CN104650779B - Adhesive composition and surface protection film - Google Patents

Adhesive composition and surface protection film Download PDF

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Publication number
CN104650779B
CN104650779B CN201410588424.4A CN201410588424A CN104650779B CN 104650779 B CN104650779 B CN 104650779B CN 201410588424 A CN201410588424 A CN 201410588424A CN 104650779 B CN104650779 B CN 104650779B
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methyl
compound
acrylate
monomer
adhesive composition
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CN104650779A (en
Inventor
长仓毅
岛口龙介
长谷川良
新见洋人
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
    • 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
    • C09J155/00—Adhesives based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09J123/00 - C09J153/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides that a kind of the balance of cohesive force is excellent with excellent antistatic property, under low peeling rate and high peeling rate and durability and re-workability also excellent adhesive composition and surface protection film.Adhesive composition of the invention includes: (methyl) acrylate monomer for being C4~C18 containing the carbon atom number selected from (A) alkyl, (B) copolymerisable monomer of hydroxyl, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) not hydroxyl and the acrylic polymer of the copolymer of at least one of nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxy；Moreover, also containing isocyanate compound, the non-ring type aliphatic isocyanates compound of (G) two function, (H) antistatic agent more than (F) trifunctional.

Description

Adhesive composition and surface protection film
Technical field
The present invention relates to the surface protection films in a kind of manufacturing process for liquid crystal display.More specifically, this hair It is bright to be related to a kind of being used to protect and being pasted onto the surface for constituting the optical components such as polarizer, phase plate of liquid crystal display The surface protection film adhesive composition on the surface of the optical components such as polarizer, phase plate, and used the binder The surface protection film of composition.
Background technique
All the time, in the manufacture as optical components such as polarizer, the phase plates of component for constituting liquid crystal display In process, in order to temporary protection optical component surface and adhesive surface protective film.This surface protection film is only in manufacture optics It is used in the process of component, when optical component is assembled into liquid crystal display, it is removed from optical component and is removed.Due to It is this to be used to that the surface protection film of optical component surfaces to be protected only to use in manufacturing process, therefore, generally also it is referred to as " process Film ".
Used in so process of manufacture optical component for surface protection film, poly- with optical transparence It is formed with adhesive layer on the single side of ethylene glycol terephthalate (PET) resin film, also, is fitted on the adhesive layer By the stripping film of lift-off processing, to protect the adhesive layer until fitting on optical component.
In addition, for the optical components such as polarizer, phase plate, due in the state of being bonded surface protection film into Row is mixed into etc. the examination and test of products of optical assessments with display capabilities, tone, contrast, the impurity of LCD panel, so, as To the performance requirement of surface protection film, it is desirable that without bubble, impurity in adhesive layer.
In addition, in recent years, when removing surface protection film from the optical components such as polarizer, phase plate, along with from quilt Adherend, which is removed, removes electrostatic caused by the electrostatic occurred when adhesive layer, it is possible to influence whether the automatically controlled of liquid crystal display The failure of circuit processed, it is therefore desirable to which adhesive layer has excellent antistatic property.
In addition, due to various reasons, can be deposited in coating surface protective film on the optical components such as polarizer, phase plate The case where re-pasting surface protection film again after temporarily removing surface protection film, requires to be easy from as adherend at this time Optical component on remove (re-workability).
In addition, when finally removing surface protection film from optical components such as polarizer, phase plates, it is desirable that can rapidly shell From.I.e., it is desirable that cohesive force is because the variation of peeling rate is small, can rapidly to shell in the case where high speed is removed From.
So, in recent years, from the viewpoint of easy to operate when using surface protection film, it is desirable that constitute surface protection film Adhesive layer have following performance: (1) under low peeling rate and high peeling rate, obtain the balance of cohesive force；(2) it prevents The generation of glue residue；(3) excellent antistatic property；And (4) reprocessing (ReWork) performance etc..
But allow to meet the performance requirement to the adhesive layer for constituting surface protection film respectively, that is, allow to Meet individual performance requirements in above-mentioned (1)~(4) respectively, but the adhesive layer for meeting the requirements surface protection film simultaneously has (1) requirement of~(4) over-all properties, is very difficult project.
For example, obtaining the balance of cohesive force and (2) under low peeling rate and high peeling rate about (1) prevents from gluing Tie the remaining generation of agent, it is known to suggestion as described below.
With (methyl) alkyl acrylate with the alkyl below of carbon atom number 7 and the copolymerizable chemical combination containing carboxyl The copolymer of object carries out crosslinking Treatment and manufactured acrylic adhesive layer to it as main component, and with crosslinking agent In, by being bonded for a long time, there are binders to be attached to adherend to the movement of adherend side, and To the bonding force of adherend through when ascending big problem.In order to avoid the problem, it is known to which one kind is provided with following viscous The technical solution of oxidant layer is tied, the adhesive layer is (methyl) acrylic acid alkyl using the alkyl with carbon atom number 8~10 The copolymer of ester and the copolymerizable compound with alcoholic extract hydroxyl group, and binder made of crosslinking Treatment is carried out to it with crosslinking agent Layer (patent document 1).
In addition, it is also proposed that a kind of technical solution for being provided with following adhesive layers, the adhesive layer be by with In above-mentioned identical copolymer, cooperate the copolymerization of a small amount of (methyl) alkyl acrylate and the copolymerizable compound containing carboxyl Object, and adhesive layer made of crosslinking Treatment is carried out to it with crosslinking agent.But when being used for, surface tension is low and surface light When in the surface protection of sliding plastic plate etc., has when processing or the heating of the when of preservation due to generates the peelings such as separation and asks The problem of releasable difference when topic, the high speed in field hand-manipulated are removed.
In order to solve these problems, a kind of adhesive composition is proposed, the adhesive composition is: a) to have (methyl) alkyl acrylate of the alkyl of carbon atom number 8~10 makees 100 weight of (methyl) alkyl acrylate as main component It measures in part, b) the copolymerizable compound containing carboxyl of 1~15 parts by weight and c) carbon atom number of 3~100 parts by weight is added The vinyl esters of 1~5 aliphatic carboxylic acid and obtain the copolymer of monomer mixture, and cooperate into the copolymer it is above-mentioned b) Adhesive composition made of the crosslinking agent more than equivalent of the carboxyl of ingredient (patent document 2).
In adhesive composition described in Patent Document 2, in processing or the when of preservation, will not generate the removing of separation etc. Phenomenon, also, bonding force through when it is ascending small, so that releasable is excellent, even long-term preservation, particularly in high temperature ring Long-term preservation under border can also be removed again with small strength, at this time the not remaining binder in adherend, and even if It can also be removed again with small strength in the case where carrying out high speed removing.
In addition, for the antistatic property excellent to (3), as the side for assigning antistatic property to surface protection film Method proposes the method etc. that antistatic agent is mixed into base material film.As antistatic agent, such as disclose (a) quaternary ammonium salt, pyridine Salt, the various cationic antistatic agents with the cationic base such as primary~tertiary amino；(b) have sulfonate group, sulfuric ester alkali, The anionic antistatic agents of the anion base of phosphate alkali, phosphonic acids alkali etc.；(c) amino acids, amidosulphuric acid esters etc. Both sexes antistatic agent；(d) non-ionic antistatic agent of alkamine, glycerols, polyethylene glycols etc.；(e) make as described above Antistatic agent carries out (patent documents 3) such as the Polymer Antistatic Agents that molecular weight obtains.
Antistatic agent so is directly contained in adhesive layer in addition, proposing in recent years, without being contained within base Material film or the scheme for being coated on substrate film surface.
In addition, for example, proposing a kind of adhesive composition, the adhesive composition is about (4) re-workability: Relative to 100 parts by weight propylene acid resins, cooperate the isocyanate ester compound of 0.0001~10 parts by weight curing agent and Specific silicate oligomer and obtain (patent document 4).
In patent document 4, record: with the carbon atom number of alkyl be 2~12 or so alkyl acrylate, alkyl Alkyl methacrylate that carbon atom number is 4~12 or so etc. is used as main monomer component, can contain for example carboxylic list The monomer component containing other functional groups such as body.Typically, the above-mentioned principal monomer of 50 weight % or more is preferably comprised, and it is desirable that The content of monomer component containing functional group is 0.001~50 weight %, preferably 0.001~25 weight %, more preferably 0.01 ~25 weight %.This adhesive composition described in Patent Document 4, even if at high temperature or under high temperature and humidity, cohesion The ongoing change of power and bonding force is also small, and excellent effect is also showed that the bonding force of curved surface, therefore has re-workability.
In general, being easy to produce glue residue, re-workability is also easily reduced if adhesive layer is soft character.That is, It is difficult to remove again after mistake fitting, and is difficult to re-paste.From this viewpoint, in order to make it have re-workability, Need will to have the functional groups such as carboxyl it is monomer crosslinked in host agent so that adhesive layer has certain hardness.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application 63-225677 bulletin
Patent document 2: Japanese Unexamined Patent Publication 11-256111 bulletin
Patent document 3: Japanese Unexamined Patent Publication 11-070629 bulletin
Patent document 4: Japanese Unexamined Patent Publication 8-199130 bulletin
Summary of the invention
Subject to be solved by the invention
In the prior art, as the performance requirement to the adhesive layer for constituting surface protection film, it is required all the time The balance of cohesive force can be obtained under low peeling rate and high peeling rate and with excellent antistatic property and again Processing performance etc..But allow to meet performance requirements respectively, also it is unable to satisfy the binder as surface protection film Over-all properties requirement required by layer.
The present invention has been made in view of the above-described circumstances, and project is, provide it is a kind of with excellent antistatic property, The balance of cohesive force under low peeling rate and high peeling rate is excellent and endurance quality and cycling processability are also excellent Adhesive composition and surface protection film.
The method to solve the problem
In order to solve the above problems, the present invention provides a kind of adhesive composition, wherein
The adhesive composition includes: (methyl) acrylate monomer that the carbon atom number containing (A) alkyl is C4~C18 At least one of and selected from by (B) hydroxyl copolymerisable monomer, (C) carboxylic copolymerisable monomer, (D) gather Asia Alkyl diol list (methyl) acrylate monomer and (E) not hydroxyl and nitrogenous vinyl monomer or (methyl) containing alkoxy The acrylic polymer of the copolymer of at least one of copolymerisable monomer group composed by alkyl acrylate monomer,
Also, also containing isocyanate compound, the non-ring type aliphatic isocyanic acid of (G) two function more than (F) trifunctional Ester compounds and (H) antistatic agent.
In addition, when setting the total amount of acrylic polymer of aforementioned copolymer as 100 parts by weight, preferably:
The content of (methyl) acrylate monomer that the carbon atom number of aforementioned (A) alkyl is C4~C18 is 50~91 weight Part,
The content of the copolymerisable monomer of aforementioned (B) hydroxyl is 0.1~10 parts by weight,
The content of aforementioned (C) carboxylic copolymerisable monomer is 0~1.0 parts by weight,
The content of aforementioned (D) polyalkylene glycol mono (methyl) acrylate monomer is 0~50 parts by weight,
Aforementioned (E) not hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxy Content be 0~20 parts by weight.
In addition, more than aforementioned (F) trifunctional isocyanate compound and the non-ring type aliphatic isocyanates of (G) two function The weight ratio (F/G) of compound is 1~90, relative to 100 parts by weight foregoing acrylic polymer, preferably aforementioned (F) three official The total amount of more than energy isocyanate compound and the non-ring type aliphatic isocyanates compound of (G) two function is 0.1~5.0 Parts by weight.
In addition, the aforementioned non-ring type aliphatic isocyanates compound of (G) two function, is to make diisocyanate cpd and two Alcoholic compound reacts and the compound that generates.It is aliphatic diisocyanate as aforementioned diisocyanates compound, it is excellent It gated selected from by tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl One of compound group composed by hexamethylene diisocyanate, lysine diisocyanate is constituted.In addition, as preceding Diol compound is stated, preferably by selected from by 2- methyl 1,3-PD, 2,2-dimethyl-1,3-propanediol, 2- methyl- 2- propyl -1,3- propylene glycol, 2- ethyl -2- butyl -1,3- propylene glycol, 3- methyl-1,5- pentanediol, 2,2- dimethyl -1,3- One of propylene glycol monohydroxy pivalate, polyethylene glycol, compound group composed by polypropylene glycol are constituted.
Additionally, it is preferred that the copolymerisable monomer of aforementioned (B) hydroxyl be selected from by (methyl) acrylic acid 8- hydroxyl monooctyl ester, The own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) acrylic acid 4- hydroxybutyl, (methyl) acrylic acid 2- hydroxy methacrylate, N- hydroxyl (methyl) acrylamide, N- methylol (methyl) acrylamide, compound group composed by N- ethoxy (methyl) acrylamide At least one of more than.
Additionally, it is preferred that aforementioned (C) carboxylic copolymerisable monomer is selected from by (methyl) acrylic acid, (methyl) acrylic acid Carboxylic ethyl ester, (methyl) carboxypentyl acrylate, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2- (methyl) acryloyl Oxygroup propyl hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl phthalic acid, 2- (methyl) acryloxy second Base succinic acid, 2- (methyl) acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) third It is more than at least one of compound group composed by alkene trimethylammonium tetrahydrophthalic acid.
Additionally, it is preferred that (D) polyalkylene glycol mono (methyl) acrylate monomer is selected from polyalkylene glycol mono (first Base) acrylate, methoxypolyalkylene glycol (methyl) acrylate, ethyoxyl polyalkylene glycol (methyl) acrylate At least one of more than.
Isocyanate compound more than aforementioned (F) trifunctional, is preferably selected from by hexamethylene diisocyanate Close the isocyanuric acid ester of object, the isocyanuric acid ester of isophorone diisocyanate compound, hexamethylene diisocyanate chemical combination The addition product of object, the addition product of isophorone diisocyanate compound, hexamethylene diisocyanate compound biuret, The biuret of isophorone diisocyanate compound, the isocyanuric acid ester of tolunediisocyanate compound, xyxylene two The isocyanuric acid ester of isocyanate compound, the isocyanuric acid ester of hydrogenated xylylene diisocyanate compound, toluene two are different The addition product of cyanate esters, the addition product of xylylene diisocyanate compound, hydrogenated xylylene diisocyanate It is more than at least one of compound group composed by the addition product of compound.
Additionally, it is preferred that foregoing acrylic polymer contain aforementioned copolymerisable monomer group aforementioned (E) not hydroxyl and contain It is more than at least one of the vinyl monomer of nitrogen or (methyl) alkyl acrylate monomer containing alkoxy.
Additionally, it is preferred that aforementioned (H) antistatic agent is to contain 0.01~5.0 weight relative to the aforementioned copolymers of 100 parts by weight Amount part and 30~50 DEG C of fusing point of ionic compound or be copolymerization amount in aforementioned copolymer be 0.1~5.0 weight % And the ionic compound containing acryloyl group.
Additionally, it is preferred that adhesive layer made of being crosslinked foregoing adhesives composition is at low peeling rate 0.3m/min Cohesive force is 0.05~0.1N/25mm, and the cohesive force at high peeling rate 30m/min is 1.0N/25mm or less.
Additionally, it is preferred that the surface resistivity of adhesive layer made of being crosslinked foregoing adhesives composition is 5.0 × 10+10 Ω/ is hereinafter, removing electrostatic pressure is ± 0~1kV.
Also, the present invention provides a kind of surface protection film, which is characterized in that is formed on the single or double of resin film viscous Knot oxidant layer forms, and the adhesive layer is to be crosslinked foregoing adhesives composition.
In addition, the purposes that surface protection film of the invention can be used as the surface protection film of polarizer be subject to using.
In addition, in surface protection film of the invention, preferably aforementioned resin film be formed with the one of foregoing adhesives layer Side is implemented with antistatic treatment and antifouling process on opposite face.
Invention effect
Based on the present invention, can satisfy required by the insurmountable adhesive layer to surface protection film in the prior art Over-all properties, and excellent antistatic property can be obtained, the generation of glue residue phenomenon can be prevented.Specifically, Excellent antistatic property can not only be kept, but also the additive amount of antistatic agent can be reduced, can also improve prevents from bonding The remaining performance of agent.
In addition, passing through isocyanate compound and the non-ring type aliphatic isocyanic acid of (G) two function more than (F) trifunctional Ester compounds are used in combination, and can make that bridging property is excellent, stain resistance also becomes well, and then in low peeling rate and high peeling rate Under cohesive force balance it is excellent.
Specific embodiment
In the following, illustrating the present invention based on preferred embodiment.
Adhesive composition of the invention, which is characterized in that
At least one in (methyl) acrylate monomer that its host agent is C4~C18 by the carbon atom number containing (A) alkyl Kind and selected from as copolymerisable monomer group by the copolymerisable monomer of (B) hydroxyl, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) hydroxyl and nitrogenous vinyl monomer or do not contain alkoxy (methyl) alkyl acrylate monomer composed by least one of copolymerisable monomer group copolymer acrylic polymer Object is closed to constitute,
Also, it is non-that the adhesive composition also contains the isocyanate compound of (F) trifunctional or more, (G) two function Ring type aliphatic isocyanates compound and (H) antistatic agent.
In addition, being preferably comprised when setting the total amount of acrylic polymer of aforementioned copolymer as 100 parts by weight: The carbon atom number of aforementioned (A) alkyl of 50~91 parts by weight is (methyl) acrylate monomer of C4~C18,0.1~10 parts by weight Before the copolymerisable monomer of aforementioned (B) hydroxyl, the carboxylic copolymerisable monomer of 0~1.0 parts by weight aforementioned (C), 0~50 parts by weight State (D) polyalkylene glycol mono (methyl) acrylate monomer and 0~20 parts by weight aforementioned (E) not hydroxyl and it is nitrogenous Vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxy.
(methyl) acrylate monomer that carbon atom number as (A) alkyl is C4~C18, can enumerate: (methyl) third Olefin(e) acid butyl ester, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid heptan Ester, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) acrylic acid nonyl Ester, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid hendecane Base ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) acrylic acid tetradecane base ester, (first Base) acrylic acid pentadecane base ester, (methyl) aliphatic acrylate, (methyl) acrylic acid heptadecane base ester, (methyl) propylene Sour stearyl, (methyl) myristyl ester, the different tetradecane base ester of (methyl) acrylic acid, (methyl) acrylic acid spermaceti Ester, (methyl) acrylic acid isohexadecane base ester, (methyl) stearyl acrylate acyl ester, (methyl) acrylic acid isooctadecane base ester etc..
When setting the total amount of acrylic polymer of copolymer as 100 parts by weight, the preferred carbon atom of (A) alkyl The content of (methyl) acrylate monomer that number is C4~C18 is 50~91 parts by weight.
It as the copolymerisable monomer of (B) hydroxyl, can enumerate: (methyl) acrylic acid 8- hydroxyl monooctyl ester, (methyl) propylene (methyl) dihydroxypropyls such as the own ester of sour 6- hydroxyl, (methyl) acrylic acid 4- hydroxybutyl, (methyl) acrylic acid 2- hydroxy methacrylate Alkyl esters；N- hydroxyl (methyl) acrylamide, N- methylol (methyl) acrylamide, N- ethoxy (methyl) acrylamide etc. (methyl) acrylic amide containing hydroxyl etc..
It is preferred that the copolymerisable monomer of above-mentioned hydroxyl is selected from by (methyl) acrylic acid 8- hydroxyl monooctyl ester, (methyl) propylene The own ester of sour 6- hydroxyl, (methyl) acrylic acid 4- hydroxybutyl, (methyl) acrylic acid 2- hydroxy methacrylate, N- hydroxyl (methyl) acryloyl At least one of amine, N- methylol (methyl) acrylamide, compound group composed by N- ethoxy (methyl) acrylamide More than.
When setting the total amount of acrylic polymer of copolymer as 100 parts by weight, preferably aforementioned (B) hydroxyl The content of copolymerisable monomer is 0.1~10 parts by weight.
It is preferred that (C) carboxylic copolymerisable monomer be selected from by (methyl) acrylic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2- (methyl) acryloxy third Base hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl phthalic acid, 2- (methyl) acryloyl-oxyethyl amber Acid, 2- (methyl) acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) acryloyl-oxy It is more than at least one of compound group composed by base ethyl tetrahydrophthalic acid.
When setting the total amount of acrylic polymer of copolymer as 100 parts by weight, preferably aforementioned (C) is carboxylic The content of copolymerisable monomer is 0~1.0 parts by weight.Adhesive composition in adhesive layer of the invention can also not contain (C) carboxylic copolymerisable monomer.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, as long as more possessed by polyalkylene glycol A hydroxyl in a hydroxyl is esterified as the compound of (methyl) acrylate.It is poly- since (methyl) is acrylate-based Conjunction property base, therefore can be copolymerized with host agent polymer.Other hydroxyls can both keep the state of OH, can also become first The alkyl ether of ether, ether etc., or saturated carboxylic acids esters such as acetate etc. can be become.
As alkylidene possessed by polyalkylene glycol, vinyl, acrylic, cyclobutenyl etc. can be enumerated, but not It is defined in these.Polyalkylene glycol is also possible to the two or more poly- alkylenes in polyethylene glycol, polypropylene glycol, polytetramethylene glycol etc. The copolymer of base glycol.As the copolymer of polyalkylene glycol, polyethylene glycol propylene glycol, polyethylene glycol can be enumerated Butanediol, polypropylene glycol-polytetramethylene glycol, polyethylene glycol propylene glycol-polytetramethylene glycol etc., which can be block copolymerization Object, random copolymer.
It is preferred that the alkylene oxide of polyalkylene glycol chain is constituted in (D) polyalkylene glycol mono (methyl) acrylate monomer Averaged repeating numbers are 3~14.So-called " averaged repeating numbers of alkylene oxide " refer to (D) polyalkylene glycol mono (methyl) acrylic acid The duplicate average of alkylene oxide unit in " polyalkylene glycol chain " part contained in the molecular structure of ester monomer.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, it is preferably selected from polyalkylene glycol mono (first Base) acrylate, methoxypolyalkylene glycol (methyl) acrylate, ethyoxyl polyalkylene glycol (methyl) acrylate At least one of more than.
More specifically, it can enumerate: mono- (methyl) acrylate of polyethylene glycol-, mono- (methyl) acrylic acid of polypropylene glycol- Mono- (methyl) acrylate of ester, polytetramethylene glycol-, polyethylene glycol propylene glycol-mono- (methyl) acrylate, polyethylene glycol fourth Mono- (methyl) acrylate of glycol-, mono- (methyl) acrylate of polypropylene glycol-polytetramethylene glycol-, polyethylene glycol propylene glycol-are poly- Mono- (methyl) acrylate of butanediol-；Methoxy poly (ethylene glycol)-(methyl) acrylate, methoxyl group polypropylene glycol-(methyl) third Olefin(e) acid ester, methoxyl group polytetramethylene glycol-(methyl) acrylate, methoxypolyethylene glycol-polypropylene glycol-(methyl) acrylate, Methoxypolyethylene glycol-polytetramethylene glycol-(methyl) acrylate, methoxyl group-polypropylene glycol-polytetramethylene glycol-(methyl) acrylic acid Ester, methoxypolyethylene glycol-polypropylene glycol-polytetramethylene glycol-(methyl) acrylate；Ethyoxyl polyethylene glycol-(methyl) propylene Acid esters, ethyoxyl polypropylene glycol-(methyl) acrylate, ethyoxyl polytetramethylene glycol-(methyl) acrylate, the poly- second of ethyoxyl- Glycol-polypropylene glycol-(methyl) acrylate, ethyoxyl-polyethylene glycol butanediol-(methyl) acrylate, ethyoxyl- Polypropylene glycol-polytetramethylene glycol-(methyl) acrylate, ethyoxyl-polyethylene glycol propylene glycol-polytetramethylene glycol-(methyl) propylene Acid esters etc..
When setting the total amount of acrylic polymer of copolymer as 100 parts by weight, preferably aforementioned (D) polyalkylene The content of glycol list (methyl) acrylate monomer is 0~50 parts by weight.Adhesive composition in adhesive layer of the present invention (D) polyalkylene glycol mono (methyl) acrylate monomer can not included.
In (E), the vinyl monomer nitrogenous as (E-1) can be enumerated: the vinyl monomer containing amido bond contains Vinyl monomer, vinyl monomer with nitrogenous heterocycle structure for having amino etc..More specifically, it can enumerate: N- second Alkenyl -2-Pyrrolidone, n-vinyl pyrrolidone, methyl ethylene pyrrolidones, N- vinylpyridine, N- vinylpiperidine Ketone, N- vinyl pyrimidine, N- vinyl piperazine, N- vinylpyrazine, N- vinyl pyrrole, N- vinyl imidazole, N- vinyl Replacing with N- vinyl for oxazole, N- polyvinyl morpholinone, N- caprolactam, N- vinyl lauric lactam etc. is miscellaneous The cyclic annular nitrogen vinyl compound of ring structure；N- (methyl) acryloyl morpholine, N- (methyl) acryloylpiperazines, N- (methyl) Propylene acyl group aziridine, N- (methyl) acryloyl group azetidine, N- (methyl) acryloyl group pyrrolidines, N- (methyl) acryloyl group Piperidines, N- (methyl) acryloyl group azepan, N- (methyl) acryloyl group Azacyclooctane etc. have N- (methyl) third The cyclic annular nitrogen vinyl compound for the heterocycle structure that enoyl- replaces；N- N-cyclohexylmaleimide, N-phenylmaleimide Deng the cyclic annular nitrogen vinyl compound with the heterocycle structure containing nitrogen-atoms and vinyl-based unsaturated bond in ring；(methyl) Acrylamide, N- methyl (methyl) acrylamide, N- isopropyl (methyl) acrylamide, N- tert-butyl (methyl) acrylamide etc. (methyl) acrylamide that unsubstituted or monoalkyl replaces；N, N- dimethyl (methyl) acrylamide, N, N- diethyl (first Base) acrylamide, N, N- dipropyl acrylamide, N, N- diisopropyl (methyl) acrylamide, N, N- dibutyl (methyl) third Acrylamide, N- ethyl-N-methyl (methyl) acrylamide, N- Methyl-N-propyl (methyl) acrylamide, N- methyl-N-isopropyl third The dialkyl group such as base (methyl) acrylamide replace (methyl) acrylamide；N, N- dimethylaminomethyl (methyl) acrylate, N, N- dimethyl aminoethyl (methyl) acrylate, N, N- dimethylaminopropyl (methyl) acrylate, N, N- dimethyl Amino isopropyl (methyl) acrylate, N, N- dimethrlaminobutyl (methyl) acrylate, N, N- diethylamino methyl (methyl) acrylate, N, N- diethylamino ethyl (methyl) acrylate, N- ethyl-N-methylamino ethyl (methyl) third Olefin(e) acid ester, N- methyl-N-propylamino ethyl (methyl) acrylate, N- methyl-N-isoproylamino ethyl (methyl) propylene Acid esters, N, the dialkyl aminos such as N- Dibutylaminoethyl (methyl) acrylate, t-butylamino ethyl (methyl) acrylate Base (methyl) acrylate；N, N- dimethylaminopropyl (methyl) acrylamide, N, N- diethyl amino propyl (methyl) third Acrylamide, N, N- dipropylamino propyl (methyl) acrylamide, N, N- diisopropylaminoethyl propyl (methyl) acrylamide, N- Ethyl-N-methylamino propyl (methyl) acrylamide, N- methyl-N-propylamino propyl (methyl) acrylamide, N- methyl- The N of N- isopropylaminopropyl (methyl) acrylamide etc., N- dialkyl group substituted-amino propyl (methyl) acrylamide；N- ethylene The N- vinylcarboxylic acid amide types such as base formamide, N- vinyl acetamide, N- vinyl-N-methylacetaniide；N- methoxy methyl Base (methyl) acrylamide, N- ethoxyethyl group (methyl) acrylamide, N- butoxymethyl (methyl) acrylamide, diacetone Acrylamide, N, (methyl) acrylic amide such as N- di-2-ethylhexylphosphine oxide (methyl) acrylamide；The unsaturation carboxylic such as (methyl) acrylonitrile Sour nitrile；Deng.
The vinyl monomer nitrogenous as (E-1), preferably not hydroxyl, more preferably not hydroxyl and carboxyl.As this Monomer, the monomer being preferably illustrated above, such as: containing N, N- dialkyl group substituted-amino, N, N- dialkyl group substituted amido Acrylic monomer；The N- vinyl such as n-vinyl-2-pyrrolidone, N- caprolactam, N- vinyl -2- piperidones Substituted lactams class；N- (methyl) acryloyl groups such as N- (methyl) acryloyl morpholine, N- (methyl) acryloyl group pyrrolidines take For cyclic amine.
In (E), (methyl) alkyl acrylate monomer as (E-2) containing alkoxy can be enumerated: (methyl) propylene Sour 2- methoxy acrylate, (methyl) acrylic acid 2- ethoxy ethyl ester, (methyl) acrylic acid 2- propoxy ethyl, (methyl) acrylic acid 2- isopropoxyethyl cyanoacrylate, (methyl) acrylic acid 2- butoxyethyl, (methyl) acrylic acid 2- methoxyl group propyl ester, (methyl) acrylic acid 2- ethyoxyl propyl ester, (methyl) acrylic acid 2- propoxyl group propyl ester, (methyl) acrylic acid 2- isopropoxy propyl ester, (methyl) acrylic acid 2- butoxy propyl ester, (methyl) acrylic acid 3- methoxyl group propyl ester, (methyl) acrylic acid 3- ethyoxyl propyl ester, (methyl) acrylic acid 3- Propoxyl group propyl ester, (methyl) acrylic acid 3- isopropoxy propyl ester, (methyl) acrylic acid 3- butoxy propyl ester, (methyl) acrylic acid 4- Methoxybutyl, (methyl) acrylic acid 4- Ethoxybutyl, (methyl) acrylic acid 4- propoxyl group butyl ester, (methyl) acrylic acid 4- are different Propoxyl group butyl ester, (methyl) acrylic acid 4- butoxy butyl ester etc..
These (methyl) alkyl acrylate monomers containing alkoxy, with the alkyl in (methyl) alkyl acrylate The structure that atom is replaced by alkoxy.
When setting the total amount of acrylic polymer of copolymer as 100 parts by weight, preferably (E-1) not hydroxyl and The content of (methyl) alkyl acrylate monomer of nitrogenous vinyl monomer or (E-2) containing alkoxy is 0~20 parts by weight. For (E-1) not hydroxyl and nitrogenous vinyl monomer and (methyl) alkyl acrylate monomer of (E-2) containing alkoxy, Both it using one kind or can be used together two or more respectively.It, can also be in the adhesive composition of adhesive layer of the invention Not comprising (E) not hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxy.
As isocyanate compound more than (F) trifunctional, as long as at least tool is there are three more than in a molecule At least one of polyisocyanate compounds of isocyanates (NCO) base or two or more.Polyisocyanate chemical combination Object includes aliphatic category isocyanates, aromatic isocyanates, non-ring type kind isocyanate, ester ring type kind isocyanate equal part Class, the present invention can be any kind therein.It as the specific example of polyisocyanate compounds, can enumerate: six methylenes The rouge such as group diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethyl hexamethylene diisocyanate (TMDI) Fat same clan isocyanate compound；Methyl diphenylene diisocyanate (MDI), xylylene diisocyanate (XDI), hydrogenation of benzene Diformazan group diisocyanate (H6XDI), dimethyl diphenylene diisocyanate (TOID), toluene di-isocyanate(TDI) (TDI) etc. Aromatic isocyanate compound.
As isocyanate compound more than trifunctional, can enumerate: diisocyanates (have two in a molecule The compound of a NCO base) biuret modified body or isocyanurate-modified body, with trimethylolpropane (TMP) or glycerol etc. The addition product of polyalcohol (at least having the compound there are three the above OH base in a molecule) more than trivalent is (polyalcohol modified Body) etc..Relative to the aforementioned copolymer of 100 parts by weight, aforementioned (F) trifunctional of 0.5~5.0 parts by weight or more is preferably comprised Isocyanate compound.
Also, isocyanate compound more than (F) trifunctional used in the present invention is preferably included selected from (F- 1) at least one of first aliphatic category isocyanate compound group is above and is selected from (F-2) second aromatic isocyanates More than at least one of compound group, wherein (F-1) first aliphatic category isocyanate compound group is by six methylenes The isocyanuric acid ester of group diisocyanate compound, the isocyanuric acid ester of isophorone diisocyanate compound, hexa-methylene The addition product of diisocyanate cpd, the addition product of isophorone diisocyanate compound, hexamethylene diisocyanate The biuret of compound, the biuret of isophorone diisocyanate compound are formed；(F-2) second aromatic is different Cyanate esters group is isocyanuric acid ester, the xylylene diisocyanate compound by tolunediisocyanate compound Isocyanuric acid ester, the isocyanuric acid ester of hydrogenated xylylene diisocyanate compound, tolunediisocyanate compound plus At the addition product institute of object, the addition product of xylylene diisocyanate compound, hydrogenated xylylene diisocyanate compound Composition.(F-1) the first aliphatic category isocyanate compound group and (F-2) second aromatic isocyanates chemical combination is preferably used in combination Object group.In the present invention, as isocyanate compound more than (F) trifunctional, by and be selected from (F-1) first aliphatic At least one of kind isocyanate compound group is above and in (F-2) second aromatic isocyanate compound group More than at least one, it can further improve the balance of low speed stripping area and the cohesive force in high speed stripping area.
Additionally, it is preferred that isocyanate compound more than (F) trifunctional includes different selected from aforementioned (F-1) the first aliphatic category At least one of cyanate esters group is above and in aforementioned (F-2) second aromatic isocyanate compound group It is more than at least one, and the aforementioned copolymer relative to 100 parts by weight, it is somebody's turn to do the isocyanate compound of (F) trifunctional or more Total content be 0.5~5.0 parts by weight.In addition, as in (F-1) first aliphatic category isocyanate compound group At least one above mixing ratio with more than at least one of (F-2) second aromatic isocyanate compound group Rate, being calculated with weight ratio is preferably (F-1): (F-2) is in the range of 10%:90%~90%:10%.
Also, the non-ring type aliphatic isocyanates compound of (G) two function used in the present invention is two function isocyanic acids Non- ring type in ester compounds and belong to aliphatic compound.As the non-ring type aliphatic isocyanates of (G) two function Close object, preferably diisocyanate cpd and diol compound react and the compound that generates.
For example, when indicating diisocyanate chemical combination with general formula " O=C=N-X-N=C=O " (wherein, X is divalent group) Object, when indicating diol compound with general formula " HO-Y-OH " (wherein, Y be divalent group), as diisocyanate cpd and two Alcoholic compound reacts compound generated, for example, the compound that following general formula Z is indicated can be enumerated.
[general formula Z]
O=C=N-X- (NH-CO-O-Y-O-CO-NH-X)n- N=C=O
Here, the integer that n is 0 or more.When n is 0, general formula Z is expressed as " O=C=N-X-N=C=O ".As (G) two The non-ring type aliphatic isocyanates compound of function also may include in general formula Z n be 0 compound (relative to diol compound Unreacted diisocyanate cpd), contain the compound that n is 1 or more integer preferably as neccessary composition.(G) two function Non- ring type aliphatic isocyanates compound is also possible to the mixing as composed by the different multiple compounds of the n in general formula Z Object.
The diisocyanate cpd that general formula " O=C=N-X-N=C=O " indicates is aliphatic diisocyanate.It is preferred that X For the aliphatic divalent group of non-ring type.As aforementioned aliphatic diisocyanate, preferably by selected from different by tetramethylene two Cyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysine One or more of compound group composed by diisocyanate is constituted.
The diol compound that general formula " HO-Y-OH " indicates is aliphatic diol.It is preferred that Y is the aliphatic divalent base of non-ring type Group.As foregoing glycols compound, preferably by selected from by 2- methyl 1,3-PD, 2,2- dimethyl -1,3- the third two Alcohol, 2- methyl-2-propyl -1,3- propylene glycol, 2- ethyl -2- butyl -1,3- propylene glycol, 3- methyl-1,5- pentanediol, 2,2- bis- One or both of methyl-1,3-propanediol monohydroxy pivalate, polyethylene glycol, compound group composed by polypropylene glycol It constitutes above.
More than aforementioned (F) trifunctional isocyanate compound and the non-ring type aliphatic isocyanates chemical combination of (G) two function The weight ratio (F/G) of object is 1~90.
Isocyanates chemical combination relative to 100 parts by weight foregoing acrylic polymer, more than preferably aforementioned (F) trifunctional The total amount of object and the non-ring type aliphatic isocyanates compound of (G) two function is 0.1~5.0 parts by weight.
It is preferred that (H) antistatic agent is that the ionic compound that (H-1) fusing point is 30~50 DEG C or (H-2) contain propylene The ionic compound of acyl group.
In the present invention, as (H) antistatic agent, the ionic compound that (H-1) fusing point is 30~50 DEG C is made an addition to Ionic compound in copolymer, or by (H-2) containing acryloyl group is copolymerized in copolymer.Speculate due to these (H) The fusing point of antistatic agent is low and has chain alkyl, therefore, high with the compatibility of acrylic copolymer.
The ionic compound for being 30~50 DEG C as (H-1) fusing point is ionicization with cation and anion Close object, can enumerate: cation is pyridylium, glyoxaline cation, pyrimidine cation, pyrazoles cation, pyrrole The cationic nitrogenous , Huo person phosphonium cation, sulfonium cation etc. of cation, ammonium cation etc. are coughed up, anion is hexafluorophosphoric acid Root (PF6 -), thiocyanate radical (SCN-), benzene sulfonamide acid group (RC6H4SO3 -), perchlorate (ClO4 -), tetrafluoroborate (BF4 -) Deng inorganic or organic anion compound.It is preferred that being solid under room temperature (such as 30 DEG C), and pass through the chain of selection alkyl Length, the position of substituent group, number etc. can obtain the compound that fusing point is 30~50 DEG C.Preferred cationic be quaternary nitrogen sun from Son can be enumerated: 1- alkyl pyridine (2~6 carbon atoms both can have substituent group or not have substituent group) etc. Season pyridylium, (2,4,5 carbon atoms both can have substituent group not to be had 1,3- dialkylimidazolium Substituent group) etc. season glyoxaline cation, the quaternary ammonium cation of tetra-allkylammonium etc. etc..
Relative to the copolymer of 100 parts by weight, the content of ionic compound that preferably (H-1) fusing point is 30~50 DEG C is 0.01~5.0 parts by weight.
Ionic compound as (H-2) containing acryloyl group is the ionic chemical combination with cation and anion Object can be enumerated: cation is (methyl) acryloxyalkyl trialkyl ammonium (R3N+-CnH2n- OCOCQ=CH2, wherein Q= H or CH3, R=alkyl) etc. the cation containing (methyl) acryloyl group；Anion is hexafluoro-phosphate radical (PF6 -), thiocyanic acid Root (SCN-), organic sulfonic acid root (RSO3 -), perchlorate (ClO4 -), tetrafluoroborate (BF4 -), the acid imide root containing F (RF 2N-) etc. inorganic or organic anion compound.As the acid imide root (R containing FF 2N-) RF, fluoroform can be enumerated Perfluoroalkyl group sulfonyl, the fluorosulfonyl of sulfonyl, five fluorine ethylsulfonyls etc..As the acid imide root containing F, can enumerate double (fluorosulfonyl) acid imide root ((FSO2)2N-), bis- (trifyl) acid imide root ((CF3SO2)2N-), bis- (five fluorine second sulphurs Acyl group) acid imide root ((C2F5SO2)2N-) etc. double sulfonyl acid imide roots.
It is preferred that the copolymerization amount of the ionic compound of (H-2) containing acryloyl group in the copolymer is 0.1~5.0 weight Measure %.
As the specific example of (H) antistatic agent, be not particularly limited, but as (H-1) fusing point be 30~50 DEG C from The specific example of sub- property compound can enumerate 1- octylpyridinium hexafluorophosphate, 1- nonylpyridine hexafluorophosphate, 2- Methyl-1-dococylpyridinium hexafluorophosphate, 1- octylpyridinium dodecyl benzene sulfonate, 1- dococylpyridinium Rhodanate, 1- dococylpyridinium dodecyl benzene sulfonate, 4- methyl-1-octylpyridinium hexafluorophosphate etc..Separately Outside, the specific example of the ionic compound as (H-2) containing acryloyl group can enumerate dimethylaminomethyl (methyl) Acrylate hexafluorophosphoric acid methyl salt ((CH3)3N+CH2OCOCQ=CH2·PF6 -, wherein, Q=H or CH3), dimethylaminoethyl Bis- (trifyl) acid imide the methyl salt ((CH of base (methyl) acrylate3)3N+(CH2)2OCOCQ=CH2·(CF3SO2)2N-, wherein Q=H or CH3), bis- (fluorosulfonyl) acid imide the methyl salt ((CH of dimethylamine methyl esters3)3N+ CH2OCOCQ=CH2·(FSO2)2N?, wherein Q=H or CH3) etc..
Adhesive composition can arbitrarily contain polyether modified siloxane compound.Polyether-modified silicone compounds are tools There are the silicone compounds of polyether-based, in addition to common siloxane unit (- SiR1 2- O-) except, also have and includes polyether-based Siloxane unit (- SiR1(R2O(R3O)nR4)-O-).Here, R1Indicate one or more kinds of alkyl or aryls, R2And R3Table Show one or more kinds of alkylidenes, R4Indicate (terminal groups) such as one or more kinds of alkyl, acyl groups.As polyether-based It can enumerate: polyethylene oxide base ((C2H4O)n) or polypropylene oxide base ((C3H6O)n) etc. polyoxyalkylenes.
Preferred, polyethers modified silicone com is the polyether modified siloxane compound that HLB value is 7~12.In addition, phase For the copolymer of 100 parts by weight, the content of preferred, polyethers modified silicone com is 0.01~0.5 parts by weight, more preferably For 0.1~0.5 parts by weight.
HLB refer to such as JIS K3211 (surfactant term) as defined in hydrophile-lipophile balance (hydrophily and oleophylic The ratio of property).
Polyether modified siloxane compound, for example, can obtain by the following method: by hydrosilylation reactions, making to have There is the organic compound of unsaturated bond and polyoxyalkylene to be grafted on the main chain with the polysiloxane of silylation and obtain ?.Specifically, can enumerate: dimethyl siloxane-methyl (polyethylene glycol oxide) silicone copolymers, dimethyl siloxane- Methyl (polyethylene glycol oxide) siloxane-methyl (polypropylene oxide) silicone copolymers, dimethyl siloxane-methyl (polyoxygenated Propylene) silicone copolymers etc..
By the way that polyether modified siloxane compound is matched with adhesive composition, can improve binder cohesive force and Cycling processability.When adhesive composition is free of polyether modified siloxane compound, cost can be made lower.
Also, as other ingredients, the copolymerizable (first containing alkylene oxide (alkylene oxide) can be mated properly into Base) acrylic monomers, (methyl) acrylamide monomer, dialkyl group substituted acrylamide monomer, surfactant, solidification promotion Additive well known to agent, plasticizer, filler, curing inhibitors, processing aid, age resister, antioxidant etc..These both may be used To be used alone, can also be used in combination of two or more.
It, can be by by the carbon atom of (A) alkyl as the copolymer of host agent used in adhesive composition of the invention At least one of (methyl) acrylate monomer that number is C4~C18, with selected from being contained by (B) as copolymerisable monomer group The copolymerisable monomer of hydroxyl, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) not copolymerizable composed by hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxy At least one of monomer group is copolymerized to synthesize.To the polymerization of copolymer, there is no particular limitation, can be used molten The polymerizations appropriate such as liquid polymerization, emulsion polymerization.
When using (H-2) ionic compound containing acryloyl group as (H) antistatic agent, as bonding of the invention The copolymer of host agent used in agent composition can pass through (methyl) acrylate by the carbon atom number of (A) alkyl for C4~C18 At least one of monomer, with selected from as copolymerisable monomer group by the copolymerisable monomer of (B) hydroxyl, (C) containing carboxyl Copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) not hydroxyl and nitrogenous vinyl list At least one of copolymerisable monomer group composed by body or (methyl) alkyl acrylate monomer containing alkoxy and (H- 2) ionic compound containing acryloyl group is copolymerized to synthesize.
Adhesive composition of the invention can pass through the isocyanation esterification in above-mentioned copolymer more than cooperation (F) trifunctional Close object, the non-ring type aliphatic isocyanates compound of (G) two function, (H) antistatic agent, there are also any additive appropriate come into Row is prepared.In addition, if the ionic compound by (H-2) containing acryloyl group polymerize the situation in host agent copolymer Under, (H) antistatic agent both can be added further to the copolymer, (H) antistatic agent can not also be added.
It is preferred that aforementioned copolymer is acrylic polymer, (methyl) acrylate of 50~100 weight % is preferably comprised The acrylic monomers such as monomer or (methyl) acrylic acid, (methyl) acrylic amide.
Additionally, it is preferred that the acid value of acrylic polymer is 0.01~8.0.Thereby, it is possible to improve pollution and improve The performance for preventing glue residue phenomenon from occurring.
Here, " acid value " is to indicate one of index of acid content, it is to neutralize 1g and contain required for the polymer of carboxyl The mg number of potassium hydroxide indicates.
It is preferred that bonding of the adhesive layer at low peeling rate 0.3m/min made of being crosslinked foregoing adhesives composition Power is 0.05~0.1N/25mm, and the cohesive force at high peeling rate 30m/min is 1.0N/25mm or less.Thereby, it is possible to obtain The cohesive force performance small with the variation of peeling rate is obtained, even can also remove rapidly in the case where high speed is removed.Also, Even if temporarily remove surface protection film to re-paste, without excessive strength, it is easy to remove from adherend.
It is preferred that the surface resistivity of adhesive layer made of being crosslinked foregoing adhesives composition is 5.0 × 10+10Ω/□ Hereinafter, removing electrostatic pressure is ± 0~1kV.In addition, in the present invention, so-called " ± 0~1kV's " is meant that " 0~-1kV " " 0~+1kV ", i.e. " -1~+1kV ".If surface resistivity is big, the electrostatic generated when to removing by electrification discharges Performance it is poor, therefore, by keeping surface resistivity sufficiently small, can reduce with generation when removing adhesive layer from adherend Electrostatic caused by remove electrostatic pressure, be able to suppress the influence to the electric control circuit of adherend etc..
It is preferred that the gel point of adhesive layer (binder after crosslinking) made of being crosslinked adhesive composition of the invention Number is 95~100%.Since gel fraction is so high, cohesive force will not become excessive in the case where low peeling rate, reduce The phenomenon that unconverted monomer or oligomer are dissolved out from copolymer, it is so as to improve resistance under re-workability, high temperature/high humidity Long property, and inhibit the pollution of adherend.
Adhesive film of the invention be resin film single or double formed adhesive layer form, the adhesive layer is to make Adhesive composition of the invention is crosslinked.In addition, surface protection film of the invention is the single or double shape in resin film It is formed at adhesive layer, the adhesive layer is to be crosslinked adhesive composition of the invention.In binder of the invention In composition, due to being combined with each ingredient of above-mentioned (A)~(H) with good balance, so having excellent antistatic property Can, the balance of the cohesive force under low peeling rate and high peeling rate is excellent, and endurance quality and cycling processability (after being described on surface protection film with ball pen across adhesive layer, not transferring the pollution to adherend) is also excellent. Thus, it may be preferable to the surface protection film purposes as polarizer be subject to using.
As adhesive layer base material film, protect adhesive surface stripping film (diaphragm), the resin films such as polyester film can be used Deng.
For base material film, it can implement to pass through silicone on the face opposite with adhesive layer side is formed with of resin film The antifouling process of the progress such as class, the release agent of fluorine class or coating agent, silicon dioxide microparticle, the implementable coating by antistatic agent Or the antistatic treatment of progress such as it is mixed into.
It for stripping film, is carried out on the face for being bonded side with the adhesive surface of adhesive layer, implements to pass through silicone, fluorine The demoulding of the progress such as release agent of class is handled.
Embodiment
In the following, illustrating the present invention based on embodiment.
<manufacture of acrylic copolymer>
[embodiment 1]
Nitrogen is imported into the reaction unit equipped with blender, thermometer, reflux condenser and nitrogen ingress pipe, to use nitrogen Gas has replaced the air in reaction unit.Then, joined into reaction unit 100 parts by weight 2-EHA, The acrylic acid 8- hydroxyl monooctyl ester of 3.0 parts by weight, the polypropylene glycol mono acrylic ester of 10 parts by weight (constitute polyalkylene glycol chain The averaged repeating numbers n=12 of alkylene oxide), and joined the solvent (ethyl acetate) of 60 parts by weight simultaneously.Then, by 2 hours The azodiisobutyronitrile as polymerization initiator for instilling 0.1 parts by weight reacts it 6 hours, and it is equal to obtain weight Molecular weight be 500,000, acrylic acid copolymer soln 1 for embodiment 1.A part of acrylic copolymer is taken, is used as aftermentioned Acid value measuring sample.
[embodiment 2~9 and comparative example 1~4]
It is and above-mentioned other than (A) in such as table 1~(E) and (H-2) have adjusted separately the composition of each monomer describedly Acrylic acid copolymer soln 1 for embodiment 1 is carried out similarly operation, obtains for embodiment 2~9 and comparative example 1~4 In acrylic acid copolymer soln.
Table 1
<manufacture of adhesive composition and surface protection film>
[embodiment 1]
1.5 parts by weight 1- octyl pyrroles are added in acrylic acid copolymer soln 1 to the embodiment 1 manufactured as described above Pyridine hexafluorophosphate and after being stirred, 2.0 parts by weight Coronate HX are added, and (U ロ ネ ー ト HX, hexa-methylene two are different The isocyanuric acid ester of cyanate esters), the non-ring type aliphatic isocyanates compound of two functions of 0.5 parts by weight synthesis example 1 It is stirred after G-1, obtains the adhesive composition of embodiment 1.The adhesive composition is coated on by being coated with silicone tree On the stripping film that polyethylene terephthalate (PET) film of rouge is constituted, then it is dried at 90 DEG C and removes solvent, Adhesive layer is obtained with a thickness of 25 μm of bonding sheet.
Then, prepare the polyethylene terephthalate that antistatic treatment and antifouling process are implemented on a face (PET) film, and bonding sheet is transferred to polyethylene terephthalate (PET) film be implemented with antistatic treatment and anti- On the opposing face in the face of dirt processing, is had and " be implemented with PET film/adhesive layer/stripping of antistatic treatment and antifouling process From film (PET film for being coated with silicone resin) " stacking constitute embodiment 1 surface protection film.
[embodiment 2~9 and comparative example 1~4]
Other than (F) of such as table 2~(H) has adjusted separately the composition of each additive describedly, with above-described embodiment 1 Surface protection film is carried out similarly operation, obtains the surface protection film of embodiment 2~9 and comparative example 1~4.
Table 2
Tables 1 and 2 is the table that the whole table for indicating each components matching ratio is divided into two parts, the equal table of numerical value in bracket Show the numerical value for each Parts by Ingredients that the total weight organized with (A) is set as 100 parts by weight and finds out.In addition, will be with Tables 1 and 2 Used in the corresponding compound name of abbreviation of each ingredient be shown in table 3 and table 4.In addition, Coronate (U ロ ネ ー ト, note Volume trade mark) HX, Coronate HL and Coronate L be Nippon Polyurethane Industry Co., Ltd. (Nippon Polyurethane Industry Co., Ltd.) product name, Takenate (タ ケ ネ ー ト, registered trademark) D-140N, D-127N, D- 110N, D-120N are the product names of Mitsui Chemicals, Inc.
In table 1, by (H) antistatic agent, quaternary of (H-2) containing acryloyl group in copolymer of copolymerization from (H) antistatic agent added after sub- property compound and polymerization, is recorded in respectively in different columns.
Table 3
Table 4
The synthesis > of the non-ring type aliphatic isocyanates compound of bis- function of <
The non-ring type aliphatic isocyanates compound of two functions of synthesis example 1~3 is synthesized using following methods.Such as table 5 With shown in table 6, diisocyanate and diol compound are mixed with the ratio of molar ratio NCO/OH=16, react 3 at 120 DEG C Hour, it then, removes unreacted diisocyanate under reduced pressure using thin film evaporation unit, it is non-to obtain desired two function Ring type aliphatic isocyanates compound.
Table 5
Synthesis example 1G-1 Synthesis example 2G-2 Synthesis example 3G-3
Diisocyanate cpd HDI HDI HDI
Diol compound K-1 K-2 K-3
Table 6
<test method and evaluation>
In the environment of 23 DEG C, 50%RH, after surface protection film aging 7 days of Examples 1 to 9 and comparative example 1~4, Stripping film (PET film for being coated with silicone resin) is peeled off, to keep adhesive layer exposed, and the examination as measurement surface resistivity Sample.
In turn, the surface protection film that the adhesive layer is exposed, is fitted in by adhesive layer and has been pasted onto liquid crystal cells On polarizer surface, place 1 day after under 50 DEG C, 5 atmospheric pressure carry out pressure cooker handle 20 minutes, further in room temperature After lower placement 12 hours, as the sample for measuring cohesive force, removing electrostatic pressure, re-workability and durability.
<cohesive force>
Using cupping machine, with low peeling rate (0.3m/min) and high peeling rate (30m/min), to 180 ° of directions Above-mentioned obtained measurement sample (surface protection film of 25mm wide is fitted in into sample made of polarisation plate surface) is removed, is measured Peel strength, and using the peel strength as cohesive force.
<surface resistivity>
After weathering, it is bonded before polarizer, peels stripping film (PET film for being coated with silicone resin) off and make outside adhesive layer Dew, using resistivity meter HirestaUP-HT450 (Ha イ レ ス タ UP-HT450, Mitsubishi, Co., Ltd. chemical analysis technology (Mitsubishi Chemical Analytech Co., Ltd.) manufacture), determine the surface resistivity of adhesive layer.
<removing electrostatic pressure>
Using high-precision electrostatic transducer SK-035, SK-200 (Co., Ltd.'s Keyemce (Keyence Corporation) Manufacture), it measures when carrying out 180 ° of removings to above-mentioned obtained measurement sample with the tensile speed of 30m/min, polarizer band Electric and generation voltage (electrostatic pressure), using the maximum value of measured value as removing electrostatic pressure.
<re-workability>
Described (load 500g, back and forth 3 on the surface protection film of measurement sample obtained above with ball pen It is secondary) after, surface protection film is removed from polarizer, the surface of polarizer is observed, is confirmed whether to transfer the pollution to polarizer.Evaluate mesh Mark benchmark: "○" is evaluated as when not transferring the pollution to polarizer；When the track that confirmation is described along ball pen is at least to office Portion is evaluated as " △ " when displaced pollution；When confirmation along the track that ball pen is described has pollution transportation and from adhesive surface Also "×" is evaluated as when confirmation has the disengaging of binder.
<durability>
After placing above-mentioned obtained measurement sample 250 hours under 60 DEG C, 90%RH environment, it is drawn off being placed in room temperature Under further place 12 hours, then measure cohesive force, whether confirmation has apparent increase compared with initial stage cohesive force.It comments Valence target fiducials: cohesive force after test is that 1.5 times of initial stage cohesive force or less of situation is evaluated as "○", more than 1.5 times The case where be evaluated as "×".
It shows the results of the evaluation in table 7.In addition, indicating " m × 10 by " mE+n " in surface resistivity+n" (its In, m is arbitrary real number, and n is positive integer).
Table 7
For the surface protection film of Examples 1 to 9, the cohesive force at low peeling rate 0.3m/min is 0.05~ 0.1N/25mm, the cohesive force at high peeling rate 30m/min is 1.0N/25mm or less；Surface resistivity is 5.0 × 10+10 Ω/ is hereinafter, removing electrostatic pressure is ± 0~1kV；Also, it is being carried out across adhesive layer in surface protection film using ball pen It after description, does not transfer the pollution to adherend, and the durability after being placed 250 hours in the environment of 60 DEG C, 90%RH It is also excellent.
That is, meeting the performance requirement of following whole simultaneously: (1) obtaining the bonding under low peeling rate and high peeling rate The balance of power；(2) generation of glue residue is prevented；(3) excellent antistatic property；And (4) cycling processability.
For the surface protection film of comparative example 1, it may be possible to due to not containing more than as (F) trifunctional of crosslinking agent The reason of isocyanate compound and the non-ring type aliphatic isocyanates compound of (G) two function, in low peeling rate 0.3m/ Cohesive force under min and high peeling rate 30m/min is excessive, surface resistivity and removing electrostatic pressure are high, re-workability and durable Property is poor.
For the surface protection film of comparative example 2, the non-ring type aliphatic isocyanates chemical combination of (G) two function is not contained Object, but the diisocyanate cpd containing the ring of diketone containing urea as two function ring type isocyanate compounds, therefore, Cohesive force at high peeling rate 30m/min is excessive, durability is poor.
For the surface protection film of comparative example 3, it may be possible to since isocyanate compound more than (F) trifunctional is excessive And the reason of the non-ring type aliphatic isocyanates compound of (G) two function is not contained, storage period is too short, has carried out before coating Crosslinking, therefore, it is impossible to be coated.
For the surface protection film of comparative example 4, it may be possible to due to the non-ring type aliphatic isocyanates chemical combination of (G) two function Reason of the object more than isocyanate compound more than (F) trifunctional, the cohesive force mistake at high peeling rate 30m/min Greatly, durability is poor.
As described above, the performance requirement of following whole can not be met simultaneously in the surface protection film of comparative example 1~4: (1) balance of low peeling rate and the cohesive force under high peeling rate is obtained；(2) generation of glue residue is prevented；(3) excellent Different antistatic property；And (4) cycling processability.

Claims (11)

1. a kind of adhesive composition, containing acrylic polymer, when the total amount for setting the acrylic polymer When for 100 parts by weight, copolymer acrylic polymer made of the acrylic polymer is copolymerized as following monomer is formed,
Total amount is in (methyl) acrylate monomer that the carbon atom number of (A) alkyl of 50~91 parts by weight is C4~C18 It is at least one；
Total amount is at least one of the copolymerisable monomer of (B) hydroxyl of 0.1~10 parts by weight；And
As copolymerisable monomer group, total amount is the carboxylic copolymerizable list of 0.2/115.7 × 100~1.0 parts by weight (C) At least one of body, (D) polyalkylene glycol mono (methyl) acrylic acid that total amount is 5/119.9 × 100~50 parts by weight At least one of ester monomer and total amount are (E) not hydroxyl and nitrogenous ethylene of 2/116.7 × 100~20 parts by weight At least one of (methyl) alkyl acrylate monomer of base monomer or not hydroxyl containing alkoxy,
Also, the adhesive composition further includes the isocyanate compound of (F) trifunctional or more, the non-ring type of (G) two function Aliphatic isocyanates compound and (H) antistatic agent, and polyether modified siloxane compound is not contained,
(H) antistatic agent be at 30 DEG C of temperature be solid fusing point be 30~50 DEG C ionic compound, the ion Property compound be selected from by 1- octylpyridinium hexafluorophosphate, 1- nonylpyridine hexafluorophosphate, 2- methyl-1-dodecane Yl pyridines hexafluorophosphate, 1- octylpyridinium dodecyl benzene sulfonate, 1- dococylpyridinium rhodanate, 1- ten Dioxane yl pyridines dodecyl benzene sulfonate and 4- methyl-1-octylpyridinium hexafluorophosphate composition one of group More than；Or
(H) antistatic agent is ionic compound containing acryloyl group of the copolymerization in the copolymer, described to contain The ionic compound of acryloyl group is selected from by dimethylaminomethyl (methyl) acrylate hexafluorophosphoric acid methyl salt, diformazan Bis- (trifyl) the acid imide methyl salts of base amino-ethyl (methyl) acrylate and dimethylamine first One or more of the group of bis- (fluorosulfonyl) the acid imide methyl salt compositions of ester,
More than (F) trifunctional isocyanate compound and the non-ring type aliphatic isocyanates compound of (G) two function Weight ratio F/G is 1~90,
The copolymerisable monomer of (B) hydroxyl is selected from by (methyl) acrylic acid 8- hydroxyl monooctyl ester, (methyl) acrylic acid 6- The own ester of hydroxyl, (methyl) acrylic acid 4- hydroxybutyl, (methyl) acrylic acid 2- hydroxy methacrylate, N- hydroxyl (methyl) acrylamide, At least one of compound group composed by N- methylol (methyl) acrylamide, N- ethoxy (methyl) acrylamide with On,
The not hydroxyl and nitrogenous vinyl monomer, to replace (methyl) acrylamide, dialkyl amido selected from dialkyl group (methyl) acrylate, N, N- dialkyl group substituted-amino propyl (methyl) acrylamide, N- vinyl substituted lactams class, N- The compound in compound group that (methyl) acryloyl group substituted cyclic amine is constituted.
2. adhesive composition as described in claim 1, wherein relative to acrylic polymer described in 100 parts by weight, institute State the isocyanate compound of (F) trifunctional or more and the total amount of the non-ring type aliphatic isocyanates compound of (G) two function For 0.1~5.0 parts by weight.
3. adhesive composition as claimed in claim 1 or 2, wherein
The non-ring type aliphatic isocyanates compound of (G) two function is that diisocyanate cpd and diol compound occur The compound of reaction and generation,
The diisocyanate cpd is aliphatic diisocyanate and passes through selected from by tetramethylene diisocyanate, five Methylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysine diisocyanate One of composed compound group is constituted,
The diol compound is by selected from by 2- methyl-1,3-propanediol, 2,2- dimethyl -1,3- propylene glycol, 2- first Base -2- propyl -1,3- propylene glycol, 2- ethyl -2- butyl -1,3- propylene glycol, 3- methyl-1,5- pentanediol, dimethyl -1 2,2-, One of 3-propanediol monohydroxy pivalate, polyethylene glycol, compound group composed by polypropylene glycol are constituted.
4. adhesive composition as claimed in claim 1 or 2, wherein (C) the carboxylic copolymerisable monomer is to be selected from By (methyl) acrylic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, 2- (methyl) acryloyl-oxyethyl six Hydrogen phthalic acid, 2- (methyl) acryloxypropyl hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl neighbour's benzene Dioctyl phthalate, 2- (methyl) acryloyl-oxyethyl succinic acid, 2- (methyl) acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone In compound group composed by single (methyl) acrylate, 2- (methyl) acryloyl-oxyethyl tetrahydrophthalic acid at least More than one.
5. adhesive composition as claimed in claim 1 or 2, wherein (D) polyalkylene glycol mono (methyl) acrylic acid Ester monomer is selected from polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, second It is more than at least one of oxygroup polyalkylene glycol (methyl) acrylate.
6. adhesive composition as claimed in claim 1 or 2, wherein isocyanates chemical combination more than (F) trifunctional Object is selected from isocyanuric acid ester, the isophorone diisocyanate compound by hexamethylene diisocyanate compound Isocyanuric acid ester, the addition product of hexamethylene diisocyanate compound, isophorone diisocyanate compound addition product, The biuret of hexamethylene diisocyanate compound, the biuret of isophorone diisocyanate compound, toluene diisocyanate The isocyanuric acid ester of ester compound, the isocyanuric acid ester of xylylene diisocyanate compound, hydrogenated xylylene two are different The isocyanuric acid ester of cyanate esters, the addition product of tolunediisocyanate compound, xylylene diisocyanate chemical combination At least one of compound group composed by the addition product of object, the addition product of hydrogenated xylylene diisocyanate compound with On.
7. adhesive composition as claimed in claim 1 or 2, wherein
Cohesive force 0.05 of the adhesive layer at low peeling rate 0.3m/min made of being crosslinked the adhesive composition ~0.1N/25mm, the cohesive force at high peeling rate 30m/min are 1.0N/25mm or less.
8. adhesive composition as claimed in claim 1 or 2, wherein
The surface resistivity 5.0 × 10 of adhesive layer made of being crosslinked the adhesive composition+10Ω/ or less, removing Electrostatic pressure is ± 0~1kV.
It is to form adhesive layer in the single or double of resin film and form, the adhesive layer is 9. a kind of surface protection film It is crosslinked adhesive composition according to any one of claims 1 to 8.
10. surface protection film as claimed in claim 9, the surface protection film purposes as polarizer be subject to using.
11. surface protection film as claimed in claim 10, wherein
On the face opposite with the side for being formed with the adhesive layer of the resin film, it is implemented with antistatic and antifouling place Reason.
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