CN105358584A - Active-energy-ray-polymerizable resin composition and laminate - Google Patents

Active-energy-ray-polymerizable resin composition and laminate Download PDF

Info

Publication number
CN105358584A
CN105358584A CN201480037713.3A CN201480037713A CN105358584A CN 105358584 A CN105358584 A CN 105358584A CN 201480037713 A CN201480037713 A CN 201480037713A CN 105358584 A CN105358584 A CN 105358584A
Authority
CN
China
Prior art keywords
compound
energy ray
active energy
methyl
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201480037713.3A
Other languages
Chinese (zh)
Other versions
CN105358584B (en
Inventor
石崎慎治
冈本淳二
稲垣大
于越
江川良
小出昌史
有吉泰
小清水渉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyochem Co Ltd
Artience Co Ltd
Original Assignee
Toyo Ink SC Holdings Co Ltd
Toyochem Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2013173290A external-priority patent/JP6260143B2/en
Priority claimed from JP2013252456A external-priority patent/JP6303460B2/en
Priority claimed from JP2013252465A external-priority patent/JP5688519B1/en
Application filed by Toyo Ink SC Holdings Co Ltd, Toyochem Co Ltd filed Critical Toyo Ink SC Holdings Co Ltd
Priority to CN201810249292.0A priority Critical patent/CN108424745B/en
Priority claimed from PCT/JP2014/067786 external-priority patent/WO2015002269A1/en
Publication of CN105358584A publication Critical patent/CN105358584A/en
Application granted granted Critical
Publication of CN105358584B publication Critical patent/CN105358584B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/24—Organic non-macromolecular coating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a novel active-energy-ray-polymerizable resin composition having excellent adhesiveness, and a laminate using the same, the laminate being, in particular, a laminate for an optical device and having better punching workability and durability to heat and humidity than in the past. The present invention relates to: an active-energy-ray-polymerizable resin composition containing an [alpha], [belta]-ethylenic unsaturated double bond group-containing compound (M) and boric acid and/or a boric acid derivative; an active-energy-ray-polymerizable resin composition containing a cationic-polymerizable compound (K), boric acid and/or a boric acid derivative, and a cationic polymerization initiator (KE); and also an active-energy-ray-polymerizable resin composition using both the [alpha], [belta]-ethylenic unsaturated double bond group-containing compound (M) and the cationic-polymerizable compound (K), and containing boric acid and/or a boric acid derivative.

