CN108795348A - Adhesion agent composition and surface protection film - Google Patents

Adhesion agent composition and surface protection film Download PDF

Info

Publication number
CN108795348A
CN108795348A CN201711053007.XA CN201711053007A CN108795348A CN 108795348 A CN108795348 A CN 108795348A CN 201711053007 A CN201711053007 A CN 201711053007A CN 108795348 A CN108795348 A CN 108795348A
Authority
CN
China
Prior art keywords
methyl
weight
parts
acrylate
composition
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.)
Granted
Application number
CN201711053007.XA
Other languages
Chinese (zh)
Other versions
CN108795348B (en
Inventor
长仓毅
吉田弘幸
大津贺健太郎
铃木史惠
菱沼昌世
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.)
Fujimori Kogyo Co Ltd
Original Assignee
Fujimori Kogyo Co Ltd
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 Fujimori Kogyo Co Ltd filed Critical Fujimori Kogyo Co Ltd
Publication of CN108795348A publication Critical patent/CN108795348A/en
Application granted granted Critical
Publication of CN108795348B publication Critical patent/CN108795348B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/0091—Complexes with metal-heteroatom-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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—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
    • C09J2301/30—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
    • 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
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a kind of adhesion agent composition and surface protection film that excellent antistatic property and stain resistance can be achieved at the same time.The adhesion agent composition contains acrylic polymer, antistatic agent and crosslinking agent, the acrylic polymer has 0 DEG C of glass transition temperature below, the crosslinking agent is the isocyanate compound of trifunctional or more, the antistatic agent is the ionic compound that the fusing point formed by cation and anion is 25 DEG C or more, the anion is selected from by trifluoromethayl sulfonic acid root anion, pentafluoroethane azochlorosulfonate acid anion, heptafluoro-propane azochlorosulfonate acid anion, one kind in the group of nine fluorine butane azochlorosulfonate acid anions composition, the acrylic polymer relative to 100 parts by weight, contain the antistatic agent as required ingredient using the ratio of 0.01~10 parts by weight.

