WO2017047547A1 - Composition durcissable et produit durci de cette dernière - Google Patents

Composition durcissable et produit durci de cette dernière Download PDF

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WO2017047547A1
WO2017047547A1 PCT/JP2016/076818 JP2016076818W WO2017047547A1 WO 2017047547 A1 WO2017047547 A1 WO 2017047547A1 JP 2016076818 W JP2016076818 W JP 2016076818W WO 2017047547 A1 WO2017047547 A1 WO 2017047547A1
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meth
acrylate
group
monofunctional
ring
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PCT/JP2016/076818
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Japanese (ja)
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孝治 小西
慎一郎 塚田
信輔 宮内
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大阪ガスケミカル株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G

Definitions

  • the present invention relates to a novel curable composition capable of forming a cured product having a high refractive index and the cured product thereof.
  • polyfunctional (meth) acrylates having a plurality of (two or more) (meth) acryloyl groups in the molecule are used in various fields.
  • the polyfunctional (meth) acrylate having a fluorene skeleton has excellent optical properties (for example, high refractive index, high transparency, etc.) derived from the fluorene skeleton (for example, 9,9-bisarylfluorene skeleton, etc.). ) And the like, it is used as an optical material.
  • polyfunctional (meth) acrylate having a fluorene skeleton typically, 9,9-bis [(meth) acryloyloxy (poly) alkoxyaryl] fluorene and the like are known.
  • polyfunctional (meth) acrylates especially polyfunctional (meth) acrylates having a fluorene skeleton
  • polyfunctional (meth) acrylates having a fluorene skeleton often have a relatively high viscosity, and are usually monofunctional (metafunctional) for improving handling properties.
  • a reactive diluent such as acrylate.
  • Patent Document 1 discloses 9,9-bis [(meth) acryloyloxypolyalkoxyphenyl] fluorene in which the average value of the number of oxyalkylene groups added is adjusted to a specific range. , Curable compositions containing the fluorene compound, and cured products thereof. It is described that the compound having a fluorene skeleton and the curable composition containing the compound are excellent in handling properties and curability, and the cured product can achieve both a high refractive index and scratch resistance.
  • aryloxyalkyl (meth) acrylates that are aromatic (meth) acrylates [for example, C 6-10 aryloxy C 1-10 alkyl (meth) acrylates such as phenoxyethyl (meth) acrylate] have a high refractive index. It is also described that it is a monofunctional (meth) acrylate that can balance both excellent handling properties and excellent handling properties and can efficiently maintain scratch resistance.
  • curable compositions comprising a wide variety of mono- or polyfunctional acrylates such as phenoxyethyl acrylate
  • curable compositions and cured products thereof have high handling properties and exhibit high refractive index and scratch resistance in the cured products, further improvements have been required in the field of optical materials.
  • an object of the present invention is to provide a novel curable composition capable of forming a cured product having a high refractive index even if it contains a reactive diluent, a cured product thereof, and a method for producing the cured product. is there.
  • Another object of the present invention is to provide a novel curable composition capable of forming a cured product having high handling properties (low viscosity) and having a high refractive index, and a cured product thereof.
  • Still another object of the present invention is to provide a curable composition capable of forming a cured product having excellent scratch resistance (flexibility), and a cured product thereof.
  • Another object of the present invention is to provide a method and a viscosity reducing agent capable of effectively lowering the viscosity even with a high-viscosity polyfunctional (meth) acrylate.
  • the present inventors combined a polyfunctional (meth) acrylate with a monofunctional (meth) acrylate having a condensed polycyclic aryl group as a reactive diluent. Even if it contains a reactive diluent, it can form a cured product having a high refractive index, and even if the monofunctional (meth) acrylate is solid at room temperature, it has a high-viscosity polyfunctional (meth) acrylate.
  • the present invention has been completed by finding that the viscosity can be lowered and the handleability can be improved.
  • the curable composition of the present invention contains a polyfunctional (meth) acrylate and a novel first monofunctional (meth) acrylate represented by the following formula (1).
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a linear or branched alkylene group
  • R 3 is an alkyl group
  • Ar 1 is a condensed polycyclic arene ring
  • a is an integer of 1 to 4
  • b represents 0 or an integer of 1 or more.
  • the first monofunctional (meth) acrylate represented by the formula (1) may be a condensed polycyclic C 10-14 aryloxy C 2-4 alkyl (meth) acrylate.
  • Multifunctional (meth) acrylate is represented by the following formula (2)
  • R 4a and R 4b and R 5a and R 5b are the same or different non-reactive substituents
  • R 6a and R 6b are direct
  • R 7a and R 7b are hydrogen atoms or methyl groups
  • k1 and k2 are 0 or an integer of 1 or more
  • m1 and m2 are 0 or an integer of 1 or more
  • n1 and n2 are 0 or 1
  • At least one high-viscosity multifunctional selected from the group consisting of fluorene skeleton-containing (meth) acrylates, alicyclic or aromatic epoxy (meth) acrylates, urethane (meth) acrylates and polyester (meth) acrylates (Meth) acrylate may be included.
  • the rings Z 1 and Z 2 and the rings Z 3 and Z 4 may each be a benzene ring or a naphthalene ring
  • k1 and k2 may be 0, and R 5a and R 5b are It may be a C 1-6 alkyl group or a C 6-10 aryl group
  • m1 and m2 may be 0 or an integer of 1 to 2
  • R 6a and R 6b are linear C 2-6 alkylene It may be a group
  • n1 and n2 may be an integer of 1 to 10
  • p1 and p2 may be 1.
  • the polyfunctional (meth) acrylate may contain at least fluorene (meth) acrylate represented by the formula (2) and urethane (meth) acrylate.
  • the polyfunctional (meth) acrylate may contain di (meth) acrylate of an alkylene oxide adduct of biphenols or bisphenols in addition to the high-viscosity polyfunctional (meth) acrylate.
  • the aromatic epoxy (meth) acrylate may be an aromatic epoxy (meth) acrylate represented by the following formula (3).
  • R 8 represents a hydrogen atom, an alkyl group or an aryl group, respectively, and two R 8 may be bonded to each other to form a hydrocarbon ring which may have an alkyl group, R 9a and R 9b is an alkyl group or an aryl group, R 10a and R 10b are linear or branched alkylene groups, R 11a and R 11b are hydrogen atoms or methyl groups, q1 and q2 are integers of 0 to 4, r1 and r2 is 0 or an integer of 1 or more, and t is 0 or 1.
  • the urethane (meth) acrylate may be a polyester type urethane (meth) acrylate, a polyether type urethane (meth) acrylate, a polycarbonate type urethane (meth) acrylate, or the like.
  • the viscosity (25 ° C.) of the polyfunctional (meth) acrylate may be high viscosity, for example, 3000 mPa ⁇ s or more.
  • the curable composition further includes at least one second unit selected from the group consisting of alkylthio (meth) acrylates, arylthio (meth) acrylates, aralkylthio (meth) acrylates, and arylthioalkyl (meth) acrylates.
  • Functional (meth) acrylate sulfur atom-containing monofunctional (meth) acrylate
  • the curable composition may further contain a third monofunctional (meth) acrylate represented by the following formula (4).
  • R 12 is a hydrogen atom or a methyl group
  • R 13 is an alkylene group
  • R 14 is an alkyl group
  • Ar 2 is a benzene ring or a ring-arene ring
  • c is an integer of 1 to 4
  • d is 0 or 1 or more. Indicates an integer.
  • the curable composition may further contain a polymerization initiator.
  • the present invention includes a cured product obtained by curing the curable composition, and further includes a method of producing the cured product by applying active energy to the curable composition and curing the composition.
  • the present invention also includes a viscosity reducing agent for reducing the viscosity of the polyfunctional (meth) acrylate, the viscosity reducing agent including the first monofunctional (meth) acrylate.
  • the viscosity reducing agent may further contain the second monofunctional (meth) acrylate.
  • the present invention also includes a method of reducing the viscosity of the polyfunctional (meth) acrylate by adding the first monofunctional (meth) acrylate to the polyfunctional (meth) acrylate.
  • the present invention also includes the first monofunctional (meth) acrylate, which is a novel compound.
  • (poly) alkoxy means both an alkoxy group and a polyalkoxy group.
  • the curable composition of the present invention contains a polyfunctional (meth) acrylate and a monofunctional (meth) acrylate having a condensed polycyclic aryl group (first monofunctional (meth) acrylate), Even when a reactive diluent (monofunctional (meth) acrylate or the like) is contained, a cured product having a high refractive index can be formed. Therefore, the amount of expensive multifunctional (meth) acrylate used can be effectively reduced. Further, the first monofunctional (meth) acrylate can function as a viscosity reducing agent, improves the handling property (low viscosity) of the curable composition, and forms a cured product having a high refractive index. You can also Furthermore, the cured product can achieve both a high refractive index and scratch resistance (flexibility).
  • FIG. 1 is a graph showing the refractive index before curing of the compositions of Comparative Examples 1 to 5 and Examples 1 to 5 with respect to the blending ratio of the diluent.
  • FIG. 2 is a graph showing the viscosity with respect to the blending ratio of the compositions of Comparative Examples 1 to 5 and Examples 2 to 5.
  • FIG. 3 is a graph showing the viscosity (calculated value) of a composition that achieves a target refractive index in a BPEFA / reactive diluent blending system.
  • the curable composition of the present invention contains a polyfunctional (meth) acrylate and a first monofunctional (meth) acrylate having a condensed polycyclic aryl group as a reactive diluent.
  • This first monofunctional (meth) acrylate is a novel compound.
  • the first monofunctional (meth) acrylate having a condensed polycyclic aryl group is a compound represented by the following formula (1).
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a linear or branched alkylene group
  • R 3 is an alkyl group
  • Ar 1 is a condensed polycyclic arene ring
  • a is an integer of 1 to 4
  • b represents 0 or an integer of 1 or more.
  • the group R 1 is a hydrogen atom or a methyl group.
  • the group R 2 is a linear or branched alkylene group.
  • linear alkylene group examples include linear C 2-6 alkylene groups such as ethylene group, trimethylene group, tetramethylene group (preferably Can be exemplified by a linear C 2-4 alkylene group, more preferably a linear C 2-3 alkylene group, particularly an ethylene group.
  • branched alkylene group examples include a propylene group and 1,2-butanediyl.
  • a branched C 3-6 alkylene group such as a 1,3-butanediyl group (preferably a branched C 3-4 alkylene group, particularly a propylene group).
  • a linear or branched C 2-6 alkylene group (eg, a linear or branched C 2-4 alkylene group) is preferable, and a linear or branched group is more preferable. It may be a chain C 2-3 alkylene group (particularly an ethylene group or a propylene group).
  • the repeating number a of the group (R 2 O) can be selected from an integer of about 1 to 4, for example, an integer of about 1 to 3, preferably 1 or 2, and more preferably 1. If the repetition number a is too large, the refractive index of the cured product may be reduced. When a is 2 or more, the two or more groups R 2 may be the same or different.
  • the ring Ar 1 is a condensed polycyclic arene ring, such as a condensed bicyclic arene ring (for example, a condensed bicyclic C 10-16 arene ring such as a naphthalene ring), a condensed tricyclic ring, etc.
  • a condensed bi to tetracyclic arene rings such as a formula arene ring (for example, anthracene ring, phenanthrene ring, etc.).
  • Preferable ring Ar 1 includes a condensed polycyclic C 10-16 arene ring (preferably a condensed polycyclic C 10-14 arene ring) such as a naphthalene ring and an anthracene ring, and a naphthalene ring is particularly preferable.
  • the group R 3 may be an alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t- Linear or branched C 1-12 alkyl group such as butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, preferably linear or A branched C 1-9 alkyl group, more preferably a linear or branched C 1-6 alkyl group (for example, a linear or branched C 1-4 alkyl group) and the like can be mentioned.
  • alkyl group for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group
  • the substitution number b of the group R 3 may be 0 or an integer of 1 or more, for example, an integer of about 0 to 4, preferably an integer of about 0 to 2, more preferably 0 or 1, particularly 0. Good.
  • the types of the two or more groups R 3 may be the same or different.
  • aryloxyalkyl (meth) acrylate for example, 2- (2-naphthoxy) ethyl (meth) acrylate, 2- (1-naphthoxy) ethyl (meth) acrylate, 2- (2-naphthoxy) propyl (meth) acrylate, etc.
  • the first monofunctional (meth) acrylate represented by the formula (1) can be used individually or in combination of 2 or more types.
  • Such a first monofunctional (meth) acrylate represented by the formula (1) has a condensed polycyclic aryl group, or a cured product even if mixed in a large amount in the curable composition. Can maintain or improve the refractive index, and has a high viscosity reducing effect. Therefore, for example, both high refractive index and low viscosity characteristics can be achieved, and the blending ratio (or usage amount) of expensive polyfunctional (meth) acrylate can be effectively reduced.
  • the reactive diluent is a liquid compound exhibiting high fluidity at the operating temperature (for example, at room temperature of about 25 ° C.). Surprisingly, it is represented by the formula (1).
  • the first monofunctional (meth) acrylate to be produced is in the form of powder or viscous material, and is a compound that exhibits almost no fluidity, but has high viscosity and multifunctionality (meta). )
  • the viscosity of the acrylate can be significantly reduced. Therefore, the first monofunctional (meth) acrylate can also function as a viscosity reducing agent for reducing the viscosity of the polyfunctional (meth) acrylate.
  • a method of mixing a polyfunctional (meth) acrylate with a viscosity reducing agent containing at least the first monofunctional (meth) acrylate is particularly preferable.
  • the resulting curable composition can be effectively reduced in viscosity, and the refractive index can be maintained or improved.
  • the blending ratio of the first monofunctional (meth) acrylate and the polyfunctional (meth) acrylate may be the same as the ratio in the curable composition described later.
  • the compound represented by the formula (1) is a known method (for example, a method according to the method described in JP 2012-222040 A (paragraph [0014])), for example, a hydroxy-fused polycyclic arene.
  • a (meth) acrylic acid component for example, (meth) acrylic acid or an ester-forming derivative thereof (for example, acid halide, acid anhydride, lower alkyl ester, etc.)).
  • a (meth) acrylic acid component for example, (meth) acrylic acid or an ester-forming derivative thereof (for example, acid halide, acid anhydride, lower alkyl ester, etc.)
  • Examples of the hydroxy-fused polycyclic arene include compounds corresponding to the compound represented by the formula (1) (for example, 1-naphthol, 2-naphthol, etc.).
  • Examples of the alkylene oxide or alkylene carbonate include alkylene oxide or alkylene carbonate (for example, ethylene oxide) corresponding to the alkylene group exemplified in the above R 2 section.
  • Typical examples of the alkylene oxide or alkylene carbonate adduct of the hydroxy-fused polycyclic arene include 2- (2-naphthyloxy) ethanol (NEO), 2- (1-naphthyloxy) propanol, 2- (2- Examples thereof include hydroxy (mono to tetra) C 2-4 alkoxy-C 10-14 condensed polycyclic arenes such as (2-naphthyloxy) ethoxy) ethanol.
  • 90/10 to 3/97 preferably 80/20 to 5/95 (eg 70/30 to 10/90), more preferably 65/35 to 13/87 (eg 60/40 to 17/83), particularly 55/45 to 20/80 (for example, 50/50 to 22/78).
  • the proportion of the first monofunctional (meth) acrylate represented by the formula (1) is too small, there is a possibility that the refractive index and / or the viscosity cannot be sufficiently reduced.
  • the ratio of the total amount of the polyfunctional (meth) acrylate and the first monofunctional (meth) acrylate represented by the formula (1) with respect to the entire polymerizable component in the curable composition is, for example, 30 to 100% by weight (50 to 100% by weight), preferably 60 to 100% by weight (for example, 70 to 100% by weight), more preferably about 80 to 100% by weight (for example, 90 to 100% by weight).
  • it may be substantially 100% by weight (only the polyfunctional (meth) acrylate and the first monofunctional (meth) acrylate represented by the formula (1)).
  • the polyfunctional (meth) acrylate is not particularly limited as long as it has a plurality of (two or more) (meth) acryloyl groups.
  • the number of (meth) acryloyl groups per molecule may be, for example, about 2 to 10, preferably 2 to 6, and more preferably about 2 to 4 (eg 2).
  • there are too many (meth) acryloyl groups there exists a possibility that the scratch resistance of hardened
  • Typical polyfunctional (meth) acrylates include, for example, polyfunctional (meth) acrylates having a 9,9-bisarylfluorene skeleton; aliphatic epoxy (meth) acrylates [for example, 1,6-hexanediol Di (meth) acrylate such as di (meth) acrylate of alkylene glycol diglycidyl ether such as di (meth) acrylate of glycidyl ether, poly (alkylene glycol diglycidyl ether such as di (meth) acrylate of polypropylene glycol diglycidyl ether] Alicyclic epoxy (meth) acrylate; aromatic epoxy (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylate; alkylene glycol di (meth) acrylate [for example, ethylene glycol Poly C, such as polyalkylene glycol di (meth) acrylates [for example, diethylene glycol di (meth
  • the polyfunctional (meth) acrylate may be viscous or solid at room temperature (for example, 25 ° C.).
  • the viscosity (25 ° C.) of the polyfunctional (meth) acrylate may be, for example, 1000 mPa ⁇ s or more, preferably 3000 mPa ⁇ s or more, more preferably 5000 mPa ⁇ s or more.
  • the upper limit of the viscosity is not particularly limited, and for example, it may exceed the measurement limit value (for example, 352 Pa ⁇ s) of the viscometer described in Examples described later.
  • a polyfunctional (meth) acrylate having a 9,9-bisarylfluorene skeleton for example, a fluorene skeleton-containing (meth) acrylate represented by the formula (2)
  • a fat It is preferable to include at least one selected from the group consisting of cyclic epoxy (meth) acrylates, aromatic epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates.
  • a polyfunctional (meth) acrylate having a 9,9-bisarylfluorene skeleton for example, a fluorene skeleton-containing (meth) represented by the formula (2)
  • Acrylates aromatic epoxy (meth) acrylates
  • urethane (meth) acrylates are often used.
  • Polyfunctional (meth) acrylates having a 9,9-bisarylfluorene skeleton have various properties such as optical properties (eg, high refractive index, low birefringence, transparency), mechanical properties, and heat resistance. Since it is excellent, it is suitable for improving the properties of the obtained cured product.
  • optical properties eg, high refractive index, low birefringence, transparency
  • mechanical properties e.g., heat resistance
  • heat resistance e.g., heat resistance to improve the properties of the obtained cured product.
  • “having a 9,9-bisarylfluorene skeleton” means that the molecular structure includes at least a 9,9-bisarylfluorene skeleton, and forms a fluorene ring of the skeleton.
  • a typical polyfunctional (meth) acrylate having a 9,9-bisarylfluorene skeleton is a compound represented by the following formula (2) (sometimes referred to as a fluorene skeleton-containing (meth) acrylate). Good.
  • rings Z 1 and Z 2 and rings Z 3 and Z 4 arene rings, R 4a and R 4b and R 5a and R 5b are the same or different non-reactive substituents, and R 6a and R 6b are direct
  • a linear or branched alkylene group R 7a and R 7b are hydrogen atoms or methyl groups, k1 and k2 are 0 or an integer of 1 or more, m1 and m2 are 0 or an integer of 1 or more, and n1 and n2 are 0 or 1 (The above integers, p1 and p2 represent integers of 1 or more.)
  • examples of the arene ring represented by the rings Z 1 and Z 2 include a monocyclic arene ring such as a benzene ring, a polycyclic arene ring, and the like.
  • a polycyclic arene ring fused polycyclic aromatic hydrocarbon ring
  • a ring assembly arene ring ring assembly aromatic hydrocarbon
  • Examples of the condensed polycyclic arene ring include the condensed polycyclic arene ring exemplified in the description of the ring Ar 1 in the formula (1), and the preferred embodiment is the same as the ring Ar 1 .
  • ring-assembled arene ring examples include a bearene ring (for example, a bi-C 6-12 arene ring such as a biphenyl ring, a binaphthyl ring, and a phenylnaphthalene ring (such as a 1-phenylnaphthalene ring and a 2-phenylnaphthalene ring)), a tellarene ring (for example, a tel C 6-12 arene ring such as a terphenylene ring) can be exemplified.
  • Preferred ring-assembled arene rings include bi-C 6-10 arene rings, and biphenyl rings are particularly preferred.
  • the two rings Z 1 and Z 2 bonded to the 9-position of fluorene may be the same or different and are usually the same.
  • a benzene ring, a naphthalene ring, a biphenyl ring and the like are preferable, and a benzene ring is particularly preferable.
  • substitution positions of the rings Z 1 and Z 2 bonded to the 9-position of fluorene are not particularly limited.
  • the groups corresponding to the rings Z 1 and Z 2 bonded to the 9-position of fluorene may be 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, etc. There may be.
  • examples of the arene ring represented by the rings Z 3 and Z 4 include a monocyclic arene ring such as a benzene ring, a condensed polycyclic arene ring (a condensed polycyclic aromatic hydrocarbon ring). ) And the like.
  • examples of the condensed polycyclic arene ring include the condensed polycyclic arene ring exemplified in the description of the ring Ar 1 in the formula (1), and the preferred embodiment is the same as the ring Ar 1 .
  • preferred rings Z 3 and Z 4 include a benzene ring and a naphthalene ring.
  • Rings Z 3 and Z 4 form a condensed ring skeleton together with a 5-membered ring interposed between them, for example, one of the rings Z 3 and Z 4 , a benzofluorene skeleton in which one is a benzene ring and the other is a naphthalene ring, A dibenzofluorene skeleton in which is a naphthalene ring may be formed.
  • Ring Z 3 and Z 4 is a fused polycyclic arene ring
  • the ring Z 3 and Z 4 bonding position of the 5-membered ring interposed therebetween (or, in the ring Z 3 and Z 4, wherein
  • the position of two adjacent carbon atoms shared with a 5-membered ring) is not particularly limited as long as it can be bonded (or shared), and for example, 1,2-position, 2,3-position of the naphthalene ring, or The carbon atom at any position in the 3,4-position may be shared with the 5-membered ring.
  • the condensed ring skeleton structure in the above formula (2) may be any of the structures represented by the following formulas (a) to (i).
  • Particularly preferred ring Z 3 and Z 4 is a benzene ring, a condensed ring structure 5 membered ring interposed ring Z 3 and Z 4 as well as between them form both the ring Z 3 and Z 4 is a benzene ring
  • a fluorene skeleton is particularly preferred.
  • the non-reactive substituents (or non-radically polymerizable substituents) R 4a and R 4b may be hydrocarbon groups [eg, alkyl groups (eg, methyl, ethyl, propyl, isopropyl, A linear or branched C 1-6 alkyl group such as a group, a butyl group or a t-butyl group), an aryl group (eg, a C 6-10 aryl group such as a phenyl group)], a cyano group, A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) etc. are mentioned.
  • alkyl groups eg, methyl, ethyl, propyl, isopropyl, A linear or branched C 1-6 alkyl group such as a group, a butyl group or a t-butyl group
  • an aryl group eg, a C 6
  • an alkyl group for example, a linear or branched C 1-4 alkyl group (particularly a C 1-3 alkyl group such as a methyl group)), a cyano group, a halogen atom are preferable, and an alkyl group is particularly preferable.
  • substitution numbers k1 and k2 of the groups R 4a and R 4b are 0 or an integer of 1 or more and can be selected according to the rings Z 3 and Z 4 .
  • the number of substitutions k1 and k2 can usually be selected from an integer of about 0 to 6, for example, an integer of about 0 to 4 (eg, 0 to 3), preferably an integer of about 0 to 2, and more preferably 0 or 1 , Especially 0.
  • the substitution numbers k1 and k2 in the rings Z 3 and Z 4 may be the same or different from each other, and the types of the groups R 4a and R 4b may be the same or different from each other.
  • the types of the two or more groups R 4a and R 4b in the respective rings Z 3 and Z 4 may be the same or different from each other. Further, the substitution position of the groups R 4a and R 4b is not particularly limited. For example, when the rings Z 3 and Z 4 and the 5-membered ring interposed therebetween form a fluorene ring, the 2-position of the fluorene ring Or 7-position (2-position, 3-position, 7-position, etc.).
  • a halogen atom for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom
  • a hydrocarbon group ⁇
  • an alkyl group a linear or branched C 1-10 alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, preferably Linear or branched C 1-6 alkyl group, more preferably linear or branched C 1-4 alkyl group, etc .
  • cycloalkyl group eg, C 5-10 such as cyclopentyl group, cyclohexyl group, etc.
  • Cycloalkyl group etc. aryl group [eg, phenyl group, alkylphenyl
  • C 6-10 aryl -C 1-4 alkyl group such as a phenethyl group
  • an alkoxy group e.g., Linear or branched C 1-10 alkoxy group such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, t-butoxy group, etc., cycloalkyloxy group (for example, cyclohexyloxy group, etc.) C 5-10 cycloalkyloxy group, etc.), aryloxy group (eg, C 6-10 aryloxy group such as phenoxy group), aralkyloxy group (eg, C 6-10 aryl-C such as benzyloxy group) 1-4 alkyloxy group), alkylthio group (eg, methylthio group, ethylthio group, pro C 1-10 alkylthio such as a pyrthio group, n-butylthio group, t-butyl
  • R 5a and R 5b typically, a halogen atom, a hydrocarbon group (alkyl group, cycloalkyl group, aryl group, aralkyl group), alkoxy group, acyl group, nitro group, cyano group, substituted An amino group etc. are mentioned.
  • R 5a and R 5b include an alkyl group (such as a linear or branched C 1-6 alkyl group such as a methyl group), an aryl group (such as a C 6-14 aryl group such as a phenyl group), an alkoxy group A group (a linear or branched C 1-4 alkoxy group such as a methoxy group), in particular, an alkyl group (particularly a linear or branched C 1-4 alkyl group such as a methyl group), an aryl group (C 6-10 aryl group such as phenyl group).
  • an alkyl group such as a linear or branched C 1-6 alkyl group such as a methyl group
  • an aryl group such as a C 6-14 aryl group such as a phenyl group
  • an alkoxy group A group a linear or branched C 1-4 alkoxy group such as a methoxy group
  • an alkyl group particularly a linear or branched C 1-4
  • the groups R 5a and R 5b are aryl groups
  • the groups R 5a and R 5b may form the ring assembly arene ring together with the rings Z 1 and Z 2 .
  • the types of the groups R 5a and R 5b may be the same or different.
  • the number of substitutions m1 and m2 is 2 or more
  • the types of two or more groups R 2a and R 2b substituted on the same ring Z 1 and Z 2 may be the same or different.
  • the substitution numbers m1 and m2 of the groups R 5a and R 5b may be 0 or an integer of 1 or more, and can be appropriately selected depending on the types of the rings Z 1 and Z 2 .
  • it may be an integer of about 0 to 8, preferably an integer of about 0 to 4 (eg, 0 to 3), more preferably an integer of about 0 to 2 (eg, 0 or 1), particularly 0.
  • the substitution numbers m1 and m2 may be the same or different from each other.
  • the rings Z 1 and Z 2 may be benzene rings, naphthalene rings or biphenyl rings, and the groups R 5a and R 5b may be methyl groups.
  • the alkylene groups R 6a and R 6b include a linear or branched alkylene group.
  • Representative alkylene groups R 6a and R 6b include, for example, a linear or branched alkylene group exemplified in the description relating to the group R 2 in the above formula (1), and a preferable embodiment also includes the group R 2 . It is the same.
  • the types of alkylene groups R 6a and R 6b may be the same or different and are usually the same. is there.
  • the repeating numbers n1 and n2 are 2 or more
  • the types of alkylene groups R 6a and R 6b in the same (meth) acryloyl group-containing group may be different, but are preferably the same.
  • the number of repetitions n1 and n2 of the oxyalkylene group can be selected from 0 or an integer of 1 or more (for example, an integer of about 0 to 20), for example, an integer of about 1 to 15, preferably May be an integer of about 1 to 10 (eg 2 to 8), more preferably an integer of about 3 to 7 (eg 4 to 6).
  • n 1 and n 2 may be the same or different.
  • the number of repeating oxyalkylene groups refers to oxyalkylene in one molecule of a compound. It is used to mean both the number of groups (integer) and the average value (or arithmetic average value, arithmetic average value) of the number of oxyalkylene groups in the molecular assembly of the compound [that is, average added mole number]. Therefore, the repeating numbers n1 and n2 may be an average value (arithmetic average or arithmetic average) in the molecular assembly of the compound represented by the formula (2), and the range is equivalent to the integer range. It may be a degree.
  • the total number of repeating numbers n1 and n2 means the total number (total number of additions) of oxyalkylene groups in one molecule of the fluorene skeleton-containing (meth) acrylate represented by the formula (2), and is simply referred to as n1 + n2. There is a case.
  • n1 + n2 means the total number of all n1 and n2 which exists by the number of p1 and p2, when p1 and / or p2 are two or more.
  • n1 + n2 can be selected from an integer range of about 0 to 30, for example, an integer of about 1 to 25 (eg, 2 to 20), preferably an integer of about 3 to 18 (eg, 4 to 16), Preferably, it may be an integer of about 5 to 14 (eg, 6 to 12), particularly an integer of about 7 to 11 (eg, 8 to 10).
  • n1 + n2 may be an integer as described above, but may be an average added mole number in the molecular assembly of the fluorene skeleton-containing (meth) acrylate represented by the formula (2), and the range thereof is For example, it may be equivalent to the integer range.
  • n1 + n2 When the value of n1 + n2 is too small, the viscosity of the curable composition tends to increase, and the handling property may be lowered. Moreover, there exists a possibility that the scratch resistance of hardened
  • the refractive index can be maintained or improved, so even if the value of n1 + n2 is relatively small. , Can effectively improve handling properties (decrease viscosity).
  • N1 + n2 can be measured by a conventional method. For example, it has a 9,9-bisarylfluorene skeleton used as a raw material in the preparation of the fluorene skeleton-containing (meth) acrylate represented by the formula (2).
  • the ratio of the amount of the hydroxy compound and the amount of alkylene oxide or alkylene carbonate consumed in the reaction can be measured by a method of calculating as an arithmetic average or arithmetic average value (for example, the method described in Patent Document 1). .
  • the groups R 7a and R 7b are a hydrogen atom or a methyl group.
  • group R 7a and R 7b may be the same or different, usually the same.
  • the substitution number p1 and p2 of the (meth) acryloyl group-containing group is an integer of 1 or more, for example, an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2 (especially 1) may be sufficient. If p1 and p2 are too large, the scratch resistance may decrease.
  • substituents which p1 and p2, in each ring Z 1 and Z 2 may be the same or different.
  • (Meth) acryloyl group-containing groups can be substituted in a suitable position on the ring Z 1 and Z 2, for example, when ring Z 1 and Z 2 is a benzene ring, the suitable position 2 to position 6
  • p1 and p2 are 1, it is often substituted at any position of 2-position, 3-position, 4-position (particularly 3-position or 4-position) of the phenyl group .
  • p1 and p2 are 2, when substituted at 2-position and 4-position, 3-position and 4-position, 3-position and 5-position (especially 3-position and 5-position), etc. There are many.
  • the substitution position is not particularly limited.
  • the rings Z 1 and Z 2 are naphthalene rings, they are often substituted at any of the 5- to 8-positions of the naphthyl group.
  • p1 and p2 are 1, The 1-position or 2-position of the naphthalene ring is substituted with respect to the 9-position (substitution is carried out in relation to 1-naphthyl or 2-naphthyl), and the 1,5-position, 2,6 with respect to this substitution position
  • the (meth) acryloyl group-containing group is substituted in a relationship such as a -position (particularly a relationship in the 2,6-position).
  • p1 and p2 are 2 or more, a substitution position is not specifically limited.
  • the substitution position of the (meth) acryloyl group-containing group is not particularly limited.
  • the ring and / or the arene ring adjacent to the arene ring may be substituted.
  • the 3-position or 4-position of the biphenyl rings Z 1 and Z 2 may be bonded to the 9-position of fluorene.
  • (meth) substitution position of acryloyl group-containing groups 2-position of the biphenyl ring, 4-position, 5-position , 6-position, 2′-position, 3′-position, 4′-position, usually 6-position, 3′-position, 4′-position, preferably 6-position, 4 It may be substituted at any position of the '-position (particularly the 6-position).
  • the substitution position of the (meth) acryloyl group-containing group is the 2-position, 3-position, 2′-position of the biphenyl ring.
  • Position, 3′-position, 4′-position usually 2-position, 3′-position, 4′-position, preferably any position of 2-position, 4′-position (Especially 2-position) may be substituted.
  • a substitution position is not specifically limited.
  • the fluorene skeleton-containing (meth) acrylate represented by the formula (2) typically, in the formula (2), the ring Z 3 and Z 4 are benzene rings, that is, the following formula (2a)
  • rings Z 1 and Z 2 , R 4a and R 4b , R 5a and R 5b , R 6a and R 6b , R 7a and R 7b , k1 and k2, m1 and m2, n1 and n2, and p1 and p2 is the same as the formula (2) including preferred embodiments.
  • the compound represented by these is mentioned.
  • 9,9-bis [(meth) acryloyloxyphenyl] fluorenes in the above formula (2a), the ring Z 1 and Z 2 are benzene rings, n1 and n2 are 0, p1 and p2 are 1,
  • 9,9-bis [(meth) acryloyloxyphenyl] fluorene eg, 9,9-bis [4- (meth) acryloyloxyphenyl] fluorene, 9,9-bis [3- (meth) acryloyloxyphenyl) 9,9-bis [(meth) acryloyloxy-mono or dialkylphenyl] fluorene (eg, 9,9-bis [4- (meth) acryloyloxy-3-methylphenyl] fluorene, 9,9) -Bis [4- (meth) acryloyloxy-3-tert-butylphenyl] fluorene, 9,9-bis [4- (meth) Acryl
  • rings Z 1 and Z 2 are benzene rings, and n1 and n2 are 1 to 10 (preferably 1 6), compounds wherein p1 and p2 are 1, for example, 9,9-bis [(meth) acryloyloxy (poly) alkoxyphenyl] fluorene (for example, 9,9-bis [4- (2- (meth)) Acryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloyloxypropoxy) phenyl] fluorene, 9,9-bis [4- (2- (2- (meth) acryloyloxyethoxy) ) ethoxy) phenyl] 9,9-bis fluorene [(meth) acryloyloxy (mono- to deca) C 2-4 alkoxyphen
  • 9,9-bis [(meth) acryloyloxynaphthyl] fluorenes in the above formula (2a), the ring Z 1 and Z 2 are naphthalene rings, n1 and n2 are 0, p1 and p2 are 1,
  • 9,9-bis [(meth) acryloyloxynaphthyl] fluorene eg, 9,9-bis [6- (meth) acryloyloxy-2-naphthyl] fluorene, 9,9-bis [5- (meth)) Acryloyloxy-1-naphthyl] fluorene and the like.
  • rings Z 1 and Z 2 are naphthalene rings, and n1 and n2 are 1 to 10 (preferably 1 6), compounds wherein p1 and p2 are 1, for example, 9,9-bis [(meth) acryloyloxy (poly) alkoxynaphthyl] fluorene (for example, 9,9-bis [6- (2- (meth)) [Acryloyloxyethoxy) -2-naphthyl] fluorene, 9,9-bis [5- (2- (meth) acryloyloxypropoxy) -1-naphthyl] fluorene, 9,9-bis [6- (2- (2- (meth) acryloyloxy) ethoxy) -2-naphthyl] fluorene such as 9,9-
  • fluorene skeleton-containing (meth) acrylates can be used alone or in combination of two or more.
  • the rings Z 1 and Z 2 are benzene rings, n1 and n2 are 1 to 10 (preferably 1 to 6), and p1 and p2 are 1.
  • 9,9-bis [(meth) acryloyloxy (poly) alkoxyphenyl] fluorenes among which 9,9-bis [(meth) acryloyloxy (poly) alkoxyphenyl] fluorene (
  • 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene 9,9-bis [4- (2- (2- (2- (meth) acryloyloxypropoxy) propoxy) phenyl) fluorene 9,9-bis such [(meth) acryloyloxy (mono- to deca) C 2-4 alkoxyphenyl] fluorene ); 9,9-bis [(meth) acryloyloxy (poly) alkoxy-mono or dialkylphenyl] fluorene (eg, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) -3-methylphenyl
  • fluorene skeleton-containing (meth) acrylates may be commercially available or may be prepared by a conventional method (for example, the method described in Patent Document 1).
  • the alicyclic epoxy (meth) acrylate may be a polyfunctional epoxy (meth) acrylate having at least one alicyclic hydrocarbon ring (aliphatic ring), and examples of the aliphatic ring include C Examples thereof include 5-8 cycloalkane rings (eg, cyclopentane ring, cyclohexane ring), C 7-10 bi- or tricycloalkane rings (eg, norbornane ring, adamantane ring, etc.).
  • alicyclic hydrocarbon ring aliphatic ring
  • examples of the aliphatic ring include C Examples thereof include 5-8 cycloalkane rings (eg, cyclopentane ring, cyclohexane ring), C 7-10 bi- or tricycloalkane rings (eg, norbornane ring, adamantane ring, etc.).
  • alicyclic epoxy (meth) acrylate for example, di (meth) acrylate of an epoxy compound having a C 5-10 aliphatic ring such as di (meth) acrylate of 1,4-cyclohexanedimethanol diglycidyl ether. ) Acrylate and the like.
  • di (meth) acrylate of an epoxy compound having a C 5-10 aliphatic ring such as di (meth) acrylate of 1,4-cyclohexanedimethanol diglycidyl ether. ) Acrylate and the like.
  • These alicyclic epoxy (meth) acrylates can be used alone or in combination of two or more.
  • the aromatic epoxy (meth) acrylate may be any polyfunctional epoxy (meth) acrylate having at least an aromatic ring, and examples of the aromatic ring include C 10-14 such as a benzene ring and a naphthalene ring. Examples thereof include a condensed polycyclic arene ring. Since the aromatic epoxy (meth) acrylate has the aromatic ring, it is suitable for obtaining a cured product having a high refractive index.
  • Representative aromatic epoxy (meth) acrylates include, for example, di (meth) acrylates of diglycidyl ethers of biphenols or bisphenols (or their alkylene oxide adducts), poly (meth) acrylates of novolac type epoxy resins. Etc. These aromatic epoxy (meth) acrylates can be used alone or in combination of two or more.
  • Preferred aromatic epoxy (meth) acrylates include di (meth) acrylates of diglycidyl ethers (epoxy compounds) of biphenols or bisphenols (or their alkylene oxide adducts).
  • the biphenols include p, p′-biphenol, m, m′-biphenol, o, o′-biphenol, and the like.
  • the bisphenols include general-purpose bisphenols such as bisphenol A, bisphenol F, bisphenol B, bisphenol AP, bisphenol AF, and bisphenol S.
  • the alkylene oxide include C 2-4 alkylene oxide such as ethylene oxide and propylene oxide, preferably C 2-3 alkylene oxide.
  • the alkylene oxide adduct may be an alkylene carbonate adduct corresponding to the exemplified alkylene oxide.
  • di (meth) acrylates of diglycidyl ethers of typical biphenols or bisphenols (or their alkylene oxide adducts) include aromatic epoxy (meth) acrylates represented by the following formula (3).
  • R 8 represents a hydrogen atom, an alkyl group or an aryl group, respectively, and two R 8 may be bonded to each other to form a hydrocarbon ring which may have an alkyl group, R 9a and R 9b is an alkyl group or an aryl group, R 10a and R 10b are linear or branched alkylene groups, R 11a and R 11b are hydrogen atoms or methyl groups, q1 and q2 are integers of 0 to 4, r1 and r2 is 0 or an integer of 1 or more, and t is 0 or 1.
  • the alkyl group represented by R 8 is, for example, a linear or branched C 1-6 alkyl group such as a methyl group, an ethyl group, an isopropyl group, or a t-butyl group, preferably a linear group.
  • the aryl group for R 8 may be, for example, a C 6-10 aryl group (particularly a phenyl group) such as a phenyl group or a naphthyl group.
  • the type of R 8 may be the same or different.
  • the hydrocarbon ring that may be formed by bonding two R 8 to each other may be a C 5-8 cycloalkane ring such as a cyclopentane ring or a cyclohexane ring.
  • alkyl group which may be substituted on the hydrocarbon ring examples include the alkyl groups exemplified in the section of the alkyl group of R 8 above, and the same may be included including preferred embodiments.
  • the number and position of substitution of the alkyl group substituted on the hydrocarbon ring may be, for example, an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, particularly 0.
  • the substitution position may be substituted, for example, at any position from the 3-position to the 5-position.
  • R 9a and R 9b include the alkyl groups and aryl groups exemplified in R 8 , and may be the same including preferred embodiments.
  • the number of substitutions q1 and q2 of R 9a and R 9b is an integer of 0 to 4, for example, an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, particularly 0. Good.
  • the types of R 9a and R 9b may be the same or different. When q1 and q2 are 2 or more, the types of two or more R 9a and R 9b bonded to the same benzene ring are the same or different. May be.
  • the substitution position of R 9a and R 9b is not particularly limited, and may be substituted at any position (2-position, 3-position, etc.) of the benzene ring.
  • Examples of the linear or branched alkylene group represented by R 10a and R 10b include the straight chain exemplified in the section of R 2 of the formula (1) (and R 6a and R 6b of the formula (2)). Or a branched alkylene group, and the same applies to preferred embodiments. Note that the types of R 10a and R 10b may be the same or different from each other. In addition, when the number of repetitions r1 and r2 of the oxyalkylene group (OR 10a and OR 10b ) is 2 or more, the types of the two or more R 10a and R 10b may be different but are preferably the same. .
  • the total number of r1 and r2 and r1 and r2 [the total number of oxyalkylene groups (total number of additions), sometimes simply referred to as r1 + r2. ] Is the same as the values (integer or average value) exemplified in the terms of n1 and n2 and n1 + n2 in the formula (2), including preferred embodiments. If the value of r1 + r2 is too small, the viscosity of the curable composition tends to increase, and the handling properties may be reduced.
  • the refractive index can be maintained or improved even if a large amount of the first monofunctional (meth) acrylate represented by the above formula (1) is mixed, so even if the value of r1 + r2 is relatively small. , Can effectively improve handling properties (decrease viscosity). If the value of r1 + r2 is too large, the aromatic ring content (for example, the number of moles contained) is also reduced, so that excellent properties such as a high refractive index may be reduced. Note that r1 + r2 may be measured with reference to the method exemplified in the section of n1 + n2 in the formula (2).
  • R 11a and R 11b may be the same or different from each other, and are usually the same.
  • T is 0 or 1, and is preferably 1.
  • the aromatic epoxy (meth) acrylate represented by the formula (3) can be used alone or in combination of two or more.
  • Compounds in which 8 is a hydrogen atom or an alkyl group are preferable.
  • Urethane (meth) acrylate has a main chain skeleton (a skeleton of a urethane oligomer or urethane polymer portion) formed of units derived from a reaction product of a polyol component and a polyisocyanate component.
  • the polyol component may be a low molecular weight polyol component (for example, alkylene glycol such as ethylene glycol), but is preferably a high molecular weight polyol component from the viewpoint of improving scratch resistance in a cured product.
  • the high molecular weight polyol component may be a polymer or an oligomer having a relatively small number of repeating units.
  • the weight average molecular weight (Mw) of the polymer polyol component can be measured by gel permeation chromatography (GPC) or the like, and can be selected from a range of, for example, about 300 or more (for example, 400 to 50000) in terms of standard polystyrene. It may be about 500 to 10000 (for example, 600 to 5000), preferably about 700 to 3000 (for example, 800 to 2000). If the molecular weight (weight average molecular weight) of the polyol component is too low, the scratch resistance of the cured product may be reduced, and if it is too high, the viscosity becomes high and the handling property may be reduced. In the present invention, by combining with the first monofunctional (meth) acrylate, even a relatively high-viscosity polyfunctional (meth) acrylate can be effectively reduced in viscosity.
  • GPC gel permeation chromatography
  • Examples of the high molecular weight polyol component include polyether polyol, polyester polyol, and polycarbonate polyol.
  • Examples of the polyether polyol (particularly, polyether diol) include polyalkylene oxide [or polyalkylene glycols such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide (tetrahydrofuran), etc.
  • C 2-6 alkylene oxide homo- or copolymers eg, polyoxy C 2-6 alkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polyethylene oxide-polypropylene oxide block copolymers, etc., especially polytetra Methylene ether glycol), etc.
  • These polyether polyols can be used alone or in combination of two or more.
  • Polyester polyols include diol components and dicarboxylic acid components [dicarboxylic acids or derivatives thereof (for example, lower alkyl esters (such as C 1-2 alkyl esters such as methyl esters), acid halides, acid anhydrides, etc.) ] Or a lactone (C 3-10 lactone such as ⁇ -caprolactone, ⁇ -valerolactone) or a copolymer (poly- ⁇ -). Caprolactone, etc.), a copolymer of the diol component, dicarboxylic acid component, hydroxyalkanecarboxylic acid and / or lactone, etc.
  • dicarboxylic acid components dicarboxylic acids or derivatives thereof (for example, lower alkyl esters (such as C 1-2 alkyl esters such as methyl esters), acid halides, acid anhydrides, etc.)
  • a lactone C 3-10 lactone such as ⁇ -caprolactone, ⁇ -valerolactone
  • dicarboxylic acid component examples include aromatic dicarboxylic acids (for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid) Alicyclic dicarboxylic acids (e.g., cyclohexane dicarboxylic acid), aliphatic dicarboxylic acids (e.g., adipic acid, straight-chain C 4-12 dicarboxylic acid such as sebacic acid), and derivatives of these dicarboxylic acids.
  • aromatic dicarboxylic acids for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid
  • Alicyclic dicarboxylic acids e.g., cyclohexane dicarboxylic acid
  • aliphatic dicarboxylic acids e.g., adipic acid, straight-chain C 4-12 dicarboxylic acid such as sebacic acid
  • diol component examples include alkanediols (for example, C 2 such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol). such as -10 alkanediol), polyoxyalkylene glycols (e.g., poly alkanediol) polyether diols, such as such as diethylene glycol, alicyclic diols (e.g., 1,4-cyclohexanediol, cyclohexanedimethanol, etc.), etc.
  • alkanediols for example, C 2 such as ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol.
  • polyester polyols include polyester diols having terminal hydroxyl groups such as polyethylene adipate and polydiethylene glycol adipate. , Polypropylene adipate, polytetramethylene adipate, polyhexamethylene adipate, copolymers thereof, etc. These polyester polyols can be used alone or in combination of two or more.
  • polycarbonate polyol examples include a polyol (such as the low molecular weight polyol, polyether polyol, and polyester polyol exemplified above) and a dialkyl carbonate (such as dimethyl carbonate) or alkylene carbonate (such as ethylene carbonate). And polycarbonate diol (for example, polyhexamethylene carbonate diol) obtained by the reaction with).
  • a polyol such as the low molecular weight polyol, polyether polyol, and polyester polyol exemplified above
  • dialkyl carbonate such as dimethyl carbonate
  • alkylene carbonate such as ethylene carbonate
  • polycarbonate diol for example, polyhexamethylene carbonate diol obtained by the reaction with
  • the polyisocyanate component is not particularly limited, and examples thereof include aliphatic polyisocyanates (for example, hexamethylene diisocyanate (HDI), 1,3,6-hexamethylene triisocyanate); alicyclic polyisocyanates [for example, isophorone diisocyanate (for example, IPDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), hydrogenated diphenylmethane-4,4′-diisocyanate (hydrogenated MDI), etc.]; araliphatic polyisocyanates [eg, xylylene diisocyanate (XDI), tetramethylxylylene Range isocyanate (TMXDI) and the like]; aromatic polyisocyanate (eg, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), Lysine diisocyan
  • the polyisocyanate component is a modified product [or derivative such as a multimer (dimer, trimer (triisocyanurate ring, etc.)), carbodiimide body, biuret body, allophanate body, uretdione body, polyamine modified body. Etc.]. These polyisocyanate components can be used alone or in combination of two or more.
  • Typical urethane (meth) acrylates include polyester-type urethane (meth) acrylate, polyether-type urethane (meth) acrylate, and polycarbonate-type urethane (meth) acrylate having a polyol component. These urethane (meth) acrylates can be used alone or in combination of two or more. These urethane (meth) acrylates can effectively improve the scratch resistance of the cured product, and among them, it is preferable to include polyester type urethane (meth) acrylate and / or polyether type urethane (meth) acrylate.
  • the polyester (meth) acrylate can be prepared by a reaction of the same polyester polyol as described above and (meth) acrylic acid, including preferred embodiments.
  • the polyester polyol has an aliphatic monomer component (for example, an aliphatic diol component (such as C 2-12 alkylene glycol such as butylene glycol) and an aliphatic dicarboxylic acid component [adipic acid, C 4-20 alkanecarboxylic acid such as dodecanedioic acid or derivatives thereof (acid halide, acid anhydride, lower alkyl ester, etc.), aliphatic lactone component ( ⁇ -caprolactone, etc.), aliphatic hydroxycarboxylic acid component (3- Etc.) may be formed from units derived from such as hydroxybutyric acid, 5-hydroxyvaleric acid and the like.
  • These polyester polyols can be used alone or in combination of two or more.
  • the content of the high-viscosity polyfunctional (meth) acrylate can be selected from the range of, for example, 10% by weight or more, for example, 30% by weight or more, preferably 50% by weight, based on the entire multifunctional (meth) acrylate. More preferably, it may be 60% by weight or more (for example, 80% by weight or more), in particular, substantially 100% by weight. If the proportion of the high-viscosity polyfunctional (meth) acrylate is too small, the viscosity may not be effectively reduced.
  • these high-viscosity polyfunctional (meth) acrylates may be used alone or in combination of two or more depending on the application, etc., and each characteristic (for example, refractive index, scratch resistance, heat resistance) Property, mechanical properties, etc.) may be adjusted.
  • each characteristic for example, refractive index, scratch resistance, heat resistance
  • a cured product having a high refractive index tends to have a large rigidity and lack flexibility, but in the present invention, both a high refractive index and scratch resistance (flexibility) can be achieved at a high level.
  • a polyfunctional (meth) acrylate is a polyfunctional (meth) acrylate having a 9,9-bisarylfluorene skeleton excellent in optical properties such as a high refractive index (for example, represented by the above formula (2)). Fluorene skeleton-containing (meth) acrylate and the like) and urethane (meth) acrylate excellent in scratch resistance of the cured product.
  • a polyfunctional (meth) acrylate can form a cured product having a high refractive index and excellent scratch resistance in a balanced manner.
  • the ratio of the polyfunctional (meth) acrylate having a 9,9-bisarylfluorene skeleton (for example, the fluorene skeleton-containing (meth) acrylate represented by the formula (2)) and the urethane (meth) acrylate is, for example,
  • the former / the latter (weight ratio) can be selected from a range of about 50/50 to 99/1, for example, 53/47 to 90/10, preferably 55/45 to 80/20, and more preferably 58/42 to It may be about 70/30 (for example, 60/40 to 65/35). If the amount of the polyfunctional (meth) acrylate having a 9,9-bisarylfluorene skeleton is too small, the refractive index of the cured product may be lowered.
  • the multifunctional (meth) acrylate may further contain di (meth) acrylate of an alkylene oxide adduct of biphenols or bisphenols in addition to the high-viscosity multifunctional (meth) acrylate.
  • di (meth) acrylate of an alkylene oxide adduct of biphenols or bisphenols in addition to the high-viscosity multifunctional (meth) acrylate.
  • Such a polyfunctional (meth) acrylate is easy to improve the low viscosity in the curable composition and the high refractive index and scratch resistance in the cured product in a balanced manner.
  • examples of the biphenols, bisphenols, and alkylene oxides include diglycidyl of the biphenols or bisphenols (or their alkylene oxide adducts).
  • Biphenols, bisphenols, and alkylene oxides exemplified in the section of ether di (meth) acrylate are exemplified, and the same applies to preferred embodiments.
  • the total number of oxyalkylene groups (total addition number) (integer or average addition mole number) derived from addition of alkylene oxide (or alkylene carbonate) can be selected from a range of about 1 to 30, for example, 2 to 25 Preferably, it may be about 3 to 20, more preferably about 5 to 15 (for example, 8 to 12). If the total number of oxyalkylene groups is too low, scratch resistance may not be improved.
  • di (meth) acrylate of an alkylene oxide adduct of biphenols or bisphenols examples include, for example, di (meth) acrylate of an alkylene oxide adduct of biphenol [for example, to 1 mol of p, p′-biphenol.
  • adduct di (meth) in which about 2 to 25 mol of C 2-4 alkylene oxide is added to 1 mol biphenols such as di (meth) acrylate in adduct with about 10 mol of ethylene oxide added.
  • di (meth) acrylates of alkylene oxide adducts of bisphenols for example, di (meth) acrylates of adducts in which about 10 mol of ethylene oxide is added to 1 mol of bisphenol A, 1 mol of bisphenol For F, propylene oxide is 0 one mole of C 2-4 di (meth) acrylate adducts of alkylene oxide are added about 2 to 25 mol relative to bisphenol such as di (meth) acrylate of moles added was adduct], and the like It is done.
  • di (meth) acrylates of alkylene oxide adducts of biphenols or bisphenols may be used alone or in combination of two or more.
  • biphenols or di (meth) acrylates of alkylene oxide adducts of bisphenols di (meth) acrylates of alkylene oxide adducts of bisphenols are preferred, and C 2-3 alkylene per mole of bisphenols
  • An adduct di (meth) acrylate added with about 3 to 20 moles of oxide for example, an adduct di (meth) acrylate with about 10 moles of ethylene oxide added to 1 mole of bisphenol A
  • Commercially available products may be used as the di (meth) acrylates of these biphenols or alkylene oxide adducts of bisphenols.
  • weight ratio about 50/50 to 99/1
  • the curable composition of the present invention further includes other monofunctional polymerizable components.
  • (Or monomer) may be included.
  • the curable composition contains other monofunctional polymerizable components to adjust or improve properties such as handling properties (low viscosity), refractive index, and scratch resistance (flexibility) according to the application.
  • Any compound may be used, for example, a monofunctional vinyl monomer [eg, ⁇ -olefin monomer (eg, ethylene, propylene, etc.); styrene monomer (eg, styrene, ⁇ -methylstyrene, vinyl toluene, etc.); vinyl Examples thereof include ester monomers (for example, vinyl acetate); N-vinylpyrrolidone, etc.], monofunctional (meth) acrylic monomers, and the like. These monofunctional polymerizable components can be used alone or in combination of two or more. Of these monofunctional polymerizable components, monofunctional (meth) acrylic monomers are preferred.
  • a monofunctional vinyl monomer eg, ⁇ -olefin monomer (eg, ethylene, propylene, etc.); styrene monomer (eg, styrene, ⁇ -methylstyrene, vinyl toluene, etc.); vinyl Examples thereof include ester monomers (for
  • Examples of the monofunctional (meth) acrylic monomer include (meth) acrylic acid, (meth) acrylamide, N-substituted (meth) acrylamide (for example, N-methylol (meth) acrylamide, N, N-dimethyl (meth) ) Acrylamide), (meth) acrylonitrile, etc., but monofunctional (meth) acrylates are often used.
  • monofunctional (meth) acrylates include aliphatic monofunctional (meth) acrylates [for example, C 1-20 alkyl such as methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.
  • (meth) acrylate, etc.] alicyclic monofunctional (meth) acrylates [e.g., cyclohexyl (meth) C 5-10 cycloalkyl (meth) acrylates such as acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) Bridged cyclic (meth) acrylates such as acrylates, etc.]; aromatic monofunctional (meth) acrylates (however, the monofunctional (meth) acrylates represented by the above formula (1) are not included); sulfur atoms And monofunctional (meth) acrylates containing These monofunctional (meth) acrylates can be used alone or in combination of two or more.
  • alicyclic monofunctional (meth) acrylates e.g., cyclohexyl (meth) C 5-10 cycloalkyl (meth) acrylates such as acrylate, dicyclopentenyl (meth) acrylate, isobornyl (
  • the curable composition contains a sulfur atom because it can improve the handleability of the curable composition and the high refractive index and scratch resistance of the cured product in a well-balanced manner. It is preferable to include a monofunctional (meth) acrylate (sometimes simply referred to as a second monofunctional (meth) acrylate), and the second monofunctional (meth) acrylate has an aromatic ring. You may have. Moreover, from the point which can improve the refractive index of hardened
  • a preferred monofunctional (meth) acrylate may be a monofunctional (meth) acrylate having an aromatic ring and having a sulfur atom.
  • Examples of the second monofunctional (meth) acrylate containing a sulfur atom include alkylthio (meth) acrylate (for example, C 1-6 alkylthio (meth) acrylate such as methylthio (meth) acrylate), arylthio (meta) ) Acrylates (eg C 6-10 arylthio (meth) acrylates such as phenylthio (meth) acrylate), aralkylthio (meth) acrylates (eg C 6-10 aryl C 1-6 alkylthio such as benzylthio (meth) acrylate) (Meth) acrylates), arylthioalkyl (meth) acrylates (eg, C 6-10 arylthio C 2-6 alkyl (meth) acrylates such as phenylthioethyl (meth) acrylate), and the like.
  • alkylthio (meth) acrylate for example, C 1-6 al
  • These 2nd monofunctional (meth) acrylate containing a sulfur atom can also be used individually or in combination of 2 or more types.
  • arylthio can be particularly improved from the viewpoint of improving the handleability of the curable composition and the refractive index and scratch resistance of the cured product.
  • a commercial item etc. may be used for the 2nd monofunctional (meth) acrylate containing such a sulfur atom.
  • the ratio of the first monofunctional (meth) acrylate is too small, the handling property and the refractive index of the cured product may be reduced.
  • aromatic monofunctional (meth) acrylate examples include aryl (meth) acrylate (for example, phenyl (meth) acrylate), aralkyl (meth) acrylate ( For example, benzyl (meth) acrylate, etc.), mono (meth) acrylate of bisphenols (or alkylene oxide adducts thereof) (for example, mono (meth) acrylate of ethylene oxide adducts of bisphenol A), fluorene skeleton ( (Meth) acrylate (for example, 9- (meth) acryloyloxymethylfluorene), the following formula (4)
  • R 12 is a hydrogen atom or a methyl group
  • R 13 is an alkylene group
  • R 14 is an alkyl group
  • Ar 2 is a benzene ring or a ring-arene ring
  • c is an integer of 1 to 4
  • d is 0 or 1 or more.
  • monofunctional (meth) acrylates represented by These third monofunctional (meth) acrylates can be used alone or in combination of two or more.
  • the third represented by the above formula (4) is able to improve the refractive index of the cured product while improving the handleability of the curable composition.
  • the monofunctional (meth) acrylate is preferably included.
  • the group R 12 is a hydrogen atom or a methyl group.
  • the base R 13 is a linear or branched alkylene group, for example, the group R 2 can be exemplified include (as well as radicals R 6a and R 6b) alkylene group exemplified in the preferred embodiment also the radical R 2 (And groups R 6a and R 6b ).
  • the repeating number c of the group (R 13 O) can be selected from an integer of about 1 to 4, for example, an integer of about 1 to 3, preferably 1 or 2, and more preferably 1. If the number of repetitions c is too large, the refractive index of the cured product may be reduced. In addition, when c is 2 or more, two or more groups R 13 may be the same or different.
  • the ring Ar 2 is a benzene ring or a ring assembly arene ring, and examples of the ring assembly arene ring include the ring assembly arene rings exemplified in the rings Z 1 and Z 2.
  • the embodiment is also the same as the ring assembly arene ring of the rings Z 1 and Z 2 .
  • a benzene ring or a biphenyl ring is preferable.
  • the group R 14 is an alkyl group, and examples thereof include the alkyl group exemplified in the group R 3 in the formula (1), and the preferred embodiment is the same as the group R 3 .
  • the substitution number d of the group R 14 may be 0 or an integer of 1 or more, for example, an integer of about 0 to 4, preferably an integer of about 0 to 2, more preferably 0 or 1, particularly 0. .
  • d is 2 or more, the types of the two or more groups R 14 may be the same or different.
  • the substitution position of the group R 14 is not particularly limited.
  • the ring Ar 2 is a benzene ring, and the bonding position of the group [—O— (R 13 O) c —CO—CR 12 ⁇ CH 2 ] is 1
  • the 1-phenyl group may be substituted at any position from 2 to 6-position, for example, any position from 3 to 5-position (for example, 4-position) May be substituted.
  • the ring Ar 2 is a biphenyl ring and the group [—O— (R 13 O) c —CO—CR 12 ⁇ CH 2 ] is bonded to the 2-position, 3 to 6 of the 2-biphenylyl group It may be substituted at any position of the -position and the 2 'to 6'-position.
  • Compound, ie, alkylphenoxyalkyl (meth) acrylate [eg, C 1-12 alkylphenoxy C 2-4 alkyl (meth) acrylate such as 2- (nonylphenoxy) ethyl (meth) acrylate, etc.];
  • third monofunctional (meth) acrylates represented by the formula (4) can be used alone or in combination of two or more.
  • the compound represented by Formula (4) may use a commercial item, for example, an alkylene oxide or alkylene carbonate adduct of phenol or a hydroxy ring assembly polycyclic arene, such as sulfuric acid, may be used. It can be prepared by a method of reacting with (meth) acrylic acid in the presence of an esterification catalyst, a polymerization inhibitor such as hydroquinone and, if necessary, a solvent.
  • the ratio of the first monofunctional (meth) acrylate represented by the formula (1) and the third monofunctional (meth) acrylate represented by the formula (4) is the former / the latter (weight).
  • Ratio) 100/0 to 20/80 (for example, 80/20 to 20/80) or so, for example, 70/30 to 25/75, preferably 65/35 to 30/70 (for example, 60/40 to 35/65), more preferably about 55/45 to 40/60 (for example, 50/50 to 43/57). If the ratio of the first monofunctional (meth) acrylate represented by the formula (1) is too small, the handling property and the refractive index of the cured product may be lowered.
  • the other monofunctional polymerizable component for example, the second monofunctional (meth) acrylate 3rd monofunctional (meth) acrylate (especially 2nd monofunctional (meth) acrylate) etc.
  • the other monofunctional polymerizable components may be the same as described above, including preferred embodiments (representative compounds, ratios with the first monofunctional (meth) acrylate, etc.) and the like.
  • the curable composition may contain a polymerization initiator in addition to the polymerizable component (or monomer component).
  • the polymerization initiator may be a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photo radical generator).
  • thermal polymerization initiator examples include organic peroxides [eg, dialkyl peroxides (eg, di-tert-butyl peroxide), diacyl peroxides (eg, lauroyl peroxide, benzoyl peroxide, etc.), Peracids (or peracid esters) (for example, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peracetate, etc.), ketone peroxides, peroxycarbonates, peroxyketals, etc.], azo Examples include compounds [for example, azonitrile compounds such as 2,2′-azobis (isobutyronitrile), azoamide compounds, azoamidine compounds, etc.]. These thermal polymerization initiators can be used alone or in combination of two or more.
  • organic peroxides eg, dialkyl peroxides (eg, di-tert-butyl peroxide), diacyl peroxides (eg, lauroy
  • photopolymerization initiator examples include benzoins (for example, benzoin alkyl ethers such as benzoin and benzoin ethyl ether) and acetophenones (for example, acetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1- ), Aminoacetophenones ⁇ eg 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone-1 ⁇ , anthraquinones (eg anthraquinone, 2-methylanthraquinone etc.), Thioxanthones (eg, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, etc.), ketals (eg, acetophenone dimethyl ketal, benzyldimethyl ketal, etc.), benzophenones (eg, Benzophenone), such as x
  • the ratio of the polymerization initiator is 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight (for example, 1 to 1 part by weight based on 100 parts by weight of the total amount of the polymerizable components). 8 parts by weight), more preferably about 2 to 5 parts by weight.
  • the photopolymerization initiator may be combined with a photosensitizer.
  • the photosensitizer include tertiary amines ⁇ eg, trialkylamine, trialkanolamine (eg, triethanolamine), ethyl N, N-dimethylaminobenzoate [eg, p- (dimethylamino). ) Ethyl benzoate, etc.], N, N-dimethylaminobenzoic acid amyl [eg, p- (dimethylamino) benzoic acid amyl etc.], etc., dialkylaminobenzoic acid alkyl esters, 4,4-bis (diethylamino) benzophenone, etc.
  • photosensitizers such as bis (dialkylamino) benzophenone, dialkylaminobenzophenone such as 4- (dimethylamino) benzophenone ⁇ and the like. These photosensitizers may be used alone or in combination of two or more.
  • the ratio of the photosensitizer may be 1 to 200 parts by weight, preferably 5 to 150 parts by weight, and more preferably about 10 to 100 parts by weight with respect to 100 parts by weight of the polymerization initiator.
  • the curable composition may contain the solvent as needed.
  • the solvent is not particularly limited.
  • hydrocarbons for example, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, etc.
  • Halogenated hydrocarbons eg, methylene chloride, chloroform, 1,2-dichloroethane, etc.
  • ethers eg, dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran, dioxane, etc.
  • ketones eg, , Dialkyl ketones such as acetone and methyl ethyl ketone, cyclic ketones such as cyclohexanone, etc .
  • esters eg, acetate esters such as methyl acetate, ethyl acetate, butyl
  • the curable composition can be prepared by using conventional additives such as colorants, stabilizers (thermal stabilizers, antioxidants, ultraviolet absorbers, etc.), fillers, antistatic agents, flame retardants, surfactants, plasticizers.
  • additives such as colorants, stabilizers (thermal stabilizers, antioxidants, ultraviolet absorbers, etc.), fillers, antistatic agents, flame retardants, surfactants, plasticizers.
  • An agent, a curing agent, a polymerization inhibitor and the like may be included. These additives can be used alone or in combination of two or more.
  • the curable composition of this invention hardens
  • active energy thermal energy and / or light energy (for example, ultraviolet rays, X-rays, etc.) are useful.
  • the heating temperature may be, for example, 50 to 200 ° C., preferably 60 to 150 ° C., more preferably about 70 to 120 ° C.
  • the amount of light irradiation energy can be appropriately selected according to the application, for example, 50 to 10000 mJ / cm 2 , preferably 70 to 8000 mJ / cm 2. More preferably, it may be about 100 to 5000 mJ / cm 2 (for example, 500 to 3000 mJ / cm 2 ).
  • the shape of the cured product is not particularly limited, and may be a cured product having a three-dimensional structure (for example, a lens), a cured product having a two-dimensional structure (or a cured film) (for example, a film or a sheet), a primary
  • the cured product may have a base structure (for example, linear, rod-like, tubular, etc.).
  • the method for producing a cured product is not particularly limited.
  • the curable composition is molded according to the shape of the cured product or in a predetermined mold. After being cast (injected), it may be produced by curing (heating and / or light irradiation).
  • the curable composition is used as a base material or a substrate [for example, metal (for example, aluminum), ceramics (for example, titanium oxide, glass, quartz, etc.), etc.
  • Inorganic materials organic materials such as plastics (for example, cyclic olefin-based resins, polycarbonate-based resins, etc., porous materials such as wood, etc.) to form a film-like coating film (or thin film), You may manufacture by giving a hardening process.
  • plastics for example, cyclic olefin-based resins, polycarbonate-based resins, etc., porous materials such as wood, etc.
  • the curable composition of the present invention contains a polyfunctional (meth) acrylate and the first monofunctional (meth) acrylate represented by the formula (1), it has a relatively low viscosity, It has excellent handling properties and can form a cured product having a high refractive index.
  • the viscosity (temperature 25 ° C.) of the curable composition may be, for example, about 1 to 500,000 mPa ⁇ s (for example, 50 to 100,000 mPa ⁇ s), depending on the type of polyfunctional (meth) acrylate, etc.
  • it can be selected from a range of about 1 to 50000 mPa ⁇ s (for example, 5 to 25000 mPa ⁇ s), for example, 10 to 20000 mPa ⁇ s (for example, 20 to 10000 mPa ⁇ s), preferably 30 to 6000 mPa ⁇ s (for example, 50 to 2000 mPa ⁇ s), more preferably about 70 to 1000 mPa ⁇ s (for example, 90 to 300 mPa ⁇ s).
  • a viscosity can be effectively reduced by combining with 1st monofunctional (meth) acrylate.
  • the viscosity (temperature 60 ° C.) of the curable composition can be selected from a range of about 100 Pa ⁇ s or less (eg, 0.1 to 50 Pa ⁇ s), for example, 30 Pa ⁇ s or less (eg, 1 to 1). 27 Pa ⁇ s), preferably about 25 Pa ⁇ s or less (eg, 10 to 23 Pa ⁇ s).
  • the viscosity can be measured by the method described in Examples described later.
  • the refractive index (refractive index before curing) (temperature 25 ° C., wavelength 589 nm) of the curable composition before curing can be selected from the range of about 1.5 to 1.7, for example, 1.52 to 1. It may be 65 (for example, 1.53 to 1.62), preferably 1.54 to 1.61, and more preferably about 1.55 to 1.60.
  • the curable composition usually has a tendency to improve the refractive index by curing, and a curable composition prepared by heating and mixing 3 parts by weight of a photopolymerization initiator with respect to 100 parts by weight of the polymerizable component is prepared.
  • the refractive index (temperature 25 ° C., wavelength 589 nm) of a cured product cured by UV irradiation (500 mJ / cm 2 ) (for example, a cured product cured by the method described in the Examples section below) is, for example, 1. It can be selected from a range of about 5 to 1.7, and may be, for example, about 1.52 to 1.66, preferably 1.54 to 1.63, and more preferably about 1.56 to 1.6.
  • a refractive index can be measured by the method as described in the Example mentioned later.
  • viscosity Using a TV-22 type viscometer (cone plate type, “TVE-22L” manufactured by Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. was measured using an optional rotor (01: 1 ° 34 ′ ⁇ R24, 07: 3 ° ⁇ R7.7) was selected, and the measurement was performed at a rotational speed of 0.5 to 20 rpm.
  • the viscosity at 60 ° C. was measured using an E-type melt viscometer (“CAP2000 +” manufactured by BROOK FIELD).
  • the obtained solution was washed with 20% by weight saline solution, neutralized with 10% by weight sodium hydroxide aqueous solution and 20% by weight saline solution, and it was confirmed that the aqueous layer had a pH of 10 or more. Thereafter, 500 ppm of 4-methoxyphenol was added to the organic layer to homogenize the solution. This solution was washed twice with 20% by weight saline and three times with distilled water. After confirming that the aqueous layer had a pH of 7, the organic layer was concentrated and filtered through Celite. After filtration, the filtrate was concentrated and dried to obtain NEOA as a powdery white solid.
  • NEOA had a refractive index (25 ° C., 589 nm) of 1.59 and a melting point of 62 ° C. The melting point was measured with a differential scanning calorimeter (DSC) (“EXSTAR DSC 6220” manufactured by SII Nanotechnology Inc.).
  • DSC differential scanning calorimeter
  • the comparative example maintains a relatively high refractive index and has a viscosity of the same level even though it contains a large amount of diluent, as compared with the Comparative Examples. Can be reduced.
  • POA is a transparent liquid like a general reactive diluent
  • NEOA is a powdery white solid that does not exhibit fluidity at all, and has a viscosity. Only when mixed with BPEFA, which was a solid, became liquid and showed low viscosity, which was a very surprising result.
  • FIG. 2 are equations showing approximate lines based on the measured values of Comparative Examples 1 to 5 and Examples 1 to 5, where x is the mixing ratio of each reactive diluent and y is the refractive index or viscosity.
  • x is the mixing ratio of each reactive diluent
  • y is the refractive index or viscosity.
  • the approximate line was calculated using “Microsoft Excel (Microsoft Office Standard 2010)” manufactured by Microsoft Corporation, linear approximation was used for the refractive index, and power approximation was used for the viscosity.
  • the viscosity of the curable composition that achieves each target refractive index is lower than that in the BPEFA / POA blending system, and in particular, the target refractive index is large. It turns out that the difference in viscosity becomes very large. Moreover, in the BPEFA / NEOA blending system, it can be seen that the proportion of the reactive diluent is large in the blending ratio for achieving the target refractive index, and the use proportion of BPEFA can be reduced.
  • each prepared curable composition (polymerizable component), and the mixture was heated and melted and mixed.
  • Each obtained curable composition was applied on a TAC (cellulose acetate) film to a film thickness of 200 ⁇ m using an applicator, and UV irradiation (500 mJ / cm 2 ) was performed once to prepare a cured product. .
  • Each of the obtained cured products was a film having a film thickness of 100 ⁇ m, and the refractive index (after curing) was measured using this cured product.
  • a mold is placed on the glass to which the release agent is attached by spraying, and each curable composition mixed with the photopolymerization initiator is poured into this mold, and the mold is sandwiched between the glass subjected to the same treatment, UV irradiation (500 mJ / cm 2 ) was repeated four times to produce a cured product having a size of 50 mm ⁇ 15 mm ⁇ 2 mm. Scratch resistance was measured using the obtained cured product.
  • Table 3 shows the blending ratio and evaluation results.
  • the number in () of Table 3 means the weight part of each structural component in a curable composition (hereinafter, Table 4 is also the same).
  • Comparative Example 6 has a high refractive index, but has a high viscosity, so that the handling property is not sufficient, and the handling property and the high refractive index cannot be achieved at the same time. On the other hand, Example 6 has excellent handling properties and high refractive index while maintaining scratch resistance.
  • each of the properties is different because it contains a soft bifunctional (meth) acrylate or maintains a relatively good handling property and achieves both a high refractive index and scratch resistance. Excellent balance.
  • the UV-3200B mixed in Example 7 shows relatively good handling properties even though the viscosity at 60 ° C. is as high as 40,000 to 60,000 mPa ⁇ s.
  • Examples 9 to 12 other monofunctional acrylates (second monofunctional (meth) acrylate containing a sulfur atom or third monofunctional (meth) represented by the above formula (3)) are used. (Acrylate) in combination achieves both excellent handling properties and a high refractive index. In particular, in Example 10, not only the handling property and the high refractive index are compatible at a high level, but also the scratch resistance is improved.
  • cured products of the respective curable compositions prepared by the same method as in Comparative Example 6 and Examples 6 to 12 (a cured film having a film thickness of 100 ⁇ m and a cured product having a size of 50 mm ⁇ 15 mm ⁇ 2 mm) Were used, and the refractive index (after curing) and scratch resistance were measured using these cured products.
  • Table 4 shows the blending ratio and the evaluation results.
  • the curable composition of the present invention is excellent in properties such as low viscosity, high refractive index, and scratch resistance, it can be used in various applications.
  • ink materials for example, light emitting materials (for example, organic EL light emitting materials), organic semiconductors, graphitized precursors, gas separation membranes (for example, CO 2 gas separation membranes), coating agents (for example, LEDs (light emitting diodes))
  • Optical overcoat agent or hard coat agent such as a coating agent for an optical element
  • lens eg, pickup lens (eg, pickup lens for DVD (digital versatile disk)), micro lens (eg, for liquid crystal projector) Micro lenses, etc.), spectacle lenses, etc.]
  • polarizing films eg, polarizing films for liquid crystal displays
  • antireflection films or antireflection films, eg, antireflection films for display devices
  • touch panel films flexible substrates Film
  • display film for example, PDP ( Laser display), LCD (liquid crystal display), VFD (vacuum fluorescent display
  • the curable composition of the present invention can be suitably used for optical material applications.
  • the shape of such an optical material include a film shape (or sheet shape), a plate shape, a lens shape, and a tubular shape. It is done.
  • first monofunctional (meth) acrylate of the present invention can also be used as a viscosity reducing agent for reducing the viscosity of the polyfunctional (meth) acrylate.

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Abstract

L'invention concerne : une composition durcissable capable de former un produit durci qui présente un indice de réfraction élevé ; et un produit durci de cette composition durcissable. Cette composition durcissable contient un (méth)acrylate polyfonctionnel et un (méth)acrylate monofonctionnel représentés par la formule (1). (Dans la formule, R1 représente un atome d'hydrogène ou un groupe méthyle ; R2 représente un groupe alkylène ; R3 représente un groupe alkyle ; Ar1 représente un cycle arène polycyclique condensé ; a représente un entier de 1 à 4 ; et b représente 0 ou un entier égal ou supérieur à 1.)
PCT/JP2016/076818 2015-09-16 2016-09-12 Composition durcissable et produit durci de cette dernière WO2017047547A1 (fr)

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WO2017209004A1 (fr) * 2016-05-30 2017-12-07 日産化学工業株式会社 Agent de faible viscosité pour un composé polymérisable ayant un indice de réfraction élevé et composition polymérisable le contenant
EP4043502A1 (fr) * 2021-02-11 2022-08-17 Xetos AG Composition hoe photopolymérisable

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WO2017209004A1 (fr) * 2016-05-30 2017-12-07 日産化学工業株式会社 Agent de faible viscosité pour un composé polymérisable ayant un indice de réfraction élevé et composition polymérisable le contenant
EP4043502A1 (fr) * 2021-02-11 2022-08-17 Xetos AG Composition hoe photopolymérisable
WO2022171821A1 (fr) * 2021-02-11 2022-08-18 Xetos Ag Composition d'eoh photopolymérisable

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