Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
• • 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
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere

Definitions

• the present invention relates to compositions, additives, plasticizers, curable compositions, adhesives, cured products, and pressure-sensitive adhesives.
• optical resins are used as adhesives and pressure sensitive adhesives.
• Optical resins have a relatively high refractive index.
• optical resins may be required to be flexible. For this reason, the addition of plasticizers to optical resins is being considered.
• dioctyl phthalate (DOP, bis(2-ethylhexyl) phthalate) is known as a plasticizer (see, for example, Patent Document 1).
• the crystallinity of the optical resin decreases and its flexibility improves.
• the refractive index of the optical resin may decrease.
• the crystallinity of the optical resin may not be sufficiently reduced, and flexibility may not improve.
• plasticizers that can improve flexibility without lowering the refractive index. Furthermore, depending on the application, optical resins are required to have excellent transparency (suppression of cloudiness) and weather resistance.
• the present invention relates to a composition, an additive, a plasticizer, a curable composition, an adhesive, a cured product, and a pressure-sensitive adhesive for obtaining a cured product that combines a refractive index, flexibility, transparency, and weather resistance.
• the present invention [1] includes a composition that contains a first compound that is a reaction product between a thiol compound having a functional group represented by the following formula (1) and a carbon-carbon double bond-containing compound represented by the following formula (2), and a second compound represented by the following formula (3).
• A represents an alkylene group having 2 to 3 carbon atoms.
• R1, R2, and R3 represent a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an aromatic aliphatic hydrocarbon group. R1, R2, and R3 may be the same or different.
• the present invention [2] includes the composition described in [1] above, in which the thiol compound has a functional group represented by the following formula (4), and the second compound is a compound represented by the following formula (5).
• R1, R2, R3, and Ar have the same meanings as R1, R2, R3, and Ar in formula (2).
• the present invention [3] includes the composition described in [1] or [2] above, in which the thiol compound is a compound represented by the following formula (6) and the carbon-carbon double bond-containing compound is styrene.
• the present invention [4] includes the composition according to any one of the above [1] to [3], in which the area ratio of the peak corresponding to the first compound to the area of all peaks is 45 to 95% and the area ratio of the peak corresponding to the second compound to the area of all peaks in a chromatogram measured by high performance liquid chromatography at a detection wavelength of 254 nm is 0.5 to 10%.
• the present invention [5] includes a plasticizer containing the composition described in any one of [1] to [4] above.
• the present invention [6] includes a curable composition that contains the plasticizer described in [5] above and a curable compound.
• the present invention [7] includes an adhesive containing the curable composition described in [6] above.
• the present invention [8] includes a cured product that contains the plasticizer described in [5] above and a cured resin.
• the present invention includes the cured product described in [8] above, in which the cured resin includes a reaction product between a base agent containing an acrylic polyol and a curing agent containing a polyisocyanate.
• the present invention includes the cured product described in [8] above, in which the cured resin includes a cured acrylic resin.
• the present invention [11] includes an adhesive containing the cured product described in [8] above.
• composition, additive, plasticizer, curable composition, and adhesive of the present invention can produce a cured product that has a refractive index, flexibility, transparency, and weather resistance.
• the cured product and adhesive of the present invention contain the above-mentioned composition, and therefore have a refractive index, flexibility, transparency, and weather resistance.
• composition Constitution of the Composition
• the composition of the present invention contains at least a first compound described in detail below and a second compound described in detail below.
• the first compound is a reaction product of a thiol compound and a carbon-carbon double bond-containing compound.
• the thiol compound and the carbon-carbon double bond-containing compound will be described in detail below.
• the thiol compound has a functional group represented by the following formula (1).
• A represents an alkylene group having 2 to 3 carbon atoms.
• A represents an alkylene group having 2 to 3 carbon atoms.
• the alkylene group having 2 to 3 carbon atoms include an ethylene group (-CH 2 CH 2 -), a triethylene group (-CH 2 CH 2 CH 2 -), a propylene group (1-methylethylene group, -CH 2 CH(CH 3 )-), and a 2-methylethylene group -CH(CH 3 )CH 2 -), and preferably an ethylene group (-CH 2 CH 2 -). That is, in the above formula (1), A preferably represents an ethylene group (-CH 2 CH 2 -).
• the thiol compound has a functional group represented by the following formula (4):
• the functional group represented by the above formula (4) is a mercaptoethylthio group (HS-CH 2 CH 2 -S-).
• the thiol compound is a compound containing a mercaptoethylthio group (a mercaptoethylthio group-containing compound).
• the dashed line represents the bond of the mercaptoethylthio group.
• the number of functional groups represented by the above formula (1) (preferably the above formula (4)) per molecule of the thiol compound is, for example, 1 to 8, preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 4.
• the functional group represented by the above formula (1) has a mercapto group.
• the thiol compound has at least one mercapto group derived from the functional group represented by the above formula (1).
• the thiol compound can contain a mercapto group that is not derived from the functional group represented by the above formula (1).
• the number of mercapto groups per molecule of the thiol compound is, for example, 1 to 8, preferably 1 to 6, more preferably 1 to 4, even more preferably 3 to 4, and especially preferably 3.
• thiol compounds include thiol compounds having one mercapto group per molecule (hereinafter, monovalent thiol compounds), thiol compounds having two mercapto groups per molecule (hereinafter, divalent thiol compounds), thiol compounds having three mercapto groups per molecule (hereinafter, trivalent thiol compounds), thiol compounds having four mercapto groups per molecule (hereinafter, tetravalent thiol compounds), thiol compounds having five mercapto groups per molecule (hereinafter, pentavalent thiol compounds), thiol compounds having six mercapto groups per molecule (hereinafter, hexavalent thiol compounds), thiol compounds having seven mercapto groups per molecule (hereinafter, heptavalent thiol compounds), and thiol compounds having eight mercapto groups per molecule (hereinafter, octavalent thiol compounds). These can benzol compounds having one
• Examples of monovalent thiol compounds include mercaptoethylthiomethane. These can be used alone or in combination of two or more. Examples of divalent thiol compounds include bis(mercaptoethylthio)methane and 2,3-dimercapto-1-propanol. Examples of trivalent thiol compounds include tris(mercaptoethylthio)methane and 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST).
• tetravalent thiol compounds include tetra(mercaptoethylthio)methane and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH). These can be used alone or in combination of two or more.
• the thiol compound is preferably a trivalent thiol compound or a tetravalent thiol compound, and more preferably 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST) or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH).
• GST 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
• FSH 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane
• a more preferred example of a compound having one functional group represented by the above formula (1) is a trivalent thiol compound, and even more preferred is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST).
• the thiol compound more preferably contains 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST), and even more preferably consists of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST).
• 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane is, for example, represented by the following formula (6). That is, the thiol compound is more preferably a compound represented by the following formula (6). In other words, the thiol compound is more preferably a compound represented by the following formula (6).
• Carbon-carbon double bond-containing compounds The carbon-carbon double bond-containing compound is represented by the following formula (2).
• R1, R2, and R3 represent a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group.
• R1, R2, and R3 may be the same or different.
• Ar represents an aromatic hydrocarbon group or an araliphatic hydrocarbon group.
• R1, R2, and R3 represent a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an aromatic aliphatic hydrocarbon group.
• aliphatic hydrocarbon group examples include aliphatic hydrocarbon groups having 1 to 20 carbon atoms. More specific examples of the aliphatic hydrocarbon group include linear aliphatic hydrocarbon groups having 1 to 20 carbon atoms and cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms.
• Examples of cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms include cyclic saturated aliphatic hydrocarbon groups having 3 to 20 carbon atoms, and cyclic unsaturated aliphatic hydrocarbon groups having 3 to 20 carbon atoms.
• Examples of cyclic saturated aliphatic hydrocarbon groups having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl groups.
• Examples of cyclic unsaturated aliphatic hydrocarbon groups having 3 to 20 carbon atoms include cyclopentenyl and cyclohexenyl groups. These can be used alone or in combination of two or more types.
• aromatic hydrocarbon groups include aromatic hydrocarbon groups having 6 to 20 carbon atoms.
• aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 3,4,5-trimethylphenyl, 2,4,6-trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 1-naphthyl, and 2-naphthyl groups. These can be used alone or in combination of two or more types.
• aromatic aliphatic hydrocarbon groups include aromatic aliphatic hydrocarbon groups having 7 to 20 carbon atoms.
• aromatic aliphatic hydrocarbon groups having 7 to 20 carbon atoms include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, o-methylbenzyl, m-methylbenzyl, p-methylbenzyl, o-ethylbenzyl, m-ethylbenzyl, p-ethylbenzyl, o-isopropylbenzyl, m-isopropylbenzyl, p-isopropylbenzyl, 2,3,4-trimethylbenzyl, 3,4,5-trimethylbenzyl, and 2,4,6-trimethylbenzyl. These can be used alone or in combination of two or more types.
• the aliphatic hydrocarbon group, aromatic hydrocarbon group, and aromatic aliphatic hydrocarbon group can have a substituent.
• substituents include a halogeno group, a cyano group, an amino group, a carboxy group, a sulfonyl group, and an alkoxy group (an alkoxy group that does not contain an aromatic ring). These may be used alone or in combination of two or more types.
• the number of substituents is appropriately set depending on the purpose and application.
• the substitution position is appropriately set depending on the purpose and application.
• R1, R2 and R3 preferably all represent a hydrogen atom or an aliphatic hydrocarbon group, and more preferably all represent a hydrogen atom.
• R1, R2 and R3 may be the same as each other, or may be different from each other.
• R1, R2 and R3 are preferably the same as each other. That is, it is particularly preferable that R1, R2 and R3 all represent a hydrogen atom.
• Ar represents an aromatic hydrocarbon group or an aromatic aliphatic hydrocarbon group.
• Aromatic hydrocarbon groups include, for example, the aromatic hydrocarbon groups described above, and more specifically, the aromatic hydrocarbon groups having 6 to 20 carbon atoms described above. These can be used alone or in combination of two or more types.
• aromatic aliphatic hydrocarbon groups include the aromatic aliphatic hydrocarbon groups described above, and more specifically, the aromatic hydrocarbon groups having 7 to 20 carbon atoms described above. These can be used alone or in combination of two or more types.
• the aromatic hydrocarbon group and the aromatic aliphatic hydrocarbon group can have the above-mentioned substituents.
• the substitution positions are appropriately set depending on the purpose and application.
• Ar preferably represents an aromatic hydrocarbon group, and more preferably represents a phenyl group.
• compounds containing carbon-carbon double bonds include styrene, ⁇ -methylstyrene, ⁇ -ethylstyrene, ⁇ -propylstyrene, ⁇ -butylstyrene, and ⁇ -methylstyrene. These can be used alone or in combination of two or more types.
• the carbon-carbon double bond-containing compound represented by the above formula (2) is preferably styrene, ⁇ -methylstyrene, and ⁇ -butylstyrene, and more preferably styrene.
• the carbon-carbon double bond-containing compound more preferably contains styrene, and even more preferably consists of styrene.
• the carbon-carbon double bond-containing compound is even more preferably styrene.
• A has the same position as A in formula (1).
• R1, R2, R3, and Ar have the same meanings as R1, R2, R3, and Ar in formula (2).
• the functional group of the thiol compound represented by the above formula (4) reacts with the carbon-carbon double bond-containing compound represented by the above formula (2) to form, for example, a functional group represented by the following formula (8).
• R1, R2, R3, and Ar have the same meanings as R1, R2, R3, and Ar in formula (2).
• the thiol compound is the thiol compound represented by the above formula (6) (4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST))
• the main product of the ene-thiol reaction between the thiol compound and the carbon-carbon double bond-containing compound is, for example, represented by the following formula (9).
• the first compound preferably contains a compound represented by the above formula (9), and more preferably consists of a compound represented by the above formula (9).
• the thiol compound is the compound represented by the above formula (6) (4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (GST)) and the carbon-carbon double bond-containing compound is styrene
• the main product of the ene-thiol reaction is, for example, represented by the following formula (10).
• the first compound preferably contains a compound represented by the above formula (10), and particularly preferably consists of a compound represented by the above formula (10).
• the compound represented by the above formula (10) is 4-phenethylthiomethyl-1,8-bisphenethylthio-3,6-dithiaoctane.
• 4-phenethylthiomethyl-1,8-bisphenethylthio-3,6-dithiaoctane may be referred to as "PE-GST.”
• Second Compound The second compound is represented by the following formula (3).
• R1, R2, R3, and Ar have the same meanings as R1, R2, R3, and Ar in formula (2).
• R1, R2, and R3 each represent a hydrogen atom, the above-mentioned aliphatic hydrocarbon group, the above-mentioned aromatic hydrocarbon group, or the above-mentioned araliphatic hydrocarbon group.
• R1, R2, and R3 each preferably represent a hydrogen atom or an aliphatic hydrocarbon group, and more preferably each represent a hydrogen atom.
• R1, R2 and R3 may be the same or different from each other.
• R1, R2 and R3 are preferably the same. That is, R1, R2 and R3 are particularly preferably all hydrogen atoms.
• Ar represents the above aromatic hydrocarbon group or the above aromatic aliphatic hydrocarbon group. From the viewpoints of refractive index, flexibility, transparency, and weather resistance, Ar preferably represents an aromatic hydrocarbon group, and more preferably represents a phenyl group.
• the second compound can be, for example, S,S'-diphenethyldimercaptoethane (a compound in which R1, R2, and R3 represent hydrogen atoms and Ar represents a phenyl group).
• the second compound can also be, for example, S,S'-bis(2-phenylpropionyl)dimercaptoethane and phenethyl(2-(2-phenylpropionyl)thio)ethyl)sulfane. These can be used alone or in combination of two or more types.
• the second compound represented by the above formula (3) is preferably S,S'-diphenethyldimercaptoethane (a compound in which R1, R2, and R3 represent hydrogen atoms and Ar represents a phenyl group).
• the second compound preferably contains S,S'-diphenethyldimercaptoethane, and more preferably consists of S,S'-diphenethyldimercaptoethane (DPE-DME).
• DPE-DME S,S'-diphenethyldimercaptoethane
• the second compound is more preferably S,S'-diphenethyldimercaptoethane.
• S,S'-diphenethyldimercaptoethane is, for example, represented by the following formula (11):
• the second compound is more preferably a compound represented by the following formula (11).
• S,S'-diphenethyldimercaptoethane may be referred to as "DPE-DME".
• the second compound is, for example, a by-product in an ene-thiol reaction between the thiol compound and the carbon-carbon double bond-containing compound.
• the second compound is produced as a by-product by subjecting the thiol compound and the carbon-carbon double bond-containing compound to an ene-thiol reaction.
• a side reaction causes the thiol compound to be cleaved, and for example, a thiyl radical corresponding to the above formula (1) is formed.
• the thiyl radical corresponding to the above formula (1) is, for example, shown in the following formula (12).
• a thiyl radical corresponding to the functional group shown in formula (4) above i.e., A is an ethylene group
• the thiyl radical corresponding to the functional group shown in formula (4) above is, for example, shown in formula (13) below.
• a HSCH 2 CH 2 S radical is produced as a by-product.
• the above-mentioned thiyl radical undergoes radical polymerization.
• the compound obtained by radical polymerization and the carbon-carbon double bond-containing compound undergo an ene-thiol reaction.
• the second compound represented by the above formula (2) is formed as a by-product.
• composition may contain other compounds.
• the other compounds are compounds other than the first compound and the second compound.
• Other compounds include, for example, by-products (excluding the second compound) in the ene-thiol reaction between the thiol compound and the carbon-carbon double bond-containing compound.
• Other compounds include, more specifically, for example, phenethyl(2-(2,4-diphenylbutyl)thio)ethyl)sulfane, 4-(2,4-diphenylbutyl)thiomethyl-1,8-bisphenethylthio-3,6-dithiaoctane, and structural isomers thereof. These may be used alone or in combination of two or more types.
• the other compound is formed, for example, by radical polymerization of the HSCH 2 CH 2 S radical and an ene-thiol reaction, analogous to the preparation of the second compound described above.
• the radical polymerization initiator is not particularly limited, and may be any known radical polymerization initiator.
• examples of the radical polymerization initiator include an active energy ray radical polymerization initiator described later, and a thermal radical polymerization initiator described later. These may be used alone or in combination of two or more.
• a thermal radical polymerization initiator is preferably used, more preferably an azo compound is more preferably used, and further preferably azoisobutyronitrile (AIBN) or 2,2'-azobis(2,4-dimethylvaleronitrile) is particularly preferably used, and 2,2'-azobis(2,4-dimethylvaleronitrile) is particularly preferably used.
• the mixing ratio of the radical polymerization initiator is set so that the first compound and the second compound are produced in the desired ratio.
• the mixing ratio of the thiol compound and the carbon-carbon double bond-containing compound is set so that the first compound and the second compound are produced in a desired ratio. More specifically, the mixing ratio of the thiol compound and the carbon-carbon double bond-containing compound is adjusted based on the equivalent ratio of the carbon-carbon double bonds in the carbon-carbon double bond-containing compound to the mercapto groups in the thiol compound (carbon-carbon double bond/mercapto group).
• the equivalent ratio of the carbon-carbon double bonds in the carbon-carbon double bond-containing compound to the mercapto groups in the thiol compound is, for example, 0.9 to 5.0, preferably 1.0 to 3.0, and more preferably 1.01 to 1.5.
• reaction conditions The reaction conditions for the ene-thiol reaction are selected to produce the first and second compounds in the desired ratio.
• the lower limit of the reaction temperature is, for example, 0°C or higher, preferably 10°C or higher, more preferably 20°C or higher, even more preferably 30°C or higher, and particularly preferably 40°C or higher.
• the upper limit of the reaction temperature is, for example, 150°C or less, preferably 100°C or less, more preferably 80°C or less, even more preferably 60°C or less, and particularly preferably 50°C or less.
• the reaction temperature is, for example, 0 to 150°C, preferably 10 to 100°C, more preferably 20 to 80°C, even more preferably 30 to 60°C, and particularly preferably 40 to 50°C.
• the reaction time is, for example, 3 to 120 hours, preferably 6 to 72 hours, more preferably 12 to 60 hours, and even more preferably 24 to 48 hours.
• the ene-thiol reaction includes a main reaction and a side reaction.
• the first compound is produced. More specifically, in the main reaction, the radical polymerization initiator first extracts a hydrogen atom from the mercapto group of the thiol compound to generate a thiyl radical.
• the thiyl radical undergoes radical addition to the carbon-carbon double bond of a carbon-carbon double bond-containing compound to generate a carboradical.
• the carboradical then abstracts a hydrogen atom from another mercapto group, completing the alkylation of the mercapto group.
• the first compound is obtained as the main product in the ene-thiol reaction.
• a second compound is produced. More specifically, in the side reaction, as in the main reaction, the radical polymerization initiator extracts a hydrogen atom from the mercapto group of the thiol compound to generate a thiyl radical.
• the thiyl radical breaks the molecular chain in the thiol compound to generate another thiyl radical.
• a thiyl radical (formula (12)) corresponding to the functional group represented by formula (1) is generated. More specifically, when the thiol compound has a functional group represented by formula (4), a HSCH2CH2S radical (formula (13)) is generated.
• the thiyl radical (formula (12) above) undergoes radical polymerization. Furthermore, the compound obtained by radical polymerization and the carbon-carbon double bond-containing compound undergo an ene-thiol reaction. As a result, the second compound represented by formula (2) above is formed. More specifically, when the thiol compound has a functional group represented by formula (4) above, the second compound is represented by, for example, formula (5) above.
• the second compound is produced as a by-product in the ene-thiol reaction.
• the by-product in the ene-thiol reaction is not limited to the second compound.
• the other compounds are produced based on the thiyl radical (formula (12)) corresponding to the functional group shown in formula (1).
• reaction solvent In the ene-thiol reaction, a reaction solvent is used as necessary. That is, the thiol compound and the carbon-carbon double bond-containing compound may react in the absence of a reaction solvent, or may react in the presence of a reaction solvent. Preferably, the thiol compound and the carbon-carbon double bond-containing compound react in the presence of a reaction solvent.
• Reaction solvents include, for example, alcohols, ketones, nitriles, alkyl esters, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, ethers, glycol ether esters, halogenated aliphatic hydrocarbons, and polar aprotic solvents.
• Alcohols include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, cyclohexanol, and benzyl alcohol.
• Ketones include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
• Nitriles include, for example, acetonitrile.
• Alkyl esters include, for example, methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate.
• Aliphatic hydrocarbons include, for example, n-hexane, n-heptane, and octane.
• Alicyclic hydrocarbons include, for example, cyclohexane and methylcyclohexane. Examples of aromatic hydrocarbons include toluene, xylene, and ethylbenzene.
• ethers include diethyl ether, tetrahydrofuran, and dioxane.
• glycol ether esters include methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, and ethyl-3-ethoxypropionate.
• halogenated aliphatic hydrocarbons include methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide, and dichloroethane.
• polar aprotic compounds include N-methylpyrrolidone, dimethylformamide, N,N'-dimethylacetamide, dimethylsulfoxide, and hexamethylphosphonylamide. These can be used alone or in combination of two or more.
• the organic solvent is preferably selected so that the first compound and the second compound are produced in a desired ratio.
• alkyl esters preferably, ethyl acetate
• aromatic hydrocarbons preferably, toluene
• the organic solvent is selected, for example, depending on the ratio of the first compound and the second compound.
• the organic solvent preferably, alkyl esters and aromatic hydrocarbons are used, and more preferably, alkyl esters are used.
• the reaction product of the ene-thiol reaction is purified by a known method as necessary.
• the purification method is not particularly limited, and examples thereof include washing, dehydration, impurity adsorption, liquid-liquid extraction, distillation, and recrystallization. These methods may be used alone or in combination of two or more.
• the content ratio of the first compound and the second compound can be adjusted by purifying the reaction product. It is also possible to adjust the content ratio of the first compound and the second compound by setting the reaction conditions without purifying the reaction product.
• the ene-thiol reaction (and purification) produces a composition containing the first compound and the second compound as a reaction product.
• the content ratio of the first compound and the content ratio of the second compound in the composition are calculated, for example, from a chromatogram (hereinafter, high-performance liquid chromatogram) obtained when the composition is subjected to high-performance liquid chromatography measurement (specifically, high-performance liquid chromatographic measurement at a detection wavelength of 254 nm in accordance with the Examples described later).
• high-performance liquid chromatogram a chromatogram obtained when the composition is subjected to high-performance liquid chromatography measurement (specifically, high-performance liquid chromatographic measurement at a detection wavelength of 254 nm in accordance with the Examples described later).
• the composition contains the first compound and the second compound
• the high performance liquid chromatography measurement specifically, high performance liquid chromatography measurement at a detection wavelength of 254 nm in accordance with the examples described below
• the high performance liquid chromatogram has a peak corresponding to the first compound and a peak corresponding to the second compound.
• the peak corresponding to the first compound has a peak top at a retention time according to the molecular structure and polarity of the first compound in a chromatogram (high-performance liquid chromatogram) obtained by high-performance liquid chromatographic measurement at a detection wavelength of 254 nm. Note that the retention time of the peak top depends on the measurement conditions of the high-performance liquid chromatographic measurement.
• the lower limit of the area ratio of the peak corresponding to the first compound in the above high performance liquid chromatogram is, for example, 20% or more, preferably 40% or more, more preferably 45% or more, even more preferably 50% or more, and particularly preferably 60% or more, relative to the area of all peaks.
• the upper limit of the area ratio of the peak corresponding to the first compound in the above high performance liquid chromatogram is, for example, 99.5% or less, preferably 99% or less, more preferably 95% or less, even more preferably 90% or less, and particularly preferably 80% or less, relative to the area of all peaks.
• the area ratio of the peak corresponding to the first compound in the above high performance liquid chromatogram is, for example, 20 to 99.5%, preferably 40 to 99%, more preferably 45 to 95%, even more preferably 50 to 90%, and particularly preferably 60 to 80%.
• the area ratio of the peak corresponding to the first compound in the high performance liquid chromatogram of the composition corresponds to the mass ratio of the first compound in the composition.
• the lower limit of the content of the first compound is, for example, 20 mass% or more, preferably 40 mass% or more, more preferably 45 mass% or more, even more preferably 50 mass% or more, and particularly preferably 60 mass% or more, based on the total amount of the composition.
• the upper limit of the content of the first compound is, for example, 99.5% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 80% by mass or less, based on the total amount of the composition.
• the content of the first compound is, for example, 20 to 99.5 mass%, preferably 45 to 95 mass%, more preferably 50 to 90 mass%, and particularly preferably 60 to 80 mass%, relative to the total amount of the composition.
• the peak corresponding to the second compound has a peak top at a retention time corresponding to the molecular weight of the second compound in a chromatogram (high-performance liquid chromatogram) obtained by high-performance liquid chromatographic measurement at a detection wavelength of 254 nm. Note that the retention time of the peak top depends on the measurement conditions of the high-performance liquid chromatographic measurement.
• the lower limit of the area ratio of the peak corresponding to the second compound in the above high performance liquid chromatogram is, for example, 0.1% or more, preferably 0.3% or more, more preferably 0.5% or more, even more preferably 0.7% or more, and particularly preferably 1.0% or more, relative to the area of all peaks.
• the upper limit of the area ratio of the peak corresponding to the second compound in the above high performance liquid chromatogram is, for example, 30% or less, preferably 20% or less, more preferably 10% or less, even more preferably 5.0% or less, and particularly preferably 2.0% or less, relative to the area of all peaks.
• the peaks corresponding to the other compounds have peak tops at retention times corresponding to the molecular weights of the other compounds in a chromatogram (high performance liquid chromatogram) obtained by measurement using a high performance liquid chromatograph with a detection wavelength of 254 nm.
• additives include plasticizers and refractive index adjusters, and preferably, plasticizers.
• the plasticizer preferably contains the above-mentioned composition.
• the above-mentioned composition is preferably used as a plasticizer.
• the above composition makes it possible to obtain a cured product (described below) that has excellent refractive index, flexibility, transparency, and weather resistance.
• Curable composition (1) Main component
• the curable composition contains a plasticizer and a curable compound as main components.
• the main component is a component whose content ratio to the whole is a predetermined value or more.
• the content ratio of the main component to the whole is, for example, 90 mass% or more.
• the total solid content of the plasticizer and the curable compound is 90 mass% or more with respect to the total solid content of the curable composition.
• a curable compound is an uncured compound that is cured by a known method to produce a cured resin (described below).
• a plasticizer is an additive that improves the flexibility of the cured resin (described below). Plasticizers and curable compounds are described in detail below.
• the plasticizer contains the above-mentioned composition (i.e., a composition containing the first compound and the second compound).
• the plasticizer is preferably composed of the above-mentioned composition (i.e., a composition containing the first compound and the second compound). If the plasticizer contains the above-mentioned composition, the flexibility, transparency, and weather resistance of the cured product (described below) can be improved. In addition, if the plasticizer contains the above-mentioned composition, the decrease in the refractive index of the cured product (described below) can be suppressed, or the refractive index can be improved.
• Curable Compound is not particularly limited, and examples thereof include resin raw materials capable of producing a cured resin (described below).
• cured resins include cured polyurethane resins, cured polyolefin resins, cured polyamine resins, cured amide resins, cured urea resins, cured phenolic resins, cured epoxy resins, cured acrylic resins, cured melamine resins, and cured alkyd resins. These may be used alone or in combination of two or more types.
• the cured resin (described below) is a cured polyurethane resin or a cured acrylic resin.
• the curable compound is selected according to the type of cured resin (described below).
• the curable compound when a cured polyurethane resin is used as the cured resin, the curable compound may be, for example, a polyurethane resin raw material.
• the curable compound when a cured acrylic resin is used as the cured resin, the curable compound may be, for example, an acrylic resin raw material.
• the polyurethane resin raw materials and acrylic resin raw materials are described in detail below.
• Polyisocyanate has a plurality of isocyanate groups in one molecule.
• examples of polyisocyanate include polyisocyanate monomers and polyisocyanate derivatives.
• polyisocyanate monomers examples include aliphatic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates.
• Aliphatic polyisocyanates include, for example, ethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methyl caproate. These can be used alone or in combination of two or more types.
• examples of the aliphatic polyisocyanate monomer include alicyclic polyisocyanate monomers.
• alicyclic polyisocyanate monomers include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, methylene bis(cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatomethyl)cyclohexane. These can be used alone or in combination of two or more types.
• Aromatic polyisocyanates include, for example, tolylene diisocyanate, phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, and 4,4'-diphenyl ether diisocyanate. These can be used alone or in combination of two or more types.
• aromatic aliphatic polyisocyanates examples include xylylene diisocyanate, tetramethyl xylylene diisocyanate, and ⁇ , ⁇ '-diisocyanate-1,4-diethylbenzene. These can be used alone or in combination of two or more types.
• the polyisocyanate derivative is derived from the polyisocyanate monomer described above.
• examples of the polyisocyanate derivative include isocyanurate modified products, iminooxadiazinedione modified products, triol adducts, allophanate modified products, biuret modified products, urea modified products, oxadiazinetrione modified products, carbodiimide modified products, uretdione modified products, and uretonimine modified products. These can be used alone or in combination of two or more types.
• a preferred example of the polyisocyanate derivative is an isocyanurate modified product.
• the polyisocyanate may be used alone or in combination of two or more kinds.
• the polyisocyanate preferably includes a polyisocyanate derivative, and more preferably consists of a polyisocyanate derivative.
• the polyisocyanate derivative is preferably a polyisocyanate derivative derived from an aromatic aliphatic polyisocyanate (an aromatic aliphatic polyisocyanate derivative).
• aromatic aliphatic polyisocyanate derivative a derivative of xylylene diisocyanate is more preferred, and a triol adduct of xylylene diisocyanate is even more preferred.
• the average number of isocyanate groups in the polyisocyanate is, for example, 2 or more, preferably 2.5 or more.
• the average number of isocyanate groups in the polyisocyanate is, for example, 4 or less, preferably 3.5 or less.
• the isocyanate group content (NCO%) of the polyisocyanate is, for example, 5% by mass or more, preferably 7% by mass or more.
• the isocyanate group content (NCO%) of the polyisocyanate is, for example, 30% by mass or less, preferably 25% by mass or less.
• Polyol Polyols include, for example, macropolyols. Macropolyols have two or more hydroxyl groups in one molecule. Macropolyols are organic compounds with relatively high molecular weights.
• the number average molecular weight of the macropolyol is, for example, 400 or more and, for example, 20,000 or less.
• the number average molecular weight can be calculated by a known method from the hydroxyl group equivalent and the average number of hydroxyl groups.
• the number average molecular weight can be measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (hereinafter the same).
• macropolyols examples include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, and vinyl monomer modified polyols. These macropolyols can be used alone or in combination of two or more types.
• the number average molecular weight of the macropolyol is, for example, more than 400, preferably 500 or more, and more preferably 1000 or more.
• the number average molecular weight of the macropolyol is, for example, 20000 or less, preferably 15000 or less, more preferably 10000 or less, and even more preferably 5000 or less.
• the hydroxyl value of the macropolyol is, for example, 5 mgKOH/g or more, preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more, and even more preferably 20 mgKOH/g or more.
• the hydroxyl value of the macropolyol is, for example, 500 mgKOH/g or less, preferably 300 mgKOH/g or less, more preferably 200 mgKOH/g or less, even more preferably 100 mgKOH/g or less, and especially preferably 50 mgKOH/g or less.
• the hydroxyl value is measured in accordance with the description of JIS K 1557-1 (2007) (hereinafter the same).
• the macropolyol is preferably an acrylic polyol.
• an acrylic polyol is a copolymer of an acrylic raw material component.
• the acrylic raw material component contains, for example, a hydroxyl group-containing (meth)acrylate and a copolymerizable vinyl monomer.
• (Meth)acrylate refers to acrylate and/or methacrylate.
• copolymerizable vinyl monomer refers to a vinyl monomer that can be polymerized together with a hydroxyl group-containing (meth)acrylate.
• Hydroxyl group-containing (meth)acrylates contain a hydroxyl group and an alkyl group.
• alkyl group include alkyl groups having 1 to 4 carbon atoms.
• Specific examples of hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and 2,2-dihydroxymethylbutyl (meth)acrylate. These may be used alone or in combination of two or more.
• Preferred examples of hydroxyl group-containing (meth)acrylates include hydroxyalkyl (meth)acrylates, more preferably 2-hydroxyethyl (meth)acrylate, and even more preferably 2-hydroxyethyl methacrylate.
• Examples of copolymerizable vinyl monomers include alkyl (meth)acrylates.
• Alkyl (meth)acrylates do not contain hydroxyl groups, but contain an alkyl group.
• Examples of the alkyl group include alkyl groups having 1 to 4 carbon atoms and alkyl groups having 5 to 8 carbon atoms.
• alkyl (meth)acrylates having an alkyl group having 1 to 4 carbon atoms examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, and t-butyl (meth)acrylate.
• alkyl (meth)acrylates having an alkyl group having 5 to 8 carbon atoms examples include pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate. These can be used alone or in combination of two or more types.
• examples of the copolymerizable vinyl monomer include aromatic ring-containing vinyl monomers.
• examples of the aromatic ring-containing vinyl monomer include aromatic ring-containing (meth)acrylates.
• Aromatic ring-containing (meth)acrylates contain aromatic rings. Examples of aromatic rings include benzene rings, naphthalene rings, anthracene rings, and phenanthrene rings. More specifically, aromatic ring-containing (meth)acrylates include benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, m-phenoxybenzyl (meth)acrylate, and 1-naphthylmethyl (meth)acrylate. These can be used alone or in combination of two or more.
• aromatic ring-containing (meth)acrylates include preferably m-phenoxybenzyl (meth)acrylate and naphthylmethyl (meth)acrylate, and more preferably m-phenoxybenzyl acrylate and naphthylmethyl acrylate.
• aromatic ring-containing vinyl monomers include styrene, ⁇ -methylstyrene, vinyltoluene, vinylbiphenyl, and divinylbenzene. These can be used alone or in combination of two or more.
• Preferred examples of aromatic ring-containing vinyl monomers include aromatic ring-containing (meth)acrylates.
• examples of the copolymerizable vinyl monomer include vinyl monomers containing functional groups (excluding hydroxyl groups).
• the vinyl monomers containing functional groups (excluding hydroxyl groups) include carboxyl group-containing vinyl monomers, glycidyl group-containing vinyl monomers, amino group-containing vinyl monomers, cyano group-containing vinyl monomers, acetoacetoxy group-containing vinyl monomers, sulfonic acid group-containing vinyl monomers, and phosphate group-containing vinyl monomers.
• examples of the carboxyl group-containing vinyl monomer include acrylic acid.
• Examples of the glycidyl group-containing vinyl monomer include glycidyl (meth)acrylate.
• Examples of the amino group-containing vinyl monomer include 2-aminoethyl (meth)acrylate.
• Examples of the cyano group-containing vinyl monomer include (meth)acrylonitrile.
• Examples of the acetoacetoxy group-containing vinyl monomer include acetoacetoxyethyl (meth)acrylate.
• Examples of the sulfonic acid group-containing vinyl monomer include allylsulfonic acid and its salts.
• Examples of the phosphate group-containing vinyl monomer include 2-methacryloyloxyethyl acid phosphate. These may be used alone or in combination of two or more.
• a vinyl monomer containing a functional group excluding a hydroxyl group
• acrylic acid is more preferred.
• examples of the copolymerizable vinyl monomer include alicyclic group-containing vinyl monomers and (meth)acryloyl group-containing rubbers.
• examples of the alicyclic group-containing vinyl monomer include dicyclopentenyloxyethyl (meth)acrylate.
• examples of the (meth)acryloyl group-containing rubber include (meth)acryloyl group-containing isoprene rubber.
• examples of the copolymerizable vinyl monomer include, in addition to the above, vinyl esters, N-substituted unsaturated carboxylic acid amides, heterocyclic vinyl compounds, vinylidene halides, ⁇ -olefins, dienes, and crosslinkable vinyl monomers.
• crosslinkable vinyl monomer examples include polyfunctional (meth)acrylates, more specifically, bifunctional (meth)acrylates, trifunctional (meth)acrylates, and tetrafunctional or higher (meth)acrylates.
• bifunctional (meth)acrylates include ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, and oligoethylene glycol di(meth)acrylate.
• trifunctional (meth)acrylates examples include trimethylolpropane tri(meth)acrylate.
• tetrafunctional or higher (meth)acrylates examples include pentaerythritol tetra(meth)acrylate. These may be used alone or in combination of two or more.
• copolymerizable vinyl monomers can be used alone or in combination of two or more types.
• the copolymerizable vinyl monomer preferably, an aromatic ring-containing vinyl monomer can be used. If the copolymerizable vinyl monomer contains an aromatic ring-containing vinyl monomer, the acrylic polyol contains an aromatic ring. In other words, the acrylic polyol is preferably an aromatic ring-containing acrylic polyol. With an aromatic ring-containing acrylic polyol, a cured product (described later) having excellent refractive index, excellent flexibility, excellent transparency, and excellent weather resistance can be obtained.
• a carboxy group-containing vinyl monomer is preferably used as the copolymerizable vinyl monomer. If the acrylic polyol contains a carboxy group-containing vinyl monomer, the acrylic polyol contains a carboxy group. In other words, the acrylic polyol is preferably a carboxy group-containing acrylic polyol. With the carboxy group-containing acrylic polyol, a cured product (described later) having an excellent refractive index, excellent flexibility, excellent transparency, and excellent weather resistance can be obtained.
• the mixing ratio of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer is appropriately set depending on the purpose and application.
• the amount of the hydroxyl group-containing (meth)acrylate is, for example, 1 part by mass or more, preferably 3 parts by mass or more, per 100 parts by mass of the total amount of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer.
• the amount of the hydroxyl group-containing (meth)acrylate is, for example, 30 parts by mass or less, preferably 10 parts by mass or less, per 100 parts by mass of the total amount of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer.
• the copolymerizable vinyl monomer (total amount) is, for example, 70 parts by mass or more, preferably 90 parts by mass or more, per 100 parts by mass of the total amount of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer.Further, the copolymerizable vinyl monomer (total amount) is, for example, 99 parts by mass or less, preferably 97 parts by mass or less, per 100 parts by mass of the total amount of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer.
• the amount of the aromatic ring-containing vinyl monomer is, for example, 70 parts by mass or more, preferably 90 parts by mass or more, per 100 parts by mass of the total amount of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer.
• the amount of the aromatic ring-containing vinyl monomer is, for example, 99 parts by mass or less, preferably 97 parts by mass or less, per 100 parts by mass of the total amount of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer.
• the content of the carboxyl group-containing vinyl monomer is appropriately set so that the total acid value and hydroxyl value of the acrylic polyol (carboxyl group-containing acrylic polyol) falls within the range described below.
• the amount of the carboxyl group-containing vinyl monomer is, for example, 1 part by mass or more, preferably 5 parts by mass or more, per 100 parts by mass of the total amount of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer.
• the amount of the carboxyl group-containing vinyl monomer is, for example, 99 parts by mass or less, preferably 97 parts by mass or less, per 100 parts by mass of the total amount of the hydroxyl group-containing (meth)acrylate and the copolymerizable vinyl monomer.
• the method for producing the acrylic polyol is not particularly limited.
• the above acrylic raw material components are copolymerized in the presence of a known organic solvent.
• An example of the organic solvent is toluene.
• the blending ratio and blending timing of the organic solvent are appropriately set according to the purpose and application.
• a known polymerization initiator In the production of acrylic polyol, a known polymerization initiator is used as necessary.
• the polymerization initiator include known radical polymerization initiators (described below), more preferably azo compounds (described below) and peroxides (described below), even more preferably peroxides (described below), and particularly preferably t-butylperoxy-2-ethylhexanoate.
• the mixing ratio and timing of the polymerization initiator are appropriately set depending on the purpose and application.
• the polymerization conditions for the acrylic raw material components are set appropriately depending on the purpose and application.
• the polymerization temperature is, for example, 50°C or higher, preferably 70°C or higher.
• the polymerization temperature is, for example, 150°C or lower, preferably 130°C or lower.
• the polymerization time is, for example, 30 minutes or longer, preferably 1 hour or longer.
• the polymerization time is, for example, 12 hours or shorter, preferably 6 hours or shorter.
• Acrylic polyol is thus obtained.
• an organic solvent is used in the above polymerization method, a solution and/or dispersion of acrylic polyol is obtained as the reaction product liquid.
• the solids concentration of the acrylic polyol solution and/or dispersion is adjusted by a known method.
• an organic solvent can be added to the reaction product liquid as necessary. Also, a portion of the organic solvent can be removed from the reaction product liquid.
• the solids concentration of the acrylic polyol solution and/or dispersion is, for example, 30% by mass or more, preferably 40% by mass or more.
• the solids concentration of the acrylic polyol solution and/or dispersion is, for example, 60% by mass or less, preferably 50% by mass or less.
• the number average molecular weight of the acrylic polyol is, for example, more than 400, preferably 500 or more, and more preferably 1000 or more.
• the number average molecular weight of the acrylic polyol is, for example, 20000 or less, preferably 15000 or less, more preferably 10000 or less, and even more preferably 5000 or less.
• the hydroxyl value of the acrylic polyol is, for example, 1 mgKOH/g or more, preferably 3 mgKOH/g or more.
• the hydroxyl value of the acrylic polyol is, for example, 500 mgKOH/g or less, preferably 300 mgKOH/g or less.
• the hydroxyl value is measured in accordance with the description of JIS K 1557-1 (2007) (hereinafter the same).
• the hydroxyl value of the acrylic polyol is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, even more preferably 15 mgKOH/g or more, and particularly preferably 20 mgKOH/g or more.
• the hydroxyl value of the acrylic polyol is preferably 200 mgKOH/g or less, more preferably 100 mgKOH/g or less, and particularly preferably 50 mgKOH/g or less.
• the total of the acid value and hydroxyl value of the acrylic polyol is preferably 1 mgKOH/g or more, more preferably 3 mgKOH/g or more.
• the total of the acid value and hydroxyl value of the acrylic polyol (carboxyl group-containing acrylic polyol) is preferably 20 mgKOH/g or less, more preferably 10 mgKOH/g or less.
• the total of the acid value and hydroxyl value is measured in accordance with the description of JIS K 1557-5 (2007) (hereinafter the same).
• the acid value of the acrylic polyol is, for example, 1 mgKOH/g or more, preferably 3 mgKOH/g or more.
• the acid value of the acrylic polyol (carboxyl group-containing acrylic polyol) is, for example, 20 mgKOH/g or less, preferably 10 mgKOH/g or less.
• the acid value is measured in accordance with the description of JIS K 1557-5 (2007) (hereinafter the same).
• the polyol may include a low molecular weight polyol in addition to the macropolyol.
• a low molecular weight polyol has two or more hydroxyl groups in one molecule.
• a low molecular weight polyol is an organic compound with a relatively low molecular weight.
• the molecular weight of the low molecular weight polyol is, for example, 40 or more, for example, 400 or less.
• Examples of low molecular weight polyols include dihydric alcohols, trihydric alcohols, and tetrahydric or higher alcohols.
• Examples of dihydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and dipropylene glycol.
• Examples of trihydric alcohols include glycerin and trimethylolpropane.
• Examples of tetrahydric or higher alcohols include pentaerythritol and diglycerin.
• low molecular weight polyols include polymers obtained by addition polymerization of alkylene (C2-3) oxide with dihydric to tetrahydric alcohols so that the number average molecular weight is less than 400. These can be used alone or in combination of two or more types.
• Examples of low molecular weight polyols include preferably dihydric alcohols and trihydric alcohols, and more preferably dihydric alcohols.
• the polyols can be used alone or in combination of two or more kinds.
• a macro polyol is used alone, and more preferably, an acrylic polyol is used alone.
• polyurethane resin raw material examples include one-component curing polyurethane resin and two-component curing polyurethane resin.
• a preferred form of the polyurethane resin raw material is a two-component curing polyurethane resin.
• a two-component curing polyurethane resin has a curing agent and a base agent, each of which is independent of each other.
• the curing agent includes, for example, the polyisocyanate described above.
• the base agent includes, for example, the polyol described above. The curing agent and base agent are mixed at the time of use to form a urethane cured product (cured resin described below).
• the polyol may be diluted with a known organic solvent.
• the polyisocyanate may be diluted with a known organic solvent.
• the two-component curing polyurethane resin preferably comprises a base agent containing the above-mentioned acrylic polyol and a curing agent containing the above-mentioned polyisocyanate. This produces a cured product (described below) that has an excellent refractive index, excellent flexibility, excellent transparency, and excellent weather resistance.
• the polyisocyanate and polyol undergo a urethane reaction by a known method to produce a cured polyurethane resin.
• the mixing ratio of the polyisocyanate and the polyol is adjusted, for example, based on the equivalent ratio (OH/NCO) of the hydroxyl groups in the polyol to the isocyanate groups in the polyisocyanate.
• the equivalent ratio (OH/NCO) of the hydroxyl groups in the polyol to the isocyanate groups in the polyisocyanate is, for example, 0.5 or more, preferably 0.8 or more, and more preferably 0.95 or more.
• the equivalent ratio (OH/NCO) of the hydroxyl groups in the polyol to the isocyanate groups in the polyisocyanate is, for example, 2.0 or less, preferably 1.5 or less, and more preferably 1.1 or less.
• the mixing ratio of the polyisocyanate and the polyol is adjusted, for example, based on the equivalent ratio (OH+COOH/NCO) of the hydroxyl groups and carboxyl groups (total amount) in the polyol to the isocyanate groups in the polyisocyanate.
• the equivalent ratio (OH+COOH/NCO) of the hydroxyl groups and carboxyl groups (total amount) in the polyol to the isocyanate groups in the polyisocyanate is, for example, 0.5 or more, preferably 0.8 or more, and more preferably 0.95 or more.
• the equivalent ratio (OH+COOH/NCO) of the hydroxyl groups and carboxyl groups (total amount) in the polyol to the isocyanate groups in the polyisocyanate is, for example, 2.0 or less, preferably 1.5 or less, and more preferably 1.1 or less.
• the acrylic resin raw material is a curable compound for producing a cured acrylic resin (described later).
• the acrylic resin raw material contains, for example, a monomer component and a polymerization initiator.
• the monomer component contains, for example, a radically polymerizable monomer.
• the radically polymerizable monomer is a monomer that can generate a cured acrylic resin by radical polymerization.
• the radical polymerizable monomer may, for example, be the monomers mentioned above as the raw material for the acrylic polyol. More specifically, the radical polymerizable monomer may, for example, be the alkyl (meth)acrylate, the hydroxyl group-containing (meth)acrylate, the aromatic ring-containing vinyl monomer, the carboxyl group-containing vinyl monomer, the glycidyl group-containing vinyl monomer, the amino group-containing vinyl monomer, the cyano group-containing vinyl monomer, the acetoacetoxy group-containing vinyl monomer, the sulfonic acid group-containing vinyl monomer, the phosphoric acid group-containing vinyl monomer, the alicyclic group-containing vinyl monomer, the (meth)acryloyl group-containing rubber, the vinyl esters, the N-substituted unsaturated carboxylic acid amide, the heterocyclic vinyl compound, the vinylidene halide compound, the ⁇ -olefins, the dienes, and the crosslinkable vinyl mono
• radical polymerizable monomer preferably, an alicyclic group-containing vinyl monomer and a (meth)acryloyl group-containing rubber are used, and more preferably, dicyclopentenyloxyethyl (meth)acrylate and a (meth)acryloyl group-containing isoprene rubber are used.
• the polymerization initiator may be a known radical polymerization initiator, such as an active energy ray radical polymerization initiator or a thermal radical polymerization initiator.
• active energy ray radical polymerization initiators include photoradical polymerization initiators.
• photoradical polymerization initiators include alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, carbazolephenone-based photopolymerization initiators, acridine-based photopolymerization initiators, triazine-based photopolymerization initiators, and benzoyl-based photopolymerization initiators. These can be used alone or in combination of two or more types.
• thermal radical polymerization initiators include azo compounds and peroxides.
• azo compounds include azoisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethylazoisobutyrate.
• peroxides include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, t-butylperoxy-2-ethylhexanoate, and peroxydicarbonate. These can be used alone or in combination of two or more types.
• active energy ray radical polymerization initiators may also act as thermal radical polymerization initiators.
• thermal radical polymerization initiators may also act as active energy ray radical polymerization initiators.
• the radical polymerization initiator may be commercially available.
• examples of commercially available radical polymerization initiators include the Azo Polymerization Initiator V series manufactured by Fujifilm Wako Pure Chemical Industries, the Omnirad series manufactured by IGM Resins B.V., and the Percure series manufactured by NOF Corporation. These may be used alone or in combination of two or more types.
• the polymerization initiator preferably, an active energy ray radical polymerization initiator is used, and more preferably, a photopolymerization initiator is used.
• the mixing ratio and mixing timing of the polymerization initiator are appropriately set according to the purpose and application.
• the form of the acrylic resin raw material may be, for example, a mixture containing the above radical polymerizable monomer and the above polymerization initiator.
• the acrylic resin raw material may also contain a known organic solvent.
• the acrylic resin raw material preferably does not contain an organic solvent and is composed of the above radical polymerizable monomer and the above polymerization initiator.
• the curable composition contains, for example, a plasticizer and a curable compound as described above.
• the curable composition contains a plasticizer and a polyurethane resin raw material and/or an acrylic resin raw material as a curable compound. More preferably, the curable composition contains a plasticizer and a polyurethane resin raw material, or a plasticizer and an acrylic resin raw material.
• the mixing ratio of the plasticizer and the curable compound is not particularly limited and is set appropriately depending on the purpose and application.
• the plasticizer is, for example, 1 part by mass (phr) or more, preferably 5 parts by mass (phr) or more, per 100 parts by mass of the solid content of the curable compound.
• the plasticizer is, for example, 70 parts by mass (phr) or less, preferably 50 parts by mass (phr) or less, per 100 parts by mass of the solid content of the curable compound.
• the plasticizer is, for example, 1 mass% or more, preferably 3 mass% or more, based on the total amount (solid content basis) of the plasticizer and the curable compound.Furthermore, the plasticizer is, for example, 50 mass% or less, preferably 35 mass% or less, based on the total amount (solid content basis) of the plasticizer and the curable compound.
• the amount of the curable compound is, for example, 50 mass% or more, preferably 65 mass% or more, based on the total amount (solid content) of the plasticizer and the curable compound.
• the amount of the curable compound is, for example, 99 mass% or less, preferably 97 mass% or less, based on the total amount (solid content) of the plasticizer and the curable compound.
• the plasticizer may be added to the curing agent (polyisocyanate) of the two-component curing polyurethane resin.
• the plasticizer may be added to the base agent (polyol) of the two-component curing polyurethane resin.
• the plasticizer may be added to both the base agent and the curing agent of the two-component curing polyurethane resin.
• the plasticizer may also be prepared separately from the base agent and hardener of the two-component curing polyurethane resin. If the plasticizer is prepared separately, it may be added at the same time as the base agent and hardener are mixed, or it may be added to the mixture of the base agent and hardener after they are mixed.
• the plasticizer may be mixed in advance with the radical polymerizable monomer.
• the plasticizer may be mixed in advance with the polymerization initiator.
• the plasticizer may be added simultaneously when the radical polymerizable monomer and the polymerization initiator are mixed, or may be added to the mixture after the radical polymerizable monomer and the polymerization initiator are mixed.
• the curable composition may contain an additive as a subcomponent, if necessary.
• the subcomponent is a component whose content ratio to the whole is equal to or less than a predetermined value.
• the content ratio of the subcomponent to the whole is, for example, 10 mass% or less. In other words, the proportion of the additive is 10 mass% or less with respect to the total solid content of the curable composition.
• Additives include, for example, ultraviolet absorbers (UV absorbers), light stabilizers (photostabilizers) and antioxidants.
• Further additives include, for example, heat stabilizers, crosslinking agents, silane coupling agents, defoamers, leveling agents, mildew inhibitors, rust inhibitors, matting agents, flame retardants, thixotropic agents, tackifiers, thickeners, lubricants, antistatic agents, surfactants, reaction retarders, hydrolysis inhibitors, dyes, inorganic pigments, organic pigments, tack inhibitors, inorganic fillers and organic fillers. These may be used alone or in combination of two or more types. The amount and timing of the additives to be added are appropriately set depending on the purpose and application.
• the additives preferably include ultraviolet absorbers (UV absorbers), light stabilizers (light stabilizers) and antioxidants. That is, the curable composition preferably contains at least one selected from the group consisting of ultraviolet absorbers, light stabilizers and antioxidants.
• the ratio of the additive is, for example, 1 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, preferably 10 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, more preferably 100 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, relative to 1 part by mass of the curable composition (total amount).
• the ratio of the additive is, for example, 100,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, preferably 10,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, and more preferably 1,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, per part by mass of the above-mentioned curable composition (total amount).
• the ultraviolet absorber is not particularly limited, and examples thereof include known ultraviolet absorbers (for example, those described in the ADEKA catalog and the CLARIANT catalog). More specifically, examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzylidene-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. These are used alone or in combination of two or more. From the viewpoint of the weather resistance of the cured product (described later), the ultraviolet absorber is preferably a benzotriazole-based ultraviolet absorber.
• the blending ratio of the ultraviolet absorber is, for example, 1 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, preferably 10 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, more preferably 100 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, relative to 1 part by mass of the curable composition described above.
• the blending ratio of the ultraviolet absorber is, for example, 100,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, preferably 10,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, and more preferably 1,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, relative to 1 part by mass of the above-mentioned curable composition.
• the light resistance stabilizer is not particularly limited, and may be a known light resistance stabilizer (for example, as described in the ADEKA catalog). More specifically, the light resistance stabilizer may be a hindered amine-based (HALS) light resistance stabilizer and a benzoate-based light resistance stabilizer. These may be used alone or in combination of two or more kinds. From the viewpoint of the weather resistance of the cured product (described later), the light resistance stabilizer may preferably be a hindered amine-based (HALS) light resistance stabilizer.
• HALS hindered amine-based
• the blending ratio of the light resistance stabilizer is, for example, 1 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, preferably 10 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, more preferably 100 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, relative to 1 part by mass of the curable composition.
• the blending ratio of the light resistance stabilizer is, for example, 100,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, preferably 10,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, more preferably 1000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, relative to 1 part by mass of the curable composition.
• the antioxidant is not particularly limited, and examples thereof include known antioxidants (for example, those described in the ADEKA catalog). More specific examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and thiophene-based antioxidants. These are used alone or in combination of two or more. From the viewpoint of weather resistance of the cured product (described later), the antioxidant is preferably a phenol-based antioxidant.
• the blending ratio of the antioxidant is, for example, 1 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, preferably 10 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, more preferably 100 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, relative to 1 part by mass of the curable composition described above.
• the mixing ratio of the antioxidant is, for example, 100,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, preferably 10,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, and more preferably 1,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, relative to 1 part by mass of the above-mentioned curable composition.
• curable composition is suitably used in various industrial fields.
• examples of uses of the curable composition include coating agents, paints, and adhesives.
• a preferred use of the curable composition is an adhesive.
• the adhesive is an uncured curable composition, and when cured, a cured adhesive product (a cured product described below) is formed.
• the cured adhesive product adheres the adherend.
• the above curable composition can provide a cured product having an excellent refractive index, excellent flexibility, excellent transparency, and excellent weather resistance. Therefore, the above curable composition is preferably used as an optical curable composition. Examples of applications of the optical curable composition include optical coating agents, optical paints, and optical adhesives.
• Main Component The cured product contains the above-mentioned plasticizer and cured resin as main components.
• the main component is a component whose content ratio to the whole is a predetermined value or more.
• the content ratio of the main component to the whole is, for example, 90 mass% or more.
• the total solid content of the plasticizer and cured resin is 90 mass% or more with respect to the total solid content of the cured product.
• the cured product is formed by curing the above-mentioned curable composition by a known method.
• the method for curing the curable composition is appropriately selected depending on the type of curable compound.
• the cured resin contains, for example, a cured product of the above-mentioned curable compound, and preferably consists of the above-mentioned cured product of the curable compound.
• cured resins include cured polyurethane resins, cured polyolefin resins, cured polyamine resins, cured amide resins, cured urea resins, cured phenolic resins, cured epoxy resins, cured acrylic resins, cured melamine resins, and cured alkyd resins. These may be used alone or in combination of two or more types.
• the cured resin is a cured polyurethane resin or a cured acrylic resin, and more preferably, a cured acrylic resin.
• the cured polyurethane resin may be, for example, a cured product of the polyurethane resin raw material described above. More specifically, the cured polyurethane resin may be a reaction product of a base agent containing the above-mentioned polyol and a curing agent containing the above-mentioned polyisocyanate. Such a cured resin can provide a cured product that has a better refractive index, better flexibility, better transparency, and better weather resistance.
• the cured resin contains a cured polyurethane resin (a reaction product of a base agent containing the above-mentioned acrylic polyol and a curing agent containing the above-mentioned polyisocyanate), a cured product that satisfies the physical properties (refractive index and flexibility) described below can be more easily obtained.
• a cured polyurethane resin a reaction product of a base agent containing the above-mentioned acrylic polyol and a curing agent containing the above-mentioned polyisocyanate
• the cured acrylic resin may be, for example, a cured product of the above-mentioned acrylic resin raw material. More specifically, the cured acrylic resin may be a reaction product obtained by a radical polymerization reaction of the above-mentioned radical polymerizable monomer.
• the method for obtaining the cured acrylic resin is not particularly limited. For example, when an active energy ray radical polymerization initiator is used, an active energy ray having a predetermined wavelength is irradiated onto the acrylic resin raw material. When a thermal radical polymerization initiator is used, the acrylic resin raw material is heated to a predetermined temperature. This activates the polymerization initiator, and the radical polymerizable monomer undergoes a radical polymerization reaction to obtain a cured acrylic resin. In particular, if the cured resin contains a cured acrylic resin (a radical polymerization product of the above-mentioned monomer components), a cured product having excellent flexibility and an especially excellent refractive index can be obtained.
• the cured product may contain the above-mentioned additives (excluding plasticizers) as subcomponents, if necessary.
• the subcomponent is a component whose content in the whole is equal to or less than a predetermined value.
• the content of the subcomponent in the whole is, for example, 10% by mass or less. In other words, the proportion of the additive is 10% by mass or less with respect to the total solid content of the cured product.
• the additives preferably include ultraviolet absorbers (UV absorbers), light stabilizers (light stabilizers) and antioxidants. That is, the cured product preferably contains at least one selected from the group consisting of ultraviolet absorbers, light stabilizers and antioxidants. From the viewpoint of weather resistance of the cured product, the ratio of the additive (at least one additive selected from the group consisting of ultraviolet absorbers, light stabilizers and antioxidants) is, for example, 1 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, preferably 10 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, more preferably 100 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, per part by mass of the cured product (total amount).
• the ratio of the additive is, for example, 100,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, preferably 10,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, and more preferably 1,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, per part by mass of the above-mentioned cured product (total amount).
• the ultraviolet absorber is not particularly limited, and may be a known ultraviolet absorber (for example, as described in the ADEKA catalog). More specifically, the ultraviolet absorber may be, for example, a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a benzylidene-based ultraviolet absorber, or a triazine-based ultraviolet absorber. These may be used alone or in combination of two or more. From the viewpoint of weather resistance of the cured product, the ultraviolet absorber may preferably be a benzotriazole-based ultraviolet absorber.
• the blending ratio of the ultraviolet absorber is, for example, 1 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, preferably 10 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, more preferably 100 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, per part by mass of the cured product.
• the blending ratio of the ultraviolet absorber is, for example, 100,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, preferably 10,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, and more preferably 1,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, per 1 part by mass of the above-mentioned cured product.
