CN103820058A - Adhesive composition, adhesive film, and surface-protective film - Google Patents
Adhesive composition, adhesive film, and surface-protective film Download PDFInfo
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- CN103820058A CN103820058A CN201310556876.XA CN201310556876A CN103820058A CN 103820058 A CN103820058 A CN 103820058A CN 201310556876 A CN201310556876 A CN 201310556876A CN 103820058 A CN103820058 A CN 103820058A
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- methyl
- adhesive composition
- vinylformic acid
- ester
- 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
-
- 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
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 invention provides a kind of adhesive composition with antistatic property and adopt this adhesive composition at least one side of resin molding, to form adhesive film and the surface protection film of the adhesive layer with antistatic property.
In addition, the present invention relates to a kind of surface protection film of the manufacturing process for liquid-crystal display.More specifically, the present invention relates to a kind of surperficial surface protection film adhesive composition that sticks on the optics such as Polarizer, polarizer, antireflection film that forms liquid-crystal display, and use the surface protection film of this adhesive composition.
Adhesive film of the present invention and surface protection film have good especially antistatic property.Therefore, it is applied to easily to produce on the surface of the plastic film of static as the blooming of the Polarizer of component parts, polarizer, antireflection film etc., to protect this surface.
Background technology
All the time, as forming in the manufacturing process of the optics such as Polarizer, polarizer, antireflection film of parts of liquid-crystal display, on the surface of optics, paste the surface protection film for temporary protection.This surface protection film only uses in the operation of manufacturing optics, in the time that optics is inserted to liquid-crystal display, it is peeled off and is removed from optics.Because this surface protection film for the protection of optical component surfaces only uses in manufacturing process, therefore, be conventionally also known as " operation film ".
For so manufacturing the surface protection film using in the operation of optics, on the one side with the polyethylene terephthalate of optical transparence (PET) resin molding, be formed with adhesive layer.On adhesive layer, be fitted with for the protection of stripping film this adhesive layer, process lift-off processing, until fit on optics.
In addition; for opticses such as Polarizer, polarizer, antireflection films; the examination and test of products of optical assessment such as sneak into owing to following display capabilities, tone, contrast gradient, the impurity of LCD panel under the state of surface protection film of having fitted; so; as the performance requriements of effects on surface protective membrane, require in adhesive layer without bubble, impurity.
In addition; in recent years; from the opticses such as Polarizer, polarizer, antireflection film when stripper surface protective membrane; be accompanied by occur when being peeled off adhesive layer by adherend static produced peels off static; likely can have influence on the fault of the electric control circuit of liquid-crystal display; therefore, require adhesive layer to there is good antistatic property.
In addition, on the opticses such as Polarizer, polarizer, antireflection film when adhesive surface protective membrane, due to a variety of causes, can there is temporary transient stripper surface protective membrane and the situation of adhesive surface protective membrane again again.Now, require surface protection film to there is the easily characteristic (re-workability) from being stripped down by the optics of adherend.In addition, now, require the adhesive layer of surface protection film not pollute by adherend, require not occur the phenomenon of so-called glue residue.
In addition, during from optics stripper surface protective membranes such as final Polarizer, polarizer, antireflection films, requirement can be peeled off rapidly.That is, require cohesive force because of the variation of peeling rate little, even if so that also can peel off rapidly in the situation that peeling off at a high speed.
So, in recent years, maneuverable viewpoint during from use surface protection film, requires the adhesive layer that forms surface protection film to have following performance: (1), under the peeling rate of low-speed region and high-speed region, obtains bonding equilibrium of forces; (2) prevent the generation of glue residue; (3) there is good antistatic property; And (4) have reprocessing (ReWork) performance.
But; allow to meet respectively the performance requriements of the adhesive layer to forming surface protection film;; allow to meet respectively the indivedual performance requriementss in above-mentioned (1)～(4); but the over-all properties requirement of (1) that the adhesive layer of the surface protection film that simultaneously meets the demands has～(4) is very difficult problem.
In this manual, " low-speed region " refers near the region of peeling rate 0.3m/min; " high-speed region " refers near the region of peeling rate 30m/min.
For example, obtain bonding equilibrium of forces and (2) and prevent the generation of glue residue about (1) under the peeling rate of low-speed region and high-speed region, known have a suggestion as described below.
At (methyl) alkyl acrylate to there is the alkyl of carbonatoms below 7 with the multipolymer of the copolymerization compound that contains carboxyl as main component, and in the acrylic adhesive layer that with linking agent, it is carried out to crosslinking Treatment and make, in the situation that process is long-time bonding, exist binding agent to being attached to by adherend by adherend one side shifting, and to by the bonding force of adherend through time rising property large problem.For fear of this problem, known have a kind of technical scheme that is provided with following adhesive layer, described adhesive layer is (methyl) alkyl acrylate and the multipolymer of copolymerization compound with alcoholic extract hydroxyl group that uses the alkyl with carbonatoms 8～10, and it is carried out to the adhesive layer (patent documentation 1) that crosslinking Treatment forms with linking agent.
In addition, a kind of technical scheme that is provided with following adhesive layer has also been proposed, described adhesive layer is by multipolymer same as described above, coordinate the multipolymer of a small amount of (methyl) alkyl acrylate and the copolymerization compound that contains carboxyl, and it is carried out to the adhesive layer that crosslinking Treatment forms with linking agent.But; when in the surface protection of using it for the low and ganoid plastic plate of surface tension etc., the poor problem of releasable when thering is heating when adding man-hour or preserve and producing the problem of the peelings such as separation, high speed in field hand-manipulated and peel off.
In order to address these problems, a kind of adhesive composition has been proposed, described adhesive composition is: a) using (methyl) alkyl acrylate of alkyl with carbonatoms 8～10 in (methyl) alkyl acrylate 100 weight parts of main component, add b) the copolymerization compound that contains carboxyl of 1～15 weight part, and c) aliphatic carboxylic acid of the carbonatoms 1～5 of 3～100 weight parts vinyl ester and obtain the multipolymer of monomer mixture, and the adhesive composition (patent documentation 2) forming to the linking agent coordinating in this multipolymer more than the equivalent of carboxyl of above-mentioned b) composition.
In the adhesive composition of recording at patent documentation 2, in the time adding man-hour or preserve, can not produce the peeling of separation etc., and, bonding force not through time significantly rising, thereby releasable is good.In addition, preserve, particularly under hot environment, preserve for a long time even long-term, also can peel off with little strength again, now not residual binding agent on by adherend, even and if also can peel off with little strength in the situation that peeling off at a high speed again.
In addition, the antistatic property good for (3), as the method for giving static resistance for effects on surface protective membrane, has proposed method of sneaking in base material film by static inhibitor etc.As static inhibitor, for example, disclose (a) quaternary ammonium salt, pyridinium salt, there are the various cationic antistatic agents of the primary～cation radicals such as tertiary amino; (b) there is the anionic antistatic agents of the anion-radicals of sulfonic acid base, sulfuric ester base, phosphoric acid ester base, phosphonic acids base etc.; (c) the both sexes static inhibitor of amino acids, amidosulphuric acid ester class etc.; (d) non-ionic antistatic agent of alkamine, glycerols, polyethylene glycols etc.; (e) make static inhibitor as above carry out polymer and quantize (patent documentations 3) such as the Polymer Antistatic Agents obtaining.
In addition, proposed in recent years will be so static inhibitor be directly contained in adhesive layer, rather than be contained in base material film or coat the scheme on base material film surface.
In addition, about (4) re-workability, for example, a kind of adhesive composition has been proposed, described adhesive composition is: with respect to 100 parts by weight of acrylic acid resinoids, coordinate the solidifying agent of the isocyanate ester compound of 0.0001～10 weight part to obtain (patent documentation 4) with specific silicate oligopolymer.
In patent documentation 4, record: the alkyl acrylate using the carbonatoms of alkyl as 2～12 left and right, the carbonatoms of alkyl be as the alkyl methacrylate of 4～12 left and right etc. is as principal monomer composition, can contain the monomer component containing other functional group such as such as carboxylic monomer.Typically, preferably contain above-mentioned principal monomers more than 50 % by weight, and wish that the content of the monomer component that contains functional group is 0.001～50 % by weight, be preferably 0.001～25 % by weight, more preferably 0.01～25 % by weight.The adhesive composition that this patent documentation 4 is recorded, even at high temperature or under hot and humid, the rheological parameters' change with time of its cohesive force and bonding force is also little, and also demonstrates good effect to the bonding force of curved surface, therefore has re-workability.
Conventionally,, if adhesive layer is soft proterties, easily produces glue residue, re-workability and also easily reduce., after mistake laminating, peel off difficulty, and be difficult to again paste.From this viewpoint, in order to make it have re-workability, need to by there is the functional groups such as carboxyl monomer crosslinked in host so that adhesive layer has certain hardness.
In technology in the past, require the adhesive layer that forms surface protection film to there is following performance: under the peeling rate of low-speed region and high-speed region, to obtain bonding equilibrium of forces; There is good antistatic property; And there is cycling processability.But, allow to meet respectively the performance requriements of individual term in above-mentioned (1)～(4), also cannot meet the over-all properties requirement of adhering agent layer desired (1)～(4) of surface protection film.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 63-225677 communique
Patent documentation 2: Japanese kokai publication hei 11-256111 communique
Patent documentation 3: Japanese kokai publication hei 11-070629 communique
Patent documentation 4: Japanese kokai publication hei 8-199130 communique
Summary of the invention
The problem that invention will solve
The present invention In view of the foregoing completes; its problem is, also good adhesive composition, adhesive film and surface protection film of the good and endurance quality of a kind of balance with good antistatic property, cohesive force under the peeling rate of low-speed region and high-speed region and cycling processability is provided.
Solve the method for problem
In order to solve above-mentioned problem, the invention provides a kind of adhesive composition, it is the adhesive composition that contains static inhibitor, wherein,
Described adhesive composition comprise to have carbonatoms be (methyl) alkyl acrylate of 4～10 alkyl as the acrylic polymers of main component,
With respect to the aforementioned acrylic polymers of 100 weight parts, the aforementioned main component that contains 85～98.5 weight parts i.e. (methyl) alkyl acrylate, the copolymerization monomer that contains hydroxyl of 0.1～15 weight part, the copolymerization monomer that contains carboxyl of 0.1～2 weight part and the linking agent of 0.1～5 weight part
Aforementioned static inhibitor is that fusing point is the ionic compound of 30～50 ℃.
In addition, for i.e. (methyl) alkyl acrylate of aforementioned main component, be preferably and be selected from more than one in the compound group being formed by (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate.
In addition, for the aforementioned copolymerization monomer that contains hydroxyl, more than being preferably at least one being selected from the compound group being formed by (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide.
In addition, the aforementioned copolymerization monomer that contains carboxyl, to be selected from by (methyl) vinylformic acid, (methyl) vinylformic acid carboxylic ethyl ester, (methyl) vinylformic acid carboxylic pentyl ester, 2-(methyl) acryloxy ethyl hexahydrophthalic acid, 2-(methyl) acryloxy propyl group hexahydrophthalic acid, 2-(methyl) acryloxy ethyl phthalic acid, 2-(methyl) acryloxy ethyl succsinic acid, 2-(methyl) acryloxy ethyl toxilic acid, carboxyl polycaprolactone list (methyl) acrylate, 2-(methyl) more than one in the compound group that forms of acryloxy ethyl tetrahydrophthalic acid.
In addition, preferred aforementioned linking agent is isocyanate compound more than trifunctional.
And, the invention provides a kind of adhesive film, it is on the single or double of resin molding, to form adhesive layer to form, described adhesive layer is aforementioned adhesive composition to be cross-linked form.
And, the invention provides a kind of surface protection film, it is on the one side of resin molding, to form adhesive layer to form, described adhesive layer is aforementioned adhesive composition to be cross-linked form.
The effect of invention
Based on the present invention, can meet the desired over-all properties of adhesive layer of insurmountable effects on surface protective membrane in the prior art.
Embodiment
Below, based on the present invention is preferred embodiment described.
