CN104302720A - Ultraviolet light curing adhesive composition and adhesive layer - Google Patents
Ultraviolet light curing adhesive composition and adhesive layer Download PDFInfo
- Publication number
- CN104302720A CN104302720A CN201380022223.1A CN201380022223A CN104302720A CN 104302720 A CN104302720 A CN 104302720A CN 201380022223 A CN201380022223 A CN 201380022223A CN 104302720 A CN104302720 A CN 104302720A
- Authority
- CN
- China
- Prior art keywords
- methyl
- composition
- acrylate
- adhesive composition
- bonding coat
- 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
Links
Classifications
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
-
- 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
- C08G18/28—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
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
-
- 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
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
-
- 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
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
- C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
- C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- 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
- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
Abstract
The purpose of the present invention is to provide an ultraviolet light curing adhesive composition that is an optical, solvent-free adhesive composition for use in touch panels and the like, wherein a thick adhesive layer can be formed by a single coating operation; the layer has excellent transparency, adhesive force, and durability under conditions of heat and humidity; and after overlaying, peeling is possible without glue remaining. The present invention pertains to an ultraviolet light curing adhesive composition comprising (A) a polyfunctional urethane (meth)acrylate oligomer having a weight-average molecular weight of 10,000 to 100,000, (B) an adhesion promoter, (C) a monofunctional epoxy ester (meth)acrylate, and (D) a photopolymerization initiator; the solvent content being less than 1 wt%, the viscosity at 25DEG C being 100 to 10,000 mPas, and the color tone being 1 or less on the Gardner color scale.
Description
Technical field
The present invention relates to ultraviolet-curing adhesive composition and bonding coat.
Background technology
In recent years, the display unit of the indicating meter, TV etc. of vehicle boarded use, outdoor measuring instrument use, PC etc. requires lightweight or slimming, and therefore widely use liquid crystal indicator, its demand has the trend day by day increased.And, especially nearest, in the ATM of bank and other financial mechanism, vending machine, mobile phone, portable information terminal, digital audio-frequency player, portable game, e-dictionary, duplicating machine, facsimile recorder, navigationsystem digital information equipment, mostly use the contact panel utilizing liquid crystal indicator.
Above-mentioned contact panel is the electronic unit that display unit and location input device are combined and obtained, and has the image information display from external reception in liquid-crystal display and the screen location information that touches of perception the function externally exported with the form of information signal.The location input device of contact panel mainly contains the control modes such as resistive film mode, electrostatic capacitance mode, way of electromagnetic induction, optical mode, sound equipment mode, and wherein, resistive film mode and electrostatic capacitance mode are conventional control method.
Above-mentioned resistive film mode and electrostatic capacitance mode contact panel by foremost protective membrane, be provided with the transparency conducting layer such as glass and Indium sesquioxide (being denoted as below " ITO ") film the display unit such as film, glass, liquid crystal, other functional form.Wherein, film, glass and functional utilize optics tackiness agent to fit usually.
As mentioned above; the optics tackiness agent used in contact panel purposes, for foremost protective membrane or glass and the laminating etc. being provided with the film of transparency conducting layer or the laminating of glass, the film being provided with transparency conducting layer or the display unit such as glass and liquid crystal, therefore requires the optical property such as the transparency, weathering resistance.
As this optics tackiness agent, propose the optics binder composition (referenced patent document 1 and 2) comprising various high molecular weight acrylic polymers and various linking agent.
On the other hand, recently, in order to improve the shock-resistance of contact panel, absorb the printing jump etc. of foremost protective membrane or glass, the thick bonding coat of more than 100 μm is required.(having the thickness of more than 100 μm) bonding coat of this thick film can by be formed bonding coat that thickness is 25 μm or 50 μm and their superimposed stickups obtained by above-mentioned optics binder composition.But, the method exist because process number is many Expenses Cost, the transparency due to laminating the problem such as reduction.On the other hand, if want to form the bonding coat with the thickness of more than 100 μm by single application, then coating solvent bubbles when drying, in film, produce bubble, thus there is the problem do not met as the performance of optics.
As the method for bonding coat being obtained the thickness with more than 100 μm when not making it bubble by single application, consider to use non-solvent adhesive composition.As non-solvent adhesive composition, propose the ultra-violet solidified non-solvent adhesive composition (referenced patent document 3) containing various (methyl) origoester acrylate or (methyl) acrylate monomer.
But the weather resistance of above-mentioned non-solvent adhesive composition under the transparency, bounding force, heating and humidified condition, when producing position skew when fitting, the time of stripping remains adhesive paste etc. and has problems as the aspect of performance of tackiness agent.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2011-195651 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2011-225835 publication
Patent documentation 3: Japanese Unexamined Patent Application Publication 2005-530024 publication
Summary of the invention
Invent problem to be solved
Major subjects of the present invention is to provide a kind of ultraviolet hardening optics binder composition, it is the solvent-free optics binder composition for contact panel etc., this ultraviolet hardening optics binder composition can form the bonding coat of thick film by single application, excellent durability under the transparency, bounding force, heating and humidified condition, and can peel off and not produce generation of adhesive deposit after laminating.
For the method for dealing with problems
Present inventor has performed further investigation, found that, in ultraviolet-curing adhesive composition, solvent is adjusted to and is less than 1 % by weight, by the viscosity adjustment to 100 at 25 DEG C ~ 10000mPas, tone is adjusted to and counts less than 1 with Gardner color, and coordinate (A) weight-average molecular weight (based on the polystyrene conversion value of gel permeation chromatography, lower with) be 10000 ~ 100000 polyfunctional carbamate (methyl) origoester acrylate, (B) tackifier, (C) monofunctional epoxy ester (methyl) acrylate and (D) Photoepolymerizationinitiater initiater, thus, can solve the problem.
In addition, the present inventor also finds, if use above-mentioned binder composition, then can provide the bonding coat that can solve the problem.
That is, the present invention relates to following ultraviolet-curing adhesive composition and bonding coat.
1. a ultraviolet-curing adhesive composition, is characterized in that, solvent is less than 1 % by weight, and the viscosity at 25 DEG C is 100 ~ 10000mPas, and tone counts less than 1 with Gardner color, and containing following (A) ~ (D),
(A) weight-average molecular weight be 10000 ~ 100000 polyfunctional carbamate (methyl) origoester acrylate,
(B) tackifier,
(C) monofunctional epoxy ester (methyl) acrylate,
(D) Photoepolymerizationinitiater initiater.
2. the ultraviolet-curing adhesive composition as described in above-mentioned 1st, wherein, above-mentioned (A) composition is polyfunctional carbamate (methyl) origoester acrylate that (methyl) acrylate reactions of (methyl) acrylate of polyether glycol, polyisocyanates and hydroxyl or isocyanato group containing is obtained.
3. the ultraviolet-curing adhesive composition as described in the above-mentioned 1st or 2, wherein, above-mentioned (B) composition is that tone counts the tackifier of less than 1 with Gardner color.
4. as the ultraviolet-curing adhesive composition according to any one of above-mentioned 1st ~ 3, wherein, take weight part as benchmark, above-mentioned (A) ~ (D) composition in binder composition with (A): (B): (C): the ratio of (D)=10 ~ 60:0.5 ~ 15:15 ~ 89.4:0.1 ~ 10 coordinates.
5. a bonding coat, it obtains by making the ultraviolet-curing adhesive composition according to any one of above-mentioned 1st ~ 4 solidify.
6. the bonding coat as described in above-mentioned 5th, wherein, the thickness of bonding coat is 10 ~ 1000 μm.
Invention effect
Binder composition of the present invention may be used for contact panel, Plasmia indicating panel etc., due to solvent-free and do not need the drying of solvent, can be formed the bonding coat of thick film by single application.In addition, the excellent durability under the transparency of binder composition of the present invention, bounding force, heating and humidified condition, and can peel off after laminating and residual adhesive paste.Thus, the binding property of the bonding coat of the present invention formed by this binder composition, the transparency and excellent durability thereof, be suitable as the bonding coat for contact panel, Plasmia indicating panel etc.
Embodiment
The present invention is a kind of ultraviolet-curing adhesive composition, wherein, solvent is less than 1 % by weight, viscosity at 25 DEG C is 100 ~ 10000mPas, tone counts less than 1 with Gardner color, and containing polyfunctional carbamate (methyl) origoester acrylate (below also referred to as " (A) composition ") that (A) weight-average molecular weight is 10000 ~ 100000, (B) tackifier (below also referred to as " (B) composition "), (C) monofunctional epoxy ester (methyl) acrylate (below also referred to as " (C) composition ") and (D) Photoepolymerizationinitiater initiater (below also referred to as " (D) composition ").
If above-mentioned solvent is more than 1 % by weight, then when the bonding coat of thick film (thickness more than 100 μm) will be formed, there is coating solvent drying, bubbling when solidifying, in film, producing the problems such as bubble.
When above-mentioned viscosity departs from the scope of 100 ~ 10000mPas, be difficult to the bonding coat being formed thick film under normal temperature and pressure by single application.
By making the tone of above-mentioned binder composition count less than 1 with Gardner Color, the bonding coat of the transparency and excellent color tone can be formed.
By making the weight-average molecular weight of above-mentioned (A) composition be more than 10000, the bounding force of bonding coat can be improved.In addition, by making the weight-average molecular weight of (A) composition be less than 100000, the viscosity of polyfunctional carbamate (methyl) origoester acrylate can be reduced, improving the operability of tackiness agent.
Above-mentioned (A) composition by (methyl) acrylate of polyvalent alcohol, polyisocyanates and hydroxyl or (methyl) acrylate of isocyanato group containing reaction and obtain.
As above-mentioned polyvalent alcohol, be not particularly limited, the polyether polyols alcohols such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol and their multipolymer can be enumerated; The polyester polyols alcohols such as the polycondensate of the polycondensate of the polycondensate of hexanodioic acid and polyvalent alcohol, sebacic acid and polyvalent alcohol, phthalic acid and polyvalent alcohol, the addition polymer that obtained by the ring-opening reaction of lactone and polyvalent alcohol; By the reaction of the glycol such as 1,3-PD, BDO, 1,5-PD, 1,6-hexylene glycol, cyclohexanedimethanol and phosgene and the polycarbonate polyol class obtained; The polyolefin polyhydric alcohol classes such as polybutadiene diol, hydrogenated butadiene polymer polyvalent alcohol; Etc..These polyvalent alcohols can be used alone or also can combine.Wherein, from the viewpoint of the lowering viscousity of tackiness agent and the high adhesion of bonding coat, more preferably use polyether polyols alcohols.
As above-mentioned polyisocyanates, can enumerate: 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-Xylene Diisocyanate, ditan-4, the aromatic diisocyanate compounds such as 4-vulcabond, 3-MDPM vulcabond, 1,5-naphthalene diisocyanate; The aliphatic diisocyanate compounds such as dicyclohexyl methane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate; Their 2 ~ 6 aggressiveness; Deng.These polyisocyanates can be used alone or also can combine.Wherein, from the viewpoint of high adhesion and the weather resistance of the lowering viscousity of tackiness agent, bonding coat, more preferably aliphatic diisocyanate is used.
The carbamate prepolymer containing terminal isocyanate acidic group reacting by making (methyl) acrylate of hydroxyl and above-mentioned polyvalent alcohol and polyisocyanates and obtain reacts, or the carbamate prepolymer containing terminal hydroxyl making (methyl) acrylate of isocyanato group containing and above-mentioned polyvalent alcohol and polyisocyanates react and obtain reacts, and can obtain polyfunctional carbamate (methyl) origoester acrylate.
As (methyl) acrylate of above-mentioned hydroxyl, simple function (methyl) acrylate such as 2-hydroxyl (methyl) acrylate (2-ヒ De ロ キ シ (メ タ) ア Network リ レ ー ト), (methyl) Propylene glycol monoacrylate, 4-hydroxyl (methyl) acrylate (4-ヒ De ロ キ シ (メ タ) ア Network リ レ ー ト), (methyl) vinylformic acid 2-hydroxy-2-methyl propyl ester can be enumerated; Pentaerythritol triacrylate, Dipentaerythritol Pentaacrylate etc. multifunctional (methyl) acrylate; Epoxy compounds and (methyl) vinylformic acid are reacted and epoxy ester (methyl) acrylate etc. that obtains.These materials can be used alone or also can combine.
As (methyl) acrylate of above-mentioned isocyanato group containing, (methyl) vinylformic acid 2-isocyanatoethyl methacrylate, 1,1-(two acryloyloxymethyl) ethyl isocyanate can be enumerated.These materials can be used alone or also can combine.
The average functional group number of polyfunctional carbamate (methyl) origoester acrylate is at least 1.5, is preferably more than 1.8.The average functional group number of carbamate (methyl) origoester acrylate is represent the quantity that on average there are how many acryls in 1 molecules of ammonia carbamate (methyl) origoester acrylate.When synthesis of carbamates (methyl) origoester acrylate, by controlling the reaction equivalent of (methyl) acrylic compound of hydroxyl or (methyl) acrylic compound of isocyanato group containing, the average functional group number of carbamate (methyl) origoester acrylate can be controlled.By use average functional group number be more than 1.5 carbamate (methyl) origoester acrylate, the optics tackiness agent of excellent durability can be obtained.
Above-mentioned (B) composition is tackifier.As (B) composition, specifically, petroleum resin, resol, xylene resin, coumarone resin, rosin based resin, terpenoid resin, hydrogenated petroleum resin, staybelite resinoid, hydriding terpene resinoid etc. can be enumerated.Wherein, preferred hue counts the material of less than 1 with Gardner color.Count the material of less than 1 as tone with Gardner color, such as hydrogenated petroleum resin, staybelite resinoid can be enumerated.The tone of these hydrogenated resins counts less than 1 with Gardner color usually, because of but the tackifier of excellent transparency, the transparency of optics tackiness agent and bonding coat can be improved.In addition, these hydrogenated resins are also few to the suppression of polymerization when utilizing uviolizing to be polymerized, and thus by using them, form the optics tackiness agent that solidified nature is excellent.
As above-mentioned staybelite resinoid, as long as the resin carrying out hydrogenation to rosin based resin and obtain is not particularly limited, known material can be used.As above-mentioned rosin based resin, the natural rosin classes such as such as gum resin, toll oil rosin, wood rosin and the rosin based (below also referred to as " processing rosin based ") of natural rosin class etc. being undertaken processing by least one method be selected from polymerization, modification, disproportionation and esterification and obtaining, rosin metal salt etc. by making natural rosin class or metal species such as processing rosin based and calcium, magnesium, zinc etc. react and obtain can be enumerated.
To in above-mentioned processing rosin based processed by polymerization process and the manufacture method of the rosin based (below also referred to as " polymerized rosin ") obtained is not particularly limited, known method can be adopted.Can enumerate and such as use polymerizing catalyst to above-mentioned natural rosin class or the method that natural rosin class heated by the rosin based being selected from modification, at least one method of disproportionation and esterification is processed and obtained.As polymerizing catalyst, be not particularly limited, known polymerizing catalyst can be used.As polymerizing catalyst, specifically, the acid such as such as sulfuric acid, phosphoric acid, hydrofluoric acid can be enumerated; The metal halides such as boron fluoride, aluminum chloride, zinc chloride.
The manufacture method of the rosin based (below also referred to as " modified rosin ") obtained above by method of modifying carries out processing is not particularly limited, and can adopt known method.Natural rosin class mixes with phenols or unsaturated acid and carries out the method that heats by usual use.As above-mentioned phenols, be not particularly limited, specifically, such as phenol, alkylphenol etc. can be enumerated.As above-mentioned unsaturated acid, be not particularly limited, specifically, fumaric acid, toxilic acid, (methyl) vinylformic acid etc. can be enumerated.
The manufacture method of the rosin based (below also referred to as " nilox resin ") obtained above by disproportionation process carries out processing is not particularly limited, and can adopt known method.Usually following method can be enumerated: natural rosin class or processing rosin based are reacted 2 ~ 6 hours at 220 ~ 250 DEG C under the condition of not adding hydrogen under the existence of the reducing catalysts such as nickel, platinum, palladium or C catalyst and carry out saponification.
The manufacture method of the rosin based (below also referred to as " rosin ester ") obtained above by esterification process carries out processing is not particularly limited, and can adopt known method.Usually can enumerate natural rosin class or processing rosin based are mixed the method also carrying out as required heating under the existence of esterifying catalyst with alcohol.As esterifying catalyst, can use such as: the acid catalyst such as acetic acid, tosic acid; The alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide; The oxyhydroxide of the alkaline-earth metal such as calcium hydroxide, magnesium hydroxide; The metal oxides etc. such as calcium oxide, magnesium oxide, zinc oxide, plumbous oxide, stannic oxide.
As above-mentioned alcohol, aliphatic unitary or polyvalent alcohol that carbonatoms is 1 ~ 20 can be enumerated.As such alcohol, can enumerate such as: the monohydroxy-alcohols such as methyl alcohol, ethanol, Virahol, primary isoamyl alcohol, n-hexyl alcohol, 2-Ethylhexyl Alcohol, n-Octanol, dodecanol, lauryl alcohol, stearyl alcohol, dihydro rosin alcohol; The dibasic alcohol such as ethylene glycol, Diethylene Glycol, propylene glycol, neopentyl glycol; The trivalent alcohols such as glycerine, trimethylolethane, TriMethylolPropane(TMP); The tetravalent alcohols such as tetramethylolmethane, two glycerine; Deng.
Above-mentioned rosin based resin can be used alone the one in them, also can be used in combination two or more.In addition, the two or more method in polymerization, modification, disproportionation and esterification also can be used to process natural rosin class etc.When manufacturing rosin based resin by two or more methods, the order of its method is not particularly limited, can based on known method.Such as, carrying out modified polymerization to natural rosin class or processing rosin based, also esterification can be carried out after polymerisation.
As the hydrogenated petroleum resin of above-mentioned (B) composition, as long as the resin carrying out hydrogenation to petroleum resin and obtain is not particularly limited, known hydrogenated petroleum resin can be used.As petroleum resin, such as, be roughly divided into aliphatic category petroleum resin, fragrant same clan petroleum resin and dicyclopentadiene class petroleum resin according to the kind of starting monomer (cut).As aliphatic category petroleum resin, C5 class petroleum resin, C5-C9 class petroleum resin etc. can be enumerated.As fragrant same clan petroleum resin, C9 class petroleum resin etc. can be enumerated.C5 class petroleum resin are by carrying out cationoid polymerisation to C5 class petroleum fractions (such as amylene, methyl butene, isoprene, cyclopentenes etc.) and obtain.As C9 class petroleum resin, be not particularly limited, usually can use and cationoid polymerisation be carried out to the C9 class petroleum fractions obtained by naphtha cracking (such as vinylbenzene, Vinyl toluene, alpha-methyl styrene, indenes class etc.) and the petroleum resin obtained.C5-C9 class petroleum resin are to the petroleum resin that above-mentioned C5 class petroleum fractions and C9 class petroleum fractions are carried out copolymerization and obtained in the same manner as the manufacture of C5 class petroleum resin.Dicyclopentadiene class petroleum resin carry out thermopolymerization or cationoid polymerisation and the petroleum resin obtained to dicyclopentadiene.These petroleum resin also can utilize hydroxyl by generally well-known method, ester group isopolarity group carries out modification.In addition, the tone of petroleum resin counts about 5 ~ about 15 with Gardner color usually.
Above-mentioned (C) composition is monofunctional epoxy ester (methyl) acrylate monofunctional epoxy compound and (methyl) vinylformic acid being reacted and obtains, and can use various known monofunctional epoxy ester (methyl) acrylate without particular limitation.As (C) composition, specifically, can enumerate: phenyl glycidyl ether and (methyl) vinylformic acid reacts and obtain monofunctional epoxy ester (methyl) acrylate, (aminomethyl phenyl) glycidyl ether and (methyl) vinylformic acid are reacted and obtain monofunctional epoxy ester (methyl) acrylate, (tert-butyl-phenyl) glycidyl ether and (methyl) vinylformic acid are reacted and monofunctional epoxy ester (methyl) acrylate etc. that obtains has (methyl) acrylate of aromatic structure; (ethylhexyl) glycidyl ether methyl (methyl) acrylate and (methyl) vinylformic acid are reacted and monofunctional epoxy ester (methyl) acrylate etc. that obtains has (methyl) acrylate that carbonatoms is the alkyl of 1 ~ 30.Wherein, from the viewpoint of the consistency with carbamate (methyl) origoester acrylate and tackifier, preferably there is monofunctional epoxy ester (methyl) acrylate of aromatic structure.
As above-mentioned (D) composition, as long as decomposed by uviolizing and produce the Photoepolymerizationinitiater initiater of free radical, then can use various known Photoepolymerizationinitiater initiater with no particular limitation.As (D) composition, can enumerate: the Photoepolymerizationinitiater initiaters such as bitter almond oil camphor compound, acetophenone compound, acylphosphine oxide compound, two cyclopentadiene titanium compounds, thioxanthone compounds, oxime ester compound; The photosensitizers such as amine, quinone etc.As concrete compound, can enumerate: 2,2-dimethoxy-1,2-diphenylethane-1-ketone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-ketone, 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, 2-hydroxyl-1-[4-[4-(2-hydroxy-2-methyl propionyl) benzyl] phenyl]-2-methyl-propan-1-ketone, 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholino propane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, TMDPO, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, two (η 5-2,4-cyclopentadiene-1-base)-bis-(the fluoro-3-of 2,6-bis-(1H-pyrroles-1-base) phenyl) titanium, 1,2-acetyl caproyl 1-[4-(phenylsulfartyl)-2-(O-benzoyl oximes)], ethyl ketone 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-ethanoyl oxime) etc.These compositions can use independent one, also can be used together two or more.Wherein, from the viewpoint of the solidified nature improving binder composition, preferred TMDPO, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide.
Above-mentioned (A) ~ (D) composition in binder composition with weight part be benchmark preferably with (A): (B): (C): the ratio of (D)=10 ~ 60:0.5 ~ 15:15 ~ 89.4:0.1 ~ 10 coordinates.Particularly preferred mixing ratio is 20 ~ 35:5 ~ 10:30 ~ 70:0.2 ~ 5.By making the mixing ratio of above-mentioned (A) composition be above-mentioned scope, the bounding force of bonding coat can be improved, and the operability of tackiness agent can be improved.By making the mixing ratio of above-mentioned (B) composition be above-mentioned scope, the bounding force of bonding coat can be improved, and the generation of adhesive deposit of bonding coat can be eliminated.By making the mixing ratio of above-mentioned (C) composition be above-mentioned scope, the operability of tackiness agent can be improved, and suitable viscosity can be obtained, the bonding coat of thick film can be formed by single application.By making the mixing ratio of above-mentioned (D) composition be above-mentioned scope, the deviation of the polymerization utilizing ultraviolet isoreactivity energy-ray to irradiate can be prevented, and the peculiar smell that the resolvent of (D) composition brings can be prevented, and the painted of cured article can be prevented.
Ultraviolet-curing adhesive composition of the present invention can become assign to manufacture by mixing above-mentioned (A) ~ (D).Blending means is not particularly limited, and the order of addition of above-mentioned (A) ~ (D) composition does not limit.
In addition, in binder composition of the present invention can as required in the scope not damaging effect of the present invention containing various simple function or polyfunctional monomer as diluting monomer.
As the concrete example of above-mentioned monofunctional monomer, can enumerate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) 2-ethylhexyl acrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) vinylformic acid cetyl, (methyl) stearyl acrylate ester, the different stearyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid mountain Yu ester etc. has (methyl) acrylate that carbonatoms is the alkyl of 1 ~ 30, (methyl) isobornyl acrylate, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) vinylformic acid bicyclopentyl ester, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester, (methyl) vinylformic acid diamantane ester etc. have (methyl) acrylate of ester ring type structure, (methyl) acrylate, (methyl) benzyl acrylate etc. have (methyl) acrylate of aromatic structure, (methyl) tetrahydrofurfuryl acrylate etc. has (methyl) acrylate of hetero ring type structure, the vinyl compounds such as vinylbenzene, hydroxyethyl vinylethers, hydroxy butyl vinyl ether, N-vinyl formamide, NVP, N-caprolactam.
As the concrete example of above-mentioned polyfunctional monomer, can enumerate: 1,4-butyleneglycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1.6-hexylene glycol (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate etc. have two (methyl) acrylate of aliphatic structure; Cyclohexanedimethanol two (methyl) acrylate, tristane two (methyl) acrylate etc. have two (methyl) acrylate of ester ring type structure; Bisphenol-A epoxy oxide-modified two (methyl) acrylate, Bisphenol F epoxy oxide-modified two (methyl) acrylate etc. have two (methyl) acrylate of aromatic structure; Multifunctional (methyl) acrylate more than trifunctionals such as trimethylolpropane tris (methyl) acrylate, isocyanuric acid ethylene-oxide-modified three (methyl) acrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate.
In addition, various additive can be contained as required in the scope not damaging effect of the present invention in binder composition of the present invention.Such as, the additives such as surface conditioner, tensio-active agent, UV light absorber, mineral filler, silane coupling agent, colloidal silica, defoamer, wetting agent, rust-preventive agent, stablizer can be contained.
When binder composition of the present invention is made bonding coat, preferably adopt the method being referred to as casting film-forming (casting film).Specifically; be coated with on the protective membranes such as the polyethylene terephthalate film (PET film) of the strippers such as silicone resin from the teeth outwards; by binder composition with after film like casting, its polymerizing curable is made to film irradiation ultraviolet radiation, obtains bonding coat.According to such method for making, the stress putting on binder composition when film forming is also few, and the formation of defect is few.In addition, the film uniformity of the film obtained improves.
As above-mentioned ultraviolet light source, the UV irradiation equipment with xenon lamp, high voltage mercury lamp, metal halide lamp etc. can be enumerated.In addition, the condition such as light quantity, light source, transfer rate suitably regulates.Light quantity is generally about 80W/cm ~ about 160W/cm, and transfer rate is generally about 5m/ minute ~ about 50m/ minute.
In addition, the thickness of bonding coat of the present invention is not particularly limited, and is generally about 10 μm ~ about 1000 μm, is preferably about 25 μm ~ about 500 μm.By making thickness be this scope, the shock-resistance of contact panel can be improved, can the printing jump of absorbing surface, therefore, it is possible to make the excellent bonding coat that can be used as the protective membrane of foremost etc.
Embodiment
Below, the present invention is further illustrated by embodiment.But, the invention is not restricted to these embodiments.In addition, in an embodiment, unless otherwise specified, then " part " expression " weight part ".
The synthesis > of < (A) composition
Synthesis example 1
(A-1) synthesis of composition
In the reaction unit possessing whipping appts and cooling tube, add the polypropylene glycol 955 parts of weight-average molecular weight 4000, hexamethylene diisocyanate 34 parts and stannous octoate 0.2 part, be warming up to 80 DEG C, be incubated after 2 hours, utilize NCO to measure and confirm that reaction terminates and generates oligourethane, then, add methacrylic acid 2-isocyanatoethyl methacrylate 11 parts, at 80 DEG C, be incubated 2 hours.Utilize NCO to measure and confirm that reaction terminates, obtain weight-average molecular weight be 30000 and average functional group number be 2.0 urethane methacrylate oligopolymer (hereinafter referred to as " (A-1) composition ").In addition, this weight-average molecular weight uses commercially available molecular weight apparatus (main product name " HLC-8220GPC ", TOSOH Co., Ltd's system; Post ProductName " TSKGel G1000H ", " TSKGel G2000H ", TOSOH Co., Ltd's system; Developing solvent: tetrahydrofuran (THF)) and the value (lower with) that obtains.
Synthesis example 2
(A-2) synthesis of composition
The polypropylene glycol 915 parts of weight-average molecular weight 4000, isophorone diisocyanate 68 parts and stannous octoate 0.8 part is added in the reaction unit same with synthesis example 1, be warming up to 80 DEG C, be incubated after 2 hours, add 2-Hydroxy ethyl acrylate 17 parts, at 80 DEG C, be incubated 2 hours.Utilize NCO to measure and confirm that reaction terminates, obtain weight-average molecular weight be 25000 and average functional group number be 2.0 urethane acrylate oligomer (hereinafter referred to as " (A-2) composition ").
The synthesis > of < (B) composition
Synthesis example 3
(B-1) synthesis of composition
Acid number be 172, softening temperature (to utilize in JIS K 5902 ring and ball method of regulation to measure, lower with) be 75 DEG C and in the gum resin 1000 parts that produces with the People's Republic of China (PRC) that Gardner color counts 6 of tone, charcoal (hereinafter referred to as " 5% palladium charcoal ") (water ratio 50%) 0.3 part of interpolation containing 5 % by weight palladiums is as catalyzer, while stir 4 hours at 280 DEG C under nitrogen envelope, while carry out disproportionation reaction, obtain that acid number is 157, softening temperature is 77 DEG C and tone counts the nilox resin of 8 with Gardner color.Under nitrogen envelope, under decompression at 3mmHg, distillation purifying is carried out to above-mentioned nilox resin, obtain that acid number is 178, softening temperature is 78 DEG C and tone counts the purifying nilox resin of 2 with Gardner color.Get this purifying nilox resin 500 parts in the four-hole boiling flask of 1L, 180 DEG C are warming up under nitrogen envelope, add glycerine 60 parts at 200 DEG C under melting is stirred after, be warming up to 280 DEG C, carry out the esterification of 12 hours at such a temperature, obtain that acid number is 3.4, softening temperature is 99 DEG C and tone counts the purifying nilox resin ester of 3 with Gardner color.This purifying nilox resin ester 200 parts and 5% palladium charcoal (water ratio 50%) 2 parts are dropped in the oscillatory type autoclave of 2L, after the oxygen in removing system, being forced into 100kg/cm with hydrogen by system
2while be warming up to 255 DEG C, carry out the hydrogenation of 3.5 hours at such a temperature, obtain that acid number is 12.5, softening temperature is 89.5 DEG C and tone counts the hydrogenated wood rosin glycerol ester (tackifier (B-1)) (hereinafter referred to as " (B-1) composition ") of less than 1 with Gardner color.
Synthesis example 4
(B-2) synthesis of composition
By in dicyclopentadiene 100 parts, vinyl carbinol 100 parts and dimethylbenzene 80 parts of input autoclaves, under nitrogen atmosphere 270 DEG C of reactions 2 hours, obtain stand oil.By the underpressure distillation 15 minutes under 200 DEG C and 2.7kPa of this stand oil, remove unreacted solvent monomer and low-grade polymer, obtain that softening temperature is 97.5 DEG C thus, tone counts 8 with Gardner color, hydroxyl value is for 210mgKOH/g and weight-average molecular weight is the petroleum resin of the hydroxyl of 540 (the polystyrene conversion values in GPC).By in the petroleum resin 100 parts of this hydroxyl, hexanaphthene 100 parts and stabilization nickel catalyzator (Hui KCC system, trade(brand)name " N-113 ") 2.0 parts of input autoclaves, in 240 DEG C of reactions 5 hours under the high pressure hydrogen atmosphere that hydrogen pressure is 18MPa.After leaching catalyzer, underpressure distillation 30 minutes under 220 DEG C and 0.27kPa, obtains that softening temperature is 118 DEG C thus, tone counts less than 1 with Gardner color, hydroxyl value is for 180mgKOH/g and weight-average molecular weight is the hydride (tackifier (B-2)) (hereinafter referred to as " (B-2) composition ") of the petroleum resin of the hydroxyl of 600 (the polystyrene conversion values in GPC).
Synthesis example 5
(E-1) synthesis of composition
In the reaction unit same with synthesis example 1, add the polypropylene glycol 955 parts of weight-average molecular weight 4000, hexamethylene diisocyanate 34 parts and stannous octoate 0.2 part, be warming up to 80 DEG C, be incubated after 2 hours, NCO is utilized to measure to confirm reaction to terminate and after generating oligourethane, add methacrylic acid 2-isocyanatoethyl methacrylate 6 parts, 80 DEG C of insulations 2 hours.Utilize NCO to measure and confirm that reaction terminates, obtain weight-average molecular weight be 30000 and average functional group number be 1.0 urethane methacrylate oligopolymer (hereinafter referred to as " (E-1) composition ").
Synthesis example 6
(E-2) synthesis of composition
In the reaction unit same with synthesis example 1, add the polypropylene glycol 955 parts of weight-average molecular weight 4000, hexamethylene diisocyanate 34 parts and stannous octoate 0.2 part, be warming up to 80 DEG C, be incubated after 2 hours, utilize NCO to measure and confirm that reaction terminates, obtain weight-average molecular weight be 30000 and average functional group number be 0 oligourethane (hereinafter referred to as " (E-2) composition ").
The preparation > of < binder composition
Embodiment 1
Coordinate (A-1) composition 25 parts, (B-1) composition 5 parts, as vinylformic acid 3-hydroxypropyl phenyl ester (HPPA) (Kyoeisha Chemical Co., Ltd.'s system belonging to the monofunctional epoxy ester acrylate making phenyl glycidyl ether and vinylformic acid react and obtain of (C) composition, trade(brand)name " エ Port キ シ エ ス テ Le M-600A ") 45 parts, as 2 of (D) composition, 4, 6-trimethyl benzoyl diphenyl base phosphine oxide (TPO) (BASF Amada Co., Ltd. system, trade(brand)name " Le シ リ Application TPO ") 1 part, the different stearyl ester of vinylformic acid as diluting monomer (ISTA) (Osaka Organic Chemical Industry Co., Ltd.'s system, ISTA) 25 parts, prepare binder composition (table 1).In addition, use level is the ratio of solids component.The tone Gardner color of obtained composition, viscosity, solvent containing ratio and consistency are evaluated, these results are shown in Table 2.
Embodiment 2 ~ 5
For each composition, prepare binder composition with the raw material shown in each use level use table 1.The tone Gardner color of obtained each composition, viscosity, solvent containing ratio and consistency are evaluated, shows the result in table 2.
Comparative example 1
Do not use (A-1) composition, coordinate (B-1) composition 5 parts, as vinylformic acid 3-hydroxypropyl phenyl ester (HPPA) (Kyoeisha Chemical Co., Ltd.'s system belonging to the monofunctional epoxy ester acrylate making phenyl glycidyl ether and vinylformic acid react and obtain of (C) composition, trade(brand)name " エ Port キ シ エ ス テ Le M-600A ") 45 parts, as 2 of (D) composition, 4, 6-trimethyl benzoyl diphenyl base phosphine oxide (TPO) (BASF Amada Co., Ltd. system, trade(brand)name " Le シ リ Application TPO ") 1 part, the different stearyl ester of vinylformic acid as diluting monomer (ISTA) (Osaka Organic Chemical Industry Co., Ltd.'s system, ISTA) 50 parts, prepare binder composition.In addition, use level is the ratio of solids component.Similarly to Example 1 the tone Gardner color of obtained composition, viscosity, solvent containing ratio and consistency are evaluated, these results are shown in Table 2.
Comparative example 2
Do not use (B-1) composition, coordinate (A-1) composition 25 parts, as vinylformic acid 3-hydroxypropyl phenyl ester (HPPA) (Kyoeisha Chemical Co., Ltd.'s system belonging to the monofunctional epoxy ester acrylate making phenyl glycidyl ether and vinylformic acid react and obtain of (C) composition, trade(brand)name " エ Port キ シ エ ス テ Le M-600A ") 45 parts, as 2 of (D) composition, 4, 6-trimethyl benzoyl diphenyl base phosphine oxide (TPO) (BASF Japanese firm system, trade(brand)name " Le シ リ Application TPO ") 1 part, the different stearyl ester of vinylformic acid as diluting monomer (ISTA) (Osaka Organic Chemical Industry Co., Ltd.'s system, ISTA) 30 parts, prepare binder composition.In addition, use level is the ratio of solids component.Similarly to Example 1 the tone Gardner color of obtained composition, viscosity, solvent containing ratio and consistency are evaluated, these results are shown in Table 2.
Comparative example 3
Do not use (C) composition; coordinate (A-1) composition 95 parts, (B-1) composition 5 parts, as 2 of (D) composition; 4; 1 part, 6-trimethyl benzoyl diphenyl base phosphine oxide (TPO) (BASF Amada Co., Ltd. system, trade(brand)name " Le シ リ Application TPO "), prepares binder composition.In addition, use level is the ratio of solids component.Similarly to Example 1 the tone Gardner color of obtained composition, viscosity, solvent containing ratio and consistency are evaluated, these results are shown in Table 2.
Comparative example 4
Do not use (D) composition, coordinate the urethane methacrylate oligopolymer 25 parts be made up of (A-1) composition, (B-1) composition 5 parts, as vinylformic acid 3-hydroxypropyl phenyl ester (HPPA) (Kyoeisha Chemical Co., Ltd.'s system belonging to the monofunctional epoxy ester acrylate making phenyl glycidyl ether and vinylformic acid react and obtain of (C) composition, trade(brand)name " エ Port キ シ エ ス テ Le M-600A ") 45 parts, the different stearyl ester of vinylformic acid as diluting monomer (ISTA) (Osaka Organic Chemical Industry Co., Ltd.'s system, ISTA) 25 parts, prepare binder composition.In addition, use level is the ratio of solids component.Similarly to Example 1 the tone Gardner color of obtained composition, viscosity, solvent containing ratio and consistency are evaluated, these results are shown in Table 2.
Comparative example 5
(B-1) composition is replaced with Nippon Zeon Co., Ltd. manufacture trade(brand)name Quintone 1700 (softening temperature is 100 DEG C, tone counts 4 with Gardner color) (B-3), in addition, binder composition is prepared similarly to Example 1.Similarly to Example 1 the tone Gardner color of obtained composition, viscosity, solvent containing ratio and consistency are evaluated, these results are shown in Table 2.
Comparative example 6
(B-1) composition is replaced with Huang Chuan chemical company manufacture trade(brand)name ス ー パ ー エ ス テ Le A100 (softening temperature is 95 ~ 105 DEG C, tone counts 7 with Gardner color) (B-4), in addition, binder composition is prepared similarly to Example 1.Similarly to Example 1 the tone Gardner color of obtained composition, viscosity, solvent containing ratio and consistency are evaluated, these results are shown in Table 2.
Comparative example 7
(A-1) composition is replaced with (E-1) composition, in addition, prepares binder composition similarly to Example 1.Similarly to Example 1 the tone Gardner color of obtained composition, viscosity, solvent containing ratio and consistency are evaluated, these results are shown in Table 2.
Comparative example 8
(A-1) composition is replaced with (E-2) composition, in addition, prepares binder composition similarly to Example 1.Similarly to Example 1 the tone Gardner color of obtained composition, viscosity, solvent containing ratio and consistency are evaluated, these results are shown in Table 2.
[table 1]
ISTA: the different stearyl ester of vinylformic acid (Osaka Organic Chemical Industry Co., Ltd.'s system, trade(brand)name " ISTA ")
HPPA: vinylformic acid 3-hydroxypropyl phenyl ester (Kyoeisha Chemical Co., Ltd.'s system, trade(brand)name " エ Port キ シ エ ス テ Le M-600A ") L, TPO:2,4,6-trimethyl benzoyl diphenyl base phosphine oxide
(TPO) (BASF Amada Co., Ltd. system, trade(brand)name " Le シ リ Application TPO ")
[table 2]
(tone Gardner color)
Gardner color number measures according to JIS K5400.
(viscosity)
Utilize E type viscometer (Toki Sangyo Co., Ltd. TVE-10) under the condition of 25 DEG C, 5 minutes, measure the viscosity (mPas) of binder composition.
(solvent containing ratio)
The solvent containing ratio of coating fluid uses gas phase chromatographic device to measure.
< analytical equipment >
GC：Agilent，6850
< GC condition determination >
GC post: HP-1
Column temperature: 50 DEG C of (10 minutes) → 10 DEG C/min → 300 (10 minutes)
Post flow: 2.0ml/ minute
Carrier gas: helium
Sample injection method: shunting (50:1)
Detected temperatures: 300 DEG C
(consistency)
For consistency, the binder composition that visual observation obtains, judges with following benchmark.
Zero: evenly and completely transparent.
×: there is gonorrhoea, be separated completely, there is insolubles, or confirm liquid layer separation.
The making > of < bonding coat
Embodiment 6 ~ 10 and comparative example 9 ~ 14
The composition of embodiment 1 is applied on 38 μm of thick lift-off processing polyester films (パ Na ッ Network Co., Ltd. system, trade(brand)name " SP-PET-01-38BU "), makes thickness be 150 μm, make its in atmosphere, high voltage mercury lamp (35mJ/cm
2) under by once, carry out Procuring thus.The mode that this cured article coated face and 38 μm of thick lift-off processing polyester films contact with lift-off processing face is fitted, make its in atmosphere, high voltage mercury lamp (300mJ/cm
2) under by four times, be cured thus, obtain the bonding coat of embodiment 6.Composition for embodiment 2 ~ 5 and comparative example 1,2,4,6,7 and 8 operates similarly, makes the bonding coat of embodiment 7 ~ 10 and comparative example 9 ~ 14.Following test is carried out to obtained each bonding coat, shows the result in table 3.
[the various tests to bonding coat]
< binding power test >
The lift-off processing polyester film of the one side of the bonding coat of made embodiment 6 ~ 10 and comparative example 9 ~ 14 is peeled off, to fit 50 μm of thick polyester films (Toyo Boseki K.K's system, trade(brand)name " コ ス モ シ ャ イ Application A-4300 ") with 2kg roller, place 2 hours.Residual lift-off processing polyester film is peeled off, with 2kg roller laminating glass, makes 50 μm of PET/ bonding coat (150 μm)/glass test sheets thus.Place after 24 hours under 25 DEG C and 50%RH, 180 ° of directions are peeled off with the speed of 300mm/ minute, measures bounding force (N/25mm) thus.
The test > that < glass is residual
Remain about glass, evaluate and on glass, whether remain bonding coat after measuring above-mentioned bounding force.Metewand is as described below.
Zero: not residual bonding coat on glass
△: remain a part of bonding coat on glass
×: on glass, remain bonding coat
The mensuration > of < haze value
For the bonding coat of embodiment 6 ~ 10 and comparative example 9 ~ 14,50 μm of PET/ bonding coats (150 μm)/glass test sheet is made in the same manner as binding power test, use the colored haze meter (カ ラ ー へ イ ズ メ ー タ ー) of color technical institute in village, measure haze value according to JIS K 5400.In addition, each haze value is the numerical value comprised as the polyester film of base material and the haze value of glass.
< endurance test >
For the bonding coat of embodiment 6 ~ 10 and comparative example 9 ~ 14, make 50 μm of PET/ bonding coats (150 μm)/glass test sheet in the same manner as binding power test, implement endurance test.About endurance test, carry out the humidity resistance test of preserving 500 hours in the constant temperature and humidity cabinet of 85 DEG C-relative humidity 85%.Use the colored haze meter of color technical institute in village, measure the haze value after humidity resistance test according to JIS K 5400.In addition, each haze value is the numerical value comprised as the polyester film of base material and the haze value of glass.In addition, the metewand of weather resistance is as described below.
Zero: without peeling off, ooze out without bonding coat, without film albefaction
×: exist peel off, bonding coat oozes out and any one in film albefaction
[table 3]
Claims (6)
1. a ultraviolet-curing adhesive composition, is characterized in that, solvent is less than 1 % by weight, and the viscosity at 25 DEG C is 100 ~ 10000mPas, and tone counts less than 1 with Gardner color, and containing following (A) ~ (D),
(A) weight-average molecular weight be 10000 ~ 100000 polyfunctional carbamate (methyl) origoester acrylate,
(B) tackifier,
(C) monofunctional epoxy ester (methyl) acrylate,
(D) Photoepolymerizationinitiater initiater.
2. ultraviolet-curing adhesive composition as claimed in claim 1, wherein, described (A) composition is polyfunctional carbamate (methyl) origoester acrylate that (methyl) acrylate reactions of (methyl) acrylate of polyether glycol, polyisocyanates and hydroxyl or isocyanato group containing is obtained.
3. ultraviolet-curing adhesive composition as claimed in claim 1 or 2, wherein, described (B) composition is that tone counts the tackifier of less than 1 with Gardner color.
4. the ultraviolet-curing adhesive composition according to any one of claims 1 to 3, wherein, take weight part as benchmark, described (A) ~ (D) composition in binder composition with (A): (B): (C): the ratio of (D)=10 ~ 60:0.5 ~ 15:15 ~ 89.4:0.1 ~ 10 coordinates.
5. a bonding coat, it obtains by making the ultraviolet-curing adhesive composition according to any one of Claims 1 to 4 solidify.
6. bonding coat as claimed in claim 5, wherein, the thickness of bonding coat is 10 ~ 1000 μm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-102063 | 2012-04-27 | ||
| JP2012102063 | 2012-04-27 | ||
| PCT/JP2013/061915 WO2013161812A1 (en) | 2012-04-27 | 2013-04-23 | Ultraviolet light curing adhesive composition and adhesive layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104302720A true CN104302720A (en) | 2015-01-21 |
| CN104302720B CN104302720B (en) | 2016-08-17 |
Family
ID=49483121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380022223.1A Active CN104302720B (en) | 2012-04-27 | 2013-04-23 | Ultraviolet-curing adhesive composition and adhesive layer |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6024748B2 (en) |
| KR (1) | KR102062177B1 (en) |
| CN (1) | CN104302720B (en) |
| TW (1) | TWI568819B (en) |
| WO (1) | WO2013161812A1 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107532043A (en) * | 2015-04-22 | 2018-01-02 | Dic株式会社 | Ultraviolet hardening bonding sheet and bonding sheet |
| CN107614544A (en) * | 2015-05-26 | 2018-01-19 | 电化株式会社 | Composition |
| CN107683316A (en) * | 2015-06-04 | 2018-02-09 | 3M创新有限公司 | Hardware is bonded to the method for vehicle glass |
| CN108137762A (en) * | 2015-12-22 | 2018-06-08 | 日本合成化学工业株式会社 | Actinic energy ray curable resion composition and its manufacturing method |
| CN108276950A (en) * | 2018-02-27 | 2018-07-13 | 中山市精微新材料有限公司 | A kind of no acid system, high durable, the cured OCA glue of UV and preparation method thereof |
| CN108350336A (en) * | 2016-04-12 | 2018-07-31 | 株式会社Lg化学 | Adhesive composition for optical applications |
| CN108431157A (en) * | 2015-12-08 | 2018-08-21 | 思美定株式会社 | Use the adhering method of photo-curable sticker |
| CN109294509A (en) * | 2017-07-24 | 2019-02-01 | 荒川化学工业株式会社 | Ultraviolet-curing adhesive, solidfied material, bonding sheet |
| CN109554155A (en) * | 2017-09-25 | 2019-04-02 | 3M创新有限公司 | Printable, radiation-curable adhesive composition and its application |
| CN112601770A (en) * | 2018-08-29 | 2021-04-02 | 德路工业胶粘剂有限两合公司 | Curable two-component composition |
| CN113013413A (en) * | 2021-02-26 | 2021-06-22 | 华南农业大学 | Epoxy soybean oil acrylate photocuring binder, lithium-sulfur battery positive electrode, lithium-sulfur battery and preparation method thereof |
| CN113416518A (en) * | 2015-03-23 | 2021-09-21 | 阿科玛法国公司 | Pressure sensitive adhesive |
| CN113861343A (en) * | 2020-06-30 | 2021-12-31 | 荒川化学工业株式会社 | Urethane (meth) acrylate, active energy ray-curable resin composition, cured product, and laminate |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102200661B1 (en) * | 2014-02-06 | 2021-01-08 | 아라까와 가가꾸 고교 가부시끼가이샤 | Uv-curable adhesive composition for optical use, cured layer thereof and optical member |
| JP6529070B2 (en) * | 2014-03-28 | 2019-06-12 | リンテック株式会社 | Method of producing adhesive |
| JP6418672B2 (en) * | 2014-03-31 | 2018-11-07 | 日東電工株式会社 | Resin composition for optical parts and optical part using the same |
| WO2015190563A1 (en) * | 2014-06-11 | 2015-12-17 | 日本化薬株式会社 | Uv-curable resin composition for use in touchscreen, and bonding method and article using said uv-curable resin |
| JP6625534B2 (en) * | 2014-06-11 | 2019-12-25 | 日本化薬株式会社 | UV curable adhesive composition for touch panel and article |
| CN106459674A (en) * | 2014-06-11 | 2017-02-22 | 日本化药株式会社 | UV-curable resin composition for use in touchscreen, and bonding method and article using said uv-curable resin |
| TWI638874B (en) * | 2014-06-11 | 2018-10-21 | 日本化藥股份有限公司 | Ultraviolet-curable resin composition for touch panel, bonding method and article using the same |
| WO2016013510A1 (en) * | 2014-07-22 | 2016-01-28 | 日本合成化学工業株式会社 | Active energy ray-curable pressure sensitive adhesive composition, and pressure sensitive adhesive and pressure sensitive adhesive sheet using same |
| JP6798104B2 (en) * | 2014-12-25 | 2020-12-09 | 三菱ケミカル株式会社 | Urethane (meth) acrylate manufacturing method |
| CN107406737B (en) * | 2015-04-01 | 2020-03-17 | 霓达株式会社 | Temperature sensitive adhesive composition |
| WO2016158414A1 (en) * | 2015-04-03 | 2016-10-06 | ニッタ株式会社 | Temperature-sensitive adhesive tape and temperature-sensitive adhesive sheet |
| JP6545994B2 (en) * | 2015-04-07 | 2019-07-17 | 株式会社イノアック技術研究所 | Adhesive composition, method for producing adhesive composition, and viscous fluid |
| KR101999583B1 (en) | 2015-05-08 | 2019-07-12 | 반도 카가쿠 가부시키가이샤 | Optical transparent adhesive sheet, method for producing optical transparent adhesive sheet, laminate and display device with touch panel |
| US11530337B2 (en) | 2015-09-29 | 2022-12-20 | Bando Chemical Industries, Ltd. | Optically transparent pressure-sensitive adhesive sheet, laminate, process for producing laminate, and display device with touch panel |
| KR102062225B1 (en) | 2015-11-26 | 2020-01-03 | 반도 카가쿠 가부시키가이샤 | Display apparatus which has an optically transparent adhesive sheet, a manufacturing method of an optically transparent adhesive sheet, a laminated body, and a touch panel |
| JP6567399B2 (en) * | 2015-12-02 | 2019-08-28 | 積水フーラー株式会社 | UV curable adhesive composition |
| CN108699409A (en) * | 2016-02-26 | 2018-10-23 | 阪东化学株式会社 | Optical clear adhesive sheet, the manufacturing method of optical clear adhesive sheet, laminated body and the display device with touch screen |
| KR102061117B1 (en) * | 2016-03-16 | 2020-01-02 | 주식회사 엘지화학 | Clear adhesives for touch panel |
| JP6819871B2 (en) * | 2016-03-22 | 2021-01-27 | 荒川化学工業株式会社 | Method of manufacturing a laminate |
| KR101683800B1 (en) * | 2016-05-03 | 2016-12-09 | 지스마트 주식회사 | Ultraviolet curing resin composition, method of preparing the same and cured product using the same |
| WO2018039096A1 (en) | 2016-08-22 | 2018-03-01 | 3M Innovative Properties Company | Propenylamines and methods of making and using same |
| JP6969235B2 (en) * | 2016-09-05 | 2021-11-24 | 荒川化学工業株式会社 | UV curable adhesive, cured product, adhesive sheet |
| KR101923545B1 (en) * | 2016-11-17 | 2019-02-28 | 황진상 | Waterproof polyurethane resin compounds and mobile device bezel adhesive tape using the same |
| KR101879849B1 (en) * | 2016-11-17 | 2018-07-20 | 황진상 | Polyurethane adhesive resin compound including rubber particle and mobile device bezel adhesive tape using the same |
| CN106810670B (en) * | 2017-01-06 | 2020-02-07 | 浙江新迪在龙涂料科技有限公司 | Preparation method of polyurethane acrylate oligomer |
| KR102258325B1 (en) * | 2017-09-04 | 2021-05-28 | 아라까와 가가꾸 고교 가부시끼가이샤 | Ultraviolet ray-curable adhesive agent composition for protecting film, adhesive agent layer and protecting sheet |
| KR102019587B1 (en) * | 2018-01-16 | 2019-09-06 | 방현수 | Urethan acrylate oligomer and adhesive composition comprising the same |
| JP7183579B2 (en) * | 2018-06-06 | 2022-12-06 | Dic株式会社 | Active energy ray hardening type concrete protective material |
| CN111548739B (en) * | 2019-02-11 | 2022-03-01 | 3M创新有限公司 | Ultraviolet light curing adhesive |
| KR102247297B1 (en) | 2019-10-30 | 2021-05-03 | (주)화인테크놀리지 | Water soluble adhesive tape |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712849A (en) * | 2008-09-30 | 2010-05-26 | 荒川化学工业株式会社 | Active energy line solidification type adhesive composition |
| CN101792641A (en) * | 2010-02-08 | 2010-08-04 | 胡云睿 | Environment-friendly adhesive for quickly adhering aluminum alloy and PVC thin film and preparation and application thereof |
| CN102203200A (en) * | 2008-10-31 | 2011-09-28 | 巴斯夫欧洲公司 | (meth)acrylate phosphonic esters as adhesion promoters |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1375617A1 (en) | 2002-06-19 | 2004-01-02 | 3M Innovative Properties Company | Radiation-curable, solvent-free and printable precursor of a pressure-sensitive adhesive |
| JP4482463B2 (en) * | 2005-02-01 | 2010-06-16 | 日本ユピカ株式会社 | Radical curable resin composition |
| JP2008540709A (en) * | 2005-05-02 | 2008-11-20 | サイテック サーフェース スペシャリティーズ、エス．エイ． | Radiation curable urethane (meth) acrylate polymers and adhesives formulated with them |
| JP2006316203A (en) * | 2005-05-13 | 2006-11-24 | Emulsion Technology Co Ltd | Adhesive composition |
| JP2007056210A (en) * | 2005-08-26 | 2007-03-08 | Emulsion Technology Co Ltd | Adhesive resin composition for back grinding, adhesive sheet for back grinding, and its manufacturing method |
| JP2007182557A (en) * | 2005-12-06 | 2007-07-19 | Jsr Corp | Impact resisting adhesive layer, method for producing the same and impact resisting adhesive laminated structure |
| JP5367990B2 (en) * | 2008-01-25 | 2013-12-11 | リンテック株式会社 | Laser dicing sheet and chip body manufacturing method |
| TWI485214B (en) * | 2008-09-05 | 2015-05-21 | Kyoritsu Chemical Co Ltd | And a photohardenable resin composition for bonding an optical functional material |
| JP2010085578A (en) * | 2008-09-30 | 2010-04-15 | Toray Advanced Film Co Ltd | Method of manufacturing ultraviolet curing pressure-sensitive adhesive layer and display filter including this ultraviolet curing pressure-sensitive adhesive layer |
| JP5544954B2 (en) | 2010-03-18 | 2014-07-09 | サイデン化学株式会社 | Optical pressure-sensitive adhesive composition |
| JP2011225835A (en) | 2010-03-30 | 2011-11-10 | Nippon Synthetic Chem Ind Co Ltd:The | Adhesive composition, adhesive, double sided adhesive sheet, adhesive for optical member, and touch panel |
| JP2012121978A (en) * | 2010-12-08 | 2012-06-28 | Toray Advanced Film Co Ltd | Adhesive sheet and display device |
| JP5834606B2 (en) * | 2011-08-05 | 2015-12-24 | Dic株式会社 | UV-curable adhesive resin composition, adhesive and laminate |
-
2013
- 2013-04-23 JP JP2014512610A patent/JP6024748B2/en active Active
- 2013-04-23 CN CN201380022223.1A patent/CN104302720B/en active Active
- 2013-04-23 WO PCT/JP2013/061915 patent/WO2013161812A1/en active Application Filing
- 2013-04-23 KR KR1020147029431A patent/KR102062177B1/en active IP Right Grant
- 2013-04-26 TW TW102115079A patent/TWI568819B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712849A (en) * | 2008-09-30 | 2010-05-26 | 荒川化学工业株式会社 | Active energy line solidification type adhesive composition |
| CN102203200A (en) * | 2008-10-31 | 2011-09-28 | 巴斯夫欧洲公司 | (meth)acrylate phosphonic esters as adhesion promoters |
| CN101792641A (en) * | 2010-02-08 | 2010-08-04 | 胡云睿 | Environment-friendly adhesive for quickly adhering aluminum alloy and PVC thin film and preparation and application thereof |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113416518A (en) * | 2015-03-23 | 2021-09-21 | 阿科玛法国公司 | Pressure sensitive adhesive |
| CN107532043A (en) * | 2015-04-22 | 2018-01-02 | Dic株式会社 | Ultraviolet hardening bonding sheet and bonding sheet |
| CN107614544B (en) * | 2015-05-26 | 2020-10-30 | 电化株式会社 | Composition comprising a metal oxide and a metal oxide |
| CN107614544A (en) * | 2015-05-26 | 2018-01-19 | 电化株式会社 | Composition |
| CN107683316A (en) * | 2015-06-04 | 2018-02-09 | 3M创新有限公司 | Hardware is bonded to the method for vehicle glass |
| CN108431157A (en) * | 2015-12-08 | 2018-08-21 | 思美定株式会社 | Use the adhering method of photo-curable sticker |
| CN108431157B (en) * | 2015-12-08 | 2021-02-05 | 思美定株式会社 | Bonding method using photocurable adhesive |
| CN108137762A (en) * | 2015-12-22 | 2018-06-08 | 日本合成化学工业株式会社 | Actinic energy ray curable resion composition and its manufacturing method |
| CN108350336A (en) * | 2016-04-12 | 2018-07-31 | 株式会社Lg化学 | Adhesive composition for optical applications |
| CN109294509A (en) * | 2017-07-24 | 2019-02-01 | 荒川化学工业株式会社 | Ultraviolet-curing adhesive, solidfied material, bonding sheet |
| CN109294509B (en) * | 2017-07-24 | 2022-02-15 | 荒川化学工业株式会社 | Ultraviolet-curable adhesive, cured product, and adhesive sheet |
| CN109554155A (en) * | 2017-09-25 | 2019-04-02 | 3M创新有限公司 | Printable, radiation-curable adhesive composition and its application |
| CN109554155B (en) * | 2017-09-25 | 2021-04-02 | 3M创新有限公司 | Printable, radiation-curable adhesive composition and use thereof |
| CN108276950A (en) * | 2018-02-27 | 2018-07-13 | 中山市精微新材料有限公司 | A kind of no acid system, high durable, the cured OCA glue of UV and preparation method thereof |
| CN112601770A (en) * | 2018-08-29 | 2021-04-02 | 德路工业胶粘剂有限两合公司 | Curable two-component composition |
| US11834540B2 (en) | 2018-08-29 | 2023-12-05 | Delo Industrie Klebstoffe Gmbh & Co. Kgaa | Curable two-component mass |
| CN112601770B (en) * | 2018-08-29 | 2024-03-01 | 德路工业胶粘剂有限两合公司 | Curable two-component composition |
| CN113861343A (en) * | 2020-06-30 | 2021-12-31 | 荒川化学工业株式会社 | Urethane (meth) acrylate, active energy ray-curable resin composition, cured product, and laminate |
| CN113861343B (en) * | 2020-06-30 | 2023-11-10 | 荒川化学工业株式会社 | Urethane (meth) acrylate, active energy ray-curable resin composition, cured product, and laminate |
| CN113013413A (en) * | 2021-02-26 | 2021-06-22 | 华南农业大学 | Epoxy soybean oil acrylate photocuring binder, lithium-sulfur battery positive electrode, lithium-sulfur battery and preparation method thereof |
| CN113013413B (en) * | 2021-02-26 | 2022-06-10 | 华南农业大学 | Epoxy soybean oil acrylate photocuring binder, lithium-sulfur battery positive electrode, lithium-sulfur battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20150005552A (en) | 2015-01-14 |
| TWI568819B (en) | 2017-02-01 |
| CN104302720B (en) | 2016-08-17 |
| JP6024748B2 (en) | 2016-11-16 |
| KR102062177B1 (en) | 2020-01-03 |
| WO2013161812A1 (en) | 2013-10-31 |
| JPWO2013161812A1 (en) | 2015-12-24 |
| TW201402755A (en) | 2014-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104302720A (en) | Ultraviolet light curing adhesive composition and adhesive layer | |
| CN102361947B (en) | Adhesive protective film, screen panel, and portable electronic terminal | |
| CN1989164B (en) | Curable composition | |
| CN104169388B (en) | Optics light solidified slice-type binder composition | |
| TWI512075B (en) | Composition of photohardenable transparent adhesive sheet | |
| JP5854404B2 (en) | Composition for photocurable transparent adhesive sheet | |
| CN103509516B (en) | Ultraviolet-curing adhesive resin combination and adhesive | |
| CN104830266A (en) | Ultraviolet light solidified-type adhesive composition for optics and solidified layer and optical component thereof | |
| CN111534244B (en) | Protective film applied to curved surface display screen | |
| JP2016186007A (en) | Ultraviolet-curable adhesive composition | |
| CN104093761A (en) | Urethane (meth)acrylate and moisture-proof insulating coating material | |
| CN106947033A (en) | Ultraviolet-curing resin composition, solidfied material and article | |
| CN106753184A (en) | Ultraviolet-curing transparent adhesive composition | |
| JP5098722B2 (en) | Curable resin composition, film laminate for sticking, and laminate for impact absorption | |
| CN103666304B (en) | The manufacture method of icon sheet, icon sheet and use the contact panel of this icon sheet | |
| JP2017052885A (en) | Manufacturing method of photosetting resin composition, photosetting resin composition, adhesive composition, composite structure and manufacturing method and decomposing method of composite structure | |
| CN105378020A (en) | Ultraviolet curable adhesive composition, adhesive and adhesive film | |
| JP2013246535A (en) | Display device | |
| JP2014065818A (en) | Ultraviolet-curable adhesive composition for optical use, and adhesive layer | |
| JP2019023292A (en) | Ultraviolet curable adhesive, cured product and adhesive sheet | |
| JP2010265402A (en) | Light and heat curing combined use-type resin composition, light and heat curing combined use-type moisture-proof sealing material for electronic paper, electronic paper, and method for producing the electronic paper | |
| JP2017206654A (en) | Adhesive composition, adhesive sheet, touch panel, and image display device | |
| JP2018070788A (en) | Adhesive composition, adhesive sheet, touch panel, and image display apparatus | |
| CN104011099A (en) | Liquid curable resin composition, method for manufacturing image display device using same, and image display device | |
| CN112752817A (en) | Adhesive composition for surface protection sheet and surface protection sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |