the polyfunctional aliphatic epoxy compound include compounds represented by the following formula (1-6).
  • Y 1 is an alkylene group having 1 to 20 carbon atoms, a divalent aliphatic hydrocarbon group having 6 to 20 carbon atoms having a cycloalkyl ring, or the alkylene group or the divalent aliphatic hydrocarbon group having cycloalkyl rings. It represents a group having a structure in which one or more methylene groups in a valent aliphatic hydrocarbon group are substituted with oxygen atoms.
  • the alkylene group having 1 to 20 carbon atoms used in Y 1 in the above formula (1-6) is the alkyl group having 1 to 20 carbon atoms used in R 1 to R 10 in the above formula (1-1). Examples include groups obtained by removing one hydrogen atom from the groups listed above.
  • the divalent aliphatic hydrocarbon group having 6 to 20 carbon atoms and having a cycloalkyl ring used for Y 1 in (1-6) above is a cycloalkylene group obtained by removing one hydrogen atom from a cycloalkyl group. , a combination of a cycloalkylene group and an alkylene group.
  • cycloalkyl group examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a methylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, Monocyclic aliphatic hydrocarbon groups such as tetramethylcyclohexyl group, pentamethylcyclohexyl group, ethylcyclohexyl group and methylcycloheptyl group; bicyclo[2.1.1]hexyl group, bicyclo[2.2.1]heptyl group , bicyclo[2.2.2]octyl group, bicyclo[4.3.1]decyl
  • the above Y 1 is preferably an alkylene group having 1 to 20 carbon atoms, particularly preferably an alkylene group having 2 to 8 carbon atoms, and particularly an alkylene group having 3 to 6 carbon atoms. It is more preferable that This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the alkylene group used for Y 1 may be linear or branched, but is preferably branched. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Y 1 is a divalent aliphatic hydrocarbon group having a cycloalkyl ring and having 6 to 20 carbon atoms
  • the number of carbon atoms in Y 1 is preferably 3 or more and 20 or less, and 6 or more. It is more preferably 18 or less, particularly preferably 10 or more and 15 or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • examples of the polyfunctional aliphatic epoxy compound include compounds represented by the following formula (1-7).
  • R is a t-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms, s represents an integer of 1 to 30, and t represents an integer of 1 to 10. represent.
  • t is 2 or more, the plurality of s may be different from each other. Further, the sum of s and t is 2 or more.
  • the t-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R in the above formula (1-7) is obtained by removing t-1 hydrogen atoms from an alkyl group having 1 to 10 carbon atoms.
  • the following groups are mentioned.
  • a predetermined number of carbon atoms can be used. Examples include groups having
  • R in the above formula (1-7) is preferably an alkyl group having 2 to 10 carbon atoms, particularly preferably a branched alkyl group having 3 to 8 carbon atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • t is preferably an integer of 1 or more and 10 or less in terms of ease of obtaining the compound, more preferably an integer of 2 or more and 8 or less, particularly preferably an integer of 2 or more and 6 or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the molecular weight of the compound represented by the above formula (1-7) may be any one that can form a cured product with excellent heat and humidity resistance and weather resistance, and is between 1,000 and 5,000. It is preferably 1,500 or more and 4,000 or less, particularly preferably 2,000 or more and 3,000 or less. This is because, by having the above-mentioned molecular weight, the above-mentioned composition can form a cured product having better heat-and-moisture resistance and weather resistance.
  • the above molecular weight means a weight average molecular weight (Mw). Further, the weight average molecular weight can be determined by gel permeation chromatography (GPC) as a standard polystyrene equivalent value.
  • the above weight average molecular weights are, for example, using GPC (LC-2000plus series) manufactured by JASCO Corporation, using tetrahydrofuran as the elution solvent, and using polystyrene standards for the calibration curve as Mw 1,110,000, 707,000, 397,000, 189,
  • the measurement columns were KF-804 and KF-803. , KF-802 (manufactured by Showa Denko).
  • the measurement temperature can be 40° C.
  • the flow rate can be 1.0 mL/min.
  • the sample concentration during measurement can be 0.1% by mass to 0.2% by mass.
  • the number of functional groups in the polyfunctional aliphatic epoxy compound is preferably 2 or more and 5 or less, more preferably 2 or more and 3 or less, and particularly preferably 2. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the polyfunctional aliphatic epoxy compound is at least one compound selected from compounds represented by the above formula (1-6) and in which Y 1 is an alkylene group having 1 to 20 carbon atoms. It is preferable to include. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the molecular weight of the polyfunctional aliphatic epoxy compound is preferably 100 or more and 400 or less, more preferably 120 or more and 300 or less, and particularly preferably 150 or more and 250 or less. This is because, by having the above-mentioned molecular weight, the above-mentioned composition can form a cured product having better heat-and-moisture resistance and weather resistance.
  • the epoxy equivalent of the polyfunctional aliphatic epoxy compound is 50 g/eq. More than 200g/eq. It is preferably less than 60g/eq. More than 150g/eq. It is more preferable that it is not more than 70 g/eq. More than 130g/eq. It is preferable that it is below. This is because, by having the above-mentioned epoxy equivalent, the composition can form a cured product having better heat-and-moisture resistance and weather resistance.
  • polyfunctional aliphatic epoxy compounds examples include 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, and trimethylol.
  • Glycidyl ethers of polyhydric alcohols such as triglycidyl ether of propane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, propylene glycol, trimethylolpropane,
  • Examples include polyglycidyl etherified polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as glycerin, and diglycidyl esters of aliphatic long-chain dibasic acids.
  • Further examples include epoxidized soybean oil, epoxidized polybutadiene, and the like.
  • the content of the polyfunctional aliphatic epoxy compound is preferably 0 parts by mass or more and 98 parts by mass or less based on a total of 100 parts by mass of the alicyclic epoxy compound, aliphatic epoxy compound, aromatic epoxy compound, and oxetane compound. Among these, it is preferably 10 parts by mass or more and 50 parts by mass or less, and particularly preferably 15 parts by mass or more and 40 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the polyfunctional aliphatic epoxy compound is preferably 0 parts by mass or more and 98 parts by mass or less, especially 10 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component. Preferably, it is particularly preferably 15 parts by mass or more and 40 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the total content of the alicyclic epoxy compound and polyfunctional aliphatic epoxy compound is preferably 8 parts by mass or more and 100 parts by mass or less, particularly 10 parts by mass or more and 100 parts by mass, based on 100 parts by mass of the cationically polymerizable component. It is more preferably at most 20 parts by mass and at most 70 parts by mass, particularly preferably at least 25 parts by mass and at most 60 parts by mass. In particular, it is preferably 32 parts by mass or more and 55 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the monofunctional aliphatic epoxy compound is a compound having one epoxy group in the molecule. Moreover, the above-mentioned monofunctional aliphatic epoxy compounds may be used in combination of two or more types. Examples of the monofunctional epoxy compound include compounds represented by the following formula (1-8).
  • R A1 represents an alkyl group having 1 to 20 carbon atoms
  • X 1 represents an ether bond or an ester bond.
  • Examples of the alkyl group used for R A1 in the above general formula (1-8) include alkyl groups having 1 to 20 carbon atoms used for R 1 to R 10 in the above formula (1-1). Groups similar to those described above can be used.
  • R A1 is preferably an alkyl group having 6 to 20 carbon atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Examples of the monofunctional aliphatic epoxy compound include butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, and the like.
  • Commercially available monofunctional aliphatic epoxy compounds include ADEKA Glycilol ED-502 (manufactured by ADEKA, a compound in which R A1 in the above formula (1-8) is an alkyl group having 12 to 13 carbon atoms), Denacol Examples include EX-1113 (manufactured by Nagase ChemteX, a compound in which R A1 in the above formula (1-8) has an alkyl group having 17 carbon atoms).
  • the monofunctional aliphatic epoxy compound When the monofunctional aliphatic epoxy compound is contained, its content is preferably 0.5 parts by mass or more and 30 parts by mass or less, particularly 1 part by mass or more and 20 parts by mass, based on 100 parts by mass of the cationically polymerizable component. It is preferably at most 2 parts by mass and at most 10 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the aliphatic epoxy compound is 0 parts by mass or more and 90 parts by mass or less in a total of 100 parts by mass of the alicyclic epoxy compound, aliphatic epoxy compound, aromatic epoxy compound, and oxetane compound. It is preferably 5 parts by mass or more and 70 parts by mass or less, particularly preferably 10 parts by mass or more and 50 parts by mass or less, especially 15 parts by mass or more and 40 parts by mass or less. It is preferable that This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the aliphatic epoxy compound is preferably 0 parts by mass or more and 90 parts by mass or less, particularly preferably 5 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component. , preferably 10 parts by mass or more and 50 parts by mass or less, particularly preferably 15 parts by mass or more and 40 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the aliphatic epoxy compound is preferably 0 parts by mass or more and 90 parts by mass or less, and particularly preferably 5 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the solid content of the composition.
  • the content is preferably 10 parts by mass or more and 40 parts by mass or less, particularly preferably 15 parts by mass or more and 30 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Aromatic epoxy compound represents a compound that has an epoxy group and an aromatic ring, and does not have an alicyclic epoxy group. Moreover, the above-mentioned aromatic epoxy compounds may be used in combination of two or more types.
  • aromatic epoxy compounds examples include monohydric phenols such as phenol, cresol, butylphenol, glycidyl etherified products of alkylene oxide adducts thereof, polyhydric phenols having two or more aromatic rings, and alkylene phenols thereof.
  • Polyglycidyl ethers of polyhydric phenols such as oxide adducts, phenol novolak type epoxy compounds; Glycidyl ethers of phenols having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone and catechol; benzenedimethanol, benzenediethanol and benzene
  • Polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups such as dibutanol
  • Glycidyl esters of benzoic acids such as benzoic acid, toluic acid and naphthoic acid; epoxidized products of styrene oxide and divinylbenzene; and the like.
  • the content of the aromatic epoxy compound is preferably 30 parts by mass or less, preferably 20 parts by mass or less, particularly 10 parts by mass in 100 parts by mass of the cationically polymerizable component. It is preferably at most 5 parts by mass, particularly preferably at most 5 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance. Further, when an aromatic epoxy compound is contained, the content thereof may be 0.1 parts by mass or more, 0.3 parts by mass or more, and 0.3 parts by mass or more, based on 100 parts by mass of the cationically polymerizable component. May be 5 parts by mass or more
  • the content thereof is preferably 0.5 parts by mass or more and 50 parts by mass or less in 100 parts by mass of the solid content of the composition, particularly 0.5 parts by mass. It is preferably at least 1 part by mass and at most 20 parts by mass, particularly preferably at least 1 part by mass and at most 10 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • oxetane compound represents a compound that has at least one oxetanyl group in the molecule and does not have an epoxy group.
  • examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and the like. Further, two or more oxetane compounds may be used in combination.
  • the monofunctional oxetane compound described above represents an oxetane compound having only one oxetanyl group in the molecule.
  • Examples of the monofunctional oxetane compound include compounds represented by the following formula (1-9).
  • R A2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R A3 represents an alkyl group having 1 to 10 carbon atoms.
  • Examples of the alkyl group having 1 to 10 carbon atoms represented by R A2 and R A3 in the above formula (1-9) are the carbon atoms used in R 1 to R 10 in the above formula (1-1).
  • Examples of the alkyl group having a number of 1 to 20 include groups having a predetermined number of carbon atoms.
  • the above R A2 is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and particularly an alkyl group having 1 to 3 carbon atoms. is preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the above R A3 is preferably an alkyl group having 3 to 10 carbon atoms, more preferably an alkyl group having 5 to 10 carbon atoms, particularly an alkyl group having 6 to 9 carbon atoms. is preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Specific examples of the compound represented by the above formula (1-9) include 3-ethyl-3-(methoxymethyl)oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-( Examples include 2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(cyclohexyloxymethyl)oxetane, and 3-ethyl-3-(butyloxymethyl)oxetane.
  • the content of the monofunctional oxetane compound is 1 part by mass out of 100 parts by mass of the total amount of the monofunctional oxetane compound and the bifunctional oxetane compound described below. It is preferably at least 50 parts by mass, particularly preferably at least 5 parts by mass and at most 40 parts by mass, particularly preferably at least 10 parts by mass and at most 30 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • bifunctional Oxetane Compound represents an oxetane compound having two oxetanyl groups in the molecule.
  • Examples of the above-mentioned bifunctional oxetane compound include compounds represented by the following formula (1-10).
  • R A4 and R A5 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • Z represents a linking group having 2 to 20 carbon atoms
  • n2 represents an integer from 0 to 3.
  • Examples of the alkyl group having 1 to 10 carbon atoms represented by R A4 and R A5 in the above formula (1-10) are the carbon atoms represented by R 1 to R 10 in the above formula (1-1).
  • Examples of the alkyl group having 1 to 20 atoms include groups having a predetermined number of carbon atoms.
  • the linking group having 2 to 20 carbon atoms represented by Z in the above formula (1-10) includes an alkylene group having 2 to 10 carbon atoms, an aromatic ring-containing group having 8 to 20 carbon atoms, etc. Can be mentioned.
  • the above R A4 and R A5 are each independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and particularly an alkyl group having 1 to 5 carbon atoms. It is preferable that it is an alkyl group of 3. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Examples of the alkylene group having 2 to 10 carbon atoms represented by Z in the above formula (1-10) include a group obtained by removing one hydrogen atom from an alkyl group having 2 to 10 carbon atoms; Examples of the group include groups having a predetermined number of carbon atoms among the alkyl groups listed as the alkyl groups represented by R 1 to R 10 in formula (1-1) above. Specific examples include methylmethine group, isopropylidene group, ethylene group, trimethylene group, and tetramethylene group.
  • the aromatic ring-containing group having 8 to 20 carbon atoms represented by Z in the above formula (1-10) includes 1 to 2 benzene rings, an alkylene group, a carbonate group, an amide group, or more than one of these. Examples include groups that are a combination of groups in which are linked.
  • the hydrogen atom of the benzene ring may be substituted with an alkyl group having 1 to 4 carbon atoms or a hydroxy group.
  • Specific examples of the aromatic ring-containing group include groups represented by any of the following formulas (2a) to (2d).
  • Specific examples of the compound represented by the above formula (1-10) include 3,7-bis(3-oxetanyl)-5-oxanonane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy) ) methyl]benzene, 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-oxetanyl
  • Examples of commercially available oxetane compounds include aron oxetane OXT-212, OXT-121, OXT-221 (manufactured by Toagosei Co., Ltd.), HBOX, OXBP, and OXIPA (manufactured by Ube Industries, Ltd.). .
  • the content of the bifunctional oxetane compound is 50 parts by mass or more out of 100 parts by mass of the total amount of the monofunctional oxetane compound and the bifunctional oxetane compound.
  • the content is preferably 100 parts by mass or less, particularly preferably 55 parts by mass or more and 95 parts by mass or less, and particularly preferably 70 parts by mass or more and 88 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the oxetane compound contains at least one type of monofunctional oxetane compound or a difunctional oxetane compound, and it is particularly preferable that the oxetane compound contains a bifunctional oxetane compound, and especially a monofunctional oxetane compound and a difunctional oxetane compound. Preferably, it contains an oxetane compound. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the total amount of monofunctional oxetane compounds and difunctional oxetane compounds in the oxetane compound is preferably 50% by mass or more, and 80% by mass or more. is more preferable, and particularly preferably 95% by mass or more.
  • the oxetane compound contains at least one compound selected from the compounds represented by the above formula (1-9) and the above formula (1-10). It is preferable to contain at least one compound represented by formula (10), and particularly preferably to contain at least one compound each of formula (1-9) and formula (1-10). This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the molecular weight of the oxetane compound is preferably 100 or more and 400 or less, more preferably 120 or more and 300 or less, and particularly preferably 150 or more and 250 or less. This is because, by having the above-mentioned molecular weight, the above-mentioned composition can form a cured product having better heat-and-moisture resistance and weather resistance.
  • the oxetane equivalent of the above oxetane compound is 250 g/eq.
  • the following is preferable, 50g/eq. More than 200g/eq. It is more preferably less than 60g/eq. More than 150g/eq. It is more preferable that it is not more than 70 g/eq. More than 130g/eq. It is preferable that it is below. This is because, by having the above-mentioned oxetane equivalent, the composition can form a cured product having better heat-and-moisture resistance and weather resistance.
  • the content of the oxetane compound may be 0 parts by mass or more and 92 parts by mass or less in a total of 100 parts by mass of the alicyclic epoxy compound, aliphatic epoxy compound, aromatic epoxy compound, and oxetane compound.
  • the content is preferably 10 parts by mass or more and 80 parts by mass or less, particularly preferably 40 parts by mass or more and 80 parts by mass or less, particularly preferably 50 parts by mass or more and 75 parts by mass or less. is preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the oxetane compound is preferably 0 parts by mass or more and 92 parts by mass or less, particularly preferably 0.5 parts by mass or more and 80 parts by mass or less, in 100 parts by mass of the cationically polymerizable component.
  • it is preferably 10 parts by mass or more and 80 parts by mass or less, particularly preferably 40 parts by mass or more and 80 parts by mass or less, and even more preferably 50 parts by mass or more and 75 parts by mass or less.
  • the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the above cationically polymerizable components include other cationically polymerizable compounds that are cationically polymerizable compounds other than alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, and oxetane compounds. can be included.
  • the content of the other cationically polymerizable compounds is preferably 50 parts by mass or less, particularly 40 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component. It is particularly preferable that the amount is 10 parts by mass or less, and it is especially preferable that it is not included.
  • the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the cationically polymerizable component contains another cationically polymerizable compound
  • examples of the other cationically polymerizable compound include vinyl ether compounds.
  • Vinyl ether compound is a compound that has a vinyl ether group and does not have an epoxy group or an oxetane group.
  • vinyl ether compounds include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, Examples include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether, and 1,6-cyclohexanedimethanol divinyl ether.
  • antioxidants examples include compounds that suppress thermal decomposition, oxidative decomposition, coloring due to heat, etc. of the resin.
  • antioxidants include sulfur-based antioxidants, phenolic antioxidants, phosphorus-based antioxidants, and the like.
  • the above-mentioned antioxidants may be used in combination of two or more types.
  • the antioxidant contains a sulfur-based antioxidant as an essential component, and may contain other antioxidants such as a phenolic antioxidant and a phosphorus-based antioxidant as an optional component. .
  • the above antioxidant may contain only a sulfur-based antioxidant, or may contain only a sulfur-based antioxidant and a phenolic antioxidant, or may contain only a sulfur-based antioxidant and a phenolic antioxidant. It may contain only a sulfur-based antioxidant and a phosphorus-based antioxidant, or it may contain a sulfur-based antioxidant, a phenol-based antioxidant, and a phosphorus-based antioxidant.
  • the antioxidant preferably contains a sulfur-based antioxidant, and particularly preferably contains a sulfur-based antioxidant and a phenolic antioxidant. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • sulfur-based antioxidant represents an antioxidant containing a thioether in the molecule. Moreover, the above-mentioned sulfur-based antioxidants can be used alone or in combination of two or more.
  • the above-mentioned sulfur-based antioxidant may be any known sulfur-based antioxidant, including, for example, the sulfur-based antioxidant described in JP-A No. 2022-11537.
  • the sulfur-based antioxidant preferably contains a compound represented by the following formula (2-1). This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • A represents a carbon atom or a sulfur atom
  • X 2 is a single bond, an alkylene group having 1 to 4 carbon atoms, a phenylene group having 6 to 18 carbon atoms, a carbonyl group, an ether bond, a thioether bond, an ester bond, a carbonate group, an amide group, or more than one of these represents a linked group
  • R B1 represents an alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
  • m1 represents 2
  • X 2 represents a group containing a thioether bond in its structure.
  • the alkylene group having 1 to 4 carbon atoms represented by X 2 in formula (2-1) is the same as the alkylene group having 1 to 4 carbon atoms represented by X in formula (1-5). It can be done.
  • the phenylene group having 6 to 18 carbon atoms represented by The above may be substituted with an alkyl group having 1 to 4 carbon atoms.
  • an alkylene group having 1 to 4 carbon atoms represented by X 2 a phenylene group having 6 to 18 carbon atoms, a carbonyl group, an ether bond, a thioether bond, an ester bond, a carbonate group, an amide
  • the group in which a plurality of these are connected is selected from an alkylene group, a phenylene group, a carbonyl group, an ether group, a thioether bond, an ester bond, a carbonate group, and an amide group.
  • a plurality of groups may be bonded together such that oxygen atoms are not adjacent to each other.
  • the alkyl group having 6 to 20 carbon atoms represented by R B1 in formula (2-1) is the alkyl group having 1 to 20 carbon atoms represented by R 1 in formula (1-1). , a group having a predetermined number of carbon atoms.
  • the aryl group having 6 to 20 carbon atoms represented by R B1 in formula (2-1), has the hydrogen atom of the aryl group substituted with an alkyl group or hydroxy group having 1 to 4 carbon atoms. Good too. Specific examples of the above aryl group having 6 to 20 carbon atoms include 3,5-di-tert-butyl-4-hydroxyphenyl group, 3-tert-butyl-4-hydroxy-5-methylphenyl group, 3, Examples include 4-di-tert-butyl-4-hydroxyphenyl group.
  • the compound represented by the above formula (2-1) include didodecyl 3,3'-thiodipropionate, ditridecyl 3,3'-thiodipropionate, ditetradecyl 3,3'-thiodipropionate, 3,3'- Dipentadecyl thiodipropionate, diotadecyl 3,3'-thiodipyropionate, dodecyl-3-((3-octadecyloxy-3-oxopropyl)thio)propionate, 2,2-bis ⁇ [3-(dodecylthio)-1-oxo propoxy]methyl ⁇ propane-1,3-diyl bis[3-(dodecylthio)propionate], (thiobis(ethane-2,1-diyl))bis(2-tert-butyl)-5-methyl-4,1- phenylene)bis(3-dodecylthio)propionate
  • sulfur-based antioxidants examples include ADEKA STAB (registered trademark) AO-412S, AO-503, AO-26 (manufactured by ADEKA Co., Ltd.), Sumilizer (registered trademark) TPM, TPS, and TP. -D (manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) PS 800 FL, PS 802FL, 1035, 1081, 1192, 1726 (manufactured by BASF), Cyanox (registered trademark) 1212 (manufactured by Solbey) ) etc.
  • the composition of the present disclosure is not limited to the exemplified commercial products, and known sulfur-based antioxidants can be used.
  • X 2 in formula (2-1) is a direct bond, an alkylene group having 1 to 4 carbon atoms, a group in which an alkylene group having 1 to 4 carbon atoms and an ester bond are connected, or a group having a number of carbon atoms
  • a group in which a 6 to 18 phenylene group, an ester bond, an alkylene group having 1 to 4 carbon atoms, and a thioether bond are connected is preferable, and among them, an alkylene group having 1 to 4 carbon atoms and an ester bond are preferable.
  • a group in which a phenylene group having 6 to 18 carbon atoms, an ester bond, an alkylene group having 1 to 4 carbon atoms, and a thioether bond are connected and in particular, a group in which a phenylene group having 6 to 18 carbon atoms is connected to 2, a group in which an alkylene group and an ester bond are connected, a group in which a phenylene group having 6 to 18 carbon atoms, an ester bond, an alkylene group having 1 to 2 carbon atoms and a thioether bond are connected, Among these, a group in which an alkylene group having 1 to 2 carbon atoms and an ester bond are connected is particularly preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the sulfur-based antioxidant contains a compound represented by formula (2-2) among the compounds represented by formula (2-1). This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • R B2 and R B3 each independently represent an alkyl group having 6 to 20 carbon atoms.
  • the alkyl group having 6 to 20 carbon atoms represented by R B2 and R B3 in formula (2-2) is the alkyl group having 1 to 20 carbon atoms represented by R 1 in formula (1-1).
  • Examples of the alkyl group include groups having a predetermined number of carbon atoms.
  • R B2 and R B3 in formula (2-2) are both preferably an alkyl group having 6 to 18 carbon atoms, particularly an alkyl group having 8 to 18 carbon atoms. It is particularly preferred to be an alkyl group having 12 to 18 carbon atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the molecular weight of the sulfur-based antioxidant is preferably 200 or more and 1,200 or less, particularly preferably 300 or more and 1,000 or less, particularly preferably 350 or more and 600 or less, In particular, it is preferably 350 or more and 550 or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the sulfur content of the sulfur-based antioxidant is preferably within the range of 3% by mass to 20% by mass, particularly preferably within the range of 4% by mass to 15% by mass, and particularly, It is preferably within the range of 5% by mass to 13% by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the sulfur content can be measured in accordance with JIS K 2541.
  • the content of the sulfur-based antioxidant is equal to the amount of the sulfur-based antioxidant and the phenolic antioxidant.
  • the total amount of 100 parts by mass it is preferably 10 parts by mass or more and 99 parts by mass, particularly preferably 15 parts by mass or more and 90 parts by mass or less, and especially 20 parts by mass or more and 80 parts by mass or less. It is preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the sulfur-based antioxidant is preferably 10 parts by mass or more and 100 parts by mass or less, particularly preferably 20 parts by mass or more and 80 parts by mass or less, based on 100 parts by mass of the antioxidant. In particular, it is preferably 30 parts by mass or more and 70 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the sulfur-based antioxidant is preferably 0.001 parts by mass or more and 10 parts by mass or less, particularly 0.1 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component.
  • the content is preferably 0.5 parts by mass or more and 3 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the sulfur-based antioxidant is preferably 0.01 parts by mass or more and 10 parts by mass or less, particularly 0.1 parts by mass or more and 5 parts by mass, based on 100 parts by mass of the solid content of the composition.
  • the content is preferably at least 0.2 parts by mass or more and 3 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Phenolic antioxidant represents an antioxidant that does not contain a thioether and contains a phenolic hydroxyl group in its molecule.
  • Specific examples of the above-mentioned phenolic antioxidant include, for example, the phenolic antioxidant described in JP-A No. 2022-11537.
  • ADEKA STAB registered trademark
  • AO-20 AO-30
  • AO-40 AO-60
  • AO-80 AO-330
  • Sumilizer registered trademark
  • GP manufactured by Sumitomo Chemical Co., Ltd.
  • Irganox registered trademark
  • BASF BASF
  • the phenolic antioxidant is preferably a compound having a hindered phenol group. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the above-mentioned hindered phenol group represents a group in which one hydrogen atom has been extracted from a benzene ring containing two tert-butyl groups and a hydroxyl group, and specifically, 3,5-di-tert-butyl- A preferred example is a 4-hydroxyphenyl group.
  • phenolic antioxidant having a hindered phenol group examples include Adekastab (registered trademark) AO-20, AO-50, AO-60, AO-330, and the like.
  • the content of the phenolic antioxidant is preferably 10 parts by mass or more and 100 parts by mass or less, based on 100 parts by mass of the antioxidant. However, it is preferably 20 parts by mass or more and 90 parts by mass or less, particularly preferably 30 parts by mass or more and 80 parts by mass or less, particularly preferably 30 parts by mass or more and 75 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the phenolic antioxidant is 0.001 parts by mass or more and 10 parts by mass or less in 100 parts by mass of the cationically polymerizable component. is preferable, and more preferably 0.01 parts by mass or more and 10 parts by mass or less, particularly preferably 0.1 parts by mass or more and 5 parts by mass or less, especially 0.2 parts by mass.
  • the amount is preferably 3 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the phenolic antioxidant is 0.01 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the solid content of the composition.
  • the content is preferably 0.05 parts by mass or more and 5 parts by mass or less, particularly preferably 0.2 parts by mass or more and 3 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Phosphorus-based antioxidant represents an antioxidant that contains a phosphorus atom and does not contain a thioether or phenolic hydroxyl group in its molecule.
  • Commercially available products of the above-mentioned phosphorus antioxidants include ADEKA STAB (registered trademark) TPP, 3010, 135A, C, 1500, 1178, 2112, HP-10, PEP-36, and PEP-8 (manufactured by ADEKA Co., Ltd.). ) etc.
  • the antioxidant contains a compound represented by the above formula (2-1) and the above phenolic antioxidant, and in particular, a compound represented by the above formula (2-2). It is preferable to contain the represented compound and the above-mentioned phenolic antioxidant. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the antioxidant includes a sulfur-based antioxidant and a phenolic antioxidant
  • the content of the sulfur-based antioxidant is higher than that of the phenolic antioxidant.
  • the mass ratio of inhibitor/phenolic antioxidant is preferably within the range of 0.1 to 20, particularly preferably within the range of 0.2 to 10, particularly 0.3 to 20. It is preferably within the range of 5. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the sulfur-based antioxidant and the phenolic antioxidant relative to 100 parts by mass of the antioxidant is preferably 50 parts by mass or more, particularly preferably 70 parts by mass or more, and particularly , is preferably 90 parts by mass or more, and particularly preferably 100 parts by mass, that is, the antioxidant contains only the sulfur-based antioxidant and the phenolic antioxidant. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the antioxidant including a sulfur-based antioxidant and a phenolic antioxidant as the above-mentioned antioxidant is preferably 0.01 parts by mass or more and 10 parts by mass or less in 100 parts by mass of the cationic polymerizable component. Among them, it is preferably 0.1 parts by mass or more and 5 parts by mass or less, and particularly preferably 0.2 parts by mass or more and 3 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance. Further, the content of the antioxidant including a sulfur-based antioxidant and a phenolic antioxidant as the above-mentioned antioxidant is 0.001 parts by mass or more and 10 parts by mass or less in 100 parts by mass of the solid content of the composition. The content is preferably 0.1 parts by mass or more and 5 parts by mass or less, particularly preferably 0.2 parts by mass or more and 4 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the antioxidant is 0 in 100 parts by mass of the cationic polymerizable component.
  • the content is preferably .01 parts by mass or more and 10 parts by mass or less, particularly preferably 0.1 parts by mass or more and 5 parts by mass or less, and particularly preferably 0.2 parts by mass or more and 3 parts by mass or less. preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the antioxidant is based on 100 parts by mass of the solid content of the composition. , preferably 0.001 parts by mass or more and 10 parts by mass or less, particularly preferably 0.1 parts by mass or more and 5 parts by mass or less, particularly 0.2 parts by mass or more and 3 parts by mass or less. It is preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the black coloring material includes one or more selected from the group consisting of black pigments and black dyes.
  • the above black coloring materials may be used alone or in combination of two or more.
  • a black coloring material may be obtained by combining a plurality of coloring agents that cannot be used alone as a black coloring material and adjusting the coloring agent to produce a black color as a whole.
  • a black pigment as a pigment that expresses black color by itself
  • a plurality of pigments each having a color other than black may be used in combination as a black pigment.
  • a plurality of dyes having colors other than black may be used in combination as a black dye.
  • the black coloring material refers to a coloring material that can absorb light with a wavelength of 400 nm to 700 nm.
  • a composition is prepared that contains a coloring material, a transparent resin matrix (acrylic resin, etc.), and a solvent, and the content of the coloring material is 60% by mass based on the total solid content.
  • the obtained composition is applied onto a glass substrate so that the coating film after drying has a thickness of 1 ⁇ m to form a coating film.
  • the light-shielding properties of the dried coating film are evaluated using an ultraviolet-visible-near-infrared spectrophotometer (V-670, manufactured by JASCO Corporation). If the maximum value of the transmittance of the dried coating film in the wavelength range of 400 nm to 700 nm is less than 10%, it can be determined that the composition is useful for applications requiring light-shielding properties, for example.
  • the black coloring material is preferably a black pigment.
  • a black pigment a known black pigment can be used.
  • the black pigment may be an inorganic pigment or an organic pigment, but a pigment that alone expresses black color is preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • pigments that express black color by themselves include Group 4 metal elements such as titanium and zirconium, Group 5 metal elements such as vanadium and niobium, cobalt, chromium, copper, manganese, ruthenium, iron, nickel, Examples include metal oxides, metal nitrides, metal oxynitrides, etc. containing metal elements such as tin and silver.
  • the black pigment include carbon black. Specific examples of carbon black include commercially available C. I. Pigment Black 1 and other organic pigments, and C.I. I. Examples include inorganic pigments such as Pigment Black 7.
  • the content of the black pigment is preferably 0.1 parts by mass or more and 15 parts by mass or less, particularly 0.3 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the cationic polymerizable component.
  • the content is preferably 1 part by mass or more and 5 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the black pigment is preferably 0.1 parts by mass or more and 15 parts by mass or less, particularly 0.3 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the solid content of the composition.
  • the content is preferably 1 part by mass or more and 5 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • a black dye is preferable because it dissolves in the composition of the present disclosure and is easily dispersed, so that it is easy to form a uniformly colored cured product. Further, it is preferable because it has excellent transparency and haze.
  • the above-mentioned black dye is soluble in a solvent and can be colored black by absorbing light in the wavelength range of visible light.
  • the black dye is at least one selected from azo black dyes and nigrosine black dyes.
  • DirectFastBlackAB C.I.DirectBlack32, manufactured by Sumitomo Chemical Industries, Ltd.
  • DirectDeepBlackEX C.I.DirectBlack38, manufactured by Sumitomo Chemical Industries, Ltd.
  • DirectFastBlackConc. C.I. Direct Black 51, manufactured by Hodogaya Chemical Industry Co., Ltd.
  • KayarusSupra Gray VGN C.I. Direct Black 71, manufactured by Nippon Kayaku Co., Ltd.
  • Acid BlueBlack 10B C.I. Acid Black 1
  • Sumino l Milling Black 8BX C.I. Acid Black 24, manufactured by Sumitomo Chemical Co., Ltd.
  • Kayanol Milling Black VLG C.I.
  • Acid Black 109 manufactured by Nippon Kayaku Co., Ltd.
  • Suminol Milling Black B C.I. Acid Black 109 , manufactured by Sumitomo Chemical Industries, Ltd.
  • Kayanol Milling Black TLR C.I. Acid Black 110, manufactured by Nippon Kayaku Co., Ltd.
  • the nigrosine black dye is a compound having a phenazine skeleton obtained by condensing aniline and nitrobenzene, such as a compound having a triphenazine oxazine structure represented by the following chemical formula (I) or (II), or a compound having the following chemical formula (III).
  • Examples include compounds having a phenazineazine structure represented by (VI). Note that X ⁇ in formulas (I) to (VI) represents a counter anion.
  • R 90 , R 91 , R 92 and R 93 are each independently a hydrogen atom or a phenyl group.
  • the nigrosine black dye mentioned above includes C.I. I. No. Examples include Acid Black 2, Solvent Black 5, Solvent Black 7, Solvent Black 22, Solvent Black 27, Solvent Black 29, and Solvent Black 34.
  • Examples of commercially available nigrosine black dyes include NUBIAN BLACK NH-805, NH-815 (manufactured by Orient Chemical Industry Co., Ltd.) (C.I.Solvent Black 5)), NUBIAN BLACK TN-870, TH-807 (manufactured by Orient Chemical Industry Co., Ltd.) (C.I. Solvent Black 7), VALIFAST BLACK1821 (organic acid salt (salt-forming dye) of C.I. Solvent Black 7), oil-soluble dye manufactured by Orient Chemical Industry Co., Ltd. dyes), etc.
  • the black dye includes a nigrosine-based black dye. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the black dye is a metal complex dye in which a metal such as chromium, cobalt, nickel, copper, or iron is complexed in the skeleton, or a salt-forming dye in which an acidic dye and a basic dye are reacted.
  • salt-forming dyes such as salt-forming dyes produced by salt-forming an acidic dye with a base such as an organic amine
  • salt-forming dyes such as salt-forming dyes produced by salt-forming a basic dye with an acid such as an organic acid.
  • salt-forming dyes are preferable.
  • the dye is preferably a salt-forming dye obtained by salt-forming a basic dye with an acid such as an organic acid. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • organic acids used to form the salt-forming dye include alkylbenzenesulfonic acids, naphthalenesulfonic acids, naphthalenesulfonic acid-formaldehyde condensates, alkyldiphenyl ether disulfonic acids, and polyoxyethylene alkylphenyl ether phosphoric acids.
  • alkylbenzenesulfonic acids are particularly preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the metal complex dye C.I. I. Solvent Black 21, 22, 23, 27, 28, 29, 31 etc., C.I. I. Acid Black 52, 60, 99, etc. are mentioned.
  • the salt forming dye include VALIFAST BLACK 1807, 1821, 3804, 3806, 3808, 3810, 3820, 3830, 3840, 3870, 3877 (manufactured by Orient Chemical Industry Co., Ltd.).
  • the black dye is a nigrosine-based black dye and contains a dye that is a metal complex salt dye or a salt-forming dye, particularly a nigrosine-based black dye, and a dye that is a salt-forming dye. It is preferred to include dyes that are salt dyes, especially C.I. I. An organic acid salt of Solvent Black 7 is preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the black dye is preferably 0.1 parts by mass or more and 15 parts by mass or less, particularly 0.3 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component.
  • the content is preferably 1 part by mass or more and 5 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the black dye is preferably 0.1 parts by mass or more and 15 parts by mass or less, particularly 0.3 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the solid content of the composition.
  • the content is preferably 1 part by mass or more and 5 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Photoacid generator The photoacid generator described above generates acid upon irradiation with active energy rays (hereinafter sometimes simply referred to as "energy rays") such as visible light, ultraviolet rays, X-rays, electron beams, and high frequency waves. It is a compound that can.
  • energy rays active energy rays
  • the above-mentioned photoacid generators include double salts that are onium salts or derivatives thereof, oxime sulfonate compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, diazomethane compounds, nitrobenzyl compounds, benzointosylate compounds, iron. -arene complexes, acetophenone derivative compounds, etc., and these can be used alone or in combination of two or more.
  • the photoacid generator is a double salt that is an onium salt or a derivative thereof. This is because, by using such a photoacid generator, the composition can yield a cured product with excellent sensitivity and adhesion.
  • double salts that are onium salts or derivatives thereof include salts of cations and anions represented by the following formula (i).
  • the cation [A] m+ is onium, and its structure can be represented by the following formula, for example.
  • R 300 represents an organic group having 1 to 60 carbon atoms and which may contain any number of atoms other than carbon atoms.
  • a represents an integer from 1 to 5.
  • the a pieces of R 300 are each independent and may be the same or different.
  • At least one of a R 300 represents the above organic group having an aromatic ring.
  • anion [B] m- is preferably a halide complex, and its structure can be represented by, for example, the following formula (iii). This is because the composition of the present disclosure has excellent sensitivity.
  • L represents a metal or metalloid that is the central atom of the halide complex, and includes B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn. , Sc, V, Cr, Mn or Co.
  • X 3 represents a halogen atom.
  • b represents an integer from 3 to 7.
  • anion [LX 3 b ] m- in formula (iii) above include tetrakis(pentafluorophenyl)borate [(C 6 F 5 ) 4 B] - , tetrafluoroborate (BF 4 ) -, hexafluoroborate (BF 4 ) - , Fluorophosphate (PF 6 ) - , hexafluoroantimonate (SbF 6 ) - , hexafluoroarsenate (AsF 6 ) - , hexachloroantimonate (SbCl 6 ) - , tris(pentafluoromethyl)trifluorophosphate ion (FAP anion) ) etc.
  • anion [B] m- may have a structure represented by the following formula (iv).
  • L, X3 and b are the same as above.
  • Other anions include perchlorate ion (ClO 4 ) - , trifluoromethylsulfite ion (CF 3 SO 3 ) - , fluorosulfonate ion (FSO 3 ) - , toluenesulfonate anion, and trinitrobenzene.
  • Sulfonic acid anions, camphor sulfonate, nonafluorobutane sulfonate, hexadecafluorooctane sulfonate, tetraarylborate, tetrakis(pentafluorophenyl)borate, and the like can be mentioned.
  • onium salts it is particularly effective to use the following aromatic onium salts (a) to (c).
  • aromatic onium salts (a) to (c) one kind can be used alone or two or more kinds can be used in combination.
  • Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, etc.
  • Diaryl such as diphenyliodonium hexafluoroantimonate, di(4-methylphenyl)iodonium hexafluorophosphate, di(4-tert-butylphenyl)iodonium hexafluorophosphate, tolylcumyliodonium tetrakis(pentafluorophenyl)borate, etc. iodonium salt
  • photoacid generators include ( ⁇ 5-2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6- ⁇ )-(1-methylethyl)benzene] - Iron-arene complexes such as iron-hexafluorophosphate, aluminum complexes such as tris(acetylacetonato)aluminum, tris(ethylacetonatoacetato)aluminum, tris(salicylaldehydato)aluminum, and silanols such as triphenylsilanol. Also included are mixtures with other types.
  • aromatic iodonium salts, aromatic sulfonium salts and iron-arene complexes are preferable as photoacid generators, and aromatic sulfonium salts are especially preferable.
  • a triarylsulfonium salt having a structure in which three aromatic rings are bonded to a sulfur atom (S) is more preferable, and a triarylsulfonium salt represented by the following formula (4) is particularly preferable. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 and R 114 are Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, R 115 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or any substituent selected from the following formulas (4a) to (4c), An q- represents a q-valent anion, p represents a coefficient that neutralizes the charge.
  • R 116 , R 117 , R 118 , R 119 , R 120 , R 121 , R 122 , R 123 , R 124 , R 125 , R 126 , R 127 , R 128 , R 129 , R 130 , R 131 , R 132 , R 133 , R 134 , R 135 , R 136 , R 137 , R 138 , R 139 , R 140 , R 141 , R 142 and R 143 are each independently, Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, * represents the bonding position with S.
  • Examples of the alkyl group having 1 to 10 carbon atoms include those listed as the ⁇ al
  • the alkoxy group having numbers 1 to 10 is a predetermined one among those listed as the "alkoxy group having 1 to 20
  • Examples of the q-valent anion represented by pAn q- in the above formula (4) include anions with a predetermined valence among those listed as the above-mentioned anion [B] m- .
  • Examples of the q-valent anion represented by pAn q- include tetrakis(pentafluorophenyl)borate [(C 6 F 5 ) 4 B] - , tetrafluoroborate (BF 4 ) - , hexafluorophosphate (PF 6 ) - , hexafluoroantimonate (SbF 6 ) - , hexafluoroarsenate (AsF 6 ) - , hexachloroantimonate (SbCl 6 ) - , tris(pentafluoromethyl)trifluorophosphate ion (FAP anion), perchloric acid ion (ClO 4 ) - ,
  • R 115 is preferably selected from the above formulas (4a) to (4c), more preferably the above formula (4a) or (4c). This is because when R 115 has the above-described structure, the composition can form a cured product with better heat-and-moisture resistance and weather resistance.
  • R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 , R 112 , R 113 and R 114 are hydrogen atom, halogen atom, carbon It is preferably an alkyl group having 1 to 10 atoms or an alkoxy group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or a halogen atom. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • R116 , R117 , R118 , R119 , R120, R121 , R122, R123, R124 , R125 , R126 , R127 , R128 , R129 , R130 , R131 , R132 , R 133 , R 134 , R 135 , R 136 , R 137 , R 138 , R 139 , R 140 , R 141 , R 142 and R 143 are a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms. or an alkoxy group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or a halogen atom. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the photoacid generator is preferably 0.1 parts by mass or more and 10 parts by mass or less, and 0.5 parts by mass or more and 8 parts by mass or less, based on 100 parts by mass of the cationically polymerizable component. It is more preferably 1 part by mass or more and 7 parts by mass or less, particularly preferably 1 part by mass or more and 4.5 parts by mass or less. This is because by setting the content within such a range, the composition can form a cured product with better heat and humidity resistance and weather resistance.
  • the content of the photoacid generator is preferably 0.1 parts by mass or more and 10 parts by mass or less, and 0.5 parts by mass or more and 7 parts by mass, based on 100 parts by mass of the solid content of the composition. It is more preferably at most 1 part by mass and at most 5 parts by mass. This is because the above composition can form a cured product with better moist heat resistance and weather resistance. Note that commercially available photoacid generators are sometimes sold in a state dispersed or dissolved in a solvent, but the content of the photoacid generator in this disclosure refers to the content as a solid content excluding the solvent. It represents.
  • composition of the present disclosure contains a cationic polymerizable component and an antioxidant, and further contains a photoacid generator and a black coloring material as necessary, but as long as the effects of the present invention are not impaired.
  • Other ingredients may be included depending on the requirements.
  • Other ingredients include sensitizers, solvents, leveling agents, fillers, silane coupling agents, antifoaming agents, thickeners, thixotropic agents, surfactants, dispersants, flame retardants, plasticizers, stabilizers, Examples include various additives such as polymerization inhibitors, ultraviolet absorbers, antistatic agents, fluidity regulators, and adhesion promoters.
  • the composition of the present disclosure preferably contains a sensitizer and a leveling agent as additives. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • Sensitizer The above composition preferably contains a sensitizer together with the above-mentioned cationically polymerizable component and antioxidant in order to improve the sensitivity and curability of the composition.
  • a carbazole-based sensitizer made of a compound having a carbazole skeleton can be preferably used as the sensitizer. This is because the above composition can be easily cured. Further, the above composition can form a cured product having better heat and humidity resistance and weather resistance.
  • carbazole-based sensitizers examples include compounds represented by chemical formulas selected from the following formulas (5-1), (5-2), (5-3), and (5-4). Can be mentioned.
  • R 201 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a vinyl group, or an aryl group having 6 to 30 carbon atoms
  • R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, or a group having 6 to 30 carbon atoms; 30 aryl group, an alkoxy group having 1 to 30 carbon atoms, a cyano group, a hydroxyl group, or a carboxyl group.
  • R 211 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a vinyl group, or an aryl group having 6 to 30 carbon atoms
  • R 212 , R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 219 , R 220 and R 221 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms.
  • R 231 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a vinyl group, or an aryl group having 6 to 30 carbon atoms
  • R 232 , R 233 , R 234 , R 235 , R 236 , R 237 , R 238 , R 239 , R 240 and R 241 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms.
  • R 251 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, a vinyl group, or an aryl group having 6 to 30 carbon atoms
  • R 252 , R 253 , R 254 , R 255 , R 256 , R 257 , R 258 , R 259 , R 260 and R 261 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 30 carbon atoms.
  • alkyl group having 1 to 30 carbon atoms represented by R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 in the above formula (5-1),
  • R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 in the above formula (5-1) For example, in addition to those exemplified as the "alkyl group having 1 to 20 carbon atoms" in formula (1-1) described in the section "1.
  • Cationically polymerizable component above, n-tricosyl groups and Examples include n-tetracosyl group.
  • the aryl group having 6 to 30 carbon atoms represented by R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 in the above formula (5-1) is Examples include phenyl group, tolyl group, 3,4,5-trimethoxyphenyl group, 4-tert-butylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthracenyl group, and phenanthryl group.
  • alkoxy group having 1 to 30 carbon atoms represented by R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 in the above formula (5-1),
  • R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 represented by R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 in the above formula (5-1)
  • alkoxy group having 1 to 20 carbon atoms represented by R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 in the above formula (5-1)
  • alkoxy group having 1 to 20 carbon atoms represented by R 201 , R 202 , R 203 ,
  • the number of carbon atoms represented by R 211 , R 212 , R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 219 , R 220 and R 221 in the above formula (5-2) is 1 to
  • the alkyl group 30 is the same as the alkyl group having 1 to 30 carbon atoms represented by R 201 in formula (5-1).
  • the number of carbon atoms represented by R 211 , R 212 , R 213 , R 214 , R 215 , R 216 , R 217 , R 218 , R 219 , R 220 and R 221 in the above formula (5-2) is 6 or more
  • the aryl group of 30 is the same as the aryl group having 6 to 30 carbon atoms represented by R 201 in formula (5-1).
  • the number of carbon atoms represented by R 231 , R 232 , R 233 , R 234 , R 235 , R 236 , R 237 , R 238 , R 239 , R 240 and R 241 in the above formula (5-3) is 1 to
  • the alkyl group 30 is the same as the alkyl group having 1 to 30 carbon atoms represented by R 201 in formula (5-1).
  • the number of carbon atoms represented by R 231 , R 232 , R 233 , R 234 , R 235 , R 236 , R 237 , R 238 , R 239 , R 240 and R 241 in the above formula (5-3) is 6 or more
  • the aryl group of 30 is the same as the aryl group having 6 to 30 carbon atoms represented by R 201 in formula (5-1).
  • the number of carbon atoms represented by R 251 , R 252 , R 253 , R 254 , R 255 , R 256 , R 257 , R 258 , R 259 , R 260 and R 261 in the above formula (5-4) is 1 to
  • the alkyl group 30 is the same as the alkyl group having 1 to 30 carbon atoms represented by R 201 in formula (5-1).
  • the number of carbon atoms represented by R 251 , R 252 , R 253 , R 254 , R 255 , R 256 , R 257 , R 258 , R 259 , R 260 and R 261 in the above formula (5-4) is 6 or more
  • the aryl group of 30 is the same as the aryl group having 6 to 30 carbon atoms represented by R 201 in formula (5-1).
  • R 201 in the above formula (5-1) is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, In particular, an alkyl group having 1 to 5 carbon atoms is preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • R 211 in the above formula (5-2), R 231 in the above formula (5-3), and R 251 in the above formula (5-4) may be an alkyl group having 1 to 30 carbon atoms. It is preferably an alkyl group having 3 to 15 carbon atoms, more preferably an alkyl group having 5 to 12 carbon atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • R 202 , R 203 , R 204 and R 205 and at least one of R 206 , R 207 , R 208 and R 209 each independently have a carbon atom number of 1 to It is preferable that R 203 and R 208 are each independently an alkoxy group having 1 to 30 carbon atoms, and is preferably an alkoxy group having 1 to 10 carbon atoms. More preferably, it is an alkoxy group having 1 to 5 carbon atoms, and particularly preferably an alkoxy group having 1 to 3 carbon atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • R 203 and R 208 are alkoxy groups
  • R 202 , R 204 , R 205 , R 206 , R 207 and R 209 are preferably hydrogen atoms. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the sensitizer is preferably 0.1 parts by mass or more and 5 parts by mass or less, and 0.1 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the solid content of the composition. More preferably 2 parts by mass or more and 3 parts by mass or less, particularly preferably 0.5 parts by mass or more and 2 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the sensitizer is preferably 1 part by mass or more and 70 parts by mass or less, and 5 parts by mass or more, based on 100 parts by mass of the photoacid generator. It is more preferably 50 parts by mass or less, particularly preferably 10 parts by mass or more and 40 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the composition of the present disclosure can contain a solvent as necessary.
  • the above-mentioned solvent is liquid at room temperature (25° C.) under atmospheric pressure, is capable of dispersing or dissolving each component in the composition, and does not react with the above-mentioned cationically polymerizable component. Therefore, even if it is liquid at room temperature (25° C.) and atmospheric pressure, the cationically polymerizable compound described in the above “A1. Cationically polymerizable component” is not included in the above solvent.
  • the antioxidant described in "A2. Antioxidant” and the antioxidant described in "A3. Black coloring material” above are used.
  • a solvent either water or an organic solvent can be used, and an organic solvent can be preferably used.
  • organic solvents examples include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, , 2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol, etc.
  • ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl
  • Ester solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol, diacetone alcohol; Ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethylpropionate, 1-t-butoxy Ether ester solvents such as -2-propanol, 3-methoxybutyl acetate, and cyclohexanol acetate; Aromatic solvents such as benzene, toluene, and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, oc
  • ketones, ether ester solvents, etc. especially propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc. can be mentioned, and these solvents can be used as a single type or a mixed solvent of two or more types. can.
  • organic solvents ketones, alcohol solvents, ether ester solvents, aromatic solvents, etc. are preferred, and ether ester solvents and alcohol solvents are particularly preferred. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the content of the above-mentioned solvent may be such that the above-mentioned composition can form a cured product having better heat-and-moisture resistance and weather resistance.
  • the content of the above-mentioned solvent in 100 parts by mass of the above-mentioned composition is 50 parts by mass or less, which provides excellent drying properties and the above-mentioned composition. It is preferable in that the degree of freedom in selecting the destination for forming the cured film is widened, and it is particularly preferable that the amount is 30 parts by mass or less, and particularly preferably 10 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • composition of the present disclosure may contain a filler as another component.
  • the filler include fumed silica, particulate silica, silica, diatomaceous earth, clay, kaolin, diatomaceous earth, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder, vermiculite, attapulgite, talc, Examples include mica, minnesotaite, pyrophyllite, silica, glass fiber, and calcium carbonate.
  • the content of the filler can be appropriately set depending on the use of the composition of the present disclosure.
  • components other than the cationic polymerizable component, antioxidant, black coloring material, photoacid generator, and sensitizer is preferably 5 parts by mass or less, and particularly preferably 1 part by mass or less, based on 100 parts by mass of the solid content of the composition of the present disclosure. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • the amount thereof is preferably 20 parts by mass or less, particularly 10 parts by mass or less, per 100 parts by mass of the cationically polymerizable component. The amount is preferably 5 parts by mass or less, particularly preferably 5 parts by mass or less. This is because the above composition can form a cured product with better moist heat resistance and weather resistance.
  • compositions There is no problem in producing the above composition as long as it is possible to form a composition containing the desired amounts of each of the above components, and examples include methods using known mixing means.
  • the composition of the present invention can be produced by mixing each component using a mixer such as a homodisper, a homomixie, a universal mixer, a planetary mixer, a kneader, or a three-roll mixer.
  • the use of the above composition preferably requires a cured product with excellent heat and humidity resistance and weather resistance, such as optical filters including light blocking filters, paints, coating agents, lining agents, adhesives, printing plates, insulating varnishes, etc.
  • color filters, electrode materials for plasma display panels, printing inks, dental compositions, stereolithography resins, both liquid and dry films, micromechanical components, glass fiber cable coatings, and holographic recording materials. can be mentioned.
  • the cured product of the present disclosure is obtained by curing the above-mentioned composition.
  • the composition is used as an optical filter, particularly as a light-blocking filter (ND filter) that reduces the transmittance of visible light as a whole, and in particular, as an image filter.
  • ND filter light-blocking filter
  • a light-shielding film such as a black matrix used in a display device; a color adjustment filter for an image display device; a light-shielding filter for improving antireflection properties, etc. This is because the cured product can exhibit excellent light-shielding properties in the form of a thin film, and is particularly useful in the above-mentioned applications where thin films are highly demanded.
  • the composition described above can be preferably used for solder resists used in printed circuit boards. This is because it provides excellent protection for the wiring.
  • the cured product may be used to achieve two purposes at the same time.
  • the thicker portion may be used as a black matrix, and the thinner portion may be used as a color adjustment filter.
  • reducing the transmittance of the entire visible light means, for example, when a cured film of the above composition is formed so that the transmittance at 500 nm is 45%, the transmittance at 400 nm is reduced.
  • the transmittance and transmittance at 600 nm may be in the range of 40% to 50%.
  • the transmittance at 700 nm is also preferably within the range of 40% to 50%.
  • the color adjustment filter can be one that adjusts each color of light. More specifically, the color adjustment filter is the color of light transmitted through a color filter used as an optical filter, in which pixels of R (red), G (green), B (blue) and other colors are arranged.
  • the light emitters of each color are arranged so as to overlap with the color filter in plan view. Examples include those arranged so as to overlap in plan view.
  • the material of the adherend on which the cured product of the above composition is formed is not particularly limited, and commonly used materials can be used, such as metal bases such as aluminum, titanium, stainless steel, mild steel, and plated steel.
  • Inorganic materials such as wood, glass; cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, and nitrocellulose; polyamide; polyimide; polyurethane; epoxy resin; polycarbonate; polyethylene terephthalate; Polyesters such as polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polybutylene terephthalate; polystyrene; polyethylene, polypropylene , polyolefins such as polymethylpentene; vinyl compounds such as polyvinyl a
  • the cured product of the present disclosure is characterized by being a cured product of the above-mentioned composition. Since the cured product is obtained by curing the composition described above, it has excellent heat-humidity resistance and weather resistance. The cured product has a long service life in a high-humidity, high-temperature environment.
  • the cured product of the present disclosure will be explained in detail. Note that the above-mentioned composition is the same as described in the section "A. Composition" above.
  • the above-mentioned cured product usually contains a polymer of a cationically polymerizable component.
  • the planar shape, thickness, etc. of the cured product can be appropriately set depending on the intended use of the cured product.
  • the thickness may be, for example, 0.05 ⁇ m or more and 300 ⁇ m or less.
  • the total light transmittance and Haze value of the cured product are appropriately set depending on the use of the cured product, and are adjusted depending on the thickness, concentration of the black coloring material, etc.
  • the method for producing the cured product is not particularly limited as long as it can form the cured product of the composition into a desired shape.
  • the step of curing the composition described above may be mentioned.
  • the step of curing is a step of curing the above-mentioned composition.
  • the method for curing the composition may be any method as long as the cationically polymerizable components can be polymerized with each other, such as a method of irradiating the coating film of the composition with light (energy rays). This is because the cationically polymerizable component can be easily polymerized.
  • the light sources of energy rays used for polymerizing the cationically polymerizable component include ultra-high pressure mercury lamps, high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, and carbon arc lamps.
  • electromagnetic wave energy with a wavelength of 2000 angstroms to 7000 angstroms obtained from metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, etc., and high-energy rays such as electron beams, X-rays, and radiation. can be used.
  • an ultra-high pressure mercury lamp a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, a light emitting diode, etc. that emit light with a wavelength of 300 to 450 nm is used.
  • a mercury vapor arc lamp a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, a light emitting diode, etc. that emit light with a wavelength of 300 to 450 nm
  • the cationically polymerizable component can be easily polymerized.
  • the amount of energy ray irradiation is preferably in the range of 100 mJ/cm 2 to 2000 mJ/cm 2 at 365 nm from the viewpoint of preventing deterioration of the components in the composition.
  • the curing method is a method that uses a method of irradiating energy rays and a method of heating in combination, and more specifically, a method of irradiating energy rays and a method of heating are performed in this order. It is preferable. This is because the polymerization of the cationically polymerizable component can proceed efficiently.
  • Examples of the method for heating the coating film of the composition in this step include methods using a hot plate such as a hot plate, an atmospheric oven, an inert gas oven, a vacuum oven, a hot air circulation oven, and the like.
  • the heating temperature when heating the coating film is not particularly limited, but from the viewpoint of facilitating polymerization of the cationic polymerizable component, it is preferably 70°C or more and 200°C or less, and especially 90°C or more and 150°C or less. It is preferable that there be.
  • the heating time when heating the coating film is not particularly limited, but from the viewpoint of improving productivity, it is preferably in the range of 1 minute to 60 minutes, particularly in the range of 1 minute to 30 minutes. is preferred.
  • the above manufacturing method may include other steps as necessary.
  • Such a step may include a step of applying the composition to a substrate before the step of curing the composition.
  • known methods such as a spin coater, roll coater, bar coater, die coater, curtain coater, various printing methods, and dipping methods can be used.
  • the above-mentioned base material can be appropriately selected depending on the intended use of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, metals, paper, plastics, and the like. Moreover, after the cured product is formed on a base material, it may be peeled off from the base material and used, or it may be used after being transferred from the base material to another adherend.
  • Examples 1 to 28 and Comparative Examples 1 to 5 Each component was blended according to the formulations in Tables 1 to 5 below to obtain a composition. In addition, the following materials were used for each component. Note that the blending amounts in the table represent parts by mass of each component.
  • the compounding amount of the photoacid generator represents the compounding amount including the solvent.
  • A1-1 Alicyclic epoxy compound (bifunctional, compound represented by the following formula (A1-1), epoxy equivalent 80 g/eq., THI-DE manufactured by JXTG Energy)
  • A1-2 Alicyclic epoxy compound ( Bifunctional, compound represented by the following formula (A1-2), epoxy equivalent: 122 g/eq., manufactured by JXTG Energy DE-102)
  • A1-3 Alicyclic epoxy compound (bifunctional, compound represented by the following formula (A1-3), epoxy equivalent 128 to 145 g/eq., Celoxide 2021P manufactured by Daicel)
  • A1-4 Alicyclic epoxy compound (bifunctional, compound represented by the following formula (A1-4), epoxy equivalent 100 g/eq., Celoxide 8000 manufactured by Daicel)
  • A2-1 Polyfunctional aliphatic epoxy compound (bifunctional, compound represented by the following formula (A2-1).
  • A2-2 Monofunctional aliphatic epoxy compound (monofunctional, compound represented by the following formula (A2-2).
  • R A6 is an alkyl group having 12 to 13 carbon atoms
  • A3-1 Adeka Resin (registered trademark) EP-4100 (manufactured by ADEKA Co., Ltd., bisphenol A type epoxy resin (epoxy equivalent: 190 g/eq.))
  • A4-1 Aronoxetane (registered trademark) OXT-221 (manufactured by Toagosei Co., Ltd., bifunctional oxetane compound represented by the following formula (A4-1))
  • A4-2 Aronoxetane (registered trademark) OXT-212 (manufactured by Toagosei Co., Ltd., monofunctional oxetane compound represented by the following formula (A4-2))
  • B1-1 Compound represented by the following formula (B1-1) (compound represented by formula (2-1) and formula (2-2), sulfur content: 5.91% by mass)
  • B1-2 Compound represented by the following formula (B1-2) (compound represented by formula (2-1), sulfur content: 11.04% by mass)
  • B1-3 Compound represented by the following formula (B1-3) (sulfur content: 10.43% by mass)
  • Antioxidant phenolic antioxidant
  • B2-1 ADEKA STAB (registered trademark) AO-60 (manufactured by ADEKA Co., Ltd., compound represented by the following formula (B2-1)) "tBu” in formula (B2-1) represents a tert-butyl group. represent.
  • black color material C1-1 Nigrosine black dye (compound represented by the following formula (C1-1))
  • Leveling agent F1-1 Megafac (registered trademark) F-554 (manufactured by DIC Corporation)
  • compositions of Examples and Comparative Examples were spin-coated onto a 10 cm x 10 cm glass substrate to form a coating film (hereinafter sometimes referred to as "pre-cured coating film").
  • pre-cured coating film a coating film
  • each composition was cured by irradiating 2,000 mJ/cm 2 of 365 nm light using a UV-LED light source to form a cured film.
  • the thickness of the coating film before curing was adjusted to 4 ⁇ m.
  • a double-sided adhesive tape (manufactured by 3M, thickness: 25 ⁇ m, manufacturer product number: 8146-1) was applied on the obtained cured film, and a PET film (manufactured by Toyobo Co., Ltd., thickness: 100 ⁇ m, Lumirror T60) was applied on top of it. ) to prepare a test piece.
  • the obtained test piece was left in a constant temperature and humidity tester at 60° C. and 90% RH for 1,000 hours.
  • the transmittance of the test piece at 540 nm was measured using an ultraviolet-visible-near-infrared spectrophotometer (V-670, manufactured by JASCO Corporation), and the transmittance at 540 nm was compared with that of the test piece before the test. For comparison, when the transmittance before the test is A and the transmittance after the test is B, (BA) (%) is the change in transmittance, and the evaluation was made according to the following evaluation criteria.
  • a test piece was prepared in the same manner as in "1. Moisture and Heat Resistance” above. The obtained test piece was subjected to a weather resistance test for 200 hours using SUN TEST The transmittance at 540 nm of the test piece was measured in the same manner as in "1. Humid heat resistance”, and compared with the transmittance at 540 nm of the test piece before the test, the transmittance before the test was A, and the transmittance after the test was A. When the transmittance is B, (B-A) (%) is the change in transmittance, and the evaluation was made according to the following evaluation criteria.

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JP2005307148A (ja) * 2004-03-24 2005-11-04 Hitachi Chem Co Ltd プリプレグ及びこれを用いた金属箔張積層板、印刷回路板。
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JP2017031247A (ja) * 2015-07-29 2017-02-09 日本化薬株式会社 硫黄系酸化防止剤を含有する硬化性樹脂組成物およびエポキシ樹脂組成物とその硬化物
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JP2017228414A (ja) * 2016-06-22 2017-12-28 積水化学工業株式会社 有機エレクトロルミネッセンス表示素子用封止剤
JP2019156955A (ja) * 2018-03-12 2019-09-19 信越化学工業株式会社 白色熱硬化性エポキシ樹脂の高強度硬化物、光半導体素子用リフレクター基板、及びこれらの製造方法、並びに硬化物の高強度化方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10279778A (ja) * 1997-04-07 1998-10-20 Hitachi Chem Co Ltd 印刷配線板用エポキシ樹脂組成物及び該組成物を用いたプリプレグ、金属張り積層板
JPH11279375A (ja) * 1998-03-27 1999-10-12 Hitachi Chem Co Ltd 印刷配線板用樹脂組成物及びそれを用いた印刷配線板
JP2005307148A (ja) * 2004-03-24 2005-11-04 Hitachi Chem Co Ltd プリプレグ及びこれを用いた金属箔張積層板、印刷回路板。
JP2006152044A (ja) * 2004-11-26 2006-06-15 Toyo Ink Mfg Co Ltd 封止用組成物
WO2014119777A1 (ja) * 2013-02-04 2014-08-07 日本ゼオン株式会社 感放射線樹脂組成物および電子部品
JP2016053108A (ja) * 2014-09-03 2016-04-14 株式会社ダイセル 硬化性エポキシ樹脂組成物
JP2017031247A (ja) * 2015-07-29 2017-02-09 日本化薬株式会社 硫黄系酸化防止剤を含有する硬化性樹脂組成物およびエポキシ樹脂組成物とその硬化物
WO2017158914A1 (ja) * 2016-03-14 2017-09-21 富士フイルム株式会社 組成物、膜、硬化膜、光学センサおよび膜の製造方法
JP2017228414A (ja) * 2016-06-22 2017-12-28 積水化学工業株式会社 有機エレクトロルミネッセンス表示素子用封止剤
JP2019156955A (ja) * 2018-03-12 2019-09-19 信越化学工業株式会社 白色熱硬化性エポキシ樹脂の高強度硬化物、光半導体素子用リフレクター基板、及びこれらの製造方法、並びに硬化物の高強度化方法

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