CN107011835A - Adhesive composition, adhesive member, optical component and electronic component - Google Patents
Adhesive composition, adhesive member, optical component and electronic component Download PDFInfo
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- CN107011835A CN107011835A CN201710060531.3A CN201710060531A CN107011835A CN 107011835 A CN107011835 A CN 107011835A CN 201710060531 A CN201710060531 A CN 201710060531A CN 107011835 A CN107011835 A CN 107011835A
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- adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Abstract
The present invention provides adhesive composition, adhesive member, optical component and electronic component.Adhesive composition, the adhesive member with the adhesive phase formed by the adhesive composition, the optical component for possessing the adhesive member, the electronic component for forming the excellent adhesive phase of stress dispersiveness are provided.The adhesive composition of the present invention includes polymer (A), the polymer (A) has the monomeric unit from (methyl) alkyl acrylate, wherein, in 40 DEG C~150 DEG C of whole temperature province, adhesive phase being solidified to form the adhesive composition losstangenttanδ is more than 0.10.
Description
Technical field
Adhesive member the present invention relates to adhesive composition, with the adhesive phase formed by the adhesive composition,
Possess optical component, the electronic component of the adhesive member.
Background technology
In optical component, the electronic components such as LCD touch panel, the lens section of camera, electronic equipment has been used, it is
Rigidity, impact resistance are assigned, adhesive films (such as patent document 1) are pasted with exposing surface side sometimes.Such bonding
Property film generally have substrate layer and adhesive phase.
For optical component as described above, electronic component, in assembling, the when of processing, when conveying, the various feelings such as when of use
Under condition, apply the load based on extruding force sometimes, can produce causes optical component, electronic component damaged because of the load of application
The problem of.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2014-234460 publications
The content of the invention
Problems to be solved by the invention
It is conceived to using the stress dispersed film with excellent stress dispersiveness as adhesive films to being arranged at this
The formation material of adhesive phase on the stress dispersed film of sample is studied.
The problem of the present invention be to provide to be formed the excellent adhesive phase of stress dispersiveness adhesive composition, with by
Adhesive member, the optical component for possessing the adhesive member, the electronic component of the adhesive phase of adhesive composition formation.
The solution used to solve the problem
The adhesive composition of the present invention includes polymer (A), and the polymer (A), which has, is derived from (methyl) alkyl acrylate
The monomeric unit of base ester, wherein,
It is in -40 DEG C~150 DEG C of whole temperature province, adhesive phase being solidified to form the adhesive composition
Losstangenttanδ is more than 0.10.
In one embodiment, the above-mentioned monomeric unit from (methyl) alkyl acrylate is monomeric unit (I), institute
State monomeric unit (I) and be derived from the alkyl with carbon number 1~20 as (methyl) alkyl acrylate of alkylester moieties.
In one embodiment, above-mentioned polymer (A) has monomeric unit (II), and the monomeric unit (II), which is derived from, divides
(methyl) acrylate with OH bases and/or COOH bases in sub.
In one embodiment, adhesive composition of the invention includes organic multiple isocyanate systems more than 2 functions
Crosslinking agent and/or epoxy crosslinking agent.
In one embodiment, adhesive composition includes organic multiple isocyanate more than polymer and 2 functions
It is crosslinking agent and/or epoxy crosslinking agent, the polymer has monomeric unit (I) and monomeric unit (II), the monomer list
First (I) is derived from the alkyl with carbon number 1~20 and is used as (methyl) alkyl acrylate of alkylester moieties, the monomeric unit
(II) being derived from intramolecular has (methyl) acrylate of OH bases and/or COOH bases, by the NCO bases in the adhesive composition
Mole containing ratio is set to [NCO], a mole containing ratio for the epoxy radicals in the adhesive composition is set to [epoxy radicals], will
Mole containing ratio of OH bases in the adhesive composition is set to [OH], mole by the COOH bases in the adhesive composition
When containing ratio is set to [COOH], 0<([NCO]+[epoxy radicals])/([OH]+[COOH])<0.05.
In one embodiment, adhesive composition of the invention includes polymer (B), and the polymer (B) has
Monomeric unit and weight average molecular weight from structure containing ester ring type (methyl) acrylate shown in formula (1) be 1000 with
Above and less than 30000.
CH2=C (R1)COOR2…(1)
(in formula (1), R1For hydrogen atom or methyl, R2For the alkyl with ester ring type structure.)
The adhesive member of the present invention has the adhesive phase formed by above-mentioned adhesive composition.
The optical component of the present invention possesses above-mentioned adhesive member.
The electronic component of the present invention possesses above-mentioned adhesive member.
The effect of invention
In accordance with the invention it is possible to provide to be formed the excellent adhesive phase of stress dispersiveness adhesive composition, with by
Adhesive member, the optical component for possessing the adhesive member, the electronic component of the adhesive phase of adhesive composition formation.
Brief description of the drawings
Fig. 1 is the schematic cross-section of the adhesive member based on an embodiment of the invention.
Description of reference numerals
10 base materials
20 adhesive phases
30 barrier films
100 adhesive members
Embodiment
In the case of the statement for having " (methyl) acrylic acid " in this manual, refer to " acrylic acid and/or metering system
Acid ", in the case of the statement for having " (methyl) acrylate ", refers to " acrylate and/or methacrylate ".In addition,
In the case of the statement for having " weight " in this specification, it can also be substituted for usual as the SI systems unit for representing weight
" quality ".
In the case of the statement for having " monomeric unit (A) for being derived from (a) " in this manual, monomeric unit (A) is monomer
(a) by polymerizeing construction unit formed by fracture occurs for the unsaturated double-bond having.It should be noted that unsaturated double-bond is logical
Cross polymerization occur fracture formed by construction unit refer to " RpRqC=CRrRs " structure (Rp, Rq, Rr, Rs be by singly-bound
With carbon atom with reference to any appropriate group) unsaturated double-bond " C=C " by polymerize occur fracture formed by "-
RpRqC-CRrRs- " construction unit.
In this manual, the containing ratio of the monomeric unit in polymer for example can be by the various knots of the polymer
Structure parsing is learnt (such as NMR).Even if in addition, without various structure elucidations as described above, system can also will be based on
The containing ratio conduct for the monomeric unit from the various monomers made the consumption of the various monomers used during polymer and calculated
The containing ratio of monomeric unit in polymer.I.e., it is possible to certain in the whole monomer components that will be used when manufacturing polymer
The containing ratio of monomer (m) is handled as the containing ratio of the monomeric unit from monomer (m) in the polymer.
<<<<A. adhesive composition》》
The adhesive composition of the present invention includes polymer (A), and the polymer (A), which has, is derived from (methyl) alkyl acrylate
The monomeric unit of base ester.
The containing ratio of above-mentioned polymer (A) in the adhesive composition of the present invention is preferably the weight of 80 weight %~100
Measure the weight % of %, the more preferably weight % of 85 weight %~100, more preferably 90 weight %~100, particularly preferably
The weight % of 92.5 weight %~100, it is most preferably the weight % of 95 weight %~100.By the adhesive composition for making the present invention
In above-mentioned polymer (A) containing ratio within the above range, using the teaching of the invention it is possible to provide form the more excellent bonding of stress dispersiveness
The adhesive composition of oxidant layer.
It is in -40 DEG C~150 DEG C of whole temperature province, by the adhesive group for the adhesive composition of the present invention
The losstangenttanδ for the adhesive phase that compound is solidified to form is more than 0.10.By the whole temperature for making -40 DEG C~150 DEG C
The above-mentioned losstangenttanδ spent in region is more than 0.10, using the teaching of the invention it is possible to provide form the excellent adhesive phase of stress dispersiveness
Adhesive composition.Wherein, the assay method of above-mentioned losstangenttanδ will be described later.
It is in -40 DEG C~150 DEG C of whole temperature province, by the adhesive group for the adhesive composition of the present invention
The upper limit of the losstangenttanδ for the adhesive phase that compound is solidified to form is preferably less than 2.40, more preferably 2.20 with
Under, more preferably less than 2.00, particularly preferably less than 1.80.By being in the upper limit of above-mentioned losstangenttanδ
In above range, using the teaching of the invention it is possible to provide form the adhesive composition of the more excellent adhesive phase of stress dispersiveness.
It is in -40 DEG C~150 DEG C of whole temperature province, by the adhesive group for the adhesive composition of the present invention
The lower limit of the losstangenttanδ for the adhesive phase that compound is solidified to form is preferably more than 0.12, more preferably 0.14 with
Above, more preferably more than 0.16, particularly preferably more than 0.18.By being in the lower limit of above-mentioned losstangenttanδ
In above range, using the teaching of the invention it is possible to provide form the adhesive composition of the more excellent adhesive phase of stress dispersiveness.
Polymer (A) has the monomeric unit from (methyl) alkyl acrylate.(methyl) is derived from polymer (A)
The monomeric unit of alkyl acrylate can be only a kind, or two or more.
The containing ratio of the monomeric unit from (methyl) alkyl acrylate in polymer (A) is preferably 90 weight %
The weight % of~99.5 weight %, more preferably the weight % of 91 weight %~99, more preferably 92 weight %~98.5, especially
The weight % of preferably 93 weight %~98.2, it is most preferably the weight % of 94 weight %~98.By making being derived from polymer (A)
The containing ratio of the monomeric unit of (methyl) alkyl acrylate is within the above range, using the teaching of the invention it is possible to provide form stress dispersiveness more
The adhesive composition of excellent adhesive phase.
The above-mentioned monomeric unit from (methyl) alkyl acrylate can be with the range of the effect of the present invention is not damaged
Using any appropriate monomeric unit from (methyl) alkyl acrylate.It is further from energy as such monomeric unit
Set out in terms of the effect for showing the present invention, preferably monomeric unit (I), the monomeric unit (I), which is derived from, has carbon number 1~20
Alkyl as alkylester moieties (methyl) alkyl acrylate.
As (methyl) alkyl acrylate of the alkyl with carbon number 1~20 as alkylester moieties, for example, it can lift
Go out：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate,
(methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid-2-ethyl oneself
Ester, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, the positive nonyl ester of (methyl) acrylic acid, the different nonyl of (methyl) acrylic acid
Ester, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl) isodecyl acrylate, (methyl) acrylic acid n-dodecane base ester, (methyl) propylene
Sour n-tridecane base ester, (methyl) n-myristyl base ester etc..
Polymer (A) preferably have monomeric unit (II), the monomeric unit (II) be derived from intramolecular have OH bases and/or
(methyl) acrylate of COOH bases.(methyl) third in polymer (A), that there is OH bases and/or COOH bases from intramolecular
The monomeric unit (II) of olefin(e) acid ester can be only a kind, or two or more.Intramolecular is derived from by having polymer (A)
The monomeric unit (II) of (methyl) acrylate with OH bases and/or COOH bases, using the teaching of the invention it is possible to provide form stress dispersiveness more excellent
The adhesive composition of different adhesive phase.
The monomeric unit of (methyl) acrylate in polymer (A), that there is OH bases and/or COOH bases from intramolecular
(II) containing ratio is preferably the weight % of the weight % of 0.5 weight %~10, more preferably 1 weight %~9, more preferably
The weight % of the weight % of 1.5 weight %~8, particularly preferably 1.8 weight %~7, it is most preferably the weight % of 2 weight %~6.Pass through
Make the monomeric unit (II) of (methyl) acrylate in polymer (A), that there is OH bases and/or COOH bases from intramolecular
Containing ratio is within the above range, using the teaching of the invention it is possible to provide form the adhesive composition of the more excellent adhesive phase of stress dispersiveness.
There is (methyl) acrylate of OH bases as intramolecular, for example, can enumerate：(methyl) acrylic acid -2- hydroxyl second
Ester, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -4- hydroxybutyls, the own ester of (methyl) acrylic acid -6- hydroxyls,
(methyl) acrylic acid -8- hydroxyls monooctyl ester, (methyl) acrylic acid -10- hydroxyls last of the ten Heavenly stems ester, (methyl) acrylic acid -12- hydroxylaurics ester,
(4- Hydroxymethyl-cyclo-hexyls) methacrylate, N- methylols (methyl) acrylamide, vinyl alcohol, allyl alcohol, 2- hydroxyls
Ethyl vinyl ether, 4- hydroxybutyl vinyl ethers, diethylene glycol monovinyl base ether etc..
There is (methyl) acrylate of COOH bases as intramolecular, for example, can enumerate：(methyl) acrylic acid, (methyl)
Carboxyethyl acrylates, (methyl) acrylic acid carboxyl pentyl ester, itaconic acid, maleic acid, fumaric acid, crotonic acid, iso-crotonic acid etc..
Polymer (A) can have the monomeric unit (III) from other monomers.Other lists are derived from polymer (A)
The monomeric unit (III) of body can be only a kind, or two or more.
As other monomers, for example, it can enumerate：Cyano-containing monomer, vinyl ester monomers, aromatic vinyl monomer, contain
Amide groups monomer, monomer containing imide, emulsion stability, containing epoxy based monomers, vinyl ether monomers, N- acryloyl groups
Quinoline, containing sulfomonomer, phosphorous acid-based monomers, monomer containing anhydride group etc..
The adhesive composition of the present invention preferably comprises organic multiple isocyanate system crosslinking agent and/or rings more than 2 functions
Oxygen system crosslinking agent.The organic multiple isocyanate system crosslinking agent more than 2 functions that can contain in the adhesive composition of the present invention
And/or epoxy crosslinking agent can be only a kind, or two or more.
More than in the adhesive composition of the present invention, above-mentioned 2 function organic multiple isocyanate system crosslinking agent and epoxy
The total containing ratio for being crosslinking agent relative to the parts by weight of polymer (A) 100 is preferably the parts by weight of 0.001 parts by weight~0.4, more excellent
Elect parts by weight of the parts by weight of 0.0025 parts by weight~0.3, more preferably 0.005 parts by weight~0.2, particularly preferably as
The parts by weight of 0.0075 parts by weight~0.15, it is most preferably the parts by weight of 0.01 parts by weight~0.1.By the adhesive group for making the present invention
Total containing ratio of more than above-mentioned 2 function organic multiple isocyanate system crosslinking agent and epoxy crosslinking agent in compound relative to
The parts by weight of polymer (A) 100 are within the above range, using the teaching of the invention it is possible to provide form the bonding of the more excellent adhesive phase of stress dispersiveness
Agent composition.
As organic multiple isocyanate system crosslinking agents more than 2 functions, for example, it can enumerate：Tetramethylene diisocyanate,
The lower aliphatic polyisocyanates such as hexamethylene diisocyanate；Cyclopentylene diisocyanate, the isocyanide of cyclohexylidene two
The alicyclic isocyanate class such as acid esters, IPDI；2,4 toluene diisocyanate, 4,4 '-diphenyl methane
The aromatic isocyanate class such as diisocyanate, xylyl diisocyanate；Trimethylolpropane/toluene di-isocyanate(TDI) three
Aggressiveness addition product (for example, Nippon Polyurethane Industry Co., Ltd.s system, trade name " CORONATE L "),
Trimethylolpropane/hexamethylene diisocyanate trimer addition product is (for example, Nippon Polyurethane Industry
Co., Ltd.'s system, trade name " CORONATE HL "), the isocyanuric acid ester body of hexamethylene diisocyanate is (for example, Nippon
Polyurethane Industry Co., Ltd. system, trade name " CORONATE HX ") etc. isocyanate addition product；Deng.
As epoxy crosslinking agent, for example, it can enumerate：Bisphenol-A, the epoxy system resin of epoxychloropropane type, ethylidene contracting
Water glycerin ether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, T 55,1,6-HD contracting
Water glycerin ether, trihydroxymethylpropanyltri diglycidyl ether, diglycidylaniline, two amido glycidyl group amines, N, N, N ',
N '-four glycidyl group-m-xylene diamine (for example, Mitsubishi Gas Chemical Co., Ltd's system, trade name " TETRAD-X "), 1,
Double (N, the N- diglycidyl amino methyl) hexamethylenes of 3- are (for example, Mitsubishi Gas Chemical Co., Ltd's system, trade name
" TETRAD-C ") etc..
For the adhesive composition of the present invention, it is preferred that it is comprising more than polymer and 2 functions organic
Polyisocyanates system crosslinking agent and/or epoxy crosslinking agent, the polymer have monomeric unit (I) and monomeric unit (II),
The monomeric unit (I) is derived from the alkyl with carbon number 1~20 as (methyl) alkyl acrylate of alkylester moieties, described
Monomeric unit (II), which is derived from intramolecular, has (methyl) acrylate of OH bases and/or COOH bases, by the adhesive composition
Mole containing ratios of NCO bases be set to [NCO], be set to a mole containing ratio for the epoxy radicals in the adhesive composition
[epoxy radicals], a mole containing ratio for the OH bases in the adhesive composition is set to [OH], by the adhesive composition
When a mole containing ratio for COOH bases is set to [COOH], 0<([NCO]+[epoxy radicals])/([OH]+[COOH])<0.05.By making
([NCO]+[epoxy radicals])/([OH]+[COOH]) is in above range, using the teaching of the invention it is possible to provide form the more excellent bonding of stress dispersiveness
The adhesive composition of oxidant layer.
The adhesive composition of the present invention can include polymer (B), and the polymer (B), which has, is derived from formula (1) institute
The monomeric unit and weight average molecular weight of structure containing ester ring type (methyl) acrylate shown are 1000 less than 30000.
CH2=C (R1)COOR2…(1)
(in formula (1), R1For hydrogen atom or methyl, R2For the alkyl with ester ring type structure.)
Polymer (B) can be only a kind, or two or more.
The weight average molecular weight of polymer (B) is preferably 1000~30000, is more preferably 1250~25000, further preferably
For 1500~20000, particularly preferably 1750~15000, most preferably 2000~10000.By making the weight of polymer (B) equal
Molecular weight within the above range, even if the amount of increase crosslinking agent, can also provide to form the more excellent bonding of stress dispersiveness
The adhesive composition of oxidant layer.
The containing ratio of polymer (B) in the adhesive composition of the present invention is excellent relative to polymer (A) 100 parts by weight
Elect the parts by weight of the parts by weight of 0.5 parts by weight~50, more preferably 1 parts by weight~45 as, the weight of more preferably 2 parts by weight~40
Part, particularly preferably the parts by weight of 3 parts by weight~35, be most preferably the parts by weight of 4 parts by weight~30.By the adhesive for making the present invention
The containing ratio of polymer (B) in composition relative to the parts by weight of polymer (A) 100 within the above range, even if increase
The amount of crosslinking agent, can also provide the adhesive composition to form the more excellent adhesive phase of stress dispersiveness.
Monomeric unit in polymer (B), from structure containing ester ring type (methyl) acrylate shown in formula (1)
Containing ratio is preferably the weight % of the weight % of 40 weight %~99.5, more preferably 42.5 weight %~99, more preferably
The weight % of the weight % of 45 weight %~98.5, particularly preferably 47.5 weight %~98, it is most preferably the weight of 50 weight %~97.5
Measure %.By making the monomeric unit for being derived from structure containing ester ring type (methyl) acrylate shown in formula (1) in polymer (B)
Containing ratio within the above range, even if increase crosslinking agent amount, can also provide to be formed stress dispersiveness it is more excellent
The adhesive composition of adhesive phase.
As structure containing ester ring type (methyl) acrylate shown in above-mentioned formula (1), for example, it can enumerate：(methyl) third
Olefin(e) acid cyclohexyl, (methyl) acrylic acid bicyclopentyl ester, methacrylic acid bicyclopentyl epoxide ethyl ester, acrylic acid bicyclopentyl oxygen
Base ethyl ester, the ring pentyl ester of methacrylic acid three, the ring pentyl ester of acrylic acid three, 1- adamantyl methacrylates, 1- adamantyls third
Olefin(e) acid ester, 2- methyl -2- adamantyl methacrylates, 2- methyl -2- adamantyl acrylates, 2- ethyl -2- Buddha's warrior attendants
Alkylmethacrylate, 2- ethyl -2- adamantyl acrylates etc..
Polymer (B) can have the monomeric unit (IV) from other monomers.Other monomers are derived from polymer (B)
Monomeric unit (IV) can be only a kind, or two or more.
As the other monomers that can contain in polymer (B), for example, it can enumerate：(methyl) methyl acrylate, (methyl)
Ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) third
Olefin(e) acid isobutyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid-2-ethyl caproite, (methyl) n-octyl, (methyl)
Isooctyl acrylate monomer, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, the positive last of the ten Heavenly stems ester of (methyl) acrylic acid, (methyl)
Isodecyl acrylate, (methyl) acrylic acid n-dodecane base ester, (methyl) acrylic acid n-tridecane base ester, (methyl) acrylic acid are just
Tetradecane base ester, acrylic acid, methacrylic acid, carboxyethyl acrylates, acrylic acid carboxyl pentyl ester, itaconic acid, maleic acid, rich horse
Acid, crotonic acid, iso-crotonic acid etc..
, can be by any appropriate in the range of the effect of the present invention is not damaged for polymer (A), polymer (B)
Method manufacture.As such manufacture method, for example, it can enumerate：Polymerisation in solution, emulsion polymerization, polymerisation in bulk, suspension
Polymerization, photopolymerization (active energy beam polymerization) etc..Among these manufacture methods, from the viewpoint of cost, productivity ratio, preferably
For polymerisation in solution.Obtained polymer (A) can be random copolymer, block copolymer, alternate copolymer, graft copolymer etc.
In it is any number of.Obtained polymer (B) can be random copolymer, block copolymer, alternate copolymer, graft copolymer etc.
In it is any number of.
As the method for polymerisation in solution, solvent is dissolved in such as can enumerate monomer component, polymerization initiator, is carried out
Heating, polymerization, so that obtain the method for polymer solution etc..
Heating-up temperature when polymerizeing as the progress heating in polymerisation in solution, for example, can enumerate 50 DEG C~90 DEG C.As
Heat time in polymerisation in solution, for example, it can enumerate 1 hour~24 hours.
As the solvent used in polymerisation in solution, in the range of the effect of the present invention is not damaged, it can use any suitable
When solvent.As such solvent, for example, it can enumerate：Toluene, benzene, dimethylbenzene etc. are aromatic hydrocarbon；Ethyl acetate, acetic acid
The esters such as N-butyl；The aliphatic hydrocarbons such as n-hexane, normal heptane；The ester ring type hydro carbons such as hexamethylene, hexahydrotoluene；MEK,
The ketones such as methyl iso-butyl ketone (MIBK)；Deng organic solvent etc..Solvent can be only a kind, or two or more.
Polymerization initiator can be used in polymer (A), the manufacture of polymer (B).Such polymerization initiator can be with
It is only a kind, or two or more.As such polymerization initiator, for example, it can enumerate：2,2 '-azodiisobutyronitrile,
Double (2- amidine propanes) dihydrochlorides of 2,2 '-azo, double [2- (5- methyl -2- imidazoline -2- bases) propane] disalts of 2,2 '-azo
Double (the 2- methyl-props amidine) dithionates of hydrochlorate, 2,2 '-azo, 2,2 '-azo double (N, N '-dimethyleneisobutylamidine), 2,2 '-
The azo systems such as double [N- (2- the carboxy ethyls) -2- methyl-props amidine] hydrates (and the pure medicine Co. Ltd. system of light, VA-057) of azo draw
Send out agent；The persulfates such as potassium peroxydisulfate, ammonium persulfate；Two (2- ethylhexyls) peroxycarbonates, two (4- t-butylcyclohexyls
Base) peroxycarbonates, di-sec-butyl peroxycarbonates, tert-butyl hydroperoxide neodecanoic acid ester, tertiary hexyl peroxidating pivalic acid
Ester, tert-butyl hydroperoxide pivalate, dilauroyl peroxide, two positive sim peroxides, 1,1,3,3- tetramethyls
Butyl peroxy -2 ethyl hexanoic acid ester, peroxidating two (4- toluyls), dibenzoyl peroxide, tert-butyl hydroperoxide are different
The peroxide series initiators such as butyrate, 1,1- bis- (tertiary hexyl peroxidating) hexamethylene, TBHP, hydrogen peroxide；
The combination of persulfate and sodium hydrogensulfite, peroxide and the combination of sodium ascorbate etc. combine peroxide with deoxidizer
Redox series initiators；Deng.
, can be using any appropriate in the range of the effect of the present invention is not damaged for the consumption of polymerization initiator
Consumption.As such consumption, such as it is preferably the parts by weight of 0.01 parts by weight~5 relative to the parts by weight of monomer component 100.
In polymer (A), the manufacture of polymer (B), chain-transferring agent can be used.Such chain-transferring agent can be only
1 kind, or two or more.As such chain-transferring agent, for example, it can enumerate：Lauryl mercaptan, glycidyl sulphur
Alcohol, TGA, 2 mercapto ethanol, TGA, methyl thioglycolate, 2-ethylhexyl mercaptoacetate, 2,3- dimercaptos -1-
Propyl alcohol etc..
, can be using any appropriate use in the range of the effect of the present invention is not damaged for the consumption of chain-transferring agent
Amount.As such consumption, for example, being preferably the parts by weight of 0.01 parts by weight~5 relative to the parts by weight of monomer component 100.
In polymer (A), the manufacture of polymer (B), other that usually can use in the polymerization can be used
Any appropriate additive.
The adhesive composition of the present invention can include crosslinking catalyst.As crosslinking catalyst, the present invention is not being damaged
Effect in the range of can be using any appropriate crosslinking catalyst.As such crosslinking catalyst, for example, it can enumerate：
The crosslinking of the metal systems such as tetra-n-butyl titanate, tetraisopropyl titanate, ferric acetyl acetonade, butyl tin oxide, dioctyl tin laurate is urged
Agent (particularly tin system crosslinking catalyst) etc..Crosslinking catalyst can be only a kind, or two or more.
, can be using any appropriate in the range of the effect of the present invention is not damaged for the consumption of crosslinking catalyst
Consumption.As such consumption, for example, being preferably the weight of 0.001 parts by weight~0.05 relative to the parts by weight of monomer component 100
Part.
The adhesive composition of the present invention can contain any appropriate its in the range of the effect of the present invention is not damaged
His additive.As other such additives, for example, it can enumerate：Silane coupler, crosslinking delay agent, emulsifying agent, coloring
It is the powders such as agent, pigment, dyestuff, surfactant, plasticizer, cohesive imparting agent, surface lubricant, levelling agent, softening agent, anti-
Oxidant, antiaging agent, light stabilizer, ultra-violet absorber, polymerization inhibitor, inorganic filler, organic filler, metal powder,
Granular, foil-like thing etc..Other such additives can be only a kind, or two or more.
《《B. adhesive member》》
The adhesive member of the present invention has the adhesive phase that the adhesive composition by the present invention is formed.
The adhesive member of the present invention can be formed only by adhesive phase, can also include adhesive phase and other components.
, can be at this in the case of the form that adhesive phase exposes as outermost layer in the adhesive member of the present invention
Expose surface side and any appropriate barrier film (stripping film) is set.Barrier film (stripping film) can double as base material described later.
Adhesive phase is formed by the adhesive composition of the present invention.For example, the adhesive composition of the present invention is applied
Cloth is dried on any appropriate base material, adhesive phase is formed on base material as needed.Then, if peeling base,
It then can obtain the adhesive member of the invention only formed by adhesive phase.In addition, for example, the adhesive composition of the present invention is applied
Cloth is dried on any appropriate base material, adhesive phase is formed on base material as needed, and base material is retained as former state, from
And obtain the adhesive member comprising adhesive phase and base material.In addition, for example, the adhesive composition of the present invention is coated on arbitrarily
On appropriate base material, it is dried as needed, adhesive phase is formed on base material, peeling base is obtained to adhesive phase load
It is placed on other components (such as other base materials), so as to obtain the adhesive member comprising adhesive phase and base material.In addition, for example,
The adhesive composition of the present invention is coated on any appropriate base material, is dried as needed, forms viscous on base material
Mixture layer, will form adhesive phase on base material and be transferred on other components (such as other base materials), so as to obtain comprising bonding
The adhesive member of oxidant layer and base material.
As the method for the coating of adhesive composition, for example, it can enumerate：Roller coat, reversely intaglio plate coating, coating, roller
Brush, spraying, air knife coating method, utilize the extrusion coated etc. of die coating machine etc..
Base material can be formed by individual layer, can also be formed by multilayer.Base material can be stretched.
The thickness of base material can be set as any appropriate thickness according to purposes.From the sight of the effect of the abundant performance present invention
Point sets out, and the thickness of base material is preferably 4 μm~500 μm, more preferably 10 μm~400 μm, more preferably 15 μm~350 μ
M, particularly preferably 20 μm~300 μm.
, can be using any appropriate material according to purposes as the material of base material.As such material, for example may be used
To enumerate：Plastics, paper, metallic film, non-woven fabrics etc..Among such material, from the effect that can further show the present invention
Aspect is set out, preferably plastics.
As above-mentioned plastics, for example, it can enumerate：Polyester based resin, polyolefin-based resins, polyamide series resin, polyamides are sub-
Amine system resin etc..As polyester based resin, for example, it can enumerate：Polyethylene terephthalate, poly terephthalic acid fourth two
Alcohol ester, PEN etc..As polyolefin-based resins, for example, it can enumerate：Homopolymer, the alkene of olefinic monomer
Copolymer of monomer etc..As polyolefin-based resins, specifically, for example, it can enumerate：Homo-polypropylene；Using ethene composition as
The propylene series copolymer of the block system of copolymer composition, random system, grafting system etc.；Reactive TPO；It is low-density, high density, linear low
The ethylene-based polymer of density, extremely-low density etc.；Ethylene propylene copolymer, EVAc, ethene
Methyl acrylate copolymer, ethylene ethyl acrylate copolymer, ethylene butyl acrylate copolymer, ethylene methyl propylene
The vinyl copolymers such as acid copolymer, ethylenemethylmethacrylate copolymer；Deng.From can further show the present invention effect
Set out in terms of fruit, as above-mentioned plastics, among these, preferably polyester based resin, more preferably poly terephthalic acid second two
Alcohol ester.
Base material can be as needed containing any appropriate additive.As the additive that can contain in base material, for example
It can enumerate：Antioxidant, ultra-violet absorber, light stabilizer, antistatic additive, filler, pigment etc..It can contain in base material
Species, number, the amount of additive can suitably be set according to purpose.
Fig. 1 is the schematic cross-section of the adhesive member based on an embodiment of the invention.In Fig. 1, of the invention is viscous
Component 100 is closed to be formed by base material 10, adhesive phase 20 and barrier film 30.
《《C. optical component, electronic component》》
The adhesive member of the present invention has the excellent adhesive phase of stress dispersiveness.It therefore, it can function properly as to protect
Optical component, electronic component are protected from the protection materials for the purpose of outside impact etc..That is, optical component tool of the invention
The adhesive member of the standby present invention.In addition, the electronic component of the present invention possesses the adhesive member of the present invention.
[embodiment]
Hereinafter, by embodiment, specifically the present invention will be described, but the present invention is not by any limit of these embodiments
It is fixed.It should be noted that the experiment and evaluation method in embodiment etc. are as follows.It should be noted that being recited as the situation of " part "
Under, as long as no specified otherwise, refer to " parts by weight ", in the case of being recited as " % ", as long as no specified otherwise, refer to " weight
Measure % ".
<The measure of weight average molecular weight>
For the weight average molecular weight (Mw) of polymer, TOSOH CORPORATION GPC devices (HLC- is used
8220GPC) it is measured.It should be noted that weight average molecular weight (Mw) is obtained using polystyrene scaled value.
Condition determination is for example following.
Sample concentration：0.2 weight % (THF solution)
Sample injection rate：10 μ l eluents
THF flow velocitys：0.6ml/ minutes
Determine temperature：40℃
Sample column：TSKguardcolumn SuperHZ-H (1)+TSKgel Super HZM-H (2)
Reference column：TSKgelSuperH-RC (1)
Detector：Differential refractometer (RI)
<The making of bonding sheet>
Lift-off processing is being carried out to one side with organosilicon in the way of dried thickness turns into 50 μm with fountain type roller
38 μm of thickness polyester film (trade name：MRF, Mitsubishi Chemical's polyester Co. Ltd. system) lift-off processing face on be coated with and obtain
Adhesive composition, under conditions of 130 DEG C of drying temperature, 3 minutes drying times solidify, dry.So operation, in base material
Upper making adhesive phase.Then, the polyester film (commodity of 38 μm of the thickness of lift-off processing will have been carried out to one side with organosilicon
Name：MRF, Mitsubishi Chemical's polyester Co. Ltd. system) it is coated in the way of the lift-off processing face of the film turns into adhesive phase side
On the surface of adhesive phase.So operation, makes bonding sheet.
<Glass transition temperature (Tg), storage modulus, loss modulus, tan δ (loss angle tangent) measure>
Using Measurement of Dynamic Viscoelasticity device (Rheometrics company systems, ARES), obtained according to following methods.
Only adhesive phase is taken out from obtained bonding sheet, is laminated, about 2mm thickness is formed, is punched to
φ 7.9mm, the columned particle of making, are used as test sample.Said determination sample is fixed on to the folder of φ 7.9mm parallel-plates
Tool, using above-mentioned Measurement of Dynamic Viscoelasticity device, the temperature dependency to storage modulus G ', loss modulus G " is measured, with
Tan δ=G "/G ' form calculates tan δ.It should be noted that temperature when obtained tan δ curves are changed into very big is used as glass
Glass transition temperature (Tg) (DEG C).
Condition determination is for example following.
Determine：Shear mode
Temperature range：- 70 DEG C~150 DEG C
Programming rate：5 DEG C/min
Frequency：1Hz
(Production Example 1)：(methyl) acrylic acid series polymeric compounds (1)
Acrylic acid-2-ethyl is put into the four-hole boiling flask for possessing stirring vane, thermometer, nitrogen ingress pipe, condenser
Own ester (Nippon Shokubai Co., Ltd. system)：100 parts by weight, 2-Hydroxy ethyl acrylate (Toagosei Co., Ltd
System)：4 parts by weight, 2,2 '-azodiisobutyronitrile (and the pure medicine Co. Ltd. system of light) as polymerization initiator：0.2 parts by weight,
Ethyl acetate：156 parts by weight, side is slowly stirred, and side imports nitrogen, and the liquid temperature in flask is remained near 65 DEG C, 6 are carried out
Hour polymerisation, prepares the solution (40 weight %) of (methyl) acrylic acid series polymeric compounds (1) of weight average molecular weight 550,000.
(Production Example 2)：(methyl) acrylic acid series polymeric compounds (2)
Acrylic acid-2-ethyl is put into the four-hole boiling flask for possessing stirring vane, thermometer, nitrogen ingress pipe, condenser
Own ester (Nippon Shokubai Co., Ltd. system)：100 parts by weight, acrylic acid -4- hydroxybutyl (Osaka Organic Chemical Industries
Co. Ltd. system)：10 parts by weight, acrylic acid (Toagosei Co., Ltd's system)：0.02 parts by weight, 2 as polymerization initiator,
2 '-azodiisobutyronitrile (and the pure medicine Co. Ltd. system of light)：0.2 parts by weight, ethyl acetate：156 parts by weight, side is slowly stirred
Mix, side imports nitrogen, the liquid temperature in flask is remained near 65 DEG C, 6 hours polymerisations are carried out, weight average molecular weight 54 is prepared
The solution (40 weight %) of ten thousand (methyl) acrylic acid series polymeric compounds (2).
(Production Example 3)：(methyl) acrylic acid series polymeric compounds (3)
Butyl acrylate is put into the four-hole boiling flask for possessing stirring vane, thermometer, nitrogen ingress pipe, condenser
(Nippon Shokubai Co., Ltd. system)：99 parts by weight, acrylic acid -4- hydroxybutyls (Osaka Organic Chemical Industry strain formula
Commercial firm's system)：1 parts by weight, 2,2 '-azodiisobutyronitrile (and the pure medicine Co. Ltd. system of light) as polymerization initiator：1 weight
Part, ethyl acetate：156 parts by weight, side is slowly stirred, and side imports nitrogen, and the liquid temperature in flask is remained near 60 DEG C, entered
7 hours polymerisations of row, prepare the solution (39 weight %) of (methyl) acrylic acid series polymeric compounds (3) of weight average molecular weight 1,600,000.
(Production Example 4)：(methyl) acrylic acid series polymeric compounds (4)
Butyl acrylate is put into the four-hole boiling flask for possessing stirring vane, thermometer, nitrogen ingress pipe, condenser
(Nippon Shokubai Co., Ltd. system)：92 parts by weight, N- acryloyl morpholines (Kohjinco., Ltd. system)：5 weight
Part, acrylic acid (Toagosei Co., Ltd's system)：2.9 parts by weight, as polymerization initiator 2,2 '-azodiisobutyronitrile (and
The pure medicine Co. Ltd. system of light)：0.1 parts by weight, ethyl acetate：200 parts by weight are put into, and side is slowly stirred, and side imports nitrogen, will
Liquid temperature in flask remains near 55 DEG C, carries out 8 hours polymerisations, prepares (methyl) propylene of weight average molecular weight 1,800,000
The solution (33 weight %) of sour based polymer (4).
(Production Example 5)：(methyl) acrylic acid series polymeric compounds (5)
Butyl acrylate is put into the four-hole boiling flask for possessing stirring vane, thermometer, nitrogen ingress pipe, condenser
(Nippon Shokubai Co., Ltd. system)：95 parts by weight, acrylic acid (Toagosei Co., Ltd's system)：5 parts by weight, conduct
The 2,2 ' of polymerization initiator-azodiisobutyronitrile (and the pure medicine Co. Ltd. system of light)：0.2 parts by weight, ethyl acetate：156 weight
Part, side is slowly stirred, and side imports nitrogen, and the liquid temperature in flask is remained near 63 DEG C, 10 hours polymerisations, system is carried out
The solution (40 weight %) of (methyl) acrylic acid series polymeric compounds (5) of standby weight average molecular weight 700,000.
(Production Example 6)：Structure containing ester ring type (methyl) acrylic acid series polymeric compounds (6)
Using as the cyclohexyl methacrylate of monomer component, [vitrifying of homopolymer (polycyclohexyl methacrylate) turns
Temperature：66℃]：95 parts by weight, acrylic acid：5 parts by weight, the 2 mercapto ethanol as chain-transferring agent：3 parts by weight, as poly-
Close 2,2 '-azodiisobutyronitrile of initiator：0.2 parts by weight and the toluene as polymer solvent：103.2 parts by weight are put into
In removable flask, side imports nitrogen, and side is stirred 1 hour.So operation, after the oxygen in polymerization system is removed, is warming up to 70
DEG C, it is reacted 3 hours, and then, it is reacted 2 hours at 75 DEG C, obtain (methyl) acrylic acid of weight average molecular weight 4000
The solution (50 weight %) of based polymer (6).
(Production Example 6)：Structure containing ester ring type (methyl) acrylic acid series polymeric compounds (7)
Toluene is put into 4 mouthfuls of flasks for possessing stirring vane, thermometer, nitrogen ingress pipe, condenser, dropping funel：
100 parts by weight, methacrylic acid two ring pentyl ester (DCPMA) (trade name：FA-513M, Hitachi Chemical Co., Ltd.'s system)：60
Parts by weight, methyl methacrylate (MMA)：40 parts by weight and the methyl thioglycolate as chain-transferring agent：3.5 parts by weight.So
Afterwards, after being stirred 1 hour under 70 DEG C, nitrogen atmosphere, input is used as the 2 of polymerization initiator, 2 '-azodiisobutyronitrile：0.2 weight
Part, it is reacted at 70 DEG C 2 hours, after then being reacted 4 hours at 80 DEG C, react 1 hour, divided equally again at 90 DEG C
The solution (51 weight %) of (methyl) acrylic acid series polymeric compounds (7) of son amount 4000.
(embodiment 1)
To the solution of (methyl) acrylic acid series polymeric compounds (1), with the solution relative to (methyl) acrylic acid series polymeric compounds (1)
The parts by weight of solid constituent 100, all solids composition turn into 25 weight % mode be diluted with ethyl acetate, use dispersion machine
Stirring, obtains including the adhesive composition (1) of acrylic resin.Show the result in table 1.
(embodiment 2)
Added into the solution of (methyl) acrylic acid series polymeric compounds (1)：Relative to (methyl) acrylic acid series polymeric compounds (1)
The parts by weight of solid constituent 100 of solution, being converted using solid constituent is calculated as the CORONATE L as crosslinking agent of 0.01 parts by weight
(Nippon Polyurethane Industry Co., Ltd. system), using solid constituent convert be calculated as 0.005 parts by weight as
The ferric acetyl acetonade (chemistry Industry Co., Ltd of Japan system) of crosslinking catalyst, turns into 25 weight % side with all solids composition
Formula is diluted with ethyl acetate, is stirred with dispersion machine, obtains including the adhesive composition (2) of acrylic resin.Will knot
Fruit is shown in table 1.
(embodiment 3)
Added into the solution of (methyl) acrylic acid series polymeric compounds (1)：Relative to (methyl) acrylic acid series polymeric compounds (1)
The parts by weight of solid constituent 100 of solution, being converted using solid constituent is calculated as the CORONATE L as crosslinking agent of 0.1 parts by weight
(Nippon Polyurethane Industry Co., Ltd. system), using solid constituent convert be calculated as 0.005 parts by weight as
The ferric acetyl acetonade (chemistry Industry Co., Ltd of Japan system) of crosslinking catalyst, turns into 25 weight % side with all solids composition
Formula is diluted with ethyl acetate, is stirred with dispersion machine, obtains including the adhesive composition (3) of acrylic resin.Will knot
Fruit is shown in table 1.
(embodiment 4)
Added into the solution of (methyl) acrylic acid series polymeric compounds (1)：Relative to (methyl) acrylic acid series polymeric compounds (1)
The parts by weight of solid constituent 100 of solution, being converted using solid constituent is calculated as the CORONATE L as crosslinking agent of 0.05 parts by weight
(Nippon Polyurethane Industry Co., Ltd. system), using solid constituent convert be calculated as 0.005 parts by weight as
The ferric acetyl acetonade (Japan chemistry Industry Co., Ltd system) of crosslinking catalyst, being converted with solid constituent is calculated as the (first of 5 parts by weight
Base) acrylic acid series polymeric compounds (6) solution, by all solids composition turn into 25 weight % in the way of carried out with ethyl acetate it is dilute
Release, stirred with dispersion machine, obtain including the adhesive composition (4) of acrylic resin.Show the result in table 1.
(embodiment 5)
Added into the solution of (methyl) acrylic acid series polymeric compounds (1)：Relative to (methyl) acrylic acid series polymeric compounds (1)
The parts by weight of solid constituent 100 of solution, being converted using solid constituent is calculated as the CORONATE L as crosslinking agent of 0.1 parts by weight
(Nippon Polyurethane Industry Co., Ltd. system), using solid constituent convert be calculated as 0.005 parts by weight as
The ferric acetyl acetonade (Japan chemistry Industry Co., Ltd system) of crosslinking catalyst, being converted with solid constituent is calculated as the (first of 5 parts by weight
Base) acrylic acid series polymeric compounds (6) solution, by all solids composition turn into 25 weight % in the way of carried out with ethyl acetate it is dilute
Release, stirred with dispersion machine, obtain including the adhesive composition (5) of acrylic resin.Show the result in table 1.
(embodiment 6)
Added into the solution of (methyl) acrylic acid series polymeric compounds (1)：Relative to (methyl) acrylic acid series polymeric compounds (1)
The parts by weight of solid constituent 100 of solution, being converted using solid constituent is calculated as the CORONATE L as crosslinking agent of 0.3 parts by weight
(Nippon Polyurethane Industry Co., Ltd. system), using solid constituent convert be calculated as 0.005 parts by weight as
The ferric acetyl acetonade (Japan chemistry Industry Co., Ltd system) of crosslinking catalyst, being converted with solid constituent is calculated as the (first of 5 parts by weight
Base) acrylic acid series polymeric compounds (6) solution, by all solids composition turn into 25 weight % in the way of carried out with ethyl acetate it is dilute
Release, stirred with dispersion machine, obtain including the adhesive composition (6) of acrylic resin.Show the result in table 1.
(embodiment 7)
Added into the solution of (methyl) acrylic acid series polymeric compounds (1)：Relative to (methyl) acrylic acid series polymeric compounds (1)
The parts by weight of solid constituent 100 of solution, being converted using solid constituent is calculated as the CORONATE L as crosslinking agent of 0.1 parts by weight
(Nippon Polyurethane Industry Co., Ltd. system), using solid constituent convert be calculated as 0.005 parts by weight as
The ferric acetyl acetonade (Japan chemistry Industry Co., Ltd system) of crosslinking catalyst, being converted with solid constituent is calculated as the (first of 5 parts by weight
Base) acrylic acid series polymeric compounds (7) solution, by all solids composition turn into 25 weight % in the way of carried out with ethyl acetate it is dilute
Release, stirred with dispersion machine, obtain including the adhesive composition (7) of acrylic resin.Show the result in table 1.
(embodiment 8)
Added into the solution of (methyl) acrylic acid series polymeric compounds (1)：Relative to (methyl) acrylic acid series polymeric compounds (1)
The parts by weight of solid constituent 100 of solution, being converted using solid constituent is calculated as the CORONATE L as crosslinking agent of 0.3 parts by weight
(Nippon Polyurethane Industry Co., Ltd. system), using solid constituent convert be calculated as 0.005 parts by weight as
The ferric acetyl acetonade (Japan chemistry Industry Co., Ltd system) of crosslinking catalyst, being converted with solid constituent is calculated as the (first of 5 parts by weight
Base) acrylic acid series polymeric compounds (7) solution, by all solids composition turn into 25 weight % in the way of carried out with ethyl acetate it is dilute
Release, stirred with dispersion machine, obtain including the adhesive composition (8) of acrylic resin.Show the result in table 1.
(embodiment 9)
To the solution of (methyl) acrylic acid series polymeric compounds (2), with the solution relative to (methyl) acrylic acid series polymeric compounds (2)
The parts by weight of solid constituent 100, all solids composition turn into 25 weight % mode be diluted with ethyl acetate, use dispersion machine
Stirring, obtains including the adhesive composition (9) of acrylic resin.Show the result in table 1.
(embodiment 10)
Added into the solution of (methyl) acrylic acid series polymeric compounds (2)：Relative to (methyl) acrylic acid series polymeric compounds (2)
The parts by weight of solid constituent 100 of solution, being converted using solid constituent is calculated as the CORONATE L as crosslinking agent of 0.1 parts by weight
(Nippon Polyurethane Industry Co., Ltd. system), being converted with solid constituent is calculated as 0.05 parts by weight
TETRAD-C (Mitsubishi Gas Chemical Co., Ltd's system), converted using solid constituent be calculated as 0.005 parts by weight be used as cross-linking catalyst
The ferric acetyl acetonade (chemistry Industry Co., Ltd of Japan system) of agent, acetic acid is used in the way of all solids composition turns into 25 weight %
Ethyl ester is diluted, and is stirred with dispersion machine, obtains including the adhesive composition (10) of acrylic resin.Show the result in table
1。
(embodiment 11)
Added into the solution of (methyl) acrylic acid series polymeric compounds (3)：Relative to (methyl) acrylic acid series polymeric compounds (3)
The parts by weight of solid constituent 100 of solution, being converted using solid constituent is calculated as the CORONATE L as crosslinking agent of 0.02 parts by weight
(Nippon Polyurethane Industry Co., Ltd. system), using solid constituent convert be calculated as 0.005 parts by weight as
The ferric acetyl acetonade (chemistry Industry Co., Ltd of Japan system) of crosslinking catalyst, turns into 25 weight % side with all solids composition
Formula is diluted with ethyl acetate, is stirred with dispersion machine, obtains including the adhesive composition (11) of acrylic resin.Will knot
Fruit is shown in table 1.
(embodiment 12)
Added into the solution of (methyl) acrylic acid series polymeric compounds (4)：Relative to (methyl) acrylic acid series polymeric compounds (4)
The parts by weight of solid constituent 100 of solution, being converted using solid constituent is calculated as the CORONATE L as crosslinking agent of 0.3 parts by weight
(Nippon Polyurethane Industry Co., Ltd. system), using solid constituent convert be calculated as 0.005 parts by weight as
The ferric acetyl acetonade (chemistry Industry Co., Ltd of Japan system) of crosslinking catalyst, turns into 25 weight % side with all solids composition
Formula is diluted with ethyl acetate, is stirred with dispersion machine, obtains including the adhesive composition (12) of acrylic resin.Will knot
Fruit is shown in table 1.
(embodiment 13)
Added into the solution of (methyl) acrylic acid series polymeric compounds (5)：Relative to (methyl) acrylic acid series polymeric compounds (5)
The parts by weight of solid constituent 100 of solution, being converted using solid constituent is calculated as the TETRAD-C as crosslinking agent of 0.075 parts by weight
(Mitsubishi Gas Chemical Co., Ltd's system), being converted using solid constituent is calculated as the acetyl as crosslinking catalyst of 0.005 parts by weight
Acetone iron (chemistry Industry Co., Ltd of Japan system), is carried out in the way of all solids composition turns into 25 weight % with ethyl acetate
Dilution, is stirred with dispersion machine, obtains including the adhesive composition (13) of acrylic resin.Show the result in table 1.
(embodiment 14)
Added into the solution of (methyl) acrylic acid series polymeric compounds (5)：Relative to (methyl) acrylic acid series polymeric compounds (5)
The parts by weight of solid constituent 100 of solution, being converted using solid constituent is calculated as the TETRAD-C as crosslinking agent of 0.075 parts by weight
(Mitsubishi Gas Chemical Co., Ltd's system), being converted using solid constituent is calculated as the acetyl as crosslinking catalyst of 0.005 parts by weight
Acetone iron (Japan chemistry Industry Co., Ltd system), being converted with solid constituent is calculated as (methyl) acrylic polymeric of 20 parts by weight
The solution of thing (6), is diluted with ethyl acetate in the way of all solids composition turns into 25 weight %, is stirred with dispersion machine,
Obtain including the adhesive composition (14) of acrylic resin.Show the result in table 1.
(comparative example 1)
Added into the solution of (methyl) acrylic acid series polymeric compounds (1)：Relative to (methyl) acrylic acid series polymeric compounds (1)
The parts by weight of solid constituent 100 of solution, being converted using solid constituent is calculated as the CORONATE L as crosslinking agent of 0.5 parts by weight
(Nippon Polyurethane Industry Co., Ltd. system), using solid constituent convert be calculated as 0.005 parts by weight as
The ferric acetyl acetonade (chemistry Industry Co., Ltd of Japan system) of crosslinking catalyst, turns into 25 weight % side with all solids composition
Formula, is diluted with ethyl acetate, is stirred with dispersion machine, obtains including the adhesive composition (C1) of acrylic resin.Will
As a result it is shown in table 1.
(comparative example 2)
Added into the solution of (methyl) acrylic acid series polymeric compounds (2)：Relative to (methyl) acrylic acid series polymeric compounds (2)
The parts by weight of solid constituent 100 of solution, being converted using solid constituent is calculated as the CORONATE L as crosslinking agent of 0.45 parts by weight
(Nippon Polyurethane Industry Co., Ltd. system), being converted with solid constituent is calculated as 0.3 parts by weight
TETRAD-C (Mitsubishi Gas Chemical Co., Ltd's system), converted using solid constituent be calculated as 0.005 parts by weight be used as cross-linking catalyst
The ferric acetyl acetonade (chemistry Industry Co., Ltd of Japan system) of agent, acetic acid is used in the way of all solids composition turns into 25 weight %
Ethyl ester is diluted, and is stirred with dispersion machine, obtains including the adhesive composition (C2) of acrylic resin.Show the result in table
1。
[table 1]
(embodiment 15)
Peel off polyester film, patch in one face of the bonding sheet that the adhesive composition (1) obtained from by embodiment 1 is obtained
It is attached on the Polarizer (Nitto Denko Corp's system, trade name " TEG1465DUHC ") as optical component, is pasted with
The optical component of bonding sheet.
(embodiment 16)
Peel off polyester film, patch in one face of the bonding sheet that the adhesive composition (2) obtained from by embodiment 2 is obtained
It is attached on the Polarizer (Nitto Denko Corp's system, trade name " TEG1465DUHC ") as optical component, is pasted with
The optical component of bonding sheet.
(embodiment 17)
Peel off polyester film, patch in one face of the bonding sheet that the adhesive composition (4) obtained from by embodiment 4 is obtained
It is attached on the Polarizer (Nitto Denko Corp's system, trade name " TEG1465DUHC ") as optical component, is pasted with
The optical component of bonding sheet.
(embodiment 18)
Peel off polyester film, patch in one face of the bonding sheet that the adhesive composition (7) obtained from by embodiment 7 is obtained
It is attached on the Polarizer (Nitto Denko Corp's system, trade name " TEG1465DUHC ") as optical component, is pasted with
The optical component of bonding sheet.
(embodiment 19)
Peel off polyester film, patch in one face of the bonding sheet that the adhesive composition (9) obtained from by embodiment 9 is obtained
It is attached on the Polarizer (Nitto Denko Corp's system, trade name " TEG1465DUHC ") as optical component, is pasted with
The optical component of bonding sheet.
(embodiment 20)
Polyester film is peeled off in one face of the bonding sheet that the adhesive composition (10) obtained from by embodiment 10 is obtained,
Attach on the Polarizer (Nitto Denko Corp's system, trade name " TEG1465DUHC ") as optical component, attached
There is the optical component of bonding sheet.
(embodiment 21)
Polyester film is peeled off in one face of the bonding sheet that the adhesive composition (11) obtained from by embodiment 11 is obtained,
Attach on the Polarizer (Nitto Denko Corp's system, trade name " TEG1465DUHC ") as optical component, attached
There is the optical component of bonding sheet.
(embodiment 22)
Polyester film is peeled off in one face of the bonding sheet that the adhesive composition (12) obtained from by embodiment 12 is obtained,
Attach on the Polarizer (Nitto Denko Corp's system, trade name " TEG1465DUHC ") as optical component, attached
There is the optical component of bonding sheet.
(embodiment 23)
Polyester film is peeled off in one face of the bonding sheet that the adhesive composition (13) obtained from by embodiment 13 is obtained,
Attach on the Polarizer (Nitto Denko Corp's system, trade name " TEG1465DUHC ") as optical component, attached
There is the optical component of bonding sheet.
(embodiment 24)
Polyester film is peeled off in one face of the bonding sheet that the adhesive composition (14) obtained from by embodiment 14 is obtained,
Attach on the Polarizer (Nitto Denko Corp's system, trade name " TEG1465DUHC ") as optical component, attached
There is the optical component of bonding sheet.
(embodiment 25)
Peel off polyester film, patch in one face of the bonding sheet that the adhesive composition (1) obtained from by embodiment 1 is obtained
It is attached to the conductive membrane (Nitto Denko Corp's system, trade name " ELECRYSTA V270L-TFMP ") as electronic component
On, obtain being pasted with the electronic component of bonding sheet.
(embodiment 26)
Peel off polyester film, patch in one face of the bonding sheet that the adhesive composition (2) obtained from by embodiment 2 is obtained
It is attached to the conductive membrane (Nitto Denko Corp's system, trade name " ELECRYSTA V270L-TFMP ") as electronic component
On, obtain being pasted with the electronic component of bonding sheet.
(embodiment 27)
Peel off polyester film, patch in one face of the bonding sheet that the adhesive composition (4) obtained from by embodiment 4 is obtained
It is attached to the conductive membrane (Nitto Denko Corp's system, trade name " ELECRYSTA V270L-TFMP ") as electronic component
On, obtain being pasted with the electronic component of bonding sheet.
(embodiment 28)
Peel off polyester film, patch in one face of the bonding sheet that the adhesive composition (7) obtained from by embodiment 7 is obtained
It is attached to the conductive membrane (Nitto Denko Corp's system, trade name " ELECRYSTA V270L-TFMP ") as electronic component
On, obtain being pasted with the electronic component of bonding sheet.
(embodiment 29)
Peel off polyester film, patch in one face of the bonding sheet that the adhesive composition (9) obtained from by embodiment 9 is obtained
It is attached to the conductive membrane (Nitto Denko Corp's system, trade name " ELECRYSTA V270L-TFMP ") as electronic component
On, obtain being pasted with the electronic component of bonding sheet.
(embodiment 30)
Polyester film is peeled off in one face of the bonding sheet that the adhesive composition (10) obtained from by embodiment 10 is obtained,
Attach to conductive membrane (Nitto Denko Corp's system, trade name " the ELECRYSTA V270L- as electronic component
TFMP ") on, obtain being pasted with the electronic component of bonding sheet.
(embodiment 31)
Polyester film is peeled off in one face of the bonding sheet that the adhesive composition (11) obtained from by embodiment 11 is obtained,
Attach to conductive membrane (Nitto Denko Corp's system, trade name " the ELECRYSTA V270L- as electronic component
TFMP ") on, obtain being pasted with the electronic component of bonding sheet.
(embodiment 32)
Polyester film is peeled off in one face of the bonding sheet that the adhesive composition (12) obtained from by embodiment 12 is obtained,
Attach to conductive membrane (Nitto Denko Corp's system, trade name " the ELECRYSTA V270L- as electronic component
TFMP ") on, obtain being pasted with the electronic component of bonding sheet.
(embodiment 33)
Polyester film is peeled off in one face of the bonding sheet that the adhesive composition (13) obtained from by embodiment 13 is obtained,
Attach to conductive membrane (Nitto Denko Corp's system, trade name " the ELECRYSTA V270L- as electronic component
TFMP ") on, obtain being pasted with the electronic component of bonding sheet.
(embodiment 34)
Polyester film is peeled off in one face of the bonding sheet that the adhesive composition (14) obtained from by embodiment 14 is obtained,
Attach to conductive membrane (Nitto Denko Corp's system, trade name " the ELECRYSTA V270L- as electronic component
TFMP ") on, obtain being pasted with the electronic component of bonding sheet.
Industrial applicability
The adhesive member of the adhesive phase formed with the adhesive composition by the present invention can function properly as to protect
Protection materials for the purpose of protecting such as optical component, electronic component are from from outside impact.
Claims (9)
1. a kind of adhesive composition, it includes polymer (A), and the polymer (A), which has, is derived from (methyl) acrylic acid alkyl
The monomeric unit of ester, wherein,
In -40 DEG C~150 DEG C of whole temperature province, adhesive phase being formed by the adhesive composition loss angle tangent
Tan δ are more than 0.10.
2. adhesive composition according to claim 1, wherein, the monomer list from (methyl) alkyl acrylate
Member is monomeric unit (I), and the monomeric unit (I) is derived from the alkyl with carbon number 1~20 as (methyl) of alkylester moieties
Alkyl acrylate.
3. adhesive composition according to claim 1 or 2, wherein, the polymer (A) has monomeric unit (II),
The monomeric unit (II), which is derived from intramolecular, has (methyl) acrylate of OH bases and/or COOH bases.
4. the adhesive composition according to any one of claims 1 to 3 is comprising more than 2 functions organic more
Isocyanates system crosslinking agent and/or epoxy crosslinking agent.
5. adhesive composition according to claim 1, it includes organic many isocyanides more than polymer and 2 functions
Acid esters system crosslinking agent and/or epoxy crosslinking agent, the polymer have monomeric unit (I) and monomeric unit (II), the list
Body unit (I) is derived from the alkyl with carbon number 1~20 and is used as (methyl) alkyl acrylate of alkylester moieties, the monomer list
First (II), which is derived from intramolecular, has (methyl) acrylate of OH bases and/or COOH bases,
Mole containing ratio of NCO bases in the adhesive composition is set to [NCO], by the epoxy in the adhesive composition
Mole containing ratio of base is set to [epoxy radicals], a mole containing ratio for the OH bases in the adhesive composition is set to [OH],
When a mole containing ratio for COOH bases in the adhesive composition is set into [COOH], 0<([NCO]+[epoxy radicals])/([OH]
+[COOH])<0.05。
6. adhesive composition according to claim 5, it includes polymer (B), and the polymer (B), which has to be derived from, leads to
The monomeric unit and weight average molecular weight of (methyl) acrylate of the structure containing ester ring type shown in formula (1) be more than 1000 and
Less than 30000,
CH2=C (R1)COOR2…(1)
In formula (1), R1For hydrogen atom or methyl, R2For the alkyl with ester ring type structure.
7. a kind of adhesive member, it has the bonding formed as the adhesive composition described in any one of claim 1~6
Oxidant layer.
8. a kind of optical component, it possesses the adhesive member described in claim 7.
9. a kind of electronic component, it possesses the adhesive member described in claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111137217.3A CN113831867B (en) | 2016-01-27 | 2017-01-25 | Adhesive composition, adhesive member, optical member, and electronic member |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-013090 | 2016-01-27 | ||
| JP2016013090A JP2017132871A (en) | 2016-01-27 | 2016-01-27 | Adhesive composition, adhesive member, optical member, and electronic member |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111137217.3A Division CN113831867B (en) | 2016-01-27 | 2017-01-25 | Adhesive composition, adhesive member, optical member, and electronic member |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107011835A true CN107011835A (en) | 2017-08-04 |
Family
ID=59440023
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|---|---|---|---|
| CN202111137217.3A Active CN113831867B (en) | 2016-01-27 | 2017-01-25 | Adhesive composition, adhesive member, optical member, and electronic member |
| CN201710060531.3A Pending CN107011835A (en) | 2016-01-27 | 2017-01-25 | Adhesive composition, adhesive member, optical component and electronic component |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111137217.3A Active CN113831867B (en) | 2016-01-27 | 2017-01-25 | Adhesive composition, adhesive member, optical member, and electronic member |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2017132871A (en) |
| KR (1) | KR20170089764A (en) |
| CN (2) | CN113831867B (en) |
| TW (1) | TWI789344B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017132872A (en) * | 2016-01-27 | 2017-08-03 | 日東電工株式会社 | Adhesive composition, adhesive member, optical member, and electronic member |
| WO2020262048A1 (en) | 2019-06-27 | 2020-12-30 | 日東電工株式会社 | Adhesive sheet and method for producing adhesive sheet-attached article |
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| CN1918254A (en) * | 2004-04-23 | 2007-02-21 | Lg化学株式会社 | Acrylic pressure-sensitive adhesive composition for polarizing film |
| JP2008231358A (en) * | 2007-03-23 | 2008-10-02 | Dic Corp | Image display module for electronic terminal and pressure-sensitive adhesive sheet for whole surface lamination |
| JP2009057394A (en) * | 2006-08-30 | 2009-03-19 | Dic Corp | Repeelable self-adhesive sheet |
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| JP4548679B2 (en) * | 1999-10-08 | 2010-09-22 | 大日本印刷株式会社 | Adhesive for pressure-sensitive adhesive layer in volume hologram laminate |
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| JP4515118B2 (en) * | 2004-03-12 | 2010-07-28 | 日東電工株式会社 | Transparent double-sided adhesive tape or sheet and touch panel |
| JP5199917B2 (en) * | 2009-02-25 | 2013-05-15 | 日東電工株式会社 | Adhesive sheet, method for producing the same, and adhesive functional film |
| JP2013142162A (en) * | 2012-01-10 | 2013-07-22 | Mitsubishi Shindoh Co Ltd | Copper or copper alloy plate for base plate with excellent warp workability, and method for producing the same |
| JP2017132872A (en) * | 2016-01-27 | 2017-08-03 | 日東電工株式会社 | Adhesive composition, adhesive member, optical member, and electronic member |
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2016
- 2016-01-27 JP JP2016013090A patent/JP2017132871A/en active Pending
-
2017
- 2017-01-17 KR KR1020170007894A patent/KR20170089764A/en not_active Application Discontinuation
- 2017-01-25 CN CN202111137217.3A patent/CN113831867B/en active Active
- 2017-01-25 TW TW106102834A patent/TWI789344B/en active
- 2017-01-25 CN CN201710060531.3A patent/CN107011835A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20170089764A (en) | 2017-08-04 |
| CN113831867B (en) | 2023-09-26 |
| JP2017132871A (en) | 2017-08-03 |
| CN113831867A (en) | 2021-12-24 |
| TW201728725A (en) | 2017-08-16 |
| TWI789344B (en) | 2023-01-11 |
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