• the light resistance stabilizer is not particularly limited, and may be a known light resistance stabilizer (for example, as described in the ADEKA catalog). More specifically, the light resistance stabilizer may be, for example, a hindered amine-based (HALS) light resistance stabilizer or a benzoate-based light resistance stabilizer. These may be used alone or in combination of two or more. From the viewpoint of weather resistance of the cured product, the light resistance stabilizer may preferably be a hindered amine-based (HALS) light resistance stabilizer.
• HALS hindered amine-based
• the blending ratio of the light resistance stabilizer is, for example, 1 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, preferably 10 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, more preferably 100 ⁇ 10 ⁇ 6 parts by mass (ppm) or more, per part by mass of the cured product described above.
• the blending ratio of the light resistance stabilizer is, for example, 100,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, preferably 10,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, and more preferably 1,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, per 1 part by mass of the above-mentioned cured product.
• the mixing ratio of the antioxidant is, for example, 100,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, preferably 10,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, and more preferably 1,000 ⁇ 10 ⁇ 6 parts by mass (ppm) or less, per 1 part by mass of the above-mentioned cured product.
• the cured product contains the composition (i.e., a composition containing the first compound and the second compound), it has an excellent refractive index, excellent flexibility, excellent transparency, and excellent weather resistance.
• the refractive index of the cured product is relatively high.
• the refractive index of the cured product is, for example, 1.45 or more, preferably 1.50 or more, more preferably 1.55 or more, even more preferably 1.60 or more, and particularly preferably 1.61 or more.
• the refractive index of the cured product is, for example, 1.80 or less, preferably 1.70 or less. The refractive index is measured in accordance with the examples described later.
• the tensile storage modulus (E') of the cured product at 25°C is relatively low.
• the tensile storage modulus (E') of the cured product at 25°C is, for example, 1000 MPa or less, preferably 800 MPa or less, more preferably 500 MPa or less, even more preferably 300 MPa or less, even more preferably 200 MPa or less, even more preferably 100 MPa or less, and particularly preferably 50 MPa or less.
• the tensile storage modulus (E') of the cured product at 25°C is, for example, 1 MPa or more.
• the tensile storage modulus (E') is measured in accordance with the examples described later.
• curable composition contains the above-mentioned plasticizer. Therefore, such a curable composition can provide a cured product that has an excellent refractive index, excellent flexibility, excellent transparency, and excellent weather resistance.
• Plasticizer Example 1 A composition containing 4-phenethylthiomethyl-1,8-bisphenethylthio-3,6-dithiaoctane (PE-GST) and S,S'-diphenethyldimercaptoethane (DPE-DME) as plasticizers was synthesized in the following manner.
• AIBN azobisisobutyronitrile
• the equivalent ratio of styrene to GST was 3.1.
• the equivalent ratio of the carbon-carbon double bond of styrene to the mercapto group of GST was 1.03.
• the ratio of the radical polymerization initiator to GST was 0.5 mol%.
• the flask was then allowed to cool until the temperature of the reaction product reached room temperature.
• the reaction product was then dried under reduced pressure at 60°C, and the ethyl acetate was distilled off.
• reaction products were then analyzed by high performance liquid chromatography/mass spectrometry (hereinafter referred to as LC/MS analysis). More specifically, the reaction products were separated by high performance liquid chromatography (UV detector: 254 nm, mobile phase: acetonitrile), and the molecular weights of the components contained in each separated peak were analyzed by mass spectrometry (detector: ESI).
• LC/MS analysis high performance liquid chromatography/mass spectrometry
• Mass spectrometry detected a peak containing a compound with a molecular weight of 572.17 (a compound equivalent to PE-GST) and a peak containing a compound with a molecular weight of 302.12 (a compound equivalent to DPE-DME).
• reaction product was a composition containing PE-GST and DPE-DME.
• the peak area ratio of the peak corresponding to PE-GST was 61.0% of the total peak area, and the peak area ratio of the peak corresponding to DPE-DME was 1.2% of the total peak area.
• the resulting composition was a colorless, transparent liquid.
• the viscosity of the composition (25°C) was 430 mPa ⁇ s.
• the refractive index (nD) of the composition was 1.617.
• Example 2 The amount of AIBN as a radical polymerization initiator was changed from 204.9 mg (1.25 mmol) to 2049 mg (12.5 mmol). The ratio of the radical polymerization initiator to GST was 5.0 mol%. The reaction temperature was changed from 60° C. to 80° C. Other than the above, the reaction product was obtained in the same manner as in Example 1.
• reaction product was a composition (plasticizer) containing PE-GST and DPE-DME.
• the peak area of the peak corresponding to PE-GST was 56.5% of the total peak area
• the peak area of the peak corresponding to DPE-DME was 1.4% of the total peak area.
• Example 3 The reaction solvent was changed from ethyl acetate to toluene. Other than the above, the reaction product was obtained in the same manner as in Example 2.
• reaction product was a composition (plasticizer) containing PE-GST and DPE-DME.
• the peak area ratio of the peak corresponding to PE-GST to the total peak area was 48.5%, and the peak area ratio of the peak corresponding to DPE-DME to the total peak area was 2.2%.
• the resulting composition was a colorless, transparent liquid.
• the viscosity of the composition (25°C) was 380 mPa ⁇ s.
• the refractive index (nD) of the composition was 1.617.
• Example 4 As the radical polymerization initiator, trade name V-65 (2,2'-azobis(2,4-dimethylvaleronitrile), manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used instead of AIBN. The amount of V-65 was adjusted to 3100 mg (12.5 mmol). The ratio of the radical polymerization initiator to GST was 5.0 mol %. The reaction temperature was changed from 60°C to 40°C. Apart from the above, a reaction product was obtained in the same manner as in Example 2.
• V-65 2,2'-azobis(2,4-dimethylvaleronitrile), manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.
• reaction product was a composition containing PE-GST and DPE-DME.
• reaction product was a composition (plasticizer) containing PE-GST and DPE-DME.
• the peak area of the peak corresponding to PE-GST was 62.1% of the total peak area
• the peak area of the peak corresponding to DPE-DME was 1.2% of the total peak area.
• Example 5 The reaction temperature was changed from 60° C. to 100° C. Except for the above, the reaction product was obtained in the same manner as in Example 1.
• reaction product was a composition (plasticizer) containing PE-GST and DPE-DME.
• the peak area ratio of the peak corresponding to PE-GST to the total peak area was 59.9%, and the peak area ratio of the peak corresponding to DPE-DME to the total peak area was 1.4%.
• the recovery flask was removed from the oil bath, and the solution was allowed to cool at room temperature, and then left to stand at room temperature for 18 hours.
• the activated carbon was then filtered out of the solution using pleated filter paper.
• the filtrate was then dried under reduced pressure at 60°C to distill off the ethyl acetate.
• a composition (plasticizer) containing PE-GST and DPE-DME was obtained.
• the recovered amount of the composition was 4.9 g.
• reaction solution was then cooled in an ice bath. Next, 53.4 g (380.0 mmol) of benzoyl chloride was added dropwise to the reaction solution while maintaining the internal temperature of the reaction solution at 10°C or less.
• the concentrate was diluted with 100 mL of dichloromethane to obtain a diluted solution.
• the diluted solution was passed through 100 mL of silica gel.
• 300 mL of dichloromethane was used to drain the diluted solution.
• the diluted solution was then concentrated in an evaporator.
• 4-benzoylthiomethyl-1,8-bisbenzoylthio-3,6-dithiaoctane (Bz-GST) was obtained as the reaction product.
• reaction solution was then cooled in an ice bath.
• 100.0 g (593.1 mmol) of 3-phenylpropionyl chloride was added dropwise to the reaction solution while maintaining the internal temperature of the reaction solution at 15°C or less.
• reaction solution was stirred for 2 hours while maintaining the internal temperature at 15°C or below.
• the cleaning solution was passed through activated alumina (300 mesh, for chromatography, basic).
• 120 g of toluene was used to flush out the reaction products remaining in the alumina.
• PP-GST was a pale yellow, transparent liquid.
• the yield of PP-GST was 119.0 g.
• the viscosity of PP-GST (25°C) was 400 mPa ⁇ s.
• the refractive index (nD) of PP-GST was 1.60.
• the PP-GST was identified by 1 H-NMR (400 MHz, CDCl 3 ) as follows.
• Curable Compositions Examples 8 to 17 and Comparative Examples 5 to 8
• Curable Compound The following curable compounds were prepared.
• FA512-AS radical polymerizable monomer, dicyclopentenyloxyethyl acrylate, manufactured by Resonac
• UC-102M radical polymerizable monomer, methacryloyl group-containing isoprene rubber, manufactured by Kuraray

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