CN108138004B - Stress dispersion film, optical member, and electronic member - Google Patents

Stress dispersion film, optical member, and electronic member Download PDF

Info

Publication number
CN108138004B
CN108138004B CN201680058899.XA CN201680058899A CN108138004B CN 108138004 B CN108138004 B CN 108138004B CN 201680058899 A CN201680058899 A CN 201680058899A CN 108138004 B CN108138004 B CN 108138004B
Authority
CN
China
Prior art keywords
weight
meth
sensitive adhesive
pressure
adhesive layer
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.)
Active
Application number
CN201680058899.XA
Other languages
Chinese (zh)
Other versions
CN108138004A (en
Inventor
佐佐木翔悟
徐创矢
设乐浩司
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to CN201810824492.4A priority Critical patent/CN109181561B/en
Publication of CN108138004A publication Critical patent/CN108138004A/en
Application granted granted Critical
Publication of CN108138004B publication Critical patent/CN108138004B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene 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
    • 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
    • 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
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • 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
    • 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
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
    • 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
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C09J2423/046—Presence of homo or copolymers of ethene in the substrate
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2463/00—Presence of epoxy resin
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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
    • C09J2475/00—Presence of polyurethane
    • 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
    • C09J2477/00—Presence of polyamide
    • C09J2477/006—Presence of polyamide in the substrate
    • 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
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a stress dispersion film having excellent stress dispersion. Also disclosed are an optical member and an electronic member each provided with such a stress dispersion film. The stress dispersion film of the present invention comprises a laminate of a plastic film and an adhesive layer, wherein the press-in energy when a load is applied in a direction perpendicular to the laminate from the plastic film side of the laminate is 260 [ mu ] J or more.

Description

Stress dispersion film, optical member, and electronic member
Technical Field
The present invention relates to a stress dispersion film, and an optical member and an electronic member each including the stress dispersion film.
Background
In order to impart rigidity and impact resistance to touch panels using lcds (liquid crystal displays), lens units of cameras, optical members such as electronic devices, and electronic members, an adhesive film may be bonded to the exposed surface side (for example, patent document 1). Such an adhesive film generally has a base layer and an adhesive layer.
In various cases such as during assembly, processing, transportation, and use, the optical member and the electronic member may be loaded by the press-fitting force, and the optical member and the electronic member may be damaged by the load applied thereto.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2014-234460
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a stress dispersion film having excellent stress dispersibility. Also disclosed are an optical member and an electronic member each provided with such a stress dispersion film.
Means for solving the problems
The stress dispersion film of the present invention comprises a laminate of a plastic film and an adhesive layer, wherein,
the press-in energy when a load is applied in a direction perpendicular to the laminate from the plastic film side of the laminate is 260 [ mu ] J or more.
In one embodiment, the thickness of the plastic film is 4 to 500 μm.
In one embodiment, the adhesive layer has a thickness of 1 to 300 μm.
In one embodiment, the adhesive layer is formed from an adhesive composition containing a polymer (A) having a monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms as an alkyl ester moiety and a monomer unit (II) derived from a (meth) acrylate having an OH group and/or a COOH group in the molecule.
In one embodiment, when the molar content ratio of NCO groups in the adhesive composition is [ NCO ], the molar content ratio of EPOXY groups in the adhesive composition is [ EPOXY ], the molar content ratio of OH groups in the adhesive composition is [ OH ], and the molar content ratio of COOH groups in the adhesive composition is [ COOH ] ([ NCO ] + [ EPOXY ])/([ OH ] + [ COOH ]) < 0.05.
In one embodiment, the adhesive composition contains an organic polyisocyanate-based crosslinking agent and/or an epoxy-based crosslinking agent having a functionality of 2 or more.
In one embodiment, the pressure-sensitive adhesive composition comprises a polymer (B) having a monomer unit derived from a (meth) acrylate ester having an alicyclic structure represented by the general formula (1) and having a weight-average molecular weight of 1000 or more and less than 30000,
CH2＝C(R1)COOR2···(1)
in the general formula (1), R1Is a hydrogen atom or a methyl group, R2Is a hydrocarbon group having an alicyclic structure.
In one embodiment, the adhesive layer has a loss tangent tan δ of 0.10 or more in the entire temperature range of-40 ℃ to 150 ℃.
The optical member of the present invention includes the stress dispersion film.
The electronic component of the present invention includes the stress dispersion film.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a stress dispersion film having excellent stress dispersibility can be provided. Further, an optical member and an electronic member provided with such a stress dispersion film can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view of a stress dispersion film according to an embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view of a stress dispersion film according to another embodiment of the present invention.
Description of the symbols
10 Plastic film
20 adhesive layer
100 stress dispersion film
Detailed Description
In the present specification, the expression "acrylic acid and/or methacrylic acid" means "acrylic acid and/or methacrylic acid" when the expression "meth (acrylic acid ester)" "is present, and the expression" acrylic acid ester and/or methacrylic acid ester "when the expression" meth (acrylic acid ester) "" is present. In the present specification, when the expression "weight" is used, the expression "mass" may be replaced with an SI-based unit representing weight.
In the present specification, when the expression "monomer unit (a) derived from (a)" is present, the monomer unit (a) is a structural unit in which an unsaturated double bond of the monomer (a) is broken by polymerization. The structural unit formed by breaking a bond by polymerization of an unsaturated double bond means a structural unit of "-RpRqC-CRrRs-" formed by breaking a bond by polymerization of an unsaturated double bond "C ═ C" having a structure of "RpRqC ═ CRrRs" (Rp, Rq, Rr, Rs are arbitrary suitable groups bonded to carbon atoms in the form of a single bond).
In the present specification, the content ratio of the monomer unit in the polymer can be known, for example, by various structural analyses (for example, NMR and the like) of the polymer. Further, without performing the various structural analyses as described above, the content ratio of the monomer unit derived from each monomer calculated based on the usage amount of each monomer used in the production of the polymer can be regarded as the content ratio of the monomer unit in the polymer. That is, the content ratio of a certain monomer (m) in the total monomer components used in the production of a polymer can be defined as the content ratio of a monomer unit derived from the monomer (m) in the polymer.
"A. stress Dispersion Membrane
The stress dispersion film of the present invention comprises a laminate of a plastic film and an adhesive layer. The plastic film may have 1 layer or 2 or more layers. The pressure-sensitive adhesive layer may be 1 layer or 2 or more layers.
Fig. 1 is a schematic cross-sectional view of a stress dispersion film according to an embodiment of the present invention. In fig. 1, a stress dispersion film 100 of the present invention is composed of a laminate of a plastic film 10 and an adhesive layer 20. Although not shown in fig. 1, the surface of the adhesive layer 20 may be provided with any suitable strong adhesive layer.
Fig. 2 is a schematic cross-sectional view of a stress dispersion film according to another embodiment of the present invention. In fig. 2, the stress dispersion film 100 of the present invention is composed of a pressure-sensitive adhesive layer 20, a plastic film 10, and a pressure-sensitive adhesive layer 20, and includes the pressure-sensitive adhesive layer 20, the plastic film 10, and the pressure-sensitive adhesive layer 20 in this order. That is, in fig. 2, the stress dispersion film 100 of the present invention is composed of a laminate of an adhesive layer 20, a plastic film 10, and an adhesive layer 20. Although not shown in fig. 2, any suitable strong adhesive layer may be provided on one or both surfaces of the adhesive layer 20.
In the case of the mode in which the pressure-sensitive adhesive layer is exposed as the outermost layer, an arbitrary suitable separator (release sheet) may be provided on the exposed surface side.
The stress dispersion film of the present invention has a press-in energy of 260 [ mu ] J or more when a load is applied from the plastic film side of a laminate of a plastic film and an adhesive layer in a direction perpendicular to the laminate. The method of measuring the indentation energy is described below. The indentation energy is preferably 260. mu.J to 10000. mu.J, more preferably 270. mu.J to 9000. mu.J, still more preferably 280. mu.J to 8000. mu.J, and particularly preferably 290. mu.J to 7000. mu.J. Since the press-in energy is in the above range, a stress dispersion film having excellent stress dispersibility can be provided.
The thickness of the plastic film is preferably 4 to 500. mu.m, more preferably 10 to 400. mu.m, still more preferably 15 to 350. mu.m, and particularly preferably 20 to 300. mu.m. Since the thickness of the plastic film is within the above range, a stress dispersion film having more excellent stress dispersibility can be provided.
The thickness of the pressure-sensitive adhesive layer is preferably 1 to 300. mu.m, more preferably 2 to 250. mu.m, still more preferably 4 to 200. mu.m, and particularly preferably 5 to 150. mu.m. Since the thickness of the adhesive layer is within the above range, a stress dispersion film having more excellent stress dispersibility can be provided.
As the plastic film, any suitable plastic film may be used within a range not impairing the effects of the present invention. Such a plastic film preferably has a compressive strength of 100Kg/cm, for example, under ASTM D6952～3000Kg/cm2More preferably 200Kg/cm2～2900Kg/cm2More preferably 300Kg/cm2～2800Kg/cm2Particularly preferably 400Kg/cm2～2700Kg/cm2. Specific examples of such plastic films include: polyester resins, polyolefin resins, polyamide resins, polyimide resins, and the like. Examples of the polyester-based resin include: polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like. Examples of the polyolefin-based resin include: homopolymers of olefin monomers, copolymers of olefin monomers, and the like. Specific examples of the polyolefin resin include: homopolymerizing propylene; block, random, graft and other propylene copolymers containing an ethylene component as a copolymerization component; reactor TPO; low density, high density, linear low density, ultra low density, and the like ethylene-based polymers; ethylene copolymers such as ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, ethylene-methacrylic acid copolymers, and ethylene-methyl methacrylate copolymers.
The plastic film may contain any suitable additive as required. Examples of additives that can be contained in the plastic film include: antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, pigments, and the like. The kind and amount of the additives that can be contained in the plastic film can be appropriately set according to the purpose.
As the adhesive layer, any suitable adhesive layer may be used within a range not impairing the effects of the present invention. Examples of such a pressure-sensitive adhesive layer include: a pressure-sensitive adhesive layer formed of an acrylic pressure-sensitive adhesive, a pressure-sensitive adhesive layer formed of a rubber pressure-sensitive adhesive, a pressure-sensitive adhesive layer formed of a silicone pressure-sensitive adhesive, a pressure-sensitive adhesive layer formed of a urethane pressure-sensitive adhesive, and the like.
The adhesive layer is preferably formed of an adhesive composition.
The pressure-sensitive adhesive layer is formed, for example, by applying the pressure-sensitive adhesive composition to any suitable substrate and drying the composition as needed. Then, when the substrate is peeled off, an adhesive layer is obtained. In addition, for example, a stress dispersion film including an adhesive layer and a plastic film is obtained by applying the adhesive composition to an arbitrary suitable plastic film, drying the adhesive composition as needed to form an adhesive layer on the plastic film, and leaving the plastic film in this state. Further, for example, a stress dispersion film including a pressure-sensitive adhesive layer and a plastic film is obtained by applying the pressure-sensitive adhesive composition to an arbitrary suitable substrate, drying the composition as needed to form a pressure-sensitive adhesive layer on the substrate, and placing the pressure-sensitive adhesive layer obtained by peeling the substrate on the plastic film. In addition, for example, a stress dispersion film including a pressure-sensitive adhesive layer and a plastic film is obtained by applying the pressure-sensitive adhesive composition to an arbitrary suitable substrate, drying the composition as needed to form a pressure-sensitive adhesive layer on the substrate, and transferring the pressure-sensitive adhesive layer formed on the substrate to the plastic film.
Examples of the method for applying the adhesive composition include: roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater, and the like.
The adhesive composition preferably contains a polymer (A) having a monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms as an alkyl ester moiety and a monomer unit (II) derived from a (meth) acrylate having an OH group and/or a COOH group in the molecule.
The content of the polymer (a) in the adhesive composition is preferably 80 to 100% by weight, more preferably 85 to 100% by weight, even more preferably 90 to 100% by weight, particularly preferably 92.5 to 100% by weight, and most preferably 95 to 100% by weight. Since the content ratio of the polymer (a) in the adhesive composition is within the above range, a stress dispersion film having more excellent stress dispersibility can be provided.
The polymer (A) has a monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group with 1-20 carbon atoms as an alkyl ester moiety. The number of monomer units (I) derived from an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms as an alkyl ester moiety in the polymer (A) may be only 1, or 2 or more.
The content ratio of the monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms as an alkyl ester moiety in the polymer (a) is preferably 90 to 99.5% by weight, more preferably 91 to 99% by weight, still more preferably 92 to 98.5% by weight, particularly preferably 93 to 98.2% by weight, and most preferably 94 to 98% by weight. The content ratio of the monomer unit (I) derived from the alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms as an alkyl ester moiety in the polymer (A) is within the above range, and therefore a stress dispersion film having more excellent stress dispersion can be provided.
Examples of the alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms as an alkyl ester moiety include: methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, and the like.
The polymer (A) has a monomer unit (II) derived from a (meth) acrylate having an OH group and/or a COOH group in the molecule. The number of monomer units (II) derived from a (meth) acrylate having an OH group and/or a COOH group in the molecule in the polymer (a) may be only 1, or 2 or more. Since the polymer (a) has the monomer unit (II) derived from a (meth) acrylate having an OH group and/or a COOH group in the molecule, a stress dispersion film having more excellent stress dispersibility can be provided.
The content ratio of the monomer unit (II) derived from a (meth) acrylate having an OH group and/or a COOH group in the molecule in the polymer (a) is preferably 0.5 to 10% by weight, more preferably 1 to 9% by weight, still more preferably 1.5 to 8% by weight, particularly preferably 1.8 to 7% by weight, and most preferably 2 to 6% by weight. Since the content ratio of the monomer unit (II) derived from a (meth) acrylate having an OH group and/or a COOH group in the molecule in the polymer (a) is in the above range, a stress dispersion film having more excellent stress dispersibility can be provided.
Examples of the (meth) acrylate having an OH group in the molecule include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, methyl (4-hydroxymethylcyclohexyl) acrylate, N-methylol (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol vinyl ether, and the like.
Examples of the (meth) acrylate having a COOH group in the molecule include: (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.
The polymer (A) may also have a monomer unit (III) derived from another monomer. The number of the monomer units (III) derived from other monomers in the polymer (a) may be only 1, or may be 2 or more.
Examples of the other monomers include: cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, amide group-containing monomers, imide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, vinyl ether monomers, N-acryloyl morpholine, sulfonic group-containing monomers, phosphoric group-containing monomers, acid anhydride group-containing monomers, and the like.
In the adhesive composition, ([ NCO ] + [ EPOXY ])/([ OH ] + [ COOH ]) is less than 0.05, where [ NCO ] is a molar content ratio of NCO groups in the adhesive composition, [ EPOXY ] is a molar content ratio of EPOXY groups in the adhesive composition, [ OH ] is a molar content ratio of OH groups in the adhesive composition, and [ COOH ] is a molar content ratio of COOH groups in the adhesive composition. Since ([ NCO ] + [ EPOXY ])/([ OH ] + [ COOH ]) is in the above range, a stress dispersion film having more excellent stress dispersion can be provided. When no NCO group is present in the adhesive composition, [ NCO ] ═ 0, and when no EPOXY group is present in the adhesive composition, [ EPOXY ] ═ 0. That is, the lower limit value of ([ NCO ] + [ EPXY ])/([ OH ] + [ COOH ]) is 0.
The adhesive composition preferably contains an organic polyisocyanate-based crosslinking agent having 2 or more functions and/or an epoxy-based crosslinking agent. The number of the organic polyisocyanate-based crosslinking agent and/or epoxy-based crosslinking agent having 2 or more functions which can be contained in the adhesive composition of the present invention may be only 1, or 2 or more.
The total content of the 2-or more-functional organic polyisocyanate-based crosslinking agent and the epoxy-based crosslinking agent in the adhesive composition is preferably 0.001 to 0.4 parts by weight, more preferably 0.0025 to 0.3 parts by weight, much more preferably 0.005 to 0.2 parts by weight, particularly preferably 0.0075 to 0.15 parts by weight, and most preferably 0.01 to 0.1 parts by weight, based on 100 parts by weight of the polymer (a). Since the total content ratio of the 2 or more functional organic polyisocyanate-based crosslinking agent and the epoxy-based crosslinking agent in the adhesive composition of the present invention is within the above range with respect to 100 parts by weight of the polymer (a), a stress dispersion film having more excellent stress dispersibility can be provided.
Examples of the organic polyisocyanate-based crosslinking agent having 2 or more functions include: lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; aromatic isocyanates such as 2, 4-tolylene diisocyanate, 4' -diphenylmethane diisocyanate, and xylylene diisocyanate; trimethylolpropane-tolylene diisocyanate trimer adduct (for example, product name "Coronate L" manufactured by japan polyurethane industries), trimethylolpropane-hexamethylene diisocyanate trimer adduct (for example, product name "Coronate HL" manufactured by japan polyurethane industries), isocyanurate of hexamethylene diisocyanate (for example, product name "Coronate HX" manufactured by japan polyurethane industries), and the like.
Examples of the epoxy crosslinking agent include: bisphenol A, an epoxy resin of the epichlorohydrin type, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, 1, 6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamine glycidylamine, N, N, N ', N' -tetraglycidyl m-xylylenediamine (for example, trade name "TETRAD-X" manufactured by Mitsubishi gas chemical corporation), 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane (for example, trade name "TETRAD-C" manufactured by Mitsubishi gas chemical corporation), and the like.
The adhesive composition may also contain a polymer (B) having a monomer unit derived from a (meth) acrylate ester having an alicyclic structure represented by the general formula (1), a weight average molecular weight of 1000 or more and less than 30000,
CH2＝C(R1)COOR2···(1)
in the general formula (1), R1Is a hydrogen atom or a methyl group, R2Is a hydrocarbon group having an alicyclic structure.
The number of the polymers (B) may be only 1, or may be 2 or more.
The weight average molecular weight of the polymer (B) is preferably 1000 to 30000, more preferably 1250 to 25000, further preferably 1500 to 20000, particularly preferably 1750 to 15000, and most preferably 2000 to 10000. Since the weight average molecular weight of the polymer (B) is within the above range, a stress dispersion film having more excellent stress dispersibility can be provided even if the amount of the crosslinking agent is increased.
The content of the polymer (B) in the adhesive composition is preferably 0.5 to 50 parts by weight, more preferably 1 to 45 parts by weight, even more preferably 2 to 40 parts by weight, particularly preferably 3 to 35 parts by weight, and most preferably 4 to 30 parts by weight, based on 100 parts by weight of the polymer (a). Since the content ratio of the polymer (B) in the adhesive composition is in the above range with respect to 100 parts by weight of the polymer (a), even if the amount of the crosslinking agent is increased, a stress dispersion film having more excellent stress dispersibility can be provided.
The content ratio of the monomer unit derived from the (meth) acrylate ester having an alicyclic structure represented by the general formula (1) in the polymer (B) is preferably 40 to 99.5% by weight, more preferably 42.5 to 99% by weight, still more preferably 45 to 98.5% by weight, particularly preferably 47.5 to 98% by weight, and most preferably 50 to 97.5% by weight. Since the content ratio of the monomer unit derived from the (meth) acrylate containing an alicyclic structure represented by the general formula (1) in the polymer (B) is in the above range, a stress dispersion film having more excellent stress dispersibility can be provided even if the amount of the crosslinking agent is increased.
Examples of the (meth) acrylate having an alicyclic structure represented by the above general formula (1) include: cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl methacrylate, dicyclopentanyloxyethyl acrylate, tricyclopentanyl methacrylate, tricyclopentanyl acrylate, 1-adamantyl methacrylate, 1-adamantyl acrylate, 2-methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl acrylate, and the like.
The polymer (B) may have a monomer unit (IV) derived from another monomer. The number of the monomer units (IV) derived from other monomers in the polymer (B) may be only 1, or may be 2 or more.
Examples of other monomers that may be included in the polymer (B) include: methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, methacrylic acid, and the like.
The polymer (a) and the polymer (B) can be produced by any suitable method within a range not impairing the effects of the present invention. Examples of such a production method include: solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, photopolymerization (active energy ray polymerization), and the like. Among these production methods, solution polymerization is preferred from the viewpoint of cost and productivity. The polymer (a) obtained may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like. The polymer (B) obtained may be a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, or the like.
Examples of the method of solution polymerization include a method of dissolving a monomer component, a polymerization initiator, and the like in a solvent and heating and polymerizing the solution to obtain a polymer solution.
The heating temperature in the heating polymerization in the solution polymerization is, for example, 50 to 90 ℃. The heating time in the solution polymerization may be, for example, 1 to 24 hours.
As the solvent used in the solution polymerization, any suitable solvent may be used within a range not impairing the effects of the present invention. Examples of such solvents include: aromatic hydrocarbons such as toluene, benzene, and xylene; esters such as ethyl acetate and n-butyl acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and organic solvents such as ketones, e.g., methyl ethyl ketone and methyl isobutyl ketone. The number of the solvents may be only 1, or 2 or more.
In the production of the polymer (a) and the polymer (B), a polymerization initiator may be used. Such a polymerization initiator may be 1 kind or 2 or more kinds. Examples of such a polymerization initiator include: azo initiators such as 2,2' -azobisisobutyronitrile, 2' -azobis (2-amidinopropane) dihydrochloride, 2' -azobis [2- (5-methyl-2-imidazolin-2-yl) propane ] dihydrochloride, 2' -azobis (2-methylamidino) disulfate, 2' -azobis (N, N ' -dimethylisobutylamidine), and 2,2' -azobis [ N- (2-carboxyethyl) -2-methylamidino ] hydrate (Wako pure chemical industries, Ltd., VA-057); persulfates such as potassium persulfate and ammonium persulfate; peroxide initiators such as di (2-ethylhexyl) peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, di-sec-butyl peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,3, 3-tetramethylbutyl peroxy2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, tert-butyl peroxyisobutyrate, 1-di (tert-hexylperoxy) cyclohexane, tert-butyl hydroperoxide, and hydrogen peroxide; combinations of persulfates with sodium bisulfite, combinations of peroxides with sodium ascorbate, and redox initiators in which a peroxide is combined with a reducing agent.
As for the amount of the polymerization initiator used, any suitable amount may be employed within a range not impairing the effects of the present invention. The amount of such a monomer is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the monomer component.
In the production of the polymer (a) and the polymer (B), a chain transfer agent may be used. Such a chain transfer agent may be 1 type or 2 or more types. Examples of such chain transfer agents include: lauryl mercaptan, glycidyl mercaptan, thioglycolic acid, 2-mercaptoethanol, thioglycolic acid, methyl thioglycolate, 2-ethylhexyl thioglycolate, 2, 3-dimercapto-1-propanol, and the like.
As for the amount of the chain transfer agent to be used, any suitable amount may be employed within a range not impairing the effects of the present invention. The amount of such a monomer is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the monomer component.
In the production of the polymer (A) and the polymer (B), any other suitable additive generally used in polymerization reactions may be used.
The adhesive composition of the invention may also contain a crosslinking catalyst. As the crosslinking catalyst, any suitable crosslinking catalyst may be used within a range not impairing the effects of the present invention. Examples of such a crosslinking catalyst include: metal-based crosslinking catalysts (particularly tin-based crosslinking catalysts) such as tetra-n-butyl titanate, tetra-isopropyl titanate, iron acetylacetonate, butyltin oxide, and dioctyltin dilaurate. The number of crosslinking catalysts may be only 1, or may be 2 or more.
As for the amount of the crosslinking catalyst used, any suitable amount may be employed within a range not impairing the effects of the present invention. The amount of such a monomer is preferably 0.001 to 0.05 parts by weight based on 100 parts by weight of the monomer component.
The adhesive composition may also contain any suitable other additives within a range not impairing the effects of the present invention. Examples of such other additives include: silane coupling agents, delayed crosslinking agents, emulsifiers, colorants, powders such as pigments, dyes, surfactants, plasticizers, adhesion imparting agents, surface lubricants, leveling agents, softeners, antioxidants, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic fillers, organic fillers, metal powders, particles, foils, and the like. Such other additives may be only 1 type or 2 or more types.
The adhesive layer preferably has a loss tangent tan delta of 0.10 or more over the entire temperature range of-40 ℃ to 150 ℃. By setting the loss tangent tan delta of the pressure-sensitive adhesive layer to 0.10 or more in the entire temperature range of-40 ℃ to 150 ℃, a stress dispersion film having more excellent stress dispersion can be provided. The method for measuring the loss tangent tan δ is described below.
The upper limit of the loss tangent tan δ of the pressure-sensitive adhesive layer is preferably 2.40 or less, more preferably 2.20 or less, further preferably 2.00 or less, and particularly preferably 1.80 or less, over the entire temperature range of-40 to 150 ℃. By setting the upper limit of the loss tangent tan δ within the above range, a stress dispersion film having more excellent stress dispersibility can be provided.
The lower limit of the loss tangent tan δ of the pressure-sensitive adhesive layer in the entire temperature range of-40 ℃ to 150 ℃ is preferably 0.12 or more, more preferably 0.14 or more, still more preferably 0.16 or more, and particularly preferably 0.18 or more. By setting the lower limit of the loss tangent tan δ within the above range, a stress dispersion film having more excellent stress dispersibility can be provided.
Optical and electronic Components
The stress dispersion film of the present invention has excellent stress dispersion. Therefore, the resin composition can be suitably used as a protective material for the purpose of protecting an optical member and an electronic member from external impact or the like. That is, the optical member of the present invention includes the stress dispersion film of the present invention. The electronic component of the present invention includes the stress dispersion film of the present invention.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The test and evaluation methods in examples and the like are as follows. In the case where "part" is described, it means "part by weight" unless otherwise specified, and in the case where "%" is described, "wt%" unless otherwise specified.
< determination of weight average molecular weight >
The weight average molecular weight (Mw) of the polymer was measured using a GPC apparatus (HLC-8220GPC) manufactured by Tosoh corporation. The weight average molecular weight (Mw) is determined by a polystyrene conversion value.
The measurement conditions are as follows.
Sample concentration: 0.2 wt% (THF solution)
Sample injection amount: 10 μ l of eluate
Flow rate of THF: 0.6ml/min
Measuring temperature: 40 deg.C
Sample column: TSKguardcolumn SuperHZ-H (1 root) + TSKgel SuperHZM-H (2 roots)
Reference column: TSKgel SuperH-RC (1 root)
A detector: differential Refractometer (RI)
< production of adhesive sheet (A) >
(examples 1,3, 5, 7, 9, 11, 13, 15, 17, 19, 21, 23, 25, 26, comparative examples 1,3, 5, 7)
The obtained adhesive composition was applied to a polyester resin substrate "lumiror S10" (thickness 50 μm, manufactured by toray corporation) by a liquid feeding roll so that the thickness after drying became 10 μm, and cured and dried under the conditions of a drying temperature of 130 ℃ and a drying time of 30 seconds. In this manner, an adhesive layer is produced on the substrate. Next, the silicone-treated surface of the base material made of a polyester resin having a thickness of 25 μm, on which the silicone treatment was performed on the other surface, was bonded to the surface of the pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive sheet (a).
(examples 2,4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, comparative examples 2,4, 6, 8)
The obtained adhesive composition was applied to a polyester resin substrate "lumiror S10" (thickness 38 μm, manufactured by toray corporation) by a liquid feeding roll so that the dried thickness became 22 μm, and cured and dried under the conditions of a drying temperature of 130 ℃ and a drying time of 30 seconds. In this manner, an adhesive layer is produced on the substrate. Next, the silicone-treated surface of the base material made of a polyester resin having a thickness of 25 μm, on which the silicone treatment was performed on the other surface, was bonded to the surface of the pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive sheet (a).
< determination of indentation energy >
The measurement temperature was measured using "SAICASDN-20" manufactured by Daipla Wintes, Inc.: 25 ℃ and pressing speed: the energy for pressing was calculated at 5 μm/sec in the following order.
(sequence 1)
The pressure-sensitive adhesive layer side of the obtained pressure-sensitive adhesive sheet (a) was attached to a flat indenter (load detection side), and the pressure-sensitive adhesive sheet (a) attached to the flat indenter was pressed from the substrate side thereof with a spherical indenter, and the press-in depth (μm) at the time of detection of a load of 20N was calculated.
(sequence 2)
The pressure-sensitive adhesive layer side of the obtained pressure-sensitive adhesive sheet (a) was stuck to a glass slide, and the pressure-sensitive adhesive sheet (a) stuck to the glass slide was press-fitted from the base material side (load detection side) thereof by a ball indenter to the press-fitting depth determined in sequence 1.
When the vertical load applied to the spherical indenter is defined as y ═ f (x) (x: press-in depth), press-in energy W (μ J) until 20N is applied to the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet (a) is calculated by the following formula (r is the press-in depth when 20N of load is applied to the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet (a)).
[ mathematical formula 1]
Figure BDA0001622171850000131
< production of adhesive sheet (B) >
The obtained pressure-sensitive adhesive composition was applied to a release-treated surface of a polyester film (trade name: MRF, manufactured by Mitsubishi chemical polyester Co., Ltd.) having a thickness of 38 μm, one surface of which was release-treated with silicone, by a doctor roll so that the thickness after drying became 50 μm, and cured and dried under conditions of a drying temperature of 130 ℃ and a drying time of 3 minutes. In this manner, an adhesive layer is produced on the substrate. Then, the surface of the pressure-sensitive adhesive layer was coated with a 38 μm thick polyester film (trade name: MRF, manufactured by Mitsubishi chemical polyester Co., Ltd.) whose one surface was peeled off with silicone so that the peeled surface of the film was on the pressure-sensitive adhesive layer side. Thus, a pressure-sensitive adhesive sheet (B) was produced.
< measurement of glass transition temperature (Tg), storage modulus, loss modulus, tan delta (loss tangent) >)
The measurement was carried out by the following method using a dynamic viscoelasticity measuring apparatus (ARES, manufactured by Rheometric Co., Ltd.).
Only the pressure-sensitive adhesive layer was taken out from the obtained pressure-sensitive adhesive sheet (B), laminated to a thickness of about 2mm, and pressed to 7.9mm to prepare cylindrical pellets, which were used as a measurement sample. The jig in which the measurement sample was fixed to a 7.9mm parallel plate was used to measure the temperature dependence of the storage elastic modulus G 'and the loss elastic modulus G ″ with the dynamic viscoelasticity measuring apparatus, and tan δ was calculated as G ═ G "/G'. The temperature at which the obtained tan δ curve becomes maximum is defined as the glass transition temperature (Tg) (° c).
The measurement conditions are as follows.
And (3) determination: a shearing mode,
Temperature range: -70 ℃ to 150 DEG C
Temperature rise rate: 5 ℃/min
Frequency: 1Hz
[ production example 1 ]: (meth) acrylic Polymer (1)
2-ethylhexyl acrylate (manufactured by Nippon catalyst Co., Ltd.) was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser: 100 parts by weight of 2-hydroxyethyl acrylate (manufactured by Toyo Synthesis Co., Ltd.): 4 parts by weight of 2,2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 0.2 part by weight, ethyl acetate: 156 parts by weight of a (meth) acrylic polymer (1) solution (40% by weight) having a weight-average molecular weight of 55 ten thousand was prepared by conducting polymerization for 6 hours while introducing nitrogen gas with gentle stirring while keeping the liquid temperature in the flask at about 65 ℃.
[ production example 2 ]: (meth) acrylic acid-based Polymer (2)
2-ethylhexyl acrylate (manufactured by Nippon catalyst Co., Ltd.) was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser: 100 parts by weight of 4-hydroxybutyl acrylate (manufactured by Osaka organic chemical industries, Ltd.): 10 parts by weight of acrylic acid (manufactured by Toyo Synthesis Co., Ltd.): 0.02 part by weight of 2,2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 0.2 part by weight, ethyl acetate: 156 parts by weight of a (meth) acrylic polymer (2) solution (40% by weight) having a weight-average molecular weight of 54 ten thousand was prepared by conducting polymerization for 6 hours while introducing nitrogen gas with gentle stirring while keeping the liquid temperature in the flask at about 65 ℃.
[ production example 3 ]: (meth) acrylic acid-based Polymer (3)
Butyl acrylate (manufactured by japan catalyst corporation) was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser: 99 parts by weight of 4-hydroxybutyl acrylate (manufactured by osaka organic chemical industries, inc.): 1 part by weight of 2,2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 1 part by weight, ethyl acetate: 156 parts by weight of a (meth) acrylic polymer (3) solution (39% by weight) having a weight average molecular weight of 160 ten thousand was prepared by conducting polymerization for 7 hours while introducing nitrogen gas with gentle stirring while maintaining the liquid temperature in the flask at about 60 ℃.
[ production example 4 ]: (meth) acrylic acid-based Polymer (4)
Butyl acrylate (manufactured by japan catalyst corporation) was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser: 92 parts by weight of N-acryloyl morpholine (manufactured by Kyoho Co., Ltd.): 5 parts by weight of acrylic acid (manufactured by Toyo Synthesis Co., Ltd.): 2.9 parts by weight of 2,2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 0.1 part by weight, ethyl acetate: 200 parts by weight of a (meth) acrylic polymer (4) solution (33% by weight) having a weight-average molecular weight of 180 ten thousand was prepared by conducting polymerization for 8 hours while introducing nitrogen gas with gentle stirring while maintaining the liquid temperature in the flask at about 55 ℃.
[ production example 5 ]: (meth) acrylic acid-based Polymer (5)
Butyl acrylate (manufactured by japan catalyst corporation) was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser: 95 parts by weight of acrylic acid (manufactured by Toyo Synthesis Co., Ltd.): 5 parts by weight of 2,2' -azobisisobutyronitrile (Wako pure chemical industries, Ltd.) as a polymerization initiator: 0.2 part by weight, ethyl acetate: 156 parts by weight of a (meth) acrylic polymer (5) solution (40% by weight) having a weight-average molecular weight of 70 ten thousand was prepared by conducting polymerization for 10 hours while introducing nitrogen gas with gentle stirring while maintaining the liquid temperature in the flask at about 63 ℃.
[ production example 6 ]: (meth) acrylic polymer (6) having an alicyclic structure
The glass transition temperature of cyclohexyl methacrylate [ homopolymer (polycyclohexyl methacrylate) ] as a monomer component was measured: 66 ℃ C. ]: 95 parts by weight, acrylic acid: 5 parts by weight of 2-mercaptoethanol as a chain transfer agent: 3 parts by weight of 2,2' -azobisisobutyronitrile as a polymerization initiator: 0.2 parts by weight, and toluene as a polymerization solvent: 103.2 parts by weight of the reaction solution was put into a separable flask, and stirred for 1 hour while introducing nitrogen gas. After removing the oxygen in the polymerization system in this manner, the temperature was raised to 70 ℃ and the reaction was carried out for 3 hours, and further at 75 ℃ for 2 hours, to obtain a solution (50 wt%) of the (meth) acrylic polymer (6) having a weight average molecular weight of 4000.
[ production example 6 ]: (meth) acrylic polymer (7) having alicyclic structure
Into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, a condenser, and a dropping funnel were charged toluene: 100 parts by weight of dicyclopentyl methacrylate (DCPMA) (trade name: FA-513M, manufactured by Hitachi chemical industries, Ltd.): 60 parts by weight, Methyl Methacrylate (MMA): 40 parts by weight, and methyl thioglycolate as a chain transfer agent: 3.5 parts by weight. Next, after stirring at 70 ℃ under a nitrogen atmosphere for 1 hour, 2' -azobisisobutyronitrile: 0.2 part by weight, at 70 ℃ for 2 hours, then at 80 ℃ for 4 hours, after which at 90 ℃ for 1 hour, to obtain a weight average molecular weight 4000 (meth) acrylic polymer (7) solution (51 wt%).
[ examples 1 and 2 ]
The solution of the (meth) acrylic polymer (1) was diluted with ethyl acetate so that the total solid content became 25 wt% with respect to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (1), and the diluted solution was stirred with a disperser to obtain an acrylic resin-containing pressure-sensitive adhesive composition (1). The results are shown in table 1.
[ examples 3 and 4 ]
To a solution of the (meth) acrylic polymer (1), 0.01 part by weight of Coronate L (manufactured by japan polyurethane industries) as a crosslinking agent in terms of solid content and 0.005 part by weight of iron acetylacetonate (manufactured by japan chemical industries) as a crosslinking catalyst in terms of solid content were added to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (1), and the resultant was diluted with ethyl acetate so that the total solid content became 25 wt%, and stirred with a disperser to obtain an acrylic resin-containing pressure-sensitive adhesive composition (2). The results are shown in table 1.
[ examples 5 and 6 ]
To a solution of the (meth) acrylic polymer (1), 0.1 part by weight of Coronate L (manufactured by japan polyurethane industries) as a crosslinking agent in terms of solid content and 0.005 part by weight of iron acetylacetonate (manufactured by japan chemical industries) as a crosslinking catalyst in terms of solid content were added to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (1), and the resultant was diluted with ethyl acetate so that the total solid content became 25 wt%, and stirred with a disperser to obtain an acrylic resin-containing pressure-sensitive adhesive composition (3). The results are shown in table 1.
[ examples 7 and 8 ]
To a solution of the (meth) acrylic polymer (1), 0.05 parts by weight of Coronate L (manufactured by japan polyurethane industries) as a crosslinking agent in terms of solid content, 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical industries) as a crosslinking catalyst in terms of solid content, and 5 parts by weight of a solution of the (meth) acrylic polymer (6) in terms of solid content were added to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (1), and the solution was diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred with a disperser, to obtain an acrylic resin-containing pressure-sensitive adhesive composition (4). The results are shown in table 1.
[ examples 9 and 10 ]
To a solution of the (meth) acrylic polymer (1), 0.1 part by weight of Coronate L (manufactured by japan polyurethane industries) as a crosslinking agent in terms of solid content, 0.005 part by weight of iron acetylacetonate (manufactured by japan chemical industries) as a crosslinking catalyst in terms of solid content, and 5 parts by weight of a solution of the (meth) acrylic polymer (6) in terms of solid content were added to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (1), and the solution was diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred by a disperser, to obtain an acrylic resin-containing pressure-sensitive adhesive composition (5). The results are shown in table 1.
[ examples 11 and 12 ]
To a solution of the (meth) acrylic polymer (1), 0.3 parts by weight of Coronate L (manufactured by japan polyurethane industries) as a crosslinking agent in terms of solid content, 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical industries) as a crosslinking catalyst in terms of solid content, and 5 parts by weight of a solution of the (meth) acrylic polymer (6) in terms of solid content were added to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (1), and the solution was diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred with a disperser, to obtain an acrylic resin-containing pressure-sensitive adhesive composition (6). The results are shown in table 1.
[ examples 13 and 14 ]
To a solution of the (meth) acrylic polymer (1), 0.1 part by weight of Coronate L (manufactured by japan polyurethane industries) as a crosslinking agent in terms of solid content, 0.005 part by weight of iron acetylacetonate (manufactured by japan chemical industries) as a crosslinking catalyst in terms of solid content, and 5 parts by weight of a solution of the (meth) acrylic polymer (7) in terms of solid content were added to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (1), and the solution was diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred by a disperser, to obtain an acrylic resin-containing pressure-sensitive adhesive composition (7). The results are shown in table 1.
[ examples 15 and 16 ]
To a solution of the (meth) acrylic polymer (1), 0.3 parts by weight of Coronate L (manufactured by japan polyurethane industries) as a crosslinking agent in terms of solid content, 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical industries) as a crosslinking catalyst in terms of solid content, and 5 parts by weight of a solution of the (meth) acrylic polymer (7) in terms of solid content were added to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (1), and the solution was diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred by a disperser, to obtain an acrylic resin-containing pressure-sensitive adhesive composition (8). The results are shown in table 1.
[ examples 17 and 18 ]
In the solution of the (meth) acrylic polymer (2), the total solid content was diluted with ethyl acetate so that the total solid content became 25 wt% with respect to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (2), and the resultant was stirred with a disperser to obtain an acrylic resin-containing pressure-sensitive adhesive composition (9). The results are shown in table 2.
[ examples 19 and 20 ]
To a solution of the (meth) acrylic polymer (2), 0.1 part by weight of Coronate L (manufactured by japan polyurethane industries) as a crosslinking agent in terms of solid content, 0.05 part by weight of TETRAD-C (manufactured by mitsubishi gas chemical corporation) in terms of solid content, and 0.005 part by weight of iron acetylacetonate (manufactured by japan chemical industries) as a crosslinking catalyst in terms of solid content were added to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (2), and the entire solution was diluted with ethyl acetate and stirred with a disperser so that the total solid content became 25 wt%. The results are shown in table 2.
[ examples 21 and 22 ]
To a solution of the (meth) acrylic polymer (3), 0.02 part by weight of Coronate L (manufactured by japan polyurethane industries) as a crosslinking agent in terms of solid content and 0.005 part by weight of iron acetylacetonate (manufactured by japan chemical industries) as a crosslinking catalyst in terms of solid content were added to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (3), and the resultant was diluted with ethyl acetate so that the total solid content became 25 wt%, and stirred with a disperser to obtain an acrylic resin-containing pressure-sensitive adhesive composition (11). The results are shown in table 2.
[ examples 23 and 24 ]
In the solution of the (meth) acrylic polymer (5), 0.075 part by weight of TETRAD-C (manufactured by mitsubishi gas chemical company) as a crosslinking agent in terms of solid content and 0.005 part by weight of iron acetylacetonate (manufactured by japan chemical industry company) as a crosslinking catalyst in terms of solid content were added to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (5), and the mixture was diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred by a disperser to obtain an acrylic resin-containing adhesive composition (12). The results are shown in table 2.
[ example 25 ]
An adhesive composition (13) containing a rubber-based resin was obtained by diluting with toluene so that the total solid content became 25 wt% with respect to 100 parts by weight of HYBRAR 5125 (manufactured by KURARAY). The results are shown in table 2.
[ example 26 ]
An adhesive composition (14) containing a rubber-based resin was obtained by diluting with toluene so that the total solid content became 25 wt% with respect to 100 parts by weight of HYBRAR 5127 (manufactured by KURARAY). The results are shown in table 2.
[ comparative examples 1 and 2 ]
To a solution of the (meth) acrylic polymer (1), 0.5 parts by weight of Coronate L (manufactured by japan polyurethane industries) as a crosslinking agent in terms of solid content and 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical industries) as a crosslinking catalyst in terms of solid content were added to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (1), and the resultant was diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred by a disperser to obtain an acrylic resin-containing pressure-sensitive adhesive composition (C1). The results are shown in table 2.
[ comparative examples 3 and 4 ]
To a solution of the (meth) acrylic polymer (2), 0.45 parts by weight of Coronate L (manufactured by japan polyurethane industries) as a crosslinking agent in terms of solid content, 0.3 parts by weight of TETRAD-C (manufactured by mitsubishi gas chemical corporation) in terms of solid content, and 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical industries) as a crosslinking catalyst in terms of solid content were added to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (2), and the mixture was diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred by a disperser to obtain an acrylic resin-containing adhesive composition (C2). The results are shown in table 2.
[ comparative examples 5 and 6 ]
To a solution of the (meth) acrylic polymer (4), 0.3 parts by weight of Coronate L (manufactured by japan polyurethane industries) as a crosslinking agent in terms of solid content and 0.005 parts by weight of iron acetylacetonate (manufactured by japan chemical industries) as a crosslinking catalyst in terms of solid content were added to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (4), and the resultant was diluted with ethyl acetate so that the total solid content became 25% by weight, and stirred by a disperser to obtain an acrylic resin-containing pressure-sensitive adhesive composition (C3). The results are shown in table 2.
[ comparative examples 7 and 8 ]
In the solution of the (meth) acrylic polymer (5), 0.075 part by weight of TETRAD-C (manufactured by mitsubishi gas chemical company) as a crosslinking agent in terms of solid content, 0.005 part by weight of iron acetylacetonate (manufactured by japan chemical industry company) as a crosslinking catalyst in terms of solid content, and 20 parts by weight of the solution of the (meth) acrylic polymer (6) in terms of solid content were added to 100 parts by weight of the solid content of the solution of the (meth) acrylic polymer (5) to dilute the solution with ethyl acetate so that the total solid content became 25% by weight, and the resulting solution was stirred by a disperser to obtain an acrylic resin-containing adhesive composition (C4). The results are shown in table 2.
Figure BDA0001622171850000211
Figure BDA0001622171850000221
[ example 27 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive compositions (1) obtained in examples 1 and 2 was peeled from one side of the polyester film, and bonded to a polarizing plate (trade name "TEG 1465 DUHC", manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which the pressure-sensitive adhesive sheet was bonded.
[ example 28 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive compositions (2) obtained in examples 3 and 4 was peeled from one side of the polyester film, and bonded to a polarizing plate (trade name "TEG 1465 DUHC", manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which the pressure-sensitive adhesive sheet was bonded.
[ example 29 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive compositions (4) obtained in examples 7 and 8 was peeled from one side of the polyester film, and bonded to a polarizing plate (trade name "TEG 1465 DUHC", manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which the pressure-sensitive adhesive sheet was bonded.
[ example 30 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive compositions (7) obtained in examples 13 and 14 was peeled from one side of the polyester film, and bonded to a polarizing plate (trade name "TEG 1465 DUHC", manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which the pressure-sensitive adhesive sheet was bonded.
[ example 31 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive compositions (9) obtained in examples 17 and 18 was peeled from one side of the polyester film, and bonded to a polarizing plate (trade name "TEG 1465 DUHC", manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which the pressure-sensitive adhesive sheet was bonded.
[ example 32 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive compositions (10) obtained in examples 19 and 20 was peeled from one side of the polyester film, and bonded to a polarizing plate (trade name "TEG 1465 DUHC", manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which the pressure-sensitive adhesive sheet was bonded.
[ example 33 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive compositions (11) obtained in examples 21 and 22 was peeled from one side of the polyester film, and bonded to a polarizing plate (trade name "TEG 1465 DUHC", manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which the pressure-sensitive adhesive sheet was bonded.
[ example 34 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive compositions (12) obtained in examples 23 and 24 was peeled from one side of the polyester film, and bonded to a polarizing plate (trade name "TEG 1465 DUHC", manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which the pressure-sensitive adhesive sheet was bonded.
[ example 35 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive composition (13) obtained in example 25 was peeled from one side of the polyester film, and bonded to a polarizing plate (product name "TEG 1465 DUHC") as an optical member, to obtain an optical member to which the pressure-sensitive adhesive sheet was bonded.
[ example 36 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive composition (14) obtained in example 26 was peeled from one side of the polyester film, and bonded to a polarizing plate (product name "TEG 1465 DUHC") as an optical member, to obtain an optical member to which the pressure-sensitive adhesive sheet was bonded.
[ example 37 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive compositions (1) obtained in examples 1 and 2 was peeled from one side of the polyester film and bonded to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by hitong electrical corporation) as an electronic component, to obtain an electronic component to which the pressure-sensitive adhesive sheet was bonded.
[ example 38 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive compositions (2) obtained in examples 3 and 4 was peeled from one side of the polyester film and bonded to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by hitong electrical corporation) as an electronic component, to obtain an electronic component to which the pressure-sensitive adhesive sheet was bonded.
[ example 39 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive compositions (4) obtained in examples 7 and 8 was peeled from one side of the polyester film and bonded to a conductive film (product name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component to which the pressure-sensitive adhesive sheet was bonded.
[ example 40 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive compositions (7) obtained in examples 13 and 14 was peeled from one side of the polyester film and bonded to a conductive film (product name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component to which the pressure-sensitive adhesive sheet was bonded.
[ example 41 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive compositions (9) obtained in examples 17 and 18 was peeled from one side of the polyester film and bonded to a conductive film (product name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component to which the pressure-sensitive adhesive sheet was bonded.
[ example 42 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive compositions (10) obtained in examples 19 and 20 was peeled from one side of the polyester film and bonded to a conductive film (product name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component to which the pressure-sensitive adhesive sheet was bonded.
[ example 43 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive compositions (11) obtained in examples 21 and 22 was peeled from one side of the polyester film and bonded to a conductive film (product name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component to which the pressure-sensitive adhesive sheet was bonded.
[ example 44 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive compositions (12) obtained in examples 23 and 24 was peeled from one side of the polyester film and bonded to a conductive film (product name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component to which the pressure-sensitive adhesive sheet was bonded.
[ example 45 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive composition (13) obtained in example 25 was peeled from one surface of the polyester film and bonded to a conductive film (product name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component to which the pressure-sensitive adhesive sheet was bonded.
[ example 46 ]
Each of the pressure-sensitive adhesive sheets (a) and (B) obtained from the pressure-sensitive adhesive composition (14) obtained in example 26 was peeled from one surface of the polyester film and bonded to a conductive film (product name: ELECRYSTA V270L-TFMP) as an electronic component, to obtain an electronic component to which the pressure-sensitive adhesive sheet was bonded.
Industrial applicability
The stress dispersion film of the present invention can be suitably used as a protective material for the purpose of protecting an optical member and an electronic member from external impact, for example.

Claims (7)

1. A stress dispersion film comprising a laminate of a plastic film and an adhesive layer, wherein,
the thickness of the plastic film is 38-300 μm,
the thickness of the adhesive layer is 1-300 μm,
the adhesive layer is formed from an adhesive composition containing a polymer (A) or a rubber-based resin, wherein the polymer (A) has a monomer unit (I) derived from an alkyl (meth) acrylate having an alkyl group with 1-20 carbon atoms as an alkyl ester part and a monomer unit (II) derived from a (meth) acrylate having an OH group and/or a COOH group in the molecule,
the press-in energy when a load is applied in a direction perpendicular to the laminate from the plastic film side of the laminate is 280 to 7000 muJ,
wherein the measurement of the indentation energy is performed as follows:
the measurement temperature was measured using "SAICASDN-20" manufactured by Daipla Wintes, Inc.: 25 ℃ and pressing speed: the indentation energy was calculated at 5 μm/sec in the following order,
sequence 1:
the adhesive layer side of the laminate was attached to a flat indenter, and the laminate was pressed from the plastic film side of the laminate attached to the flat indenter with a ball indenter, and the press-in depth at the time of detection of a load of 20N was calculated, the press-in depth having a unit of μm,
sequence 2:
the pressure-sensitive adhesive layer side of the laminate was stuck to a glass slide, and the laminate was press-fitted from the plastic film side of the slide with a spherical indenter to the press-fitting depth determined in the sequence 1,
when the vertical load applied to the spherical indenter is defined as y ═ f (x), the pressing energy W until 20N is applied to the pressure-sensitive adhesive layer side of the laminate is calculated by the following formula, where r is the pressing depth when 20N of load is applied to the pressure-sensitive adhesive layer side of the laminate, x is the pressing depth, and the unit of the pressing energy W is μ J,
Figure FDA0003247534890000011
2. the stress dispersion film according to claim 1,
the thickness of the adhesive layer is 1-150 μm.
3. The stress dispersion film according to claim 1,
[ NCO ] + [ EPOXY ])/([ OH ] + [ COOH ]) < 0.05 when the molar content ratio of NCO groups in the adhesive composition is [ NCO ], the molar content ratio of EPOXY groups in the adhesive composition is [ EPOXY ], the molar content ratio of OH groups in the adhesive composition is [ OH ], and the molar content ratio of COOH groups in the adhesive composition is [ COOH ].
4. The stress dispersion film according to claim 1,
the adhesive composition contains an organic polyisocyanate-based crosslinking agent having 2 or more functions and/or an epoxy-based crosslinking agent.
5. The stress dispersion film according to claim 1,
the adhesive layer has a loss tangent tan delta of 0.10 or more over the entire temperature range of-40 ℃ to 150 ℃.
6. An optical member provided with the stress dispersion film according to any one of claims 1 to 5.
7. An electronic component comprising the stress dispersion film according to any one of claims 1 to 5.
CN201680058899.XA 2016-01-27 2016-08-16 Stress dispersion film, optical member, and electronic member Active CN108138004B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810824492.4A CN109181561B (en) 2016-01-27 2016-08-16 Stress dispersion membrane, optical component and electronic component

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2016013092 2016-01-27
JP2016-013092 2016-01-27
PCT/JP2016/073903 WO2017130444A1 (en) 2016-01-27 2016-08-16 Stress distributing film, optical member, and electronic member

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN201810824492.4A Division CN109181561B (en) 2016-01-27 2016-08-16 Stress dispersion membrane, optical component and electronic component

Publications (2)

Publication Number Publication Date
CN108138004A CN108138004A (en) 2018-06-08
CN108138004B true CN108138004B (en) 2021-11-23

Family

ID=59082005

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201810824492.4A Active CN109181561B (en) 2016-01-27 2016-08-16 Stress dispersion membrane, optical component and electronic component
CN201680058899.XA Active CN108138004B (en) 2016-01-27 2016-08-16 Stress dispersion film, optical member, and electronic member

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201810824492.4A Active CN109181561B (en) 2016-01-27 2016-08-16 Stress dispersion membrane, optical component and electronic component

Country Status (6)

Country Link
JP (2) JP6151416B1 (en)
KR (3) KR102035955B1 (en)
CN (2) CN109181561B (en)
SG (2) SG10201802306WA (en)
TW (2) TWI679265B (en)
WO (1) WO2017130444A1 (en)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111876095A (en) 2017-09-28 2020-11-03 日东电工株式会社 Reinforced film
JP6467548B1 (en) 2017-09-28 2019-02-13 日東電工株式会社 Reinforcement film
JP6581694B1 (en) 2018-06-27 2019-09-25 日東電工株式会社 Reinforcement film
JP6581704B1 (en) 2018-08-27 2019-09-25 日東電工株式会社 Reinforcement film
JP7111558B2 (en) 2018-08-27 2022-08-02 日東電工株式会社 laminate
JP2020033400A (en) 2018-08-27 2020-03-05 日東電工株式会社 Laminate
JP6995033B2 (en) * 2018-09-27 2022-01-14 日東電工株式会社 Reinforcing film
CN111325071A (en) * 2018-12-17 2020-06-23 上海箩箕技术有限公司 Optical adhesive and optical sensor module
WO2020158349A1 (en) 2019-02-01 2020-08-06 日東電工株式会社 Intermediate laminate, method for producing intermediate laminate, and method for producing product laminate
JP2020132659A (en) 2019-02-12 2020-08-31 日東電工株式会社 Reinforcement film, manufacturing method thereof, manufacturing method of device and reinforcement method
JP7257165B2 (en) 2019-02-12 2023-04-13 日東電工株式会社 Device with reinforcing film, manufacturing method thereof, and reinforcing method
TWI779211B (en) 2019-02-12 2022-10-01 日商日東電工股份有限公司 Reinforcing film, manufacturing method and reinforcing method of device
KR20200098401A (en) 2019-02-12 2020-08-20 닛토덴코 가부시키가이샤 Reinforcing film, method for making device and reinforcing method
JP7348727B2 (en) 2019-02-12 2023-09-21 日東電工株式会社 reinforcing film
JP6803426B2 (en) 2019-05-14 2020-12-23 日東電工株式会社 Laminated body and its manufacturing method
JP6916836B2 (en) 2019-05-14 2021-08-11 日東電工株式会社 Method of manufacturing a laminate
JP2020196820A (en) 2019-06-03 2020-12-10 日東電工株式会社 Pressure sensitive adhesive sheet, pressure sensitive adhesive kit and laminate
USD922701S1 (en) 2019-12-23 2021-06-15 Samsung Electronics Co., Ltd. Shoe care machine
KR102566606B1 (en) 2021-11-19 2023-08-16 울산과학기술원 Method of polymer material analysis on surface and interfacial cutting analysis system

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW554025B (en) * 2000-04-13 2003-09-21 Lintec Corp Adhesive compositions and adhesive optical elements using thereof
JP2006036843A (en) * 2004-07-23 2006-02-09 Diatex Co Ltd Heat-resistant and moisture-resistant adhesive and adhesive sheet
CN101405359A (en) * 2006-03-14 2009-04-08 日东电工株式会社 Adhesive sheet for glass protection, and protective film for automotive glass
JP2009108122A (en) * 2007-10-26 2009-05-21 Saiden Chemical Industry Co Ltd Optical pressure-sensitive adhesive composition and optical functional film
JP2012067315A (en) * 2011-11-02 2012-04-05 Nitto Denko Corp Pressure sensitive adhesive composition, double-sided pressure sensitive adhesive tape, and method for bonding
JP2013134481A (en) * 2011-12-27 2013-07-08 Asahi Kasei E-Materials Corp Pellicle
JP2013209586A (en) * 2012-03-30 2013-10-10 Lintec Corp Adhesive composition, adhesive and adhesive sheet
JP2014221864A (en) * 2013-05-13 2014-11-27 積水化学工業株式会社 Adhesive sheet for electronic apparatus
JP2015212326A (en) * 2014-05-02 2015-11-26 積水化学工業株式会社 Double-sided adhesive tape for fixation of optical film

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001294834A (en) * 2000-04-13 2001-10-23 Lintec Corp Pressure-sensitive adhesive composition and pressure- sensitive adhesive optical member using the same
US7208206B2 (en) * 2003-03-10 2007-04-24 Nitto Denko Corporation Glass crack prevention laminate and liquid crystal display device
JP5288733B2 (en) * 2007-05-31 2013-09-11 出光ユニテック株式会社 Surface protection film
JP5115218B2 (en) * 2008-01-30 2013-01-09 株式会社デンソー Starter
KR102071103B1 (en) * 2013-04-11 2020-01-29 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 Laminate
JP6229926B2 (en) 2013-06-03 2017-11-15 大日本印刷株式会社 Adhesive composition and adhesive sheet using the same
JP6037990B2 (en) * 2013-09-30 2016-12-07 大王製紙株式会社 Toilet roll packaging film and toilet roll packaging

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW554025B (en) * 2000-04-13 2003-09-21 Lintec Corp Adhesive compositions and adhesive optical elements using thereof
JP2006036843A (en) * 2004-07-23 2006-02-09 Diatex Co Ltd Heat-resistant and moisture-resistant adhesive and adhesive sheet
CN101405359A (en) * 2006-03-14 2009-04-08 日东电工株式会社 Adhesive sheet for glass protection, and protective film for automotive glass
JP2009108122A (en) * 2007-10-26 2009-05-21 Saiden Chemical Industry Co Ltd Optical pressure-sensitive adhesive composition and optical functional film
JP2012067315A (en) * 2011-11-02 2012-04-05 Nitto Denko Corp Pressure sensitive adhesive composition, double-sided pressure sensitive adhesive tape, and method for bonding
JP2013134481A (en) * 2011-12-27 2013-07-08 Asahi Kasei E-Materials Corp Pellicle
JP2013209586A (en) * 2012-03-30 2013-10-10 Lintec Corp Adhesive composition, adhesive and adhesive sheet
JP2014221864A (en) * 2013-05-13 2014-11-27 積水化学工業株式会社 Adhesive sheet for electronic apparatus
JP2015212326A (en) * 2014-05-02 2015-11-26 積水化学工業株式会社 Double-sided adhesive tape for fixation of optical film

Also Published As

Publication number Publication date
KR20180091962A (en) 2018-08-16
SG11201800572XA (en) 2018-02-27
CN108138004A (en) 2018-06-08
JP2017160451A (en) 2017-09-14
TW201900804A (en) 2019-01-01
TWI638878B (en) 2018-10-21
SG10201802306WA (en) 2018-04-27
KR101888811B1 (en) 2018-08-14
JP2017132977A (en) 2017-08-03
WO2017130444A1 (en) 2017-08-03
CN109181561B (en) 2019-09-27
JP6193525B1 (en) 2017-09-06
KR101888341B1 (en) 2018-08-13
JP6151416B1 (en) 2017-06-21
CN109181561A (en) 2019-01-11
KR20180038077A (en) 2018-04-13
TW201803955A (en) 2018-02-01
KR102035955B1 (en) 2019-10-23
TWI679265B (en) 2019-12-11
KR20180022978A (en) 2018-03-06

Similar Documents

Publication Publication Date Title
CN108138004B (en) Stress dispersion film, optical member, and electronic member
JP6367599B2 (en) Double-sided adhesive sheet
JP2017065217A (en) Laminate, touch panel, laminate formation kit, and, method of improving bending resistance of transparent conductive film
CN107011834B (en) Adhesive composition, adhesive member, optical member, and electronic member
CN111492007A (en) Resin composition, resin layer, and laminate sheet
KR20180107252A (en) Pressure-sensitive adhesive composition and pressure-sensitive adhesive tape
CN113831867B (en) Adhesive composition, adhesive member, optical member, and electronic member
CN112449649A (en) Adhesive and adhesive sheet
KR102706292B1 (en) Pressure-sensitive adhesive composition, pressure-sensitive adhesive member, optical member and electronic member
KR20230047163A (en) Reinforcing film, optical member and electronic member
WO2023105906A1 (en) Reinforcement film
WO2022163165A1 (en) Acrylic adhesive agent, acrylic adhesive agent composition, adhesive film, and flexible device
KR20240065076A (en) Reinforcement film, device manufacturing method and reinforcement method
KR20240125456A (en) Reinforcement film, manufacturing method of device, and reinforcement method
KR20240125455A (en) Reinforcement film, manufacturing method of device, and reinforcement method
KR20230098039A (en) Optical adhesive sheet
JP2023131574A (en) Reinforcement film
TW202309229A (en) Optical Adhesive Layer
CN116790192A (en) Optical adhesive sheet for image equipment

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant