CN103764708A - Photopolymerizable composition, photopolymerizable coating agent, laminate, and polarizing plate - Google Patents

Photopolymerizable composition, photopolymerizable coating agent, laminate, and polarizing plate Download PDF

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Publication number
CN103764708A
CN103764708A CN201280041470.1A CN201280041470A CN103764708A CN 103764708 A CN103764708 A CN 103764708A CN 201280041470 A CN201280041470 A CN 201280041470A CN 103764708 A CN103764708 A CN 103764708A
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Prior art keywords
compound
ring
optical polymerism
ketone
methyl
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CN201280041470.1A
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CN103764708B (en
Inventor
石崎慎治
冈本淳二
丹羽聪子
小出昌史
滨田直宏
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Toyochem Co Ltd
Artience Co Ltd
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Toyo Ink SC Holdings Co Ltd
Toyochem Co Ltd
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Priority claimed from JP2011184037A external-priority patent/JP5304859B2/en
Priority claimed from JP2012080883A external-priority patent/JP5824747B2/en
Application filed by Toyo Ink SC Holdings Co Ltd, Toyochem Co Ltd filed Critical Toyo Ink SC Holdings Co Ltd
Publication of CN103764708A publication Critical patent/CN103764708A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polarising Elements (AREA)

Abstract

Provided is a photopolymerizable composition which is characterized by containing (A) a three-membered cyclic oxirane compound and one or more compounds that are selected from among (B1) four- or more-membered cyclic compounds having two or more oxygen atoms, (B2) four- or more-membered cyclic compounds having one or more oxygen atoms and one or more sulfur atoms, and (C) compounds having both at least one cyclic structure and a hydroxyl group and having a molecular weight of 500 or less.

Description

Optical polymerism composition, optical polymerism coating agent, duplexer and Polarizer
Technical field
The present invention is about a kind of optical polymerism composition, the coating agent that uses it, duplexer and Polarizer.
Background technology
In recent years, due to the progress at full speed of electronic product, the various flat-panel monitors (FPD) such as liquid-crystal display (LCD), plasma display (PDP), rear projection display (RPJ), EL indicating meter (ELD), light emitting diode indicator, are used as the display unit in various fields.For example, these FPD are not only take the indicating meter of Personal Computer, LCD TV as representative is in indoor use, also can with being loaded into vehicle indicating meter etc., use as navigation.
For such display unit, conventionally according to purposes, use the various films that prevent from the anti-reflective film of the reflection of external light source, prevent protective membrane (Protect film) that the surface of display unit is injured etc.For example, at the liquid crystal cells that forms LCD with in part, by stacked to Polarizer, phase retardation film.
And; these anti-reflective films, prevent protective membrane (Protect film) that the surface of display unit is injured etc.; especially for surfaces such as PDP, LCD, ELD, it is the coat film of the image display device of plane; except optical characteristics; owing to requiring scuff resistance, pencil hardness, resistance to chemical reagents, weathering resistance; conventionally by optical polymerism resins such as thermohardening type resin or ultraviolet hardenings, on transparency carrier, directly form or form the thin film of 4 to 20 μ m degree and manufacture across undercoat (primer layer).
But traditional coat film, even if the hardness of its coat is abundant, in the case of the thin transparency carrier distortion causing down below of its coating thickness, exists relatively coat to be also out of shape, the problem of the lower hardness of coat film entirety.On the other hand, if just make common 0.5 to the 20 μ m of the Thickness Ratio of coat thicker, although the hardness of the coat film of gained improves, exist become easy generation coat destruction, peel off, because of cure shrinkage, cause the large problem of curling change of coat film simultaneously.And, take the hardness that further improves coat as object, be improved the method for the crosslinking rate of optical polymerism resin, but similarly the curling change of coat film is large.
Curling when large, because the weather resistance after productivity or the laminating of the display surface laminating step at next step etc. significantly reduces, therefore in the situation that coat is located on transparency carrier, thickness that must restriction coat, the crosslinking rate of optical polymerism resin.So for not hindering the thickness of coat of next step, the situation of pencil hardness take 2H to 3H as limit is many.
In order to have low curling and high pencil hardness concurrently, at the face of at least one side of transparent film or thin slice base material, Vickers (Vickers) hardness of regulation optical polymerism resin, the method that 2 layers of coat are set is recorded in patent documentation 1(and refers to Patent Document 1).
But when its record the method is only used optical polymerism composition, curling change is large, curling in order to improve, and makes coat contain the particulates such as silicon oxide.But, such containing fine-grained coat, because the transmitance of film reduces, while being used in various image display device, the problem that has contrast gradient to reduce.
And further, FPD is not only and utilizes as display unit, sometimes also on its surface, contact panel function is set, and utilizes as input unit.For contact panel, also can use protective membrane, anti-reflective film, ITO evaporation resin molding etc.
And, for display unit, from back side illuminaton, make the luminous mode backlight of liquid crystal layer universal, in the lower face side of liquid crystal layer, the back light unit of installing side light type, full run-down type etc.About such side light type backlight unit, substantially possess square tabular light guiding plate, the light diffusing sheet that is disposed in the face side of light guiding plate configuring as the wire el lamp of light source, along the end of lamp, the prismatic lens that is disposed in the face side of light diffusing sheet.Recently, for light source, because of from cold-cathode tube (COFL), become and use color reprodubility, the good photodiode (LED) of province's power, the requirement that therefore further improves thermotolerance, dimensional stability.
Such film is attached at across caking agent and is attached body, thereby is used in display unit.The caking agent that display unit is used, first, because requirement is transparent, thermotolerance is good, is generally used the 2 solution curing type caking agents that contain solvent take acrylic resin as host.
Herein, in aforementioned various films, light polarizing film be generally polyvinyl alcohol (PVA) be polarisation two sides with triacetyl cellulose (TAC) be, cycloolefin (COP) is protective membrane clamping, with the 3-tier architecture of water system caking agent laminating.Therefore,, with regard to light polarizing film, owing to forming the dimensional change characteristic difference of material of each layer, along with the variation of temperature, humidity, easily produce the warpage that dimensional change causes.
TAC mesentery, is used water system caking agent because Water Vapour Permeability is high, can non-volatile moisture according to former state with PVA be under the overlapping state of polarisation, make water dry carry out simultaneously bonding.
As protective membrane, proposed (patent documentations 2,3,4) such as the good polyester mesentery of the optical characteristics such as low cost, the transparency, polyvinyl chloride mesentery, polycarbonate mesentery, vinylformic acid mesentery, amorphism polyolefine mesentery, cycloolefin mesenterys and replaced TAC mesentery.These protective membranes because than TAC film have more hydrophobicity, Water Vapour Permeability is low, with PVA be polarisation overlapping front must fully dry moisture, but the water capacity is easily residual, when water is residual, has the problem of bonding strength deficiency, bad order etc.
So, for polyethenol series polarisation and the hydrophobicity protective membrane of fitting, replace water caking agent with optical polymerism caking agent.
So the Polarizer that liquid crystal indicator is used fits in liquid crystal cells across bond layer.Now there is foreign matter to sneak into etc. in the situation of laminating fault, peel off Polarizer, liquid crystal cells is recycled.If PVA is the bonding force deficiency of polarisation and protective membrane, is to peel off between polarisation and protective membrane at PVA when Polarizer is peeled off, protective membrane residues in liquid crystal cells, and liquid crystal cells cannot be recycled.So to require PVA be bonding force between polarisation and protective membrane than for Polarizer is higher with the bonding force of the caking agent of liquid crystal cells laminating, further, more preferably PVA is that polarisation and protective membrane can not be peeled off.
And, liquid crystal indicator because of at high temperature, the inferior various environment of high humidity use, Polarizer also requires its damp and hot patience very harshly.At PVA, being in the bonding hypodynamic situation of polarisation and protective membrane, if expose for a long time (exposing damp and hot) under hot and humid degree, is the dimensional change of polarisation because of PVA, at PVA, is to produce and peel off between polarisation and protective membrane.
At TOHKEMY 2004-245925(patent documentation 5) in, the caking agent that to disclose as hydrogenation (also referred to as the hydrogenation) bispheno type epoxy ethane colophony that is not resin containing the oxyethane (oxirane) of aromatic nucleus be principal constituent, has proposed by heating or irradiating active energy beam and photopolymerisable bonding method.
But, the caking agent that patent documentation 5 is recorded, its viscosity is high, and coating is had any problem.
Moreover; as the caking agent that patent documentation 5 is recorded; if take A Hydrogenated Bisphenol A type oxirane compound during as principal constituent, in the situation that using the protective membranes such as polyester mesentery, polyvinyl chloride mesentery, polycarbonate mesentery, vinylformic acid mesentery, there is the problem that these protective membranes completely cannot be bonding.
In addition, laminating PVA is the thickness of the bond layer of polarisation and protective membrane, in order to improve the transmitance of light, in order to reduce costs, requires thin as much as possible.Particularly, to require be the thickness of 0.1 to 6 μ m and level and smooth to bond layer.
For the industrial bond layer that such film is set, during coating optical cement, preferably use miniature intaglio plate coating machine.The intaglio plate coating machine that diameter is little, by using more tiny intaglio plate, can form film.But, when the viscosity of caking agent is high, may the thin intaglio plate (for example 500 line/inches) of limit even if use, also cannot form the bond layer of 0.1 to 6 μ m thickness.
So in order to form the bond layer of 0.1 to 6 μ m thickness, the viscosity of caking agent is necessary for 1 to 1500mPas.
In TOHKEMY 2008-63397 communique (patent documentation 6), disclose the more low viscous caking agent take aliphatic epoxy ethane compounds as principal constituent, proposed by heating or irradiating active energy beam and photopolymerisable bonding method.While using the caking agent that patent documentation 5 records, do not exposing under damp and hot state, PVA is that polarisation is that polarisation can be bonding with abundant intensity with cycloolefin mesentery with TAC mesentery, PVA.
But, in the case of using the caking agent recorded of patent documentation 6, be exposed to when damp and hot, PVA be polarisation with the protective membrane of either side between or PVA be that between sub and two protective membranes of polarisation, generation is peeled off.
Moreover; if as the caking agent that patent documentation 6 is recorded; take aliphatic epoxy ethane compounds as principal constituent,, in the situation that using the protective membranes such as polyester mesentery, polyvinyl chloride mesentery, polycarbonate mesentery, vinylformic acid mesentery, these protective membranes have problem that completely cannot be bonding.
In TOHKEMY 2008-257199 communique (patent documentation 7), disclose to comprise and in molecule, there is the caking agent in the multiple functional radical oxyethane resin of more than 1 ester ring type epoxy group(ing) and molecule without the multiple functional radical oxyethane resin of the three membered cyclic ether that is incorporated into ester ring type ring.
The light solidified of general alicyclic epoxy resin is good, but viscosity height is more than 200mPas.
On the other hand, with regard to not having the multiple functional radical oxyethane resin of the three membered cyclic ether that is incorporated into ester ring type ring, light solidified is low, but is the low viscosity below so-called 100mPas.Therefore, for coated thin film, reduce caking agent viscosity, cannot not increase the content of the multiple functional radical oxyethane resin without the three membered cyclic ether that is incorporated into ester ring type ring.But result solidified nature reduces, adaptation is bad, and being exposed to when damp and hot is to produce and peel off between polarisation and protective membrane at PVA.
On the other hand, in order to maintain solidified nature, cannot not increase the resin with the three membered cyclic ether that is incorporated into ester ring type ring, caking agent viscosity rise, result becomes cannot coated thin film.
Moreover while increasing alicyclic epoxy resin, in the situation that using the protective membranes such as polyester mesentery, polyvinyl chloride mesentery, polycarbonate mesentery, vinylformic acid mesentery, these protective membranes have problem that completely cannot be bonding.
Moreover, in order to reduce the viscosity of caking agent, there is the so-called with an organic solvent method of dilution.
But if with an organic solvent, coating apparatus is necessary for explosion-proof specification, and special solvent recovery unit must be set.
So for the optical polymerism caking agent of Polarizer formation use, requiring substantially not contain under the state of organic solvent is low viscosity.
And, recently in order to improve production rate, require to solidify with low exposure.In the invention of document 5 to 7 records, owing to needing in fact 1000mJ/cm 2above accumulated light, production efficiency is poor.
And disclosing by three membered cyclic oxirane compound, Photoepolymerizationinitiater initiater and phenol in patent documentation 8 is the composition that resole (resol) or the compound that contains hydroxyl form.
But, at the composition that uses patent documentation 8, in the situation of stacked optical film, cannot meet the desired thermotolerance of optical applications, humidity resistance.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2000-127281 communique
Patent documentation 2: TOHKEMY 2001-324616 communique
Patent documentation 3: TOHKEMY 2009-300768 communique
Patent documentation 4: TOHKEMY 2007-140092 communique
Patent documentation 5: TOHKEMY 2004-245925 communique
Patent documentation 6: TOHKEMY 2008-63397 communique
Patent documentation 7: TOHKEMY 2008-257199 communique
Patent documentation 8: No. 2005-520007 report of Japanese Unexamined Patent Application Publication
Summary of the invention
The problem that invention will solve
Even take the optical polymerism composition of dimensional stability, weathering resistance etc. that provides low-light (level) also to there is good solidified nature, there is good thermotolerance, wet fastness, heat while solidifying as problem.And, no matter to be provided in the kind of various bloomings in the laminating of various bloomings, can be easy and firm bonding, in fact containing organic solvent, because the good optical polymerism coating agent of low viscosity film coated is problem.Moreover, to provide the good Polarizer of the good and damp and hot weather resistance of perforation processibility as object.Moreover in the present invention, so-called coating agent, refers to arrange new layer in the general name of the material of base material, according to purposes, is expressed as caking agent, easy bonding coating agent, coating etc.
Solve the means of problem
The inventor etc., in order to solve aforementioned problems, repeat the result of wholwe-hearted research, find to utilize optical polymerism composition shown below, can reach aforementioned target.
That is to say, embodiments of the present invention are about a kind of optical polymerism composition, it is characterized in that, the oxirane compound (A) that contains three membered cyclic and be selected from more than the tetra-atomic ring with more than 2 Sauerstoffatom ring compound (B1), there is ring compound (B2) more than the tetra-atomic ring of more than 1 Sauerstoffatom and more than 1 sulphur atom and there is at least 1 ring texture and the compound (C) of the two molecular weight of hydroxyl below 500 in more than 1 compound.With respect to the aforementioned oxirane compound (A) of 100 weight parts, preferably contain the aforementioned ring compound (B1) of 0.5 to 60 weight part.With respect to the aforementioned oxirane compound (A) of 100 weight parts, preferably contain the aforementioned ring compound (B2) of 0.5 to 60 weight part.With respect to the aforementioned oxirane compound (A) of 100 weight parts, preferably contain the aforesaid compound (C) of 0.5 to 40 weight part.Moreover, with respect to the aforementioned oxirane compound (A) of 100 weight parts, preferably contain the moisture of 0.05 to 3 weight part.Aforementioned oxirane compound (A) preferably contains the compound (a-2) that has the oxirane compound (a-1) of aromatic nucleus and/or have the oxyethane ring of more than 2 three membered cyclic.Aforementioned ring compound (B1) preferably contains the a kind of above compound that is selected from the group that cyclic ester compound (b1-1), cyclic formals compound (b1-2) and cyclic carbonate compound (b1-3) form.Aforementioned cyclic ester compound (b1-1) preferably contains lactone (b1-1-1), and aforementioned cyclic formals compound (b1-2) preferably contains and is selected from dioxolane (dioxolane) class (compound of the group that b1-2-1), diox (dioxane) class (b1-2-2) and trioxane (trioxane) class (b1-2-3) form.The substituting group that aforementioned ring compound (B1) preferably contains through having F atom replaces fluorine-containing ring compound (b1-4) more than at least 1 place.Aforementioned ring compound (B2) preferably ring in have be selected from sulfoxide skeleton, sulfone skeleton, sulfite skeleton, sulfuric ester skeleton, sulphonate skeleton and thioesters skeleton in wantonly more than a kind structure.The ring texture of aforesaid compound (C) is preferably and is selected from wantonly a kind of above ring texture in the above condensation polycyclic class of naphthenic, cyclenes class, phenyl ring and two rings.Aforesaid compound (C) is preferably hydroxyl and is bonded directly to the compound of ring structure and/or hydroxyl by having C 1to C 18the alkylidene group of carbonatoms be bonded to the compound of ring structure.Aforesaid compound (C) is preferably to have and is selected from the two compound (c-1) of more than wantonly a kind ring texture in cyclohexane ring, cyclohexene ring, norcamphane ring, norcamphene ring, diamantane ring, dihydroisobenzofuran (phthalan) ring, Dihydrobenzofuranes (coumaran) ring, piperonyl (piperonyl) ring and look alkane (chromane) ring and hydroxyl.Aforesaid compound (c-1) is hexalin, phenylcarbinol, falls baras camphor, adamantanol, piperitol or 3,4-methylenedioxyphenol.Moreover, with respect to the aforementioned oxirane compound (A) of 100 weight parts, preferably contain the ethene unsaturated compound (D) of 5 to 1000 weight parts.Aforementioned ethene unsaturated compound (D) preferably contains the ethene unsaturates (d-1) with hydroxyl.Preferably further contain Photoepolymerizationinitiater initiater (E).Aforementioned Photoepolymerizationinitiater initiater (E) is for producing the A of acid active specy by rayed +b -the salt representing, this cation A +be preferably and be selected from the group that aromatic series iodide ion and aromatic matte ion form.Optical polymerism composition does not preferably contain in fact organic solvent, and the mensuration viscosity 23 ℃ time is 1 to 1500mPas.
And embodiments of the present invention relate to the optical polymerism coating agent that uses aforementioned optical polymerism composition to become.
Moreover embodiments of the present invention relate to the duplexer in the one or two sides of base material (G) with the layer that aforementioned optical polymerism coating agent forms.Aforementioned substrates (G) is preferably transparent film (H).Aforementioned transparent film (H) is preferably blooming (I).Aforementioned blooming (I) is preferably cellulose acetate mesentery, norcamphene mesentery, vinylformic acid mesentery, polycarbonate mesentery, polyester mesentery or polyvinyl alcohol mesentery.
Moreover embodiments of the present invention relate to the Polarizer in the one or two sides of polyethenol series polarisation with aforementioned duplexer.
Moreover, the present invention relates to following embodiment I.
That is to say, the embodiment of the present application relates to optical polymerism oxyethane based resin composition, its oxirane compound take three membered cyclic is principal constituent, and further contain the ring compound more than tetra-atomic ring with more than 2 Sauerstoffatom, do not contain in fact organic solvent, and the viscosity 23 ℃ time is 1 to 1500mPas's.With respect to the oxirane compound of the aforementioned three membered cyclic of 100 weight parts, preferably contain the ring compound more than tetra-atomic ring with more than 2 Sauerstoffatom of 0.5 to 60 weight part.There is the ring compound more than tetra-atomic ring of more than 2 Sauerstoffatom, be preferably and there is the ring texture that is selected from lactonic ring, carbonic ether ring, dioxolane, diox ring at least a kind.Have the ring compound more than tetra-atomic ring of more than 2 Sauerstoffatom, the substituting group preferably containing through having F atom replaces fluorine-containing ring compound more than at least 1 place.The oxirane compound of three membered cyclic, preferably contains the compound with aromatic nucleus.The oxirane compound of three membered cyclic, preferably contains the compound of the oxyethane ring with more than 2 three membered cyclic.Preferably further contain Photoepolymerizationinitiater initiater.Photoepolymerizationinitiater initiater is the A that produces acid active specy by rayed +b -the salt representing, this cation A +be preferably selected from the group that aromatic series iodide ion and aromatic matte ion form.
And the embodiment of the present application relates to the duplexer that uses the bonding blooming of aforementioned optical polymerism coating agent to become.
Moreover the embodiment of the present application relates to the Polarizer that uses optical polymerism coating agent to form at the bonding protective membrane of one or two sides of polyethenol series polarisation.At least one of the protective membrane of preferred aforementioned Polarizer for cellulose acetate mesentery or norcamphene mesentery, vinylformic acid mesentery, poly-carbonic acid be ester film.
Moreover, the present invention relates to following embodiment II.
That is to say, the embodiment of the present application relates to a kind of optical polymerism oxyethane based resin composition, it is characterized in that oxirane compound take three membered cyclic is as principal constituent, and further contain the ring compound more than tetra-atomic ring with more than 1 Sauerstoffatom and sulphur atom, do not contain in fact organic solvent, and the viscosity 23 ℃ time is 1 to 1500mPas.With respect to the oxirane compound of the three membered cyclic of the aforementioned principal constituent of 100 weight parts, preferably contain the ring compound more than tetra-atomic ring with more than 1 Sauerstoffatom and sulphur atom of 0.5 to 60 weight part.There is the ring compound more than tetra-atomic ring of more than 1 Sauerstoffatom and sulphur atom, preferably in ring, have be selected from sulfoxide skeleton, sulfone skeleton, sulfite skeleton, sulfuric ester skeleton, sulphonate skeleton,-sulfinic acid ester skeleton, thioesters skeleton in any more than a kind structure.The oxirane compound of three membered cyclic, preferably contains the compound with aromatic nucleus.The oxirane compound of three membered cyclic, preferably contains the compound of the oxyethane ring with more than 2 three membered cyclic.Moreover, preferably contain the ring compound more than tetra-atomic ring with more than 2 Sauerstoffatom.There is the ring compound more than tetra-atomic ring of more than 2 Sauerstoffatom, be preferably and there is the ring texture that is selected from lactonic ring, carbonic ether ring, dioxolane, diox ring, trioxane ring at least a kind.Preferably further contain Photoepolymerizationinitiater initiater.Photoepolymerizationinitiater initiater is the A that produces acid active specy by rayed +b -the salt representing, aforementioned male ion A +be preferably selected from the group that aromatic series iodide ion and aromatic matte ion form.
And the embodiment of the present application relates to the duplexer that uses the bonding blooming of aforementioned optical polymerism coating agent to become.
Moreover the embodiment of the present application relates to the Polarizer that uses above-mentioned optical polymerism coating agent to form at the bonding protective membrane of one or two sides of polyethenol series polarisation.At least one of the protective membrane of preferred aforementioned Polarizer for cellulose acetate mesentery or norcamphene mesentery, vinylformic acid mesentery, poly-carbonic acid be ester film.
Moreover, the present invention relates to following embodiment III.
That is to say, the embodiment of the present application relates to a kind of optical polymerism oxyethane based resin composition, its oxirane compound take three membered cyclic is principal constituent, and further contain the ring compound more than tetra-atomic ring with more than 2 Sauerstoffatom and there is at least 1 ring texture and the compound of the two molecular weight of hydroxyl below 500, do not contain in fact organic solvent, and the viscosity 23 ℃ time is 1 to 1500mPas.With respect to the oxirane compound of the aforementioned three membered cyclic of 100 weight parts, preferably contain the ring compound more than tetra-atomic ring with more than 2 Sauerstoffatom of 0.5 to 60 weight part, what preferably contain 0.5 to 40 weight part has the compound of the two molecular weight of at least 1 ring texture and hydroxyl below 500.The ring compound having more than the tetra-atomic ring of more than 2 Sauerstoffatom is cyclic ester compound, cyclic formals compound and/or cyclic carbonate compound, preferably at least contains more than a kind.As cyclic ester, be preferably lactone, as cyclic formals compound, be preferably dioxolane class, dioxane, trioxa alkanes.There is the ring structure of the compound of the two molecular weight of at least 1 ring texture and hydroxyl below 500, be preferably naphthenic, cyclenes class, phenyl ring, the above condensation polycyclic class of two rings.The hydroxyl preferably with the compound of the two molecular weight of at least 1 ring texture and hydroxyl below 500 on ring structure directly and/or by thering is C 1-18the alkylidene group of carbonatoms replaces 1 above compound.There is the compound of the two molecular weight of at least 1 ring texture and hydroxyl below 500, be preferably there is cyclohexane ring, the two compound of the ring texture of at least a kind and hydroxyl in cyclohexene ring, norcamphane ring, norcamphene ring, diamantane ring, dihydroisobenzofuran ring, Dihydrobenzofuranes ring, pepper basic ring and look alkane ring.There is in cyclohexane ring, cyclohexene ring, norcamphane ring, norcamphene ring, diamantane ring, dihydroisobenzofuran ring, Dihydrobenzofuranes ring, pepper basic ring and look alkane ring the ring texture of at least a kind and the compound of hydroxyl, be preferably hexalin, phenylcarbinol, fall baras camphor, adamantanol, piperitol or 3,4-methylenedioxyphenol.The oxirane compound of three membered cyclic, preferably contains the compound with aromatic nucleus.The oxirane compound of three membered cyclic, preferably contains the compound of the oxyethane ring with more than 2 three membered cyclic.
And the embodiment of the present application relates to the optical polymerism coating agent that contains Photoepolymerizationinitiater initiater in aforementioned optical polymerism ethylene oxide resin system: compositions.Photoepolymerizationinitiater initiater is the A that produces acid active specy by rayed +b -the salt representing, aforementioned male ion A +be preferably selected from the group that aromatic series iodide ion and aromatic matte ion form.
Moreover the embodiment of the present application relates to the duplexer that uses the bonding blooming of aforementioned optical polymerism coating agent to become.Moreover the embodiment of the present application relates to the aforementioned optical polymerism coating agent of use, the Polarizer forming at the bonding protective membrane of one or two sides of polyethenol series polarisation.At least one of preferred aforementioned protective membrane is cellulose acetate mesentery or norcamphene mesentery, vinylformic acid mesentery, polycarbonate mesentery.
Moreover, the present invention relates to following embodiment IV.
That is to say, the embodiment of the present application relates to a kind of optical polymerism composition, it is characterized in that, for the oxirane compound of the three membered cyclic with respect to 100 weight parts, the optical polymerism composition of the Photoepolymerizationinitiater initiater that contains 0.5 to 10 weight part, in this optical polymerism composition of 100 weight parts, the moisture that contains 0.05 to 3 weight part, and further do not contain in fact organic solvent.The oxirane compound of three membered cyclic is preferably and contains the oxirane compound with alicyclic structure.The oxirane compound with alicyclic structure more preferably has the compound of aromatic nucleus, optical polymerism composition is preferably with respect to the oxirane compound of 100 weight parts, further contains the ring compound more than tetra-atomic ring with more than 2 Sauerstoffatom of 0.5 to 60 weight part.There is the ring compound more than tetra-atomic ring of more than 2 Sauerstoffatom, be preferably the compound with the ring texture that is selected from cyclic ester compound, cyclic formals compound, cyclic carbonate compound at least a kind.Cyclic ester compound is preferably lactone.And in the present application, above-mentioned cyclic formals compound is preferably dioxolane class, dioxane, trioxa alkanes at least a kind.Moreover ethene unsaturated compound, preferably contains 5 to 1000 weight parts with respect to the oxirane compound (A) of 100 weight parts.Ethene unsaturated compound (D) preferably contains the ethene unsaturated compound (d1) with hydroxyl.The ethene unsaturated compound with hydroxyl is preferably the ethene unsaturated compound (d1-1) of carbonatoms 2 to 18.
And the embodiment of the present application relates to easy the to be bonding coating agent and/or the optical polymerism caking agent that use above-mentioned optical polymerism composition to form.
Moreover the embodiment of the present application relates to any one that use in above-mentioned optical polymerism composition and/or easy bonding coating agent and/or optical polymerism caking agent, is laminated in the duplexer that blooming forms.Aforementioned blooming is preferably cellulose acetate mesentery or norcamphene mesentery, vinylformic acid mesentery, polycarbonate mesentery, polyethylene terephthalate mesentery or polyvinyl alcohol mesentery.
Moreover the embodiment of the present application relates to any one that use in above-mentioned optical polymerism composition and/or easy bonding coating agent and/or optical polymerism caking agent, the duplexer forming at the bonding protective membrane of one or two sides of polyethenol series polarisation.
The disclosure of the specification relates to the theme comprising in the Japanese Patent Application 2012-080883 of the Japanese Patent Application 2011-184037 of application on August 25th, 2011, the Japanese Patent Application 2011-280020 of application on December 21st, 2011, the Japanese Patent Application 2012-053614 of application on March 9th, 2012, the Japanese Patent Application 2012-077306 of application on March 29th, 2012, application on March 30th, 2012, for reference, the disclosure entirety of these specification sheetss is incorporated in this specification sheets.
The effect of invention
According to the embodiment of the present invention, can obtain polymerisable optical polymerism oxyethane based resin composition under low-light (level).And, utilize and use its optical polymerism coating agent, can easy and firmly bonding blooming, the good duplexer of processibility, thermotolerance and humidity resistance can obtain boring a hole.Moreover, can obtain good Polarizer.
Embodiment
The embodiment of the present application relates to a kind of optical polymerism composition, its oxirane compound that contains three membered cyclic (A), and be selected from more than the tetra-atomic ring with more than 2 Sauerstoffatom ring compound (B1), there is ring compound (B2) more than the tetra-atomic ring of more than 1 Sauerstoffatom and more than 1 sulphur atom and there is at least 1 ring texture and the compound (C) of the two molecular weight of hydroxyl below 500 in more than 1 compound.Each composition is below described.
Be explained, in this specification sheets, " optical polymerism composition " is recited as " Photocurable composition " or " Photocurable resin composition ".
Oxirane compound (A) > of < three membered cyclic
The oxirane compound (A) of so-called three membered cyclic, for having the ring-type ether of more than 1 three membered cyclic in molecule as the compound of reactive functional group, can be used with no particular limitation.Below, " oxirane compound (A) of three membered cyclic " is also recited as " oxirane compound (A) ".
As the ring-type ether of three membered cyclic, can enumerate for example oxyethane, methyl oxirane, phenyl ethylene oxide, 1,2-phenylbenzene oxyethane, methylene radical oxyethane, epoxy ethyl methyl esters, epoxy ethyl methyl alcohol, oxiranecarboxylic acid, (chloromethyl) oxyethane, (brooethyl) oxyethane, the aliphatics ring-type ethers such as epoxy ethyl nitrile, for example 3,4-oxyethane hexahydrobenzoic acid 3,4-oxyethane cyclohexyl methyl esters, 3,4-oxyethane-6-methylcyclohexanecarboxylic acid 3,4-oxyethane-6-methylcyclohexyl methyl esters, two (3,4-oxyethane hexahydrobenzoic acid) ethyl, two (3, the 4-oxyethane cyclohexyl methyl) esters of hexanodioic acid, two (3, the 4-oxyethane-6-methyl cyclohexane ylmethyl) esters of hexanodioic acid, diethylene glycol bis-(3,4-oxyethane cyclohexyl methyl ether), ethylene glycol bis (3,4-oxyethane cyclohexyl methyl ether), 2,3,14,15-diepoxide for example-7, 11,18,21-, tetra-oxa-triple helical [5.2.2.5.2.2] heneicosanes (or can called after 3,4-oxyethane hexanaphthene spiral-2', 6'-diox spiral-3 ", 5 "-diox spiral-3 ' ", 4 ' " compound of oxyethane hexanaphthene), 4-(3,4-oxyethane cyclohexyl)-2,6-dioxa-8,9-oxyethane spiral [5.5] undecane, dioxidized 4-vinyl cyclohexene, two-2,3-oxyethane cyclopentyl ether and titanium dioxide Dicyclopentadiene (DCPD) etc. are incorporated into the ring-type ether of the three membered cyclic of ester ring type ring.The group that hydrogen atom in the compound of the ring-type ether that these are contained to three membered cyclic is removed the form of one or more gained is incorporated into the compound of other chemical structures, can become oxirane compound (A).
Illustrative oxirane compound herein, can distinguish separately and use, and also can mix use by multiple oxirane compounds.
The oxyethane equivalent of oxirane compound (A), is generally 30 to 3000g/eq, is preferably 50 to 1500g/eq.Oxyethane equivalent is 30g/eq when above, and the pliability of the blooming after solidifying is good, and bonding strength is high.On the other hand, when 3000g/eq is following, good with the intermiscibility of other compositions.
Oxirane compound (A), preferably contains the compound (a-2) that has the oxirane compound (a-1) of aromatic nucleus and/or have the oxyethane ring of more than 2 three membered cyclic.
< has oxirane compound (a-1) > of aromatic nucleus
The oxirane compound (A) of three membered cyclic, in order to improve thermotolerance, humidity resistance, preferably contains oxirane compound (a-1).Below, " there is the oxirane compound (a-1) of aromatic nucleus " and be also recited as " oxirane compound (a-1) ".
As preferred aromatic nucleus substituting group, more specifically, can enumerate for example phenyl, phenylene, tolyl, methylene phenyl, phenmethyl, α-tolylene, inferior phenmethyl, xylyl, xylylene, phthalal (phthalylidene), mphenylenedimethylim-, terephthalylidene, styrene (phenethylidene), styrene, styryl, sub-styryl, the inclined to one side trimethylphenyl of as-(pseudocumyl), the inclined to one side trimethylphenyl of v-, the inclined to one side trimethylphenyl of s-, sym-trimethylbenzene base, cumyl (cumenyl), α-cumyl (cumyl), hydrogen cinnamyl (hydrocinnamyl), cinnamyl, cinnamylidene, inferior cinnamyl, tetramethylphenyl (duryl), durylene, thymyl (thymyl), carvacryl (carvacryl), p-isopropylbenzyl (cuminyl), p-isopropylbenzylidene (cuminylidene), the benzene tertiary butyl (neophyl), xenyl (xenyl), diphenyl-methyl (benzhydryl), diphenylmethylene (benzhydrylidene), the substituting group of the representative such as trityl (trityl).Among these, can enumerate benzene, toluene, dimethylbenzene, vinylbenzene, hemimellitol (hemimellitene), unsym-trimethyl benzene (pseudocumene), sym-trimethylbenzene (mesitylene), isopropyl benzene, プ レ ー ニ Application グ, isodurene (isodurene), durol (durene), isopropyl toluene (cymene), the group that hydrogen atom in the benzene derivatives such as mellitene (mellitene) is removed the form of one or more gained is incorporated into the aromatic nucleus of other chemical structure gained.
Other, can enumerate the cyclenes classes such as such as cyclopropylene, cyclobutene, cyclopentenes, tetrahydrobenzene, suberene, cyclooctene, cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene;
The carbonatoms that for example have carbonatoms beyond benzene, forms ring is more than 3 [4n+2] annulene (annulene).
Can enumerate the such as aromatic series such as biphenyl, triphenyl methane polynuclear compound;
For example pentalene (pentalene), indenes (indene), indane (indane), triketohydrindene hydrate (ninhydrin), naphthalene, tetraline, naphthane, sapotalene (sapotalene), cadalin (cadalene), eudalene (eudalene), naphthols, dihydro naphthoquinones (menadiol), gossypol (gossypol), naphthoquinones, regianin (juglone), vitamin k4 (Menadione), plumbagin (plumbagin), phthiocol (phthiocol), echinochrome (echinochrome) A, Shikonin (alkannin), Shikonin (shikonin), acetonaphthone (acetonaphthone), naphthoic acid, naphthoyl (naphthoyl), naphthalic acid, naphthalate, acetomenaphthone (acetomenaphthone), napthylamine sulfonic acid (naphthionicacid), napthylamine sulfonic acid ester, napthylamine sulfonic acid base (naphthionyl), red sulphonyl (dansyl), Bayer acid (croceic acid), flavianic acid (flavianic acid), chromotropic acid (chromotropic acid), neocupferron (neocupferron), camomile Azulene (azulene), chrysanthemum Azulene (chamazulene), melon camomile Azulene (guaiazulene), triolefin between heptan (heptalene), aldrin (octalene), the carbon condensations two such as purple times phenol (purpurogallin) encircle,
For example as-indenes reaches alkene (indacene), s-indenes reaches alkene, as-hydrogen indenes reaches alkene, s-hydrogen indenes reaches alkene, biphenylene, acenaphthylene (acenaphthylene), acenaphthene naphthalene (acenaphthene), acenaphthenequinone (acenaphthoquinone), fluorenes (fluorene), non-that alkene (phenalene), perinaphthene (perinaphthene), luxuriant and rich with fragrance (phenanthrene), phenanthryl, luxuriant and rich with fragrance (phenanthrylium), luxuriant and rich with fragrance subunit (phenanthrylidene), phenanthrylene (phenanthrylene), phenanthrol (phenanthrol), morphol (morphol), phenanthrenone (phenanthrone), phenanthrenequione, pimanthrene (pimanthrene), retene (retene), anthracene, anthryl, anthracene, anthracene subunit, anthrylene, hydroxyl anthracene (anthrol), anthrol (anthranol), grace dream refined (anthrarobin), anthralin (anthralin), Dithranol (dithranol), anthracene acyl group (anthroyl), anthrone (anthrone), dianthrone, anthraquinone, anthraquinonyl, sub-anthraquinonyl, alizarin (alizarin), quinizarin (quinizarin), anthrarufine (anthrarufin), chrysazin (chrysazin), trihydroxyanthraquinone (anthragallol), purpurin (purpurin), flavopurpurin (flavopurpurin), anthracene violet element (anthrapurpurin), skyrin (quinalizarin), teak quinone (tectoquinone), chrysophanol (chrysophanol), chrysophanic acid, Schuttgelb (emodin), large sulfonic acid (Rhein), kermesic acid (kermesic acid), coccinic acid (carminic acid), two anthracene imines (dianthrimide), anthracene imines (anthrimide), golden yellow anthraquinonic acid (chrysamminic acid), the carbon condensations three such as colchicine (colchicine) encircle,
For example three indenes (trindene), three indanes, fluoranthene (fluoranthene), the luxuriant and rich with fragrance alkene of vinegar (acephenanthrylene), vinegar phenanthrene (acephenanthrene), benzo acenaphthene (aceanthrylene), aceanthrene (aceanthrene), three acenes (triphenylene), pyrene (pyrene), thick dinaphthyl (chrysene), benzanthrene (tetraphene), thick four benzene (tetracene), thick four benzene (naphthacene), lycid alkene (rubene), tsiklomitsin (tetracycline), Uromycin, oxytetracycline, seven days of the week alkene (pleiadene), the carbon condensation Fourth Rings such as benzanthrone (benzanthrone),
Li is as Pi (the carbon condensation five rings such as picene), perylene (perylene), dibenzphenanthrene (pentaphene), thick pentaphene (pentacene), four sub-benzene (tetraphenylene), sub-cholanthrenyl (cholanthrylene), cholanthrene (cholanthrene);
For example bowl alkene (corannulene), rich bright alkene (fluminene), dibenzo pyrene (anthanthrene), thick four benzene of dibenzo (zethrene), six helicenes (hexahelicene), hexaphene (hexaphene), thick six benzene (hexacene), rubicene (rubicene), coronene (coronene), trinaphthylene (trinaphthylene), heptaphene (heptaphene), thick seven benzene (heptacene), pyrrole anthracene (pyranthrene), Xin Fen (octaphene), thick eight benzene (octacene), terylene (terylene), thick four benzene of thick four benzos (naphthacenonaphthacene), sweet smell in the ninth of the ten Heavenly Stems (nonaphene), thick nine benzene (nonacene), violanthrene (violanthrene), violanthrone (violanthrone), isoviolanthrene (isoviolanthrene), iso-violanthrone (isoviolanthrone), ovalene (ovalene), sweet smell in the last of the ten Heavenly stems (decaphene), thick ten benzene (decacene), decacyclene (decacyclene), thick pentaphene thick pentaphene (pentacenopentacene), quaterrylene (quaterrylene), the more than 6 carbon condensed rings of number of rings such as thick six benzene of thick six benzos (hexacenohexacene), the group that hydrogen atom in isocyclic compound is removed the form of one or more gained is incorporated into the aromatic nucleus of other chemical structure gained.
< has compound (a-2) > of the oxyethane ring of more than 2 three membered cyclic
The oxirane compound (A) of three membered cyclic preferably contains the compound (a-2) of the oxyethane ring with more than 2 three membered cyclic.By the oxyethane ring that contains multiple three membered cyclics, the bridging property of Polymerizable composition described later improves, and can effectively maintain bonding force and thermotolerance, humidity resistance.Below, " there is the compound (a-2) of the oxyethane ring of more than 2 three membered cyclic " and be also recited as " compound (a-2) ".
As compound (a-2), for example can enumerate 3,4-epoxy-cyclohexane carboxylic acid 3,4-epoxy group(ing) cyclohexyl methyl esters, 2-(3,4-epoxy group(ing) cyclohexyl-5,5-spiral-3,4-epoxy group(ing)) hexanaphthene--diox, two (3, the 4-epoxy group(ing) cyclohexyl methyl) esters of hexanodioic acid, two (3, the 4-epoxy group(ing)-6-methyl cyclohexane ylmethyl) esters of hexanodioic acid, 1,2,8,9-bicyclic oxygen limonene, 6-caprolactone modification 3', 4'-epoxy-cyclohexane carboxylic acid 3,4-epoxy group(ing) cyclohexyl methyl esters, 3,4,3', 4'-bicyclic oxygen bis cyclohexane, the glycidyl ethers of dihydroxyphenyl propane, the glycidyl ethers of Bisphenol F, diglycidyl terephthalate, neo-pentyl diepoxy propyl ether, 1,6-hexylene glycol diepoxy propyl ether, ethylene glycol bisthioglycolate glycidyl ethers, 2,2-pair [4-(2,3-epoxy group(ing) propoxy-) cyclohexyl] propane, 2,2-pair [3,5-dimethyl-4-(2,3-epoxy group(ing) propoxy-) cyclohexyl] propane, two [o, o-(2,3-epoxy group(ing) propoxy-) cyclohexyl] methane, two [o, p-(2,3-epoxy group(ing) propoxy-) cyclohexyl] methane, two [p, p-(2,3-epoxy group(ing) propoxy-) cyclohexyl] methane, two [3,5-dimethyl-4-(2,3-epoxy group(ing) propoxy-) cyclohexyl] methane, A Hydrogenated Bisphenol A type epoxy compounds etc. has the compound of 2 oxyethane rings, glycerol is gathered glycidyl ethers, two glycerol are gathered glycidyl ethers, TriMethylolPropane(TMP) gathers glycidyl ethers, tetramethylol methane gathers glycidyl ethers, the poly-glycidyl ethers of sorbyl alcohol etc. has the compound of more than 3 oxyethane ring.
Herein, even with aforesaid compound (a-1) with (a-2) be same compound, namely there is aromatic nucleus and there is the also no problem of compound (a-12) of more than 2 oxyethane ring, can use.Their content in oxirane compound (A), in (A) 100 % by weight, compound (a-1), (a-2) and (a-12) any one be 50 % by weight above on the point of polymerizability, humidity resistance preferably, particularly preferably more than 70 % by weight.
And, even do not belong to compound (a-1), (a-2) and any one also no problem of oxirane compound (A) (a-12), can use (as compound (a-3)).They can only use a kind, also can be used together multiple.
< has ring compound (B1) the > more than tetra-atomic ring of more than 2 Sauerstoffatom
Below, " there is ring compound (B1) more than the tetra-atomic ring of more than 2 Sauerstoffatom " and be also recited as " ring compound (B1) ".Ring compound (B1) is preferably the compound that is selected from cyclic ester compound (b1-1), cyclic formals compound (b1-2), cyclic carbonate compound (b1-3), fluorine-containing ring compound (b1-4) on the point of optical polymerism.
Moreover cyclic ester compound (b1-1) is preferably lactone (b1-1-1).Cyclic formals compound (b1-2) is more preferably selected from the compound of dioxolane class (b1-2-1), dioxane (b1-2-2) and trioxa alkanes (b1-2-3).
< cyclic ester compound (b1-1) >
So-called cyclic ester compound (b1-1), can enumerate the hydroxyl of hydroxycarboxylic acid and carboxylic acid in molecule or intermolecular dehydrating condensation and form the oxygen acid condenses of ring structure, carboxylic acid dehydrating condensations more than 2 molecules and form the lactide etc. of ring structure.
As cyclic ester compound (b1-1), can enumerate lactone (b1-1-1) and lactide class (b1-1-2), preferably lactone (b1-1-1).As lactone (b1-1-1), be preferably the hydroxyl of hydroxycarboxylic acid and carboxylic acid in molecule or intermolecular dehydrating condensation and form the oxygen acid condenses of ring structure, also can be its dipolymer or polymer more than trimer.So, as aforementioned hydroxycarboxylic acid, can use the compound of aliphatics, ester ring type, aromatic series and hetero ring type.
As aliphatic hydroxyl carboxylic acid, can enumerate for example oxyacetic acid, 2 hydroxy propanoic acid, hydroxyl acrylic, α-oxy butyrate, Alpha-hydroxy isobutyric acid, hydroxypentanoic acid, Alpha-hydroxy caproic acid, δ-hydroxycaproic acid, 2,3-dihydroxypropionic acid, 2-carbonyl propionic acid, hydroxy-butanedioic acid, 2-hydroxy propane-1,2,3-tricarboxylic acid, Hydroxyoctanoic acid, hydroxyl dodecanoic acid, hydroxyl (9Z, 12Z)-Linolenic Acid, 12-diolefinic acid, Alpha-hydroxy lacceroic acid (dotriacontanoic acid), Alpha-hydroxy gheddic acid, Alpha-hydroxy ceroplastic acid, Alpha-hydroxy three stearic acids, Alpha-hydroxy 40 acid, hydroxyl-PA, hydroxy-propionic acid, 6-hydroxypentanoic acid, Alpha-hydroxy enanthic acid, 10-hydroxy octadecadienoic acid, 12-hydroxy octadecadienoic acid, 10-hydroxydecanoic acid, sabinic acid, 3-hydroxy tetradecanoic acid, 16-hydroxy-palmitic acid, 15-hydroxy-pentadecanoic acid, Alpha-hydroxy 20 acid, Alpha-hydroxy behenic acid, Alpha-hydroxy tetracosanoic acid, Alpha-hydroxy hydroxyhexacosanoic acid, Alpha-hydroxy octacosanoic acid, Alpha-hydroxy triacontanoic acid, beta-hydroxy TETRADECONIC ACID, two (hydroxymethyl) propionic acid of 1,3-etc.
As ester ring type, aromatic series and hetero ring type hydroxycarboxylic acid, for example 2 hydroxybenzoic acid, 3,5-bis--tertiary butyl-2 hydroxybenzoic acid, 3-hydroxy-benzoic acid, 3,4-resorcylic acid, 4-hydroxyl-3-Phenylbenzoic acid, vanillic acid, 4-hydroxyl-3,5-dimethoxybenzoic acid, 4'-hydroxyl-4-carboxyl biphenyl, 6-Hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 5-hydroxyl-1-naphthoic acid etc.
These hydroxycarboxylic acids, as long as having the organic compound of carboxylic acid and hydroxyl in 1 molecule, are not limited to above-mentioned illustration.
In above-mentioned oxygen acid condenses, from reactive viewpoint, preferably lactone.Particularly, can enumerate α-second lactone, beta-propiolactone, beta-butyrolactone, gamma-butyrolactone, γ-valerolactone, δ-valerolactone, 6-caprolactone, γ-hexalactone, δ-caprolactone, γ-heptalactone, γ-octalactone, δ-octalactone, ε-caprylolactone, δ-nonalactone, 6-caprolactone glycollide (ε-caprolactoneglycolide), pivalolactone, 7-oenantholacton (7-heptanolide), 8-caprylolactone, 11-undecane lactone, 12-dodecane lactone, 15-pentadecane lactone, 10-oxa-n-Hexadecane lactone, 2-nonane-4-lactone, 16-n-Hexadecane lactone, 7-decene-4-lactone, 9-decene-5-lactone, 2-decene-5-lactone, 7-decene-5-lactone, 6-decene-4-lactone, 8-decene-5-lactone, 8-hendecene-5-lactone, 4-methyl-cis-7-decene-4-lactone, 2-butylene-4-lactone, 2-methyl-4-butyrolactone, 3-methyl-4-caprylolactone, 3-methyl-4-nonalactone, 4-methyl-4-decalactone, pentadecanolide, 2,4-decadiene-5-lactone, 4-methyl-5-hexene-4-lactone, penta-4-lactone, 4-vinyl-γ-valerolactone, Glucuronic acid lactone (glucuronolactone), jasmine lactone (jasmolactone), ア ッ ソ イ ラ Network ト Application, peppermint lactone (menthalactone), chirality methyl valerolactone (mintlactone), massoia lactone (massoialactone), grape wine lactone (winelactone), pantolactone (pantolactone), Kosé amino acid lactone (homoserine lactone), mevalonolactone (mevalonic lactone), Gluconolactone (glucono delta lactone), bergapten (bergaptene), cyclohexa decen-7-olide (ambrettolide), Sclareolide (sclareolide), alpha-angelica lactone (α-Angelica lactone), β-angelica lactone, 7-decylene-1,4-lactone, 9-decene-5-lactone, 2,3-dimethyl-2,4-nonadiene-4-lactone, dihydroxyl Chinese goosebeery lactone (actinidiolide), 5-hydroxyl-8-undecylenic acid-delta-lactone, 2-hydroxyl-3,3-dimethyl-4-butyrolactone, Isosorbide-5-Nitrae-diox ring heptadecane-5,17-diketone, α-ethanoyl-gamma-butyrolactone, Alpha-Methyl-beta-propiolactone, Beta-methyl-α-propiolactone, α, alpha-alpha-dimethyl-beta-propiolactone, maltonic acid-1,5-lactone, 4-hydroxy-4-methyl tetrahydropyrans-2-ketone, phenanthrene-1,10:9,8-bis-phosphinylidyne lactones (phenanthrene-1,10:9,8-dicarbolactone), 3 α-courage matter-24, Alpha-hydroxy-5,17-lactone (3 α-hydroxy-5 α-cholano-24,17-lactone) etc.
As the cyclic dimer of hydroxycarboxylic acid that can be used as cyclic ester compound (b1-1) and use, can enumerate and utilize 3 of lactic acid, 6-dimethyl-1,4-diox-2,5-diketone, utilize 1 of oxyacetic acid, 4-diox-2,5-diketone, glycollide (glycolide), lactic acid lactide (lactide), further can enumerate alpha-hydroxybutyric acid, Alpha-hydroxy isobutyric acid, Alpha-hydroxy valeric acid, Alpha-hydroxy isovaleric acid, Alpha-hydroxy-α-methyl butyric acid, Alpha-hydroxy caproic acid, Alpha-hydroxy isocaproic acid, HMV, Alpha-hydroxy enanthic acid etc.
In above-mentioned lactone (b1-1-1), from the side chain lengths that forms by open loop, with the aspect of the ring-opening copolymerization of the oxirane compound (A) of three membered cyclic, the preferably material in the scope of carbonatoms 4 to 18 that forms ester ring, particularly particularly preferably propiolactone, butyrolactone, valerolactone, caprolactone.
< cyclic formals compound (b1-2) >
Cyclic formals compound (b1-2) is more preferably selected from the compound of dioxolane class (b1-2-1), dioxane (b1-2-2) and trioxa alkanes (b1-2-3).
As dioxolane class (b1-2-1), can be by the carbonyl acetalation of ethylene glycol be obtained.More specifically, can enumerate 1,2-dioxolane, DOX, 2,2-dimethyl-DOX, 2,2-dimethyl-DOX-4-methyl alcohol, (R)-(-)-2,2-dimethyl-DOX-4-methyl alcohol, (+)-4, two [hydroxyl (phenylbenzene) methyl]-2 of 5-, 2-dimethyl-DOX, (4S)-α, α, α ', α-tetraphenyl-2,2-dimethyl-DOX-4 α, 5 β-dimethanol, 4 α, 5 β-bis-(hydroxyl diphenyl methyl)-2,2-dimethyl-DOX, (4S, 5S)-2,2-dimethyl-α, α, α ', α '-tetraphenyl-DOX-4,5-dimethanol, 2,2-dimethyl-DOX-4 α, 5 β-bis-bases two (diphenyl-carbinol), (4S)-2,2-dimethyl-4 α, 5 β-bis-(Alpha-hydroxy diphenyl-methyl)-DOX, α, α, α ', α '-tetraphenyl-2,2-dimethyl-DOX-4 α, 5 β-dimethanol, 2,2-dimethyl-α, α, α ', α '-tetraphenyl-DOX-4 α, 5 β-dimethanol, (4S, 5S)-2,2-dimethyl-DOX-4,5-two (diphenyl-carbinol), α, α '-(2,2-dimethyl-DOX-4,5-bis-bases) two (α-phenyl benzil alcohols), (4S, 5S)-2,2-dimethyl-α, α, α ', α '-tetraphenyl-DOX-4,5-two (diphenyl-carbinol), (4S)-2,2-dimethyl-4 α, 5 β-bis-(Alpha-hydroxy-α-phenyl phenmethyl)-DOX, (4S, 5S)-α, α, α ', α '-tetraphenyl-2,2-dimethyl-DOX-4 α, 5 β-dimethanol, [(4S, 5S)-2,2-dimethyl-4,5-dihydro-DOX]-4,5-bis-bases two (diphenyl-carbinol), α, α '-[(4S, 5S)-2,2-dimethyl-DOX-4,5-bis-bases] two (α-phenyl benzil alcohols), α, α, α ', α '-tetraphenyl-2,2-dimethyl-DOX-4,5-dimethanol, α, α, α ', α '-tetraphenyl-2,2-dimethyl-DOX-4 α, 5 β-bis-methyl alcohol, α, α '-(2,2-dimethyl-DOX-4,5-bis-bases) two (diphenyl-carbinols), (4S, 5S)-α, α, α ', α '-tetraphenyl-2,2-dimethyl-DOX-4,5-dimethanol, (+)-trans-α, α '-(2,2-dimethyl-DOX-4,5-bis-bases) two (diphenyl-carbinols), 1, Isosorbide-5-Nitrae, 4-tetraphenyl-2-O, 3-O-isopropylidene-D-threitol (threitol), [(4S, 5S)-2,2-dimethyl-DOX-4,5-bis-bases] two (diphenyl-carbinols), (4S)-2,2-dimethyl-4 α, 5 β-bis-(hydroxy diphenyl phenmethyl)-DOX, 2,2-dimethyl-DOX-4,5-pair (α ', α '-diphenyl-carbinol), (4S)-2,2-dimethyl-α, α, α ', α '-tetraphenyl-DOX-4 α, 5 β-dimethanol, (4S, 5S)-2,2-dimethyl-4 α, 5 β-bis-(Alpha-hydroxy-α-phenyl phenmethyl)-DOX, 2,2-dimethyl-DOX-4 α, 5 β-bis-(α ', α '-diphenyl-carbinol), α ', α '-(2,2-dimethyl-DOX-4 α, 5 β-bis-bases) two (diphenyl-carbinol) dioxs, methacrylic acid (2-methyl-2-ethyl-DOX-4-yl) methyl esters, vinylformic acid [hexanaphthene spiral-2-(DOX-4-yl)] methyl esters, methacrylic acid [hexanaphthene spiral-2-(DOX-4-yl)] methyl esters, vinylformic acid (2-methyl-2-carbonyl-DOX-4-yl) methyl esters, methacrylic acid (2-methyl-2-carbonyl-DOX-4-yl) methyl esters, 2,2'-two (DOX), 2-phenyl-2,2'-two (DOX) etc.
In above-mentioned dioxolane class (b1-2-1), from with the aspect of the ring-opening copolymerization of the oxirane compound (A) of three membered cyclic, particularly preferably DOX, methacrylic acid (2-methyl-2-ethyl-DOX-4-yl) methyl esters.
As dioxane (b1-2-2), the method that can react under the existence of the mineral acids such as sulfuric acid, aromatic sulphonic acid catalyzer by (gathering) ethylene glycol, use the acid catalysts such as sulfuric acid, boron trifluoride to make the method for oxyethane Cyclodimerization synthetic.More specifically, for example can enumerate, 1, 2-diox, 4-ethanoyl-6-hexyl-3-methyl isophthalic acid, 2-diox-3-alcohol, 4-ethanoyl-3, 4-dimethyl-6, 6-phenylbenzene-1, 2-diox-3-alcohol, 4-ethanoyl-6-phenyl-3-methyl isophthalic acid, 2-diox-3-alcohol, 6, 6-phenylbenzene-4-(phenyl amido carbonyl)-3-methyl isophthalic acid, 2-diox-3-alcohol, 6, 6-phenylbenzene-4-benzoyl-3-methyl isophthalic acid, 2-diox-3-alcohol, (3S)-3 β, 6 alpha-alpha-dimethyl-4 α, 5 β-bis-(4-acetoxy-3-p-methoxy-phenyl)-1, 2-diox, 6, 6-phenylbenzene-4-ethanoyl-3-methyl-4-ethyl-1, 2-diox-3-alcohol, (3S)-4 α-ethanoyl-6, 6-phenylbenzene-3-methyl isophthalic acid, 2-diox-3 α-ol, (3S)-3 β, 6 alpha-alpha-dimethyl-4 α, 5 β-bis-(4-hydroxy 3-methoxybenzene base)-1, 2-diox, 4-ethanoyl-6, two (4-the aminomethyl phenyl)-3-methyl isophthalic acids of 6-, 2-diox-3-alcohol, 4-ethanoyl-6, two (4-the chloro-phenyl-)-3-methyl isophthalic acids of 6-, 2-diox-3-alcohol, 4-ethanoyl-6, two (4-the p-methoxy-phenyl)-3-methyl isophthalic acids of 6-, 2-diox-3-alcohol, 4-ethanoyl-6, two (4-the fluorophenyl)-3-methyl isophthalic acids of 6-, 2-diox-3-alcohol, α, 6-dimethyl-6-[4-methyl-6-(2, 6, 6-trimethylammonium-1-tetrahydrobenzene-1-yl)-3-hexenyl]-1, 2-diox-3-acetic acid, 4-ethyl-6-(2-ethyl-3-hexenyl)-6-methyl isophthalic acid, 2-diox-3-methyl acetate, (3R, α R, 6R)-6-[2-[[(4aR, 8aS)-1, 4, 4 α β, 7, 8, 8 α β-six hydrogen-1, 1, 3, 6-tetramethyl-naphthalene]-2-yl] ethyl]-α, 6-dimethyl-1, 2-diox-3-acetic acid, (R)-2-[(3R, 6R)-6 Beta-methyls-6-[[(2S)-2, 3, 3 α, 4, 5, 9 β-six hydrogen-3a α, 4 α, 7, 9b α-tetramethyl-naphthalene [1, 2-b] furans]-2 α-yl]-1, 2-diox-3 beta-yl] methyl propionate, (2S)-2-[(3S, 6S)-6-[2-[(1S, 2R, 4a α, 8 α β)-decahydro-1, 2 α, 4a-trimethylammonium-5-methanonaphthalene-1 beta-yl] ethyl]-6-methyl isophthalic acid, 2-diox-3-yl] propionic acid, (R)-2-[(3R, 6S)-6 Beta-methyls-6-[2-[[(2R, 4a β, 8a β)-decahydro-1, 1-dimethyl-3, 6-dimethylene naphthalene]-2-yl] ethyl]-1, 2-diox-3 beta-yl] propionic acid etc. 1, 2-dioxane derivatives class,
For example, 1,3-diox, 2,4-phenylbenzene-1,3-diox, 5-hydroxyl-1,3-diox, 2-cyclohexyl-1,3-diox, 1,3-diox-2-ketone, 2 α, 4 alpha-alpha-dimethyl-1,3-diox, 5,6-dimethyl-1,3-diox, 5,5-diethyl-1,3-diox, 4,6-dibutyl-1,3-diox, 2-ethyl-1,3-diox, 2-methylene radical-1,3-diox, 4,6-dimethyl-1,3-diox, 2,2-hexichol Oxy-1,3-diox, 2,2,4-trimethylammonium-1,3-diox, 5,5-bis-is fluoro-1,3-diox, Alpha-Methyl-1,2 α-tertiary butyl-4,3-diox, 2-phenyl-4-methyl isophthalic acid, 3-diox, 4-methyl 4-phenyl-1,3-diox, 4,6-dimethyl-2-methylene radical-1,3-diox, 4,5,5-trimethylammonium-1,3-diox, 4,6-di neo-pentyl-1,3-diox, 2-ethyl-5-methyl isophthalic acid, 3-diox, 2,5-dimethyl-5-phenyl-1,3-diox, 2-pentadecyl-1,3-diox, 2-hexyl-1,3-diox, 2-butyl-2,5,5-trimethylammonium-1,3-diox, 5-(1-methylethyl)-1,3-diox, 2-phenyl-2-benzoyl-1,3-diox, 4-phenyl-1,3-diox-2-ketone, 2,4,4,6-tetramethyl--1,3-diox, 2 α, 4 α, 5 α-trimethylammonium-1,3-diox, 2 α-hexyl-1,3-diox-5 β-ol, 5,5-dimethyl-2-vinyl-1,3-diox, 4-(1-methyl ethylene)-1,3-diox, 2-methyl isophthalic acid, 3-diox-2-(1-propyl alcohol), 4,5-dimethanol-1,3-diox-5-methyl alcohol, 4,5-dimethanol-1,3-diox-4-methyl alcohol, 4,4,5-trimethylammonium-1,3-diox-5-alcohol, 5-ethyl-2-(2-furyl)-4-propyl group-1,3-diox, 5,5 '-spiral two [1,3-diox], 4-methyl isophthalic acid, 3-diox, 2,2-dimethyl-5-phenyl-1,3-diox-4,6-diketone, 3,3-dimethyl-1,5-dioxy spiral [5,5] undecane-9-ketone, 2-(1,3-diox-2-yl) ethyl triphenyl bromination sulfonium, 2,2-dimethyl-5-methyl isophthalic acid, 3-diox-4,6-diketone, 4-phenyl-1,3-diox, 5,5-dimethyl-1,3-diox-2-ketone, 5-is bromo-2,2,5-trimethylammonium-1,3-diox-4,6-diketone, 5-propyl group-2-[2-(4-trifluoromethyl) ethyl]-1,3-diox, 5-propyl group-2-[4-(3,4,5-trifluorophenyl) cyclohexyl]-1,3-diox, 5-propyl group-2-[4-(3,5-difluorophenyl) ethyl]-1,3-diox, 5-propyl group-2-[4-(the fluoro-4-Trifluoromethoxyphen-l of 3-) cyclohexyl]-1,3-diox, 5-propyl group-2-[4-(4-trifluoromethyl) butyl]-1,3-diox, 5-propyl group-2-[4-(3,5-difluorophenyl) cyclohexyl]-1,3-diox, 5-propyl group-2-[4-{4-(the fluoro-4-chloro-phenyl-of 3-)-3,5-difluorophenyl } cyclohexyl]-1,3-diox, 4-(5-amyl group-1,3-diox-2-basic ring hexane) carboxylic acid, 4-[5-amyl group-(1,3-diox)-2-yl]-hexahydrobenzoic acid 3,4,5-trifluoro phenyl ester, 1-[2-(1,3-diox-2-yl) ethyl] cyclohexyl 3,4,5-trifluoro-benzene, 1-[2-(5-amyl group-1,3-diox-2-yl) ethyl] cyclohexyl-3,4,5-trifluoro-benzene, (Z)-6-(2-(2-chloro-phenyl-)-4-(2-hydroxy phenyl)-1,3-diox-5-yl) oneself-obtusilic acid, (Z)-6-(2-[4-methoxyphenoxy-o-phenyl] o-hydroxy phenyl-1 of-4-, 3-diox-cis-5-yl) oneself-obtusilic acid, (Z)-6-(the chloro-4-oxygen-4H-of the chloro-4H-chromene of 2-3-[6-(chromene)-4-ketone 6-chromene-3-yl]-4-(2-hydroxy phenyl-1,3-diox-cis-5-yl) oneself-obtusilic acid, (Z)-6-((2R, 4R, 5S)-2-(2-chloro-phenyl-)-4-(2-hydroxy phenyl)-1,3-diox-5-yl) oneself-obtusilic acid, (Z)-6-((2S, 4S, 5R)-2-(2-chloro-phenyl-)-4-(2-p-methoxy-phenyl)-1,3-diox-5-yl) oneself-obtusilic acid, (Z)-6-((2S, 4S, 5R)-2-(2-chloro-phenyl-)-4-(2-acetoxyl group phenyl)-1,3-diox-5-yl) oneself-obtusilic acid, (Z)-6-((2S, 4S, 5R)-2-(2-chloro-phenyl-)-4-(2-hydroxy phenyl)-1,3-diox-5-yl) oneself-obtusilic acid methyl esters, (Z)-6-((2S, 4S, 5R)-2-(2-chloro-phenyl-)-4-(2-hydroxy phenyl)-1,3-diox-5-yl) oneself-obtusilic acid methyl esters, (Z)-6-((2S, 4S, 5R)-2-(2-acetoxyl group phenyl)-2-(2-chloro-phenyl-)-1,3-diox-5-yl) oneself-obtusilic acid etc. 1,3-dioxane derivatives class,
For example Isosorbide-5-Nitrae-dioxs, Isosorbide-5-Nitrae-diox-2,3-dithione, 2,5-dimethyl-Isosorbide-5-Nitrae ,-dioxs, 5 α, 6 alpha-alpha-dimethyls-Isosorbide-5-Nitrae ,-dioxs-2-ketone, 2,5-divinyl-Isosorbide-5-Nitrae ,-dioxs, 2,2'-joins (Isosorbide-5-Nitrae-dioxs), 2,2,3,3,5,6,6-heptachlor-Isosorbide-5-Nitrae ,-dioxs, methylene radical-Isosorbide-5-Nitrae-dioxs, (2R, 3S)-2, the chloro-Isosorbide-5-Nitrae-diox of 3-bis-, 2-methyl-3-methylene radical-Isosorbide-5-Nitrae-dioxs, 2,5-dimethyl-3-methylene radical-Isosorbide-5-Nitrae ,-dioxs, 2-ethyl-5-methyl isophthalic acid, 4-diox, 3,6-diethyl-Isosorbide-5-Nitrae ,-diox-2,5-diketone, 2,6-dimethyl-Isosorbide-5-Nitrae ,-dioxs, 2-methyl isophthalic acid, 4-diox-2,3-glycol, 2-(2-furyl)-Isosorbide-5-Nitrae-dioxs, 3,6-diisobutyl-Isosorbide-5-Nitrae ,-diox-2,5-diketone, 2,2,3,3,5,6-hexafluoro-5, the chloro-Isosorbide-5-Nitrae-diox of 6-bis-, two (epoxy ethyl methyl)-Isosorbide-5-Nitrae-dioxs of 2,3-, hydroperoxidation Isosorbide-5-Nitrae-dioxs-2-base, 3,6-dipropyl-Isosorbide-5-Nitrae ,-diox-2,5-diketone, 2,5,6-trimethylammonium-Isosorbide-5-Nitrae ,-diox-2,3-glycol, the fluoro-2-of 2,3,3-tri-(trifluoromethyl)-Isosorbide-5-Nitrae-diox, 5,6-dimethyl-Isosorbide-5-Nitrae ,-diox-2,3-glycol, 2-[(tetrahydrochysene-2H-pyrans)-2-ylmethyl]-Isosorbide-5-Nitrae-dioxs, acetic acid (Isosorbide-5-Nitrae-dioxs-2-yl) methyl esters, 2,2,3,3-tetrafluoro-5,5,6,6-tetrachloro-Isosorbide-5-Nitrae ,-dioxs, Isosorbide-5-Nitrae-diox-2,6-dimethanol, 2-(Isosorbide-5-Nitrae-dioxs-2-yl)-1,4-naphthoquinone, Isosorbide-5-Nitrae-diox-2, the two methyl alcohol of 5-, N, two (the benzyloxy)-Isosorbide-5-Nitraes of N'--diox-2,5-diimine, two [(TMS) oxygen base]-Isosorbide-5-Nitrae-diox-2 of 3,6-, 5-diketone, 2,3,3-tri-is fluoro-5,5,6,6-tetrachloro-2-(trifluoromethyl)-Isosorbide-5-Nitrae-diox, 2,3-epoxy group(ing)-2, the fluoro-6-of 3,5,5,6-five (trifluoromethyl)-Isosorbide-5-Nitrae-dioxs, 2,2'-(3,6-dimethoxy-Isosorbide-5-Nitrae ,-diox-2,5-bis-subunits (diylidene)) oxalic acid dimethyl ester, two [morpholine-4-(two sulphur formic acid)], Isosorbide-5-Nitrae-diox-2 α, 3 β-bis-bases, two (chloromethyl)-Isosorbide-5-Nitrae-dioxs of 2,5-, the chloro-5-of 3,3-bis-(1-methyl propoxy-)-Isosorbide-5-Nitrae-diox-2-ketone, 2,5-dimethyl-Isosorbide-5-Nitrae ,-dioxs, 2-(the fluoro-2-phenyl sulfonyl of 2-ethyl)-Isosorbide-5-Nitrae-dioxs, the fluoro-2-of 2,3,3,5,6-five (trifluoromethyl)-5, the chloro-Isosorbide-5-Nitrae-diox of 6-bis-, (2H8)-Isosorbide-5-Nitrae-dioxs, trans-2, the chloro-Isosorbide-5-Nitrae-diox of 3-bis-, 2-[3-(3,3-dimethyl-2-isopropyl epoxy ethyl)-1-methylene radical-2-propynyl]-Isosorbide-5-Nitrae-dioxs, 2,5-dihydroxyl-3,6-dimethyl-3,6-bis-phosphono-2,5-bis-phosphorus (V)-Isosorbide-5-Nitrae-diox-2,5-diketone, N, N'-[(1,4-diox-2,5-bis-bases) two (methylene radical)] two [N-(carboxyl methyl) glycines], (3S, 5R)-3 α-sec.-propyl-5 α-[(2S)-1-[butoxy carbonyl] Pyrrolizidine-2-yl]-6-[(E)-bromine methylene radical]-Isosorbide-5-Nitrae-dioxs-2-ketone, 3,5,5,6-tetrafluoro-3, two (the trifluoromethyl)-Isosorbide-5-Nitrae-dioxs-2-ketone of 6-, the fluoro-5-of 2,2,3,5,6-five (five fluorine oxyethyl groups)-3, two (trifluoromethyl)-Isosorbide-5-Nitrae-dioxs of 6-, (3S, 5S)-3 α-sec.-propyl-5 β-[(2S)-1-[butoxy carbonyl] Pyrrolizidine-2-yl]-6-[(E)-bromine methylene radical]-Isosorbide-5-Nitrae-dioxs-2-ketone, (3S, 5S)-3 α-sec.-propyl-5 β-[(2S)-1-[butoxy carbonyl] Pyrrolizidine-2-yl]-6-methylene radical-Isosorbide-5-Nitrae-dioxs-2-ketone, 3,3,6,6-tetramethyl--Isosorbide-5-Nitrae ,-diox-2,5-diketone, [(2S, 3R)-Isosorbide-5-Nitrae-diox-2,3-bis-bases] two (sulphur) two (phosphine sulfide acid 0,0-diethyl esters), α-[(3,3-dimethyl-2-isopropyl epoxy ethyl ethynyl)]-Alpha-Methyl-Isosorbide-5-Nitrae-dioxs-2-methyl alcohol, 2,3-bis-chloro-right-diox, two (methyl acetate mercury)-Isosorbide-5-Nitrae-dioxs of 3,6-, Isosorbide-5-Nitrae-dioxs-2-ketone, (3S, 5S)-3 α-sec.-propyl-5 α-[(2S)-1-[N-(4-methoxyl group-Isosorbide-5-Nitrae-bis-oxygen-butyl)-L-Ala-L-Ala-] Pyrrolizidine-2-yl]-6-methylene radical-Isosorbide-5-Nitrae-diox-2-ketone, 5-methoxyl group-Isosorbide-5-Nitrae-dioxy hexanaphthene, 2,2,3,5,6-, five methyl fluorides-5-[(trifluoroacetyl group) oxygen base]-3, two (trifluoromethyl)-Isosorbide-5-Nitrae-dioxs of 6-, 2,3,5,6-tetramethyl--Isosorbide-5-Nitrae ,-diox-2,5-glycol, (3S, 5S)-3 α-sec.-propyl-5 β-[(2S)-1-[N-(4-methoxyl group-Isosorbide-5-Nitrae-bis-oxygen-butyl)-L-Ala-L-Ala-] Pyrrolizidine-2-yl]-6-methylene radical-Isosorbide-5-Nitrae-diox-2-ketone, 1,1,1,2,4,5,5,5-octafluoro-2,4-two [[2,3,5,5,6-five fluoro-3, two (trifluoromethyl)-Isosorbide-5-Nitrae-diox-2 bases of 6-] oxygen base]-propione, 1,3-Dihydroxyacetone (dipolymer), Isosorbide-5-Nitrae-diox-2 α, 5 beta-diols, Isosorbide-5-Nitrae-diox-2,3-glycol, Isosorbide-5-Nitrae-diox-2,5-diketone, Isosorbide-5-Nitrae-dioxane derivatives such as [(Isosorbide-5-Nitrae-diox-2,3-bis-bases) two sulphur] two (phosphine sulfide acid 0,0-diethyl esters) etc.
In above-mentioned dioxane (b1-2-2), from the aspect of the ring-opening copolymerization of the oxirane compound (A) of three membered cyclic, particularly preferably 1,2-diox, 1,3-diox, Isosorbide-5-Nitrae-dioxs, 1,3-diox-2 ketone.The ring compound (B1) that these have more than the tetra-atomic ring of more than 2 Sauerstoffatom, can be used independent a kind, also can be used together multiple.
As trioxa alkanes (b1-2-3), can be by formaldehyde condensation etc. and synthesizing under acid catalyst.Particularly, can enumerate 1,3,5-trioxane, paraldehyde (paraldehyde), cyamelide (cyamelide), 2,4,6-tri-(chloromethyl)-1,3,5-trioxane, 2,4,6-triisopropyl-1,3,5-trioxane, 2,4,6-trivinyl-1,3,5-trioxane, 2,4,6-tripropyl-1,3,5-trioxane, 2-(1,1-dimethyl ethyl)-1,3,5-trioxane, 2,4,6-triethyl-1,3,5-trioxane, 2,4,6-tributyl-1,3,5-trioxane, 2,4-diethyl-6-methyl isophthalic acid, 3,5-trioxane, 2-ethyl-4,6-dimethyl-1,3,5-trioxane, 2,4,6-tri-(dichloromethyl)-1,3,5-trioxane, 2,4,6-tri-(2-chloroethyl)-1,3,5-trioxane, 1,3,5-trioxane-2,4,6-, tri-propionitrile, 2,4,6-trityl-1,3,5-trioxane, 2,4,6-triisobutyl-1,3,5-trioxane, 11 β-(methoxymethoxy) spiral [male solid alkane-Isosorbide-5-Nitrae-diene-17,2'-[1,3,5] trioxanes]-3-ketone, 11 β-(methoxymethoxy) spiral [male solid alkane-Isosorbide-5-Nitrae-diene-17,2'-[1,3,5] trioxanes]-3-thioketones, 1,7,9-trimethylammonium-3,5,12-, tri-oxygen Fourth Rings [5.3.1.12,6.04,9] dodecane, 2,4,6-tri-(1-chloroethyl)-1,3,5-trioxane, 2,4,6-, tri-styroyl-1,3,5-trioxane, 2,4,6-thricyclohexyl-1,3,5-trioxane, 2-cyclohexyl-4,6-dimethyl-1,3,5-trioxane, 2-cyclohexyl-4,6-diphenyl-methyl-1,3,5-trioxane, 2,2,4,4,6,6-vegolysen, 3,5-trioxane, 4,4', 4 " (1,3,5-trioxane-2,4,6-, tri-bases) three butyric acid, three (p-toluenesulphonic acidss) 1,3,5-trioxane-2,4,6-, tri-base triethylenes, 1,3,5,7-tetramethyl--6-[3-(1,3,5,7-tetramethyl--2,4,9-trioxa-6-phospha-adamantane (phosphaadamantane)-6-yl) propyl group]-2,4,8-trioxa-6-phospha-adamantane, 2,4,6-triacetyl-1,3,5-trioxane, 1,3,5-trioxane-2-ketone, 2,2,4,4,6,6-hexafluoro-1,3,5-trioxane, 2,2-bis-is chloro-1,3,5-trioxane, 1,3,5-trioxane-2,4-diketone, 1,3,5-trioxane-2,4,6-triketone, 2-(triethyl silyl)-1,3,5-trioxane, 2-(TMS)-1,3,5-trioxane, 2,4,6-, tri-hexyl-1,3,5-trioxane, 2,4,6-trioctylphosphine-1,3,5-trioxane, 1,3,5-trioxane-2,4,6-tri-(methyl propionate), 2,2', 2 " (1,3,5-trioxane-2,4,6-, tri-bases) three acetonitriles, 2,4,6-, tri-cyclopentyl-1,3,5-trioxane, 2,4,6-tri-(2,6-dimethyl heptyl)-1,3,5-trioxane, 2,4,6-tri-(9-decene base)-1,3,5-trioxane, 2,4,6-tri-(4-pentenyl)-1,3,5-trioxane, 2,4,6-tri-[3-(benzyloxy) propyl group]-1,3,5-trioxane, 2,4,6-tri-[4-benzoyloxy butyl]-1,3,5-trioxane, 2,4,6-tri-(3-methoxycarbonyl propyl group)-1,3,5-trioxane, 2,4,6-tri-[4-(methoxycarbonyl) butyl]-1,3,5-trioxane, 2,4,6-tri-[5-(methoxycarbonyl) amyl group]-1,3,5-trioxane, 2,4,6-tri-[2-(benzoyloxy carbonyl) ethyl]-1,3,5-trioxane, 2,4,6-tri-(5-bromine amyl group)-1,3,5-trioxane, 2,4,6-tri-(3-methyl-5-bromine amyl group)-1,3,5-trioxane, 2,4,6-tri-(5-azido-amyl group)-1,3,5-trioxane, 2,4,6-tri-[2-(acetoxy-methyl)-3-acetoxyl group propyl group]-1,3,5-trioxane, 2,2', 2 " (1,3,5-trioxane-2,4,6-, tri-bases) three ethanol, 5,5', 5 " (1,3,5-trioxane-2,4,6-, tri-bases) three valeric acids, 3,3', 3 " (1,3,5-trioxane-2,4,6-, tri-bases) three propionic acid, 2,4,6-tri-(5-amido amyl group)-1,3,5-trioxane, 2,2', 2 " [(1,3,5-trioxane-2,4,6-, tri-bases) trimethylene] three (1,3-PDs), (2H6)-1,3,5-trioxane, 2,4,6-, tri--tertiary butyl-1,3,5-trioxane, 2,4,6-, tri-nonyl-1,3,5-trioxane, 2,4,6-, tri-heptyl-1,3,5-trioxane, 1,3,5-trioxane-2,4,6-tricarboxylic acid triethyl, 2,4,6-tri-(1-phenylethyl)-1,3,5-trioxane, 2,4,6-tri-(2,6-dimethyl-5-heptene-1-yl)-1,3,5-trioxane, 2,4,6,8,9,10-, six oxa-diamantane etc.
In above-mentioned trioxa alkanes (b1-2-3), from the aspect of the ring-opening copolymerization of the oxirane compound (A) of three membered cyclic, particularly preferably 1,3,5-trioxane.
< cyclic carbonate compound (b1-3) >
As cyclic carbonate compound (b1-3), can obtain the method (with reference to Japanese kokai publication hei 2-56356 communique) that polymkeric substance depolymerizes by glycol and reacting of dialkyl carbonate, maybe can synthesize with reacting of carbonic acid gas by corresponding epoxy alkane (alkylene oxide).Cyclic carbonate has 5 rings, 6 rings or structures more than 7 rings, with regard to 5 rings, comprise DOX class, with regard to 6 rings, comprise 1,3-diox, with regard to 7 rings, comprises Dioxepane (dioxepane) class, because the carbon of 2 is carbonyl carbon, thereby independent sorting is cyclic carbonate.As its concrete example, can enumerate for example ethylene carbonate (being also called DOX-2-ketone), propylene carbonate, butylene carbonate, 4-amyl group-DOX-2-ketone, 4-butyl-DOX-2-ketone, 4-propyl group-DOX-2-ketone, 4-(isopropoxy methyl)-DOX-2-ketone, 4-hexyl-DOX-2-ketone, 4-hexyl-5-methylene-DOX-2-ketone, 4,5-dimethyl-DOX-2-ketone, 4,4,5,5-tetramethyl-DOX-2-ketone, 4-octyl group-DOX-2-ketone, 4-nonyl-5-vinyl-DOX-2-ketone, 4-decyl-DOX-2-ketone, 4,5-dimethylene-DOX-2-ketone, 4,4-dimethyl-DOX-2-ketone, 4,4,5,5-tetraethyl-DOX-2-ketone, six hydrogen-DOX-2-ketone, 4-isopropyl-4-methyl-5-methylene-DOX-2-ketone, vinylene carbonate, carbonic acid pi-allyl ethyl, pi-allyl succinyl oxide, 4-vinyl-DOX-2-ketone, 4-phenethyl-5-vinyl-DOX-2-ketone, 4-methylene-DOX-2-ketone, 4-(3-cyclobutenyl)-DOX-2-ketone, 4-(5-hydroxyl-6,6-dimethyl tetrahydro-2H-pyrans-2-yl)-DOX-2-ketone, 4-[(E)-iodine methylene]-5-cyclopropyl-DOX-2-ketone, 4-cyclohexyl-5-vinyl-DOX-2-ketone, 4-(allyloxy)-4,5,5-trimethyl-DOX-2-ketone, 4-[(1E)-1,3-butadiene base]-DOX-2-ketone, 4-ethyl-4-methyl-5-methylene-DOX-2-ketone, 4-(2-methyl-2-allylidene)-5,5-dimethyl-DOX-2-ketone, 4-[4-(methoxyl group carbonyl oxygen base) butyl]-DOX-2-ketone, 4-vinyl-5,5-diethyl-DOX-2-ketone, 4-phenyl-5-vinyl-DOX-2-ketone, 4,5,5-trimethyl-4-(1-acrylic)-DOX-2-ketone, 4-vinyl-5, two (the 2-cyclohexyl ethyl)-DOX-2-ketone of 5-, 4,5,5-trimethyl-4-(3-methyl-3-butene-1-alkynyl)-DOX-2-ketone, 4-(vinyl oxygen ylmethyl)-DOX-2-ketone, 4,4-dimethyl-5-[(E)-3-butene-1-subunit]-DOX-2-ketone,4-[(E)-3-butene-1-subunit]-DOX-2-ketone, 4,4-dimethyl-5-[(Z)-1-phenyl-3-butene-1-subunit]-DOX-2-ketone, methacrylic acid (2-oxygen-DOX-4-yl) methyl esters, 4-methyl-5-[(E)-3-butene-1-subunit]-DOX-2-ketone, 4-methyl-5-[(Z)-3-butene-1-subunit]-DOX-2-ketone, 4,4-dimethyl-5-[(Z)-3-butene-1-subunit]-DOX-2-ketone, 4,4-dimethyl-5-[(E)-ethylidene]-DOX-2-ketone, 4,4-dimethyl-5-[(Z)-3-butene-1-subunit]-DOX-2-ketone, 4-(1-hexin base)-4-methyl isophthalic acid, 3-dioxolan-2-one, 4-(1-propenyloxy group methyl)-DOX-2-ketone, 4-[(1E)-1-methyl-3-butenylidene]-DOX-2-ketone, 4-[(1Z)-1-phenyl-3-butenylidene]-DOX-2-ketone, 4,4-diamyl-5-[(1E)-1,3-butadiene base]-DOX-2-ketone, 4-phenyl-5-methylene-DOX-2-ketone, 4-methyl-5-methylene-DOX-2-ketone, 4-methyl-4-vinyl-5-methylene-DOX-2-ketone, 4-propargyl-5-methylene-DOX-2-ketone, 4-[(E)-bromine methylene]-DOX-2-ketone, [(E)-2-carbonyl-5,5-dimethyl-DOX-4-subunit] ethyl acetate, 4-[(E)-2-(tert-butyl group carbonyl oxygen base) ethylidene]-DOX-2-ketone, 4-ethyl-5-methylene-DOX-2-ketone, 4-(hydroxymethyl)-DOX-2-ketone, 4-[(E)-2-(tert-butyl group carbonyl oxygen base) ethylidene]-5-methyl isophthalic acid, 3-dioxolan-2-one, 4,5-divinyl-DOX-2-ketone, 4-(1-naphthyl)-5-vinyl-DOX-2-ketone, two (2-cyclohexyl the ethyl)-5-[(1E of 4,4-)-1,3-butadiene base]-DOX-2-ketone, (4S)-4-phenyl-4-methyl-5-(1,3-butadiene base)-DOX-2-ketone, 4-(2-propylene-1-subunit)-5,5-dimethyl-DOX-2-ketone, 4,4-dimethyl-5-methylene-DOX-2-ketone, 5-butyl-5-methyl-4-methylene-DOX-2-ketone, carbonic acid glyceryl ester, 4-(butoxymethyl)-DOX-2-ketone,4-(allyloxy methyl)-DOX-2-ketone, 4-(hydroxymethyl)-DOX-2-ketone, 4-(methoxy)-DOX-2-ketone, 4-(4-vinyl benzene methoxy)-DOX-2-ketone, 4-ethyl-4-methyl-5-(3-phenyl propylidene)-DOX-2-ketone, 4-ethyl-4-methyl-5-benzylidene-DOX-2-ketone, 4-(own sulfenyl methyl)-DOX-2-ketone, 4,4-dimethyl-5-[(E)-2-phenyl ethylidene]-DOX-2-ketone, 4-(p-tolyl)-DOX-2-ketone, 4-methyl-5-phenyl-DOX-2-ketone, 4-benzyl-DOX-2-ketone, 4-(benzyl oxygen ylmethyl)-DOX-2-ketone, 4-phenyl-DOX-2-ketone, 4-phenyl-4-methyl-5-methylene-DOX-2-ketone, 4-phenyl-DOX-2-ketone, 4-methyl 4-phenyl-DOX-2-ketone, 4-phenoxy group-DOX-2-ketone, 4-butoxy-4,5-dimethyl-5-phenyl-DOX-2-ketone, (4S)-4 β-(phenylene-ethynylene)-4-phenethyl-5-[(Z)-benzylidene]-DOX-2-ketone, 4-[4-(phenoxy group carbonyl oxygen base) butyl]-DOX-2-ketone, 4-[4-(glycidyl amine formyloxy) butyl]-DOX-2-ketone, 4-epoxy ethyl-DOX-2-ketone, 4-[4-(2-carbonyl-DOX-4-ylmethyl amine formyloxy) butyl]-DOX-2-ketone, 4-(2-carbonyl-DOX-4-ylmethyl amine formyloxy methyl)-DOX-2-ketone, 4,4'-joins [DOX-2-ketone], 4,4'-tetramethylene two [DOX-2-ketone], 4,4'-(the two tetramethylenes of ethylenebis sulphur) two [DOX-2-ketone], 4,4'-[1,6-hexane two bases two (Oxymethylene)] two (DOX-2-ketone), 4,4'-[hexa-methylene two (sulphur ethylidene)] two (DOX-2-ketone), two (4,1-phenylene) the dioxygen dimethylenes of 4,4'-[isobutylidene] two (DOX-2-ketone), 4,4'-[isopropylidene two [(4,1-phenylene) Oxymethylene]] two (DOX-2-ketone), 4,4-dimethyl-5-[(Z)-benzylidene]-DOX-2-ketone, 4-[2-(benzyl oxygen base) ethyl]-DOX-2-ketone,4-[2-(trityl oxygen base) ethyl]-DOX-2-ketone, 4,5-diphenyl-DOX-2-ketone, 4,4-dimethyl-5-[1-(1-naphthyl) vinyl]-DOX-2-ketone, 4,4-dimethyl-5-[1-(2-naphthyl) vinyl]-DOX-2-ketone, 4,4-dimethyl-5-[1-(4-aminomethyl phenyl) vinyl]-DOX-2-ketone, 4,4-dimethyl-5-[1-(4-methoxyphenyl) vinyl]-DOX-2-ketone, 4,4-dimethyl-5-[1-(4-hydroxy phenyl) vinyl]-DOX-2-ketone, 4,4-dimethyl-5-(1-methylene-2-phenyl-2-acrylic)-DOX-2-ketone, 4,4-dimethyl-5-[(E)-1-methylene-3-phenyl-2-acrylic]-DOX-2-ketone, 4,4-dimethyl-5-(1-phenyl vinyl)-DOX-2-ketone, 4-methyl-5-(1-phenyl vinyl)-DOX-2-ketone, 4,4-dimethyl-5-[(E)-3-phenyl-1-acrylic]-DOX-2-ketone, 4-(1-phenyl vinyl)-DOX-2-ketone, 4,4-dimethyl-5-(1-phenyl-1-acrylic)-DOX-2-ketone, 4,4-dimethyl-5-(1,2-diphenylacetylene)-DOX-2-ketone, 4,4-dimethyl-5-(2-methyl isophthalic acid-phenyl-1-acrylic)-DOX-2-ketone, 4,4,5-trimethyl-5-(1-phenyl vinyl)-DOX-2-ketone, 4-(benzyloxy methyl)-DOX-2-ketone, 4,4-diphenyl-DOX-2-ketone, 4,4 '-[(1,3-phenylene) two (Oxymethylenes)] two (DOX-2-ketone), 4,4-dimethyl-5-[(Z)-1-naphthyl methylene]-DOX-2-ketone, 4,4-dimethyl-5-[(Z)-4-methoxybenzene methylene]-DOX-2-ketone, 4,4-dimethyl-5-[(Z)-4-phenol methylene]-DOX-2-ketone, 4-(phenylene-ethynylene)-4-methyl isophthalic acid, 3-dioxolan-2-one, 4-(phenylene-ethynylene)-4,5-dimethyl-DOX-2-ketone, 4-[1-(4-methoxyphenoxy) vinyl]-5,5-diethyl-DOX-2-ketone, 4-[1-(4-methoxyphenoxy) vinyl]-5,5-dimethyl-DOX-2-ketone, 4-[3-(benzyloxy) propyl group]-5-methyl isophthalic acid, 3-dioxolan-2-one,7-[2-(2-carbonyl-DOX-4-yl) ethyoxyl]-2H-1-chromen-2-one, 7-[2-(2-carbonyl-4-methyl isophthalic acid, 3-dioxolanes-4-yl) ethyoxyl]-2H-1-chromen-2-one, 5-(benzyloxy)-DOX-2-ketone, 4-(isobutoxy methyl)-DOX-2-ketone, 4-(4-nonyl benzene methoxy)-DOX-2-ketone, 4-(4-chlorphenyl sulfidomethyl)-DOX-2-ketone, 4-[3-(chloromethyl) phenyl]-DOX-2-ketone, 4-[4-(chloromethyl) phenyl]-DOX-2-ketone, 4,4-dipropyl-5-[1-(4-methoxyphenoxy) vinyl]-DOX-2-ketone, 4,4-diamyl-5-[1-(4-methoxyphenoxy) vinyl]-DOX-2-ketone, 4,4-diisopropyl-5-[1-(4-methoxyphenoxy) vinyl]-DOX-2-ketone, 4,4-, bis-phenethyls-5-[1-(4-methoxyphenoxy) vinyl]-DOX-2-ketone, two (2-cyclohexyl the ethyl)-5-[1-(4-methoxyphenoxy) of 4,4-]-DOX-2-ketone, 4-[1-(thiophenyl) cyclohexyl]-DOX-2-ketone, 4-(3-methoxyl group-4-ethoxyl phenenyl)-5-(hydroxymethyl)-DOX-2-ketone, 4-(phenoxy group carbonyl oxy-methyl)-DOX-2-ketone, 4-benzylidene-5,5-dimethyl-DOX-2-ketone, 4-[(2-naphthyl) methylene]-5,5-dimethyl-DOX-2-ketone, 4-(4-chlorobenzene methylene)-5,5-dimethyl-DOX-2-ketone, 5-methyl-5-phenyl-4-(3-phenyl propylidene)-DOX-2-ketone, 5,5-dimethyl-4-(3-phenyl propylidene)-DOX-2-ketone, 4-[4-(chloroformyl oxygen base) butyl]-DOX-2-ketone, 4-chlorine-1,3-dioxolane-2-ketone, 4-is chloro-4,5-dimethyl-DOX-2-ketone, 4-(chlorine carbonyl oxy-methyl)-DOX-2-ketone, 4-(p-chlorophenoxy methyl)-DOX-2-ketone, 4-(chloromethyl)-DOX-2-ketone, chloro-DOX-the 2-of 4,5-bis-ketone, (4S, 5R)-4,5-diphenyl-DOX-2-ketone, 4 α, 5 alpha-alpha-dimethyls-DOX-2-ketone, (4R, 5R)-4,5-dimethyl-DOX-2-ketone, (4S, 5S)-4,5-dimethyl-DOX-2-ketone,(4S)-4 Beta-methyls-DOX-2-ketone, (R)-4-methyl isophthalic acid, 3-dioxolan-2-one, (S)-5-ethyl-DOX-2-ketone, 4-[(tri-phenyl-silane base) methyl]-5,5-dimethyl-DOX-2-ketone, 4-[9-(3-thienyl) nonyl]-DOX-2-ketone, 4-(methyl amine ylmethyl)-DOX-2-ketone, 4-(4-chlorobenzene sulfenyl)-DOX-2-ketone, 4-(thiophenyl)-DOX-2-ketone, 4-(4-methoxybenzene sulfenyl)-DOX-2-ketone, 4-(4-bromobenzene sulfenyl)-DOX-2-ketone, 4-(thiophenyl methyl)-DOX-2-ketone, 4,4 '-[sulfonyl two (p-sub-phenoxy group methylene)] two (DOX-2-ketone), 4-(4-methylbenzene sulfenyl)-DOX-2-ketone, 4,4,5,5-tetramethyl-2-(phenyl sulfonyl oxygen base imido grpup)-DOX-2-ketone, 2-(4-nitrophenoxy)-4-methyl-2-phosphorus (V)-DOX-2-ketone, 4-(glycidyl oxygen ylmethyl)-DOX-2-ketone, glycidyl amine formic acid (2-carbonyl-DOX-4-yl) methyl esters, 4-(falling camphane-5-alkene-2-yl)-DOX-2-ketone, 4-[2-(2-naphthyl) ethyl]-5-methoxyl group-DOX-2-ketone, 4-[2-(1-naphthyl) ethyl]-5-methoxyl group-DOX-2-ketone, 4,4-dimethyl-5-(3-thienyl methene)-DOX-2-ketone, 4-[2-[dimethyl (TMS oxygen base) silylation] ethyl]-DOX-2-ketone, 4-[2-[(methyl) two (TMS oxygen base) silylation] ethyl]-DOX-2-ketone, 4-[2-(TMS) ethyl]-DOX-2-ketone, 4-[4-(glycidyl amine formyloxy) butyl]-DOX-2-ketone, 4-[4-(2-carbonyl-DOX-4-ylmethyl amine formyloxy) butyl]-DOX-2-ketone, 4-[4-(glycidyl amine formyloxy) butyl]-DOX-2-ketone, 5 ring carbonates of 4-(2-carbonyl-DOX-4-ylmethyl amine formyloxy methyl)-DOX-2-ketone etc.,
For example trimethylene carbonate (being also called 1,3-diox-2-ketone), 4-methyl isophthalic acid, 3-diox-2-ketone, carbonic acid 2,2-dimethoxy the third-1,3-diester, 5-methyl isophthalic acid, 3-diox-2-ketone, 5,5-dimethyl-1,3-diox-2-ketone (being also called new penta diester of carbonic acid), 5-methyl-5-propyl group-1,3-diox-2-ketone, 5-hydroxymethyl-5-methyl isophthalic acid, 3-diox-2-ketone, 4-phenyl-1,3-diox-2-ketone, 5-(hydroxymethyl)-5-ethyl-1,3-diox-2-ketone, 4-methylene radical-1,3-diox-2-ketone, 5,5-dimethyl-4-vinyl-1,3-diox-2-ketone, 5-cyano group-5-methyl isophthalic acid, 3-diox-2-ketone, 4,4-dimethyl-1,3-diox-2-ketone, 5-butyl-1,3-diox-2-ketone, 5,5-diethyl-1,3-diox-2-ketone, 5-ethyl-5-phenyl-1,3-diox-2-ketone, methacrylic acid 2-carbonyl-5-ethyl-1,3-diox-5-base methyl esters, 5-methyl-5-phenyl-1,3-diox-2-ketone, 4-styryl-5,5-dimethyl-1,3-diox-2-ketone, 4-styryl-1,3-diox-2-ketone, 4-(1-heptenyl)-1,3-diox-2-ketone, 4-vinyl-6-phenyl-1,3-diox-2-ketone, 4-pseudoallyl-6-phenyl-1,3-diox-2-ketone, 4-allyl group-6-phenyl-1,3-diox-2-ketone, 4-vinyl-6-the tertiary butyl-1,3-diox-2-ketone, 4-styryl-5,5-dimethyl-6-sec.-propyl-1,3-diox-2-ketone, 5-[2-(2-amido-9H-purine-9-yl) ethyl]-1,3-diox-2-ketone, 4-(1-phenyl vinyl)-1,3-diox-2-ketone, 5,5-phenylbenzene-1,3-diox-2-ketone, 5-methyl-4-(1-phenyl vinyl)-1,3-diox-2-ketone, 4,4-dimethyl-6-(1-phenyl vinyl)-1,3-diox-2-ketone, 5-methylene radical-1,3-diox-2-ketone, 4-[(E)-styryl]-1,3-diox-2-ketone, 5-octyl group-1,3-diox-2-ketone, 5-dodecyl-1,3-diox-2-ketone, 2-carbonyl-5-methyl isophthalic acid, 3-diox-5-carboxylic acid benzene methyl, 4,6-dimethyl-1,3-diox-2-ketone, 4-methoxybenzoic acid 2-carbonyl-5-methyl isophthalic acid, 3-diox-5-base methyl esters, phenylformic acid 2-carbonyl-5-methyl isophthalic acid, 3-diox-5-base methyl esters, 4-nitrobenzoic acid 2-carbonyl-5-methyl isophthalic acid, 3-diox-5-base methyl esters, 4,4,6-trimethylammonium-1,3-diox-2-ketone, 5-ethyl-5-(methoxycarbonyl oxygen ylmethyl)-1,3-diox-2-ketone, 5-ethyl-5-(ethoxy carbonyl oxygen ylmethyl)-1,3-diox-2-ketone, 5-(4-butoxy phenyl)-1,3-diox-2-ketone, 5-[4-(pentyloxy) phenyl]-1,3-diox-2-ketone, 5-(4-propoxy-phenyl)-1,3-diox-2-ketone, 5-[4-(hexyloxy) phenyl]-1,3-diox-2-ketone, 5-allyl group-1,3-diox-2-ketone, 5-(benzyloxy carbonyl)-1,3-diox-2-ketone, 5-methyl-4-(4-phenmethyl benzoxy ylmethyl)-1,3-diox-2-ketone, 5-methyl-4-(4-nitrobenzoyl acyloxy methyl)-1,3-diox-2-ketone, 5-methyl-4-(4-methoxybenzoyl oxygen ylmethyl)-1,3-diox-2-ketone, 5-(4-methylene radical-5-hexene-1-subunit)-1,3-diox-2-ketone, 5-ethyl-5-(4-vinyl benzene methoxymethyl)-1,3-diox-2-ketone, 5-ethyl-5-(4-vinyl benzene methoxymethyl)-1,3-diox-2-ketone, 5-(benzyloxy)-1,3-diox-2-ketone, 5-hydroxyl-1,3-diox-2-ketone, 4-methylene radical-5,5-dimethyl-1,3-diox-2-ketone, 5-ethyl-5-(2-hydroxyethyl)-1,3-diox-2-ketone, 4-[1-(thiophenyl) cyclohexyl]-1,3-diox-2-ketone, 4-[4-(octyloxy) phenylazo]-6-hexyl-1,3-diox-2-ketone, 4-(4-p-methoxy-phenyl azo-group)-6-hexyl-1,3-diox-2-ketone, 4-[4-(octyloxy) phenylazo]-6-decyl-1,3-diox-2-ketone, 2-carbonyl-5-methyl isophthalic acid, 3-diox-5-allyl carboxylate, 4-[1-(thiophenyl) cyclohexyl]-5,5-dimethyl-1,3-diox-2-ketone, 4-allyl group-6-methyl isophthalic acid, 3-diox-2-ketone, 5-ethyl-5-(benzyloxy methyl)-1,3-diox-2-ketone, 5-[2-(benzyloxy) oxyethyl group]-1,3-diox-2-ketone, 5-(allyloxy)-1,3-diox-2-ketone, 5-[3-(2-hydroxyl ethylmercapto group) propoxy-]-1,3-diox-2-ketone, 5-(benzyloxy carbonyl amido)-1,3-diox-2-ketone, 5-[6-[4-(4-amyl group cyclohexyl) phenoxy group] hexyloxy]-1,3-diox-2-ketone, 4-(iodomethyl)-6-[2-(4-anisole methoxyl group) ethyl]-1,3-diox-2-ketone, (5S)-4-vinyl-5 β-(2,2-dimethoxy-ethyl)-1,3-diox-2-ketone, 5-allyl group-5-propargyl-1,3-diox-2-ketone, 4-vinyl-5-(1-methyl-5-imidazolyl methyl)-1,3-diox-2-ketone, 5-α-tolylene-1,3-diox-2-ketone, 5-(epoxypropyl oxygen ylmethyl)-5-ethyl-1,3-diox-2-ketone, 5-(allyloxy methyl)-5-ethyl-1,3-diox-2-ketone, two (the azido-methyl)-5-of 5,5-ethyl-1,3-diox-2-ketone, 5-methyl-5-[[2-(vinylsulfonyl) ethyl] thiomethyl]-1,3-diox-2-ketone, 5-(allyloxy methyl)-5-ethyl-1,3-diox-2-ketone, 5,5'-(oxygen dimethylene) two (5-ethyl-1,3-diox-2-ketone), 5,5'-(4,7-, bis-Tiadenol-1,10-bis-bases) two (1,3-diox-2-ketone), 5,5'-(the two tetramethylenes of ethylenebis sulphur) two (1,3-diox-2-ketone), 5-methyl-5-(2-carbonyl-1,3-dioxane-4-yl methyl)-1,3-diox-2-ketone, 5-ethyl-5-(2-carbonyl-1,3-dioxane-4-yl methyl)-1,3-diox-2-ketone, 5-[(2-carbonyl-1,3-dioxane-4-yl) methyl]-5-propyl group-1,3-diox-2-ketone, 5-(2-carbonyl-1,3-dioxane-4-yl methyl)-5-ethyl-1, the 6 ring carbonates such as 3-diox-2-ketone,
For example tetramethylene carbonic ether (is also called 1, 3-Dioxepane-2-ketone), 5-methyl isophthalic acid, 3-Dioxepane-2-ketone, 4-methyl isophthalic acid, 3-Dioxepane-2-ketone, 5, 5-dimethyl-1, 3-Dioxepane-2-ketone, 5-phenyl-1, 3-Dioxepane-2-ketone, 4-phenyl-1, 3-Dioxepane-2-ketone, 4-[1-(thiophenyl) cyclohexyl]-1, 3-Dioxepane-2-ketone, 5, 5'-(the two trimethylenes of ethylenebis sulphur) two (1, 3-Dioxepane-2-ketone) etc. 7 ring carbonates, on reactive point, preferably use ethylene carbonate, Texacar PC, the 5 ring carbonates such as carbonic acid glyceryl ester.
The fluorine-containing ring compound of < (b1-4) >
For ring compound (B1), in order further to improve thermotolerance, humidity resistance, can be in the ring texture of ring compound (B1), the substituting group further comprising through having F atom replaces fluorine-containing ring compound (b1-4) more than 1 place.As the substituting group that preferably contains F atom, more specifically, can illustrate for example F-, CF 3-, CF 2h-, CFH 2-, CF 3cF 2-, CHF 2cF 2-, CH 3cF 2-, CF 3cH 2-, CF 3cF 2cH 2-, CF 3cF 2cF 2-, CH (CF 3) 2-, CHF 2cF 3cH 2-, CHF 2cF 2cH 2-, CF 3cH 2cH 2-, CF 3cF 2cF 2cF 2-, CHF 2cF 2cF 2cH 2-, CF 3cHFCF 2cH 2-, CHF 2cF(CF 3) CH 2-, CF 3cF 2cH 2cH 2-, CHF 2cF 2cF 2cF 2cH 2-, CF 3cF 2cF 2cF 2cF 2-etc., wherein F atom be independent substituting group or carbonatoms below 3 containing fluoroalkyl, on the point that can maintain effective bonding force and thermotolerance, humidity resistance particularly preferably.
And, in the structure of ring compound (B1), arbitrary position all can, can fully effectively bring into play.
And, as the fluorine-containing ring compound (b1-4) replacing through the substituting group with F atom more than 1 place, on the point of thermotolerance, humidity resistance, preferably there is at least a kind in Fluorine-containing lactones class (b1-4-1), fluorine-containing carbonates (b1-4-2), fluorine-containing dioxolane class (b1-4-3).
As Fluorine-containing lactones class (b1-4-1), more specifically, can enumerate for example α-fluoro-gamma-butyrolactone, β-fluoro-gamma-butyrolactone, γ-fluoro-gamma-butyrolactone, α-trifluoromethyl-gamma-butyrolactone, 2-(4-fluorophenoxy)-4 hydroxybutyric acid lactone, the fluoro-11-oxygen of 1-dehydrogenation-9-testolactone (oxotestololactone), the fluoro-11-hydroxyl of 10-undeeanoic acid lactone, 5-(1'-fluoro ethyl)-5-phenyl-2-carbonyl tetrahydrofuran (THF), the Fluorine-containing lactones class of 5-methyl fluoride-5-phenyl-2-carbonyl tetrahydrofuran (THF), on reactive point, preferably use the Fluorine-containing lactones class of fluoro-gamma-butyrolactone.
