CN105143388B - Ultraviolet-curing adhesive composition and binding agent - Google Patents

Ultraviolet-curing adhesive composition and binding agent Download PDF

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Publication number
CN105143388B
CN105143388B CN201480022518.3A CN201480022518A CN105143388B CN 105143388 B CN105143388 B CN 105143388B CN 201480022518 A CN201480022518 A CN 201480022518A CN 105143388 B CN105143388 B CN 105143388B
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methyl
acrylate
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ultraviolet
mass parts
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CN105143388A (en
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纲岛启次
大地尉夫
佐藤浩司
小西真理子
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The problem to be solved in the present invention is to provide the ultraviolet-curing adhesive composition that bonding force, wet-heat resisting albefaction and wet-heat resisting xanthochromia are excellent.The present invention provides ultraviolet-curing adhesive composition and the binding agent using said composition to obtain, described ultraviolet-curing adhesive composition is characterised by, it contains carbamate (methyl) acrylate (X), (methyl) acrylic monomer (Y) and Photoepolymerizationinitiater initiater (Z), described carbamate (methyl) acrylate (X) is the polyhydric alcohol (a) making to comprise Polyethylene Glycol (a1), polyisocyanates (b) and (methyl) acrylic compounds (c) with hydroxyl or NCO react and obtain.The binding agent using the ultraviolet-curing adhesive composition of the present invention to obtain can be suitably used as the binding agent for optics.Especially can be suitably employed in the IT Related products such as manufacture contact panel, liquid crystal display, plasma display, organic EL, PC, mobile phone.

Description

Ultraviolet-curing adhesive composition and binding agent
Technical field
The present invention relates to the ultraviolet-curing adhesive group that bonding force, wet-heat resisting albefaction and wet-heat resisting xanthochromia are excellent Compound and binding agent.
Background technology
Since Yi Wang, acrylic adhesive is used for purposes widely.The most in recent years, it is correlated with at IT such as slim TVs Purposes in product expands, and is advancing high performance, multifunction.But, the price of IT Related product is also falling, Do not require nothing more than high performance, also require high production rate.
Wherein, owing to need not in the case of the binding agent (solvent system, water system) of conventional type as must the solvent of operation Drying process and ageing time etc. required before being machined to show performance, therefore can expect large-duty purple Outside line curing adhesive receives publicity.Additionally, due to the thick-film of adhesive phase is easy compared with the binding agent of conventional type, because of And the advantage that can expect high performance etc. can be enumerated, expect development from now on.
As the ultraviolet-curing adhesive that can be used in above-mentioned IT Related product, the most known a kind of binding agent combination Thing, it is characterised in that relative to possessing monomer 100 mass parts of unsaturated double-bond, comprise more than 5 mass parts and 200 mass parts Following has ammonia ester bond and has the high molecular thing that weight average molecular weight is more than 20,000 of unsaturated double-bond in polymer ends (see for example patent documentation 1).
But, for above-mentioned binding agent, after using binding agent under wet heat condition, if placing in room temperature, then exist The problems such as binding agent overlay film generation albefaction or subsequently generation xanthochromia.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-104296 publication
Summary of the invention
The problem to be solved in the present invention is for providing a kind of bonding force, wet-heat resisting albefaction and the purple of wet-heat resisting xanthochromia excellence Outside line curing adhesive composition.
Means for solving the above
The present inventor etc., among the further investigation carried out to solve above-mentioned problem, are conceived to carbamate (first Base) acrylate, studied.
It is it was found that pass through to contain Polyethylene Glycol as the raw material as carbamate (methyl) acrylate Polyhydric alcohol, above-mentioned problem can be solved, thus complete the present invention.
That is, the present invention provides a kind of ultraviolet-curing adhesive composition and the binding agent using said composition to obtain, Described ultraviolet-curing adhesive composition is characterised by, it contains carbamate (methyl) acrylate (X), (first Base) acrylic monomer (Y) and Photoepolymerizationinitiater initiater (Z), described carbamate (methyl) acrylate (X) be make to comprise poly- The polyhydric alcohol (a) of ethylene glycol (a1), polyisocyanates (b) and (methyl) the acrylic acid series chemical combination with hydroxyl or NCO Thing (c) reacts and obtains.
Invention effect
The binding agent using the ultraviolet-curing adhesive composition of the present invention to obtain possesses the bonding force of excellence, holding Power, wet-heat resisting albefaction and wet-heat resisting xanthochromia.
The binding agent using the ultraviolet-curing adhesive composition of the present invention to obtain can be suitably used as light The binding agent of department of the Chinese Academy of Sciences's part.Especially can be suitably employed in manufacture contact panel, liquid crystal display, plasma display, organic EL, The IT Related product such as PC, mobile phone.
Detailed description of the invention
The ultraviolet-curing adhesive composition of the present invention contains carbamate (methyl) acrylate (X), (first Base) acrylic monomer (Y) and Photoepolymerizationinitiater initiater (Z), described carbamate (methyl) acrylate (X) be make to comprise poly- The polyhydric alcohol (a) of ethylene glycol (a1), polyisocyanates (b) and (methyl) the acrylic acid series chemical combination with hydroxyl or NCO Thing (c) reacts and obtains.
Above-mentioned Polyethylene Glycol (a1) improves the hydrophilic of ultraviolet-curing adhesive composition, owing to binding agent overlay film exists Suppression binding agent overlay film can be thus helped in after wet-heat resisting with uniform pickup dampness and moisture when being exposed under wet heat condition Albefaction.It addition, by using above-mentioned Polyethylene Glycol (a1), thus reduce the making of (methyl) acrylic monomer of easy xanthochromia Consumption or make to use (methyl) acrylic monomer of easy xanthochromia, thus bonding force can also be kept and compose Give the wet-heat resisting xanthochromia of excellence.
Above-mentioned Polyethylene Glycol (a1) is used as the raw material of carbamate (methyl) acrylate (X), but from bonding force, resistance to The aspect of damp and hot albefaction and wet-heat resisting xanthochromia is set out, it is possible to use in straight-chain Polyethylene Glycol, branched Polyethylene Glycol Any one, above-mentioned Polyethylene Glycol (a1) can be with the form of the grafted chain in above-mentioned carbamate (methyl) acrylate (X) Exist, it is also possible to presented in block chain.
As the number-average molecular weight of above-mentioned Polyethylene Glycol (a1), from can further improve wet-heat resisting albefaction and wet-heat resisting The aspect of xanthochromia is set out, preferably 200～5, the scope of 000, and then the reactive control in time can further improving synthesis The easiness of system, set out at the aspect of the storage stability etc. of low temperature, more preferably 200～2, the scope of 000, further preferably It it is the scope of 200～1,000.It should be noted that the number-average molecular weight of above-mentioned Polyethylene Glycol (a1) represents passes through gel infiltration The value that chromatograph (GPC) method measures with following condition.
Determinator: high speed GPC device (TOSOH Co., Ltd's system " HLC-8220GPC ")
Post: the following post of TOSOH Co., Ltd is connected in series use.
" TSKgel G5000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G4000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G3000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgel G2000 " (7.8mmI.D. × 30cm) × 1 piece
Detector: RI (differential refractometer)
Column temperature: 40 DEG C
Eluent: oxolane (THF)
Flow velocity: 1.0mL/ minute
Injection rate: 100 μ L (tetrahydrofuran solution of sample solution concentration 0.4 mass %)
Standard specimen: use following polystyrene standard to make standard curve.
(polystyrene standard)
TOSOH Co., Ltd's system " TSKgel polystyrene standard A-500 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard A-1000 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard A-2500 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard A-5000 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-1 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-2 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-4 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-10 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-20 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-40 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-80 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-128 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-288 "
TOSOH Co., Ltd's system " TSKgel polystyrene standard F-550 "
As the usage amount of above-mentioned Polyethylene Glycol (a1), from can further improve bonding force, retentivity, wet-heat resisting albefaction Property and the aspect of wet-heat resisting xanthochromia set out, the scope of 1～60 mass % in the most above-mentioned polyhydric alcohol (a), more preferably 3～ The scope of 50 mass %, more preferably 5～the scope of the scope of 40 mass %, particularly preferably 10.5～33 mass %.
It addition, as the content of the above-mentioned Polyethylene Glycol (a1) in carbamate (methyl) acrylate (X), from can be more The aspect improving bonding force, retentivity, wet-heat resisting albefaction and wet-heat resisting xanthochromia further is set out, preferably 0.1～50 matter The scope of the scope of amount %, the more preferably scope of 5～35 mass %, more preferably 9～25 mass %.
As the spendable above-mentioned polyhydric alcohol (a) beyond above-mentioned Polyethylene Glycol (a1), it is possible to use such as Polyethylene Glycol Polyether polyol in addition, PEPA, polycarbonate polyol, acrylic acid series multiple alcohol, butadiene polyhydric alcohol etc..These Polyhydric alcohol can be used alone or share two or more.Among these, from can further improve bonding force, retentivity, resistance to The aspect of damp and hot albefaction and wet-heat resisting xanthochromia is set out, and above-mentioned polyether polyol, polycarbonate polyol are preferably used.
As above-mentioned polyether polyol, it is possible to use such as: make the alkylene oxides such as oxirane, expoxy propane, epoxy butane One or more addition polymerizations in the product that there is the compound of two or more reactive hydrogen and obtain；Oxolane is made to open Cyclopolymerization and the polytetramethylene glycol that obtains；Make the modified polytetramethylene glycol that oxolane and alkyl substituted tetrahydro furan are copolymerized into；Make new The modified polytetramethylene glycol that pentanediol and oxolane are copolymerized into；Etc..
As the above-mentioned compound with two or more reactive hydrogen, it is possible to use such as: ethylene glycol, diethylene glycol, three second Glycol, TEG, 1,2-PD, 1,3-PD, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3 butylene glycol, BDO, 2,3-butanediol, 1,5-PD, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol, decamethylene-glycol, 1,11-undecane, 1,12-dodecanediol, 2-methyl isophthalic acid, 3- Propylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1,3-PD, 3-methyl isophthalic acid, 5-pentanediol, 2-ethyl-1,3-PD, 3-methyl isophthalic acid, 5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl isophthalic acid, 8-ethohexadiol, hydroquinone, resorcinol, bis-phenol A, Bisphenol F, 4, the dihydroxy compounds of the lower molecular weight such as 4 '-bis-phenol；1,2-cyclobutanediol, 1,3-ring pentanediol, Isosorbide-5-Nitrae-ring Hexanediol, cycloheptyl glycol, ring ethohexadiol, 1,4-CHDM, hydroxypropyl Hexalin, three rings [5,2,1,0,2, the 6] last of the ten Heavenly stems Alkane dimethanol, dicyclo [4,3,0] nonanediol, two cyclohexanediols, three rings [5,3,1,1] dodecanediol, dicyclo [4,3,0] nonane Dimethanol, three rings [5,3,1,1] dodecane diethanol, hydroxypropyl three ring [5,3,1,1] lauryl alcohol, spiral shell [3,4] ethohexadiol, fourth Basic ring hexanediol, 1,1 '-bis-cyclohexylene, phloroglucite, hydrogenated bisphenol A, 1, the ester ring type such as 3-diamantane (obsolete) glycol is polynary Alcohol；The polyether polyol such as Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol；Polyhexamethylene adipate ester, polyhexamethylene succinic acid The PEPA such as ester, polycaprolactone；Etc..
As the number-average molecular weight of above-mentioned polyether polyol, preferably 200～3, the scope of 000, more preferably 500～2, The scope of 000, more preferably 500～1, the scope of 500.It should be noted that the equal molecule of the number of above-mentioned polyether polyol Amount represents the value being measured as the number-average molecular weight of above-mentioned Polyethylene Glycol (a1) and obtain.
As above-mentioned polycarbonate polyol, such as, can use carbonic ester and/or phosgene and above-mentioned there are two The polycarbonate polyol that the compound of above reactive hydrogen reacts and obtains.
As above-mentioned carbonic ester, it is possible to use such as methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, ring Carbonic ester, diphenyl carbonate etc..
As the hydroxyl value of above-mentioned polycarbonate polyol, from improving the aspect of bonding force further, preferably 30～ The scope of 230mgKOH/g, more preferably 50～the scope of 230mgKOH/g.It should be noted that above-mentioned polycarbonate polyol Hydroxyl value represent the value being measured according to JIS K0070-1992.
As above-mentioned polyisocyanates (b), it is possible to use such as XDI, phenylene diisocyanate, The aromatic diisocyanates such as toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, naphthalene diisocyanate；Hexa-methylene two Isocyanates, lysinediisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4 '-dicyclohexyl first Aliphatic such as alkane diisocyanate, methylcyclohexane diisocyanate, tetramethyl xylylene diisocyanate or there is alicyclic ring The diisocyanate etc. of structure.These polyisocyanates can be used alone or share two or more.Among these, from more entering One step improves the aspect of bonding force, retentivity and wet-heat resisting xanthochromia and sets out, and two Carbimide .s with alicyclic structure are preferably used Ester, more preferably use HMDI, isophorone diisocyanate, cyclohexane diisocyanate, Methylcyclohexane diisocyanate.
Above-mentioned (methyl) acrylic compounds (c) with hydroxyl or NCO is in order to carbamate (methyl) acrylate (X) imports the purpose of (methyl) acryloyl group and uses.
As can serve as above-mentioned (methyl) acrylic compounds with hydroxyl of above-claimed cpd (c), can make With such as: (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, acrylic acid 3-hydroxy propyl ester, (methyl) Acrylic acid 3-hydroxybutyl, (methyl) acrylic acid 4-hydroxybutyl, the own ester of acrylic acid 6-hydroxyl, hydroxyethyl acrylamide etc. have (methyl) alkyl acrylate of hydroxyl；Trimethylolpropane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylic acid Ester, dipentaerythritol five (methyl) acrylate etc. have multifunctional (methyl) acrylate of hydroxyl；Polyethyleneglycol propylene Acid esters, polypropylene glycol mono acrylic ester etc..Among these, from further improve curable based on ultraviolet in terms of go out Send out, more preferably use the acrylic compounds with hydroxyl, from further improving the accessibility of raw material, curable and gluing The aspect of compound is set out, and further preferably uses the alkyl acrylate with hydroxyl, particularly preferably uses acrylic acid 2-hydroxyl Base ethyl ester, acrylic acid 4-hydroxybutyl.
It addition, as can be used as (methyl) acrylic compounds with NCO of above-claimed cpd (c), can To use such as: 2-(methyl) acryloyloxyethyl isocyanate, 2-(2-(methyl) acryloyloxyethoxy) ethyl are different Cyanate, 1, double ((methyl) acryloyloxymethyl) ethyl isocyanates of 1-etc..Among these, from the easiness obtaining raw material Aspect set out, 2-(methyl) acryloyloxyethyl isocyanate, more preferably 2-acryloyl-oxyethyl isocyanide are preferably used Acid esters.
As using, there is above-mentioned as in the case of above-claimed cpd (c) of (methyl) acrylic compounds of hydroxyl The manufacture method of carbamate (methyl) acrylate (X), it is possible to use such as: under solvent-free, by above-mentioned polyhydric alcohol (a) After putting in reaction system with above-mentioned (methyl) acrylic compounds (c), supply above-mentioned polyisocyanates (b), be allowed to mix, Reaction, the method thus carrying out manufacturing；Under solvent-free, by making above-mentioned polyhydric alcohol (a) and above-mentioned polyisocyanates (b) react And obtain the carbamate prepolymer with NCO, then, supply has above-mentioned (methyl) acrylic acid series of hydroxyl Compound (c), is allowed to mix, react, the method thus carrying out manufacturing；Etc..Above-mentioned reaction the most preferably exists Substantially carry out under conditions of 20～120 DEG C 30 minutes～about 24 hours.
It addition, there is (methyl) acrylic compounds of NCO as above-claimed cpd (c) as using In the case of the manufacture method of carbamate (methyl) acrylate (X), it is possible to use such as: under solvent-free, in input State polyhydric alcohol (a) and above-mentioned polyisocyanates (b), be allowed to reaction and obtain the carbamate prepolymer with hydroxyl, then, Supply has above-mentioned (methyl) acrylic compounds (c) of NCO, is allowed to mix, react, and thus carries out manufacturing Method etc..Above-mentioned reaction the most preferably substantially carries out 30 minutes～24 hours left sides under conditions of 20～120 DEG C Right.
The manufacture of above-mentioned carbamate (methyl) acrylate (X) can be in the presence of organic solvent, water-medium Carry out.It addition, as organic solvent, the replacement of water-medium, it is also possible to depositing of (methyl) acrylic monomer (Y) described later Manufacture under.
Above-mentioned polyhydric alcohol (a) exists with the reaction of above-mentioned polyisocyanates (b) with above-mentioned (methyl) acrylic compounds (c) Hydroxyl that above-mentioned polyhydric alcohol (a) is had and the total amount of the hydroxyl that above-mentioned (methyl) acrylic compounds (c) is had and Equivalents ratio [total amount of NCO/hydroxyl]=0.75 between the NCO that polyisocyanates (b) is had ～1 scope in carry out, this control obtained by carbamate (methyl) acrylate (X) molecular weight from the standpoint of It is preferred, the scope of more preferably 0.79～0.995.Alternatively, it is also possible to be allowed in the case of above-mentioned equivalents ratio is more than 1 Lower reaction, but now, so that for the purpose of the NCO inactivation of carbamate (methyl) acrylate (X), being preferably used The alcohol such as methanol.Now, hydroxyl and above-mentioned (methyl) acrylic acid series being had so that above-mentioned polyhydric alcohol (a) preferably it is adjusted Hydroxyl that compound (c) is had and the total amount of the hydroxyl that alcohol is had and above-mentioned polyisocyanate-based between equivalents ratio In [total amount of NCO/hydroxyl] is above-mentioned scope.
It addition, as can be so that the NCO inactivation of above-mentioned carbamate (methyl) acrylate (X) is for mesh And the alcohol that uses, it is possible to use the monofunctional alcohols such as such as methanol, ethanol, propanol, butanol；1,2-PD, 1,3 butylene glycol Etc. two functional alcohol etc. comprising primary hydroxyl and secondary hydroxyl.
It addition, when manufacturing carbamate (methyl) acrylate (X), polymerization inhibitor, amino can be used as required Formic acid esterification catalyst etc..
As above-mentioned polymerization inhibitor, it is possible to use such as BHT, hydroquinone, methyl are to benzene Diphenol, hydroquinone monomethyl ether (p methoxy phenol), p-tert-butyl catechol methoxyphenol, 2,6-di-tertiary butyl methyl phenol, fen thiophene Piperazine, tetramethyl thiuram disulfide, diphenylamines, dinitro benzene etc..
As above-mentioned urethanation catalyst, it is possible to use such as triethylamine, triethylene diamine, N-methylmorpholine etc. Nitrogen-containing compound；The slaines such as potassium acetate, zinc stearate, tin octoate；The organic metal such as dibutyl tin laurate, acetylacetone,2,4-pentanedione zirconium Compound etc..
Above-mentioned carbamate (methyl) acrylate (X) has and carries out radical polymerization by light irradiation, heating etc. (methyl) acryloyl group.As the equivalent of above-mentioned (methyl) acryloyl group, from further improving bonding force, jump close property etc. Aspect set out, the scope of preferably 1,000～200,000g/eq., the scope of more preferably 5,000～100,000g/eq.. It should be noted that the equivalent of above-mentioned (methyl) acryloyl group represents above-mentioned polyhydric alcohol (a) and polyisocyanates (b) and (first Base) the total quality of acrylic compounds (d) is divided by present in above-mentioned carbamate (methyl) acrylate (X) Value after the equivalent of (methyl) acryloyl group.It addition, in the present invention, " (methyl) acrylic compounds " refers to metering system One or both in acid based compound and acrylic compounds, " (methyl) acrylate " is methacrylate and third One or both in olefin(e) acid ester, " (methyl) acryloyl group " refers to the side or double in methylacryloyl and acryloyl group Side, " (methyl) acrylic acid " is one or both in methacrylic acid and acrylic acid, and " (methyl) acrylic monomer " is One or both in finger, methacrylic monomers and acrylic monomer.
As the weight average molecular weight of above-mentioned carbamate (methyl) acrylate (X), from the bonding force that can take into account excellence With retentivity and from the viewpoint of good coating workability can be given, the scope of preferably 5,000～200,000, more excellent Elect the scope of 10,000～100,000 as.It should be noted that the weight average of above-mentioned carbamate (methyl) acrylate (X) Molecular weight represents the value being measured in the same manner as the number-average molecular weight of above-mentioned Polyethylene Glycol (a1) and obtain.
As above-mentioned (methyl) acrylic monomer (Y), it is possible to use such as: (methyl) acrylic acid methyl ester., (methyl) third Olefin(e) acid ethyl ester, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid are secondary Butyl ester, (methyl) Isobutyl 2-propenoate, (methyl) acrylic acid 2-ethyl butyl ester, (methyl) acrylic acid n-pentyl ester, (methyl) propylene Acid own ester, (methyl) acrylic acid-2-ethyl caproite, (methyl) heptylacrylate, (methyl) 1-Octyl acrylate, (methyl) acrylic acid Nonyl ester, (methyl) dodecyl acrylate, (methyl) acrylic acid 3-methylbutyl butenoate, (methyl) Isooctyl acrylate monomer, (methyl) propylene Acid lauryl, (methyl) tridecyl acrylate, (methyl) stearyl acrylate ester, (methyl) acrylic acid peopentyl ester, (methyl) propylene Acid aliphatic (methyl) acrylate such as hexadecyl ester, (methyl) isoamyl acrylate；(methyl) isobornyl acrylate, (methyl) Ester ring type (methyl) acrylate such as cyclohexyl acrylate, (methyl) tetrahydrofurfuryl acrylate；(methyl) acrylic acid 3-methoxyl group Butyl ester, (methyl) acrylic acid 2-methoxy acrylate, (methyl) acrylic acid 3-methoxyl group propyl ester, (methyl) acrylic acid 2-methoxyl group fourth Ester, the methoxy polyethylene glycol acrylate of the scope that addition molal quantity is 1～15 of oxygen ethylene, ethoxydiglycol (first Base) acrylate, ethyl carbitol (methyl) acrylate etc. have (methyl) acrylate of ether；(methyl) acrylic acid 2- Hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxybutyl etc. have (methyl) propylene of hydroxyl Acid esters；(methyl) benzyl acrylate, (methyl) benzyl acrylate, (methyl) acrylate, phenoxy group Polyethylene Glycol Aromatic series (methyl) acrylic acid such as acrylate, (methyl) phenyl acrylate, (methyl) acrylic acid 2-hydroxyl-3-phenoxy-propyl Ester；(methyl) acrylamide, dimethyl (methyl) acrylamide, acryloyl morpholine, dimethylamino-propyl (methyl) acrylamide, Isopropyl (methyl) acrylamide, diethyl (methyl) acrylamide, ethoxy (methyl) acrylamide, diacetone (methyl) third Acrylamides etc. have (methyl) acrylic monomer etc. of nitrogen-atoms.These (methyl) acrylic monomers can be used alone or Person share two or more.
It should be noted that as above-mentioned (methyl) acrylic monomer (Y), in order to give the wet-heat resisting albefaction of excellence Property, sometimes use above-mentioned (methyl) acrylic monomer with nitrogen-atoms.Now, wet-heat resisting xanthochromia declines sometimes, because of This preferred addition is few, is below 40 mass % preferably with respect to above-mentioned (methyl) acrylic monomer (Y) total amount, more preferably Below 35 mass %.In the present invention, the hydrophilic of binding agent overlay film can be improved by using above-mentioned Polyethylene Glycol (a1), Therefore wet-heat resisting albefaction can be shown with less addition.
As the usage amount of above-mentioned (methyl) acrylic monomer (Y), from the aspect of bonding force, relative to above-mentioned ammonia Carbamate (methyl) acrylate (X) 100 mass parts, preferably in the scope of 30～200 mass parts use, more preferably 50～ The scope of 150 mass parts, the scope of particularly preferred 70～130 mass parts.
Above-mentioned Photoepolymerizationinitiater initiater (Z) produces free radical by light irradiation, heating etc., causes above-mentioned carbamate (methyl) acrylate (X) and the radical polymerization of above-mentioned (methyl) acrylic monomer (Y).
As above-mentioned Photoepolymerizationinitiater initiater (Z), it is possible to use such as: 4-phenoxydichloroacetophenone, diethoxybenzene second Ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxyl Butylcyclohexyl phenyl ketone, 4-(2-hydroxyl-oxethyl)-phenyl (2-hydroxyl-2-propyl group) ketone, 2-methyl-[4-(methyl mercapto) benzene Base]-2-morpholino-1-acetone, 2, the acetophenone compound such as 2-dimethoxy-2-phenyl acetophenone；Benzoin, benzoin first The benzoin compound benzophenone such as ether, benzoin diisopropyl ether, benzoin iso-propylether, benzoin isobutyl ether, benzoylbenzoic acid, Methyl benzoylbenzoate, 4-phenyl benzophenone, dihydroxy benaophenonel, 4-benzoyl-4 '-methyldiphenyl thioether, 3,3 '- The benzophenone cpds such as dimethyl-4-methoxy benzophenone；Thiaxanthone, CTX, 2,4-bis-clopenthixal ketone, 2-first Base thiaxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropylthioxanthone etc. Thioxanthone compounds；4,4 '-dimethylamino thiaxanthone (another name: ミ ネ ラ mono-ズ ケ ト Application), 4,4 '-lignocaine benzophenone, The anthraquinone compounds such as α-acyl group oxime ester, benzil, methyl benzoylformate (" バ イ ア キ ユ ア 55 "), 2-ethyl-anthraquinone；2, 4,6-trimethyl benzoyl diphenyl base phosphine oxides (" LucirinTPO "), double (2,4,6-trimethylbenzoyl) phenyl aoxidize The acylphosphine oxide compounds such as phosphine (" IRGACURE 819 ")；3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone [" BTTB " of NOF Corp], acrylated benzophenone etc..
As above-mentioned Photoepolymerizationinitiater initiater (Z), from further improving bonding force, retentivity, wet-heat resisting xanthochromia and consolidating Change property aspect set out, be preferably used 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2,4, 6-trimethyl benzoyl diphenyl base phosphine oxide, double (2,4,6-trimethylbenzoyl) phenyl phosphine oxide.
The usage amount of above-mentioned Photoepolymerizationinitiater initiater (Z) is relative to above-mentioned carbamate (methyl) acrylate (X) 100 matter Amount part preferably uses with the scope of 0.1～20 mass parts, the scope of more preferably 0.5～15 mass parts, particularly preferably 1～5 The scope of mass parts.
The ultraviolet-curing adhesive composition of the present invention contain above-mentioned carbamate (methyl) acrylate (X), Above-mentioned (methyl) acrylic monomer (Y) and above-mentioned Photoepolymerizationinitiater initiater (Z), as neccessary composition, can contain it as required Its additive.
As other additive above-mentioned, it is possible to use such as silane coupler, antioxidant, light stabilizer, solvent, antirust Agent, thixotropy conferring agents, sensitizer, polymerization inhibitor, levelling agent, viscosifier, antistatic additive, fire retardant etc..Among these, from entering The aspect of the bonding physical property after one step raising wet-heat resisting is set out, and preferably comprises silane coupler.It addition, it is resistance to from can further improve The aspect of damp and hot xanthochromia etc. is set out, and preferably comprises antioxidant, light stabilizer.
As above-mentioned silane coupler, it is possible to use such as: 3-glycydoxy trimethoxy silane, 3-contract Water glycerin ether epoxide propyl-triethoxysilicane, 3-glycidoxypropyl diethoxy silane, 3-glycidyl ether oxygen Base hydroxypropyl methyl dimethoxysilane etc. has the silane coupler of epoxy radicals；2-(3,4-epoxycyclohexyl) ethyl triethoxy Silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl-methyl dimethoxy silicon Alkane, 2-(3,4-epoxycyclohexyl) ethyl-methyl diethoxy silane, 2-(3,4-epoxycyclohexyl) propyl trimethoxy silicane, 2-(3,4-epoxycyclohexyl) hydroxypropyl methyl dimethoxysilane, 2-(3,4-epoxycyclohexyl) propyl-triethoxysilicane, 2- (3,4-epoxycyclohexyl) hydroxypropyl methyl diethoxy silane etc. has the silane coupler of alicyclic epoxy group；Vinyl trichlorine silicon Alkane, vinyltrimethoxy silane, VTES, to styryl trimethoxy silane, 3-methacryl Epoxide hydroxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxy third Ylmethyl diethoxy silane, 3-methacryloxypropyl, 3-acryloxypropyl trimethoxy Silane, 3-mercaptopropyi methyl dimethoxysilane, 3-mercaptopropyi trimethoxy silane, oxyalkylsiloxane oligomer etc.. These silane couplers can be used alone or share two or more.Among these, after can further improve wet-heat resisting The aspect of bonding force etc. is set out, the silane coupler silane coupler with epoxy radicals is preferably used, having alicyclic epoxy group, More preferably use selected from 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy In base silane, 3-glycydoxy trimethoxy silane and 3-glycydoxy triethoxysilane More than one.
As the usage amount of above-mentioned silane coupler, the aspect of the bonding force after can further improve wet-heat resisting, Relative to above-mentioned carbamate (methyl) acrylate (X) 100 mass parts, the amount of being preferably used is the model of 0.01～10 mass parts Enclose, the scope of more preferably 0.05～5 mass parts, the scope of further preferred 0.05～1 mass parts.
As above-mentioned antioxidant, it is possible to use the hindered phenol compound catching the free radical produced by heat deterioration is (main anti- Oxidant) and by the phosphorus compound of peroxide decomposition produced by heat deterioration, sulphur compound (secondary antioxidant) etc..
As above-mentioned hindered phenol compound, it is possible to use such as: the double [3-(the 3-tert-butyl group-5-methyl-4-hydroxyl of triethylene glycol Base phenyl) propionic ester], tetramethylolmethane four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], 3-(3,5-di-t-butyls- 4-hydroxy phenyl) propanoic acid stearyl, sulfur is for diethylene double [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], benzene Propane acid-3, double (1,1-the dimethyl ethyl)-4-hydroxyl-C of 5-7-C9Pendant alkyl group ester, 4,6-double (dodecylthiomethyl) is adjacent Cresol, N-phenylaniline and 2, the product of 4,4-trimethylpentenes, the acrylic acid 2-tert-butyl group-6-(the 3-tert-butyl group-2-hydroxyl Base-5-methyl-benzyl)-4-aminomethyl phenyl ester, 3,9-double [2-(3-(tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)- 1,1-dimethyl ethyl] 2,4,8,10-tetra-oxaspiro [5.5] hendecanes, 2,6-di-tert-butyl-4-methy phenol, 2,2 '-methylene Base double (4-methyl-6-tert-butylphenol), 2,5-bis-tertiary pentyl hydroquinone etc..
As above-mentioned phosphorus compound, such as, triphenylphosphine, double (2,4-di-t-butyl-6-aminomethyl phenyl) ethyl phosphorous acid Ester, triphenyl phosphite, trisnonylphenyl phosphite, three (2,4-dibutylphenyl) phosphite ester, three (2,4-dibutyl- 5-aminomethyl phenyl) phosphite ester, three (2-tributyl-4-(3-butyl-4-hydroxy-5-methyl base phenyl)-5-methylbenzene Base) phosphite ester, three (2,4-di-tert-butyl-phenyl) phosphite ester, tridecyl phosphite, octyl diphenyl phosphite ester, Two (decyl) single phenyl phosphites, two (tridecyl) pentaerythritol diphosphites, two (nonyl phenyl) tetramethylolmethane two Phosphite ester, double (2,4-dibutylphenyl) pentaerythritol diphosphites, double (2,6-dibutyl-4-aminomethyl phenyl) Ji Wusi Alcohol diphosphites, double (2,4,6-tributyl phenyl) pentaerythritol diphosphites, double (2,4-dicumylphenyl) Ji Wusi Alcohol diphosphites, four (tridecyl) isopropylidenediphenol diphosphites, four (tridecyl)-4,4 '-positive butylidene Double (2-butyl-5-methylphenol) diphosphites, six (tridecyl)-1,1,3-tri-(2-methyl-4-hydroxyl-5-butyl benzene Base) butane triphosphite ester, four (2,4-dibutylphenyl) biphenylen, 9,10-dihydro-9-oxy miscellaneous-10-phosphorus Miscellaneous phenanthrene-10-oxide, 2,2 '-di-2-ethylhexylphosphine oxide (4,6-butyl phenyl)-2-ethylhexyl phosphite ester, 2,2 '-di-2-ethylhexylphosphine oxide (4,6-butyl phenyl)-octadecyl phosphite ester, 2,2 '-ethylenebis (4,6-dibutylphenyl) fluorophosphites, three (2- [(2,4,8,10-tetrabutyl dibenzo [d, f] [1,3,2] dioxaphosphepin cycloheptadiene-6-base) epoxide] ethyl) amine, 2-second Base-2-butyl propylene glycol and 2, the phosphite ester etc. of 4,6-tributyl phenols.
As above-mentioned sulphur compound, it is possible to use such as: 3, the double dodecyl ester of 3 '-propane thioic acid, 3,3 '-sulfur is for dipropyl Acid dilauryl, sulfur for bisthiosulfate lauryl (ラ ウ ジ リ Le チ オ ジ チ オ ネ mono-ト), 3,3 '-thio-2 acid two (tridecyl) ester, 3,3 '-thio-2 acid two myristin, 3,3 '-distearylthiodi-propionate, four-methylene-3-moon Osmanthus base thiopropionate methane, 3,3 '-methyl-3,3 '-distearylthiodi-propionate, 3,3 '-thio-2 acid lauryl is hard Aliphatic radical ester, double [2-methyl-4-(3-alkyl thiopropionyl epoxide)-5-tert-butyl-phenyl] sulfide, β-lauryl sulfur generation Propionic ester, 2-mercaptobenzimidazole, 2-sulfydryl-5-tolimidazole, 3,3 '-thio-2 acid two (octadecyl) ester etc..
Among these, from can further improve bonding force and the aspect of wet-heat resisting xanthochromia, phosphatization is preferably used and closes Thing, more preferably uses selected from triphenylphosphine, double (2,4-di-t-butyl-6-aminomethyl phenyl) ethide phosphite ester and three (2,4-bis- Tert-butyl-phenyl) antioxidant of in phosphite ester more than a kind, particularly preferably use triphenylphosphine, double (2,4-bis-tertiary fourths Base-6-aminomethyl phenyl) ethide phosphite ester.
As the usage amount of above-mentioned antioxidant, from can further improve the aspect of wet-heat resisting xanthochromia, relative to Above-mentioned carbamate (methyl) acrylate (X) 100 mass parts, the scope of preferably 0.01～10 mass parts.
Above-mentioned light stabilizer catches the free radical produced by light deterioration, it is possible to use such as: mercaptan compound, thioether chemical combination The free radical scavenger such as thing, hindered amine compound and the UV absorbent such as benzophenone cpd, benzoic acid ester compounds Deng.Among these, from further improving the aspect of wet-heat resisting xanthochromia, hindered amine compound is preferably used.
As above-mentioned hindered amine compound, it is possible to use such as: hexamethylene and peroxidating N-butyl 2,2,6,6-tetramethyl- 4-piperidinamine-2, the product of 4,6-trichlorine 1,3,5-triazines and 2-ethylaminoethanol product, decanedioic acid double (2,2,6, 6-tetramethyl-1-(octyloxy)-4-piperidyl) ester, 1, the tool such as the product of 1-dimethyl ethyl hydrogen peroxide and octane There is the hindered amine compound of amino ether；N-acetyl group-3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl) pyrroles Alkane-2, the N-acetyl base system hindered amine compound such as 5-diketone；Double (1,2,2,6, the 6-pentamethyl-4-piperidyl) ester of decanedioic acid, double (1,2,2,6,6 ,-pentamethyl-4-piperidyl) { [3,5-double (1,1-dimethyl ethyl)-4-hydroxy phenyls] methyl } butyl the third two Acid esters, dimethyl succinate 1-(2-hydroxyethyl)-4-hydroxyl-2,2,6,6-tetramethyl piperidine condensation polymers, malonic acid [{ 4- Methoxyphenyl } methylene] the N-alkyl hindered amine compound etc. of-bis-(1,2,2,6,6-pentamethyl-4-piperidyl) ester.
As the usage amount of above-mentioned light stabilizer, from can further improve the aspect of wet-heat resisting xanthochromia, relatively In above-mentioned carbamate (methyl) acrylate (X) 100 mass parts, the scope of preferably 0.01～10 mass parts.
As the viscosity of the ultraviolet-curing adhesive composition of the present invention, when good screening characteristics and coating The aspect of the good treatability of binder solution is set out, preferably 500～20, the scope of 000mPa s, more preferably 1,000～ The scope of 15,000mPa s.It should be noted that above-mentioned viscosity represents 25 DEG C of values measured with Brookfield viscometer.
The ultraviolet-curing adhesive composition of the present invention can make solid by the irradiation of ultraviolet homenergic ray Change is carried out.
As the method making the ultraviolet-curing adhesive composition of the present invention solidify, can be by using such as xenon The known ultraviolet illumination injection device such as lamp, xenon-mercury lamp, metal halide lamp, high voltage mercury lamp, low pressure mercury lamp irradiates the purple of regulation Outside line is allowed to solidify.
Above-mentioned ultraviolet irradiation is preferably 0.05～5J/cm2, more preferably 0.1～3J/cm2, particularly preferably 0.3～ 1.5J/cm2Scope.It should be noted that ultraviolet irradiation amount uses UV detector (checker) UVR-N1 (GS-YUASA Co., Ltd.'s system) value of mensuration in the wave-length coverage of 300～390nm.
As the ultraviolet-curing adhesive composition of the present invention can be coated with to form the base material of adhesive phase, can make With plastic basis material, flexible printing element, glass baseplate and base material etc. after evaporation ITO on the substrate.
As above-mentioned plastic basis material, it is possible to use normally used comprise the base material of acrylic resin etc., PC (poly-carbonic acid Ester), PBT (polybutylene terephthalate), PPS (polyphenylene sulfide), MODIFIED PP E (polyphenylene oxide), PET (poly terephthalic acid second Diester), COP (cyclic olefin polymer), TAC (cellulose triacetate), antireflection film, anti-soil film, composition contact panel transparent The film etc. of conducting film.
Embodiment
Hereinafter, use embodiment that the present invention is described in more detail.
[synthesis example 1]
<synthesis of urethane acrylate (X-1)>
In the reaction vessel possessing blender, reflux cooling pipe, nitrogen ingress pipe, thermometer, (number is all to add polytetramethylene glycol Molecular weight: 1,000, hereafter abbreviated with " PTMG1000 ") 410 mass parts, Polyethylene Glycol (number-average molecular weight: 400, abridge below For " PEG-1 ") 27.5 mass parts, 2-Hydroxy ethyl acrylate (hereafter abbreviated with HEA) 6.1 mass parts, 2,6-di-t-butyl first Phenol 2 mass parts, p methoxy phenol 0.3 mass parts.Heat up until after temperature reaches 40 DEG C in reaction vessel, adding isophorone Diisocyanate (hereafter abbreviated with IPDI) 105 mass parts.Then, two neodecanoic acid dioctyl tin 0.1 mass parts, used time 1 are added Hour it is warming up to 80 DEG C.Afterwards, keeping 12 hours at 80 DEG C, after confirming that whole NCOs disappears, cooling obtains amino Formic acid esters acrylate (X-1).The equivalent of the acryloyl group of obtained urethane acrylate (X-1) is 10,441 (round up below arithmetic point.The molecular weight of 2-Hydroxy ethyl acrylate is 116.1.Lower with), weight average molecular weight be 30, 000。
[synthesis example 2]
<synthesis of urethane acrylate (X-2)>
In the reaction vessel possessing blender, reflux cooling pipe, nitrogen ingress pipe, thermometer, add polycarbonate polyol Alcohol (Chemicals Co., Ltd. of " Duranol T-5651 " Asahi Chemical Industry system, number-average molecular weight: 1000) 390 mass parts, poly-second two Alcohol (number-average molecular weight: 600, hereafter abbreviated with " PEG-2 ") 43.4 mass parts, HEA9 mass parts, 2,6-di-tertiary butyl methyl phenol 2 matter Amount part, p methoxy phenol 0.3 mass parts.Heat up until after temperature reaches 40 DEG C in reaction vessel, adding IPDI102 mass Part.Then, adding two neodecanoic acid dioctyl tin 0.1 mass parts, 1 hour used time was warming up to 80 DEG C.Afterwards, little 80 DEG C of holdings 12 Time, after confirming that whole NCOs disappears, cooling obtains urethane acrylate (X-2).Obtained amino first The equivalent of the acryloyl group of acid esters acrylate (X-2) is 7,023, weight average molecular weight is 19,000.
[synthesis example 3]
<synthesis of urethane acrylate (X-3)>
In the reaction vessel possessing blender, reflux cooling pipe, nitrogen ingress pipe, thermometer, add PTMG1000 351 Mass parts, PEG-1 51.4 mass parts, HEA 5.7 mass parts, 2,6-di-tertiary butyl methyl phenol 2 mass parts, p methoxy phenol 0.3 Mass parts.Heat up until after temperature reaches 40 DEG C in reaction vessel, adding IPDI 104 mass parts.Then, two neodecanoic acids are added Dioctyl tin 0.1 mass parts, 1 hour used time was warming up to 80 DEG C.Afterwards, keep 12 hours at 80 DEG C, confirm whole Carbimide .s After ester group disappears, cooling obtains urethane acrylate (X-3).Obtained urethane acrylate (X-3) The equivalent of acryloyl group is 10,431, weight average molecular weight is 21,000.
[synthesis example 4]
<synthesis of urethane acrylate (X-4)>
In the reaction vessel possessing blender, reflux cooling pipe, nitrogen ingress pipe, thermometer, (number is all to add polypropylene glycol Molecular weight: 3,000, hereafter abbreviated with " PPG3000 ") 180 mass parts, PTMG1000 143 mass parts, PEG-1 109 mass Part, HEA 6 mass parts, 2,6-di-tertiary butyl methyl phenol 2 mass parts, p methoxy phenol 0.3 mass parts.Heat up until reaction vessel After interior temperature reaches 40 DEG C, add IPDI 105 mass parts.Then, two neodecanoic acid dioctyl tin 0.1 mass parts, used time 1 are added Hour it is warming up to 80 DEG C.Afterwards, keeping 12 hours at 80 DEG C, after confirming that whole NCOs disappears, cooling obtains amino Formic acid esters acrylate (X-4).Obtained by the equivalent of acryloyl group of urethane acrylate (X-4) be 10,507, Weight average molecular weight is 26,000.
[synthesis example 5]
<synthesis of urethane acrylate (X-5)>
In the reaction vessel possessing blender, reflux cooling pipe, nitrogen ingress pipe, thermometer, add Duranol T- 5652 442 mass parts, Polyethylene Glycol (" Ymer N120 " Perstorp company system, number-average molecular weight: 1,000) 246 mass parts, HEA 9.5 mass parts, 2,6-di-tertiary butyl methyl phenol 2 mass parts, p methoxy phenol 0.3 mass parts.Heat up until reaction vessel After interior temperature reaches 40 DEG C, add IPDI 102 mass parts.Then, two neodecanoic acid dioctyl tin 0.1 mass parts, used time 1 are added Hour it is warming up to 80 DEG C.Afterwards, keeping 12 hours at 80 DEG C, after confirming that whole NCOs disappears, cooling obtains amino Formic acid esters acrylate (X-5).The equivalent of the acryloyl group of obtained urethane acrylate (X-5) is 9,771, weight Average molecular weight is 20,000.
[synthesis example 6]
<synthesis of urethane acrylate (X-6)>
In the reaction vessel possessing blender, reflux cooling pipe, nitrogen ingress pipe, thermometer, add Duranol T- 5651 467 mass parts, HEA 9.6 mass parts, 2,6-di-tertiary butyl methyl phenol 2 mass parts, p methoxy phenol 0.3 mass parts.Rise Temperature is until after temperature reaches 40 DEG C in reaction vessel, adding IPDI 101 mass parts.Then, two neodecanoic acid dioctyl tins are added 0.1 mass parts, 1 hour used time was warming up to 80 DEG C.Afterwards, keep 12 hours at 80 DEG C, confirm that whole NCOs disappears After, cooling obtains urethane acrylate (X-6).The acryloyl group of obtained urethane acrylate (X-6) Equivalent be 6,985, weight average molecular weight be 19,000.
[synthesis example 7]
<synthesis of urethane acrylate (X-7)>
In the reaction vessel possessing blender, reflux cooling pipe, nitrogen ingress pipe, thermometer, add PTMG1000 460 Mass parts, HEA 6.5 mass parts, 2,6-di-tertiary butyl methyl phenol 2 mass parts, p methoxy phenol 0.3 mass parts.Heat up until anti- After answering temperature in container to reach 40 DEG C, add IPDI 105 mass parts.Then, add two neodecanoic acid dioctyl tin 0.1 mass parts, 1 hour used time was warming up to 80 DEG C.Afterwards, keeping 12 hours at 80 DEG C, after confirming that whole NCOs disappears, cooling obtains Urethane acrylate (X-7).The equivalent of the acryloyl group of obtained urethane acrylate (X-7) is 10, 208, weight average molecular weight is 22,000.
[embodiment 1]
<preparation of ultraviolet-curing adhesive composition>
In the reaction vessel possessing blender, reflux cooling pipe, thermometer, put into above-mentioned urethane acrylate (X-1) 100 mass parts, butyl acrylate (hereafter abbreviated with " BA ") 105 mass parts, DMAA (hereafter abbreviated with DMAA) 10 mass parts, 80 DEG C of stirrings until uniformly.Afterwards, it is cooled to room temperature, under agitation adds 2,4,6-trimethylbenzene first Double (2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl) ester 0.5 mass of aminosulfonylphenyl phosphine oxide 3 mass parts, decanedioic acid Part, triphenylphosphine 0.5 mass parts, 3-glycydoxy triethoxysilane 0.1 mass parts, stirring is until uniformly. Afterwards, with 200 mesh metal mesh filters, ultraviolet-curing adhesive composition has been obtained.
[embodiment 2～6, comparative example 1～2]
Carbamate (methyl) acrylate, (methyl) the acrylic acid series list used is changed as Ru Biao1Suo Shi The kind of body and amount, in addition, obtained ultraviolet-curing adhesive composition similarly to Example 1.
[manufacture method of bonding film]
The table of the polyethylene terephthalate film (demoulding PET50) of thickness 50 μm after surface is carried out demoulding process Face, the mode that thickness is 175 μm after irradiating according to making UV is coated in embodiment and comparative example the ultraviolet curing obtained Type adhesive resin composition, fit demoulding PET50.Afterwards, utilize UV irradiation unit, according to through the UV-after demoulding PET50 The accumulative light quantity of the wavelength of a-quadrant reaches 1J/cm2Mode carry out UV irradiation, made bonding film.
[assay method of bonding force]
The one side of the bonding film utilizing aforesaid method to make is fitted in the polyethylene terephthalate of thickness 75 μm Film (PET75), is made for being fitted with the bonding film of PET75 base material in one side.It is cut into after 25mm width as test film.With This test film is attached to the glass plate as clung body, Merlon (PC) plate by 2kg roller × 2 time reciprocal condition respectively.? After attaching 1 hour, 23 DEG C, measure 180 degree of peel strengths, as bonding force under the atmosphere of humidity 50%.
[evaluation methodology of wet-heat resisting albefaction]
The one side of the bonding film utilizing aforesaid method to make is fitted in the polyethylene terephthalate of thickness 100 μm Film (PET100), has made the bonding film being fitted with PET100 base material in one side.It is cut into vertical 50mm, horizontal 40mm, with 2kg roller × 2 reciprocal conditions are attached to after glass plate as test film.For this test film, utilize scopometer " NDH5000 " (electricity Se Industrial Co., Ltd of Japan system) measures mist degree (%) according to JIS K7361-1-1997, using this value as initial value.Connect , by this test film 85 DEG C, place 10 minutes under the atmosphere of humidity 85% after take out, utilize within latter 10 minutes turbid in taking-up Degree meter " NDH5000 " (electricity Se Industrial Co., Ltd of Japan system) measures mist degree (%) according to JIS K7361-1-1997.
[evaluation methodology of wet-heat resisting xanthochromia]
The one side of the bonding film utilizing aforesaid method to make is attached at glass plate, and then peels off 1 demoulding again As test film after PET50.For this test film, utilize light source C, 2 ° of the visual field, spectral photometric colour measuring meter " CM-5000d " (Konica Minolta Sensing company system), measure xanthochromia degree (b*) according to JIS K7105-1981.It addition, above-mentioned test film is existed 80 DEG C, place 500 hours under the atmosphere of humidity 85% after, similarly measure xanthochromia degree (b*).
[table 1]
Additionally, the translation in table 1～2 is illustrated.
ACMO: acryloyl morpholine
NOA: n-octyl
IOA: Isooctyl acrylate monomer
TDA: tridecyl acrylate
CHA: cyclohexyl acrylate
IBXA: isobornyl acrylate
Understand, use the present invention ultraviolet-curing adhesive composition obtain the bonding force of binding agent, wet-heat resisting Albefaction and wet-heat resisting xanthochromia are excellent.
On the other hand understanding, comparative example 1 is do not use Polyethylene Glycol as carbamate (methyl) acrylate former The scheme of material, wet-heat resisting albefaction is bad.
Understanding, comparative example 2 is not use Polyethylene Glycol as the raw material of carbamate (methyl) acrylate and use The high ACMO of substantial amounts of xanthochromia is as the scheme of (methyl) acrylic monomer, and wet-heat resisting xanthochromia is bad.

Claims (3)

1. a ultraviolet-curing adhesive composition, it is characterised in that it contains carbamate (methyl) acrylate (X), (methyl) acrylic monomer (Y) and Photoepolymerizationinitiater initiater (Z), described carbamate (methyl) acrylate (X) is Make comprise the polyhydric alcohol (a) of Polyethylene Glycol (a1), polyisocyanates (b) and there is (methyl) propylene of hydroxyl or NCO Acid based compound (c) is reacted and is obtained, and the usage amount of described Polyethylene Glycol (a1) is 1～60 matter in described polyhydric alcohol (a) The scope of amount %, the content of (methyl) acrylic monomer with nitrogen-atoms in described (methyl) acrylic monomer (Y) It is below 40 mass %.
2. ultraviolet-curing adhesive composition as claimed in claim 1, wherein, the number of described Polyethylene Glycol (a1) is divided equally Son amount is the scope of 200～5,000.
3. a binding agent, it is characterised in that it is to use the ultraviolet-curing adhesive combination described in claim 1 or 2 Thing and obtain.
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