Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
  • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
  • C07C69/54—Acrylic acid esters; Methacrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/02—Ortho- or ortho- and peri-condensed systems
  • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
  • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
  • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
  • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
  • C07C2603/18—Fluorenes; Hydrogenated fluorenes

Definitions

• the present invention relates to optical material applications (optical overcoating agent, hard coating agent, antireflection film)
• the present invention relates to a polymerizable composition (and a cured product thereof) composed of a polyfunctional (meth) acrylate.
• Thermoplastic resins such as polycarbonate
• thermosetting resins are used for optical materials such as optical overcoating agents, hard coating agents, antireflection films, spectacle lenses, optical fibers, optical waveguides, and holograms.
• Cured products eg, polyfunctional aliphatic acrylates such as diethylene glycol bisaryl carbonate (CR-39)
• Such optical materials are required to have improved properties such as moisture resistance, heat resistance, and high refractive index, and development of various optical materials is being studied.
• Patent Document 1 discloses, as a plastic lens material, a compound obtained by reacting 9,9 bis (4-hydroxyphenyl) fluorene with (meth) acrylic acid chloride, or 9, Disclosed is a copolymer containing, as a main component, a compound obtained by adding ethylene oxide or propylene oxide to bis (4-hydroxyphenyl) fluorene and then reacting with (meth) acrylic acid.
• Patent Document 1 Japanese Patent Laid-Open No. 4 325508 (Claim 1, Paragraph No. [0010])
• an object of the present invention is to improve the properties such as hardness, heat resistance and moisture resistance. It is an object of the present invention to provide a functional (meth) atalylate and a method for producing the same.
• Another object of the present invention is to provide a polyfunctional (meth) acrylate which can improve the crosslink density.
• Still another object of the present invention is to provide a method capable of easily producing a novel polyfunctional (meth) acrylate having a fluorene skeleton at a high yield.
• the inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that the polyfunctionality of the conjugated product (or alkylene oxide adduct thereof) in which fluorene is substituted with a polyvalent phenol at the 9-position ) It has been found that the use of acrylate allows the crosslink density to be improved and the properties (hardness, heat resistance, etc.) of the material (such as an optical material) to be significantly improved, and the present invention has been completed.
• the polyfunctional (meth) acrylate of the present invention is a (meth) acrylate having a fluorene skeleton represented by the following formula (1).
• R la , R lb , R 2a and R also represent a substituent, R 3a and R 3b represent an alkylene group, R 1 ⁇ 2 and R 4b represent a hydrogen atom or a methyl group, and kl and k2 are the same.
• R 3a and R 3b represent an alkylene group
• R 1 ⁇ 2 and R 4b represent a hydrogen atom or a methyl group
• kl and k2 are the same.
• ml and m2 are the same or different and represent an integer of 0 or 13
• n1 and n2 are the same or different and represent an integer of 0 or 1 or more
• pi and p2 are the same or different and each represent an integer of 2 to 4, where ml + pl and m2 + p2 are integers of 2 to 5
• R 3a and R 31 ⁇ C are an alkylene group
• nl + n2 force may be about 24.
• R la and! ⁇ Alkyl group, kl and k2 are 0 or 1
• R 2a and R 2b are C alkyl
• a C alkoxy group or a C aryl group, ml and m2 are 0-2,
• nl and n2 are 1 or more include R 3a and R 3 C
• nl and n2 are about 114, nl + n2 force is about 18, and pi and p2 are each 2 and include polyfunctional (meth) acrylates .
• Representative polyfunctional (meth) atalylates represented by the above formula (1) include (meta) of a kazane compound with a C alkylene oxide of 9,9 bis (dihydroxyphenyl) fluorene. ) Atarilate, 9
• the polyfunctional (meth) atalylate represented by the formula (1) is not particularly limited, but is usually a polyhydric alcohol having a fluorene skeleton represented by the following formula (2), and (meth) It can be produced by reacting with acrylic acid or a derivative thereof.
• the present invention includes a polymerizable composition composed of the polyfunctional (meth) atalylate represented by the formula (1) and a polymerization initiator (for example, a photopolymerization initiator).
• the ratio of the polymerization initiator may be about 0.1 to 30 parts by weight based on 100 parts by weight of the polyfunctional (meth) acrylate which is represented by the above formula (1).
• the polymerizable composition may further contain a polysilane.
• a polysilane includes a polysilane having at least one structural unit among the structural units represented by the following formulas (3) to (5).
• the amount may be, for example, about 0.1 to 50 parts by weight based on 100 parts by weight of the polyfunctional (meth) acrylate which is represented by the following formula.
• R 5 -R 7 are the same or different and each represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkenyl group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkyl group, an aryl group
• x, y and z each represent 0 or an integer of 1 or more, and the total of x, y and z is 5 to 400.
• the present invention relates to a cured product obtained by polymerizing or curing the polymerizable composition (or the polyfunctional (meth) atalylate represented by the formula (1)), and a material (optical material) composed of the cured product. Material).
• (meth) acrylate means atalylate or metathalilate.
• (meth) atalyloyloxy means atariloyloxy or metharyloyloxy.
• the polyfunctional (meth) atalylate of the present invention has a fluorene skeleton and a large number of highly polymerizable (meth) atalyloyl groups, so that the crosslink density can be improved and the material (optical) Properties such as hardness and heat resistance can be significantly improved. Further, in the present invention, a large number of (meth) atalyloyl groups can be introduced, and a novel polyfunctional (meth) atalylate having a fluorene skeleton can be easily produced at a high yield.
• the polyfunctional (meth) atalylate of the present invention is represented by the following formula (1), wherein a polyhydric alcohol (or its alkylenoxy) is substituted with two polyphenols at the 9-position of fluorenes. (Ad)) as a polyol component.
• R la , R lb , R 2a and R 2b represent a substituent, R 3a and R 3b represent an alkylene group, R 1 ⁇ 2 and R 4b represent a hydrogen atom or a methyl group.
• Kl and k2 represent The same or different, and represent an integer of 0 or 14; ml and m2 represent the same or different and represent an integer of 0 or 13; n1 and n2 represent the same or different and represent an integer of 0 or 1 or more; , Pi and p2 are the same or different and each represent an integer of 2 to 4, where ml + pl and m2 + p2 are integers of 2 to 5)
• the substituent represented by the groups R la and R lb is not particularly limited, but is usually an alkyl group in many cases.
• the alkyl group include C 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 alkyl group,
• a methyl group can be exemplified.
• the groups R la and R lb can be different or identical.
• the groups R la (or R lb ) may be different or the same on the same benzene ring.
• the bonding position (substitution position) of the group R la (or R lb ) to the benzene ring constituting the fluorene skeleton is not particularly limited.
• Preferred substitution numbers kl and k2 are 0 or 1, especially 0.
• the substitution numbers kl and k2 may be different, but are usually the same.
• alkyl groups C alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, and the like.
• Alkyl group more preferably C alkyl group, etc.
• C cycloalkyl groups such as tyl and cyclohexyl groups, preferably C cycloalkyl
• aryl group preferably C cycloalkyl group
• aryl group preferably C cycloalkyl group
• aryl group preferably C cycloalkyl group
• aryl group preferably C cycloalkyl group
• aryl group preferably C cycloalkyl group
• Carbohydrates such as benzyl and phenethyl groups, etc.
• alkoxy group such as a c-alkoxy group such as a methoxy group
• a hydroxyl group such as a c-alkoxy group such as a methoxy group
• a halogen atom (such as a fluorine atom or a chlorine atom).
• Nitro group ; cyano group and the like.
• the hydroxyl group or hydroxy (poly) alkylenoxy group may be used as a starting material for a polyhydric alcohol residue ((meth)) according to a method for producing a polyfunctional (meth) atalylate described below.
• the substituent R 2a is an alkyl group (C alkyl group), a cycloalkyl group (
• R 2a (or R 2b ) may be used alone or in combination of two or more.
• the benzene ring may be substituted in combination.
• the groups R 2a and R 2b may be the same or different from each other, but are usually the same.
• the groups R 2a (or R 2b ) may be different or the same in the same benzene ring.
• the substitution position of the substituent R 2a is not particularly limited, and may be a (meth) atalyloyloxy group or a (meth) atalyloyloxy (poly) alkoxy group (hereinafter, (meth) atariloyloxy).
• the substitution position of the group which may be collectively referred to as a group-containing group
• it can be substituted at the 2- to 6-positions (for example, the 2-, 5-, and 2,5-positions) of the fuel group.
• the preferred number of substitutions ml and m2 is 0-2, more preferably 0-1 (particularly 0), though it depends on the number of substitutions of the (meth) atalyloyloxy group-containing group.
• the substitution numbers ml and m2 may be different, but usually are often the same.
• the alkylene group represented by R 3a and R 3b is not limited.
• R 3a and R 3b may be the same or different alkylene groups, but are usually the same anoalkylene group.
• substitution numbers (addition numbers) nl and n2 of the alkoxy group are the same or different, and a force in the range of about 0 to 15 can be selected.
• 0 to 12 for example, 1 to 12
• preferably 0 to 8 for example, 1 to 8
• more preferably about 0 to 6 for example, 1 to 6
• particularly about 0 to 4 for example, 1 to 4.
• nl and n2 can be selected from a range of about 0-30, for example, 0-24 (for example, 2-24), preferably 0-16 (for example, 2-12), More preferably, it may be about 0 to 12 (for example, 2 to 10), particularly about 0 to 8 (for example, 2 to 8).
• the polyalkoxy (polyalkyleneoxy) group may be a different alkoxy group (for example, an ethoxy group and a propyleneoxy group) which may be composed of the same alkoxy group. ) May be present in combination, but usually they are often composed of the same alkoxy group.
• the number of substitutions pi and P2 of the (meth) atalyloyloxy group-containing group are preferably 2-3, particularly preferably 2! / ⁇ .
• the number of pi (p + p2) between pi and p2 may be about 418, preferably about 416 (particularly 4,) if f rows are used.
• the substitution numbers pi and ⁇ 2 may be different, but are usually the same in many cases.
• the substitution position of the (meth) atalyloyloxy group-containing group is not particularly limited. Depending on the number of pi (or ⁇ 2), the 2-6 position of the fluorene substituted at the 9-position of fluorene is also selected. When pi (or ⁇ 2) is 2, the position may be, for example, the first, third or fourth position, or the third or fifth position.
• One (meth) atalyloyloxy group-containing group may be usually substituted at the 4-position.
• the plurality of (meth) atalyloyloxy group-containing groups substituted on the same benzene ring may be the same or different.
• Representative polyfunctional (meth) acrylates represented by the above formula (1) include, for example, 9,9-bis (di (meth) atalyloyloxyphenyl) fluorenes, 9 , 9-Bis (tri (meth) ataryloxyphenyl) fluorenes and their corresponding polyhydric alcohols [9,9-bis (di- or trihydroxyphenyl) fluorenes] alkylene oxides (C alkylene oxides)
• 9,9-bis (di (meth) atalyloyloxyphenol) fluorenes include, for example, 9,9-bis (di (meth) atalyloyloxyphenyl) fluorene [9, 9] Bis (3,4-di (meth) acryloyloxyphenyl) fluorene, 9,9 bis (2,4-di (meth) atalyloyloxyphenyl) fluorene, 9,9 bis (2 , 5-di (meth) atalyloyloxyphenyl) fluorene, etc.], and substituted 9,9 bis (di (meth) atalyloyloxyphenyl) fluorene ⁇ eg, 9,9 bis ( Alkyldi (meth) atalyloyloxyphenyl) fluorene [9,9 bis (3,4-di (meth) atalyloyloxy 5-methylphenyl) fluorene, 9,9
• the 9,9-bis (tri (meth) atalyloyloxyphenyl) fluorenes include the 9,9-bis
• Fluorenes corresponding to (di (meth) atalyloyloxyphenyl) fluorenes for example, 9,9 bis (2,4,6 -— (meth) atalyloyloxyphenyl) fluorene, 9,9 Screw (2, 9, 9-bis (such as 4,5-tri (meth) atalyloyloxyphenyl) fluorene and 9,9 bis (3,4,5-tri (meth) atalyloyloxyphenyl) fluorene Tri (meta) atariloyloxyphenyl) fluorene and the like.
• Examples of the (meth) atalylate of an alkylene oxide-carrying compound of 9,9 bis (dihydroxyphenyl) fluorene include, for example, 9,9 bis [3,4-di (2- (meta) Atariloyloxyethoxy) phenyl] fluorene and other 9,9 bis [di (2- (meth) ataliloyloxy C alkoxy]
• (Meth) acrylates of alkylene oxide-carrying bodies of 9,9 bis (trihydroxyphenyl) fluorenes include, for example, 9,9 bis [3,4,5-tri (2- 9,9-bis [di (2- (meth) atalyloyloxy C al) such as (meth) atariloyloxyethoxy) phenyl] fluorene
• (Meta) acrylates such as 9,9-bis [tri (2- (meth) atalyloyloxy C alkoxy) phenyl] fluorene, 9,9-bis ⁇ tri [2— (2 — (Meth) atariloyloxy
• the polyfunctional (meth) atalylate of the present invention has a large number of (meth) atalyloyloxy group-containing groups (particularly, (meth) atalyloyloxy (poly)) having a fluorene skeleton and having high reactivity. C alkoxy group), it has various excellent properties (particularly high refractive index
• the polyfunctional (meth) atalylate of the present invention is not particularly limited, but is prepared by reacting a polyhydric alcohol having a fluorene skeleton represented by the following formula (2) with (meth) acrylic acid or a derivative thereof. It can be manufactured from this.
• polyhydric alcohol represented by the above formula (2) preferable groups and substitution numbers (R, k, m, n, p) are the same as described above.
• Representative polyhydric alcohols include, for example, 9,9-bis (dihydroxyphenyl) fluorene [9,9-bis (3,4-dihydroxyphenyl) fluorene (biscatecholfluorene (BCAF)), 9,9-bis (2,4-dihydroxyphenyl) fluorene, 9,9-bis (2,5-dihydroxyphenyl) fluorene], substituted 9,9-bis (dihydroxyphenyl) fluorene ⁇
• 6,9-bis (dihydroxyphenyl) fluorene such as 6-8 Lyldihydroxyphenyl) fluorene [9,9-bis (3,4-dihydroxy-5-phenylphenyl) fluorene, etc.]
• the purity of the polyhydric alcohol is not particularly limited, but is usually 95% by weight or more, preferably 96% by weight or more, and more preferably 98% by weight or more. is there.
• the polyhydric alcohol represented by the above formula (2) is a novel compound and can be usually easily produced by the following method.
• the method for producing the polyhydric alcohol represented by the formula (2) is not particularly limited, but is usually a fluorenone represented by the following formula (2a) and a fluorenone represented by the following formula (2b) in the presence of an acid catalyst.
• R 2 represents a substituent
• m represents an integer of 0 or 13
• p represents an integer of 2-4.
• m + p is an integer of 2-5.
• R la , R lb , kl, and k2 are the same as above
• polyhydric alcohols (9,9-bis (polyhydroxyphenyl) fluorenes) in which nl and n2 are 0 are converted to fluorenone represented by the above formula (2a) in the presence of an acid catalyst.
• the polyhydric alcohol wherein nl and Z or n2 is 1 or more is converted to the above-mentioned formula (I) in the presence of an acid catalyst.
• the resulting 9,9-bis (polyhydroxyphenyl) fluorene is Further, it can be produced by reacting an alkylene oxide or an alkylene carbonate.
• R 2 corresponds to R 2a or R 2b
• m corresponds to ml or m2
• p corresponds to pi or This corresponds to p2, and preferred embodiments and the like are as described above.
• the fluorenone represented by the above formula (2a) corresponds to the fluorene skeleton of the polyhydric alcohol represented by the above formula (2), and A typical fluorenone is 9 fluorenone.
• the purity of the fluorenone used is not particularly limited, but is usually 95% by weight or more, preferably 99% by weight or more.
• polyphenol polyhydric phenols represented by the above formula (2b)
• polyhydroxybenzenes include, for example, dihydroxybenzene (catechol, resorcinol, hydroquinone), alkyldihydroxybenzene [dihydroxytoluene (3,5-dihydroxytoluene (orcinol) ), 3-methylcatechol, 4-methylcatechol, etc.), 4 t-butylcatechol, dihydroxyxylene (2,6-dihydroxy-p-xylene, etc.)
• Chlorocatechol mono- or dihalodihydroxybenzenes such as 2,4-difluorohydroquinone, etc., nitrodihydroxybenzenes (such as nitrocatechol), and alkoxy dihydroxybenzenes (3-methoxycatechol, 4,6-di-tert-butyl) Mono- or di-C alkoxydihydroxybenzene such as 3-methoxycatechol), acyldihydroxyben
• dihydroxybenzenes which dihydroxybenzenes; trihydroxybenzenes corresponding to these dihydroxybenzenes [for example, trihydroxybenzenes (pyrogallol, hydroxyhydroquinone, fluoro Loglucinol), trihydroxyacetophenone, etc.].
• the polyhydric phenols may be reacted with fluorenones alone or in combination of two or more.
• the amount of the polyhydric phenol used is, for example, 2 to 20 mol per mol of the fluorenone.
• the reaction (condensation reaction) between the polyvalent phenols and the fluorenones is not particularly limited, but can usually be carried out in the presence of an acid catalyst.
• the acid catalyst include inorganic acids [sulfuric acid, hydrogen chloride, hydrochloric acid, phosphoric acid, etc.] and organic acids [sulfonic acid (alkanesulfonic acid such as methanesulfonic acid)].
• the sulfuric acid includes dilute sulfuric acid, concentrated sulfuric acid, fuming sulfuric acid and the like, and sulfur trioxide may be used as a sulfuric acid precursor as long as it can be converted into sulfuric acid in the reaction system.
• the acid catalysts may be used alone or in combination of two or more. Preferred acid catalysts are hydrochloric acid or sulfuric acid.
• the amount of the acid catalyst to be used can be selected according to the type of the acid catalyst. For example, for fluorenone 100 parts by weight, 0.0001 to 150 parts by weight is preferable. ⁇ ⁇ More [preferably 0.01 to 50 parts by weight.
• sulfuric acid in terms of H SO
• the amount of sulfuric acid is usually small if it is very small.
• hydrochloric acid used as a catalyst, the amount of hydrochloric acid used is, in terms of hydrogen chloride, 100 parts by weight of fluorenone, 100 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 50 parts by weight. It may be about 30 parts by weight.
• the condensation reaction may be carried out using a thiol as a co-catalyst in addition to the acid catalyst.
• a thiol as a co-catalyst in addition to the acid catalyst.
• the condensation reaction can proceed effectively and the yield can be improved in many cases.
• thiols include conventional thiols that function as cocatalysts, such as mercaptocarboxylic acids (mercaptoacetic acid, j8-mercaptopropionic acid, ⁇ -mercaptopropionic acid, thioglycolic acid, mercaptosuccinic acid, mercaptobenzoic acid, etc.
• Thiocarboxylic acids thioacetic acid, thiooxalic acid, etc.
• alkyl mercaptans methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, ⁇ -butyl mercaptan, dodecyl mercaptan, and other C alkyl mercaptans (especially C Alkenyl mercaptan), aralkyl mercaptan (benzyl mercaptan, etc.) or salts thereof.
• the salt include an alkali metal salt (eg, a sodium salt).
• thiols mercapto C carboxylic acid (for example, ⁇ -methyl)
• Rucaptopropionic acid is preferred.
• the thiols can be used alone or in combination of two or more.
• the amount of the thiol used can be selected from a range of about 0 to 0.2 part by weight per 1 part by weight of fluorenone. For example, 0.001 to 0.1 part by weight, preferably 0.003 part by weight. -0.03 parts by weight, more preferably about 0.005-0.015 parts by weight.
• the amount of the thiols used can be selected from a range of about 0 to 10 parts by weight per 1 part by weight of the acid catalyst, and is, for example, 0.001 to 10 parts by weight, preferably 0.01 to 10 parts by weight. It may be 10 parts by weight (for example, 0.01 to 5 parts by weight), more preferably about 0.01 to 2 parts by weight.
• the thiols are preferably 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, more preferably 0.01 to 0.3 part by weight based on 1 part by weight of sulfuric acid. It may be about parts by weight.
• hydrochloric acid When hydrochloric acid is used, 0.1 to 13 parts by weight, preferably 0.3 to 1 part by weight, more preferably 0.5 to 1 part by weight per 1 part by weight of hydrochloric acid (in terms of hydrogen chloride). It may be about 5 parts by weight.
• the condensation reaction may be carried out in the absence of a solvent or in a solvent.
• the solvent is not particularly limited as long as it is non-reactive with the above-mentioned acidic catalyst and can dissolve fluorenones and polyvalent phenols, and can be used in a wide range.
• Representative solvents include ether solvents (dialkyl ethers such as getyl ether, cyclic ethers such as tetrahydrofuran and dioxane), and halogen solvents (methylene chloride, chloroform, Halogenated hydrocarbons such as carbon chloride); and aromatic solvents (such as aromatic hydrocarbons such as benzene, toluene and xylene, and alcohol).
• an excess of polyhydric phenols may be used as a solvent.
• solvents cyclic ethers (such as tetrahydrofuran and 1,4-dioxane) are preferred.
• the solvents may be used alone or in combination of two or more.
• the amount of the solvent to be used can be selected from the range of about 0 to 20 parts by weight, based on 1 part by weight of the fluorenones, for example, 0.5 to 10 parts by weight, preferably 18 to 18 parts by weight, more preferably Is 2— 5 It may be about parts by weight.
• the condensation reaction varies depending on the type of polyhydric phenols, acid catalysts, thiols, etc. used, but is usually 10 to 150 ° C, preferably 20 to 120 ° C, and more preferably 30 to 100 ° C. It is often performed at about ° C.
• the reaction time can be adjusted according to the type of the starting material, the reaction temperature, the concentration in the solvent, and the like, and is, for example, 30 minutes to 48 hours, usually, about 24 hours, and preferably about 110 hours.
• the reaction may be carried out with stirring or in the air or in an inert atmosphere (nitrogen, rare gas, etc.) or at normal pressure or under pressure.
• an inert atmosphere nitrogen, rare gas, etc.
• the reaction mixture after completion of the reaction usually contains, in addition to the produced polyhydric alcohol (9,9 bis (polyhydroxypropyl) fluorenes), unreacted fluorenones and unreacted polyhydric phenols. , Catalysts (acid catalysts, thiols), by-products, etc. Therefore, separation and purification can be performed by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, and column chromatography, or a separation means combining these. For example, after removal of the acid catalyst (and thiols) by a conventional method, crystallization may be performed by adding a crystallization solvent, followed by cooling to crystallize, followed by filtration and separation for purification.
• crystallization solvent examples include hydrocarbons [aliphatic hydrocarbons (hexane, heptane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogens Hydrocarbons (dichloromethane, etc.)], water, alcohols (alkyl alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, cyclohexanol, etc.), ketones (acetone, methylethylketone, methyl Alkyl ketones such as isobutyl ketone, getyl ketone, ethyl propyl ketone, di-propyl ketone, diisopropyl ketone, cyclohexanone, etc., ethers (dialkyl ethers such as getyl ether, diisopropyl ether, etc.), nit
• the crystallization solvent may be used alone or in combination of two or more.
• the amount of the crystallization solvent is not particularly limited, and is 0.5 to 50 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 10 parts by weight, based on 1 part by weight of the reaction mixture (in terms of solid content). It may be about 5 parts by weight.
• JP-A-6-145087, JP-A-8-217713 hydrohalide gas and mercaptocarboxylic acid
• a method of reacting a fluorenone with a phenol in the presence of a phenol (b) JP-A-2000-26349 [Reacting 9 fluorenone with an alkylphenol in the presence of an acid catalyst (and alkylmercaptan)] Method), (c) JP-A-2002-47227 (method of reacting fluorenones with phenols in the presence of hydrochloric acid and thiols), (d) JP-A-2003-221352 (sulfuric acid and thiols) A method in which fluorenone and phenol are reacted in the presence of water and crystallized with a crystallization solvent composed of a hydrocarbon and an polar solvent).
• the polyvalent phenols (compounds represented by the formula (3)) are used in place of the phenols, and the synthesis method (the purification method and the Polyhydric alcohols [9,9 bis (polyhydroxyphenyl) fluorenes] may be produced with reference to the addition ratio).
• the synthesis method the purification method and the Polyhydric alcohols [9,9 bis (polyhydroxyphenyl) fluorenes] may be produced with reference to the addition ratio.
• alkylene oxide examples include C alkylene oxides (particularly, C alkylene oxides) such as ethylene oxide, propylene oxide, and butylene oxide.
• alkylene carbonate examples include C alkylene carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate (particularly,
• Lencarbonate may be used alone or in combination of two or more.
• an alkylene carbonate is used, an alkylene oxide unit (alkoxy unit) is introduced because a decarboxylation reaction occurs after the addition of the alkylene carbonate.
• the amount of the alkylene oxide or alkylene carbonate to be used can be adjusted according to the number of alkylene oxide units to be added, and is, for example, 1 to 50 mol per mol of the hydroxyl group constituting the polyhydric alcohol. , Preferably 110 moles, more preferably 110 moles. It may be about the same.
• the purity of the polyhydric alcohol (9,9 bis (polyhydroxyphenyl) fluorenes) which is nl and n2 O to be reacted is not particularly limited, but is usually 95% by weight or more, preferably 99% by weight or more! / ,.
• the reaction with the 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.
• a base catalyst can be used.
• the base catalyst include metal hydroxides (eg, alkali metal or alkaline earth metal hydroxides such as sodium hydroxide) and metal carbonates (eg, alkali metal or alkaline earth metal carbonates such as sodium carbonate).
• Inorganic bases such as alkali metal or alkaline earth metal hydrogen carbonate such as sodium hydrogencarbonate; amines [eg, tertiary amines (trialkylamine such as triethylamine, N, N-diamine; Aromatic tertiary amines such as methyla-phosphorus, heterocyclic tertiary amines such as 1-methylimidazole), and metal salts of carboxylic acids (alkali metal or alkaline earth metals such as sodium acetate and calcium acetate).
• Organic bases such as salts).
• the catalysts base catalysts
• the catalysts may be used alone or in combination of two or more.
• the amount of the catalyst to be used can be adjusted according to the type of the catalyst, and is 0 to 1 part by weight of the polyhydric alcohol (bis (polyhydroxyphenyl) fluorenes) produced by the method (i).
• the polyhydric alcohol bis (polyhydroxyphenyl) fluorenes
• the reaction may be performed in a solvent.
• the solvent is not particularly limited and can be selected according to the raw materials used.
• an alkylene oxide is used, the above-mentioned solvents and the like can be used.
• alkylene carbonate is used, alcohols (such as methanol and ethanol) can be used in addition to the above-mentioned solvents.
• C alkylene such as alcohol and ethylene glycol
• the amount of the solvent used is about 120 parts by weight, preferably about 1.5 to 10 parts by weight, more preferably about 2 to 5 parts by weight, based on 1 part by weight of the polyhydric alcohol produced by the method (i). There may be.
• the reaction can be adjusted according to the kind of the compound to be added (alkylene oxide, alkylene carbonate) or the like, and is, for example, 0 to 170 ° C, preferably 10 to 150 ° C, more preferably 20 to 130 ° C. In most cases, it is performed at about C In particular, when an alkylene carbonate is used, the reaction is often performed at, for example, about 70 to 150 ° C., preferably about 80 to 120 ° C. in order to efficiently perform the decarboxylation reaction.
• the reaction time is, for example, 30 minutes to 48 hours, usually, 124 hours, preferably about 110 hours.
• the reaction may be carried out with stirring or in the air or in an inert atmosphere (such as nitrogen or a rare gas), or at normal pressure or under pressure. Further, the reaction may be carried out while removing generated gas (such as carbon dioxide) as necessary. Further, in the same manner as described above, the reaction mixture after completion of the reaction is purified by using a conventional purification method (extraction, crystallization, etc.) to obtain a polyhydric alcohol-containing alkylene oxide-cured product.
• an inert atmosphere such as nitrogen or a rare gas
• generated gas such as carbon dioxide
• the (meth) acrylic acid derivative to be reacted with a polyhydric alcohol includes lower alkyl (meth) acrylates (eg, methyl (meth) acrylate, C alkyl, such as ethyl (meth) acrylate and butyl (meth) acrylate
• lower alkyl (meth) acrylates eg, methyl (meth) acrylate, C alkyl, such as ethyl (meth) acrylate and butyl (meth) acrylate
• (meth) acrylic acid acrylate and the ride commercially available products or synthesized products may be used.
• (meth) acrylic acid chloride can be prepared by reacting chloride salt with (meth) acrylic acid.
• the amount of (meth) acrylic acid or a derivative thereof used is, for example, 110 mol, preferably 115 mol, per 1 mol of a hydroxyl group (hydroxyl group corresponding to P) of a polyhydric alcohol. Mole, more preferably about 113 mole.
• a catalyst (acid catalyst, base catalyst, or the like) may be appropriately used.
• an acid catalyst is preferably used.
• a base may be suitably used for trapping (trapping) halogenated hydrogen (eg, salted hydrogen).
• the acid catalyst is not particularly limited as long as it is an esterified acid catalyst.
• inorganic acids sulfuric acid, hydrochloric acid, phosphoric acid, etc.
• organic acids sulfonic acids (methanesulfonic acid, ethanesulfonic acid, Alkanesulfonic acid such as fluoromethanesulfonic acid, and aranesulfonic acid such as p-toluenesulfonic acid), and the like
• solidified acids inorganic acids such as acids (sulfuric acid, phosphoric acid, heteropolyacid) Acid (organic acid), solid acid (solid phosphoric acid, etc.)], cation exchange resin, metal oxide (ZnO, etc.), metal halide (CuCl, etc.), metal salt
• the acid catalysts may be used alone or in combination of two or more!
• the base is not particularly limited as long as it is an inert base with respect to (meth) acrylic acid or a derivative thereof (such as (meth) acrylic anhydride).
• Alkali metal or alkaline earth metal bicarbonate such as potassium metal or alkaline earth metal carbonate, sodium bicarbonate, etc., metal carboxylate (alkali metal or alkaline earth metal acetate such as sodium acetate, calcium acetate, etc.)
• Inorganic bases such as metal hydroxides (such as alkali metal hydroxides such as sodium hydroxide and sodium hydroxide and alkaline earth metal hydroxides such as calcium hydroxide); amines [ For example, tertiary amines (trialkylamines such as triethylamine, triisopropylamine and tributylamine, and aromatic tertiary amines such as ⁇ , ⁇ ⁇ ⁇ dimethylaniline) Emissions, such as organic bases, such as heterocyclic tertiary Amin
• the amount of the catalyst (acid catalyst, base) used depends on the type of the catalyst, but is, for example, 0.01 to 10 parts by weight per 100 parts by weight of (meth) acrylic acid or a derivative thereof. Preferably it may be about 0.05-5 parts by weight, more preferably about 0.1-3 parts by weight.
• the reaction may be carried out in the presence of a polymerization inhibitor (thermal polymerization inhibitor), if necessary.
• a polymerization inhibitor thermal polymerization inhibitor
• the polymerization inhibitor include hydroxyphenols (hydroquinones such as hydroquinone and hydroquinone monomethyl ether, catechols such as t-butyl catechol, etc.), amines (such as diphenylamine), 2,2-diphenyl-1-picuril. Examples thereof include ruhydrazyl, 4-hydroxy-2,2,6,6-tetramethylpiperazine, 1-year-old xyl, and the like.
• the polymerization inhibitors may be used alone or in combination of two or more.
• the amount of the polymerization inhibitor to be used is, for example, 0.001 to 5 parts by weight per 100 parts by weight of (meth) acrylic acid or a derivative thereof. Preferably, it may be about 0.005 to 3 parts by weight, more preferably about 0.01 to 1 part by weight.
• the reaction may be carried out without a solvent, but can usually be carried out in a solvent.
• the solvent organic solvent
• examples of the solvent include hydrocarbons (aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene); and halogenated hydrocarbons (methylene chloride, Solvent, dialkyl ethers such as getyl ether, cyclic ethers such as tetrahydrofuran, dioxane, etc., ketones (acetone, methyl ethyl ketone, etc.) Dialkyl ketones).
• the solvents may be used alone or in combination of two or more.
• the amount of the solvent to be used is, for example, 10 to 500 parts by weight, preferably 30 to 100 parts by weight of the total amount of the polyhydric alcohol represented by the formula (2) and (meth) acrylic acid (or a derivative thereof). — 300 parts by weight, more preferably about 50 to 200 parts by weight.
• the reaction temperature varies depending on the type of (meth) acrylic acid or a derivative thereof used, but is usually 30 to 180 ° C, preferably 40 to 150 ° C, and more preferably about 50 to 130 ° C. Often, it is done.
• the reaction time can be adjusted according to the type of the raw material, the reaction temperature, the concentration in the solvent, and the like, and is, for example, about 30 minutes to 48 hours, usually about 124 hours, preferably about 110 hours.
• the reaction may be carried out while refluxing, while removing water or alcohol by-produced.
• the reaction may be carried out in air or under an inert atmosphere (nitrogen, rare gas, etc.) with stirring or at normal pressure or under pressure.
• the produced polyfunctional (meth) atarylate can be obtained by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, and column chromatography, or a separation method combining these. It may be separated and purified by a means.
• separation means such as filtration, concentration, extraction, crystallization, recrystallization, and column chromatography, or a separation method combining these. It may be separated and purified by a means.
• the present invention includes a polymerizable composition composed of a polyfunctional (meth) acrylate (the compound represented by the formula (1)).
• the polymerizable composition can usually be composed of at least a polyfunctional (meth) acrylate (the compound represented by the formula (1)) and a polymerization initiator.
• the polyfunctional (meth) acrylates may be used alone or in combination of two or more to form a polymerizable composition. [0077] (Polymerization initiator)
• the polymerization initiator includes a thermal polymerization initiator and a photopolymerization initiator.
• thermal polymerization initiator include dialkyl peroxides (di-butyl peroxide, dicumyl peroxide, etc.), disilver oxides (dialkanol peroxide (lauroyl peroxide, etc.), diaroyl peroxide, etc.).
• a photopolymerizable composition can be formed by combining with a photopolymerization initiator.
• the photopolymerization initiator include various known and commonly used photopolymerization initiators, for example, benzoins (benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether), and acetophenones (acetophenone). 2-hydroxy-2-methyl-1-phenylpropane 1one, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,
• anthraquinones anthraquinone, 2-methyl Luangthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, etc.
• thioxanthones (2,4 dimethylthioxanthone, 2,4-dimethylthioxanthone, 2-cycloethylthoxanthone, 2,4- Examples thereof include diisopropyl thioxanthone, ketals (acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.), benzophenones (benzophenone, etc.), and xanthones.
• These photopolymerization initiators may be used alone or in combination of two or more.
• the photopolymerization initiator may be combined with a photosensitizer.
• photosensitizers include tertiary amines ⁇ eg, trialkylamine, trialkanolamine (such as triethanolamine), N, N-dimethylaminoethyl benzoate [p (dimethylamino) ethyl benzoate, etc.
• N, N-dimethylamino benzoate [amyl p (dimethylamino) benzoate etc.], alkyl dialkylamino benzoates, and bis (dialkylamino) such as 4,4 bis (getylamino) benzophenone (Michler's ketone)
• Conventional photosensitizers such as benzophenone, dialkylaminobenzozophenone such as 4- (dimethylamino) benzophenone, and the like.
• the photosensitizers may be used alone or in combination of two or more.
• the amount of the polymerization initiator (and the total amount of the photosensitizer) used is 0.1 to 30 parts by weight (for example, 110 to 30 parts by weight) per 100 parts by weight of the polyfunctional (meth) acrylate. ), Preferably about 11 to 20 parts by weight (for example, 5 to 25 parts by weight), and more preferably about 1.5 to 10 parts by weight. If the amount of the photopolymerization initiator is too small, the polymerizability (or photocurability) of the composition is reduced, while if it is too large, the photopolymerization initiator itself absorbs and the photocurability in a thick film is reduced. May decrease.
• the amount of the photosensitizer used is 5 to 200 parts by weight, preferably 10 to 150 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of the polymerization initiator (photopolymerization initiator). It may be about parts by weight.
• the polymerization initiator may be composed of a thermal polymerization initiator and a photopolymerization initiator.
• the polymerization initiator is usually often composed of at least a photopolymerization initiator.
• the polymerizable composition may contain a diluent (reactive diluent, non-reactive diluent).
• a diluent reactive diluent, non-reactive diluent.
• the reactive diluent (polymerizable diluent) include a monofunctional monomer and a polyfunctional monomer.
• Monofunctional monomers include alkyl (meth) acrylates [C alkyl (meth) acrylates such as methyl (meth) acrylate] and cycloalkyl (meth) acrylates.
• Di- or tetracycloalkyl (meth) acrylates such as isobutyl acrylate], aryl (meth) acrylate [poly (meth) acrylate], hydroxyalkyl (meth) acrylate [ Hydroxy C alkyl (meta) such as (2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate
• (Meth) acrylic acid C such as glycol mono (meth) acrylate, alkoxyalkyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, and 3-methoxybutyl (meth) acrylate
• N-substituted (meth) acrylamides N, N-diCalkyl (meth) acrylamides such as N, N-dimethyl (meth) atarylamide, N-methylol (meth) ataryl
• N-hydroxy C alkyl (meth) acrylamides such as
• acrylic monomers such as atalylate (such as N, N-dimethylaminoethyl acrylate), glycidyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate.
• Polyfunctional monomers include bifunctional (meth) acrylate, polyfunctional (meth) acrylate, epoxy group-containing compounds (glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl iso- Poly (glycidyl ethers such as cyanurate) (for example, di to penta) (meth) acrylate and melamine acrylate.
• Examples of the bifunctional (meth) acrylate include alkylene glycol di (meth) atalylate [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di C-alkylene glycol di (meth) atalyles such as (meth) atalylate, hexanediol di (meth) atalylate, and neopentyl alcoholic di (meth) atalylate Etc.), (poly) oxyalkylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol (Poly) oxy C alkylene glycols such as di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly
• Di (meth) atalylate eg, glycerin di (meth) atalylate, trimethylolpropane di (meth) atalylate, tris (hydroxyethyl) isocyanurate di (meta) acrylate
• Atelylate pentaerythritol di (meth) atalylate, and the like, and tetra (di (meth) atalylate).
• Polyfunctional (meth) acrylates include polyhydric alcohols (or C alkylene oxides thereof).
• Trifunctional or polyfunctional (meth) acrylates such as glycerin tri (meth) atalylate, trimethylolethanetri (meth) atalylate, trimethylolpropane tri (meth) atalylate, trimethylol Triol (tri) (meth) acrylates such as propane ethoxy tri (meth) acrylate and tris (hydroxyethyl) isocyanurate tri (meth) acrylate; pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meta) ) Triol or tetra (meth) atalylate of tetraol such as acrylate; ditrimethylolpropane tetra (meth) atalylate; dipentaerythritol tetra (meth) atalylate; dipentaerythritol hexa (meth) atalylate; Can be illustrated
• the reactive diluents may be used alone or in combination of two or more.
• the amount of the reactive diluent to be used can be selected from the range of 0 to 100 parts by weight based on 100 parts by weight of the polyfunctional (meth) acrylate, for example, 1 to 100 parts by weight, preferably 1 to 50 parts by weight. Parts, more preferably about 1 to 30 parts by weight.
• the diluent also includes a non-reactive diluent.
• a non-reactive diluent can improve the coatability of the polymerizable composition.
• the non-reactive diluent (or solvent) include organic solvents, for example, aliphatic hydrocarbons such as hexane, heptane, octane, and decane; ketones such as ethyl methyl ketone and cyclohexanone; toluene, xylene, and tetramethyl Benze Aromatic hydrocarbons such as cellosolve, methylcellosolve, butylcellosolve, carbitone, methinorecanolebitone, butinorecanolebitone, propylene glycol monomethyl ether, dipropylene glycolone monomethinole ether, Glyconorethenoates such as dipropylene glycol jet and tripropylene glycol monomethino
• the use amount (addition amount) of the non-reactive diluent varies depending on the application method and the like, but a range force of 0 to 500 parts by weight can be selected with respect to 100 parts by weight of the polyfunctional (meta) acrylate. Usually, it may be about 10 to 400 parts by weight, preferably about 20 to 300 parts by weight, and more preferably about 30 to 200 parts by weight.
• the polymerizable composition may further include a polysilane.
• Polysilane can be effectively added to a polymerizable composition used for optical or electrical use (particularly for optical use) because it can efficiently lower the dielectric constant and increase the refractive index.
• flame retardancy and water repellency can be improved depending on the type of polysilane (such as a three-dimensional structure such as linear, branched, network, or cyclic structure, and the type of terminal group), flame retardancy and water repellency can be improved.
• the polysilane is not particularly limited as long as it is a linear, cyclic, branched, or network compound having a Si-Si bond.
• the polysilane is represented by the following formulas (3) to (5). Examples include polysilanes (including oligosilanes and copolysilanes) having at least one structural unit among the structural units. [0093] [I-Dori 7]
• R 5 -R 7 are the same or different and each represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkenyl group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkyl group, an aryl group
• x, y and z each represent 0 or an integer of 1 or more, and the total of x, y and z is 5 to 400.
• Examples of such a polysilane include a linear or cyclic polysilane having a structural unit represented by the formula (3), a branched or cyclic polysilane having a structural unit represented by the formula (4) or (5).
• Reticulated polysilane, polysilane having a combination of the structural units represented by the above formulas (3) to (5) (cyclic, branched or reticulated polysilane, for example, represented by the above formulas (3) and (4)) And the like).
• the alkyl group is a C alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl (preferably a C alkyl group, particularly a C alkyl group).
• Alkoxy groups include methoxy, ethoxy, etc.
• alkoxy group preferably C alkoxy group, particularly C alkoxy group.
• Examples of the keninole group include a C phenol group such as vinylol and alinole (preferably a C
• cycloalkyl group examples include C cycloalkyl groups such as cyclohexyl and methylcyclohexyl (preferably C cycloalkyl groups, more preferably
• Cycloalkyl group As the cycloalkyloxy group, cyclohexyl
• C cycloalkyloxy group such as oxy (preferably C cycloalkyloxy group)
• Cycloalkenyl groups include C cycloalkenyl such as cyclohexenyl.
• a kenyl group (preferably a c cycloalkyl group) is mentioned.
• a reel group As a reel group,
• C aryl groups such as methyl, methyl and dimethyl (preferably C And more preferably a C aryl group).
• aryloxy group As an aryloxy group,
• C aryloxy groups such as phenoxy (preferably C aryloxy groups);
• Aralkyl groups include C aryl C alkyl such as benzyl and phenethyl.
• a C aryl C alkyloxy group such as benzyloxy (preferably C
• silyl group silyl group, disila
• Si silyl group preferably a Si silanyl group
• R 5 to R 7 are the aforementioned organic substituent or silyl group
• at least one hydrogen atom thereof is substituted by a substituent such as an alkyl group, an aryl group or an alkoxy group.
• a substituent such as an alkyl group, an aryl group or an alkoxy group.
• Examples of such a substituent include the same groups as described above.
• a hydrogen atom, a hydroxyl group, an alkoxy group, and a silyl group are often substituted with terminal groups.
• the substituents R 5 to R 7 are usually hydrocarbon groups such as an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group.
• aryl group C aryl group such as phenol
• the terminal substituent is usually a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a silyl group, a halogen atom (chlorine Atom) and is preferably composed of at least a hydroxyl group.
• the structural unit of a specific polysilane, for example, R 5 and R 6 months ⁇ , structural units (3) shift is also Ariru group, R 5 is a Ariru group and R 6 is an alkyl group Structural unit (3), wherein R 5 is an alkyl group or an aryl group, and R 6 is a hydrogen atom, a hydroxyl group, an alkoxy group, an alkenyl group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkyl group, Aryl group, aryloxy group, aralkyl group, aralkyloxy group and silyl group Structural unit (3) which is at least one selected group, structural unit (4) in which R 7 is an alkyl group, and R 7 is an aryl group There are certain structural units (4) and structural units (5).
• Preferred polysilanes at least one of R 5 and R 6 are structural units of a Ariru group (3) and, polysilane R 7 contains a structural unit (4) is Ariru group, in particular, R 5 and R 6 Structural units (3) each of which is an aryl group (especially a phenyl group), and structural units (3) in which R 5 is an aryl group (especially a phenyl group) and R 6 is an alkyl group (especially a methyl group) And polysilanes composed of structural units (4) in which R 7 is an aryl group (particularly a phenyl group).
• the structure of the polysilane is preferably cyclic, branched, or mesh-like, and particularly preferably branched.
• the polysilane copolymer may be a random copolymer, a block copolymer, or a graft copolymer.
• Typical polysilanes include cyclic polydiaryl silanes (eg, cyclic polydiphenylsilanes (5- to 8-membered rings)), linear polyalkylaryl silanes (such as linear polymethylphenylsilane), and straight-chain polydiarylsilanes.
• cyclic polydiaryl silanes eg, cyclic polydiphenylsilanes (5- to 8-membered rings
• linear polyalkylaryl silanes such as linear polymethylphenylsilane
• straight-chain polydiarylsilanes straight-chain polydiarylsilanes.
• Polysilin means a branched polysilane composed of the structural unit (4).
• the degree of polymerization of the polysilane that is, the sum of x, y and z in the structural unit (3)-(5) may be about 5 to 400, preferably about 10 to 350, and more preferably about 20 to 300. .
• the molecular weight of the polysilane is 300 to 100000, preferably 400 to 50,000 in number average molecular weight, and more preferably about 500 to 20000! / !.
• the polysilane can be prepared using various known methods.
• a silicon-containing monomer having a specific structural unit such as mono- or tetrahalosilanes
• magnesium is used as a reducing agent to remove halosilanes
• Polycondensation method (“magnesium reduction method”, W098Z29476, JP 2001-48987, JP 2002-226586, etc.)
• halosilanes in the presence of alkali metal Dehalogen condensation polymerization (“Kipping method", J. Am. Chem.
• the magnesium reduction method (particularly, the method described in JP-A-2001-48987 and JP-A-2002-226586) is most preferable.
• the method of introducing the silanol group (terminal hydroxyl group) is not particularly limited, but for example, it can be easily introduced by adding water to the polysilane obtained by the above method.
• the ratio of the polysilane can be selected from a range of 0 to 100 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate, and is usually 0.1 to 50 parts by weight, preferably 0.5 to 0.5 parts by weight. — It may be 20 parts by weight, more preferably about 11 to 20 parts by weight.
• the polymerizable composition may be, if necessary, a conventional additive such as a coloring agent or a stabilizer (a heat stabilizer, an antioxidant, or an ultraviolet absorber) within a range that does not impair the original characteristics. ), Fillers, antistatic agents, flame retardants (phosphorus-containing compounds such as organic phosphorus compounds and inorganic phosphorus compounds, halogen-containing flame retardants, metal oxides, metal hydroxides, metal sulfides, etc.), flame retardant aids Agents, leveling agents, silane coupling agents, polymerization inhibitors (or thermal polymerization inhibitors), and the like.
• the additives may be used alone or in combination of two or more.
• the proportion of the additive can be appropriately selected according to the type of the additive.
• 0.5 to 100 parts by weight, 100 parts by weight of the polyfunctional (meth) acrylate Preferably it may be about 50 parts by weight, more preferably about 120 parts by weight.
• the polymerizable composition can be prepared by mixing or mixing a polyfunctional (meth) acrylate and at least a polymerization initiator.
• the mixing method is not particularly limited, and a conventional method can be used.
• the polyfunctional (meth) acrylate and the polymerization initiator and other components such as polysilane
• the diluent particularly, non-reactive Dissolve (or suspend) in a diluent containing a diluent
• coating Coating
• the polymerizable composition (particularly, the photopolymerizable composition) (or the polyfunctional (meth) acrylate) of the present invention can be used to obtain a polymerized or cured (or crosslinked) cured product (molded article).
• a cured product a cured product of the polymerizable composition composed of the polyfunctional (meth) acrylate and the polymerization initiator, a cured product of the polyfunctional (meth) acrylate
• a cured product of the polyfunctional (meth) acrylate is a molded article
• it can be obtained by subjecting the polymerizable composition to a curing treatment (heating treatment or light irradiation treatment) during or after the molding.
• a film-shaped cured product may be obtained by applying a polymerizable composition to a substrate to form a coating film (or a thin film), and then performing a curing treatment.
• a coating film or a thin film
• Such coatings (or thin films) can be formed by conventional methods such as flow coating, spin coating, spray coating, screen printing, casting, bar coating, curtain coating, and roll coating. , A dip method or the like can be used.
• the composition may be dried by a conventional method, and may be dried by heating if necessary. The heating temperature in drying can be appropriately selected depending on the type of the polymerization initiator and the diluent (non-reactive diluent).
• the drying treatment may be performed in an atmosphere of an inert gas such as nitrogen or argon or in air, or may be performed under normal pressure or reduced pressure.
• the thickness of the coating film may be, for example, about 0.01 to 100 / zm, preferably about 0.1 to 10 ⁇ m, and more preferably about 0.1 to 1 ⁇ m. .
• Curing treatment for the polymerizable composition can be selected according to the type of polymerization initiator (thermal polymerization initiator and Z or photopolymerization initiator), and can be performed by heat treatment and Z or light irradiation treatment.
• the heating temperature is a force depending on the type of the polymerization initiator, for example, about 50 to 250 ° C, preferably about 60 to 150 ° C, and more preferably about 70 to 120 ° C.
• light irradiation sources include, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a hydrogen lamp, a deuterium lamp, a fluorescent lamp, a halogen lamp, an excimer laser, and a nitrogen laser.
• the light irradiation amount of energy, application, coating thickness, etc. by different forces typically, 0. 1- lOOOOmjZcm 2, preferably about 0.
• the exposure time is, for example, 1 second to 13 hours, preferably 5 seconds to 12 hours, and more preferably 10 seconds to 11 hours.
• Light irradiation may be performed in an atmosphere of an inert gas such as nitrogen or argon or in the air, or may be performed under normal pressure, increased pressure, or reduced pressure.
• the heat treatment and the light irradiation treatment may be combined!
• a polymerizable composition containing a photopolymerization initiator may be further heated after light irradiation (or with light irradiation) in order to promote curing or crosslinking.
• the shape of the cured product (molded product) is not particularly limited, and examples thereof include a two-dimensional structure (such as a film, a sheet, and a plate) and a three-dimensional structure (such as a tube, a rod, and a tube). And the like).
• the cured product of the present invention has a high refractive index and is excellent in optical properties.
• the cured product (or the cured product of the polyfunctional (meth) acrylate) has a refractive index of 1.55 or more (for example, about 1.59-1.7), preferably 1.60 or more (for example, , About 1.60-1.7).
• the refractive index is, for example, about 1.60 to 1.7, preferably about 1.62 to 1.7.
• the cured product of the present invention is particularly suitable as an optical material (coating agent such as an optical overcoat agent, a hard coat agent, an antireflection film, an eyeglass lens, an optical fiber, an optical waveguide, a hologram, etc.).
• an optical material coating agent such as an optical overcoat agent, a hard coat agent, an antireflection film, an eyeglass lens, an optical fiber, an optical waveguide, a hologram, etc.
• Examples of the shape of such an optical material include a film or sheet, a plate, a lens, and a tube.
• the polyfunctional (meth) atalylate (and the polymerizable composition thereof) of the present invention has a high refractive index and has light transmittance, hardness, weather resistance, flexibility, mechanical strength, and dimensional stability. It is excellent in plasticity and processability, and is useful as a plastic raw material that meets various required performances. In particular, it is excellent in heat resistance and moisture resistance, and has a high refractive index and high hardness, so that it is used for optical materials, such as optical overcoating agents, hard coating agents, antireflection films, spectacle lenses, optical fibers, etc. , Optical waveguides, holograms and the like.
• polyhydric alcohol 40 g (0.06 mol) was obtained, acrylic acid 43 g (0.6 mol), 70 weight 0/0 of methanesulfonic acid solution lg, hydroquinone 0. OLG and toluene lOOmL fitted with Dinshi Yu Tak trap The mixture was placed in a reactor, and the esterification reaction was carried out for 5 hours under reflux of toluene. Water generated during the esterification reaction was removed with a Dean-Stark trap to obtain 45 g of the polyhydric alcohol tetraatalylate. Analysis by high performance liquid chromatography 1 revealed that the purity of tetraatalylate was 98%.
• Polysilane was synthesized by the magnesium reduction method of chlorosilanes described in W098Z29476. That is, THF (tetrahydrofuran) 400ml, Mg (magnesium) 37g , 10 g of iron chloride (FeCl) and 15 g of lithium bromide in a reactor, and
• Example 2 To 40 g of the tetraphthalate obtained in Example 1, 0.6 g of 2-hydroxy-2-methyl-1 phenylpropane 1 on was added, and after UV (ultraviolet) light irradiation, the mixture was further cured at 80 ° A cured product was obtained as a transparent film by heat curing with C for 1 hour.
• the glass transition temperature Tg of the obtained cured product was 225 ° C., and the refractive index was 1.630 (D line).
• Example 2 Cured as a transparent film by photocuring and heat curing in the same manner as in Example 2 except that 8 g of the polysilane obtained in Synthesis Example 1 was added to 40 g of the tetraacrylate obtained in Example 1 I got something.
• the Tg of the obtained cured product was 220 ° C., and the refractive index was 1.645 (D line).

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