As fluorine-containing carbonates (b1-4-2), more specifically, can enumerate for example carbonic acid fluoroethylene, carbonic acid trifluoromethyl ethyl, 4-(trifluoromethyl)-5-(thiophenyl)-DOX-2-ketone, 4-[4-(trifluoromethyl) α-tolylene]-5,5-dimethyl-DOX-2-ketone, the fluoro-4-methyl isophthalic acid of 4-, 3-dioxolan-2-one, the fluoro-5-methyl isophthalic acid of 4-, 3-dioxolan-2-one, 4-trifluoromethyl-4-methyl isophthalic acid, 3-dioxolan-2-one, 4-(trifluoromethyl)-DOX-2-ketone, 4-(2,2,3,3,4,4,5,5,5-, nine fluorine amyl groups)-DOX-2-ketone, fluoro-DOX-the 2-of 4,5-bis-ketone, the fluoro-4-ethyl-DOX-2-of 4-ketone, fluoro-DOX-the 2-of 4,4-bis-ketone, 4-(α, α-difluorobenzene methyl)-DOX-2-ketone, 4-[(tetrahydrofuran (THF)-3-yl) difluoromethyl]-DOX-2-ketone, the fluoro-4-[(4-p-methoxy-phenyl of 4-) sulphur]-DOX-2-ketone, the fluoro-4-of 4-(4-bromobenzene sulfenyl)-DOX-2-ketone, 4-(thiophenyl methyl fluoride)-DOX-2-ketone, 4-(thiophenyl difluoromethyl)-DOX-2-ketone, 4-[difluoro (phenyl sulfonyl) methyl]-DOX-2-ketone, 4-[difluoro (phenyl sulfinyl) methyl]-DOX-2-ketone, the fluoro-4-of 4-(4-methylbenzene sulfenyl)-DOX-2-ketone, 4-[[4-(methyl fluoride) phenyl] sulphur]-DOX-2-ketone, the fluoro-4-of 4-(thiophenyl)-DOX-2-ketone, the fluoro-4-of 4-(4-chlorobenzene sulfenyl)-fluorine-containing carbonates of 5 ring such as DOX-2-ketone,
For example 4-fluoro-1,3-diox-2-ketone, the fluoro-4-methyl isophthalic acid of 4-, 3-diox-2-ketone, the fluoro-5-methyl isophthalic acid of 4-, 3-diox-2-ketone, 4,5-bis-is fluoro-1,3-diox-2-ketone, 4-Trifluoromethyl-1,3-diox-2-ketone, 4,5-bis-(trifluoromethyl)-1, the fluorine-containing carbonates of 6 ring such as 3-diox-2-ketone;
For example 4-fluoro-1,3-Dioxepane-2-ketone, 5-fluoro-1,3-Dioxepane-2-ketone, the fluoro-4-methyl isophthalic acid of 4-, 3-Dioxepane-2-ketone, 4-Trifluoromethyl-1, the fluorine-containing carbonates of 7 ring such as 3-Dioxepane-2-ketone are preferably used carbonic acid fluoroethylene, carbonic acid trifluoromethyl ethyl, 4 on reactive point, 4-bis-fluoro-1,3-dioxolan-2-one, 4, the fluorine-containing carbonates of 5 ring such as the fluoro-DOX-2-of 5-bis-ketone.
As fluorine-containing dioxolane class (b1-4-3), more specifically, can enumerate for example 2-fluoro-1, 3-dioxolane, 4-fluoro-1, 3-dioxolane, 2-(fluorine methylene radical)-1, 3-dioxolane, 2-(trifluoromethyl)-1, 3-dioxolane, 2-difluoromethyl-1, 3-dioxolane, α-methyl fluoride-1,2-carbonyl-4, 3-dioxolane, 2, 2-dimethyl-4-(methyl fluoride)-1, 3-dioxolane, cis-4-methyl fluoride-2-methyl isophthalic acid, 3-dioxolane, 2-(3-chloropropyl)-2-(p-fluorophenyl)-1, 3-dioxolane etc. fluorine-containing 1, 3-dioxolane class, on reactive point, preferably use 2-fluoro-1, 3-dioxolane, 4-fluoro-1, 3-dioxolane.
These replace fluorine-containing ring compound (b1-4) more than 1 place through having the substituting group of F atom, can only use a kind, or also can be also with multiple.
In optical polymerism composition, for the ring compound (B1) more than thering is the tetra-atomic ring of more than 2 Sauerstoffatom, with respect to the oxirane compound (A) of the three membered cyclic as principal constituent of 100 weight parts, preferably in the scope of 0.5 to 60 weight part, contain (B1), more preferably in the scope of 1 to 30 weight part, contain.If the ring compound (B) having more than the tetra-atomic ring of more than 2 Sauerstoffatom is more than 0.5 weight part, while carrying out photopolymerization, improve the polymerization velocity of the oxirane compound (A) of three membered cyclic, improve cohesive force, can obtain effectively crosslinked film.On the other hand, if below 60 weight parts,, in the situation that using Polymerizable composition as optical polymerism caking agent, the polarity of crosslinked film becomes applicable scope, and the bonding force of nonpolar blooming (polyester mesentery, norcamphene film etc.) is good.
From the viewpoint of polymerization velocity, more than the ring compound (b1-1) in ring compound (B1) 100 % by weight, ring compound (b1-2), compound (b1-3) preferably contain 80 % by weight altogether, more preferably more than 90 % by weight.And from the viewpoint of the cohesive force of crosslinked film, these are preferably allocated than being respectively (b1-1)/(b1-2)/(b1-3)=5 to 10/5 to 10/70 to 60, more preferably (b1-1)/(b1-2)/(b1-3)=0 to 5/0 to 5/80 to 70.
For fluorine-containing ring compound (b1-4), in ring compound (B1) 100 % by weight, preferably contain (b1-4) of the scope of 10 to 100 % by weight, more preferably contain the scope of 50 to 100 % by weight.By using and replace fluorine-containing ring compound (b1-4) more than 1 place through thering is the substituting group of F atom, can give thermotolerance and humidity resistance under more harsh condition, therefore more preferably within the scope of this.
< has ring compound (B2) the > more than tetra-atomic ring of more than 1 Sauerstoffatom and more than 1 sulphur atom
Below, " there is ring compound (B2) more than the tetra-atomic ring of more than 1 Sauerstoffatom and more than 1 sulphur atom " and be also recited as " ring compound (B2) ".On the point of optical polymerism, ring compound (B2) preferably in ring, have be selected from sulfoxide skeleton, sulfone skeleton, sulfite skeleton, sulfuric ester skeleton, sulphonate skeleton,-sulfinic acid ester skeleton, thioesters skeleton in any structure.
As the ring compound (b2-1) with sulfoxide skeleton, can enumerate Thietane-1-oxide compound (being also called trimethylene sulfoxide), 3-hydroxyl Thietane-1-oxide compound, 3-methyl Thietane-1-oxide compound, 1, 3-dithietane-1-oxide compound, 3-tertiary butyl Thietane-1-oxide compound, tetrahydrochysene-2H-sulphur pyrans-1-oxide compound, 2-methyl tetrahydrochysene-2H-sulphur pyrans-1-oxide compound, 2-ethyl tetrahydrochysene-2H-sulphur pyrans-1-oxide compound, 2-sec.-propyl tetrahydrochysene-2H-sulphur pyrans-1-oxide compound, 3, 5-dimethyl tetrahydro-2H-sulphur pyrans-1-oxide compound, 4-methyl tetrahydrochysene-2H-sulphur pyrans-1-oxide compound, 4-ethyl tetrahydrochysene-2H-sulphur pyrans-1-oxide compound, 4-neo-pentyl tetrahydrochysene-2H-sulphur pyrans-1-oxide compound, 4-sec.-propyl tetrahydrochysene-2H-sulphur pyrans-1-oxide compound, 4-tertiary butyl tetrahydrochysene-2H-sulphur pyrans-1-oxide compound etc.
And, as the ring compound (b2-2) with sulfone skeleton, can enumerate tetramethylene sulfone (sulfolane), 3-methyl sulfolane, dimethylsulfolane, 3-cyclobufene sultone, 2,5-dimethylsulfolane, 4,4-dicarbapentaborane-1,4-oxathiane (4,4-oxo-1,4-oxathiane) etc.
As the ring compound (b2-3) with sulfite skeleton, can enumerate 1,3,2-dioxy thiacyclopentane 2-oxide compound (1,3,2-dioxathiolane-2-oxide) (being also called sulfurous acid second diester (glycol sulfite)), 4,5-dimethyl-1,3,2-dioxy thiacyclopentane 2-oxide compound, 4,4,5,5-tetramethyl--1,3,2-dioxy thiacyclopentane 2-oxide compound, 4,5-phenylbenzene-1,3,2-dioxy thiacyclopentane-2-oxide compound, 4-(hydroxymethyl)-1,3,2-dioxy thiacyclopentane-2-oxide compound, 4-butyl-1,3,2-dioxy thiacyclopentane-2-oxide compound, 5-methyl-4-carbonyl-1,3,2-dioxy thiacyclopentane-2-oxide compound, 4-phenyl-1,3,2-dioxy thiacyclopentane-2-oxide compound, 4-methyl isophthalic acid, 3,2-dioxy thiacyclopentane-2-oxide compound, 4-butyl-4-phenyl-1,3,2-dioxy thiacyclopentane-2-oxide compound, 4-propyl group-1,3,2-dioxy thiacyclopentane-2-oxide compound, 4-methyl 4-phenyl-1,3,2-dioxy thiacyclopentane-2-oxide compound etc.
As the ring compound (b2-4) with sulfuric ester skeleton, can enumerate 1,3,2-dioxy thiacyclopentane-2,2-dioxide (1,3,2-dioxathiolane-2,2-dioxide) (being also called sulfuric acid second diester (glycol sulfate)), 4-ethyl-1,3,2-dioxy thiacyclopentane-2,2-dioxide, 4-methyl isophthalic acid, 3,2-dioxy thiacyclopentane-2,2-dioxide, 4-(3-methyl butyl)-1,3,2-dioxy thiacyclopentane-2,2-dioxide, the 4-tertiary butyl-1,3,2-dioxy thiacyclopentane 2,2-dioxide, 4-(benzyloxy methyl)-1,3,2-dioxy thiacyclopentane 2,2-dioxide, 4-sec.-propyl-1,3,2-dioxy thiacyclopentane 2,2-dioxide, 4-propyl group-1,3,2-dioxy thiacyclopentane 2,2-dioxide, 4-(4-phenyl butyl)-4-methyl isophthalic acid, 3,2-dioxy thiacyclopentane 2,2-dioxide, 4-hexyl-1,3,2-dioxy thiacyclopentane 2,2-dioxide, 4,4-diethyl-1,3,2-dioxy thiacyclopentane 2,2-dioxide, 4-carboxyl-4-methyl isophthalic acid, 3,2-dioxy thiacyclopentane 2,2-dioxide, 4-styroyl-1,3,2-dioxy thiacyclopentane 2,2-dioxide etc.
As the ring compound (b2-5) with sulphonate skeleton, can enumerate 3-hydroxyl-2-perfluoroetane sulfonic acid lactone (sultone), 1,3-propane sultone, 1-methyl isophthalic acid, 3-propane sultone, 1,4-butane sultones, 2,4-butane sultones, 4-hydroxyl-2-perfluoroetane sulfonic acid lactone, 3-hydroxyl-1-propylene-1-sultones, γ-butane sultones, 1,8-naphthene sulfonic acid lactone, δ-n-Hexadecane sultones, 1-phenmethyl-4-hydroxyl butane-1-sultones etc.
As the ring compound (b2-6) with-sulfinic acid ester skeleton, can enumerate 1,2-oxathiolane-2-oxide compound, 3-methyl isophthalic acid, 2-oxathiolane 2-oxide compound, 3-propyl group-1,2-oxathiolane 2-oxide compound, 3,3,5-trimethylammonium-1,2-oxathiolane 2-oxide compound, 3-amyl group-5-methyl isophthalic acid, 2-oxathiolane 2-oxide compound, 3,3-dimethyl-1,2-oxathiolane 2-oxide compound etc.
As the ring compound (b2-7) with thioesters skeleton, can enumerate Thietane-2-ketone, 3,3-dimethyl Thietane-2-ketone, 4-methyl Thietane-2-ketone, 3-methyl Thietane-2-ketone, 3-ethyl Thietane-2-ketone, 3-methyl-3-ethyl Thietane-2-ketone, γ-thia butyrolactone, 3-methyl dihydroxyl thiophene-2 (3H)-one, 3-ethyl tetramethylene sulfide-2-ketone, 4,5-dihydro-3-sec.-propyl thiophene-2 (3H)-one, 4,5-dihydro-3-tertiary butyl thiophene-2 (3H)-one, 3,3-dimethyl tetrahydro thiophene-2-ketone, 4,5-dihydro-3,3-diethyl thiophene-2 (3H)-one, 4,5-dihydro-3-sec.-propyl-3 methyl thiophene-2 (3H)-one, 4,5-dihydro-3,3-di-isopropyl thiophene-2 (3H)-one, 5-methyl dihydro-thiophene-2 (3H)-one, 4-methyl dihydro-thiophene-2 (3H)-one, 5-butyl dihydro-thiophene-2 (3H)-one, 5-hexyl tetramethylene sulfide-2 (3H)-one, 5-octyl group dihydro-thiophene-2 (3H)-one, 4-butyl dihydro-thiophene-2 (3H)-one, 5-ethyl tetramethylene sulfide-2-ketone, 4-methyl dihydro-thiophene-2 (3H)-one, α-ethyl-Alpha-Methyl-γ-thia butyrolactone, 4-ethyl-3-methyl isophthalic acid-thiacyclopentane-2-ketone, 3-ethyl-4-methyl isophthalic acid-thiacyclopentane-2-ketone, β-ethyl-Beta-methyl-γ-thia butyrolactone, tetrahydrochysene-2H-sulphur pyran-2-one, 6-methyl tetrahydrochysene-2H-sulphur pyran-2-one, 6-propyl group tetrahydrochysene-2H-sulphur pyran-2-one, 6-amyl group tetrahydrochysene-2H-sulphur pyran-2-one, 6-heptyl tetrahydrochysene-2H-sulphur pyran-2-one, 6-hexyl tetrahydrochysene-2H-sulphur pyran-2-one etc.
Ring compound (B2), can be used independent a kind, or also can combine two or more use.
In ring compound (B2), on the point of reactivity and lowering viscousity, preferably use tetramethylene sulfone, 1,3,2-dioxy thiacyclopentane-2-oxide compound, 1,3,2-dioxy thiacyclopentane-2,2-dioxide, 1,3-propane sultone, Isosorbide-5-Nitrae-butane sultones.
With respect to the oxirane compound as principal constituent (A) of 100 weight parts, ring compound (B2) preferably contains in the scope of 0.5 to 60 weight part, more preferably in the scope of 1 to 30 weight part, contains.If ring compound (B2) is more than 0.5 weight part, while carrying out photopolymerization, improve the polymerization velocity of the oxirane compound (A) of three membered cyclic, improve cohesive force, can obtain effectively crosslinked film.On the other hand, if below 60 weight parts,, in the situation that using Polymerizable composition as optical polymerism caking agent, the polarity of crosslinked film becomes applicable scope, good to the bonding force of nonpolar blooming (polyester mesentery, norcamphene film etc.).
< has compound (C) > of the two molecular weight of at least 1 ring texture and hydroxyl below 500
Below, " there is the compound (C) of the two molecular weight of at least 1 ring texture and hydroxyl below 500 " and be also recited as " compound (C) ".
So-called compound (C), be have ring compound that at least 1 aromatic nucleus, cycloalkanes, cyclenes etc. only consist of carbon, thiirane (thiirane), azetidine (azetidine), tetrahydrofuran, thiacyclopentane etc. contain heteroatomic ring compound and 1 to 10 hydroxyl the two, the compound of molecular weight below 500, hydroxyl is any one of phenol hydroxyl or alcohol hydroxyl group.
Compound (C), not only with the reacting of oxirane compound (A), ring compound (B1) and ring compound (B2), improve the polymerization degree, also promote the reaction of oxirane compound (A), ring compound (B1) and ring compound (B2).The molecular weight of compound (C) is below 500 time, and reaction facilitation effect is high, good with the reactivity of oxirane compound (A), ring compound (B1) and ring compound (B2).
Moreover the measuring method of molecular weight, is used clear and electrician company GPC(gel permeation chromatography processed instrument) " ShodexGPC System-21 ".GPC passes through the quantitative liquid chromatography of differential liberation of its molecular size by the material that is dissolved in solvent, and tetrahydrofuran (THF) as solvent, is determined as number average molecular weight (Mn) as molecular weight, carried out polystyrene conversion.
The ring compound of so-called compound (C), can enumerate for example benzene particularly, phenylene, tolyl, methylene phenyl, phenmethyl, α-tolylene, inferior phenmethyl, xylyl, xylylene, phthalal, mphenylenedimethylim-, terephthalylidene, styrene, styrene, styryl, sub-styryl, the inclined to one side trimethylphenyl of as-, the inclined to one side trimethylphenyl of v-, the inclined to one side trimethylphenyl of s-, sym-trimethylbenzene base, cumyl, α-cumyl, hydrogen cinnamyl, cinnamyl, cinnamylidene, inferior cinnamyl, tetramethylphenyl, durylene, thymyl, carvacryl, p-isopropylbenzyl, p-isopropylbenzylidene, the benzene tertiary butyl, xenyl, diphenyl-methyl, diphenylmethylene, the substituting group of the representative such as trityl, among these, benzene, toluene, dimethylbenzene, vinylbenzene, hemimellitol, unsym-trimethyl benzene, sym-trimethylbenzene, isopropyl benzene, プ レ ー ニ Application グ, isodurene, durol, isopropyl toluene, the group that hydrogen atom in the benzene derivatives such as mellitene is removed the form of one or more gained is incorporated into the compound that contains aromatic nucleus of other chemical structure gained.
Can enumerate the such as aromatic series such as biphenyl, triphenyl methane polynuclear compound;
For example pentalene, indenes, indane, triketohydrindene hydrate, naphthalene, tetraline, naphthane, sapotalene, cadalin, eudalene, naphthols, dihydro naphthoquinones, gossypol, naphthoquinones, regianin, vitamin k4, plumbagin, phthiocol, echinochrome A, Shikonin, Shikonin, acetonaphthone, naphthoic acid, naphthoyl, naphthalic acid, naphthalate, acetomenaphthone, napthylamine sulfonic acid, napthylamine sulfonic acid ester, napthylamine sulfonic acid base, red sulphonyl, Bayer acid, flavianic acid, chromotropic acid, neocupferron, camomile Azulene, chrysanthemum Azulene, melon camomile Azulene, triolefin between heptan, aldrin, the carbon condensations two such as purple times phenol encircle,
For example as-indenes reaches alkene, s-indenes reaches alkene, as-hydrogen indenes reaches alkene, s-hydrogen indenes reaches alkene, biphenylene, acenaphthylene, acenaphthene naphthalene, acenaphthenequinone, fluorenes, non-that alkene, perinaphthene, luxuriant and rich with fragrance, phenanthryl, luxuriant and rich with fragrance, luxuriant and rich with fragrance subunit, phenanthrylene, phenanthrol, morphol, phenanthrenone, phenanthrenequione, pimanthrene, retene, anthracene, anthryl, anthracene, anthracene subunit, anthrylene, hydroxyl anthracene, anthrol, grace dream is refined, anthralin, Dithranol, anthracene acyl group, anthrone, dianthrone, anthraquinone, anthraquinonyl, sub-anthraquinonyl, alizarin, quinizarin, anthrarufine, chrysazin, trihydroxyanthraquinone, purpurin, flavopurpurin, anthracene violet element, skyrin, teak quinone, chrysophanol, chrysophanic acid, Schuttgelb, rhubarb yellow, kermesic acid, coccinic acid, two anthracene imines, anthracene imines (anthrimide), golden yellow anthraquinonic acid, the carbon condensations three such as colchicine encircle,
The carbon condensation Fourth Rings such as for example three indenes, three indanes, fluoranthene, the luxuriant and rich with fragrance alkene of vinegar, vinegar phenanthrene, benzo acenaphthene, aceanthrene, three acenes, pyrene, thick dinaphthyl, benzanthrene, thick four benzene, thick four benzene, lycid alkene, tsiklomitsin, Uromycin, oxytetracycline, seven days of the week alkene, benzanthrone;
Li is as carbon condensation five rings such as Pi, perylene, dibenzphenanthrene, thick pentaphene, four sub-benzene, sub-cholanthrenyl, cholanthrene;
For example bowl alkene, rich bright alkene, dibenzo pyrene, thick four benzene of dibenzo, six helicenes, hexaphene, thick six benzene, rubicene, coronene, trinaphthylene, heptaphene, thick seven benzene, pyrrole anthracene, Xin Fen, thick eight benzene, terylene, thick four benzene of thick four benzos, the ninth of the ten Heavenly Stems sweet smell, thick nine benzene, violanthrene, violanthrone, isoviolanthrene, ovalene, the last of the ten Heavenly stems the more than 6 carbon condensed ring of number of rings such as sweet smell, thick ten benzene, decacyclene, thick pentaphene thick pentaphene, quaterrylene, thick six benzene of thick six benzos; The group that hydrogen atom in isocyclic compound is removed the form of one or more gained is incorporated into the aromatic nucleus of other chemical structure gained.
Other can enumerate the cyclenes classes such as such as cyclopropylene, cyclobutene, cyclopentenes, tetrahydrobenzene, suberene, cyclooctene, cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene;
The carbonatoms that for example have carbonatoms beyond benzene, forms ring is more than 3 [4n+2] annulene.
For example furans, furyl (furyl), furyl (furanyl), furans subunit, inferior furyl, furylidene, furans two bases, furfuryl, furfuryl, furfurylidene, furfurylidene, inferior furfurylidene, 2-furans methyne, 2 furan carboxyaldehyde, 2,2 '-furoin (furoin), furancarbonyl, tetronic acid (tetronic acid), tetrahydrofuran (THF)-2,4-diketone, succinyl oxide, MALEIC ANHYDRIDE, methyl-maleic acid acid anhydride, itaconic anhydride, 2H-pyrans, pyrrone (pyrone), pyrone (pyranone), trimethylene oxide (oxetane), malonic anhydride, glycollide (diglycolide), lactic acid lactide (dilactide), 2-cumarone, dihydroisobenzofuran (phthalan), O-phthalic lactone (phthalide), O-phthalic lactone group, sub-O-phthalic lactone group, dimethoxy phthalein (meconin), anhydride phthalic acid, trihemellitic acid acid anhydride (trimellitic acid anhydride), coumarone (coumarone), Dihydrobenzofuranes (coumaran), heterochromatic alkene (isochromene), heterochromatic alkane (isochromane), Isocoumarin (isocoumarin), heterochromatic alkene (isochromenylium), chromene, tonka bean camphor, chromene (chromenylium), xanthene (xanthylium), oxygen anthracene (oxanthrene), piperonyl, piperonylidene, rise piperonyl (homopiperonyl), meliatin (loganin), diphenylene-oxide, the ether ring shape compounds such as phenol (morphenol).
For example thiophene, thienyl, thiophene subunit, sub-thienyl, thenyl (thenyl), sub-thenyl, inferior thenyl, thiophenecarboxaldehyde, thiophenecarboxaldehyde oxime (thenaldoxime), tetramethylene sulfide (tetramethylene sulfide), thiapyran (thiopyran), different thiochromene (isothiochromene), different thiochromene, thiochromene (thiochromene), thioxanthone (thioxanthone), thianthrene (thianthrene), phenoxazine (phenoxathiine), thiirane (thiirane), Thietane, thionaphthene (thianaphthene), the sulphur-containing cyclic compounds such as aphthothiophenes (thiophanthrene).
For example pyrroles, imidazoles, pyrazoles (pyrazole), selenazoles (selenazole), thiazole, oxazole (oxazole), furan Xanthones (furazan), piperidines (piperidine), pyridine, pyrazine (pyrazine), piperazine (piperazine), pyrimidine, pyridazine (pyridazine), tellurium morpholine (telluromorpholine), selenium morpholine, parathiazan, morpholine, sub-ethyliminum, sub-tetrahydroform, sub-own imines, anistree nitramine (octogen), Pyrrolizidine, benzazole (pyrindine), indolizine (indolizine), indoles (indole), indazole (indazole), purine (purine), quinolizine (quinolizine), quinoline, the nitrogenous ring compounds such as naphthyridines (naphthyridine).
Such as phosphorus piperazine (phosphindolizine), different phosphorus diindyl (isophosphindole), phosphorus diindyl (phosphindole), phosphorus pyridine (phosphinolidine), phosphorus quinoline (phosphinoline), (phosphanthridine), acridine phosphorus (acridophosphine), phosphorus anthracene (the phosphorous ring compound such as phosphanthrene), Fen Evil phosphorus (phenoxaphosphinine), fen phosphorus piperazine (phenophosphazinine).
As ring compound, cyclohexane ring, cyclohexene ring, norcamphane ring, norcamphene ring, diamantane ring, dihydroisobenzofuran ring, Dihydrobenzofuranes ring, pepper basic ring and look alkane ring because of solidified nature under low-light (level) better, so preferably.
As compound (C), can enumerate and for example encircle propyl alcohol, cyclobutanol, cyclopentanol, hexalin, phenol, phenylcarbinol, phenylbenzene alcohol, phenmethyl ethanol, cyclohexenol, baras camphor falls, norcamphene alcohol, Buddha's warrior attendant alcohol, dihydroisobenzofuran alcohol, Dihydrobenzofuranes alcohol, piperitol, look alkanol, the such ring compound of phenol is directly or across the alkyl of carbonatoms 1 to 18 and the material of 1 hydroxyl bonding, as 1,3-CHDM, saligenol, saleripol (gentisyl alcohol), VANILLYL ALCOHOL MIN 98, syringyl alcohol, phenylethyl alcohol, high VANILLYL ALCOHOL MIN 98 (homovanillyl alcohol), quinhydrones, Resorcinol, the compound with multiple hydroxyls of pyrocatechol, or as 3-hydroxyl hexalin, pmethoxybenzyl alcohol, (3,4-Dimethoxyphenyl) methyl alcohol, (4-isopropyl phenyl) methyl alcohol, 3-phenyl third-2-alkene-1-alcohol, 3-(4-hydroxy 3-methoxybenzene base) third-2-alkene-1-alcohol, the such hydroxyl-removal of cresols is with bonding alkyl on external ring compound, alkane, alkene, ether, the functional group's of ester etc. compound, or across alkyl, alkane, alkene, ether, the functional groups such as ester and with compound of hydroxyl bonding etc.
As compound (C), particularly hexalin, phenylcarbinol, baras camphor, Buddha's warrior attendant alcohol, piperitol, 3 fall, 4-methylenedioxyphenol, under low-light (level), solidified nature is good, so more preferably.
With respect to the aforementioned oxirane compound (A) of 100 weight parts, compound (C) preferably contains 0.5 to 40 weight part, more preferably 1 to 30 weight part.Being 0.5 weight part when above, reacting facilitation effect high with oxirane compound (A), ring compound (B1) or ring compound (B2), is 40 weight parts when following, reactive good.
In optical polymerism composition, more than the viscosity of the oxirane compound of three membered cyclic (A) is mostly 200mPas, the viscosity with the compound (a-1) of aromatic nucleus is mostly solid more than being mostly 5000mPas.
Other optical polymerism compositions except oxirane compound (A), ring compound (B1), ring compound (B2), compound (C), in optical polymerism composition 100 % by weight, can comprise the scope below 80 % by weight.
< ethene unsaturated compound (D) >
In optical polymerism composition, as other optical polymerism compositions, preferably comprise ethene unsaturated compound (D).So-called ethene unsaturated compound (D), refers to have in molecular structure the compound of unsaturated double-bond.
In the situation that containing ethene unsaturated compound (D), with respect to the aforementioned oxirane compound (A) of 00 weight part, can use the ratio of 5 to 1000 weight parts.When ethene unsaturated compound (D) is less than 5 weight part, the viscosity of optical polymerism composition cannot fully reduce, and during more than 1000 weight part, hinders the raising of the polymerizability of the oxirane compound (A) of three membered cyclic.
As ethene unsaturated compound (D), preferred viscosities is 0.5 to 2000mPas, and more preferably 1 to 1000mPas.By using such ethene unsaturated compound (D), can suppress the high viscosity of optical polymerism composition, improved thin film coating, and maintain optical polymerism, maintain bonding force, the processibility of caking agent described later simultaneously.
As ethene unsaturated compound (D), while considering with the adaptation of blooming, be preferably the ethene unsaturated compound (d-1) that contains hydroxyl and/or there is cycloalkanes skeleton and/or the ethene unsaturated compound of cyclenes skeleton (d-2).
As the ethene unsaturated compound (d-1) that contains hydroxyl, as long as thering is the material of hydroxyl in its structure, be not particularly limited, [vinylformic acid 2-hydroxy methacrylate and 2-hydroxyethyl methacrylate merge and are designated as " (methyl) vinylformic acid 2-hydroxy methacrylate " can to enumerate for example (methyl) vinylformic acid 2-hydroxy methacrylate.Identical below], (methyl) vinylformic acid 1-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 1-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 3-hydroxyl butyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 8-hydroxyl monooctyl ester, (methyl) vinylformic acid 10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid 12-hydroxyl ten diester, (methyl) vinylformic acid ethyl-α-(hydroxymethyl) ester, monofunctional (methyl) vinylformic acid glyceryl ester, or (methyl) acrylic acid epoxy propyl group laurate, (methyl) acrylic acid epoxy propyl group oleic acid ester, fatty acid ester system (methyl) acrylate such as (methyl) acrylic acid epoxy propyl group stearate, or by the open loop addition of lactonic ring, there is endways polylactone system (methyl) acrylate of hydroxyl or oxyethane, epoxy alkane addition system (methyl) acrylate endways with hydroxyl of the repetition addition of the epoxy alkane such as propylene oxide, aliphatics (methyl) esters of acrylic acid that (methyl) vinylformic acid 2-hydroxyethyl phosphoric acid ester etc. contains hydroxyl,
For example (methyl) vinylformic acid 1,2-hexanaphthene dimethyl ester, (methyl) vinylformic acid 1,3-hexanaphthene dimethyl ester, (methyl) vinylformic acid Isosorbide-5-Nitrae-hexanaphthene dimethyl ester, (methyl) cyclohexyl acrylate glycidyl ethers, (methyl) phenyl acrylate glycidyl ethers, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group methyl esters, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy ethyl, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group butyl ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group ester in the last of the ten Heavenly stems, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group octadecyl ester, (methyl) vinylformic acid monohydroxy ethyl phthalic ester, (methyl) vinylformic acid 2-(4-benzoyl-3-hydroxyphenoxy) ethyl ester, two (methyl) vinylformic acid Isosorbide-5-Nitrae-bis-(2-hydroxy propyl ester) benzene, two (methyl) vinylformic acid 1, alicyclic ring or aromatic series (methyl) esters of acrylic acid that two (2-hydroxy propyl ester) benzene etc. of 3-contains hydroxyl,
For example 2-(2'-hydroxyl-5'-(methyl) acryloxy ethylphenyl)-2H-benzotriazole, [2-(2'-hydroxyl-5'-acryloxy ethylphenyl)-2H-benzotriazole and 2-(2'-hydroxyl-5'-methacryloxyethyl phenyl)-2H-benzotriazole merge and are designated as " 2-(2'-hydroxyl-5'-(methyl) acryloxy ethylphenyl)-2H-benzotriazole ".Identical below], 2-(2'-hydroxyl-5'-(methyl) acryloxy ethylphenyl) the chloro-2H-benzotriazole of-5-, 2-(2'-hydroxyl-5'-(methyl) acryloxy propyl group phenyl)-2H-benzotriazole, 2-(2'-hydroxyl-5'-(methyl) acryloxy propyl group phenyl) the chloro-2H-benzotriazole of-5-, 2-(the 2'-hydroxyl-3'-tertiary butyl-5'-(methyl) acryloxy ethylphenyl)-2H-benzotriazole, benzotriazole system (methyl) esters of acrylic acid that 2-(the 2'-hydroxyl-3'-tertiary butyl-5'-(methyl) acryloxy ethylphenyl) the chloro-2H-benzotriazole of-5-etc. contains hydroxyl,
For example 2-hydroxyl-4-{2-(methyl) acryloxy } ethoxy diphenyl base ketone, 2-hydroxyl-4-{2-(methyl) acryloxy } butoxy diphenylketone, 2,2'-dihydroxyl-4-{2-(methyl) acryloxy } ethoxy diphenyl base ketone, 2-hydroxyl-4-{2-(methyl) acryloxy } oxyethyl group-4'-(2-hydroxyl-oxethyl) diphenylketone etc. diphenylketone system (methyl) esters of acrylic acid of containing hydroxyl;
For example 2, 4-phenylbenzene-6-[2-hydroxyl-4-{2-(methyl) acryloyl-oxy base oxethyl }]-S-triazine (triazine), 2, two (2-aminomethyl phenyl)-6-[2-hydroxyl-4-{2-(methyl) acryloyl-oxy base oxethyls of 4-}]-S-triazine, 2, two (2-p-methoxy-phenyl)-6-[2-hydroxyl-4-{2-(methyl) acryloyl-oxy base oxethyls of 4-}]-S-triazine, 2, two (2-ethylphenyl)-6-[2-hydroxyl-4-{2-(methyl) acryloyl-oxy base oxethyls of 4-}]-S-triazine, 2, two (2-ethoxyl phenenyl)-6-[2-hydroxyl-4-{2-(methyl) acryloyl-oxy base oxethyls of 4-}]-S-triazine, 2, 4-two (2, 4-3,5-dimethylphenyl)-6-[2-hydroxyl-4-{2-(methyl) acryloyl-oxy base oxethyl }]-S-triazine, 2, 4-two (2, 4-diethoxy phenyl)-6-[2-hydroxyl-4-{2-(methyl) acryloyl-oxy base oxethyl }]-S-triazine, 2, 4-two (2, 4-diethyl phenyl)-6-[2-hydroxyl-4-{2-(methyl) acryloyl-oxy base oxethyl }]-triazine that S-triazine etc. contains hydroxyl system (methyl) esters of acrylic acid,
Glucose ring system (methyl) esters of acrylic acids such as for example (methyl) vinylformic acid candy glycosides base (glycosyl) methyl esters, (methyl) vinylformic acid candy glycosides base ethyl ester, (methyl) vinylformic acid candy glycosides base propyl ester, (methyl) vinylformic acid candy glycosides base butyl ester;
The end of the repetition addition of the epoxy alkane such as such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyl hexyl vinyl ether, hydroxyl octyl group vinyl ether, hydroxyl decave, hydroxyl dodecyl vinyl ether, hydroxyl octadecyl vinyl ether, epoxypropyl vinyl ether or oxyethane, propylene oxide has the aliphatic ethylene base ethers that epoxy alkane addition vinyl ether of hydroxyl etc. contains hydroxyl;
For example 1, 2-cyclohexanedimethanol mono vinyl ether, 1, 3-cyclohexanedimethanol mono vinyl ether, 1, 4-cyclohexanedimethanol mono vinyl ether, 2-hydroxyl-3-phenoxymethyl mono vinyl ether, 2-hydroxyl-3-phenoxy group ethyl mono vinyl ether, 2-hydroxyl-3-phenoxy propyl mono vinyl ether, 2-hydroxyl-3-phenoxy group butyl mono vinyl ether, 2-hydroxyl-3-phenoxy group decyl mono vinyl ether, 2-hydroxyl-3-phenoxy group octadecyl mono vinyl ether, the alicyclic ring that has that 2-(4-benzoyl-3-hydroxyphenoxy) ethyl mono vinyl ether etc. contains hydroxyl, the vinyl ethers of aromatic nucleus,
For example 2-hydroxy styrenes, 3-hydroxy styrenes, 4-Vinyl phenol, 2-hydroxyl-alpha-vinyl toluene, 3-hydroxyl-alpha-vinyl toluene, 4-hydroxyl-alpha-vinyl toluene, 2-methyl-3-hydroxy styrenes, 4-methyl-3-hydroxy styrenes, 5-methyl-3-hydroxy styrenes, 2-methyl-4-Vinyl phenol, 3-methyl-4-Vinyl phenol, 3,4-dihydroxy-benzene ethene, 2, the aromatic ethenyl compound class that 4,6-trihydroxybenzene ethene, 2-hydroxyl-6-vinyl naphthalene etc. contain hydroxyl;
[vinyl carbinol and methallyl alcohol merging are designated as " (methyl) vinyl carbinol " to for example (methyl) vinyl carbinol.Identical below.], isopropyl enol, dimethyl (methyl) vinyl carbinol, hydroxyethyl (methyl) allyl ether, hydroxypropyl (methyl) allyl ether, hydroxybutyl (methyl) allyl ether, hydroxyl hexyl (methyl) allyl ether, hydroxyl octyl group (methyl) allyl ether, hydroxyl decyl (methyl) allyl ether, hydroxyl dodecyl (methyl) allyl ether, hydroxyl octadecyl (methyl) allyl ether, epoxypropyl (methyl) allyl ether or oxyethane, aliphatics (methyl) allyl alcohol or (methyl) allyl ethers that epoxy alkane addition (methyl) allyl ether etc. endways with hydroxyl of the repetition addition of the epoxy alkane such as propylene oxide contains hydroxyl,
For example 1, 2-cyclohexanedimethanol list (methyl) allyl ether, 1, 3-cyclohexanedimethanol list (methyl) allyl ether, 1, 4-cyclohexanedimethanol list (methyl) allyl ether, o-(methyl) allyl phenol, m-(methyl) allyl phenol, p-(methyl) allyl phenol, 2-hydroxyl-3-phenoxymethyl list (methyl) allyl ether, 2-hydroxyl-3-phenoxy group ethyl list (methyl) allyl ether, 2-hydroxyl-3-phenoxy propyl list (methyl) allyl ether, 2-hydroxyl-3-phenoxy group butyl list (methyl) allyl ether, 2-hydroxyl-3-phenoxy group decyl list (methyl) allyl ether, 2-hydroxyl-3-phenoxy group octadecyl list (methyl) allyl ether, the alicyclic ring that has that 2-(4-benzoyl-3-hydroxyphenoxy) ethyl list (methyl) allyl ether etc. contains hydroxyl, (methyl) allyl ethers of aromatic nucleus,
Such as propylene glycol, butylene glycol, heptene glycol, octene glycol, two (methyl) vinylformic acid glyceryl ester, o-two (methyl) allyl group dihydroxyphenyl propane etc. have the ethylene unsaturated monomer class of multiple hydroxyls;
[N-hydroxyethyl acrylamide and the merging of N-hydroxyethyl Methacrylamide are designated as " N-hydroxyethyl (methyl) acrylamide " to for example N-hydroxyethyl (methyl) acrylamide.Identical below.], N-hydroxypropyl (methyl) acrylamide, N-hydroxybutyl (methyl) acrylamide, N-hydroxyl hexyl (methyl) acrylamide, N-hydroxyl octyl group (methyl) acrylamide etc. (methyl) acrylic amide of containing hydroxyl;
Such as hydroxy styrenes, vinyl alcohol etc. have the monomer class of hydroxyl and thiazolinyl etc., are not particularly limited.They can only use a kind, or also can be also with multiple.
There is the ethene unsaturated compound (d-2) of cycloalkanes skeleton and/or cyclenes skeleton, for thering is the compound with polymerizable functional groups of cycloalkanes skeleton and/or cyclenes skeleton and more than 1 ethene unsaturated double-bond; Have in the cycloalkanes skeleton and/or cyclenes skeleton of more than 2 ring structure, ring structure can be separation due to alkyl, ether, ester group etc. with ring structure, can be as the bridging structure of the ring of norcamphane, norcamphene, adamantane structure, but based on thermotolerance compared with good and preferred norcamphane, norcamphene, adamantane framework.
As the ethene unsaturated compound (d-2) with cycloalkanes skeleton and/or cyclenes skeleton, more specifically, for example can enumerate (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 1-methyl isophthalic acid-ring pentyl ester, (methyl) vinylformic acid 1-ethyl-1-encircles pentyl ester, (methyl) vinylformic acid 1-sec.-propyl-1-encircles pentyl ester, (methyl) vinylformic acid 1-methyl isophthalic acid-cyclohexyl, (methyl) vinylformic acid 1-ethyl-1-cyclohexyl, (methyl) vinylformic acid 1-sec.-propyl-1-cyclohexyl, (methyl) vinylformic acid 1-ethyl-1-encircles monooctyl ester, (methyl) vinylformic acid benzene methyl, the different camphane ester of (methyl) vinylformic acid, (methyl) phenyl acrylate, (methyl) vinylformic acid 2-phenoxy ethyl, (methyl) vinylformic acid 2-carbonyl-1,2-phenyl chlorocarbonate, (methyl) vinylformic acid 2-carbonyl-1,2-phenylbenzene ethyl ester, (methyl) vinylformic acid 1-naphthalene ester, (methyl) vinylformic acid 2-naphthalene ester, (methyl) vinylformic acid 1-naphthyl methyl esters, (methyl) vinylformic acid 1-anthracene ester, (methyl) vinylformic acid 2-anthracene ester, (methyl) vinylformic acid 9-anthracene ester, (methyl) vinylformic acid 9-anthryl methyl esters, (methyl) vinylformic acid 2-methyl adamantane-2-ester, (methyl) vinylformic acid 2-ethyl diamantane-2-ester, (methyl) vinylformic acid 2-n-propyl diamantane-2-ester, (methyl) vinylformic acid 2-sec.-propyl diamantane-2-ester, (methyl) vinylformic acid 1-(diamantane-1-yl)-1-methyl ethyl ester, (methyl) vinylformic acid 1-(diamantane-1-yl)-1-diethyl acetamidomalonate, (methyl) vinylformic acid 1-(diamantane-1-yl)-1-methyl propyl ester, (methyl) vinylformic acid 1-(diamantane-1-yl)-1-ethyl propyl ester, (methyl) vinylformic acid-5-carbonyl-4-oxa--tri-encircle [4.2.1.03, the 7] ninth of the ten Heavenly Stems-2-ester, assorted oxygen-tri-ring of (methyl) vinylformic acid-5-carbonyl-4-[5.2.1.03, the 8] last of the ten Heavenly stems-2-ester, (methyl) vinylformic acid dihydro-α-terpinyl acetate (terpinyl), (methyl) vinylformic acid-6-carbonyl-7-is assorted, and oxygen-dicyclo [3.2.1] is pungent-2-ester, (methyl) vinylformic acid-7-carbonyl-8-oxa--dicyclo [3.2.1] is pungent-(methyl) vinylformic acid cyclic ester classes such as 2-ester,
For example 5-vinyl dicyclo [2.2.1] hept-2-ene", 2, two (allyloxy) norcamphanes of 5-, 5-vinyl-2,3-oxyethane norcamphane, 2-(2-propenyl) the ring compound class that contains thiazolinyl such as dicyclo [2.2.1] heptane, 5-vinyl dicyclo [2.2.1] hept-2-ene", 2-ethylidene diamantane, 3-allyl group diamantane-1-alcohol, 1-allyl group diamantane.
And, for example, as long as the Hydrogenated Bisphenol A of aromatic ring structure hydrogenation etc. have ethene unsaturated double-bond, also can be contained in (d-2).They can only use a kind, or also can be also with multiple.
< Photoepolymerizationinitiater initiater (E) >
Optical polymerism composition preferably contains Photoepolymerizationinitiater initiater (E).Above-mentioned Photoepolymerizationinitiater initiater (E), for producing acid active specy with A by rayed +b -the salt representing, is not particularly limited, the general known salt that has.As salt, can enumerate lewis acidic diazonium (diazonium) salt, lewis acidic salt compounded of iodine, lewis acidic sulfonium salt etc.This cation A +be preferably aromatic series iodide ion and/or aromatic matte ion.
As Photoepolymerizationinitiater initiater (E), can enumerate such as UVACURE1590(Daicel (Daicel Cytec) company's system), CPI-110P(tri-general (Sanpro) company system) etc. sulfonium salt, IRGACURE250(Chiba special chemical (Chiba.Specialty chemicals) company's system), WPI-113(and Guang Chun medicine company system), sub-(Rhodia Japan) the company's system in Rp-2074(dream ground) etc. salt compounded of iodine, but be not limited to these.
And, as Photoepolymerizationinitiater initiater (E), can there is optical free radical polymerization starter.As such optical free radical polymerization starter; for example IRGACURE-184,907,651,1700,1800,819,369,261, DAROCUR-TPO(Chiba special chemical company system, 2; 4,6-trimethylbenzoyl-phenylbenzene-phosphine oxide), DAROCUR-1173(Merck (Merck) company system), Ezacure-KIP150, TZT(Japan DKSH company system), Kayacure BMS, Kayacure DMBI(Japan chemical drug company system) etc.
The allotment ratio of Photoepolymerizationinitiater initiater (E), with respect to the optical polymerism composition of 100 weight parts, is preferably 0.5 to 20 weight part, 0.5 to 10 weight part.
< light sensitizer (F) >
In order to improve the performance of Photoepolymerizationinitiater initiater (E), can and use light sensitizer.As light sensitizer, such as anthracene system, diphenylketone system, thioxanthone system, thiodiphenylamine (phenothiazine), rose-red (Rose Bengal) etc.
The allotment ratio of light sensitizer, with respect to the optical polymerism composition of 100 weight parts, is preferably 0.1 to 20.
< antioxidant >
Optical polymerism composition can further comprise antioxidant.By comprising antioxidant, can suppress bond layer after photocuring through time after painted.
As antioxidant, can enumerate ADEKA STAB AO-50, ADEKA STAB AO-80(Asahi Electro-Chemical Co. Ltd system) etc. be phenolic antioxidant, IRGANOX-PS-800FD(Chiba special chemical company system) etc. sulphur be that the hindered amines such as antioxidant, TINUBIN622LD, TINUBIN144, TINUBIN765 are photostabilizer etc., but be not limited to these.The allotment ratio of antioxidant, with respect to the optical polymerism composition of 100 weight parts, is preferably 0 to 5 weight part, more preferably 0.01 to 3 weight part.
< organic solvent >
Optical polymerism composition does not preferably comprise in fact organic solvent.Preferably do not comprise organic solvent completely, but Photoepolymerizationinitiater initiater (E) is insoluble in polymerizability composition mostly.Therefore,, in order to dissolve Photoepolymerizationinitiater initiater (E), can comprise a small amount of organic solvent.The content of the organic solvent in optical polymerism composition is preferably in 5 % by weight.
< moisture >
Optical polymerism composition preferably comprises the moisture of 0.05 to 3 weight part.In the photopolymerization reaction of the general oxirane compound at three membered cyclic, known moisture worsens solidified nature, but finds that the scope that comprises 0.05 to 3 weight part improves solidified nature on the contrary.Moisture is 0.05 weight part when above, can find the raising of solidified nature, and when 3 weight parts are following, solidified nature is good.
Other additives of < >
As long as do not damaging under the scope of effect of the present invention, optical polymerism composition can be according to needs, not damaging in the scope of effect of the present invention, the various known additive that comprises polymerizable monomer, oligomer, silane coupling agent, stopper, tenderizer, dyestuff, pigment, defoamer, tackifier, plasticizer, weighting agent and antiaging agent etc.
< optical polymerism composition >
By by oxirane compound (A) be selected from ring compound (B1), ring compound (B2) and compound (C) compound and according to need other compositions mix, can obtain optical polymerism composition.
The viscosity of optical polymerism composition in the time of 23 ℃ is preferably 1 to 1500mPas, and more preferably 10 to 1300mPas, is more preferably 20 to 1000mPas.Viscosity is 1500mPas when following, and in the situation that coating protective membrane, the film coated of 0.1 to 6 μ m can fully be carried out, and the optical characteristics of transmitance etc. is good.On the other hand, viscosity is 1mPas when above, and the film thickness monitoring of bond layer is good.
The viscosity of optical polymerism composition, because substantially being determined by the viscosity of oxirane compound (A), is 1 to 1500mPas scope by the viscosity of management oxirane compound (A), the viscosity that can manage optical polymerism composition.
Optical polymerism composition can solidify by the irradiation of active energy beam, and the light source using is not particularly limited, and preferably has the energy-ray of the luminescence distribution below wavelength 500nm.For example can use low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, chemical lamp, black lamp, microwave-excitation mercury lamp, metal halide lamp, photodiode etc.
As rayed intensity, be preferably 10 to 500mW/cm 2.Rayed intensity is 10mW/cm 2when above, solidify and can complete in the short period of time, 500mW/cm 2when following, can be because not producing the deteriorated of base material from the radiant heat of lamp.The accumulated light that represents the product of exposure intensity and irradiation time is preferably 50 to 5000mJ/cm 2.Accumulated light is 50mJ/cm 2when above, solidify and can complete in the short period of time, 5000mJ/cm 2when following, irradiation time is short, and productivity is good.
< duplexer >
Use optical polymerism composition as optical polymerism coating agent, according to ordinary method, by proper method, coating optical polymerism composition, in base material (G), can form duplexer.
In the situation that using optical polymerism coating agent as caking agent, be preferably the film coated of 0.1 to 6 μ m, the more preferably film of 0.1 to 3 μ m coating.0.1 μ m when above, can obtain sufficient bonding force, even if exceed 6 μ m, the characteristics such as bonding force can not improve more as a rule yet.
In the situation that using optical polymerism coating agent as easy bonding coating agent, coating, from the viewpoint of the hardness of coat, be preferably the film coating of 0.1 to 20 μ m, the more preferably film of 1 to 10 μ m coating.
As the method for optical polymerism composition being coated to base material, be not particularly limited, the various coating processes such as such as Mai Er rod painting method (Mayer bar), applicator (applicator), bristle, spraying, roller coat, intaglio plate coating method, die coating method, nick version coating method, lip mouth coating method (lip coating), unfilled corner wheel coating method (comma coating), heavy curtain coating method (curtain coating), scraper for coating method, reversion coating method, method of spin coating, as long as carrying out film coated, be not particularly limited.
As base material (G), using optical polymerism composition as coating agent, be used in the situation on one side, two sides of one deck base material (G), can use cloth, timber, metal sheet, plastic plate, membranaceous base material, sheet glass, paper conversion product etc., be not particularly limited.On the other hand, in the situation that the caking agent of optical polymerism composition more than 2 base material (G) as laminating is used, in order to irradiate active energy beam, make its polymerization, the base material that easily sees through active energy beam be must use, transparent film (H), transparency glass plate particularly preferably used.Even use and be difficult to see through base material such as timber, metal sheet, plastic plate, the paper conversion product etc. of active energy beam in one side, as long as can use transparent film (H), transparency glass plate at another side, from transparent film (H), transparency glass plate side, irradiate and carry out polymerizing curable, can use.
As base material (G), preferably use membranaceous base material, as membranaceous base material, can enumerate the membranaceous base materials such as glassine paper (cellophane), various plastic film, paper, preferably use transparent various plastic films.And, as membranaceous base material, as long as transparent, can be individual layer, also can use the base material of the multilayered state that multiple base materials are stacked formed.
About using optical polymerism coating agent, be laminated in the duplexer that the one or two sides of base material (G) forms herein, and carry out generality explanation.
Utilize the situation of the polyreaction of passing through active energy beam of optical polymerism composition, be preferred for forming and possess in aforementioned substrates (G) as the transparent film (H) of membranaceous base material and be positioned at the duplexer of the optical polymerism composition layer of the face of at least one side of this transparent film (H).
Can obtain in the following manner the duplexer of transparent film (H).
In the situation that using optical polymerism composition as coating agent, at the single spreading coating agent of the transparent film as membranaceous base material (H), thereby can obtain duplexer.Now, coat can be used as the undercoat of easy bondingization use.
And, use in the situation of optical polymerism composition as optical polymerism caking agent, at the one side of the transparent film as membranaceous base material (H), coating optical polymerism caking agent, other transparent film (H) is laminated in to the surface of adhesive linkage, further, at one side, the two sided coatings caking agent of this duplexer, be further laminated in other transparent film (H), glass or transparent molded article, thereby can obtain duplexer.
The active energy beam polyreaction of optical polymerism coating agent is when coating coating agent or when stacked, further at stacked rear irradiation active energy beam, carries out, and preferably at stacked rear irradiation active energy beam, carries out polyreaction.
Transparent film (H), can be used in the blooming (I) of information communication machines such as indicating meter, contact panel etc.
Duplexer used for optical elements is carried out to general remark herein.
Optical polymerism coating agent, can be used for forming duplexer used for optical elements.
About the basic stacked formation of optical laminated body, in the situation that using optical polymerism coating agent as easy bonding coating agent, be that the such laminar optics of transparent film/coat or coat/transparent film/coat applies duplexer.
And, in the situation that being used as caking agent, be the such bonding duplexer of laminar two sides sensitization solidified nature of transparent film/adhesive linkage/transparent film or transparent film/adhesive linkage/transparent film/adhesive linkage/transparent film.Moreover, be used as multi-layer optical film such to transparent film/adhesive linkage/transparent film/adhesive linkage/transparent film/adhesive linkage/transparent film, glass or optical molded body is immobilized onto to the duplexer used for optical elements that optical element forms.
Be used as the various transparent films (H) of blooming (I) for example can use the good thermoplastic resins of characteristic such as the transparency, physical strength, thermostability, moisture shielding.As various transparent films (H), also referred to as various plastic films, plastic tab, can enumerate the polyester mesentery, polycarbonate mesentery, poly-norcamphene mesentery, Aromatic polyester mesentery, vinylformic acid mesentery, polyphenylene sulfide mesentery, polystyrene mesentery, vinyl mesentery, polymeric amide mesentery, polyimide mesentery, oxyethane mesentery of the polyolefine mesentery, polyethylene terephthalate, polybutylene terephthalate etc. of polyvinyl alcohol film such as, triacetyl cellulose mesentery, polypropylene, polyethylene, poly-cycloolefin, vinyl-vinyl acetate copolymer etc. etc.
Transparent film (H), in the situation that using multilayer, can be same composition, also can be different compositions.For example, can use cycloolefin mesentery at one side, at another side, use vinylformic acid mesentery.
The thickness of transparent film (H), can suitably determine, general according to the point of the operability such as intensity, usability, thin layer etc., is 1 to 500 μ m degree.Particularly preferably 1 to 300 μ m, more preferably 5 to 200 μ m.Transparent film (H) is to be particularly suitable in the situation of 5 to 150 μ m.
Moreover, both sides at polarisation of the Polarizer as blooming arrange transparent film (H), can use the transparent film (H) forming for identical polymer materials in its table, the transparent film (H) that also can use different polymer materials etc. to form.
As optical laminated body, in above-mentioned various transparent films (H), applicable use is mainly used in the blooming (I) of optical applications.As blooming (I), will be called blooming as above-mentioned transparent film (H) being imposed to film special processing, that there is optical function (the various functions such as printing opacity, light diffusion, optically focused, refraction, scattering, atomization (HAZE)).These bloomings individually or by stacked with optical polymerism coating agent multiple blooming be multilayer, as duplexer use used for optical elements.For example, can enumerate hard coat film, anti-charged coat film, anti-dizzy coat film, light polarizing film, phase retardation film, elliptical polarized light film, anti-reflective film, optical diffusion film, brightness enhancement film, prism film (also referred to as prismatic lens), light guiding film (being also called light guiding plate) etc.
Light polarizing film; also be called Polarizer, its for by the two sides of polyethenol series polarisation using 2 triacetyl celluloses as cellulose acetate mesentery be protective membrane (hereinafter referred to as " TAC film ") clamping, duplexer laminar used for optical elements by the one side of polyethenol series polarisation, two sides using the multilayered structure of the clampings such as the cycloolefin mesentery as norcamphene mesentery, vinylformic acid mesentery, polycarbonate mesentery, polyester mesentery.
Use the duplexer of the blooming of optical polymerism caking agent to be preferably attached at the transparent film (H) of sheet glass, the above-mentioned various plastic films etc. such as liquid crystal indicator, PDP module, touch panel module, organic EL module, thereby be used as duplexer used for optical elements.
Polarizer more specifically for example can obtain by following (I) to (III) either method.
(I) at the face of a side of the protective membrane as the 1st transparent film (H), (2') coating optical polymerism caking agent, form the 1st optical polymerism adhesive linkage,
At the face of a side of the 2nd protective membrane, coating optical polymerism caking agent, forms the 2nd optical polymerism adhesive linkage,
Then, at each face of polyethenol series polarisation, simultaneously/or sequentially after overlapping the 1st optical polymerism adhesive linkage and the 2nd optical polymerism adhesive linkage, irradiate active energy beam, polymerizing curable the 1st optical polymerism adhesive linkage and the 2nd optical polymerism adhesive linkage, thereby the method for manufacturing.
(II) at the face of a side of polyethenol series polarisation; coating optical polymerism caking agent; form the 1st optical polymerism adhesive linkage; the surface of the 1st optical polymerism adhesive linkage forming is covered with the 1st protective membrane; then; at the face of the opposite side of polyethenol series polarisation; coating optical polymerism caking agent; form the 2nd optical polymerism adhesive linkage; the surface of the 2nd optical polymerism adhesive linkage forming is covered with the 2nd protective membrane; irradiate active energy beam, polymerizing curable the 1st optical polymerism adhesive linkage and the 2nd optical polymerism adhesive linkage, thereby the method for manufacturing.
(III) in the overlapping end of the protective membrane as the 1st transparent film (H) and polyethenol series polarisation and with the end of overlapping the 2nd protective membrane of the face without the 1st protective membrane of polyethenol series polarisation; drip after optical polymerism caking agent; it is passed through between running roller, and diffusion bonding agent is in each interlayer.Then, irradiate active energy beam, polymerizing curable optical polymerism coating agent, thereby the method for manufacturing, but be not particularly limited.
Embodiment
Below, merge explanation specific embodiments of the invention and comparative example, but the invention is not restricted to following embodiment.In following embodiment and comparative example, " part " and " % ", represents respectively " weight part " and " % by weight ".
Below, about embodiment I.
[allocating routine 1-1 to 1-34]
Replacing to oxygen concentration, be in the mayonnaise bottle (マ ヨ ネ ー ズ bottle) of the 300cc of the shading below 10%, according to table, the ratio shown in 1-1 is put into three membered cyclic oxirane compound (A), is had more than the tetra-atomic ring of more than 2 Sauerstoffatom ring compound (B1), ethene unsaturated compound (D), Photoepolymerizationinitiater initiater (E), sensitizing agent and antioxidant, with pneumatic motor (air motor), fully stir, fully, after deaeration, obtain being expressed as the routine optical polymerism coating agent of allotment.
The optical polymerism coating agent of the allotment example shown in table 1-1, its solution appearance, viscosity are tried to achieve according to following methods, and result is shown in 1-2.
< < outward appearance > >
The liquid appearance of the optical polymerism coating agent of the routine gained of each allotment, evaluates with visual.
< < viscosity > >
By the optical polymerism coating agent of the routine gained of each allotment, under the environment of 23 ℃, with E type viscometer (TV-22 processed of Dong Ji industry company), using approximately 1.2 milliliters as test sample, under the condition of speed of rotation rotation in 0.5 to 100rpm, 1 minute, measure, as soltion viscosity (mPas).
[table 1]
Figure BDA0000469466250000491
Figure BDA0000469466250000501
Figure BDA0000469466250000511
Figure BDA0000469466250000521
[table 2]
Table 1-2 Outward appearance Viscosity (mPas)
Allocate routine 1-1 Water white transparency 410
Allocate routine 1-2 Water white transparency 425
Allocate routine 1-3 Water white transparency 420
Allocate routine 1-4 Water white transparency 403
Allocate routine 1-5 Water white transparency 388
Allocate routine 1-6 Water white transparency 475
Allocate routine 1-7 Water white transparency 391
Allocate routine 1-8 Water white transparency 399
Allocate routine 1-9 Water white transparency 391
Allocate routine 1-10 Water white transparency 393
Allocate routine 1-11 Water white transparency 140
Allocate routine 1-12 Water white transparency 143
Allocate routine 1-13 Water white transparency 361
Allocate routine 1-14 Water white transparency 382
Allocate routine 1-15 Water white transparency 264
Allocate routine 1-16 Water white transparency 281
Allocate routine 1-17 Water white transparency 213
Allocate routine 1-18 Water white transparency 205
Allocate routine 1-19 Faint yellow transparent 428
Allocate routine 1-20 Water white transparency 1600
Allocate routine 1-21 Water white transparency 136
Allocate routine 1-22 Water white transparency 91
Allocate routine 1-23 Water white transparency 17
Allocate routine 1-24 Water white transparency 84
Allocate routine 1-25 Water white transparency 4
Allocate routine 1-26 Water white transparency 415
Allocate routine 1-27 Water white transparency 3
Allocate routine 1-28 Water white transparency 400
Allocate routine 1-29 Water white transparency 380
Allocate routine 1-30 Water white transparency 390
Allocate routine 1-31 Water white transparency 350
Allocate routine 1-32 Water white transparency 365
Allocate routine 1-33 Water white transparency 383
Allocate routine 1-34 Water white transparency 377
Allocate routine 1-35 Water white transparency 500
Allocate routine 1-36 Water white transparency 480
[embodiment 1-1]
Use the optical polymerism coating agent of the routine 1-1 gained of allotment, make following duplexer.
As protective membrane (1); use the triacetyl cellulose mesentery that contains UV light absorber of film company of Fuji system: trade(brand)name " FUJITAC:80 μ m "; as protective membrane (2); use the triacetyl cellulose mesentery that does not contain UV light absorber of supply corporation of Fuji film enterprise system: trade(brand)name " TAC50 μ " (thickness 50 μ m), respectively on its surface with 300Wmin/m 2discharge capacity carry out corona treatment (corona discharge); after surface treatment in 1 hour; use line rod spreader; optical polymerism coating agent shown in the routine 1-1 of coating allotment; make thickness become 4 μ m; form optical polymerism coat, clamp above-mentioned polyethenol series polarisation between aforementioned optical polymerism coat, obtaining protective membrane (1)/optical polymerism coat/PVA is the duplexer that polarisation/optical polymerism coat/protective membrane (2) forms.
Protective membrane (1) is connected with sheet tin, fixes, is fixed on sheet tin for four jiaos of this duplexer with cellotape.
With UV irradiating unit (Toshiba's high voltage mercury lamp processed), maximal illumination 300mW/cm 2, accumulated light 300mJ/cm 2ultraviolet ray from protective membrane (2) side irradiate, make Polarizer.
[comparative example 1-1]
Replace the optical polymerism coating agent (allocating routine 1-1) of embodiment 1-1, change to the optical polymerism coating agent shown in the allotment example 1-20 of the ring compound (B1) not using more than the tetra-atomic ring with more than 2 Sauerstoffatom, in addition, similarly make Polarizer with embodiment 1-1.
[comparative example 1-2]
Replace the optical polymerism coating agent (allocating routine 1-1) of embodiment 1-1, change to the optical polymerism coating agent shown in the allotment example 1-27 that does not use three membered cyclic oxirane compound (A), in addition, similarly make Polarizer with embodiment 1-1.
[embodiment 1-2 to 1-25,1-39,1-40]
Replace the optical polymerism coating agent (allocating routine 1-1) of embodiment 1-1, change to allotment routine 1-2 to 1-19,1-21 to 1-26,1-35,1-36, in addition, similarly make Polarizer with embodiment 1-1.
[embodiment 1-26 to 1-28]
The protective membrane (2) that embodiment 1-3 is used changes to respectively Japanese lucky grace (Zeon) company norcamphene mesentery processed (trade(brand)name " Zeonor ZF-14:100 μ m ") (embodiment 1-26), company of Mitsubishi beautiful sun (Rayon) vinylformic acid mesentery processed (trade(brand)name " HDB-002:50 μ m ") (embodiment 1-27), Ka Neika (Kaneka) company polycarbonate mesentery processed (trade(brand)name " R-140:43 μ m ") (embodiment 1-28) in addition; similarly make with embodiment 1-3 and obtain Polarizer, similarly evaluating.
[embodiment 1-29 to 1-31]
The protective membrane (1) that embodiment 1-3 is used change to respectively east match (Tohcello) company polypropylene mesentery processed (trade(brand)name " OPU-1:50 μ m ") (embodiment 1-29), east match (Tohcello) company polyethylene mesentery processed (trade(brand)name " TUX-HZ:50 μ m ") (embodiment 1-30), You Niji can (Unitika) company polyester mesentery processed (trade(brand)name " Emblet S:50 μ m ") (embodiment 1-31); in addition; similarly make with embodiment 1-1 and obtain Polarizer, similarly evaluating.
[embodiment 1-32 to 1-38]
Replace the optical polymerism coating agent (allocating routine 1-1) of embodiment 1-1, change to the allotment example 1-28 to 1-34 shown in table 1-1, in addition, similarly make with embodiment 1-1 and obtain Polarizer, similarly evaluate.
The duplexer (Polarizer) of embodiment, comparative example gained, tries to achieve according to following methods for its stripping strength, gel ratio, perforation processibility and humidity resistance, and result is shown in 1-3.
< < stripping strength > >
Bonding force, according to 4 of bonding strength testing method-of JIS K6854-4 caking agent-peel off: the running roller method of floating is measured.
That is to say, by the Polarizer of gained, use cutter cuts into the size of 25mm × 150mm, as test sample.Sample is used to two sides jointing tape (DF8712S processed of Toyo Ink manufacturing company), be attached on metal sheet with laminator (laminater), obtain the mensuration duplexer of Polarizer and metal sheet.For mensuration duplexer, making a start of peeling off is in advance set between protective membrane and polarisation, by this mensuration with duplexer under 23 ℃, the condition of relative humidity 50%, the speed strip off dividing with 300mm/, as peeling force.Now, measure the two peeling force of polyethenol series polarisation and protective membrane (1) and polyethenol series polarisation and protective membrane (2).This peeling force is as bonding force, evaluates with 4 stages.
◎: not peelable, or Polarizer destroys
Zero: peeling force is 2.0(N/25mm) above to being less than 5.0(N/25mm)
△: peeling force is 1.0(N/25mm) above to being less than 2.0(N/25mm)
×: peeling force is less than 1.0(N/25mm)
< < gel ratio > >
To not implementing lucky grace (Zeon) the company norcamphene film processed of Japan (trade(brand)name " Zeonor ZF-14:100 μ m ") of corona treatment, use line rod spreader, the optical polymerism coating agent of coating gained, makes thickness become 20 to 25 μ m, forms optical polymerism coat.Further, on optical polymerism coat, the overlapping Zeonor ZF-14 that does not implement corona treatment, obtains after 3 layers of duplexer forming, and with UV irradiating unit (Toshiba's high voltage mercury lamp processed), irradiates maximal illumination 300mW/cm 2, accumulated light 300mJ/cm 2ultraviolet ray, make optical polymerism coat solidify.The Zeonor ZF-14 that peels off 3 layers of duplexer forming, obtains bond layer.
After the weight of mensuration bond layer (weight 1), the bond layer clipping between wire netting and wire netting is not overlapped each other, in methyl ethyl ketone (MEK), reflux 3 hours.With 80 ℃, within-30 minutes, be dried again, measure the weight (weight 2) of bond layer.By following formula, try to achieve gel ratio, evaluate with 3 stages.
Gel ratio (%)=and 1-(weight 1-weight 2)/weight 1} × 100
Zero: gel ratio is more than 90%
△: gel ratio is more than 80% to being less than 90%
×: gel ratio is less than 80%
< < perforation processibility > >
Use the blade of Deng Shi (Dumbbell) 100mm × 100mm processed of company, by the Polarizer of making from protective membrane (1) side perforation.
With chi, measure the peel distance of the surrounding of the Polarizer of perforation, with the 4 following stages, evaluate.
◎：0mm
Zero: below 1mm
△: 1 to 3mm
×: more than 3mm
< < thermotolerance > >
The Polarizer of each embodiment, comparative example gained cuts into the size of 50mm × 40mm, under 80 ℃-dry and 100 ℃-dry condition, exposes respectively 1000 hours.For the end of Polarizer after exposing peel off have or not, evaluate with 3 stages below visual use.
◎: under 100 ℃-dry condition completely without peeling off
Under zero: 80 ℃-dry condition completely without peeling off
Zero △: have and be less than peeling off of 1mm under 80 ℃-dry condition
△: have 1mm to be less than above peeling off of 2mm under 80 ℃-dry condition
×: under 80 ℃-dry condition, there is more than 2mm peeling off
< < humidity resistance > >
The Polarizer of each embodiment, comparative example gained is cut into the size of 50mm × 40mm, under the condition of 60 ℃-90%RH and under the condition of 85 ℃-85%RH, expose 1000 hours.After exposing the end of Polarizer peel off have or not, evaluate with 3 stages below visual use.
◎: under the condition of 85 ℃-85%RH, nothing is peeled off completely
Under the condition of zero: 60 ℃-90%RH, nothing is peeled off completely
Zero △: have under the condition of 60 ℃-90%RH and be less than peeling off of 1mm
△: have 1mm to be less than above peeling off of 2mm under the condition of 60 ℃-90%RH
×: under the condition of 60 ℃-90%RH, there is more than 1mm peeling off
[table 3]
Figure BDA0000469466250000581
Figure BDA0000469466250000582
According to the optical polymerism coating agent of present embodiment, as shown in table 1-3, in embodiment 1-1 to 1-10,1-13 to 1-19,1-26 to 1-40, some viscosity is high, but without special problem.In three membered cyclic oxirane compound (A), all not containing the embodiment 1-20 to 1-22 of aromatic nucleus because of the cured coating film of optical polymerism coating agent a bit soft, though have the difficulty of humidity resistance, without special problem.And, containing aromatic nucleus and only there is the embodiment 1-24 of a three membered cyclic oxyethane ring, though there is the difficulty of gel ratio, perforation processibility and humidity resistance, without special problem.And, embodiment 1-32 to 1-38, because using fluorine-containing ring compound (b1-4) as ring compound (B1), thereby thermotolerance, humidity resistance significantly improve.
Hence one can see that, and in arbitrary embodiment, the viscosity of the optical polymerism resin combination using, for below 1500mPas, can form bonding force, perforation processibility, thermotolerance, the good Polarizer of humidity resistance.
Relatively, the known comparative example 1-1 for not containing ring compound (B1) more than the tetra-atomic ring with more than 2 Sauerstoffatom, the viscosity of the optical polymerism resin combination using is up to 1600mPas, and gel ratio is low, solidified nature is poor, and the processibility of therefore boring a hole, thermotolerance, humidity resistance are poor.And for comparative example 1-2, because not having three membered cyclic oxirane compound (A), it is insufficient that light solidified becomes, bonding force, gel ratio, perforation processibility and thermotolerance, humidity resistance are all poor.
Below about embodiment II.
[allocating routine 2-1 to 2-28]
Replacing to oxygen concentration, be in the mayonnaise bottle of 300cc of the shading below 10%, according to table, the ratio shown in 2-1 is put into three membered cyclic oxirane compound (A), has more than the tetra-atomic ring of more than 1 Sauerstoffatom and sulphur atom ring compound (B2), is had more than the tetra-atomic ring of more than 2 Sauerstoffatom ring compound (B1), ethene unsaturated compound (D), Photoepolymerizationinitiater initiater (E), sensitizing agent and antioxidant, with pneumatic motor, fully stir, fully, after deaeration, obtain being expressed as the routine optical polymerism coating agent of allotment.
The optical polymerism coating agent of the allotment example shown in table 2-1, its solution appearance, viscosity are tried to achieve according to above-mentioned identical method, and result is shown in 2-2.
[table 4]
Figure BDA0000469466250000601
Figure BDA0000469466250000611
Figure BDA0000469466250000621
[table 5]
Table 2-2 Outward appearance Viscosity (mPas)
Allocate routine 2-1 Water white transparency 430
Allocate routine 2-2 Water white transparency 450
Allocate routine 2-3 Water white transparency 435
Allocate routine 2-4 Water white transparency 452
Allocate routine 2-5 Water white transparency 450
Allocate routine 2-6 Water white transparency 451
Allocate routine 2-7 Water white transparency 440
Allocate routine 2-8 Water white transparency 431
Allocate routine 2-9 Water white transparency 150
Allocate routine 2-10 Water white transparency 380
Allocate routine 2-11 Water white transparency 392
Allocate routine 2-12 Water white transparency 265
Allocate routine 2-13 Water white transparency 285
Allocate routine 2-14 Water white transparency 250
Allocate routine 2-15 Water white transparency 263
Allocate routine 2-16 Water white transparency 255
Allocate routine 2-17 Water white transparency 230
Allocate routine 2-18 Water white transparency 235
Allocate routine 2-19 Water white transparency 240
Allocate routine 2-20 Water white transparency 213
Allocate routine 2-21 Water white transparency 150
Allocate routine 2-22 Water white transparency 145
Allocate routine 2-23 Faint yellow transparent 265
Allocate routine 2-24 Water white transparency 240
Allocate routine 2-25 Water white transparency 102
Allocate routine 2-26 Water white transparency 1600
Allocate routine 2-27 Water white transparency 10
Allocate routine 2-28 Water white transparency 3
[embodiment 2-1]
Use the optical polymerism coating agent of the routine 2-1 gained of allotment, make following duplexer.
As protective membrane (1); use the triacetyl cellulose mesentery that contains UV light absorber of film company of Fuji system: trade(brand)name " FUJITAC:80 μ m "; as protective membrane (2); use the triacetyl cellulose mesentery that does not contain UV light absorber of supply corporation of Fuji film enterprise system: trade(brand)name " TAC50 μ " (thickness 50 μ m), respectively on its surface with 300Wmin/m 2discharge capacity carry out corona treatment; after surface treatment in 1 hour; use line rod spreader; optical polymerism coating agent shown in the routine 2-1 of coating allotment; make thickness become 4 μ m; form optical polymerism coat, clamp above-mentioned polyethenol series polarisation between aforementioned optical polymerism coat, obtaining protective membrane (1)/optical polymerism coat/PVA is the duplexer that polarisation/optical polymerism coat/protective membrane (2) forms.
Protective membrane (1) is connected with sheet tin, fixes, is fixed on sheet tin for four jiaos of this duplexer with cellotape.
With UV irradiating unit (Toshiba's high voltage mercury lamp processed), maximal illumination 300mW/cm 2, accumulated light 300mJ/cm 2ultraviolet ray from protective membrane (2) side irradiate, make Polarizer.
[comparative example 2-1]
Replace the optical polymerism coating agent (allocating routine 2-1) of embodiment 2-1, change to the optical polymerism coating agent shown in the allotment example 2-26 of the ring compound (B2) not using more than the tetra-atomic ring with more than 1 Sauerstoffatom and sulphur atom, in addition, similarly make Polarizer with embodiment 2-1.
[comparative example 2-2]
Replace the optical polymerism coating agent (allocating routine 2-1) of embodiment 2-1, change to the optical polymerism coating agent shown in the allotment example 2-27 that does not use three membered cyclic oxirane compound (A), in addition, similarly make Polarizer with embodiment 2-1.
[comparative example 2-3]
Replace the optical polymerism coating agent (allocating routine 2-1) of embodiment 2-1, change to the optical polymerism coating agent shown in the allotment example 2-28 that does not use three membered cyclic oxirane compound (A), in addition, similarly make Polarizer with embodiment 2-1.
[embodiment 2-2 to 2-25]
Replace the optical polymerism coating agent (allocating routine 2-1) of embodiment 2-1, change to the allotment example 2-2 to 2-25 shown in table 2-1, in addition, similarly make Polarizer with embodiment 2-1.
[embodiment 2-26 to 2-28]
The protective membrane (2) that embodiment 2-15 is used changes to respectively Japanese lucky grace (Zeon) company norcamphene film processed (trade(brand)name " Zeonor ZF-14:100 μ m ") (embodiment 2-26), company of Mitsubishi beautiful sun (Rayon) vinylformic acid mesentery processed (trade(brand)name " HDB-002:50 μ m ") (embodiment 2-27), Ka Neika (Kaneka) company polycarbonate mesentery processed (trade(brand)name " R-140:43 μ m ") (embodiment 2-28); in addition; similarly make with embodiment 2-1 and obtain Polarizer, similarly evaluating.
[embodiment 2-29 to 2-31]
The protective membrane (1) that embodiment 2-15 is used change to respectively east match (Tohcello) company polypropylene mesentery processed (trade(brand)name " OPU-1:50 μ m ") (embodiment 2-29), east match (Tohcello) company polyethylene mesentery processed (trade(brand)name " TUX-HZ:50 μ m ") (embodiment 2-30), You Niji can (Unitika) company polyester mesentery processed (trade(brand)name " Emblet S:50 μ m ") (embodiment 2-31); in addition; similarly make with embodiment 2-1 and obtain Polarizer, similarly evaluating.
The duplexer (Polarizer) of embodiment, comparative example gained, method that its stripping strength, gel ratio, perforation processibility and humidity resistance are recorded according to embodiment I, tries to achieve according to following method, and result is shown in 2-3.
< < humidity resistance > >
The duplexer (Polarizer) of each embodiment, comparative example gained cuts into the size of 50mm × 40mm, under the condition of 60 ℃-90%RH, exposes 500 hours.After exposing the end of Polarizer peel off have or not, evaluate with 4 stages below visual use.
Under the condition of zero: 60 ℃-90%RH, nothing is peeled off completely
Zero △: have under the condition of 60 ℃-90%RH and be less than peeling off of 1mm
△: have 1mm to be less than above peeling off of 2mm under the condition of 60 ℃-90%RH
×: the 2mm having under the condition of 60 ℃-90%RH peels off above
[table 6]
Figure BDA0000469466250000681
Figure BDA0000469466250000682
According to the optical polymerism coating agent of present embodiment, as shown in table 2-3, for embodiment 2-1 to 2-8,2-10 to 2-13,2-20, in a part, viscosity is high sometimes, and stripping strength, gel ratio are had any problem, but without special problem.And for embodiment 2-14 to 2-19,2-21 to 2-24, because comprising ring compound (B1) more than the tetra-atomic ring with more than 2 Sauerstoffatom, reactivity improves, cohesive force improves, although viscosity is high, without special problem.And, in three membered cyclic oxirane compound (A), all, not containing embodiment 2-9, the 2-25 of aromatic nucleus, because the cured coating film of optical polymerism coating agent is a bit soft, there is the difficulty of humidity resistance, but without special problem.Hence one can see that, and in arbitrary embodiment, viscosity is below 1500mPas, can form bonding force, perforation processibility, the good Polarizer of humidity resistance.
Relatively, known for not containing more than the tetra-atomic ring with more than 1 Sauerstoffatom and sulphur atom ring compound (B1) and comparative example 2-1 (B1), viscosity is up to 1600mPas, and gel ratio is low again, solidified nature is poor, and the processibility of therefore boring a hole, humidity resistance are poor.And for comparative example 2-2,2-3, because not having three membered cyclic oxirane compound (A), it is insufficient that light solidified becomes, bonding force, gel ratio, perforation processibility and humidity resistance are all poor.
Below, about embodiment III.
[allocating routine 3-1 to 3-49]
Replacing to oxygen concentration, be in the mayonnaise bottle of 300cc of the shading below 10%, according to table, the ratio shown in 3-1 is put into three membered cyclic oxirane compound (A), has more than the tetra-atomic ring of more than 2 Sauerstoffatom ring compound (B1), is had compound (C), ethene unsaturated compound (D), Photoepolymerizationinitiater initiater (E), sensitizing agent and the antioxidant of the two molecular weight of at least 1 ring texture and hydroxyl below 500, with pneumatic motor, fully stir, fully, after deaeration, obtain being expressed as the routine optical polymerism coating agent of allotment.
The optical polymerism coating agent of the allotment example shown in table 3-1, its solution appearance, viscosity are tried to achieve according to above-mentioned identical method, and result is shown in 3-2.
[table 7]
Figure BDA0000469466250000711
Figure BDA0000469466250000721
[table 8]
Table 3-2 Outward appearance Viscosity (mPas)
Allocate routine 3-1 Water white transparency 355
Allocate routine 3-2 Water white transparency 360
Allocate routine 3-3 Water white transparency 371
Allocate routine 3-4 Water white transparency 366
Allocate routine 3-5 Water white transparency 345
Allocate routine 3-6 Water white transparency 364
Allocate routine 3-7 Water white transparency 353
Allocate routine 3-8 Water white transparency 346
Allocate routine 3-9 Water white transparency 353
Allocate routine 3-10 Water white transparency 342
Allocate routine 3-11 Water white transparency 121
Allocate routine 3-12 Water white transparency 122
Allocate routine 3-13 Water white transparency 332
Allocate routine 3-14 Water white transparency 336
Allocate routine 3-15 Water white transparency 232
Allocate routine 3-16 Water white transparency 239
Allocate routine 3-17 Water white transparency 178
Allocate routine 3-18 Water white transparency 181
Allocate routine 3-19 Faint yellow transparent 371
Allocate routine 3-20 Water white transparency 1242
Allocate routine 3-21 Water white transparency 117
Allocate routine 3-22 Water white transparency 265
Allocate routine 3-23 Water white transparency 264
Allocate routine 3-24 Water white transparency 256
Allocate routine 3-25 Water white transparency 261
Allocate routine 3-26 Water white transparency 269
Allocate routine 3-27 Water white transparency 254
Allocate routine 3-28 Water white transparency 259
Allocate routine 3-29 Water white transparency 256
Allocate routine 3-30 Water white transparency 279
Allocate routine 3-31 Water white transparency 221
Allocate routine 3-32 Water white transparency 287
Allocate routine 3-33 Water white transparency 203
Allocate routine 3-34 Water white transparency 298
Allocate routine 3-36 Water white transparency 286
Allocate routine 3-37 Water white transparency 224
Allocate routine 3-38 Water white transparency 14
Allocate routine 3-39 Water white transparency 266
Allocate routine 3-40 Water white transparency 7
Allocate routine 3-41 Water white transparency 356
Allocate routine 3-42 Water white transparency 4
Allocate routine 3-44 Water white transparency 265
Allocate routine 3-45 Water white transparency 288
Allocate routine 3-46 Water white transparency 276
Allocate routine 3-47 Water white transparency 247
Allocate routine 3-48 Water white transparency 256
Allocate routine 3-49 Water white transparency 275
[embodiment 3-1]
Use the optical polymerism coating agent of the routine 3-1 gained of allotment, make following duplexer.
As protective membrane (1); use the triacetyl cellulose mesentery that contains UV light absorber of film company of Fuji system: trade(brand)name " FUJITAC:80 μ m "; as protective membrane (2); use supply corporation of Fuji film enterprise system not contain the triacetyl cellulose mesentery of UV light absorber: trade(brand)name " TAC50 μ " (thickness 50 μ m), respectively on its surface with 300Wmin/m 2discharge capacity carry out corona treatment; after surface treatment in 1 hour; use line rod spreader; optical polymerism coating agent shown in the routine 3-1 of coating allotment; make thickness become 4 μ m; form optical polymerism coat, clamp above-mentioned polyethenol series polarisation between aforementioned optical polymerism coat, obtaining protective membrane (1)/optical polymerism coat/PVA is the duplexer that polarisation/optical polymerism coat/protective membrane (2) forms.Protective membrane (1) is connected with sheet tin, fixes, is fixed on sheet tin for four jiaos of this duplexer with cellotape.With UV irradiating unit (Toshiba's high voltage mercury lamp processed), maximal illumination 200mW/cm 2, accumulated light 200mJ/cm 2ultraviolet ray from protective membrane (2) side irradiate, make Polarizer.
[embodiment 3-2 to 3-36 and 3-43 to 3-48, comparative example 3-6 to 3-8]
The allotment example 3-1 that replaces the optical polymerism coating agent of embodiment 3-1, changes to allotment example 3-2 to 3-34,3-38 to 3-42 and the 3-44 to 3-49 shown in table 3-1, in addition, similarly makes Polarizer with embodiment 3-1.
[embodiment 3-37 to 3-39]
The protective membrane (2) that embodiment 3-21 is used changes to respectively Japanese lucky grace (Zeon) company norcamphene film processed (trade(brand)name " Zeonor ZF-14:100 μ m ") (embodiment 3-37), company of Mitsubishi beautiful sun (Rayon) vinylformic acid mesentery processed (trade(brand)name " HDB-002:50 μ m ") (embodiment 3-38), Ka Neika (Kaneka) company polycarbonate mesentery processed (trade(brand)name " R-140:43 μ m ") (embodiment 3-39); in addition; similarly make Polarizer with embodiment 3-21, similarly evaluate.
[embodiment 3-40 to 3-42]
The protective membrane (1) that embodiment 3-21 is used change to respectively east match (Tohcello) company polypropylene mesentery processed (trade(brand)name " OPU-1:50 μ m ") (embodiment 3-40), east match (Tohcello) company polyethylene mesentery processed (trade(brand)name " TUX-HZ:50 μ m ") (embodiment 3-41), You Niji can (Unitika) company polyester mesentery processed (trade(brand)name " Emblet S:50 μ m ") (embodiment 3-42) outside; similarly make Polarizer with embodiment 3-21, similarly evaluate.
The duplexer (Polarizer) of embodiment, comparative example gained, the method for recording, tries to achieve according to following method for gel ratio for its stripping strength, gel ratio, perforation processibility and humidity resistance according to embodiment I, and result is shown in 3-3.
< < gel ratio > >
To not implementing lucky grace (Zeon) the company norcamphene film processed of Japan (trade(brand)name " Zeonor ZF-14:100 μ m ") of corona treatment, use line rod spreader, the optical polymerism coating agent of coating gained, makes thickness become 20 to 25 μ m, forms optical polymerism coat.Further be on optical polymerism coat, the overlapping Zeonor ZF-14 that does not implement corona treatment, obtains after 3 layers of duplexer forming, and with UV irradiating unit (Toshiba's high voltage mercury lamp processed), irradiates maximal illumination 200mW/cm 2, accumulated light 200mJ/cm 2ultraviolet ray, make optical polymerism coat solidify.The Zeonor ZF-14 that peels off 3 layers of duplexer forming, obtains bond layer.After the weight of mensuration bond layer (weight 1), the bond layer clipping between wire netting and wire netting is not overlapped each other, in methyl ethyl ketone (MEK), reflux 3 hours.With 80 ℃, within-30 minutes, be dried again, measure the weight (weight 2) of bond layer.By following formula, try to achieve gel ratio, evaluate with 3 stages.
Gel ratio (%)=and 1-(weight 1-weight 2)/weight 1} × 100
Zero: gel ratio is more than 90%
△: gel ratio is more than 80% to being less than 90%
×: gel ratio is less than 80%
[table 9]
Figure BDA0000469466250000781
According to the optical polymerism coating agent of present embodiment, as shown in table 3-3, for embodiment 3-1 to 3-19,3-21 to 3-28,3-34,3-36 to 3-42, in whole assessment items, without special problem.In three membered cyclic oxirane compound (A), not containing embodiment 3-20, the 3-33 of aromatic nucleus, because the cured coating film of optical polymerism coating agent is a bit soft, there is the difficulty of thermotolerance, humidity resistance completely, but without special problem.And, containing aromatic nucleus and do not there is the embodiment 3-35 of three membered cyclic oxyethane ring, though there is the difficulty of gel ratio, thermotolerance and humidity resistance, without special problem.And, there is embodiment 3-29 that more than tetra-atomic ring of more than 2 Sauerstoffatom ring compound (B1) is few, there is the many embodiment 3-30 of ring compound (B1) more than the tetra-atomic ring of more than 2 Sauerstoffatom, though have gel ratio and stable on heating difficulty, without special problem.There is embodiment 3-31 that the compound (C) of the two molecular weight of ring texture and hydroxyl below 500 is few, there is compound (C) the many embodiment 3-32 of the two molecular weight of ring texture and hydroxyl below 500, though have the difficulty of gel ratio, thermotolerance and humidity resistance, without special problem.Hence one can see that, and in arbitrary embodiment, viscosity is below 1500mPas, can form bonding force, perforation processibility, thermotolerance, the good Polarizer of humidity resistance.Comparative example 3-8 is large because having the two the molecular weight ratio 500 of compound of ring texture and hydroxyl, with three membered cyclic oxirane compound (A) and/or have ring compound (B1) more than the tetra-atomic ring of more than 2 Sauerstoffatom reactivity, to react facilitation effect low, gel ratio step-down, perforation processibility, thermotolerance, humidity resistance are poor.Comparative example 3-7 is because have the compound without the hydroxyl of ring texture, three membered cyclic oxirane compound (A) and/or to have the reaction facilitation effect of ring compound (B1) more than the tetra-atomic ring of more than 2 Sauerstoffatom low, gel ratio step-down, perforation processibility, thermotolerance, humidity resistance are poor.And comparative example 3-6 is not because having three membered cyclic oxirane compound (A), solidified nature is poor, and stripping strength, perforation processibility, thermotolerance, humidity resistance are poor.
Below, about embodiment IV.
[allocating routine 4-1]
Replacing to oxygen concentration, be in the mayonnaise bottle of 300cc of the shading below 10%, ratio according to table 4-1 is put into three membered cyclic oxirane compound (A) and Photoepolymerizationinitiater initiater (E), with pneumatic motor, fully stir, fully, after deaeration, obtain being expressed as the routine optical polymerism coating agent of allotment.
In the optical polymerism composition of gained, the method for recording according to embodiment I according to following method, for viscosity for amount of moisture is tried to achieve, and result is shown in 4-1.
< < moisture determination > >
By Ka Shi moisture volumetry (Karl Fischer), according to JIS K0113-2005, measure.
[allocating routine 4-2 to 4-5]
With allotment routine 4-1 similarly, obtain after composition ring compound (B1) more than the tetra-atomic ring with more than 2 Sauerstoffatom shown in interpolation table 4-1, add purified water, become the amount of moisture shown in table 4-1, with pneumatic motor, fully stir, obtain optical polymerism coating agent.
[allocating routine 4-6 to 4-35]
With the ratio shown in table 4-1, put into three membered cyclic oxirane compound (A), there is more than the tetra-atomic ring of more than 1 Sauerstoffatom and sulphur atom ring compound (B2), there is more than the tetra-atomic ring of more than 2 Sauerstoffatom ring compound (B1), ethene unsaturated compound (D), Photoepolymerizationinitiater initiater (E) and sensitizing agent, routine 4-2 similarly adjusts amount of moisture with allotment, with pneumatic motor, fully stir, fully, after deaeration, obtain being expressed as the routine optical polymerism coating agent of allotment.
[table 10]
Figure BDA0000469466250000801
Figure BDA0000469466250000811
Figure BDA0000469466250000821
[Chemical formula 1]
Figure BDA0000469466250000841
[embodiment 4-1]
Use the optical polymerism coating agent of the routine 4-2 gained of allotment, make following duplexer.
As blooming, use the triacetyl cellulose mesentery that contains UV light absorber of film company of Fuji system: trade(brand)name " FUJITAC:80 μ m ".On the surface of blooming, with 300Wmin/m 2discharge capacity carry out corona treatment, after surface treatment in 1 hour, use line rod spreader, the optical polymerism coating agent shown in the routine 4-1 of coating allotment, makes thickness become 4 μ m, forms the easy bonding coating agent layer of optical polymerism.
Blooming is connected with sheet tin, fixes, is fixed on sheet tin for four jiaos of this duplexer with cellotape.
After replacing with drying nitrogen in UV irradiating unit (Toshiba's high voltage mercury lamp processed), the maximal illumination 200mW/cm of wavelength 365nm 2, accumulated light 200mJ/cm 2ultraviolet ray from easy bonding coating agent layer side, irradiate, make the duplexer with easy bonding coating agent layer.
[embodiment 4-2 to 4-34 and 4-71, comparative example 4-1 to 4-5]
Replace the optical polymerism coating agent (allocating routine 4-1) of embodiment 4-1, change to allotment example, the blooming shown in table 4-2, in addition, similarly make duplexer with embodiment 4-1.
The duplexer of embodiment 4-2 to 4-34 and 4-71, comparative example 4-1 to 4-5 gained, the method for recording according to embodiment II according to following method, for gel ratio for its closing force and thermotolerance is tried to achieve, and result is shown in table 4-2.
< < closing force > >
According to JIS K5400, implement checker and peel off test.The lattice number of peeling off in 100 lattice, evaluated with 4 stages.
◎: 0 lattice
Zero: 1 to 10 lattice
△: 11 to 30 lattice
×: more than 31 lattice
< < thermotolerance > >
The duplexer of each embodiment, comparative example gained cuts into the size of 50mm × 40mm, under 80 ℃-dry condition, exposes 1000 hours.After exposing the end of duplexer peel off have or not, evaluate with 3 stages below visual use.
Zero: completely without peeling off
Zero △: have and be less than peeling off of 1mm
△: have 1mm to be less than above peeling off of 2mm
×: there is more than 2mm peeling off
[table 11]
Figure BDA0000469466250000851
Figure BDA0000469466250000861
Blooming Content
FIJITAC (80 μ m) for the TAC film that film company of Fuji system contains UV light absorber
ZF14 Japan Zeon company system does not contain the norcamphene film of UV light absorber, and (100 μ m)
HBD-002 Li Yang company of Mitsubishi system does not contain the vinylformic acid mesentery of UV light absorber, and (50 μ m)
R-140 Kaneka company system does not contain the polycarbonate mesentery of UV light absorber, and (43 μ m)
Emblet?S (50 μ m) for the polyester mesentery that Unitika company system contains UV light absorber
TUX-HZ (50 μ m) for the polyethylene mesentery that Tohcello company system contains UV light absorber
[embodiment 4-35]
Use the optical polymerism coating agent of the routine 4-2 gained of allotment, make following Polarizer.
As protective membrane (1); use the triacetyl cellulose mesentery that contains UV light absorber of film company of Fuji system: trade(brand)name " FUJITAC:80 μ m "; as protective membrane (2); use supply corporation of Fuji film enterprise system not contain the triacetyl cellulose mesentery of UV light absorber: trade(brand)name " TAC50 μ " (thickness 50 μ m), respectively on its surface with 300Wmin/m 2discharge capacity carry out corona treatment; after surface treatment in 1 hour; use line rod spreader; optical polymerism coating agent shown in the routine 4-2 of coating allotment; make thickness become 4 μ m; form optical polymerism coat, clamp above-mentioned polyethenol series polarisation between aforementioned optical polymerism coat, obtaining protective membrane (1)/optical polymerism coat/PVA is the duplexer that polarisation/optical polymerism coat/protective membrane (2) forms.
Protective membrane (1) is connected with sheet tin, fixes, is fixed on sheet tin for four jiaos of this duplexer with cellotape.
With UV irradiating unit (Toshiba's high voltage mercury lamp processed), the maximal illumination 200mW/cm of wavelength 365nm 2, accumulated light 200mJ/cm 2ultraviolet ray from protective membrane (2) side irradiate, make Polarizer.
[embodiment 4-36 to 4-69 and 4-149, comparative example 4-6 to 4-10]
Replace the optical polymerism coating agent (allocating routine 4-2) of embodiment, change to allotment example, the blooming shown in table 4-3, in addition, similarly make duplexer with embodiment 4-35.
The polarisation plate body of embodiment 4-35 to 4-69 and 4-149, comparative example 4-6 to 4-10 gained, tries to achieve for the method for recording according to embodiment I according to following method, for perforation processibility in stripping strength and thermotolerance, and result is shown in table 4-3.
< < stripping strength > >
Bonding force, according to 4 of bonding strength testing method-of JIS K6854-4 caking agent-peel off: the running roller method of floating is measured.
That is to say, by the Polarizer of gained, use cutter cuts into the size of 25mm × 150mm, as test sample.Sample is used to two sides jointing tape (DF8712S processed of Toyo Ink manufacturing company), be attached on metal sheet with laminator, obtain the mensuration duplexer of Polarizer and metal sheet.For mensuration duplexer, making a start of peeling off is in advance set between protective membrane and polarisation, by this mensuration with duplexer under 23 ℃, the condition of relative humidity 50%, the speed strip off dividing with 300mm/, as peeling force.Now, measure the two peeling force of polyethenol series polarisation and protective membrane (1) and polyethenol series polarisation and protective membrane (2).This peeling force is as bonding force, evaluates with 4 stages.
◎: peeling force is 5.0(N/25mm) above or Polarizer destruction
Zero: peeling force is 2.0(N/25mm) above to being less than 5.0(N/25mm)
△: peeling force is 1.0(N/25mm) above to being less than 2.0(N/25mm)
×: peeling force is less than 1.0(N/25mm)
[table 12]
Figure BDA0000469466250000891
Figure BDA0000469466250000892
In the situation that optical polymerism coating agent is used as easy bonding coating agent, embodiment 4-1 to 4-6,4-27 to 4-29 shown in table 4-2 form adaptation, gel ratio, all good optical film laminate of thermotolerance.
On the other hand, comparative example 4-1,4-4 that amount of moisture is few, the comparative example 4-2 that amount of moisture is many, because of at maximal illumination 200mW/cm 2, accumulated light 200mJ/cm 2low irradiation dose time solidified nature poor, thereby gel ratio is low, closing force, poor heat resistance.
Similarly, comprise ring compound (B1) more than the tetra-atomic ring with more than 2 Sauerstoffatom, embodiment 4-7 to 4-21, the 4-22 to 4-26 of ethene unsaturated compound (D) also forms good optical film laminate.
On the other hand, do not contain the comparative example 4-5 of three membered cyclic oxirane compound (A), gel ratio is high, but closing force, poor heat resistance.
And embodiment 4-30 to 4-34, in the evaluation result of various bloomings, from hydrophobic norcamphene mesentery to hydrophilic cellulose acetate mesentery, forms good optical film laminate.
The evaluation result that table 4-3 is Polarizer.There is the tendency identical with the evaluation result of table 4-2; but the in the situation that of Polarizer; optical polymerism coating agent between protective membrane 1 and polyethenol series polarisation; because of the absorption of the active energy beam by protective membrane 2 and optical polymerism coating agent, polyethenol series polarisation; become more weak irradiation dose, show more significant bonding force difference.
Embodiment 4-35 to 4-69, though form good Polarizer, comparative example 4-6,4-8,4-9, amount of moisture comparative example 4-7 how that amount of moisture is few, solidified nature is poor, and particularly the bonding force of protective membrane 1 side is poor terrifically.The comparative example 4-10 adaptation that does not contain three membered cyclic oxirane compound (A) is poor, thereby bore a hole processibility, poor heat resistance.
[embodiment 4-72 to 4-143, comparative example 4-11 to 4-28]
The optical polymerism coating agent that embodiment 4-1 is used and blooming change shown in table 4-4, in addition, similarly make duplexer with embodiment 4-1.
To the duplexer of gained, its closing force, gel ratio, thermotolerance are tried to achieve according to the method identical with embodiment 4-1, and result is shown in 4-4.
[table 13]
Figure BDA0000469466250000911
Figure BDA0000469466250000921
Blooming Content
FIJITAC (80 μ m) for the TAC film that film company of Fuji system contains UV light absorber
ZF14 Japan Zeon company system does not contain the norcamphene film of UV light absorber, and (100 μ m)
HBD-002 Li Yang company of Mitsubishi system does not contain the vinylformic acid mesentery of UV light absorber, and (50 μ m)
R-140 Kaneka company system does not contain the polycarbonate mesentery of UV light absorber, and (43 μ m)
Emblet?S (50 μ m) for the polyester mesentery that Unitika company system contains UV light absorber
TUX-HZ (50 μ m) for the polyethylene mesentery that Tohcello company system contains UV light absorber
As show as shown in 4-4, while using according to the optical polymerism coating agent of present embodiment, the adaptation of the duplexer of gained, gel ratio, thermotolerance are good.

Claims (34)

1. an optical polymerism composition, is characterized in that, contains:
The oxirane compound (A) of three membered cyclic; And
Be selected from more than the tetra-atomic ring with more than 2 Sauerstoffatom ring compound (B1), there is ring compound (B2) more than the tetra-atomic ring of more than 1 Sauerstoffatom and more than 1 sulphur atom and there is at least 1 ring texture and the compound of the group that the compound (C) of the two molecular weight of hydroxyl below 500 forms.
2. optical polymerism composition according to claim 1, is characterized in that, with respect to the described oxirane compound (A) of 100 weight parts, and the described ring compound (B1) that contains 0.5 to 60 weight part.
3. optical polymerism composition according to claim 1, is characterized in that, with respect to the described oxirane compound (A) of 100 weight parts, and ring compound (B2) more than the described tetra-atomic ring that contains 0.5 to 60 weight part.
4. optical polymerism composition according to claim 1, is characterized in that, with respect to the described oxirane compound (A) of 100 weight parts, and the described compound (C) that contains 0.5 to 40 weight part.
5. optical polymerism composition according to claim 1, is characterized in that, with respect to the described oxirane compound (A) of 100 weight parts, further contains the moisture of 0.05 to 3 weight part.
6. according to the optical polymerism composition described in any one in claim 1 to 5, wherein said oxirane compound (A) contains the compound (a-2) that has the compound (a-1) of aromatic nucleus and/or have the oxyethane ring of more than 2 three membered cyclic.
7. according to the optical polymerism composition described in any one in claim 1 to 5, it is characterized in that, described ring compound (B1) contains the compound that is selected from the group that cyclic ester compound (b1-1), cyclic formals compound (b1-2) and cyclic carbonate compound (b1-3) form.
8. optical polymerism composition according to claim 6, it is characterized in that, described ring compound (B1) contains the compound that is selected from the group that cyclic ester compound (b1-1), cyclic formals compound (b1-2) and cyclic carbonate compound (b1-3) form.
9. optical polymerism composition according to claim 7, is characterized in that, described cyclic ester compound (b1-1) contains lactone (b1-1-1);
Described cyclic formals compound (b1-2) contains the compound that is selected from the group that dioxolane class (b1-2-1), dioxane (b1-2-2) and trioxa alkanes (b1-2-3) form.
10. optical polymerism composition according to claim 8, is characterized in that, described cyclic ester compound (b1-1) contains lactone (b1-1-1);
Described cyclic formals compound (b1-2) contains the compound that is selected from the group that dioxolane class (b1-2-1), dioxane (b1-2-2) and trioxa alkanes (b1-2-3) form.
11. according to the optical polymerism composition described in any one in claim 1 to 5, it is characterized in that, the substituting group that described ring compound (B1) contains through having F atom replaces fluorine-containing ring compound (b1-4) more than at least 1 place.
12. optical polymerism compositions according to claim 6, is characterized in that, the substituting group that described ring compound (B1) contains through having F atom replaces fluorine-containing ring compound (b1-4) more than at least 1 place.
13. according to the optical polymerism composition described in any one in claim 1 to 5, it is characterized in that, described ring compound (B2) has the skeleton structure that is selected from the group that sulfoxide skeleton, sulfone skeleton, sulfite skeleton, sulfuric ester skeleton, sulphonate skeleton and thioesters skeleton form in ring.
14. optical polymerism compositions according to claim 6, it is characterized in that, described ring compound (B2) has the skeleton structure that is selected from the group that sulfoxide skeleton, sulfone skeleton, sulfite skeleton, sulfuric ester skeleton, sulphonate skeleton and thioesters skeleton form in ring.
15. optical polymerism compositions according to claim 8, it is characterized in that, described ring compound (B2) has the skeleton structure that is selected from the group that sulfoxide skeleton, sulfone skeleton, sulfite skeleton, sulfuric ester skeleton, sulphonate skeleton and thioesters skeleton form in ring.
16. optical polymerism compositions according to claim 10, it is characterized in that, described ring compound (B2) has the skeleton structure that is selected from the group that sulfoxide skeleton, sulfone skeleton, sulfite skeleton, sulfuric ester skeleton, sulphonate skeleton and thioesters skeleton form in ring.
17. according to the optical polymerism composition described in any one in claim 1 to 5, it is characterized in that the ring texture that the ring texture of described compound (C) is the group that is selected from naphthenic, cyclenes class, phenyl ring and the above condensation polycyclic class of two rings and forms.
18. optical polymerism compositions according to claim 17, is characterized in that, described compound (C) is bonded directly to the compound of ring structure for hydroxyl, and/or hydroxyl is by having C 1to C 18carbonatoms alkylidene group and be bonded to the compound of ring structure.
19. optical polymerism compositions according to claim 18, it is characterized in that, described compound (C) is selected from the two compound (c-1) of the ring texture of the group that cyclohexane ring, cyclohexene ring, norcamphane ring, norcamphene ring, diamantane ring, dihydroisobenzofuran ring, Dihydrobenzofuranes ring, pepper basic ring and look alkane ring form and hydroxyl for having.
20. optical polymerism compositions according to claim 19, is characterized in that, described compound (c-1) is hexalin, phenylcarbinol, falls baras camphor, adamantanol, piperitol or 3,4-methylenedioxyphenol.
21. optical polymerism compositions according to claim 6, is characterized in that, described compound (C) is hexalin, phenylcarbinol, falls baras camphor, adamantanol, piperitol or 3,4-methylenedioxyphenol.
22. optical polymerism compositions according to claim 8, is characterized in that, described compound (C) is hexalin, phenylcarbinol, falls baras camphor, adamantanol, piperitol or 3,4-methylenedioxyphenol.
23. optical polymerism compositions according to claim 10, is characterized in that, described compound (C) is hexalin, phenylcarbinol, falls baras camphor, adamantanol, piperitol or 3,4-methylenedioxyphenol.
24. according to the optical polymerism composition described in any one in claim 1 to 5, it is characterized in that, with respect to the described oxirane compound (A) of 100 weight parts, further contains the ethene unsaturated compound (D) of 5 to 1000 weight parts.
25. optical polymerism compositions according to claim 24, is characterized in that, described ethene unsaturated compound (D) contains the ethene unsaturates (d-1) with hydroxyl.
26. according to the optical polymerism composition described in any one in claim 1 to 5, it is characterized in that, further contains Photoepolymerizationinitiater initiater (E).
27. optical polymerism compositions according to claim 26, is characterized in that, described Photoepolymerizationinitiater initiater (E) is for producing the A of acid active specy by rayed +b -the salt representing, this cation A +for aromatic series iodide ion and/or aromatic matte ion.
28. according to the optical polymerism composition described in any one in claim 1 to 5, it is characterized in that, does not contain in fact organic solvent, and the mensuration viscosity in the time of 23 ℃ is 1 to 1500mPas.
29. 1 kinds of optical polymerism coating agents, its right to use requires the optical polymerism composition described in any one in 1 to 28 to form.
30. 1 kinds of duplexers, is characterized in that, in the one or two sides of base material (G), have the layer that the optical polymerism coating agent described in claim 29 forms.
31. duplexers according to claim 30, is characterized in that, described base material (G) is transparent film (H).
32. duplexers according to claim 31, is characterized in that, described transparent film (H) is blooming (I).
33. duplexers according to claim 32, is characterized in that, described blooming (I) is cellulose acetate mesentery, norcamphene mesentery, vinylformic acid mesentery, polycarbonate mesentery, polyester mesentery or polyvinyl alcohol mesentery.
34. 1 kinds of Polarizers, is characterized in that, the one or two sides that the duplexer described in claim 33 is adhered to polyethenol series polarisation forms.
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