CN111793439B - Adhesive sheet for image display device - Google Patents
Adhesive sheet for image display device Download PDFInfo
- Publication number
- CN111793439B CN111793439B CN202010235490.9A CN202010235490A CN111793439B CN 111793439 B CN111793439 B CN 111793439B CN 202010235490 A CN202010235490 A CN 202010235490A CN 111793439 B CN111793439 B CN 111793439B
- Authority
- CN
- China
- Prior art keywords
- adhesive sheet
- image display
- display device
- adhesive
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000853 adhesive Substances 0.000 title claims abstract description 88
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 88
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 150000002148 esters Chemical class 0.000 claims abstract description 22
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 21
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012790 adhesive layer Substances 0.000 claims abstract description 17
- 238000003860 storage Methods 0.000 claims abstract description 17
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 12
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
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- MXYATHGRPJZBNA-KRFUXDQASA-N isopimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@](C=C)(C)CC2=CC1 MXYATHGRPJZBNA-KRFUXDQASA-N 0.000 claims description 4
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 claims description 2
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- KGMSWPSAVZAMKR-ONCXSQPRSA-N Neoabietic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CCC(=C(C)C)C=C2CC1 KGMSWPSAVZAMKR-ONCXSQPRSA-N 0.000 claims description 2
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- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 claims description 2
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- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 210000002489 tectorial membrane Anatomy 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- 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
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
- C08L93/04—Rosin
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
-
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- 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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides an adhesive sheet for an image display device and an adhesive sheet laminate for an image display device, which can prevent the film from cracking and peeling when the film is mounted on the image display device. The adhesive sheet for image display device of the present invention comprises an adhesive layer comprising a crosslinked product of an adhesive composition comprising, as main components, a (meth) acrylate copolymer, an isocyanate-based crosslinking agent and a rosin ester-based tackifying resin, wherein the adhesive composition comprises 1 to 40 parts by weight of the rosin ester-based tackifying resin per 100 parts by weight of the (meth) acrylate copolymer, the maximum value of tan delta at 1Hz of the adhesive layer is-20 ℃ or less, and the storage modulus at 1Hz and 25 ℃ of the adhesive layer is 1.0X10 ° 5 Pa or below.
Description
Technical Field
The present invention relates to an adhesive sheet for an image display device and an adhesive sheet laminate for an image display device.
Background
In recent years, for laminating and laminating a film, an electrode film, a casing, and the like constituting a touch panel display used for a smart phone and the like, an adhesive sheet described in patent document 1 is used, for example.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2012-025808
Disclosure of Invention
Technical problem to be solved by the invention
However, in recent years, image display devices such as touch panel displays have curved surfaces or curved surfaces and are sometimes repeatedly curved and used, and therefore, films and the like as constituent members thereof also need to be attached to follow the curved surfaces and the like. However, when the coating film is stuck on such a curved surface, the coating film may be broken or peeled off, and improvement of this is desired. The present invention has been made to solve the above-described problems, and an object of the present invention is to provide an adhesive sheet for an image display device and an adhesive sheet laminate for an image display device, which can prevent the occurrence of cracking and peeling of a coating film when the coating film is attached to the image display device.
Technical scheme for solving technical problems
Item 1. An adhesive sheet for an image display device having an adhesive layer containing a crosslinked product of an adhesive composition containing:
(meth) acrylate copolymers as a main component;
an isocyanate-based crosslinking agent; and
the rosin ester is an adhesive-imparting resin,
the adhesive composition contains 1 to 40 parts by weight of the rosin ester based tackifying resin per 100 parts by weight of the (meth) acrylate copolymer,
the maximum value of tan delta at 1Hz of the adhesive layer is below-20 ℃,
the adhesive layer has a storage elastic modulus of 1.0X10 at 25 ℃ at 1Hz 5 Pa or below.
The adhesive sheet for an image display device according to item 1, wherein the storage elastic modulus at 1 Hz-20 ℃ is 1.0X10 5 Pa or below.
The pressure-sensitive adhesive sheet for an image display device according to item 1 or 2, wherein the thickness is 5 to 100. Mu.m.
Item 4. An adhesive sheet laminate for an image display device, comprising: the adhesive sheet for an image display device according to any one of items 1 to 3; and a base sheet for peeling attached to at least one surface of the adhesive sheet for an image display device.
Effects of the invention
When the adhesive sheet according to the present invention is used to attach a film to an image display device, the film can be prevented from being broken or peeled off.
Drawings
Fig. 1 is a cross-sectional view of an adhesive sheet laminate according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view of a test piece for bending test.
Fig. 3 is a diagram showing a method of bending test.
Symbol description
1. First release sheet
2. Adhesive sheet (adhesive layer)
3. Second release sheet
Detailed Description
An embodiment of the pressure-sensitive adhesive sheet according to the present invention will be described below. The pressure-sensitive adhesive sheet is used for mounting a film, an electrode film, a casing, or the like constituting an image display device such as a touch panel display, and is particularly suitable for mounting a film on a display having a curved or bent surface. The adhesive sheet is obtained by crosslinking an adhesive composition containing a (meth) acrylate copolymer, an isocyanate-based crosslinking agent and a rosin ester-based tackifying resin as main components. The following is a detailed description.
(meth) acrylate copolymer >
The (meth) acrylate polymer preferably contains, as monomer units, an alkyl (meth) acrylate having an alkyl group with 2 to 20 carbon atoms and a monomer having a reactive functional group in the molecule (a monomer containing a reactive functional group). This can exhibit preferable adhesion.
The alkyl (meth) acrylate having 2 to 20 carbon atoms as the alkyl group is preferably a compound having a glass transition temperature (Tg) of-40 ℃ or lower (hereinafter, sometimes referred to as "specific acrylate") as a homopolymer. By containing such a specific acrylate as a constituent monomer unit, the maximum value of tan δ of the adhesive sheet according to the present embodiment can be easily set to the range described below.
As specific acrylic esters, for example, n-butyl acrylate (Tg-55deg.C), n-octyl acrylate (Tg-65deg.C), isooctyl acrylate (Tg-58deg.C), 2-ethylhexyl acrylate (Tg-70deg.C), isononyl acrylate (Tg-58 deg.C), isodecyl acrylate (Tg-60 deg.C), isodecyl methacrylate (Tg-41 deg.C), n-lauryl methacrylate (Tg-65deg.C), tridecyl acrylate (Tg-55deg.C), tridecyl methacrylate (-40 deg.C) and the like are preferably used. Among these, from the viewpoint of more effectively reducing the storage elastic modulus, the Tg of the homopolymer is more preferably-45℃or less, particularly preferably-50℃or less, as the specific acrylic ester. In particular, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred. These acrylates may be used alone or in combination of 2 or more. The alkyl group in the alkyl (meth) acrylate having 2 to 20 carbon atoms in the alkyl group refers to a linear, branched or cyclic alkyl group.
The (meth) acrylate polymer preferably contains 60 mass% or more, more preferably 80 mass% or more, and particularly preferably 90 mass% or more of a specific acrylate as a monomer unit. When the specific acrylic acid ester is contained in an amount of 60 mass% or more, the maximum value of tan δ of the pressure-sensitive adhesive sheet according to the present embodiment can be more easily set to the range described below.
The (meth) acrylate polymer preferably contains 99.9 mass% or less, more preferably 99 mass% or less, and particularly preferably 98 mass% or less of a specific acrylate as a monomer unit. By containing 99.9 mass% or less of the above specific acrylic acid ester, a suitable amount of other monomer components (particularly, a reactive functional group-containing monomer) can be introduced into the (meth) acrylic acid ester polymer.
The (meth) acrylate polymer has a monomer unit containing a reactive functional group, and reacts with a crosslinking agent described later via the reactive functional group derived from the monomer containing a reactive functional group, thereby forming a crosslinked structure (three-dimensional network structure) and obtaining an adhesive sheet having a desired cohesive force.
In the (meth) acrylate polymer, as the monomer having a reactive functional group in the monomer unit, a monomer having a hydroxyl group in the molecule (hydroxyl group-containing monomer), a monomer having an amino group in the molecule (amino group-containing monomer), and the like are preferable. Among these, hydroxyl group-containing monomers are particularly preferable. Most hydroxyl group-containing monomers have a glass transition temperature (Tg) of 0 ℃ or less, and the maximum value of tan δ of the pressure-sensitive adhesive sheet according to the present embodiment can be easily set to the range described below.
Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Among them, at least one of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate and 4-hydroxybutyl acrylate is preferable from the viewpoints of glass transition temperature (Tg), reactivity of hydroxyl groups in the obtained (meth) acrylate polymer with a crosslinking agent, and copolymerizability with other monomers. These hydroxyl group-containing monomers may be used alone or in combination of 2 or more.
The hydroxyl value of the (meth) acrylate copolymer is not particularly limited, and from the viewpoint of suppressing peeling from the adherend when the pressure-sensitive adhesive sheet is repeatedly bent in a state of being in contact with the adherend, the lower limit is preferably 5mgKOH/g or more, more preferably 10mgKOH/g or more. On the other hand, the upper limit is preferably 100mgKOH/g or less, more preferably 90mgKOH/g or less.
The (meth) acrylate polymer preferably contains 0.1 mass% or more, more preferably 0.5 mass% or more, and particularly preferably 1 mass% or more of a reactive functional group-containing monomer as a monomer unit. The (meth) acrylate polymer preferably contains 30 mass% or less, more preferably 20 mass% or less, and particularly preferably 8 mass% or less of a monomer containing a reactive functional group as a monomer unit.
Among them, the (meth) acrylate polymer according to the present embodiment does not contain a carboxyl group-containing monomer, particularly does not contain acrylic acid as a monomer unit. Since the carboxyl group is an acid component, the absence of the carboxyl group-containing monomer can suppress occurrence of defects due to acid in the object to be adhered to the pressure-sensitive adhesive sheet, and even in the case where a transparent conductive film such as Indium Tin Oxide (ITO), a metal film, a metal mesh, or the like is present, the defects (corrosion, change in resistance value, or the like) due to acid can be suppressed.
The polymerization system of the (meth) acrylic acid ester polymer may be a random copolymer or a block copolymer.
The lower limit of the weight average molecular weight of the (meth) acrylate polymer is preferably 20 ten thousand or more, more preferably 30 ten thousand or more, and particularly preferably 40 ten thousand or more. When the lower limit value of the weight average molecular weight of the (meth) acrylate polymer is not less than the above, the adhesive sheet can be processed to suppress defects such as bleeding of the adhesive. The weight average molecular weight in the present specification is a value in terms of standard polystyrene measured by Gel Permeation Chromatography (GPC).
The upper limit of the weight average molecular weight of the (meth) acrylic acid ester polymer is preferably 100 ten thousand or less, more preferably 90 ten thousand or less, and particularly preferably 80 ten thousand or less. When the upper limit value of the weight average molecular weight of the (meth) acrylate polymer is not more than the above, the adhesion force and storage modulus of the obtained adhesive sheet to the adherend easily fall within preferable ranges described later.
In the pressure-sensitive adhesive according to the present embodiment, 1 of the above-mentioned (meth) acrylate polymers may be used alone, or 2 or more may be used in combination.
< 2 isocyanate-based crosslinking agent >
When the adhesive composition according to the present embodiment is heated, the isocyanate-based crosslinking agent crosslinks the (meth) acrylate polymer to form a three-dimensional network structure. Thus, the cohesive force of the obtained adhesive sheet is improved.
The isocyanate-based crosslinking agent contains at least a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, and hydrogenated diphenylmethane diisocyanate, and the like, biuret and isocyanurate thereof, and adducts as a reactant with compounds containing low molecular active hydrogen such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil. Among them, from the viewpoint of reactivity with hydroxyl groups, trimethylolpropane-modified aromatic polyisocyanates, in particular, trimethylolpropane-modified toluene diisocyanate and trimethylolpropane-modified xylylene diisocyanate are preferable.
The content of the isocyanate-based crosslinking agent in the adhesive composition is preferably 0.01 parts by mass or more, particularly preferably 0.05 parts by mass or more, and further preferably 0.1 parts by mass or more, based on 100 parts by weight of the (meth) acrylate polymer. The content is preferably 10 parts by mass or less, particularly preferably 8 parts by mass or less, and further preferably 5 parts by mass or less.
< 3. Rosin ester based tackifying resin >
The rosin ester-based tackifying resin according to the present embodiment is a rosin ester-based tackifying resin comprising resin acids such as abietic acid, palustric acid, neoabietic acid, pimaric acid, isopimaric acid, dehydroabietic acid and the like as main components, and esters of various alcohols.
The content of the rosin ester tackifying resin in the adhesive composition is preferably 1 to 40 parts by weight, more preferably 1.5 to 35 parts by weight, and even more preferably 2 to 30 parts by weight, based on 100 parts by weight of the (meth) acrylate polymer. When the content is 1 part by weight or more, the bending resistance is improved when the film is mounted on an image display device by using an adhesive sheet. On the other hand, by setting the content to 40 parts by weight or less, the cloudiness of the adhesive sheet can be suppressed.
< 4 additive >
Various additives commonly used for acrylic adhesives, for example, a silane coupling agent, an ultraviolet absorber, an antistatic agent, an adhesion promoter, an antioxidant, a light stabilizer, a softener, a filler, a refractive index adjuster, and the like may be added to the adhesive composition as needed. Among them, the polymerization solvent and the dilution solvent described later are not contained in the additives constituting the adhesive composition.
< 5 Properties of adhesive sheet >
< 5-1. Thickness of adhesive sheet >
The thickness of the adhesive sheet is preferably 5 to 100. Mu.m, more preferably 10 to 50. Mu.m. This is because when the thickness is less than 5. Mu.m, the coating film may be easily peeled off. On the other hand, if the thickness exceeds 100 μm, the coating film tends to sink when pressed, and thus pencil hardness may be lowered.
< 5-2. Storage modulus and tan delta >
The adhesive sheet according to the present embodiment has a maximum value of tan delta at 1Hz (glass transition temperature) of-20 ℃ or lower and a storage elastic modulus at 1Hz and 25 ℃ of 1.0X10 5 Pa or below. the lower the maximum value of tan delta, the lower the storage elastic modulus and the softer the adhesive sheet. Therefore, the maximum value of tan delta at 1Hz of the pressure-sensitive adhesive sheet is preferably-30℃or lower, more preferably-50℃or lower. The adhesive sheet preferably has a storage elastic modulus at 25℃at 1Hz of less, preferably 1.0X10 5 Pa or less, more preferably 8.0X10 4 Pa or less, more preferably 5.0X10 4 Pa or less, particularly preferably 3.0X10 4 Pa or below. In order to maintain softness even at low temperature, the adhesive sheet preferably has a storage elastic modulus of 1.0X10 at-20 Hz 5 Pa or less, more preferably 7.0X10 4 Pa or less, particularly preferably 5.5X10 4 Pa or below.
The maximum value of tan. Delta. Can be measured, for example, using "Discovery HR-3" manufactured by TA Instruments, and the storage modulus can be measured by a method based on JIS K7244-6.
< 6. Method for producing adhesive sheet >
The method for producing the pressure-sensitive adhesive sheet according to the present embodiment is not particularly limited, and may be performed, for example, as follows.
First, a (meth) acrylate polymer, an isocyanate-based crosslinking agent, and a rosin ester-based tackifying resin are mixed, and the above-described additives are added as needed.
The (meth) acrylate polymer can be produced by polymerizing a mixture of monomers constituting the polymer by a usual radical polymerization method. The polymerization of the (meth) acrylate polymer is preferably carried out by a solution polymerization method using a polymerization initiator, if necessary. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, and methyl ethyl ketone, and 2 or more kinds thereof may be used in combination.
The polymerization initiator may be an azo compound, an organic peroxide, or the like, or may be used in combination of 2 or more. As the azo-based compound, a compound having a hydroxyl group, examples thereof include 2,2' -azobisisobutyronitrile, 2' -azobis (2-methylbutyronitrile), 1' -azobis (cyclohexane 1-carbonitrile), 2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobis (2, 4-dimethyl-4-methoxyvaleronitrile), and dimethyl 2,2' -azobis (2-methylpropionate), 4' -azobis (4-cyanovaleric acid), 2' -azobis (2-hydroxymethylpropionitrile), 2' -azobis [2- (2-imidazolin-2-yl) propane ], and the like.
Examples of the organic peroxide include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, (3, 5-trimethylhexanoyl) peroxide, dipropyl peroxide, and diacetyl peroxide.
In the polymerization step, a chain transfer agent such as 2-mercaptoethanol is blended to adjust the weight average molecular weight of the polymer obtained.
If a (meth) acrylate polymer is obtained, an isocyanate-based crosslinking agent, a rosin ester-based tackifying resin, a desired additive, and a diluting solvent are added to a solution of the (meth) acrylate polymer and thoroughly mixed, thereby obtaining an adhesive composition (coating solution) diluted with the solvent.
In addition, in the case where a solid substance is used or in the case where precipitation occurs when the solid substance is mixed with other components in an undiluted state, any of the above components may be dissolved or diluted in advance by a diluting solvent and then mixed with the other components.
Examples of the diluent solvent include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and dichloroethane, alcohols such as methanol, ethanol, propanol, butanol and 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate, cellosolve solvents such as ethyl cellosolve, and the like.
The concentration and viscosity of the coating solution prepared in this way may be appropriately selected according to the situation as long as the coating solution can be applied. For example, the concentration of the adhesive composition may be diluted to 10 to 60 mass%. In addition, the addition of a diluting solvent or the like is not necessarily required in obtaining the coating solution, and the diluting solvent may not be added as long as the adhesive composition has a coatable viscosity or the like. In this case, the adhesive composition is a coating solution in which the polymerization solvent of the (meth) acrylate polymer is directly used as a diluting solvent.
The crosslinking of the adhesive composition described above can be generally performed by a heat treatment. The heat treatment may be used in combination with a drying treatment for evaporating the diluting solvent or the like from the coating film of the adhesive composition applied to the desired object.
The heating temperature of the heating treatment is preferably 50 to 150 ℃, more preferably 70 to 120 ℃. The heating time is, for example, preferably 10 seconds to 10 minutes, more preferably 50 seconds to 2 minutes.
After the heat treatment, a curing period of about 1 to 2 weeks at normal temperature (e.g., 23 ℃ C., 50% RH) may be set as needed. When this curing period is required, an adhesive sheet is formed after the curing period. On the other hand, when the curing period is not required, the adhesive sheet is formed after the completion of the heat treatment.
By the above-mentioned heat treatment (and curing), the (meth) acrylate polymer is sufficiently crosslinked via the isocyanate-based crosslinking agent to form a crosslinked structure, thereby obtaining an adhesive sheet.
< 7. Adhesive sheet laminate >
Next, the adhesive sheet laminate according to the present embodiment will be described. As shown in fig. 1, the pressure-sensitive adhesive sheet laminate according to the present embodiment includes a first release sheet 1, a pressure-sensitive adhesive layer 2 laminated on the first release sheet 1, and a second release sheet 3 disposed on the pressure-sensitive adhesive layer 2. The first and second release sheets 1, 3 are known release sheets having a release surface on at least one side.
The adhesive sheet laminate can be produced, for example, as follows. First, the first release sheet 1 is pulled out from the guide roller around which the first release sheet 1 is wound. Then, the adhesive composition is applied with the coating liquid on the release surface of the first release sheet 1, and heat-treated to thermally crosslink the adhesive composition, thereby forming the adhesive layer 2. The adhesive layer 2 corresponds to the adhesive sheet of the present invention. After that, the second release sheet 3 is attached so as to cover the adhesive layer 2. At this time, the release surface of the second release sheet 3 is in contact with the adhesive layer 2. Thus, an adhesive sheet laminate shown in FIG. 1 was formed.
< 8. Tectorial membrane >)
The film to be adhered to the image display device via the pressure-sensitive adhesive sheet is not particularly limited, and a known film may be used. There are various methods for attaching the adhesive sheet to the cover film. For example, the first or second release sheet of the adhesive sheet laminate described above can be attached to a coating film by transferring the exposed adhesive layer to the coating film after being released. Alternatively, the adhesive layer (adhesive sheet) can be formed by applying the coating liquid of the adhesive composition described above to one surface of the film, and performing a heat treatment to thermally crosslink the adhesive composition.
< 9. Features >
Since the adhesive sheet according to the present invention has a low storage elastic modulus and contains a rosin ester adhesive resin, when a film provided with the adhesive sheet is attached along an image display device having a curved portion, stress acting on the film due to bending can be relaxed by the adhesive sheet. Therefore, when the coating film is bent, cracking and peeling including cracking can be prevented from occurring.
Examples
Next, an embodiment of the present invention will be described. However, the present invention is not limited to the following examples.
< 1. Preparation of examples and comparative examples >
Adhesive sheets according to examples 1 to 7 and comparative examples 1 to 4 were prepared. Then, the film was adhered to the target film by each adhesive sheet, and a laminate shown in fig. 2 was produced. The coating film and the object film are as follows.
(1) And (3) film coating: acrylic resin film having a thickness of 100 μm and not causing cracking when r=3.0 mm in bending test
(2) Object film: polyimide resin film 30 μm thick
The target film is assumed to be an image display device to which the coating film is attached.
The compositions of the adhesives according to examples 1 to 7 and comparative examples 1 to 4 are as follows. Coronate L-55E, which is an isocyanate-based crosslinking agent, is manufactured by Tosoh corporation, BXX8515 is manufactured by Toyo ink corporation, and Duranate TPA-100 is manufactured by Asahi chemical Co. Further, PINECRYSTAL ME-GH constituting the rosin ester tackifying resin was manufactured by Dekkera chemical Co. For the acrylate copolymer, the weight average molecular weight and the hydroxyl number are indicated.
TABLE 1
Physical properties of the adhesive sheets according to examples 1 to 7 and comparative examples 1 to 4 are as follows.
The storage modulus and loss tangent tan. Delta. Of the adhesive sheet were measured using "Discovery HR-3" manufactured by TA Instruments. The measurement conditions are as follows.
(measurement conditions)
Measurement mode: shear mode
Deformation: 0.1%
Measuring frequency: 1Hz
Measuring temperature: -60-25 ℃ (heating 5 ℃/min)
Measuring a sample: the adhesive layers of the adhesive sheets were overlapped and measured at a total thickness of about 1 mm.
TABLE 2
The total light transmittance and haze of each adhesive sheet were measured using a glass/adhesive sheet/PET film laminate. The results of the total light transmittance measured in accordance with JIS K7136-1 and the results of the haze measured in accordance with JIS K7136 are shown in Table 3.
Further, a bending test was performed on the laminate shown in fig. 2 using each adhesive sheet. The bending test used the no-load U-tester shown in fig. 3. The tester has 2 rotatable movable plates, and the rotation axes of the movable plates are arranged in parallel so as to be close to each other. Then, a laminate as a sample sheet is disposed on the movable plate in a horizontal state shown in fig. 3 (a). At this time, the laminate is disposed such that the film-coated surface of the laminate is in contact with the movable plate. Next, as shown in fig. 3 (b), the sample piece was bent into a U shape by rotating the two movable plates by 90 degrees. Such bending was repeated at room temperature at a test speed of 0.85 seconds/time. After the test, whether or not the film of the sample piece had developed cracks was checked, and the bending resistance was evaluated according to the following criteria (1) to (3). Tests were conducted so that the bending radii R of the sample pieces were 2.5mm and 3.0mm, and as a result, it was tested whether the test was equivalent to any of the following (1) to (3).
(1) When r=2.5 mm, the number of bending times was 10 ten thousand times or more, and no crack was generated (when r=2.5 mm, no crack was generated)
(2) When r=2.5 mm, the number of bending times was less than 10 ten thousand times, and cracks were generated, but when r=3.0 mm, the number of bending times was 10 ten thousand times or more, and no cracks were generated (when r=3.0 mm, no cracks were generated)
(3) When r=3.0 mm, the number of bending times was less than 10 ten thousand times, and cracks were generated (when r=3.0 mm, cracks were generated)
TABLE 3
| Total light transmittance (%) | Haze (%) | Bending test | |
| Example 1 | 90.6 | 0.7 | (1) R=2.5 no cracking |
| Example 2 | 90.6 | 0.7 | (1) R=2.5 no cracking |
| Example 3 | 90.4 | 0.8 | (1) R=2.5 no cracking |
| Example 4 | 90.5 | 0.7 | (1) R=2.5 no cracking |
| Example 5 | 90.2 | 0.7 | (1) R=2.5 no cracking |
| Example 6 | 90.6 | 0.7 | (2) R=3.0 no cracks |
| Example 7 | 90.2 | 1.1 | (1) R=2.5 no cracking |
| Comparative example 1 | 90.6 | 0.7 | (3) R=3.0 crack initiation |
| Comparative example 2 | 90.6 | 0.7 | (3) R=3.0 crack initiation |
| Comparative example 3 | 90.6 | 0.7 | (3) R=3.0 crack initiation |
| Comparative example 4 | 90.6 | 0.7 | (3) R=3.0 crack initiation |
According to table 3, examples 1 to 7 were bent 10 ten thousand times or more at r=2.5 mm or 3.0mm, and the coating film did not crack, but comparative examples 1 to 4 were bent less than 10 ten thousand times at r=3.0 mm, and cracks were generated. In example 6, when r=2.5 mm, the number of bending times was less than 10 ten thousand times, and cracks were generated, considering that the content of the rosin ester based tackifying resin was small.
The flexural properties of comparative examples 1 to 4 were considered to be low because the storage modulus at 25℃was high. Further, as described above, comparative example 2 has a high storage modulus, and therefore, even when a rosin ester-based tackifying resin is contained, it is considered that the bending resistance is low.
Claims (4)
1. An adhesive sheet for an image display device, characterized in that,
which has an adhesive layer containing a crosslinked product of an adhesive composition,
the adhesive composition comprises:
(meth) acrylate copolymers as a main component;
an isocyanate-based crosslinking agent; and
a rosin ester based tackifying resin,
the adhesive composition contains 5 to 40 parts by weight of the rosin ester based tackifying resin per 100 parts by weight of the (meth) acrylate copolymer,
the rosin ester tackifying resin is an ester of a rosin ester tackifying resin comprising abietic acid, palustric acid, neoabietic acid, pimaric acid, isopimaric acid or dehydroabietic acid as a main component,
the maximum value of tan delta at 1Hz of the adhesive layer is below-20 ℃,
the adhesive layer has a storage elastic modulus at 25 ℃ of 1.0X10 at 1Hz 5 Pa or below.
2. The adhesive sheet for an image display device according to claim 1, wherein:
storage elastic modulus at-20 ℃ at 1Hz is 1.0X10 5 Pa or below.
3. The adhesive sheet for an image display device according to claim 1 or 2, wherein: the thickness is 5-100 mu m.
4. An adhesive sheet laminate for an image display device, comprising:
the adhesive sheet for an image display device according to any one of claims 1 to 3; and
a base sheet for peeling attached to at least one surface of the adhesive sheet for an image display device.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2019072360A JP7398203B2 (en) | 2019-04-04 | 2019-04-04 | Adhesive sheet for image display devices |
| JP2019-072360 | 2019-04-04 |
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| CN111793439A CN111793439A (en) | 2020-10-20 |
| CN111793439B true CN111793439B (en) | 2024-03-26 |
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| JP (1) | JP7398203B2 (en) |
| KR (1) | KR20200117874A (en) |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007091896A (en) * | 2005-09-29 | 2007-04-12 | Sekisui Chem Co Ltd | Pressure-sensitive adhesive agent |
| JP2017095654A (en) * | 2015-11-27 | 2017-06-01 | 三星エスディアイ株式会社Ｓａｍｓｕｎｇ ＳＤＩ Ｃｏ． | Adhesive for optical film, adhesive layer, optical member and image display device |
| CN107828354A (en) * | 2016-09-16 | 2018-03-23 | 琳得科株式会社 | Flexible display sticker, adhesive sheet, flexible lamination part and flexible display |
| CN107922808A (en) * | 2015-08-21 | 2018-04-17 | 郡是株式会社 | Adhesive composition, bonding sheet and the contact panel and display device that possess the bonding sheet |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009167281A (en) | 2008-01-15 | 2009-07-30 | Sekisui Chem Co Ltd | Double-sided adhesive tape and liquid crystal display device |
| JP5614706B2 (en) | 2009-05-22 | 2014-10-29 | 荒川化学工業株式会社 | Tackifying resin emulsion, method for producing the same, and water-based adhesive / adhesive composition |
| JP2012025808A (en) | 2010-07-21 | 2012-02-09 | Nippon Synthetic Chem Ind Co Ltd:The | Acrylic adhesive, adhesive sheet, and acrylic resin composition |
| JP2014173011A (en) | 2013-03-08 | 2014-09-22 | Nitto Denko Corp | Double-sided adhesive tape |
| JP6807234B2 (en) | 2017-01-10 | 2021-01-06 | 日東電工株式会社 | Adhesive sheet |
-
2019
- 2019-04-04 JP JP2019072360A patent/JP7398203B2/en active Active
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2020
- 2020-02-26 TW TW109106147A patent/TWI818157B/en active
- 2020-03-30 CN CN202010235490.9A patent/CN111793439B/en active Active
- 2020-03-30 KR KR1020200038086A patent/KR20200117874A/en not_active Application Discontinuation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007091896A (en) * | 2005-09-29 | 2007-04-12 | Sekisui Chem Co Ltd | Pressure-sensitive adhesive agent |
| CN107922808A (en) * | 2015-08-21 | 2018-04-17 | 郡是株式会社 | Adhesive composition, bonding sheet and the contact panel and display device that possess the bonding sheet |
| JP2017095654A (en) * | 2015-11-27 | 2017-06-01 | 三星エスディアイ株式会社Ｓａｍｓｕｎｇ ＳＤＩ Ｃｏ． | Adhesive for optical film, adhesive layer, optical member and image display device |
| CN107828354A (en) * | 2016-09-16 | 2018-03-23 | 琳得科株式会社 | Flexible display sticker, adhesive sheet, flexible lamination part and flexible display |
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| 橡胶工业原材料与装备简明手册 2016年版.橡胶工业原材料与装备简明手册 2016年版.《橡胶工业原材料与装备简明手册 2016年版》.2016, * |
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| Publication number | Publication date |
|---|---|
| TW202041640A (en) | 2020-11-16 |
| KR20200117874A (en) | 2020-10-14 |
| CN111793439A (en) | 2020-10-20 |
| TWI818157B (en) | 2023-10-11 |
| JP2020169289A (en) | 2020-10-15 |
| JP7398203B2 (en) | 2023-12-14 |
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