WO2011033872A1 - Novel episulfide compounds, curable resin compositions containing the episulfide compounds, and cured products thereof - Google Patents
Novel episulfide compounds, curable resin compositions containing the episulfide compounds, and cured products thereof Download PDFInfo
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- WO2011033872A1 WO2011033872A1 PCT/JP2010/063088 JP2010063088W WO2011033872A1 WO 2011033872 A1 WO2011033872 A1 WO 2011033872A1 JP 2010063088 W JP2010063088 W JP 2010063088W WO 2011033872 A1 WO2011033872 A1 WO 2011033872A1
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- 0 *c1ccccc1 Chemical compound *c1ccccc1 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D331/00—Heterocyclic compounds containing rings of less than five members, having one sulfur atom as the only ring hetero atom
- C07D331/02—Three-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/06—Polythioethers from cyclic thioethers
- C08G75/08—Polythioethers from cyclic thioethers from thiiranes
Definitions
- the present invention relates to a novel episulfide compound, a curable resin composition containing the episulfide compound, a curing agent and / or an energy ray-sensitive cation initiator, and a cured product thereof.
- optical materials such as lenses.
- active development has been made in the field of electronic materials and optical materials due to the excellent electrical properties, heat resistance, adhesiveness, optical properties and the like of the cured resin combined with a curing agent.
- examples thereof include a semiconductor sealing material, an antireflection film such as a liquid crystal display, a protective film for a color filter, an optical waveguide, a lens, a mirror, and a prism that are used in an optical device such as a camera.
- Patent Document 1 reports branched alkyl sulfide-type episulfide compounds
- Patent Document 2 reports linear alkyl sulfide-type episulfide compounds
- Patent Document 3 reports bisphenol S-type episulfide compounds.
- Patent Document 4 reports an episulfide compound having a fluorene skeleton having high heat resistance as an optical material.
- a resin composition for obtaining a cured product exhibiting a high refractive index cannot be produced due to poor solubility in a diluent or the like.
- An object of the present invention is to provide a compound that is excellent in curability, transparency, etc., and is particularly useful for optical applications, and a curable resin composition using the compound.
- an episulfide compound having a specific structure is excellent in solubility, and further that a curable resin composition containing the episulfide compound is excellent in storage stability, and that the cured product is high. It was found that it is a refractive index and excellent in transparency, and it was found that the above problem can be solved by using this.
- the present invention has been made based on the above findings, and provides a novel episulfide compound represented by the following general formula (I) or (II).
- a 1 and A 2 represent an oxygen atom or a sulfur atom (wherein at least one of A 1 and A 2 represents a sulfur atom)
- Cy represents a cycloalkyl group having 3 to 10 carbon atoms.
- X and Z are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic ring having 2 to 20 carbon atoms.
- Aromatic ring is halogen source And n represents an integer of 0 to 10, p represents an integer of 0 to 5, and r represents an integer of 0 to 4.
- the optical isomer present when n is not 0 may be any isomer.
- Y 1 , Y 2 and Z are each independently, An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, and a cyclohexane having 3 to 10 carbon atoms.
- the optical isomer present in can be any isomer.
- this invention provides the curable resin composition containing the novel episulfide compound represented by the said general formula (I) or (II), and a hardening
- the present invention also provides a curable resin composition containing a novel episulfide compound represented by the above general formula (I) or (II) and an energy ray-sensitive cation initiator.
- this invention provides the hardened
- the episulfide compound of the present invention has excellent solubility, and the curable resin composition containing the episulfide compound has excellent curability and storage stability, and gives a cured product having high refractive index and excellent transparency.
- the episulfide compound of the present invention is a novel compound represented by the above general formula (I) or (II). First, the episulfide compound represented by the general formula (I) will be described.
- Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by Cy, X and Z in the general formula (I) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl and cyclononyl. And cyclodecyl.
- Examples of the alkyl group having 1 to 10 carbon atoms represented by X and Z in the general formula (I) include methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl and the like.
- Examples of the group in which the methylene group in the alkyl group is interrupted by —O— include methoxy, ethoxy, propyloxy, isopropyloxy, methoxymethyl, ethoxymethyl, 2-methoxyethyl and the like.
- Examples of the group in which the methylene group is interrupted by —S— include methylthio, ethylthio, butylthio, pentylthio and the like, and examples of the group in which the methylene group in the alkyl group is interrupted by a double bond include allyl, 3-butenyl Etc.
- Examples of the aryl group having 6 to 20 carbon atoms represented by X and Z in the general formula (I) include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 1-phenanthryl, o-tolyl, m-tolyl, p-tolyl, 3-fluorenyl, 9-fluorenyl, 1-tetrahydronaphthyl, 2-tetrahydronaphthyl, 1-acenaphthenyl, 1-indanyl, 2-indanyl, biphenyl and the like.
- Groups interrupted by —O— include phenoxy, 1-naphthoxy, 2-naphthoxy, 1-anthryloxy, 1-phenanthryloxy, o-tolyloxy, m-tolyloxy, p-tolyloxy, 9-fluore Nyloxy, 1-indanyloxy, 2-indanyloxy and the like, and the bond part of the aryl group is-
- the groups interrupted by — include phenylthio, 1-naphthylthio, 2-naphthylthio, 1-anthrylthio, 1-phenanthrylthio, o-tolylthio, m-tolylthio, p-tolylthio, 9-fluorenylthio, 1-tetrahydronaphthylthio, Examples include 2-tetrahydronaphthylthio, 1-indanylthio, 2-indanylthio and the like, and examples of the group in which the bond
- Examples of the arylalkyl group having 7 to 20 carbon atoms represented by X and Z in the general formula (I) include benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl and the like.
- Examples of the group in which the methylene group in the arylalkyl group is interrupted by —O— include benzyloxy, phenoxymethyl, phenoxyethyl, 1-naphthylmethoxy group, 2-naphthylmethoxy group, 1-anthrylmethoxy, and the like.
- Examples of the group in which the methylene group in the arylalkyl group is interrupted by —S— include benzylthio, phenylthiomethyl, phenylthioethyl, etc., and the methylene group in the arylalkyl group is interrupted by a double bond. Examples of the group include cinnamyl.
- heterocyclic group having 2 to 20 carbon atoms represented by X and Z in the general formula (I) examples include pyrrolyl, pyridyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolidyl, quinolyl.
- Examples of the aromatic ring formed by adjacent Zs in the general formula (I) include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring.
- halogen atom represented by X and Z in the above general formula (I) and the alkyl group, aryl group, arylalkyl group, heterocyclic group, cycloalkyl group and X and Z represented by the above general formula (I) and Examples of the halogen atom that may substitute the aromatic ring formed between adjacent Zs include fluorine, chlorine, bromine, and iodine.
- the alkyl group, the aryl group, the arylalkyl group, the heterocyclic group, the cycloalkyl group and the aromatic ring formed between Z and represented by X and Z in the general formula (I) may have a substituent.
- the alkyl group, aryl group, arylalkyl group, heterocyclic group, cyclohexyl represented by X and Z in the general formula (I) including the substituent The number of carbon atoms of the aromatic ring formed by the group and adjacent Zs shall satisfy the specified range of the number of carbon atoms.
- an optical isomer may exist in the episulfide compound represented by the general formula (I) and the episulfide compound represented by the general formula (II) described later.
- an optical isomer may exist in the episulfide compound represented by the general formula (I) and the episulfide compound represented by the general formula (II) described later.
- the compounds shown in the following text are not limited to specific optical isomers.
- Examples of the episulfide compound represented by the general formula (I) include the following compound No. 1-No. The compound shown by 13 is mentioned. In the chemical formula below, n represents a number from 0 to 10. However, the present invention is not limited by the following compounds.
- X and Z are alkyl groups having 1 to 10 carbon atoms or aryl groups having 6 to 20 carbon atoms
- p And compounds in which r is 0 to 2 and n is 0 to 5 are preferred because of their good storage stability.
- the following compounds i) to iii) are easy to obtain from raw materials and have good productivity. Further preferred.
- the optical isomer present when n is not 0 may be any isomer.
- X is an aryl group having 6 to 20 carbon atoms
- p is 0 or 1
- n is 0 to 2.
- the method for producing the episulfide compound represented by the general formula (I) is not particularly limited. For example, as shown in the following reaction formula, by reacting the epoxy derivative (1) with thiourea, The episulfide compound represented by the general formula (I) can be easily produced.
- the amount of thiourea used in the reaction and the reaction time it is possible to arbitrarily control the ratio of substitution of oxygen atoms to sulfur atoms in the oxirane ring (sulfur substitution rate) in the epoxy derivative as a raw material.
- sulfur substitution rate the ratio of substitution of oxygen atoms to sulfur atoms in the oxirane ring
- it may be used as an episulfide compound of the present invention while leaving an unsubstituted oxirane ring in the product, or an epoxy derivative as a part of the raw material.
- the alkyl group having 1 to 10 carbon atoms represented by Y 1 , Y 2 and Z, and the methylene group in the alkyl group are —O—, —S—, or a double bond.
- Examples of the interrupted group include the groups exemplified in the description of the general formula (I).
- the aryl group having 6 to 20 carbon atoms represented by Y 1 , Y 2 and Z, and the bond part of the aryl group are interrupted by —O—, —S— or a double bond.
- Examples of the group include those exemplified in the description of the general formula (I).
- Examples of the group interrupted in the above include the groups exemplified in the description of the general formula (I).
- heterocyclic group having 2 to 20 carbon atoms represented by Y 1 , Y 2 and Z in the general formula (II) include groups exemplified in the description of the general formula (I).
- Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by Y 1 , Y 2 and Z in the general formula (II) include groups exemplified in the description of the general formula (I).
- the ring structure formed by bonding adjacent Y 1 in the general formula (II) includes, in addition to those exemplified as the aromatic ring in the general formula (I), a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, Examples thereof include 5- to 7-membered rings such as piperidine ring, morpholine ring, lactone ring and lactam ring, and condensed rings such as fluorene ring, acenaphthene ring, indane ring and tetralin ring.
- Examples of the halogen atom that may substitute the ring structure formed by bonding of the heterocyclic group, the cycloalkyl group and the adjacent Y 1 include the groups exemplified in the description of the general formula (I).
- Ring structure formed by bonding of alkyl group, aryl group, arylalkyl group, heterocyclic group, cycloalkyl group and adjacent Y 1 represented by Y 1 , Y 2 and Z in the general formula (II) May have a substituent, and examples of these substituents include the groups exemplified in the description of the general formula (I), and these groups may be further substituted.
- an alkyl group represented by Y 1 , Y 2 and Z, an aryl group, an arylalkyl group, which can be placed in the general formula (II) including the substituent when substituted with a substituent having a carbon atom, an alkyl group represented by Y 1 , Y 2 and Z, an aryl group, an arylalkyl group, which can be placed in the general formula (II) including the substituent,
- the number of carbon atoms in a ring structure formed by a heterocyclic group, a cycloalkyl group, and adjacent Z's shall satisfy the specified range of carbon atoms.
- n a number from 0 to 10.
- the present invention is not limited by the following compounds.
- the following compounds iv) to ix) are preferable because the raw materials are easily available, the productivity is high, and a cured product having a high refractive index is obtained.
- x is 2 or 3
- y is 0,
- Y 1 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or adjacent Y
- the ring formed by 1 is an aromatic ring,
- Y 2 and Z are an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, and q and r are 0 to 2 A compound.
- Y 1 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms.
- the method for producing the episulfide compound represented by the general formula (II) is not particularly limited.
- the episulfide compound represented by the general formula (II) can be easily produced.
- the episulfide compound of the present invention includes a curable resin composition described below, and uses as a cured product obtained by heating and / or irradiating the curable resin composition with energy rays, as well as concrete and cement mortar. Paints or adhesives for various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc .; adhesive tape for packaging, adhesive labels, frozen food labels, removable labels, POS labels, adhesive wallpaper, adhesive flooring, etc.
- Adhesives Art paper, lightweight coated paper, cast coated paper, coated paperboard, carbonless copying machine, impregnated paper and other processed paper; natural fibers, synthetic fibers, glass fibers, carbon fibers, metal fibers and other sizing agents, Used for a wide range of applications such as anti-fraying agents, fiber treatment agents such as processing agents, building materials such as sealing agents, cement admixtures, waterproofing materials, and sealants for electronic and electrical equipment. Rukoto can.
- the curable resin composition of the present invention (hereinafter also referred to as the first curable resin composition) containing the novel episulfide compound represented by the general formula (I) or (II) and a curing agent. explain.
- the description of the episulfide compound is appropriately applied to portions that are not particularly described.
- the curing agent examples include polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; polyether polyamines such as polyoxypropylenediamine and polyoxypropylenetriamine; 1,2-diaminocyclohexane, 1, 4-diamino-3,6-diethylcyclohexane, isophoronediamine, mensendiamine, norbornenediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminomethylpiperazine Alicyclic polyamines such as 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane; m-xylenediamine, ⁇ - (m / p amide) Phenyl) ethylamine,
- these polyamines and glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-glycidyl ether, or various epoxy resins such as glycidyl esters of carboxylic acid are used in a conventional manner.
- latent curing agents such as dicyandiamide, acid anhydrides, and imidazoles such as 2-ethyl-4methylimidazole can also be used.
- the polyamines, modified products of the polyamines, and imidazoles are preferable, and imidazoles are more preferable in terms of storage stability and curability.
- the content of the curing agent is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the episulfide compound. .
- the content of the curing agent is less than 0.01 parts by weight, the curing rate is slow or the curing is insufficient, and when it exceeds 20 parts by weight, the strength of the cured product is insufficient.
- the first curable resin composition may include a curing catalyst; reactive and / or non-reactive, such as an epoxy compound, an oxetane compound, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and coal tar.
- a curing catalyst reactive and / or non-reactive, such as an epoxy compound, an oxetane compound, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and coal tar.
- epoxy compound that may be used as the reactive and / or non-reactive diluent (plasticizer) include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.
- oxetane compound that may be used as a reactive and / or non-reactive diluent (plasticizer) include soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized polybutadiene, and the like.
- the first curable resin composition may contain a solvent.
- the amount of the solvent used is such that the total content of the episulfide compound and the curing agent is preferably 5 to 90% by mass, more preferably 10 to 50% by mass in the first curable resin composition. It should be in the range.
- the solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1 Ether solvents such as 1,2-diethoxyethane and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, and n-butyl acetate; ethylene glycol monomethyl ether, ethylene glycol Cellosolve solvents such as monoethyl ether, propylene glycol monomethyl ether acetate; methanol, ethanol, iso- or n-propanol, iso- or n-butan
- the first curable resin composition can be cured by heat treatment.
- the heat treatment is preferably performed in the range of 100 to 300 ° C. for 10 to 240 minutes.
- the curable resin composition of the present invention (hereinafter referred to as the second curable resin composition) containing the novel episulfide compound represented by the general formula (I) or (II) and an energy ray-sensitive cationic polymerization initiator. (Also called things).
- the content of the description in the said episulfide compound and the 1st curable resin composition is applied suitably about the part which is not demonstrated especially.
- the energy beam sensitive initiator is a compound capable of releasing a substance that initiates cationic polymerization by energy beam sensitive irradiation, more specifically, energy beam irradiation as described later.
- the energy ray-sensitive cationic polymerization initiator include a double salt that is an onium salt that releases a Lewis acid by energy ray-sensitive irradiation, or a derivative thereof.
- a typical example of such a compound is a salt of a cation and an anion represented by the general formula [A] y + [B] y- .
- the cation [A] y + is preferably onium, and the structure can be represented by, for example, [(R) x Q] y + .
- R is an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon, and x is an integer of 1 to 5.
- the x Rs are independent and may be the same or different. Further, at least one of x R is preferably an aromatic group.
- the anion [B] y ⁇ is preferably a halide complex, and the structure thereof can be represented by [LX s ] y ⁇ , for example.
- L is a metal or metalloid which is a central atom of a halide complex
- B P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like.
- X is a halogen atom.
- anion [LX s ] y ⁇ of the above general formula examples include tetrafluoroborate (BF 4 ) ⁇ , hexafluorophosphate (PF 6 ) ⁇ , hexafluoroantimonate (SbF 6 ) ⁇ , hexafluoroarsenate.
- PF 6 hexafluorophosphate
- SbF 6 hexafluoroantimonate
- hexafluoroarsenate hexafluoroarsenate.
- AsF 6 ) ⁇ hexachloroantimonate (SbCl 6 ) ⁇ and the like can be mentioned, and hexafluoroantimonate (SbF 6 ) ⁇ is preferable.
- a structure represented by [LX s ⁇ 1 (OH)] y ⁇ can also be used.
- L, X, and s are the same as described above.
- Other anions that can be used include perchlorate ion (ClO 4 ) ⁇ , trifluoromethyl sulfite ion (CF 3 S O 3 ) ⁇ , fluorosulfonic acid ion (FSO 3 ) ⁇ , toluenesulfonic acid anion, trinitrobenzenesulfonic acid anion, and the like.
- tetrakis (pentafluorophenyl) borate can be used as the anion [B] y ⁇ .
- aromatic onium salts among such onium salts.
- aromatic halonium salts described in JP-A-50-151997, JP-A-50-158680, JP-A-50-151997, JP-A-52-30899, JP-A-56- No. 55420, JP-A 55-125105, etc. Group VIA aromatic onium salts, JP-A-50-158698, Group VA aromatic onium salts, JP-A 56-8428, Oxosulfoxonium salts described in JP-A-56-149402, JP-A-57-192429, etc., aromatic diazonium salts described in JP-A-49-17040, US Pat. No. 4,139,655
- the thiopyrylium salt described in 1 is preferable.
- aromatic onium salts the following general formula (V), (VI) or (VII) is particularly preferable.
- R1 to R14 may be the same or different from each other, a hydrogen atom, a halogen atom, an oxygen atom or a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent, Ar is one or more.
- a hydrogen atom is a phenyl group which may be substituted.
- a compound having a sulfonium cation represented by: a compound having a (tricumyl) iodonium cation; a compound having a bis (t-butylphenyl) iodonium cation; Examples thereof include a compound having a phenylsulfonium cation.
- xylene-cyclopentadienyl iron (II) hexafluoroantimonate cumene-cyclopentadienyl iron (II) hexafluorophosphate
- xylene-cyclopentadienyl iron (II) -tris examples thereof include iron / allene complexes such as (trifluoromethylsulfonyl) methanide, aluminum complexes / photolytic silicon compound-based initiators, and the like.
- the energy ray sensitive cationic polymerization initiator can be used alone or in combination of two or more. Moreover, the hardening
- the amount of the energy ray sensitive cationic polymerization initiator used or the total amount of the energy ray sensitive cationic polymerization initiator and the curing agent used is 0.05 to 20 parts by mass with respect to 100 parts by mass of the episulfide compound. When the amount used is less than 0.05 parts by mass, the curable resin composition is not sufficiently cured, and distortion or unevenness occurs, or cracks occur during heating.
- a more preferable amount of the energy ray-sensitive cationic polymerization initiator is 0.5 to 15 parts by mass with respect to 100 parts by mass of the episulfide compound.
- any additive exemplified in the description of the first curable resin composition may be added to the second curable resin composition.
- these optional additives are preferably 500 parts by mass or less in total with respect to 100 parts by mass of the episulfide compound.
- the second curable resin composition may contain a solvent.
- the amount of the solvent used is such that the total content of the episulfide compound, the energy ray-sensitive cationic polymerization initiator and / or the curing agent is preferably 5 to 90 mass in the second curable resin composition. %, More preferably 10 to 50% by mass.
- Specific examples of the solvent include the solvents exemplified in the first curable resin composition, and among them, ketones or cellosolve solvents are preferable. Moreover, you may make it contain in the 2nd curable resin composition as it is, without removing the solvent used when synthesize
- the second curable resin composition can be cured to a dry-to-touch state or a solvent-insoluble state usually after 0.1 seconds to several minutes by irradiation with energy rays such as ultraviolet rays.
- energy rays such as ultraviolet rays.
- Any suitable energy ray may be used as long as it induces decomposition of the cationic polymerization initiator, but preferably an ultra-high, high, medium, low-pressure mercury lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, From 2000 angstroms obtained from tungsten lamp, excimer lamp, germicidal lamp, excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source, etc.
- High energy rays such as electromagnetic energy having a wavelength of 7000 angstroms, electron beams, X-rays
- the second curable resin composition can be cured by heat treatment.
- a heat treatment is appropriately performed before and after the energy beam irradiation, a cured product with good quality can be obtained.
- the first and second curable resin compositions described above are used as cured products described below, as well as inks, protective films, paints, coating agents, adhesives, insulating materials, structural materials, optical disks, and sealings. It can also be used as an agent or an optical modeling agent.
- the cured product of the present invention obtained by heating the first and / or second curable resin composition and / or irradiating energy rays will be described.
- the content of the description in the said episulfide compound and the 1st and 2nd curable resin composition is applied suitably about the part which is not demonstrated especially.
- the shape of the cured product of the present invention is not particularly limited, and examples thereof include a lens shape, a film, a prism shape, and a plate shape. Furthermore, the material may be coated or sealed by curing on other materials.
- the cured product of the present invention is useful for optical parts such as an optical lens, an optical film, a light guide plate, a waveguide, an optical element, and an optical connector.
- Examples 1-1 to 1-3 show production examples of the novel episulfide compound of the present invention
- Examples 2-1 to 2-8 show production examples and evaluation examples of the first and second curable resin compositions.
- Comparative Examples 2-1 to 2-7 show production examples and evaluation examples of comparative curable resin compositions.
- Examples 3-1 to 3-3 show production examples and evaluation examples of cured products obtained by curing the first curable resin composition
- Comparative Example 3-1 shows production examples and evaluation examples of comparative cured products.
- Examples 4-1 and 4-2 show production examples and evaluation examples of cured products obtained by curing the second curable resin composition
- Comparative Examples 4-1 to 4-3 are productions of comparative cured products. Examples and evaluation examples are shown.
- Example 1-1 Production of episulfide compound A-1
- 1,1-bis (4- (2,3-epoxypropyloxy) phenyl) -3-phenylindane was added.
- 100.0 g of tetrahydrofuran, 250 g of tetrahydrofuran, and 60.0 g of ethanol were charged and dissolved with sufficient stirring. This was charged with 44.2 g of thiourea, heated to 45 ° C. and stirred for 18 hours.
- the sulfur substitution rate of the oxirane ring to the thiirane ring determined from the elemental analysis value was 98%. The analysis results are shown below.
- Example 1-2 Production of episulfide compound A-2.
- the organic layer was washed twice with 300 mL of 10% saline and dried well over anhydrous magnesium sulfate, and then the solvent was removed to obtain 50.2 g of a colorless solid (episulfide compound (A-2)) in a yield of 95. %.
- a colorless solid episulfide compound (A-2)
- the sulfur substitution rate of the oxirane ring to the thiirane ring determined from the elemental analysis value was 96%. The analysis results are shown below.
- Example 1-3 Production of episulfide compound A-3.
- 30.0 g of bis [4- (2,3-epoxypropyloxy) phenyl] cyclohexyl (4-biphenyl) methane 150 g of 1,4-dioxane, and 30. ethanol. 0 g was charged and dissolved by stirring well. This was charged with 10.2 g of thiourea and stirred at 50 ° C. for 24 hours.
- the comparative curable resin composition was prepared in the same manner using the following comparative compounds (B-1) to (B-3) instead of the episulfide compound of the present invention. No. 9-No. 15 was produced. The solubility of the obtained composition was evaluated. The results are shown in [Table 1] and [Table 2].
- the composition using the comparative compound (B-2) was poor in solubility and storage stability, whereas the examples using the episulfide compound of the present invention were used.
- the compositions of 2-1 to 2-8 are excellent in solubility in a diluent. Further, in Comparative Examples 2-1 and 2-4, the curable resin composition was not obtained because it was not dissolved, and in Comparative Example 2-7, crystals were precipitated after cooling to room temperature.
- Examples 3-1 to 3-3 and Comparative Example 3-1 The obtained curable resin composition No. 1-No. 3 and comparative curable resin composition No. Each 10 was heated to 60 ° C. and applied to a glass substrate subjected to a release treatment. The glass was sandwiched with another glass with a 1.00 mm spacer and bonded together, and heated at 100 ° C. for 1 hour and at 150 ° C. for 1 hour. The cured product was evaluated as ⁇ , and the cured product was evaluated as ⁇ . Moreover, what was obtained as hardened
- Examples 4-1 and 4-2 and Comparative Examples 4-1 to 4-3 The obtained curable resin composition No. 4 and no. 5 and comparative curable resin composition No. 11, No. 13, and No. 11; Each 14 was heated to 60 ° C. and applied to a glass substrate subjected to a release treatment. Laminated by sandwiching the other piece of glass with 1.00mm spacer, which after exposure at 3000 mJ / cm 2 per glass sided high pressure mercury lamp (total 6000 mJ / cm 2), for 2 hours at 0.99 ° C., cooled to room temperature And peeled from the glass substrate. The curability was evaluated as ⁇ for those obtained as cured products, and x for those that were not cured. Moreover, what was obtained as hardened
- the episulfide compound of the present invention is excellent in solubility, and the curable resin composition of the present invention characterized by containing these compounds is a cured product having a high refractive index excellent in curability and transparency. Obviously, it is useful for optical material applications.
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Abstract
Description
本発明のエピスルフィド化合物は、上記一般式(I)又は(II)で表わされる新規化合物である。
先ず、上記一般式(I)で表わされるエピスルフィド化合物について説明する。 Hereinafter, the episulfide compound, curable resin composition, and cured product thereof of the present invention will be described in detail based on preferred embodiments.
The episulfide compound of the present invention is a novel compound represented by the above general formula (I) or (II).
First, the episulfide compound represented by the general formula (I) will be described.
i)下記一般式(III)で表される化合物。
ii)上記一般式(I)中、Xが炭素原子数6~20のアリール基であり、pが0又は1であり、nが0~2である化合物。
iii)上記一般式(III)中、nが0~2である化合物。 Among the episulfide compounds represented by the general formula (I), in the general formula (I), X and Z are alkyl groups having 1 to 10 carbon atoms or aryl groups having 6 to 20 carbon atoms, p And compounds in which r is 0 to 2 and n is 0 to 5 are preferred because of their good storage stability. In particular, the following compounds i) to iii) are easy to obtain from raw materials and have good productivity. Further preferred.
i) A compound represented by the following general formula (III).
ii) A compound in which, in the above general formula (I), X is an aryl group having 6 to 20 carbon atoms, p is 0 or 1, and n is 0 to 2.
iii) A compound wherein n is 0-2 in the above general formula (III).
造は置換基を有してもよく、これらの置換基としては、上記一般式(I)の説明で例示した基が挙げられ、これらの基は更に置換されてもよい。尚、炭素原子を有する置換基で置換される場合は、該置換基を含めた上記一般式(II)に置けるY1、Y2及びZで表されるアルキル基、アリール基、アリールアルキル基、複素環基、シクロアルキル基、及び隣接するZ同士で形成される環構造の炭素原子数が規定された炭素原子数の範囲を満たすものとする。 Ring structure formed by bonding of alkyl group, aryl group, arylalkyl group, heterocyclic group, cycloalkyl group and adjacent Y 1 represented by Y 1 , Y 2 and Z in the general formula (II) May have a substituent, and examples of these substituents include the groups exemplified in the description of the general formula (I), and these groups may be further substituted. In addition, when substituted with a substituent having a carbon atom, an alkyl group represented by Y 1 , Y 2 and Z, an aryl group, an arylalkyl group, which can be placed in the general formula (II) including the substituent, The number of carbon atoms in a ring structure formed by a heterocyclic group, a cycloalkyl group, and adjacent Z's shall satisfy the specified range of carbon atoms.
iv)上記一般式(II)中、xが2又は3であり、yが0であり、Y1が炭素原子数1~10のアルキル基、炭素原子数6~20のアリール基又は隣接するY1同士で形成した環が芳香環となる基であり、Y2及びZは炭素原子数1~10のアルキル基、炭素原子数6~20のアリール基であり、q及びrが0~2である化合物。
v)下記一般式(IV)で表される化合物。
vi)上記一般式(II)又は(IV)中、nが0~5である化合物。
vii)上記一般式(II)又は(IV)中、Y2がフェニル基である化合物。
viii)上記一般式(II)又は(IV)中、qが0又は1であり、qが1の時、Y1が炭素原子数1~10のアルキル基又は炭素原子数6~20のアリール基である化合物。
ix)上記一般式(II)中、xは2であり、yは0であり、Y2はフェニル基であり、qは0であり、q’は0であり、qは1であり、rは0であり、nは0~2である化合物。 Among the episulfide compounds represented by the above general formula (II), the following compounds iv) to ix) are preferable because the raw materials are easily available, the productivity is high, and a cured product having a high refractive index is obtained.
iv) In the above general formula (II), x is 2 or 3, y is 0, Y 1 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or adjacent Y The ring formed by 1 is an aromatic ring, Y 2 and Z are an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, and q and r are 0 to 2 A compound.
v) A compound represented by the following general formula (IV).
vi) A compound wherein n is 0 to 5 in the above general formula (II) or (IV).
vii) A compound wherein Y 2 is a phenyl group in the above general formula (II) or (IV).
viii) In the above general formula (II) or (IV), when q is 0 or 1, and q is 1, Y 1 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. A compound that is
ix) In the general formula (II), x is 2, y is 0, Y 2 is a phenyl group, q is 0, q ′ is 0, q is 1, r Is a compound in which n is 0 and n is 0-2.
O3)-、フルオロスルホン酸イオン(FSO3)-、トルエンスルホン酸陰イオン、トリニトロベンゼンスルホン酸陰イオン等が挙げられる。 As the anion [B] y− , a structure represented by [LX s −1 (OH)] y− can also be used. L, X, and s are the same as described above. Other anions that can be used include perchlorate ion (ClO 4 ) − , trifluoromethyl sulfite ion (CF 3 S
O 3 ) − , fluorosulfonic acid ion (FSO 3 ) − , toluenesulfonic acid anion, trinitrobenzenesulfonic acid anion, and the like.
攪拌装置及び温度計を付した三口フラスコに、1,1-ビス(4-(2,3-エポキシプロピルオキシ)フェニル)-3-フェニルインダンの100.0g、テトラヒドロフラン250g、及びエタノール60.0gを仕込みよく攪拌して溶解させた。これにチオ尿素の44.2gを仕込み、45℃に加熱し18時間攪拌した。この後トルエン300mL、酢酸エチル200mL及び水300mLを加え、分液ろうとで洗浄し、水層を廃棄した。更に有機層を10%食塩水の300mLで2度洗浄した後無水硫酸マグネシウムでよく乾燥させ、脱溶媒を行い粗生成物を得た。この粗生成物をシリカゲルカラムクロマトグラフィー(展開溶媒:トルエン)で分離精製を行い、73.0gの無色粘稠性固体(エピスルフィド化合物(A-1))を収率69%で得た。各種分析の結果、該無色粘稠性固体は本発明のエピスルフィド化合物(化合物No.53におけるn=0の化合物)であることを確認した。元素分析値から求められるオキシラン環のチイラン環への硫黄置換率は98%であった。分析結果を下記に示す。 [Example 1-1] Production of episulfide compound A-1 In a three-necked flask equipped with a stirrer and a thermometer, 1,1-bis (4- (2,3-epoxypropyloxy) phenyl) -3-phenylindane was added. 100.0 g of tetrahydrofuran, 250 g of tetrahydrofuran, and 60.0 g of ethanol were charged and dissolved with sufficient stirring. This was charged with 44.2 g of thiourea, heated to 45 ° C. and stirred for 18 hours. Thereafter, 300 mL of toluene, 200 mL of ethyl acetate and 300 mL of water were added, washed with a separatory funnel, and the aqueous layer was discarded. Further, the organic layer was washed twice with 300 mL of 10% saline, and then thoroughly dried over anhydrous magnesium sulfate, and the solvent was removed to obtain a crude product. This crude product was separated and purified by silica gel column chromatography (developing solvent: toluene) to obtain 73.0 g of a colorless viscous solid (episulfide compound (A-1)) in a yield of 69%. As a result of various analyses, it was confirmed that the colorless viscous solid was an episulfide compound of the present invention (a compound of n = 0 in Compound No. 53). The sulfur substitution rate of the oxirane ring to the thiirane ring determined from the elemental analysis value was 98%. The analysis results are shown below.
(1)1H-NMRのケミカルシフト(DMSO-d6、35℃):(ppm)
2.42-2.45(m:2H)、2.49-2.73(m:3H)、3.15-3.20(m:1H)、3.26-3.37(m:2H)、3.95-4.02(m:2H)、4.07-4.16(m:3H)、6.78(d:1H)、6.86-6.96(m:4H)、7.01-7.07(m:3H)、7.08-7.13(m:2H)、7.15-7.26(m:5H)、7.30-7.35(m:2H)。
(2)元素分析による硫黄含量(ダイアインスルメンツ社製TOX-100による測定含量)
実測値:12.1%、理論値:12.3%。
(3)IR(cm-1)
3027、2868、1605、1579、1507、1468、1454、1397、1292、1245、1181、1118、1032、1011、828、779、756、736、701 (result of analysis)
(1) 1 H-NMR chemical shift (DMSO-d6, 35 ° C.): (ppm)
2.42-2.45 (m: 2H), 2.49-2.73 (m: 3H), 3.15-3.20 (m: 1H), 3.26-3.37 (m: 2H) ), 3.95-4.02 (m: 2H), 4.07-4.16 (m: 3H), 6.78 (d: 1H), 6.86-6.96 (m: 4H), 7.01-7.07 (m: 3H), 7.08-7.13 (m: 2H), 7.15-7.26 (m: 5H), 7.30-7.35 (m: 2H) ).
(2) Sulfur content by elemental analysis (measured content by TOIN-100 manufactured by Diainstruments)
Found: 12.1%, Theoretical value: 12.3%.
(3) IR (cm -1 )
3027, 2868, 1605, 1579, 1507, 1468, 1454, 1397, 1292, 1245, 1181, 1118, 1032, 1011, 828, 779, 756, 736, 701
攪拌装置及び温度計を付した三口フラスコに、1,1-ビス(4-(2,3-エポキシプロピルオキシ)フェニル)-3,5-ジフェニルインダンの50.0g、テトラヒドロフラン270g、及びエタノール30.0gを仕込みよく攪拌して溶解させた。これにチオ尿素の14.8gを仕込み、室温で48時間攪拌した。この後トルエン1000mL、と水300mLを加え、分液ろうとで洗浄し、水層を廃棄した。更に有機層を10%食塩水の300mLで2度洗浄し、無水硫酸マグネシウムでよく乾燥させた後、脱溶媒を行い、50.2gの無色固体(エピスルフィド化合物(A-2))を収率95%で得た。各種分析の結果、該無色固体は本発明のエピスルフィド化合物(化合物No.44におけるn=0の化合物)であることを確認した。元素分析値から求められるオキシラン環のチイラン環への硫黄置換率は96%であった。分析結果を下記に示す。 [Example 1-2] Production of episulfide compound A-2.
In a three-necked flask equipped with a stirrer and a thermometer, 50.0 g of 1,1-bis (4- (2,3-epoxypropyloxy) phenyl) -3,5-diphenylindane, 270 g of tetrahydrofuran, and 30. 0 g was charged and dissolved by stirring well. This was charged with 14.8 g of thiourea and stirred at room temperature for 48 hours. Thereafter, 1000 mL of toluene and 300 mL of water were added, washed with a separatory funnel, and the aqueous layer was discarded. Further, the organic layer was washed twice with 300 mL of 10% saline and dried well over anhydrous magnesium sulfate, and then the solvent was removed to obtain 50.2 g of a colorless solid (episulfide compound (A-2)) in a yield of 95. %. As a result of various analyses, it was confirmed that the colorless solid was an episulfide compound of the present invention (a compound of n = 0 in Compound No. 44). The sulfur substitution rate of the oxirane ring to the thiirane ring determined from the elemental analysis value was 96%. The analysis results are shown below.
(1)1H-NMRのケミカルシフト(DMSO-d6、35℃):(ppm)
2.50(d:1H)、2.65(d:1H)、2.68-2.71(m:2H)、2.76-2.82(m:1H)、3.21-3.36(m:3H)、3.80-3.86(m:1H)、4.00-4.03(m:1H)、4.10-4.15(m:1H)、4.18-4.24(m:1H)、4.26-4.31(m:1H)、6.88-6.92(m:4H)、6.98(s:1H)、7.05-7.09(m:2H)、7.14-7.20(m:3H)、7.25-7.41(m:8H)、7.48-7.55(m:3H)(2)元素分析による硫黄含量(ダイアインスルメンツ社製TOX-100による測定含量)
実測値:10.3%、理論値:10.7%。
(3)IR(cm-1)
3027、2925、1604、1579、1508、1475、1298、1245、1181、1035、914、830、763、701 (result of analysis)
(1) 1 H-NMR chemical shift (DMSO-d6, 35 ° C.): (ppm)
2.50 (d: 1H), 2.65 (d: 1H), 2.68-2.71 (m: 2H), 2.76-2.82 (m: 1H), 3.21-3. 36 (m: 3H), 3.80-3.86 (m: 1H), 4.00-4.03 (m: 1H), 4.10-4.15 (m: 1H), 4.18- 4.24 (m: 1H), 4.26-4.31 (m: 1H), 6.88-6.92 (m: 4H), 6.98 (s: 1H), 7.05-7. 09 (m: 2H), 7.14-7.20 (m: 3H), 7.25-7.41 (m: 8H), 7.48-7.55 (m: 3H) (2) Elemental analysis Sulfur content (measured by Diax Instruments TOX-100)
Actual value: 10.3%, theoretical value: 10.7%.
(3) IR (cm -1 )
3027, 2925, 1604, 1579, 1508, 1475, 1298, 1245, 1181, 1035, 914, 830, 763, 701
攪拌装置及び温度計を付した三口フラスコに、ビス[4-(2,3-エポキシプロピルオキシ)フェニル]シクロヘキシル(4-ビフェニル)メタンの30.0g、1,4-ジオキサン150g、及びエタノール30.0gを仕込みよく攪拌して溶解させた。これにチオ尿素の10.2gを仕込み、50℃で24時間攪拌し、この後トルエン300mL、酢酸エチル200mL及び水300mLを加え、分液ろうとで洗浄し、水層を廃棄した。更に有機層を10%食塩水の300mLで2度洗浄し、無水硫酸マグネシウムでよく乾燥させた後脱溶媒を行い、白色粉末状の結晶を析出させた。この結晶をトルエンとヘキサンで洗浄し、よく乾燥させて22.5gの無色結晶(エピスルフィド化合物(A-3))を収率71%で得た。各種分析の結果、該無色結晶は本発明のエピスルフィド化合物(化合物No.1におけるn=0の化合物)であることを確認した。元素分析値から求められるオキシラン環のチイラン環への硫黄置換率は92%であった。分析結果を下記に示す。 [Example 1-3] Production of episulfide compound A-3.
In a three-necked flask equipped with a stirrer and a thermometer, 30.0 g of bis [4- (2,3-epoxypropyloxy) phenyl] cyclohexyl (4-biphenyl) methane, 150 g of 1,4-dioxane, and 30. ethanol. 0 g was charged and dissolved by stirring well. This was charged with 10.2 g of thiourea and stirred at 50 ° C. for 24 hours. After that, 300 mL of toluene, 200 mL of ethyl acetate and 300 mL of water were added, washed with a separatory funnel, and the aqueous layer was discarded. Further, the organic layer was washed twice with 300 mL of 10% saline, dried thoroughly with anhydrous magnesium sulfate, and then the solvent was removed to precipitate white powdery crystals. The crystals were washed with toluene and hexane and dried well to obtain 22.5 g of colorless crystals (episulfide compound (A-3)) with a yield of 71%. As a result of various analyses, it was confirmed that the colorless crystals were the episulfide compound of the present invention (the compound of n = 0 in Compound No. 1). The sulfur substitution rate of the oxirane ring to the thiirane ring determined from elemental analysis values was 92%. The analysis results are shown below.
(1)1H-NMRのケミカルシフト(DMSO-d6、25℃):(ppm)
0.99-1.10(m:3H)、1.30-1.52(m:5H)、2.07(d:2H)、2.30(d:2H)、2.51(d:2H)、3.14-3.22(m:2H)、3.80(dd:2H)、3.86(s:1H)、3.96(dd:2H)、6.61-6.66(m:4H)、6.86-6.92(m:6H)、7.20-7.25(m:1H)、7.31-7.37(m:2H)、7.44(d:2H)、7.57(d:2H)
(2)元素分析による硫黄含量(ダイアインスルメンツ社製TOX-100による測定含量)
実測値:10.1%、理論値:11.0%
(3)IR(cm-1)
2929、2845、1606、1508、1236、1181、1032、824、764、763 (result of analysis)
(1) 1 H-NMR chemical shift (DMSO-d6, 25 ° C.): (ppm)
0.99-1.10 (m: 3H), 1.30-1.52 (m: 5H), 2.07 (d: 2H), 2.30 (d: 2H), 2.51 (d: 2H), 3.14-3.22 (m: 2H), 3.80 (dd: 2H), 3.86 (s: 1H), 3.96 (dd: 2H), 6.61-6.66 (M: 4H), 6.86-6.92 (m: 6H), 7.20-7.25 (m: 1H), 7.31-7.37 (m: 2H), 7.44 (d : 2H), 7.57 (d: 2H)
(2) Sulfur content by elemental analysis (measured content by TOIN-100 manufactured by Diainstruments)
Measured value: 10.1%, theoretical value: 11.0%
(3) IR (cm -1 )
2929, 2845, 1606, 1508, 1236, 1181, 1032, 824, 764, 763
上記製造例1~3で製造したエピスルフィド化合物(A-1)~(A-3)及び希釈剤(C-1)又は(C-2)を[表1]の配合比率に従い混合し、100℃に加熱して攪拌溶解させた後、60℃まで降温し、熱硬化剤(D-1)又はカチオン重合開始剤(D-2)を加えて10分撹拌し、それぞれ硬化性樹脂組成物No.1~No.8を作製した。また、[表2]の配合比率に従い、本発明のエピスルフィド化合物に替えて、下記に示す比較化合物(B-1)~(B-3)を用いて同様の操作で、比較硬化性樹脂組成物No.9~No.15を作製した。得られた組成物の溶解性を評価した。結果を[表1]及び[表2]に示す。
(B-1)2,2-ビス(4-(2,3-エピチオプロピルオキシ)フェニル)プロパン(B-2)9,9-ビス(4-(2,3-エピチオプロピルオキシ)フェニル)フルオレン
(B-3)1,1-ビス(4-(2,3-エポキシプロピルオキシ)フェニル)-3-フェニルインダン
(C-1)アデカレジンEP-4100E((株)ADEKA製):ビスフェノールA型エポキシ樹脂):希釈剤
(C-2)グリシジルフェニルエーテル:希釈剤
(D-1)2-エチル-4-メチルイミダゾール:熱硬化剤
(D-2)4-(2-クロロ-4-ベンゾイルフェニルチオ)フェニルビス(4-フルオロフェニル)スルホニウムヘキサフルオロアンチモネート(アデカオプトマーSP-172、(株)ADEKA製):エネルギー線感受性カチオン重合開始剤
(B-1) 2,2-bis (4- (2,3-epithiopropyloxy) phenyl) propane (B-2) 9,9-bis (4- (2,3-epithiopropyloxy) phenyl Fluorene (B-3) 1,1-bis (4- (2,3-epoxypropyloxy) phenyl) -3-phenylindane (C-1) Adeka Resin EP-4100E (manufactured by ADEKA Corporation): Bisphenol A Type epoxy resin): diluent (C-2) glycidyl phenyl ether: diluent (D-1) 2-ethyl-4-methylimidazole: thermosetting agent (D-2) 4- (2-chloro-4-benzoyl) Phenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate (Adekaoptomer SP-172, manufactured by ADEKA Corporation): Energy ray sensitive cation Polymerization initiator
得られた硬化性樹脂組成物を60℃で10分撹拌後、室温まで冷却し、溶解性について評価した。尚、評価基準は、室温まで冷却しても析出物が確認されない場合は○、加熱時に溶解するが室温まで冷却後1日で析出物が確認される場合を△、加熱しても溶解しない場合は×とした。 <Solubility>
The obtained curable resin composition was stirred at 60 ° C. for 10 minutes, cooled to room temperature, and evaluated for solubility. The evaluation criteria are ○ when the precipitate is not confirmed even after cooling to room temperature, △ when the precipitate is confirmed after cooling to room temperature but one day after cooling to room temperature, when it does not dissolve even when heated Is x.
得られた硬化性樹脂組成物No.1~No.3及び比較硬化性樹脂組成物No.10をそれぞれ60℃に加熱し、離形処理を施したガラス基板に塗布した。1.00mmのスペーサーと共にもう一枚のガラスで挟み込んで張り合わせ、100℃で1時間、150℃で1時間加熱し、硬化したものを○、硬化しなかったものを×として硬化性を評価した。また、硬化物として得られたものは、屈折率及び透明性を評価した。結果を[表3]に示す。 [Examples 3-1 to 3-3 and Comparative Example 3-1]
The obtained curable resin composition No. 1-No. 3 and comparative curable resin composition No. Each 10 was heated to 60 ° C. and applied to a glass substrate subjected to a release treatment. The glass was sandwiched with another glass with a 1.00 mm spacer and bonded together, and heated at 100 ° C. for 1 hour and at 150 ° C. for 1 hour. The cured product was evaluated as ◯, and the cured product was evaluated as ×. Moreover, what was obtained as hardened | cured material evaluated the refractive index and transparency. The results are shown in [Table 3].
得られた硬化物についてアタゴ(株)製アッベ屈折計DR-M2にて、25℃におけるD線及びe線の屈折率nd及びneの測定を行った。 <Refractive index>
At resulting cured product for Atago Co. Abbe refractometer DR-M2, it was measured D line and e-line refractive index n d and n e at 25 ° C..
得られた硬化性樹脂組成物No.4及びNo.5並びに比較硬化性樹脂組成物No.11、No、13及びNo.14をそれぞれ60℃に加熱し、離形処理を施したガラス基板に塗布した。1.00mmのスペーサーと共にもう一枚のガラスで挟み込んで張り合わせ、これを高圧水銀灯でガラス片面につき3000mJ/cm2(計6000mJ/cm2)で露光後に、150℃で2時間処理し、室温まで冷却してガラス基板から剥離させた。硬化物として得られたものについて○、硬化していないものは×として、硬化性を評価した。また、硬化物として得られたものは、屈折率及び透明性を評価した。結果を[表4]に示す。 [Examples 4-1 and 4-2 and Comparative Examples 4-1 to 4-3]
The obtained curable resin composition No. 4 and no. 5 and comparative curable resin composition No. 11, No. 13, and No. 11; Each 14 was heated to 60 ° C. and applied to a glass substrate subjected to a release treatment. Laminated by sandwiching the other piece of glass with 1.00mm spacer, which after exposure at 3000 mJ / cm 2 per glass sided high pressure mercury lamp (total 6000 mJ / cm 2), for 2 hours at 0.99 ° C., cooled to room temperature And peeled from the glass substrate. The curability was evaluated as ◯ for those obtained as cured products, and x for those that were not cured. Moreover, what was obtained as hardened | cured material evaluated the refractive index and transparency. The results are shown in [Table 4].
得られた硬化物について、アタゴ(株)製アッベ屈折計DR-M2にて、25℃におけるD線及びe線の屈折率nd及びneの測定を行った。 <Refractive index>
The obtained cured product at Atago Co. Abbe refractometer DR-M2, were measured D line and e-line refractive index n d and n e at 25 ° C..
日本電色工業(株)製ヘーズメーターNDH5000にて、得られた硬化物の全光線透過率を測定した。 <Transparency>
The total light transmittance of the resulting cured product was measured with a haze meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.
これに対して、本発明のエピスルフィド化合物A-1を用いた硬化性樹脂組成物No.4及び5(実施例4-4及び4-5)は、硬化性、屈折率及び透明性に優れることは明らかである。 From [Table 4], comparative curable resin composition No. using comparative compound (B-1) was obtained. 11 (Comparative Example 4-1) has good solubility but poor curability, and the curable resin composition No. 11 using the comparative compound (B-3) was not good. 13 (Comparative Example 4-2), and comparative curable resin composition No. 1 comprising a diluent and an energy ray-sensitive cationic polymerization initiator. 14 (Comparative Example 4-3) has good curability but poor refractive index and transparency.
In contrast, the curable resin composition No. 1 using the episulfide compound A-1 of the present invention was used. It is clear that 4 and 5 (Examples 4-4 and 4-5) are excellent in curability, refractive index and transparency.
Claims (9)
- 下記一般式(I)で表されるエピスルフィド化合物。
- 下記一般式(II)で表されるエピスルフィド化合物。
- 下記一般式(III)で表される、請求項1に記載のエピスルフィド化合物。
- 下記一般式(IV)で表される、請求項2に記載のエピスルフィド化合物。
- 上記一般式(IV)のx’が1である請求項4に記載のエピスルフィド化合物。 The episulfide compound according to claim 4, wherein x 'in the general formula (IV) is 1.
- 請求項1~5の何れか1項に記載のエピスルフィド化合物と硬化剤を含有する硬化性樹脂組成物。 A curable resin composition comprising the episulfide compound according to any one of claims 1 to 5 and a curing agent.
- 請求項1~5の何れか1項に記載のエピスルフィド化合物とエネルギー線感受性カチオン重合開始剤を含有する硬化性樹脂組成物。 A curable resin composition comprising the episulfide compound according to any one of claims 1 to 5 and an energy ray-sensitive cationic polymerization initiator.
- 請求項6又は7に記載の硬化性樹脂組成物を加熱して得られる硬化物。 A cured product obtained by heating the curable resin composition according to claim 6 or 7.
- 請求項7に記載の硬化性樹脂組成物にエネルギー線を照射して得られる硬化物。 A cured product obtained by irradiating the curable resin composition according to claim 7 with energy rays.
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KR1020117027059A KR101758726B1 (en) | 2009-09-18 | 2010-08-03 | Novel episulfide compounds, curable resin compositions containing the episulfide compounds, and cured products thereof |
CN201080021087.0A CN102421826B (en) | 2009-09-18 | 2010-08-03 | Novel episulfide compounds, curable resin compositions containing the episulfide compounds, and cured products thereof |
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TW202346275A (en) * | 2022-03-08 | 2023-12-01 | 日商三菱瓦斯化學股份有限公司 | Production method for episulfide compound |
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JP2001151888A (en) * | 1999-11-22 | 2001-06-05 | Nippon Steel Chem Co Ltd | Resin composition for optical material |
JP2002173533A (en) * | 2000-12-06 | 2002-06-21 | Yokohama Rubber Co Ltd:The | Hardening resin composition |
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JP4651768B2 (en) * | 1999-12-27 | 2011-03-16 | 新日鐵化学株式会社 | Novel aromatic episulfide compound, composition containing the same, and cured product |
JP2001288177A (en) * | 2000-04-05 | 2001-10-16 | Kyoeisha Chem Co Ltd | Episulfide compound containing fluorene skeleton, its cured substance and method for producing the same |
JP2006276066A (en) | 2005-03-25 | 2006-10-12 | Fuji Xerox Co Ltd | Raw material solution for manufacturing nonlinear optical material, nonlinear optical material, and nonlinear optical element |
KR20090074187A (en) * | 2006-09-19 | 2009-07-06 | 미츠비시 가스 가가쿠 가부시키가이샤 | Resin composition for optical material and optical material using the same |
US8252512B2 (en) * | 2007-05-09 | 2012-08-28 | Adeka Corporation | Epoxy compound, alkali-developable resin composition, and alkali-developable photosensitive resin composition |
JP2009198548A (en) | 2008-02-19 | 2009-09-03 | Toppan Printing Co Ltd | Color filter, and liquid crystal display device using the same |
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JP2001151888A (en) * | 1999-11-22 | 2001-06-05 | Nippon Steel Chem Co Ltd | Resin composition for optical material |
JP2002173533A (en) * | 2000-12-06 | 2002-06-21 | Yokohama Rubber Co Ltd:The | Hardening resin composition |
JP2003176332A (en) * | 2001-12-12 | 2003-06-24 | Mitsubishi Chemicals Corp | Heterocycle-containing compound and composition containing the same |
JP2003261648A (en) * | 2002-03-12 | 2003-09-19 | Mitsubishi Chemicals Corp | Heterocycle-containing compound and composition containing this |
JP2006063192A (en) * | 2004-08-26 | 2006-03-09 | Matsushita Electric Works Ltd | Powdery resin composition for sealing semiconductor and semiconductor device |
WO2009116618A1 (en) * | 2008-03-21 | 2009-09-24 | 積水化学工業株式会社 | Curable composition, anisotropic conductive material and connection structure |
WO2010035459A1 (en) * | 2008-09-25 | 2010-04-01 | 積水化学工業株式会社 | Episulfide compound, episulfide compound-containing mixture, method for producing episulfide compound-containing mixture, curable composition and connection structure |
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