CN108300365A - Adhesive composition, adhesive film and surface protection film - Google Patents
Adhesive composition, adhesive film and surface protection film Download PDFInfo
- Publication number
- CN108300365A CN108300365A CN201710881073.XA CN201710881073A CN108300365A CN 108300365 A CN108300365 A CN 108300365A CN 201710881073 A CN201710881073 A CN 201710881073A CN 108300365 A CN108300365 A CN 108300365A
- Authority
- CN
- China
- Prior art keywords
- methyl
- weight
- parts
- acrylate
- surface protection
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
A kind of surface protection film,Be resin film single or double formed adhesive layer form,The adhesive layer is made containing acrylic polymer,The adhesive composition of crosslinking agent and antistatic agent is crosslinked,The acrylic polymer is using (methyl) alkyl acrylate for the alkyl for being 4~10 with carbon atom number as main component,Copolymer is constituted obtained by relative to the main component that the acrylic polymer of 100 parts by weight is 85~99.5 parts by weight, i.e. (methyl) alkyl acrylate and the combined polymerization monomer containing hydroxyl of 5~15 parts by weight are copolymerized,The acrylic polymer relative to 100 parts by weight,The adhesive composition contains the crosslinking agent of 0.1~5 parts by weight,The crosslinking agent is the isocyanate compound of trifunctional or more,The antistatic agent is that fusing point is 30~50 DEG C and is the ionic compound of solid when temperature is 30 DEG C.
Description
The application be the applying date be on November 11st, 2013, application No. is 201310556382.1, entitled " bond
The divisional application of the application of agent composition, adhesive film and surface protection film ".
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 on at least single 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 surfaces of the optical components such as polarizer, phase plate, antireflection film being pasted onto composition liquid crystal display
Surface protection film adhesive composition, and using the adhesive composition surface protection film.
The adhesive film and surface protection film of the present invention has particularly excellent antistatic property.Therefore, it is applied to hold
On the surface of the optical film of the polarizer, phase plate, antireflection film of plastic foil easy to produce static electricity as component parts etc., with
Protect the surface.
Background technology
All the time, as optical sections such as polarizer, phase plate, the antireflection films of component 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
It only uses in the process of manufacture optical component, when optical component is inserted into liquid crystal display, it is removed from optical component
And it removes.Due to this for protecting the surface protection film of optical component surfaces only to be used in manufacturing process, generally also
Referred to as " process film ".
For the surface protection film used in the process for so manufacturing optical component, poly- with optical transparence
It is formed with adhesive layer on the single side of ethylene glycol terephthalate (PET) resin film.It is fitted on adhesive layer for protecting
The adhesive layer, stripping film by lift-off processing are protected, until fitting on optical component.
In addition, for the optical components such as polarizer, phase plate, antireflection film, due to being bonded surface protection film
In the state of carry out the product inspection that optical assessments are mixed into etc. with display capabilities, tone, contrast, the impurity of LCD panel
It tests, so, as the performance requirement to 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, antireflection film, companion
Electrostatic is removed with caused by the electrostatic occurred when removing 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 which adhesive layer has excellent antistatic property.
In addition, in adhesive surface protective film on the optical components such as polarizer, phase plate, antireflection film, due to various
Reason, the case where having temporarily stripping surface protection film and re-paste surface protection film again.At this time, it is desirable that surface protection
Film has the characteristic (re-workability) for being easy to be stripped down from the optical component of adherend.In addition, at this time, it is desirable that surface is protected
The adhesive layer of cuticula does not pollute adherend, that is, requires not that there is a phenomenon where so-called glue residues.
In addition, when removing surface protection film from optical components such as final polarizer, phase plate, antireflection films, it is desirable that
It can rapidly remove.I.e., it is desirable that cohesive force is because the variation of peeling rate is small, in order to even if in the case where high speed is removed
It can rapidly remove.
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 the peeling rate of low-speed region and high-speed region, the balance of cohesive force is obtained；
(2) generation of glue residue is prevented；(3) there is excellent antistatic property；And (4) have reprocessing (ReWork) property
Energy.
But allow to meet respectively the performance requirement of the adhesive layer to constituting surface protection film, 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) the over-all properties requirement of~(4), is very difficult project.
In the present specification, " 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, balance and (2) of cohesive force are obtained under the peeling rate of low-speed region and high-speed region about (1)
Prevent the generation of glue residue, it is known to suggestion as described below.
With with 7 alkyl below of carbon atom number (methyl) alkyl acrylate and contain the combined polymerization of carboxyl
The copolymer of object is closed as main component, and crosslinking Treatment carried out and manufactured acrylic adhesive layer to it 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 combined polymerization compound with alcoholic extract hydroxyl group, and it bond made of crosslinking Treatment with crosslinking agent
Oxidant layer (patent document 1).
In addition, it is also proposed that a kind of technical solution being provided with following adhesive layers, the adhesive layer be by with
In above-mentioned identical copolymer, coordinate being total to for a small amount of (methyl) alkyl acrylate and the combined polymerization compound containing carboxyl
Polymers is used in combination crosslinking agent to carry out adhesive layer made of crosslinking Treatment to it.But when using it for, surface tension is low and surface
When in the surface protection of smooth plastic plate etc., has when processing or the heating of the when of preservation due to generates the peelings such as separation
The problem of releasable difference when problem, the high speed in field hand-manipulated are removed.
In order to solve these problems, it is proposed that a kind of adhesive composition, the adhesive composition are：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 combined polymerization compound containing carboxyl of 1~15 parts by weight and c) carbon atom of 3~100 parts by weight is added
The vinyl esters of the aliphatic carboxylic acid of number 1~5 and obtain the copolymer of monomer mixture, and coordinate into the copolymer above-mentioned
B) adhesive composition (patent document 2) made of the crosslinking agent more than equivalent of the carboxyl of ingredient.
In adhesive composition described in Patent Document 2, in processing or the when of preservation, not will produce the stripping of separation etc.
Phenomenon, also, bonding force not through when be substantially increased, to releasable it is excellent.Even in addition, long-term preservation, especially
It is long-term preservation under high temperature environment, also can be again removed with small strength, not remain bonding in adherend at this time
Agent, and can again be removed with small strength in the case where high speed is removed.
In addition, for the antistatic property excellent to (3), as the side for assigning antistatic property to surface protection film
Method, it is proposed that 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 sulfonic acid base, sulfuric ester base,
The anionic antistatic agents of the anion base of phosphate base, phosphonic acids base 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 base material film surface.
In addition, about (4) re-workability, such as, it is proposed that a kind of adhesive composition, the adhesive composition are：
Relative to 100 parts by weight propylene acid resins, coordinate 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, it records：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 be 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,
The ongoing change of cohesiveness and bonding force is also small, and excellent effect is also showed that the bonding force of curved surface, therefore has and add again
Work.
In general, if adhesive layer is soft character, glue residue is easy tod produce, re-workability is also easily reduced.That is,
Difficulty is removed after mistake is bonded, and is difficult to re-paste.From this viewpoint, it in order to make it have re-workability, needs
By with functional groups such as carboxyls it is monomer crosslinked in host agent so that adhesive layer is with certain hardness.
In previous technology, it is desirable that 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 there is re-workability
Energy.But allow to the performance requirement for meeting individual term in above-mentioned (1)~(4) respectively, it also cannot be satisfied surface protection film
The over-all properties requirement of (1)~(4) required by adhering agent layer.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Application 63-225677 bulletins；
Patent document 2：Japanese Unexamined Patent Publication 11-256111 bulletins；
Patent document 3：Japanese Unexamined Patent Publication 11-070629 bulletins；
Patent document 4：Japanese Unexamined Patent Publication 8-199130 bulletins.
Invention content
The present invention has been made in view of the above-described circumstances, and project is, provide it is a kind of have excellent antistatic property,
The balance of 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.
In order to solve the above problems, the present invention provides a kind of adhesive composition, is the binder containing antistatic agent
Composition, wherein
The adhesive composition includes to be made with (methyl) alkyl acrylate for the alkyl for being 4~10 with carbon atom number
Acrylic polymer as main component,
Relative to the foregoing acrylic polymer of 100 parts by weight, the aforementioned main component containing 85~99.5 parts by weight
That is (methyl) alkyl acrylate, the combined polymerization monomer containing hydroxyl of 0.5~15 parts by weight and 0.1~5 parts by weight
Crosslinking agent,
Foregoing antistatic agents are the ionic compounds that fusing point is 30~50 DEG C.
In addition, for aforementioned main component i.e. (methyl) alkyl acrylate, it is preferably selected from by (methyl) propylene
Acid butyl ester, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate,
(methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) acrylic acid nonyl ester,
One or more of the compound group that the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate are formed.
In addition, for the aforementioned combined polymerization monomer containing hydroxyl, it is preferably selected from by (methyl) acrylic acid 8- hydroxyls
Base monooctyl ester, the own ester of (methyl) acrylic acid 6- hydroxyls, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxy methacrylates,
The change that N- hydroxyls (methyl) acrylamide, N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide are formed
Close at least one of object group or more.
Additionally, it is preferred that aforementioned crosslinking agent is the isocyanate compound of trifunctional or more.
Also, the present invention provides a kind of adhesive film, is to form adhesive layer on the single or double of resin film to form,
The adhesive layer is that foregoing adhesives composition is made to be crosslinked.
Also, the present invention provides a kind of surface protection film, is to form adhesive layer on the single side of resin film to form, institute
It is that foregoing adhesives composition is made to be crosslinked to state adhesive layer.
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 implementation mode
In the following, illustrating the present invention based on preferred embodiment.
The adhesive composition of the present invention is the adhesive composition containing antistatic agent, wherein the binder combination
Object includes to make acrylic polymer as main component with (methyl) alkyl acrylate for the alkyl for being 4~10 with carbon atom number
Object is closed, relative to the foregoing acrylic polymer of 100 parts by weight, the aforementioned main component containing 85~99.5 parts by weight is
(methyl) alkyl acrylate, the combined polymerization monomer containing hydroxyl of 0.5~15 parts by weight and the friendship of 0.1~5 parts by weight
Join agent, foregoing antistatic agents are the ionic compounds that fusing point is 30~50 DEG C.
Preferably it is 4~10 alkyl containing carbon atom number for making (methyl) alkyl acrylate as main component
(methyl) alkyl acrylate, be preferably selected from by (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl)
Amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid are different
Monooctyl ester, (methyl) 2-EHA, (methyl) acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) acrylic acid
One or more of the compound group that last of the ten Heavenly stems ester is formed.
Relative to the foregoing acrylic polymer of 100 parts by weight, (methyl) alkyl acrylate of main component contains
Amount is preferably 85~99.5 parts by weight.
As the combined polymerization monomer containing hydroxyl, can enumerate：(methyl) acrylic acid 8- hydroxyls monooctyl ester, (methyl) acrylic acid
(methyl) the dihydroxypropyl alkane such as the own ester of 6- hydroxyls, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxy methacrylates
Base ester class；N- hydroxyls (methyl) acrylamide, N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide etc. contain
There is (methyl) acrylic amide etc. of hydroxyl.
It is preferred that the above-mentioned combined polymerization monomer containing hydroxyl is selected from by (methyl) acrylic acid 8- hydroxyls 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) third
In the compound group that acrylamide, N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide are formed at least
More than one.
