CN103154060A - Resin composition - Google Patents
Resin composition Download PDFInfo
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- CN103154060A CN103154060A CN2011800485261A CN201180048526A CN103154060A CN 103154060 A CN103154060 A CN 103154060A CN 2011800485261 A CN2011800485261 A CN 2011800485261A CN 201180048526 A CN201180048526 A CN 201180048526A CN 103154060 A CN103154060 A CN 103154060A
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- methyl
- acrylate
- hydroxyl
- resin combination
- photoepolymerizationinitiater initiater
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- 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
-
- 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
- C08G18/67—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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
- C09K19/3885—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Laminated Bodies (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
In response to the problem of providing a resin composition having good transparency, pencil hardness, and adhesiveness, the present invention provides a resin composition comprising (D) a urethane acrylate obtained by reacting (A) a (meth)acrylic acid ester monomer having hydroxyl groups, (B) a photopolymerization initiator having hydroxyl groups, and (C) an isocyanate having isocyanate groups; (E) a polymerizable (meth)acrylate; and (F) a silane coupling agent. This resin composition is used as an adhesive or hard coating agent, and further, is ideal for the production of a touch panel laminate or liquid crystal panel laminate.
Description
Technical field
The present invention relates to resin combination.The present invention relates to caking agent for example, hard paint and use its electronics.
Background technology
Be equipped on touch panel on the display body such as LCD resistance membrane type, condenser type, induction, optical profile type etc. are arranged.Sometimes fit on these touch panels decorative sheet, icon board (icon sheet).Decorative sheet uses for the designability that makes outward appearance is good.Icon board is used for the position of specifying touch.Capacitive touch panels has and is forming transparency electrode on transparency carrier and the structure of applying transparent panel on this transparency electrode.
In the past, the applying of the applying of above-mentioned decorative sheet and touch panel, icon board and touch panel, the formation in capacitive touch panels the applying of the transparency carrier of transparency electrode and transparent panel be that two sides adhesive sheet with sheet carries out, or carry out being carried out bonding processing by the single face of convered structure.Exist bonding insufficient or sneak into the problem of bubble at binding face in the technology of using such tackiness agent.Particularly, if carried out printing processing at binding face, have bubble and easily remain in the part of printing and the problem of the difference of altitude part of the part of nothing printing.
In recent years, the thickness of glass attenuation gradually of the display body such as LCD.If the glass attenuation, LCD easily distortion due to external stress.When the optical functional materialses such as the display body such as the LCD of this thin glass and acrylic board, polycarbonate plate are fitted, deformation during due to the plastic shaping material moulding such as polar expansion difference, acrylic board or polycarbonate of glass and acrylic etc., cause mitigation, the hygroscopic desiccation of moulding deformation in oven test, humidity test, cause the surface accuracies such as dimensional change, warpage to change.Want with in the past caking agent (for example, patent documentation 1～2) when suppressing this distortion, exist bonding plane to peel off, LCD breaks, LCD shows the problem that inequality is such.
As the solution of the problems referred to above, the UV gel-type resin in patent documentation 3 is arranged.Because it is with the rigid backbone monomer of (methyl) isobornyl acrylate and so on the snappiness resin as matrix, peel off so might can't tolerate by the dilation of convered structure in the high temperature reliability test.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-77887 communique
Patent documentation 2:WO2010/027041 communique
Patent documentation 3: Japanese kokai publication sho 64-85209 communique
Summary of the invention
The invention provides a kind of caking agent, hard paint, it has solved such as will be for the decorative sheet of the display body such as touch panel, when icon board is fitted, or when the transparency carrier that is formed with transparency electrode in capacitive touch panels and transparency carrier are fitted, be difficult to give sufficient cementability, be difficult to not contain the prior art problem of fitting in bubble ground.The invention provides a kind of caking agent, hard paint, it has for example solved when display body and optical functional materials are fitted, and bonding plane peels off or the prior art problem of the glass breakage of display body.
That is, on the one hand, the invention provides resin combination.This resin combination is the resin combination that contains urethane acrylate (D), polymerisable (methyl) acrylate (E) and silane coupling agent (F), and isocyanic ester (C) reaction that above-mentioned urethane acrylate (D) makes (methyl) acrylate monomer (A) with hydroxyl, the Photoepolymerizationinitiater initiater (B) with hydroxyl and has isocyanate group obtains.
In an embodiment of this resin combination, (methyl) acrylate monomer (A) with hydroxyl is the compound with (methyl) acryl more than 2.In addition, in another embodiment, the Photoepolymerizationinitiater initiater (B) with hydroxyl has 2 above hydroxyls.
On the other hand, the invention provides the cured article of this resin combination.
On the other hand, the invention provides by this cured article coating or engage the complex body that is formed by convered structure.
In an embodiment of this complex body, this complex body by convered structure be selected from cellulose triacetate, fluorine based polymer, polyester, polycarbonate, polyolefine, glass, metal more than a kind.
From another point of view, the invention provides with this resin combination fit by convered structure and the touch panel duplexer, and then the invention provides the indicating meter that has utilized this touch panel duplexer.
From another point of view, the invention provides with this resin combination fit by convered structure and the liquid crystal panel duplexer, and then the invention provides the indicating meter that has utilized this liquid crystal panel duplexer.
From another point of view, the invention provides the caking agent that is consisted of by above-mentioned resin combination.In addition, from another point of view, the invention provides the hard paint that is consisted of by this resin combination.
Resin combination of the present invention has the effect that the transparency is large, pencil hardness is large, cementability is large.Embodiment
Isocyanic ester (C) reaction that urethane acrylate (D) with Photoepolymerizationinitiater initiater makes (methyl) acrylate monomer (A) with hydroxyl, the Photoepolymerizationinitiater initiater (B) with hydroxyl and has the isocyanate group more than 2 obtains.
(methyl) acrylate monomer (A) with hydroxyl is the monomer with at least 1 (methyl) acrylate-based and hydroxyl.As (methyl) acrylate with 1 (methyl) acrylate-based and hydroxyl, such as enumerating (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester and propylene glycol (methyl) acrylate etc.As (methyl) acrylic compound with the acrylate-based and hydroxyl of (methyl) more than 2, such as enumerating glycerine two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, hydroxypropyl trimethylolpropane tris (methyl) acrylate, Dipentaerythritol hydroxyl five (methyl) acrylate, two (tetramethylolmethane) four (methyl) acrylate, tetramethylol methane-three (methyl) acrylate, 2-hydroxyl-3-(methyl) acryloxy propyl methyl acid esters etc.(methyl) acrylate-based number with (methyl) acrylate monomer (A) of hydroxyl is preferably more than 2, more preferably more than 3.The number of hydroxyl with (methyl) acrylate monomer (A) of hydroxyl is preferably more than 2.
Photoepolymerizationinitiater initiater (B) with hydroxyl has at least 1 hydroxyl.As the Photoepolymerizationinitiater initiater with 1 hydroxyl, for example can enumerate 2-hydroxy-methyl-1-phenyl-propane-1-ketone (Ciba Japan company system, ProductName Darocur1173), 1-hydroxyl-cyclohexyl-phenyl-ketone (Ciba Japan company system, ProductName Irgacure184) etc.As the Photoepolymerizationinitiater initiater with 2 above hydroxyls; for example can enumerate 1-［ 4-(hydroxyl-oxethyl)-phenyl ］-2-hydroxyl-2 methyl isophthalic acids-propane-1-ketone (Ciba Japan company system; ProductName Irgacure2959), 2-hydroxyl-1-{ 4-［ 4-(2-hydroxy-2-methyl-propionyl)-benzyl ］-phenyl }-2-methyl-propane-1-ketone (Ciba Japan company system, ProductName Irgacure127) etc.The number of hydroxyl with Photoepolymerizationinitiater initiater (B) of hydroxyl is preferably more than 2.This is because by having more than 2, the light trigger that ftractures after radiation exposure can enter the reaction system of the acryl of (methyl) acrylate monomer (A), so can suppress migration.Should illustrate, be not particularly limited for the upper limit of the number of hydroxyl.
Isocyanic ester (C) with isocyanate group preferably has the isocyanate group more than 2.Have the isocyanic ester (C) of the isocyanate group more than 2 such as enumerating aromatic diisocyanate, alicyclic diisocyanate and aliphatic diisocyanate etc., can preferably use aromatic isocyanate or alicyclic isocyanate.As the form of isocyanate compound, monomer, dimer and tripolymer are arranged, preferably use tripolymer.
As aromatic diisocyanate, for example can enumerate inferior cresyl vulcabond, 4,4-diphenylmethanediisocyanate and eylylene diisocyanate etc.
As alicyclic diisocyanate, such as enumerating isophorone diisocyanate, methylene-bis (4-cyclohexyl isocyanate) etc.
As aliphatic diisocyanate, such as enumerating hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate etc.
Can also use well the trimethylolpropane adduct of above-mentioned vulcabond, with the biuret body of water reaction, have 3 aggressiveness of isocyanurate ring etc.
The total (A)+(B)=10 of the mole number of the hydroxyl of the mole number of above-mentioned (methyl) acrylate monomer (A) with hydroxyl and above-mentioned Photoepolymerizationinitiater initiater (B) with hydroxyl o'clock (A) is preferably more than 6, more preferably more than 9.(A) be preferably below 9.9, more preferably below 9.8.
The total (A)+(B)=10 of the mole number of the hydroxyl of the mole number of the hydroxyl of above-mentioned (methyl) acrylate monomer (A) with hydroxyl and above-mentioned Photoepolymerizationinitiater initiater (B) with hydroxyl o'clock, the mole number of isocyanate group with isocyanic ester (C) of 2 above isocyanate group is preferably 8～12, and more preferably 9～11.
Manufacture method with urethane acrylate (D) of above-mentioned Photoepolymerizationinitiater initiater is not particularly limited.Urethane acrylate (D) with above-mentioned Photoepolymerizationinitiater initiater for example can followingly obtain, namely, stir the Photoepolymerizationinitiater initiater (B) that has (methyl) acrylate monomer (A) of hydroxyl and have hydroxyl on one side in the ethyl acetate equal solvent, heat after 40 ℃ on one side, isocyanic ester (C) with 2 hours continuous addings have 2 above isocyanate group further stirred 6 hours.
Polymerisable (methyl) acrylate (E) be so long as polymerisable (methyl) acrylic acid series composition and can carry out radical polymerization just can use any (methyl) acrylate, shown in it is for example lower.Here, (methyl) acrylic acid series composition refers to the general name (below be designated as～(methyl) acrylate) of methacrylic ester and acrylate.as polymerisable (methyl) acrylate (E), for example can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) isodecyl acrylate, (methyl) dodecylacrylate, (methyl) vinylformic acid stearyl, (methyl) phenyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid two cyclopentyl esters, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) isobornyl acrylate, methoxylation cyclotriene (methyl) acrylate, (methyl) vinylformic acid dicyclopentenyl oxygen ethyl ester, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, polyoxyethylene glycol (methyl) acrylate, alkyl oxygen polypropylene glycol (methyl) acrylate, (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) glycidyl acrylate, caprolactone modification four furfuryl groups (methyl) acrylate, ethoxy carbonyl methyl (methyl) acrylate, phenol ring oxidative ethane modification (methyl) acrylate, to cumyl phenol ethylidene oxygen modification (methyl) acrylate, nonylphenol oxyethane modification (methyl) acrylate, nonylphenol poly(propylene oxide) modification (methyl) acrylate, (methyl) vinylformic acid 2-ethylhexyl carbitol ester, polyglycerol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate, BDO (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, epoxy group(ing) (methyl) acrylate (Osaka organic chemistry society system, " VISCOTE#540 "), polyester (methyl) acrylate (East Asia synthetic society system, " ARONIXM-6100 ", common prosperity chemistry society system, " EPOXY ESTER3000M "), carbamate (methyl) acrylate (society's system, " ARONIX M-1100 " are synthesized in East Asia), polyoxyethylene glycol urethane-modified two (methyl) acrylate, polypropylene glycol urethane-modified two (methyl) acrylate, epoxy group(ing) (methyl) acrylate (society's system, " ARONIX M-5710 " are synthesized in East Asia), polyhutadiene two (methyl) acrylate (Japanese Cao Da society system, " TE-2000 "), acrylonitrile butadiene (methyl) acrylate (emerging product society of space section system, " HyCAr VTBNX "), (methyl) benzyl acrylate, glycerol (methyl) acrylate, glycerol two (methyl) acrylate, phenoxy group Diethylene Glycol (methyl) acrylate, two (4-(methyl) the acryloxy phenyl of 2,2-) propane, two (4-(methyl) the acryloxy diethoxy phenyl of 2,2-) propane, two (4-(methyl) the acryloxy ethoxyl phenenyls of 2,2-) propane, two (4-(methyl) the acryloxy propoxy-phenyl of 2,2-) propane, two (4-(methyl) the acryloxy tetraethoxy phenyl of 2,2-) propane, 2,2-pair [the 4-((methyl) the acryloxy polyethoxye) phenyl ］ propane, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate etc.
Above-mentioned (E) composition can use one kind or two or more, be preferably be selected from (methyl) isobornyl acrylate, dicyclopentenyl two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate more than a kind.Above from showing that the aspect consideration of high conservation rate is favourable take high temperature and humidity test, atmospheric exposure test as the endurance test of representative.
In the present invention, for improving glass so that the purpose of the closing force of plastics as (F) composition, can contain silane coupling agent.as silane coupling agent, for example can enumerate γ-r-chloropropyl trimethoxyl silane, vinyltrimethoxy silane, vinyl trichloro silane, vinyltriethoxysilane, vinyl-three ('beta '-methoxy oxyethyl group) silane, γ-(methyl) acryloxy propyl trimethoxy silicane, β-(3, 4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ mercaptopropyitrimethoxy silane, γ aminopropyltriethoxy silane, N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane, N-β-(amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane, γ-urea groups propyl-triethoxysilicane etc.Wherein, consider preferred γ-glycidoxypropyltrime,hoxysilane and/or γ-(methyl) acryloxy propyl trimethoxy silicane, more preferably γ-glycidoxypropyltrime,hoxysilane from the adaptation aspect to glass etc.
In resin combination of the present invention, in total 100 mass parts of (D) composition, (E) composition, preferably contain (D) composition 5～95 mass parts, (E) composition 5～95 mass parts, more preferably contain (D) composition 10～90 mass parts, (E) composition 10～90 mass parts, most preferably contain (D) composition 30～80 mass parts, (E) composition 20～70 mass parts.
From composition, and solidified nature high especially by the cementability of convered structure good aspect is considered, (F) usage quantity of composition is with respect to total 100 mass parts of (D) composition, (E) composition, the situation that preferably contains 0.01～10 mass parts more preferably contains the situation of 0.1～5 mass parts.
For the purpose of keeping storage stability, can use commercially available antioxidant that contains stopper etc.
In addition, can also use as required the known materials such as softening agent, weighting agent, tinting material or rust-preventive agent.
The present invention solidifies composition to resin combination irradiation visible rays or ultraviolet ray and bonding.
Visible rays or ultraviolet accumulated light are at the preferred 100～40000mJ/cm of 365nm
2, more preferably 500～4000mJ/cm
2
Resin combination of the present invention becomes the protection base material as the substitute of transparency carrier on the transparency carrier that is formed with transparency electrode in touch panel.Resin combination of the present invention can not contain bubble and fits, and guarantees sufficient cementability.Resin combination of the present invention can use as caking agent, hard paint.
In the present invention, can utilize the cured article of resin combination engage or made complex body by the cover convered structure.For by the various materials of convered structure, be preferably selected from polyolefine, glass, the metals such as cellulose triacetate, fluorine based polymer, polyester, polycarbonate, cyclic olefin polymer more than a kind, more preferably be selected from polyester, polycarbonate, glass more than a kind.
By fitting by convered structure with resin combination of the present invention, can make duplexer.As duplexer, can enumerate the electronicss such as touch panel duplexer, liquid crystal panel duplexer.Touch panel duplexer, liquid crystal panel duplexer etc. can be used for indicating meter.
Embodiment
Below, with table 1～3 explanation the present invention.The invention is not restricted to these.Table 1 expression has the cooperation of the compound that uses in the urethane acrylate (D) of Photoepolymerizationinitiater initiater, and table 2 and table 3 have gathered cooperation and the evaluation thereof of composition.
The preparation of＜experiment material＞
Related caking agent in embodiment so that hard paint with following formula manufacturing.
In table 1, each compound of record is as follows.
Has (methyl) acrylate monomer (A) of hydroxyl-first: 2-hydroxyethyl methacrylate;
Has (methyl) acrylate monomer (A) of hydroxyl-second: pentaerythritol triacrylate (Osaka organic chemistry society system, ProductName V#300);
(methyl) acrylate monomer (A)-third with hydroxyl: glycerine dimethacrylate (chemical society of common prosperity society system, ProductName LIGHT ESTER G-101P);
Has the Photoepolymerizationinitiater initiater (B) of hydroxyl-first: 1-hydroxyl-cyclohexyl-phenyl-ketone (CibaJapan company system, ProductName Irgacure184);
Has the Photoepolymerizationinitiater initiater (B) of hydroxyl-second: 2-hydroxyl-1-{ 4-［ 4-(2-hydroxy-2-methyl-propionyl)-benzyl ］-phenyl }-2-methyl-propane-1-ketone (Ciba Japan company system, ProductName Irgacure127);
Photoepolymerizationinitiater initiater (B)-third with hydroxyl: 1-［ 4-(hydroxyl-oxethyl)-phenyl ］-2-hydroxyl-2 methyl isophthalic acids-propane-1-ketone (Ciba Japan company system, ProductName Irgacure2959);
Has the isocyanic ester (C) of 2 above isocyanate group-first: 3 aggressiveness of hexamethylene diisocyanate (Asahi Kasei Chemicals company system, ProductName Duranate TPA-100);
Has the isocyanic ester (C) of 2 above isocyanate group-second: inferior cresyl vulcabond;
Polymerisable (methyl) acrylate (E)-first: dicyclopentenyl diacrylate;
Polymerisable (methyl) acrylate (E)-second: Viscoat 295;
Silane coupling agent (F)-first: γ-methacryloxypropyl trimethoxy silane;
Silane coupling agent (F)-second: γ-glycidoxypropyltrime,hoxysilane
Following the obtaining of urethane acrylate (D) with Photoepolymerizationinitiater initiater, namely, under the shading condition, stir the Photoepolymerizationinitiater initiater (B) that has (methyl) acrylate monomer (A) of hydroxyl and have hydroxyl on one side in ethyl acetate, heat after 40 ℃ on one side, add continuously the isocyanic ester (C) with 2 above isocyanate group with 2 hours, further stirred 6 hours.
(embodiment and comparative example)
The caking agent of corresponding each embodiment and comparative example so that the main component amount of being mated of hard paint as shown in table 1～3.In the preparation, except the composition shown in these tables 1, above-mentioned (E) composition and (F) composition have also been coordinated.
In comparative example 1～2, replace having the urethane acrylate (D) of Photoepolymerizationinitiater initiater, coordinate urethane acrylate oligomer (industrial society system on root, ProductName UN-3320HS) 50～100 mass parts and Photoepolymerizationinitiater initiater (Ciba Japan company system, ProductName Irugacure651) 3 mass parts, prepare composition with it.
The following mensuration of various physical property.
(light solidified)
Measure 23 ℃ of temperature.About light solidified, (surface of 25mm * 25mm * 2mm) is coated with curable resin composition in the mode that thickness reaches 0.1mm at Tempax glass.Then, utilize the FUSION company solidification equipment processed that has used electrodeless discharge lamp, at accumulated light 2000mJ/cm
2Condition under illumination wavelength 365nm UV light and be cured.As light solidified, the record curing degree.Curing degree uses FT-IR and utilizes and calculate with following formula.
(curing degree)=intensity of the absorption spectrum of the carbon-carbon double bond after 100-((solidifies)/(intensity of the absorption spectrum of the carbon-carbon double bond before solidifying)) * 100(%)
The evaluation of light solidified is as follows.
Zero: (curing degree of being calculated by FT-IR: more than 90%), △ are not clamminess on the surface: the part on surface be clamminess (curing degree of being calculated by FT-IR: 50%-89%), *: the surface integral (curing degree of being calculated by FT-IR: 0-49%) that is clamminess.
(estimate and use component manufacturing method: the embodiment comparative example is common)
The mode that the composition that obtains is reached 10 μ m with thickness with metering bar coater is coated Tempax glass and (on 25mm * 25mm * 2mmt), after solidifying according to (light solidified), is formed being touched of composition.
Full light transmittance, mist degree, the result of pencil hardness and the end value of light fastness test of each film of obtaining are shown in table 1～3 in the lump.
Method for testing performance is as follows.
(full light transmittance and mist degree)
Use haze meter (SUGA TEST INSTRUMENTS company system), measure according to JISK7361 and JIS K7136.
(pencil hardness)
Use scratch test machine (KASAI company system), measure with load 1kg according to JIS K5600-5-4.
(light fastness test)
Use Sunshine Weather Meter(SUGA TEST INSTRUMENTS company system), to the coated face side irradiation ultraviolet radiation of sample, expose 200 hours (there is no water spray).To the sample determination pencil hardness after exposing.
(to the tensile shear bonding strength (bonding strength, glass) of glass)
Measure according to JIS K6850.(25mm * 25mm * 2mm) is as by adhesives to use Tempax glass.Making bonding position is 8mm φ (it is 8mm φ that what is called makes bonding position, refers to that bonding position is the circle of diameter 8mm), uses 2 Tempax glass of resin combination applying.By having used the FUSION company solidification equipment processed of electrodeless discharge lamp, at the accumulated light 2000mJ/cm of the wavelength of 365nm
2Condition under make its curing, make tensile shear bonding strength test film.For test film, use universal testing machine, under the environment of 23 ℃ of temperature, humidity 50%, measure the tensile shear bonding strength with draw speed 10mm/min.
(to the bonding strength (bonding strength, polyester) of polyester)
Use PET film (10mm * 50mm * 185 μ m) conduct by adhesives.Making bonding position is 10mm * 30mm, uses 2 PET films of resin combination applying.By having used the FUSION company solidification equipment processed of electrodeless discharge lamp, at the accumulated light 2000mJ/cm of the wavelength of 365nm
2Condition under make its curing, made and peeled off the bonding strength test film.For test film, use universal testing machine, under the environment of 23 ℃ of temperature, humidity 50%, measure with draw speed 50mm/min and peel off bonding strength.
(to the tensile shear bonding strength (bonding strength, polycarbonate) of polycarbonate)
Measure according to JIS K6850.(25mm * 25mm * 2mm) is as by adhesives to use polycarbonate plate.Making bonding position is 8mm φ (so-called make bonding position be that 8mm φ refers to that bonding position is the circle of diameter 8mm), uses resin combination 2 polycarbonate plates of fitting.By having used the FUSION company solidification equipment processed of electrodeless discharge lamp, at the accumulated light 2000mJ/cm of the wavelength of 365nm
2Condition under make its curing, made tensile shear bonding strength test film.For test film, use universal testing machine, under the environment of 23 ℃ of temperature, humidity 50%, measure the tensile shear bonding strength with draw speed 10mm/min.
Table 1
Table 2
Table 3
As seen from table, resin combination of the present invention has following characteristics.
(1) resin combination of the present invention can not contain bubble ground applying, and the transparency is large.Resin combination of the present invention becomes the protection base material of transparency carrier.
(2) pencil hardness after the pencil hardness of resin combination of the present invention, particularly light fastness test is large.Even if can providing to use, resin combination of the present invention also is difficult to injured hard paint under the environment that light exposes.
(3) resin combination of the present invention is guaranteed sufficient cementability.Resin combination of the present invention can be used as caking agent.
Claims (12)
1. resin combination, contain urethane acrylate (D), polymerisable (methyl) acrylate (E), silane coupling agent (F), isocyanic ester (C) reaction that described urethane acrylate (D) makes (methyl) acrylate monomer (A) with hydroxyl, the Photoepolymerizationinitiater initiater (B) with hydroxyl and has isocyanate group obtains.
2. resin combination according to claim 1, wherein, (methyl) acrylate monomer (A) with hydroxyl is the compound with (methyl) acryl more than 2.
3. resin combination according to claim 1 and 2, wherein, have the Photoepolymerizationinitiater initiater (B) of hydroxyl for having the compound of 2 above hydroxyls.
4. a cured article, be the cured article of the described resin combination of claim 1～3.
5. a species complex, formed by convered structure by cured article coating claimed in claim 4 or joint.
6. complex body according to claim 5, wherein, by convered structure be selected from cellulose triacetate, fluorine based polymer, polyester, polycarbonate, polyolefine, glass, metal more than a kind.
7. a touch panel duplexer, formed by convered structure with the described resin combination applying of claim 1～3.
8. a liquid crystal panel duplexer, formed by convered structure with the described resin combination applying of claim 1～3.
9. an indicating meter, used touch panel duplexer claimed in claim 7.
10. an indicating meter, used liquid crystal panel duplexer claimed in claim 8.
11. a caking agent is made of the described resin combination of claim 1～3.
12. a hard paint is made of the described resin combination of claim 1～3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-228138 | 2010-10-08 | ||
| JP2010228138 | 2010-10-08 | ||
| PCT/JP2011/073113 WO2012046810A1 (en) | 2010-10-08 | 2011-10-06 | Resin composition |
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| Publication Number | Publication Date |
|---|---|
| CN103154060A true CN103154060A (en) | 2013-06-12 |
| CN103154060B CN103154060B (en) | 2015-08-12 |
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| CN201180048526.1A Active CN103154060B (en) | 2010-10-08 | 2011-10-06 | Resin combination |
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| Country | Link |
|---|---|
| JP (1) | JP5847724B2 (en) |
| KR (1) | KR101848401B1 (en) |
| CN (1) | CN103154060B (en) |
| TW (1) | TWI532808B (en) |
| WO (1) | WO2012046810A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105745240A (en) * | 2013-11-15 | 2016-07-06 | 富士胶片株式会社 | Curable composition, method for producing cured film, cured film, and display device |
| CN110872483A (en) * | 2018-09-03 | 2020-03-10 | 荒川化学工业株式会社 | Active energy ray-curable adhesive composition, cured product, and adhesive sheet |
| CN111278944A (en) * | 2017-08-31 | 2020-06-12 | 三星Sdi株式会社 | Adhesive film, adhesive composition for the same, and display member comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| ES2626506T3 (en) * | 2012-05-30 | 2017-07-25 | Igm Malta Limited | Radiation curable compounds |
| JP2014062195A (en) * | 2012-09-21 | 2014-04-10 | Ksm Kk | Photocurable composition and method for producing photocurable composition |
| KR102307244B1 (en) | 2014-12-02 | 2021-10-01 | 삼성디스플레이 주식회사 | Display device |
| EP3784497A1 (en) * | 2018-04-25 | 2021-03-03 | Basf Se | Process for the production of strongly adherent liquid crystal films on flexible substrates |
| KR102184587B1 (en) * | 2019-02-28 | 2020-12-01 | 주식회사 케이씨씨 | Adhesive Composition |
| JP2020164840A (en) * | 2019-03-27 | 2020-10-08 | 荒川化学工業株式会社 | Ultraviolet curable adhesive composition for protective film, cured product, and protective sheet |
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- 2011-10-06 WO PCT/JP2011/073113 patent/WO2012046810A1/en active Application Filing
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| CN110872483B (en) * | 2018-09-03 | 2021-10-15 | 荒川化学工业株式会社 | Active energy ray-curable adhesive composition, cured product, and adhesive sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012046810A1 (en) | 2012-04-12 |
| KR101848401B1 (en) | 2018-04-12 |
| KR20130120474A (en) | 2013-11-04 |
| JP5847724B2 (en) | 2016-01-27 |
| CN103154060B (en) | 2015-08-12 |
| TWI532808B (en) | 2016-05-11 |
| TW201224098A (en) | 2012-06-16 |
| JPWO2012046810A1 (en) | 2014-02-24 |
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