Adhesive composition of the present invention is the adhesive composition that contains static inhibitor, wherein, it is that (methyl) alkyl acrylate of 4～10 alkyl is as the acrylic polymers of main component that described adhesive composition comprises to have carbonatoms, with respect to the aforementioned acrylic polymers of 100 weight parts, the aforementioned main component that contains 85～98.5 weight parts i.e. (methyl) alkyl acrylate, the copolymerization monomer that contains hydroxyl of 0.1～15 weight part, the copolymerization monomer that contains carboxyl of 0.1～2 weight part and the linking agent of 0.1～5 weight part, aforementioned static inhibitor is that fusing point is the ionic compound of 30～50 ℃.
As (methyl) alkyl acrylate of main component, be preferably and contain (methyl) alkyl acrylate that carbonatoms is 4～10 alkyl, be preferably and be selected from by (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, more than one in the compound group that (methyl) decyl acrylate forms.
With respect to the aforementioned acrylic polymers of 100 weight parts, the content of (methyl) alkyl acrylate of main component is preferably 85～98.5 weight parts.
As the copolymerization monomer that contains hydroxyl, can enumerate: (methyl) vinylformic acid hydroxyalkyl acrylate classes such as (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxy methacrylate; (methyl) acrylic amide that N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide etc. contain hydroxyl etc.
Preferably the above-mentioned copolymerization monomer that contains hydroxyl is more than at least one being selected from the compound group being made up of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide.
With respect to the aforementioned acrylic polymers of 100 weight parts, the content of the copolymerization monomer that contains hydroxyl is preferably 0.1～15 weight part.
As the copolymerization monomer that contains carboxyl, be preferably and be selected from by (methyl) vinylformic acid, (methyl) vinylformic acid carboxylic ethyl ester, (methyl) vinylformic acid carboxylic pentyl ester, 2-(methyl) acryloxy ethyl hexahydrophthalic acid, 2-(methyl) acryloxy propyl group hexahydrophthalic acid, 2-(methyl) acryloxy ethyl phthalic acid, 2-(methyl) acryloxy ethyl succsinic acid, 2-(methyl) acryloxy ethyl toxilic acid, carboxyl polycaprolactone list (methyl) acrylate, 2-(methyl) more than one in the compound group that forms of acryloxy ethyl tetrahydrophthalic acid.
With respect to the aforementioned acrylic polymers of 100 weight parts, the content that preferably contains the copolymerization monomer of carboxyl is 0.1～2 weight part.
For adhesive composition of the present invention, preferably in the time forming adhesive layer, adhesive composition is cross-linked.As causing the method for crosslinking reaction, also can be cross-linked by the photo-crosslinking of ultraviolet (UV) etc., but preferred binder composition contains linking agent.
As linking agent, can enumerate: two senses or isocyanate compound more than trifunctional, two senses or epoxide more than trifunctional, two senses or more than trifunctional acrylic compound, metallo-chelate etc.Wherein, be preferably polyisocyanate compounds (two senses or isocyanate compound more than trifunctional), more preferably isocyanate compound more than trifunctional.
Preferably linking agent is 0.1～5 weight part with respect to the content of the aforementioned acrylic polymers of 100 weight parts.
As isocyanate compound more than trifunctional, as long as at least there is the polyisocyanate compounds of more than three isocyanic ester (NCO) bases in a part.Polyisocyanate compounds comprises the classification such as aliphatic category isocyanic ester, aromatic series kind isocyanate, non-ring type kind isocyanate, ester ring type kind isocyanate, and the present invention can be any kind wherein.As the object lesson of polyisocyanate compounds, can enumerate: the aliphatic category isocyanate compounds such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethyl hexamethylene diisocyanate (TMDI); The aromatic series kind isocyanate compounds such as diphenylmethanediisocyanate (MDI), xylylene vulcabond (XDI), hydrogenation of benzene dimethyl vulcabond (H6XDI), dimethyl diphenylene vulcabond (TOID), tolylene diisocyanate (TDI).
As isocyanate compound more than trifunctional, can enumerate: biuret modified body or the isocyanurate-modified body of diisocyanates (thering is the compound of two NCO bases in a part), the affixture (polyalcohol modified body) of the polyvalent alcohol (at least thering is the compound of more than three OH base in a part) with TriMethylolPropane(TMP) (TMP) or glycerine etc. more than trivalent etc.
It is that the ionic compound of 30～50 ℃ is as static inhibitor that adhesive composition of the present invention contains fusing point.Static inhibitor can be the quaternary ionic compound that contains acryl.
Because the fusing point of these static inhibitor is low and have the cause of chain alkyl, infer that the affinity of they and acrylic polymers is high.
It is the static inhibitor of the ionic compound of 30～50 ℃ as fusing point, it is the ionic compound with positively charged ion and negatively charged ion, can enumerate: positively charged ion is the cationic nitrogenous of pyridylium, glyoxaline cation, pyrimidine positively charged ion, pyrazoles positively charged ion, pyrroles's positively charged ion, ammonium positively charged ion etc. or phosphorus positively charged ion, sulphur positively charged ion etc., and negatively charged ion is phosphorus hexafluoride acid group (PF
6 -), thiocyanate ion (SCN
-), benzene sulfonamide acid group (RC
6h
4sO
3 -), perchlorate (ClO
4 -), tetrafluoride borate (BF
4 -) etc. the compound of inorganic or organic anion.For example, under normal temperature (30 ℃), be preferably solid, and be the compound of 30～50 ℃ by selecting the chain length, substituent position, number etc. of alkyl, can obtaining fusing point.Preferred cationic is quaternary nitrogen positively charged ion, can enumerate: the season pyridylium, 1 of 1-alkyl pyridine (carbon atom of 2～6 both can have substituting group also can not have substituting group) etc., the quaternary ammonium cation of season glyoxaline cation, the tetra-allkylammonium etc. of 3-dialkylimidazolium (carbon atom of 2,4,5 both can have substituting group also can not have substituting group) etc. etc.
With respect to the aforementioned acrylic polymers of 100 weight parts, the content that is the static inhibitor of the ionic compound of 30～50 ℃ as fusing point is preferably 0.1～5.0 weight part.
As the aforementioned quaternary ionic compound that contains acryl, be the ionic compound with positively charged ion and negatively charged ion, can enumerate: positively charged ion is (methyl) acryloxyalkyl trialkyl ammonium (R
3n
+-C
nh
2n-OCOCQ=CH
2, wherein, Q=H or CH
3, R=alkyl) etc. the quaternary ammonium that contains (methyl) acryl, negatively charged ion is phosphorus hexafluoride acid group (PF
6 -), thiocyanate ion (SCN
-), organic sulfonic acid root (RSO
3 -), perchlorate (ClO
4 -), tetrafluoride borate (BF
4 -), containing the imide root (R of F
f 2n
-) etc. the compound of inorganic or organic anion.As the imide root (R containing F
f 2n
-) R
f, can enumerate perfluoroalkyl group sulfonyl, the fluorosulfonyl of trifyl, five fluorine ethylsulfonyls etc.As the imide root containing F, can enumerate two (fluorosulfonyl) imide root ((FSO
2)
2n
-), two (trifyl) imide root ((CF
3sO
2)
2n
-), two (five fluorine ethylsulfonyls) imide root ((C
2f
5sO
2)
2n
-) etc. two alkylsulfonyl imide roots.
Preferably the copolymerization in aforementioned acrylic polymers of the aforementioned quaternary ionic compound that contains acryl has 0.1～5.0 % by weight.
As the object lesson of static inhibitor, be not particularly limited, but be the object lesson of the ionic compound of 30～50 ℃ as aforementioned fusing point, can enumerate 1-octyl group pyridine dodecylbenzene sulfonate, 1-dodecyl pyridinium thiocyanate-, 3-methyl isophthalic acid-dodecyl pyridine hexafluorophosphate, 1-dodecyl pyridinium dodecylbenzene sulfonate, 4-methyl isophthalic acid-octyl group pyridine hexafluorophosphate etc.
In addition, as the object lesson of the aforementioned quaternary ionic compound that contains acryl, can enumerate dimethylaminomethyl (methyl) acrylate phosphorus hexafluoride acid methyl salt ((CH
3)
3n
+cH
2oCOCQ=CH
2pF
6 -, wherein, Q=H or CH
3), two (trifyl) imide methyl salt ((CH of dimethyl aminoethyl (methyl) acrylate
3)
3n
+(CH
2)
2oCOCQ=CH
2(CF
3sO
2)
2n
-, wherein, Q=H or CH
3), two (fluorosulfonyl) imide methyl salt ((CH of dimethylaminomethyl (methyl) acrylate
3)
3n
+cH
2oCOCQ=CH
2(FSO
2)
2n
-, wherein, Q=H or CH
3) etc.
Adhesive composition of the present invention can contain cross-linked inhibitor.As cross-linked inhibitor, can enumerate: the 'beta '-ketoester of methyl acetoacetate, methyl aceto acetate, etheric acid monooctyl ester, etheric acid oil base ester, etheric acid lauryl, etheric acid stearyl ester etc., methyl ethyl diketone, 2, the beta-diketon of 4-hexanedione, benzoyl acetone etc.These are keto-enol tautomerism compounds, in the adhesive composition using polyisocyanate compounds as linking agent, seal by the isocyanate group that linking agent is had, can suppress to coordinate the excess stickiness of adhesive composition after linking agent to rise or the phenomenon of gelation, can extend the storage period of adhesive composition.
Preferred aforementioned cross-linked inhibitor is keto-enol tautomerism compound, more than being particularly preferably at least one being selected from the compound group that methyl ethyl diketone, methyl aceto acetate form.
In the situation that adding aforementioned cross-linked inhibitor, aforementioned cross-linked inhibitor is preferably 1.0～5.0 weight parts with respect to the content of the aforementioned acrylic polymers of 100 weight parts.
Adhesive composition of the present invention can contain crosslinking catalyst.Using polyisocyanate compounds as linking agent in the situation that, crosslinking catalyst is as long as the material that reacts (crosslinking reaction) and play catalyst action to aforementioned acrylic polymers and linking agent.As crosslinking catalyst, can enumerate: organometallic compound such as the aminated compounds of tertiary amine etc., organo-tin compound, organo-lead compound, organic zinc compound etc.
Can enumerate as tertiary amine: trialkylamine, N, N, N', N'-tetraalkyl diamines, N, N-dialkyl amido alcohol, triethylene diamine, morpholine derivative, bridged piperazine derivatives etc.
As organo-tin compound, can enumerate: the soap of dialkyl tin oxide, dialkyl tin, the soap of sub-tin etc.
Preferred aforementioned crosslinking catalyst is organo-tin compound, more than being particularly preferably at least one being selected from the compound group being made up of di-n-octyltin oxide, two dioctyltin laurate.
In the time adding aforementioned crosslinking catalyst, with respect to the aforementioned acrylic polymers of 100 weight parts, the content of aforementioned crosslinking catalyst is preferably 0.01～0.5 weight part.
Adhesive composition of the present invention can contain polyether modified siloxane compound.Polyether modified siloxane compound is the silicone compounds with polyether-based, except common siloxane unit (SiR
1 2-O-) outside, the siloxane unit (SiR with polyether-based also comprised
1(R
2o (R
3o)
nr
4)-O-).At this, R
1represent one or more alkyl or aryl, R
2and R
3represent one or more alkylidene group, R
4represent one or more alkyl, acyl group etc. (terminal group).Can enumerate as polyether-based: polyoxyethylene thiazolinyl ((C
2h
4o)
n) or polyoxytrimethylene base ((C
3h
6o)
n) etc. polyoxyalkylene.
Preferred aforementioned polyether modified siloxane compound is that HLB value is 7～12 polyether modified siloxane compound.In addition, in the time adding, preferred aforementioned polyether modified siloxane Compound Phase is 0.01～0.5 weight part for the content of the aforementioned acrylic polymers of 100 weight parts.More preferably 0.1～0.5 weight part.
HLB refers to such as JIS K3211(tensio-active agent term) etc. in regulation hydrophilic-lipophilic balance (wetting ability and oil loving ratio).
Polyether modified siloxane compound, for example, can obtain by the following method: by hydrosilylation reactions, make the organic compound with unsaturated link(age) and polyoxyalkylene be grafted on the main chain of the organopolysiloxane with silylation and obtain.Particularly, can enumerate: dimethyl siloxane-methyl (polyoxyethylene) silicone copolymers, dimethyl siloxane-methyl (polyoxyethylene) siloxanes-methyl (polyoxytrimethylene) silicone copolymers, dimethyl siloxane-methyl (polyoxytrimethylene) silicone copolymers etc.
By aforementioned polyether modified siloxane compound is matched with to adhesive composition, can improve cohesive force and the cycling processability of binding agent.
Adhesive composition of the present invention can contain polyether compound.As polyether compound, be the compound with polyalkylene oxide base (poly alkylene oxide), can enumerate the polyether glycols such as polyalkylene glycol and their derivative.As the alkylidene group having in polyalkylene glycol and polyalkylene oxide base, can enumerate ethylidene, propylidene, butylidene etc., but be not limited to these.Polyalkylene glycol can be also the multipolymer of the two or more polyalkylene glycol in polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol etc.As the multipolymer of polyalkylene glycol, can enumerate polyethylene glycol-propylene glycol, polyethylene glycol-butyleneglycol, polypropylene glycol-polytetramethylene glycol, polyethylene glycol-propylene glycol-polytetramethylene glycol etc., this multipolymer can be segmented copolymer, random copolymers.
As the derivative of polyalkylene glycol, can enumerate: polyoxyalkylene monoalky lether, the polyoxyalkylene alkyl oxides such as polyoxyalkylene dialkyl ether, polyoxyalkylene mono alkenyl ether, the polyoxyalkylene alkene ethers such as polyoxyalkylene dialkylene ether, polyoxyalkylene list aryl ethers, the polyoxyalkylene aryl ethers such as polyoxyalkylene diaryl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene glycol mono fatty acid ester, the polyoxyalkylene glycol fatty acid esters such as polyoxyalkylene glycol di fatty acid ester, polyoxyalkylene sorbitan-fatty acid ester, polyoxyalkylene alkylamine, polyoxyalkylene diamines etc.
At this, as the alkyl oxide in polylalkylene glycol derivatives, can enumerate: the lower alkyl ether such as methyl ether, ether, the senior alkyl oxides such as lauryl ether, octadecyl ether.As the alkene ether in polylalkylene glycol derivatives, can enumerate vinyl ether, allyl ethers, oleyl ether etc.In addition, as the fatty acid ester in polylalkylene glycol derivatives, can enumerate: the polyunsaturated fatty acid esters such as acetic ester, stearate, the unsaturated fatty acid esters such as (methyl) acrylate, oleic acid ester.
Preferred, polyethers compound is the compound that contains oxyethylene group (ethylene oxide), more preferably contains the compound of polyoxyethylene thiazolinyl.
In the time that polyether compound has polymerizability functional group, also can make itself and (methyl) acrylic polymers carry out copolymerization.As polymerizability functional group, be preferably the ethene functional groups such as (methyl) propenyl, vinyl, allyl group.As the polyether compound with polymerizability functional group, can enumerate: polyalkylene glycol mono (methyl) acrylate, polyalkylene glycol two (methyl) acrylate, alkoxyl group polyalkylene glycol (methyl) acrylate, polyalkylene glycol mono allyl ether, polyalkylene glycol diallyl ether, alkoxyl group polyalkylene glycol allyl ether, polyalkylene glycol mono Vinyl Ether, polyalkylene glycol divinyl ether, alkoxyl group polyalkylene glycol Vinyl Ether etc.
And, as other composition, can suitably coordinate contain alkylene oxide (alkylene oxide) can copolymerization the known additive such as (methyl) Acrylic Acid Monomer, (methyl) acrylamide monomer, dialkyl group substituted acrylamide monomer, tensio-active agent, curing catalyst, softening agent, weighting agent, curing inhibitors, processing aid, antiaging agent, antioxidant.These both may be used singly or in combination of two or more use.
By being that (methyl) alkyl acrylate of 4～10 alkyl and the copolymerization monomer that contains hydroxyl and the copolymerization monomer that contains carboxyl carry out copolymerization by thering is carbonatoms, can synthesize the acrylic polymers as the host of adhesive composition of the present invention.To the polymerization process of acrylic polymers, there is no particular limitation, can use the suitable polymerization process such as solution polymerization, letex polymerization.
In acrylic polymers, also can make polyalkylene glycol mono (methyl) acrylate monomer, hydroxyl and nitrogenous vinyl monomer, other monomer such as (methyl) alkyl acrylate monomer, the quaternary ionic compound that contains acryl that contains alkoxyl group do not carry out copolymerization.
Adhesive composition of the present invention can be by coordinating linking agent, static inhibitor, also having suitable any additive to prepare in aforesaid propylene acids polymkeric substance.
Preferably making the cohesive force of the crosslinked adhesive layer forming of aforementioned adhesive composition under the peeling rate 0.3m/min of low-speed region is 0.05～0.1N/25mm, and the cohesive force under the peeling rate 30m/min of high-speed region is below 1.0N/25mm.Thus, can obtain cohesive force with the little performance of the variation of peeling rate, even also can peel off rapidly in the situation that peeling off at a high speed.And, even, also without excessive strength, be easy to from being peeled off by adherend when temporary transient stripper surface protective membrane in order again to paste.
Preferably make surface resistivity that aforementioned adhesive composition is cross-linked the adhesive layer forming 5.0 × 10
+ 11below Ω/, peeling off static voltage is ± 0～0.5kV.In addition, in the present invention, the meaning of so-called " ± 0～0.5kV " refers to " 0～-0.5kV " and " 0～+ 0.5kV ", i.e. " 0.5～+ 0.5kV ".In the case of the surface resistivity of adhesive layer is large, when surface protection film is peeled off, adhesive layer discharges the poor performance because of the charged static producing.By making the surface resistivity of adhesive layer enough little, can reduce follow occur when being peeled off adhesive layer by adherend static produced peels off static voltage, can suppress by the impact of electric control circuit of adherend etc.
Preferably making the gel fraction of the crosslinked adhesive layer forming of adhesive composition of the present invention (binding agent after crosslinked) is 95～100%.Because gel fraction is so high, the in the situation that of low peeling rate, cohesive force can not become excessive, reduce the phenomenon of from acrylic polymers stripping unconverted monomer or oligomer, thereby can improve the weather resistance under re-workability, high temperature/high humidity, and suppressed by the pollution of adherend.
Adhesive film of the present invention is to form adhesive layer at the single or double of resin molding to form, and described adhesive layer is adhesive composition of the present invention to be cross-linked form.In addition, surface protection film of the present invention is to form adhesive layer at the one side of resin molding to form, and described adhesive layer is adhesive composition of the present invention to be cross-linked form.In adhesion agent composition of the present invention, because balance has coordinated each composition of aforesaid propylene acids polymkeric substance well, so it is good to have the balance of good antistatic property, clinging power under the peeling rate of low-speed region and high-speed region.And endurance quality and cycling processability be good (after adhesive layer is described on surface protection film, not having to being transferred the pollution by adherend with ballpoint pen).Therefore, can preferably be used as the surface protection film purposes of Polarizer.
As the base material film of adhesive layer, the stripping film (barrier film) of protection adhesive surface, can use the resin moldings such as polyester film etc.
For base material film, can be on the face contrary with being formed with adhesive layer one side of resin molding, implement the antifouling processing undertaken by releasing agent or coating-forming agent, the silicon dioxide microparticle etc. of silicone, fluorine class, the antistatic treatment that can implement the coating by static inhibitor or sneak into etc. carried out.
For stripping film, fitting on the face of a side with the adhesive surface of adhesive layer, implement the demoulding processing that releasing agent by silicone, fluorine class etc. carries out.
Embodiment
Illustrate the present invention based on embodiment below.
The manufacture > of < acrylic polymers
[embodiment 1]
Import nitrogen to being furnished with in the reaction unit of agitator, thermometer, reflux exchanger and nitrogen ingress pipe, thus with nitrogen replacement the air in reaction unit.Then, in reaction unit, add the 2-EHA of 93 weight parts, the vinylformic acid 8-hydroxyl monooctyl ester of 5.5 weight parts, the vinylformic acid of 1.5 weight parts, and added the solvent (ethyl acetate) of 60 weight parts simultaneously.Then, through within 2 hours, splashing into the Diisopropyl azodicarboxylate as polymerization starter of 0.1 weight part, at 65 ℃, make its reaction 6 hours, to have obtained weight-average molecular weight be 500,000, for the acrylic polymers solution 1 of embodiment 1.
[embodiment 2～6 and comparative example 1～3]
Except having adjusted respectively the composition of each monomer as described in (A) as in table 1～(C), similarly operate with the above-mentioned acrylic polymers solution 1 for embodiment 1, obtained the acrylic polymers solution for embodiment 2～6 and comparative example 1～3.
In addition, in table 1, table 2, (A) being (methyl) alkyl acrylate of main component, (B) being the copolymerization monomer that contains hydroxyl, is (C) the copolymerization monomer that contains carboxyl.
The manufacture > of < adhesive composition and surface protection film
[embodiment 1]
To the acrylic polymers solution 1 according to the embodiment of manufacture described above 1, after adding 2.0 weight part 1-octyl group pyridine dodecylbenzene sulfonates and stirring, add the Coronate HX(コ ロ ネ ー ト HX of 1.5 weight parts, the isocyanuric acid ester of hexamethylene diisocyanate compound) after be uniformly mixed, obtained the adhesive composition of embodiment 1.This adhesive composition is coated on the stripping film being made up of the polyethylene terephthalate that scribbles silicone resin (PET) film, then at 90 ℃, be dried and remove solvent, having obtained adhesive layer thickness is the bonding sheet of 25 μ m.
Then; prepare to implement on a face polyethylene terephthalate (PET) film of antistatic treatment and antifouling processing; and bonding sheet is transferred to this polyethylene terephthalate (PET) film with implement on the opposing face of face of antistatic treatment and antifouling processing, obtained the surface protection film of the embodiment 1 of the stacked formation with " the PET film/adhesive layer/stripping film (scribbling the PET film of silicone resin) that implements antistatic treatment and antifouling processing ".
[embodiment 2～6 and comparative example 1～3]
Except having adjusted respectively the composition of each additive as described in (D) of table 1～(E), similarly operate with the surface protection film of above-described embodiment 1 and obtained embodiment 2～6 and 1～3 surface protection film relatively.
In addition, in table 1, table 2, (D) being linking agent, is (E) static inhibitor.
Table 1
In table 1, the numerical value in bracket all represents to be made as 100 weight parts and the numerical value of each composition weight part of obtaining with the total weight of (A)～(C) group.In addition, the compound title corresponding with the abbreviation of the each composition using in table 1 is shown in Table 2.In addition, Coronate(コ ロ ネ ー ト, registered trademark) HX, Coronate HL and Coronate L be (the Nippon Polyurethane Industry Co. of Nippon Polyurethane Industry Co., Ltd., Ltd.) trade name, Takenate(タ ケ ネ ー ト, registered trademark) D-140N, D-127N, D-110N be the trade name of Mitsui Chemicals, Inc.
Table 2
< test method and evaluation >
Under 23 ℃, the environment of 50%RH, by after aging the surface protection film of embodiment 1～6 and comparative example 1～3 7 days, peel stripping film (scribbling the PET film of silicone resin) off, thereby adhesive layer is exposed, and as the sample of measuring surface resistivity.
And then; the surface protection film that this adhesive layer is exposed; fit in the surface that sticks on the Polarizer on liquid crystal cells by adhesive layer; place and after 1 day, under 50 ℃, 5 normal atmosphere, carry out pressure kettle and process 20 minutes; further at room temperature place 12 hours, using the surface protection film obtaining thus as measuring cohesive force, peeling off the sample of static voltage, re-workability and weather resistance.
< cohesive force >
Adopt tensile testing machine; with the peeling rate (0.3m/min) of low-speed region and the peeling rate (30m/min) of high-speed region; peel off above-mentioned obtained mensuration sample (surface protection film wide 25mm is fitted in to the sample that Polarizer surface forms) to 180 ° of directions; measure stripping strength, and using this stripping strength as cohesive force.
< surface resistivity >
After aging, fit in Polarizer before, peel stripping film (scribbling the PET film of silicone resin) off and adhesive layer is exposed, adopt resistivity meter (trade name be " Hiresta(Ha イ レ ス タ) UP-HT450 ", Mitsubishi Chemical of Co., Ltd. analytical technology (Mitsubishi Chemical Analytech Co., Ltd.) manufacture), measure the surface resistivity of adhesive layer.
< peels off static voltage >
(model is SK-035, SK-200 to adopt high precision electrostatic transducer, Co., Ltd.'s Keyemce (Keyence Corporation) is manufactured), measure and carry out 180 ° while peeling off with the draw speed of 30m/min when the mensuration sample to above-mentioned obtained, Polarizer charged and produce voltage (static voltage), using the maximum value of measured value as peeling off static voltage.
< re-workability >
On the surface protection film of mensuration sample obtained above, describe after (load be 500g, 3 times back and forth) with ballpoint pen, from Polarizer stripper surface protective membrane, observe the surface of Polarizer, confirm not transfer the pollution to Polarizer.The metewand of re-workability: when be not evaluated as "○" in the time that Polarizer is transferred the pollution; When confirming that the track of describing along ballpoint pen is at least evaluated as " △ " in the time that pollution has been shifted in part; When confirming that the track described along ballpoint pen has pollution transportation and be evaluated as "×" in the time that adhesive surface also confirms to have the disengaging of binding agent.Evaluate re-workability according to said reference.
< weather resistance >
Transfer to be set up and state obtained mensuration sample after 250 hours at 60 ℃, 90%RH environment, its taking-up is placed under room temperature and is placed further 12 hours, then measure cohesive force, the significantly increase of confirming to compare with initial stage cohesive force not.The metewand of weather resistance: when the cohesive force after test is that the average evaluation below 1.5 times of initial stage cohesive force is "○", the average evaluation that exceedes 1.5 times is "×".Evaluate weather resistance according to said reference.
Evaluation result is shown in Table 3.In addition, in surface resistivity, represent " m × 10 by " mE+n "
+ n" (wherein, m is real number arbitrarily, 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, and the cohesive force under the peeling rate 30m/min of high-speed region is below 1.0N/25mm; Surface resistivity is 5.0 × 10
+ 11below Ω/, peeling off static voltage is ± 0～0.5kV; And, use ballpoint pen across adhesive layer after surface protection film is described, not to being transferred the pollution by adherend, and weather resistance after giving placing for 250 hours under 60 ℃, the environment of 90%RH is also good.
, met following whole performance requriements: (1) obtains the balance of the cohesive force under the peeling rate of low-speed region and high-speed region simultaneously; (2) prevent the generation of glue residue; (3) there is excellent antistatic property; And (4) have cycling processability.
For the surface protection film of comparative example 1; may be because main component (methyl) alkyl acrylate be very few, the copolymerization monomer of hydroxyl is too much and not containing the cause of copolymerization monomer with carboxyl; cohesive force under the peeling rate 0.3m/min of its low-speed region is little; surface resistivity and to peel off static voltage high, poor durability.
For the surface protection film of comparative example 2; because the copolymerization monomer that contains carboxyl is many with respect to (methyl) alkyl acrylate content too much and isocyanates solidifying agent of main component; thereby validity period becomes too short and is cross-linked before coating, therefore cannot be coated with.
For the surface protection film of comparative example 3; may be due to not containing the cause of copolymerization monomer, linking agent and static inhibitor with carboxyl, cohesive force under the peeling rate 30m/min of its cohesive force under the peeling rate 0.3m/min of low-speed region and high-speed region is excessive, surface resistivity and peel off that static voltage is high, re-workability and poor durability.
As mentioned above, in the surface protection film of comparative example 1～3, cannot meet following whole performance requriements: (1) obtains the balance of the cohesive force under the peeling rate of low-speed region and high-speed region simultaneously; (2) prevent the generation of glue residue; (3) there is excellent antistatic property; And (4) have cycling processability.
Claims (7)
1. an adhesive composition, it is the adhesive composition that contains static inhibitor, wherein,
Comprise to have carbonatoms and be (methyl) alkyl acrylate of 4～10 alkyl as the acrylic polymers of main component,
With respect to the described acrylic polymers of 100 weight parts, the described main component that contains 85～98.5 weight parts i.e. (methyl) alkyl acrylate, the copolymerization monomer that contains hydroxyl of 0.1～15 weight part, the copolymerization monomer that contains carboxyl of 0.1～2 weight part and the linking agent of 0.1～5 weight part
Described static inhibitor is that fusing point is the ionic compound of 30～50 ℃.
2. adhesive composition as claimed in claim 1, wherein, described main component (methyl) alkyl acrylate be to be selected from more than one in the compound group being formed by (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate.
3. adhesive composition as claimed in claim 1 or 2, wherein, the copolymerization monomer that contains hydroxyl described in is more than at least one being selected from the compound group being made up of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide.
4. the adhesive composition as described in any one in claim 1～3, wherein, the described copolymerization monomer that contains carboxyl, to be selected from by (methyl) vinylformic acid, (methyl) vinylformic acid carboxylic ethyl ester, (methyl) vinylformic acid carboxylic pentyl ester, 2-(methyl) acryloxy ethyl hexahydrophthalic acid, 2-(methyl) acryloxy propyl group hexahydrophthalic acid, 2-(methyl) acryloxy ethyl phthalic acid, 2-(methyl) acryloxy ethyl succsinic acid, 2-(methyl) acryloxy ethyl toxilic acid, carboxyl polycaprolactone list (methyl) acrylate, 2-(methyl) more than one in the compound group that forms of acryloxy ethyl tetrahydrophthalic acid.
5. the adhesive composition as described in any one in claim 1～4, wherein, described linking agent is isocyanate compound more than trifunctional.
6. an adhesive film, it is to form adhesive layer at the single or double of resin molding to form, described adhesive layer is to make in claim 1～5 that the adhesive composition described in any one is crosslinked to be formed.
7. a surface protection film, it is to form adhesive layer at the one side of resin molding to form, described adhesive layer is to make in claim 1～5 that the adhesive composition described in any one is crosslinked to be formed.
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| 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 true CN103820058A (en) | 2014-05-28 |
| CN103820058B CN103820058B (en) | 2017-04-12 |
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| JP (1) | JP6187896B2 (en) |
| KR (2) | KR101554870B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110982447A (en) * | 2019-12-18 | 2020-04-10 | 苏州赛伍应用技术股份有限公司 | Double-sided adhesive tape and preparation method and application thereof |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| TWI620804B (en) * | 2015-04-10 | 2018-04-11 | Mitsubishi Chemical Corporation | Adhesive composition and adhesive using the adhesive composition and adhesive for polarizing plate |
| 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 |
| 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 |
| CN117413037A (en) * | 2021-05-31 | 2024-01-16 | 日东电工株式会社 | Adhesive composition, adhesive, and surface protective film |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060088670A1 (en) * | 2004-10-21 | 2006-04-27 | Se-Ra Kim | Acrylic pressure sensitive adhesive with good antistatic property |
| JP2009251281A (en) * | 2008-04-07 | 2009-10-29 | Soken Chem & Eng Co Ltd | Adhesive composition for polarizing plate and preparation method of the same |
| WO2011152616A2 (en) * | 2010-06-01 | 2011-12-08 | 동우화인켐 주식회사 | Adhesive composition and polarizing plate including same |
| 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 |
| CN102746811A (en) * | 2011-04-22 | 2012-10-24 | 藤森工业株式会社 | Adhesive combination and surface protective film |
| CN103131362A (en) * | 2011-11-21 | 2013-06-05 | 藤森工业株式会社 | Adhesive composition, and surface protection film |
| CN103305157A (en) * | 2012-03-06 | 2013-09-18 | 藤森工业株式会社 | Adhesive composition and surface-protective adhesive film |
| CN103361010A (en) * | 2012-04-05 | 2013-10-23 | 藤森工业株式会社 | Adhesive composition and surface-protective film |
| CN103509502A (en) * | 2012-06-20 | 2014-01-15 | 藤森工业株式会社 | Adhesive composition and surface-protective film |
| CN103571400A (en) * | 2012-07-27 | 2014-02-12 | 藤森工业株式会社 | Adhesive composition and surface-protective adhesive film |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4149473B2 (en) * | 2005-09-21 | 2008-09-10 | サイデン化学株式会社 | Polymer composition for pressure-sensitive adhesive, pressure-sensitive adhesive composition for surface protective film, and surface protective film |
| JP5332315B2 (en) * | 2007-09-03 | 2013-11-06 | 住友化学株式会社 | Optical laminate |
| JP5354673B2 (en) * | 2008-08-11 | 2013-11-27 | 住友化学株式会社 | Optical film with adhesive and optical laminate using the same |
| WO2010143643A1 (en) * | 2009-06-09 | 2010-12-16 | 日本合成化学工業株式会社 | Pressure-sensitive adhesive composition, pressure-sensitive adhesive, pressure-sensitive adhesive for optical member, and optical member with pressure-sensitive adhesive layer obtained using same |
| KR20110130693A (en) * | 2010-05-28 | 2011-12-06 | 동우 화인켐 주식회사 | Adhesive composition and polarizing plate comprising the same |
| JP5716364B2 (en) | 2010-11-29 | 2015-05-13 | 株式会社リコー | Electromechanical transducer, liquid jet head, and method of manufacturing electromechanical transducer |
-
2012
- 2012-11-16 JP JP2012251871A patent/JP6187896B2/en active Active
-
2013
- 2013-11-06 KR KR1020130134209A patent/KR101554870B1/en active IP Right Grant
- 2013-11-11 TW TW102140935A patent/TWI557199B/en active
- 2013-11-11 CN CN201310556876.XA patent/CN103820058B/en active Active
-
2015
- 2015-05-14 KR KR1020150067094A patent/KR101578376B1/en active IP Right Grant
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060088670A1 (en) * | 2004-10-21 | 2006-04-27 | Se-Ra Kim | Acrylic pressure sensitive adhesive with good antistatic property |
| JP2009251281A (en) * | 2008-04-07 | 2009-10-29 | Soken Chem & Eng Co Ltd | Adhesive composition for polarizing plate and preparation method of the same |
| WO2011152616A2 (en) * | 2010-06-01 | 2011-12-08 | 동우화인켐 주식회사 | Adhesive composition and polarizing plate including same |
| CN102746811A (en) * | 2011-04-22 | 2012-10-24 | 藤森工业株式会社 | Adhesive combination 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 |
| CN103131362A (en) * | 2011-11-21 | 2013-06-05 | 藤森工业株式会社 | Adhesive composition, and surface protection film |
| CN103305157A (en) * | 2012-03-06 | 2013-09-18 | 藤森工业株式会社 | Adhesive composition and surface-protective adhesive film |
| CN103361010A (en) * | 2012-04-05 | 2013-10-23 | 藤森工业株式会社 | Adhesive composition and surface-protective film |
| CN103509502A (en) * | 2012-06-20 | 2014-01-15 | 藤森工业株式会社 | Adhesive composition and surface-protective film |
| CN103571400A (en) * | 2012-07-27 | 2014-02-12 | 藤森工业株式会社 | Adhesive composition and surface-protective adhesive film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110982447A (en) * | 2019-12-18 | 2020-04-10 | 苏州赛伍应用技术股份有限公司 | Double-sided adhesive tape and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101554870B1 (en) | 2015-09-22 |
| JP6187896B2 (en) | 2017-08-30 |
| TWI557199B (en) | 2016-11-11 |
| KR101578376B1 (en) | 2015-12-17 |
| CN103820058B (en) | 2017-04-12 |
| JP2014098131A (en) | 2014-05-29 |
| KR20150060641A (en) | 2015-06-03 |
| KR20140063418A (en) | 2014-05-27 |
| TW201432002A (en) | 2014-08-16 |
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