CN110951421B - Adhesive composition - Google Patents

Adhesive composition Download PDF

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Publication number
CN110951421B
CN110951421B CN201910339799.XA CN201910339799A CN110951421B CN 110951421 B CN110951421 B CN 110951421B CN 201910339799 A CN201910339799 A CN 201910339799A CN 110951421 B CN110951421 B CN 110951421B
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meth
adhesive
weight
acrylate
parts
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CN110951421A (en
Inventor
长仓毅
铃木史惠
塚田高士
大津贺健太郎
吉田弘幸
菱沼昌世
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Fujimori Kogyo Co Ltd
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Fujimori Kogyo Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • 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
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J133/04—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
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/017—Additives being an antistatic agent
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

The invention provides an adhesive composition which has excellent adhesive performance such as balanced adhesive force under low-speed stripping speed and high-speed stripping speed and can simultaneously achieve antistatic performance and anti-pollution performance, and an adhesive film and a surface protective film using the adhesive composition. In the adhesive composition, (F) the antistatic agent is represented by the general formula K + ·A ‑ The ionic compound with the melting point of 25-80 ℃, wherein K + Is a cation selected from the group consisting of pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, guanidinium, ammonium, isouronium, thiouronium, piperidinium, pyrazolium, methylcarbonium, morpholinium, A ‑ An anion selected from the group consisting of trifluoromethanesulfonate and pentafluoroethanesulfonate, which do not contain an imide group, and an ionic compound in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the acrylic polymer.

Description

Adhesive composition
Technical Field
The present invention relates to an adhesive composition containing an antistatic agent, and an adhesive film and a surface protective film using the same. More particularly, the present invention relates to an adhesive composition which has excellent adhesive properties such as adhesive force in a balanced manner at a low peeling speed and a high peeling speed and which can achieve both antistatic properties and antifouling properties, and an adhesive film and a surface protective film using the adhesive composition.
Background
Conventionally, in a process for manufacturing an optical member such as a polarizing plate as a member constituting a liquid crystal display, a surface protective film is bonded to temporarily protect the surface of the optical member. Such a surface protective film is used only in a process of manufacturing an optical member, and is peeled and removed from the optical member when the optical member is mounted on a liquid crystal display. Such a surface protective film for protecting the surface of an optical member is generally also called a process film since it is used only in the process of manufacturing the optical member.
In the surface protective film used in the process of producing the optical member, an adhesive layer is formed on one surface of a polyethylene terephthalate (PET) resin film having optical transparency. Before being bonded to an optical member, a release film subjected to release treatment is bonded to the surface of an adhesive agent layer in order to protect the adhesive agent layer of the surface protective film.
Optical members such as polarizing plates are subjected to product inspection involving optical evaluations such as display capability, color tone, contrast, and impurity contamination of the liquid crystal display panel in a state where a surface protective film is bonded thereto. Therefore, as a performance requirement for the surface protective film, it is required that the adhesive layer does not adhere to bubbles or impurities and low molecular weight components of the adhesive composition, that is, has a stain resistance.
In addition, when the surface protective film is peeled from an optical member such as a polarizing plate, peeling static electricity generated along with static electricity generated when the adhesive layer and an adherend are peeled may affect a failure of an electric control circuit of a liquid crystal display. Therefore, the adhesive layer of the surface protective film is required to have excellent antistatic performance.
Further, in recent years, as a protective layer (also referred to as a protective film) of a polarizer of a polarizing plate, in addition to conventionally used Triacetylcellulose (TAC), use of a material which is likely to generate peeling static electricity when peeling a surface protective film of a polarizing plate, such as acrylic resin such as polymethyl methacrylate (PMMA), polyester resin such as polyethylene terephthalate (PET), cyclic olefin polymer, polycarbonate, or the like, has been expanded. Therefore, the antistatic performance required of the adhesive layer for the surface protective film of the polarizing plate is required to be more excellent than ever.
In addition, when the surface protective film is finally peeled from an optical member such as a polarizing plate, it is required to be quickly peeled. That is, the variation of the adhesive force due to the peeling speed is required to be small so that peeling can be performed quickly even in the case of high-speed peeling.
As described above, in recent years, from the viewpoint of ease of use in using a surface protective film, the adhesive layer constituting the surface protective film is required to have the following properties: (1) the adhesive force is balanced under the low-speed peeling speed and the high-speed peeling speed; (2) has anti-pollution performance; (3) has excellent antistatic performance.
However, it is very difficult to satisfy the required performances of the adhesive agent layer constituting the surface protective film, even if the individual required performances of (1) to (3) described above can be satisfied, and at the same time, all the required performances of (1) to (3) required for the adhesive agent layer of the surface protective film can be satisfied.
In order to solve such problems, for example, (1) adhesion is balanced between a low peeling speed and a high peeling speed, (2) anti-contamination performance is provided, and (3) excellent anti-static performance is provided.
With respect to (1) the balance of the adhesive force at a low peeling speed and a high peeling speed, in an acrylic adhesive layer obtained by crosslinking a copolymer of an alkyl (meth) acrylate having an alkyl group having 7 or less carbon atoms and a carboxyl group-containing copolymerizable compound as a main component with a crosslinking agent, when the adhesive is bonded for a long time, there is a problem that the adhesive moves toward the adherend and adheres to the adherend, or the adhesive force to the adherend is greatly increased with time. In order to avoid this problem, a technique is known in which an adhesive agent layer is provided in which a copolymer of an alkyl (meth) acrylate having an alkyl group with 8 to 10 carbon atoms and a copolymerizable compound having an alcoholic hydroxyl group is used and the copolymer is crosslinked using a crosslinking agent (patent document 1).
In addition, there has been proposed a method of providing an adhesive layer in which a copolymer of a small amount of alkyl (meth) acrylate and a carboxyl group-containing copolymerizable compound is blended with the same copolymer, and the resultant is crosslinked with a crosslinking agent. However, when these are used for surface protection of a plastic sheet or the like having a low surface tension and a smooth surface, there are problems that a peeling phenomenon such as floating occurs due to heating at the time of processing or storage, and that removability is poor at the time of high-speed peeling in the field of manual operation.
In order to solve these problems, an adhesive composition has been proposed which comprises a) 100 parts by weight of an alkyl (meth) acrylate containing an alkyl (meth) acrylate having 8 to 10 carbon atoms as a main component, 1 to 15 parts by weight of b) a carboxyl group-containing copolymerizable compound and 3 to 100 parts by weight of c) a vinyl ester of an aliphatic carboxylic acid having 1 to 5 carbon atoms as a main component to form a copolymer of a monomer mixture, and a crosslinking agent having an equivalent weight or more to the carboxyl group of the component b) is blended into the copolymer (patent document 2).
The pressure-sensitive adhesive composition described in patent document 2 is free from a peeling phenomenon such as floating at the time of processing or storage, has a small increase in adhesive strength with time, is excellent in removability, can be remounted with a small force even when stored for a long period of time, particularly in a high-temperature atmosphere, does not cause adhesive residue on an adherend at this time, and can be remounted with a small force even when peeled at a high speed.
However, in the adhesive composition described in patent document 2, since the gel fraction of the adhesive layer in examples 1 to 3 is 90%, unpolymerized monomers or oligomers are easily eluted from the copolymer. Further, patent document 2 does not describe antistatic performance and anti-contamination performance, and there is a problem that it is difficult to form an adhesive layer having excellent antistatic performance and anti-contamination performance when a material that is likely to generate peeling static electricity is used as an adherend.
Further, as to (2) having anti-contamination property, disclosed is an adhesive composition containing: 100 parts by mass of a (meth) acrylic copolymer having a weight average molecular weight of 10 to less than 100 million, the (meth) acrylic copolymer being composed of 0 to less than 0.5 parts by mass of a carboxyl group-containing monomer, 0.6 to 9 parts by mass of a hydroxyl group-containing (meth) acrylic monomer, and 99.4 to 90.5 parts by mass of a (meth) acrylic ester monomer; and 0.1 to 5 parts by mass of a carbodiimide-based crosslinking agent (patent document 3).
The adhesive composition described in patent document 3 is characterized in that a carbodiimide-based crosslinking agent is used as a crosslinking agent for a (meth) acrylic copolymer having a specific composition. This makes it possible to form a crosslinked structure in the adhesive layer that can follow shrinkage caused by pressure and temperature during the autoclave treatment. Therefore, the adhesive layer formed using the adhesive composition described in patent document 3 can suppress and prevent foaming even under high-temperature and high-pressure conditions (at the time of autoclave treatment), and is excellent in anti-contamination performance and transparency.
However, the adhesive composition described in patent document 3 has improved anti-contamination performance, but fails to achieve both excellent adhesion performance and antistatic performance, and there remains a problem that needs to be further solved.
Further, regarding (3) having excellent antistatic performance, as a method for imparting antistatic property to the surface protective film, a method of kneading an antistatic agent into the base film, and the like are known. Examples of the antistatic agent include (a) various cationic antistatic agents having a cationic group such as a quaternary ammonium salt, pyridinium, and primary to tertiary amino groups; (b) anionic antistatic agent with sulfonate base (スルホン salt), sulfate base (エステル salt), phosphate base (リン acid エステル salt), phosphonate base (ホスホン acid salt) and other anionic groups; (c) amphoteric antistatic agents such as amino acids and amino sulfates; (d) nonionic antistatic agents such as aminoalcohols, glycerols, and polyethylene glycols; (e) and a polymer type antistatic agent obtained by polymerizing the above antistatic agent with a high molecular weight (patent document 4).
However, although the surface protective film described in patent document 4 has been described about imparting antistatic performance to an adherend in relation to adhesion of dust, there is no description of a method of achieving both excellent adhesion performance and stain resistance, and there remains a problem that needs to be further solved.
In addition, in recent years, it has been proposed to directly contain an antistatic agent in an adhesive layer, instead of containing an antistatic agent in a base film or applying an antistatic agent to the surface of a base film. For example, an antistatic pressure-sensitive adhesive composition is disclosed, which is characterized by comprising a salt of an anion containing a fluoro group and a sulfonyl group dispersed in a state dissolved in a polyether ester plasticizer containing a polyether group in the main chain (patent document 5).
With respect to the adhesive composition described in patent document 5, it is disclosed that a plasticizer composed of the following ester is used as the plasticizer: an ester of a monocarboxylic acid or a dicarboxylic acid having a saturated or unsaturated acyclic hydrocarbon group and an alcohol having an acyclic hydrocarbon group having 1 to 20 carbon atoms; or an ester in which an unsaturated group in the unsaturated acyclic hydrocarbon group is epoxidized. Consider that: by making such a monocarboxylic acid or dicarboxylic acid having a saturated or unsaturated acyclic hydrocarbon group have a carbon number close to the carbon number of the acrylic monomer constituting the acrylic copolymer for the adhesive layer, compatibility in the antistatic adhesive composition becomes good, and the plasticizer is appropriately retained in the plasticizer acrylic antistatic adhesive composition, so bleeding is suppressed.
However, although the antistatic adhesive composition described in patent document 5 discloses a technique for improving antistatic performance and bleeding, it does not describe an adhesive composition having excellent adhesive performance such as balance of adhesive force at a low peeling speed and a high peeling speed, and there remains a problem in that an adhesive composition having excellent adhesive performance is obtained.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 63-225677
Patent document 2: japanese laid-open patent publication No. 11-256111
Patent document 3: japanese patent laid-open publication No. 2011-
Patent document 4: japanese laid-open patent publication No. 11-070629
Patent document 5: japanese laid-open patent publication No. 2014-118469
Disclosure of Invention
Technical problem to be solved by the invention
As described above, none of the prior arts can simultaneously solve the following required performances for the adhesive agent layer constituting the surface protective film: (1) the adhesive force is balanced under the low-speed peeling speed and the high-speed peeling speed; (2) has anti-pollution performance; (3) has excellent antistatic performance.
In addition, conventionally, in an adhesive layer formed using an adhesive composition having antistatic performance and a surface protective film using the adhesive layer, the antistatic performance and the anti-contamination performance to an adherend are in a trade-off relationship, and it has been difficult to improve the anti-contamination performance while maintaining the antistatic performance.
Further, in recent years, the kinds of materials of adherends to which the surface protective films are bonded have increased, and the surface treatments of the adherends have been diversified, and thus it has become more difficult to simultaneously exhibit the anti-contamination performance and the antistatic performance on all the adherends.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an adhesive composition which has excellent adhesive performance such as an adhesive force in a balanced manner at a low peeling speed and a high peeling speed and which can achieve both antistatic performance and anti-contamination performance, and an adhesive film and a surface protective film using the adhesive composition.
Means for solving the problems
The inventors of the present application have found that an adhesive composition containing an ionic compound having a melting point of 25 to 80 ℃ and having a trifluoromethanesulfonate anion or a pentafluoroethanesulfonate anion and being solid at room temperature, as an antistatic agent, can exhibit both antistatic properties and anti-contamination properties to an adherend, and have completed the present invention.
The adhesive composition containing an ionic compound as an antistatic agent, and an adhesive film and a surface protective film using the same of the present invention can achieve excellent adhesion performance and can achieve both antistatic performance and anti-contamination performance, and solve the technical problems of the prior art, wherein the ionic compound has a melting point of 25 to 80 ℃, and comprises one kind of cation selected from the group consisting of pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, guanidinium, ammonium, isouronium, thiouronium, piperidinium, pyrazolium, methylcarbapentanium, and morpholinium, and a trifluoromethanesulfonate anion or a pentafluoroethanesulfonate anion, and is solid at room temperature.
In order to solve the above-mentioned problems, the present invention provides an adhesive composition comprising an acrylic polymer, (F) an antistatic agent and (C) a crosslinking agent, wherein the antistatic agent (F) is an ionic compound represented by the following general formula (1) and having a melting point of 25 to 80 ℃,
K + ·A - (1)
in the general formula (1), K + Is a cation selected from the group consisting of pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, guanidinium, ammonium, isouronium, thiouronium, piperidinium, pyrazolium, methylcarbonium, morpholinium, A - Is an anion selected from the group consisting of a trifluoromethanesulfonate anion and a pentafluoroethanesulfonate anion which do not contain an imide group.
The acrylic polymer is an acrylic polymer having a glass transition temperature of 0 ℃ or lower, and the ionic compound is contained as an essential component in a proportion of 0.01 to 10 parts by weight relative to 100 parts by weight of the acrylic polymer.
Preferably: the acrylic polymer is a copolymer obtained by copolymerization of at least one or more (B-1) copolymerizable vinyl monomers containing hydroxyl groups in a proportion of 0.01 to 10 parts by weight in total and/or at least one or more (B-2) copolymerizable vinyl monomers containing carboxyl groups in a proportion of 0.01 to 0.5 part by weight in total relative to 100 parts by weight in total of at least one or more (meth) acrylate monomers containing alkyl groups and having carbon atoms of C1 to 18, wherein at least one selected from the group consisting of isooctyl (meth) acrylate, isononyl (meth) acrylate and 2-ethylhexyl (meth) acrylate is contained in a proportion of 50 parts by weight or more in total of 100 parts by weight in total of at least one or more (meth) acrylate monomers containing alkyl groups and having carbon atoms of C1 to 18, the adhesive composition further contains (D) a crosslinking accelerator for a metal chelate compound and (E) a keto-enol tautomer compound, and the isocyanate compound having a functionality of 3 or more is contained as the crosslinking agent (C) in a proportion of 0.1 to 10 parts by weight relative to 100 parts by weight of the acrylic polymer.
Preferably: the surface resistivity of the adhesive layer obtained by crosslinking the adhesive composition is 1.0 x 10 +12 Omega/□ or less, wherein the adhesive layer has a peeling electrostatic voltage of + -0.3 kV or less with respect to a low refractive index layer formed on the surfaces of a PMMA substrate and a TAC substrate using a resin composition for forming a low refractive index layer containing a fluoride, and a peeling electrostatic voltage of a planar layer which is not treated on the surfaces of the PMMA substrate and the TAC substrate, the adhesive layer is bonded to an adherend, the adhesive layer is left in an atmosphere of 60 ℃ and 90% RH for 48 hours, the anti-contamination performance after being taken out from the atmosphere for 1 day is "non-contamination" with respect to the surface of the adherend, the adherend is a polarizing plate in which a protective layer is laminated on a polarizer and the surface of the protective layer is subjected to a low reflection surface treatment with respect to the surface of the protective layer using a composition containing a fluoride, and the adhesive force of the adhesive layer with respect to the low refractive index layer applied on the surface of the PMMA substrate is 0.04 to 0.2N/25mm at a peeling speed of 0.3m/min, and the adhesive force at a high peeling speed of 30m/min is 2.0N/25mm or less.
Preferably: the (B-1) copolymerizable vinyl monomer containing a hydroxyl group is at least one selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-methylol (meth) acrylamide and N-hydroxyethyl (meth) acrylamide;
the (B-2) carboxyl group-containing copolymerizable vinyl monomer is at least one selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone mono (meth) acrylate, and 2- (meth) acryloyloxyethyltetrahydrophthalic acid.
Preferably, the following components: the adhesive composition contains the crosslinking accelerator of the metal chelate compound (D) in a proportion of 0.001-0.5 part by weight and the keto-enol tautomer compound (E) in a proportion of 0.1-300 parts by weight relative to 100 parts by weight of the acrylic polymer, wherein the crosslinking accelerator of the metal chelate compound (D) is at least one selected from the group consisting of an aluminum chelate compound, a titanium chelate compound and an iron chelate compound, and the weight ratio of (E)/(D) is 70-1000.
The present invention also provides an adhesive film, wherein an adhesive layer obtained by crosslinking the adhesive composition is laminated on one surface of a resin film.
The present invention also provides a surface protective film using the adhesive film.
The present invention also provides a surface protective film for a polarizing plate, which uses the adhesive film.
The present invention also provides an optical film with an adhesive layer, wherein the adhesive layer obtained by crosslinking the adhesive composition is laminated on at least one surface of the optical film.
The present invention also provides an adhesive film, wherein the resin film is subjected to an antistatic treatment and an antifouling treatment on one surface of the resin film opposite to the side on which the adhesive layer is formed.
Effects of the invention
The adhesive composition of the present invention has excellent adhesion performance and excellent antistatic performance without deterioration with time, compared with the conventional adhesive composition for a surface protective film.
In particular, in the case where the adherend is a low refractive index layer formed using a low refractive index layer forming composition containing a fluoride, or a stain-proofing layer containing a fluoride, which is laminated on the surface of the optical film, as compared with the surface protective film of the related art, the surface protective film of the present invention has excellent adhesion performance and excellent antistatic property against peeling without deterioration with time, and has a remarkable effect of simultaneously satisfying both the antistatic property and the stain-proofing property.
That is, the adhesive composition of the present invention and the surface protective film using the same have excellent adhesive performance and excellent antistatic property against peeling without time deterioration, and thus have a great industrial utility value.
Detailed Description
The present invention will be described below based on preferred embodiments.
The adhesive composition of the present embodiment is an adhesive composition containing an acrylic polymer, (F) an antistatic agent, and (C) a crosslinking agent, wherein the (F) antistatic agent is an ionic compound having a melting point of 25 to 80 ℃ represented by the following general formula (1),
K + ·A - (1)
in the general formula (1), K + Is a cation selected from the group consisting of pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, guanidinium, ammonium, isouronium, thiouronium, piperidinium, pyrazolium, methylcarbonium, morpholinium, A - Is an anion selected from the group consisting of a trifluoromethanesulfonate anion and a pentafluoroethanesulfonate anion which do not contain an imide group;
the acrylic polymer has a glass transition temperature of 0 ℃ or lower, and contains the ionic compound as an essential component in a proportion of 0.01 to 10 parts by weight relative to 100 parts by weight of the acrylic polymer.
The acrylic polymer used in the adhesive composition of the present embodiment is a main component polymer of the adhesive composition, and is an acrylic polymer having a glass transition temperature of 0 ℃ or lower. The acrylic polymer is preferably a copolymer mainly composed of (A) a (meth) acrylate monomer having an alkyl group and having carbon atoms of from C1 to C18.
Examples of the (meth) acrylate monomer having an alkyl group having C1-18 include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, and the like, Heptadecyl (meth) acrylate, octadecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. The alkyl group of the alkyl (meth) acrylate monomer may be any of linear, branched, and cyclic.
The acrylic polymer used in the adhesive composition of the present embodiment preferably contains at least one selected from the group consisting of isooctyl (meth) acrylate, isononyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate in a proportion of 50 parts by weight or more, more preferably 60 parts by weight or more, and particularly preferably 75 parts by weight or more, based on 100 parts by weight of the total of at least one (meth) acrylate monomer having an alkyl group with carbon atoms of C1 to 18.
The acrylic polymer used in the adhesive composition of the present embodiment is preferably an acrylic polymer of a copolymer obtained by copolymerizing (B-1) at least one or more copolymerizable vinyl monomers containing a hydroxyl group and/or (B-2) at least one or more copolymerizable vinyl monomers containing a carboxyl group. The acrylic polymer may be copolymerized with at least one of (B-1) a copolymerizable vinyl monomer having a hydroxyl group and (B-2) a copolymerizable vinyl monomer having a carboxyl group, or both of these monomers.
Preferably the acrylic polymer is: an acrylic polymer which is a copolymer obtained by copolymerizing (A) 100 parts by weight in total of at least one or more (meth) acrylic acid ester monomers having an alkyl group of C1-18 in a proportion of 0.01-10 parts by weight in total of (B-1) at least one or more copolymerizable vinyl monomers containing a hydroxyl group and/or 0.01-0.5 parts by weight in total of (B-2) at least one or more copolymerizable vinyl monomers containing a carboxyl group.
The acrylic polymer used in the adhesive composition of the present embodiment is copolymerized with (B-1) a copolymerizable monomer containing a hydroxyl group. The hydroxyl group-containing copolymerizable monomer (B-1) is preferably at least one selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide and the like.
When the (B-1) hydroxyl group-containing copolymerizable monomer is copolymerized, the (B-1) hydroxyl group-containing copolymerizable monomer is contained preferably in a proportion of 0.01 to 10.0 parts by weight, more preferably in a proportion of 0.5 to 7.0 parts by weight, particularly preferably in a proportion of 1.0 to 6.0 parts by weight, based on 100 parts by weight of the total of at least one (meth) acrylate monomer having an alkyl group of C1 to 18.
The acrylic polymer used in the adhesive composition of the present embodiment is copolymerized with (B-2) a carboxyl group-containing copolymerizable monomer. The carboxyl group-containing copolymerizable monomer (B-2) is preferably at least one selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyltetrahydrophthalic acid and the like.
When the (B-2) carboxyl group-containing copolymerizable vinyl monomer is copolymerized, the (B-2) carboxyl group-containing copolymerizable vinyl monomer is contained preferably in an amount of 0.01 to 0.5 parts by weight, more preferably 0.01 to 0.4 parts by weight, and particularly preferably 0.01 to 0.3 parts by weight, based on 100 parts by weight of the total of at least one (meth) acrylate monomer having an alkyl group of C1 to 18.
The method for producing the acrylic polymer contained in the pressure-sensitive adhesive composition of the present embodiment is not particularly limited, and an appropriate and known polymerization method such as a solution polymerization method or an emulsion polymerization method can be used. The weight average molecular weight of the copolymer of the acrylic polymer is, for example, 50 to 300 ten thousand. The acid value of the acrylic polymer is preferably 0.1 to 1.0. Whereby the anti-contamination performance can be improved. Here, "acid value" is one of indexes indicating the acid content, and is expressed in mg of potassium hydroxide required for neutralizing 1g of a carboxyl group-containing polymer.
The adhesive composition of the present embodiment contains (F) an antistatic agent. The antistatic agent (F) of the present embodiment is an ionic compound having a melting point of 25 to 80 ℃ represented by the following general formula (1).
K + ·A - (1)
In the general formula (1), K + Is a cation selected from the group consisting of pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, guanidinium, ammonium, isouronium, thiouronium, piperidinium, pyrazolium, methylcarbonium, morpholinium, A - Is an anion selected from the group consisting of a trifluoromethanesulfonate anion and a pentafluoroethanesulfonate anion which do not contain an imide group.
Preferably, the ionic compound is solid at ordinary temperature. The ordinary temperature is, for example, a temperature of less than 25 ℃, and specifically, an ionic compound which is solid at 23 ℃ is preferable. The adhesive composition of the present embodiment contains the ionic compound as an essential component in a proportion of 0.01 to 10 parts by weight relative to 100 parts by weight of the acrylic polymer.
Specific examples of the antistatic agent (F) include 1-octyl-2-methylpyridinium trifluoromethanesulfonate, 1,2, 3-trimethylimidazolium pentafluoroethane sulfonate, 1-butyl-2, 3-dimethylimidazolium trifluoromethanesulfonate, 1-hexyl-4-methylpyridinium pentafluoroethane sulfonate, 1-octyl-3-methylpyridinium trifluoromethanesulfonate and n-octylpyridinium trifluoromethanesulfonate.
The adhesive composition of the present embodiment further contains an isocyanate compound having a functionality of 3 or more as the (C) crosslinking agent. Examples of the isocyanate compound having a functionality of 3 or more include biuret modified products or isocyanurate modified products of diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and xylylene diisocyanate, and adducts with polyols having a valence of 3 or more such as trimethylolpropane and glycerin. The proportion of the isocyanate compound having a functionality of 3 or more, which is the crosslinking agent (C), is, for example, preferably 0.1 to 10 parts by weight, more preferably 0.1 to 6 parts by weight, based on 100 parts by weight of the acrylic polymer.
The adhesive composition of the present embodiment may further contain (E) a keto-enol tautomer compound. Examples of the keto-enol tautomer compound (E) include β -keto esters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate (oleyl acetoacetate), lauryl acetoacetate, and stearyl acetoacetate, and β -diketones such as acetylacetone, 2, 4-hexanedione, and benzoylacetone. In an adhesive composition containing a polyisocyanate compound as a crosslinking agent, these keto-enol tautomer compounds can suppress excessive viscosity increase and gelation of the adhesive composition after blending with the crosslinking agent by blocking (blocking) the isocyanate group of the crosslinking agent, and can prolong the pot life of the adhesive composition. (E) The keto-enol tautomer compound is particularly preferably at least one compound selected from the group consisting of acetylacetone and ethyl acetoacetate. The (E) keto-enol tautomer compound is preferably contained in a proportion of 0.1 to 300 parts by weight relative to 100 parts by weight of the acrylic polymer.
The adhesive composition of the present embodiment may further contain (D) a crosslinking accelerator for the metal chelate compound. In the case where a polyisocyanate compound is used as the crosslinking agent, (D) the crosslinking accelerator for the metal chelate compound may be any one that functions as a catalyst for the reaction (crosslinking reaction) between the copolymer and the crosslinking agent. (D) The crosslinking accelerator for a metal chelate compound is a compound in which 1 or more polydentate ligands L are bonded to a central metal atom M. The metal chelate compound may or may not have 1 or more monodentate ligands X bonded to the metal atom M. Specific examples of the metal chelate compound include iron (III) tris (2, 4-pentanedionate), iron (III) triacetylacetonate, titanium triacetylacetonate, ruthenium triacetylacetonate, zinc bisacetoacetonate, aluminum triacetylacetonate, zirconium tetraacetoacetonate, iron (III) tris (2, 4-hexanedionate), zinc bis (2, 4-hexanedionate), titanium tris (2, 4-hexanedionate), aluminum tris (2, 4-hexanedionate), zirconium tetrakis (2, 4-hexanedionate), and the like.
The crosslinking accelerator for the metal chelate compound (D) is preferably at least one metal chelate compound selected from the group consisting of aluminum chelate compounds, titanium chelate compounds and iron chelate compounds. The crosslinking accelerator containing (D) a metal chelate compound is preferably contained in an amount of 0.001 to 0.5 part by weight based on 100 parts by weight of the acrylic polymer.
(E) The keto-enol tautomer compound has an effect of inhibiting crosslinking, as opposed to the crosslinking accelerator of the (D) metal chelate compound, and therefore the ratio of the (E) keto-enol tautomer compound to the crosslinking accelerator of the (D) metal chelate compound is preferably set appropriately. In order to prolong the storage life of the adhesive composition and improve the storage stability, the weight part ratio of (E)/(D) is preferably 70-1000, more preferably 70-700, and particularly preferably 70-300. Here, the weight part ratio of (E)/(D) is a value obtained by dividing the weight part of (E) by the weight part of (D).
The pressure-sensitive adhesive composition of the present embodiment may further contain (H) a polyether-modified silicone compound as an optional component. (H) The polyether-modified silicone compound is a silicone compound having a polyether group, except for having a general siloxane unit [ -SiR ] 1 2 -O-]In addition, it has siloxane units [ -SiR ] with polyether groups 1 (R 2 O(R 3 O) n R 4 )-O-]. Here, R 1 Represents one or more alkyl or aryl groups, R 2 And R 3 Represents one or more alkylene groups, R 4 Represents one or two or more kinds of alkyl groups, acyl groups, or the like (terminal groups). The polyether group includes polyoxyethylene [ (C) 2 H 4 O) n ]Or polyoxypropylene [ (C) 3 H 6 O) n ]And the like. In the siloxane unit having a polyether group, the end of the polyether group may be an OH group (R in the above formula (1)) 4 ＝H)。
(H) The polyether modified siloxane compound is preferably a polyether modified siloxane compound with an HLB value of 6-12. Further, the (H) polyether-modified silicone compound is preferably contained in an amount of 0.01 to 0.5 part by weight, more preferably 0.02 to 0.35 part by weight, and particularly preferably 0.02 to 0.25 part by weight, based on 100 parts by weight of the acrylic polymer. The HLB value refers to, for example, a hydrophilic-lipophilic balance value (ratio of lipophilic to hydrophilic) specified in JIS K3211 (surfactant terminology) and the like.
The polyether-modified siloxane compound can be obtained, for example, by: an organic compound having an unsaturated bond and a polyoxyalkylene group is grafted to the main chain of a polyorganosiloxane having a silicon hydride group by a hydrosilylation reaction. Specific examples thereof include dimethylsiloxane-methyl (polyoxyethylene) siloxane copolymers, dimethylsiloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxypropylene) siloxane copolymers, and dimethylsiloxane-methyl (polyoxypropylene) siloxane polymers.
By incorporating (H) the polyether-modified siloxane compound into the adhesive composition, the adhesive force and the reworkability of the adhesive layer can be improved. (H) The polyether-modified siloxane compound preferably has a weight average molecular weight of 10000 or less. From the viewpoint of compatibility with acrylic polymers, although compatibility is better when the HLB value is low and the molecular weight is low, excellent antistatic properties can be obtained even when the HLB value is high and the compatibility with polymers is slightly low in the case of polyether-modified silicone compounds having a low molecular weight.
The pressure-sensitive adhesive composition of the present embodiment is not limited to the above additives, and may be appropriately blended with known additives such as a surfactant, a curing accelerator, a plasticizer, a filler, a curing retarder, a processing aid, an antioxidant, and an antioxidant. These additives can be used singly or in combination of 2 or more.
The adhesive composition of the present embodiment is suitable as an adhesive composition for a surface protective film to be attached to a protective layer of a polarizer of a polarizing plate. Here, the protective layer of the polarizer of the polarizing plate may be one selected from the group consisting of a TAC-based film, a PMMA-based film, and a PET-based film. Here, TAC is an abbreviation for cellulose triacetate, PMMA is an abbreviation for polymethyl methacrylate, and PET is an abbreviation for polyethylene terephthalate.
Further, the surface treatment applied on the surface of the protective layer of the polarizer of the polarizing plate may be one selected from the group consisting of no treatment, AG treatment, LR treatment, AR treatment, AG-LR treatment, and AG-AR treatment. Here, AG means Anti-Glare (Anti Glare), LR means Low Reflection (Low Reflection), and AR means Anti-Reflection (Anti Reflection).
In the adhesive layer obtained by crosslinking the adhesive composition of the present embodiment, the surface resistivity of the adhesive layer is preferably 1.0 × 10 +12 Omega/□ or less, more preferably 5.0X 10 +11 Omega/□ or less, particularly preferably 1.0X 10 +11 Omega/□ or less. When the surface resistivity is high, the performance of releasing static electricity generated when the adhesive layer is peeled from an adherend is poor. Therefore, by sufficiently reducing the surface resistivity, the peeling electrostatic voltage generated by static electricity generated when the adhesive layer is peeled from the adherend can be reduced, and the influence on the adherend can be suppressed.
In the adhesive layer obtained by crosslinking the adhesive composition of the present embodiment, the electrostatic voltage for peeling off the low refractive index layer formed using the resin composition for forming a low refractive index layer containing a fluoride is preferably ± 0.3kV or less, that is, preferably in the range of-0.3 to +0.3 kV. Examples of the fluoride used in the composition for forming a low refractive index layer include a fluorinated copolymer of one or two or more kinds of polymers selected from fluorinated olefins, fluorinated vinyl ethers, fluorinated alkyl (meth) acrylates, and the like, and a condensate of a silane compound containing a fluorinated alkyl group. In addition to the fluorinated monomer, a non-fluorinated monomer such as an olefin, a vinyl ether, or a (meth) acrylate may be copolymerized in the fluorine-containing copolymer. The low refractive index layer may be combined with a high refractive index layer or the like to constitute an antireflection layer.
When the peeling electrostatic voltage of the low refractive index layer is measured, a PMMA substrate and a TAC substrate can be used as the substrate for forming the low refractive index layer on the surface. Further, the electrostatic pressure for peeling of the adhesive layer obtained by crosslinking the adhesive composition of the present embodiment from a flat layer which is not subjected to any treatment on the surfaces of the PMMA substrate and the TAC substrate is preferably. + -. 0.3kV or less, that is, preferably in the range of-0.3 to +0.3 kV.
The anti-contamination performance after the adhesive layer is bonded to an adherend and left to stand in an atmosphere of 60 ℃ and 90% RH for 48 hours and taken out from the atmosphere for 1 day is preferably "no contamination" with respect to the surface of the adherend. Examples of the adherend include a polarizing plate in which a protective layer is laminated on a polarizer and the surface of the protective layer is subjected to a low reflection surface treatment with a fluoride-containing composition. The composition containing a fluoride for the low reflection surface treatment may be the same as or different from the resin composition for forming a low refractive index layer containing a fluoride. Examples of the protective layer include a PMMA substrate and a TAC substrate.
The adhesive layer obtained by crosslinking the adhesive composition of the present embodiment preferably has an adhesive force of 0.04 to 0.2N/25mm at a low peeling speed of 0.3m/min, an adhesive force of 2.0N/25mm or less at a high peeling speed of 30m/min, and more preferably an adhesive force of 0.2 to 1.6N/25mm at a high peeling speed of 30m/min, with respect to the adhesive force of the adhesive layer to the low refractive index layer applied to the surface of the PMMA substrate. This provides a property of reducing a change in the adhesive force due to the peeling speed, and allows rapid peeling even in the case of high-speed peeling. Further, even when the surface protective film is temporarily peeled off for re-attachment, the surface protective film can be easily peeled off from the adherend without requiring an excessive force.
The gel fraction of the adhesive layer obtained by crosslinking the adhesive composition of the present embodiment is preferably 95 to 100%, and more preferably 97 to 100%. Since the gel fraction of the adhesive layer is so high, the adhesive force does not become excessively high at a low peeling speed, elution of unpolymerized monomer or oligomer from the copolymer is reduced, and the reworkability and durability at high temperature and high humidity can be improved, and contamination of an adherend can be suppressed.
The adhesive film of the present embodiment is obtained by forming an adhesive layer obtained by crosslinking the adhesive composition of the present embodiment on one surface or both surfaces of a resin film. The surface protective film of the present embodiment is a surface protective film in which an adhesive layer obtained by crosslinking the adhesive composition of the present embodiment is formed on one surface of a resin film. The adhesive composition of the present embodiment has excellent antistatic performance, and has excellent balance of adhesive force at a low peeling speed and a high peeling speed, and further has anti-contamination performance. Therefore, the composition can be suitably used for the surface protective film of a polarizing plate.
As a base film of the adhesive layer or a release film (separator) for protecting the adhesive surface, a resin film such as a polyester film can be used.
The resin film may be subjected to an antistatic treatment and an antifouling treatment on one surface thereof which is opposite to the side on which the adhesive layer is formed. Examples of the antistatic treatment include coating or kneading of an antistatic agent. Examples of the antifouling treatment include a treatment with a silicone-based release agent, a fluorine-based release agent, a coating agent, silica fine particles, and the like. The surface of the release film on the side to be bonded to the adhesive surface of the adhesive layer may be subjected to release treatment using a silicone-based, fluorine-based, or long chain alkyl-based release agent.
Further, an optical film with an adhesive layer can be obtained by laminating an adhesive layer obtained by crosslinking the adhesive composition of the present embodiment on at least one surface of an optical film. Examples of the optical film include a polarizing film, a retardation film, an antireflection film, an anti-glare (anti-glare) film, an ultraviolet absorbing film, an infrared absorbing film, an optical compensation film, and a brightness enhancement film. Examples of devices to which the optical member is applied include a liquid crystal panel, an organic EL panel, and a touch panel.
In the case of an optical surface protective film or adhesive film such as a surface protective film for a polarizing plate, the base film and the adhesive layer preferably have sufficient transparency.
Examples
The present invention will be specifically described below with reference to examples.
< preparation of acrylic Polymer >
[ example 1]
Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, thereby replacing the air in the reaction apparatus with nitrogen gas. Then, 100 parts by weight of 2-ethylhexyl acrylate, 6.0 parts by weight of 8-hydroxyoctyl acrylate, 0.1 part by weight of acrylic acid, and a solvent (ethyl acetate) were simultaneously added to the reaction apparatus. Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and reacted at 65 ℃ for 6 hours to obtain an acrylic polymer used in example 1.
Examples 2 to 6 and comparative examples 1 to 3
Acrylic polymer solutions used in examples 2 to 6 and comparative examples 1 to 3 were obtained in the same manner as the acrylic polymer solution used in example 1, except that the monomer compositions were adjusted to the compositions shown in (A), (B-1), and (B-2) in Table 1, respectively.
Production of adhesive composition and surface protective film
[ example 1]
To the acrylic polymer solution of example 1 prepared as described above, 2.5 parts by weight of a crosslinking agent (CORONATE HX), 1.5 parts by weight of an antistatic agent (1-octyl-2-methylpyridinium trifluoromethanesulfonate), 0.1 part by weight of a crosslinking catalyst (titanium triacetylacetonate) and 8.5 parts by weight of acetylacetone were added and mixed with stirring to obtain an adhesive composition of example 1. The adhesive composition was applied to a release film (silicone resin-coated PET film), and then the solvent was removed by drying at 90 ℃ to obtain an adhesive layer having a thickness of 20 μm. Then, the adhesive layer with the release film was transferred onto the surface of the base film (PET film with one surface subjected to the antistatic and antifouling treatment) opposite to the surface subjected to the antistatic and antifouling treatment, to obtain the surface protective film of example 1 having a laminated structure of "base film/adhesive layer/release film".
Examples 2 to 6 and comparative examples 1 to 3
Surface protective films of examples 2 to 6 and comparative examples 1 to 3 were obtained in the same manner as the surface protective film of example 1 above, except that the compositions of the additives were adjusted to the respective compositions (C) to (F) in table 1.
[ Table 1]
Figure BDA0002040361160000191
In table 1, the weight parts of each component were determined assuming that the total of (meth) acrylate monomers (a) having an alkyl group with carbon atoms of C1 to 18 was 100 weight parts.
In table 1, the content ratio (parts by weight) of each component is represented by a numerical value in parentheses () in each column of (C) to (F) assuming that the acrylic polymer is 100 parts by weight.
In addition, the compound names of the abbreviations used in table 1 for the respective components are shown in table 2. Cornate (registered trademark) HX, cornate HL, and cornate L are trade names of TOSOH CORPORATION, and TAKENATE (registered trademark) D-140N, D-127N, D-110N are trade names of Mitsui Chemicals, inc.
[ Table 2]
Figure BDA0002040361160000201
In the antistatic agent (F), F-1 to F-6 and F-9 are ionic compounds having a melting point of 25 ℃ to 80 ℃ and being solid at ordinary temperature. F-7 and F-8 are ionic compounds having a melting point of more than 80 ℃ and being solid at ordinary temperature.
< test method and evaluation >
The surface protective films of examples 1 to 6 and comparative examples 1 to 3 were cured for 7 days in an atmosphere of 23 ℃ and 50% RH, and then evaluated by the following test methods.
< test method of adhesion >
The release film was peeled off, and the surface protective film with the adhesive layer exposed was bonded to the surface of the polarizing plate via the adhesive layer, and after leaving for 1 day, the sheet was subjected to a autoclaving treatment at 50 ℃ under 5 atmospheres for 20 minutes, and further left for 12 hours at room temperature, to obtain a sample for measuring the adhesive strength. The obtained measurement sample was peeled at a low speed (0.3m/min) or a high speed (30m/min) in a 180 ° direction using a tensile tester, and the peel strength measured was taken as the adhesive force.
Here, the protective layer of the polarizer is one selected from the group consisting of Triacetylcellulose (TAC), Polymethylmethacrylate (PMMA), and polyethylene terephthalate (PET).
In addition, a low reflection surface treatment was applied to the surface of the protective layer of the polarizer of the LR polarizing plate and the AG-LR polarizing plate using a composition containing a fluoride.
< test method of surface resistivity >
After curing the surface protective film and before bonding it to the polarizing plate, the release film was peeled off to expose the adhesive layer, and the surface resistivity of the adhesive layer was measured using a resistivity meter HIRESTAUP-HT450 (manufactured by Mitsubishi Chemical analytical co.
< test method of Peel Electrostatic Voltage >
The release film was peeled off, and the surface protective film with the adhesive layer exposed was bonded to a polarizing plate having a low refractive index layer formed by using a composition for forming a low refractive index layer containing a fluoride on the surface to be bonded. A voltage (electrostatic voltage) generated by electrification of an adherend when the surface protective film was peeled at 180 ℃ at a stretching speed of 30m/min was measured using high-precision electrostatic inductors SK-035 and SK-200 (manufactured by KEYENCE CORPORATION), and the maximum value of the measured values was defined as the peeling electrostatic voltage.
< test method of anti-contamination Property >
A polarizing plate subjected to Low Reflection (LR) surface treatment was bonded to one surface of a glass plate via an adhesive layer (double-sided adhesive tape) using a bonding machine. Then, a surface protective film was attached to the surface of the polarizing plate using a laminator. After the sheet was adhered to an adherend, the sheet was left to stand in an atmosphere of 60 ℃ and 90% RH for 48 hours, and taken out from the atmosphere for 1 day, and then the surface protective film was peeled off, and the state of contamination of the surface of the polarizing plate was visually observed. As criteria for judging the anti-contamination performance, the case where the surface of the polarizing plate was not contaminated was evaluated as "o", the case where the surface was slightly contaminated was evaluated as "Δ", and the case where the surface was contaminated was evaluated as "x".
The evaluation results of the surface protective films of examples 1 to 6 and comparative examples 1 to 3 are shown in Table 3. "surface resistivity" is determined by mixing "m.times.10 +n "mE + n" (where m is an arbitrary real number and n is a positive integer) is used.
The column "peeling electrostatic voltage" indicates the material (TAC or PMMA) and surface treatment (Plain or AG-LR) of the protective layer of the polarizer used in the test. "surface treated" Plain refers to untreated. The column "anti-contamination performance" also refers to the material (PMMA) and surface treatment (AG-LR) of the protective layer of the polarizer used in the test.
[ Table 3]
Figure BDA0002040361160000221
The surface protective films of examples 1 to 6 had an adhesive force of 0.04 to 0.2N/25mm at a low peeling speed of 0.3m/min and an adhesive force of 2.0N/25mm or less at a high peeling speed of 30m/min, respectively, to a polarizing plate as an adherend, and were excellent in adhesive performance.
In addition, the surface resistivity of the adhesive layer of the surface protective films of examples 1 to 6 was 1.0X 10 +12 Omega/□ or less, the adhesive layer has excellent antistatic performance, and the peeling electrostatic pressure of the adhesive layer to the low refractive index layer formed by using the composition for forming the low refractive index layer containing fluoride is in the range of-0.3 to +0.3 kV.
Further, the surface protective films of examples 1 to 6 had a peel electrostatic voltage in the range of-0.3 to +0.3kV for the adhesive layer even for the untreated PMMA substrate and TAC substrate having no low refractive index layer, and were excellent in antistatic performance.
Further, even after the surface protective films of examples 1 to 6 were bonded to an adherend, and left to stand in an atmosphere at a temperature of 60 ℃ and a humidity of 90% RH for 48 hours and taken out from the atmosphere for 1 day, the polarizing plate to which the low reflection surface treatment was applied as the adherend was free from contamination and was excellent in the anti-contamination performance.
That is, the evaluation results shown in table 3 regarding the surface protective films of examples 1 to 6 confirmed that the technical problem of the present invention could be solved.
The surface protective film of comparative example 1 contains an antistatic agent having a melting point of more than 80 ℃. Therefore, the adhesive layer of the surface protective film of comparative example 1 had a large adhesive force, high peeling static voltage, and poor anti-contamination performance.
In addition, the surface protective film of comparative example 2 contains an antistatic agent having a melting point of more than 80 ℃. Therefore, the adhesive layer of the surface protective film of comparative example 2 had a large adhesive force, high peeling static voltage, and poor anti-contamination performance.
In addition, the surface protection film of comparative example 3 contains an antistatic agent having an anionic imide group even though the melting point is 25 to 80 ℃. Therefore, the surface protective film of comparative example 3 has high peeling static voltage against the PMMA base material and also has poor anti-contamination performance.
As described above, the surface protective films of comparative examples 1 to 3 failed to solve the technical problems of the present invention.

Claims (10)

1. An adhesive composition comprising an acrylic polymer, (F) an antistatic agent and (C) a crosslinking agent, characterized in that,
the antistatic agent (F) is an ionic compound with a melting point of 25-80 ℃ shown in the general formula (1),
K + ·A - (1)
in the general formula (1), K + Is a cation selected from the group consisting of pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, guanidinium, ammonium, isouronium, thiouronium, piperidinium, pyrazolium, methylcarbonium, morpholinium, A - Is an anion selected from the group consisting of a trifluoromethanesulfonate anion and a pentafluoroethanesulfonate anion which do not contain an imide group,
the acrylic polymer is: an acrylic polymer which is a copolymer obtained by copolymerizing (A) 100 parts by weight of at least one or more (meth) acrylic acid ester monomers having an alkyl group of C1-18 in total, at a ratio of 0.01-10 parts by weight in total of (B-1) at least one or more copolymerizable vinyl monomers containing a hydroxyl group, and/or at a ratio of 0.01-0.5 parts by weight in total of (B-2) at least one or more copolymerizable vinyl monomers containing a carboxyl group,
at least one selected from the group consisting of isooctyl (meth) acrylate, isononyl (meth) acrylate and 2-ethylhexyl (meth) acrylate is contained in an amount of 50 parts by weight or more based on 100 parts by weight in total of at least one (meth) acrylate monomer having an alkyl group of C1 to 18,
the acrylic polymer is an acrylic polymer having a glass transition temperature of 0 ℃ or lower,
the ionic compound is contained as an essential component in a proportion of 0.01 to 10 parts by weight relative to 100 parts by weight of the acrylic polymer.
2. Adhesive composition according to claim 1,
an isocyanate compound having a functionality of 3 or more is contained as the crosslinking agent (C) in a proportion of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic polymer,
the adhesive composition further contains (D) a crosslinking accelerator for the metal chelate compound and (E) a keto-enol tautomer compound.
3. Adhesive composition according to claim 2,
the surface resistivity of the adhesive layer obtained by crosslinking the adhesive composition is 1.0 x 10 +12 Below the value of omega/□, the ratio of omega/□,
the adhesive layer has a peeling electrostatic voltage of + -0.3 kV or less for a low refractive index layer formed on the surface of a PMMA substrate and a TAC substrate by using a resin composition for forming a low refractive index layer containing a fluoride, and for a flat layer which is not treated on the surface of the PMMA substrate and the TAC substrate,
the adhesive layer is bonded to an adherend, which is a polarizing plate having a protective layer laminated on a polarizer and having a low reflection surface treatment of the surface of the protective layer with a fluoride-containing composition, and then left to stand in an atmosphere of 60 ℃ and 90% RH for 48 hours, and the anti-contamination performance after 1 day of removal from the atmosphere is "no contamination" with respect to the surface of the adherend,
the adhesive layer has an adhesive force to the low refractive index layer applied to the surface of the PMMA substrate, the adhesive force at a low peeling speed of 0.3m/min is 0.04-0.2N/25 mm, and the adhesive force at a high peeling speed of 30m/min is 2.0N/25mm or less.
4. The adhesive composition according to any one of claims 1 to 3,
the (B-1) copolymerizable vinyl monomer having a hydroxyl group is at least one selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-methylol (meth) acrylamide and N-hydroxyethyl (meth) acrylamide,
the (B-2) carboxyl group-containing copolymerizable vinyl monomer is at least one selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone mono (meth) acrylate, and 2- (meth) acryloyloxyethyltetrahydrophthalic acid.
5. Adhesive composition according to claim 2 or 3,
the adhesive composition contains the crosslinking accelerator of the metal chelate compound (D) in a proportion of 0.001 to 0.5 parts by weight and the keto-enol tautomer compound (E) in a proportion of 0.1 to 300 parts by weight with respect to 100 parts by weight of the acrylic polymer,
the crosslinking accelerator for the metal chelate compound (D) is at least one selected from the group consisting of an aluminum chelate compound, a titanium chelate compound and an iron chelate compound,
the weight part ratio of the (E)/the (D) is 70-1000.
6. An adhesive film characterized in that an adhesive layer obtained by crosslinking the adhesive composition according to any one of claims 1 to 5 is laminated on one surface of a resin film.
7. A surface protective film using the adhesive film according to claim 6.
8. A surface protective film for a polarizing plate, which uses the adhesive film according to claim 6.
9. An optical film with an adhesive layer, wherein the adhesive layer obtained by crosslinking the adhesive composition according to any one of claims 1 to 5 is laminated on at least one surface of the optical film.
10. The adhesive film according to claim 6, wherein an antistatic treatment and an antifouling treatment are applied to one surface of the resin film opposite to the side on which the adhesive layer is formed.
CN201910339799.XA 2018-09-27 2019-04-25 Adhesive composition Active CN110951421B (en)

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