WO2013022065A1 - (meth)acrylate multifonctionnel ayant un squelette de fluorène et composition durcissable le contenant - Google Patents

(meth)acrylate multifonctionnel ayant un squelette de fluorène et composition durcissable le contenant Download PDF

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WO2013022065A1
WO2013022065A1 PCT/JP2012/070351 JP2012070351W WO2013022065A1 WO 2013022065 A1 WO2013022065 A1 WO 2013022065A1 JP 2012070351 W JP2012070351 W JP 2012070351W WO 2013022065 A1 WO2013022065 A1 WO 2013022065A1
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meth
acrylate
polyfunctional
formula
fluorene
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PCT/JP2012/070351
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English (en)
Japanese (ja)
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渓子 三ノ上
佐季子 福西
信輔 宮内
長嶋　太一
光宏 服部
祐一郎 安田
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大阪ガスケミカル株式会社
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Priority to CN201280039281.0A priority Critical patent/CN103890018B/zh
Priority to JP2013528066A priority patent/JP6158084B2/ja
Priority to KR1020147006073A priority patent/KR101868665B1/ko
Publication of WO2013022065A1 publication Critical patent/WO2013022065A1/fr

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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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings 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
    • C08F220/26—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
    • 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
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
    • C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Definitions

  • the present invention relates to a novel multifunctional (meth) acrylate having scratch resistance, a curable composition containing this multifunctional (meth) acrylate, and a cured product thereof.
  • a curable material that can be used as an optical material a polyfunctional (meth) acrylate having a fluorene skeleton (particularly a 9,9-bisarylfluorene skeleton) that is a material having a high refractive index and heat resistance (for example, 9 , 9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene and the like) have been proposed.
  • Patent Document 1 JP-A-2007-91870 discloses a polyfunctional (meth) acrylate as a constituent of the polymerizable composition. Following formula (1)
  • R 1a , R 1b , R 2a and R 2b represent a substituent
  • R 3a and R 3b represent an alkylene group
  • R 4a and R 4b represent a hydrogen atom or a methyl group
  • k 1 and k 2 represent Identical or different and represent an integer of 0 to 4
  • m1 and m2 are identical or different and represent an integer of 0 to 3
  • n1 and n2 are identical or different and represent an integer of 0 or 1
  • p1 and p2 are the same
  • it is different and represents an integer of 1 to 4 where m1 + p1 and m2 + p2 are each an integer of 1 to 5
  • the compound represented by these is disclosed.
  • n1 and n2 corresponding to the number of oxyalkylene groups (R 3a , R 3b ) (or the number of added moles of alkylene oxide) in Formula (1) is 1 is described.
  • such a polyfunctional (meth) acrylate is inferior in scratch resistance.
  • an object of the present invention is to provide a multifunctional (meth) acrylate having a novel fluorene skeleton having scratch resistance, a curable composition containing the multifunctional (meth) acrylate, and a cured product thereof. is there.
  • Another object of the present invention is to provide a polyfunctional (meth) acrylate having a novel fluorene skeleton capable of achieving both a high refractive index and scratch resistance, a curable composition containing this polyfunctional (meth) acrylate, and curing thereof.
  • Still another object of the present invention is to provide a polyfunctional (meth) acrylate having a novel fluorene skeleton capable of balancing handling and curability in a well-balanced manner, a curable composition containing the polyfunctional (meth) acrylate, and its It is to provide a cured product.
  • the present inventors have intensively studied to achieve the above problems, and as a result, surprisingly, excellent scratch resistance can be imparted by setting the number of oxyalkylene groups added within a specific range. Moreover, the expected decrease in the refractive index by increasing the number of oxyalkylene groups added and the characteristics that are usually considered difficult to achieve at the same time, that is, excellent scratch resistance and high refractive index, are at a high level.
  • a polyfunctional (meth) acrylate that can be realized by the above-mentioned method is obtained, and such a polyfunctional (meth) acrylate has a relatively low viscosity and good curability, and further improves handling properties (low).
  • the present inventors have found that a curable composition capable of maintaining excellent scratch resistance and high refractive index can be obtained even when used in combination with other monomers, for example, for increasing the viscosity.
  • the polyfunctional (meth) acrylate of the present invention has the following formula (1)
  • R 1a and R 1b are non-radically polymerizable substituents
  • R 2a and R 2b are alkylene groups
  • R 3a and R 3b are hydrogen atoms or methyl groups
  • R 4a and R 4b are non-radical polymerizable substituents.
  • K1 and k2 are each an integer of 0 to 4
  • m1 and m2 are each an integer of 0 or more
  • n1 and n2 are each an integer of 1 to 4
  • p1 and p2 are each an integer of 0 to 4.
  • the average value of m1 + m2 is 8.5 to 17 polyfunctional (meth) acrylate.
  • n1 and n2 may each be 1, m1 and m2 may each be 1 or more, and the average value of m1 + m2 may be 8.5 to 16.5 (for example, 9 to 15) .
  • the average value of m1 + m2 may be 9.5 to 11.5 (for example, 10 to 11).
  • R 5a and R 5b represent a hydrogen atom or a (meth) acryloyl group
  • R 1a , R 1b , R 2a , R 2b , R 4a , R 4b , k1, k2, m1, m2, n1, n2, p1, p2 are the same.
  • at least one of R 5a and R 5b is (meth) acryloyl groups, all of R 5a and R 5b are (meth) never becomes acryloyl group.
  • the polyfunctional (meth) acrylate composition containing the compound represented by these is included.
  • polyfunctional (meth) acrylate composition has the following formula (A)
  • R 1a , R 1b , R 2a , R 2b , R 4a , R 4b , k1, k2, m1, m2, n1, n2, p1, and p2 are the same as above. It can obtain by making the compound (polyhydroxy compound) represented by and (meth) acrylic acid component react.
  • the ratio of the compound represented by the formula (2) is represented by, for example, the polyfunctional (meth) acrylate represented by the formula (1) and the formula (2).
  • the area ratio (area ratio or area%) by high performance liquid chromatography may be about 5 to 30% with respect to the total amount of the compound.
  • n1 and n2 are each 1
  • m1 and m2 are each 1 or more
  • the average value of m1 + m2 is 9 to 15
  • the ratio of the compound represented by formula (1) is the ratio of the area by high performance liquid chromatography (area ratio) to the total amount of the polyfunctional (meth) acrylate represented by formula (1) and the compound represented by formula (2).
  • Or area%) may be about 8 to 20%.
  • the multifunctional (meth) acrylate (or multifunctional (meth) acrylate composition, hereinafter the same) of the present invention has a low viscosity despite being a high refractive index.
  • the refractive index ( 589 nm) may be 1.53 or more, and the viscosity (25 ° C.) may be 20000 mPa ⁇ s or less.
  • the present invention includes a curable composition containing a curable component including the polyfunctional (meth) acrylate or the polyfunctional (meth) acrylate composition.
  • the curable component may be composed only of a polyfunctional (meth) acrylate, and may further contain a non-fluorene-based monofunctional monomer (that is, multifunctional). (Meth) acrylate and non-fluorene-based monofunctional monomer may be used).
  • the non-fluorene monofunctional monomer may contain a monofunctional (meth) acrylate, typically a branched alkyl (meth) acrylate, an alicyclic (meth) acrylate, or an aromatic (meth) acrylate. And at least one monofunctional (meth) acrylate selected from sulfur-containing (meth) acrylates.
  • the non-fluorene-based monofunctional monomer may contain at least one monofunctional (meth) acrylate selected from aromatic (meth) acrylate and sulfur-containing (meth) acrylate.
  • Non-fluorene monofunctional monomers are aryl (meth) acrylate, aralkyl (meth) acrylate, aryloxyalkyl (meth) acrylate, aryloxy (poly) alkoxyalkyl (meth) acrylate, alkylaryloxy (poly) alkoxy Monofunctional (meth) acrylate (A) selected from alkyl (meth) acrylate, arylthio (meth) acrylate, aralkylthio (meth) acrylate, and arylthioalkyl (meth) acrylate, and arylaryloxyalkyl (meth) Selected from acrylates, arylaryloxy (poly) alkoxyalkyl (meth) acrylates, and mono (meth) acrylates of bisphenols or their alkylene oxide adducts Functional (meth) acrylate (B) and may contain.
  • A selected from alkyl (meth) acrylate, ary
  • the scratch resistance can be maintained at a high level.
  • the curable component may further contain a non-fluorene bifunctional (meth) acrylate.
  • the ratio of the polyfunctional (meth) acrylate (or polyfunctional (meth) acrylate composition) to the non-fluorene bifunctional (meth) acrylate is, for example, the former / the latter (Weight ratio) may be about 99/1 to 50/50.
  • the curable component may further contain another fluorene-based monomer, for example, a compound represented by the following formula (3).
  • R 6 is a direct bond or a divalent hydrocarbon group
  • R 7 is a substituent
  • m 3 is an integer of 0 or more
  • q is 0 or 1
  • R 1a , R 1b , R 2a , R 3a , k1 and k2 are the same as above.
  • the present invention includes a cured product obtained by curing the curable composition. Since such a cured product has a high refractive index and excellent scratch resistance, the cured product for optical use that requires them, such as a prism sheet (for example, a prism sheet for a liquid crystal display) A cured product (or a touch panel sheet) for use in a prism sheet) or a touch panel (for example, a liquid crystal display touch panel) may be used.
  • a prism sheet for example, a prism sheet for a liquid crystal display
  • a cured product (or a touch panel sheet) for use in a prism sheet) or a touch panel (for example, a liquid crystal display touch panel) may be used.
  • the present invention further includes a method for producing the cured product in which active energy is applied to the curable composition to be cured.
  • the scratch resistance of a cured product containing a polyfunctional (meth) acrylate having a fluorene skeleton can be improved. Therefore, the present invention includes the following formula (1A)
  • R 1a and R 1b are non-radically polymerizable substituents
  • R 2a and R 2b are alkylene groups
  • R 3a and R 3b are hydrogen atoms or methyl groups
  • R 4a and R 4b are non-radical polymerizable substituents.
  • K1 and k2 are each an integer of 0 to 4
  • m1 and m2 are each an integer of 0 or more
  • n1 and n2 are each an integer of 1 to 4
  • p1 and p2 are each an integer of 0 to 4.
  • n1 + p1 ⁇ 5, n2 + p2 ⁇ 5. Is a method for improving or improving the scratch resistance of a cured product obtained by curing a curable composition comprising a curable component composed of a polyfunctional (meth) acrylate represented by formula (1A): m1 + m2 A method for improving or improving the scratch resistance is also included, in which the average value is adjusted to 8.5 to 17.
  • the scratch resistance may be improved or improved while the refractive index (589 nm) at 25 ° C. is 1.53 or more and the viscosity (25 ° C.) is 20000 mPa or less.
  • polyfunctional (meth) acrylate represented by formula (1) means “aggregate” or “molecular aggregate” of compounds belonging to the category of formula (1), and m1 + m2 Such a value may mean an average value in such an “aggregate” or “molecular aggregate”.
  • scratch resistance can be imparted to a polyfunctional (meth) acrylate having a fluorene skeleton.
  • a polyfunctional (meth) acrylate can maintain a high refractive index, and can achieve both a high refractive index and scratch resistance.
  • scratch resistance and high refractive index are not unexpectedly damaged (or high levels) even in combination with other curable monomers (for example, non-fluorene (meth) acrylate). Therefore, a curable composition that can realize scratch resistance and high refractive index can be easily formed according to a desired viscosity (handling property).
  • handling property can be improved (viscosity reduction), without impairing sclerosis
  • the polyfunctional (meth) acrylate (polyfunctional (meth) acrylate aggregate) of the present invention has the following formula (1):
  • R 1a and R 1b are non-radically polymerizable substituents
  • R 2a and R 2b are alkylene groups
  • R 3a and R 3b are hydrogen atoms or methyl groups
  • R 4a and R 4b are non-radical polymerizable substituents.
  • K1 and k2 are each an integer of 0 to 4
  • m1 and m2 are each an integer of 0 or more
  • n1 and n2 are each an integer of 1 to 4
  • p1 and p2 are each an integer of 0 to 4.
  • the average value of m1 + m2 is a polyfunctional (meth) acrylate represented by (or a compound represented by the above formula (1) or an aggregate of polyfunctional (meth) acrylates).
  • the polyfunctional (meth) acrylate is adjusted to a specific range with respect to the entire polyfunctional (meth) acrylate (aggregate).
  • the groups R 1a and R 1b may be non-radical polymerizable groups such as cyano group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), carboxyl group, hydrocarbon, etc.
  • Group for example, alkyl group, aryl group (C 6-10 aryl group such as phenyl group) and the like], and the like.
  • alkyl group examples include C 1-12 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C 1-8 alkyl group, particularly a C 1-1 such as a methyl group). 4 alkyl group) and the like.
  • k1 or k2 is plural (2 to 4)
  • the plural groups R 1a or R 1b may be different from each other or the same.
  • the groups R 1 and R 1b may be the same or different.
  • the bonding position (substitution position) of the groups R 1a and R 1b is not particularly limited, and examples thereof include the 2nd, 7th, 2nd and 7th positions of the fluorene ring.
  • the preferred substitution number k1 or k2 is 0 to 1, in particular 0.
  • the substitution numbers k1 and k2 may be the same or different.
  • examples of the alkylene group represented by the groups R 2a and R 2b include C 2-6 alkylene such as ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, and tetramethylene group.
  • a group preferably a C 2-4 alkylene group, more preferably a C 2-3 alkylene group, particularly an ethylene group.
  • the alkylene group may be composed of different alkylene groups, and usually may be composed of the same alkylene group.
  • the groups R 2 and R 2b may be the same or different and may usually be the same.
  • m1 and m2 which are the substitution numbers of the oxyalkylene group corresponding to these alkylene groups may be the same or different.
  • the number of oxyalkylene groups (OR 2a and OR 2b ) (addition moles) m1 and m2 may be any integers of 0 or more, for example, selected from the range of about 0 to 30 (eg, 0 to 25). Usually 1 or more (eg 1 to 22), preferably 2 or more (eg 2 to 20), more preferably 2 to 15 (eg 2 to 10), especially 3 to 8 (eg 3 to 7). ) Degree.
  • the total of m1 and m2 with respect to the entire polyfunctional (meth) acrylate is within a specific range. adjust.
  • the sum of m1 and m2 (m1 + m2) can be selected from the range of 8.5 to 17 (for example, 8.5 to 16.7) as an average (arithmetic average or arithmetic average). 5 to 16.5 (eg, 8.6 to 16.3), preferably 8.8 to 16.2 (eg, 8.9 to 16), and more preferably 9 to 15.8 (eg, 9.1).
  • the average of m1 + m2 is, for example, 9 to 13 (eg, 9.3 to 12.5), preferably 9.5 to 12 (eg, 9.7 to 11.7), and more preferably 10 to 11. It may be about 5 (for example, 10.2 to 11.3), and usually about 9.5 to 11.5 (for example, 10 to 11). If the value of m1 + m2 is too large, a cured product having a sufficient refractive index cannot be obtained.
  • Each value of m1 and m2 can be selected from an average (arithmetic average or arithmetic average), for example, in the range of 4.1 to 8.5 (eg, 4.2 to 8.4). 4.3 to 8.3 (eg 4.3 to 8.2), preferably 4.4 to 8.1 (eg 4.4 to 8), more preferably 4.5 to 7.9 (eg 4.5 to 7.8), particularly 4.6 to 7.8 (for example, 4.8 to 7.6).
  • an average arithmetic average or arithmetic average
  • the average (arithmetic average or arithmetic average) can be measured by a conventional method, and the measurement method is not particularly limited.
  • a polyhydroxy compound (a compound represented by the formula (A) described below) described below can be used.
  • it is easily obtained as an arithmetic average or arithmetic average value from the ratio of the amount of the starting compound (compound represented by the formula (B) described later) and the amount of the consumed alkylene oxide. be able to.
  • the groups R 3a and R 3b may be different from each other, but they may usually be the same group (that is, a hydrogen atom or a methyl group).
  • the number of substitutions n1 and n2 may be 1 to 4, for example, 1 to 3, preferably 1 to 2, particularly 1. Also good.
  • the numbers of substitutions n1 and n2 may be the same or different and are usually the same in many cases.
  • substitution position of the (meth) acryloyl group-containing group is not particularly limited, and it may be substituted at an appropriate substitution position on the benzene ring.
  • the (meth) acryloyl group-containing group may be substituted at an appropriate position (especially at least the 4th position) of the 2-6th position of the benzene ring substituted at the 9th position of fluorene.
  • the compound represented by a formula may be sufficient.
  • R 1a , R 1b , R 2a , R 2b , R 3a , R 3b , R 4a , R 4b , k1, k2, m1, m2, p1, and p2 are the same as above.
  • the substituents R 4a and R 4b are usually non-radically polymerizable substituents such as alkyl groups (for example, C 1-12 alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl groups, preferably C 6, such as C 5-8 cycloalkyl group etc.), an aryl group (e.g., phenyl group, tolyl group, xylyl group, naphthyl group, such as C 1-8 an alkyl group), a cycloalkyl group (cyclohexyl group is -10 and aryl group), a hydrocarbon group such as an aralkyl group (a benzyl group and C 6-10
  • a group such as an alkylthio group such as a C 1-8 alkylthio group such as a methylthio group) —SR 5 (wherein R 5 is as defined above); an acyl group (such as a C 1-6 acyl group such as an acetyl group) ); Alkoxycarbonyl group (C 1-4 alkoxy-carbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.); nitro group; cyano group; substituted amino group (for example, And a dialkylamino group such as a dimethylamino group).
  • R 5 is as defined above
  • an acyl group such as a C 1-6 acyl group such as an acetyl group
  • Alkoxycarbonyl group C 1-4 alkoxy-carbonyl group such as methoxycarbonyl group
  • halogen atom fluorine atom, chlorine atom
  • R 4a and R 4b include, for example, a hydrocarbon group [eg, alkyl group (eg, C 1-6 alkyl group), cycloalkyl group (eg, C 5-8 cycloalkyl group), aryl group (eg, , C 6-10 aryl group), aralkyl group (eg C 6-8 aryl-C 1-2 alkyl group)], alkoxy group (C 1-4 alkoxy group etc.) and the like.
  • R 4a and R 4b are preferably an alkyl group [C 1-4 alkyl group (especially methyl group) etc.], an aryl group [eg C 6-10 aryl group (especially phenyl group)], etc. .
  • the groups R 4a or R 4b may be different from each other or the same.
  • the groups R 4a and R 4b may be the same or different.
  • the preferred substitution numbers p1 and p2 may be, for example, 0 to 3, preferably 0 to 2, and more preferably 0 to 1, respectively.
  • the substitution numbers p1 and p2 may be the same or different from each other, and may be usually the same.
  • R 1a , R 1b , R 2a , R 2b , R 4a , R 4b , k1, k2, m1, m2, n1, n2, p1, and p2 are the same as above. It can obtain by making the compound (polyhydroxy compound) represented by and (meth) acrylic acid component react.
  • the polyhydroxy compound (compound represented by the formula (A)) is not particularly limited, but usually a compound represented by the following formula (B) and an alkylene oxide or alkylene carbonate corresponding to the group OR 2a or the group OR 2b It can obtain by making it react.
  • a polyhydroxy compound (an assembly of polyhydroxy compounds) having a range of values (or molecular weights) of m1, m2, and m1 + m2 in the formula (1) is usually obtained.
  • Examples of the polyhydroxy compound include conventional methods [for example, a method of reacting 9-fluorenone and phenol in the presence of an acid catalyst (for example, the method described in Patent Document 1), 9-fluorenone and phenoxy. Those synthesized by a method of reacting with alkanols (for example, 2-phenoxyethanol etc.) may be used, or commercially available products may be used.
  • Specific polyhydroxy compounds include, for example, 9,9-bis (hydroxyphenyl) fluorene [eg, 9,9-bis (4-hydroxyphenyl) fluorene], 9,9-bis (alkyl-hydroxyphenyl) fluorene [For example, 9,9-bis (mono or di-C) such as 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (3,5-dimethyl-4-hydroxyphenyl) fluorene 1-4 alkyl-hydroxyphenyl) fluorene], 9,9-bis (aryl-hydroxyphenyl) fluorene [for example, 9,9-bis (9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene, etc.
  • 9,9-bis (hydroxyphenyl) fluorene eg, 9,9-bis (4-hydroxyphenyl) fluorene]
  • 9,9-bis (mono or di-C)
  • Examples of the alkylene oxide corresponding to the group OR 2a or the group OR 2b include C 2-6 alkylene oxide such as ethylene oxide, propylene oxide and butylene oxide, preferably C 2-4 alkylene oxide, more preferably C 2-3 alkylene oxide ( In particular, ethylene oxide) may be mentioned.
  • Examples of the alkylene carbonate corresponding to the group OR 2a or the group OR 2b include C 2-6 alkylene carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, preferably C 2-4 alkylene carbonates, more preferably C 2-3 alkylene carbonates. (Especially ethylene carbonate).
  • an oxyalkylene unit (group OR 2a or group OR 2b ) can be introduced through the hydroxyl group of the compound represented by the formula (B).
  • oxyalkylene units are introduced by decarboxylation after addition of alkylene carbonate.
  • the amount of alkylene oxide or alkylene carbonate corresponding to group OR 2a or a group OR 2b can be adjusted according to the value of the m1 in formula (1), m2, m1 + m2.
  • the reaction between the compound represented by the formula (B) and alkylene oxide or alkylene carbonate may be carried out in the absence of a catalyst, but can usually be carried out in the presence of a catalyst.
  • the catalyst include a base catalyst and an acid catalyst, and usually a base catalyst can be used.
  • Base catalysts include metal hydroxides (alkali metals such as sodium hydroxide or alkaline earth metal hydroxides), metal carbonates (alkali metals such as sodium carbonate or alkaline earth metal carbonates, sodium hydrogen carbonate, etc.) Inorganic bases such as alkali metals or alkaline earth metal hydrogen carbonates of the above; metal alkoxides (such as alkali metal alkoxides such as sodium methoxide), amines [eg, tertiary amines (eg, trialkylamines such as triethylamine, Aromatic tertiary amines such as N, N-dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole, etc.], carboxylic acid metal salts (sodium acetate, calcium acetate and other alkali metal acetates or alkaline earths) Organic bases such as metal salts).
  • the catalyst (base catalyst) may be used alone or in combination of two or more.
  • the amount of the catalyst used can be adjusted according to the type of the catalyst. For example, 0.001 to 1 part by weight (for example, 0.003 to 0.005 parts by weight) with respect to 1 part by weight of the compound represented by the formula (B). 5 parts by weight), preferably 0.005 to 0.3 parts by weight, more preferably about 0.01 to 0.1 parts by weight.
  • the reaction may be performed in a solvent.
  • the solvent is not particularly limited and can be selected according to the raw material to be used.
  • an ether solvent dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane, Anisole, etc.
  • halogen solvents halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride
  • hydrocarbon solvents aromatic hydrocarbons such as benzene, toluene, xylene, etc.
  • alkylene carbonate in addition to the solvents exemplified above, alcohols (C 1-4 alcohols such as methanol and ethanol, (poly) C 2 such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol) are used. -3 alkylene glycol, etc.) may be used.
  • the solvents may be used alone or in combination of two or more.
  • the amount of the solvent used is, for example, about 1 to 30 parts by weight, preferably about 1.5 to 20 parts by weight, and more preferably about 2 to 10 parts by weight with respect to 1 part by weight of the compound represented by the formula (B). It may be.
  • the reaction is often carried out, for example, at about 0 to 170 ° C., preferably 10 to 150 ° C., more preferably about 20 to 130 ° C., depending on the type of compound to be added (alkylene oxide, alkylene carbonate) and the like.
  • alkylene carbonate in order to efficiently perform the decarboxylation reaction, for example, the reaction is often performed at 70 to 150 ° C., preferably about 80 to 120 ° C.
  • the reaction time is, for example, 30 minutes to 48 hours, usually 1 to 24 hours, preferably about 2 to 10 hours.
  • the reaction may be performed with stirring, may be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.), or may be performed at normal pressure or under pressure. Moreover, you may react, removing the gas (carbon dioxide etc.) which generate
  • the target product (compound represented by formula (A)) may be purified from the reaction mixture after completion of the reaction using a conventional purification method (extraction, crystallization, etc.).
  • R 3b ) —a group represented by —CO—] is not particularly limited as long as it is a compound capable of introducing a group, such as (meth) acrylic acid, (meth) acrylic acid derivatives [eg, (meth) acrylic acid lower alkyl esters (eg, C 1-4 alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate), (meth) acrylic acid halides (for example, (meth) acrylic acid chloride) Etc.), (meth) acrylic anhydride, etc.].
  • a group represented by —CO— is not particularly limited as long as it is a compound capable of introducing a group, such as (meth) acrylic acid, (meth) acrylic acid derivatives [eg, (meth) acrylic acid lower alkyl esters (eg, C 1-4 alkyl (meth) acrylates such as methyl (meth) acrylate,
  • the proportion of the (meth) acrylic acid component is, for example, 0.7 mol or more (for example, 0.8 to 10 mol), preferably 0 with respect to 1 mol of the hydroxyl group of the compound represented by the formula (A). It may be 0.9 mol or more (for example, 0.95 to 8 mol), more preferably 1 mol or more (for example, 1.1 to 5 mol).
  • (meth) acrylic acid used for the reaction time and reaction You may adjust the quantity of a component.
  • a catalyst such as an acid catalyst or a base catalyst
  • the acid catalyst is not particularly limited as long as it is an esterification acid catalyst.
  • inorganic acid sulfuric acid, hydrochloric acid, phosphoric acid, etc.
  • organic acid sulfonic acid (methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, etc.) And alkane sulfonic acids, and arene sulfonic acids such as p-toluene sulfonic acid etc.], etc.]
  • solidified acids supporting an acid (an inorganic acid such as sulfuric acid, phosphoric acid, heteropoly acid, organic acid) on a carrier]
  • Solid acid such as solid phosphoric acid
  • cation exchange resin metal oxide (such as ZnO), metal halide (such as CuCl 2 )
  • metal salt catalyst metal sulfate (such as NiSO 4
  • the base examples include metal carbonate (alkali metal or alkaline earth metal carbonate such as sodium carbonate, alkali metal or alkaline earth metal hydrogen carbonate such as sodium hydrogen carbonate), carboxylate metal salt (sodium acetate, Inorganic bases such as alkali metal acetates or alkaline earth metal salts such as calcium acetate), metal hydroxides (alkali metal hydroxides such as sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide) Amines [eg tertiary amines (trialkylamines such as triethylamine, triisopropylamine and tributylamine, aromatic tertiary amines such as N, N-dimethylaniline, and heterocyclic tertiary amines such as pyridine; And an organic base such as amine).
  • the bases may be used alone or in combination of two or more.
  • the amount of the catalyst (acid catalyst, base) used depends on the type of the catalyst, but for example 0.01 to 10 mol, preferably 0, with respect to 1 mol of the compound represented by the formula (A). .05 to 5 mol, more preferably about 0.1 to 3 mol.
  • reaction may be carried out in the presence of a polymerization inhibitor (thermal polymerization inhibitor) as necessary.
  • Polymerization inhibitors include hydroquinones (eg, hydroquinone; hydroquinone monoalkyl ethers such as hydroquinone monomethyl ether (methoquinone)), catechols (eg, alkyl catechols such as t-butylcatechol), amines (eg, diphenylamine) And 2,2-diphenyl-1-picrylhydrazyl, 4-hydroxy-2,2,6,6-tetramethylpiperazine-1-oxyl and the like.
  • the polymerization inhibitors may be used alone or in combination of two or more.
  • the amount of the polymerization inhibitor used is, for example, 0.1 to 10 parts by weight, preferably 0.3 to 8 parts by weight, and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid component. It may be about a part.
  • the reaction may be performed in the absence of a solvent or in a solvent.
  • Solvents organic solvents
  • organic solvents include hydrocarbons (aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as benzene, toluene, and xylene), halogenated hydrocarbons (methylene chloride, chloroform, etc.) And carbon tetrachloride), ether solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane, anisole and the like), ketones (dialkyl ketones such as acetone and methyl ethyl ketone), and the like.
  • the solvents may be used alone or in combination of two or more.
  • the reaction temperature and reaction time can be appropriately selected according to the type of (meth) acrylic acid component to be used.
  • the reaction time is, for example, 30 minutes to 48 hours, usually 1 to 36 hours, preferably 2 to 24 hours.
  • the reaction temperature and reaction time may be adjusted. .
  • the reaction may be performed while refluxing, or may be performed while removing by-product water and alcohols.
  • the reaction may be performed with stirring, may be performed in air or in an inert atmosphere (such as nitrogen or a rare gas), and may be performed under normal pressure, increased pressure, or reduced pressure. In particular, when the reaction is performed under reduced pressure, coloring can be reduced and the reaction time can be shortened.
  • the produced compound (compound represented by the formula (1)) can be separated by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination means combining these. It may be separated and purified by
  • Multifunctional (meth) acrylate composition The reaction mixture obtained by reacting the compound represented by the formula (A) with the (meth) acrylic acid component as described above contains a product (polyfunctionality represented by the formula (1) ( In addition to (meth) acrylate), some or all of the hydroxyl groups of the compound represented by formula (A) may contain a compound that remains without reacting with the (meth) acrylic acid component. Such a compound (compound represented by the following formula (2)) may be separated from the compound represented by the above formula (1), but is usually multifunctional represented by the above formula (1). As a composition with (meth) acrylate, it can be used as it is.
  • R 5a and R 5b represent a hydrogen atom or a (meth) acryloyl group
  • R 1a , R 1b , R 2a , R 2b , R 4a , R 4b , k1, k2, m1, m2, n1, n2, p1, p2 are the same.
  • R 5a and R 5b are (meth) acryloyl groups, all of R 5a and R 5b are (meth) never becomes acryloyl group.
  • R since the compound represented by Formula (2) is a component normally produced
  • the average value of m1 + m2 is selected from the same range as described above.
  • the number of (meth) acryloyl groups may be 1 or more and smaller than n1 + n2.
  • the number of (meth) acryloyl groups is the average value of the whole compound represented by the formula (2) as in the case of the polyfunctional (meth) acrylate. Represented as:
  • a typical polyfunctional (meth) acrylate composition includes a polyfunctional (meth) acrylate in which n1 and n2 are each 1 in the formula (1), and n1 and n2 in the formula (2).
  • Examples thereof include compositions each containing 1, a compound in which R 5a is a hydrogen atom and R 5b is a (meth) acryloyl group (that is, a monofunctional (meth) acrylate compound represented by the following formula (2A)).
  • the ratio (or concentration) of the compound represented by the formula (2) is the multifunctional (meth) acrylate represented by the formula (1) and the formula (2).
  • the ratio (or concentration) of the compound represented by the formula (2) is the multifunctional (meth) acrylate represented by the formula (1) and the formula (2).
  • the range of 3 to 40% eg, 4 to 35%), for example, 5 to 30% (eg, 6 to 27%), preferably 6.5. Even if it is about 26 to 26% (for example, 7 to 25%), more preferably about 7.5 to 22% (for example, 8 to 20%), especially about 8.5 to 18% (for example, 9 to 16%). Usually, it may be about 8 to 20% (for example, 8.5 to 17%, preferably 9 to 15.5%).
  • the reaction rate of (meth) acrylation is about 85 to 98%.
  • the range can be selected, for example, 87 to 97.5% (for example, 87.5 to 97.5%), preferably 89 to 96.5% (for example, 89.5 to 96.5%), and more preferably It may be about 90 to 96% (for example, 90.5 to 96%), particularly about 91 to 95.5% (for example, 91.5 to 95.5%).
  • the (meth) acrylation reaction rate indicates the degree (index) of (meth) acrylation generally used in (meth) acrylic resins, and is a polyfunctional (meth) represented by the formula (1). It can be easily determined from the ratio (concentration) of acrylate and the ratio (concentration) of the compound represented by the formula (2).
  • the ratio of the compound represented by Formula (1) and the compound represented by Formula (2) is a measurement of the hydroxyl value based on the usage-amount of the compound represented by Formula (A) used for the raw material ( Molar ratio, molar ratio), purity (area ratio) measurement by high performance liquid chromatography (HPLC), GPC measurement, NMR measurement, and the like.
  • the polyfunctional (meth) acrylate composition may further contain a solvent (solvent used in the reaction), an unreacted polyhydroxy compound (a compound represented by the formula (A)), and the like.
  • a solvent or polyhydroxy compound may be separated and usually contained in a composition as it is because it is often a trace amount after purification.
  • the ratio (or concentration) of the solid content (components other than the solvent) is, for example, 95% by weight or more, preferably 97% by weight or more, and more preferably 98% by weight. In particular, it may be 99% by weight or more (for example, 99.5% by weight or more).
  • the polyfunctional (meth) acrylate of the present invention (including a composition containing the compound represented by the formula (2) (including the polyfunctional (meth) acrylate composition), the same shall apply hereinafter)) has a high refractive index. Despite being, it has excellent scratch resistance after curing.
  • the refractive index of the polyfunctional (meth) acrylate at a wavelength of 589 nm is 1.52 or more (eg, 1.525 to 1.65), preferably 1.53 or more (eg, 1.535 to 1.6), more preferably 1.54 or more (eg 1.545 to 1.58), usually 1.53 to 1.58 (eg 1.535 to 1.575, preferably It may be about 1.54 to 1.57).
  • the properties of the polyfunctional (meth) acrylate of the present invention may be liquid at normal temperature (for example, 15 to 25 ° C.).
  • a liquid polyfunctional (meth) acrylate has a relatively low viscosity despite its high refractive index as described above, and is excellent in handling properties.
  • the viscosity of the polyfunctional (meth) acrylate is, for example, 20000 mPa ⁇ s or less (eg, 50 to 17000 mPa ⁇ s), preferably 15000 mPa ⁇ s or less (eg, 100 to 13000 mPa ⁇ s) at 25 ° C.
  • the viscosity of the polyfunctional (meth) acrylate may be about 400 to 15000 mPa ⁇ s, preferably 500 to 13000 mPa ⁇ s, more preferably about 600 to 12000 mPa ⁇ s at 25 ° C.
  • the viscosity can be measured with a TV-22 viscometer (cone plate type) or the like (hereinafter the same).
  • the hue (APHA) of the polyfunctional (meth) acrylate (or curable composition) of the present invention may be, for example, 100 or less, preferably 70 or less, and more preferably 50 or less.
  • the glass transition temperature of the cured product of the polyfunctional (meth) acrylate (or curable composition) of the present invention is, for example, 0 to 40 ° C., preferably 10 to 35 ° C., more preferably 15 to 30 ° C. There may be.
  • Such a polyfunctional (meth) acrylate of the present invention is composed of a curable polyfunctional (meth) acrylate, it is useful as a component for forming a curable composition for obtaining a cured product. It is. Below, a curable composition is explained in full detail.
  • the curable composition (polymerizable composition, radical polymerizable composition) of the present invention includes a curable component (polymerizable component, radical polymerizable component) composed of the polyfunctional (meth) acrylate.
  • the curable component may be composed only of (i) a polyfunctional (meth) acrylate, or (ii) a monomer that does not belong to the category of the polyfunctional (meth) acrylate (non-fluorene monomer). Good.
  • hardenable component is only polyfunctionality (meth) acrylate, it can form hardened
  • scratch resistance and high refractive index derived from polyfunctional (meth) acrylate can be maintained.
  • non-fluorene monomer for example, non-fluorene monofunctional monomer such as monofunctional (meth) acrylate
  • the handling property is further improved (lowering the viscosity)
  • a cured product having a high refractive index can be obtained efficiently.
  • the non-fluorene monomer has a polymerizable unsaturated bond or a polymerizable group [for example, an alkenyl group (vinyl group, allyl group, etc.), (meth) acryloyl group].
  • a non-fluorene-based monomer includes a monofunctional monomer (or a monofunctional polymerizable monomer, a monomer having one polymerizable unsaturated bond), a polyfunctional monomer [or a polyfunctional polymerizable monomer, Monomers having 2 or more polymerizable unsaturated bonds (for example, 2 to 8, preferably 2 to 6, more preferably 2 to 4)].
  • the polymerizable groups may be the same or different groups.
  • Such non-fluorene monomers can be used for the purpose of adjusting curability, hardness, viscosity, and the like, and monofunctional monomers are mainly used for adjusting viscosity and curability.
  • the non-fluorene-based monomer may be composed of at least a monofunctional monomer.
  • Monofunctional monomers include (meth) acrylic monomers, non- (meth) acrylic monomers [for example, styrene-based monomers (for example, styrene, ⁇ -methylstyrene, vinyltoluene, etc.), vinyl esters Type monomers (for example, vinyl acetate), N-vinylpyrrolidone, etc.].
  • the monofunctional monomer may usually contain at least a (meth) acrylic monomer.
  • the ratio of the non (meth) acrylic monomer to the whole monofunctional monomer is preferably 30% by weight or less, preferably May be 20% by weight or less, more preferably 10% by weight or less, especially 5% by weight or less.
  • Monofunctional (meth) acrylic monomers include (meth) acrylic acid, (meth) acrylamide, N-substituted (meth) acrylamide (N, N-diC 1-4 such as N, N-dimethyl (meth) acrylamide) (Meth) acrylic acid ester (or (meth) acrylate) and the like are included in addition to alkyl (meth) acrylamide and the like.
  • Monofunctional (meth) acrylates include aliphatic (meth) acrylates ((meth) acrylates having an aliphatic skeleton), aromatic (meth) acrylates ((meth) acrylates having an aromatic skeleton), sulfur-containing (meta) ) Acrylate and the like.
  • Monofunctional aliphatic (meth) acrylates include alkyl (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate , T-butyl (meth) acrylate, isobutyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) ) Acrylate, C 1-20 alkyl (meth) acrylate such as stearyl (meth) acrylate], alicyclic (meth) acrylate ⁇ eg cycloalkyl (meth) acrylate [
  • Examples of monofunctional aromatic (meth) acrylates include aryl (meth) acrylates (eg, C 6-10 aryl (meth) acrylates such as phenyl (meth) acrylate), aralkyl (meth) acrylates (eg, benzyl) C 6-10 aryl C 1-4 alkyl (meth) acrylate such as (meth) acrylate), aryloxyalkyl (meth) acrylate (eg C 6-10 aryloxy C 1-10 such as phenoxyethyl (meth) acrylate) Alkyl (meth) acrylate), arylaryloxyalkyl (meth) acrylate (for example, C 6-10 aryl C 6-10 aryloxy C 1-10 alkyl such as 2- (o-phenylphenoxy) ethyl (meth) acrylate ( Meta) Acrelay ), Aryloxy (poly) alkoxyalkyl (meth) acrylates [for example,
  • Adducts of about 10 alkylene oxides Adducts of about 10 alkylene oxides), the same applies hereinafter) mono (meth) acrylates, aromatic epoxy (meth) acrylates ⁇ eg 2-hydroxy-3-aryloxypropyl (meth) acrylates [eg 2 -Hydroxy-3-C 6-10 aryloxypropyl (meth) acrylate such as hydroxy-3-phenoxypropyl (meth) acrylate] ⁇ , arylthio (meth) acrylate, aralkylthio (meth) acrylate, arylthioa described later Examples include rualkyl (meth) acrylate.
  • aromatic epoxy (meth) acrylates ⁇ eg 2-hydroxy-3-aryloxypropyl (meth) acrylates [eg 2 -Hydroxy-3-C 6-10 aryloxypropyl (meth) acrylate such as hydroxy-3-phenoxypropyl (meth) acrylate] ⁇ ,
  • the aromatic (meth) acrylate (monofunctional (meth) acrylate) usually does not contain phenoxybenzyl (meth) acrylate.
  • sulfur-containing (meth) acrylate examples include alkylthio (meth) acrylate (for example, C 1-10 alkylthio (meth) acrylate such as methylthio (meth) acrylate), arylthio (meth) acrylate (for example, phenylthio (meth) acrylate) , Tolylthio (meth) acrylate, 2-naphthylthio (meth) acrylate, C 6-10 arylthio (meth) acrylate such as chlorophenylthio (meth) acrylate), aralkylthio (meth) acrylate (eg benzylthio (meth) acrylate, etc.) C 6-10 and aryl C 1-4 alkylthio (meth) acrylate), arylthioalkyl (meth) acrylate (e.g., phenyl thio (meth) C 6-10, such as acrylate Riruch
  • Monofunctional monomers may be used alone or in combination of two or more.
  • monofunctional (meth) acrylates are preferable, and among monofunctional (meth) acrylates, they may be used properly depending on the application.
  • monofunctional monomers from the viewpoint of improving handling properties, aliphatic (meth) acrylate [particularly branched alkyl (meth) acrylate (particularly branched C 3-10 alkyl such as isoamyl (meth) acrylate) ( (Meth) acrylates, preferably branched C 3-6 alkyl (meth) acrylates, alicyclic (meth) acrylates, etc.] can be suitably used.
  • aromatic (meth) acrylates, sulfur-containing (meth) acrylates, and the like can be suitably used from the viewpoint of achieving a balance between high refractive index and excellent handling properties.
  • monofunctional (meth) acrylates monofunctional (meth) acrylates (monofunctional) that can efficiently maintain scratch resistance in combination with the polyfunctional (meth) acrylate (or composition thereof).
  • (Meth) acrylate (sometimes referred to as (A)) may be suitably used.
  • monofunctional (meth) acrylate (A) for example, aryl (meth) acrylate, aralkyl (meth) acrylate, aryloxyalkyl (meth) acrylate, aryloxy (poly) alkoxyalkyl (meth) acrylate, alkylaryloxy (Poly) alkoxyalkyl (meth) acrylate, sulfur-containing (meth) acrylate [for example, arylthio (meth) acrylate, aralkylthio (meth) acrylate, arylthioalkyl (meth) acrylate, etc.] etc. are mentioned.
  • the monofunctional (meth) acrylate (A) may be used alone or in combination of two or more.
  • Such a monofunctional (meth) acrylate (A) has a relatively high refractive index, and even when combined with the polyfunctional (meth) acrylate, the scratch resistance is often not impaired. Low viscosity), high refractive index, and scratch resistance are easily realized in a balanced manner.
  • sulfur-containing (meth) acrylates such as arylthioalkyl (meth) acrylates are preferable because they have a high effect of maintaining or improving scratch resistance despite having a high refractive index.
  • a monofunctional (meth) acrylate (A) and a monofunctional (meth) acrylate (sometimes referred to as a monofunctional (meth) acrylate (B)) that is particularly excellent in terms of increasing the refractive index. You may combine.
  • the monofunctional (meth) acrylate (B) include, for example, arylaryloxyalkyl (meth) acrylate, arylaryloxy (poly) alkoxyalkyl (meth) acrylate, bisphenols, or mono (meth) of alkylene oxide adducts thereof. An acrylate etc. are mentioned.
  • the monofunctional (meth) acrylate (B) may be used alone or in combination of two or more.
  • Such a monofunctional (meth) acrylate (B) has a high refractive index among monofunctional monomers, but when combined with a polyfunctional (meth) acrylate at a very high concentration, scratch resistance and handling properties are improved. Although it may be damaged, by combining with the monofunctional (meth) acrylate (A), a high refractive index can be realized while preventing or suppressing a decrease in scratch resistance and handling properties.
  • the viscosity of the monofunctional monomer is not particularly limited, and may be selected from a range of about 200 mPa ⁇ s or less at 25 ° C., for example, 100 mPa ⁇ s or less (eg, 0.01 to 100 mPa ⁇ s), preferably May be 50 mPa ⁇ s or less (eg, 0.1 to 50 mPa ⁇ s), more preferably 30 mPa ⁇ s or less (eg, 0.3 to 30 mPa ⁇ s), particularly 20 mPa ⁇ s or less [eg, 0 0.01 to 20 mPa ⁇ s, preferably 0.05 to 10 mPa ⁇ s, more preferably 0.1 to 5 mPa ⁇ s (for example, 0.5 to 3 mPa ⁇ s).
  • the viscosity of the monofunctional (meth) acrylate (A) is 100 mPa ⁇ s or less (for example, 0.1 to 70 mPa ⁇ s), preferably 50 mPa ⁇ s at 25 ° C. Or less (for example, 0.3 to 40 mPa ⁇ s), more preferably 30 mPa ⁇ s or less (for example, 0.5 to 25 mPa ⁇ s), particularly about 20 mPa ⁇ s or less (for example, 0.5 to 15 mPa ⁇ s). There may be.
  • the viscosity of the monofunctional (meth) acrylate (B) is 30 mPa ⁇ s or higher (for example, 40 to 300 mPa ⁇ s), preferably 50 mPa ⁇ s or higher (for example, 70 to 250 mPa ⁇ s) at 25 ° C. More preferably, it may be 100 mPa ⁇ s or more (for example, 110 to 200 mPa ⁇ s), particularly 120 mPa ⁇ s or more (for example, 130 to 180 mPa ⁇ s).
  • the refractive index of the monofunctional monomer may be, for example, 1.4 or more at 25 ° C. and 589 nm, for example, 1.4 to 1.65, preferably 1.41 to 1.62, Preferably, it may be about 1.42 to 1.6.
  • the refractive index of the monofunctional monomer may be 1.5 or more, for example, 1.5 to 1.65, preferably 1.51 to 1.62, and more preferably 1.515 to 1. It may be about 6, particularly 1.53 or more (for example, about 1.54 to 1.6, preferably about 1.55 to 1.59).
  • the refractive index of the monofunctional (meth) acrylate (A) is, for example, 1.4 to 1.57, preferably 1.45 to 1. 565, more preferably 1.5 to 1.56, especially 1.51 to 1.56 (eg 1.53 to 1.56), usually 1.5 to 1.565 (eg It may be about 1.515 to 1.56).
  • the refractive index of the monofunctional (meth) acrylate (B) is, for example, 1.57 to 1.65, preferably 1.571 to 1.62, more preferably 1.573 to 1.5 at 25 ° C. and 589 nm. It may be about 1.6, particularly about 1.575 to 1.59.
  • 99/1 to 15/85 for example, 98/2 to 20/80
  • preferably 97/3 to 25/75 for example, 96/4 to 30/70.
  • More preferably 95/5 to 35/65 for example, 94/6 to 40/60
  • particularly about 93/7 to 45/55 for example, 92/8 to 45/55).
  • a polyfunctional monomer For the purpose of improving hard coat properties, a polyfunctional monomer may be used as long as the effects of the present invention (improvement of scratch resistance) are not impaired.
  • the multifunctional monomer include a multifunctional (meth) acrylic monomer ⁇ for example, a bifunctional (meth) acrylate ⁇ for example, an alkylene glycol di (meth) acrylate [ethylene glycol di C 2-10 alkylene glycol di (meth) acrylate such as (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc.], ( Poly) oxyalkylene glycol di (meth) acrylate [for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth)
  • the polyfunctional (meth) acrylic monomer includes, for example, a polyfunctional oligomer having a (meth) acryloyl group such as urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate.
  • the number (average number) of (meth) acryloyl groups in the polyfunctional oligomer may be 2 or more (for example, 2 to 8), for example, 2 to 6, preferably 2 to 4, and more preferably 2 to 3 In particular, it may be 2.
  • the polyfunctional monomer may be composed of at least polyfunctional (meth) acrylate.
  • the number of functional groups of the polyfunctional monomer (for example, the number of (meth) acryloyl groups) is, for example, 2 to 10 (for example, 2 to 8), preferably 2 to 6, more preferably 2 to 4, particularly 2 It may be.
  • Polyfunctional monomers may be used alone or in combination of two or more.
  • Preferred polyfunctional monomers include polyfunctional (meth) acrylates having an aromatic skeleton [for example, bisphenol A or its C 2-3 alkylene oxide adduct (for example, 1 mol of bisphenol A).
  • Non-fluorene-based polyfunctionality (such as urethane (meth) acrylate having urethane (meth) acrylate, particularly urethane (meth) acrylate having two (meth) acryloyloxy groups))
  • meth) acrylates especially non-fluorene bifunctional (meth) acrylates
  • the ratio of the polyfunctional (meth) acrylate represented by the formula (1) and the polyfunctional monomer is as follows:
  • the former / the latter (weight ratio) 99.9 / 0.1 to 30/70 (for example, 99.9 / 0.1 to 50/50) can be selected, and 99.9 / 0.1 to 60/40 (for example, 99.7 / 0.3 to 65/35), preferably 99.5 / 0.5 to 70/30 (for example, 99.3 / 0.7 to 75/25), more preferably May be about 99/1 to 80/20 (for example, 98/2 to 85/15), and usually 99/1 to 50/50 (for example, 95/5 to 60/40, preferably 90/10).
  • 99.9 / 0.1 to 50/50 can be selected
  • 99.9 / 0.1 to 60/40 for example, 99.7 / 0.3 to 65/35
  • the ratio of the former / the latter 99/1 to 5/95, preferably 97/3 to 10/90, more preferably Is about 95/5 to 20/80 (for example, 93/7 to 30/70), particularly 90/10 to 40/60 (for example, 88/12 to 50/50, preferably 85/15 to 55/45). It may be.
  • the ratio of the polyfunctional monomer to the entire curable component can be selected from the range of about 60% by weight or less (for example, 50% by weight or less), for example, 30% by weight or less, preferably 20% by weight or less, more preferably May be 10% by weight or less, and usually 40% by weight or less (for example, 25% by weight or less).
  • the curable component may further contain another fluorene-based monomer (a fluorene-based monomer that does not belong to the category of the polyfunctional (meth) acrylate represented by the formula (1) or the composition thereof).
  • another fluorene-based monomer a fluorene-based monomer that does not belong to the category of the polyfunctional (meth) acrylate represented by the formula (1) or the composition thereof.
  • the other fluorene-based monomer is usually a fluorene compound having a polymerizable unsaturated bond, in other words, a polymerizable unsaturated compound having a fluorene skeleton.
  • a fluorene-based monomer as the polymerizable unsaturated bond (polymerizable unsaturated group), a carbon-carbon unsaturated bond (carbon-carbon) such as alkenylene group (for example, vinyl group), (meth) acryloyl group, etc. Unsaturated group).
  • a typical fluorene-based monomer is a fluorene compound having a (meth) acryloyl group (or (meth) acryloyloxy group).
  • the number of polymerizable unsaturated bonds is, for example, 1 or more (eg, 1 to 8, preferably 1 to 6, more preferably 1 to 4, particularly preferably 1 or 2).
  • Such other fluorene monomers include (i) a fluorene monomer having one polymerizable unsaturated bond (especially a (meth) acryloyl group) and (ii) a polymerizable unsaturated bond (especially (meta And fluorene-based monomers having two or more acryloyl groups).
  • a fluorene monomer having one polymerizable unsaturated bond especially a (meth) acryloyl group
  • a polymerizable unsaturated bond especially (meta And fluorene-based monomers having two or more acryloyl groups.
  • the fluorene monomer (i) is not particularly limited as long as it is a monofunctional compound having a fluorene skeleton (that is, having one polymerizable unsaturated group).
  • the fluorene monomer (i) is represented by the following formula (3). Examples thereof include monofunctional (meth) acrylates having a fluorene skeleton such as compounds.
  • the number (number of added moles) m3 of the oxyalkylene group (OR 2a ) can be selected, for example, from the range of about 0 to 15 (for example, 0 to 10), for example, 0 to 8 (for example, 1 to 8), preferably 0 to 6 (eg 1 to 6), more preferably 0 to 4 (eg 1 to 4).
  • m3 may be about 0-2.
  • the divalent hydrocarbon group may be an aromatic hydrocarbon group (for example, a C 6-10 arylene group such as a phenylene group or a naphthylene group). It may be a hydrocarbon group.
  • Non-aromatic hydrocarbon groups include, for example, alkylidene groups (eg, C 1-10 alkylidene groups such as methylene group, ethylidene group, propylidene group, propane-2,2-diyl group, preferably C 1-6 alkyl).
  • a lidene group more preferably a C 1-4 alkylidene group
  • an alkylene group for example, a C 2-10 alkylene group such as an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, preferably a C 2-6 alkylene group, Preferably a C 2-4 alkylene group
  • a cycloalkylene group for example, a C 5-10 cycloalkylene group such as a cyclohexylene group, preferably a C 5-8 cycloalkylene group
  • a cycloalkanedimethylene group for example, 1, 4-cyclohexanedimethylene group and the like.
  • Representative divalent non-aromatic hydrocarbon groups include alkylidene groups and alkylene groups.
  • Preferred groups R 6 are a direct bond, an alkylidene group (eg, a C 1-4 alkylidene group, particularly a methylene group), and an alkylene group (eg, a C 2-4 alkylene group such as an ethylene group).
  • the substituent R 7 is the same as the above R 4a or R 4b , for example, a hydrocarbon group [eg, alkyl group (eg, C 1-6 alkyl group), cycloalkyl] Group (for example, C 5-8 cycloalkyl group), aryl group (for example, C 6-10 aryl group), aralkyl group (for example, C 6-8 aryl-C 1-2 alkyl group), etc.], alkoxy group ( C 1-4 alkoxy group, etc.).
  • alkyl group eg, C 1-6 alkyl group
  • cycloalkyl Group
  • aryl group for example, C 6-10 aryl group
  • aralkyl group for example, C 6-8 aryl-C 1-2 alkyl group
  • alkoxy group C 1-4 alkoxy group, etc.
  • R 1a , R 1b , R 2a , R 3a , k1, and k2 are the same as in Formula (1), including the preferred embodiment.
  • Representative fluorene-based monomer (i) includes a compound in which R 6 is a direct bond in formula (3) [for example, 9- (meth) acryloyloxyfluorene, 9- (meth) acryloyloxy-9-alkylfluorene, 9- (meth) acryloyloxy-9-arylfluorene, etc.], a compound in which R 6 is a methylene group in formula (3) [eg 9- (meth) Acryloyloxymethyl fluorene (9-fluorenylmethyl (meth) acrylate, etc.)] and the like.
  • R 6 is a direct bond in formula (3)
  • R 6 for example, 9- (meth) acryloyloxyfluorene, 9- (meth) acryloyloxy-9-alkylfluorene, 9- (meth) acryloyloxy-9-arylfluorene, etc.
  • R 6 is a direct bond in formula (3)
  • R 6 is
  • fluorene monomer (ii) a polyfunctional (meth) acrylate having a fluorene skeleton, for example, two or more (especially two) (meth) acryloyl groups such as a compound represented by the following formula (4) are used. 9,9-bisarylfluorenes are included.
  • ring Z represents an aromatic hydrocarbon ring
  • m4 and m5 each represent a number of less than 8.5
  • R 1a , R 1b , R 2a , R 2b , R 3a , R 3b , R 4a , R 4b , K1, k2, n1, n2, p1, and p2 are the same as above.
  • examples of the aromatic hydrocarbon ring represented by ring Z include a benzene ring and a condensed polycyclic arene (or condensed polycyclic aromatic hydrocarbon) ring.
  • condensed polycyclic arene (or condensed polycyclic aromatic hydrocarbon) ring for example, a condensed bicyclic arene ring (for example, a C 8-20 condensed bicyclic arene ring such as an indene ring or a naphthalene ring, preferably And C 10-16 condensed bicyclic arene rings), condensed tricyclic arene rings (eg, anthracene ring, phenanthrene ring, etc.) and the like.
  • the two rings Z may be the same or different rings, and may usually be the same ring.
  • a typical ring Z is a benzene ring or a naphthalene ring.
  • the number of oxyalkylene groups (OR 2a and OR 2b ) (addition moles) m4 and m5 may be less than 8.5, for example, 0 to 8 (for example, 0 to 6), preferably 0 to 4 (eg 0 to 3), more preferably 0 to 2 (eg 0 to 1), especially 1.
  • R 1a , R 1b , R 2a , R 2b , R 3a , R 3b , R 4a , R 4b , k1, k2, n1, n2, p1, and p2 are those in the formula (1). It is the same including a case and a preferable aspect.
  • Representative fluorene monomers (ii) include 9,9-bis ((meth) acryloyloxyaryl) fluorenes, 9,9-bis ((meth) acryloyl) Oxy (poly) alkoxyaryl) fluorenes are included.
  • 9,9-bis ((meth) acryloyloxyaryl) fluorenes for example, 9,9-bis ((meth) acryloyloxyphenyl) fluorene [for example, 9,9-bis (4- (meth) acryloyloxy) Phenyl) fluorene and the like], 9,9-bis (alkyl- (meth) acryloyloxyphenyl) fluorene [9,9-bis (4- (meth) acryloyloxy-3-methylphenyl) fluorene, 9,9-bis ( 9,9-bis (mono or diC 1-4 alkyl- (meth) acryloyloxyphenyl) fluorene, etc.] such as 4- (meth) acryloyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis ( Aryl (meth) acryloyloxyphenyl) fluorene [9,9-bis (4- (meth) acryloyl
  • the 9,9-bis ((meth) acryloyloxy (poly) alkoxyaryl) fluorenes correspond to the 9,9-bis ((meth) acryloyloxyaryl) fluorenes, and in formula (4), m4 and m5 Is one or more (eg, about 1 to 4), for example, 9,9-bis ((meth) acryloyloxyalkoxyphenyl) fluorene [eg, 9,9-bis (4- (2- (meth) acryloyl) 9,9-bis ((meth) acryloyloxy C 2-4 alkoxyphenyl) fluorene and the like], 9,9-bis ((meth) acryloyloxydialkoxyphenyl) fluorene (for example, 9 , 9-bis ⁇ 4- [2- (2- (meth) acryloyloxyethoxy) ethoxy] phenyl ⁇ Fluorene] 9,9-bis such ⁇ [2- (2-
  • the ratio of the other fluorene-type monomer with respect to the whole curable component can be selected from the range of about 70 weight% or less, for example, 60 weight% or less, Preferably it is 50 weight% or less, More preferably, it is 40 weight% or less. It may be.
  • the ratio of the fluorene-based monomer (ii) to the entire curable component may be, for example, 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, particularly 7% by weight or less.
  • the curable composition of this invention may contain the polymerization initiator further as needed.
  • a polymerization initiator may be a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photo radical generator).
  • a preferred polymerization initiator is a photopolymerization initiator.
  • photopolymerization initiator or photo radical generator examples include benzoins (benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether); acetophenones (acetophenone, p- Dimethylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-phenyl-2-hydroxy-acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc.); propiophenones (p-dimethylaminopropiophenone) 2-hydroxy-2-methyl-propiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc.); buty
  • a photoinitiator can be obtained as a commercial item, for example, a brand name "Irgacure” "Darocur” (made by Ciba Japan Co., Ltd.), a brand name “Syracure” (made by Union Carbide), etc.
  • thermal polymerization initiators examples include dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides (diaalkanoyl peroxide (lauroyl peroxide, etc.), dialoyl peroxide (benzoyl peroxide).
  • the ratio of the polymerization initiator is a curable component (for example, the polyfunctional (meth) acrylate represented by the formula (1) alone, the polyfunctional represented by the formula (1).
  • a curable component for example, the polyfunctional (meth) acrylate represented by the formula (1) alone, the polyfunctional represented by the formula (1).
  • 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably 1 to 10 parts by weight (total amount of the functional (meth) acrylate and the monofunctional monomer) For example, it may be about 2 to 7 parts by weight.
  • the photopolymerization initiator may be combined with a photosensitizer.
  • the photosensitizer include conventional components such as tertiary amines [for example, trialkylamine, trialkanolamine (such as triethanolamine), ethyl N, N-dimethylaminobenzoate, N, N-dimethyl.
  • Dialkylaminobenzoic acid alkyl esters such as amyl aminobenzoate, bis (dialkylamino) benzophenones such as 4,4-bis (dimethylamino) benzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone], triphenylphosphine, etc.
  • Examples include phosphine, toluidines such as N, N-dimethyltoluidine, anthracene such as 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene and 2-ethyl-9,10-diethoxyanthracene. It is done.
  • the photosensitizers may be used alone or in combination of two or more.
  • the amount of the photosensitizer used is, for example, 0.1 to 150 parts by weight, preferably 1 to 100 parts by weight, more preferably 5 to 75 parts by weight (particularly 10 parts by weight) with respect to 100 parts by weight of the photopolymerization initiator. About 50 parts by weight).
  • the curable composition of the present invention further contains conventional additives such as resin components, solvents, thermal polymerization inhibitors (hydroquinone, hydroquinone monoethyl ether, etc.), antifoaming agents, coating property improvers, thickeners, lubricants. , Stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.), plasticizers, surfactants, dissolution accelerators, colorants, fillers, antistatic agents, silane coupling agents, leveling agents, dispersants, A dispersion aid or the like may be included.
  • additives may be used alone or in combination of two or more.
  • the curable composition of the present invention is excellent in curability (particularly photocurability) and has characteristics such as a high refractive index even before curing.
  • the refractive index of the curable composition can be selected from a range of about 1.5 or more (eg, 1.5 to 1.65) at 25 ° C. and 589 nm, and 1.51 or more (eg, 1.515 to 1.62), preferably 1.52 or more (eg 1.525 to 1.61), more preferably 1.53 or more (eg 1.535 to 1.6), especially 1.54 or more (eg 1.545 to 1.58), usually 1.53 to 1.58 (eg, 1.535 to 1.575, preferably 1.54 to 1.57, more preferably 1.545 to 1.545). It may be about 1.565).
  • the curable composition of the present invention has excellent handling properties despite having a high refractive index. Therefore, the curable composition of the present invention may be usually liquid at normal temperature (for example, 15 to 25 ° C.).
  • the viscosity of such a curable composition is, for example, 15000 mPa ⁇ s or less (eg, 1 to 13000 mPa ⁇ s), preferably 12000 mPa ⁇ s or less (eg, 5 to 11000 mPa ⁇ s), more preferably at 25 ° C.
  • the viscosity can be lowered by using a monofunctional monomer as compared with the case of using a polyfunctional (meth) acrylate alone.
  • Such a curable composition of this invention can be prepared by mixing each component.
  • the curable composition of this invention hardens
  • the curable composition of the present invention is often excellent in photocurability and may be cured by applying at least light energy (light irradiation).
  • the cured product may have a three-dimensional structure and is usually a cured film in many cases.
  • the cured film may be a film pattern (particularly a thin film pattern).
  • the cured film can be formed by applying the resin composition to a base material or a substrate and drying it if necessary, and then heating or exposing to an actinic ray. Then, it can be formed by selectively exposing and developing the generated latent image pattern.
  • the base material or the substrate can be selected according to the use, and may be a porous material such as wood, a metal such as aluminum or copper, a ceramic such as glass or quartz, a plastic such as polymethyl methacrylate or polycarbonate.
  • the curable composition of the present invention is excellent in adhesion to a substrate, and has a high refractive index and high transparency. Therefore, the curable composition of the present invention is suitable for optical applications, and among these substrates, by coating on a transparent film. You may utilize as a laminated body with a transparent base material or a transparent film. As the transparent film, for example, it is excellent in transparency and has excellent adhesion to the curable composition.
  • cyclic olefin resin for example, cyclic olefin resin, styrene resin, (meth) acrylic resin (polymethyl methacrylate, etc.), acrylonitrile type, etc.
  • a transparent film composed of a resin, a polyester-based resin, a polyamide-based resin, a cellulose ester (such as triacetyl cellulose) or the like is preferable.
  • the thickness of the transparent film can be selected depending on the application, and may be, for example, about 1 to 1000 ⁇ m, preferably 10 to 500 ⁇ m, and more preferably about 30 to 300 ⁇ m.
  • the coating method is not particularly limited. For example, flow coating method, spin coating method, spray coating method, screen printing method, casting method, bar coating method, curtain coating method, roll coating method, gravure coating method, dipping method, slit method. It may be.
  • the curable composition may be applied and then dried (for example, dried at about 40 to 150 ° C.).
  • the thickness of the coating film varies depending on the application, but can be selected from the range of about 0.01 to 1000 ⁇ m, and may be, for example, 1 to 500 ⁇ m, preferably 5 to 400 ⁇ m, and more preferably about 10 to 300 ⁇ m.
  • the curable composition is usually in a liquid state at room temperature, and when such a liquid resin composition is used, a coating film can be formed without passing through a step of melting the resin composition.
  • the heating temperature may be, for example, 60 to 200 ° C. (eg, 80 to 180 ° C.), preferably about 100 to 150 ° C. Since the curable composition of this invention is excellent in photopolymerizability, it can also obtain hardened
  • the entire surface may be exposed depending on the application, or a patterned latent image may be formed by selective exposure using a photomask or the like.
  • radiation gamma rays, X-rays, etc.
  • ultraviolet rays visible rays, etc.
  • the light source for example, in the case of ultraviolet rays, a deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, a laser light source (light source such as helium-cadmium laser or excimer laser), etc. Can be used.
  • the amount of irradiation light varies depending on the thickness of the coating film, but can be selected from a range of, for example, about 50 to 10,000 mJ / cm 2 , 75 to 5000 mJ / cm 2 , more preferably 100 to 3000 mJ / cm 2 (for example, 100 to 2000 mJ / cm 2 ).
  • the heating temperature may be, for example, about 60 to 200 ° C., preferably about 100 to 150 ° C.
  • a developed coating film pattern can be formed by developing the latent image pattern.
  • Developers include water, alkaline aqueous solutions (eg, tetramethylammonium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc.), acidic aqueous solutions, hydrophilic solvents (eg, alcohols such as methanol, ethanol, isopropanol, Ketones such as acetone, ethers such as dioxane and tetrahydrofuran, cellosolves, cellosolve acetates, etc.), and mixtures thereof.
  • the development can be performed using immersion, washing, spraying or spray development.
  • a cured product (cured film or the like) is obtained.
  • Such a cured product has scratch resistance and is excellent in optical properties such as high transparency and high refractive index.
  • scratch resistance is not impaired even when a curable composition is constituted in combination with a monofunctional monomer or the like, and a cured product having excellent scratch resistance and a high refractive index is obtained.
  • the refractive index of the cured product of the present invention can be selected from a range of about 1.5 or more (eg, 1.5 to 1.65) at 25 ° C. and 589 nm, and 1.51 or more (eg, 1.515).
  • 1.62 preferably 1.52 or more (eg 1.525 to 1.61), more preferably 1.53 or more (eg 1.535 to 1.6), especially 1.54 or more (eg 1.545 to 1.58), usually 1.55 or more (eg 1.555 to 1.59), 1.56 or more [eg 1.56 to 1.6, preferably 1 565 or more (for example, 1.565 to 1.59), more preferably 1.57 or more (for example, 1.57 to 1.585)].
  • IAA Isoamyl acrylate, manufactured by NOF Corporation, viscosity (25 ° C.) 1 mPa ⁇ s, refractive index (25 ° C., 589 nm) 1.419
  • POA Phenoxyethyl acrylate, “Light acrylate PO-A” manufactured by Kyoeisha Chemical Co., Ltd., viscosity (25 ° C.) 8 mPa ⁇ s, refractive index (25 ° C., 589 nm) 1.518
  • BZA benzyl acrylate, “FA-BZA” manufactured by Hitachi Chemical Co., Ltd., viscosity (25 ° C.) 2 mPa ⁇ s, refractive index (25 ° C., 589 nm) 1.515
  • PTEA Phenylthioethyl acrylate BIMAX Co., Ltd., viscosity (25 ° C.) 6 m
  • 9-FMA 9-fluorenylmethyl acrylate, synthesized by the following method: 9-fluorenylmethanol (manufactured by Kanto Chemical Co., Inc.) 196.2 g (1.0 mol) in a four-necked flask and acrylic An acid 93.7 g (1.3 mol), p-toluenesulfonic acid 23.8 g (0.13 mol), toluene 577 g, and methoquinone 2.1 g were charged, and a stirrer, thermometer, condenser, and water separator were attached. Thereafter, dehydration esterification reaction was performed for 3.3 hours while refluxing at 110 to 120 ° C.
  • reaction solution was neutralized with 10% sodium hydroxide and washed with 20% saline. After drying over magnesium sulfate and filtration, 2.1 g of methoquinone was added, and toluene was removed by concentration under reduced pressure. As a result, 237 g (yield: 95%) of 9-fluorenylmethyl acrylate as a target product was obtained.
  • BPEFA 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd.).
  • Photopolymerization initiator “IRGACURE 184” manufactured by Ciba Japan Co., Ltd.
  • various properties and evaluations were measured as follows.
  • Refractive index A multi-wavelength Abbe refractometer (manufactured by Atago, DR-M2 ⁇ using circulating water bath 60-C3>) was used, and the refractive index at 589 nm (refractive index before and after curing) was measured while maintaining a temperature of 25 ° C.
  • the glass transition temperature of the cured product was measured using DSC 6220 manufactured by SII NanoTechnology at a measurement temperature of 30 to 220 ° C. and a heating time of 10 ° C./min.
  • A No damage at 200 g load, no damage at 1 kg load, or complete recovery within 5 minutes at room temperature (about 25 ° C.)
  • B Damage at 200 g load There is no scratch and the wound is immediately after moving with 1 kg load, and the wound does not recover after 5 minutes at room temperature (about 25 ° C). But the wound does not recover after 5 minutes.
  • Solid content concentration Using a halogen moisture meter HG53 manufactured by METTLER TOLEDO Co., Ltd., the volatile residue at 200 ° C. was measured as a solid content.
  • Example 1 1 mol of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd., hereinafter referred to as BPEF) in the same manner as in Example 1 of JP-A-2001-139651
  • BPEF 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene
  • EO ethylene oxide
  • BPF 9,9- (4-hydroxyphenyl) fluorene
  • the ratio (HPLC purity) of BPF-9.0EO-1A to the total amount of BPF-9.0EO-2A and BPF-9.0EO-1A was 11.5%, and the polyfunctionality determined from this ratio
  • the reaction rate of the functional acrylate (acrylation reaction rate) was 94.2%.
  • the solid content concentration of the polyfunctional acrylate was 99.9% by weight, the refractive index (25 ° C., 589 nm) was 1.563, and the viscosity (25 ° C.) was 10500 mPa ⁇ s.
  • UV ultraviolet light
  • a photopolymerization initiator was added to 100 parts by weight of the obtained polyfunctional acrylate and melt-mixed, followed by ultraviolet light (UV) irradiation (500 mJ / cm 2 , 20 seconds).
  • UV ultraviolet light
  • the cured product had a refractive index (25 ° C., 589 nm) of 1.583 and a glass transition temperature of 30 ° C.
  • Example 2 A compound in which 10.5 mol of EO was added to 1 mol of BPF was obtained in the same manner as in Example 1 except that the amount of EO used was changed to 9.5 mol in Example 1. APHA of the obtained compound (referred to as BPF-10.5EO) was 76.
  • the polyfunctional acrylate (composition) includes a compound obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-10.5EO (referred to as BPF-10.5EO-2A), and 1 mol of BPF-10.5EO. Also included was a compound (referred to as BPF-10.5EO-1A) in which 1 mol of acrylic acid had reacted.
  • the ratio (HPLC purity) of BPF-10.5EO-1A to the total amount of BPF-10.5EO-2A and BPF-10.5EO-1A is 14.9%, and the polyfunctionality determined from this ratio
  • the reaction rate of the functional acrylate (acrylation reaction rate) was 92.5%.
  • the solid content concentration of the polyfunctional acrylate was 99.7% by weight, the refractive index (25 ° C., 589 nm) was 1.556, and the viscosity (25 ° C.) was 7900 mPa ⁇ s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared in the same manner as in Example 1 was 1.575, the scratch resistance was evaluated as A, and the glass transition temperature was 24 ° C.
  • Example 3 In Example 1, except that the amount of EO used was changed to 9.9 mol, a compound in which 10.9 mol of EO was added to 1 mol of BPF was obtained in the same manner as in Example 1. APHA of the obtained compound (referred to as BPF-10.9EO) was 59.
  • the polyfunctional acrylate (composition) includes a compound obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-10.9EO (referred to as BPF-10.9EO-2A), and 1 mol of BPF-10.9EO. Also included was a compound (referred to as BPF-10.9EO-1A) in which 1 mol of acrylic acid had reacted.
  • the ratio (HPLC purity) of BPF-10.9EO-1A to the total amount of BPF-10.9EO-2A and BPF-10.9EO-1A was 9.9%, and the polyfunctionality determined from this ratio
  • the reaction rate of the functional acrylate (acrylation reaction rate) was 95.1%.
  • the solid content concentration of the polyfunctional acrylate was 99.7% by weight, the refractive index (25 ° C., 589 nm) was 1.554, and the viscosity (25 ° C.) was 6600 mPa ⁇ s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared in the same manner as in Example 1 was 1.574, the scratch resistance was evaluated as A, and the glass transition temperature was 18 ° C.
  • Example 4 In Example 1, except that the amount of EO used was changed to 10 mol, a compound in which 11.0 mol of EO was added to 1 mol of BPF was obtained in the same manner as in Example 1. APHA of the obtained compound (referred to as BPF-11.0EO) was 30.
  • the polyfunctional acrylate (composition) contains 1 mol of BPF-11.0EO. Also included was a compound (referred to as BPF-11.0EO-1A) in which 1 mol of acrylic acid had reacted.
  • the ratio (HPLC purity) of BPF-11.0EO-1A to the total amount of BPF-11.0EO-2A and BPF-11.0EO-1A was 10.1%, and the polyfunctionality determined from this ratio
  • the reaction rate of the functional acrylate (acrylation reaction rate) was 94.9%.
  • the solid content concentration of the polyfunctional acrylate was 99.6% by weight, the refractive index (25 ° C., 589 nm) was 1.552, and the viscosity (25 ° C.) was 5000 mPa ⁇ s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared in the same manner as in Example 1 was 1.572, the scratch resistance was evaluated as B, and the glass transition temperature was 16 ° C.
  • Example 5 In Example 1, except that the amount of EO used was changed to 11 mol, a compound in which 12.0 mol of EO was added to 1 mol of BPF was obtained in the same manner as in Example 1. APHA of the obtained compound (referred to as BPF-12.0EO) was 25.
  • the polyfunctional acrylate (composition) contains 1 mol of BPF-12.0EO. Also included was a compound (referred to as BPF-12.0EO-1A) in which 1 mol of acrylic acid had reacted.
  • the ratio (HPLC purity) of BPF-12.0EO-1A to the total amount of BPF-12.0EO-2A and BPF-12.0EO-1A is 10.5%, and the polyfunctionality determined from this ratio
  • the reaction rate of the functional acrylate (acrylation reaction rate) was 94.7%.
  • the solid content concentration of the polyfunctional acrylate was 99.7% by weight, the refractive index (25 ° C., 589 nm) was 1.547, and the viscosity (25 ° C.) was 2100 mPa ⁇ s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared in the same manner as in Example 1 was 1.567, the scratch resistance was evaluated as B, and the glass transition temperature was 14 ° C.
  • Example 6 In Example 1, except that the amount of EO used was changed to 13 mol, a compound in which 14.2 mol of EO was added to 1 mol of BPF was obtained in the same manner as in Example 1. APHA of the obtained compound (referred to as BPF-14.2EO) was 40.
  • the polyfunctional acrylate (composition) includes a compound obtained by reacting 2 moles of acrylic acid with 1 mole of BPF-14.2EO (referred to as BPF-14.2EO-2A), and 1 mole of BPF-14.2EO. Also included was a compound (referred to as BPF-14.2EO-1A) in which 1 mol of acrylic acid had reacted.
  • BPF-14.2EO-1A a compound obtained by reacting 2 moles of acrylic acid with 1 mole of BPF-14.2EO
  • BPF-14.2EO-1A a compound obtained by reacting 2 moles of acrylic acid with 1 mole of BPF-14.2EO
  • BPF-14.2EO-1A a compound obtained by reacting 2 moles of acrylic acid with 1 mole of BPF-14.2EO
  • BPF-14.2EO-1A a compound obtained by reacting 2 moles of acrylic acid with 1 mole of BPF-14.2EO
  • BPF-14.2EO-1A a compound obtained by reacting 2 moles of acrylic acid with 1 mole of BPF-14.2EO
  • the solid content concentration of the polyfunctional acrylate was 99.8% by weight, the refractive index (25 ° C., 589 nm) was 1.539, and the viscosity (25 ° C.) was 900 mPa ⁇ s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared in the same manner as in Example 1 was 1.559, the scratch resistance was evaluated as B, and the glass transition temperature was 13 ° C.
  • Example 7 In Example 1, except that the amount of EO used was changed to 15 mol, a compound in which 16.0 mol of EO was added to 1 mol of BPF was obtained in the same manner as in Example 1. APHA of the obtained compound (referred to as BPF-16.0EO) was 58.
  • a polyfunctional acrylate was obtained in a yield of 97% in the same manner as in Example 1, except that 1 mol of BPF-16.0EO was used and the reaction time was changed to 2.7 hours.
  • the polyfunctional acrylate (composition) includes a compound obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-16.0EO (referred to as BPF-16.0EO-2A), and 1 mol of BPF-16.0EO. Also included was a compound (referred to as BPF-16.0EO-1A) in which 1 mol of acrylic acid had reacted.
  • the ratio (HPLC purity) of BPF-16.0EO-1A to the total amount of BPF-16.0EO-2A and BPF-16.0EO-1A was 16.0%, and the polyfunctionality determined from this ratio
  • the reaction rate of the functional acrylate (acrylation reaction rate) was 92.0%.
  • the solid content concentration of the polyfunctional acrylate was 99.7% by weight, the refractive index (25 ° C., 589 nm) was 1.530, and the viscosity (25 ° C.) was 400 mPa ⁇ s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared in the same manner as in Example 1 was 1.548, the scratch resistance was evaluated as B, and the glass transition temperature was 11 ° C.
  • a polyfunctional acrylate was obtained in a yield of 96% in the same manner as in Example 1 except that 1 mol of BPF-6.6EO was used and the reaction time was changed to 2.4 hours.
  • the polyfunctional acrylate (composition) contains 1 mol of BPF-6.6EO. Also included was a compound (referred to as BPF-6.6EO-1A) in which 1 mol of acrylic acid had reacted.
  • BPF-6.6EO-1A a compound in which 1 mol of acrylic acid had reacted.
  • the ratio of BPF-6.6EO-1A to the total amount of BPF-6.6EO-2A and BPF-6.6EO-1A (HPLC purity) was 18.1%, and the polyfunctionality determined from this ratio
  • the reaction rate of the functional acrylate (acrylation reaction rate) was 91.0%.
  • the solid content concentration of the polyfunctional acrylate was 99.95% by weight, the refractive index (25 ° C., 589 nm) was 1.588, and the viscosity (25 ° C.) was 134,000 mPa ⁇ s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared in the same manner as in Example 1 was 1.596, the scratch resistance was evaluated as C, and the glass transition temperature was 62 ° C.
  • Example 2 In Example 1, except that the amount of EO used was changed to 7 mol, a compound in which 8.0 mol of EO was added to 1 mol of BPF was obtained in the same manner as in Example 1. APHA of the obtained compound (referred to as BPF-8.0EO) was 106.
  • the polyfunctional acrylate (composition) includes a compound obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-8.0EO (referred to as BPF-8.0EO-2A), and 1 mol of BPF-8.0EO. Also included was a compound (referred to as BPF-8.0EO-1A) in which 1 mol of acrylic acid had reacted.
  • BPF-8.0EO-1A a compound obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-8.0EO
  • BPF-8.0EO-1A a compound obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-8.0EO
  • BPF-8.0EO-1A a compound obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-8.0EO
  • BPF-8.0EO-1A a compound obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-8.0EO
  • BPF-8.0EO-1A a compound obtained by reacting 2 mol of acrylic acid with 1 mol of BPF-8.0EO
  • the solid content concentration of the polyfunctional acrylate was 99.7% by weight, the refractive index (25 ° C., 589 nm) was 1.573, and the viscosity (25 ° C.) was 62000 mPa ⁇ s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared in the same manner as in Example 1 was 1.591, the scratch resistance was evaluated as C, and the glass transition temperature was 55 ° C.
  • the polyfunctional acrylates of the Examples could form a cured product having a high refractive index and excellent scratch resistance despite having a low viscosity.
  • the polyfunctional acrylates of Reference Example 1, Reference Example 2 and Comparative Example 1 have a high refractive index, but are poor in handling properties with high viscosity, and are also poor in scratch resistance of the obtained cured product. It was a thing.
  • Comparative Examples 2 and 3 urethane acrylate having flexibility was used, but the refractive index was low, and a cured product sufficient in scratch resistance could not be obtained.
  • Comparative Example 2 had tack and poor handling properties, and the refractive index was smaller than that of the Examples.
  • Comparative Example 3 had a lower viscosity than Comparative Example 2, but the refractive index was remarkably reduced as the viscosity was lowered, and scratch resistance was not obtained.
  • Example 8 90 parts by weight of the polyfunctional acrylate obtained in Example 3, 10 parts by weight of isoamyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.541
  • the viscosity (25 degreeC) was 2100 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.563, the scratch resistance evaluation was A, and the curability evaluation was A.
  • Example 9 90 parts by weight of the polyfunctional acrylate obtained in Example 3, 10 parts by weight of phenoxyethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.551
  • the viscosity (25 degreeC) was 3000 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.574, the scratch resistance evaluation was A, and the curability evaluation was A.
  • Example 10 70 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of phenoxyethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.543
  • the viscosity (25 degreeC) was 1800 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.568, the scratch resistance evaluation was A, and the curability evaluation was A.
  • Example 11 50 parts by weight of the polyfunctional acrylate obtained in Example 3, 50 parts by weight of phenoxyethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.536
  • the viscosity (25 degreeC) was 600 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.561, the scratch resistance evaluation was B, and the curability evaluation was A.
  • Example 12 90 parts by weight of the polyfunctional acrylate obtained in Example 3, 10 parts by weight of benzyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.550
  • the viscosity (25 degreeC) was 1500 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.572, the scratch resistance evaluation was A, and the curability evaluation was A.
  • Example 13 70 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of benzyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.542
  • the viscosity (25 degreeC) was 500 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.565, the scratch resistance evaluation was A, and the curability evaluation was A.
  • Example 14 50 parts by weight of the polyfunctional acrylate obtained in Example 3, 50 parts by weight of benzyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.534
  • the viscosity (25 degreeC) was 100 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.559, the scratch resistance evaluation was B, and the curability evaluation was A.
  • Example 15 90 parts by weight of the polyfunctional acrylate obtained in Example 3, 10 parts by weight of phenylthioethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.554
  • the viscosity (25 degreeC) was 3000 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.574, the scratch resistance evaluation was A, and the curability evaluation was A.
  • Example 16 70 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of phenylthioethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.555
  • the viscosity (25 degreeC) was 800 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.577, the scratch resistance evaluation was A, and the curability evaluation was A.
  • Example 17 50 parts by weight of the polyfunctional acrylate obtained in Example 3, 50 parts by weight of phenylthioethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.555
  • the viscosity (25 degreeC) was 200 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.578, the scratch resistance evaluation was A, and the curability evaluation was A.
  • Example 18 90 parts by weight of the polyfunctional acrylate obtained in Example 3, 10 parts by weight of o-phenylphenol monoethoxy acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.557
  • the viscosity (25 degreeC) was 4500 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.578, the scratch resistance evaluation was A, and the curability evaluation was A.
  • Example 19 70 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of o-phenylphenol monoethoxy acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.561
  • the viscosity (25 degreeC) was 2500 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.586
  • the scratch resistance evaluation was B
  • the curability evaluation was A.
  • Example 20 70 parts by weight of the polyfunctional acrylate obtained in Example 2, 30 parts by weight of benzyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.544
  • the viscosity (25 degreeC) was 1000 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.566, the scratch resistance evaluation was A, and the curability evaluation was A.
  • Example 21 60 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of phenoxyethyl acrylate, 10 parts by weight of o-phenylphenol monoethoxy acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition. Obtained.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.544
  • the viscosity (25 degreeC) was 600 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.567, the scratch resistance evaluation was A, and the curability evaluation was A.
  • Example 22 40 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of phenoxyethyl acrylate, 30 parts by weight of o-phenylphenol monoethoxy acrylate, and 3 parts by weight of a photopolymerization initiator are melt-mixed to obtain a curable composition. Obtained.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.548
  • the viscosity (25 degreeC) was 500 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.575, the scratch resistance evaluation was B, and the curability evaluation was A.
  • Example 23 60 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of phenylthioethyl acrylate, 10 parts by weight of o-phenylphenol monoethoxy acrylate, and 3 parts by weight of a photopolymerization initiator are melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.557
  • the viscosity (25 degreeC) was 600 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.577, the scratch resistance evaluation was A, and the curability evaluation was A.
  • Example 24 40 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of phenylthioethyl acrylate, 30 parts by weight of o-phenylphenol monoethoxy acrylate, and 3 parts by weight of a photopolymerization initiator are melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.561
  • the viscosity (25 degreeC) was 500 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.579, the scratch resistance was evaluated as B, and the curability was evaluated as A.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.586
  • the viscosity (25 degreeC) was 7000 mPa * s.
  • the refractive index (25 ° C., 589 nm) of the cured product prepared from the curable composition in the same manner as in Example 1 was 1.608, the scratch resistance evaluation was C, and the curability evaluation was A.
  • a cured product having a good balance of excellent scratch resistance, high refractive index and handling property while maintaining or improving scratch resistance by combining POA, PTEA and OPPEOA. could get.
  • Example 25 80 parts by weight of the polyfunctional acrylate obtained in Example 3, 20 parts by weight of urethane acrylate (UV-3200B), and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.545
  • the viscosity (25 degreeC) was 11100 mPa * s.
  • Example 26 80 parts by weight of the polyfunctional acrylate obtained in Example 3, 20 parts by weight of urethane acrylate (EBECRYL8402), and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • EBECRYL8402 urethane acrylate
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.542
  • the viscosity (25 degreeC) was 11100 mPa * s.
  • Example 27 80 parts by weight of the polyfunctional acrylate obtained in Example 3, 20 parts by weight of diacrylate (FA-321A) of an ethylene oxide adduct of bisphenol A, and 3 parts by weight of a photopolymerization initiator are melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.546
  • the viscosity (25 degreeC) was 4500 mPa * s.
  • Example 28 80 parts by weight of the polyfunctional acrylate obtained in Example 3, 20 parts by weight of 9-fluorenylmethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.564
  • the viscosity (25 degreeC) was 4000 mPa * s.
  • Example 29 70 parts by weight of the polyfunctional acrylate obtained in Example 3, 30 parts by weight of 9-fluorenylmethyl acrylate, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.57
  • the viscosity (25 degreeC) was 1000 mPa * s.
  • Example 30 95 parts by weight of the polyfunctional acrylate obtained in Example 3, 5 parts by weight of BPEFA, and 3 parts by weight of a photopolymerization initiator were melt-mixed to obtain a curable composition.
  • the refractive index (25 degreeC, 589 nm) of the curable composition was 1.558
  • the viscosity (25 degreeC) was 8400 mPa * s.
  • the polyfunctional (meth) acrylate or curable composition of the present invention is, for example, an ink material, a light emitting material (for example, a light emitting material for organic EL), an organic semiconductor, a graphitization precursor, a gas separation membrane (for example, CO 2 gas separation membrane, etc.), coating agents (for example, optical overcoat agents such as coating agents for LED (light emitting diode) elements or hard coating agents), lenses [pickup lenses (eg, DVD (digital versatile tiles) Disc) pick-up lens, etc.), microlens (eg, microlens for liquid crystal projector), spectacle lens, etc.], polarizing film (eg, polarizing film for liquid crystal display), composite sheet, brightness enhancement film, prism sheet, reflection Anti-reflection film (or anti-reflection film such as anti-reflection film for display device) ), Touch panel film, flexible substrate film, display film [eg, PDP (plasma display), LCD (liquid crystal display), VFD (vacuum fluorescent display), SED
  • the multifunctional (meth) acrylate or curable composition of the present invention can balance a high refractive index and excellent scratch resistance in a well-balanced manner, so that it can be used for optical materials that require scratch resistance [for example, It can be suitably used for a prism sheet (for example, a prism sheet for a display such as a prism sheet for a liquid crystal display), a sheet for a touch panel (or a film for a touch panel, for example, a touch panel sheet for a liquid crystal display) and the like.
  • a prism sheet for example, a prism sheet for a display such as a prism sheet for a liquid crystal display
  • a sheet for a touch panel or a film for a touch panel, for example, a touch panel sheet for a liquid crystal display
  • the shape of the optical material include a film or sheet shape, a plate shape, a lens shape, and a tubular shape.

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Abstract

L'invention concerne un (méth)acrylate multifonctionnel contenant un squelette de fluorène, qui présente un bon équilibre entre une excellente résistance à la rayure et un indice de réfraction élevé. Dans la formule (1), la moyenne de m1 + m2 est régulée à 8,5-17. (Dans la formule, R1a et R1b représentent chacun un substituant non-polymérisable par voie radicalaire ; R2a et R2b représentant chacun un groupe alkylène, R3a et R3b représentent chacun un atome d'hydrogène ou un groupe méthyle ; R4a et R4b représentent chacun un substituant non polymérisable par voie radicalaire ; k1 et k2 représentent chacun un entier de 0-4 ; m1 et m2 représentent chacun un entier de 0 ou plus ; n1 et n2 représentent chacun un entier de 1-4 ; et p1 et p2 représentent chacun un entier de 0-4. A cet égard, n1 + p1 ≤ 5 et n2 + p2 ≤ 5).
PCT/JP2012/070351 2011-08-11 2012-08-09 (meth)acrylate multifonctionnel ayant un squelette de fluorène et composition durcissable le contenant WO2013022065A1 (fr)

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