CN103890028A - Ultraviolet ray cured resin composition, cured product, and article - Google Patents
Ultraviolet ray cured resin composition, cured product, and article Download PDFInfo
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- CN103890028A CN103890028A CN201280051831.0A CN201280051831A CN103890028A CN 103890028 A CN103890028 A CN 103890028A CN 201280051831 A CN201280051831 A CN 201280051831A CN 103890028 A CN103890028 A CN 103890028A
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
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Abstract
[Problem] The present invention pertains to an ultraviolet ray cured resin composition characterized by containing a compound (A) having a structure indicated by general formula (1) (in the formula, n is an integer from 0 to 40, m is an integer from 10 to 50, R1 and R2 may be the same or different, and R1 and R2 are an aryl group, an alkynyl group, an alkenyl group, or an alkyl group having 1-18 carbon atoms), a (meth) acrylate compound (B) having one or two (meth)acryloyl groups, and a photoinitiator (C). The resin composition has the characteristics of being able to result in a cured product having superior curability, low contraction during curing, and superior flexibility, adhesion to a substrate, and transparency, and of being suited to forming an optical member resulting from pasting together optical substrates.
Description
Technical field
The present invention relates to the ultraviolet-curing resin composition that is fitted with use to optical clear member.
Background technology
In recent years, thus the display unit that sticking touch control panel can carry out screen input on the display screen of the display unit such as liquid-crystal display, plasma display, OLED display extensively utilized.This display unit has following structure: on its display screen, be laminated with and will be formed with the sheet glass of transparency electrode or the contact panel that resin-made membrane obtains so that transparency electrode mode is in opposite directions fitted, then in the touch surface of contact panel, be laminated with glass system or resinous transparent protection plate.In addition, for not thering is the display unit of contact panel, become the structure that is laminated with glass or resinous transparent protection plate on display screen.
Have in the laminating etc. of the contact panel on laminating or display unit and its screen of the transparent protection plate on the sheet glass that is formed with transparency electrode or the touch surface of film and the laminating of glass or resinous transparent protection plate or display unit and its screen in contact panel and use the technology of double-sided adhesive sheet, but have the problem that easily produces bubble.The technology of double-sided adhesive sheet as an alternative, has proposed the technology (patent documentation 1～3) that uses light-cured type resin combination to fit.
On the other hand, the slimming of display unit and giant-screenization develop.Therefore, for example, the also attenuation gradually such as the sheet glass that the display screen in the transparent protection plate of contact panel or substrate and display unit is used or resin transparent panel.Therefore,, in above-mentioned stacked or laminating, while using light-cured type resin combination to fit, there is the problem that makes contact panel, display screen distortion due to the cure shrinkage of this resin combination.In addition, in the case of by the two material in adhesive be the material such as glass/acrylic resin, glass/polycarbonate resin different, due to the thermal expansion of two kinds of materials, hygroscopic difference, there is gluing surface is peeled off in hot resistance test problem.In order to address these problems, require to provide the light-cured type resin combination of the cured article that the contraction while suppressing to solidify, the tackiness to base material and flexibility are good.But the polyisoprene of recording at use patent documentation 1, as main component, must use the organic solvent such as heptane, hexane to be removed in the time of reprocessing, has the poor problem of re-workability.In addition, in the time using the epoxy resin with naphthenic hydrocarbon skeleton of being recorded as patent documentation 2, flexibility is poor, in the composition of being recorded as patent documentation 3, also has the worry that xanthochromia occurs while solidifying.Therefore, patent documentation 1～3 cannot obtain gratifying light-cured type resin combination.
Prior art document
Patent documentation
Patent documentation 1: No. 2010/027041st, International Publication
Patent documentation 2: TOHKEMY 2010-248387 communique
Patent documentation 3: Japanese Unexamined Patent Application Publication 2011-511851 communique
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide and can obtain that solidified nature is good, the transparency of little, the cured article of contraction while solidifying, with the ultraviolet-curing resin composition of the tackiness of base material and the good optical clear tackiness agent of flexibility, use this ultraviolet-curing resin composition and optical component, such as contact panel or the display unit, the electronics that is assembled with them etc. that obtain.
For the means of dealing with problems
The inventor conducts in-depth research in order to address the above problem, the ultraviolet-curing resin composition that found that the compound, (methyl) acrylic compound and the Photoepolymerizationinitiater initiater that contain the structure with following formula (1) has been realized the problems referred to above, thereby has completed the present invention.
, the present invention relates to following (1)～(22).
(1) a kind of ultraviolet-curing resin composition, compound (A), (methyl) acrylic compound (B) and Photoepolymerizationinitiater initiater (C) that it contains the structure with following general formula (1) expression
In formula (1), the integer that n is 0～40, the integer that m is 10～80, R
1and R
2can be the same or different separately, is the alkyl of carbonatoms 1～18, thiazolinyl, the alkynyl of carbonatoms 2～18 or the aryl of carbonatoms 5～18 of carbonatoms 2～18.
(2) ultraviolet-curing resin composition as described in above-mentioned (1), wherein, R
1and R
2be the alkyl of carbonatoms 1～10 or the thiazolinyl of carbonatoms 3～10 independently of one another.
(3) ultraviolet-curing resin composition as described in above-mentioned (1), wherein, above-claimed cpd (A) is for selecting at least one in the group of free polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dibutyl ether, polypropylene glycol allyl group butyl ether, polyethylene glycol-propylene glycol diallyl ether, polyethylene glycol-propylene glycol dibutyl ether and polyethylene glycol-propylene glycol allyl group butyl ether composition.
(4) ultraviolet-curing resin composition as described in any one in above-mentioned (1)～(3); wherein, contain (methyl) acrylic compound that there is (methyl) acrylic compound (B ') of 1 (methyl) acryl or there are 2 (methyl) acryls as (methyl) acrylic compound (B).
(5) ultraviolet-curing resin composition as described in any one in above-mentioned (1)～(4), wherein, contain carbamate (methyl) acrylate (D) as (methyl) acrylic compound (B).
(6) ultraviolet-curing resin composition as described in any one in above-mentioned (1)～(5); wherein, (methyl) acrylic compound (B ') that contains carbamate (methyl) acrylate (D) and have 1 (methyl) acryl is as (methyl) acrylic compound (B).
(7) ultraviolet-curing resin composition as described in any one in above-mentioned (1)～(6), wherein, the content of above-claimed cpd (A) is 10～60 % by weight, the content of Photoepolymerizationinitiater initiater (C) is 0.2～5 % by weight, and remainder is (methyl) acrylic compound (B).
(8) ultraviolet-curing resin composition as described in above-mentioned (6), wherein, contain the freely alkyl ester of (methyl) vinylformic acid carbonatoms 10～30 of choosing, poly-C2～C4 aklylene glycol (methyl) acrylate, (methyl) vinylformic acid nonyl phenyl ester of poly(propylene oxide) modification, (methyl) vinylformic acid has the alkyl ester of the carbonatoms 1～5 of hydroxyl, acryloyl morpholine, at least one in the group of (methyl) tetrahydrofurfuryl acrylate and (methyl) vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester composition is as (methyl) acrylic compound (B ') with 1 (methyl) acryl.
(9) ultraviolet-curing resin composition as described in any one in above-mentioned (4)～(8), wherein, contain freely (methyl) lauryl acrylate of choosing, 2-ethylhexyl Trivalin SF acrylate, acryloyl morpholine, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) tetrahydrofurfuryl acrylate, the different stearyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid nonyl phenyl ester of poly(propylene oxide) modification, (methyl) vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester, the different stearyl ester of (methyl) vinylformic acid, at least one in the group of (methyl) vinylformic acid 2-decyl tetradecane ester composition is as (methyl) acrylic compound (B ') with 1 (methyl) acryl.
(10) ultraviolet-curing resin composition as described in any one in above-mentioned (4)～(9), wherein,
Above-claimed cpd (A) is for selecting at least one in the group of free polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dibutyl ether, polypropylene glycol allyl group butyl ether, polyethylene glycol-propylene glycol diallyl ether, polyethylene glycol-propylene glycol dibutyl ether and polyethylene glycol-propylene glycol allyl group butyl ether composition
Contain freely (methyl) lauryl acrylate of choosing, 2-ethylhexyl Trivalin SF acrylate, acryloyl morpholine, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) tetrahydrofurfuryl acrylate, the different stearyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid nonyl phenyl ester of poly(propylene oxide) modification, (methyl) vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester, the different stearyl ester of (methyl) vinylformic acid, at least one in the group of (methyl) vinylformic acid 2-decyl tetradecane ester composition is as (methyl) acrylic compound (B ') with 1 (methyl) acryl.
(11) ultraviolet-curing resin composition as described in any one in above-mentioned (1)～(10); wherein; contain (methyl) acrylic compound (B ') and carbamate (methyl) acrylate (D) with 1 (methyl) acryl, the integer that the m in general formula (1) is 10～50.
(12) ultraviolet-curing resin composition as described in any one in above-mentioned (1)～(11), wherein, carbamate (methyl) acrylate (D) is the reaction product of (methyl) acrylate of polyether glycol and polyisocyanates and hydroxyl.
(13) ultraviolet-curing resin composition as described in any one in above-mentioned (1)～(12), wherein, (methyl) acrylic compound (B ') that contains carbamate (methyl) acrylate (D) and have 1 (methyl) acryl is as (methyl) acrylic compound (B), with respect to the total amount of composition, the above-claimed cpd (A) that contains 1～60 % by weight, carbamate (methyl) acrylate (D) of 20～80 % by weight, the Photoepolymerizationinitiater initiater (C) of (methyl) acrylic compound with 1 (methyl) acryl of 10～70 % by weight (B ') and 0.2～5 % by weight.
(14) ultraviolet-curing resin composition as described in above-mentioned (13); wherein, (methyl) acrylic compound (B ') that has 1 (methyl) acryl is at least 40 % by weight with the total content of carbamate (methyl) acrylate (D) with respect to the total amount of resin combination.
(15) ultraviolet-curing resin composition as described in any one in above-mentioned (1)～(14), wherein, cure shrinkage is below 3.0%.
(16) ultraviolet-curing resin composition as described in any one in above-mentioned (6)～(15), wherein,
(i) above-claimed cpd (A) is for selecting at least one in the group of free polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dibutyl ether, polypropylene glycol allyl group butyl ether, polyethylene glycol-propylene glycol diallyl ether, polyethylene glycol-propylene glycol dibutyl ether and polyethylene glycol-propylene glycol allyl group butyl ether composition
(ii) contain freely (methyl) lauryl acrylate of choosing, 2-ethylhexyl Trivalin SF acrylate, acryloyl morpholine, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) tetrahydrofurfuryl acrylate, the different stearyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid nonyl phenyl ester of poly(propylene oxide) modification, (methyl) vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester, the different stearyl ester of (methyl) vinylformic acid, at least one in the group of (methyl) vinylformic acid 2-decyl tetradecane ester composition is as (methyl) acrylic compound (B ') with 1 (methyl) acryl,
(iii) carbamate (methyl) acrylate (D) is the reaction product of (methyl) acrylate of polyether glycol and polyisocyanates and hydroxyl.
(17) ultraviolet-curing resin composition as described in any one in above-mentioned (6)～(16), wherein, the weight-average molecular weight of carbamate (methyl) acrylate (D) is 7000～25000.
(18) ultraviolet-curing resin composition as described in any one in above-mentioned (6)～(18), wherein,
Above-claimed cpd (A) is the R in general formula (1)
1and R
2can be the same or different separately and R
1and R
2for the compound of the alkyl of carbonatoms 1～10 or the thiazolinyl of carbonatoms 3～10,
Carbamate (methyl) acrylate (D) is that the reaction product of (methyl) acrylate and the weight-average molecular weight of this reaction product of polyether glycol and polyisocyanates and hydroxyl is 7000～25000,
(methyl) acrylic compound (B ') that contains carbamate (methyl) acrylate (D) and have 1 (methyl) acryl is as (methyl) acrylic compound (B), and
With respect to the total amount of composition, the above-claimed cpd (A) that contains 1～60 % by weight, carbamate (methyl) acrylate (D) of 20～80 % by weight, the Photoepolymerizationinitiater initiater (C) of (methyl) acrylic compound with 1 (methyl) acryl of 10～70 % by weight (B ') and 0.2～5 % by weight, and (methyl) acrylic compound (B ') with 1 (methyl) acryl is 40～90 % by weight with the total content of carbamate (methyl) acrylate (D) with respect to the total amount of composition.
(19) optical component, the cured article layer of the ultraviolet-curing resin composition in its above-mentioned by utilizing (1)～(18) described in any one is by least two gluing obtaining of optical element.
(20) cured article, it obtains by the ultraviolet-curing resin composition described in any one in above-mentioned (1)～(18) is irradiated to active energy beam.
(21) contact panel, the cured article layer of the ultraviolet-curing resin composition in its above-mentioned by utilizing (1)～(18) described in any one is by least two gluing obtaining of optical element.
(22) there is the protection display unit of optical element or contact panel, the cured article layer of the ultraviolet-curing resin composition in its above-mentioned by utilizing (1)～(18) described in any one by protection with optical element or contact panel and display unit is gluing obtains.
Invention effect
According to the present invention, can provide can be good as solidified nature, contraction while solidifying is little, the transparency of cured article, the ultraviolet-curing resin composition using with the tackiness of base material and the good optical clear tackiness agent of flexibility, the cured article laminating that uses this resin combination close and the optical component that obtains.
Embodiment
Ultraviolet-curing resin composition of the present invention (following, to be called resin combination of the present invention or composition of the present invention) contains compound (A), (methyl) acrylic compound (B) and the Photoepolymerizationinitiater initiater (C) with the structure being represented by general formula (1).
Resin combination of the present invention contains the compound (A) with the structure being represented by following general formula (1),
In formula, n represents 0～40 integer, and m represents 10～80 integer.R
1and R
2can be the same or different separately.R
1and R
2for the alkyl of carbonatoms 1～18, thiazolinyl, the alkynyl of carbonatoms 2～18 or the aryl of carbonatoms 5～18 of carbonatoms 2～18.
In formula (1), as a preferred mode, can enumerate n and be 0 or n be 5～40, more preferably 10～30 mode.M preferably 20～80, more preferably 30～70.At this, from giving with the adaptation of base material and making the viewpoint improving with the consistency of carbamate (methyl) acrylate, m/ (m+n) is preferably 0.2～1, and more preferably 0.4～1.
In addition, R
1and R
2be preferably the alkyl of carbonatoms 1～18 or the thiazolinyl of carbonatoms 2～18, the more preferably thiazolinyl of the alkyl of carbonatoms 1～10 or carbonatoms 3～10 independently of one another.More preferably R
1and R
2be the alkyl of carbonatoms 1～6 or the thiazolinyl of carbonatoms 3～5 independently of one another.A most preferred mode is that n is 5～40, m is 10～40, R
1and R
2in any be that butyl and another are allylic mode, or n is 0, m is 20～80, R
1and R
2independently of one another for the alkyl of carbonatoms 1～4, be preferably the mode of methyl.
There is the flexibility that the compound (A) of structure that represented by general formula (1) can be given tackiness agent.As thering is the compound (A) of structure being represented by general formula (1), as long as in the integer that is 0～40 at n, scope that m is 10～80, can use ad lib.
As the concrete example of this compound (A), for example can enumerate: polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dibutyl ether, polypropylene glycol allyl group butyl ether, polyethylene glycol-propylene glycol diallyl ether, polyethylene glycol-propylene glycol dibutyl ether, polyethylene glycol-propylene glycol allyl group butyl ether.
This compound (A) also can easily obtain in the mode of commercially available product.For example, can obtain in the mode of polyethylene glycol-propylene glycol allyl group butyl ether (ユ ニ セ ー Off PKA-5015, PKA-5016, PKA-5017, Japan Oil Co manufacture), polypropylene glycol diallyl ether (ユ ニ セ ー Off PKA-5018, Japan Oil Co manufacture).Particularly polyethylene glycol-propylene glycol allyl group butyl ether (PKA-5016, PKA-5017, Japan Oil Co manufacture) is good with the consistency of carbamate (methyl) acrylate, thereby preferably.
The number-average molecular weight of this compound (A) is generally 100～10000, is preferably 500～8000, and more preferably 1000～8000, be particularly preferably 1500～5000.This be because, when number-average molecular weight is too small, flexibility, tackiness may be poor, when number-average molecular weight is excessive, consistency may be poor.
The part by weight of this compound (A) in light-cured type transparent adhesive composition of the present invention is preferably approximately 1 % by weight～approximately 60 % by weight, is particularly preferably approximately 10 % by weight～approximately 50 % by weight.When very few, flexibility is poor, solidified nature variation too much time.
In composition of the present invention, contain (methyl) acrylic compound (B) (below also referred to as (B) composition).As long as (methyl) acrylic compound and be known compound, can be not particularly limited to use.
As (methyl) acrylic compound (B); (methyl) acrylic compound preferably with 1 or 2 (methyl) acryl, more preferably these compositions reach the situation of 100 % by weight of (B) composition.
As (B) composition, particularly preferably following (methyl) acrylic compound with 1 (methyl) acryl (B ') (below also referred to as (B ') composition) and aftermentioned carbamate (methyl) acrylate (D) (below also referred to as (D) composition).Also can use other multifunctional (methyl) acrylate.As preferred mode, can enumerate the total amount with respect to (methyl) acrylic compound (B), (B ') composition and (D) the total content of composition are 50～100 % by weight (as long as following not dated especially, % refers to % by weight), 70～100%, more preferably 90～100% mode more preferably.Remainder is other (methyl) acrylic compound.Most preferably (B) composition is by the above-mentioned situation that both form (both amount to 100% the situation of (B) composition).
In addition, in this specification sheets, " (methyl) acrylate " refers to any one or two kinds in methacrylic ester and acrylate.
As (methyl) acrylic compound (B) containing in resin combination of the present invention, preferably use (methyl) acrylic compound (B ') with 1 (methyl) acryl.
Particularly, can enumerate: the alkyl ester of (methyl) vinylformic acid carbonatomss 5～30 such as (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid isopentyl ester, (methyl) lauryl acrylate, (methyl) isodecyl acrylate, (methyl) stearyl acrylate ester, (methyl) vinylformic acid cetyl, the different myristin of (methyl) vinylformic acid, (methyl) vinylformic acid tridecane ester, (methyl) vinylformic acid 2-decyl tetradecane ester, the more preferably alkyl ester of (methyl) vinylformic acid carbonatoms 10～30, (methyl) benzyl acrylate, (methyl) tetrahydrofurfuryl acrylate, acryloyl morpholine, (methyl) vinylformic acid phenyl glycidyl ester, tristane (methyl) acrylate, vinylformic acid dihydro dicyclopentadiene base ester, (methyl) vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid tetrahydrochysene dicyclopentadiene base ester, vinylformic acid 1-diamantane ester, vinylformic acid 2-methyl-2-diamantane ester, vinylformic acid 2-ethyl-2-diamantane ester, methacrylic acid 1-diamantane ester, (methyl) vinylformic acid dihydro dicyclopentadiene oxygen base ethyl ester etc. has (methyl) acrylate of ring texture, preferably there are 3～10 rings that contain 3～10 carbon atoms and can contain any one or two kinds in Sauerstoffatom or nitrogen-atoms, more preferably (methyl) acrylate of these 3～10 yuan of aliphatics rings or benzyl, (methyl) vinylformic acid such as (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester have the alkyl ester of the carbonatoms 1～5 of hydroxyl, (methyl) vinylformic acid nonyl phenyl ester of polyalkylene glycol (methyl) acrylate such as (methyl) vinylformic acid nonyl phenyl ester of oxyethyl group Diethylene Glycol (methyl) acrylate, 2-ethylhexyl Diethylene Glycol (methyl) acrylate (another name 2-ethylhexyl Trivalin SF (methyl) acrylate), polypropylene glycol (methyl) acrylate, poly(propylene oxide) modification or polyalkylene glycol modification, preferably (methyl) vinylformic acid nonyl phenyl ester of poly-C2～C4 aklylene glycol (methyl) acrylate or poly(propylene oxide) modification, phenoxylation or C3～C10 alkoxylate phosphoric acid (methyl) acrylate etc. of the oxyethane modifications such as octyloxy phosphoric acid (methyl) acrylate of phenoxylation phosphoric acid (methyl) acrylate of oxyethane modification, butoxy phosphoric acid (methyl) acrylate of oxyethane modification and oxyethane modification.
As the preferred compound of (B ') composition, can enumerate: the alkyl ester of (methyl) vinylformic acid carbonatoms 10～30; Poly-C2～C4 aklylene glycol (methyl) acrylate; (methyl) vinylformic acid nonyl phenyl ester of poly(propylene oxide) modification; (methyl) vinylformic acid has the alkyl ester of the carbonatoms 1～5 of hydroxyl; Acryloyl morpholine; (methyl) tetrahydrofurfuryl acrylate and/or (methyl) vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester.
Wherein, (methyl) vinylformic acid nonyl phenyl ester ((methyl) vinylformic acid nonyl phenyl esters of for example 2～10 moles of epoxy pronane modifications) of the alkyl ester of preferred (methyl) vinylformic acid carbonatoms 10～30,2-ethylhexyl Trivalin SF acrylate, acryloyl morpholine, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester, poly(propylene oxide) modification.Particularly from the viewpoint of the flexibility of resin, preferably alkyl ester, (methyl) vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester, (methyl) vinylformic acid nonyl phenyl ester ((methyl) vinylformic acid nonyl phenyl esters of for example 2～10 moles of epoxy pronane modifications) of poly(propylene oxide) modification, (methyl) tetrahydrofurfuryl acrylate of (methyl) vinylformic acid carbonatoms 10～30.
On the other hand, from improving the viewpoint of the adaptation to glass, preferably (methyl) vinylformic acid has alkyl ester, the acryloyl morpholine of the carbonatoms 1～5 of hydroxyl, particularly preferably acryloyl morpholine.
More preferably (B ') composition all (100%) formed by above-mentioned preferred compound.
As the alkyl ester of (methyl) vinylformic acid carbonatoms 10～30, preferred compound is the alkyl ester of (methyl) vinylformic acid carbonatoms 12～25, be particularly the exemplary compounds till from above-mentioned illustrative (methyl) lauryl acrylate to (methyl) vinylformic acid 2-decyl tetradecane ester, most preferably be (methyl) lauryl acrylate and (methyl) vinylformic acid 2-decyl tetradecane ester.
In resin combination of the present invention, can contain multifunctional (methyl) acrylic compound in the scope of not damaging characteristic of the present invention.For example can enumerate: tristane dimethanol two (methyl) acrylate, dioxane glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate, oxirane modified bisphenol A type two (methyl) acrylate, caprolactone modification hydroxypivalic acid neopentyl glycol two (methyl) acrylate and oxyethane modified phosphate two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trishydroxymethyl C2～C10 alkane three (methyl) acrylate such as trishydroxymethyl octane three (methyl) acrylate, TriMethylolPropane(TMP) polyethoxye three (methyl) acrylate, TriMethylolPropane(TMP) gathers propoxy-three (methyl) acrylate, poly-alkoxyl group three (methyl) acrylate of trishydroxymethyl C2～C10 alkane such as poly-propoxy-three (methyl) acrylate of TriMethylolPropane(TMP) polyethoxye, three [(methyl) acryloxy ethyl] isocyanuric acid ester, tetramethylolmethane three (methyl) acrylate, oxyethane modification trimethylolpropane tris (methyl) acrylate, oxirane modification trimethylolpropane tris (methyl) acrylate such as epoxy pronane modification trimethylolpropane tris (methyl) acrylate, tetramethylolmethane polyethoxye four (methyl) acrylate, tetramethylolmethane gathers propoxy-four (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, ditrimethylolpropane four (methyl) acrylate, Dipentaerythritol four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate etc.
In the present invention, in order to suppress cure shrinkage, preferably use simple function or dual functional (methyl) acrylate.
In order further to reduce cure shrinkage, in resin combination of the present invention, as carbamate (methyl) acrylate (D) (B) composition in addition, with respect to the total amount of (B) composition beyond this (D) composition, contain at least 50 % by weight, preferably at least 70 % by weight, more preferably at least 80 % by weight, further preferably at least 90 % by weight, above-mentioned (B ') composition of 100 % by weight most preferably.
In resin combination of the present invention, above-mentioned carbamate (methyl) acrylate (D) (B) composition in addition can use a kind or mix two or more and use with arbitrary proportion.The part by weight of carbamate (methyl) acrylate (D) (B) composition in addition in light-cured type transparent adhesive composition of the present invention is generally 5～70 % by weight, be preferably 5～50 % by weight, more preferably 10～40%.
The situation that (methyl) acrylic compound (B ') particularly preferably with 1 (methyl) acryl is above-mentioned content.
When the content of carbamate (methyl) acrylate (D) above-mentioned (B) composition is in addition very few, lack solidified nature, too much time, shrink and become large.
For carbamate (methyl) acrylate (D) that can contain in composition of the present invention, as long as carbamate (methyl) acrylate, all can use.Be preferably carbamate (methyl) acrylate that (methyl) acrylate reactions by making polyvalent alcohol, polyisocyanates and hydroxyl obtains.More preferably there is polyethers carbamate (methyl) acrylate of polyether structure.
As the polyvalent alcohol of use in carbamate (methyl) acrylate synthetic, for example can enumerate: neopentyl glycol, 3-methyl isophthalic acid, 5-pentanediol, ethylene glycol, propylene glycol, BDO, 1, the aklylene glycol of the carbonatomss 1～10 such as 6-hexylene glycol; The trivalent alcohol such as TriMethylolPropane(TMP), tetramethylolmethane; Tristane dimethanol, two [methylol] hexanaphthene etc. have the alcohol of cyclic skeleton etc.; And the polyester polyol for example, obtaining by the reaction of above-mentioned polyvalent alcohol and polyprotonic acid (, succsinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, hexanodioic acid, nonane diacid, Tetra Hydro Phthalic Anhydride etc.); The caprolactone alcohol obtaining with reacting of 6-caprolactone by polyvalent alcohol; Polycarbonate polyol (polycarbonate diol for example obtaining with reacting of diphenyl carbonate by 1,6-hexylene glycol etc.); Or polyether glycol (such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, oxyethane modified bisphenol A etc.) etc.The viewpoint of the flexibility of the resin from solidifying, preferred, polyethers polyvalent alcohol.From with the viewpoint of the consistency of (A) composition, more preferably polypropylene glycol, from the viewpoint of the adaptation to base material, particularly preferably molecular weight is more than 2000 polypropylene glycol.
As organic multiple isocyanate, for example can enumerate: isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, Xylene Diisocyanate, ditan-4,4 '-vulcabond or tetrahydrochysene dicyclopentadiene based isocyanate etc.
From transparent viewpoint, preferably isophorone diisocyanate or tolylene diisocyanate.
In addition, as (methyl) acrylate of hydroxyl, for example, can use: (methyl) vinylformic acid hydroxyl C2～C4 alkyl esters such as (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid hydroxy propyl ester, (methyl) vinylformic acid hydroxyl butyl ester, list (methyl) vinylformic acid dihydroxymethyl cyclohexyl, hydroxyl caprolactone (methyl) acrylate etc.
Above-mentioned reaction is for example carried out as follows.; in polyvalent alcohol with respect to every 1 equivalent of its hydroxyl; the isocyanate group of organic multiple isocyanate is preferably 1.1～2.0 equivalents, more preferably the mode of 1.1～1.5 equivalents is mixed organic multiple isocyanate, makes its reaction and synthesis of carbamates oligopolymer under the temperature of reaction that is preferably 70～90 DEG C.Then, with every 1 equivalent of the isocyanate group with respect to oligourethane, the hydroxyl of hydroxyl (methyl) acrylic compound is preferably the mode of 1～1.5 equivalent and mixes hydroxyl (methyl) acrylic compound, at 70～90 DEG C, make its reaction, thereby can obtain carbamate (methyl) acrylate as target.
As the weight-average molecular weight of carbamate (methyl) acrylate (D), preferably approximately 7000～approximately 25000, more preferably from about 10000～approximately 20000.When weight-average molecular weight is too small, shrinks and become large, when weight-average molecular weight is excessive, solidified nature variation.
In resin combination of the present invention, these (D) compositions can use a kind or mix two or more and use with arbitrary proportion.(D) part by weight of composition in light-cured type transparent adhesive composition of the present invention is generally 20～80 % by weight, is preferably 25～50 % by weight.
In resin combination of the present invention; the total content of above-mentioned (D) composition and above-mentioned (methyl) acrylic compound with 1 (methyl) acryl (B ') is preferably at least 40 % by weight with respect to the total amount of this resin combination, more preferably at least 50 % by weight.
In resin combination of the present invention, can contain (methyl) origoester acrylate with polyisoprene and/or polyhutadiene skeleton as (methyl) acrylic compound (B).As (methyl) origoester acrylate with polyisoprene and/or polyhutadiene skeleton, as long as known compound, can be not particularly limited to use.
As above-mentioned (methyl) origoester acrylate with polyisoprene and/or polyhutadiene skeleton, can preferably use (a) first synthetic isoprene copolymer, butadiene polymer or their multipolymer, then make unsaturated acid anhydride and these polymer reactions, then the oligopolymer that makes hydroxyl (methyl) acrylic compound react with part or all in obtained polymkeric substance and to obtain, or (b) make unsaturated carboxylic acid or derivatives thereof and C-terminal isoprene copolymer, C-terminal butadiene polymer or their copolymer reaction and the oligopolymer that obtains.
First, to (a) first synthetic isoprene copolymer, butadiene polymer or their multipolymer, then make unsaturated acid anhydride and these polymer reactions, then make hydroxyl (methyl) acrylic compound react with part or all in obtained polymkeric substance and the oligopolymer that obtains describes.
As above-mentioned isoprene copolymer, butadiene polymer, can use isoprene copolymer or butadiene polymer by a kind of homopolymerization in isoprene and/or divinyl is obtained, the isoprene-butadiene multipolymer that also can use the mixture copolymerization by making isoprene and divinyl to obtain.Below, by them in the lump referred to as oligopolymer polymkeric substance.
As the method that makes its polymerization, can obtain by isoprene and/or divinyl are carried out to anionoid polymerization using lithium alkylide, sodium naphthalene complex compounds such as lithium methide, lithium ethide, s-butyl lithium, n-Butyl Lithium, amyl group lithiums as initiator, also can manufacture by carrying out radical polymerization using the azo such as superoxide, Diisopropyl azodicarboxylate dinitrile compounds such as benzoyl peroxides as initiator.
In addition, these polyreactions can be reacted 0.5～100 hour and be carried out under the existence of hexane, heptane, toluene, dimethylbenzene equal solvent, at-100 DEG C～200 DEG C.
From giving the viewpoint of flexibility, the number-average molecular weight of the above-mentioned oligopolymer polymkeric substance using in the present invention is generally 2000～100000, and preferably 5000～50000, particularly preferably 20000～50000.
Then, make unsaturated acid anhydride and the oligopolymer polymer reaction obtaining by aforesaid method.This reaction for example can by make above-mentioned polymkeric substance and unsaturated acid anhydride at hexane, heptane, toluene, dimethylbenzene equal solvent etc. to conventionally reacting and carry out for 0.5～100 hour at normal temperature～300 DEG C under reacting for the existence of the solvent of inertia or under condition of no solvent.
As unsaturated acid anhydride, for example, can use: maleic anhydride, Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride etc.
The usage quantity of this acid anhydrides is preferably the scope of 0.1～200 weight part conventionally with polymkeric substance 100 weight parts with respect to above-mentioned oligopolymer, more preferably in the scope of 0.1～100 weight part.
Utilize the reaction of anhydride group in the addition of above-mentioned polymkeric substance, by making under these conditions its reaction, the adduct number of every 1 molecule is the scope of 1～30 conventionally, is preferably the scope of 2～20.
Then, by hydroxyl (methyl) acrylic compound is reacted with part or all of the anhydride group importing in above-mentioned polymkeric substance, can obtain having polyisoprene skeleton (methyl) origoester acrylate, there is (methyl) origoester acrylate of polyhutadiene skeleton or there is (methyl) origoester acrylate of polyisoprene-polybutadiene copolymer skeleton.
Reaction can be by under hexane, heptane equal solvent or solvent-free existence, conventionally by hydroxyl (methyl) acrylic compound so that its hydroxyl be preferably that the mode of 1～1.5 equivalent is mixed and at 20～200 DEG C, react 0.1～100 hour and obtain.
As hydroxyl (methyl) acrylic compound, for example, can use: (methyl) vinylformic acid hydroxyl C2～C4 alkyl esters such as (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid hydroxy propyl ester, (methyl) vinylformic acid hydroxyl butyl ester, list (methyl) vinylformic acid dihydroxymethyl cyclohexyl, hydroxyl caprolactone (methyl) acrylate etc.
Then, (b) passed the method for the oligopolymer that unsaturated carboxylic acid or derivatives thereof obtains with the isoprene copolymer, butadiene polymer or their copolymer reaction that contain hydroxyl is described.
By unsaturated carboxylic acid or derivatives thereof is reacted with part or all of C-terminal isoprene copolymer, C-terminal butadiene polymer or C-terminal isoprene-butadiene multipolymer, can obtain having polyisoprene skeleton (methyl) origoester acrylate, there is (methyl) origoester acrylate of polyhutadiene skeleton or there is (methyl) origoester acrylate of isoprene-butadiene copolymer skeleton.
Reaction can, by under hexane, heptane equal solvent or under solvent-free existence, make unsaturated carboxylic acid or derivatives thereof at 20～200 DEG C, react 0.1～100 hour and obtain conventionally.
As unsaturated carboxylic acid or derivatives thereof, for example, can use: the derivatives such as the unsaturated carboxylic acids such as vinylformic acid, methacrylic acid, toxilic acid, α-ethylacrylate, fumaric acid, methylene-succinic acid, citraconic acid, tetrahydrophthalic acid, methyl tetrahydrophthalic acid and their carboxylic acid halides, acid amides, imide, acid anhydride, ester.
As the concrete example of the compound obtaining like this, can illustrate: the NISSO-PB TE-2000 (the acrylate modified butadiene type oligopolymer of two terminal methyl group) of the UC-203 (the carboxylate oligopolymer of the maleic anhydride adduct of isoprene copolymer and 2-hydroxyethyl methacrylate) that Kuraray company manufactures, the manufacture of Japanese Cao Da company etc.
In resin combination of the present invention, these (methyl) origoester acrylates with polyisoprene, polyhutadiene skeleton can use a kind or mix two or more and use with arbitrary proportion.The part by weight of (methyl) origoester acrylate with polyisoprene, polyhutadiene skeleton in ultraviolet hardening tackiness agent of the present invention is generally 5～90 % by weight, is preferably 20～80 % by weight, more preferably 25～50 % by weight.
(methyl) origoester acrylate can with above-mentioned carbamate (methyl) acrylate (D) use, according to circumstances, also can replace carbamate (methyl) acrylate (D) and use.
As the Photoepolymerizationinitiater initiater containing in composition of the present invention (C), be not particularly limited, for example can enumerate: 1-hydroxy-cyclohexyl phenyl ketone (イ Le ガ キ ュ ア (registered trademark, lower same) 184; BASF AG manufacture), 2-hydroxy-2-methyl [4-(1-methyl ethylene) phenyl] propyl alcohol oligopolymer (エ サ キ ュ ア ONE; Ning Baidi company manufacture), 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone (イ Le ガ キ ュ ア 2959; BASF AG manufacture), 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl propionyl) benzyl] phenyl-2-methylpropane-1-ketone (イ Le ガ キ ュ ア 127; BASF AG manufacture), 2,2-dimethoxy-2-phenyl methyl phenyl ketone (イ Le ガ キ ュ ア 651; BASF AG manufacture), 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone (ダ ロ キ ュ ア (registered trademark) 1173; BASF AG manufacture), 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl propane-1-ketone (イ Le ガ キ ュ ア 907; BASF AG manufactures), oxygen base phenylacetic acid 2-[2-oxo-2-phenyl-acetoxyl group-oxyethyl group] ethyl ester and oxygen base phenylacetic acid 2-[2-hydroxyl-oxyethyl group] mixture (the イ Le ガ キ ュ ア 754 of ethyl ester; BASF AG manufactures), 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butane-1-ketone, CTX, 2; 4-dimethyl thioxanthone, 2; 4-di-isopropyl thioxanthone, isopropyl thioxanthone, 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4; 6-trimethylbenzoyl) phenyl phosphine oxide, two (2; 6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide etc.Consider from the transparency, preferably 1-hydroxy-cyclohexyl phenyl ketone (イ Le ガ キ ュ ア 184; BASF manufacture), 2-hydroxy-2-methyl [4-(1-methyl ethylene) phenyl] propyl alcohol oligopolymer (エ サ キ ュ ア KIP-150; Ning Baidi company manufacture), phenyl glyoxalic acid methylester (ダ ロ キ ュ ア MBF; BASF manufactures), oxygen base phenylacetic acid 2-[2-oxo-2-phenyl-acetoxyl group-oxyethyl group] ethyl ester and oxygen base phenylacetic acid 2-[2-hydroxyl-oxyethyl group] mixture (the イ Le ガ キ ュ ア 754 of ethyl ester; BASF AG manufactures).In addition, from making the viewpoint that tackiness agent inside solidification is good, preferably TMDPO (ス ピ ー De キ ュ ア TPO; LAMBSON company manufactures).
In resin combination of the present invention, these (C) compositions can use a kind or mix two or more and use with arbitrary proportion.(C) part by weight of composition in light-cured type transparent adhesive composition of the present invention is generally 0.2～5 % by weight, is preferably 2～5 % by weight.
At this; while only using TMDPO as Photoepolymerizationinitiater initiater in order to improve the transparency; preferred part by weight in light-cured type transparent adhesive composition of the present invention is generally 0.3～1.0 % by weight, is particularly preferably 0.3～0.8 % by weight.
In addition, as above-mentioned (A), (B) and (C) other compositions in addition, also can be as required using the amine etc. that can cause auxiliary agent as photopolymerization with above-mentioned Photoepolymerizationinitiater initiater and use.As operable amine etc., can enumerate: phenylformic acid 2-dimethylaminoethyl, dimethylamino methyl phenyl ketone, (dimethylamino)-ethyl benzoate or IADB etc.While using the photopolymerization such as this amine to cause auxiliary agent, being of the present inventionly gluingly generally 0～5 % by weight with the content in resin combination, is 0.005～5 % by weight when interpolation, is preferably 0.01～3 % by weight.
In addition, as other compositions, can contain as required oxetane compound.Operable oxetane compound, as long as known compound, is not particularly limited.
As the concrete example of oxetane compound, for example can enumerate: two [(3-ethyl-3-trimethylene oxide ylmethoxy) methyl] benzene of 4-, two [(3-methyl-3-trimethylene oxide ylmethoxy) methyl] benzene of 4-, 3-methyl-3-glycidyl trimethylene oxide, 3-ethyl-3-methylol trimethylene oxide, 3-methyl-3-methylol trimethylene oxide, two (1-ethyl (3-oxetanyl)) methyl ether, 3-ethyl-3-(phenoxymethyl) trimethylene oxide, 3-(cyclohexyloxy) methyl-3-Ethyloxetane, the two trimethylene oxide of phenylenedimethylidyne, phenol phenolic varnish trimethylene oxide etc.As long as normally used oxetane compound, be not limited to this.These oxetane compounds can use separately, also can use two or more.
In ultraviolet hardening tackiness agent of the present invention, these oxetane compounds can use a kind or mix two or more and use with arbitrary proportion.The part by weight of oxetane compound in light-cured type adhesive compound of the present invention is generally 0～70 % by weight, when interpolation, is 5～70 % by weight, is preferably 5～50 % by weight.
In addition, in composition of the present invention, not damaging in the scope of characteristic of the present invention, can use epoxy (methyl) acrylate as other compositions.Epoxy (methyl) acrylate has the solidified nature of making raising and makes the hardness of cured article, the function that curing speed improves.In addition, as epoxy (methyl) acrylate, as long as by making glycidyl ether type epoxy compounds react epoxy (methyl) acrylate obtaining with (methyl) vinylformic acid, all can use, as preferred use for obtaining the glycidyl ether type epoxy compounds of epoxy (methyl) acrylate, can enumerate the diglycidylether of dihydroxyphenyl propane or its oxirane affixture, the diglycidylether of Bisphenol F or its oxirane affixture, the diglycidylether of Hydrogenated Bisphenol A or its oxirane affixture, the diglycidylether of A Hydrogenated Bisphenol A F or its oxirane affixture, ethylene glycol diglycidylether, propylene glycol diglycidylether, neopentylglycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexanedimethanodiglycidyl diglycidyl ether, polypropylene glycol diglycidyl ether etc.
Epoxy (methyl) acrylate can be by making these glycidyl ether type epoxy compoundss react and obtain under condition as described below with (methyl) vinylformic acid.
Taking epoxy group(ing) 1 equivalent with respect to glycidyl ether type epoxy compounds make (methyl) vinylformic acid as 0.9～1.5 mole, more preferably the ratio of 0.95～1.1 mole reacts.Temperature of reaction is preferably 80～120 DEG C, and the reaction times is approximately 10 hours～approximately 35 hours.In order to promote reaction, preferably use the catalyzer such as such as triphenylphosphine, TAP, trolamine, etamon chloride.In addition, in reaction, in order to prevent polymerization, also can use such as p methoxy phenol, toluhydroquinone etc. as stopper.
As the epoxy that can preferably use in the present invention (methyl) acrylate, it is bisphenol type epoxy (methyl) acrylate being obtained by the epoxy compounds of bisphenol A-type.In the present invention, as the weight-average molecular weight of epoxy (methyl) acrylate (G), preferably 500～10000.
In resin combination of the present invention, these epoxies (methyl) acrylate can use a kind or mix two or more and use with arbitrary proportion.The part by weight of epoxy (methyl) acrylate in light-cured type transparent adhesive composition of the present invention is generally 0～90 % by weight, when interpolation, is 5～90 % by weight, is preferably 10～85 % by weight.
In resin combination of the present invention, can use as required softening ingredient as other compositions.As the concrete example of operable softening ingredient, can enumerate: there is (methyl) origoester acrylate of polyisoprene, polyhutadiene skeleton or its carboxylate, polymkeric substance, oligopolymer, phthalate, phosphoric acid ester, diol-lipid, aliphatic dibasic acid ester, fatty acid ester, citric acid ester type, epoxy plasticiser, castor-oil plant oils, terpenes hydrogenated resin etc.As the example of oligopolymer, polymkeric substance, can illustrate oligopolymer or the polymkeric substance of polyisoprene class, polybutadiene or xylene.
The part by weight of this softening ingredient in light-cured type transparent adhesive composition is generally 10～80 % by weight, is preferably 10～70 % by weight.
In addition, can use (methyl) acrylate copolymer as softening ingredient.
(methyl) acrylate copolymer can be enumerated other polymerizable monomers beyond polymkeric substance or this monomer forming as polymerizable raw material using acrylic acid or the like or methacrylic monomer and the multipolymer of this monomer, can manufacture by usual methods such as solution polymerization, suspension polymerization, mass polymerizations.
As particularly preferred manufacture method, preferably at high temperature carry out radical polymerization continuously and manufacture.Particularly, manufacture by following technique.First,, with respect to acrylic acid or the like or methacrylic monomer, mix micro-polymerization starter and micro-solvent.Then,, at the temperature more than 150 DEG C, it is under high pressure reacted more than 10 minutes.Then, can use separating machine to be separated into unreacted component obtains with reacting (methyl) acrylate copolymer obtaining.
At this, if sneak into polymerization starter, storage stability possible deviation, therefore, preferred limit is heated up in a steamer trimming by solvent and is reacted, or, separate and obtain after (methyl) acrylate copolymer, solvent being heated up in a steamer.
As acrylic acid or the like or the methacrylic monomer of the raw material as (methyl) acrylate copolymer, can enumerate: (methyl) vinylformic acid, α-ethylacrylate, (methyl) methyl acrylate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid 2-ethyl butyl ester, (methyl) vinylformic acid 1, 3-dimethyl butyl ester, (methyl) Ethyl acrylate, (methyl) 2-EHA, (methyl) Octyl acrylate, (methyl) vinylformic acid 3-oxyethyl group propyl ester, (methyl) vinylformic acid 3-oxyethyl group butyl ester, (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid hydroxyl butyl ester, (methyl) vinylformic acid α-(methylol) ethyl ester, (methyl) phenyl acrylate, (methyl) benzyl acrylate, ester class (methyl) acrylate such as (methyl) vinylformic acid phenyl chlorocarbonate etc., can use the one kind or two or more of these monomers.
As other polymerizable monomers that can copolymerization, can use the known compound with unsaturated double-bond, for example can enumerate: vinylbenzene, 3-nitrostyrolene, 4-methoxy styrene; The ring-alkylated styrenes classes such as alpha-methyl styrene, Beta-methyl vinylbenzene, 2,4-DMS, Vinyl toluene, α-ethyl styrene, α-butylstyrene, α-hexyl benzene ethene; The halogenated styrenes classes such as 4-chloro-styrene, 3-chloro-styrene, 3-bromstyrol; β-crotonic acid, tiglic acid, α-ethyl crotonic acid, iso-crotonic acid, toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid, paraconic acid, propene dicarboxylic acid etc. have the carboxylic-acid of unsaturated double-bond.
Wherein, from the solvability of other compositions to composition, set out in the tackiness aspect of cured article, as acrylic acid or the like or methacrylic monomer, preferred: (methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid C1～C10 alkyl esters such as (methyl) Octyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid such as (methyl) vinylformic acid hydroxyl butyl ester have C1～C10 alkyl ester of hydroxyl, as other polymerizable monomer, optimization styrene etc.
In the present invention, the weight-average molecular weight of (methyl) acrylate copolymer is 1500～30000, is preferably 3000～20000, is particularly preferably 5000～15000.When weight-average molecular weight is too small, the tackiness of cured article has the tendency of variation, and on the other hand, when excessive, be not easy to be dissolved in other monomers, or produce gonorrhoea, thereby not preferred.
(methyl) acrylate copolymer also can easily obtain in the mode of commercially available product.For example, can enumerate " ARUFON series " that Toagosei Co., Ltd manufactures, can obtain in the mode of UP-1170, UH-2190.
The part by weight of (methyl) acrylate copolymer in light-cured type adhesive compound of the present invention is generally 20 % by weight～95 % by weight, preferably 50 % by weight～95 % by weight, more preferably from about 70 % by weight～approximately 95 % by weight, particularly preferably 70 % by weight～90 % by weight.
In resin combination of the present invention, can further add as required the additives such as antioxidant, organic solvent, silane coupling agent, stopper, flow agent, static inhibitor, surface lubricant, white dyes, photostabilizer (for example, hindered amine compound etc.), weighting agent as other compositions.
As the concrete example of antioxidant, for example can enumerate: BHT, two (n-octyl sulfenyl)-6-(4-hydroxyl-3,5-di-tert-butyl the amido)-1,3,5-triazines of 2,4-, tetramethylolmethane four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], 2,2-sulfenyl di ethylene bis [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], triethylene glycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionic ester], 1,6-hexylene glycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionic ester], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester, N, N-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide), 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-t-butyl-4-acrinyl) benzene, three (3,5-di-t-butyl-4-acrinyl) isocyanuric acid ester, octylated diphenylamine, two [(pungent sulfenyl) methyl] ortho-cresols of 2,4-, iso-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], butylated hydroxytoluene etc.
As the concrete example of organic solvent, for example can enumerate: the alcohols such as methyl alcohol, ethanol, Virahol, dimethyl sulfone, methyl-sulphoxide, tetrahydrofuran (THF), dioxane, toluene, dimethylbenzene etc.
As the concrete example of silane coupling agent, for example can enumerate: 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, N-(2-aminoethyl) 3-aminopropyl methyl dimethoxysilane, γ mercaptopropyitrimethoxy silane, N-(2-aminoethyl) 3-aminopropyl methyltrimethoxy silane, 3-aminopropyl triethoxysilane, 3-sulfydryl propyl trimethoxy silicane, vinyltrimethoxy silane, N-(2-(vinyl benzyl amino) ethyl) 3-aminopropyl trimethoxysilane hydrochloride, 3-methyl-prop acyloxy propyl trimethoxy silicane, 3-chloropropylmethyldimethoxysilane, the silane coupling agents such as 3-r-chloropropyl trimethoxyl silane, sec.-propyl (N-ethyl aminoethyl amino) titanic acid ester, sec.-propyl three isostearoyl base titanic acid ester, two (dioctylphyrophosphoric acid esters) contain titanium coupling agent containing fluoroacetic acid titanium, tetra isopropyl two (dioctyl phosphorous acid ester) titanic acid ester, new alkoxyl group three (p-N-(β-aminoethyl) aminophenyl) titanic acid ester etc., methyl ethyl diketone zirconium, methacrylic acid zirconium, propionic acid zirconium, new alkoxy zirconium ester, the new new decanoyl zirconate of alkoxyl group three, new alkoxyl group three (lauroyl) benzenesulfonyl zirconate, new alkoxyl group three (ethylene amino-ethyl) zirconate, new alkoxyl group three (m-aminophenyl base) zirconate, zirconium carbonate ammonium, aluminium acetylacetonate, aluminium methacrylate, propionic acid aluminium etc. are containing zirconium coupling agent or contain aluminum coupling agent etc.
As the concrete example of stopper, can enumerate: p methoxy phenol, toluhydroquinone etc.
As the concrete example of photostabilizer, for example can enumerate: 1, 2, 2, 6, 6-pentamethyl--4-piperidine alcohols, 2, 2, 6, 6-tetramethyl--4-piperidine alcohols, (methyl) vinylformic acid 1, 2, 2, 6, (Ai Dike Co., Ltd. manufactures 6-pentamethyl--4-piperidine ester, LA-82), 1, 2, 3, 4-ethylene-dimalonic acid four (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) ester, 1, 2, 3, 4-ethylene-dimalonic acid four (2, 2, 6, 6-tetramethyl--4-piperidyl) ester, 1, 2, 3, 4-ethylene-dimalonic acid and 1, 2, 2, 6, 6-pentamethyl--4-piperidine alcohols and 3, two (2-hydroxyl-1 of 9-, 1-dimethyl ethyl)-2, 4, 8, the undecanoic mixed ester compound of 10-tetra-oxaspiros [5.5], sebacic acid two (2, 2, 6, 6-tetramethyl--4-piperidyl) sebate, two (1-undecane oxygen base-2, 2, 6, 6-tetramethyl piperidine-4-yl) carbonic ether, methacrylic acid 2, 2, 6, 6-tetramethyl--4-piperidine ester, sebacic acid two (2, 2, 6, 6-tetramethyl--4-piperidyl) ester, sebacic acid two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) ester, 4-benzoyloxy-2, 2, 6, 6-tetramethyl piperidine, 1-[2-[3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl]-4-[3-(3, 5-di-t-butyl-4-hydroxyphenyl) propionyloxy]-2, 2, 6, 6-tetramethyl piperidine, methacrylic acid 1, 2, 2, 6, 6-pentamethyl--4-piperidine ester, two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) [[3, 5-two (1, 1-dimethyl ethyl)-4-hydroxyphenyl] methyl] butyl malonic acid ester, sebacic acid two (2, 2, 6, 6-tetramethyl--1 (octyloxy)-4-piperidyl) ester, 1, the reaction product of 1-dimethyl ethyl hydrogen peroxide and octane, N, N ', N ' ', N ' ' '-tetra-(4, two (butyl (N-methyl-2 of 6-, 2, 6, 6-tetramethyl piperidine-4-yl) amino) triazine-2-yl)-4, 7-diaza decane-1, 10-diamines, dibutylamine-1, 3, 5-triazine-N, N '-bis-(2, 2, 6, 6-tetramethyl--4-piperidyl-1, 6-hexamethylene-diamine and N-(2, 2, 6, 6-tetramethyl--4-piperidyl) polycondensate of butylamine, poly-[[6-(1, 1, 3, 3-tetramethyl butyl) amino-1, 3, 5-triazine-2, 4-bis-bases] [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-] hexa-methylene [(2, 2, 6, 6-tetramethyl--4-piperidyl) imino-]], Succinic acid dimethylester and 4-hydroxyl-2, 2, 6, the polymkeric substance of 6-tetramethyl--1-piperidines ethanol, 2, 2, 4, 4-tetramethyl--20-(β-bay oxygen base carbonyl) ethyl-7-oxa--3, 20-diaza two spiral shells [5.1.11.2] heneicosane-21-ketone, Beta-alanine N,-(2, 2, 6, 6-tetramethyl--4-piperidyl) dodecane ester/tetradecane ester, N-ethanoyl-3-dodecyl-1-(2, 2, 6, 6-tetramethyl--4-piperidyl) tetramethyleneimine-2, 5-diketone, 2, 2, 4, 4-tetramethyl--7-oxa--3, 20-diaza two spiral shells [5, 1, 11, 2] heneicosane-21-ketone, 2, 2, 4, 4-tetramethyl--21-oxa--3, 20-diazabicylo [5, 1, 11, 2] heneicosane-20-propionic acid dodecane ester/tetradecane ester, propanedioic acid [(4-p-methoxy-phenyl) methylene radical] two (1, 2, 2, 6, 6-pentamethyl--4-piperidyl) ester, 2, 2, 6, the high-grade aliphatic ester of 6-tetramethyl--4-piperidine alcohols, N, N '-bis-(2, 2, 6, 6-tetramethyl--4-piperidyl)-1, the hindered aminess such as 3-benzenedicarboxamide, the benzophenone compounds such as octabenzone, 2-(2H-benzotriazole-2-yl)-4-(1, 1, 3, 3-tetramethyl butyl) phenol, 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2-[2-hydroxyl-3-(3, 4, 5, 6-tetrahydric phthalimide-methyl)-5-aminomethyl phenyl] benzotriazole, 2-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenyl)-5-chlorobenzotriazole, 2-(2-hydroxyl-3, 5-di-tert-pentyl-phenyl) benzotriazole, the reaction product of 3-(3-(2H-benzotriazole-2-yl)-5-tertiary butyl-4-hydroxyphenyl) methyl propionate and polyoxyethylene glycol, the benzotriazole compounds such as 2-(2H-benzotriazole-2-yl)-6-dodecyl-4-cresols, 2, 4-di-tert-butyl-phenyl-3, the benzoates such as 5-di-tert-butyl-4-hydroxybenzoic acid ester, 2-(4, 6-phenylbenzene-1, 3, 5-triazine-2-yl)-5-[(hexyl) oxygen base] compound in triazine class such as phenol etc., be particularly preferably hindered amine compound.
As the concrete example of weighting agent, for example can enumerate: the powder of crystalline silica, fused silica, aluminum oxide, zircon, Calucium Silicate powder, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconium white, forsterite, steatite, spinel, titanium dioxide, talcum etc. or make their spheroidizations and bead of obtaining etc.
Various additives are optional member, can be also therefore zero conventionally.While there is various additive in composition, the part by weight of various additives in light-cured type transparent adhesive composition is 0.01～3 % by weight, is preferably 0.01～1 % by weight, more preferably 0.02～0.5 % by weight.
In order to improve consistency, adaptation, resin combination of the present invention preferably combines with the composition with propylidene skeleton.
Particularly, can preferably use that to contain by m value/(m value+n value) in general formula (1) be the resin combination of carbamate (methyl) acrylate that obtains of 0.4～1.0 compound and polypropylene glycol.
Resin combination of the present invention can, by above-mentioned each composition mixed dissolution at normal temperature～80 DEG C is obtained, can wait operation that inclusion is removed by filtration as required.Consider coating, of the present invention gluing preferred so that the mode of the scope that the viscosity of 25 DEG C is 300～15000mPas suitably regulates the proportioning of composition with resin combination.
The cure shrinkage of resin combination of the present invention is preferably below 3.0%, is particularly preferably below 2.0%.Thus, in the time that ultraviolet-curing resin composition solidifies, the internal stress that can reduce to accumulate in resin cured matter, can prevent from producing strain in base material and the interface of the layer being made up of the cured article of ultraviolet-curing resin composition effectively.
In addition, in the situation that the base materials such as glass are thin, when cure shrinkage is large, it is large that the warpage while solidifying becomes, and therefore can cause large detrimentally affect to display performance, and from this viewpoint, also preferred consolidation shrinking percentage is less.
(thickness 200 μ m) are preferably more than 90% in the average transmittance of 400nm～800nm the cured article of resin combination of the present invention.This be because, when transmissivity is too low, light is difficult to transmission, while being used in display unit, visibility reduce.
In addition, cured article, in the time that the transmissivity of 400～450nm is high, can further be expected the raising of visibility, and therefore, the transmissivity of 400～450nm is preferably more than 90%.Transmissivity is more high better, and the upper limit can reach 100%.Be actually below 99%.
Resin combination of the present invention contain have the structure being represented by general formula (1) compound, carbamate (methyl) acrylate, there is (methyl) acrylate of 1 (methyl) acryl, re-workability is also good.
Conventionally, in order reprocessing, after fitted base material heating, to use metal wire incision adhesive layer, to carry out thus peeling off of base material and adhesive layer.Now, use solvent in order easily to peel off, but in the present invention, because the separability of the composition of composition is good, even if therefore use the alcohols such as Virahol also can easily peel off as solvent.
Below, illustrate the optimal way of resin combination of the present invention.
(i) a kind of ultraviolet-curing resin composition, the compound (A), (methyl) acrylic compound (B) and the Photoepolymerizationinitiater initiater (C) that contain formula (1), wherein, the molecular weight of the compound (A) of formula (1) is 100～10000.
(ii) ultraviolet-curing resin composition as described in above-mentioned (i), wherein, the molecular weight of the compound (A) of formula (1) is 500～8000.
(iii) ultraviolet-curing resin composition as described in above-mentioned (i), wherein, the molecular weight of the compound (A) of formula (1) is 1000～8000.
(iv) ultraviolet-curing resin composition as described in above-mentioned (i), wherein, the molecular weight of the compound (A) of formula (1) is 1500～5000.
(v) ultraviolet-curing resin composition as described in any one in above-mentioned (i)～(iv), wherein, the R in the compound (A) of formula (1)
1and R
2be the alkyl of carbonatoms 1～10 or the thiazolinyl of carbonatoms 3～10 independently of one another.
(vi) ultraviolet-curing resin composition as described in above-mentioned (v), wherein, R
1and R
2be the alkyl of carbonatoms 1～6 or the thiazolinyl of carbonatoms 3～5 independently of one another.
(vii) ultraviolet-curing resin composition as described in any one in above-mentioned (i)～(vi), wherein, m/ (m+n) is 0.2～1.
(viii) ultraviolet-curing resin composition as described in above-mentioned (vii), wherein, m/ (m+n) is 0.4～1.
(ix) ultraviolet-curing resin composition as described in above-mentioned (vi), wherein, n is that 5～40, m is 10～40, R
1and R
2in any be butyl, another is allyl group, or n is that 0, m is 20～80, R
1and R
2be the alkyl of carbonatoms 1～4 independently of one another, be preferably methyl.
(x) ultraviolet-curing resin composition as described in above-mentioned (vi), wherein, above-claimed cpd (A) is for selecting at least one in the group of free polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dibutyl ether, polypropylene glycol allyl group butyl ether, polyethylene glycol-propylene glycol diallyl ether, polyethylene glycol-propylene glycol dibutyl ether and polyethylene glycol-propylene glycol allyl group butyl ether composition.
(xi) ultraviolet-curing resin composition as described in any one in above-mentioned (i)～(x); wherein, (methyl) acrylic compound (B ') that contains carbamate (methyl) acrylate (D) and have 1 (methyl) acryl is as (methyl) acrylic compound (B).
(xii) ultraviolet-curing resin composition as described in above-mentioned (xi), wherein, the weight-average molecular weight of carbamate (methyl) acrylate (D) is 7000～25000.
(xiii) ultraviolet-curing resin composition as described in above-mentioned (xi), wherein, the weight-average molecular weight of carbamate (methyl) acrylate (D) is 10000～20000.
(xiv) ultraviolet-curing resin composition as described in any one in above-mentioned (xi)～(xiii), wherein, carbamate (methyl) acrylate (D) is the reaction product of (methyl) acrylate of polyether glycol and polyisocyanates and hydroxyl.
(xv) ultraviolet-curing resin composition as described in any one in above-mentioned (xi)～(xiv), wherein, contain the freely alkyl ester of (methyl) vinylformic acid carbonatoms 10～30 of choosing, poly-C2～C4 aklylene glycol (methyl) acrylate, (methyl) vinylformic acid nonyl phenyl ester of poly(propylene oxide) modification, (methyl) vinylformic acid has the alkyl ester of the carbonatoms 1～5 of hydroxyl, acryloyl morpholine, at least one in the group of (methyl) tetrahydrofurfuryl acrylate and (methyl) vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester composition is as (methyl) acrylic compound (B ') with 1 (methyl) acryl.
(xvi) ultraviolet-curing resin composition as described in above-mentioned (xv), wherein, contain freely (methyl) lauryl acrylate of choosing, 2-ethylhexyl Trivalin SF acrylate, acryloyl morpholine, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) tetrahydrofurfuryl acrylate, the different stearyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid nonyl phenyl ester of poly(propylene oxide) modification, (methyl) vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester, the different stearyl ester of (methyl) vinylformic acid, at least one in the group of (methyl) vinylformic acid 2-decyl tetradecane ester composition is as (methyl) acrylic compound (B ') with 1 (methyl) acryl.
(xvii) ultraviolet-curing resin composition as described in any one in above-mentioned (xi)～(xiv), wherein, the content of above-claimed cpd (A) is 10～60 % by weight, the content of Photoepolymerizationinitiater initiater (C) is 0.2～5 % by weight, and remainder is (methyl) acrylic compound (B).
(xviii) ultraviolet-curing resin composition as described in above-mentioned (xvii); wherein; with respect to the total amount of (methyl) acrylic compound (B), carbamate (methyl) acrylate (D) and the total content with (methyl) acrylic compound (B ') of 1 (methyl) acryl are 50～100 % by weight.
(xix) ultraviolet-curing resin composition as described in above-mentioned (xviii), wherein, with respect to the total amount of (B) composition, (D) the total content of composition and (B ') composition is 90～100 % by weight.
(xx) ultraviolet-curing resin composition as described in any one in above-mentioned (i)～(xix), wherein, cure shrinkage is below 3%.
(xxi) ultraviolet-curing resin composition as described in above-mentioned (xx), wherein, cure shrinkage is below 2%.
(xxii) ultraviolet-curing resin composition as described in any one in above-mentioned (i)～(xxi), wherein, the cured article of thickness 200 μ m is at least 90% in the average transmittance of 400～800nm.
(xxiii) ultraviolet-curing resin composition as described in any one in above-mentioned (i)～(xxii), wherein, the cured article of thickness 200 μ m is at least 90% in the average transmittance of 400～450nm.
Resin combination of the present invention is used to the apparatus for coating such as slit coater, roller coating machine, spin coater, silk screen print method, so that the mode that the thickness of the resin after coating is 10～300 μ m is coated on a base material, another base material of fitting, as near the light of for example ultraviolet～near ultraviolet (wavelength 200～400nm) of active energy beam, it is solidified from the irradiation of transparent substrate side, can make thus it gluing.Irradiation dose is preferably about 100mJ/cm
2～about 4000mJ/cm
2, be particularly preferably about 200mJ/cm
2～about 3000mJ/cm
2.While being cured by irradiating ultraviolet～near ultraviolet light, as long as irradiating the lamp of ultraviolet～near ultraviolet light, no matter how light source all can use.For example, can enumerate low pressure, high pressure or ultrahigh pressure mercury lamp, metal halid lamp, (pulse) xenon lamp or electrodeless lamp etc.
Resin combination of the present invention can be suitable for the optical elements of fitting more than 2.And optical component of the present invention can be by obtaining at least two above-mentioned optical element laminatings.More specifically, after at least two optical elements are used to resin combination laminating of the present invention, to being clipped in two ultraviolet-curing resin composition layer irradiation ultraviolet radiations between optical element, make thus this resin combination layer be solidified to form cured article layer, can obtain thus optical component of the present invention.
For the laminating of optical element, for example on the binding face of an optical element, be coated with resin combination of the present invention, or on these two faces of binding face of two optical elements of fitting in wish, be coated with resin combination of the present invention, fit in the mode of clamping the coating layer of resin combination of the present invention with the binding face of two optical elements.
As this optical element, be not particularly limited, preferably the optical element of tabular or sheet.As the optical element of tabular or sheet, can enumerate the following plate that comprises transparent panel, sheet, display body (or display body unit), contact panel (or contact panel unit) etc. as an example.
As one of preferred optical component of the present invention, can enumerate the contact panel with protection optical element.
For example, for contact panel, will on a surface, there is the glass system of the transparency electrodes such as electrode ITO film or resinous transparent sheet-like or transparent 2 tabular optical elements use tackiness agent so that transparent electrical pole-face mode in opposite directions separates the gap of a little and fits.An optical element is substrate, and another optical element is the optical element that touch surface is used.And then, there is as required the structure that uses the protections such as tackiness agent laminating screening glass (or plate), icon sheet (or plate) or cosmetic sheet (or plate) to form with optical element on the surface of touch surface side of the optical element of using in touch surface.It is the contact panel that uses resin combination of the present invention to obtain as the tackiness agent of at least one position in the contact panel of this structure as the contact panel of optical component of the present invention.Therefore, this contact panel is the gluing contact panel forming of cured article layer that at least two optical elements utilize resin combination of the present invention.
As the contact panel of optimal way of the present invention, can be set forth in the touch surface of contact panel and above it, there is the contact panel that utilizes the gluing protection of cured article layer of resin combination of the present invention to use optical element.
In addition, one of other optimal way can be enumerated and utilize the cured article layer of resin combination of the present invention to be adhesive in by having the protection contact panel of optical element the display unit with contact panel forming on display surface.
In addition, as one of other preferred optical components of the present invention, can enumerate to contain and utilize the image of the gluing optical component forming of cured article layer of resin combination of the present invention to show the display unit of use at least two above-mentioned optical elements.As a most representative example, can enumerate and utilize the cured article laminating of resin combination of the present invention to be combined in the display unit forming on the surface of image display screen protection optical element or contact panel.In this case, in the present invention, optical element comprise contact panel before laminating and display body the two.
In addition, resin combination of the present invention can be suitable as the tackiness agent use of fit in contact panel multiple transparent panels or sheet.
As transparent panel or sheet, can use the transparent panel or the sheet that adopt various materials.
Particularly, can use by polyethylene terephthalate (PET), polycarbonate (PC), polymethylmethacrylate (PMMA), the mixture of PC and PMMA, glass, cyclic olefine copolymer (COC), cyclic olefin polymer (COP), triacetyl cellulose (TAC), transparent panel or sheet that the resins such as acrylic resin (plastics) are made, or functional transparent layer lamination or the sheets such as the polarization plates that its multi-disc is laminated, { unorganic glass plate and processed goods thereof are (for example for the transparent panel of being made up of unorganic glass, lens, prism, ito glass) } etc.
In addition, in the present invention, the optical element of tabular or sheet, except comprising functional transparent layer lamination such as above-mentioned transparent panel or sheet, polarization plates etc. or sheet, also comprises as the duplexer (below also referred to as functional stacked body) of multiple feature boards such as display body such as contact panel, LCD panel or LED or sheet.
In the present invention, the preferably optical element of above-mentioned tabular or sheet.
Resin combination of the present invention also can be used as the tackiness agent of contact panel and sheet or plate laminating is used.
At this, as sheet, can enumerate icon sheet, cosmetic sheet, screening glass, as plate, can enumerate decorative sheet, protecting sheet.And, as the material of sheet or plate, can apply the material cited as the material of transparent panel.In addition, as the material of contact panel face, can enumerate mixture, COC, the COP of glass, PET, PC, PMMA, PC and PMMA.
Resin combination of the present invention also can be applicable to being used in optical functional materials is fitted on the display surface of display unit.As display unit, can be set forth in the display unit such as the LCD that is pasted with polarization plates on glass, EL indicating meter, EL illumination, Electronic Paper, plasma display.In addition, as optical functional materials, can enumerate: the transite plates such as acrylic resin board, PC plate, PET plate, PEN plate, chilled glass, contact panel etc.
While use as the adhesive material of laminating transparent panel, in order to improve visibility, the specific refractory power of preferred consolidation thing is 1.45～1.55.
In the scope of this specific refractory power time, can reduce and the specific refractivity of base material using as transparent panel, can suppress the diffuse-reflectance of light and reduce optical loss.
In addition, the electronics that is assembled with the display unit for example, with the optical element (optical functional materials) that uses resin combination laminating of the present invention, such as televisor, small game machine, mobile phone, Personal Computer etc. are also contained in optical component of the present invention.
Below, the optimal way of optical component of the present invention is shown below.
(I) optical component, the cured article layer of the ultraviolet-curing resin composition in above-mentioned (i) of its application of the invention～(xxiii) described in any one will at least two optical elements laminating and is obtained.
(II) optical component as described in above-mentioned (I), wherein, the optical element of laminating is the optical element of tabular or sheet.
(III) optical component as described in above-mentioned (II); wherein; an optical element tabular or sheet of laminating is protection optical element; another optical element tabular or sheet is contact panel, and the optical component obtaining is the contact panel with protection optical element.
(IV) a kind of display unit; wherein; an optical element is optical element or contact panel for protection; another optical element is display unit, and the optical component obtaining has protection optical element or the contact panel on the display screen that uses above-mentioned cured article laminating to be combined in display unit.
[embodiment]
Below, be described more specifically the present invention by embodiment, but the present invention is not subject to any restriction of these embodiment.
Embodiment 1～11 and comparative example 1
By each ultraviolet-curing resin composition that each starting compound mixes and preparation comprises even composition, obtain the present invention and the resin combination of use relatively in the mode that reaches the composition shown in following table 1.
In addition, as described below to be called for short the each composition representing in table 1.
ユ ニ セ ー Off PKA-5016 (trade(brand)name): polyethylene glycol-propylene glycol allyl group butyl ether (in general formula (1), R
1for allyl group, R
2for butyl, n=15, m=15, the number-average molecular weight compound that is 1600), Japan Oil Co manufactures
ユ ニ セ ー Off PKA-5017 (trade(brand)name): polyethylene glycol-propylene glycol allyl group butyl ether (in general formula (1), R
1for allyl group, R
2for butyl, n=23, m=23, the number-average molecular weight compound that is 2500), Japan Oil Co manufactures
PPG2000-DME: polypropylene glycol dimethyl ether (in general formula (1), R
1for methyl, R
2for the compound of methyl, n=0, m=34, number-average molecular weight 2000)
PPG4000-DME: polypropylene glycol dimethyl ether (in general formula (1), R
1for methyl, R
2for the compound of methyl, n=0, m=68, number-average molecular weight 4000)
UA-l: the reaction product that the mol ratio that makes polypropylene glycol (molecular weight 3000), isophorone diisocyanate, these 3 kinds of compositions of vinylformic acid 2-hydroxy methacrylate is 1:1.3:2.
ACMO: acryloyl morpholine, Xing Ren Co., Ltd. manufactures
4-HBA: vinylformic acid 4-hydroxyl butyl ester, Osaka Organic Chemical Industry Co., Ltd. manufactures
LA: lauryl acrylate, Osaka Organic Chemical Industry Co., Ltd. manufactures
FA-512AS: vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester, Hitachi Chemical Co., Ltd. manufactures
THFA: tetrahydrofurfuryl acrylate, Osaka Organic Chemical Industry Co., Ltd. manufactures
The vinylformic acid nonyl phenyl ester of M-117:2.5 mole of epoxy pronane modification, Toagosei Co., Ltd manufactures
The vinylformic acid nonyl phenyl ester of NP-5P:5 mole of epoxy pronane modification, Di-ichi Kogyo Seiyaku Co., Ltd. manufactures
S-1800A: the different stearyl ester of vinylformic acid, chemical industry Co., Ltd. of Xin Zhong village manufactures
DTD-A: vinylformic acid 2-decyl tetradecane ester, chemical industry Co., Ltd. of common prosperity society manufacture
イ Le ガ キ ュ ア ー 184 (trade(brand)names): 1-hydroxy-cyclohexyl phenyl ketone, BASF AG manufactures
KIP-150 (trade(brand)name): 2-hydroxy-2-methyl-[4-(1-methyl ethylene) phenyl] propyl alcohol oligopolymer, Ning Baidi company manufactures
ス ピ ー De キ ュ ア TPO (trade(brand)name): TMDPO, LAMBSON company manufactures
Z-6062 (goods number): 3-sulfydryl propyl trimethoxy silicane, Dong Li Dow Corning Corporation manufactures
Use the resin combination of the present invention obtaining to carry out following evaluation.
Solidified nature:
So that the slide glass that the mode that the thickness of the resin combination obtaining is 200 μ m is 1mm by 2 thickness laminating.Use high voltage mercury lamp (80W/cm, ozone free), across glass, the resin combination of being clamped by slide glass is carried out to 2000mJ/cm
2uviolizing, make resin combination solidify, confirm its solid state.
Zero ... completely curing
△ ... semi-cured state
× ... uncured
Cure shrinkage:
The slide glass that is 1mm by 2 thickness that are coated with fluorine-containing demoulding agent so that the mode that the thickness of the resin combination obtaining is 200 μ m fit.Use high voltage mercury lamp (80W/cm, ozone free), across glass, the resin combination of being clamped by slide glass is carried out to 2000mJ/cm
2uviolizing, it is solidified, make the cured article that film specific gravity test is used.Measure the proportion (DS) of cured article according to JIS K7112B method.In addition, at 25 DEG C, measure the liquid specific gravity (DL) of resin combination, calculate cure shrinkage by following formula.
Cure shrinkage (%)=(DS-DL) ÷ DS × 100
◎ ... be less than 2.0%
Zero ... more than 2.0% and be less than 3.0%
× ... more than 3.0%
Tackiness:
By the acrylic resin board of the slide glass of thickness 0.8mm and thickness 0.8mm so that the mode that the thickness of the ultraviolet-curing resin composition obtaining is 200 μ m fit.Use high voltage mercury lamp (80W/cm, ozone free), across glass, the resin combination of being clamped by slide glass is carried out to 2000mJ/cm
2uviolizing and make evaluation sample.It is placed 250 hours under 85 DEG C, the environment of 85%RH, confirm to peel off by visual.
Zero ... without peeling off
× ... peel off
Flexibility:
Obtained ultraviolet-curing resin composition is solidified fully, measure sclerometer E hardness according to JIS K7215, evaluate flexibility.
◎ ... be less than 10
Zero ... more than 10 and be less than 20
× ... more than 20
The transparency:
The slide glass that is 1mm by 2 thickness that are coated with fluorine-containing demoulding agent so that the mode that the thickness of the cured article layer of the ultraviolet-curing resin composition obtaining is 200 μ m fit.Use high voltage mercury lamp (80W/cm, ozone free), across glass, the resin combination of being clamped by slide glass is carried out to 2000mJ/cm
2uviolizing and make the transparency and measure the cured article of use.For the transparency, use spectrophotometer (U-3310, new and high technology Co., Ltd. of Hitachi) to measure the transmissivity of 400～800nm and 400～450nm.
◎ ... the transmissivity of 400～800nm is more than 90% and the transmissivity of 400～450nm is 90%
Zero ... the transmissivity of 400～800nm is more than 90% and the transmissivity of 400～450nm is 88～90%
× ... the transmissivity of 400～800nm is less than 90%
Result by table 1 can confirm, contains the transparency that the resin combination of the present invention with the polyether compound ((B) composition) of structure that represented by general formula (1) and the embodiment 1～11 of (methyl) acrylic compound ((A) composition) can obtain the little and cured article of solidified nature contraction good, while solidifying, and the tackiness of base material and the good optical clear tackiness agent of flexibility.
Claims (22)
1. a ultraviolet-curing resin composition, compound (A), (methyl) acrylic compound (B) and Photoepolymerizationinitiater initiater (C) that it contains the structure with following general formula (1) expression,
In formula (1), the integer that n is 0～40, the integer that m is 10～80, R
1and R
2can be the same or different separately, is the alkyl of carbonatoms 1～18, thiazolinyl, the alkynyl of carbonatoms 2～18 or the aryl of carbonatoms 5～18 of carbonatoms 2～18.
2. ultraviolet-curing resin composition as claimed in claim 1, wherein, R
1and R
2be the alkyl of carbonatoms 1～10 or the thiazolinyl of carbonatoms 3～10 independently of one another.
3. ultraviolet-curing resin composition as claimed in claim 1, wherein, described compound (A) is for selecting at least one in the group of free polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dibutyl ether, polypropylene glycol allyl group butyl ether, polyethylene glycol-propylene glycol diallyl ether, polyethylene glycol-propylene glycol dibutyl ether and polyethylene glycol-propylene glycol allyl group butyl ether composition.
4. ultraviolet-curing resin composition as claimed in claim 1; wherein, contain (methyl) acrylic compound that there is (methyl) acrylic compound (B ') of 1 (methyl) acryl or there are 2 (methyl) acryls as (methyl) acrylic compound (B).
5. the ultraviolet-curing resin composition as described in claim 1 or 4, wherein, contains carbamate (methyl) acrylate (D) as (methyl) acrylic compound (B).
6. ultraviolet-curing resin composition as claimed in claim 1; wherein, (methyl) acrylic compound (B ') that contains carbamate (methyl) acrylate (D) and have 1 (methyl) acryl is as (methyl) acrylic compound (B).
7. ultraviolet-curing resin composition as claimed in claim 1, wherein, the content of described compound (A) is 10～60 % by weight, the content of Photoepolymerizationinitiater initiater (C) is 0.2～5 % by weight, and remainder is (methyl) acrylic compound (B).
8. ultraviolet-curing resin composition as claimed in claim 6, wherein, contain the freely alkyl ester of (methyl) vinylformic acid carbonatoms 10～30 of choosing, poly-C2～C4 aklylene glycol (methyl) acrylate, (methyl) vinylformic acid nonyl phenyl ester of poly(propylene oxide) modification, (methyl) vinylformic acid has the alkyl ester of the carbonatoms 1～5 of hydroxyl, acryloyl morpholine, at least one in the group of (methyl) tetrahydrofurfuryl acrylate and (methyl) vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester composition is as (methyl) acrylic compound (B ') with 1 (methyl) acryl.
9. ultraviolet-curing resin composition as claimed in claim 4, wherein, contain freely (methyl) lauryl acrylate of choosing, 2-ethylhexyl Trivalin SF acrylate, acryloyl morpholine, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) tetrahydrofurfuryl acrylate, the different stearyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid nonyl phenyl ester of poly(propylene oxide) modification, (methyl) vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester, the different stearyl ester of (methyl) vinylformic acid, at least one in the group of (methyl) vinylformic acid 2-decyl tetradecane ester composition is as (methyl) acrylic compound (B ') with 1 (methyl) acryl.
10. ultraviolet-curing resin composition as claimed in claim 5, wherein,
Described compound (A) is for selecting at least one in the group of free polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dibutyl ether, polypropylene glycol allyl group butyl ether, polyethylene glycol-propylene glycol diallyl ether, polyethylene glycol-propylene glycol dibutyl ether and polyethylene glycol-propylene glycol allyl group butyl ether composition
Contain freely (methyl) lauryl acrylate of choosing, 2-ethylhexyl Trivalin SF acrylate, acryloyl morpholine, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) tetrahydrofurfuryl acrylate, the different stearyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid nonyl phenyl ester of poly(propylene oxide) modification, (methyl) vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester, the different stearyl ester of (methyl) vinylformic acid, at least one in the group of (methyl) vinylformic acid 2-decyl tetradecane ester composition is as (methyl) acrylic compound (B ') with 1 (methyl) acryl.
11. ultraviolet-curing resin compositions as claimed in claim 1; wherein; contain (methyl) acrylic compound (B ') and carbamate (methyl) acrylate (D) with 1 (methyl) acryl, the integer that the m in general formula (1) is 10～50.
12. ultraviolet-curing resin compositions as claimed in claim 5, wherein, carbamate (methyl) acrylate (D) is the reaction product of (methyl) acrylate of polyether glycol and polyisocyanates and hydroxyl.
13. ultraviolet-curing resin compositions as claimed in claim 1, wherein, (methyl) acrylic compound (B ') that contains carbamate (methyl) acrylate (D) and have 1 (methyl) acryl is as (methyl) acrylic compound (B), with respect to the total amount of composition, the described compound (A) that contains 1～60 % by weight, carbamate (methyl) acrylate (D) of 20～80 % by weight, the Photoepolymerizationinitiater initiater (C) of (methyl) acrylic compound with 1 (methyl) acryl of 10～70 % by weight (B ') and 0.2～5 % by weight.
14. ultraviolet-curing resin compositions as claimed in claim 13; wherein, (methyl) acrylic compound (B ') that has 1 (methyl) acryl is at least 40 % by weight with the total content of carbamate (methyl) acrylate (D) with respect to the total amount of resin combination.
15. ultraviolet-curing resin compositions as claimed in claim 12, wherein, cure shrinkage is below 3.0%.
16. ultraviolet-curing resin compositions as claimed in claim 6, wherein,
(i) described compound (A) is for selecting at least one in the group of free polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dibutyl ether, polypropylene glycol allyl group butyl ether, polyethylene glycol-propylene glycol diallyl ether, polyethylene glycol-propylene glycol dibutyl ether and polyethylene glycol-propylene glycol allyl group butyl ether composition
(ii) contain freely (methyl) lauryl acrylate of choosing, 2-ethylhexyl Trivalin SF acrylate, acryloyl morpholine, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) tetrahydrofurfuryl acrylate, the different stearyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid nonyl phenyl ester of poly(propylene oxide) modification, (methyl) vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester, the different stearyl ester of (methyl) vinylformic acid, at least one in the group of (methyl) vinylformic acid 2-decyl tetradecane ester composition is as (methyl) acrylic compound (B ') with 1 (methyl) acryl,
(iii) carbamate (methyl) acrylate (D) is the reaction product of (methyl) acrylate of polyether glycol and polyisocyanates and hydroxyl.
17. ultraviolet-curing resin compositions as described in claim 6 or 16, wherein, the weight-average molecular weight of carbamate (methyl) acrylate (D) is 7000～25000.
18. ultraviolet-curing resin compositions as claimed in claim 6, wherein,
Described compound (A) is the R in general formula (1)
1and R
2can be the same or different separately and R
1and R
2for the compound of the alkyl of carbonatoms 1～10 or the thiazolinyl of carbonatoms 3～10,
Carbamate (methyl) acrylate (D) is that the reaction product of (methyl) acrylate and the weight-average molecular weight of this reaction product of polyether glycol and polyisocyanates and hydroxyl is 7000～25000,
(methyl) acrylic compound (B ') that contains carbamate (methyl) acrylate (D) and have 1 (methyl) acryl is as (methyl) acrylic compound (B), and
With respect to the total amount of composition, the described compound (A) that contains 1～60 % by weight, carbamate (methyl) acrylate (D) of 20～80 % by weight, the Photoepolymerizationinitiater initiater (C) of (methyl) acrylic compound with 1 (methyl) acryl of 10～70 % by weight (B ') and 0.2～5 % by weight, and (methyl) acrylic compound (B ') with 1 (methyl) acryl is 40～90 % by weight with the total content of carbamate (methyl) acrylate (D) with respect to the total amount of composition.
19. 1 kinds of optical components, it is by utilizing the cured article layer of the ultraviolet-curing resin composition described in claim 1 by least two gluing obtaining of optical element.
20. 1 kinds of cured articles, it obtains by ultraviolet-curing resin composition claimed in claim 1 is irradiated to active energy beam.
21. 1 kinds of contact panels, it is by utilizing the cured article layer of the ultraviolet-curing resin composition described in claim 1 by least two gluing obtaining of optical element.
22. 1 kinds have the protection display unit of optical element or contact panel, and its cured article layer by utilizing the ultraviolet-curing resin composition described in claim 1 is by protection optical element or contact panel and display unit is gluing obtains.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510791254.4A CN105385405A (en) | 2011-10-21 | 2012-10-19 | Ultraviolet ray cured resin composition, cured product, and article |
| CN201710073183.3A CN106947033A (en) | 2011-10-21 | 2012-10-19 | Ultraviolet-curing resin composition, solidfied material and article |
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| JP2011-231464 | 2011-10-21 | ||
| JP2011231464 | 2011-10-21 | ||
| JP2012-149206 | 2012-07-03 | ||
| JP2012149206 | 2012-07-03 | ||
| PCT/JP2012/006707 WO2013057957A1 (en) | 2011-10-21 | 2012-10-19 | Ultraviolet ray cured resin composition, cured product, and article |
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| CN201710073183.3A Division CN106947033A (en) | 2011-10-21 | 2012-10-19 | Ultraviolet-curing resin composition, solidfied material and article |
| CN201510791254.4A Division CN105385405A (en) | 2011-10-21 | 2012-10-19 | Ultraviolet ray cured resin composition, cured product, and article |
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| CN103890028B CN103890028B (en) | 2017-03-15 |
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| CN201280051831.0A Expired - Fee Related CN103890028B (en) | 2011-10-21 | 2012-10-19 | Ultraviolet-curing resin composition, solidfied material and article |
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| JP (5) | JP5980223B2 (en) |
| CN (3) | CN106947033A (en) |
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| CN108285745A (en) * | 2016-12-20 | 2018-07-17 | 荒川化学工业株式会社 | Ultraviolet-curing adhesive, solidfied material and bonding sheet |
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| CN106662771A (en) * | 2014-06-30 | 2017-05-10 | 日本化药株式会社 | Image display device manufacturing method, hardening resin composition used therein, and image display device |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2017020025A (en) | 2017-01-26 |
| CN105385405A (en) | 2016-03-09 |
| JP2018031002A (en) | 2018-03-01 |
| CN103890028B (en) | 2017-03-15 |
| JP2017222876A (en) | 2017-12-21 |
| CN106947033A (en) | 2017-07-14 |
| JP2016188386A (en) | 2016-11-04 |
| JPWO2013057957A1 (en) | 2015-04-02 |
| JP6391195B2 (en) | 2018-09-19 |
| TWI572691B (en) | 2017-03-01 |
| JP5980223B2 (en) | 2016-08-31 |
| JP6185122B2 (en) | 2017-08-23 |
| TW201323559A (en) | 2013-06-16 |
| WO2013057957A1 (en) | 2013-04-25 |
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