Description

Adhesion agent composition and surface protection film
Technical field
The present invention relates to a kind of adhesion agent composition and surface protection film containing antistatic agent.More specifically, it is one Kind contains ionic compound as antistatic agent to the adhesion agent composition with excellent antistatic property and stain resistance And the surface protection film of the adhesion agent composition has been used, the ionic compound has the specific sulphurs such as nine fluorine butane sulfonate radicals Acid radical anion.
Background technology
Back and forth, in the system of the precise parts such as electronic equipment part, optical equipment parts, image display panel and component It makes in processing and assembling procedure, for the surface of these precise parts of temporary protection and component, to prevent from coming from operating environment gas The particle (particle) of atmosphere and the attachment of gasiform polluter or the generation of scratch, recess, in precise part and structure It is pasted with surface protection film on the surface of part.
For example, for manufacturing as optical components such as the polarizer, phase difference boards of component for constituting liquid crystal display For surface protection film used in process, although in the polyethylene terephthalate (PET) with optical transparence It is formed with adhering agent layer on the single side of resin film, but before fitting on optical component, is bonded on adhering agent layer useful In the release-treated mold release film for protecting the adhering agent layer.
In addition, the optical components such as polarizer, phase difference board are carried out with being fitted with the state of surface protection film with liquid crystal Show that display capabilities, tone, contrast, the foreign matter of plate such as are mixed at the product examination of optical evaluation.Therefore, as to surface protection The required performance of film, it is desirable that bubble-free or foreign matter are attached to adhering agent layer.
In addition, in recent years, it is believed that when surface protection film is removed from the optical components such as polarizer, phase difference board, with The stripping electrostatic the electrostatic that the when of removing adhering agent layer from adherend generates and generated may be to the electrical of liquid crystal display The failure of control circuit has an impact.Therefore, excellent antistatic property is required adhering agent layer.
As described above, in recent years, as the required performance of the adhering agent layer to constituting surface protection film, being protected from surface is used Being set out using the angle of difficulty when cuticula, it is desirable that excellent antistatic property and contamination preventing performance etc..
Oriented base is disclosed as the method for assigning surface protection film antistatic property about excellent antistatic property The method etc. that antistatic agent is mediated in material film discloses for example as antistatic agent：(a) there is quaternary ammonium salt, pyridineSalt, primary The various cationic antistatic agents of the cation groups such as amino~tertiary amino；(b) have sulfonate radical, sulfate group, it is phosphate-based, The anionic antistatic agents of the anionic groups such as phosphonate radical；(c) the both sexes antistatic agent such as amino acids, amidosulphuric acid esters；(d) The non-ionic antistatic agents such as alkamine, glycerols, polyethylene glycols；(e) by antistatic agent molecular weight as described above Made of Polymer Antistatic Agent etc. (patent document 1).
In addition, proposing in recent years, such antistatic agent is not set to be contained in base material film, or be not coated on base On the surface of material film, but directly make that it includes in adhering agent layer (patent documents 2).
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 11-070629 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2000-129235 bulletins
Invention content
The technical problem to be solved in the present invention
However, the surface protection film for being used for the optical films such as LR (low reflection) polarizing films or AG (anti-dazzle)-LR polarizing films For, antifouling process or low reflecting surface based on silicone compounds or fluorine compounds etc. have been subjected to due to the surface of optical film Processing, therefore the stripping electrostatic pressure by surface protection film from the optical film as adherend when stripping is got higher.
In addition, having the adhesion agent composition of antistatic property and having used the surface protection film of the adhesion agent composition The relationship of antistatic property and the stain resistance to adherend is the relationship of shifting (trade-off), it is difficult to remain anti- Improve stain resistance while antistatic property.
Therefore, in the adhesion agent composition of the surface protection film for the optical films such as LR polarizing films or AG-LR polarizing films In, even if seeking a kind of to be subjected to antifouling process based on silicone compounds or fluorine compounds etc. or low on the surface of optical film Reflecting surface processing in the case of, stripping electrostatic pressure when also can remove surface protection film from optical film be suppressed to it is relatively low, And adherend pollutes few adhesion agent composition.
The present invention has been made in view of the above-described circumstances, and the present invention provides a kind of adhesion agent composition and used the adhesion The surface protection film of agent composition, the adhesion agent composition can impose adherend using the composition containing fluorine compounds In the case of surface treatment, while realizing excellent antistatic property and stain resistance.
Solve the technological means of technical problem
Present inventor is prepared for a kind of new adhesion agent composition, contains：Adhesion agent composition will be constituted The carbon atom number of the alkyl of (methyl) alkyl acrylate of acrylic polymer is limited to specific range and makes specific Copolymer made of two or more (methyl) alkyl acrylate copolymers of combination；And by having nine fluorine butane sulfonate radicals etc. The antistatic agent that the ionic compound that the fusing point of specific azochlorosulfonate acid anion is 25 DEG C or more is formed.It finds as a result, available It is a kind of compared with previous surface protection film adhesion agent composition, there is excellent stain resistance, and with not passing through When the adhesion agent composition of excellent antistripping antistatic property that deteriorates, so as to complete the present invention.
Especially define：Have in adherend and is laminated in stain-proofing layers on the surface of optical film, containing fluorine compounds Or using the low-refraction formation containing fluorine compounds composition and in the case of the low-index layer that is formed, and it is existing Technology is compared, and surface protection film of the present invention has excellent stain resistance, and has and the excellent of deterioration does not occur Different antistripping antistatic property.That is, a kind of surface while realizing with antistatic property and stain resistance can be obtained Protective film.
In order to solve the technical problem, the present invention provides a kind of adhesion agent composition, containing acrylic polymer, Antistatic agent and (D) crosslinking agent, which is characterized in that
The acrylic polymer has 0 DEG C of glass transition temperature below,
(D) crosslinking agent is the isocyanate compound of trifunctional or more,
The antistatic agent is the ionic compound that the fusing point formed by cation and anion is 25 DEG C or more, described the moon Ion is selected from by trifluoromethayl sulfonic acid root anion, pentafluoroethane azochlorosulfonate acid anion, heptafluoro-propane azochlorosulfonate acid anion, nine One kind in the group of fluorine butane azochlorosulfonate acid anion composition,
Relative to the acrylic polymer of 100 parts by weight, contained with the ratio of 0.01~10 parts by weight described anti- Electrostatic agent is as required ingredient.
Furthermore it is preferred that：The acrylic polymer is the acrylic polymer of copolymer made of making following monomer be copolymerized Close object：
(A) carbon atom number of alkyl be C1~18 (methyl) acrylate monomer at least two or more, with 1~ At least one of (methyl) acrylate monomer that the carbon atom number that the ratio of 50 parts by weight contains (a1) alkyl is C1~C4, And the carbon atom number of (a2) alkyl is contained in (methyl) acrylate monomer of C5~C18 with the ratio of 50~99 parts by weight At least one, (a1) add up to 100 parts by weight with (a2's)；
(B) more than at least one of copolymerizable vinyl monomer containing hydroxyl and/or carboxyl；And
(C) more than at least one of the list containing polyalkylene glycol chain (methyl) acrylate monomer,
In (a2), contained selected from by (methyl) Isooctyl acrylate monomer, (methyl) third with ratios more than 50 parts by weight At least one of the group of the different nonyl ester of olefin(e) acid, (methyl) acrylic acid-2-ethyl caproite composition,
Further the crosslinking accelerator containing (E) metal chelate compound and (F) keto-enol are mutual for the adhesion agent composition Tautomeric compound.
The cation is preferably selected from by pyridineImidazolesPhosphonium, sulfonium, pyrrolidinesGuanidineAmmonium, isourea (isouronium), thiocarbamide(thiouronium), piperidinesPyrazoles(pyrazolium), methyl (methylium), lithium, morpholine(morpholinium) one kind in the group formed.
It is preferred that：The surface resistivity of adhering agent layer made of making the adhesion agent composition be crosslinked is 1.0 × 10+12Ω/□ Hereinafter, the low-index layer formed relative to the composition for using the low-index layer formation containing fluorine compounds, institute The stripping electrostatic pressure for stating adhering agent layer is -0.3~+0.3kV.
It is preferred that：The copolymerizable vinyl monomer of (B) containing hydroxyl and/or carboxyl is selected from by being total to containing hydroxyl It is more than polycondensation monomer and at least one of the group of copolymerisable monomer composition containing carboxyl, wherein
The copolymerisable monomer containing hydroxyl is selected from by (methyl) acrylic acid -8- hydroxyls monooctyl ester, (methyl) acrylic acid - The own ester of 6- hydroxyls, (methyl) acrylic acid -4- hydroxybutyls, (methyl) 2-Hydroxy ethyl acrylate, N- hydroxyls (methyl) acryloyl Amine, N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide composition at least one of compound group with On,
The copolymerisable monomer containing carboxyl is selected from by (methyl) acrylic acid, carboxyethyl (methyl) acrylate, carboxylic Amyl (methyl) acrylate, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) acryloxy third Base hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyls phthalic acid, 2- (methyl) acryloyl-oxyethyl amber Acid, 2- (methyl) acryloyl-oxyethyls maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) acryloyl-oxy It is more than at least one of compound group of base ethyl tetrahydrophthalic acid composition.
It is preferred that：For list (methyl) acrylate monomer of (C) containing polyalkylene glycol chain, poly- alkylene is constituted The average repeat unit number of the alkylene oxide (alkylene oxide) of base glycol chains is 3~14,
Diester component in list (methyl) acrylate monomer of (C) containing polyalkylene glycol chain be 0.2% hereinafter,
It is (methyl) acrylate of C1~18 relative to the carbon atom number of (A) alkyl described in 100 parts by weight is added up to At least two or more in monomer, contained selected from by polyalkylene glycol mono (methyl) acrylic acid with the ratio of 1~50 parts by weight The group of ester, methoxypolyalkylene glycol (methyl) acrylate, ethyoxyl polyalkylene glycol (methyl) acrylate composition At least one of above list (methyl) acrylate monomer of as described in (C) containing polyalkylene glycol chain.
It is preferred that：(E) crosslinking accelerator is selected from by aluminium chelate compound, titanium chelate compound, iron chelating compounds It is more than at least one of group of composition,
Relative to the acrylic polymer of 100 parts by weight, contained with the ratio of 0.001~0.5 parts by weight described (E) crosslinking accelerator and described (F) ketone-enol tautomers compound is contained with the ratio of 0.1~300 parts by weight, it is described (F) weight part ratio of/(E) is 70~1000.
In addition, the present invention provides a kind of adhesive film, which is characterized in that being laminated on the single side of resin film makes above-mentioned glue Adhering agent layer made of the crosslinking of agent composition.
In addition, the present invention provides a kind of surface protection film, it uses above-mentioned adhesive films.
In addition, the present invention provides a kind of surface protection film of polarizing film, it uses above-mentioned adhesive films.
In addition, the present invention provides a kind of optical film with adhering agent layer, it is laminated on the face of at least side of optical film There is adhering agent layer made of making above-mentioned adhesion agent composition be crosslinked.
In addition, the present invention provides a kind of adhesive film, wherein the resin film single side, i.e. be laminated with the adhesion The side of oxidant layer is implemented with antistatic treatment and antifouling process on opposite face.
Invention effect
The present invention provides a kind of adhesion agent composition and table that excellent antistatic property and stain resistance can be achieved at the same time Surface protective film.
Have in adherend and is laminated in stain-proofing layers on the surface of optical film, containing fluorine compounds or use contains fluorine The composition of the low-index layer formation of compound and in the case of the low-index layer that is formed, compared with prior art, this Inventing the adhesion agent composition being related to and the surface protection film for having used the adhesion agent composition has excellent stain resistance, and And with the excellent antistripping antistatic property that deterioration does not occur.
That is, adhesion agent composition of the present invention and having used the surface protection film of the adhesion agent composition due to having Excellent antistatic property and stain resistance, therefore utility value industrially is very big.
Specific implementation mode
Hereinafter, based on suitable embodiment, the present invention will be described.
The adhesion agent composition of present embodiment contains acrylic polymer, antistatic agent and (D) crosslinking agent, and described third It is the isocyanation esterification of trifunctional or more that alkene acids polymers, which have 0 DEG C of glass transition temperature below, (D) crosslinking agent, Close object, the antistatic agent be 25 DEG C or more by cation and the fusing point that is formed of anion ionic compound, described the moon from Son is selected from by trifluoromethayl sulfonic acid root anion, pentafluoroethane azochlorosulfonate acid anion, heptafluoro-propane azochlorosulfonate acid anion, nine fluorine One kind in the group of butane azochlorosulfonate acid anion composition；Relative to the acrylic polymer of 100 parts by weight, with 0.01~ The ratio of 10 parts by weight contains the antistatic agent as required ingredient.
Furthermore it is preferred that it is solid, the ionization that fusing point is 25 DEG C or more that the antistatic agent, which is at a temperature of 25 DEG C, Object is closed, the fusing point of the further preferred antistatic agent is 450 DEG C or less.
The acrylic polymer used in the adhesion agent composition of present embodiment has 0 DEG C of glass transition below Temperature.In addition, acrylic polymer is preferably (methyl) acrylate monomer for C1~18 with the carbon atom number of (A) alkyl Make copolymer as main component.
In addition, the carbon atom number as (A) alkyl is (methyl) acrylate monomer of C1~18, can enumerate (methyl) Methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid are different Butyl ester, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (first Base) Isooctyl acrylate monomer, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) acrylic acid hendecane base ester, (methyl) dodecylacrylate, (methyl) acrylic acid ten Trialkyl ester, (methyl) acrylic acid tetradecane base ester, (methyl) acrylic acid pentadecane base ester, (methyl) acrylic acid cetyl Ester, (methyl) acrylic acid heptadecane base ester, (methyl) octadecyl acrylate, (methyl) acrylic acid ring pentyl ester, (methyl) third Olefin(e) acid cyclohexyl etc..The alkyl of (methyl) alkyl acrylate monomer is any one in straight chain, branch-like, ring-type.
In addition, the carbon atom number relative to (A) alkyl for adding up to 100 parts by weight is (methyl) acrylate of C1~18 Monomer, the carbon atom number of (a1) alkyl are that the ratio of at least one of (methyl) acrylate monomer of C1~C4 is preferably 1 The ratio of at least one of~50 parts by weight, (methyl) acrylate monomer that the carbon atom number of (a2) alkyl is C5~C18 Preferably 50~99 parts by weight.In addition, the carbon atom number relative to (A) alkyl for adding up to 100 parts by weight is the (first of C1~18 Base) acrylate monomer, the carbon atom number of (a2) alkyl is in (methyl) acrylate monomer of C5~C18, preferably with 50 weights Ratio more than amount part contains selected from by (methyl) Isooctyl acrylate monomer, the different nonyl ester of (methyl) acrylic acid, (methyl) acrylic acid -2- At least one of the group of ethylhexyl composition.
The acrylic polymer used in the adhesion agent composition of present embodiment (B) can be made containing hydroxyl and/or At least one of copolymerizable vinyl monomer of carboxyl is copolymerized as any ingredient.Contain hydroxyl and/or carboxyl as (B) Copolymerizable vinyl monomer, can enumerate selected from by the copolymerisable monomer (hydroxyl monomer) containing hydroxyl and containing carboxyl It is more than at least one of group of copolymerisable monomer (carboxyl group-containing monomer) composition.I.e., it is possible to only select hydroxyl monomer or contain carboxylic In base monomer any one and be copolymerized, can also make both hydroxyl monomer and carboxyl group-containing monomer be copolymerized.
In addition, as hydroxyl monomer, can enumerate selected from by (methyl) acrylic acid -8- hydroxyls monooctyl ester, (methyl) propylene The own ester of acid -6- hydroxyls, (methyl) acrylic acid -4- hydroxybutyls, (methyl) 2-Hydroxy ethyl acrylate, N- hydroxyls (methyl) third In the compound groups of compositions such as acrylamide, N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide at least More than one.Carbon atom number relative to (A) alkyl for adding up to 100 parts by weight is (methyl) acrylate monomer of C1~18 In at least two or more, the ratio of the hydroxyl monomer contained in the adhesion agent composition of present embodiment is preferably 0.1~ The ratio of 20 parts by weight, the more preferably ratio of 4.1~16 parts by weight, the particularly preferably ratio of 5.1~14 parts by weight.
In addition, as carboxyl group-containing monomer, can enumerate selected from by (methyl) acrylic acid, carboxyethyl (methyl) acrylate, Carboxylic amyl (methyl) acrylate, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) acryloxy Propyl hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyls phthalic acid, 2- (methyl) acryloyl-oxyethyl amber Amber acid, 2- (methyl) acryloyl-oxyethyls maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) acryloyl It is more than at least one of compound groups of compositions such as oxygroup ethyl tetrahydrophthalic acid.Relative to adding up to 100 parts by weight (A) alkyl carbon atom number be C1~18 (methyl) acrylate monomer at least two or more, present embodiment relates to And adhesion agent composition in the ratio of carboxyl group-containing monomer to be preferably 0~5.0 parts by weight (also allow carboxyl group-containing monomer not to be made to be total to Poly- situation), in the case where making carboxyl group-containing monomer be copolymerized, the more preferably ratio of 0.01~5.0 parts by weight, particularly preferably The ratio of 0.02~1.3 parts by weight, the most preferably ratio of 0.02~0.8 parts by weight.
The acrylic polymer used in the adhesion agent composition of present embodiment can make (C) to contain polyalkylene glycol List (methyl) acrylate monomer of chain is copolymerized as any ingredient.As the list (methyl) of (C) containing polyalkylene glycol chain Acrylate monomer, as long as being that a hydroxyl in multiple hydroxyls possessed by polyalkylene glycol is esterified as (methyl) propylene Compound made of acid esters.It is polymerizable group since (methyl) is acrylate-based, it can be with the acrylic compounds Polymer copolymerization.In present embodiment, even if being polyalkylene glycol mono (methyl) acrylate that other hydroxyls are still OH, Also it is not classified as the copolymerizable vinyl monomer of (B) containing hydroxyl and/or carboxyl.(C) list containing polyalkylene glycol chain (methyl) acrylate monomer may be the alkoxy polyalkyleneglycol list (methyl) that other hydroxyls are transformed into alkyl ether Acrylate etc..
In addition, as the polyalkylene glycol for constituting polyalkylene glycol chain, as long as with one or more The diatomic alcohol compounds of alkylidene, such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol third can be enumerated Glycol, polyethylene glycol butanediol, polypropylene glycol-polytetramethylene glycol, polyethylene glycol propylene glycol-polytetramethylene glycol etc..
In addition, for list (methyl) acrylate monomer of (C) containing polyalkylene glycol chain, poly- alkylene is preferably comprised The average repeat unit number of the alkylene oxide of base glycol chains is 3~14." the average repeat unit number of alkylene oxide " refers at (C) containing poly- The part of " polyalkylene glycol chain " included in the molecular structure of list (methyl) acrylate monomer of alkylene glycol chain In, average that epoxy alkane unit is repeated.Furthermore it is preferred that list (methyl) acrylate of (C) containing polyalkylene glycol chain Diester component in monomer is 0.2% or less." diester component in monomer " refers to the list (first of (C) containing polyalkylene glycol chain Base) polyalkylene glycol two (methyl) acrylate included in acrylate monomer containing ratio (weight %).
In addition, as list (methyl) acrylate monomer of (C) containing polyalkylene glycol chain, it is preferably selected from by poly- alkylene Base glycol list (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, ethyoxyl polyalkylene glycol (first Base) acrylate composition at least one of group more than.
Carbon atom number relative to (A) alkyl for adding up to 100 parts by weight is (methyl) acrylate monomer of C1~18 In at least two or more, the list (first of (C) containing polyalkylene glycol chain in adhesion agent composition of the present embodiment Base) ratio of acrylate monomer is preferably the ratio of 1~50 parts by weight, the more preferably ratio of 1~30 parts by weight, and it is especially excellent It is selected as the ratio of 2~25 parts by weight.
The preparation method of the acrylic polymer contained in adhesion agent composition of the present embodiment is not special Restriction, the suitable and known polymerization such as solution polymerization process, emulsion polymerization can be used.For of the present embodiment For adhesion agent composition, the weight average molecular weight of the copolymer of preferably used acrylic polymer is 100~3,000,000.
In order to obtain antistatic property, adhesion agent composition of the present embodiment contains (G) antistatic agent.(G) resist Electrostatic agent is the ionic compound that the fusing point formed by cation and anion is 25 DEG C or more, which is selected from by trifluoro Methanesulfonate anion (CF3SO3 -), pentafluoroethane azochlorosulfonate acid anion (CF3CF2SO3 -), heptafluoro-propane azochlorosulfonate acid anion (CF3CF2CF2SO3 -), nine fluorine butane azochlorosulfonate acid anion (CF3CF2CF2CF2SO3 -) composition group in one kind.Relative to 100 The acrylic polymer of parts by weight, adhesion agent composition of the present embodiment is preferably with the ratio of 0.01~10 parts by weight Contain (G) antistatic agent as required ingredient, is needing to further increase the antistatic property of adhering agent layer to keep surface electric The lower limiting value of resistance rate is reduced to 1.0 × 10+10In the case of Ω/ is below, more preferably contained with the ratio of 0.01~15 parts by weight (G) antistatic agent.
In addition, as the cation contained by ionic compound, can enumerate selected from by pyridineImidazolesPhosphonium, sulfonium, PyrrolidinesGuanidineAmmonium, isoureaThiocarbamidePiperidinesPyrazolesMethylLithium, morpholineOne in the group of composition Kind.
In addition, the concrete example as (G) antistatic agent, can enumerate trifluoromethayl sulfonic acid lithium, nine fluorine butane Sulfonic Lithiums, 1- Methyl -3- octylpyridiniumsTrifluoro-methanyl sulfonate, 3- methyl-1s-octylpyridiniumTrifluoro-methanyl sulfonate, 1- methyl -4- OctylpyridiniumNine fluorine butane sulfonate, 4- methyl-1s-octylpyridiniumNine fluorine butane sulfonate, dimethyl dioctyl ammonium five Fluoroethane sulfonate, 1- methyl -3- octylpyridiniumsHeptafluoro-propane sulfonate, 3- methyl-1s-octylpyridiniumHeptafluoro-propane sulphur Hydrochlorate, 1- methyl -3- octylpyridiniumsNine fluorine butane sulfonate, 3- methyl-1s-octylpyridiniumNine fluorine butane sulfonate, 1- Octyl -3- methylimidazolesNine fluorine butane sulfonate etc..
Adhesion agent composition of the present embodiment further contains the isocyanate compound conduct of trifunctional or more (D) crosslinking agent.
As isocyanate compound more than trifunctional, such as hexamethylene diisocyanate, different Fo Er can be enumerated Two isocyanide such as ketone diisocyanate, methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), benzene dimethylene diisocyanate The polyalcohol more than biuret modified body or isocyanurate-modified body of esters of gallic acid, with the ternarys such as trimethylolpropane or glycerine Adduct etc..
As the ratio of (D) crosslinking agent, such as it is 0.01 that can enumerate relative to the acrylic polymer of 100 parts by weight The ratio of~5 parts by weight.
Adhesion agent composition of the present embodiment can also contain (E) crosslinking accelerator.By polyisocyanate compounds In the case of as crosslinking agent, (E) is as long as crosslinking accelerator is as catalyst and to the acrylic polymer and crosslinking The substance that the reaction (cross-linking reaction) of agent plays a role, can enumerate the aminated compounds such as tertiary amine, metal chelate compound, Organo-metallic compounds such as organo-tin compound, organo-lead compound, organic zinc compound etc..In present embodiment, as friendship Join accelerating agent, preferably metal chelate compound.
It is the multidentate ligand L that 1 or more is bonded on central metal atom M in addition, as metal chelate compound Compound.Metal chelate compound can not also have with 1 or more the monodentate ligand X being bonded on metallic atom M There is monodentate ligand X.For example, by the general formula of the metallic atom M metal chelate compounds for being 1 with M (L)m(X)nWhen expression, m >=1, n≥0.When m is 2 or more, m L can be identical ligand, or different ligands.When n is 2 or more, n X can Think identical ligand, or different ligands.
In addition, as metallic atom M, Fe, Ni, Mn, Cr, V, Ti, Ru, Zn, Al, Zr, Sn etc. can be enumerated.
As multidentate ligand L, methyl acetoacetate, ethyl acetoacetate, acetoacetate monooctyl ester, acetoacetate can be enumerated 'beta '-ketoesters, the acetylacetone,2,4-pentanediones such as oleyl alcohol ester (oleyl acetoacetate), lauryl acetoacetate, acetoacetate stearyl The beta-diketons such as (alias 2,4- pentanediones), 2,4- acetyl butyryls, benzoyl acetone.These multidentate ligands L is ketoenol tautomerization Body compound, for multidentate ligand L, or enolization compound made of enol deprotonation (such as acetylacetonate Object).
As monodentate ligand X, the halogen atoms such as chlorine atom, bromine atom can be enumerated；Valeryl, caproyl, 2- ethyl hexyls The acyloxy such as acyl group, caprylyl, pelargonyl group, capryl, dodecanoyl, octadecanoyl；It is methoxyl group, ethyoxyl, positive propoxy, different Alkoxies such as propoxyl group, butoxy etc..
In addition, the concrete example as metal chelate compound, can enumerate three (2,4- pentanedione) iron (III), triacetyl Acetone iron, praseodynium titanium, praseodynium ruthenium, bis-acetylacetonate zinc, praseodynium aluminium, four acetylacetone,2,4-pentanedione zirconiums, three (2, 4- acetyl butyryls) iron (III), bis- (2,4- acetyl butyryls) zinc, three (2,4- acetyl butyryls) titaniums, three (2,4- acetyl butyryls) aluminium, four (2,4- oneself Diketone) zirconium etc..
In addition, as (E) crosslinking accelerator, it is preferably selected from sequestration by aluminium chelate compound, titanium chelate compound, iron Close at least one of group of object composition or more.It is of the present embodiment relative to the acrylic polymer of 100 parts by weight Adhesion agent composition preferably contains (E) crosslinking accelerator with the ratio of 0.001~0.5 parts by weight.
Adhesion agent composition of the present embodiment can also contain (F) ketone-enol tautomers compound.As (F) ketone-enol tautomers compound can enumerate methyl acetoacetate, ethyl acetoacetate, acetoacetate monooctyl ester, second The 'beta '-ketoesters such as ethyl acetoacetic acid oleyl alcohol ester, lauryl acetoacetate, acetoacetate stearyl；Acetylacetone,2,4-pentanedione, 2,4- acetyl butyryls, benzene first The beta-diketons such as acyl acetone.Using polyisocyanate compounds as in the adhesion agent composition of crosslinking agent, these keto-enol changes Isomeric compound can inhibit viscous after blending crosslinking agent by isocyanate group possessed by sealing end (block) crosslinking agent The excessive viscosity for agent composition rises or gelation, can extend the storage period of adhesion agent composition.
Relative to the acrylic polymer of 100 parts by weight, adhesion agent composition of the present embodiment is preferably with 0.1 The ratio of~300 parts by weight contains (F) ketone-enol tautomers compound.
In addition, with (E) crosslinking accelerator on the contrary, (F) ketone-enol tautomers compound, which has, inhibits crosslinked effect Fruit, therefore the ratio preferably to (F) ketone-enol tautomers compound relative to (E) crosslinking accelerator is suitably set It is fixed.In order to extend the storage period of adhesion agent composition, improve bin stability, the weight part ratio of (F)/(E) is preferably 70~ 1000, more preferably 70~700, particularly preferably 80~600.Herein, the weight part ratio of (F)/(E) refers to the parts by weight of (F) Divided by (E) parts by weight and calculate gained quotient value.
Other than above-mentioned additive, the adhesion agent composition of present embodiment can also suitably blend antioxidant, It is added well known to surfactant, curing accelerator, plasticizer, filler, cure retarder, processing aid, age resister etc. Agent.These additives can be used alone or merge using two or more.
Made of so that the adhesion agent composition of present embodiment is crosslinked for adhering agent layer, the preferred table of adhering agent layer Surface resistivity is 1.0 × 10+12Ω/ is hereinafter, more preferably surface resistivity is 5.0 × 10+11Ω/ is hereinafter, particularly preferred table Surface resistivity is 2.0 × 10+11Ω/ or less.If surface resistivity is big, when adhering agent layer is removed from adherend, release The poor performance of the electrostatic generated by electrification.Therefore, by fully reducing the surface resistivity of adhering agent layer, companion can be reduced What is generated with the electrostatic generated when removing adhering agent layer from adherend removes electrostatic pressure, inhibits the influence to adherend.
For adhering agent layer made of the adhesion agent composition crosslinking for making present embodiment, contain preferably with respect to using There is the composition of the low-index layer formation of fluorine compounds and the low-index layer that is formed, adhering agent layer stripping electrostatic pressure In the range of -0.3~+0.3kV.The fluorine compounds used in composition as low-index layer formation can enumerate As the poly- of one or more of fluorinated olefins class, fluorinated vinyl ethers, (methyl) acrylic acid fluorinated alkyl esters etc. The condensation products such as the fluorinated copolymer of conjunction object, the silane compound containing fluorinated alkyl.Fluorinated copolymer in addition to perfluorinated monomer with Outside, olefines, vinyl ethers, (methyl) acrylate etc. can also be copolymerized without fluorinated monomer.Low-index layer It can be combined with high refractive index layer etc. and constitute anti-reflection layer.
The adhesive film of present embodiment is that the adhesion agent composition for making present embodiment is laminated on the single side of base material film The adhesive film of adhering agent layer made of crosslinking.The adhesive film of present embodiment can be suitably used for surface protection film, polarizing film Surface protection film, optical film surface protection film in.Make this reality by being laminated on the face of at least side of optical film Adhering agent layer made of the adhesion agent composition crosslinking of mode is applied, the optical film with adhering agent layer can be obtained.It, can as optical film Enumerate polarizing coating, phase difference film, antireflection film, anti-dazzle (anti-glare) film, ultraviolet-absorbing film, infrared absorbing film, Optical compensation films, brightness improve film etc..As the equipment that optical component is applicable in, can enumerate liquid crystal display panel, organic EL panel, Touch panel etc..
As the base material film of adhering agent layer or the mold release film (isolation film) of protection bonding plane, the resin films such as polymer PET can be used Deng.
For base material film, it can implement to be based on silicon on the face opposite with the side for being formed with adhering agent layer of resin film The antifouling process of ketone, the releasing agent of fluorine class or smears, silicon dioxide microparticle etc., coating or kneading based on antistatic agent etc. Antistatic treatment.
For mold release film, be bonded in the bonding plane with adhering agent layer using the releasing agent etc. of silicone, fluorine class one Implement demoulding processing on the face of side.
In the case of in the surface protection film of the optics such as the surface protection film of polarizing film, preferred substrates film and sticker Layer has the adequately transparency.
Embodiment
Hereinafter, being specifically explained to the present invention using embodiment.
The preparation > of < acrylic polymers
[embodiment 1]
Nitrogen is imported into the reaction unit for having blender, thermometer, reflux cooler and nitrogen ingress pipe, utilizes nitrogen Gas has replaced the air in reaction unit.Then, the methyl acrylates of 12 parts by weight, 88 parts by weight are added into reaction unit Acrylic acid-2-ethyl caproite, the acrylic acid -8- hydroxyls monooctyl esters of 12.0 parts by weight, the acrylic acid of 0.1 parts by weight, 20 parts by weight Polypropylene glycol mono acrylic ester (the average repeat unit number n=12 of alkylene oxide), while adding the solvent (second of 100 parts by weight Acetoacetic ester).Then, the azodiisobutyronitrile as 0.1 parts by weight of polymerization initiator was added dropwise using 2 hours, reacts 8 at 65 DEG C Hour, obtain the acrylic polymer solution of embodiment 1.
[embodiment 2~6 and comparative example 1~3]
Other than the composition of monomer being set to as described in Table 1, with the propylene that is used in the above embodiments 1 It is molten to have obtained the acrylic polymer used in embodiment 2~6 and comparative example 1~3 for the same mode of acids polymers solution Liquid.
The preparation > of < adhesion agent compositions and surface protection film
[embodiment 1]
To as described above and in the acrylic polymer solution of the embodiment 1 of preparation, the crosslinking agent of 2.0 parts by weight is added The antistatic agent (nine fluorine butane Sulfonic Lithiums) of (CORONATE HX), 1.0 parts by weight, crosslinking accelerator (three second of 0.1 parts by weight Acyl acetone titanium) and 9 parts by weight ketone-enol tautomers compound (acetylacetone,2,4-pentanedione), be stirred mixing, obtain The adhesion agent composition of embodiment 1.The adhesion agent composition is coated on to the poly terephthalic acid second by having been coated with silicone resin It after in the mold release film that diol ester (PET) film is formed, is dried at 90 DEG C, to remove solvent, it is 20 μ to have obtained thickness The adhering agent layer of m.Then, make the adhering agent layer with mold release film be needed on the face of side is implemented it is antistatic and antifouling process It is the base material film formed by polyethylene terephthalate (PET) film, opposite with antistatic and antifouling process face is implemented Face on, obtained with base material film/adhering agent layer/mold release film stepped construction embodiment 1 surface protection film.
[embodiment 2~6 and comparative example 1~3]
Other than being set to the composition of additive as described in Table 1, with the surface protection with the above embodiments 1 The same mode of film, has obtained the surface protection film of embodiment 2~6 and comparative example 1~3.
[table 1]
In table 1, the parts by weight of each ingredient are by that will be used as (methyl) propylene that the carbon atom number of (A) alkyl is C1~18 The total of (a1) and (a2) of acid ester monomer is set as 100 parts by weight and acquires.
In addition, in table 1, (D), (G), (E), (F) each column in, acrylic polymer is set as 100 parts by weight, with Numerical value in parantheses () illustrates the content ratio (parts by weight) of each ingredient.
In addition, the compound name of the dummy suffix notation of each ingredient used in table 1 is shown in table 2.(C) contain polyalkylene two In list (methyl) acrylate monomer of alcohol chain, for C-1~C-5, the diester component in monomer is 0.2% or less；For C- 6, the diester component in monomer is 0.8%.G-1~G-6 is that fusing point is 25 DEG C or more, is the ion combination of solid at 25 DEG C Object；G-7 is that fusing point is 15 DEG C, is the ionic compound of liquid at 25 DEG C.
[table 2]
In addition, CORONATE (registered trademark) HX, CORONATE HL and CORONATE L are TOSOH CORPORATION Trade name, D-127N, TAKENATE (registered trademark) D-140N be Mitsui Chemicals, Inc. trade name. In addition, HDI refers to hexamethylene diisocyanate, IPDI refers to isophorone diisocyanate, and XDI refers to phenylenedimethylidyne two Isocyanates, TDI refer to toluene di-isocyanate(TDI), and TMP refers to trimethylolpropane.
< test methods and evaluation >
Surface protection film in Examples 1 to 6 and comparative example 1~3 is cured 7 under 23 DEG C, the atmosphere of 50%RH respectively After it, evaluated using test method below.
The test method > of < adhesion strengths
Mold release film is peeled, the surface protection film of adhering agent layer will be exposed via adhering agent layer and fitting in polarizing film (makes The polarizing film for being TAC with the protective layer of polarizer) surface on, place 1 day after, carried out 20 minutes under 50 DEG C, 5 atmospheric pressure Autoclaving, after further placed 12 hours at room temperature, as the determination sample of adhesion strength.The polarization of adherend Piece is LR polarizing films or AG-LR polarizing films.It (30m/ minutes) will with low velocity (0.3m/ minutes) or at high speed with cupping machine It is peeled along 180 ° of directions in above-mentioned obtained determination sample, obtained peel strength will be measured as adhesion strength.
Herein, for above-mentioned LR polarizing films and AG-LR polarizing films, with the composition containing fluorine compounds to the polarization Implement low reflecting surface processing in the surface of piece.
The test method > of < surface resistivities
After surface protection film is cured, before being fitted on adherend, mold release film is peeled, exposes sticker Layer, it is right using resistrivity meter HIRESTA UP-HT450 (Mitsubishi Chemical Analytech Co., Ltd manufacture) The surface resistivity of adhering agent layer is determined.
< removes the test method > of electrostatic pressure
Mold release film is peeled, the surface protection film for exposing adhering agent layer is fitted on adherend, the adherend is in quilt The low-index layer that there is the composition using the low-index layer formation containing fluorine compounds on viscous face and formed.With 30m/ When the tensile speed of minute carries out 180 ° of strippings to surface protection film, high-precision electrostatic induction device SK-035, SK-200 are used The voltage (electrostatic pressure) that (KEYENCE CORPORATION manufactures) measures adherend electrification and generation, by the maximum value of measured value As stripping electrostatic pressure.
The test method > of < stain resistances
Using make-up machine, by the LR polarizing films for implementing low reflecting surface processing or described low reflection is implemented The AG-LR polarizing films (polarizing film that the protective layer using polarizer is TAC) of surface treatment are via adhering agent layer (two-sided adhesion glue Band) it fits on the single side of glass plate.Then, surface protection film is fitted on the surface of the polarizing film using make-up machine. After keeping during having been carried out in the environment of 23 DEG C, 50%RH 3 days and 30 days, the surface protection film is peeled, to institute The pollutional condition for stating the surface of polarizing film has carried out visual observation.The judgement benchmark of stain resistance is：It will be to the polarizing film The case where surface no-pollution, is evaluated as "○"；There will be the case where a little pollution to be evaluated as " △ "；There will be the case where pollution to comment Valence is "×".
By about the surface protection film in Examples 1 to 6 and comparative example 1~3 evaluation result is shown in table 3." sheet resistance Rate " is by by " m × 10+n" be denoted as " mE+n " mode (wherein, m be arbitrary real number value, n is positive integer) carried out table Show.The type of the polarizing film of the adherend used in the experiment of " surface treatment " column expression adhesion strength.
[table 3]
The surface protection film of Examples 1 to 6 to the polarizing film as adherend, peeling rate in low speed be 0.3m/ Adhesion strength when minute is 0.03~0.05N/25mm (for example, 0.01~0.1N/25mm), is 30m/ in the peeling rate of high speed Adhesion strength when minute is 0.4~0.6N/25mm (for example, 1.0N/25mm or less), has adhesion strength appropriate, adhesive performance It is excellent.
In addition, the surface resistivity of the adhering agent layer of the surface protection film of Examples 1 to 6 is 1.0 × 10+12Ω/ with Under, the low-index layer that is formed relative to the composition for using the low-index layer formation containing fluorine compounds, adhesion For the stripping electrostatic pressure of oxidant layer in the range of -0.3~+0.3kV, antistatic property is excellent.
Further, even if not having if after keeping of the surface protection film of Examples 1 to 6 during having carried out 3 days and 30 days There are the pollution to the polarizing film as adherend, stain resistance excellent.
That is, the evaluation result shown in table 3 about the surface protection film of Examples 1 to 6, it was confirmed that the present invention can be solved The technical issues of.
The surface protection film of comparative example 1~3 is used as (G) antistatic agent due to the use of the ionic compound of liquid, therefore The surface resistivity height of adhering agent layer, low contamination resistance.
In addition, the surface protection film of comparative example 1~2 removes electrostatic pressure since the surface resistivity of adhering agent layer is high It is high.About the surface protection film of comparative example 3, although undetermined removes electrostatic pressure, since the surface resistivity of adhering agent layer is high, Therefore it can speculate that stripping electrostatic pressure is high.
Further, for the surface protection film of comparative example 2, the acrylic contained in adhesion agent composition The glass transition temperature of object is more than 0 DEG C (calculated value is+2 DEG C).Therefore, adhesive performance is poor, and adhesion strength is excessive.In addition, comparing In the acrylic polymer used in example 2, the glass transition temperature of homopolymer is the methyl acrylate of high level (being more than 0 DEG C) And the ratio of acrylic acid is more.
As described above, the surface protection film of comparative example 1~3, can not solve the technical problem of the present invention.

Claims (12)

1. a kind of adhesion agent composition contains acrylic polymer, antistatic agent and (D) crosslinking agent, which is characterized in that
The acrylic polymer has 0 DEG C of glass transition temperature below,
(D) crosslinking agent is the isocyanate compound of trifunctional or more,
The antistatic agent is the ionic compound that the fusing point formed by cation and anion is 25 DEG C or more, the anion To be selected from by trifluoromethayl sulfonic acid root anion, pentafluoroethane azochlorosulfonate acid anion, heptafluoro-propane azochlorosulfonate acid anion, nine fluorine fourths One kind in the group of alkyl sulfonic acid root anion composition,
Relative to the acrylic polymer of 100 parts by weight, contained with the ratio of 0.01~10 parts by weight described antistatic Agent is as required ingredient.
2. adhesion agent composition according to claim 1, which is characterized in that the acrylic polymer is to make lower list The acrylic polymer of copolymer made of body copolymerization：
(A) carbon atom number of alkyl is at least two or more in (methyl) acrylate monomer of C1~18, with 1~50 weight At least one of (methyl) acrylate monomer that the carbon atom number that the ratio of amount part contains (a1) alkyl is C1~C4 and with In (methyl) acrylate monomer that the carbon atom number that the ratio of 50~99 parts by weight contains (a2) alkyl is C5~C18 at least One kind, (a1) add up to 100 parts by weight with (a2's)；
(B) more than at least one of copolymerizable vinyl monomer containing hydroxyl and/or carboxyl；And
(C) more than at least one of the list containing polyalkylene glycol chain (methyl) acrylate monomer,
In (a2), contained selected from by (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid with ratios more than 50 parts by weight At least one of the group of different nonyl ester, (methyl) acrylic acid-2-ethyl caproite composition,
The crosslinking accelerator and (F) keto-enol that the adhesion agent composition further contains (E) metal chelate compound mutually make a variation Structure body compound.
3. adhesion agent composition according to claim 1 or 2, which is characterized in that the cation is selected from by pyridine ImidazolesPhosphonium, sulfonium, pyrrolidinesGuanidineAmmonium, isoureaThiocarbamidePiperidinesPyrazolesMethylLithium, morpholine One kind in the group of composition.
4. adhesion agent composition according to claim 1 or 2, which is characterized in that make the adhesion agent composition be crosslinked and At adhering agent layer surface resistivity be 1.0 × 10+12Ω/ is hereinafter, relative to the low-refraction containing fluorine compounds is used The stripping electrostatic pressure of the composition of layer formation and the low-index layer that is formed, described adhering agent layer is -0.3~+0.3kV's In range.
5. adhesion agent composition according to claim 2, which is characterized in that (B) being total to containing hydroxyl and/or carboxyl Poly- sex ethylene base monomer is in the group being made of the copolymerisable monomer containing hydroxyl and the copolymerisable monomer containing carboxyl It is more than at least one,
The copolymerisable monomer containing hydroxyl is selected from by (methyl) acrylic acid -8- hydroxyls monooctyl ester, (methyl) acrylic acid -6- hydroxyls The own ester of base, (methyl) acrylic acid -4- hydroxybutyls, (methyl) 2-Hydroxy ethyl acrylate, N- hydroxyls (methyl) acrylamide, It is more than at least one of compound group of N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide composition,
The copolymerisable monomer containing carboxyl is selected from by (methyl) acrylic acid, carboxyethyl (methyl) acrylate, carboxylic amyl (methyl) acrylate, 2- (methyl) acryloyl-oxyethyls hexahydrophthalic acid, 2- (methyl) acryloxypropyl six Hydrogen phthalic acid, 2- (methyl) acryloyl-oxyethyls phthalic acid, 2- (methyl) acryloyl-oxyethyls succinic acid, 2- (methyl) acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) acryloxy second It is more than at least one of compound group of base tetrahydrophthalic acid composition.
6. adhesion agent composition according to claim 2, which is characterized in that contain polyalkylene glycol chain for (C) List (methyl) acrylate monomer for, constitute the alkylene oxide of polyalkylene glycol chain average repeat unit number be 3~14,
Diester component in list (methyl) acrylate monomer of (C) containing polyalkylene glycol chain be 0.2% hereinafter,
It is (methyl) acrylate monomer of C1~18 relative to the carbon atom number of (A) alkyl described in 100 parts by weight is added up to In at least two or more, contained selected from by polyalkylene glycol mono (methyl) acrylate, first with the ratio of 1~50 parts by weight In the group that oxygroup polyalkylene glycol (methyl) acrylate, ethyoxyl polyalkylene glycol (methyl) acrylate form extremely Few list (methyl) acrylate monomer of more than one as described in (C) containing polyalkylene glycol chain.
7. adhesion agent composition according to claim 2, which is characterized in that (E) crosslinking accelerator is selected from by aluminium It is more than at least one of group of chelate compound, titanium chelate compound, iron chelating compounds composition,
Relative to the acrylic polymer of 100 parts by weight, (E) is contained with the ratio of 0.001~0.5 parts by weight and is handed over Connection accelerating agent simultaneously contains described (F) ketone-enol tautomers compound with the ratio of 0.1~300 parts by weight, and (F)/ The weight part ratio of (E) is 70~1000.
8. a kind of adhesive film, which is characterized in that being laminated on the single side of resin film makes described in any one of claim 1~7 Adhesion agent composition crosslinking made of adhering agent layer.
9. a kind of surface protection film, it uses adhesive films according to any one of claims 8.
10. a kind of surface protection film of polarizing film, it uses adhesive films according to any one of claims 8.
11. a kind of optical film with adhering agent layer, being laminated on the face of at least side of optical film makes claim 1~7 Any one of described in adhesion agent composition crosslinking made of adhering agent layer.
12. adhesive film according to claim 8, wherein the resin film single side, i.e. be laminated with the sticker It is implemented with antistatic treatment and antifouling process on the opposite face in side of layer.
CN201711053007.XA 2017-04-28 2017-11-01 Adhesive composition and surface protective film Active CN108795348B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-090505 2017-04-28
JP2017090505A JP6782664B2 (en) 2017-04-28 2017-04-28 Adhesive composition and surface protective film

Publications (2)

Publication Number Publication Date
CN108795348A true CN108795348A (en) 2018-11-13
CN108795348B CN108795348B (en) 2022-03-04

Family

ID=64095130

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711053007.XA Active CN108795348B (en) 2017-04-28 2017-11-01 Adhesive composition and surface protective film

Country Status (4)

Country Link
JP (1) JP6782664B2 (en)
KR (5) KR102045734B1 (en)
CN (1) CN108795348B (en)
TW (1) TWI737849B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113817110A (en) * 2021-09-08 2021-12-21 中国乐凯集团有限公司 Acrylate polymer, pressure-sensitive adhesive composition, pressure-sensitive adhesive, protective film and display device

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1957050A (en) * 2004-08-24 2007-05-02 Lg化学株式会社 Acrylic pressure sensitive adhesive having antistatic property
EP2014738A1 (en) * 2007-07-13 2009-01-14 Cheil Industries Inc. Adhesive composition and optical member
CN101874091A (en) * 2007-11-22 2010-10-27 第一毛织株式会社 Adhesive composition, and optical member, surface protective sheet
CN103930510A (en) * 2011-11-24 2014-07-16 日东电工株式会社 Adhesive composition, adhesive layer, polarizing film having adhesive layer, and image formation device
CN103958633A (en) * 2011-10-19 2014-07-30 日东电工株式会社 Water-dispersible acrylic adhesive composition, adhesive layer, and adhesive sheet
CN104673142A (en) * 2013-11-29 2015-06-03 藤森工业株式会社 Adhesive composition and surface protection film
CN104877606A (en) * 2014-02-27 2015-09-02 日本电石工业株式会社 Adhesive composition and optical member surface protective film
CN106147673A (en) * 2015-05-11 2016-11-23 藤森工业株式会社 Adhesion agent composition and surface protection film
CN106244062A (en) * 2015-06-04 2016-12-21 藤森工业株式会社 Adhesion agent composition and surface protection film
CN106489086A (en) * 2014-06-18 2017-03-08 住友化学株式会社 Polaroid, the polarization plates with binding agent and image display device

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4106749B2 (en) 1997-06-25 2008-06-25 三菱化学ポリエステルフィルム株式会社 LCD panel surface protective film
JP2000129235A (en) 1998-10-27 2000-05-09 Minnesota Mining & Mfg Co <3M> Antistatic pressure-sensitive adhesive composition
JP5734754B2 (en) * 2011-06-10 2015-06-17 藤森工業株式会社 Adhesive composition containing antistatic agent and adhesive film
JP2013163783A (en) * 2012-02-13 2013-08-22 Fujimori Kogyo Co Ltd Adhesive composition, adhesive film and surface-protecting film
JP5909137B2 (en) * 2012-04-05 2016-04-26 藤森工業株式会社 Adhesive composition and surface protective film
JP6267854B2 (en) * 2012-04-06 2018-01-24 日東電工株式会社 Adhesive composition, adhesive sheet, and optical member
JP6742723B2 (en) 2015-01-16 2020-08-19 日東電工株式会社 Surface protection film and optical member

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1957050A (en) * 2004-08-24 2007-05-02 Lg化学株式会社 Acrylic pressure sensitive adhesive having antistatic property
EP2014738A1 (en) * 2007-07-13 2009-01-14 Cheil Industries Inc. Adhesive composition and optical member
CN101874091A (en) * 2007-11-22 2010-10-27 第一毛织株式会社 Adhesive composition, and optical member, surface protective sheet
CN103958633A (en) * 2011-10-19 2014-07-30 日东电工株式会社 Water-dispersible acrylic adhesive composition, adhesive layer, and adhesive sheet
CN103930510A (en) * 2011-11-24 2014-07-16 日东电工株式会社 Adhesive composition, adhesive layer, polarizing film having adhesive layer, and image formation device
CN104673142A (en) * 2013-11-29 2015-06-03 藤森工业株式会社 Adhesive composition and surface protection film
CN104877606A (en) * 2014-02-27 2015-09-02 日本电石工业株式会社 Adhesive composition and optical member surface protective film
CN106489086A (en) * 2014-06-18 2017-03-08 住友化学株式会社 Polaroid, the polarization plates with binding agent and image display device
CN106147673A (en) * 2015-05-11 2016-11-23 藤森工业株式会社 Adhesion agent composition and surface protection film
CN106244062A (en) * 2015-06-04 2016-12-21 藤森工业株式会社 Adhesion agent composition and surface protection film

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
魏文德 主编: "《有机化工原料大全 上卷（2版）》", 31 January 1999, 北京：化学工业出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113817110A (en) * 2021-09-08 2021-12-21 中国乐凯集团有限公司 Acrylate polymer, pressure-sensitive adhesive composition, pressure-sensitive adhesive, protective film and display device
CN113817110B (en) * 2021-09-08 2024-03-29 中国乐凯集团有限公司 Acrylic polymer, pressure-sensitive adhesive composition, pressure-sensitive adhesive, protective film and display device

Also Published As

Publication number Publication date
KR102342433B1 (en) 2021-12-22
KR20200067794A (en) 2020-06-12
KR20200096453A (en) 2020-08-12
KR20180121318A (en) 2018-11-07
TW201843278A (en) 2018-12-16
KR102265519B1 (en) 2021-06-16
KR20210111233A (en) 2021-09-10
KR20190129791A (en) 2019-11-20
JP2018188523A (en) 2018-11-29
JP6782664B2 (en) 2020-11-11
KR102300173B1 (en) 2021-09-08
CN108795348B (en) 2022-03-04
TWI737849B (en) 2021-09-01
KR102045734B1 (en) 2019-11-18

Similar Documents

Publication Publication Date Title
TW201610132A (en) Antistatic surface-protective film
CN109852280A (en) Adhesion agent composition and surface protection film
KR102647963B1 (en) Antistatic surface-protective film
JP7541132B2 (en) Pressure-sensitive adhesive composition, and pressure-sensitive adhesive film, surface protection film, and optical film with pressure-sensitive adhesive layer each using the same
KR102311150B1 (en) Adhesive composition and surface-protective film
CN108795348A (en) Adhesion agent composition and surface protection film
JP2015091988A (en) Adhesive agent composition and surface protective film
CN108795339A (en) Adhesion agent composition and adhesive film
JP7065230B2 (en) Adhesive composition and surface protective film
JP7014880B2 (en) Adhesive film
JP7041225B2 (en) Adhesive composition and surface protective film
JP2024149779A (en) Pressure-sensitive adhesive composition, and pressure-sensitive adhesive film, surface protection film, and pressure-sensitive adhesive layer-attached optical film using the same
JP2022066512A (en) Pressure sensitive adhesive film, and surface protective film and optical film using the same
JP2022040328A (en) Adhesive agent composition, adhesive film, surface protective film and optical film with adhesive agent layer
JP2023139030A (en) Adhesive film and surface protective film

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