Relative to the foregoing acrylic polymer of 100 parts by weight, the content of the combined polymerization monomer containing hydroxyl is preferred
For 0.5~15 parts by weight.
For the adhesive composition of the present invention, preferably adhesive composition is set to be handed over when forming adhesive layer
Connection.As the method for causing cross-linking reaction, can also be crosslinked by the photo-crosslinking of ultraviolet light (UV) etc., but preferred binder
Composition contains crosslinking agent.
As crosslinking agent, can enumerate：Isocyanate compounds, two functions more than two functions or trifunctional or trifunctional
More than above epoxides, two functions or trifunctional acrylate compounds, metallo-chelate etc..Wherein, preferably
Polyisocyanate compounds (isocyanate compounds more than two functions or trifunctional), more preferably isocyanide more than trifunctional
Ester compound.
It is preferred that crosslinking agent is 0.1~5 parts by weight relative to the content of the foregoing acrylic polymer of 100 parts by weight.
As isocyanate compound more than trifunctional, as long as at least there are three above isocyanides for tool in a molecule
The polyisocyanate compounds of acid esters (NCO) base.Polyisocyanate compounds include aliphatic category isocyanates, aromatic series
The classification such as kind isocyanate, non-ring type kind isocyanate, ester ring type kind isocyanate, the present invention can be therein any number of
Class.As the specific example of polyisocyanate compounds, can enumerate：Hexamethylene diisocyanate (HDI), isophorone two
The aliphatic categories isocyanate compounds such as isocyanates (IPDI), trimethyl hexamethylene diisocyanate (TMDI)；Diphenyl
Methane diisocyanate (MDI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H6XDI), two
The aromatics isocyanate compounds such as methyl diphenylene diisocyanate (TOID), toluene di-isocyanate(TDI) (TDI).
As isocyanate compound more than trifunctional, can enumerate：Diisocyanates (have two in a molecule
The compound of a NCO bases) biuret modified body or isocyanurate-modified body, with trimethylolpropane (TMP) or glycerine etc.
The addition product of polyalcohol (at least there are three the compounds of the above OH bases for tool in a molecule) more than trivalent is (polyalcohol modified
Body) etc..
The adhesive composition of the present invention contains the ionic compound that fusing point is 30~50 DEG C as antistatic agent.It is antistatic
Agent can be the quaternary ionic compound containing acryloyl group.
Due to the fusing point of these antistatic agents is low and with chain alkyl reason, thus it is speculated that they and acrylic polymer
Compatibility it is high.
It is the antistatic agent of 30~50 DEG C of ionic compound as fusing point, is the ionization with cation and anion
Object is closed, can be enumerated：Cation is pyridylium, glyoxaline cation, pyrimidine cation, pyrazoles cation, pyrrole
Cough up cationic nitrogenous or the phosphorus cation, sulphur cation etc. of cation, ammonium cation etc., anion six
Fluorinated phosphate root (PF6 -), thiocyanate radical (SCN-), benzene sulfonamide acid group (RC6H4SO3 -), perchlorate (ClO4 -), tetrafluoride boron
Acid group (BF4 -) etc. inorganic or organic anion compound.It is preferred that being solid under room temperature (such as 30 DEG C), and pass through selection
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 be enumerated：(2~6 carbon atoms both can not also be with having taken with substituent group for 1- alkyl pyridines
Dai Ji) etc. season pyridylium, (2,4,5 carbon atoms can both have substituent group or can 1,3- dialkylimidazoliums
Not have substituent group) etc. season glyoxaline cation, tetra-allkylammonium etc. quaternary ammonium cation etc..
It is 30~50 DEG C of ionic compound as fusing point relative to the foregoing acrylic polymer of 100 parts by weight
The content of antistatic agent is preferably 0.1~5.0 parts by weight.
It is the ionization with cation and anion as the aforementioned quaternary ionic compound containing acryloyl group
Object is closed, can be enumerated：Cation is (methyl) acryloxyalkyl trialkyl ammonium (R3N+-CnH2n- OCOCQ=CH2, wherein Q
=H or CH3, R=alkyl) etc. the quaternary ammonium containing (methyl) acryloyl group, anion be phosphorus hexafluoride acid group (PF6 -), sulphur cyanogen
Acid group (SCN-), organic sulfonic acid root (RSO3 -), perchlorate (ClO4 -), tetrafluoride borate (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.
Have it is preferred that the aforementioned quaternary ionic compound containing acryloyl group is copolymerized in foregoing acrylic polymer
0.1~5.0 weight %.
It as the specific example of antistatic agent, is not particularly limited, but the ionization for being 30~50 DEG C as aforementioned fusing point
Close object specific example, can enumerate 1- octylpyridiniums dodecyl benzene sulfonate, 1- dococylpyridiniums drone rhodanate,
3- methyl-1s-dococylpyridinium hexafluorophosphate, 1- dococylpyridiniums drone dodecyl benzene sulfonate, 4- methyl-1s-
Octylpyridinium hexafluorophosphate etc..
In addition, the specific example as the aforementioned quaternary ionic compound containing acryloyl group, can enumerate diformazan
Base amino methyl (methyl) acrylate phosphorus hexafluoride acid methyl salt ((CH3)3N+CH2OCOCQ=CH2·PF6 -, wherein, Q=H
Or CH3), bis- (trifyl) acid imide the methyl salt ((CH of dimethyl aminoethyl (methyl) acrylate3)3N+(CH2)2OCOCQ=CH2·(CF3SO2)2N-, wherein Q=H or CH3), bis- (the fluorine sulphonyl of dimethylaminomethyl (methyl) 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 esters, ethyl acetoacetate, acetoacetate monooctyl ester, acetoacetate oil base ester, lauryl acetoacetate, acetoacetate stearoyl
The 'beta '-ketoester of ester etc., the beta-diketon of acetylacetone,2,4-pentanedione, 2,4- acetyl butyryls, benzoyl acetone etc..These are keto-enol tautomerisms
Object is closed, in the adhesive composition using polyisocyanate compounds as crosslinking agent, by by isocyanide possessed by crosslinking agent
Perester radical is closed, and can inhibit the phenomenon that the excess stickiness rising or gelation of adhesive composition after cooperation crosslinking agent,
The storage period of adhesive composition can be extended.
It is preferred that aforementioned cross-linked inhibitor is keto-enol tautomerism compound, it is particularly preferably selected from acetylacetone,2,4-pentanedione, acetyl
It is more than at least one of compound group that ethyl acetate is formed.
In the case where adding aforementioned cross-linked inhibitor, aforementioned propylene of the aforementioned cross-linked inhibitor relative to 100 parts by weight
The content of acids polymers is preferably 1.0~5.0 parts by weight.
The adhesive composition of the present invention can contain crosslinking catalyst.Using polyisocyanate compounds as crosslinking agent
In the case of, as long as crosslinking catalyst plays catalysis to foregoing acrylic polymer with react (cross-linking reaction) of crosslinking agent
The substance of agent effect.As crosslinking catalyst, can enumerate：It is the aminated compounds of tertiary amine etc., organo-tin compound, organic
Organo-metallic compounds such as lead compound, organic zinc compound etc..
It can be enumerated as tertiary amine：Trialkylamine, N, N, N', N'- tetras, N, N- dialkyl amidos alcohol, three second
Alkene diamines, morpholine derivative, bridged piperazine derivatives etc..
As organo-tin compound, can enumerate：The fat of dialkyl tin oxide, the fatty acid salt of dialkyl tin, stannous
Fat hydrochlorate etc..
It is preferred that aforementioned crosslinking catalyst is organo-tin compound, particularly preferably it is selected from by di-n-octyltin oxide, February
It is more than at least one of compound group that cinnamic acid dioctyl tin is formed.
When adding aforementioned crosslinking catalyst, relative to the foregoing acrylic polymer of 100 parts by weight, aforementioned crosslinking is urged
The content of agent is preferably 0.01~0.5 parts by weight.
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, in addition to common siloxane unit (- SiR1 2- O-) except, also include that there is polyethers
The siloxane unit (- SiR of base1(R2O(R3O)nR4)-O-).Here, R1Indicate one or more kinds of alkyl or aryls, R2
And R3Indicate alkylidene, the R of one or more4It indicates (terminal groups) such as one or more kinds of alkyl, acyl groups.As
Polyether-based can be enumerated：Polyethylene oxide base ((C2H4O)n) or polypropylene oxide base ((C3H6O)n) etc. polyoxyalkylenes.
It is preferred that aforementioned polyether modified siloxane compound is the polyether modified siloxane compound that HLB value is 7~12.Separately
Outside, in addition, the foregoing acrylic polymer of preferably aforementioned polyether modified siloxane compound relative to 100 parts by weight
Content is 0.01~0.5 parts by weight.More preferably 0.1~0.5 parts by weight.
HLB refer to such as JIS K3211 (surfactant term) specified in hydrophile-lipophile balance (hydrophily with parent
The ratio of oiliness).
Polyether modified siloxane compound, for example, can obtain by the following method：By hydrosilylation reactions, make tool
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 aforementioned polyether modified siloxane compound is matched with adhesive composition, the bonding of binder 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
The compound of base (poly alkylene oxide), can enumerate the polyether polyol such as polyalkylene glycol and they spread out
Biology.As the alkylidene having in polyalkylene glycol and polyoxyalkylene oxygroup, ethylidene, propylidene, butylidene can be enumerated
Deng, but it is not limited to these.Polyalkylene glycol can also be two kinds in polyethylene glycol, polypropylene glycol, polytetramethylene glycol etc.
The copolymer of above polyalkylene glycol.As the copolymer of polyalkylene 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 derivative of polyalkylene glycol, can enumerate：Polyoxyalkylene monoalky lether, polyoxyalkylene two
The polyoxyalkylene alkyl ethers such as alkyl ether, the polyoxygenateds such as polyoxyalkylene mono alkenyl ether, polyoxyalkylene dialkylene ether
Alkylidene alkene ether, the polyoxyalkylenes aryl ethers such as polyoxyalkylene list aryl ether, polyoxyalkylene diaryl ether are gathered
Alkylidene oxide alkyl phenyl ether, polyoxyalkylene glycol mono fatty acid ester, polyoxyalkylene glycol di fatty acid ester etc.
Polyoxyalkylene glycol aliphatic ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene alkylamine amine gather
Alkylidene oxide diamines etc..
Here, as the alkyl ether in polylalkylene glycol derivatives, can enumerate：The lower alkyl ethers such as methyl ether, ether,
The advanced 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 aliphatic ester in polylalkylene glycol derivatives, can enumerate：
The polyunsaturated fatty acid esters such as acetate, stearate, the unsaturated fatty acid esters such as (methyl) acrylate, oleate.
Preferred, polyethers compound is the compound containing oxyethylene group (ethylene oxide), further preferably polyoxy
Change the compound of vinyl.
When polyether compound has polymerizable functional group, it can also be made to be total to (methyl) acrylic polymer
It is poly-.As polymerizable functional group, the preferably ethylene functional group such as (methyl) acrylic, vinyl, allyl.As with poly-
The polyether compound of He Xing functional groups can be enumerated：Polyalkylene glycol mono (methyl) acrylate, polyalkylene glycol two
(methyl) acrylate, alkoxy polyalkyleneglycol (methyl) acrylate, polyalkylene glycol mono allyl ether, polyalkylene
Glycol diallyl ether, alkoxy polyalkyleneglycol allyl ether, polyalkylene glycol mono vinethene, polyalkylene glycol divinyl
Ether, alkoxy polyalkyleneglycol vinethene etc..
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 promote
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.
By will have carbon atom number be 4~10 alkyl (methyl) alkyl acrylate and containing the combined polymerization of hydroxyl
Property monomer be copolymerized, can synthesize as adhesive composition of the present invention host agent acrylic polymer.To acrylic acid
There is no particular limitation for the polymerization of Type of Collective object, can use the polymerizations appropriate such as polymerisation in solution, emulsion polymerization.
In acrylic polymer, polyalkylene glycol mono (methyl) acrylate monomer, not hydroxyl can also be made
And nitrogenous vinyl monomer, (methyl) alkyl acrylate monomer, the quaternary containing acryloyl group containing alkoxy
Other monomers such as ionic compound are copolymerized.In addition, can not also contain in acrylic polymer for example carboxylic total
The arcylic acid of polymerizable monomer etc. conjunction property monomer.
The present invention adhesive composition, can by above-mentioned acrylic polymer coordinate crosslinking agent, antistatic agent,
Arbitrary additive also appropriate is prepared.
It is preferred that peeling rate 0.3m/min of the adhesive layer in low-speed region made of making foregoing adhesives composition be crosslinked
Under cohesive force be 0.05~0.1N/25mm, cohesive force at the peeling rate 30m/min of high-speed region is 1.0N/25mm
Below.Thereby, it is possible to obtain cohesive force with the small performance of the variation of peeling rate, even also may be used in the case where high speed is removed
To remove rapidly.Also, even if when temporarily removing surface protection film to re-paste, without excessive strength, it is easy to
It is removed from adherend.
It is preferred that the surface resistivity of adhesive layer is 5.0 × 10 made of so that foregoing adhesives composition is crosslinked+11
Ω/ is hereinafter, stripping electrostatic pressure is ± 0~0.5kV.In addition, in the present invention, so-called " ± 0~0.5kV's " is meant that " 0
~-0.5kV " and " 0~+0.5kV ", i.e. " -0.5~+0.5kV ".It, will in the case where the surface resistivity of adhesive layer is big
When surface protection film stripping, the poor performance for the electrostatic that adhesive layer release is generated by electrification.By the surface for making adhesive layer
Resistivity is sufficiently small, can reduce and remove electrostatic with caused by the electrostatic occurred when removing adhesive layer from adherend
Pressure, can inhibit the influence to the electric control circuit of adherend etc..
It is preferred that making the gel point of adhesive layer (binder after crosslinking) made of the adhesive composition crosslinking of the present invention
Number is 95~100%.Since gel fraction is so high, cohesive force will not become too much under the peeling rate of low-speed region, drop
Low the phenomenon that unconverted monomer or oligomer are dissolved out from acrylic polymer, so as to improve re-workability, high temperature/
Durability under high humidity, and inhibit 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 of the present invention is crosslinked.In addition, the surface protection film of the present invention is to form bonding in the single side of resin film
Oxidant layer forms, and the adhesive layer is that the adhesive composition of the present invention is made to be crosslinked.In the adhesion agent composition of the present invention
In, since balance has coordinated each ingredient of above-mentioned acrylic polymer well, so with excellent antistatic property,
The balance of 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, not to be shifted to adherend
Pollution).Thus, it may be preferable to which the surface protection film purposes as polarizer is used.
As adhesive layer base material film, protect the stripping film (diaphragm) of adhesive surface, 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 releasing agent of fluorine class or coating agent, silicon dioxide microparticle, can implement the coating by antistatic agent
Or the antistatic treatment of progress such as it is mixed into.
For stripping film, with the adhesive surface of adhesive layer be bonded on the face of side, implement through silicone, fluorine
The demoulding of the progress such as releasing agent of class is handled.
Embodiment
In the following, illustrating the present invention based on embodiment.
<The manufacture of acrylic polymer>
[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, added into reaction unit 95 parts by weight 2-EHA, 5
The acrylic acid 8- hydroxyl monooctyl esters of parts by weight, and the solvent (ethyl acetate) of 60 parts by weight is added simultaneously.Then, it was dripped by 2 hours
The azodiisobutyronitrile as polymerization initiator for entering 0.1 parts by weight makes it react at 65 DEG C 6 hours, is divided equally again
Son amount for 500,000, acrylic polymer solution 1 for embodiment 1.
[embodiment 2~6 and comparative example 1~3]
In addition to (A) in such as table 1~(B) it is described adjusted separately the composition of monomer other than, with it is above-mentioned be used for embodiment 1
Acrylic polymer solution 1 be carried out similarly operation, obtain for the propylene in embodiment 2~6 and comparative example 1~3
Acids polymers solution.
In addition, in table 1, table 2, (A) is main component (methyl) alkyl acrylate, and (B) is being total to containing hydroxyl
Polymerizable monomer.
<The manufacture of adhesive composition and surface protection film>
[embodiment 1]
1.5 parts by weight 1- octyls are added in acrylic polymer solution 1 to the embodiment 1 manufactured as described above
Pyridine dodecyl benzene sulfonate and after being stirred, the CoronateHX of 1.5 parts by weight is added, and (U ロ ネ ー ト HX, six is sub-
The isocyanuric acid ester of methyl diisocyanate compound) after be stirred, obtain the adhesive composition of embodiment 1.
The adhesive composition is coated on to the stripping film being made of polyethylene terephthalate (PET) film for being coated with silicone resin
On, it is then dried at 90 DEG C and removes solvent, obtain the bonding sheet that adhesive layer thickness is 25 μm.
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 2~6 and comparative example 1~3]
In addition to (C) of such as table 1~(D) it is described adjusted separately the composition of each additive other than, with above-described embodiment 1
Surface protection film be carried out similarly operation and obtain embodiment 2~6 and compare 1~3 surface protection film.
In addition, in table 1, table 2, (C) is crosslinking agent, and (D) is antistatic agent.
Table 1
In table 1, the numerical value in bracket indicates that the total weight organized with (A)~(B) is set as 100 parts by weight and finds out each
The numerical value of Parts by Ingredients.In addition, compound name corresponding with the abbreviation of each ingredient used in table 1 is shown in Table 2.This
Outside, Coronate (U ロ ネ ー ト, registered trademark) HX, Coronate HL and Coronate L is Japanese polyurethane industry strain formula
The trade name of commercial firm (Nippon Polyurethane Industry Co., Ltd.s), Takenate (タ ケ ネ ー ト, registration
Trade mark) D-140N, D-127N, D-110N be Mitsui Chemicals, Inc trade name.
Table 2
<Test method and evaluation>
In the environment of 23 DEG C, 50%RH, after the surface protection film aging 7 days of Examples 1 to 6 and comparative example 1~3,
Stripping film (PET film for being coated with silicone resin) is peeled off, to keep adhesive layer exposed, and as the examination for measuring surface resistivity
Sample.
In turn, it by the exposed surface protection film of the adhesive layer, 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
It is lower to place 12 hours, using thus obtained surface protection film as measurement cohesive force, stripping electrostatic pressure, re-workability and durability
Sample.
<Cohesive force>
Using cupping machine, with the peeling rate of peeling rate (0.3m/min) and high-speed region of low-speed region
(30m/min) removes above-mentioned obtained measurement sample to 180 ° of directions and (surface protection film of 25mm wide is fitted in polarizer
Sample made of surface), peel strength is determined, and using the peel strength as cohesive force.
<Surface resistivity>
After weathering, it fits in before polarizer, peels stripping film (PET film for being coated with silicone resin) off and make adhesive layer
Exposed, using resistivity meter, (for " Hiresta (Ha イ レ ス タ) UP-HT450 ", Mitsubishi of Co., Ltd. chemistry divides trade name
Analysis technology (Mitsubishi Chemical Analytech Co., Ltd.s) manufactures), determine the sheet resistance of adhesive layer
Rate.
<Remove electrostatic pressure>
Using high-precision electrostatic transducer (model SK-035, SK-200, Co., Ltd. Keyemce (Keyence
Corporation) manufacture), it measures when to above-mentioned obtained 180 ° of strippings of tensile speed progress for measuring sample with 30m/min
When, polarizer charges and the voltage (electrostatic pressure) of generation, using the maximum value of measured value as stripping electrostatic pressure.
<Re-workability>
Described (load 500g, back and forth 3 on the surface protection film obtained above for measuring sample with ball pen
It is secondary) after, surface protection film is removed from polarizer, observes the surface of polarizer, confirmation is not transferred the pollution to polarizer.Reprocessing
The evaluation criteria of property："○" is evaluated as when not transferring the pollution to polarizer；When confirming the track described along ball pen extremely
It is few to being evaluated as " △ " when local transfer pollution；When confirming that there is pollution transportation in the track described along ball pen and from bonding
Agent surface is evaluated as "×" when also confirming the disengaging for having binder.Re-workability is had rated according to said reference.
<Durability>
Above-mentioned obtained measurement 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 measure cohesive force, confirmation does not increase more significantly compared with initial stage cohesive force.It is durable
The evaluation criteria of property：Cohesive force after experiment 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 "×".Durability is had rated according to said reference.
It will be evaluation result is shown in table in 3.In addition, in surface resistivity, " m × 10 are indicated by " mE+n "+n" (its
In, m is arbitrary real number, and n is positive integer).
Table 3
For the surface protection film of Examples 1 to 6, the cohesive force at the peeling rate 0.3m/min of low-speed region is
0.05~0.1N/25mm, the cohesive force at the peeling rate 30m/min of high-speed region is 1.0N/25mm or less；Sheet resistance
Rate is 5.0 × 10+11Ω/ is hereinafter, stripping electrostatic pressure is ± 0~0.5kV；Also, exist across adhesive layer using ball pen
It after surface protection film is described, does not transfer the pollution to adherend, and gives 250 in the environment of 60 DEG C, 90%RH
Durability after hour placement is also excellent.
That is, meeting the performance requirement of following whole simultaneously：(1) under the peeling rate for obtaining low-speed region and high-speed region
Cohesive force balance；(2) generation of glue residue is prevented；(3) there is excellent antistatic property；And (4) have
Cycling processability.
For the surface protection film of comparative example 1, it may be possible to due to (methyl) alkyl acrylate of main component is very few,
The excessive reason of the combined polymerization monomer of hydroxyl, the cohesive force under the peeling rate 0.3m/min of low-speed region is small, surface
Resistivity and stripping electrostatic pressure are high, and durability is poor.
For the surface protection film of comparative example 2, it may be possible to due to (methyl) alkyl acrylate of main component is very few,
Combined polymerization monomer containing hydroxyl is excessive and is free of the reason of antistatic agent, and the peeling rate in low velocity region is
Cohesive force under 0.3m/min is small, and surface resistivity and stripping electrostatic pressure are high, and durability is poor.
For the surface protection film of comparative example 3, it may be possible to due to the reason without crosslinking agent and antistatic agent,
Cohesive force under the peeling rate 0.3m/min of low-speed region and the cohesive force mistake under the peeling rate 30m/min of high-speed region
Greatly, surface resistivity and stripping electrostatic pressure height, re-workability and durability are poor.
As described above, in the surface protection film of comparative example 1~3, the performance requirement of following whole can not be met simultaneously：
(1) balance of the cohesive force under the peeling rate of low-speed region and high-speed region is obtained；(2) hair of glue residue is prevented
It is raw；(3) there is excellent antistatic property；And (4) have cycling processability.
Claims (3)
1. a kind of surface protection film, which is characterized in that it is to form adhesive layer in the single or double of resin film and form, it is described viscous
It is that the adhesive composition containing acrylic polymer, crosslinking agent and antistatic agent is made to be crosslinked to tie oxidant layer,
The acrylic polymer with (methyl) alkyl acrylate for the alkyl for being 4~10 with carbon atom number be mainly at
Point, by being (first relative to the main component that the acrylic polymer of 100 parts by weight is 85~99.5 parts by weight
Base) alkyl acrylate and 5~15 parts by weight the combined polymerization monomer containing hydroxyl be copolymerized obtained by copolymer structure
At,
Relative to the acrylic polymer of 100 parts by weight, the adhesive composition contains the institute of 0.1~5 parts by weight
Crosslinking agent is stated,
The crosslinking agent is the isocyanate compound of trifunctional or more,
The antistatic agent is that fusing point is 30~50 DEG C and is the ionic compound of solid when temperature is 30 DEG C, and for selected from
By 1- octylpyridiniums dodecyl benzene sulfonate, 1- dococylpyridiniums rhodanate, 3- methyl-1s-dococylpyridinium
Hexafluorophosphate, 1- dococylpyridiniums dodecyl benzene sulfonate, 4- methyl-1s-octylpyridinium hexafluorophosphate with
And one or more of the group that dimethylaminomethyl (methyl) acrylate phosphorus hexafluoride acid methyl salt is formed,
The acrylic polymer does not contain arcylic acid and closes property monomer,
Cohesive force of the adhesive layer at the peeling rate 0.3m/min of low-speed region is 0.05~0.1N/25mm, in height
Cohesive force under the peeling rate 30m/min in fast region is 1.0N/25mm or less.
2. surface protection film as described in claim 1, wherein the main component is that (methyl) alkyl acrylate is to be selected from
In by (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (first
Base) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (first
Base) in the compound group that is formed of acrylic acid nonyl ester, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate it is a kind of with
On.
3. surface protection film as claimed in claim 1 or 2, wherein the combined polymerization monomer containing hydroxyl is to be selected from
By (methyl) acrylic acid 8- hydroxyls monooctyl ester, the own ester of (methyl) 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) third
It is more than at least one of compound group that acrylamide is formed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-251820 | 2012-11-16 | ||
| JP2012251820A JP6221091B2 (en) | 2012-11-16 | 2012-11-16 | Surface protection film |
| CN201310556382.1A CN103820059A (en) | 2012-11-16 | 2013-11-11 | Adhesive composition, adhesive film, and surface-protective film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310556382.1A Division CN103820059A (en) | 2012-11-16 | 2013-11-11 | Adhesive composition, adhesive film, and surface-protective film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108300365A true CN108300365A (en) | 2018-07-20 |
| CN108300365B CN108300365B (en) | 2020-12-22 |
Family
ID=50755362
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710881073.XA Active CN108300365B (en) | 2012-11-16 | 2013-11-11 | Adhesive composition, adhesive film and surface protective film |
| CN201310556382.1A Pending CN103820059A (en) | 2012-11-16 | 2013-11-11 | Adhesive composition, adhesive film, and surface-protective film |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310556382.1A Pending CN103820059A (en) | 2012-11-16 | 2013-11-11 | Adhesive composition, adhesive film, and surface-protective film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6221091B2 (en) |
| KR (1) | KR101511088B1 (en) |
| CN (2) | CN108300365B (en) |
| TW (3) | TWI630268B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2891693B1 (en) | 2013-06-19 | 2021-09-29 | LG Chem, Ltd. | Pressure-sensitive adhesive composition |
| WO2014204253A1 (en) | 2013-06-19 | 2014-12-24 | 주식회사 엘지화학 | Adhesive composition |
| JP6198275B2 (en) * | 2014-08-29 | 2017-09-20 | 藤森工業株式会社 | Antistatic surface protection film |
| CN107107543B (en) * | 2014-10-30 | 2021-07-20 | Ａｇｃ株式会社 | Substrate with antifouling film |
| WO2017145545A1 (en) * | 2016-02-25 | 2017-08-31 | 株式会社寺岡製作所 | Adhesive agent composition and adhesive tape |
| JP6952497B2 (en) * | 2017-05-31 | 2021-10-20 | 日東電工株式会社 | Adhesive composition, surface protective sheet, and optical member |
| JP6529203B2 (en) * | 2018-05-10 | 2019-06-12 | 藤森工業株式会社 | Release film for antistatic surface protection film |
| WO2021199359A1 (en) * | 2020-03-31 | 2021-10-07 | 株式会社寺岡製作所 | Crosslinking-type adhesive agent composition and adhesive tape |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI328029B (en) * | 2004-10-21 | 2010-08-01 | Lg Chemical Ltd | Acrylic pressure sensitive adhesive with good antistatic property |
| TWI340161B (en) * | 2005-01-19 | 2011-04-11 | Lg Chemical Ltd | Acrylic pressure-sensitive adhesive composition with good re-workability,adhesive sheet,and method of preparing the sheet |
| CN101243153B (en) * | 2005-09-05 | 2010-10-06 | 日东电工株式会社 | Adhesive composition, adhesive sheet and surface-protecting film |
| JP5091434B2 (en) * | 2006-07-04 | 2012-12-05 | 日本カーバイド工業株式会社 | Pressure-sensitive adhesive composition and optical member surface protective film |
| JP2009091406A (en) * | 2007-10-04 | 2009-04-30 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition and surface protection film |
| JP4963485B2 (en) | 2008-04-07 | 2012-06-27 | 綜研化学株式会社 | Adhesive composition for polarizing plate and method for producing the same |
| JP5311342B2 (en) * | 2009-02-09 | 2013-10-09 | 綜研化学株式会社 | Antistatic pressure-sensitive adhesive composition and antistatic film |
| JP5623020B2 (en) * | 2009-02-27 | 2014-11-12 | 日東電工株式会社 | Adhesive composition, adhesive layer, and adhesive sheet |
| JP2011168751A (en) * | 2010-02-22 | 2011-09-01 | Nitto Denko Corp | Surface protective film |
| KR101177563B1 (en) * | 2010-05-03 | 2012-08-27 | (주)신명에이치엠에스 | cutting device for welding bead of T-profile using a steel curtainwall |
| KR101279394B1 (en) * | 2010-06-01 | 2013-07-04 | 동우 화인켐 주식회사 | Adhesive composition and polarizing plate comprising the same |
| JP5723618B2 (en) * | 2011-02-04 | 2015-05-27 | 日東電工株式会社 | Adhesive sheet and surface protective film |
| JP5683370B2 (en) * | 2011-04-22 | 2015-03-11 | 藤森工業株式会社 | Adhesive composition and surface protective film |
| JP5683369B2 (en) * | 2011-04-22 | 2015-03-11 | 藤森工業株式会社 | Adhesive composition and surface protective film |
| CN102352206A (en) * | 2011-09-06 | 2012-02-15 | 烟台德邦电子材料有限公司 | Pressure-sensitive adhesive for polaroid |
| JP5906064B2 (en) * | 2011-11-21 | 2016-04-20 | 藤森工業株式会社 | Adhesive composition and surface protective film |
| JP5882774B2 (en) * | 2012-02-13 | 2016-03-09 | 藤森工業株式会社 | Adhesive composition, adhesive film and surface protective film |
| JP2013163783A (en) * | 2012-02-13 | 2013-08-22 | Fujimori Kogyo Co Ltd | Adhesive composition, adhesive film and surface-protecting film |
| JP5879160B2 (en) * | 2012-03-06 | 2016-03-08 | 藤森工業株式会社 | Adhesive composition and surface protective film |
| JP5909137B2 (en) * | 2012-04-05 | 2016-04-26 | 藤森工業株式会社 | Adhesive composition and surface protective film |
| JP5879208B2 (en) * | 2012-06-20 | 2016-03-08 | 藤森工業株式会社 | Adhesive composition and surface protective film |
| JP6268407B2 (en) * | 2012-07-27 | 2018-01-31 | 藤森工業株式会社 | Adhesive composition and surface protective film |
-
2012
- 2012-11-16 JP JP2012251820A patent/JP6221091B2/en active Active
-
2013
- 2013-11-06 KR KR20130134208A patent/KR101511088B1/en active IP Right Grant
- 2013-11-11 TW TW104118878A patent/TWI630268B/en active
- 2013-11-11 CN CN201710881073.XA patent/CN108300365B/en active Active
- 2013-11-11 TW TW102140934A patent/TWI491719B/en active
- 2013-11-11 TW TW105136369A patent/TWI640592B/en active
- 2013-11-11 CN CN201310556382.1A patent/CN103820059A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014098128A (en) | 2014-05-29 |
| CN108300365B (en) | 2020-12-22 |
| JP6221091B2 (en) | 2017-11-01 |
| TW201534708A (en) | 2015-09-16 |
| TWI491719B (en) | 2015-07-11 |
| TW201708476A (en) | 2017-03-01 |
| KR101511088B1 (en) | 2015-04-10 |
| TWI640592B (en) | 2018-11-11 |
| CN103820059A (en) | 2014-05-28 |
| KR20140063417A (en) | 2014-05-27 |
| TW201432036A (en) | 2014-08-16 |
| TWI630268B (en) | 2018-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103834328B (en) | Adhesive composition, adhesive film and surface protection film | |
| CN104419358B (en) | Adhesive composition, adhesive film and surface protection film | |
| CN103571400B (en) | Adhesive composition and surface protection film | |
| CN103509502B (en) | Adhesive composition and surface protection film | |
| JP5683369B2 (en) | Adhesive composition and surface protective film | |
| JP5906064B2 (en) | Adhesive composition and surface protective film | |
| CN108300365A (en) | Adhesive composition, adhesive film and surface protection film | |
| CN103820058B (en) | Adhesive composition, adhesive film, and surface-protective film | |
| CN103131357B (en) | Adhesive composition and surface-protective adhesive film | |
| CN102746810B (en) | Adhesive combination and surface protective film | |
| CN104650779A (en) | Adhesive composition and surface protection film | |
| CN105001815A (en) | Binder composition and surface protective film | |
| CN104449481A (en) | Adhesive composition and surface protection film | |
| CN104342072B (en) | Adhesive composition, adhesive film and surface protection film | |
| JP2015091988A (en) | Adhesive agent composition and surface protective film | |
| JP2019196501A (en) | Surface protective film | |
| JP7496451B2 (en) | Pressure-sensitive adhesive composition, pressure-sensitive adhesive film, and surface protection film for polarizing plate | |
| JP6573701B2 (en) | Surface protection film | |
| JP7416893B2 (en) | surface protection film | |
| JP6240275B2 (en) | Surface protection film | |
| JP6374565B2 (en) | Surface protection film | |
| JP6999735B2 (en) | Surface protective film | |
| JP6130530B2 (en) | Adhesive layer and surface protective film | |
| JP2016113623A (en) | Adhesive composition, adhesive film and surface protective film | |
| JP2018044170A (en) | Surface protective film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |