CN103820058B - Adhesive composition, adhesive film, and surface-protective film - Google Patents
Adhesive composition, adhesive film, and surface-protective film Download PDFInfo
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- CN103820058B CN103820058B CN201310556876.XA CN201310556876A CN103820058B CN 103820058 B CN103820058 B CN 103820058B CN 201310556876 A CN201310556876 A CN 201310556876A CN 103820058 B CN103820058 B CN 103820058B
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- acrylate
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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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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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
- 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
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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
- 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
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Abstract
The invention provides an adhesive composition which has excellent anti-static performance, adhesive force having excellent balance in stripping speeds in a low-speed region and a high-speed region, excellent durability and excellent reprocessing performance, and an adhesive film and a surface-protective film. An adhesive composition containing an anti-static agent includes an acrylic polymer which takes a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 6 carbon atoms as a main component, 85 to 98.5 parts, by weight, of the (meth) acrylic acid alkyl ester, the said main component, with respect to 100 parts of a (meth) acrylic acid alkyl ester by weight, 0.1 to 15 parts, by weight, of a copolymerized monomer having hydroxyl groups, 0.1 to 2 parts, by weight, of a copolymerized monomer having carboxyl groups, and 0.1 to 5 parts, by weight, of a cross-linking agent. The anti-static agent is an ion composition having a melting point of 30 to 50 DEG C.
Description
Technical field
The present invention provides a kind of adhesive composition with antistatic property and using the adhesive composition in resin
The adhesive film and surface protection film of the adhesive layer with antistatic property are formed at least one side of film.
Moreover, it relates to the surface protection film in a kind of manufacturing process for liquid crystal display.More specifically,
The present invention relates to a kind of surface of the opticses such as Polarizer, polarizer, antireflection film for being pasted onto composition liquid crystal display
Surface protection film adhesive composition, and using the surface protection film of the adhesive composition.
The adhesive film and surface protection film of the present invention has particularly excellent antistatic property.Therefore, it is applied to hold
It is also easy to produce on surface of the plastic foil of electrostatic as the blooming of Polarizer, polarizer, the antireflection film etc. of component parts, with
Protect the surface.
Background technology
All the time, as optical sections such as Polarizer, polarizer, the antireflection films of part for constituting liquid crystal display
In the manufacturing process of part, the surface protection film for temporary protection is pasted over the surfaces of the optical components.This surface protection film
Only used in the operation of manufacture opticses, when opticses are inserted into liquid crystal display, it is peeled off from opticses
And remove.Because this surface protection film for protecting optical component surfaces is only used in manufacturing process, therefore, generally also
It is referred to as " operation film ".
For the surface protection film used in so operation of manufacture opticses, poly- with optical transparence
Ethylene glycol terephthalate（PET）Adhesive layer is formed with the one side of resin film.It is fitted with adhesive layer for protecting
The adhesive layer, stripping film through lift-off processing are protected, until fitting on opticses.
In addition, for the opticses such as Polarizer, polarizer, antireflection film, due in surface protection film of having fitted
In the state of carry out being mixed into etc. the product inspection of optical assessment with the display capabilities of LCD panel, tone, contrast, impurity
Test, so, as the performance requirement to surface protection film, it is desirable to without bubble, impurity in adhesive layer.
In addition, in recent years, when peeling off surface protection film from the opticses such as Polarizer, polarizer, antireflection film, companion
With the stripping electrostatic produced by the electrostatic occurred when peeling off adhesive layer from adherend, it is possible to influence whether liquid crystal display
The failure of the electric control circuit of device, it is therefore desirable to adhesive layer has excellent antistatic property.
In addition, on the opticses such as Polarizer, polarizer, antireflection film during adhesive surface protecting film, due to various
Reason, can exist and temporarily peel off surface protection film and re-paste the situation of surface protection film again.Now, it is desirable to surface protection
Film has the characteristic for easily stripping down from the opticses of adherend（Re-workability）.In addition, now, it is desirable to which surface is protected
The adhesive layer of cuticula does not pollute adherend, that is, require the phenomenon of so-called glue residue.
In addition, from the opticses such as final Polarizer, polarizer, antireflection film peel off surface protection film when, it is desirable to
Can rapidly peel off.I.e., it is desirable to which cohesive force is little because of the change of peeling rate, even if in the case of in order to peel off in high speed
Can rapidly peel off.
So, in recent years, from using maneuverable viewpoint during surface protection film, it is desirable to constitute surface protection film
Adhesive layer there is following performance：（1）Under the peeling rate of low-speed region and high-speed region, the balance of cohesive force is obtained；
（2）Prevent the generation of glue residue；（3）With excellent antistatic property；And（4）With reprocessing（ReWork）Property
Energy.
But, that is, allow to meet the performance requirement of the adhesive layer to constituting surface protection film respectively, i.e. allow to
Meet respectively above-mentioned（1）~（4）In indivedual performance requirements, but require that the adhesive layer of surface protection film has while meeting
（1）~（4）Over-all properties require, be extremely difficult problem.
In this manual, " low-speed region " refers to region of the peeling rate near 0.3m/min；" high-speed region " is
Refer to region of the peeling rate near 30m/min.
For example, with regard to（1）Under the peeling rate of low-speed region and high-speed region obtain cohesive force balance and（2）
Prevent the generation of glue residue, it is known to suggestion as described below.
With the alkyl with carbon number below 7（Methyl）Alkyl acrylate and the combined polymerization containing carboxyl
The copolymer of compound as main component, and with cross-linking agent to it carry out crosslinking Treatment and made by acrylic adhesive layer
In, adherend is attached to the side shifting of adherend one in the case of long-time bonding, there is binding agent, and
To ascending big problem during the Jing of the bonding force of adherend.In order to avoid the problem, it is known to which one kind is provided with following viscous
The technical scheme of knot oxidant layer, the adhesive layer is using the alkyl with carbon number 8～10（Methyl）Acrylic acid alkyl
The copolymer of ester and the combined polymerization compound with alcoholic extract hydroxyl group, and the bonding of crosslinking Treatment is carried out to it with cross-linking agent
Oxidant layer（Patent documentation 1）.
In addition, it is also proposed that a kind of technical scheme for being provided with following adhesive layers, the adhesive layer be by with
In above-mentioned identical copolymer, coordinate a small amount of（Methyl）Alkyl acrylate and the combined polymerization compound containing carboxyl are total to
Polymers, and the adhesive layer of crosslinking Treatment is carried out to it with cross-linking agent.But, when using it for, surface tension is low and surface
When in the surface protection of smooth plastic plate etc., the peelings such as separation are produced with heating when adding man-hour or preserving
The problem of releasable difference when problem, the high speed in field hand-manipulated are peeled off.
In order to solve these problems, it is proposed that a kind of adhesive composition, the adhesive composition is：In a）To have
The alkyl of carbon number 8～10（Methyl）Alkyl acrylate is used as main component（Methyl）The weight of alkyl acrylate 100
In amount part, b is added）The combined polymerization compound containing carboxyl of 1～15 weight portion and c）The carbon atom of 3～100 weight portions
The vinyl esters of the aliphatic carboxylic acid of number 1～5 and obtain the copolymer of monomer mixture, and coordinate above-mentioned in the copolymer
b）The adhesive composition of the cross-linking agent more than equivalent of the carboxyl of composition（Patent documentation 2）.
In the adhesive composition that patent documentation 2 is recorded, the stripping of separation etc. will not be produced when adding man-hour or preserving
Phenomenon, also, bonding force being substantially increased when not having Jing, so as to releasable is excellent.Even preserving, especially in addition, long-term
It is to preserve for a long time in high temperature environments, it is also possible to peeled off again with little strength, bonding is not now remained in adherend
Agent, even and if also can again be peeled off with little strength in the case where high speed is peeled off.
In addition, right（3）For excellent antistatic property, as the side to surface protection film imparting antistatic behaviour
Method, it is proposed that method of antistatic additive etc. is mixed in base material film.As antistatic additive, for example, disclose（a）Quaternary ammonium salt, pyridine
Salt, the various cationic antistatic agents with the cation base such as primary～tertiary amino；（b）With sulfonic acid base, sulfuric ester base,
The anionic antistatic agents of the anion base of phosphate ester base, phosphonic acids base etc.；（c）Amino acidses, amidosulphuric acid esters etc.
Both sexes antistatic additive；（d）The non-ionic antistatic agent of alkamine, glycerols, polyethylene glycols etc.；（e）Make as above
Antistatic additive carries out Polymer Antistatic Agent that molecular weight is obtained etc.（Patent documentation 3）.
In addition, propose in recent years antistatic additive so is directly contained in adhesive layer, rather than it is contained in base
Material film coats the scheme on base material film surface.
In addition, with regard to（4）Re-workability, for example, it is proposed that a kind of adhesive composition, the adhesive composition is：
Relative to 100 parts by weight propylene acid resins, coordinate the isocyanate ester compound of 0.0001～10 weight portion firming agent and
Specific silicate oligomer and obtain（Patent documentation 4）.
In patent documentation 4, record：Carbon number with alkyl is 2～12 or so alkyl acrylate, alkyl
Carbon number be 4～12 or so alkyl methacrylate etc. as main monomer component, for example carboxylic list can be contained
The monomer component containing other functional groups such as body.Typically, above-mentioned principal monomers more than 50 weight % is preferably comprised, and is wished
The content of the monomer component containing functional group be 0.001～50 weight %, preferably 0.001～25 weight %, more preferably
0.01～25 weight %.This patent documentation 4 record adhesive composition, even if at high temperature or it is hot and humid under, its
The rheological parameters' change with time of cohesiveness and bonding force is also little, and excellent effect is also showed that to the bonding force of curved surface, thus with again plus
Work.
Generally, if adhesive layer is soft character, glue residue, re-workability are easily produced and is also easily reduced.That is,
Difficulty is peeled off after mistake laminating, and is difficult to re-paste.From this viewpoint, in order to make it have re-workability, need
By monomer crosslinked with functional groups such as carboxyls in host so that adhesive layer has certain hardness.
In conventional technology, it is desirable to which the adhesive layer for constituting surface protection film has following performance：In low-speed region and
Under the peeling rate of high-speed region, the balance of cohesive force is obtained；With excellent antistatic property；And with re-workability
Energy.But, that is, allow to meet above-mentioned respectively（1）~（4）The performance requirement of middle individual term, cannot also meet surface protection film
Required by adhering agent layer（1）~（4）Over-all properties require.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Application 63-225677 publication
Patent documentation 2：Japanese Unexamined Patent Publication 11-256111 publication
Patent documentation 3：Japanese Unexamined Patent Publication 11-070629 publication
Patent documentation 4：Japanese Unexamined Patent Publication 8-199130 publication
The content of the invention
The invention problem to be solved
The present invention is completed in view of the foregoing, and its problem is, there is provided it is a kind of with excellent antistatic property,
The balance of the cohesive force under the peeling rate of low-speed region and high-speed region is excellent and endurance quality and cycling processability
Also excellent adhesive composition, adhesive film and surface protection film.
The method for solving problem
In order to solve above-mentioned problem, the present invention provides a kind of adhesive composition, and it is the binding agent containing antistatic additive
Compositionss, wherein,
The adhesive composition is included with the alkyl that carbon number is 4～10（Methyl）Alkyl acrylate is made
For the acrylic polymer of main component,
Relative to the foregoing acrylic polymer of 100 weight portions, the aforementioned main component containing 85～98.5 weight portions
I.e.（Methyl）Alkyl acrylate, the combined polymerization monomer containing hydroxyl of 0.1～15 weight portion, 0.1～2 weight portion contain
The combined polymerization monomer of carboxyl and the cross-linking agent of 0.1～5 weight portion,
Foregoing antistatic agents are the ionic compounds that fusing point is 30～50 DEG C.
In addition, being to aforementioned main component（Methyl）For alkyl acrylate, be preferably selected from by（Methyl）Propylene
Acid butyl ester,（Methyl）Isobutyl 2-propenoate,（Methyl）Amyl acrylate,（Methyl）Hexyl 2-propenoate,（Methyl）Heptylacrylate,
（Methyl）1-Octyl acrylate,（Methyl）Isooctyl acrylate monomer,（Methyl）2-EHA,（Methyl）Acrylic acid nonyl ester,
（Methyl）The different nonyl ester of acrylic acid,（Methyl）One or more of compound group that decyl acrylate is constituted.
In addition, for the aforementioned combined polymerization monomer containing hydroxyl, be preferably selected from by（Methyl）Acrylic acid 8- hydroxyls
Base monooctyl ester,（Methyl）The own ester of acrylic acid 6- hydroxyls,（Methyl）Acrylic acid 4- hydroxybutyls,（Methyl）Acrylic acid 2- hydroxy methacrylates,
N- hydroxyls（Methyl）Acrylamide, N- methylols（Methyl）Acrylamide, N- ethoxys（Methyl）The change that acrylamide is constituted
It is more than at least one in compound group.
In addition, the aforementioned combined polymerization monomer containing carboxyl, be selected from by（Methyl）Acrylic acid,（Methyl）Acrylic acid carboxylic
Ethyl ester,（Methyl）Carboxypentyl acrylate, 2-（Methyl）Acryloyl-oxyethyl hexahydrophthalic acid, 2-（Methyl）Acryloyl-oxy
Base propyl group hexahydrophthalic acid, 2-（Methyl）Acryloyl-oxyethyl phthalic acid, 2-（Methyl）Acryloyl-oxyethyl
Succinic acid, 2-（Methyl）Acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone list（Methyl）Acrylate, 2-（Methyl）Propylene
One or more of compound group that trimethylammonium tetrahydrophthalic acid is constituted.
Additionally, it is preferred that aforementioned crosslinking agent is isocyanate compound more than trifunctional.
Also, the present invention provides a kind of adhesive film, it is to form adhesive layer on the single or double of resin film to form,
The adhesive layer is to form the crosslinking of foregoing adhesives compositionss.
Also, the present invention provides a kind of surface protection film, it is to form adhesive layer on the one side of resin film to form, institute
It is to form the crosslinking of foregoing adhesives compositionss to state adhesive layer.
The effect of invention
Based on the present invention, disclosure satisfy that required by the insurmountable adhesive layer to surface protection film in the prior art
Over-all properties.
Specific embodiment
Below, based on the preferred embodiment explanation present invention.
The adhesive composition of the present invention is the adhesive composition containing antistatic additive, wherein, the binding agent combination
Thing is included with the alkyl that carbon number is 4～10（Methyl）Acrylic polymer of the alkyl acrylate as main component
Compound, relative to the foregoing acrylic polymer of 100 weight portions, the aforementioned main component containing 85～98.5 weight portions is
（Methyl）Alkyl acrylate, the combined polymerization monomer containing hydroxyl of 0.1～15 weight portion, 0.1～2 weight portion contain carboxylic
The combined polymerization monomer of base and the cross-linking agent of 0.1～5 weight portion, foregoing antistatic agents are the ionizings that fusing point is 30～50 DEG C
Compound.
As main component（Methyl）Preferably it is 4～10 alkyl containing carbon number for alkyl acrylate
's（Methyl）Alkyl acrylate, be preferably selected from by（Methyl）Butyl acrylate,（Methyl）Isobutyl 2-propenoate,（Methyl）
Amyl acrylate,（Methyl）Hexyl 2-propenoate,（Methyl）Heptylacrylate,（Methyl）1-Octyl acrylate,（Methyl）Acrylic acid is different
Monooctyl ester,（Methyl）2-EHA,（Methyl）Acrylic acid nonyl ester,（Methyl）The different nonyl ester of acrylic acid,（Methyl）Acrylic acid
One or more of compound group that last of the ten Heavenly stems ester is constituted.
Relative to the foregoing acrylic polymer of 100 weight portions, main component（Methyl）Alkyl acrylate contains
Amount is preferably 85～98.5 weight portions.
As the combined polymerization monomer containing hydroxyl, can enumerate：（Methyl）Acrylic acid 8- hydroxyl monooctyl esters,（Methyl）Acrylic acid
The own ester of 6- hydroxyls,（Methyl）Acrylic acid 4- hydroxybutyls,（Methyl）Acrylic acid 2- hydroxy methacrylates etc.（Methyl）Dihydroxypropyl alkane
Base ester class；N- hydroxyls（Methyl）Acrylamide, N- methylols（Methyl）Acrylamide, N- ethoxys（Methyl）Acrylamide etc. contains
There is hydroxyl（Methyl）Acrylic amide etc..
It is preferred that the above-mentioned combined polymerization monomer containing hydroxyl be selected from by（Methyl）Acrylic acid 8- hydroxyl monooctyl esters,（Methyl）
The own ester of acrylic acid 6- hydroxyls,（Methyl）Acrylic acid 4- hydroxybutyls,（Methyl）Acrylic acid 2- hydroxy methacrylates, N- hydroxyls（Methyl）Third
Acrylamide, N- methylols（Methyl）Acrylamide, N- ethoxys（Methyl）In the compound group that acrylamide is constituted at least
More than one.
Relative to the foregoing acrylic polymer of 100 weight portions, the content of the combined polymerization monomer containing hydroxyl is preferred
For 0.1～15 weight portion.
As the combined polymerization monomer containing carboxyl, be preferably selected from by（Methyl）Acrylic acid,（Methyl）Acrylic acid carboxylic
Ethyl ester,（Methyl）Carboxypentyl acrylate, 2-（Methyl）Acryloyl-oxyethyl hexahydrophthalic acid, 2-（Methyl）Acryloyl-oxy
Base propyl group hexahydrophthalic acid, 2-（Methyl）Acryloyl-oxyethyl phthalic acid, 2-（Methyl）Acryloyl-oxyethyl
Succinic acid, 2-（Methyl）Acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone list（Methyl）Acrylate, 2-（Methyl）Propylene
One or more of compound group that trimethylammonium tetrahydrophthalic acid is constituted.
Relative to the foregoing acrylic polymer of 100 weight portions, the content of the combined polymerization monomer of carboxyl is preferably comprised
It is 0.1～2 weight portion.
For the adhesive composition of the present invention, preferably handed over adhesive composition when adhesive layer is formed
Connection.Method as cross-linking reaction is caused, it is also possible to by ultraviolet（UV）Deng photo-crosslinking be crosslinked, but preferred binder
Compositionss contain cross-linking agent.
As cross-linking agent, can enumerate：Isocyanate compounds, two senses or trifunctional more than two senses or trifunctional
Acrylate compounds, metallo-chelate more than epoxide above, two senses or trifunctional etc..Wherein, preferably
Polyisocyanate compounds（Isocyanate compounds more than two senses or trifunctional）, the isocyanide more preferably more than trifunctional
Ester compound.
It is preferred that cross-linking agent is 0.1～5 weight portion relative to the content of the foregoing acrylic polymer of 100 weight portions.
As isocyanate compound more than trifunctional, as long as at least there is the isocyanide of more than three in a molecule
Acid esters（NCO）The polyisocyanate compounds of base.Polyisocyanate compounds include aliphatic category isocyanates, aromatic series
Kind isocyanate, non-ring type kind isocyanate, ester ring type kind isocyanate etc. are classified, and the present invention can be therein any number of
Class.As the specific example of polyisocyanate compounds, can enumerate：Hexamethylene diisocyanate（HDI）, isophorone two
Isocyanates（IPDI）, trimethyl hexamethylene diisocyanate（TMDI）Deng aliphatic category isocyanate compound；Diphenyl
Methane diisocyanate（MDI）, xylylene diisocyanate（XDI）, hydrogenated xylylene diisocyanate（H6XDI）, two
Methyl diphenylene diisocyanate（TOID）, toluene di-isocyanate(TDI)（TDI）Deng aromatic series kind isocyanate compound.
As isocyanate compound more than trifunctional, can enumerate：Diisocyanates（Have two in a molecule
The compound of individual NCO bases）Biuret modified body or isocyanurate-modified body, with trimethylolpropane（TMP）Or glycerol etc.
Polyhydric alcohol more than trivalent（At least there is the compound of more than three OH bases in a molecule）Addition product（It is polyalcohol modified
Body）Deng.
The adhesive composition of the present invention contains ionic compound that fusing point is 30～50 DEG C as antistatic additive.Antistatic
Agent can be the quaternary ionic compound containing acryloyl group.
Because the fusing point of these antistatic additive is low and reason with chain alkyl, thus it is speculated that them and acrylic polymer
Affinity it is high.
It is the antistatic additive of 30～50 DEG C of ionic compound as fusing point, is the ionizing with cation and anion
Compound, can enumerate：Cation is pyridylium, glyoxaline cation, pyrimidine cation, pyrazoles cation, pyrrole
Cationic nitrogenous or phosphorus cation, sulfur cation of cation, ammonium cation etc. etc. are coughed up, anion is six
Fluorinated phosphate root（PF6 -）, thiocyanate radical（SCN-）, benzene sulfonamide acid group（RC6H4SO3 -）, perchlorate（ClO4 -）, tetrafluoride boron
Acid group（BF4 -）Deng inorganic or organic anion compound.It is preferred that in room temperature（Such as 30 DEG C）Under be solid, and by select
The chain length of alkyl, the position of substituent group, number etc., can obtain the compound that fusing point is 30～50 DEG C.Preferred cationic is season
Azonia, can enumerate：1- alkyl pyridines（The carbon atom of 2～6 both can have substituent group can not also have take
Dai Ji）Deng season pyridylium, 1,3- dialkylimidazoliums（2nd, the carbon atom of 4,5 can both have substituent group or can
Not have substituent group）Deng season glyoxaline cation, the quaternary ammonium cation of tetra-allkylammonium etc. etc..
It is 30～50 DEG C of ionic compound as fusing point relative to the foregoing acrylic polymer of 100 weight portions
The content of antistatic additive is preferably 0.1～5.0 weight portion.
It is the ionizing with cation and anion as the aforementioned quaternary ionic compound containing acryloyl group
Compound, can enumerate：Cation is（Methyl）Acryloxyalkyl trialkyl ammonium（R3N+-CnH2n- OCOCQ=CH2, wherein, Q
=H or CH3, R=alkyl）Deng contain（Methyl）The quaternary ammonium of acryloyl group, anion is phosphorus hexafluoride acid group（PF6 -）, sulfur cyanogen
Acid group（SCN-）, organic sulfonic acid root（RSO3 -）, perchlorate（ClO4 -）, tetrafluoride borate（BF4 -）, the acid imide root containing F
（RF 2N-）Deng inorganic or organic anion compound.As the acid imide root containing F（RF 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-), double (trifyl) acid imide root ((CF3SO2)2N-), double (five fluorine second sulphurs
Acyl group) acid imide root ((C2F5SO2)2N-) etc. double sulfonyl acid imide roots.
It is preferred that the aforementioned copolymerization in foregoing acrylic polymer of the quaternary ionic compound containing acryloyl group has
0.1～5.0 weight %.
As the specific example of antistatic additive, it is not particularly limited, but as the ionizing that aforementioned fusing point is 30～50 DEG C
The specific example of compound, can enumerate 1- octylpyridinium dodecyl benzene sulfonates, 1- dococylpyridiniums drone rhodanate,
3- methyl isophthalic acids-dococylpyridinium hexafluorophosphate, 1- dococylpyridiniums drone dodecyl benzene sulfonate, 4- methyl isophthalic acids-
Octylpyridinium hexafluorophosphate etc..
In addition, as the specific example of the aforementioned quaternary ionic compound containing acryloyl group, diformazan can be enumerated
Base amino methyl（Methyl）Acrylate phosphorus hexafluoride acid methyl salt ((CH3)3N+CH2OCOCQ=CH2·PF6 -, wherein, Q=H
Or CH3), dimethyl aminoethyl（Methyl）Double (trifyl) acid imide the methyl salt ((CH of acrylate3)3N+(CH2)2OCOCQ=CH2·(CF3SO2)2N-, wherein, Q=H or CH3), dimethylaminomethyl（Methyl）Double (the fluorine sulphonyl of acrylate
Base) acid imide methyl salt ((CH3)3N+CH2OCOCQ=CH2·(FSO2)2N-, wherein, Q=H or CH3) etc..
The adhesive composition of the present invention can contain cross-linked inhibitor.As cross-linked inhibitor, can enumerate：Acetyl second
Sour methyl ester, ethyl acetoacetate, acetoacetic acid monooctyl ester, acetoacetic acid oil base ester, lauryl acetoacetate, acetoacetic acid stearoyl
The beta-diketon of the 'beta '-ketoester of ester etc., acetylacetone,2,4-pentanedione, 2,4- acetyl butyryls, benzoyl acetone etc..These are keto-enol tautomerisms
Compound, in using polyisocyanate compounds as the adhesive composition of cross-linking agent, by the isocyanide for having cross-linking agent
Perester radical is closed, and can suppress the phenomenon of the excess stickiness rising or gelation of adhesive composition after cooperation cross-linking agent,
The storage period of adhesive composition can be extended.
It is preferred that aforementioned cross-linked inhibitor is keto-enol tautomerism compound, particularly preferably selected from acetylacetone,2,4-pentanedione, acetyl
It is more than at least one in the compound group that ethyl acetate is constituted.
In the case where aforementioned cross-linked inhibitor is added, aforementioned propylene of the aforementioned cross-linked inhibitor relative to 100 weight portions
The content of acids polymers is preferably 1.0～5.0 weight portions.
The adhesive composition of the present invention can contain crosslinking catalyst.Using polyisocyanate compounds as cross-linking agent
In the case of, as long as reaction of the crosslinking catalyst to foregoing acrylic polymer and cross-linking agent（Cross-linking reaction）Play catalysis
The material of agent effect.As crosslinking catalyst, can enumerate：It is the aminated compoundss of tertiary amine etc., organo-tin compound, organic
Organo-metallic compounds such as lead compound, organic zinc compound etc..
Can enumerate as tertiary amine：Trialkylamine, N, N, N', N'- tetra, N, N- dialkyl amido alcohol, three second
Alkene diamidogen, morpholine derivative, bridged piperazine derivatives etc..
As organo-tin compound, can enumerate：Dialkyl tin oxide, the soap of dialkyl tin, the fat of stannous
Fat hydrochlorate etc..
It is preferred that aforementioned crosslinking catalyst is organo-tin compound, particularly preferably selected from by di-n-octyltin oxide, February
It is more than at least one in the compound group that cinnamic acid dioctyl tin is constituted.
When aforementioned crosslinking catalyst is added, relative to the foregoing acrylic polymer of 100 weight portions, aforementioned crosslinking is urged
The content of agent is preferably 0.01～0.5 weight portion.
The adhesive composition of the present invention can contain polyether modified siloxane compound.Polyether modified siloxane compound
It is the silicone compounds with polyether-based, except common siloxane unit（-SiR1 2-O-）Outside, also comprising with polyethers
The siloxane unit of base（-SiR1(R2O(R3O)nR4)-O-）.Here, R1Represent one or more alkyl or aryl, R2
And R3Represent one or more alkylidene, R4Represent one or more alkyl, acyl group etc.（Terminal groups）.As
Polyether-based can be enumerated：Polyethylene oxide base（(C2H4O)n）Or polypropylene oxide base（(C3H6O)n）Deng polyoxyalkylene.
It is preferred that aforementioned polyether modified siloxane compound is the polyether modified siloxane compound that HLB value is 7～12.Separately
Outward, in addition, preferably aforementioned polyether modified siloxane compound phase is for the foregoing acrylic polymer of 100 weight portions
Content is 0.01～0.5 weight portion.More preferably 0.1～0.5 weight portion.
HLB refers to such as JIS K3211（Surfactant term）The hydrophile-lipophile balance Deng specified in（Hydrophilic and parent
The ratio of oiliness）.
Polyether modified siloxane compound, for example, can obtain by the following method：By hydrosilylation reactions, tool is made
There are unsaturated bond and the organic compound of 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 aforementioned polyether modified siloxane compound is matched with into adhesive composition, the bonding of binding agent can be improved
Power and cycling processability.
The adhesive composition of the present invention can contain polyether compound.It is with polyalkylene oxide as polyether compound
Base（poly alkylene oxide）Compound, the polyether polyol such as poly alkylene glycol can be enumerated and they spread out
It is biological.As the alkylidene having in poly alkylene glycol and polyoxyalkylene epoxide, ethylidene, propylidene, butylidene can be enumerated
Deng, but it is not limited to these.Poly alkylene glycol can also be two kinds in Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol etc.
The copolymer of poly alkylene glycol above.As the copolymer of poly alkylene glycol, polyethylene glycol the third two can be enumerated
Alcohol, polyethylene glycol butanediol, polypropylene glycol-polytetramethylene glycol, polyethylene glycol Propylene Glycol-polytetramethylene glycol etc., the copolymer
Can be block copolymer, random copolymer.
As the derivant of poly alkylene glycol, can enumerate：Polyoxyalkylene monoalky lether, polyoxyalkylene two
The polyoxygenated such as the polyoxyalkylene alkyl ethers such as alkyl ether, polyoxyalkylene mono alkenyl ether, polyoxyalkylene dialkylene ether
The polyoxyalkylene aryl ether such as alkylidene alkene ether, polyoxyalkylene list aryl ether, polyoxyalkylene diaryl ether, gather
Alkylidene oxide alkyl phenyl ether, polyoxyalkylene glycol mono fatty acid ester, polyoxyalkylene glycol di fatty acid ester etc.
Polyoxyalkylene glycol fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene alkylamine amine gathers
Alkylidene oxide diamidogen etc..
Here, as the alkyl ether in polylalkylene glycol derivatives, can enumerate：The lower alkyl ethers such as methyl ether, ether,
The senior alkyl ether such as lauryl ether, octadecyl ether.As the alkene ether in polylalkylene glycol derivatives, second can be enumerated
Alkene ether, allyl ether, oleyl ether etc..In addition, as the fatty acid ester in polylalkylene glycol derivatives, can enumerate：
The polyunsaturated fatty acid esters such as acetate, stearate,（Methyl）The unsaturated fatty acid esters such as acrylate, oleate.
Preferred, polyethers compound is containing oxyethylene group（ethylene oxide）Compound, further preferably polyoxy
Change the compound of vinyl.
When polyether compound has polymerizable functional group, it is also possible to make its with（Methyl）Acrylic polymer is carried out altogether
It is poly-.As polymerizable functional group, preferably（Methyl）The ethylene such as acrylic, vinyl, pi-allyl functional group.As with poly-
The polyether compound of He Xing functional groups, can enumerate：Polyalkylene glycol mono（Methyl）Acrylate, poly alkylene glycol two
（Methyl）Acrylate, alkoxy polyalkyleneglycol（Methyl）Acrylate, polyalkylene glycol mono allyl ether, polyalkylene
Glycol diallyl ether, alkoxy polyalkyleneglycol allyl ether, polyalkylene glycol mono vinyl Ether, poly alkylene glycol divinyl
Ether, alkoxy polyalkyleneglycol vinyl Ether etc..
Also, as other compositions, can mate properly into containing the copolymerizable of alkylene oxide (alkylene oxide)（First
Base）Acrylic monomerss,（Methyl）Acrylamide monomer, dialkyl group substituted acrylamide monomer, surfactant, solidification promote
Additive known to agent, plasticizer, filler, curing inhibitors, processing aid, age resister, antioxidant etc..These both may be used
To be used alone, it is also possible to be used in combination of two or more.
By by with the alkyl that carbon number is 4～10（Methyl）Alkyl acrylate and the combined polymerization containing hydroxyl
Property monomer and the combined polymerization monomer containing carboxyl carry out copolymerization, the host as adhesive composition of the present invention can be synthesized
Acrylic polymer.To the polymerization of acrylic polymer, there is no particular limitation, it is possible to use polymerisation in solution, breast
The appropriate polymerizations such as liquid polymerization.
In acrylic polymer, it is also possible to make polyalkylene glycol mono（Methyl）Acrylate monomer, not hydroxyl
And nitrogenous vinyl monomer, containing alkoxyl（Methyl）Alkyl acrylate monomer, the quaternary containing acryloyl group
Other monomers such as ionic compound carry out copolymerization.
The present invention adhesive composition, can by aforesaid propylene acids polymers coordinate cross-linking agent, antistatic additive,
Also appropriate any additive is being prepared.
It is preferred that making the adhesive layer that foregoing adhesives compositionss are crosslinked in the peeling rate 0.3m/min of low-speed region
Under cohesive force be 0.05～0.1N/25mm, the cohesive force under the peeling rate 30m/min of high-speed region be 1.0N/25mm
Below.Thereby, it is possible to obtain cohesive force with the little performance of the change of peeling rate, even also may be used in the case where high speed is peeled off
To peel off rapidly.Even if also, when temporarily peeling off surface protection film to re-paste, without excessive strength, it is easy to
Peel off from adherend.
It is preferred that making foregoing adhesives compositionss carry out the surface resistivity of adhesive layer being crosslinked 5.0 × 10+11
Ω/below, stripping electrostatic pressure is ± 0～0.5kV.Additionally, in the present invention, so-called " ± 0～0.5kV " is meant that " 0
～-0.5kV " and " 0～+0.5kV ", i.e. " -0.5～+0.5kV ".In the case where the surface resistivity of adhesive layer is big,
When surface protection film is peeled off, the poor performance of the electrostatic that adhesive layer release is produced because powered.By the table for making adhesive layer
Surface resistivity is sufficiently small, can reduce with the stripping electrostatic produced by the electrostatic occurred when peeling off adhesive layer from adherend
Pressure, can suppress the impact of the electric control circuit to adherend etc..
It is preferred that making the adhesive layer of the adhesive composition crosslinking of the present invention（Binding agent after crosslinking）Gel point
Number is 95～100%.Because gel fraction is so high, cohesive force will not become too much in the case of low peeling rate, reduce
The phenomenon of dissolution unconverted monomer or oligomer from acrylic polymer such that it is able to improve re-workability, high temperature/height
Durability under wet, and suppress the pollution of adherend.
The present invention adhesive film be resin film single or double formed adhesive layer form, the adhesive layer is to make
The adhesive composition crosslinking of the present invention is formed.In addition, the surface protection film of the present invention is the one side formation bonding in resin film
Oxidant layer is formed, and the adhesive layer is that the adhesive composition crosslinking for making the present invention is formed.In the adhesion agent composition of the present invention
In, because balance has coordinated well each composition of aforesaid propylene acids polymers, so with excellent antistatic property,
The balance of the adhesion strength under the peeling rate of low-speed region and high-speed region is excellent.Also, endurance quality and again plus
Work performance is also excellent（With ball pen after adhesive layer is described on surface protection film, do not have to adherend transfer
Pollution）.Thus, it may be preferable to be used as the surface protection film purposes of Polarizer.
Base material film, the stripping film of protection adhesive surface as adhesive layer（Barrier film）, it is possible to use the resin film such as polyester film
Deng.
For base material film, can implement to pass through silicone on the face contrary with adhesive layer side is formed with of resin film
The antifouling process that class, the releasing agent of fluorine class or coating agent, silicon dioxide microparticle etc. are carried out, can implement the coating by antistatic additive
Or the antistatic treatment for carrying out such as it is mixed into.
For stripping film, on the face that the adhesive surface with adhesive layer carries out fitting side, implement to pass through silicone, fluorine
The demoulding that releasing agent of class etc. is carried out is processed.
Embodiment
Below, the present invention is illustrated based on embodiment.
<The manufacture of acrylic polymer>
[embodiment 1]
Nitrogen is imported to being furnished with the reaction unit of agitator, thermometer, reflux condenser and nitrogen ingress pipe, so as to nitrogen
Gas has replaced the air in reaction unit.Then, add in reaction unit 93 weight portions 2-EHA,
The acrylic acid 8- hydroxyl monooctyl esters of 5.5 weight portions, the acrylic acid of 1.5 weight portions, and while add the solvent of 60 weight portions（Acetic acid second
Ester）.Then, the azodiisobutyronitrile as polymerization initiator of 0.1 weight portion was instilled through 2 hours, makes its anti-at 65 DEG C
Answer 6 hours, obtain weight average molecular weight be 500,000, acrylic polymer solution 1 for embodiment 1.
[embodiment 2～6 and comparative example 1～3]
Except as in table 1（A）~（C）Have adjusted respectively describedly beyond the composition of each monomer, with above-mentioned for implementing
The acrylic polymer solution 1 of example 1 is similarly operated, and is obtained for third in embodiment 2～6 and comparative example 1～3
Alkene acids polymers solution.
Additionally, in table 1, table 2,（A）It is main component（Methyl）Alkyl acrylate,（B）It is being total to containing hydroxyl
Polymerizable monomer,（C）It is the combined polymerization monomer containing carboxyl.
<The manufacture of adhesive composition and surface protection film>
[embodiment 1]
The acrylic polymer solution 1 of the embodiment 1 to manufacturing as described above, adds 2.0 weight portion 1- octyl groups
Pyridine dodecyl benzene sulfonate and after being stirred, adds the Coronate HX of 1.5 weight portions（U ロ ネ ー ト HX, six
The isocyanuric acid ester of methylene diisocyanate compound）After be stirred mixing, obtain embodiment 1 binding agent combination
Thing.The adhesive composition is coated by the polyethylene terephthalate for scribbling silicone resin（PET）The stripping that film is constituted
On film, then it is dried at 90 DEG C and removes solvent, obtains the bonding sheet that adhesive layer thickness is 25 μm.
Then, the polyethylene terephthalate that antistatic treatment and antifouling process are implemented with a face is prepared
（PET）Film, and bonding sheet is transferred to into the polyethylene terephthalate（PET）Film be implemented with antistatic treatment and anti-
On the opposing face in the face that dirt is processed, had and " be implemented with the PET film/adhesive layer/stripping of antistatic treatment and antifouling process
From film（Scribble the PET film of silicone resin）" stacking constitute embodiment 1 surface protection film.
[embodiment 2～6 and comparative example 1～3]
Except such as table 1（D）~（E）Have adjusted respectively describedly beyond the composition of each additive, with above-described embodiment 1
Surface protection film is similarly operated and is obtained embodiment 2～6 with the surface protection film for comparing 1～3.
Additionally, in table 1, table 2,（D）For cross-linking agent,（E）For antistatic additive.
Table 1
In table 1, the numerical value in bracket represent with（A）~（C）It is each that total weight of group is set to 100 weight portions and obtains
The numerical value of Parts by Ingredients.In addition, compound name corresponding with the abbreviation of each composition used in table 1 is shown in Table 2.This
Outward, Coronate（U ロ ネ ー ト, registered trade mark）HX, Coronate HL and Coronate L are Japanese polyurethane industry strain formulas
Commercial firm（Nippon Polyurethane Industry Co.,Ltd.）Trade name, Takenate（タ ケ ネ ー ト, registration
Trade mark）D-140N, D-127N, D-110N are the trade names of Mitsui Chemicals, Inc.
Table 2
<Test method and evaluation>
In the environment of 23 DEG C, 50%RH, by the surface protection film of embodiment 1～6 and comparative example 1～3 it is aging 7 days after,
Peel stripping film off（Scribble the PET film of silicone resin）, so that adhesive layer exposes, and as the examination of measure surface resistivity
Sample.
Further, the surface protection film for the adhesive layer being exposed, is fitted in by adhesive layer and be pasted onto liquid crystal cells
On Polarizer surface, place 1 day after carry out under 50 DEG C, 5 atmospheric pressure pressure cooker process 20 minutes, further in room temperature
It is lower to place 12 hours, using thus obtained surface protection film as measure cohesive force, stripping electrostatic pressure, re-workability and durability
Sample.
<Cohesive force>
Using cupping machine, with the peeling rate of low-speed region（0.3m/min）With the peeling rate of high-speed region
（30m/min）, to 180 ° of directions above-mentioned resulting measure sample is peeled off（The wide surface protection films of 25mm are fitted in into Polarizer
The sample on surface）, peel strength is determined, and using the peel strength as cohesive force.
<Surface resistivity>
After weathering, fit in before Polarizer, peel stripping film off（Scribble the PET film of silicone resin）And make adhesive layer
Expose, using resistivity meter（Trade name is " Hiresta（Ha イ レ ス タ) UP-HT450 ", Co., Ltd.'s Rhizoma Sparganii chemistry point
Analysis technology（Mitsubishi Chemical Analytech Co.,Ltd.）Manufacture）, determine the sheet resistance of adhesive layer
Rate.
<Peel off electrostatic pressure>
Using high accuracy electrostatic transducer（Model SK-035, SK-200, Co., Ltd.'s Keyemce（Keyence
Corporation）Manufacture）, determine to work as carries out 180 ° of strippings to above-mentioned resulting measure sample with the draw speed of 30m/min
When, Polarizer it is powered and produce voltage（Electrostatic pressure）, using the maximum of measured value as stripping electrostatic pressure.
<Re-workability>
Described on the surface protection film of measure sample obtained above with ball pen（Load be 500g, back and forth 3
It is secondary）Afterwards, surface protection film is peeled off from Polarizer, observes the surface of Polarizer, confirmation is no to transfer the pollution to Polarizer.Reprocessing
The metewand of property："○" is evaluated as when not transferring the pollution to Polarizer；When confirm along ball pen describe track extremely
It is evaluated as " △ " when having lacked to local transfer pollution；When there is pollution transportation the track for confirming to describe along ball pen and from bonding
Agent surface also confirms to be evaluated as "×" during the disengaging for having binding agent.Re-workability have rated according to said reference.
<Durability>
Above-mentioned resulting measure sample is placed under 60 DEG C, 90%RH environment after 250 hours, is drawn off being placed in room temperature
Under further place 12 hours, then determine cohesive force, confirm compared with initial stage cohesive force relatively without significantly increase.It is durable
The metewand of property：Cohesive force after test be the situation of less than 1.5 times of initial stage cohesive force be evaluated as "○", more than 1.5
Situation again is evaluated as "×".Durability have rated according to said reference.
Evaluation result is shown in Table 3.In addition, in surface resistivity, by " mE+n " " m × 10 are represented+n”（Its
In, m is arbitrary real number, and n is positive integer）.
Table 3
For the surface protection film of embodiment 1～6, the cohesive force under the peeling rate 0.3m/min of low-speed region is
0.05～0.1N/25mm, the cohesive force under the peeling rate 30m/min of high-speed region is below 1.0N/25mm；Sheet resistance
Rate is 5.0 × 10+11Ω/below, stripping electrostatic pressure is ± 0～0.5kV；Also, existed across adhesive layer using ball pen
It is no to transfer the pollution to adherend after surface protection film is described, and give 250 in the environment of 60 DEG C, 90%RH
Durability after hour is placed is also excellent.
That is, while meeting the performance requirement of following whole：（1）Under obtaining the peeling rate of low-speed region and high-speed region
Cohesive force balance；（2）Prevent the generation of glue residue；（3）With excellent antistatic property；And（4）Have
Cycling processability.
For the surface protection film of comparative example 1, it may be possible to due to main component（Methyl）Alkyl acrylate is very few,
The combined polymerization monomer of hydroxyl is excessively and without the reason of the combined polymerization monomer with carboxyl, the stripping of its low-speed region
Cohesive force under speed 0.3m/min is little, and surface resistivity and stripping electrostatic pressure are high, poor durability.
For the surface protection film of comparative example 2, because the combined polymerization single phase containing carboxyl is for main component
（Methyl）Alkyl acrylate is excessive and content of isocyanates firming agent is more, so as to effect duration becomes too short and in coating
It is front to be crosslinked, therefore cannot be coated.
For the surface protection film of comparative example 3, it may be possible to due to without combined polymerization monomer, cross-linking agent with carboxyl
And the reason of antistatic additive, the stripping speed of its cohesive force and high-speed region under the peeling rate 0.3m/min of low-speed region
Under degree 30m/min cohesive force is excessive, surface resistivity and peel off high electrostatic pressure, re-workability and poor durability.
As described above, in the surface protection film of comparative example 1～3, it is impossible to while meeting following whole performance requirement：
（1）Obtain the balance of the cohesive force under the peeling rate of low-speed region and high-speed region；（2）Prevent sending out for glue residue
It is raw；（3）With excellent antistatic property；And（4）With cycling processability.
Claims (6)
1. a kind of adhesive composition, it is the adhesive composition containing acrylic polymer, cross-linking agent and antistatic additive,
Wherein,
The acrylic polymer is using (methyl) alkyl acrylate with the alkyl that carbon number is 4～10 as main
Composition, the main component by 85～98.5 weight portions of the acrylic polymer relative to 100 weight portions is (first
Base) alkyl acrylate, the combined polymerization monomer containing hydroxyl of 4～15 weight portions and 1.0～2 weight portions contain carboxyl
Combined polymerization monomer carry out obtained by copolymerization copolymer and constitute,
Relative to the acrylic polymer of 100 weight portions, the adhesive composition contains the friendship of 0.1～5 weight portion
Connection agent, and crosslinking catalyst, cross-linked inhibitor and polyether modified siloxane compound are not contained,
The combined polymerization monomer containing hydroxyl is selected from by (methyl) acrylic acid 8- hydroxyl monooctyl esters, (methyl) acrylic acid 6-
The own ester of hydroxyl, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxy methacrylates, N- hydroxyls (methyl) acrylamide,
At least one in the compound group that N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide are constituted with
On,
The antistatic additive is the ionic compound that fusing point is 30～50 DEG C.
2. adhesive composition as claimed in claim 1, wherein, it is choosing that the main component is (methyl) alkyl acrylate
From in by (methyl) butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate,
(methyl) heptylacrylate, (methyl) 1-Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA,
One kind in the compound group that (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate are constituted
More than.
3. adhesive composition as claimed in claim 1 or 2, wherein, the combined polymerization monomer containing carboxyl, is to be selected from
In by (methyl) acrylic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, 2- (methyl) acryloyl-oxyethyl
Hexahydrophthalic acid, 2- (methyl) acryloxypropyl hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl are adjacent
Phthalic acid, 2- (methyl) acryloyl-oxyethyl succinic acid, 2- (methyl) acryloyl-oxyethyl maleic acid, carboxyl gather in oneself
In the compound group that ester list (methyl) acrylate, 2- (methyl) acryloyl-oxyethyl tetrahydrophthalic acid are constituted one
More than kind.
4. adhesive composition as claimed in claim 1 or 2, wherein, the cross-linking agent is isocyanates more than trifunctional
Compound.
5. a kind of adhesive film, it is formed adhesive layer and forms in the single or double of resin film, and the adhesive layer is to make power
Profit requires that the adhesive composition crosslinking any one of 1～4 is formed.
6. a kind of surface protection film, it is formed adhesive layer and forms in the one side of resin film, and the adhesive layer is to make right
It is required that the crosslinking of the adhesive composition any one of 1～4 is formed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-251871 | 2012-11-16 | ||
| JP2012251871A JP6187896B2 (en) | 2012-11-16 | 2012-11-16 | Adhesive layer, adhesive film and surface protective film |
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| CN103820058A CN103820058A (en) | 2014-05-28 |
| CN103820058B true CN103820058B (en) | 2017-04-12 |
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| CN201310556876.XA Active CN103820058B (en) | 2012-11-16 | 2013-11-11 | Adhesive composition, adhesive film, and surface-protective film |
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| JP (1) | JP6187896B2 (en) |
| KR (2) | KR101554870B1 (en) |
| CN (1) | CN103820058B (en) |
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| JP2016011363A (en) * | 2014-06-27 | 2016-01-21 | 日東電工株式会社 | Adhesive composition, adhesive sheet and optical member |
| KR102012667B1 (en) * | 2015-01-28 | 2019-08-22 | 주식회사 엘지화학 | Antistatic adhesive composition and antistatic adhesive tape using the same |
| CN106795408B (en) * | 2015-04-10 | 2018-05-04 | 日本合成化学工业株式会社 | Adhesive composition and use adhesive obtained from it and polarizer adhesive |
| JP6392798B2 (en) * | 2016-02-16 | 2018-09-19 | 藤森工業株式会社 | Surface protective film and optical component on which it is bonded |
| JP6775045B2 (en) * | 2019-02-13 | 2020-10-28 | 藤森工業株式会社 | Surface protective film |
| CN110982447B (en) * | 2019-12-18 | 2022-11-22 | 苏州赛伍应用技术股份有限公司 | Double-sided adhesive tape and preparation method and application thereof |
| JP7086153B2 (en) * | 2020-10-02 | 2022-06-17 | 藤森工業株式会社 | Surface protection film |
| JP2022183682A (en) * | 2021-05-31 | 2022-12-13 | 日東電工株式会社 | laminated film |
| WO2022255210A1 (en) * | 2021-05-31 | 2022-12-08 | 日東電工株式会社 | Adhesive agent composition, adhesive agent, and surface protection film |
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| CN103571400A (en) * | 2012-07-27 | 2014-02-12 | 藤森工业株式会社 | Adhesive composition and surface-protective adhesive film |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101578376B1 (en) | 2015-12-17 |
| KR101554870B1 (en) | 2015-09-22 |
| KR20150060641A (en) | 2015-06-03 |
| JP2014098131A (en) | 2014-05-29 |
| TW201432002A (en) | 2014-08-16 |
| KR20140063418A (en) | 2014-05-27 |
| CN103820058A (en) | 2014-05-28 |
| JP6187896B2 (en) | 2017-08-30 |
| TWI557199B (en) | 2016-11-11 |
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