CN103890028B - Ultraviolet-curing resin composition, solidfied material and article - Google Patents

Ultraviolet-curing resin composition, solidfied material and article Download PDF

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Publication number
CN103890028B
CN103890028B CN201280051831.0A CN201280051831A CN103890028B CN 103890028 B CN103890028 B CN 103890028B CN 201280051831 A CN201280051831 A CN 201280051831A CN 103890028 B CN103890028 B CN 103890028B
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methyl
acrylate
ultraviolet
curing resin
ester
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CN103890028A (en
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小林大祐
本桥隼
松尾雄朗
松尾雄一朗
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority to CN201510791254.4A priority Critical patent/CN105385405A/en
Priority to CN201710073183.3A priority patent/CN106947033A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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

Abstract

The present invention relates to a kind of ultraviolet-curing resin composition; characterized in that, containing the compound (A) with the structure represented by formula (1), (methyl) acrylate compounds (B) with 1 or 2 (methyl) acryloyl group and Photoepolymerizationinitiater initiater (C).The resin combination has following feature：The adhesivity of the little and transparent and base material of contraction when excellent curable, solidification can be provided and the solidfied material of excellent flexibility, the manufacture of the optical component for being suitable for being fitted with optical element.In formula (1), n represents that 0～40 integer, m represent 10～50 integer, R1And R2Each can be the same or different, R1And R2For the alkyl of carbon number 1～18, thiazolinyl, alkynyl, aryl.

Description

Ultraviolet-curing resin composition, solidfied material and article
Technical field
The present invention relates to the ultraviolet-curing resin composition being fitted with to optical clear component.
Background technology
In recent years, on the display screen of the display devices such as liquid crystal display, plasma scope, organic el display Sticking touch control panel thus allows for the display device of screen input and is extensively utilized.The display device has following knot Structure：The glass plate or resin-made membrane by transparency electrode is formed with is laminated with its display screen so that transparency electrode is opposite Mode fit obtained from contact panel, then be laminated with glass system or resinous transparency protected in the touch surface of contact panel Plate.In addition, for it not there is the display device of contact panel, becoming The structure of transparent protection plate.
Existing formation in contact panel has the touch surface and glass or resin-made of the glass plate or thin film of transparency electrode Transparent protection plate laminating or display device and the transparent protection plate on its screen fit or display device and its The technology of double-sided adhesive sheet used in laminating of contact panel on screen etc., but there is a problem of easily producing bubble.As Substitute the technology of double-sided adhesive sheet, it is proposed that the technology (patent documentation 1～3) that fits using photocurable resin compositionss.
On the other hand, the slimming of display device and giant-screenization develop.Thus, for example, contact panel is transparent Protection board or substrate and the glass plate of the display screen in display device or resin-made lamella lucida etc. are also gradually thinning.Cause This, in above-mentioned stacking or laminating, when being fitted using photocurable resin compositionss, is present due to the resin combination Cure shrinkage and make contact panel, display screen deformation problem.In addition, the material of both is glass in thing is glued In the case of the materials such as glass/acrylic resin, glass/polycarbonate resin difference, due to thermal expansion, the hygroscopicity of two kinds of materials Difference, there is a problem of that in hot resistance test gluing surface is peeled off.In order to solve these problems, it is desirable to when providing suppression solidification Contraction, the photocurable resin compositionss to the solidfied material of the adhesivity and excellent flexibility of base material.But, using patent In the case that the polyisoprene that document 1 is recorded is as main component, heptane, hexane etc. must be used organic molten in reprocessing Agent is removed, and there is a problem of that re-workability is poor.In addition, using as described in patent documentation 2 with cycloalkanes hydrocarbon skeleton Epoxy resin when, flexibility is poor, the load that xanthochromia, in the compositionss as described in patent documentation 3, occurs when there is also solidification Melancholy.Therefore, patent documentation 1～3 cannot obtain gratifying photocurable resin compositionss.
Prior art literature
Patent documentation
Patent documentation 1：International Publication No. 2010/027041
Patent documentation 2：Japanese Unexamined Patent Publication 2010-248387 publications
Patent documentation 3：Japanese Unexamined Patent Application Publication 2011-511851 publication
Content of the invention
Invent problem to be solved
It is an object of the invention to provide can obtain curable excellent, solidification when contraction little, solidfied material the transparency, Ultraviolet-curing resin composition with the optical clear adhesive of the adhesivity of base material and excellent flexibility, ultraviolet using this Optical component, such as contact panel or display device obtained from line curable resin composition, it is assembled with their electronics and sets Standby etc..
Means for solving the problem
The present inventor is had made intensive studies to solve the above problems, and is as a result found containing the knot with following formula (1) The ultraviolet-curing resin composition of the compound of structure, (methyl) acrylate compounds and Photoepolymerizationinitiater initiater is achieved Problem is stated, so as to complete the present invention.
That is, the present invention relates to following (1)～(22) item.
(1) a kind of ultraviolet-curing resin composition, its contain the compound of the structure represented with following formulas (1) (A), (methyl) acrylate compounds (B) and Photoepolymerizationinitiater initiater (C),
In formula (1), n is 0～40 integer, and m is 10～80 integer, R1And R2Each can be the same or different, be The alkyl of carbon number 1～18, the thiazolinyl of carbon number 2～18, the alkynyl of carbon number 2～18 or carbon number 5～18 Aryl.
(2) ultraviolet-curing resin composition described in (1) as described above, wherein, R1And R2It is each independently carbon atom The alkyl of number 1～10 or the thiazolinyl of carbon number 3～10.
(3) ultraviolet-curing resin composition described in (1) as described above, wherein, above-claimed cpd (A) is selected from poly- Propylene Glycol diallyl ether, polypropylene glycol dimethyl ether, polypropyleneglycol dibutyl ether, polypropylene glycol pi-allyl butyl ether, poly- second Glycol-polypropylene glycol diallyl ether, polyethylene glycol Propylene Glycol dibutyl ethers and polyethylene glycol Propylene Glycol pi-allyl fourth At least one in the group of base ether composition.
(4) ultraviolet-curing resin composition any one of (1)～(3) as described above, wherein, containing having 1 (methyl) acrylate compounds (B ') of individual (methyl) acryloyl group or (methyl) propylene with 2 (methyl) acryloyl groups Ester compound is used as (methyl) acrylate compounds (B).
(5) ultraviolet-curing resin composition any one of (1)～(4) as described above, wherein, containing amino first Acid esters (methyl) acrylate (D) is used as (methyl) acrylate compounds (B).
(6) ultraviolet-curing resin composition any one of (1)～(5) as described above, wherein, containing amino first Acid esters (methyl) acrylate (D) and (methyl) acrylate compounds (B ') with 1 (methyl) acryloyl group are used as (first Base) acrylate compounds (B).
(7) ultraviolet-curing resin composition any one of (1)～(6) as described above, wherein, above-claimed cpd (A) content is 10～60 weight %, and the content of Photoepolymerizationinitiater initiater (C) is 0.2～5 weight %, and remainder is (methyl) third Enoic acid ester compounds (B).
(8) ultraviolet-curing resin composition described in (6) as described above, wherein, containing being selected from (methyl) acrylic acid The Arrcostab of carbon number 10～30, poly- C2～C4 aklylene glycols (methyl) the acrylate, (first of polypropylene oxide Base) nonylphenol acrylate phenyl ester, (methyl) acrylic acid has the Arrcostab of carbon number 1～5 of hydroxyl, acryloyl morpholine, (first Base) tetrahydrofurfuryl acrylate and (methyl) propylene acid dihydride dicyclopentadiene base epoxide ethyl ester composition group at least one As (methyl) acrylate compounds (B ') with 1 (methyl) acryloyl group.
(9) ultraviolet-curing resin composition any one of (4)～(8) as described above, wherein, containing being selected from (methyl) lauryl acrylate, 2- ethylhexyl carbitol acrylate, acryloyl morpholine, (methyl) acrylic acid 4- hydroxyl fourths Ester, (methyl) tetrahydrofurfuryl acrylate, the different stearyl ester of (methyl) acrylic acid, (methyl) nonylphenol acrylate of polypropylene oxide Phenyl ester, (methyl) propylene acid dihydride dicyclopentadiene base epoxide ethyl ester, the different stearyl ester of (methyl) acrylic acid, (methyl) acrylic acid At least one in the group of 2- decyl tetradecanes ester composition is used as (methyl) acroleic acid esterification with 1 (methyl) acryloyl group Compound (B ').
(10) ultraviolet-curing resin composition any one of (4)～(9) as described above, wherein,
Above-claimed cpd (A) is selected from polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, two fourth of polypropylene glycol Base ether, polypropylene glycol pi-allyl butyl ether, polyethylene glycol Propylene Glycol diallyl ether, polyethylene glycol Propylene Glycol dibutyl At least one in the group of ether and polyethylene glycol Propylene Glycol pi-allyl butyl ether composition,
Containing selected from (methyl) lauryl acrylate, 2- ethylhexyl carbitol acrylate, acryloyl morpholine, (methyl) acrylic acid 4- hydroxybutyls, (methyl) tetrahydrofurfuryl acrylate, the different stearyl ester of (methyl) acrylic acid, poly(propylene oxide) change (methyl) nonylphenol acrylate phenyl ester of property, (methyl) propylene acid dihydride dicyclopentadiene base epoxide ethyl ester, (methyl) acrylic acid At least one in different stearyl ester, the group of (methyl) acrylic acid 2- decyl tetradecanes ester composition is used as with 1 (methyl) propylene (methyl) acrylate compounds (B ') of acyl group.
(11) ultraviolet-curing resin composition any one of (1)～(10) as described above, wherein, containing having (methyl) acrylate compounds (B ') and carbamate (methyl) acrylate (D) of 1 (methyl) acryloyl group, formula (1) m in is 10～50 integer.
(12) ultraviolet-curing resin composition any one of (1)～(11) as described above, wherein, carbamic acid Ester (methyl) acrylate (D) is the reaction product of polyether polyol and polyisocyanates and (methyl) acrylate of hydroxyl Thing.
(13) ultraviolet-curing resin composition any one of (1)～(12) as described above, wherein, containing amino Formic acid esters (methyl) acrylate (D) and (methyl) acrylate compounds (the B ') conduct with 1 (methyl) acryloyl group (methyl) acrylate compounds (B), relative to the total amount of compositionss, the above-claimed cpd containing 1～60 weight % (A), 20～ Carbamate (methyl) acrylate (D) of 80 weight the %, (first with 1 (methyl) acryloyl group of 10～70 weight % Base) acrylate compounds (B ') and 0.2～5 weight % Photoepolymerizationinitiater initiater (C).
(14) ultraviolet-curing resin composition described in (13) as described above, wherein, with 1 (methyl) acryloyl group (methyl) acrylate compounds (B ') and carbamate (methyl) acrylate (D) total content relative to resin group The total amount of compound is at least 40 weight %.
(15) ultraviolet-curing resin composition any one of (1)～(14) as described above, wherein, cure shrinkage Rate is less than 3.0%.
(16) ultraviolet-curing resin composition any one of (6)～(15) as described above, wherein,
I () above-claimed cpd (A) is selected from polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol Dibutyl ethers, polypropylene glycol pi-allyl butyl ether, polyethylene glycol Propylene Glycol diallyl ether, polyethylene glycol Propylene Glycol two At least one in the group of butyl ether and polyethylene glycol Propylene Glycol pi-allyl butyl ether composition,
(ii) containing selected from (methyl) lauryl acrylate, 2- ethylhexyl carbitol acrylate, acryloyl group Quinoline, (methyl) acrylic acid 4- hydroxybutyls, (methyl) tetrahydrofurfuryl acrylate, the different stearyl ester of (methyl) acrylic acid, polycyclic oxygen third Modified (methyl) the nonylphenol acrylate phenyl ester of alkane, (methyl) propylene acid dihydride dicyclopentadiene base epoxide ethyl ester, (methyl) third At least one in the different stearyl ester of olefin(e) acid, the group of (methyl) acrylic acid 2- decyl tetradecanes ester composition is used as with 1 (methyl) (methyl) acrylate compounds (B ') of acryloyl group,
(iii) carbamate (methyl) acrylate (D) is polyether polyol and polyisocyanates and the (first of hydroxyl Base) acrylate product.
(17) ultraviolet-curing resin composition any one of (6)～(16) as described above, wherein, carbamic acid The weight average molecular weight of ester (methyl) acrylate (D) is 7000～25000.
(18) ultraviolet-curing resin composition any one of (6)～(18) as described above, wherein,
Above-claimed cpd (A) is the R in formula (1)1And R2Each can be the same or different and R1And R2For carbon atom The compound of the thiazolinyl of the alkyl of number 1～10 or carbon number 3～10,
Carbamate (methyl) acrylate (D) is polyether polyol and polyisocyanates and (methyl) third of hydroxyl The weight average molecular weight of the product and the product of olefin(e) acid ester is 7000～25000,
(methyl) acrylic acid containing carbamate (methyl) acrylate (D) and with 1 (methyl) acryloyl group Ester compounds (B ') conduct (methyl) acrylate compounds (B), and
Relative to the total amount of compositionss, the above-claimed cpd containing 1～60 weight % (A), the amino first of 20～80 weight % Acid esters (methyl) acrylate (D), (methyl) acrylate chemical combination with 1 (methyl) acryloyl group of 10～70 weight % The Photoepolymerizationinitiater initiater (C) of thing (B ') and 0.2～5 weight %, and there is (methyl) acrylic acid of 1 (methyl) acryloyl group Ester compounds (B ') are 40～90 with total content of carbamate (methyl) acrylate (D) relative to the total amount of compositionss Weight %.
(19) a kind of optical component, which is by using the ultraviolet hardening tree any one of above-mentioned (1)～(18) The solidified material layer of oil/fat composition will be gluing at least two optical elements and be obtained.
(20) a kind of solidfied material, which is by the ultraviolet curing resin group any one of above-mentioned (1)～(18) Compound irradiates active energy beam and obtains.
(21) a kind of contact panel, which is by using the ultraviolet hardening tree any one of above-mentioned (1)～(18) The solidified material layer of oil/fat composition will be gluing at least two optical elements and be obtained.
(22) a kind of display device with protection optical element or contact panel, its by using above-mentioned (1)～ (18) solidified material layer of the ultraviolet-curing resin composition any one of is by protection optical element or contact panel Gluing with display device and obtain.
Invention effect
In accordance with the invention it is possible to provide can excellent as curable, solidification when contraction little, solidfied material the transparency, The ultraviolet-curing resin composition that uses with the optical clear adhesive of the adhesivity and excellent flexibility of base material, use this Optical component obtained from the solidified material layer laminating of resin combination.
Specific embodiment
The ultraviolet-curing resin composition of the present invention be (resin combination hereinafter referred to as of the invention or the present invention's Compositionss) containing the compound (A), (methyl) acrylate compounds (B) and photopolymerization with the structure represented by formula (1) Initiator (C).
The resin combination of the present invention contains the compound (A) with the structure represented by following formulas (1),
In formula, n represents that 0～40 integer, m represent 10～80 integer.R1And R2Each can be the same or different. R1And R2For the alkyl of carbon number 1～18, the thiazolinyl of carbon number 2～18, the alkynyl of carbon number 2～18 or carbon number 5 ～18 aryl.
In formula (1), as a preferred mode, can enumerate n be 0 or n be 5～40, more preferably 10～30 Mode.M preferably 20～80, more preferably 30～70.Here, from the adaptation given with base material and making and carbamate (methyl) From the viewpoint of the compatibility of acrylate is improved, m/ (m+n) is preferably 0.2～1, more preferably 0.4～1.
In addition, R1And R2It is preferred that the thiazolinyl of the alkyl or carbon number 2～18 of carbon number 1～18 is each independently, more The thiazolinyl of the preferably alkyl of carbon number 1～10 or carbon number 3～10.More preferably R1And R2It is each independently The alkyl of carbon number 1～6 or the thiazolinyl of carbon number 3～5.A most preferred mode be n be 5～40, m be 10～40, R1And R2In any one be butyl and another for pi-allyl mode, or n be 0, m be 20～80, R1And R2Each independent Ground for carbon number 1～4 alkyl, be preferably methyl mode.
Compound (A) with the structure represented by formula (1) can give the flexibility of adhesive.As having by leading to The compound (A) of the structure that formula (1) is represented, as long as being in the range of 10～80 in the integer, m that n is 0～40, then can not have Limit ground to use.
As the concrete example of the compound (A), can enumerate for example：Polypropylene glycol diallyl ether, polypropylene glycol diformazan Base ether, polypropyleneglycol dibutyl ether, polypropylene glycol pi-allyl butyl ether, polyethylene glycol Propylene Glycol diallyl ether, poly- second two Alcohol-polypropyleneglycol dibutyl ether, polyethylene glycol Propylene Glycol pi-allyl butyl ether.
The compound (A) can also be readily available in the way of commercially available product.For example, it is possible to polyethylene glycol the third two Alfin butyl ether (ユ ニ セ Off PKA-5015, PKA-5016, PKA-5017, Japan Oil Co's manufacture), poly- the third two The mode of alcohol diallyl ether (ユ ニ セ Off PKA-5018, Japan Oil Co's manufacture) is obtained.Particularly polyethylene glycol Propylene Glycol pi-allyl butyl ether (PKA-5016, PKA-5017, Japan Oil Co's manufacture) and carbamate (methyl) propylene The compatibility of acid esters is excellent, thus it is preferred that.
The number-average molecular weight of the compound (A) is usually 100～10000, preferably 500～8000, more preferably 1000 ～8000, particularly preferably 1500～5000.This is because, when number-average molecular weight is too small, flexibility, adhesivity may be poor, When number-average molecular weight is excessive, the compatibility may be poor.
The part by weight of the compound (A) in the light-cured type transparent adhesive compositionss of the present invention is preferably from about 1 weight Amount %～about 60 weight %, are particularly preferably for about 10 weight %～about 50 weight %.When very few, flexibility is poor, and when excessive, curable becomes Difference.
In the compositionss of the present invention, containing (methyl) acrylate compounds (B) (hereinafter also referred to (B) composition).As long as It is (methyl) acrylate compounds and for known compound, then can be not particularly limited to use.
As (methyl) acrylate compounds (B), preferably there is (methyl) third of 1 or 2 (methyl) acryloyl group Enoic acid ester compounds, more preferably these compositions reach the situation of 100 weight % of (B) composition.
As (B) composition, particularly preferably following (methyl) acrylate compounds with 1 (methyl) acryloyl group (B ') (hereinafter also referred to (B ') composition) and aftermentioned carbamate (methyl) acrylate (D) (hereinafter also referred to (D) composition). Other multifunctional (methyl) acrylate can also be used.As preferred mode, can enumerate relative to (methyl) propylene The total amount of ester compound (B), total content of (B ') composition and (D) composition is 50～100 weight % (as long as not special below Indicate, then % refers to weight %), more preferably 70～100%, more preferably 90～100% mode.Remainder is other (methyl) acrylate compounds.Most preferably by the above-mentioned situation that both are constituted, (both amount to (B) composition to (B) composition 100% situation).
In addition, in this specification, " (methyl) acrylate " is any one in methacrylate and acrylate Plant or two kinds.
(methyl) acrylate compounds (B) contained in resin combination as the present invention, preferably use with 1 (methyl) acrylate compounds (B ') of (methyl) acryloyl group.
Specifically, can enumerate：(methyl) Isooctyl acrylate monomer, (methyl) isoamyl acrylate, (methyl) acrylic acid Lauryl, (methyl) isodecyl acrylate, (methyl) stearyl acrylate ester, (methyl) acrylic acid cetyl, (methyl) acrylic acid (methyl) the acrylic acid carbon such as different myristin, (methyl) acrylic acid tridecane ester, (methyl) acrylic acid 2- decyl tetradecane esters are former The Arrcostab of the Arrcostab of subnumber 5～30, more preferably (methyl) acrylic acid carbon number 10～30；(methyl) benzyl acrylate, (methyl) tetrahydrofurfuryl acrylate, acryloyl morpholine, (methyl) phenylethyl ethylene oxidic ester, tristane (methyl) third Olefin(e) acid ester, propylene acid dihydride dicyclopentadiene base ester, (methyl) propylene acid dihydride dicyclopentadiene base epoxide ethyl ester, (first Base) isobornyl acrylate, (methyl) acrylic acid tetrahydrochysene dicyclopentadiene base ester, acrylic acid 1- Buddha's warrior attendant alkyl esters, acrylic acid 2- Methyl -2- Buddha's warrior attendant alkyl esters, acrylic acid 2- ethyl -2- Buddha's warrior attendant alkyl esters, methacrylic acid 1- Buddha's warrior attendant alkyl esters, (methyl) propylene acid dihydride (methyl) acrylate with circulus such as dicyclopentadiene epoxide ethyl ester, preferably has and contains 3～10 carbon atoms And can be containing any one in oxygen atom or nitrogen-atoms or two kinds of 3～10 yuan of rings, more preferably 3～10 yuan of aliphatic rings Or (methyl) acrylate of benzyl；(methyl) such as (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls Acrylic acid has the Arrcostab of the carbon number 1～5 of hydroxyl；Ethoxydiglycol (methyl) acrylate, 2- ethylhexyls Diethylene glycol (methyl) acrylate (another name 2- ethylhexyl carbitol (methyl) acrylate), polypropylene glycol (methyl) propylene Poly alkylene glycol (methyl) acrylate or the poly- alkylenes such as acid esters, (methyl) nonylphenol acrylate phenyl ester of polypropylene oxide (methyl) nonylphenol acrylate phenyl ester of base glycol modification, preferably poly- C2～C4 aklylene glycols (methyl) acrylate or polycyclic oxygen Modified (methyl) the nonylphenol acrylate phenyl ester of propane；Ethylene-oxide-modified phenoxylation phosphoric acid (methyl) acrylate, epoxy Oxide-modified butoxylated phosphoric acid (methyl) acrylate and ethylene-oxide-modified octyloxy phosphoric acid (methyl) acrylic acid The ethylene-oxide-modified phenoxylation such as ester or C3～C10 alkoxylated phosphates (methyl) acrylate etc..
As the preferred compound of (B ') composition, can enumerate：The Arrcostab of (methyl) acrylic acid carbon number 10～30； Poly- C2～C4 aklylene glycols (methyl) acrylate；(methyl) nonylphenol acrylate phenyl ester of polypropylene oxide；(methyl) Acrylic acid has the Arrcostab of the carbon number 1～5 of hydroxyl；Acryloyl morpholine；(methyl) tetrahydrofurfuryl acrylate and/or (methyl) propylene acid dihydride dicyclopentadiene base epoxide ethyl ester.
Wherein, preferably the Arrcostab of (methyl) acrylic acid carbon number 10～30,2- ethylhexyl carbitol acrylate, Acryloyl morpholine, (methyl) acrylic acid 4- hydroxybutyls, (methyl) tetrahydrofurfuryl acrylate, (methyl) propylene acid dihydride dimerization Cyclopentadienyl group epoxide ethyl ester, (methyl) nonylphenol acrylate phenyl ester (such as 2～10 mol propylenoxies of polypropylene oxide Modified (methyl) nonylphenol acrylate phenyl ester).Particularly from from the viewpoint of the flexibility of resin, preferred (methyl) acrylic acid carbon The Arrcostab of atomic number 10～30, (methyl) propylene acid dihydride dicyclopentadiene base epoxide ethyl ester, polypropylene oxide (methyl) nonylphenol acrylate phenyl ester (modified (methyl) the nonylphenol acrylate phenyl ester of such as 2～10 mol propylenoxies), (methyl) Tetrahydrofurfuryl acrylate.
On the other hand, from from the viewpoint of improving the adaptation to glass, preferably (methyl) acrylic acid has the carbon of hydroxyl The Arrcostab of atomic number 1～5, acryloyl morpholine, particularly preferred acryloyl morpholine.
More preferably all (100%) is made up of (B ') composition above-mentioned preferred compound.
Used as the Arrcostab of (methyl) acrylic acid carbon number 10～30, preferred compound is that (methyl) acrylic acid carbon is former The Arrcostab of subnumber 12～25, specifically from foregoing illustrative (methyl) lauryl acrylate to (methyl) acrylic acid 2- last of the ten Heavenly stems Exemplary compounds till base tetradecane ester, most preferably (methyl) lauryl acrylate and (methyl) acrylic acid 2- decyls 14 Alkyl ester.
In the resin combination of the present invention, contain in the range of characteristic of the present invention multifunctional (methyl) third not damaging Enoic acid ester compounds.Can enumerate for example：Tricyclodecane Dimethanol two (methyl) acrylate, dioxane glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate, alkylene oxide Modified bisphenol A type two (methyl) acrylate, two (methyl) acrylate of caprolactone modification 3-hydroxypivalic acid neopentyl glycol and ring Oxidative ethane modified phosphate two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, three (first of trihydroxy methyl octane Base) trihydroxy methyl C2～C10 alkane three (methyl) acrylate, the trimethylolpropane polyethoxy three (methyl) such as acrylate Poly- propoxyl group three (methyl) acrylate of acrylate, trimethylolpropane, the poly- propoxyl group three of trimethylolpropane polyethoxy The trihydroxy methyl C2 such as (methyl) acrylate～C10 alkane poly-alkoxyl three (methyl) acrylate, three [(methyl) acryloyl-oxies Base ethyl] isocyanuric acid ester, tetramethylolmethane three (methyl) acrylate, ethylene-oxide-modified trimethylolpropane tris (methyl) third The alkylene oxides such as olefin(e) acid ester, epoxy pronane modification trimethylolpropane tris (methyl) acrylate modification trimethylolpropane tris (first Base) acrylate, tetramethylolmethane polyethoxy four (methyl) acrylate, poly- propoxyl group four (methyl) acrylic acid of tetramethylolmethane Ester, tetramethylolmethane four (methyl) acrylate, double trimethylolpropane 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, simple function or dual functional (methyl) acrylate is preferably used.
In order to further reduce cure shrinkage, in the resin combination of the present invention, as carbamate (methyl) propylene (B) composition beyond acid esters (D), relative to the total amount of (B) composition beyond (D) composition, containing at least 50 weight %, preferably At least 70 weight %, more preferably at least 80 weight %, further preferably at least 90 weight %, above-mentioned (B ') of most preferably 100 weight % Composition.
In the resin combination of the present invention, (B) composition beyond above-mentioned carbamate (methyl) acrylate (D) can be with Use using a kind or so that arbitrary proportion mixes two or more.(B) beyond carbamate (methyl) acrylate (D) into Point the present invention light-cured type transparent adhesive compositionss in part by weight be usually 5～70 weight %, preferably 5～50 Weight %, more preferably 10～40%.
(methyl) acrylate compounds (B ') particularly preferably with 1 (methyl) acryloyl group are the feelings of above-mentioned content Condition.
When the content of above-mentioned (B) composition beyond carbamate (methyl) acrylate (D) is very few, lack curable, When excessive, shrink and become big.
For carbamate (methyl) acrylate (D) that can contain in the present compositions, as long as It is carbamate (methyl) acrylate, then can uses.Preferably by making polyhydric alcohol, polyisocyanates and hydroxyl (methyl) acrylate reactions obtained from carbamate (methyl) acrylate.More preferably there is the poly- of polyether structure Ether carbamate (methyl) acrylate.
As the polyhydric alcohol used in the synthesis of carbamate (methyl) acrylate, can enumerate for example：New penta The Asia of the carbon numbers 1～10 such as glycol, 3- methyl isophthalic acids, 5- pentanediols, ethylene glycol, Propylene Glycol, 1,4- butanediols, 1,6-HD Alkyl diol；The trihydroxylic alcohols such as trimethylolpropane, tetramethylolmethane；Tricyclodecane Dimethanol, double [methylol] hexamethylene etc. have Alcohol of cyclic skeleton etc.；And by above-mentioned polyhydric alcohol and polyprotic acid (for example, succinic acid, phthalic acid, hexahydro O-phthalic Anhydride, p-phthalic acid, adipic acid, Azelaic Acid, tetrabydrophthalic anhydride etc.) the PEPA that obtains of reaction；Pass through The caprolactone alcohol that the reaction of polyhydric alcohol and 6-caprolactone is obtained；Polycarbonate polyol is (for example by 1,6-HD and carbonic acid PCDL that the reaction of diphenyl ester is obtained etc.)；Or polyether polyol (such as Polyethylene Glycol, polypropylene glycol, poly- four methylene Base glycol, ethylene-oxide-modified bisphenol-A etc.) etc..From the viewpoint of the flexibility of the resin from after solidification, preferred, polyethers are polynary Alcohol.From with the compatibility of (A) composition from the viewpoint of, more preferably polypropylene glycol is from from the viewpoint of the adaptation to base material, special Other preferred molecular weight is more than 2000 polypropylene glycol.
As organic multiple isocyanate, can enumerate for example：Isophorone diisocyanate, two Carbimide. of hexa-methylene Ester, toluene di-isocyanate(TDI), XDI, diphenyl methane -4,4 ' two polycyclopentadithio.henes of-diisocyanate or tetrahydrochysene Thiazolinyl isocyanates etc..
From from the viewpoint of the transparency, preferably isophorone diisocyanate or toluene di-isocyanate(TDI).
In addition, as (methyl) acrylate of hydroxyl, such as can use：(methyl) Hydroxyethyl Acrylate, (first Base) (methyl) dihydroxypropyl C2～C4 Arrcostabs such as hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, single (methyl) Acrylic acid dihydroxymethyl cyclohexyl, hydroxyl caprolactone (methyl) acrylate etc..
Above-mentioned reaction is for example carried out as follows.That is, with relative to every 1 equivalent of its hydroxyl, organic polyisocyanic acid in polyhydric alcohol The NCO of ester is preferably 1.1～2.0 equivalents, the mode of more preferably 1.1～1.5 equivalents and mixes organic polyisocyanic acid Ester, makes which react and synthesis of carbamates oligomer under preferably 70～90 DEG C of reaction temperature.Then, with relative to ammonia Every 1 equivalent of the NCO of carbamate oligomer, the hydroxyl of hydroxyl (methyl) acrylate compounds are preferably 1～1.5 The mode of equivalent mixes hydroxyl (methyl) acrylate compounds, reacts which such that it is able to obtain conduct at 70～90 DEG C Carbamate (methyl) acrylate of target.
As the weight average molecular weight of carbamate (methyl) acrylate (D), preferably from about 7000～about 25000, more excellent Choosing about 10000～about 20000.When weight average molecular weight is too small, shrinks and become big, when weight average molecular weight is excessive, curable is deteriorated.
In the resin combination of the present invention, these (D) compositions can be using a kind or so that arbitrary proportion mixes two or more Use.(D) part by weight of the composition in the light-cured type transparent adhesive compositionss of the present invention is usually 20～80 weight %, Preferably 25～50 weight %.
In the resin combination of the present invention, above-mentioned (D) composition and above-mentioned (methyl) third with 1 (methyl) acryloyl group Total content of enoic acid ester compounds (B ') is preferably at least 40 weight % relative to the total amount of the resin combination, more preferably At least 50 weight %.
(methyl) third with polyisoprene and/or polybutadiene skeleton can be contained in the resin combination of the present invention Olefin(e) acid ester oligomer is used as (methyl) acrylate compounds (B).As with polyisoprene and/or polybutadiene skeleton (methyl) acrylate oligomer, as long as known compound, then can be not particularly limited to use.
As above-mentioned (methyl) acrylate oligomer with polyisoprene and/or polybutadiene skeleton, can be with excellent Choosing use (a) first synthesize isoprene copolymer, butadiene polymer or their copolymer, then make unsaturated acid anhydride and this A little polymer reactions, then make part or all in hydroxyl (methyl) acrylate compounds and obtained polymer anti- Should obtained from oligomer, or (b) make unsaturated carboxylic acid or derivatives thereof and C-terminal isoprene copolymer, hydroxyl end End butadiene polymer or oligomer obtained from their copolymer reaction.
First, isoprene copolymer, butadiene polymer or their copolymer are first synthesized to (a), then makes insatiable hunger With anhydride and these polymer reactions, in hydroxyl (methyl) acrylate compounds and obtained polymer is then made Divide or oligomer obtained from total overall reaction is illustrated.
As above-mentioned isoprene copolymer, butadiene polymer, it is possible to use by by isoprene and/or butadiene In a kind of homopolymerization obtained from isoprene copolymer or butadiene polymer, it is also possible to using by making isoprene and fourth Isoprene-butadiene copolymer obtained from the mixture copolymerization of diene.Hereinafter, they are referred to as oligomer use in the lump poly- Compound.
Method as making which be polymerized, can pass through isoprene and/or butadiene with lithium methide, ethyl-lithium, Zhong Ding The lithium alkylides such as base lithium, n-BuLi, amyl group lithium, sodium naphthalene complex carry out anionic polymerisation as initiator and obtain, it is also possible to By the azo such as the peroxide such as benzoyl peroxide, azodiisobutyronitrile dinitrile compound is carried out free radical as initiator It is polymerized and manufactures.
In addition, these polyreactions can in the presence of hexane, heptane, toluene, dimethylbenzene equal solvent, -100 DEG C～ React 0.5～100 hour at 200 DEG C and carry out.
From from the viewpoint of giving flexibility, the number-average molecular weight of the above-mentioned oligomer polymer used in the present invention is led to It is often 2000～100000, preferably 5000～50000, particularly preferred 20000～50000.
Then, unsaturated acid anhydride and the oligomer polymer reaction obtained by said method are made.The reaction for example may be used With by make above-mentioned polymer and unsaturated acid anhydride in hexane, heptane, toluene, dimethylbenzene equal solvent etc. to reaction as inert molten Generally react 0.5～100 hour at room temperature～300 DEG C in the presence of agent or under condition of no solvent and carry out.
As unsaturated acid anhydride, for example, can use：Maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, first Base hexahydrophthalic anhydride etc..
The usage amount of the anhydride is commonly angled relative to above-mentioned 100 weight portion of oligomer polymer and is preferably 0.1～200 weight The scope of part, in the range of more preferably 0.1～100 weight portion.
In using the addition of the reaction to above-mentioned polymer of anhydride group, reacted by making which under these conditions, generally per 1 The adduct number of molecule is the scope of 1～30, the scope of preferably 2～20.
Then, by making the part of the anhydride group imported in hydroxyl (methyl) acrylate compounds and above-mentioned polymer Or all reacted, (methyl) acrylate oligomer with polyisoprene skeleton can be obtained, there is polybutadiene (methyl) acrylate oligomer of skeleton or (methyl) acrylate with polyisoprene-polybutadiene copolymer skeleton Oligomer.
Reaction can pass through hexane, heptane equal solvent or solvent-free in the presence of, generally by hydroxyl (methyl) acrylate Compound is mixed in the way of making its hydroxyl be preferably 1～1.5 equivalent and reacts 0.1～100 hour at 20～200 DEG C and obtain Arrive.
As hydroxyl (methyl) acrylate compounds, for example, can use：(methyl) Hydroxyethyl Acrylate, (methyl) (methyl) dihydroxypropyl C2～C4 Arrcostabs such as hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, single (methyl) third Olefin(e) acid dihydroxymethyl cyclohexyl, hydroxyl caprolactone (methyl) acrylate etc..
Then, (b) is obtained by making unsaturated carboxylic acid or derivatives thereof with the isoprene copolymer containing hydroxyl, fourth The diene polymer or method of oligomer is illustrated obtained from their copolymer reaction.
By making unsaturated carboxylic acid or derivatives thereof with C-terminal isoprene copolymer, C-terminal polymerizing butadiene Part or all of reaction of thing or C-terminal isoprene-butadiene copolymer, can obtain with polyisoprene bone (methyl) acrylate oligomer of frame, (methyl) acrylate oligomer with polybutadiene skeleton have isoamyl two (methyl) acrylate oligomer of alkene-butadiene copolymer skeleton.
Reaction can pass through under hexane, heptane equal solvent or solvent-free in the presence of, generally make unsaturated carboxylic acid or its spread out Biology reacts 0.1～100 hour at 20～200 DEG C and obtains.
As unsaturated carboxylic acid or derivatives thereof, for example, can use：Acrylic acid, methacrylic acid, maleic acid, α-ethyl The unsaturated carboxylic acids such as acrylic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyl tetrahydrophthalic acid and it Carboxylic acid halides, amide, acid imide, acid anhydride, the derivant such as ester.
As the concrete example of the compound for so obtaining, can illustrate：UC-203 (the isoprene of Kuraray company manufacture The carboxylate oligomer of the maleic anhydride adduct of polymer and 2-hydroxyethyl methacrylate), Cao Da companies of Japan manufacture NISSO-PB TE-2000 (two terminal methacrylate modified butadiene quasi-oligomers) etc..
In the resin combination of the present invention, these have (methyl) acrylate of polyisoprene, polybutadiene skeleton Oligomer can be used using a kind or so that arbitrary proportion mixes two or more.There is polyisoprene, polybutadiene skeleton Part by weight of (methyl) acrylate oligomer in the ultraviolet curing adhesive of the present invention is usually 5～90 weight %, Preferably 20～80 weight %, more preferably 25～50 weight %.
(methyl) acrylate oligomer can be used in combination with above-mentioned carbamate (methyl) acrylate (D), according to feelings Condition, it is also possible to replace carbamate (methyl) acrylate (D) and use.
The Photoepolymerizationinitiater initiater (C) contained in compositionss as the present invention, is not particularly limited, can enumerate for example： 1- hydroxycyclohexyl phenyl ketones (イ Le ガ キ ュ ア (registered trade mark, similarly hereinafter) 184；BASF AG manufacture), 2- hydroxyl -2- first Base [4- (1- methyl ethylenes) phenyl] propanol oligomer (エ サ キ ュ ア ONE；Lamberti manufacture), 1- [4- (2- hydroxyls Ethyoxyl) phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone (イ Le ガ キ ュ ア 2959；BASF AG manufacture), 2- hydroxyls- 1- { 4- [4- (2- hydroxy-2-methyl propionos) benzyl] phenyl } -2- methylpropane -1- ketone (イ Le ガ キ ュ ア 127；BASF Company manufacture), 2,2- dimethoxy -2- phenyl acetophenones (イ Le ガ キ ュ ア 651；BASF AG manufacture), 2- hydroxyl -2- first Base -1- phenyl-propane -1- ketone (ダ ロ キ ュ ア (registered trade mark) 1173；BASF AG manufacture), 2- methyl isophthalic acids-[4- (first sulfur Base) phenyl] -2- morpholinopropane -1- ketone (イ Le ガ キ ュ ア 907；BASF AG manufacture), phenyl acetic acid 2- [2- oxygen Generation -2- phenyl-acetoxies-ethyoxyl] ethyl ester and phenyl acetic acid 2- [2- Hydroxy-ethoxies] ethyl ester mixture (イ ルガキュア754；BASF AG manufacture), 2- benzyl -2- dimethylamino -1- (4- morpholino phenyls) butane -1- ketone, 2- chlorine Thiaxanthone, 2,4- dimethyl thioxanthones, 2,4- diisopropylthioxanthones, isopropyl thioxanthone, 2,4,6- trimethylbenzoyls Diphenyl phosphine oxide, double (2,4,6- trimethylbenzoyls) phenyl phosphine oxides, double (2,6- Dimethoxybenzoyls) -2,4, 4- trimethylpentylphosphine oxides etc..From transparency consideration, preferably 1- hydroxycyclohexyl phenyl ketones (イ Le ガ キ ュ ア 184； BASF manufacture), 2- hydroxy-2-methyls [4- (1- methyl ethylenes) phenyl] propanol oligomer (エ サ キ ュ ア KIP-150；Rather Bai Di companies manufacture), phenylglyoxalates methyl ester (ダ ロ キ ュ ア MBF；BASF manufacture), phenyl acetic acid 2- [2- oxo -2- Phenyl-acetoxy-ethyoxyl] ethyl ester and phenyl acetic acid 2- [2- Hydroxy-ethoxies] ethyl ester mixture (イ Le ガ キ ュア754；BASF AG manufactures).In addition, from from the viewpoint of making adhesive inside solidification good, preferably 2,4,6- front threes Base benzoyl diphenyl phosphine oxide (ス ピ De キ ュ ア TPO；LAMBSON company is manufactured).
In the resin combination of the present invention, these (C) compositions can be using a kind or so that arbitrary proportion mixes two or more Use.(C) part by weight of the composition in the light-cured type transparent adhesive compositionss of the present invention is usually 0.2～5 weight %, Preferably 2～5 weight %.
Here, only using TMDPO in order to improve the transparency as photopolymerization During initiator, the part by weight preferably in the light-cured type transparent adhesive compositionss of the present invention is usually 0.3～1.0 weight Amount %, particularly preferably 0.3～0.8 weight %.
Additionally, as the other compositions beyond above-mentioned (A), (B) and (C), it is also possible to be possible to as needed poly- as light Close amine of initiation auxiliary agent etc. to be used in combination with above-mentioned Photoepolymerizationinitiater initiater.As amine that can be used etc., can enumerate：Benzene first Sour 2- dimethylaminoethyls, dimethylamino 1-Phenylethanone., (dimethylamino)-ethyl benzoate or IADB Deng.During using photopolymerization initiator auxiliary agents such as the amines, the content in the gluing use resin combination of the present invention is usually 0～5 weight Amount %, is 0.005～5 weight % during interpolation, preferably 0.01～3 weight %.
In addition, as other compositions, oxetane compound can be contained as needed.The oxa- ring fourth that can be used As long as the known compound of hydride compounds, is not particularly limited.
As the concrete example of oxetane compound, can enumerate for example：The double [(3- ethyl -3- oxetanyls of 4- Methoxyl group) methyl] benzene, 4- double [(3- methyl -3- oxetanylmethoxies) methyl] benzene, 3- methyl -3- glycidyls Oxetanes, 3- ethyl -3- hydroxymethyl-oxetanes, 3- methyl -3- hydroxymethyl-oxetanes, two (1- ethyls (3- oxygen Azetidinyl)) methyl ether, 3- ethyl -3- (phenoxymethyl) oxetanes, 3- (cyclohexyloxy) methyl -3- ethyl oxygen Azetidine, phenylenedimethylidyne dioxygen azetidine, phenol novolacs oxetanes etc..As long as the oxa- being usually used Tetramethylene. compound, then not limited to this.These oxetane compounds can be used alone, it is also possible to using two or more.
In the ultraviolet curing adhesive of the present invention, these oxetane compounds can use a kind or with any Ratio mixes two or more and uses.Weight of the oxetane compound in the light-cured type adhesive compound of the present invention Ratio is usually 0～70 weight %, is 5～70 weight % during interpolation, preferably 5～50 weight %.
In addition, in the compositionss of the present invention, not damaging in the range of characteristic of the present invention, it is possible to use epoxy (methyl) third Olefin(e) acid ester is used as other compositions.Epoxy (methyl) acrylate has to be improved curable and makes the hardness of solidfied material, solidification speed The function that degree is improved.In addition, as epoxy (methyl) acrylate, as long as by make diglycidyl ether type epoxy compound with Obtained from (methyl) propylene acid reaction, epoxy (methyl) acrylate, then can use, as preferably use for To the diglycidyl ether type epoxy compound of epoxy (methyl) acrylate, bisphenol-A or its alkylene oxide addition product can be enumerated Diglycidyl ether, the diglycidyl ether of Bisphenol F or its alkylene oxide addition product, hydrogenated bisphenol A or its alkylene oxide addition product Diglycidyl ether, the diglycidyl ether of A Hydrogenated Bisphenol A F or its alkylene oxide addition product, Ethylene glycol diglycidyl ether, the third two Alcohol diglycidyl ether, neopentylglycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, ring Hexane dimethanol diglycidyl ether, polypropylene glycol diglycidyl ether etc..
Epoxy (methyl) acrylate can be by making these diglycidyl ether type epoxy compounds and (methyl) acrylic acid React under conditions of as described below and obtain.
(methyl) acrylic acid is made to rub as 0.9～1.5 with 1 equivalent of epoxy radicals relative to diglycidyl ether type epoxy compound You, more preferably 0.95～1.1 mole of ratio are reacted.Reaction temperature is preferably 80～120 DEG C, and the response time is for about 10 Hour～about 35 hours.In order to promote to react, such as triphenylphosphine, TAP, triethanolamine, tetraethylammonium chloride etc. is preferably used Catalyst.In addition, in reaction, in order to prevent being polymerized, it is also possible to use such as p methoxy phenol, methylnaphthohydroquinone etc. as inhibition Agent.
As epoxy (methyl) acrylate that can be preferably used in the present invention, it is by the epoxy compound of bisphenol A-type Bisphenol type epoxy (methyl) acrylate that thing is obtained.In the present invention, as dividing equally for epoxy (methyl) acrylate (G) again Son amount, preferably 500～10000.
In the resin combination of the present invention, these epoxies (methyl) acrylate can use a kind or mixed with arbitrary proportion Close two or more and use.Weight of epoxy (methyl) acrylate in the light-cured type transparent adhesive compositionss of the present invention Ratio is usually 0～90 weight %, is 5～90 weight % during interpolation, preferably 10～85 weight %.
In the resin combination of the present invention, softening ingredient can be used as needed as other compositions.As can make The concrete example of softening ingredient, can enumerate：There are polyisoprene, (methyl) acrylate oligomers of polybutadiene skeleton Thing or its carboxylate, polymer, oligomer, phthalate, phosphoric acid ester, diol-lipid, aliphatic dibasic acid ester, Fatty acid ester, citric acid ester type, epoxy plasticiser, Semen Ricini oils, terpenes hydrogenated resin etc..As oligomer, polymerization The example of thing, can illustrate the oligomer or polymer of polyisoprene class, polybutadiene or xylene.
Part by weight of the softening ingredient in light-cured type transparent adhesive compositionss is usually 10～80 weight %, excellent Elect 10～70 weight % as.
Further, it is possible to use (methyl) acrylate copolymer is used as softening ingredient.
(methyl) acrylate copolymer can be enumerated using acrylic compounds or methacrylic monomer as polymerizable raw material Into polymer or the monomer beyond other polymerizable monomers and the monomer copolymer, polymerisation in solution, suspension can be passed through The usual ways such as polymerization, polymerisation in bulk are manufacturing.
As particularly preferred manufacture method, preferably continuously carry out radical polymerization at high temperature and manufacture.Concrete and Speech, is manufactured by following technique.First, relative to acrylic compounds or methacrylic monomer, mix micro polymerization Initiator and micro solvent.Then, at the temperature more than 150 DEG C so as to react more than 10 minutes under high pressure.Then, Unreacted component and (methyl) acrylate copolymer that obtains of reaction can be separated into using seperator and be obtained.
If here, being mixed into polymerization initiator, storage stability possible deviation, it is therefore preferable that when solvent is evaporated Reacted, or, solvent is evaporated after isolated (methyl) acrylate copolymer.
As the acrylic compounds or methacrylic monomer of the raw material for being used as (methyl) acrylate copolymer, Ke Yilie Lift：(methyl) acrylic acid, α-ethylacrylate；(methyl) acrylic acid methyl ester., (methyl) n-propyl, (methyl) acrylic acid Isopropyl ester, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid 2- ethyl butyl esters, (methyl) acrylic acid 1,3- dimethyl butyl esters, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid 2- ethyl hexyls Ester, (methyl) 1-Octyl acrylate, (methyl) acrylic acid 3- ethyoxyl propyl ester, (methyl) acrylic acid 3- Ethoxybutyls, (methyl) Acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) hydroxy butyl acrylate, (methyl) acrylic acid The esters such as α-(methylol) ethyl ester, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) phenylethyl acrylate (methyl) acrylate etc., it is possible to use these monomers one kind or two or more.
As can be with other polymerizable monomers of copolymerization, it is possible to use the known compound with unsaturated double-bond, can To enumerate for example：Styrene, 3- nitrostyrolenes, 4- methoxy styrenes；α-methyl styrene, Beta-methyl styrene, 2,4- The ring-alkylated styrenes classes such as dimethyl styrene, vinyltoluene, α-ethyl styrene, α-butylstyrene, α-hexyl styrene； The halogenated styrenes classes such as 4- chlorostyrenes, 3- chlorostyrenes, 3- bromstyrols；.beta.-methylacrylic acid, tiglic acid, α-ethyl crotonic The carboxylic acid with unsaturated double-bond such as acid, iso-crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, paraconic acid, glutaconate Class.
Wherein, from the other compositions to compositionss dissolubility, the adhesivity aspect of solidfied material, used as acrylic compounds Or methacrylic monomer, preferably：(methyl) acrylic acid methyl ester., (methyl) n-butyl acrylate, (methyl) acrylic acid 2- second (methyl) acrylic acid C1～C10 Arrcostabs such as the own ester of base, (methyl) 1-Octyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, (first Base) (methyl) acrylic acid such as hydroxy butyl acrylate has C1～C10 Arrcostabs of hydroxyl, as other polymerizable monomers, Optimization styrene etc..
In the present invention, the weight average molecular weight of (methyl) acrylate copolymer is 1500～30000, preferably 3000～ 20000, particularly preferably 5000～15000.When weight average molecular weight is too small, the adhesivity of solidfied material has the tendency of variation, another Aspect, when excessive, it is not easy to is dissolved in other monomers, or produces nebulousurine, thus not preferred.
(methyl) acrylate copolymer can also be readily available in the way of commercially available product.For example, it is possible to enumerate East Asia conjunction Into " the ARUFON series " of Co., Ltd.'s manufacture, can be obtained in the way of UP-1170, UH-2190.
Part by weight of (methyl) acrylate copolymer in the light-cured type adhesive compound of the present invention is usually 20 Weight %～95 weight %, preferably 50 weight %～95 weight %, more preferably from about 70 weight %～about 95 weight %, particularly preferred 70 weight Amount %～90 weight %.
Antioxidant, organic solvent, silane coupled can be further added as needed in the resin combination of the present invention Agent, polymerization inhibitor, levelling agent, antistatic additive, surface lubricant, fluorescent whitening agent, light stabilizer (for example, hindered amine compound Deng), the additive such as filler is used as other compositions.
As the concrete example of antioxidant, can enumerate for example：Double (n-octyl the sulfenyl) -6- of BHT, 2,4- (4- hydroxyl -3, 5- di-tert-butyl amidos) -1,3,5- triazines, tetramethylolmethane four [3- (3,5- di-t-butyl -4- hydroxyphenyl) propionic ester], 2,2- Double [3- (the 3- tert-butyl group -5- the first of sulfenyl di ethylene bis [3- (3,5- di-t-butyl -4- hydroxyphenyl) propionic ester], triethylene glycol Base -4- hydroxyphenyl) propionic ester], 1,6-HD double [3- (the 3- tert-butyl group -5- methyl -4- hydroxyphenyl) propionic ester], octadecane Base -3- (3,5- di-t-butyl -4- hydroxyphenyl) propionic ester, N, N- hexamethylene bis (3,5- di-t-butyl -4- hydroxy group Cortex Cinnamomis Amide), 1,3,5- trimethyls -2,4,6- three (3,5- di-t-butyl -4- acrinyls) benzene, three (3,5- di-t-butyl -4- hydroxyl benzyls Base) isocyanuric acid ester, octylated diphenylamine, double [(pungent sulfenyl) methyl] orthoresols of 2,4-, iso-octyl -3- (3,5- di-t-butyls - 4- hydroxyphenyl) propionic ester], dibenzylatiooluene etc..
As the concrete example of organic solvent, can enumerate for example：The alcohols such as methanol, ethanol, isopropanol, dimethylsulfone, diformazan Sulfoxide, tetrahydrofuran, dioxane, toluene, dimethylbenzene etc..
As the concrete example of silane coupler, can enumerate for example：3- glycidoxypropyltrime,hoxysilanes, 3- rings Oxygen propoxypropyl methyl dimethoxysilane, 3- glycidoxypropyl dimethoxysilanes, 2- (3,4- epoxy hexamethylenes Base) ethyl trimethoxy silane, N- (2- aminoethyls) 3- aminopropyltriethoxy dimethoxysilanes, γ-mercaptopropyi trimethoxy Silane, N- (2- aminoethyls) 3- aminopropyltriethoxy trimethoxy silanes, 3- aminopropyl triethoxysilanes, 3- mercaptopropyi front threes TMOS, vinyltrimethoxy silane, N- (2- (vinyl-benzylamino) ethyl) 3- aminopropyl trimethoxysilane salt Hydrochlorate, 3- methylpropionyloxy propyl trimethoxy silicanes, 3- chloropropylmethyldimethoxysilanes, 3- r-chloropropyl trimethoxyls The silane coupling agents such as silane；Isopropyl (N- ethylamino-ethyl amino) titanate esters, three isostearoyl base titanate esters of isopropyl, two (dioctylphyrophosphoric acid ester) titanium containing fluoroacetic acid, tetra isopropyl two (dioctyl phosphito ester) titanate esters, three (p- N- of new alkoxyl (β-aminoethyl) aminophenyl) titanate esters etc. contain titanium coupling agent；Acetylacetone,2,4-pentanedione zirconium, methacrylic acid zirconium, propanoic acid zirconium, new zirconium alkoxide Acid esters, three new trineodecanoyl zirconate of new alkoxyl, new alkoxyl three (lauroyl) benzenesulfonyl zirconate, new alkoxyl three (ethylene amino-ethyl) zirconate, new alkoxyl three (m-aminophenyl base) zirconate, zirconium carbonate ammonium, aluminium acetylacetonate, first Base acrylic acid aluminum, propanoic acid aluminum etc. are containing zirconium coupling agent or containing aluminum coupling agent etc..
As the concrete example of polymerization inhibitor, can enumerate：P methoxy phenol, methylnaphthohydroquinone etc..
As the concrete example of light stabilizer, can enumerate for example：1,2,2,6,6- pentamethyl -4- piperidine alcohols, 2,2,6,6- (Ai Dike Co., Ltd. manufactures, LA- for tetramethyl -4- piperidine alcohols, 1,2,2,6,6- pentamethyl -4- piperidine esters of (methyl) acrylic acid 82), 1,2,3,4- ethylene-dimalonic acids four (1,2,2,6,6- pentamethyl -4- piperidyls) ester, 1,2,3,4- ethylene-dimalonic acids four (2, 2,6,6- tetramethyl -4- piperidyls) ester, 1,2,3,4- ethylene-dimalonic acids and 1,2,2,6,6- pentamethyl -4- piperidine alcohols and 3,9- Double (2- hydroxyl -1,1- dimethyl ethyls) undecanoic mixed ester compounds of four oxaspiros of -2,4,8,10- [5.5], decanedioic acid are double (2,2,6,6- tetramethyl -4- piperidyls) sebacate, double (1- hendecane epoxide -2,2,6,6- tetramethyl piperidine -4- bases) carbon Acid esters, methacrylic acid 2,2,6,6- tetramethyl -4- piperidine esters, decanedioic acid double (2,2,6,6- tetramethyl -4- piperidyls) ester, the last of the ten Heavenly stems Diacid double (1,2,2,6,6- pentamethyl -4- piperidyls) 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 piperidines, methacrylic acid 1,2,2,6,6- pentamethyl -4- piperidine esters, double (1,2,2,6,6- pentamethyl -4- Piperidyl) [[3,5- double (1,1- dimethyl ethyls) -4- hydroxyphenyl] methyl] butylmalonic acid ester, the double (2,2,6,6- of decanedioic acid Tetramethyl -1 (octyloxy) -4- piperidyls) ester, the product of 1,1- dimethyl ethyls hydrogen peroxide and octane, N, N ', N ' ', N ' ' '-four (double (butyl (N- methyl -2,2,6,6- tetramethyl piperidine -4- bases) amino) triazine -2- bases of 4,6-) -4,7- diazas Decane -1,10- diamidogen, dibutyl amine -1,3,5- triazine-N, N '-bis- (2,2,6,6- tetramethyl -4- piperidyl -1,6- hexa-methylenes The condensation polymer of diamidogen and N- (2,2,6,6- tetramethyl -4- piperidyls) butylamine, poly- [[6- (1,1,3,3- tetramethyl butyls) amino - 1,3,5- triazine -2,4- diyls] [(2,2,6,6- tetramethyl -4- piperidyls) imino group] hexa-methylene [(2,2,6,6- tetramethyls Base -4- piperidyls) imino group]], the polymer of dimethyl succinate and 4- hydroxyl -2,2,6,6- tetramethyl -1- piperidine ethanols, Two spiral shell [5.1.11.2] 21 of 2,2,4,4- tetramethyl -20- (β-Laurel Epoxide carbonyl) ethyl -7- oxa- -3,20- diazas Alkane -21- ketone, Beta-alanine N,-(2,2,6,6- tetramethyl -4- piperidyls) dodecane ester/tetradecane ester, N- acetyl group -3- ten Dialkyl group -1- (2,2,6,6- tetramethyl -4- piperidyls) pyrrolidine-2,5-dione, 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- diazabicylos [5, 1,11,2] heneicosane -20- propanoic acid dodecane ester/tetradecane ester, malonic acid [(4- methoxyphenyls) methylene] double (1,2, 2,6,6- pentamethyl -4- piperidyls) ester, the high-grade aliphatic ester of 2,2,6,6- tetramethyl -4- piperidine alcohols, N, N '-bis- (2,2,6, 6- tetramethyl -4- piperidyls) benzophenone compound, the 2- (2H- such as hindered amines, the octabenzone such as -1,3- benzenedicarboxamides Benzotriazole -2- bases) -4- (1,1,3,3- tetramethyl butyls) phenol, 2- (2- hydroxy-5-methyl base phenyl) benzotriazole, 2- [2- Hydroxyl -3- (3,4,5,6- tetrahydric phthalimides-methyl) -5- aminomethyl phenyls] benzotriazole, 2- (the 3- tert-butyl group -2- hydroxyls Base -5- aminomethyl phenyls) -5- chlorobenzotriazoles, 2- (2- hydroxyl -3,5- di-tert-pentyl-phenyls) benzotriazole, 3- (3- (2H- benzos Triazole -2- bases) -5- the tert-butyl group -4- hydroxyphenyl) product of methyl propionate and Polyethylene Glycol, 2- (2H- benzotriazole -2- Base) benzotriazole compound, the 2,4- di-tert-butyl-phenyl -3,5- di-t-butyl -4- hydroxyls such as -6- dodecyl -4- cresol The triazines such as the benzoates such as benzoate, 2- (4,6- diphenyl -1,3,5- triazine -2- bases) -5- [(hexyl) epoxide] phenol Class compound etc., particularly preferably hindered amine compound.
As the concrete example of filler, can enumerate for example：Crystalline silica, fused silica, aluminium oxide, zirconium Stone, calcium silicates, Calcium Carbonate, carborundum, silicon nitride, boron nitride, zirconium oxide, forsterite, steatite, spinelle, Titanium Dioxide, The powder body of Talcum etc. makes beadlet etc. obtained from their spheroidizations.
Various additives are optional member, therefore can generally also be zero.When there are various additives in compositionss, various Part by weight of the additive in light-cured type transparent adhesive compositionss be 0.01～3 weight %, preferably 0.01～1 weight Amount %, more preferably 0.02～0.5 weight %.
In order to improve the compatibility, adaptation, the resin combination of the present invention is preferably entered with the composition with propylidene skeleton Row combination.
Specifically, it may be preferred to using containing by compound that m values in formula (1)/(m value+n values) is 0.4～1.0 with The resin combination of carbamate (methyl) acrylate that polypropylene glycol is obtained.
The present invention resin combination can by by above-mentioned each composition at room temperature～80 DEG C mixed dissolution and obtain, Field trash can be removed as desired by the operation such as filtration.Consider that coating, the gluing of the present invention use resin combination It is preferred that in the way of making the scope that 25 DEG C of viscosity is 300～15000mPa s appropriate modifying ingredients proportioning.
The cure shrinkage of the resin combination of the present invention is preferably less than 3.0%, particularly preferably less than 2.0%.Thus, When ultraviolet-curing resin composition solidifies, the internal stress that accumulates in resin cured matter can be reduced, can be effectively Prevent from producing strain in base material with the interface of the layer being made up of the solidfied material of ultraviolet-curing resin composition.
In addition, in the case where the base materials such as glass are thin, when cure shrinkage is big, warpage during solidification becomes big, therefore can be right Display performance causes big harmful effect, from for the viewpoint, it is also preferred that cure shrinkage is less.
The solidfied material (200 μm of thickness) of the resin combination of the present invention is preferably in the average transmittance of 400nm～800nm More than 90%.This is because, when absorbance is too low, light is difficult to transmission, and when being used in display device, visibility reduces.
In addition, solidfied material is when the absorbance of 400～450nm is high, the raising of visibility can be further expected, therefore, The absorbance of 400～450nm is preferably more than 90%.The higher the better for absorbance, and the upper limit can reach 100%.Be actually 99% with Under.
The resin combination of the present invention contains compound, the carbamate (first with the structure represented by formula (1) Base) acrylate, there is (methyl) acrylate of 1 (methyl) acryloyl group, re-workability is also excellent.
Generally, in order to be reprocessed, after the base material that is fitted is heated, gluing oxidant layer is cut using metal wire, by This carries out the stripping of base material and gluing oxidant layer.Now, use to be easily peeled off in solvent, but the present invention, due to compositionss Composition fissility excellent, even if therefore using the alcohols such as isopropanol also easily can be peeled off as solvent.
Hereinafter, the optimal way of the resin combination of the present invention is illustrated.
A kind of (i) ultraviolet-curing resin composition, the compound containing formula (1) (A), (methyl) acrylate chemical combination Thing (B) and Photoepolymerizationinitiater initiater (C), wherein, the molecular weight of the compound (A) of formula (1) is 100～10000.
(ii) ultraviolet-curing resin composition as described above described in (i), wherein, the molecule of the compound (A) of formula (1) Measure as 500～8000.
(iii) ultraviolet-curing resin composition as described above described in (i), wherein, the compound (A) of formula (1) point Son amount is 1000～8000.
(iv) ultraviolet-curing resin composition as described above described in (i), wherein, the molecule of the compound (A) of formula (1) Measure as 1500～5000.
(v) ultraviolet-curing resin composition as described above any one of (i)～(iv), wherein, the change of formula (1) R in compound (A)1And R2It is each independently the thiazolinyl of the alkyl or carbon number 3～10 of carbon number 1～10.
(vi) ultraviolet-curing resin composition as described above described in (v), wherein, R1And R2It is each independently carbon former The alkyl of subnumber 1～6 or the thiazolinyl of carbon number 3～5.
(vii) ultraviolet-curing resin composition as described above any one of (i)～(vi), wherein, m/ (m+n) For 0.2～1.
(viii) ultraviolet-curing resin composition described in (vii) as described above, wherein, m/ (m+n) is 0.4～1.
(ix) ultraviolet-curing resin composition described in (vi) as described above, wherein, it is 10～40, R that n is 5～40, m1 And R2In any one be butyl, another is pi-allyl, or n be 0, m be 20～80, R1And R2It is each independently carbon former The alkyl of subnumber 1～4, preferably methyl.
(x) ultraviolet-curing resin composition as described above described in (vi), wherein, above-claimed cpd (A) be selected from Polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropyleneglycol dibutyl ether, polypropylene glycol pi-allyl butyl ether, poly- Ethylene glycol-polypropylene glycol diallyl ether, polyethylene glycol Propylene Glycol dibutyl ethers and polyethylene glycol Propylene Glycol pi-allyl At least one in the group of butyl ether composition.
(xi) ultraviolet-curing resin composition as described above any one of (i)～(x), wherein, containing amino Formic acid esters (methyl) acrylate (D) and (methyl) acrylate compounds (the B ') conduct with 1 (methyl) acryloyl group (methyl) acrylate compounds (B).
(xii) ultraviolet-curing resin composition described in (xi) as described above, wherein, carbamate (methyl) propylene The weight average molecular weight of acid esters (D) is 7000～25000.
(xiii) ultraviolet-curing resin composition described in (xi) as described above, wherein, carbamate (methyl) third The weight average molecular weight of olefin(e) acid ester (D) is 10000～20000.
(xiv) ultraviolet-curing resin composition any one of (xi)～(xiii) as described above, wherein, amino Formic acid esters (methyl) acrylate (D) is the reaction of polyether polyol and polyisocyanates and (methyl) acrylate of hydroxyl Product.
(xv) ultraviolet-curing resin composition any one of (xi)～(xiv) as described above, wherein, containing choosing The Arrcostab of free (methyl) acrylic acid carbon number 10～30, poly- C2～C4 aklylene glycols (methyl) acrylate, polycyclic Modified (methyl) the nonylphenol acrylate phenyl ester of Ethylene Oxide, (methyl) acrylic acid have the carbon number 1～5 of hydroxyl Arrcostab, Acryloyl morpholine, (methyl) tetrahydrofurfuryl acrylate and (methyl) propylene acid dihydride dicyclopentadiene base epoxide ethyl ester are constituted Group at least one as have 1 (methyl) acryloyl group (methyl) acrylate compounds (B ').
(xvi) ultraviolet-curing resin composition described in (xv) as described above, wherein, containing being selected from (methyl) propylene Sour lauryl, 2- ethylhexyl carbitol acrylate, acryloyl morpholine, (methyl) acrylic acid 4- hydroxybutyls, (methyl) Tetrahydrofurfuryl acrylate, the different stearyl ester of (methyl) acrylic acid, (methyl) nonylphenol acrylate phenyl ester of polypropylene oxide, (first Base) propylene acid dihydride dicyclopentadiene base epoxide ethyl ester, the different stearyl ester of (methyl) acrylic acid, (methyl) acrylic acid 2- decyls ten At least one in the group of four alkyl esters composition is used as (methyl) acrylate compounds with 1 (methyl) acryloyl group (B’).
(xvii) as described above the ultraviolet-curing resin composition any one of (xi)～(xiv), wherein, above-mentioned The content of compound (A) is 10～60 weight %, and the content of Photoepolymerizationinitiater initiater (C) is 0.2～5 weight %, and remainder is (first Base) acrylate compounds (B).
(xviii) ultraviolet-curing resin composition described in (xvii) as described above, wherein, relative to (methyl) propylene The total amount of ester compound (B), carbamate (methyl) acrylate (D) and (first with 1 (methyl) acryloyl group Base) acrylate compounds (B ') total content be 50～100 weight %.
(xix) ultraviolet-curing resin composition described in (xviii) as described above, wherein, relative to the total of (B) composition Amount, (D) total content of composition and (B ') composition is 90～100 weight %.
(xx) ultraviolet-curing resin composition as described above any one of (i)～(xix), wherein, solidification is received Shrinkage is less than 3%.
(xxi) ultraviolet-curing resin composition described in (xx) as described above, wherein, cure shrinkage is less than 2%.
(xxii) ultraviolet-curing resin composition as described above any one of (i)～(xxi), wherein, thickness 200 μm of solidfied material is at least 90% in the average transmittance of 400～800nm.
(xxiii) ultraviolet-curing resin composition as described above any one of (i)～(xxii) is wherein, thick The solidfied material of 200 μm of degree is at least 90% in the average transmittance of 400～450nm.
The resin combination of the present invention is applied using slit coater, roll coater, spin coater, silk screen print method etc. and is arranged Put, the thickness of the resin after to make coating is to be coated on a base material in the way of 10～300 μm, another base material of fitting, from The irradiation of transparent base side is made as the light of for example ultraviolet～near ultraviolet (near 200～400nm of wavelength) of active energy beam Which solidifies, and thus enables which is gluing.Irradiation dose is preferably from about 100mJ/cm2～about 4000mJ/cm2, particularly preferably it is for about 200mJ/cm2～about 3000mJ/cm2.When being solidified by irradiating ultraviolet～near ultraviolet light, as long as irradiation ultraviolet～ The lamp of near ultraviolet light, then no matter how light source can use.For example, it is possible to enumerate low pressure, high pressure or ultrahigh pressure mercury lamp, gold Category Halogen light, (pulse) xenon lamp or electrodeless lamp etc..
The resin combination of the present invention can be suitable for fitting the optical element of more than 2.And, the optics of the present invention Component can be by obtaining above-mentioned at least two optical elements laminating.More specifically, by least two optical elements After using the resin combination laminating of the present invention, to the ultraviolet-curing resin composition being clipped between two optical elements Layer irradiation ultraviolet radiation, thus makes the resin composition layer be solidified to form solidified material layer, thus, it is possible to obtain the optics of the present invention Component.
For the laminating of optical element, for example, the resin group of the present invention is coated with the binding face of an optical element Compound, or be coated with the two faces of binding face of two optical elements being fitted the present invention resin combination, with The binding face of two optical elements is clamped the mode of the coating layer of the resin combination of the present invention and is fitted.
As the optical element, it is not particularly limited, preferably the optical element of tabular or lamellar.As tabular or lamellar Optical element, can enumerate following plates comprising lamella lucida, piece, display body (or show body unit), contact panel (or touch-control Panel unit) etc. as an example.
One of preferred optical component as the present invention, can enumerate the contact panel with protection optical element.
For example, for contact panel, there is the glass system of the transparency electrodes such as electrode ito film on a surface Or 2 optical elements of resinous transparent sheet-like or transparent plate mode for making transparent electrical pole-face opposite using adhesive every Open fraction of gap and fit.One optical element is substrate, optical element of another optical element for touch surface.Enter And, as needed have on the surface of the touch-control surface side of the optical element of touch surface using adhesive laminating screening glass (or Plate), the structure of the protection optical element such as icon sheet (or plate) or cosmetic sheet (or plate).Optical component as the present invention Contact panel be the resin combination for using the present invention as the gluing of at least one of the contact panel position of the structure Contact panel obtained from agent.Therefore, the contact panel is resin combination of at least two optical elements using the present invention The gluing contact panel of solidified material layer.
As the contact panel of the optimal way of the present invention, the touch surface of contact panel can be set forth in and face has thereon Contact panel using the gluing protection optical element of the solidified material layer of the resin combination of the present invention.
In addition, one of other optimal ways can be enumerated and will be had using the solidified material layer of the resin combination of the present invention The gluing display device with contact panel on the display face of the contact panel of protection optical element.
In addition, as one of other preferred optical components of the present invention, can enumerate containing by least two above-mentioned light Learn display dress of the base material using the image display of the gluing optical component of the solidified material layer of the resin combination of the present invention Put.As a most representative example, can enumerate protection optical element or contact panel using tree of the invention The solidified material layer of oil/fat composition is fitted in the display device on the surface of image display screen.In this case, the present invention In, optical element includes both the contact panel before laminating and display body.
The glue of multiple lamella lucidas or piece in addition, the resin combination of the present invention can be suitable as fitting in contact panel Stick is used.
As lamella lucida or piece, it is possible to use using lamella lucida or the piece of various materials.
Specifically, it is possible to use by polyethylene terephthalate (PET), Merlon (PC), polymethyl Sour methyl ester (PMMA), the complex of PC and PMMA, glass, cyclic olefine copolymer (COC), cyclic olefin polymer (COP), triacetyl Lamella lucida or piece that the resin such as cellulose (TAC), acrylic resin (plastics) are made, or the polarization that its multi-disc is laminated { unorganic glass plate and its processed goods are (for example, thoroughly for the functional transparent layer such as plate lamination or piece, the lamella lucida being made up of unorganic glass Mirror, prism, ito glass) } etc..
In addition, in the present invention, the optical element of tabular or lamellar is except including the function such as above-mentioned lamella lucida or piece, polarization plates Property clear layer lamination or piece beyond, also comprising such as multiple feature boards or the piece such as display body such as contact panel, LCD panel or LED Duplexer (hereinafter also referred to functional layer stack).
In the present invention, the optical element of preferably above-mentioned tabular or lamellar.
The resin combination of the present invention can also be used as using the adhesive that contact panel is fitted with piece or plate.
Here, as piece, icon sheet, cosmetic sheet, screening glass can be enumerated, as plate, decorative panel, protection can be enumerated Plate.And, as piece or the material of plate, the material cited by the material as lamella lucida can be applied.In addition, as touch surface The material of plate face, can enumerate glass, the complex of PET, PC, PMMA, PC and PMMA, COC, COP.
The resin combination of the present invention can also be suitable for being used in the display that optical functional materialses are fitted in display device On face.As display device, can be set forth on glass be pasted with the LCD of polarization plates, EL display, EL illumination, Electronic Paper, etc. The display devices such as gas ions display.In addition, as optical functional materialses, can enumerate：Acrylic resin board, PC plate, PET The transparent plastic sheets such as plate, PEN plate, strengthens glass, contact panel etc..
As laminating lamella lucida adhesive material use when, in order to improve visibility, the refractive index of preferred consolidation thing is 1.45～1.55.
When in the range of the refractive index, the specific refractivity with the base material used as lamella lucida can be reduced, can Suppress the diffuse-reflectance of light and reduce light loss.
In addition, being assembled with the optical element (such as optical functional materialses) with the resin combination laminating for using the present invention Display device electronic equipment, such as television set, mini game machine, mobile phone, personal computer etc. be also contained in the present invention In optical component.
Hereinafter, the optimal way of the optical component of the present invention is shown as follows.
(I) a kind of optical component, which is by using ultraviolet any one of above-mentioned (i)～(xxiii) of the invention At least two optical elements are fitted and are obtained by the solidified material layer of line curable resin composition.
(II) optical component described in (I) as described above, wherein, the optical element of laminating is the optics base of tabular or lamellar Material.
(III) optical component described in (II) as described above, wherein, the optical element of a tabular or lamellar of laminating is for protecting The optical element of shield optical element, another tabular or lamellar is contact panel, and obtained optical component is with protection Contact panel with optical element.
(IV) a kind of display device, wherein, an optical element is protection optical element or contact panel, another light Base material is display device, and obtained optical component has the display screen for being fitted in display device using above-mentioned solidified material layer On protection optical element or contact panel.
[embodiment]
Hereinafter, the present invention is further illustrated by embodiment, but the present invention is not by any restriction of these embodiments.
Embodiment 1～11 and comparative example 1
Each starting compound is mixed in the way of reaching the composition shown in table 1 below and prepared each comprising uniformly constituted Ultraviolet-curing resin composition, obtains the present invention and the resin combination for comparing.
In addition, as described below with each composition for referred to as representing in table 1.
ユ ニ セ Off PKA-5016 (trade name)：Polyethylene glycol Propylene Glycol pi-allyl butyl ether (in formula (1), R1 For pi-allyl, R2Compound for butyl, n=15, m=15, number-average molecular weight are 1600), Japan Oil Co manufactures
ユ ニ セ Off PKA-5017 (trade name)：Polyethylene glycol Propylene Glycol pi-allyl butyl ether (in formula (1), R1 For pi-allyl, R2Compound for butyl, n=23, m=23, number-average molecular weight are 2500), Japan Oil Co manufactures
PPG2000-DME：Polypropylene glycol dimethyl ether (in formula (1), R1For methyl, R2For methyl, n=0, m=34, number The compound of molecular weight 2000)
PPG4000-DME：Polypropylene glycol dimethyl ether (in formula (1), R1For methyl, R2For methyl, n=0, m=68, number The compound of molecular weight 4000)
UA-l：Make polypropylene glycol (molecular weight 3000), isophorone diisocyanate, this 3 kinds of acrylic acid 2- hydroxy methacrylates The mol ratio of composition is 1:1.3:2 product.
ACMO：Acryloyl morpholine, Xing Ren Co., Ltd. are manufactured
4-HBA：Acrylic acid 4- hydroxybutyls, Osaka Organic Chemical Industry Co., Ltd. are manufactured
LA：Lauryl acrylate, Osaka Organic Chemical Industry Co., Ltd. are manufactured
FA-512AS：Propylene acid dihydride dicyclopentadiene base epoxide ethyl ester, Hitachi Chemical Co., Ltd. are manufactured
THFA：Tetrahydrofurfuryl acrylate, Osaka Organic Chemical Industry Co., Ltd. are manufactured
M-117：The modified nonylphenol acrylate phenyl ester of 2.5 mol propylenoxies, Toagosei Co., Ltd are manufactured
NP-5P：The modified nonylphenol acrylate phenyl ester of 5 mol propylenoxies, Di-ichi Kogyo Seiyaku Co., Ltd. are manufactured
S-1800A：The different stearyl ester of acrylic acid, chemical industry Co., Ltd. of Xin Zhong villages are manufactured
DTD-A：Acrylic acid 2- decyl tetradecane esters, the manufacture of chemical industry Co., Ltd. of common prosperity society
イ Le ガ キ ュ ア 184 (trade name)：1- hydroxycyclohexyl phenyl ketones, BASF AG are manufactured
KIP-150 (trade name)：2- hydroxy-2-methyls-[4- (1- methyl ethylenes) phenyl] propanol oligomer, Ning Baidi Company manufactures
ス ピ De キ ュ ア TPO (trade name)：TMDPO, LAMBSON are public Department's manufacture
Z-6062 (goods number)：3-mercaptopropyi trimethoxy silane, Dong Li Dow Corning Corporations are manufactured
Following evaluation is carried out using the resin combination of the obtained present invention.
Curable：
Thickness with the resin combination obtained by making is the microscope slide laminating of 200 μm of mode by 2 thickness as 1mm. 2000mJ/cm is carried out to the resin combination that is clamped by microscope slide using high voltage mercury lamp (80W/cm, ozone free) across glass2's Ultraviolet irradiates, and makes resin composition, confirms its solid state.
Zero ... is fully cured
△ ... semi-cured states
× ... uncured
Cure shrinkage：
The thickness that fluorine-containing demoulding agent is coated with by 2 for 1mm microscope slide so that the thickness of obtained resin combination Mode for 200 μm is fitted.Using high voltage mercury lamp (80W/cm, ozone free) across glass to the resin combination clamped by microscope slide Thing carries out 2000mJ/cm2Ultraviolet irradiation so as to solidify, make film gravity test solidfied material.According to JIS K7112B Method determines the proportion (DS) of solidfied material.In addition, determining the liquid specific gravity (DL) of resin combination at 25 DEG C, calculated by following formula Cure shrinkage.
Cure shrinkage (%)=(DS-DL) ÷ DS × 100
◎ ... is less than 2.0%
Zero ... 2.0% less than 3.0%
× ... more than 3.0%
Adhesivity：
By the microscope slide of thickness 0.8mm with the acrylic resin board of thickness 0.8mm so that obtained ultraviolet hardening The thickness of resin combination is that 200 μm of mode is fitted.Using high voltage mercury lamp (80W/cm, ozone free) across glass to by load glass The resin combination that piece is clamped carries out 2000mJ/cm2Ultraviolet irradiation and make evaluation sample.By which in 85 DEG C, 85%RH In the environment of place 250 hours, by visual observation confirming to peel off.
Zero ... without peeling
× ... there is peeling
Flexibility：
Ultraviolet-curing resin composition obtained by making is cured sufficiently, and determines durometer E according to JIS K7215 hard Degree, evaluates flexibility.
◎ ... is less than 10
Zero ... 10 less than 20
× ... more than 20
The transparency：
The thickness that fluorine-containing demoulding agent is coated with by 2 for 1mm microscope slide so that obtained ultraviolet curing resin The thickness of the solidified material layer of compositionss is that 200 μm of mode is fitted.Using high voltage mercury lamp (80W/cm, ozone free) across glass pair 2000mJ/cm is carried out by the resin combination that microscope slide is clamped2Ultraviolet irradiation and make the transparency determine solidfied material. For the transparency, using spectrophotometer (U-3310, new and high technology Co., Ltd. of Hitach) determine 400～800nm and 400～ The absorbance of 450nm.
The absorbance of 400～800nm of ◎ ... is more than 90% and the absorbance of 400～450nm is 90%
The absorbance of zero ... 400～800nm is more than 90% and the absorbance of 400～450nm is 88～90%
× ... the absorbance of 400～800nm is less than 90%
By the result of table 1 it has been confirmed that containing the polyether compound ((B) composition) with the structure represented by formula (1) The invention resin composition of the embodiment 1～11 of (methyl) acrylate compounds ((A) composition) can obtain curable The optical clear of the adhesivity and excellent flexibility of the transparency and base material of the little and solidfied material of contraction during excellent, solidification is gluing Agent.

Claims (23)

1. a kind of ultraviolet-curing resin composition, its contain the structure represented with following formulas (1) compound (A), Selected from (methyl) acrylate compounds (B) and at least one and the Photoepolymerizationinitiater initiater (C) of acryloyl morpholine,
In formula (1), n is 0～40 integer, and m is 10～80 integer, R1And R2Each can be the same or different, be that carbon is former The aryl of the alkyl of subnumber 1～18, the thiazolinyl of carbon number 2～18, the alkynyl of carbon number 2～18 or carbon number 5～18.
2. ultraviolet-curing resin composition as claimed in claim 1, wherein, R1And R2It is each independently carbon number 1 ～10 alkyl or the thiazolinyl of carbon number 3～10.
3. ultraviolet-curing resin composition as claimed in claim 1, wherein, compound (A) is selected from poly- third Glycol diallyl ether, polypropylene glycol dimethyl ether, polypropyleneglycol dibutyl ether, polypropylene glycol pi-allyl butyl ether, poly- second two Alcohol-polypropylene glycol diallyl ether, polyethylene glycol Propylene Glycol dibutyl ethers and polyethylene glycol Propylene Glycol pi-allyl butyl At least one in the group of ether composition.
4. ultraviolet-curing resin composition as claimed in claim 1, wherein, containing having 1 (methyl) acryloyl group (methyl) acrylate compounds (B ') or have 2 (methyl) acryloyl groups (methyl) acrylate compounds conduct (methyl) acrylate compounds (B).
5. ultraviolet-curing resin composition as claimed in claim 1, wherein, containing carbamate (methyl) acrylic acid Ester (D) is used as (methyl) acrylate compounds (B).
6. ultraviolet-curing resin composition as claimed in claim 4, wherein, also contains carbamate (methyl) propylene Acid esters (D) is used as (methyl) acrylate compounds (B).
7. ultraviolet-curing resin composition as claimed in claim 1, wherein, containing carbamate (methyl) acrylic acid Ester (D) and (methyl) acrylate compounds (B ') with 1 (methyl) acryloyl group are used as (methyl) acrylate chemical combination Thing (B).
8. ultraviolet-curing resin composition as claimed in claim 1, wherein, the content of compound (A) is 10～ 60 weight %, the content of Photoepolymerizationinitiater initiater (C) is 0.2～5 weight %, and remainder is (methyl) acrylate compounds (B).
9. ultraviolet-curing resin composition as claimed in claim 7, wherein, former containing (methyl) acrylic acid carbon is selected from The Arrcostab of subnumber 10～30, poly- C2～C4 aklylene glycols (methyl) acrylate, (methyl) third of polypropylene oxide Olefin(e) acid nonyl phenyl ester, (methyl) acrylic acid have the Arrcostab of the carbon number 1～5 of hydroxyl, (methyl) tetrahydrofurfuryl acrylate At least one in the group of (methyl) propylene acid dihydride dicyclopentadiene base epoxide ethyl ester composition is used as with 1 (methyl) (methyl) acrylate compounds (B ') of acryloyl group.
10. ultraviolet-curing resin composition as claimed in claim 4, wherein, containing being selected from (methyl) acrylic acid moon Osmanthus ester, 2- ethylhexyl carbitol acrylate, (methyl) acrylic acid 4- hydroxybutyls, (methyl) tetrahydrofurfuryl acrylate, (first Base) the different stearyl ester of acrylic acid, (methyl) nonylphenol acrylate phenyl ester of polypropylene oxide, (methyl) propylene acid dihydride dimerization ring At least one in pentadienyl epoxide ethyl ester, the group of (methyl) acrylic acid 2- decyl tetradecanes ester composition is used as with 1 (first Base) acryloyl group (methyl) acrylate compounds (B ').
11. ultraviolet-curing resin compositions as claimed in claim 6, wherein,
Compound (A) is selected from polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dibutyl Ether, polypropylene glycol pi-allyl butyl ether, polyethylene glycol Propylene Glycol diallyl ether, polyethylene glycol Propylene Glycol dibutyl ethers At least one in the group constituted with polyethylene glycol Propylene Glycol pi-allyl butyl ether,
Containing selected from (methyl) lauryl acrylate, 2- ethylhexyl carbitol acrylate, (methyl) acrylic acid 4- hydroxyls Butyl ester, (methyl) tetrahydrofurfuryl acrylate, the different stearyl ester of (methyl) acrylic acid, (methyl) acrylic acid nonyl of polypropylene oxide Base phenyl ester, (methyl) propylene acid dihydride dicyclopentadiene base epoxide ethyl ester, (methyl) acrylic acid 2- decyl tetradecanes ester composition Group at least one as have 1 (methyl) acryloyl group (methyl) acrylate compounds (B ').
12. ultraviolet-curing resin compositions as claimed in claim 1, wherein, containing with 1 (methyl) acryloyl group (methyl) acrylate compounds (B ') and carbamate (methyl) acrylate (D) as (methyl) acrylate chemical combination Thing (B), the m in formula (1) are 10～50 integer.
13. ultraviolet-curing resin compositions as described in claim 5 or 6, wherein, carbamate (methyl) acrylic acid Ester (D) is polyether polyol and polyisocyanates and the product of (methyl) acrylate of hydroxyl.
14. ultraviolet-curing resin compositions as claimed in claim 1, wherein, containing carbamate (methyl) propylene Acid esters (D) and (methyl) acrylate compounds (B ') with 1 (methyl) acryloyl group are used as (methyl) acroleic acid esterification Compound (B), relative to the total amount of compositionss, the compound (A), the amino of 20～80 weight % containing 1～60 weight % Formic acid esters (methyl) acrylate (D), (methyl) acroleic acid esterification with 1 (methyl) acryloyl group of 10～70 weight % The Photoepolymerizationinitiater initiater (C) of compound (B ') and 0.2～5 weight %.
15. ultraviolet-curing resin compositions as claimed in claim 14, wherein, with 1 (methyl) acryloyl group Total content of (methyl) acrylate compounds (B ') and carbamate (methyl) acrylate (D) is relative to resin combination The total amount of thing is at least 40 weight %.
16. ultraviolet-curing resin compositions as claimed in claim 13, wherein, cure shrinkage is less than 3.0%.
17. ultraviolet-curing resin compositions as claimed in claim 7, wherein,
I () described compound (A) is selected from polypropylene glycol diallyl ether, polypropylene glycol dimethyl ether, two fourth of polypropylene glycol Base ether, polypropylene glycol pi-allyl butyl ether, polyethylene glycol Propylene Glycol diallyl ether, polyethylene glycol Propylene Glycol dibutyl At least one in the group of ether and polyethylene glycol Propylene Glycol pi-allyl butyl ether composition,
(ii) containing selected from (methyl) lauryl acrylate, 2- ethylhexyl carbitol acrylate, (methyl) acrylic acid 4- Hydroxybutyl, (methyl) tetrahydrofurfuryl acrylate, the different stearyl ester of (methyl) acrylic acid, (methyl) propylene of polypropylene oxide Sour nonyl phenyl ester, (methyl) propylene acid dihydride dicyclopentadiene base epoxide ethyl ester, (methyl) acrylic acid 2- decyl tetradecane esters At least one in the group of composition as have 1 (methyl) acryloyl group (methyl) acrylate compounds (B '),
(iii) carbamate (methyl) acrylate (D) is polyether polyol and polyisocyanates and (methyl) of hydroxyl The product of acrylate.
18. ultraviolet-curing resin compositions as described in claim 7 or 17, wherein, carbamate (methyl) propylene The weight average molecular weight of acid esters (D) is 7000～25000.
19. ultraviolet-curing resin compositions as claimed in claim 7, wherein,
Compound (A) is the R in formula (1)1And R2Each can be the same or different and R1And R2For carbon number 1～ The compound of the thiazolinyl of 10 alkyl or carbon number 3～10,
Carbamate (methyl) acrylate (D) is polyether polyol and polyisocyanates and (methyl) acrylic acid of hydroxyl The weight average molecular weight of the product of ester and the product is 7000～25000,
(methyl) acroleic acid esterification containing carbamate (methyl) acrylate (D) and with 1 (methyl) acryloyl group Compound (B ') conduct (methyl) acrylate compounds (B), and
Relative to the total amount of compositionss, the compound (A), the carbamic acid of 20～80 weight % containing 1～60 weight % Ester (methyl) acrylate (D), (methyl) acrylate compounds with 1 (methyl) acryloyl group of 10～70 weight % The Photoepolymerizationinitiater initiater (C) of (B ') and 0.2～5 weight %, and there is (methyl) acrylate of 1 (methyl) acryloyl group Compound (B ') is 40～90 weights with total content of carbamate (methyl) acrylate (D) relative to the total amount of compositionss Amount %.
A kind of 20. optical components, its solidified material layer by using the ultraviolet-curing resin composition described in claim 1 Will be gluing at least two optical elements and obtain.
A kind of 21. solidfied materials, its are penetrated by irradiating active-energy to the ultraviolet-curing resin composition described in claim 1 Line and obtain.
A kind of 22. contact panels, its solidified material layer by using the ultraviolet-curing resin composition described in claim 1 Will be gluing at least two optical elements and obtain.
A kind of 23. display devices with protection optical element or contact panel, which is by using the purple described in claim 1 The solidified material layer of outside line curable resin composition will be gluing with display device to protection optical element or contact panel and be obtained.
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Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013057957A1 (en) * 2011-10-21 2013-04-25 日本化薬株式会社 Ultraviolet ray cured resin composition, cured product, and article
KR20170020346A (en) * 2014-06-11 2017-02-22 닛뽄 가야쿠 가부시키가이샤 Uv-curable resin composition for use in touchscreen, and bonding method and article using said uv-curable resin
JP6499406B2 (en) * 2014-06-30 2019-04-10 日本化薬株式会社 Method for producing optical member and curable resin composition used therefor
JP6898715B2 (en) * 2016-08-01 2021-07-07 デクセリアルズ株式会社 A method for manufacturing a photocurable resin composition, an image display device, and an image display device.
WO2018110666A1 (en) * 2016-12-14 2018-06-21 デンカ株式会社 Composition
KR102280540B1 (en) * 2016-12-20 2021-07-21 아라까와 가가꾸 고교 가부시끼가이샤 Ultraviolet ray-curable adhesive agent, cured product and adhesive sheet
KR101814098B1 (en) 2017-01-18 2018-01-02 동우 화인켐 주식회사 Photocurable composition and photocurable layer formed from the same
WO2018207843A1 (en) * 2017-05-11 2018-11-15 日本化薬株式会社 Ultraviolet curable resin composition for blue light blocking films and blue light blocking film using same
CN108048006A (en) * 2017-08-14 2018-05-18 无锡海特新材料研究院有限公司 A kind of solvent-type acrylic ester pressure-sensitive for being suitable for bonding TPU and preparation method thereof
CN107502246B (en) * 2017-08-25 2020-10-27 无锡海特新材料研究院有限公司 Solvent type acrylate pressure-sensitive adhesive for crepe paper and preparation method thereof
JP6360605B1 (en) * 2017-08-30 2018-07-18 リンテック株式会社 Manufacturing method of display body
JP7105443B2 (en) * 2018-08-10 2022-07-25 三菱鉛筆株式会社 COMPOUND, DECORATIVE MATERIAL, DECORATION, AND INK COMPOSITION
JP2020196829A (en) * 2019-06-04 2020-12-10 デクセリアルズ株式会社 Photocurable resin composition and method for manufacturing image display device
JP7452206B2 (en) 2020-04-06 2024-03-19 東亞合成株式会社 Active energy ray curable adhesive composition
JP2022056388A (en) * 2020-09-29 2022-04-08 パナソニックＩｐマネジメント株式会社 Ultraviolet-curable resin composition, optical component, method for manufacturing optical component, light-emitting device, and method for manufacturing light-emitting device
KR20220097640A (en) 2020-12-30 2022-07-08 삼성디스플레이 주식회사 Resin composition and display device including adhesive layer formed from the same
KR20230077781A (en) 2021-11-25 2023-06-02 삼성디스플레이 주식회사 Method of manufacturing adhesive member, method of manufacturing display device including the same, and display device manufactured by the method of manufacturing display device

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1646591A (en) * 2002-02-19 2005-07-27 Dsmip财产有限公司 Curable liquid resin composition

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61103908A (en) * 1984-10-26 1986-05-22 Nitto Electric Ind Co Ltd Production of emulsion-type photo-curable adhesive
JPS61103574A (en) * 1984-10-26 1986-05-22 Nitto Electric Ind Co Ltd Process for forming surface protecting layer
JPS62244627A (en) * 1986-04-17 1987-10-26 電気化学工業株式会社 Glass laminate
JP3105439B2 (en) * 1995-12-07 2000-10-30 三洋化成工業株式会社 Photo solder resist composition
JP2000309618A (en) * 1999-02-26 2000-11-07 Asahi Glass Co Ltd Curable composition
JP5210631B2 (en) * 2005-05-31 2013-06-12 電気化学工業株式会社 Energy ray curable resin composition and adhesive using the same
JP5782668B2 (en) * 2007-06-19 2015-09-24 日立化成株式会社 Optical resin composition and optical resin material using the same
TWI485214B (en) * 2008-09-05 2015-05-21 Kyoritsu Chemical Co Ltd And a photohardenable resin composition for bonding an optical functional material
JP2010072471A (en) * 2008-09-19 2010-04-02 Three M Innovative Properties Co Transparent adhesive sheet, image display apparatus comprising the same, and method for producing the image display apparatus
JP4428470B1 (en) * 2009-06-08 2010-03-10 東洋インキ製造株式会社 Polarizing plate and adhesive composition for forming polarizing plate
JP5521689B2 (en) * 2009-07-22 2014-06-18 東洋インキＳｃホールディングス株式会社 Pressure-sensitive adhesive composition for conductive member and laminate using the same
JP4820443B2 (en) * 2009-11-20 2011-11-24 日東電工株式会社 Optical film adhesive composition, optical film adhesive layer, adhesive optical film, and image display device
JP2011111572A (en) * 2009-11-30 2011-06-09 Toray Advanced Film Co Ltd Adhesive sheet and display
JP5544853B2 (en) * 2009-12-09 2014-07-09 サイデン化学株式会社 Optical pressure-sensitive adhesive composition
CN102212317A (en) * 2010-04-02 2011-10-12 素塔电子科技(上海)有限公司 Adhesive agent of polaroid and preparation method for polaroid by using adhesive agent
JP2012126839A (en) * 2010-12-16 2012-07-05 Nippon Shokubai Co Ltd Ultraviolet curing resin composition for optics, cured material, and display device
WO2013057957A1 (en) * 2011-10-21 2013-04-25 日本化薬株式会社 Ultraviolet ray cured resin composition, cured product, and article

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1646591A (en) * 2002-02-19 2005-07-27 Dsmip财产有限公司 Curable liquid resin composition

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