Description

Active energy ray polymer resin composition and duplexer
Technical field
The present invention relates to a kind of active energy ray polymer resin composition being suitable for the novelty of caking agent or coating agent and the duplexer using said composition.
Background technology
Active energy ray polymer resin composition due to polymerization velocity fast, in addition, usually can solvent-free state use, so there is workability excellence and then the characteristic such as the energy level required when being polymerized be low.Representative, active energy ray polymer resin composition contains can utilize active energy ray and the resinous principle that is polymerized and have α, the monomer component of β-ethene unsaturated double-bond base.
Described resinous principle utilizes polyester based resin, polyurethane(s) system resin, gathers the lower molecular weight such as epoxy system resin and polyacrylic based resin and have α in molecular end, the oligopolymer of β-ethene unsaturated double-bond base.Utilize the irradiation of active energy ray, the polymerization together with described resinous principle of described monomer component, but to polymerization terminates, can be used as solvent and play function.Therefore, described active energy ray polymerizing resin has does not need solvent in addition, can not produce the advantage of the volatilization of solvent thus when film is formed.
In addition, in recent years, the prosperity and the universalization that comprise the information communication machine of the display unit such as indicating meter are astonishing.In these display unit, require the performance and the raising productivity that improve coating agent, caking agent or sealing agent etc. further, propose there is the multiple motion using active energy ray polymeric materials.In this kind of display unit; usually use according to purposes to prevent from the anti-reflective film of the reflection of external light source or in order to prevent the multiple films such as the protective membrane (protectfilm) of the damage on the surface of display unit; such as; at formation liquid-crystal display (LiquidCrystalDisplay; LCD), in liquid crystal cells component, Polarizer or phase retardation film is laminated with.
In addition, flat-panel monitor (flatpaneldisplay, FPD) is not only used as display unit, and can arrange the function of touch-screen to be used as input unit to the surface of described flat-panel monitor.Also protective membrane, anti-reflective film or tin indium oxide (indiumtinoxide, ITO) evaporation resin molding etc. are used on the touchscreen.
In addition, in display unit, from the back side, liquid crystal layer is irradiated and the backlight of its luminescence (backlight) mode is popularized, the lower face side of liquid crystal layer be equipped with edge-light (edgelight) type, immediately below the back light unit such as type.The back light unit of described edge-light type consists essentially of: as the wire el lamp of light source, be configured at along end the square tabular on lamp light guiding plate, be disposed in the light diffusing sheet of the face side of light guiding plate and be disposed in the prismatic lens of face side of light diffusing sheet.Recently, replace cooling pole lamp (ColdCathodeFluorescentLamp, CCFL) photodiode (lightemittingdiode of color reproduction or electric power saving excellence is used, LED) be used as light source, therefore the requirement of thermotolerance or dimensional stability improves further.
This kind of film is attached at via caking agent in adherend, and as duplexer used for optical elements, for display unit, active energy ray polymerizability caking agent uses as a kind of form.
Enumerate concrete example.The polarization element used in liquid-crystal display association area etc. normally will at polyvinyl alcohol (polyvinylalcohol, PVA) iodine is adsorbed with in or dyestuff person carries out uniaxial extension to manufacture, this polyethenol series polarization element shrinks because of heat or moisture, causes the decline of polarizing properties.Therefore, person is used as Polarizer to be fitted with protective membrane on the surface of PVA system polarization element.In the past, the caking agent in order to attach protective membrane on polarization element widely uses the aqueous solution (PVA system caking agent) (with reference to patent documentation 1, patent documentation 2) of polyvinyl alcohol resin.But aqueous adhesive needs drying step after coating, but due to the thermotolerance of PVA system polarization element low, so the long drying under needing low temperature, production efficiency is poor.Due to reason as above, propose replace water system caking agent and use the positively charged ion system active energy ray polymerizability caking agent (with reference to patent documentation 3) utilizing ultraviolet as active energy ray.
But positively charged ion system active energy ray polymerizability caking agent, owing to there is dark reaction after uv irradiation, so when rectangular hardening thing is coiled into web-like, easily produces the problem of curling tendency when there is keeping.And there is the impact of the moisture be easily subject in humidity when being polymerized sclerosis or caking agent and film in positively charged ion system active energy ray polymerizability caking agent, the problem that hardening state is easily uneven.Therefore, in order to show uniform hardening state, ambient moisture, from saying, strictly must manage the water ratio of caking agent or PVA system polarization element.Free base system active energy ray polymerizability caking agent due to this kind of problem fewer, so excellent, but usually curing shrinkage is large, is difficult to guarantee sufficient cementability.
But liquid crystal indicator expands along with its purposes and uses under circumstances, high heat resistance is required to the Polarizer forming liquid crystal indicator.Such as, in the liquid crystal indicator of the vehicle-mounted types such as auto navigation (carnavigation), require high resistance to heat durability.
In high temperature environments, if cementability is weak, then due to the difference of the percent thermal shrinkage of PVA system polarization element and protective membrane, and the problem that PVA system polarization element and protective membrane peel off can be produced.
Disclose in patent documentation 4 and have a kind of active energy ray polymerizability caking agent; it contains the hardening composition relevant with the compound with (methyl) acryl comprising N-hydroxyethyl acrylamide and N-acryloyl morpholine, and the Tg of bond layer after sclerosis is more than 60 DEG C.The endurance quality that Polarizer requires is become strict, under high humidity and under high temperature, requires the weather resistance under harsher environment.But, in described Polarizer, the weather resistance under described harsh and unforgiving environments cannot be met.
And then; in recent years; the filming of polarization element or protective membrane advances; when utilizing the active energy ray polymerizability caking agent containing the hardening composition relevant with the compound with (methyl) acryl to form Polarizer; because the curing shrinkage of caking agent is large, so gauffer or concavo-convex can be produced on Polarizer.
In addition, disclose in patent documentation 5 and have the ultraviolet active energy ray polymer resin composition of a kind of use, it comprises (methyl) acrylamide compound (A) and boric acid (B) without hydroxyl, but do not study about the strength deterioration caused by curing shrinkage, bonding strength etc. are insufficient.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 09-258023 publication
Patent documentation 2: Japanese Patent Laid-Open 2005-208456 publication
Patent documentation 3: Japanese Patent Laid-Open 2008-233874 publication
Patent documentation 4: Japanese Patent No. 4744496 publications
Patent documentation 5: Japanese Patent Laid-Open 2013-194083 publication
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide and be a kind ofly suitable for there is the active energy ray polymer resin composition of the novelty of superior adhesion and using its duplexer of caking agent or coating agent, particularly duplexer used for optical elements, described duplexer compared with in the past, punch process and the excellent in te pins of durability to heat or humidity.
The technique means of dealing with problems
The described problem of solution that the present inventor etc. are artificial and repeatedly carry out active research, found that, active energy ray polymer resin composition shown below can be utilized to reach described target, thus complete the present invention.
Namely, the present invention is a kind of active energy ray polymer resin composition, it is the active energy ray resin combination comprising polymerizable compound and boric acid and/or boric acid derivatives, and this polymerizable compound is for being selected from by least one in the cohort formed containing the compound (M) of α, β-ethene unsaturated double-bond base and cationically polymerizable compound (K).
1st aspect of the present invention is a kind of active energy ray polymer resin composition, it is the active energy ray resin combination comprising polymerizable compound and boric acid and/or boric acid derivatives, and this polymerizable compound is the compound (M) containing α, β-ethene unsaturated double-bond base.
The active energy ray polymer resin composition of the 1st aspect of the present invention preferably comprises at least one initiator in the cohort being selected from and being made up of active energy ray polymerization starter (KE) and active energy ray polymerization starter (RE).
In addition, 2nd aspect of the present invention is a kind of active energy ray polymer resin composition, it is the active energy ray resin combination comprising polymerizable compound and boric acid and/or boric acid derivatives, and this polymerizable compound is cationically polymerizable compound (K), and also containing cationic polymerization initiators (KE).
In addition, 3rd aspect of the present invention is the active energy ray resin combination comprising polymerizable compound and boric acid and/or boric acid derivatives, and this polymerizable compound is the compound (M) and the cationically polymerizable compound (K) that contain α, β-ethene unsaturated double-bond base.
The active energy ray polymer resin composition of the 3rd aspect of the present invention preferably comprises at least one initiator in the cohort being selected from and being made up of active energy ray polymerization starter (KE) and active energy ray polymerization starter (RE).
In active energy ray polymer resin composition of the present invention, containing α, the compound (M) of β-ethene unsaturated double-bond base is preferably inclusion compound (X), and described compound (X) is containing hydroxyl and containing α, β-ethene unsaturated double-bond base.
In addition, the compound (M) containing α, β-ethene unsaturated double-bond base is preferably inclusion compound (Y), and described compound (Y) is containing amino and containing α, β-ethene unsaturated double-bond base.
And then, containing α, the compound (M) of β-ethene unsaturated double-bond base preferably comprises containing α, the compound (C) of β-ethene unsaturated double-bond base, described compound (C) comprises the naphthenic hydrocarbon skeleton and/or cyclic olefin backbone with more than 2 ring structures.
The described compound (M) containing α, β-ethene unsaturated double-bond base preferably comprises the oligopolymer (D) that weight average molecular weight is 300 ~ 30,000.
In active energy ray polymer resin composition of the present invention, cationically polymerizable compound (K) preferably comprises oxirane compound (k1).
Described oxirane compound (k1) preferably comprises the oxirane compound (k1-1) with aromatic nucleus.
Active energy ray polymer resin composition of the present invention is preferably, and boric acid derivatives has the hydroxyl of more than 3 in 1 molecule.
In addition, active energy ray polymer resin composition of the present invention is preferably in said composition 100 weight part, the described boric acid containing 0.1 weight part ~ 20 weight part and/or boric acid derivatives.
The present invention relates to a kind of caking agent or coating agent, it comprises described active energy ray polymer resin composition.
The present invention relates to a kind of duplexer, it is the duplexer wherein simultaneously or on the two sides layer comprising described active energy ray polymer resin composition being laminated in base material (F).
Described base material (F) is preferably selected from least one in the cohort be made up of poly-acetylcellulose mesentery, polynorbornene mesentery, polypropylene mesentery, polyacrylic acid mesentery, polycarbonate mesentery, polyester mesentery, polyvinyl alcohol mesentery and polyimide mesentery.
The present invention relates to a kind of duplexer used for optical elements, it uses described duplexer to form.
The effect of invention
Active energy ray polymer resin composition of the present invention can provide compared with in the past, the duplexer, particularly duplexer used for optical elements of punch process and the excellent in te pins of durability to heat or humidity.
Embodiment
The present invention is a kind of active energy ray polymer resin composition, it is the active energy ray resin combination comprising polymerizable compound and boric acid and/or boric acid derivatives, and this polymerizable compound is for being selected from by least one in the cohort formed containing the compound (M) of α, β-ethene unsaturated double-bond base and cationically polymerizable compound (K).
Active energy ray polymer resin composition of the present invention is preferably contained in active energy ray polymerizability caking agent or active energy ray polymerizability coating agent.
In addition; in the present invention; when being expressed as " (methyl) acryl ", " (methyl) vinylformic acid ", " (methyl) acrylate ", " (methyl) acryloxy " and " (methyl) allyl group "; as long as no special instructions, then " acryl and/or methacryloyl ", " vinylformic acid and/or methacrylic acid ", " acrylate and/or methacrylic ester ", " acryloxy and/or methacryloxy " and " allyl group and/or methacrylic " is represented respectively.
Below, example of the present invention (the 1st aspect ~ the 3rd aspect) is described.
(explanation of the 1st aspect)
First, to by boric acid and/or boric acid derivatives and containing α, the compound (M) of β-ethene unsaturated double-bond base and active energy ray polymer resin composition (following, be sometimes referred to as " free base system active energy ray polymer resin composition "; In addition, " resin combination " is sometimes referred to as " caking agent " or " coating agent ") be described.
Free base system active energy ray polymer resin composition of the present invention comprises: containing the compound (M) of α, β-ethene unsaturated double-bond base and boric acid and/or boric acid derivatives.
The compound (M) containing α, β-ethene unsaturated double-bond base becoming the principal constituent of free base system active energy ray polymer resin composition comprises all compounds containing α, β-ethene unsaturated double-bond in molecule.With regard to the reactive viewpoint utilizing active energy ray; containing α; the compound (M) of β-ethene unsaturated double-bond is preferably designed to α contained in active energy ray polymer resin composition; in the gross weight of β-ethene unsaturated double-bond, (methyl) acryloyl fiduciary point 50 % by weight ~ 100 % by weight.
As compound (M), specifically, preferably comprise the compound of more than a kind in the cohort being selected from and being made up of following compound: containing hydroxyl containing α, the compound (X) of β-ethene unsaturated double-bond base, containing amino containing α, the compound (Y) of β-ethene unsaturated double-bond base, comprise the naphthenic hydrocarbon skeleton with more than 2 ring structures and/or cyclic olefin backbone containing α, the compound (C) of β-ethene unsaturated double-bond base and weight average molecular weight are the oligopolymer (D) of 300 ~ 30,000.
First, the compound (X) (hereinafter referred to as compound (X)) containing α, β-ethene unsaturated double-bond base containing hydroxyl is described.Compound (X) produces bond with boric acid and/or boric acid derivatives, forms crosslinked film after hardening with active energy ray.In addition, compound (X) has following effect: form bond via boric acid and/or boric acid derivatives with the surface functionalities of base material (F), makes cementability good.
Compound (X) is as long as have the compound of hydroxyl in its structure, then there is no particular restriction, include, for example: (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxybutyl, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 8-hydroxyl monooctyl ester, (methyl) vinylformic acid 12-hydroxylauric ester, (methyl) acrylic acid ethyl-α-(hydroxymethyl) ester, simple function (methyl) glycerol acrylate, or fatty acid ester system (methyl) acrylate such as (methyl) glycidyl base laurate, or for described containing hydroxyl containing α, the compound of β-ethene unsaturated double-bond base, be there is at end by the open loop addition of 6-caprolactone (methyl) acrylate of hydroxyl, or aliphatics (methyl) esters of acrylic acid to the described compound containing α, β-ethene unsaturated double-bond base containing the hydroxyl oxirane such as addition of ethylene oxide, propylene oxide, butylene oxide ring and the hydroxyls such as oxirane addition (methyl) acrylate that obtains repeatedly,
Cyclohexanedimethanol list (methyl) acrylate, list (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group methyl esters, phthalic acid (methyl) vinylformic acid monohydroxy ethyl ester, (methyl) vinylformic acid 2-(4-benzoyl-3-hydroxyphenoxy) ethyl ester etc. have (methyl) esters of acrylic acid of hydroxyl and ring texture;
Hydroxyethyl vinyl ether, hydroxydecyl Vinyl Ether etc. repeatedly addition have the aliphatic ethylene ethers at end with hydroxyls such as the oxirane addition system Vinyl Ethers of hydroxyl of oxirane;
(methyl) vinyl carbinol, isopropenyl alcohol, dimethyl (methyl) vinyl carbinol, hydroxyethyl (methyl) allyl ether or repeatedly addition have aliphatics (methyl) allyl alcohol at end with hydroxyls such as oxirane addition system (methyl) allyl ethers of hydroxyl or (methyl) allyl ethers of the oxirane such as oxyethane or propylene oxide;
Propylene glycol, butylene glycol, two (methyl) glycerol acrylate etc. have the compounds containing α, β-ethene unsaturated double-bond base of multiple hydroxyl;
(methyl) acrylic amide containing hydroxyl such as N-hydroxyethyl (methyl) acrylamide, N-hydroxypropyl (methyl) acrylamide;
Vinyl alcohols etc. have the monomer class etc. of hydroxyl and vinyl, but are not particularly limited to these compounds.These compounds can only use a kind, or also can and with multiple.
With regard to the viewpoint of the cementability with base material, compound (X) is particularly preferably: (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxybutyl, cyclohexanedimethanol list (methyl) acrylate, addition have the compound containing α, β-ethene unsaturated double-bond base of the carbon numbers 2 ~ 18 such as (methyl) vinylformic acid 2-hydroxy methacrylate of the 6-caprolactone of 1mol ~ 2mol.
Then, be described containing the amino compound (Y) containing α, β-ethene unsaturated double-bond base.
In the present invention, α is contained containing amino, the compound (Y) (hereinafter referred to as compound (Y)) of β-ethene unsaturated double-bond base is compound that is amino containing at least one in molecule and at least one α, β-ethene unsaturated double-bond base.The amino of compound (Y) and boric acid described later and/or boric acid derivatives interact, as non-water system active energy ray polymeric composition and obtain stable and uniform liquid characteristic.Further, when being used as active energy ray polymerizability caking agent of the present invention or coating agent by described interaction, large effect being brought to the raising of cementability, the good coating oxidant layer such as thermotolerance or water tolerance or bond layer can be formed.
This kind of compound (Y) can be enumerated: acyclic containing amino containing α, the compound (y1) of β-ethene unsaturated double-bond base and the compound (y2) containing α, β-ethene unsaturated double-bond base containing amino of ring-type.
The acyclic compound (y1) containing α, β-ethene unsaturated double-bond base containing amino include, for example: (methyl) vinylformic acid-mono-or two-alkylamino ester classes such as (methyl) vinylformic acid monomethylaminoethylester, (methyl) acrylate;
The list such as mono-methyl amino ethyl (methyl) acrylamide, diethyl amino propyl (methyl) acrylamide or two-alkylaminoalkyl group (methyl) acrylamide etc.
Can enumerating containing the amino compound (y2) containing α, β-ethene unsaturated double-bond base of ring-type: ring-type containing amino and compound (y2-I) containing (methyl) acryl, ring-type containing amino and compound (y2-II) containing vinyl, ring-type containing amino and containing (methyl) allylic compound (y2-III).
Include, for example containing amino and containing (methyl) acryl compound (y2-I) of ring-type: polynuclear planes such as 2-(2 '-hydroxyl-5 '-(methyl) acryloyl-oxyethyl phenyl)-2H-benzotriazole, 2-(2 '-hydroxyl-3 '-tertiary butyl-5 '-(methyl) acryloyl-oxyethyl phenyl)-2H-benzotriazole and there is amino (methyl) esters of acrylic acid;
2,4-phenylbenzene-6-[2-hydroxyl-4-{2-(methyl) acryloyloxyethoxy }]-symmetrical triazine, 2, two (2,4-diethyl the phenyl)-6-of 4-[2-hydroxyl-4-{2-(methyl) acryloyloxyethoxy }]-symmetrical triazine etc. has (methyl) esters of acrylic acid of six-ring amino;
Acrylate and methacrylic ester [are referred to as and are recited as (methyl) acrylate by (methyl) vinylformic acid pentamethvl ester; Record similarly in the following], (methyl) vinylformic acid tetramethyl piperidine ester, (methyl) vinylformic acid 4-(pyrimidine-2-base) piperazine-1-base ester etc. have (methyl) esters of acrylic acid etc. of alicyclic ring amino.
More specifically, amino and containing vinyl the compound (y2-II) that contains of ring-type include, for example: 2-vinyl pyrrole, 1-vinyl-2-tetrahydroglyoxaline, 2-vinyl-2-tetrahydroglyoxaline, 1-vinyl imidazole, 3-methyl-5-phenyl-1-vinyl pyrazoles etc. have the compounds containing vinyl of five-ring amino;
2-vinyl piperazine, 4-vinyl piperazine, 2-vinyl pyridine, 4-vinylpridine, 2-vinyl pyrimidine, 2-vinyl-4,6-diamino-1,3,5-triazines etc. have the compounds containing vinyl of six-ring amino;
1-vinyl indoles, 1-vinyl-1H-benzoglyoxaline, 2-vinylquinoline, 2-vinyl isoquinoline 99.9,2-vinyl quinoxaline, 2-vinyl quinazoline, 2-vinyl cinnolines, 1-vinylcarbazole etc. have the compounds containing vinyl of many rings amino;
1-methyl-4,5-divinyl-1H-imidazoles, 2,6-divinyl pyridine etc. have the compounds of cyclic amino and two or more vinyl.
More specifically, containing amino and containing (methyl) allylic compound (y2-III) of ring-type include, for example: 1-(methyl) allyl group-1H-imidazoles, the bromo-1-1-of 5-(methyl) allyl group-1H-pyrazoles, 1-(methyl) allyl group piperazine, N-(methyl) allyl group-4, chloro-1, the 3-5-triazine-2-amine of 6-bis-etc. have cyclic amino containing (methyl) allylic compounds;
2-(methyl) allyl group-1H-indoles, 1-(methyl) allyl group-1H-benzoglyoxaline, 2-(methyl) allyl indazole, 1,2-bis-(methyl) allyl group-1,2-dihydro-isoquinoline, 9-(methyl) allyl group-9H-carbazole etc. have many rings amino containing (methyl) allylic compounds etc.
Just consider with the viewpoint of the cementability as the various base materials (F) when active energy ray polymerizability caking agent or coating agent, more acyclic containing amino containing α, the compound (y1) of β-ethene unsaturated double-bond base, the compound (Y) used in the present invention is more preferably the compound (y2) containing α, β-ethene unsaturated double-bond base containing amino of ring-type.Wherein, when with compound (Y) beyond compound (M) and with and make active energy ray Polymerizable composition, be preferably ring-type containing amino and containing vinyl compound (y2-II).
Compound (y2-II) due to be used as compound (M) containing the relative response speed of compound of acryl or the difference of backbone structure; coating structure after the active energy ray polymerization of active energy ray polymer resin composition easily forms micro phase separation structure, especially easily forms island structure.Therefore, become the coating structure having elasticity and stress relaxation concurrently, so when being used as active energy ray polymerizability caking agent, not only show the high density of access caused by high cohesion or high adhesion, and by change from the outside atmosphere of pole low temperature to very high temperature or moistening caused floating or peel off is suppressed, practicality can be maintained, therefore most preferably.
In addition, if the α of compound (Y), β-ethene unsaturated double-bond base is (methyl) allyl group (y2-III), then easily form micro phase separation structure but speed of response slow, the polymer that therefore there is film quantizes to become insufficient situation.Therefore, when being used as active energy ray polymerizability caking agent, the situation that the cohesion that there is decline or the adhesive linkage easily producing weather resistance destroys.The preferred sequence of the α of the compound (Y) of the micro phase separation structure of easy formation film, β-ethene unsaturated double-bond base is: vinyl (y2-II) > (methyl) allyl group (y2-III) > (methyl) acryl (y2-I).
And then the ring structure containing more than 1 nitrogen-atoms in the molecule of compound (Y) is preferably more than 5 rings.If 3 rings, 4 rings, then exist and utilize heat or active energy ray and cause the situation of ring-opening reaction.
α is contained as containing amino, the compound (Y) of β-ethene unsaturated double-bond base, 2-vinyl pyrrole, 1-vinyl-2-tetrahydroglyoxaline, 2-vinyl-2-tetrahydroglyoxaline, 1-vinyl imidazole, 2-vinyl piperazine, 4-vinyl piperazine, 2-vinyl pyridine, 4-vinylpridine, 1-vinyl indoles, 1-vinyl-1H-benzoglyoxaline, 2-vinylquinoline, 2-vinyl isoquinoline 99.9,2-vinyl quinoxaline, 2-vinyl quinazoline, 2-vinyl cinnolines, 1-vinylcarbazole industrially and in price are most preferably.
In addition, the compound (C) (hereinafter referred to as compound (C)) containing α, β-ethene unsaturated double-bond base comprising naphthenic hydrocarbon skeleton and/or the cyclic olefin backbone with more than 2 ring structures is described.Compound (C) preferably has the α of the naphthenic hydrocarbon skeleton of more than 2 and/or cyclic olefin backbone and more than 1, the compound of β-ethene unsaturated double-bond.Compound (C) can be enumerated: the compound (c1) that each ring structure of more than 2 as the naphthenic hydrocarbon skeleton and/or cyclic olefin backbone with more than 2 ring structures is separated each other by alkyl or ether, ester group etc. and the compound (c2) with norbornane or norbornylene skeleton, there is adamantane structure compound (c3) as, there is the compound of the bridge crosslinking structure of ring ring.In these compounds, with regard to the aspect of excellent heat resistance, the compound (c2) with norbornane or norbornylene skeleton or the compound (c3) with adamantane framework are better than compound (c1).
Comprise the naphthenic hydrocarbon skeleton and/or cyclic olefin backbone with more than 2 ring structures and this ring structure be separated with ring structure containing α, the compound (c1) of β-ethene unsaturated double-bond base has the diacrylate or 3,3-Bicyclopropyl acrylate etc. of hydrogenated biphenyl phenol A.
Have norbornylene and/or norbornane skeleton containing α, the compound (c2) of β-ethene unsaturated double-bond base is as long as have norbornylene skeleton and/or the norbornane skeleton of more than 1, and more than 1 ethene unsaturated double-bond, include, for example: (methyl) vinylformic acid dicyclopentenyl ester, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester, (methyl) vinylformic acid two ring pentyl ester, dihydroxymethyl bicyclopentane two (methyl) acrylate, Tricyclodecane Dimethanol (methyl) acrylate, (methyl) isobornyl acrylate etc.
In described compound (c2), the compound (c2 ') particularly with more than 3 cyclic skeletons suppresses curing shrinkage by increasing volume, bonding force also improves, therefore particularly preferably, concrete compound (c2 ') is: (methyl) vinylformic acid dicyclopentenyl ester, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester, (methyl) vinylformic acid two ring pentyl ester, dihydroxymethyl bicyclopentane two (methyl) acrylate etc.
What have adamantane framework contains α, the compound (c3) of β-ethene unsaturated double-bond base is the free-radical polymerised compound with more than 3 cyclic skeletons identical with described compound (c2 '), and thermotolerance and cementability improve.Concrete compound (c3) can be enumerated: (methyl) vinylformic acid 3-hydroxyl-1-adamantane esters, (methyl) vinylformic acid 2-methyl-2-adamantane esters, (methyl) vinylformic acid 2-ethyl-2-adamantane esters, (methyl) vinylformic acid 2-propyl group-2-adamantane esters, (methyl) vinylformic acid 3, 5-dihydroxyl-1-adamantane esters, 1, 3-adamantyl glycol two (methyl) acrylate, three (methyl) vinylformic acid 1, 3, 5-adamantane esters, two (methyl) vinylformic acid 3-hydroxyl-1, 5-adamantane esters, (methyl) vinylformic acid 3, 5-dihydroxyl-1-adamantane esters etc.Wherein, with regard to aspect excellent in adhesion, be preferably vinylformic acid 3-hydroxyl-1-adamantane esters, vinylformic acid 2-methyl-2-adamantane esters, vinylformic acid 2-ethyl-2-adamantane esters that α, β-ethene unsaturated double-bond is 1.
And then, the oligopolymer (D) (hereinafter referred to as oligopolymer (D)) that weight average molecular weight is 300 ~ 30,000 is described.First, oligopolymer (D) does not comprise described compound (X), compound (Y), compound (C) and compound (m) described later.Oligopolymer (D) is preferably selected from the oligopolymer of more than at least one in the cohort be made up of Polyester oligopolymer (d1), polyurethane(s) system oligopolymer (d2) and poly-epoxy oligopolymer (d3), can use with no particular limitation.
Polyester oligopolymer (d1) can be the hydroxyl in the end of the polyester by obtaining at main chain backbone polycondensation polyprotonic acid and polyvalent alcohol or polyester chain, with there is in (methyl) vinylformic acid, maleic acid equimolecular the esterification of the compound containing α, β-ethene unsaturated double-bond base of more than 1 carboxyl and the compound that obtains.Another example also can be by the carboxyl in the end of polyester or polyester chain, with the esterification of the described compounds (X) such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester and the compound obtained.In addition, the polyester oligomer etc. obtained by acid anhydrides, (methyl) glycidyl acrylate and the compound with at least one hydroxyl also can be used as polyester oligomer (d1).
Described polyprotonic acid can enumerate fatty family, alicyclic ring family and fragrant family, can use with no particular limitation respectively.More specifically, fat family polyprotonic acid include, for example: oxalic acid, propanedioic acid, succinic acid, hexanodioic acid, sebacic acid, nonane diacid, suberic acid, maleic acid, chlorine maleic acid, FUMARIC ACID TECH GRADE, dodecanedioic acid, pimelic acid, citraconic acid, pentanedioic acid, methylene-succinic acid, Succinic anhydried, MALEIC ANHYDRIDE etc., can use these aliphatic dicarboxylic acids or its acid anhydride.
In addition, the derivative of Succinic anhydried such as also can utilize: pyrovinic acid acid anhydride thing, 2,2-dimethyl succinic acid acid anhydrides, butyl Succinic anhydried, phenylsuccinic acid acid anhydride;
The derivative of Pyroglutaric acid such as also can use: Pyroglutaric acid, 3-allyl group Pyroglutaric acid, 2,4-dimethylated pentanedioic acid acid anhydrides;
The derivative of MALEIC ANHYDRIDE such as also can utilize: the acid anhydride derivatives such as 2-methyl-maleic acid acid anhydride, 2,3-dimethyl maleate acid anhydrides, butyl MALEIC ANHYDRIDE, dodecyl MALEIC ANHYDRIDE, phenyl MALEIC ANHYDRIDE.
More specifically, alicyclic ring family polyprotonic acid such as can use: alicyclic dicarboxylic acid or its acid anhydride etc.These alicyclic ring family polyprotonic acids include, for example: dimeracid, cyclopropane-1 α, 2 α-dicarboxylic acid, tetramethylene-1 α, 2 β-dicarboxylic acid, (1R)-pentamethylene-1 β, 2 α-dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1, the saturated alicyclic dicarboxylic acids such as 1-suberane dicarboxylic acid, cubane-Isosorbide-5-Nitrae-dicarboxylic acid, 2,3-norbornane dicarboxylic acid, six hydrogen terephthalic acids, six hydrogen m-phthalic acids, hexahydrophthalic acid, tetrahydrophthalic acid; And
1-cyclobutene-1,2-dicarboxylic acid, 4-cyclopentenes-1,3-dicarboxylic acid, 1-tetrahydrobenzene-1,2-dicarboxylic acid, 2,5-hexadiene-1 α, 4 α-dicarboxylic acid etc. has the unsaturated cycloaliphatic dicarboxylic acid of 1 or 2 unsaturated double-bond in ring.
In addition, alicyclic dicarboxylic acid's acid anhydride also can use: the derivative of hexahydrophthalic anhydride, such as 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, and the derivative of Tetra Hydro Phthalic Anhydride, such as 1,2,3,6-Tetra Hydro Phthalic Anhydride, 3-methyl isophthalic acid, 2, the hydrogenated phthalic anhydride derivatives such as 3,6-Tetra Hydro Phthalic Anhydride.
More specifically, fragrant family polyprotonic acid such as can use: aromatic dicarboxylic acid or its acid anhydride etc.Aromatic dicarboxylic acid include, for example: o-phthalic acid, m-phthalic acid, terephthalic acid, toluene dicarboxylic acid, 2, 5-dimethyl terephthalic acid, 4, 4-diphenyldicarboxylic acid, 1, 4-naphthalene dicarboxylic acids, norbornene dicarboxylic acids, ditan-4, 4 '-dicarboxylic acid, phenyl indane dicarboxylic acid, 1, 2-Azulene dicarboxylic acid, 1, 3-Azulene dicarboxylic acid, 4, 5-Azulene dicarboxylic acid, (-)-1, 3-ethane closes naphthalene dicarboxylic acids, 1, 4-anthracene dicarboxylic acid, 1, the luxuriant and rich with fragrance dicarboxylic acid of 2-, and 3, 9-perylene dianhydride carboxylic acid, aromatic dicarboxylic acid acid anhydride can be enumerated: Tetra hydro Phthalic anhydride, 4-methyl nadic anhydride.
And then, polyprotonic acid also can use: hexachloroendomethylene-tetrahvdrophthalic anhydride (chlorendicanhydride), hexachloroendomethylene-tetrahvdrophthalic anhydride (HETanhydride), diphenyldicarboxylic acid's acid anhydride, interior methylene radical tetrahydrophthalic anhydride (himicanhydride), interior methylene radical-1, 2, 3, 6-Tetra Hydro Phthalic Anhydride, methyl-3, methylene radical-1 in 6-, 2, 3, 6-Tetra Hydro Phthalic Anhydride, 1, 2-cyclohexane dicarboxylic acid acid anhydride, 1-cyclopentenes-1, 2-dicarboxylic anhydride, tetrahydrotoluene dicarboxylic anhydride, 1, 8-naphthalene dicarboxylic acids acid anhydride, octahydro-1, 3-dioxo-4, the anhydrides such as 5-isobenzofuran dicarboxylic anhydride.
In addition, polyvalent alcohol can be enumerated: number average molecular weight (Mn) be about 50 ~ 500 more low-molecular-weight polyalcohols or number average molecular weight (Mn) be about 500 ~ 30, the polyalcohols of the ratio higher molecular weight of 000, can use respectively with no particular limitation.
More specifically, more low-molecular-weight polyalcohols include, for example: ethylene glycol, propylene glycol, dipropylene glycol, Diethylene Glycol, triethylene glycol, butyleneglycol, 3-methyl isophthalic acid, 5-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 2-methyl isophthalic acid, 8-ethohexadiol, 3, 3 '-dihydroxymethyl heptane, 2-butyl-2-ethyl-1, ammediol, polyoxyethylene glycol (addition mole number is less than 10), polyoxypropylene glycol (addition mole number is less than 10), propylene glycol, 1, 3-butyleneglycol, 1, 4-butyleneglycol, 1, 5-pentanediol, 1, 6-hexylene glycol, 1, 9-nonanediol, neopentyl glycol, ethohexadiol, butyl ethyl pentanediol, 2-ethyl-1, 3-hexylene glycol, cyclohexanediol, cyclohexanedimethanol, Tricyclodecane Dimethanol, cyclopentadiene dimethanol, the aliphatics such as dimer diol or alicyclic diol class,
1, two (2-hydroxyl-oxethyl) benzene, 1 of 3-, two (2-hydroxyl-oxethyl) benzene, 1 of 2-, two (2-hydroxyl-oxethyl) benzene, 4 of 4-, 4 '-methylene radical biphenol, 4,4 '-(2-sub-norbornylene) biphenol, 4,4 '-dihydroxybiphenyl phenol, o-dihydroxy benzene, Meta-dihydroxybenzene and hydroquinol, 4,4 '-isopropylidene phenol, in bis-phenol addition have the aromatic diol classes etc. such as the add-on type bis-phenol of oxirane.
The raw materials bisphenol of described add-on type bis-phenol can enumerate dihydroxyphenyl propane, Bisphenol F etc., and raw material oxirane can enumerate oxyethane, propylene oxide etc.
More specifically, include, for example than the polyalcohols of higher molecular weight: high-molecular-weight poly ester polyol, superpolyamide polyvalent alcohol, high-molecular-weight polycarbonate polyvalent alcohol and high-molecular-weight poly urethane polyol.High-molecular-weight polycarbonate polyvalent alcohol is reaction by described more low-molecular-weight glycol and carbonic ether or phosgene and obtains.
The described polyalcohols than higher molecular weight also can be used as commercially available product and obtains.Such as, the commercially available product of described high-molecular-weight poly ester polyol can be enumerated: Kao Wapoli (KyowaPaul) series that the Kuraray polyvalent alcohol P series that Ba Yilong (Vylon) series that company of twisting flax fibers and weaving of Japan manufactures, Kuraray (Kuraray) company manufacture, consonance fermentation chemistry company manufacture.
The commercially available product of described superpolyamide polyvalent alcohol can use Fuji to change into the TPAE617 etc. of industrial's manufacture.
The commercially available product of described high-molecular-weight polycarbonate polyvalent alcohol include, for example: the Kuraray polyvalent alcohol PMHC series that the PCDL series that Losec Sigma (Oxymer) N112 that Bai Situo (Perstorp) company manufactures, chemical company of Asahi Chemical Industry manufacture, Kuraray company manufacture, Kuraray polyvalent alcohol C series etc.
The commercially available product of described high-molecular-weight poly urethane polyol include, for example: Ba Yilong (Vylon) the UR series that company of twisting flax fibers and weaving of Japan manufactures, Plutarch clarke (Takelac) E158 (hydroxyl value=20 that Mitsui Chemicals urethane company manufactures, acid number < 3), Plutarch clarke (Takelac) E551T (hydroxyl value=30, acid number < 3) and Plutarch clarke (Takelac) Y2789 (hydroxyl value=10, acid number < 2) etc.
In addition, the lactone such as polycaprolactone glycol, poly-(Beta-methyl-γ-valerolactone) glycol, poly-valerolactone glycol are carried out ring-opening polymerization and the polyester polyol etc. that obtains also can be used as described high molecular weight polyols.
Polyurethane(s) system oligopolymer (d2) also can be the isocyanate group making to have at least more than one compound, carry out reacting and the compound that obtains with described compound (X).In addition, another example also can be the compound that makes to have at least one isocyanate group and described polyvalent alcohol carries out reacting and obtains the carbamate prepolymer of terminal isocyanate group, then makes the compound that described carbamate prepolymer and described compound (X) carry out reacting and obtain.And then, another example also can be the compound that makes to have at least one isocyanate group and polyvalent alcohol carries out reacting and obtains the carbamate prepolymer of terminal isocyanate group, and then make described carbamate prepolymer carry out reacting with the compound of the amino with at least more than one and obtain the carbamate prepolymer of terminal isocyanate group, then make the compound that this carbamate prepolymer and described compound (X) carry out reacting and obtain.In addition, the urea bond base person obtained containing making isocyanate group carry out reacting with amino is also contained in polyurethane(s) system oligopolymer (d2).
The compound with at least one isocyanate group can be enumerated: simple function polymeric polyisocyanate and polyfunctional isocyanate.Concrete compound can be enumerated: aromatic poly-isocyanate, aliphatic polymeric isocyanate, aromatic-aliphatic polymeric polyisocyanate, alicyclic polymeric isocyanate etc.
More specifically, simple function polymeric polyisocyanate include, for example: methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, isocyanic acid ester in the last of the ten Heavenly stems, isocyanic acid stearyl, isocyanic acid stearyl ester, NSC 87419, phenylcarbimide, benzyl mustard oil, parachlorobenzyl isocyanic ester, isocyanic acid p-nitrophenyl ester, isocyanic acid (R)-(+)-Alpha-Methyl benzyl ester, isocyanic acid (R)-(+)-1-phenyl chlorocarbonate, isocyanic acid (S)-(-)-1-phenyl chlorocarbonate, tolysulfonyl based isocyanate etc.
In polyfunctional isocyanate, more specifically, aromatic poly-isocyanate include, for example: 1, 3-phenylene diisocyanate, two isocyanic acids 4, 4 '-diphenyl ester, 1, 4-phenylene vulcabond, 4, 4 '-diphenylmethanediisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4, 4 '-toluidine diisocyanate, 2, 4, 6-triisocyanate base toluene, 1, 3, 5-triisocyanate base benzene, dianisidine vulcabond, 4, 4 '-diphenyl ether diisocyanate, 4, 4 ', 4 "-triphenylmethane triisocyanates etc.
HDI (hexamethylenediisocyanate)), pentamethylene diisocyanate, 1 aliphatic polymeric isocyanate can be enumerated: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (another name:, 2-trimethylene diisocyanate, 2,3-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate, ten dimethylene diisocyanates, 2,4,4-trimethyl hexamethylene diisocyanate etc.
Aromatic-aliphatic polymeric polyisocyanate can be enumerated: ω, ω '-diisocyanate based-1,3-dimethyl benzene, Isosorbide-5-Nitrae-tetramethyl xylylen vulcabond etc.
Alicyclic polymeric isocyanate can be enumerated: 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (another name: IPDI (isophorone diisocyanate, isophoronediisocyanate)), 1,3-pentamethylene vulcabond, 1,3-cyclohexyl diisocyanate, 1,4-cyclohexyl diisocyanate, methyl-2,4-cyclohexyl diisocyanate, methyl-2,6-cyclohexyl diisocyanate, 4,4 '-methylene-bis (cyclohexyl isocyanate), Isosorbide-5-Nitrae-bis-(isocyanatomethyl) hexanaphthene etc.
In addition, also can and add zoarium with 2-methylpentane-2, the 4-glycol of described polymeric polyisocyanate, there is the part that the trimer etc. of isocyanurate ring is used as polyurethane(s) system oligopolymer (d2).In addition, polyphenylene methane polymeric polyisocyanate (another name: PAPI (polyphenylmethanepolyisocyanate), naphthalene diisocyanate and their polymeric polyisocyanate modifier etc. can be used.In addition, polymeric polyisocyanate modifier can use and have carbon imide base, uretdion, urea imido grpup, the biuret groups, any one group of isocyanurate group or the modifier of more than two kinds of these groups that react with water.The reactant of polyvalent alcohol and vulcabond also can be used as the compound with at least two isocyanate group and uses.
In addition, more specifically, there is amino compound such as can use: ethylene diamine, trimethylene diamine, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine, Triethylenetetramine (TETA), diethylenetriamine, triaminopropane, 2, 2, 4-trimethylhexamethylenediamine, 2, 2, 4-trimethylhexamethylenediamine, 2-hydroxyethyl ethylene diamine, hexamethylene-diamine 2-hydroxyethyl ethylene diamine, N-(2-hydroxyethyl) trimethylene diamine, (2-hydroxyethyl propylidene) diamines, (two-2-hydroxyethyl ethylidene) diamines, (two-2-hydroxyethyl propylidene) diamines, (2-hydroxypropyl ethylidene) diamines, (two-2-hydroxypropyl ethylidene) diamines, the aliphatic polyamine classes such as piperazine,
The ester ring type polyamines classes such as isophorone diamine, dicyclohexyl methyl hydride-4,4 '-diamines;
Phenylenediamine, xylylene amine, 2,4-first phenylenediamine, 2,6-first phenylenediamines, diethyl toluene diamine, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, 4, the aromatic diamines etc. such as 4 '-bis--(sec-butyl) ditan.
Poly-epoxy oligopolymer (d3) be compound by having glycidyl with (methyl) vinylformic acid, maleic acid equimolecular in there is the reaction of the compound containing α, β-ethene unsaturated double-bond base of more than 1 carboxyl and the compound that obtains.Typical example can be enumerated: bisphenol type, epoxidation oil type, phenol novolak type, alicyclic ring type.Bisphenol type gathers epoxy oligopolymer be the bisphenol type diglycidylether that obtains making bisphenols and Epicholorohydrin carry out reacting with (methyl) vinylformic acid equimolecular in there is more than 1 carboxyl the compound containing α, β-ethene unsaturated double-bond base carry out reacting and obtain.
Epoxidation oil type polycyclic oxygen system oligopolymer can use the reaction of the compound containing α, β-ethene unsaturated double-bond base by having more than 1 carboxyl in epoxidised soybean wet goods oil with (methyl) vinylformic acid, maleic acid equimolecular and winner.Phenol novolak type gathers epoxy oligopolymer can use the reaction of the compound containing α, β-ethene unsaturated double-bond base by having more than 1 carboxyl in phenol novolak type epoxy resin and (methyl) vinylformic acid equimolecular and winner.Alicyclic ring type gathers epoxy oligopolymer can use the reaction of the compound containing α, β-ethene unsaturated double-bond base by having more than 1 carboxyl in alicyclic type epoxy resin and (methyl) vinylformic acid equimolecular and synthesis person.
With regard to the consistency or good weather resistance (thermotolerance, humidity resistance) of other compositions in resin combination, condense density aspect with regard to, there is in molecule at least more than one α, the weight average molecular weight (hereinafter referred to as Mw) of the oligopolymer (D) of β-ethene unsaturated double-bond base is preferably the scope of 300 ~ 30,000.And then Mw is more preferably 400 ~ 20, the scope of 000.If the Mw of oligopolymer (D) is more than 30,000, then mobility declines, or also declines with the consistency of compound (M) beyond oligopolymer (D), and therefore the coating of active energy ray polymer resin composition declines.In addition, when making active energy ray polymerizability caking agent and coating agent, the cementability or the weather resistance that there is polymerization film decline, or the situation of film albefaction.When the Mw of oligopolymer (D) is less than 300, exist when by active energy ray polymerizability caking agent and coating agent, be laminated in various base material (F) etc. upper after, easily produce the situation of the cohesion destruction of bond layer and coating oxidant layer.
About contained containing α in active energy ray polymer resin composition of the present invention, the compound (M) of β-ethene unsaturated double-bond base, except described compound (Y), compound (X), compound (C) and oligopolymer (D), can optionally the compound (m) (hereinafter referred to as compound (m)) containing α, β-ethene unsaturated double-bond base be used to be used as other compositions.
Described compound (m) include, for example: (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, the just own ester of (methyl) vinylformic acid, (methyl) lauryl acrylate and (methyl) stearyl acrylate ester;
(methyl) cyclohexyl acrylate, (methyl) vinylformic acid 1-methyl isophthalic acid-ring pentyl ester, (methyl) vinylformic acid 2-oxo-1,2-phenylbenzene ethyl ester, (methyl) vinylformic acid (ethoxylation orthoxenol), (methyl) vinylformic acid 1-naphthyl ester, (methyl) vinylformic acid 2-anthryl ester and hexahydrophthalic acid 2-(methyl) acryloyloxyethyl ester etc. have 1 naphthenic hydrocarbon skeleton or cyclic olefin backbone or have (methyl) esters of acrylic acid of aromatic ring;
(methyl) vinylformic acid (methyl) allyl ester, (methyl) vinylformic acid 1-butylene ester, (methyl) vinylformic acid 3-chlorine-2-propylene, (methyl) vinylformic acid 2-propenyl lactoyl ester, (methyl) vinylformic acid 3,7-dimethyl oct-6-ene-1-base ester, (methyl) acrylic acid rosin ester, (methyl) vinylformic acid cassia bark base ester, vinylformic acid 2-(2-vinyloxyethoxy) ethyl ester and (methyl) vinyl acrylate etc. and then (methyl) esters of acrylic acid containing unsaturated group;
(methyl) perfluoroalkyl acrylate classes such as (methyl) perfluoroethyl methyl esters, (methyl) vinylformic acid 2-perfluoro-ethyl ethyl ester and (methyl) vinylformic acid 2-perfluor hexadecyl ethyl ester;
(methyl) glycidyl acrylate, (methyl) vinylformic acid 4-(glycidoxypropyl) butyl ester, (methyl) vinylformic acid (3-methyl-3-oxetanylmethoxy) methyl esters, (methyl) vinylformic acid-4-propyl group-2-oxo tetrahydropyran-4-base ester and (methyl) vinylformic acid-3,4-expoxycyclohexyl methyl esters etc. are containing (methyl) esters of acrylic acid of heterocycle with Sauerstoffatom;
(methyl) vinylformic acid (methoxycarbonyl) methyl esters, (methyl) vinylformic acid 2-(oxyethyl group carbonyl oxygen base) own ester, (methyl) vinylformic acid 2-(propoxy-carbonyl oxygen base) ethyl ester and (methyl) vinylformic acid 2-(octyloxy carbonyl oxygen base) butyl ester etc. have fatty family (methyl) esters of acrylic acid of 1 carbonyl;
(methyl) vinylformic acid 2-oxobutanoyl ethyl ester, (methyl) vinylformic acid 3-oxobutanoyl propyl ester, (methyl) vinylformic acid 2,3-bis-(oxobutanoyl) butyl ester, (methyl) vinylformic acid 2,3-bis-(oxobutanoyl) own ester and (methyl) vinylformic acid 2,3-bis-(oxobutanoyl) monooctyl ester etc. have fatty family (methyl) esters of acrylic acid of 2 carbonyls;
3-(methyl) acryloxypropyl dimethoxysilane, 3-(methyl) acryloxypropyl ethyldimethoxysilane and 3-(methyl) acryloxypropyl tripropoxy silane etc. are containing (methyl) esters of acrylic acid of alkoxysilane group;
(methyl) vinylformic acid 3-sulphopropyl and (methyl) sulfoethyl stearyl ester etc. are containing (methyl) alkyl-acrylates of alkylsulfonyl;
Ethylsulfuric acid (methyl) acryloxy dimethyl ethyl ammoniums etc. contain metal-salt or the ammonium salt of (methyl) esters of acrylic acid of alkylsulfonyl;
4 ~ 10) etc. (methyl) vinylformic acid acid phosphorus oxygen base ethyl ester and (methyl) vinylformic acid acid phosphorus oxygen hexadecyl ethylene oxide (ethyleneoxide addition mole number: containing (methyl) esters of acrylic acid of phosphonate group;
(methyl) vinylformic acid 2-methoxy acrylate, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-propoxy ethyl, (methyl) vinylformic acid 3-propoxy ethyl, (methyl) vinylformic acid 2-butoxyethyl, (methyl) vinylformic acid 3-butoxyethyl and (methyl) vinylformic acid 4-butoxyethyl etc. are containing (methyl) esters of acrylic acid of alkoxyl group;
(methyl) acrylic acid oxirane affixtures etc. are containing (methyl) acrylic acid derivative class of oxirane;
Two (methyl) vinylformic acid ethylene glycol, two (methyl) vinylformic acid triethylene glycol, two (methyl) vinylformic acid TEG, two (methyl) vinylformic acid 2, 2-dimethyl propyl glycol, two (methyl) dihydroxypropyl pivaloyl hydroxyl trimethylacetic acid ester, two (methyl) vinylformic acid 2, 5-hexylene glycol, two (methyl) vinylformic acid 1, 2-ethohexadiol, two (methyl) vinylformic acid 2, 2-diethyl-1, ammediol, and two (methyl) vinylformic acid 2, 5-dimethyl-2, 5-hexylene glycol etc. 2 official energy (methyl) esters of acrylic acid,
Three (methyl) vinylformic acid 1,2,3-glycerol, three (methyl) vinylformic acid Trimethylolhexane, three (methyl) vinylformic acid trishydroxymethyl octane and three (methyl) vinylformic acid 1,1,1-trihydroxy methyl ethane etc. 3 official energy (methyl) esters of acrylic acid;
Four (methyl) vinylformic acid tetramethylolmethane, four (methyl) vinylformic acid 2, two (hydroxymethyl) 1 of 2-, ammediol and seven (methyl) vinylformic acid 22, multifunctional (methyl) esters of acrylic acids such as two (hydroxymethyl) 1,3-PD polyalkylene oxides of 2-;
The vinyl esters of the carboxylic acids such as vinyl formate, vinyl-acetic ester, propionate, vinyl butyrate and stearic acid vinyl ester;
Etheric acid vinyl acetate, levulinic acid vinyl acetate, 2-acetoacetoxy groups hexyl Vinyl Ether and 2-acetoacetoxy groups octyl vinyl ether etc. have the fatty family vinyl compound class of acyl group;
The aliphatic ethylene ethers such as ethyl vinyl ether, 2-propyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl Vinyl Ether, n-hexyl, 2-ethylhexyl vinyl ether and stearyl Vinyl Ether;
The vinyl compound class that perfluoro-ethylene, perfluoro propylene, perfluor (propyl vinyl ether) and vinylidene fluoride etc. are fluorine-containing;
The compounds containing α, β-ethene unsaturated double-bond base containing alkoxysilane group such as (methyl) allyl chlorosilane and (methyl) allyltrimethoxysilanis;
Vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid and vinylsulfuric acid etc. are containing the sulphonic acids of thiazolinyl;
Metal-salt or the ammonium salt classes such as vinyl sulfonic acid ammonium, sodium vinyl sulfonate, vinyl sulfonic acid potassium and vinyl alkyl sodium sulfo-succinate;
The metal-salt of the 2-methyl-2-propenyl sulfonic acid such as 2-methyl-2-propenyl ammonium sulphonate and 2-methyl-2-propenyl sodium sulfonate or ammonium salt class;
(methyl) acrylic amide of the fatty families such as (methyl) acrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-butyl (methyl) acrylamide, crotonamide, maleinamide, fumaramide, mesaconoyl amine, citraconoyl amine, clothing health acid amides and 2-methylpropane-2-enoyl-amine;
N-methoxymethyl (methyl) acrylamide, N-methoxy ethyl (methyl) acrylamide, N-methoxyethyl (methyl) acrylamide, N-ethoxyl methyl (methyl) acrylamide, N-isopropoxy hexyl (methyl) acrylamide, N-butoxy octyl group (methyl) acrylamide, N, N-bis-(methoxymethyl) (methyl) acrylamide and N, N-bis-(ethoxyl methyl) (methyl) acrylamide etc. are containing (methyl) acrylic amide of N-alkoxyl group;
N-(2-oxobutanoyl ethyl) (methyl) acrylamide, N-(2-oxobutanoyl octyl group) (methyl) acrylamide and diacetone (methyl) acrylamide etc. have (methyl) acrylic amide of carbonyl;
(methyl) acrylamide sulfonic acid, the tertiary butyl-(methyl) acrylamide sulfonic acid and (methyl) acrylamide-2-methyl isophthalic acid-propanesulfonic acid etc. are containing (methyl) acrylic amide of sulfonic acid;
The compounds containing α, β-ethene unsaturated double-bond base containing itrile group such as (methyl) vinyl cyanide, clothing health nitrile, 2-vinyl cyanide and (methyl) 2 cyanoethyl acrylate;
(methyl) allyl ester class of acetic acid (methyl) allyl ester, saturated carboxylic acid such as propionic acid (methyl) allyl ester and vinyl pivalate etc.;
TRANSCINNAMIC ACID glycidyl ester, glycidyl allyl ether and 1,3-butadiene monocycle oxidative ethane etc. are containing the vinyl esters of glycidyl;
Etheric acid (methyl) allyl ester, levulinic acid (methyl) allyl ester, propionyl acetic acid (methyl) allyl ester and butyryl radicals acetic acid (methyl) allyl ester etc. have fatty family (methyl) the allylic cpd class of acyl group;
The vinyl esters such as vinylchlorid, vinylidene chloride and allyl chlorine;
Propadiene (allene), 1，2-butadiene, 1,3-butadiene and 2-methyl isophthalic acid, the dienes such as 3-divinyl;
Cis-succinic acid diallyl, 2-sub-methyne succinic acid diallyl, (E)-but-2-ene vinyl acetate, (Z)-octadec-9-enoic acid vinyl acetate and (9Z, 12Z, 15Z)-ten eight-9,12, the polyfunctional compounds containing α, β-ethene unsaturated double-bond base containing unsaturated link(age) such as 15-trienic acid vinyl acetate;
Ethene, propylene, 1-butylene, 2-butylene, 2-methacrylic, 1-tetradecylene, 1-30 alkene (1-triacontene), 1-tri-octadecylene (1-octatriacontene) and 1-40 alkene (1-tetracontene) etc. with and composition thereof;
The olefines etc. such as polybutene-1, polypenthylene-1 and poly 4-methylpene-1.Be not particularly limited to these compounds.These compounds can only use a kind, or also can and with multiple.
With regard to reactive viewpoint, described compound (m) preferably has the compound of (methyl) acryl.And then when being used as active energy ray polymerizability caking agent and coating agent, with regard to the viewpoint of active energy ray polymerization velocity, preferably comprising 2 officials can above (methyl) esters of acrylic acid.
In addition, at use (methyl) glycidyl acrylate, (methyl) vinylformic acid 4-(glycidoxypropyl) butyl ester, (methyl) vinylformic acid (3-methyl-3-oxetanylmethoxy) methyl esters, and (methyl) vinylformic acid-3, 4-expoxycyclohexyl methyl esters etc. contain (methyl) esters of acrylic acid with the heterocycle of Sauerstoffatom of 3 rings or 4 rings, be used as containing α, when the compound (m) of β-ethene unsaturated double-bond base, and then, be preferably optionally and and with known smooth acid producing agent (hereinafter sometimes referred to cationic polymerization initiators (KE)).Thus, be cross-linked, can be formed to heat or humidity excellent in te pins of durability adhesive linkage or coating oxidant layer.This kind of cationic polymerization initiators (KE) such as can illustrate: the sulfonium salts such as You Bagu (UVACURE) 1590 (manufacture of Daicel cyanogen spy (DaicelCytec) company) and CPI-110P (manufacture of Sanya general sieve (San-Apro) company), or the Iodonium salt etc. such as gorgeous good solid (IRGACURE) 250 (manufacture of Ciba (CibaSpecialtyChemicals) company), WPI-113 (manufacturing with Guang Chun medicine company) and Rp-2074 (Japanese sub-(RhodiaJapan) company in sieve ground manufactures).
As formation containing α, the preferred ratio of the composition of the compound (M) of β-ethene unsaturated double-bond base, be preferably when by active energy ray polymer resin composition containing α, when the total amount of the compound (M) of β-ethene unsaturated double-bond base is set to 100 % by weight, compound (X) is 0 % by weight ~ 70 % by weight, compound (Y) is 0 % by weight ~ 95 % by weight, compound (C) is 0 % by weight ~ 70 % by weight, oligopolymer (D) is 0 % by weight ~ 50 % by weight, and other containing α, the compound (m) of β-ethene unsaturated double-bond base is 0 % by weight ~ 50 % by weight.Wherein, be preferably compound (Y) and add up to more than 10 % by weight, less than 100 % by weight with compound (X).If compound (Y) is less than 10 % by weight with the total of compound (X), then exist and produce the poorly soluble of boric acid and/or boric acid derivatives, can not homogeneous system be become, or when liquid leaves standstill, the situation of the problem such as crystallization along with the process of time.
Boric acid contained in active energy ray polymer resin composition of the present invention and boric acid derivatives are described.Boric acid and boric acid derivatives have with containing hydroxyl containing α, the interaction of the compound (X) of β-ethene unsaturated double-bond base, and/or contain α with containing amino, the compound (Y) of β-ethene unsaturated double-bond base forms salt, even if not moisture or organic solvent, the solution of stable and uniform active energy ray polymerizability caking agent and coating agent also can be formed.Utilize active energy ray by after this caking agent and coating agent sclerosis, form boric acid and boric acid derivatives and derive from the hydroxyl of compound (X) and/or derive from the film of amino bond of compound (Y).In addition, boric acid and boric acid derivatives have the effect improving cementability with the surface functionalities bond of aftermentioned base material (F).Boric acid and boric acid derivatives can separately use, or can be used in combination.
As long as there is in boric acid derivatives 1 molecule of the present invention the compound of the B-O-H key of more than 1 or can be hydrolyzed in presence of water and form the multiple boron-containing compound of the B-O-H key of more than 1, then can unrestrictedly be suitable for using.Boric acid derivatives concrete but can enumerate in the example of indefiniteness: boric acid oxide compound (such as B 2o 3);
By the reaction of boric acid and alcohol or phenol and winner, such as: the borate esters such as trimethyl borate, triethyl borate, boric acid three n-propyl, tri-n-butyl borate, triphenyl borate, triisopropyl borate ester, boric acid three-tert-pentyl ester, triphenyl borate, trimethoxy-boron oxygen hydrocarbon trimer (trimethoxyboroxine), boric acid three-2-cyclohexyl cyclohexyl, triethanolamine borate, boric acid triisopropylamine, boric acid mannitol, boroglyceride and boric acid tri-isopropanolamine.
In addition, borated derivative is also wrapped in boric acid derivatives of the present invention.Include, for example: alkylboronic acids or the ene boric acids such as methyl-boron-dihydroxide, ethyl-boron dihydroxide, butyl boron dihydroxide and cyclohexyl boric acid;
The aryl boric acids such as phenyl-boron dihydroxide, naphthalene boronic acids and anthracene boric acid, or there is arbitrary substituent substituted type aryl boric acid on the aryl of these boric acid.
And then other the tertiary amine salt containing amino borate and boric acid is also useful.Can enumerate in this kind of boron-containing compound: 2-(the amino isopropoxy of beta-dimethyl-)-4, 5-dimethyl-1, 3, 2-dioxy boron penta ring, 2-(β-diethyl amino base oxethyl)-4, 4, 6-trimethylammonium-1, 3, 2-dioxaborinane, 2-(beta-dimethyl-amino ethoxy)-4, 4, 6-trimethylammonium-1, 3, 2-dioxaborinane, 2-(β-diisopropylaminoethyl oxyethyl group)-1, 3, 2-dioxaborinane, 2-(β-diisopropylaminoethyl oxyethyl group)-4-methyl isophthalic acid, 3, 2-dioxaborinane, 2-(γ-dimethylamino propoxy)-1, 3, 6, 9-tetra-oxygen-2-boron heterocycle undecane, and 2-(beta-dimethyl-amino ethoxy)-4, 4-(4-hydroxybutyl)-1, 3, 2-dioxaborinane, but be not limited to these compounds.
In addition, in boric acid derivatives, easily can dissociate in an aqueous medium at it and under forming the condition of boric acid, also can enumerate the metal-salt (i.e. boric acid metal) of boric acid.In the suitable example of boric acid metal, include, for example: lime borate, potassium borate (such as potassium metaborate, potassium tetraborate, potassium pentaborate, six potassium borates and eight potassium borates), Sodium Tetraborate (such as Sodium peroxoborate, sodium metaborate, hypoboric acid sodium, sodium tetraborate, sodium pentaborate, Sodium peroxoborate, six Sodium Tetraboratees and eight Sodium Tetraboratees).Similarly, ammonium borate is also useful.
And then, in boric acid derivatives, the organic oligomer containing boracic position and polymer compound can be enumerated.Such as preferably by the polymer, boron acid esters polymkeric substance (acrylate copolymer of such as hydroxyl functional group or polysiloxane polymer) of active hydrogen (such as containing), react with boric acid and/or boric acid ester, form the polymkeric substance with boric acid ester group and the compound obtained.
Become in the polymkeric substance of the raw material of polymer, boron acid esters, any one of the multiple polymkeric substance containing active hydrogen can be enumerated, such as, be preferably selected from least one in the cohort be made up of acrylate copolymer, polyester polymers, polyurethane polymer and polyether polymer.
With regard to deliquescent aspect, the boric acid used in the present invention or boric acid derivatives are preferably the tertiary amine salt of boric acid, boric acid ester, boric acid, with regard to the viewpoint of cementability, are particularly preferably boric acid.
In addition, in the present invention, boric acid derivatives preferably has the hydroxyl of more than 3 in 1 molecule.The boric acid derivatives in 1 molecule with more than 3 hydroxyls can be enumerated: Isosorbide-5-Nitrae-benzene hypoboric acid (hydroxyl value is 4), tetrahydroxy diboron hexahydride (hydroxyl value is 4) and triethanolamine borate salt (hydroxyl value is 3) etc.
When being set to 100 weight part containing the total amount of the compound (M) of α, β-ethene unsaturated double-bond base, the boric acid used in the present invention and/or the usage quantity of boric acid derivatives will be preferably below more than 0.1 weight part, 20 weight parts.
If be less than 0.1 weight part, then cannot show required bonding force, if more than 20 weight parts, then exist to produce and separate out along with the process of time, or rise and the situation of the problems such as gelation as the excess stickiness of solution.
Especially more than 0.3 weight part is preferably, below 12 weight parts.Be particularly preferably below more than 0.3 weight part, 7 weight parts.
In addition, in considering in active energy ray polymeric composition 100 weight part, boric acid and/or boric acid derivatives are preferably 0.1 weight part ~ 20 weight part, are particularly preferably 0.3 weight part ~ 12 weight part.Especially 0.3 weight part ~ 7 weight part is preferably.
Active energy ray polymer resin composition also can comprise active energy ray polymerization starter (E).Active energy ray polymerization starter (E) can be enumerated: radical polymerization initiator (RE) and described cationic polymerization initiators (KE).
Specifically, radical polymerization initiator (RE) can be enumerated: 2, 2-dimethoxy-2-phenyl acetophenone, methyl phenyl ketone, benzophenone, xanthone, Fluorenone, phenyl aldehyde, anthraquinone, 3-methyl acetophenone, 4-chlorobenzophenone, 4, 4 '-diaminobenzophenone, st-yrax propyl ether, Benzoin ethyl ether, benzyl dimethyl ketal, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 4-xanthone, camphorquinone, and 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinopropane-1-ketone etc.Commercially available product include, for example: gorgeous good solid (Irgacure) 184, 907, 651, 1700, 1800, 819, 369, 261, moral firmly (DAROCUR)-TPO (BASF (BASF) company manufacture, 2, 4, 6-trimethylbenzoy-dipheny-phosphine oxide), moral is (DAROCURE) 1173 (manufacture of Merck (Merck) company) firmly, solid (Esacure) KIP150 of easy solarization, TZT (manufacture of Japanese Waja (NihonSiberHegner) company), block refined solid (Kayacure) BMS, block refined solid (Kayacure) DMBI (Japanese chemical drug Inc. makes) etc.In addition, the radical polymerization initiator with at least one (methyl) acryl can be used in molecule as radical polymerization initiator of the present invention (RE).
Then, as mentioned above, cationic polymerization initiators (KE) (being sometimes referred to as acid producing agent) can enumerate: the sulfonium salt cation initiators such as You Bagu (UVACURE) 1590 (manufacture of Daicel Qing Te company), CPI-110P (manufacture of Sanya Pu Luo company), the Iodonium salt cation initiators such as gorgeous good solid (IRGACURE) 250 (BASF AG's manufacture), WPI-113 (manufacturing with Guang Chun medicine company) and Rp-2074 (Japanese Rhodia manufactures).
And then, in order to improve the performance of described cationic polymerization initiators (KE), also also active energy ray sensitizing agent can be used.As active energy ray sensitizing agent, if illustrate representative person, be then amine, ureas, sulfocompound, P contained compound and chlorine-containing compound or nitrile or other nitrogenous compound etc.Be preferably and use anthracene system, benzophenone series, thioxanthone Xi, perylene (perylene), thiodiphenylamine (phenothiazine) and rose bengal (RoseBengal) etc.
These active energy ray polymerization starters (E) can be used alone or use as mixture of more than two kinds, in the 1st aspect of the present invention, are preferably containing radical polymerization initiator (RE).
With regard to reactive aspect, the allotment ratio of described active energy ray polymerization starter (E) is preferably relative to containing α, compound (M) 100 weight part of β-ethene unsaturated double-bond base, and the active energy ray polymerization starter (E) containing 0.01 weight part ~ 20 weight part.
(explanation of the 2nd aspect)
Then, to the 2nd aspect of the present invention, that is, by boric acid and/or boric acid derivatives and cationically polymerizable composition (K) and active energy ray polymer resin composition (hereinafter sometimes referred to " positively charged ion system active energy ray polymer resin composition ") be described.
Positively charged ion system active energy ray polymer resin composition comprises cationically polymerizable compound (K) and boric acid and/or boric acid derivatives.
First, the cationically polymerizable compound (K) in positively charged ion system active energy ray polymer resin composition is described.
Cationically polymerizable compound (K) comprises and utilizes positively charged ion and all compounds be polymerized.With regard to the reactive viewpoint utilizing active energy ray, cationically polymerizable compound (K) is preferably ring-type heterocompound, is particularly preferably the oxirane compound (k1) as 3 yuan of cyclic ethers.In addition, the vinyl ether compound in described compound (M) also carries out cationoid polymerisation, so can use.
Oxirane compound (k1) include, for example: oxyethane, methyl oxirane, phenyl ethylene oxide, 1,2-phenylbenzene oxyethane, sub-methyne oxyethane, oxiranylmethyl radical, Oxyranyle methyl alcohol, oxirane carboxylic acid, (chloromethyl) oxyethane, (brooethyl) oxyethane and Oxyranyle acetonitrile etc. have the compounds of fatty family cyclic ether group;
3, 4-oxyethane hexahydrobenzoic acid 3, 4-oxyethane cyclohexylmethyl, 3, 4-oxyethane-6-methylcyclohexanecarboxylic acid 3, 4-oxyethane-6-methylcyclohexyl methyl esters, two (3, 4-oxyethane hexahydrobenzoic acid) ethyl, hexanodioic acid two (3, 4-oxyethane cyclohexyl methyl) ester, hexanodioic acid two (3, 4-oxyethane-6-methylcyclohexylmethyl) ester, diethylene glycol bis-(3, 4-oxyethane cyclohexyl methyl ether), and dicyclopentadiene etc. has the compounds of the cyclic ether group of the three membered cyclic be binding on ester ring type ring.In addition, the group compound be binding in other chemical structures that the hydrogen atom these contained in the compound of the cyclic ether group of three membered cyclic removes 1 or multiple forms can become oxirane compound (k1).
Illustrative oxirane compound can individually use herein, in addition, and also can by used in combination for multiple oxirane compound.
The oxyethane equivalent of oxirane compound (k1) is generally 30g/eq ~ 3000g/eq, is preferably 50g/eq ~ 1500g/eq.When oxyethane equivalent is more than 30g/eq, the pliability of the blooming after sclerosis is excellent, and bonding strength is high.On the other hand, when below 3000g/eq, with the excellent compatibility of other compositions.
In order to improve thermotolerance or humidity resistance, oxirane compound (k1) especially preferably has the oxirane compound (k1-1) of aromatic nucleus.
Have in the oxirane compound (k1-1) of aromatic nucleus and can comprise the substituting group deriving from aromatic nucleus.These substituting groups can be enumerated: by benzene,toluene,xylene, vinylbenzene, 1,2,3-trimethylbenzene (hemimellitene), pseudocumol (pseudocumene), 1,3,5-trimethylbenzene (mesitylene), cumene, 1,2, ((isodurene), Du (durene), isopropyl toluene (cymene) and mellitene (mellitene) etc. can remove the group of 1 or multiple forms to prehnitene), Yi Du to 3,4-durene with the hydrogen atom in the benzene derivative of other chemical structure bonds.Its substituting group include, for example: phenyl, phenylene, tolyl, first phenylene, benzyl, benzylidene, benzylidyne, xylyl, xylylene, phthalal (phthalylidene), mphenylenedimethylim-, terephthalylidene, styrene (phenethylidene), styrene (phenethylidyne), styryl, sub-styryl (styrylidene), the false cumyl (as-pseudocumyl) of as-, the false cumyl of v-, the false cumyl of s-, sym-trimethylbenzene base (mesityl), cumenyl, α-cumyl, hydrogen cassia bark base, cassia bark base, sub-cassia bark base (cinnamylidene), secondary cassia bark base (cinnamylidyne), Du base (duryl), Ya Du base (durylene), auspicious vanillyl (thymyl), carvacryl (carvacryl), anisyl (cuminyl), ar-methoxy-benzylidene (cuminylidene), tert-butyl-phenyl (neophyl), xenyl (xenyl), diphenyl-methyl (benzhydryl), diphenylmethylene (benzhydrylidene), trityl (trityl) etc.
In addition, include, for example: the cyclenes hydro carbons such as cyclopropylene, cyclobutene, cyclopentenes, tetrahydrobenzene, suberene, cyclooctene, cyclobutadiene, cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene;
The carbon number forming the ring beyond benzene is [4n+2] annulene (annulene) of more than 3.
In addition, include, for example the hydrogen atom in following ring compound removed 1 or multiple forms group can with the aromatic nucleus of other chemical structure bonds: the aromatic series such as xenyl, triphenyl methane polynuclear compound class;
Pentalene (pentalene), indenes (indene), indane (indan), Ninghai LJ (ninhydrin), naphthalene, naphthane (tetralin), perhydronaphthalene (decalin), sapotalene (sapotalene), cadalin (cadalene), excellently reach woods (eudalene), naphthols (naphthol), menadiol (menadiol), gossypol (gossypol), naphthoquinones (naphthoquinone), lawsone (lawsone), regianin (juglone), vitamin k4 (menadione), plumbagin (plumbagin), phthiocol (phthiocol), sea urchin chromoprotein A (echinochromeA), Shikonin (alkannin), Shikonin (shikonin), acetonaphthone (acetonaphthone), naphthoic acid (naphthoicacid), naphthoyl (naphthoyl), naphthalic acid (naphthalicacid), naphthalate (naphthalate), acetomenaphthone (acetomenaphthone), napthylamine sulfonic acid (naphthionicacid), napthylamine sulfonic acid salt (naphthionate), naphthalene sulfinyl (naphthionyl), dansyl (dansyl), 2-naphthol-8-sulfonic acid (croceicacid), flavianic acid (flavianicacid), chromotropic acid (chromotropicacid), neocupferron (neocupferron), Azulene (azulene), lindazulene (chamazulene), melon camomile Azulene (guaiazulene), heptalene (heptalene), pungently take alkene (octalene), the carbon condensation second cycle line compounds such as purple times phenol (purpurogallin),
The red alkene (as-indacene) of asymmetric-Yin, the red alkene of symmetry-Yin, the red alkene of asymmetric-hydrogen Yin, the red alkene of symmetry-hydrogen Yin, sub-biphenyl, acenaphthene (acenaphthylene), ethane closes naphthalene (acenaphthene), acenaphthenequinone (acenaphthoquinone), fluorenes (fluorene), Fu (phenalene), perinaphthene (perinaphthene), luxuriant and rich with fragrance (phenanthrene), phenanthryl (phenanthryl), luxuriant and rich with fragrance (phenanthrylium), phenanthrylene (phenanthrylidene), phenanthrylene (phenanthrylene), phenanthrol (phenanthrol), 3,4-phenanthrahydroquinone (morphol), phenanthrenone (phenanthrone), phenanthrenequione (phenanthraquinone), pimanthrene (pimanthrene), retene (retene), anthracene, anthryl, anthracene (anthrylium), anthracene subunit (anthrylidene), anthrylene (anthrylene), anthrol (anthrol), 9-hydroxyl anthracene (anthranol), anthraline (anthrarobin), anthralin (anthralin), anthratriol (dithranol), anthracene formyl radical (anthroyl), anthrone (anthrone), dianthranide ketone (bianthrone), anthraquinone, anthraquinonyl (anthraquinonyl), sub-anthraquinonyl (anthraquinonylene), alizarin (alizarin), quinizarin (quinizarin), anthrarufine (anthrarufin), golden yellow different alizarin (chrysazin), anthracene Turkey-galls phenol (anthragallol), C.I. Natural Red 8 (purpurin), flavopurpurin (flavopurpurin), anthracene violet element (anthrapurpurin), quina A Ning (quinalizarin), teak quinone (tectoquinone), chrysophanol (chrysophanol), chrysophanic acid (chrysophanicacid), Schuttgelb (emodin), rhubarb yellow (rhein), kermesic acid (kermesicacid), coccinic acid (carminicacid), two anthracene imines (dianthrimide), anthracene imide (anthrimide), golden yellow anthraquinonic acid (chrysamminicacid), the carbon condensation tricyclic compounds classes such as colchicine (colchicine),
The luxuriant and rich with fragrance alkene (acephenanthrylene) of three indenes (trindene), three indenes alkane (trindane), 1,2-benzo acenaphthene (fluoranthene), vinegar, vinegar phenanthrene (acephenanthrene), aceanthrylene (aceanthrylene), aceanthrene (aceanthrene), connection triphenylene (triphenylene), pyrene (pyrene), (chrysene), the carbon condensation four compound ring series class such as four sweet smell (tetraphene), thick four benzene (tetracene), tetracene (naphthacene), lycid alkene (rubrene), tsiklomitsin (tetracycline), Uromycin, oxytetracycline, seven days of the week alkene (pleiadene), benzanthrone (benzanthrone);
Pi (picene), perylene, pentaphene (pentaphene), thick pentaphene (pentacene), four sub-benzene (tetraphenylene), cholanthrene (cholanthrylene), 1,2-dihydrobenzene [j] the carbon condensation five rings based compound classes such as acenaphthene (cholanthrene);
Thimble alkene (corannulene), benzo [c] Pi (benzo [c] picene) (fulminene), anthanthrene (anthanthrene), thick four benzene of dibenzo [de, mn] (dibenzo [de, mn] tetracene) (zethrene), revolve thick six benzene (hexahelicene), hexaphene (hexaphene), thick six benzene (hexacene), rubicene (rubicene), cool (coronene), connection Sanya naphthalene (trinaphthylene), heptaphene (heptaphene), thick seven benzene (heptacene), pyrrole anthracene (pyranthrene), Xin Fen (octaphene), thick eight benzene (octacene), three benzos [de, kl, rst] pentaphene (tribenzo [de, kl, rst] pentaphene) (terrylene), tetracene tetracene (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 carbon condensed ring based compound class etc. of the number of rings more than 6 such as thick six benzene (hexacenohexacene) of thick six benzos.
The oxirane compound (k1-1) with aromatic nucleus is particularly preferably: the glycidyl ether of the dihydroxyphenyl propane of thermotolerance and bonding force excellence, the glycidyl ether of Bisphenol F, 1, two (methylene radical) two (7-oxabicyclo [4.1.0] heptane-3-carboxylicesters) of 3-phenylene and two { (7-oxabicyclo [4.1.0] heptane-3-ylmethoxy) methyl } benzene of 1,3-.
Ring-type heterocompound (k2) beyond oxirane compound can be enumerated: as the cyclic ether compound more than compound of the oxygen heterocyclic ring butyl of 4 yuan of cyclic ethers, 5 rings and the compound with the assorted base beyond the oxygen of more than 2 or oxygen.
The compound of oxygen heterocyclic ring butyl can be enumerated: 3-ethyl-3-hydroxymethyl oxetane, Isosorbide-5-Nitrae-bis-[(3-ethyl-3-oxetanylmethoxy) methoxymethyl] benzene, two (1-ethyl-3-oxetanylmethoxy) methyl ether, 3-ethyl-3-(phenoxymethyl) trimethylene oxide, 3-ethyl-3-(2-Ethylhexoxymethyl) trimethylene oxide, phenol novolacs trimethylene oxide and 3-ethyl-{ (3-triethoxysilicane alkyl propoxy-) methyl } trimethylene oxide etc.The compound of oxygen heterocyclic ring butyl can be used alone, also can and use two or more.
Other ring-type heterocompound (k2) can be enumerated: cyclic ester compounds, cyclic formals compound, cyclic carbonate compound, fluorine-containing ring compound etc.Cyclic ester compounds is preferably lactone.Cyclic formals compound is more preferably the compound be selected from dioxolane class, dioxane and trioxa alkanes.
Cyclic carbonate can utilize the method (with reference to Japanese Patent Laid-Open 2-56356 publication) of to be carried out by the polymkeric substance obtained by glycol and the reaction of dialkyl carbonate depolymerizing or the reaction of corresponding oxirane and carbonic acid gas to synthesize.Cyclic carbonate has the structure of more than 5 rings, 6 rings or 7 rings, 5 rings are contained in 1, in 3-dioxolane class, 6 rings are contained in 1,3-dioxane, 7 rings are contained in 1,3-Dioxepane class, but because the carbon of 2 are carbonyl carbon, so be classified separately as cyclic carbonates.Its concrete example can be enumerated: such as ethylene carbonate (also referred to as 1,3-dioxolane-2-ketone), Texacar PC, butylene carbonate, 4-amyl group-1,3-dioxolane-2-ketone, 4-butyl-1,3-dioxolane-2-ketone, 4-propyl group-1,3-dioxolane-2-ketone, 4-(i-propoxymethyl)-1,3-dioxolane-2-ketone, 4-hexyl-1,3-dioxolane-2-ketone, 4-hexyl-5-methylene radical-1,3-dioxolane-2-ketone, 4,5-dimethyl-1,3-dioxolane-2-ketone, 4,4,5,5-tetramethyl--1,3-dioxolane-2-ketone, 4-octyl group-1,3-dioxolane-2-ketone, 4-nonyl-5-vinyl-1,3-dioxolane-2-ketone, 4-decyl-1,3-dioxolane-2-ketone, 4,5-dimethylene-1,3-dioxolane-2-ketone, 4,4-dimethyl-1,3-dioxolane-2-ketone, 4,4,5,5-tetraethyl--1,3-dioxolane-2-ketone, six hydrogen-1,3-benzodioxole (benzodioxole)-2-ketone, 4-isopropyl-4-methyl-5-methylene radical-1,3-dioxolane-2-ketone, vinylene carbonate, allyl ethyl, allyl group Succinic anhydried, the 5 membered ring carbonate classes such as 4-(2-oxo-1,3-dioxolane-4-ylmethyl carbamoyloxy group methyl)-1,3-dioxolane-2-ketone,
Such as trimethylene carbonate methyl ester is (also referred to as 1, 3-diox-2-ketone), 4-methyl isophthalic acid, 3-diox-2-ketone, carbonic acid 2, 2-Propanal dimethyl acetal-1, 3-bis-base ester, 5-methyl isophthalic acid, 3-diox-2-ketone, 5, 5-dimethyl-1, 3-diox-2-ketone (also referred to as neopentyl glycol carbonic ether), 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, 5-(2-oxo-1, 3-dioxolane-4-ylmethoxy)-5-ethyl-1, the 6 membered ring carbonate classes such as 3-diox-2-ketone,
Such as carbonic acid tetramethylene ester is (also referred to as 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 '-(ethylenebis thiobis trimethylene) two (1, 3-Dioxepane-2-ketone) etc. 7 membered ring carbonate classes, with regard to reactive aspect, preferably use ethylene carbonate, Texacar PC, glycerol carbonate etc. 5 membered ring carbonate class.
In addition, described containing α, in the compound (M) of β-ethene unsaturated double-bond base, the Vinyl Ether that also can carry out cationoid polymerisation can be enumerated: ethylene methacrylic ether, ethyl vinyl ether, 2-vinylchlorid ether, n-propyl Vinyl Ether, allyl vinyl ether, isopropyl-ethylene ether, n-butyl vinyl ether, isobutyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl Vinyl Ether, isopentyl Vinyl Ether, tert-pentyl Vinyl Ether, n-hexyl vinyl ether, isohexyl Vinyl Ether, 2-ethylbutyl vinyl ether, 2-ethylhexyl vinyl ether, n-heptyl Vinyl Ether, n-octyl Vinyl Ether, nonyl Vinyl Ether, the ethene ethers such as Dipentaerythritol six Vinyl Ether.
Boric acid contained in positively charged ion system active energy ray polymer resin composition and boric acid derivatives are described.In addition, be described with preferred system in the interaction of cationically polymerizable compound (K) especially herein.Boric acid and boric acid derivatives and cationically polymerizable compound (K) interact, even if not moisture or organic solvent, also the solution of stable and uniform active energy ray polymer resin composition can be formed, after utilizing active energy ray said composition to be hardened, formed and be polymerized with making cationically polymerizable compound (K) film that generated hydroxyl carries out bond.In addition, have and form key with the surface functionalities of aftermentioned base material (F) and the effect making cementability good.As bringing this kind of effect person, boric acid can use certainly, and following illustrated boric acid derivatives also can be used alone or used in combination with boric acid.
So-called boric acid derivatives of the present invention, as long as the B-O-H key itself with more than 1, or can be hydrolyzed in presence of water and form most boron-containing compounds of more than 1 B-O-H key, then can unrestrictedly be suitable for using.Boric acid derivatives concrete but can enumerate in the example of indefiniteness: boric acid oxide compound (such as B 2o 3), the boric acid such as ortho-boric acid, metaboric acid, peroxyboric acid, hypoborous acid, boric acid (boronicacid), two substituted boracic acids (borinicacid);
Such as by the reaction of boric acid and alcohol or phenol and the compound obtained, such as: the borate esters such as trimethyl borate, triethyl borate, boric acid three n-propyl, tri-n-butyl borate, triphenyl borate, triisopropyl borate ester, boric acid three-tert-pentyl ester, triphenyl borate, trimethoxy-boron oxygen hydrocarbon trimer, boric acid three-2-cyclohexyl cyclohexyl, triethanolamine borate, boric acid triisopropylamine, boric acid mannitol, boroglyceride and boric acid tri-isopropanolamine.
In addition, borated derivative is also wrapped in boric acid derivatives of the present invention.Can enumerate: alkyl or the ene boric acids such as such as methyl-boron-dihydroxide, ethyl-boron dihydroxide, butyl boron dihydroxide, cyclohexyl boric acid;
Aryl boric acids such as such as phenyl-boron dihydroxide, naphthalene boronic acids, anthracene boric acid or there is arbitrary substituent substituted type aryl boric acid at the aryl of these boric acid.
And then, other the borate containing amino and the tertiary amine salt of boric acid can be used.Can enumerate in this kind of boron-containing compound: 2-(the amino isopropoxy of beta-dimethyl-)-4, 5-dimethyl-1, 3, 2-dioxy boron penta ring, 2-(β-diethyl amino base oxethyl)-4, 4, 6-trimethylammonium-1, 3, 2-dioxaborinane, 2-(beta-dimethyl-amino ethoxy)-4, 4, 6-trimethylammonium-1, 3, 2-dioxaborinane, 2-(β-diisopropylaminoethyl oxyethyl group)-1, 3, 2-dioxaborinane, 2-(β-diisopropylaminoethyl oxyethyl group)-4-methyl isophthalic acid, 3, 2-dioxaborinane and 2-(beta-dimethyl-amino ethoxy)-4, 4-(4-hydroxybutyl)-1, 3, 2-dioxaborinane, but be not limited to these compounds.
In addition, in boric acid derivatives, easily can dissociate in an aqueous medium at it and under forming the condition of boric acid, also can enumerate the metal-salt (that is, boric acid metal) of boric acid.In the suitable example of boric acid metal, include, for example: lime borate, potassium borate (such as potassium metaborate, potassium tetraborate, potassium pentaborate, six potassium borates and eight potassium borates), Sodium Tetraborate (such as Sodium peroxoborate, sodium metaborate, hypoboric acid sodium, sodium tetraborate, sodium pentaborate, Sodium peroxoborate, six Sodium Tetraboratees and eight Sodium Tetraboratees).Similarly, also ammonium borate can be used.
And then, in boric acid derivatives, organic oligomer and the polymer compound containing containing boron portion can be enumerated in addition.Can enumerate in suitable example: reacted by the polymer, boron acid esters polymkeric substance (acrylate copolymer of such as hydroxyl functional group or polysiloxane polymer) of active hydrogen (such as containing) and boric acid and/or boric acid ester, form the polymkeric substance with boric acid ester group and the compound formed.
Be suitable in this purpose polymers, can be enumerated the multiple polymkeric substance containing active hydrogen any one, wherein, such as, select at least one of acrylic acid polymer, polyester polymers, polyurethane polymer, polyether polymer.
In addition, in the present invention, boric acid derivatives preferably has the hydroxyl of more than 3 in 1 molecule.The boric acid derivatives in 1 molecule with more than 3 hydroxyls can be enumerated: Isosorbide-5-Nitrae-benzene hypoboric acid (hydroxyl value is 4), tetrahydroxy diboron hexahydride (hydroxyl value is 4) and triethanolamine borate salt (hydroxyl value is 3) etc.
In active energy ray polymeric composition 100 weight part, the ratio of boric acid and/or boric acid derivatives is 0.1 weight part ~ 20 weight part, is preferably 0.3 weight part ~ 12 weight part, is especially preferably 0.3 weight part ~ 7 weight part.
If boric acid and/or boric acid derivatives are more than 0.1 weight part, then can show required bonding force, if more than 0.3 weight part, then become more remarkable.In addition, if below 20 weight parts, be then difficult to produce and separate out along with the process of time, or rise and the problems such as gelation as the excess stickiness of solution, if below 7 weight parts, then especially preferred.
By using cationically polymerizable compound (K), the bad order of the duplexer caused because curing shrinkage is large can be improved.
And then by also using boric acid and/or boric acid derivatives, the surface functionalities of the hydroxyl that cationically polymerizable compound (K) carries out being polymerized and generates and base material forms key and makes cementability good.
Preferably cationic polymerization initiators (KE) is also comprised in positively charged ion system active energy ray polymer resin composition.
Cationic polymerization initiators (KE) is described above, can enumerate: the sulfonium salt cation initiators such as You Bagu (UVACURE) 1590 (manufacture of Daicel Qing Te company), CPI-110P (manufacture of Sanya Pu Luo company), the Iodonium salt cation initiator such as gorgeous good solid (IRGACURE) 250 (BASF AG's manufacture), WPI-113 (manufacturing with Guang Chun medicine company), Rp-2074 (Japanese Rhodia manufactures).
Relative to active energy ray Polymerizable composition 100 weight part, the allotment ratio of described cationic polymerization initiators (KE) is preferably containing 0.01 weight part ~ 20 weight part.
(explanation of the 3rd aspect)
Finally, to the 3rd aspect of the present invention, namely, by boric acid and/or boric acid derivatives and containing the compound (M) of α, β-ethene unsaturated double-bond base and cationically polymerizable composition (K) and active energy ray polymer resin composition (be active energy ray polymer resin composition hereinafter sometimes referred to blending together) be described.
Blend together is that active energy ray polymer resin composition comprises: containing the compound (M) of α, β-ethene unsaturated double-bond base, cationically polymerizable compound (K) and boric acid and/or boric acid derivatives.
In addition, boric acid and/or boric acid derivatives, specifically can use containing the compound (M) of α, β-ethene unsaturated double-bond base and cationically polymerizable compound (K) exemplary compounds recorded in the 1st aspect and the 2nd aspect.
Blending together is comprising molecule containing the compound (M) of α, β-ethene unsaturated double-bond base and including α, all compounds of β-ethene unsaturated double-bond of active energy ray polymer resin composition.With regard to the reactive viewpoint utilizing active energy ray; containing α; the compound (M) of β-ethene unsaturated double-bond is preferably designed in the gross weight of α, β-ethene unsaturated double-bond, (methyl) acryloyl fiduciary point 50 % by weight ~ 100 % by weight.
As compound (M), specifically, preferably comprise: be selected from by containing hydroxyl containing α, the compound (X) of β-ethene unsaturated double-bond base, the compound of more than a kind had in the cohort formed containing the compound (C) of α, β-ethene unsaturated double-bond base of more than 2 naphthenic hydrocarbon skeletons and/or cyclic olefin backbone.
Containing α, the preferred ratio of the compound (M) of β-ethene unsaturated double-bond base, cationically polymerizable compound (K) and boric acid and/or boric acid derivatives is: in active energy ray polymeric composition 100 weight part, containing α, the compound (M) of β-ethene unsaturated double-bond base is 9 weight part ~ 99 weight parts, cationically polymerizable compound (K) is 0.5 weight part ~ 90 weight part, and boric acid and/or boric acid derivatives are 0.1 weight part ~ 20 weight part.
Be more preferably: containing α, the compound (M) of β-ethene unsaturated double-bond base is 30 weight part ~ 80 weight parts, cationically polymerizable compound (K) is 20 weight part ~ 70 weight parts, and boric acid and/or boric acid derivatives are 0.3 weight part ~ 12 weight part (being particularly preferably 0.3 weight part ~ 7 weight part).
If be less than 9 weight parts containing the compound (M) of α, β-ethene unsaturated double-bond base, then comparatively speaking, cationically polymerizable compound (K) increases, and easily produce sclerosis because of the moisture in base material or humidity bad.If contain the compound (M) of α, β-ethene unsaturated double-bond base more than 99 weight parts, then curing shrinkage becomes large, when attaching film base material, can produce gauffer and easily produce bad order.If boric acid and/or boric acid derivatives are less than 0.1 weight part, then cannot show required bonding force, if more than 20 weight parts, then exist to produce and separate out along with the process of time, or rise and the situation of the problems such as gelation as the excess stickiness of solution.
Blend together is that active energy ray polymer resin composition passes through and uses containing α, the compound (M) of β-ethene unsaturated double-bond base and cationically polymerizable compound (K), the sclerosis that namely bad order of duplexer that the curing shrinkage because of the compound (M) containing α, β-ethene unsaturated double-bond base can be suppressed to cause greatly or the feature of cationically polymerizable compound cause because of moisture is bad.
And then, by and with boric acid and/or boric acid derivatives, the hydroxyl that compound (X) and/or cationically polymerizable compound (K) carry out being polymerized and generate, form key with the hydroxyl of base material, cementability becomes good.
Blend together is also can comprise active energy ray polymerization starter (E) in active energy ray polymer resin composition.By using active energy ray polymerization starter (E), polyreaction can be promoted.In addition, blending together is that active energy ray polymerization starter (E) in active energy ray polymer resin composition can enumerate radical polymerization initiator (RE) and cationic polymerization initiators (KE).
Radical polymerization initiator (RE), cationic polymerization initiators (KE) are specifically described in the 1st aspect and the 2nd aspect.
Radical polymerization initiator (RE) and cationic polymerization initiators (KE) can be used alone or used in combination, preferably used in combination.
Relative to active energy ray Polymerizable composition 100 weight part, described initiator (radical polymerization initiator (RE), with the total amount of cationic polymerization initiators (KE)) is preferably containing 0.01 weight part ~ 20 weight part.
Below, the item " solvent, sensitizing agent, additive, viscosity, thickness, coating process, base material, duplexer, laminating method " shared in " the 1st aspect ~ the 3rd aspect " is recorded.
(solvent)
In the present invention, with regard to the viewpoint of the equipment required for drying step or energy, be preferably not moisture in fact or organic solvent.But, at active energy ray polymerization starter (E) to containing α, when the compound (M) of β-ethene unsaturated double-bond base is for insoluble, in addition in full-bodied situation, in order to be dissolved by active energy ray polymerization starter (E), also a small amount of water or organic solvent can be comprised.The content that this water or organic solvent are preferably in active energy ray polymer resin composition is less than 5 % by weight.Spendable organic solvent is not particularly limited, specifically, also and then methyl alcohol, ethanol, Virahol, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl acetate, ethyl acetate, butylacetate, hexanaphthene, toluene and dimethylbenzene can be added, the organic solvents such as other hydrocarbon system solvent, and water, adjust the viscosity of active energy ray polymer resin composition, also can heat active energy ray polymer resin composition and make viscosity degradation.
(sensitizing agent)
And then, when using cationic polymerization initiators (KE) as active energy ray polymerization starter (E), in order to improve the performance of cationic polymerization initiators (KE), also also active energy ray sensitizing agent can be used.As active energy ray sensitizing agent, if illustrate representative person, be then amine, ureas, sulfocompound, P contained compound, chlorine-containing compound or nitrile or other nitrogenous compound etc., be preferably and use anthracene system or benzophenone series, thioxanthone Xi Huo perylene, thiodiphenylamine, rose bengal etc.
(additive)
In active energy ray polymer resin composition of the present invention, as long as do not undermine the scope of effect of the present invention, then except described composition, also suitably can allocate additive.Such as, with regard to the viewpoints such as the reduction of polymerization curing shrinkage rate, coefficient of thermal expansion reduction, dimensional stability raising, Young's modulus raising, viscosity adjustment, thermal conductivity raising, intensity raising, toughness raising and painted raising, adjustable organic or inorganic weighting agent.This kind of weighting agent can use: polymkeric substance, pottery, metal, metal oxide, metal-salt and dye pigment etc.Being not particularly limited shape, such as, is particle shape and threadiness etc.In addition, when formulating polymer, also can not as weighting agents such as softness-conferring agent, fluidizer, fire-retardant agent, preserving stabilizer, antioxidant, UV light absorber, thixotropy conferring agents, dispersion stabilizer, mobility donor and defoamers, but as polymer blend (polymerblend) or polymer alloy (polymeralloy), and dissolve, half dissolve or to be micro-ly scattered in active energy ray polymerizability caking agent.
(viscosity)
Active energy ray polymer resin composition of the present invention can aqueous, paste and membranaceous arbitrary form use, but with regard to easy-to-use viewpoint, preferably aqueous.
The viscosity of active energy ray polymer resin composition of the present invention is preferably and adjusts according to the thickness of used said composition or use.Such as, when the thickness of layer being set to 0.1 μm ~ 6 μm, viscosity is 1mPas ~ 1500mPas, is preferably 10mPas ~ 1300mPas, is especially preferably 20mPas ~ 1000mPas.If viscosity is higher than 1500mPas, then when coating on base material (F), the film coated of 0.1 μm ~ 6 μm cannot be carried out, cause the deterioration in optical properties such as transmitance.On the other hand, if viscosity is lower than 1mPas, then the film thickness monitoring of active energy ray polymer resin composition layer becomes difficulty.
In addition, when the thickness of active energy ray polymer resin composition layer being set to 6 μm ~ 300 μm according to use, viscosity is 1500mPas ~ 100,000mPas, is preferably 3,000mPas ~ 50,000mPas.In fact, the viscosity of resin combination is decide by containing the compound (M) of α, β-ethene unsaturated double-bond base and/or the viscosity of cationically polymerizable compound (K) substantially.Therefore, by 1mPas ~ 100, the viscosity of management compound (M) and/or compound (K) in the scope of 000mPas, then the management of the viscosity of resin combination becomes easy.The adjustment of the viscosity of described example and the coating of resin combination can optionally by adding solvent and easily implementing in described resin combination.
(thickness)
When active energy ray polymer resin composition being used for the purposes of the duplexer used for optical elements such as aftermentioned hard coat film or light polarizing film (also referred to as Polarizer), active energy ray polymer resin composition is carried out film coated.The thickness of the resin layer formed by being coated with is preferably the film coated of 0.1 μm ~ 6 μm, is more preferably 0.1 μm ~ 3 μm.By being set to more than 0.1 μm, when resin combination is used as coating agent or caking agent, easily obtain sufficient adhesion or bonding force.On the other hand, if the thickness of resin layer is more than 6 μm, then in the characteristic such as adhesion or bonding force, do not find that situation about changing is many.
In addition, in purposes active energy ray polymer resin composition being used for the duplexers used for optical elements such as decorating film (meaning touch-screen filler piece), the thickness of the described resin layer formed by being coated with is preferably the thick film coating of 6 μm ~ 300 μm, is more preferably 20 μm ~ 250 μm.If be less than 6 μm, then sometimes cannot obtain sufficient stress relaxation, if more than 300 μm, then the situation producing the coating declines such as striped is many.
(coating process)
The method coated by energy line polymer resin composition of the present invention on base material etc. can be enumerated: Meyer rod (Meyerbar), applicator (applicator), brush (brush), atomizer (spray), roller (roller), gravure coater (gravurecoater), mould coating machine (diecoater), micro-gravure coater (microgravurecoater), lip type coating machine (lipcoater), unfilled corner wheel coating machine (commacoater), curtain application device (curtaincoater), scraper type coating machine (knifecoater), reverse coating machine (reversecoater), the multiple coating processes such as spin coater (spincoater), can use according to purposes such as film coated or thick film coatings, there is no particular restriction.
(active energy ray)
Active energy ray polymer resin composition of the present invention utilizes known customary way and coats on base material, active energy ray is irradiated to formed coating layer, thus, containing α, by radical polymerization when compound (M) of β-ethene unsaturated double-bond base, carry out polymerization when cationically polymerizable (K) by cationoid polymerisation and harden.The radiation source of active energy ray is the light source using the light of 150nm ~ 550nm wavelength region may as main body, can preferably use Cooper-Hewitt lamp, middle medium pressure mercury lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, chemical lamp, black lamp, microwave-excitation mercuryvapour lamp, LED, xenon lamp or metal halide lamp etc.In addition, laser beam, electron beam etc. also can be used as exposure active energy ray.
Ultraviolet irradiation intensity is preferably 10mW/cm 2~ 3000mW/cm 2.If photo-irradiation intensity is less than 10mW/cm 2, then sclerosis needs long-time, if more than 3000mW/cm 2, then utilize the heat given off from lamp, there is the possibility of the base material deteriorates produced in various base material (F), therefore not good enough.The long-pending accumulative irradiation dose being expressed as exposure intensity and irradiation time is preferably 50mJ/cm 2~ 20,000mJ/cm 2.If accumulative irradiation dose is less than 50mJ/cm 2, then polymerization sclerosis needs long-time, if be greater than 20,000mJ/cm 2, then irradiation time becomes very long, and productivity is poor, therefore not good enough.Representational active energy ray polymer resin composition needs 1000mJ/cm usually 2above accumulative irradiation dose.But, even if be less than 1000mJ/cm 2low accumulative irradiation dose, described resin combination of the present invention also carries out polymerization well.
(base material (F))
Then, base material (F) is described.
The applicable base material of active energy ray polymer resin composition of the present invention (F) is film-like substrate, sheet glass, paper conversion product etc., and there is no particular restriction.On the other hand, when by active energy ray polymer resin composition of the present invention as the caking agent making the base material of more than two panels (F) fit, making it be polymerized to irradiate active energy ray, needing to use easily through the base material of active energy ray.Be particularly preferably and use transparent film or transparency glass plate.Also can use to wherein a slice of fitted base material the base material be difficult to through active energy ray, such as timber, metal sheet, plastic plate, paper conversion product etc., and transparent film or transparency glass plate are used to another plate substrate, self-induced transparency film or transparency glass plate side are irradiated, and carry out polymerization sclerosis.
Active energy ray polymer resin composition of the present invention preferably uses the film-like substrate in base material (F).Film-like substrate can enumerate the film-like substrate such as glassine paper (cellophane), various plastic film, paper, preferably uses transparent various plastic films.In addition, as long as film-like substrate is transparent, then can be the base material of individual layer, also can use the base material being in multilayered state be laminated by multi-layer substrate.
(explanation of duplexer)
Herein, active energy ray polymer resin composition is used to carry out generality explanation to the duplexer on wherein one side or the two sides that are laminated in base material (F) to being characterized as.
The polyreaction of active energy ray that utilizes of active energy ray polymer resin composition of the present invention is preferably for the formation of comprising in described base material (F) as the transparent film of film-like substrate and the duplexer of active energy ray polymer resin composition layer of at least one side being positioned at this transparent film.
In the present invention, the duplexer of transparent film can obtain as follows.
By the wherein coated on one side resin combination of the present invention at the transparent film as film-like substrate, another transparent film is laminated in the surface of resin composition layer, and then at the wherein one or both sides coating resin composition of this duplexer, and then, be laminated on another transparent film, glass or transparent formed article, thus obtain duplexer.
Active energy ray polyreaction as the resin combination of the present invention of caking agent is when the coating of resin combination or time stacked and then irradiates active energy ray after lamination and carry out, but preferably irradiates active energy ray after lamination and carry out polyreaction.
In the present invention, transparent film can be used for the blooming of the information communication machine such as indicating meter or touch-screen etc.
(explanation of duplexer used for optical elements)
Herein, generality explanation is carried out to duplexer used for optical elements.
The basic stacked formation of optical laminated body is the duplexer being laminated with the active energy ray polymerizability caking agent of the sheet of multilayer as transparent film/adhesive linkage/transparent film or transparent film/adhesive linkage/transparent film/adhesive linkage/transparent film and so on.And then, use as by such as transparent film/adhesive linkage/transparent film/adhesive linkage/transparent film/adhesive linkage/transparent film, duplexer used for optical elements that the multi-layer optical film of glass or optical forming body and so on is fixed on optical component.Described adhesive linkage can use the resin combination of the 1st aspect of the present invention ~ the 3rd aspect.
Various transparent films as blooming are preferably the excellent thermoplastic resin such as the such as transparency, physical strength, thermostability, moisture barrier and isotropy.So-called various transparent film; also various plastic film or plastic sheet is referred to; include, for example: polyvinyl alcohol film; poly-tri acetyl cellulose film; the polyolefine mesenterys such as polypropylene, polyethylene, polycyclic alkene and vinyl-vinyl acetate copolymer; the polyester such as polyethylene terephthalate and polybutylene terephthalate mesentery, polycarbonate mesentery, polynorbornene mesentery; polyarylester mesentery; polyacrylic acid mesentery, polyphenylene sulfide mesentery, polystyrene mesentery; polyvinyl mesentery; polymeric amide mesentery, polyimide mesentery, and polyethylene oxide mesentery etc.
When transparent film of the present invention is used as multilayer film, each film can be same composition, also can be different.Such as, can simultaneously use polycyclic alkene mesentery wherein, and use polyacrylic acid mesentery at another side.
The thickness of transparent film can suitably determine, but usually with regard to the viewpoints such as the workability such as intensity or operability, thin layer, described thickness is 1 μm ~ about 500 μm.Be particularly preferably 1 μm ~ 300 μm, be more preferably 5 μm ~ 200 μm.Transparent film is particularly suitable for the situation of 5 μm ~ 150 μm.
In addition, in the both sides of the polarization element at the Polarizer film as blooming, transparent film is set, the back side can be shown at it and use the transparent film comprising identical polymer materials, also can use the transparent film (H) comprising different polymer materials etc.
Then, blooming is described.
Duplexer used for optical elements of the present invention is suitable for using the blooming being mainly used in optical applications in described various transparent film.Blooming is the film described transparent film being implemented to special processing, and the film with optical function various functions such as () diffusion of printing opacity, light, optically focused, refraction, scattering, mist degrees (HAZE) is called blooming.In order to give these optical functions, usually not only these functional materialss are mixed in film, or stacked by sputter, and use the caking agent containing functional materials or coating agent, or utilize caking agent to fit film containing functional materials, carry out stacked and give optical function.In addition, blooming can be used alone, or utilizes coating agent or caking agent that multiple optical film is stacked as multilayer to use.This kind of blooming include, for example: hard coat film, antistatic coated film, anti-dazzle coated film, light polarizing film, phase retardation film, elliptical polarized light film, anti-reflective film, optical diffusion film, brightness improve film, prism film (also referred to as prismatic lens) and light guiding film (also referred to as light guiding plate) etc.
Light polarizing film is also referred to as Polarizer; via caking agent; on the two sides of polyethenol series polarization element stacked 2 as the poly-tri acetyl cellulose system protective membrane (hereinafter referred to as " TAC film ") gathering acetylcellulose mesentery, or the sheet-form optical film of multilayered structure at the wherein one or both sides of polyethenol series polarization element stacked polycyclic alkene mesentery, polyacrylic acid mesentery, polycarbonate mesentery, polyester mesentery etc. as polynorbornene mesentery.This caking agent can be suitable for using active energy ray polymer resin composition of the present invention.
Use active energy ray polymer resin composition of the present invention and stacked blooming is preferably at liquid crystal indicator, plasma display (plasmadisplaypanel, PDP) module, touch screen module, organic electroluminescent (electroluminescence, on the transparent film such as sheet glass, described various plastic films of EL) module etc., and then stacked and attach active energy ray polymer resin composition of the present invention, make duplexer used for optical elements to use.
More specifically, active energy ray polymer resin composition is used can to obtain as follows as the Polarizer (light polarizing film) of caking agent.
Use the Polarizer (light polarizing film) of active energy ray polymerizability caking agent that any one method of following (I) ~ (III) such as can be utilized to obtain.
There is (I) method of being manufactured by following operation: in the wherein one side of the protective membrane as the 1st transparent film, coat activated energy line polymerizability caking agent and form the 1st polymerizability adhesive linkage (2 '),
In the wherein one side of the 2nd protective membrane as transparent film, coat activated energy line polymerizability caking agent and form the 2nd active energy ray polymerizability adhesive linkage,
Then, at each of polyethenol series polarization element, simultaneously/or successively after the overlapping bonding aspect of 1st active energy ray polymerizability and the bonding aspect of the 2nd active energy ray polymerizability, irradiate active energy ray, the 1st active energy ray polymerizability adhesive linkage and the 2nd active energy ray polymerizability adhesive linkage are carried out polymerization sclerosis;
(II) by method that following operation manufactures: in the wherein one side of polyethenol series polarization element, coat activated energy line polymerizability caking agent and form the 1st active energy ray polymerizability adhesive linkage, the surface of the 1st formed active energy ray polymerizability adhesive linkage is covered using the 1st protective membrane as transparent film, then at the another side of polyethenol series polarization element, coat activated energy line polymerizability caking agent and form the 2nd active energy ray polymerizability adhesive linkage, the surface of the 2nd formed active energy ray polymerizability adhesive linkage is covered with the 2nd protective membrane, irradiate active energy ray, 1st active energy ray polymerizability adhesive linkage and the 2nd active energy ray polymerizability adhesive linkage are carried out polymerization sclerosis, and
(III) by method etc. that following operation manufactures: in the end overlapping with polyethenol series polarization element of the protective membrane as the 1st transparent film and the end without the 2nd protective membrane on the face of the 1st protective membrane being overlapped in polyethenol series polarization element; after flowing through active energy ray polymerizability caking agent, make it by making caking agent in each inter-level diffusion between roller.Then, irradiate active energy ray, active energy ray polymerizability caking agent is carried out polymerization sclerosis; But be not particularly limited.
Embodiment
Below, specific embodiments of the invention and comparative example are described in the lump, but the present invention is not limited to following embodiment.In addition, in following embodiment and comparative example, " part " and " % " represents " weight part " and " % by weight " respectively.
In addition, " weight average molecular weight (Mw) " and " number average molecular weight (Mn) " are the numerical value that the gel permeation chromatograph " HLC-8220GPC " using Dong Cao limited-liability company to manufacture measures, tubing string will be separated: Dong Cao limited-liability company manufactures " TSK-GELSUPERH5000 ", " TSK-GELSUPERH4000 ", " TSK-GELSUPERH3000 ", and " TSK-GELSUPERH2000 " 4 is connected in series, to the tetrahydrofuran (THF) of mobile phase use temperature 40 DEG C, the polystyrene conversion weight average molecular weight obtained with the hydrometry of 0.6ml/min and number average molecular weight.
In addition, in this specification sheets, about situation active energy ray polymer resin composition of the present invention being used as 1. caking agents and 2. coating agents, be divided into the 1st aspect of the present invention, the 2nd aspect, the 3rd aspect respectively, embodiment is described.
1. caking agent
(the 1st aspect)
[embodiment 1 ~ embodiment 19 and comparative example 1 ~ comparative example 8, embodiment 20 ~ embodiment 35 and comparative example 9 ~ comparative example 24, embodiment 36 ~ embodiment 45]
At oxygen concn through being replaced into less than 10% and in the mayonnaise bottle (mayonnaisejar) of the 300ml be blocked, respectively with the composition shown in the table 1 corresponding with each embodiment and comparative example and table 2 and ratio (weight part), drop into compound (X), compound (Y), compound (C), oligopolymer (D), compound (m), boric acid or boric acid derivatives, active energy ray polymerization starter (E), sensitizing agent and acid producing agent.Then, utilize decollator, input mixture is fully stirred, then fully carry out deaeration, obtain each active energy ray polymer resin composition thus.For this active energy ray polymer resin composition, utilize following methods to make duplexer respectively, evaluate.Evaluation result is also shown in table 1 ~ table 5.
In addition, the abbreviation in table 1 ~ table 5 as described below.
4HBA: vinylformic acid 4-hydroxybutyl
HEA: vinylformic acid 2-hydroxy methacrylate
CHDMMA: cyclohexanedimethanol monomethacrylates
DMAEA: acrylate
DMAPAA: acrylate propyl ester
PMPMA: methacrylic acid pentamethvl ester
VIM:1-vinyl imidazole
VRP:4-vinyl pyridine
DCPA: vinylformic acid two ring pentyl ester
IBXA: isobornyl acrylate
DCPDMDA: Tricyclodecane Dimethanol diacrylate
Oligopolymer 1: purple light UV3000B: Japanese synthetic chemical industry company manufactures, polyacrylate and amino manthanoate, Mw=18000
Oligopolymer 2: the polyacrylate and amino manthanoate obtained in synthesis example 1, Mw=4000
Oligopolymer 3: the polyacrylate and amino manthanoate obtained in synthesis example 2, Mw=1300
Oligopolymer 4: Chinese mugwort Ba Keli (EBECRYL) 3708: Daicel Oulu Knicks (DaicelAllnex) company manufactures, modified epoxy acrylic ester, Mw=1500
Oligopolymer 5: Chinese mugwort Ba Keli (EBECRYL) 810: Daicel Oulu Knicks company manufactures, polyester acrylate, Mw=1000
TBA: tert-butyl acrylate
NBA: n-butyl acrylate
THFA: tetrahydrofurfuryl acrylate
PEA: acrylate
BzA: benzyl acrylate
EPPA: ethoxylation orthoxenol acrylate (A-LEN-10: Xin Zhong chemical industrial company of village manufactures)
VEEA: vinylformic acid 2-(2-vinyloxyethoxy) ethyl ester
BDDA:1,4-butylene glycol diacrylate
DPHA: dipentaerythritol acrylate
PET3A: pentaerythritol triacrylate
(East Asia synthetic chemistry company manufactures INATA: isocyanuric acid EO modified triacrylate: sub-Luo Nisi (Aronix) M-315)
NPDA: neopentylglycol diacrylate
GMA: glycidyl methacrylate
4HBAGE: vinylformic acid 4-hydroxybutyl glycidyl ether (Japan changes into Inc. and makes, another name: vinylformic acid 4-(glycidoxypropyl) butyl ester)
DMAA:N, N-DMAA
TPO:2,4,6-trimethylbenzoy-dipheny-phosphine oxide
Moral is (DAROCUR) 1173 firmly: moral is (DAROCUR) 1173 (Merck & Co., Inc.'s manufacture) firmly
DETX-S: Japanese chemical drug Inc. makes, thioxanthone system sensitizing agent
CPI-110P: Sanya Pu Luo company manufactures, the light acid producing agent of triarylsulfonium salt type
Synthesis example 1 (oligopolymer 2) > of < oligopolymer
In the 5 mouthfuls of separate type flasks possessing stirrer, reflux cooling pipe, gas introduction tube, thermometer and addition funnel, (hodogaya chemical (HodogayaChemical) limited-liability company manufactures: PTG850 to drop into polytetramethylene glycol, hydroxyl value is 127.1mgKOH/g) 81.6 parts, isophorone diisocyanate 41.4 parts, import dry air and be warming up to 60 DEG C.Add dibutyl tin laurate 0.05 part wherein, carry out reaction in 1 hour.In addition, in addition funnel, drop into vinylformic acid 4-hydroxybutyl 27.0 parts, hydroquinone monomethyl ether 0.15 part, spend within 1 hour, drip in separate type flask.After dropping terminates, at 80 DEG C, continue stirring after 3 hours, terminate reaction in the moment confirming the absorption peak that there is not isocyanate group in infrared absorption spectrum, obtain oligopolymer 2.The weight average molecular weight of product is 4000.
In addition, the measuring method of hydroxyl value of the present invention is as described below.The sample of about 1g is critically measured in the Erlenmeyer flask of band plug; add toluene/ethanol (volume ratio: toluene/ethanol=2/1) mixed solution 100ml and after dissolving; and then; add the acetylizing agent (carried out dissolving with pyridine by diacetyl oxide 25g and volume be set to the solution of 100ml) of 5ml exactly, stir about 1 hour.Add phenolphthalein reagent wherein as indicator, continue 30 seconds.Then, carry out titration with 0.1N alcoholic potassium hydroxide solution, till solution presents incarnadine, utilize following formula to obtain hydroxyl value.Hydroxyl value is set to the numerical value (unit: mgKOH/g) of the drying regime of resin.
Hydroxyl value (mgKOH/g)=[(b-a) × F × 28.25}/S]/(nonvolatile component concentration/100)+D
Wherein, S: the collection capacity (g) of sample
The consumption (ml) of a:0.1N alcoholic potassium hydroxide solution
B: the consumption (ml) of the 0.1N alcoholic potassium hydroxide solution of blank test
The titre of F:0.1N alcoholic potassium hydroxide solution
D: acid number (mgKOH/g)
Synthesis example 2 (oligopolymer 3) > of < oligopolymer
In the 5 mouthfuls of separate type flasks possessing stirrer, reflux cooling pipe, gas introduction tube, thermometer, addition funnel, (Daicel chemistry manufactures: skin clarke Sai Er (Placcel) FA2D to drop into the compound making addition 6-caprolactone 2mol in vinylformic acid 2-hydroxy methacrylate 1mol, hydroxyl value is 163.0mgKOH/g) 113.4 parts, isophorone diisocyanate 36.6 parts, hydroquinone monomethyl ether 0.15 part, import dry air and be warming up to 60 DEG C.Add dibutyl tin laurate 0.04 part wherein, improve temperature, at 80 DEG C, carry out reaction in 3 hours.Reaction is terminated in the moment confirming the absorption peak that there is not isocyanate group in infrared absorption spectrum.The weight average molecular weight of product is 1300.In addition, the mensuration of hydroxyl value is identical with the synthesis example 1 of oligopolymer.
Use the active energy ray polymerizability caking agent allocated with the ratio of table 1 ~ table 5, utilize following methods to make duplexer respectively.
The Production Example > of < duplexer A
The poly-tri acetyl cellulose mesentery containing UV light absorber that use Fuji Photo Film Co., Ltd. manufactures: trade(brand)name " Fuji reaches (Fujitac): 80 μm " (thickness is 80 μm) is as transparent film (1), and the poly-tri acetyl cellulose mesentery not containing UV light absorber using Fujiphoto commercial offers (FujiFilmBusinessSupply) company to manufacture: trade(brand)name " TAC50 μ " (thickness is 50 μm) is as transparent film (2).To the one-sided surface of transparent film (1), transparent film (2), with 300Wmin/m 2discharge capacity carry out corona treatment, then, within 1 hour, on the corona treatment face of each film, line rod coating machine is used, become the mode coating table 1 of 4 μm, the active energy ray polymerizability caking agent shown in table 2 and table 5 with thickness, form active energy ray polymerizability adhesive linkage.Clamp polyethenol series polarization element being formed between the active energy ray polymerizability adhesive linkage on described transparent film (1), transparent film (2), obtain the duplexer comprising transparent film (1)/adhesive linkage/PVA system polarization element/adhesive linkage/transparent film (2).In the mode that transparent film (1) contacts with sheet tin (tinplate), the surrounding of this duplexer is fixed with cellophane tape, is fixed on sheet tin.
Utilize active-energy beam irradiating apparatus (Toshiba manufactures, high pressure mercury vapour lamp), it is 300mW/cm that maximal illumination is irradiated in self-induced transparency film (2) side 2, and accumulative light quantity is 300mJ/cm 2ultraviolet, make duplexer A (Polarizer).
The Production Example > of < duplexer B
Be on polyethylene terephthalate (hereinafter referred to as the PET) film of 50 μm at thickness, utilize rod coater to be the thickness of 8 μm by the coating of the active energy ray polymerizability caking agent of table 1 ~ table 5.Utilize niproll and thereon coating thickness be after the PET film of 50 μm, utilizing active-energy beam irradiating apparatus (Toshiba manufacture, high pressure mercury vapour lamp), is 300mW/cm from single-side irradiance maximal illumination 2, and accumulative light quantity is 300mJ/cm 2ultraviolet, obtain duplexer B.
To the duplexer A of gained, obtain stripping strength, punch process, thermotolerance and humidity resistance according to following methods.In addition, in the duplexer B of gained, confirm the transmitance after hot resistance test, painted according to following methods.Result is similarly shown in table 1 ~ table 5.
The Production Example > of < duplexer C
3 kinds of following films are used to be used as transparent film (1) in table 3 and table 4 and transparent film (2) respectively:
ZF: the ZF-14 that Japanese auspicious father-in-law (ZEON) company manufactures, not containing UV light absorber polynorbornene mesentery (thickness is 100 μm),
HBD: Mitsubishi beautiful sun (MitsubishiRayon) company manufacture HBD-002, not containing UV light absorber polyacrylic acid mesentery (thickness is 50 μm) and
TAC: the TAC50 μ that Fujiphoto commercial offers company manufactures, not containing the poly-tri acetyl cellulose mesentery (thickness is 50 μm) of UV light absorber.To respective one-sided surface, with 300Wmin/m 2discharge capacity carry out corona treatment, then, within 1 hour, on the corona treatment face of each film, line rod coating machine is used, become the active energy ray polymerizability caking agent shown in the mode coating table 3 of 4 μm and table 4 with thickness, form active energy ray polymerizability adhesive linkage.Clamp polyethenol series polarization element being formed between the active energy ray polymerizability adhesive linkage on described each film, obtain the duplexer comprising transparent film (1)/adhesive linkage/PVA system polarization element/adhesive linkage/transparent film (2).In the mode that transparent film (1) contacts with sheet tin, the surrounding of this duplexer is fixed with cellophane tape, is fixed on sheet tin.
Utilize active-energy beam irradiating apparatus (Toshiba manufactures, high pressure mercury vapour lamp), it is 300mW/cm that maximal illumination is irradiated in self-induced transparency film (2) side 2, and accumulative light quantity is 300mJ/cm 2ultraviolet, make duplexer C (Polarizer).
< stripping strength >
According to JISK6854-4 caking agent-stripping bonding strength test method-4: floating roll method measures bonding force.
That is, use cutting unit, the duplexer A of gained or duplexer C is cut to the size of 25mm × 150mm, as test sample.Attach double sided adhesive tape (DF8712S that Japan's chemistry (Toyochem) company manufactures) in the wherein one side of sample, use rigging machine and be adhered on metal sheet, obtaining the mensuration duplexer of Polarizer and metal sheet.On mensuration duplexer, between transparent film and polarization element, pre-set the beginning of stripping, by this mensuration duplexer in 23 DEG C, under relative humidity is the condition of 50%, peel off, as peeling force with the angle of 90 ° with the speed of 300mm/min.Now, both peeling forces of polyethenol series polarization element and transparent film (1) and polyethenol series polarization element and transparent film (2) are measured.Using this peeling force as bonding force, evaluate with 4 grades.If ◎, zero, the evaluation of △, be then the level of practical upper no problem.
◎: cannot peel off or Polarizer destruction
Zero: peeling force is more than 2.0 (N/25mm)
△: peeling force is more than 1.0 (N/25mm) and is less than 2.0 (N/25mm)
×: peeling force is less than 1.0 (N/25mm)
< punch process >
About duplexer A or the duplexer C of gained, the blade of the 100mm × 100mm using dumbbell (Dumbbell) company to manufacture, punching press is carried out to made Polarizer in self-induced transparency film (1) side.
Utilize chi to measure the peel distance of the periphery of the Polarizer through punching press, evaluate with following 4 grades.If ◎, zero, the evaluation of △, be then the level of practical upper no problem.
◎：0mm
Zero: be less than 1mm
△: more than 1mm and be less than 3mm
×: more than 3mm
< thermotolerance >
The duplexer A utilizing each caking agent to fit or duplexer C is cut to the size of 50mm × 40mm, under the 80 DEG C-condition of dry (dry) and 100 DEG C-dry, exposes 1000 hours respectively.After exposure, by visual, with following 4 grades, the presence or absence of peeling off of the end of Polarizer is evaluated.If ◎, zero, the evaluation of △, be then the level of practical upper no problem.
◎: also completely without peeling off under the condition of 100 DEG C-drying
Zero: completely without peeling off under 80 DEG C-drying conditions
△: have under 80 DEG C-drying conditions and be less than peeling off of 1mm
×: under 80 DEG C-drying conditions, there is peeling off of more than 1mm
< humidity resistance >
The duplexer A utilizing each caking agent to fit or duplexer C is cut to the size of 50mm × 40mm, under the condition of temperature 60 C-humidity 90% and under the condition of temperature 85 DEG C-humidity 85%, exposes 1000 hours.After exposure, by visual, with following 4 grades, the presence or absence of peeling off of the end of duplexer A is evaluated.If ◎, zero, the evaluation of △, be then the level of practical upper no problem.
◎: also completely without peeling off under the condition of 85 DEG C of-85%RH
Zero: completely without peeling off under the condition of 60 DEG C of-90%RH
△: have under the condition of 60 DEG C of-90%RH and be less than peeling off of 1mm
×: under the condition of 60 DEG C of-90%RH, there is peeling off of more than 1mm
< yellowness index (yellowindex) (Δ YI) >
The duplexer B utilizing each caking agent to fit is cut to the size of 50mm × 40mm, under the condition of temperature 85 DEG C-humidity 85%, expose 1000 hours, utilize integrating sphere type spectrophotometric transmittance tester (DOT-3C that company of colouring material technical institute of village manufactures) to measure Δ YI.Herein, Δ YI be with oven test after laminated film YI value and test before the difference of YI value of PET film represent.Δ YI evaluates with following 4 grades.If ◎, zero, the evaluation of △, be then the level of practical upper no problem.
◎: be less than 0.5
More than zero: 0.5 and be less than 1.0
More than △: 1.0 and be less than 1.5
×: more than 1.5
The above results are shown in table 1 ~ table 5.
As shown in table 1, when the active energy ray polymerizability adhesive application of the present invention that will comprise boric acid or boric acid derivatives in poly-tri acetyl cellulose mesentery, stripping strength, punch process, thermotolerance and humidity resistance are all realistic scale.Particularly in embodiment 3 ~ embodiment 19, there is good stripping strength or patience.In addition, in embodiment 1, embodiment 2, although the level of patience is low, can use.
On the other hand, as shown in table 2, in the comparative example 1 ~ comparative example 8 of not boronic acid containing or boric acid derivatives, any one of stripping strength, punch process, thermotolerance and humidity resistance does not all reach usage range.
In addition, as shown in table 3, when the active energy ray polymerizability caking agent of the present invention comprising boric acid or boric acid derivatives is used for polyacrylic acid mesentery or polynorbornene mesentery, also, as embodiment 20 ~ embodiment 31, whole evaluation results of stripping strength, punch process, thermotolerance and humidity resistance are well.In the embodiment 32 ~ embodiment 35 of not inclusion compound (Y), compound (C) and oligopolymer (D), the level of thermotolerance and humidity resistance is not so high, but level that can be practical uses.
On the other hand, as shown in table 4, in the comparative example 9 ~ comparative example 24 of not boronic acid containing or boric acid derivatives, stripping strength is low, and the evaluation result of any one patience of thermotolerance and humidity resistance is all low, does not reach usage range.
And then, as shown in table 5, the active energy ray polymerizability caking agent of the present invention comprising various boric acid derivatives is also useful, particularly comprising 1, when the embodiment 42 ~ embodiment 45 of 4-benzene hypoboric acid, tetrahydroxy diboron hexahydride, stripping strength etc. are and only wrap borated situation for excellent with Shangdi on an equal basis.
(the 2nd aspect)
[embodiment 101 ~ embodiment 125, comparative example 101, comparative example 102]
Be substituted at oxygen concn and be less than 10% and in the mayonnaise bottle of the 300ml be blocked, drop into cationically polymerizable compound (K), boric acid or boric acid derivatives and cationically polymerizable initiator (KE) with the composition shown in the table 6 corresponding with each embodiment and comparative example and table 7 and ratio (weight part) respectively.Then, utilize decollator, input mixture is fully stirred, then fully carry out deaeration, obtain each active energy ray polymer resin composition thus.For this active energy ray polymer resin composition, utilize following methods to make duplexer respectively, evaluate.
In addition, the abbreviation in table 6, table 7 as described below.
JER828:2,2 '-(dimethylated methylene base) two [(to phenylene) oxygen methylene] bisoxirane (Mitsubishi Chemical Ind's manufacture)
Two (methylene radical) two (7-oxabicyclo [4.1.0] heptane-3-carboxylicesters) of CEP-01:1,3-phenylene
Two { (7-oxabicyclo [4.1.0] heptane-3-ylmethoxy) methyl } benzene of CEP-10:1,3-
ZX1658:2-[{ 4-(oxyethane-2-ylmethoxy) cyclohexyl } methoxyl group] oxyethane (Dongdu changes into company and manufactures)
2021P:3,4-epoxy-cyclohexane carboxylic acid 3,4-expoxycyclohexyl methyl esters (Daicel company manufactures, Sai Luo West Germany (Celloxide) 2021P)
OXT-101:3-ethyl-3-hydroxymethyl oxetane (East Asia Synesis Company manufactures, A Long trimethylene oxide (AronOxetane) OXT-101)
OXT-221: two (1-ethyl-3-oxetanylmethoxy) methyl ether (East Asia Synesis Company manufactures, A Long trimethylene oxide (AronOxetane) OXT-221)
B1: boric acid (hydroxyl value is 3) (also referred to as ortho-boric acid)
B2:1,4-benzene hypoboric acid (hydroxyl value is 4)
B3: tetrahydroxy diboron hexahydride (hydroxyl value is 4)
B4: triethanolamine borate salt (hydroxyl value is 3)
B5: methyl-boron-dihydroxide (hydroxyl value is 2)
B6: phenyl-boron dihydroxide (hydroxyl value is 2)
B7: triethyl borate (hydroxyl value is 0)
WPI-113: sulfonium salt cation polymerization starter (manufacturing with Guang Chun medicine company)
CPI-110P: the light acid producing agent (manufacture of Sanya Pu Luo company) of triarylsulfonium salt type
The Production Example > of < duplexer D
The poly-tri acetyl cellulose mesentery containing UV light absorber that use Fuji Photo Film Co., Ltd. manufactures: trade(brand)name " Fuji reaches (Fujitac): 80 μm " (thickness is 80 μm) is as transparent film (1), and the poly-tri acetyl cellulose mesentery not containing UV light absorber using Fujiphoto commercial offers company to manufacture: trade(brand)name " TAC50 μ " (thickness is 50 μm) is as transparent film (2).To the one-sided surface of transparent film (1), transparent film (2), with 300Wmin/m 2discharge capacity carry out corona treatment, then within 1 hour, use line rod coating machine, become the active energy ray polymer resin composition shown in the mode coating table 6 of 4 μm and table 7 with thickness, form active energy ray polymerizability adhesive linkage.Clamp polyethenol series polarization element being formed between the active energy ray polymerizability adhesive linkage on described transparent film (1), transparent film (2), obtain the duplexer comprising transparent film (1)/adhesive linkage/PVA system polarization element/adhesive linkage/transparent film (2).In the mode that transparent film (1) contacts with sheet tin, the surrounding of this duplexer is fixed with cellophane tape, is fixed on sheet tin.
Utilize active-energy beam irradiating apparatus (Toshiba manufactures, high pressure mercury vapour lamp), it is 300mW/cm that maximal illumination is irradiated in self-induced transparency film (2) side 2, and accumulative light quantity is 300mJ/cm 2ultraviolet, make duplexer D (Polarizer).For the duplexer D of gained, utilize following methods to obtain stripping strength, gel fraction, punch process, shrinking percentage, thermotolerance and humidity resistance (table 6, table 7).
" stripping strength "
Bonding force is according to JISK6854-4 caking agent-stripping bonding strength test method-4: floating roll method measures.
That is, use cutting unit, the Polarizer of gained is cut to the size of 25mm × 150mm, as test sample.Attach double sided adhesive tape (DF8712S that chemical company of Japan manufactures) in the wherein one side of sample, use rigging machine and be adhered on metal sheet, obtaining the mensuration duplexer of Polarizer and metal sheet.On mensuration duplexer, between protective membrane and polarization element, pre-set the beginning of stripping, by this mensuration duplexer 23 DEG C, under relative humidity is the condition of 50%, peel off, as peeling force with the speed of 300mm/min.Now, both peeling forces of polyethenol series polarization element and transparent film (1) and polyethenol series polarization element and transparent film (2) are measured.Using this peeling force as bonding force, evaluate with 4 grades.When ◎, zero, the evaluation of △, do not have problems especially when reality uses.
(metewand)
◎: cannot peel off or Polarizer destruction.
Zero: peeling force is more than 2.0 (N/25mm) ~ be less than 5.0 (N/25mm).
△: peeling force is more than 1.0 (N/25mm) ~ be less than 2.0 (N/25mm).
×: peeling force is less than 1.0 (N/25mm).
" gel fraction "
In the wherein one side of the polynorbornene mesentery (trade(brand)name " Ze Ouna (Zeonor) ZF-14 ": thickness is 100 μm) that the Japan not implementing corona treatment auspicious father-in-law (ZEON) company manufactures, use line rod coating machine, the mode becoming 20 μm ~ 25 μm with thickness is coated with active energy ray polymer resin composition of the present invention, forms adhesive linkage.And then overlap does not implement Ze Ouna (Zeonor) ZF-14 of corona treatment on described adhesive linkage, obtain after comprising the duplexer of 3 layers, utilize active-energy beam irradiating apparatus (Toshiba manufactures, high pressure mercury vapour lamp), irradiation maximal illumination is 300mW/cm 2, and accumulative light quantity is 300mJ/cm 2active energy ray, make adhesive linkage carry out polymerization sclerosis.Ze Ouna (Zeonor) ZF-14 formation being comprised the both sides of the adhesive linkage of the duplexer of 3 layers of Ze Ouna (Zeonor) ZF-14/ adhesive linkage/Ze Ouna (Zeonor) ZF-14 peels off, and obtains bond layer.
After the weight of mensuration bond layer (weight 1), be held between wire netting and wire netting, the mode do not overlapped each other with bond layer, in methyl ethyl ketone (methylethylketone, MEK), carry out 3 hours reflux.And then at 80 DEG C dry 30 minutes, measure the weight (weight 2) of bond layer.Obtain gel fraction by following formula, carry out the evaluation of 3 grades.When zero, the evaluation of △, do not have problems especially when reality uses.
Gel fraction (%)={ 1-(weight 1-weight 2)/weight 1} × 100
(metewand)
Zero: gel fraction is more than 90%
△: gel fraction is more than 80% ~ be less than 90%
×: gel fraction is less than 80%
" punch process "
The blade of the 100mm × 100mm using dumbbell company to manufacture, punching press is carried out to made Polarizer in self-insurance cuticula (1) side.
Utilize chi to measure the peel distance of the periphery of the Polarizer through punching press, evaluate with following 4 grades.When ◎, zero, the evaluation of △, do not have problems especially when reality uses.
(metewand)
◎：0mm
Zero: below 1mm
△：1mm～3mm
×: more than 3mm
" shrinking percentage "
Described Polarizer small pieces are positioned in the constant temperature and humidity machine of 60 DEG C-drying and 60 DEG C of-90RH%, measure the shortening amount of the bearing of trend after 60 hours, obtain the ratio of shortening amount relative to script length (100mm) as shrinking percentage, evaluate with following 3 grades.
In addition, so-called " drying ", refers in the baking oven with humidity adjustment function, only control temperature, and test conditions when not carrying out humid control.When zero, the evaluation of △, do not have problems especially when reality uses.
(metewand)
Zero: shrinking percentage is less than 0.2%
△: shrinking percentage is greater than 0.2% and is less than 0.4%
×: shrinking percentage is more than 0.4%
" thermotolerance "
The Polarizer obtained in each embodiment and comparative example is cut to the size of 50mm × 40mm, under 80 DEG C-dry and 100 DEG C-dry condition, exposes 1000 hours respectively.After exposure, by visual, with following 4 grades, the presence or absence of peeling off of the end of Polarizer is evaluated.When ◎, zero, the evaluation of △, do not have problems especially when reality uses.
(metewand)
◎: also completely without peeling off under the condition of 100 DEG C-drying.
Zero: completely without peeling off under 80 DEG C-drying conditions.
△: have under 80 DEG C-drying conditions and be less than peeling off of 1mm.
×: under 80 DEG C-drying conditions, there is peeling off of more than 1mm.
" humidity resistance "
The Polarizer obtained in each embodiment and comparative example is cut to the size of 50mm × 40mm, under the condition of 60 DEG C of-90%RH and under the condition of 85 DEG C of-85%RH, exposes 1000 hours.After exposure, by visual, with following 4 grades, the presence or absence of peeling off of the end of Polarizer is evaluated.When ◎, zero, the evaluation of △, do not have problems especially when reality uses.
(metewand)
◎: also completely without peeling off under the condition of 85 DEG C of-85%RH.
Zero: completely without peeling off under the condition of 60 DEG C of-90%RH.
△: have under the condition of 60 DEG C of-90%RH and be less than peeling off of 1mm.
×: under the condition of 60 DEG C of-90%RH, there is peeling off of more than 1mm.
In the comparative example 101 not adding any one of boric acid or boric acid derivatives and cationic polymerization initiators and comparative example 102, all physical property required by the application cannot be obtained completely.When using oxirane compound (k1) as cationically polymerizable compound (K), compared with situation about not using (embodiment 124, embodiment 125), all physical property are good.And then under using the situation (such as embodiment 103) with the K1-1 of aromatic nucleus at oxirane compound, and do not use compared with the embodiment 122 of K1-1, embodiment 123, the shrinking percentage under humidification is suitable.
And then, as boric acid and/or boric acid derivatives, hydroxyl be more than 3 situation (such as embodiment 103, embodiment 108, embodiment 110, embodiment 111) be better than the situation (such as embodiment 113 ~ embodiment 115) that hydroxyl is less than 3.
In addition we know, relative to active energy ray resin combination 100 weight part, the addition of boric acid and/or boric acid derivatives is preferably 0.3 weight part ~ 20 weight part (with reference to embodiment 101 ~ embodiment 110).
(the 3rd aspect)
[embodiment 201 ~ embodiment 220, comparative example 201]
At oxygen concn through being replaced into less than 10% and in the mayonnaise bottle of the 300ml be blocked, dropping into compound (X), compound (C), compound (m), oligopolymer, cationically polymerizable compound (B), boric acid or boric acid derivatives, active energy ray polymerization starter (E) and sensitizing agent with the composition shown in the table 8 corresponding with each embodiment and comparative example and ratio (weight part) respectively.Then, utilize decollator, input mixture is fully stirred, then fully carry out deaeration, obtain each active energy ray polymer resin composition thus.For this active energy ray polymer resin composition, utilize following method to make duplexer respectively, evaluate.Evaluation result is also shown in Table 8.
In addition, the abbreviation in table as described below.
4HBA: vinylformic acid 4-hydroxybutyl
HEA: vinylformic acid 2-hydroxy methacrylate
CHDMMA: cyclohexanedimethanol monomethacrylates
DCPA: vinylformic acid two ring pentyl ester
IBXA: isobornyl acrylate
FA-511AS: vinylformic acid dicyclopentenyl ester (Hitachi changes into company and manufactures, model gram force (Fancryl) 511AS)
NBA: n-butyl acrylate
NPDA: neopentylglycol diacrylate
PET3A: pentaerythritol triacrylate
(East Asia synthetic chemistry company manufactures INATA: isocyanuric acid EO modified triacrylate: sub-Luo Nisi (Aronix) M-315)
Oligopolymer 6: the polyacrylate and amino manthanoate obtained in synthesis example 3, Mw=4000
Compound 1:
[changing 1]
Two (methylene radical) two (7-oxabicyclo [4.1.0] heptane-3-carboxylicesters) of Isosorbide-5-Nitrae-phenylene
JER806: Bisphenol F diglycidylether (Mitsubishi Chemical Ind's manufacture)
CEL2021P:3,4-epoxy-cyclohexane carboxylic acid 3,4-expoxycyclohexyl methyl esters (Daicel company manufactures, Sai Luo West Germany (Celloxide) 2021P)
OXT-121: xylylene dioxygen azetidine (East Asia Synesis Company manufactures, A Long trimethylene oxide (AronOxetane) OXT-121)
EC: ethylene carbonate
CPI-110P: Sanya Pu Luo company manufactures, the light acid producing agent of triarylsulfonium salt type
IRG250:4-isobutyl phenenyl (4-aminomethyl phenyl) Iodonium hexafluorophosphate (BASF AG manufactures, gorgeous good solid (Irgacure) 250)
TPO:2,4,6-trimethylbenzoy-dipheny-phosphine oxide (BASF AG manufactures, XiLin, road (Lucirin) TPO)
DETX-S: Japanese chemical drug Inc. makes, thioxanthone system sensitizing agent
Synthesis example 3 (oligopolymer 6) > of < oligopolymer
In the 5 mouthfuls of separate type flasks possessing stirrer, reflux cooling pipe, gas introduction tube, thermometer and addition funnel, (hodogaya chemical company manufactures: PTG850 to drop into polytetramethylene glycol, hydroxyl value is 127.1mgKOH/g) 81.6 parts, isophorone diisocyanate 41.4 parts, import dry air and be warming up to 60 DEG C.Add dibutyl tin laurate 0.05 part wherein, carry out reaction in 1 hour.In addition, in addition funnel, drop into vinylformic acid 4-hydroxybutyl 27.0 parts, hydroquinone monomethyl ether 0.15 part, spend within 1 hour, drip in separate type flask.After dropping terminates, at 80 DEG C, Keep agitation is after 3 hours, terminates reaction in the moment confirming the absorption peak that there is not isocyanate group in infrared absorption spectrum, obtains oligopolymer 6.The weight average molecular weight of product is 4000.
In addition, the measuring method of hydroxyl value of the present invention is as described in the 1st aspect.
Use with the active energy ray polymer resin composition of the ratio allotment shown in table 8, utilize following methods to make duplexer respectively.
The Production Example > of < duplexer E
The poly-tri acetyl cellulose mesentery containing UV light absorber that use Fuji Photo Film Co., Ltd. manufactures: trade(brand)name " Fuji reaches (Fujitac): 80 μm " (thickness is 80 μm) is as transparent film (1), and the poly-tri acetyl cellulose mesentery not containing UV light absorber using Fujiphoto commercial offers company to manufacture: trade(brand)name " TAC50 μ " (thickness is 50 μm) is as transparent film (2).To the one-sided surface of transparent film (1), transparent film (2), with 300Wmin/m 2discharge capacity carry out corona treatment, then within 1 hour, use line rod coating machine, become the active energy ray polymer resin composition shown in mode coating table 8 of 4 μm with thickness, form active energy ray polymerizable resin layer.Clamp polyethenol series polarization element being formed between the active energy ray polymerizable resin layer on described transparent film (1), transparent film (2), obtain the duplexer comprising transparent film (1)/resin layer/PVA system polarization element/resin layer/transparent film (2).In the mode that transparent film (1) contacts with sheet tin, the surrounding of this duplexer is fixed with cellophane tape, is fixed on sheet tin.
Utilize active-energy beam irradiating apparatus (Toshiba manufactures, high pressure mercury vapour lamp), it is 300mW/cm that maximal illumination is irradiated in self-induced transparency film (2) side 2, and accumulative light quantity is 300mJ/cm 2ultraviolet, make duplexer E (Polarizer).
The Production Example > of < duplexer F
Being, on polyethylene terephthalate (hereinafter referred to as the PET) film of 50 μm, utilize rod coater at thickness, is the thickness of 8 μm by the coating of the active energy ray polymer resin composition of table 8.Utilize niproll and thereon coating thickness be after the PET film of 50 μm, utilizing active-energy beam irradiating apparatus (Toshiba manufacture, high pressure mercury vapour lamp), is 300mW/cm from single-side irradiance maximal illumination 2, and accumulative light quantity is 300mJ/cm 2ultraviolet, obtain duplexer F.
The Production Example > of < duplexer G
Following 3 kinds of films are used to be used as transparent film (1) and transparent film (2) respectively:
ZF: the ZF-14 that Japanese auspicious father-in-law (ZEON) company manufactures, not containing UV light absorber polynorbornene mesentery (thickness is 100 μm),
HBD: Li Yang company of Mitsubishi manufacture HBD-002, not containing UV light absorber polyacrylic acid mesentery (thickness is 50 μm) and
TAC: the TAC50 μ that Fujiphoto commercial offers company manufactures, not containing the poly-tri acetyl cellulose mesentery (thickness is 50 μm) of UV light absorber.Respectively to its one-sided surface, with 300Wmin/m 2discharge capacity carry out corona treatment, then, within 1 hour, on the corona treatment face of each film, line rod coating machine is used, become the active energy ray polymer resin composition shown in mode coating table 8 of 4 μm with thickness, form active energy ray polymerizable resin layer.Clamp polyethenol series polarization element being formed between the active energy ray polymerizable resin layer on described each film, obtain the duplexer comprising transparent film (1)/resin layer/PVA system polarization element/resin layer/transparent film (2).In the mode that transparent film (1) contacts with sheet tin, the surrounding of this duplexer is fixed with cellophane tape, is fixed on sheet tin.
Utilize active-energy beam irradiating apparatus (Toshiba manufactures, high pressure mercury vapour lamp), it is 300mW/cm that maximal illumination is irradiated in self-induced transparency film (2) side 2, and accumulative light quantity is 300mJ/cm 2ultraviolet, make duplexer G (Polarizer).
According to following methods, stripping strength, punch process, thermotolerance and humidity resistance, duplexer outward appearance are evaluated to the duplexer E of gained, duplexer outward appearance is evaluated to duplexer F.In addition, in duplexer G, confirm the transmitance after hot resistance test, painted according to following methods.Result is similarly shown in Table 8.
< stripping strength >
Bonding force is according to JISK6854-4 caking agent (polymer resin composition)-stripping bonding strength test method-4: floating roll method measures.
That is, use cutting unit, the duplexer E of gained is cut to the size of 25mm × 150mm, as test sample.Attach double sided adhesive tape (DF8712S that chemical company of Japan manufactures) in the wherein one side of sample, use rigging machine and be adhered on metal sheet, obtaining the mensuration duplexer of Polarizer and metal sheet.On mensuration duplexer, between transparent film and polarization element, pre-set the beginning of stripping, by this mensuration duplexer 23 DEG C, under relative humidity is the condition of 50%, peel off, as peeling force with the angle of 90 ° with the speed of 300mm/min.Now, both peeling forces of polyethenol series polarization element and transparent film (1) and polyethenol series polarization element and transparent film (2) are measured.Using this peeling force as bonding force, evaluate with 4 grades.When ◎, zero, the evaluation of △, do not have problems especially when reality uses.
◎: cannot peel off or Polarizer destruction
Zero: peeling force is more than 2.0 (N/25mm)
△: peeling force is more than 1.0 (N/25mm) and is less than 2.0 (N/25mm)
×: peeling force is less than 1.0 (N/25mm)
< punch process >
The blade of the 100mm × 100mm using dumbbell company to manufacture, punching press is carried out to made Polarizer in self-induced transparency film (1) side.
Utilize chi to measure the peel distance of the periphery of the Polarizer through punching press, evaluate with following 4 grades.When ◎, zero, the evaluation of △, do not have problems especially when reality uses.
◎：0mm
Zero: be less than 1mm
△: more than 1mm and be less than 3mm
×: more than 3mm
< thermotolerance >
The duplexer E utilizing each caking agent to fit is cut to the size of 50mm × 40mm, under 80 DEG C-dry and 100 DEG C-dry condition, exposes 1000 hours respectively.After exposure, by visual, with following 4 grades, the presence or absence of peeling off of the end of Polarizer is evaluated.When ◎, zero, the evaluation of △, do not have problems especially when reality uses.
◎: also completely without peeling off under the condition of 100 DEG C-drying
Zero: completely without peeling off under 80 DEG C-drying conditions
△: have under 80 DEG C-drying conditions and be less than peeling off of 1mm
×: under 80 DEG C-drying conditions, there is peeling off of more than 1mm
< humidity resistance >
The duplexer E utilizing each caking agent to fit is cut to the size of 50mm × 40mm, under the condition of temperature 60 C-humidity 90% and under the condition of temperature 85 DEG C-humidity 85%, exposes 1000 hours.After exposure, by visual, with following 4 grades, the presence or absence of peeling off of the end of duplexer A is evaluated.When ◎, zero, the evaluation of △, do not have problems especially when reality uses.
◎: also completely without peeling off under the condition of 85 DEG C of-85%RH
Zero: completely without peeling off under the condition of 60 DEG C of-90%RH
△: have under the condition of 60 DEG C of-90%RH and be less than peeling off of 1mm
×: under the condition of 60 DEG C of-90%RH, there is peeling off of more than 1mm
< duplexer outward appearance >
By visual, evaluate with the outward appearance of following 3 grades to each duplexer.When zero, the evaluation of △, do not have problems especially when reality uses.
Zero: completely non-wrinkled or concavo-convex on duplexer
△: duplexer has some gauffers or concavo-convex
×: on duplexer, there is gauffer or concavo-convex in whole face
< yellowness index (Δ YI) >
The duplexer G utilizing each caking agent to fit is cut to the size of 50mm × 40mm, under the condition of temperature 85 DEG C-humidity 85%, expose 1000 hours, utilize integrating sphere type spectrophotometric transmittance tester (DOT-3C that company of colouring material technical institute of village manufactures) to measure Δ YI.Herein, Δ YI be with oven test after laminated film YI value and test before the difference of YI value of PET film represent.Δ YI evaluates with following 4 grades.If ◎, zero, the evaluation of △, be then the level of practical upper no problem.
◎: be less than 0.5
More than zero: 0.5 and be less than 1.0
More than △: 1.0 and be less than 1.5
×: more than 1.5
As shown in table 8, when using active energy ray polymer resin composition of the present invention, in embodiment 203 ~ embodiment 210, embodiment 212, embodiment 213, embodiment 215 ~ embodiment 218, embodiment 220, there is good stripping strength or patience, duplexer outward appearance.In addition, in embodiment 201, embodiment 202, embodiment 211, embodiment 214, embodiment 219, though the test subject that the level that also there is patience is low, can use.On the other hand, in the comparative example 201 of not boronic acid containing or boric acid derivatives, stripping strength is low, and punch process patience does not reach usage range.
2. coating agent
(the 1st aspect)
[embodiment 501 ~ embodiment 536, comparative example 501 ~ comparative example 525]
In the mode identical with embodiment 1 etc., to show the composition shown in 9-1, table 9-2, table 10-1, table 10-2 and ratio (weight part), obtain the active energy ray polymer resin composition of embodiment 501 ~ embodiment 536 and comparative example 501 ~ comparative example 525.Use the resin combination of gained as active energy ray polymerizability coating agent, make following duplexer.In addition, the abbreviation shown in 9-1, table 9-2 and table 10-1, table 10-2 is identical with table 1 ~ table 5.
The Production Example > of < duplexer H
The polyacrylic acid mesentery not containing UV light absorber using Li Yang company of Mitsubishi to manufacture: trade(brand)name " HBD-002:50 μm " (thickness is 50 μm) is as blooming.To blooming surface with 300Wmin/m 2discharge capacity carry out corona treatment, after surface treatment within 1 hour, using the resin combination shown in table 9-1, table 9-2 and table 10-1, table 10-2 as active energy ray polymerizability coating agent, use line rod coating machine, the mode becoming 4 μm with thickness is coated with, and forms coating oxidant layer.
In the mode that blooming contacts with sheet tin, the surrounding of this duplexer is fixed on sheet tin with cellophane tape.
With drying nitrogen to after replacing in UV irradiating unit (Toshiba manufacture, high pressure mercury vapour lamp), the maximal illumination being 365nm from coating oxidant layer side illumination wavelength is 300mW/cm 2, and accumulative light quantity is 300mJ/cm 2ultraviolet, make have coating oxidant layer duplexer.
To the duplexer of gained, obtain contiguity power, thermotolerance according to following methods, result is similarly shown in table 9-1, table 9-2 and table 10-1, table 10-2.
" contiguity power "
According to JISK5400, implement grid method stripping test.Evaluating with the grid number of 4 grades to the stripping in 100 grid (block), is the judgement of cementability by contiguity masterpiece.When ◎, zero, the evaluation of △, do not have problems especially when reality uses.
(metewand)
◎: 0 grid
Zero: 1 ~ 10 grid
△: 11 ~ 30 grid
×: more than 31 grid
" thermotolerance "
The duplexer obtained in each embodiment and comparative example is cut to the size of 50mm × 40mm, under the condition of 80 DEG C-drying, exposes 1000 hours.After exposure, by visual, with following 3 grades, the presence or absence of peeling off of the end of duplexer is evaluated.When zero, the evaluation of △, do not have problems especially when reality uses.
(metewand)
Zero: completely without peeling off
△: have and be less than peeling off of 1mm
×: there is peeling off of more than 1mm
(the 2nd aspect)
[embodiment 601 ~ embodiment 630, comparative example 601 ~ comparative example 602]
In the mode identical with embodiment 101 etc., to show the composition shown in 11-1, table 11-2 and ratio (weight part), obtain the active energy ray polymer resin composition of embodiment 601 ~ embodiment 630 and comparative example 601 ~ comparative example 602.For the resin combination of gained, make duplexer H in the mode that the 1st aspect with described 1. coating agents is identical.In addition, show abbreviation and table 6 in 11-1, table 11-2, table 7 is identical.
For the duplexer of gained, carry out the evaluation of contiguity power, thermotolerance in the mode that the 1st aspect with described 2. coating agents is identical.Show the result in table 11-1, table 11-2.
(the 3rd aspect)
[embodiment 701 ~ embodiment 725, comparative example 701]
In the mode identical with embodiment 201 etc., to show the composition shown in 12-1, table 12-2 and ratio (weight part), obtain the active energy ray polymer resin composition of embodiment 701 ~ embodiment 725 and comparative example 701.For the resin combination of gained, make duplexer H in the mode that the 1st aspect with described 2. coating agents is identical.In addition, the abbreviation shown in 12-1, table 12-2 is identical with table 8.
For the duplexer of gained, carry out the evaluation of contiguity power, thermotolerance in the mode that the 1st aspect with described 2. coating agents is identical.Show the result in table 12-1, table 12-2.
In the present invention, as the typical example of blooming, exemplary compounds is specifically shown in described table 9 ~ table 12, but is not limited to these compounds.In addition, the illustratively statement of film, is expressed as TAC: the TAC50 μ that Fujiphoto commercial offers company manufactures, not containing the poly-tri acetyl cellulose mesentery (thickness is 50 μm) of UV light absorber; ZF: the ZF-14 that Japanese auspicious father-in-law (ZEON) company manufactures, not containing the polynorbornene mesentery (thickness is 100 μm) of UV light absorber; HBD: the HBD-002 that Li Yang company of Mitsubishi manufactures, not containing the polyacrylic acid mesentery (thickness is 50 μm) of UV light absorber; R140: the R-140 that clock deep pool chemistry (Kaneka) company manufactures, not containing the polycarbonate mesentery (thickness is 43 μm) of UV light absorber; Emblet: You Niji can (Unitika) company manufacture EmbletS, containing the polyester mesentery (thickness is 50 μm) of UV light absorber; The TUX-HZ that TUX: Dong Seluo (Tohcello) company manufactures, containing the polyethylene mesentery (thickness is 50 μm) of UV light absorber.
When using resin combination of the present invention as coating agent, in embodiment 503 ~ embodiment 536, embodiment 602 ~ embodiment 605, embodiment 607 ~ embodiment 612, embodiment 616 ~ embodiment 623, embodiment 626 ~ embodiment 630, embodiment 702 ~ embodiment 718, embodiment 720 ~ embodiment 725, do not have problems especially.In addition, in embodiment 501, embodiment 502, embodiment 601, embodiment 606, embodiment 613 ~ embodiment 615, embodiment 624, embodiment 625, embodiment 701, embodiment 719, although the level of adhesion or thermotolerance is low, can use.On the other hand, in comparative example 501 ~ comparative example 525, comparative example 601, comparative example 602, comparative example 701, known adhesion or thermotolerance are poor especially.

Claims (21)

1. an active energy ray polymer resin composition, its comprise polymerizable compound and boric acid and and/or boric acid derivatives, and described polymerizable compound is for being selected from by least one in the cohort formed containing the compound (M) of α, β-ethene unsaturated double-bond base and cationically polymerizable compound (K).
2. active energy ray polymer resin composition according to claim 1, wherein polymerizable compound is the compound (M) containing α, β-ethene unsaturated double-bond base.
3. active energy ray polymer resin composition according to claim 1 and 2, it also comprises radical polymerization initiator (RE).
4. active energy ray polymer resin composition according to any one of claim 1 to 3, it is also containing cationic polymerization initiators (KE).
5. active energy ray polymer resin composition according to claim 1, wherein polymerizable compound is cationically polymerizable compound (K), and also containing cationic polymerization initiators (KE).
6. active energy ray polymer resin composition according to claim 1, wherein polymerizable compound is the compound (M) and the cationically polymerizable compound (K) that contain α, β-ethene unsaturated double-bond base.
7. active energy ray polymer resin composition according to claim 6, it also comprises radical polymerization initiator (RE).
8. the active energy ray polymer resin composition according to claim 6 or 7, it is also containing cationic polymerization initiators (KE).
9. the active energy ray polymer resin composition according to any one of Claims 1-4 and 6 to 8, wherein containing α, compound (M) inclusion compound (X) of β-ethene unsaturated double-bond base, described compound (X) is containing hydroxyl and containing α, β-ethene unsaturated double-bond base.
10. the active energy ray polymer resin composition according to any one of Claims 1-4 and 6 to 8, wherein containing α, compound (M) inclusion compound (Y) of β-ethene unsaturated double-bond base, described compound (Y) is containing amino and containing α, β-ethene unsaturated double-bond base.
11. active energy ray polymer resin compositions according to any one of Claims 1-4 and 6 to 8, wherein containing α, the compound (M) of β-ethene unsaturated double-bond base comprises containing α, the compound (C) of β-ethene unsaturated double-bond base, described compound (C) comprises the naphthenic hydrocarbon skeleton and/or cyclic olefin backbone with more than 2 ring structures.
12. active energy ray polymer resin compositions according to any one of 1 to 4 and 6 to 8, the compound (M) wherein containing α bond base comprises the oligopolymer (D) that weight average molecular weight is 300 ~ 30,000.
13. active energy ray polymer resin compositions according to any one of claim 5 to 8, wherein cationically polymerizable compound (K) comprises oxirane compound (k1).
14. active energy ray polymer resin compositions according to claim 13, wherein oxirane compound (k1) comprises the oxirane compound (k1-1) with aromatic nucleus.
15. active energy ray polymer resin compositions according to any one of claim 1 to 14, wherein boric acid derivatives has the hydroxyl of more than 3 in 1 molecule.
16. active energy ray polymer resin compositions according to any one of claim 1 to 15, wherein in active energy ray polymer resin composition 100 weight part,
Comprise described boric acid and/or the boric acid derivatives of 0.1 weight part ~ 20 weight part.
17. 1 kinds of caking agents, it comprises the active energy ray polymer resin composition according to any one of claim 1 to 16.
18. 1 kinds of coating agents, it comprises the active energy ray polymer resin composition according to any one of claim 1 to 16.
19. 1 kinds of duplexers, it is the duplexer wherein simultaneously or on the two sides layer of the active energy ray polymer resin composition comprised according to any one of claim 1 to 16 being laminated in base material (F).
20. duplexer according to claim 19, wherein base material (F) is for being selected from least one in the cohort that is made up of poly-acetylcellulose mesentery, polynorbornene mesentery, polypropylene mesentery, polyacrylic acid mesentery, polycarbonate mesentery, polyester mesentery, polyvinyl alcohol mesentery and polyimide mesentery.
21. 1 kinds of duplexers used for optical elements, it uses the duplexer according to claim 19 or 20 to form.
CN201480037713.3A 2013-07-04 2014-07-03 Active energy ray polymer resin composition, bonding agent, smears, layered product and layered product used for optical elements Active CN105358584B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810249292.0A CN108424745B (en) 2013-07-04 2014-07-03 Active energy ray-polymerizable resin composition, adhesive, coating agent, laminate, and use of laminate

Applications Claiming Priority (19)

Application Number Priority Date Filing Date Title
JP2013-141045 2013-07-04
JP2013141045 2013-07-04
JP2013159388 2013-07-31
JP2013-159388 2013-07-31
JP2013173290A JP6260143B2 (en) 2013-08-23 2013-08-23 Active energy ray polymerizable resin composition and laminate
JP2013-173290 2013-08-23
JP2013216348 2013-10-17
JP2013-216348 2013-10-17
JP2013252456A JP6303460B2 (en) 2013-12-05 2013-12-05 Active energy ray polymerizable resin composition and laminate
JP2013-252466 2013-12-05
JP2013-252464 2013-12-05
JP2013252465A JP5688519B1 (en) 2013-07-04 2013-12-05 Active energy ray-polymerizable adhesive and laminate
JP2013-252456 2013-12-05
JP2013-252465 2013-12-05
JP2013252463A JP5703475B1 (en) 2013-07-04 2013-12-05 Active energy ray-polymerizable adhesive and laminate
JP2013-252463 2013-12-05
JP2013252464A JP5703476B1 (en) 2013-07-04 2013-12-05 Active energy ray-polymerizable adhesive and laminate
JP2013252466A JP5688520B1 (en) 2013-07-04 2013-12-05 Active energy ray-polymerizable adhesive and laminate
PCT/JP2014/067786 WO2015002269A1 (en) 2013-07-04 2014-07-03 Active-energy-ray-polymerizable resin composition and laminate

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN201810249292.0A Division CN108424745B (en) 2013-07-04 2014-07-03 Active energy ray-polymerizable resin composition, adhesive, coating agent, laminate, and use of laminate

Publications (2)

Publication Number Publication Date
CN105358584A true CN105358584A (en) 2016-02-24
CN105358584B CN105358584B (en) 2018-04-27

Family

ID=53437007

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201480037713.3A Active CN105358584B (en) 2013-07-04 2014-07-03 Active energy ray polymer resin composition, bonding agent, smears, layered product and layered product used for optical elements
CN201810249292.0A Active CN108424745B (en) 2013-07-04 2014-07-03 Active energy ray-polymerizable resin composition, adhesive, coating agent, laminate, and use of laminate

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201810249292.0A Active CN108424745B (en) 2013-07-04 2014-07-03 Active energy ray-polymerizable resin composition, adhesive, coating agent, laminate, and use of laminate

Country Status (3)

Country Link
KR (3) KR102456269B1 (en)
CN (2) CN105358584B (en)
TW (2) TWI623579B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109321145A (en) * 2017-07-31 2019-02-12 东洋油墨Sc控股株式会社 Optics active energy ray polymerism bonding agent and optical laminated body

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102336281B1 (en) * 2017-07-31 2021-12-07 토요잉크Sc홀딩스주식회사 Optical active energy ray-polymerizable adhesive and laminate obtained using said optical adhesive
WO2020017251A1 (en) * 2018-07-19 2020-01-23 Dic株式会社 Actinic energy ray curable composition, and cured film and antireflection film thereof
JP7297642B2 (en) * 2019-10-30 2023-06-26 日東電工株式会社 POLARIZING PLATE COMPOSITION FOR PROTECTING POLARIZER AND PROTECTIVE LAYER MADE FROM THE COMPOSITION
CN117866575B (en) * 2024-01-15 2024-06-18 江苏美标家居科技有限公司 Aldehyde-free flame-retardant waterproof balance artificial board and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5873991A (en) * 1996-12-20 1999-02-23 Pharmacia Biotech Ab Method for electrophoretic separation
JP2001026609A (en) * 1999-07-13 2001-01-30 Teijin Seiki Co Ltd Resin composition for optical stereolithography
US20080032127A1 (en) * 2004-01-07 2008-02-07 Minoru Kohara Pressure-Sensitive Adhesive Composition And Skin Patch
CN102012535A (en) * 2009-09-04 2011-04-13 东洋油墨制造株式会社 Polarizing plate and photocurable adhesive for forming polarizing plate

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3704786B2 (en) 1996-03-18 2005-10-12 住友化学株式会社 Polarizer
JP2004137172A (en) * 2002-10-16 2004-05-13 Konica Minolta Holdings Inc New aromatic sulfonium compound, photo acid generator comprising the same and photopolymerizable composition containing the same, ink composition for inkjet and method for inkjet recording
JP2005208456A (en) 2004-01-26 2005-08-04 Sumitomo Chemical Co Ltd Polarizing plate and its manufacturing method
JP2008001867A (en) * 2006-06-26 2008-01-10 Three Bond Co Ltd Curable resin composition
JP2008233874A (en) 2007-02-02 2008-10-02 Jsr Corp Polarizing plate and its manufacturing method
JP4744496B2 (en) 2007-04-16 2011-08-10 日東電工株式会社 Polarizing plate, optical film and image display device
CN101475790B (en) * 2008-01-04 2012-10-10 杨光 Novel timber adhesive and preparation thereof
CN101966349B (en) * 2010-09-10 2013-09-18 北京化工大学 Method for preparing photo-curable bone repairing material from epoxy group-containing siloxane-clad modified hydroxyapatite
CN102443362A (en) * 2010-10-15 2012-05-09 南通玺路贸易有限公司 Novel paper product glue and preparation method thereof
CN102634167B (en) * 2011-02-10 2014-05-07 台光电子材料股份有限公司 Resin composition
JP5304859B2 (en) * 2011-08-25 2013-10-02 東洋インキＳｃホールディングス株式会社 Photopolymerizable composition and use thereof
JP5850244B2 (en) 2012-03-16 2016-02-03 Dic株式会社 UV curable composition, adhesive and polarizing plate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5873991A (en) * 1996-12-20 1999-02-23 Pharmacia Biotech Ab Method for electrophoretic separation
JP2001026609A (en) * 1999-07-13 2001-01-30 Teijin Seiki Co Ltd Resin composition for optical stereolithography
US20080032127A1 (en) * 2004-01-07 2008-02-07 Minoru Kohara Pressure-Sensitive Adhesive Composition And Skin Patch
CN102012535A (en) * 2009-09-04 2011-04-13 东洋油墨制造株式会社 Polarizing plate and photocurable adhesive for forming polarizing plate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109321145A (en) * 2017-07-31 2019-02-12 东洋油墨Sc控股株式会社 Optics active energy ray polymerism bonding agent and optical laminated body
CN109321145B (en) * 2017-07-31 2022-01-04 东洋油墨Sc控股株式会社 Active energy ray-polymerizable adhesive for optical use and optical laminate

Also Published As

Publication number Publication date
KR20220147143A (en) 2022-11-02
TW201512284A (en) 2015-04-01
CN108424745A (en) 2018-08-21
KR20160030896A (en) 2016-03-21
TWI623579B (en) 2018-05-11
CN108424745B (en) 2021-06-15
KR20210032025A (en) 2021-03-23
KR102456269B1 (en) 2022-10-18
CN105358584B (en) 2018-04-27
TWI656137B (en) 2019-04-11
KR102619470B1 (en) 2024-01-03
TW201819426A (en) 2018-06-01
KR102230902B1 (en) 2021-03-22

Similar Documents

Publication Publication Date Title
JP6191427B2 (en) Active energy ray polymerizable resin composition and laminate
JP5703475B1 (en) Active energy ray-polymerizable adhesive and laminate
TWI344975B (en)
JP6273879B2 (en) Active energy ray polymerizable resin composition and laminate
JP6260143B2 (en) Active energy ray polymerizable resin composition and laminate
CN105358584A (en) Active-energy-ray-polymerizable resin composition and laminate
JP6343909B2 (en) Resin composition, active energy ray-polymerizable adhesive, and laminate
JP6135243B2 (en) Adhesive and adhesive sheet using the same
WO2015002269A1 (en) Active-energy-ray-polymerizable resin composition and laminate
TWI526709B (en) Optical film and optical display apparatus comprising the same
JP6613586B2 (en) Active energy ray polymerizable resin composition and laminate
JP5098722B2 (en) Curable resin composition, film laminate for sticking, and laminate for impact absorption
JP2019035031A (en) Active energy ray-polymerizable resin composition
JP6307914B2 (en) Active energy ray polymerizable resin composition and laminate
JP6331367B2 (en) Resin composition, active energy ray-polymerizable adhesive, and laminate
CN107936906A (en) A kind of OLED Protection glues and preparation method thereof
JP2015108098A (en) Active energy ray-polymerizable resin composition and laminate
JP6369018B2 (en) Active energy ray polymerizable resin composition and laminate
JP2016172801A (en) Active energy ray-polymerizable resin composition and laminate
JP2015172132A (en) active energy ray-polymerizable resin composition and laminate
JP6428031B2 (en) Optical material active energy ray polymerizable resin composition and laminate
JP2015108096A (en) Active energy ray-polymerizable resin composition and laminate
CN118255929A (en) Active energy ray polymerizable resin composition and laminate
JP6314531B2 (en) Active energy ray polymerizable resin composition and laminate
JP2023092544A (en) Active energy ray-polymerizable resin composition and laminate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant