CN103571400B - Adhesive composition and surface protection film - Google Patents
Adhesive composition and surface protection film Download PDFInfo
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- CN103571400B CN103571400B CN201310280729.4A CN201310280729A CN103571400B CN 103571400 B CN103571400 B CN 103571400B CN 201310280729 A CN201310280729 A CN 201310280729A CN 103571400 B CN103571400 B CN 103571400B
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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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
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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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Abstract
The invention provides a kind of there is excellent antistatic property, the excellent and adhesive composition that weather resistance and re-workability are also excellent of the balance of cohesive force under low peeling rate and high peeling rate.Adhesive composition of the present invention is made up of the acrylic polymers of multipolymer, the carbonatoms that the acrylic polymers of described multipolymer contains (A) alkyl be (methyl) acrylate monomer of C4 ~ C10, (B) containing hydroxyl can the monomer of copolymerization and (C) containing carboxyl can the monomer of copolymerization, and, be also the static inhibitor as ionic compound of 30 ~ 80 DEG C containing (D) fusing point.
Description
Technical field
The present invention relates to a kind of for the surface protection film in the manufacturing process of liquid-crystal display.More specifically; the present invention relates to and a kind ofly form the surface of the optics such as Polarizer, polarizer of liquid-crystal display and the surface protection film adhesive composition on the surface for the protection of the optics such as Polarizer, polarizer by being pasted onto, and use the surface protection film of this adhesive composition.
Background technology
All the time, in the manufacturing process of the optics such as Polarizer, polarizer of the parts as formation liquid-crystal display, the adhesive surface protective membrane in order to the surface of temporary protection optics.This surface protection film only uses in the operation manufacturing optics, when optics is inserted liquid-crystal display, it is peeled off from optics and removes.Because this surface protection film for the protection of optical component surfaces only uses in manufacturing process, therefore, be usually also referred to as " operation film ".
For so manufacturing the surface protection film used in the operation of optics; the one side of polyethylene terephthalate (PET) resin molding with optical transparence is formed with adhesive layer; but the stripping film be fitted with on adhesive layer through lift-off processing, to protect this adhesive layer until fit in optics.
In addition; for the optics such as Polarizer, polarizer; owing to carrying out the examination and test of products being mixed into etc. optical assessment with the display capabilities of LCD panel, tone, contrast gradient, impurity under the state of fitting surface protection film; 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 optics such as Polarizer, polarizer during stripper surface protective membrane; along with the stripping electrostatic that the electrostatic occurred when adherend peels off adhesive layer produces; likely can have influence on the fault of the electric control circuit of liquid-crystal display; therefore, require that adhesive layer has excellent antistatic property.
In addition; on the optics such as Polarizer, polarizer during coating surface protective membrane; due to a variety of causes, the situation of adhesive surface protective membrane to be there is after temporary transient stripper surface protective membrane again again, now requires easily to peel off (re-workability) from the optics as adherend.
In addition, during from optics stripper surface protective membranes such as final Polarizer, polarizers, requirement can be peeled off rapidly.That is, require cohesive force because of the change of peeling rate little, even if also can peel off rapidly when peeling off at a high speed.
So, in recent years, from maneuverable viewpoint during use surface protection film, require that the adhesive layer forming surface protection film has following performance: (1), under low peeling rate and high peeling rate, obtains the balance of cohesive force; (2) generation of glue residue is prevented; (3) excellent antistatic property; And (4) reprocessing (ReWork) performance etc.
But; although the performance requriements to the adhesive layer forming surface protection film can be met respectively; namely; although the indivedual performance requriementss in above-mentioned (1) ~ (4) can be met respectively; but the over-all properties requirement of (1) that the adhesive layer of the surface protection film that meets the demands has ~ (4) is very difficult simultaneously.
Such as, under low peeling rate and high peeling rate, obtain about (1) generation that the balance of cohesive force and (2) prevent glue residue, there will be a known suggestion as described below.
The multipolymer of (methyl) alkyl acrylate at the alkyl to have carbonatoms less than 7 and the copolymerizable compound containing carboxyl is as main component, and in the acrylic adhesive layer with linking agent, crosslinking Treatment being carried out to it and make, when through bonding for a long time, there is binding agent move to adherend side and be attached to adherend, and to the bonding force of adherend through time ascending large problem.In order to avoid this problem, there will be a known a kind of technical scheme being provided with following adhesive layer, described adhesive layer is the multipolymer using (methyl) alkyl acrylate with the alkyl of carbonatoms 8 ~ 10 and the copolymerizable compound with alcoholic extract hydroxyl group, and with linking agent, it is carried out to the adhesive layer (patent documentation 1) of crosslinking Treatment.
In addition, also proposed a kind of technical scheme being provided with following adhesive layer, described adhesive layer is by multipolymer same as described above, coordinate the multipolymer of a small amount of (methyl) alkyl acrylate and the copolymerizable compound containing carboxyl, and with linking agent, it is carried out to the adhesive layer of crosslinking Treatment.But, when using it for surface tension and be low and in the surface protection of ganoid plastic plate etc., produce the peelings such as separation because of heating when adding man-hour or preserve, high speed in field hand-manipulated when peeling off releasable poor.
In order to address these problems, propose a kind of adhesive composition, described adhesive composition is: a) to have (methyl) alkyl acrylate of the alkyl of carbonatoms 8 ~ 10 as in (methyl) alkyl acrylate 100 weight part of main component, add the copolymerizable compound containing carboxyl of b) 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 in this multipolymer, coordinate the adhesive composition (patent documentation 2) of the linking agent of more than the equivalent of the carboxyl of above-mentioned b) composition.
In the adhesive composition that patent documentation 2 is recorded, the peeling of separation etc. can not be produced when adding man-hour or preserving, and, bonding force through time ascending little, thus releasable is excellent, preserves even long-term, particularly preserve for a long time in high temperature environments, also can peel off again with little strength, now not remaining binder in adherend, even and if when carrying out also to peel off with little strength when peeling off at a high speed again.
In addition, the antistatic property excellent for (3), as the method for giving antistatic property for effects on surface protective membrane, proposes the method etc. being mixed into static inhibitor in base material film.As static inhibitor, such as, disclose the various cationic antistatic agents that (a) has the cation radicals such as quaternary ammonium salt, pyridine, primary ~ uncle amino; B () has the anionic antistatic agents of the anion-radicals of sulfonic acid base, sulfuric ester base, phosphoric acid ester base, phosphonic acids base etc.; The non-ionic antistatic agent of the both sexes static inhibitor, (d) alkamine, glycerols, polyethylene glycols etc. of (c) amino acids, amidosulphuric acid ester class etc.; E () makes static inhibitor polymer as above quantize (patent documentations 3) such as the Polymer Antistatic Agents obtained.
In addition, propose in recent years and static inhibitor so is directly contained in adhesive layer, and be not contained in base material film or coat the scheme on base material film surface.
In addition, about (4) re-workability, such as, propose a kind of adhesive composition, described adhesive composition is: relative to 100 parts by weight propylene acid resins, coordinates the solidifying agent of isocyanate ester compound of 0.0001 ~ 10 weight part and specific silicate oligomer and obtains (patent documentation 4).
In patent documentation 4, record: using the carbonatoms of alkyl be the alkyl acrylate of about 2 ~ 12, the carbonatoms of alkyl be the alkyl methacrylate of about 4 ~ 12 etc. as main monomer component, can containing the monomer component containing other functional group such as such as carboxylic monomer.Typically, preferably contain the above-mentioned principal monomer of more than 50 % by weight, and the content of wishing the monomer component containing functional group is 0.001 ~ 50 % by weight, is preferably 0.001 ~ 25 % by weight, is more preferably 0.01 ~ 25 % by weight.The adhesive composition that this patent documentation 4 is recorded, though at high temperature or hot and humid under, the rheological parameters' change with time of its cohesive force and bonding force is also little, and also demonstrates excellent effect to the bonding force of curved surface, therefore has re-workability.
Usually, if adhesive layer is soft proterties, then easily produces glue residue, re-workability also easily reduces.That is, after mistake laminating, peel off difficulty, and be difficult to again paste.From this viewpoint, in order to make it have re-workability, need by there is the functional groups such as carboxyl monomer crosslinked in host to make adhesive layer have certain hardness.
In the prior art, as the performance requriements of the adhesive layer to formation surface protection film, require that it has the balance obtaining cohesive force under low peeling rate and high peeling rate, excellent antistatic property and cycling processability etc. all the time.But, namely allow to meet properties requirement respectively, also cannot meet as the over-all properties requirement required by the adhesive layer of surface protection film.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 63-225677 publication
Patent documentation 2: Japanese Unexamined Patent Publication 11-256111 publication
Patent documentation 3: Japanese Unexamined Patent Publication 11-070629 publication
Patent documentation 4: Japanese Unexamined Patent Publication 8-199130 publication
Summary of the invention
The problem that invention will solve
The present invention completes in view of the foregoing; its problem is, provides a kind of balance excellent and the adhesive composition that endurance quality and cycling processability are also excellent and the surface protection film with excellent antistatic property, cohesive force under low peeling rate and high peeling rate.
Solve the method for problem
In order to solve above-mentioned problem, the invention provides a kind of adhesive composition, it is made up of the acrylic polymers of multipolymer, the carbonatoms that the acrylic polymers of described multipolymer contains (A) alkyl be (methyl) acrylate monomer of C4 ~ C10, (B) containing hydroxyl can the monomer of copolymerization and (C) containing carboxyl can the monomer of copolymerization, be also the static inhibitor as ionic compound of 30 ~ 80 DEG C containing (D) fusing point.
In addition, be (methyl) acrylate monomer of C4 ~ C10 relative to the carbonatoms of aforementioned (A) alkyl of 100 weight parts, aforementioned (B) containing 0.1 ~ 8.0 weight part can the monomer of copolymerization containing hydroxyl; Further, aforementioned (B) containing hydroxyl can in the monomer of copolymerization, preferably the total amount of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, (methyl) vinylformic acid own ester of 6-hydroxyl and (methyl) vinylformic acid 4-hydroxybutyl is 0 ~ 0.9 weight part.
In addition, relative to (methyl) acrylate monomer that the carbonatoms of aforementioned (A) alkyl of 100 weight parts is C4 ~ C10, aforementioned (C) preferably containing 0.35 ~ 1.0 weight part can the monomer of copolymerization containing carboxyl, and the acid number of aforementioned copolymer is 0.01 ~ 9.0.
In addition, preferably the fusing point of the static inhibitor as ionic compound of aforementioned (D) is 30 ~ 49 DEG C.
Further, preferably containing isocyanate compound more than (E) trifunctional.
In addition, isocyanate compound more than aforementioned (E) trifunctional comprises and is selected from more than at least one of (E-1) first in aliphatic category isocyanate compound group and is selected from more than at least one of (E-2) second in aromatic series kind isocyanate compound group, and relative to the aforementioned copolymer of 100 weight parts, the total content of isocyanate compound more than aforementioned (E) trifunctional is preferably 0.5 ~ 5.0 weight part.
In addition, in foregoing adhesives composition, relative to the aforementioned copolymer of 100 weight parts, preferably containing the keto-enol tautomerism compound of 1.0 ~ 5.0 weight parts as cross-linked inhibitor; Relative to the aforementioned copolymer of 100 weight parts, preferably containing the organo-tin compound of 0.01 ~ 0.5 weight part as crosslinking catalyst.
In addition, the cohesive force of the adhesive layer preferably making foregoing adhesives composition be cross-linked under low peeling rate 0.3m/min is 0.05 ~ 0.1N/25mm, and the cohesive force under high peeling rate 30m/min is below 1.0N/25mm.
In addition, the surface resistivity of the adhesive layer preferably making foregoing adhesives composition be cross-linked is 5.0 × 10
+ 11Ω/below, stripping static voltage is ± 0 ~ 0.3kV.
In addition, the invention provides a kind of adhesive film, it on the single or double of resin molding, forms adhesive layer form, and described adhesive layer foregoing adhesives composition is cross-linked form.
In addition, the invention provides a kind of surface protection film, it on the one side of resin molding, forms adhesive layer form, and described adhesive layer foregoing adhesives composition is cross-linked form.
In addition, the purposes that surface protection film of the present invention can be used as the surface protection film of Polarizer is used.
In addition, in surface protection film of the present invention, preferably on the face contrary with the side being formed with adhesive layer of resin molding, implement antistatic and antifouling process.
Invention effect
Based on the present invention, the over-all properties required by adhesive layer of insurmountable effects on surface protective membrane in the prior art can be met, but also the balance of cohesive force under low peeling rate and high peeling rate can be improved.
Embodiment
Below, based on preferred embodiment the present invention being described.
Adhesive composition of the present invention, it is characterized in that, this adhesive composition is made up of the acrylic polymers of multipolymer, the carbonatoms that the acrylic polymers of described multipolymer contains (A) alkyl be (methyl) acrylate monomer of C4 ~ C10, (B) containing hydroxyl can the monomer of copolymerization and (C) containing carboxyl can the monomer of copolymerization, be also the static inhibitor as ionic compound of 30 ~ 80 DEG C containing (D) fusing point.
Carbonatoms as (A) alkyl is (methyl) acrylate monomer of C4 ~ C10, can enumerate: (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Ethyl acrylate, (methyl) heptylacrylate, (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 etc.
As (B) containing hydroxyl can the monomer of copolymerization, can enumerate: (methyl) hydroxyalkyl acrylates classes such as (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 2-hydroxy methacrylate; (methyl) acrylic amide etc. containing hydroxyl such as N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide.
Preferably above-mentioned (B) can the monomer of copolymerization be selected from more than at least one in the compound group that is made up of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide containing hydroxyl.
Relative to (methyl) acrylate monomer that the carbonatoms of (A) alkyl of 100 weight parts is C4 ~ C10, aforementioned (B) preferably containing 0.1 ~ 8.0 weight part containing hydroxyl can the monomer of copolymerization.
And, (B) containing hydroxyl can in the monomer of copolymerization, the total amount of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl and (methyl) vinylformic acid 4-hydroxybutyl is preferably lower than 1 weight part (also allowing situation about not containing), is more preferably 0 ~ 0.9 weight part.
Preferably (C) can the monomer of copolymerization be selected from by (methyl) vinylformic acid containing carboxyl, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloxypropyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloyl-oxyethyl succsinic acid, 2-(methyl) acryloyl-oxyethyl toxilic acid, carboxy-polycaprolactone list (methyl) acrylate, 2-(methyl) more than at least one in the compound group that forms of acryloyl-oxyethyl tetrahydrophthalic acid.
Relative to (methyl) acrylate monomer that the carbonatoms of (A) alkyl of 100 weight parts is C4 ~ C10, (C) content of monomer of copolymerization can be preferably 0.35 ~ 1.0 weight part containing carboxyl, be more preferably 0.35 ~ 0.6 weight part.
Acrylic polymers used in the present invention, can also comprise polyalkylene glycol mono (methyl) acrylate monomer.As polyalkylene glycol mono (methyl) acrylate monomer, as long as the esterified compound for (methyl) acrylate of a hydroxyl in multiple hydroxyls of having of polyalkylene glycol.Be polymerizability base because (methyl) is acrylate-based, therefore, it is possible to carry out copolymerization with host polymkeric substance.Other hydroxyl, both can keep the state of OH, also can become the alkyl oxide of methyl ether, ether etc., or the saturated carboxylic acid ester etc. such as acetic ester.
As the alkylidene group that polyalkylene glycol has, vinyl, propenyl, butenyl etc. can be enumerated, but be not limited to these.Polyalkylene glycol also can be the multipolymer of the two or more polyalkylene glycols 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 aforementioned polyalkylene glycol mono (methyl) acrylate monomer, be preferably selected from more than at least one in polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate.
More specifically, can enumerate: polyoxyethylene glycol-mono-(methyl) acrylate, polypropylene glycol-mono-(methyl) acrylate, polytetramethylene glycol-mono-(methyl) acrylate, polyethylene glycol-propylene glycol-mono-(methyl) acrylate, polyethylene glycol-butyleneglycol-mono-(methyl) acrylate, polypropylene glycol-polytetramethylene glycol-mono-(methyl) acrylate, polyethylene glycol-propylene glycol-polytetramethylene glycol-mono-(methyl) acrylate; Methoxy poly (ethylene glycol)-(methyl) acrylate, methoxyl group polypropylene glycol-(methyl) acrylate, methoxyl group polytetramethylene glycol-(methyl) acrylate, methoxypolyethylene glycol-polypropylene glycol-(methyl) acrylate, methoxypolyethylene glycol-polytetramethylene glycol-(methyl) acrylate, methoxyl group-polypropylene glycol-polytetramethylene glycol-(methyl) acrylate, methoxypolyethylene glycol-polypropylene glycol-polytetramethylene glycol-(methyl) acrylate; Oxyethyl group polyoxyethylene glycol-(methyl) acrylate, oxyethyl group polypropylene glycol-(methyl) acrylate, oxyethyl group polytetramethylene glycol-(methyl) acrylate, oxyethyl group-polyethylene glycol-propylene glycol-(methyl) acrylate, oxyethyl group-polyethylene glycol-butyleneglycol-(methyl) acrylate, oxyethyl group-polypropylene glycol-polytetramethylene glycol-(methyl) acrylate, oxyethyl group-polyethylene glycol-propylene glycol-polytetramethylene glycol-(methyl) acrylate etc.
Relative to (methyl) acrylate monomer that the carbonatoms of (A) alkyl of 100 weight parts is C4 ~ C10, aforementioned polyalkylene glycol mono (methyl) acrylate monomer preferably containing 1 ~ 20 weight part.
The acrylic polymers used in the present invention, can also comprise nitrogenous vinyl monomer.As nitrogenous vinyl monomer, can enumerate: the vinyl monomer containing amido linkage, the vinyl monomer etc. containing amino vinyl monomer, there is nitrogenous heterocycle structure.More specifically, can enumerate: the ring-type nitrogen vinyl compound with the heterocycle structure of N-vinyl substituted of NVP, NVP, methyl ethylene pyrrolidone, N-vinyl pyridine, N-vinylpiperidone, N-vinyl pyrimidine, N-vinyl piperazine, N-vinylpyrazine, N-vinyl pyrrole, N-vinyl imidazole, N-Yi Xi Ji oxazole, N-polyvinyl morpholinone, N-caprolactam, N-vinyl laurolactam etc., N-(methyl) acryloyl morpholine, N-(methyl) acryloylpiperazines, N-(methyl) third rare acyl group aziridine, N-(methyl) acryl azetidine, N-(methyl) acryl tetramethyleneimine, N-(methyl) acryloylpiperidine, N-(methyl) acryl azepan, N-(methyl) acryl Azacyclooctane etc. there is N-(methyl) the ring-type nitrogen vinyl compound of heterocycle structure that replaces of acryl, N-N-cyclohexylmaleimide, N-phenylmaleimide etc. have the ring-type nitrogen vinyl compound of the heterocycle structure containing nitrogen-atoms and vinyl-based unsaturated link(age) in ring, (methyl) acrylamide that (methyl) acrylamide, N-methyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, the N-tertiary butyl (methyl) acrylamide etc. do not replace or monoalkyl replaces, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, N-dipropyl acrylamide, N, the dialkyl group such as N-di-isopropyl (methyl) acrylamide, N, N-dibutyl (methyl) acrylamide, N-ethyl-N-methyl (methyl) acrylamide, N-Methyl-N-propyl (methyl) acrylamide, N-methyl-N-isopropyl (methyl) acrylamide replace (methyl) acrylamide, N, N-dimethylaminomethyl (methyl) acrylate, N, N-dimethyl aminoethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylate, N, N-dimethylamino sec.-propyl (methyl) acrylate, N, N-dimethrlaminobutyl (methyl) acrylate, N, N-diethylamino methyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N-ethyl-N-methylamino ethyl (methyl) acrylate, N-methyl-N-propylamino ethyl (methyl) acrylate, N-methyl-N-isoproylamino ethyl (methyl) acrylate, N, N-Dibutylaminoethyl (methyl) acrylate, dialkyl amido (methyl) acrylate such as t-butylamino ethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylamide, N, N-diethyl amino propyl (methyl) acrylamide, N, N-dipropylamino propyl group (methyl) acrylamide, N, the N of N-diisopropylaminoethyl propyl group (methyl) acrylamide, N-ethyl-N-methylamino propyl group (methyl) acrylamide, N-methyl-N-propylamino propyl group (methyl) acrylamide, N-methyl-N-isoproylamino propyl group (methyl) acrylamide etc., N-dialkyl group substituted-amino propyl group (methyl) acrylamide, the N-vinylcarboxylic acid amide type such as N-vinyl formamide, N-vinyl acetamide, N-vinyl-N-methylacetaniide, (methyl) acrylic amides such as N-methoxymethyl (methyl) acrylamide, N-ethoxyethyl group (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, diacetone acrylamide, N, N-methylene-bis (methyl) acrylamide, the unsaturated carboxylic acid nitriles such as (methyl) vinyl cyanide, Deng.
As aforementioned nitrogenous vinyl monomer, preferably not hydroxyl, more preferably not hydroxyl and carboxyl.As this monomer, be preferably illustrative monomer above, such as: the acrylic monomer containing N, N-dialkyl group substituted-amino, N, N-dialkyl group substituted amido; The N-vinyl substituted lactan such as NVP, N-caprolactam, N-vinyl-2-piperidone; N-(methyl) acryloyl morpholine, N-(methyl) the N-(methyl such as acryl tetramethyleneimine) acryl substituted cyclic amine.
The acrylic polymers used in the present invention, can also comprise (methyl) alkyl acrylate monomer containing alkoxyl group.As (methyl) alkyl acrylate monomer containing alkoxyl group, can enumerate: (methyl) vinylformic acid 2-methoxy acrylate, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-propoxy ethyl, (methyl) vinylformic acid 2-isopropoxyethyl cyanoacrylate, (methyl) vinylformic acid 2-butoxyethyl, (methyl) vinylformic acid 2-methoxyl group propyl ester, (methyl) vinylformic acid 2-oxyethyl group propyl ester, (methyl) vinylformic acid 2-propoxy-propyl ester, (methyl) vinylformic acid 2-isopropoxy propyl ester, (methyl) vinylformic acid 2-butoxy propyl ester, (methyl) vinylformic acid 3-methoxyl group propyl ester, (methyl) vinylformic acid 3-oxyethyl group propyl ester, (methyl) vinylformic acid 3-propoxy-propyl ester, (methyl) vinylformic acid 3-isopropoxy propyl ester, (methyl) vinylformic acid 3-butoxy propyl ester, (methyl) vinylformic acid 4-methoxybutyl, (methyl) vinylformic acid 4-Ethoxybutyl, (methyl) vinylformic acid 4-propoxy-butyl ester, (methyl) vinylformic acid 4-isopropoxy butyl ester, (methyl) vinylformic acid 4-butoxy butyl ester etc.
These contain (methyl) alkyl acrylate monomer of alkoxyl group, the structure that the atom alkoxy with the alkyl in (methyl) alkyl acrylate replaces.
Relative to (methyl) acrylate monomer that the carbonatoms of (A) alkyl of 100 weight parts is C4 ~ C10, the content of aforementioned not hydroxyl and nitrogenous vinyl monomer or aforementioned (methyl) alkyl acrylate monomer containing alkoxyl group is preferably 1 ~ 20 weight part.To aforementioned not hydroxyl, nitrogenous vinyl monomer and aforementioned (methyl) alkyl acrylate monomer containing alkoxyl group, can use one respectively, or also can be used together two or more.
Adhesive composition of the present invention is the static inhibitor as ionic compound of 30 ~ 80 DEG C containing (D) fusing point.Static inhibitor can be the quaternary ionic compound containing acryl.
In the present invention, as static inhibitor, comprise the static inhibitor as ionic compound that (D) fusing point is 30 ~ 80 DEG C.Fusing point due to these static inhibitor is low and have chain alkyl, therefore, infers with the affinity of acrylic copolymer high.
(D) fusing point is the static inhibitor as ionic compound of 30 ~ 80 DEG C, it is the ionic compound with positively charged ion and negatively charged ion, can enumerate: positively charged ion is cationic nitrogenous or phosphorus positively charged ion, the sulphur positively charged ion etc. of pyridylium, glyoxaline cation, pyrimidine positively charged ion, pyrazoles positively charged ion, pyrroles's positively charged ion, ammonium cation 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.Be preferably solid under normal temperature (such as 30 DEG C), and by selecting the chain length, substituent position, number etc. of alkyl, the compound that fusing point is 30 ~ 80 DEG C can be obtained.Preferred cationic is quaternary nitrogen positively charged ion, can enumerate: the quaternary ammonium cation etc. of the season glyoxaline cation, tetra-allkylammonium etc. of the season pyridylium, 1,3-dialkylimidazolium (carbon atom of 2,4,5 both can have substituting group and also can not have substituting group) etc. of 1-alkyl pyridine (carbon atom of 2 ~ 6 both can have substituting group and also can not have substituting group) etc.
Relative to the multipolymer of 100 weight parts, (D) fusing point preferably containing 0.1 ~ 5.0 weight part is the static inhibitor as ionic compound of 30 ~ 80 DEG C.
In addition, preferably the fusing point of the static inhibitor as ionic compound of (D) is 30 ~ 49 DEG C.
As the aforementioned quaternary ionic compound containing 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. containing the quaternary ammonium of (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 -), imide root (R containing F
f 2n
-) etc. the compound of inorganic or organic anion.As containing F imide root (R
f 2n
-) R
f, perfluoroalkyl group sulfonyl, the fluorosulfonyl of trifyl, five fluorine ethylsulfonyls etc. can be enumerated.As containing F imide root, two (fluorosulfonyl) imide root ((FSO can be enumerated
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.
The aforementioned quaternary ionic compound containing acryl, preferably copolymerization has 0.1 ~ 5.0 % by weight in the copolymer.
As the object lesson of foregoing antistatic agents, be not particularly limited, but be the object lesson of the ionic compound of 30 ~ 80 DEG C as aforementioned fusing point, 1-octylpyridinium hexafluorophosphate, 1-nonylpyridine hexafluorophosphate, 2-methyl isophthalic acid-dococylpyridinium hexafluorophosphate, 1-octylpyridinium dodecylbenzene sulfonate, 1-dococylpyridinium thiocyanate-, 1-dococylpyridinium dodecylbenzene sulfonate, 4-methyl isophthalic acid-octylpyridinium hexafluorophosphate etc. can be enumerated.In addition, as the object lesson of the aforementioned quaternary ionic compound containing acryl, dimethylaminomethyl (methyl) acrylate phosphofluoric acid methyl salt ((CH can be enumerated
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 dimethylamine methyl esters
3)
3n
+cH
2oCOCQ=CH
2(FSO
2)
2n
-, wherein, Q=H or CH
3) etc.
Adhesive composition of the present invention, preferably makes binder polymer be cross-linked when forming adhesive layer.The method occurred as making crosslinking reaction, both can make adhesive composition contain known linking agent, also can be cross-linked by photo-crosslinkings such as ultraviolets (UV).As linking agent, can enumerate: more than more than more than two senses or trifunctional isocyanate compound, two senses or trifunctional epoxide, two senses or trifunctional acrylic compound, metallo-chelate etc.Wherein, be preferably polyisocyanate compounds (isocyanate compound more than two senses or trifunctional), be more preferably the isocyanate compound of more than (E) trifunctional.
As isocyanate compound more than (E) trifunctional, as long as at least have the polyisocyanate compounds of isocyanic ester (NCO) base of more than three 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 diisocyanate (XDI), hydrogenated xylylene vulcabond (H6XDI), dimethyl diphenylene vulcabond (TOID), tolylene diisocyanate (TDI).
As isocyanate compound more than trifunctional, can enumerate: the biuret modified body of diisocyanates (there is the compound of two NCO bases in a part) or isocyanurate-modified body, with the affixture (polyalcohol modified body) etc. of polyvalent alcohol (at least there is the compound of more than three OH bases in a part) more than the trivalents such as TriMethylolPropane(TMP) (TMP) or glycerine.
And, as isocyanate compound more than (E) trifunctional used in the present invention, preferably include and be selected from more than at least one of (E-1) first in aliphatic category isocyanate compound group and be selected from more than at least one of (E-2) second in aromatic series kind isocyanate compound group, wherein, this (E-1) first aliphatic category isocyanate compound group is by the isocyanuric acid ester of hexamethylene diisocyanate compound, the isocyanuric acid ester of isophorone diisocyanate compound, the affixture of hexamethylene diisocyanate compound, the affixture of isophorone diisocyanate compound, the biuret of hexamethylene diisocyanate compound, the biuret of isophorone diisocyanate compound formed, should (E-2) second aromatic series kind isocyanate compound group be made up of the isocyanuric acid ester of tolunediisocyanate compound, the isocyanuric acid ester of xylylene diisocyanate compound, the isocyanuric acid ester of hydrogenated xylylene diisocyanate cpd, the affixture of tolunediisocyanate compound, the affixture of xylylene diisocyanate compound, the affixture of hydrogenated xylylene diisocyanate cpd.Preferably and by (E-1) first aliphatic category isocyanate compound group and (E-2) the second aromatic series kind isocyanate compound group.In the present invention, as isocyanate compound more than (E) trifunctional, by and with being selected from more than at least one of (E-1) first in aliphatic category isocyanate compound group and being selected from more than at least one of (E-2) second in aromatic series kind isocyanate compound group, the balance of the cohesive force in low speed stripping area and high speed stripping area can be improved further.
In addition, more than isocyanate compound preferably more than (E) trifunctional comprises and is selected from more than at least one of aforementioned (E-1) first in aliphatic category isocyanate compound group and is selected from least one that aforementioned (E-2) be selected from the second aromatic series kind isocyanate compound group, and relative to the aforementioned copolymer of 100 weight parts, the total content being somebody's turn to do the isocyanate compound of more than (E) trifunctional is 0.5 ~ 5.0 weight part.In addition, as being selected from more than at least one of (E-1) first in aliphatic category isocyanate compound group and the mixture ratio being selected from more than at least one of (E-2) second in aromatic series kind isocyanate compound group, calculating with weight ratio and being preferably (E-1): (E-2) is in the scope of 10%:90% ~ 90%:10%.
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 grease, lauryl acetoacetate, etheric acid stearyl ester etc.; The beta-diketon of methyl ethyl diketone, 2,4-hexanediones, benzoyl acetone etc.These are keto-enol tautomerism compounds, using polyisocyanate compounds as in the adhesive composition of linking agent, closed by the isocyanate group that linking agent is had, the excess stickiness coordinating adhesive composition after linking agent can be suppressed to rise or the phenomenon of gelation, the storage period of adhesive composition can be extended.
Preferred aforementioned cross-linked inhibitor is keto-enol tautomerism compound, is particularly preferably and is selected from methyl ethyl diketone, be more than at least one in compound group that methyl aceto acetate forms.
Relative to the multipolymer of 100 weight parts, the content of preferred aforementioned cross-linked inhibitor is 1.0 ~ 5.0 weight parts.
Adhesive composition of the present invention can contain crosslinking catalyst.When using polyisocyanate compounds as linking agent, as long as crosslinking catalyst plays the material of function as the reaction (crosslinking reaction) of catalyzer to aforementioned copolymer and linking agent, can enumerate: the organometallic compound etc. such as aminated compounds, organo-tin compound, organo-lead compound, organic zinc compound of tertiary amine etc.
Can enumerate as tertiary amine: trialkylamine, N, N, N ', N '-tetra, N, N-dialkyl amido alcohol, triethylenediamine, morpholine derivative, bridged piperazine derivatives etc.
As organo-tin compound, can enumerate: the soap of dialkyl tin oxide, dialkyl tin, the soap etc. of sub-tin.
Preferred aforementioned crosslinking catalyst is organo-tin compound, is particularly preferably more than at least one in the compound group being selected from and being made up of di-n-octyltin oxide, tin dilaurate dioctyl tin.
Relative to the multipolymer of 100 weight parts, the content of preferred aforementioned crosslinking catalyst is 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, also there is the siloxane unit (-SiR comprising polyether-based
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 (terminal group) such as one or more alkyl, acyl groups.Can enumerate as polyether-based: polyethylene oxide base ((C
2h
4o)
n) or polyoxytrimethylene base ((C
3h
6o)
n) etc. polyoxyalkylene.
Preferred foregoing polyethers modified silicone com to be HLB value be 7 ~ 12 polyether modified siloxane compound.In addition, relative to the multipolymer of 100 weight parts, the content of foregoing polyethers modified silicone com is preferably 0.01 ~ 0.5 weight part.Be more preferably 0.1 ~ 0.5 weight part.
HLB refers to such as JISK3211(tensio-active agent term) etc. regulation hydrophilic-lipophilic balance (wetting ability and oil loving ratio).
Polyether modified siloxane compound, such as, obtains by following method: by hydrosilylation reactions, makes the organic compound with unsaturated link(age) and polyoxyalkylene be grafted on the main chain of the organopolysiloxane with silylation and obtain.Specifically, can enumerate: dimethyl siloxane-methyl (polyoxyethylene) silicone copolymers, dimethyl siloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxytrimethylene) silicone copolymers, dimethyl siloxane-methyl (polyoxytrimethylene) silicone copolymers etc.
By above-mentioned polyether modified siloxane compound is matched with adhesive composition, cohesive force and the cycling processability of binding agent can be improved.
Adhesive composition of the present invention can also contain polyether compound.As polyether compound, be the compound with polyalkylene oxide base (poly-alkylene oxide group, polyalkyleneoxidegroup), the polyether glycols such as polyalkylene glycol and their derivative can be enumerated.As the alkylidene group had in polyalkylene glycol and polyalkylene oxide base, vinyl, propenyl, butenyl etc. can be enumerated, but be not limited to these.Polyalkylene glycol also can be the multipolymer of the two or more polyalkylene glycols 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: the polyoxyalkylene alkyl ether such as polyoxyalkylene monoalky lether, polyoxyalkylene dialkyl ether; The polyoxyalkylene alkene ethers such as polyoxyalkylene mono alkenyl ether, polyoxyalkylene dialkylene ether; The polyoxyalkylene aryl ethers such as polyoxyalkylene list aryl ethers, polyoxyalkylene diaryl ether; The polyoxyalkylene glycol fatty acid esters such as polyoxyalkylene alkylamine phenyl ether, polyoxyalkylene glycol mono fatty acid ester, polyoxyalkylene glycol di fatty acid ester; Polyoxyalkylene sorbitan-fatty acid ester, polyoxyalkylene alkylamine amine, 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, Vinyl Ether, allyl ether, oily ether (oleylether) etc. can be enumerated.In addition, as the fatty acid ester in polylalkylene glycol derivatives, can enumerate: the polyunsaturated fatty acid ester such as acetic ester, stearate; Unsaturated fatty acid ester such as (methyl) acrylate, oleic acid ester etc.
Preferred, polyethers compound is the compound containing oxyethylene group (ethyleneoxidegroup), is more preferably the compound containing polyethylene oxide base (polyethyleneoxidegroup).
When polyether compound has polymerizable functional group, itself and (methyl) acrylic polymers generation copolymerization also can be made.As polymerizable functional group, be preferably the ethene functional groups such as (methyl) acryl, vinyl, allyl group.As the polyether compound with polymerizable functional group, can enumerate: 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 Vinyl Ether, polyalkylene glycol divinyl ether, alkoxy polyalkyleneglycol Vinyl Ether etc.
And, as other composition, also can suitably coordinate containing alkylene oxide (alkyleneoxide) can 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 of copolymerization.These both may be used singly or in combination of two or more use.
As the multipolymer of the host for adhesive composition of the present invention, by making that the carbonatoms of (A) alkyl is (methyl) acrylate monomer of C4 ~ C10, (B) containing hydroxyl can the monomer of copolymerization and (C) can the monomer of copolymerization carry out being polymerized synthesizing containing carboxyl.To the polymerization process of multipolymer, there is no particular limitation, can use the polymerization process that solution polymerization, letex polymerization etc. are suitable.In aforementioned copolymer, also can make polyalkylene glycol mono (methyl) acrylate monomer, not hydroxyl and other monomers such as nitrogenous vinyl monomer, (methyl) alkyl acrylate monomer containing alkoxyl group, the quaternary ionic compound containing acryl carry out copolymerization.
Adhesive composition of the present invention is that the static inhibitor as ionic compound of 30 ~ 80 DEG C and suitable any additive are prepared by coordinating (D) fusing point in above-mentioned multipolymer.
Preferred aforementioned copolymer is acrylic polymers, preferably contains (methyl) acrylate monomer or the acrylic monomer such as (methyl) vinylformic acid, (methyl) acrylic amide of 50 ~ 100 % by weight.
In addition, the acid number (acid number of acrylic polymers) of preferred aforementioned copolymer is 0.01 ~ 9.0.Thereby, it is possible to improve contaminative and improve the performance preventing glue residue phenomenon from occurring.
At this, " acid number " is one of index representing acid content, be with in and 1g contain carboxyl polymkeric substance required for the mg number of potassium hydroxide represent.
The cohesive force of the adhesive layer preferably making foregoing adhesives composition be cross-linked under low peeling rate 0.3m/min is 0.05 ~ 0.1N/25mm, and the cohesive force under high peeling rate 30m/min is below 1.0N/25mm.Thereby, it is possible to obtain cohesive force with the little performance of the change of peeling rate, even also can peel off rapidly when peeling off at a high speed.Further, even if in order to again paste during temporary transient stripper surface protective membrane, also without the need to excessive strength, be easy to peel off from adherend.
Foregoing adhesives composition is preferably made to carry out the surface resistivity of crosslinked adhesive layer 5.0 × 10
+ 11Ω/below, stripping static voltage is ± 0 ~ 0.3kV.In addition, in the present invention, the meaning of so-called " ± 0 ~ 0.3kV " refers to " 0 ~-0.3kV " and " 0 ~+0.3kV ", i.e. "-0.3 ~+0.3kV ".If surface resistivity is large, then to the poor performance that the electrostatic produced because of charged when peeling off discharges, therefore, by making surface resistivity enough little, the stripping static voltage produced with the electrostatic that occurs when peeling off adhesive layer from adherend can be reduced, the impact on the electric control circuit of adherend etc. can be suppressed.
The gel fraction of the adhesive layer (binding agent after crosslinked) preferably making adhesive composition of the present invention be cross-linked is 95 ~ 100%.Because gel fraction is so high, when low peeling rate, cohesive force can not become excessive, reduce the phenomenon of stripping unconverted monomer or oligomer from multipolymer, thus the weather resistance under re-workability, high temperature/high humidity can be improved, and suppress the pollution of adherend.
Adhesive film of the present invention forms adhesive layer at the single or double of resin molding to form, and described adhesive layer adhesive composition of the present invention is cross-linked form.In addition, surface protection film of the present invention forms adhesive layer at the one side of resin molding to form, and described adhesive layer adhesive composition of the present invention is cross-linked form.In adhesive composition of the present invention; owing to being combined with each composition of above-mentioned (A) ~ (D) with good balance; so have excellent antistatic property; the balance of the cohesive force under low peeling rate and high peeling rate is excellent; and endurance quality and cycling processability (with ballpoint pen after adhesive layer is described on surface protection film, transferring the pollution to adherend) are also excellent.Therefore, adhesive film of the present invention can be preferably used as the surface protection film of Polarizer.
As the base material film of adhesive layer, the stripping film (barrier film) of protection adhesive surface, the resin moldings etc. such as polyester film can be used.
For base material film, can on the face contrary with being formed with adhesive layer side of resin molding, implement the antifouling process undertaken by releasing agent or coating-forming agent, the silicon dioxide microparticle etc. of silicone, fluorine class, the antistatic treatment of being undertaken by the coating of static inhibitor or be mixed into etc. can be implemented.
For stripping film, carry out fitting on the face of side at the adhesive surface with adhesive layer, implement the demoulding process undertaken by the releasing agent etc. of silicone, fluorine class.
Embodiment
Below, the present invention is illustrated based on embodiment.
The manufacture > of < acrylic copolymer
[embodiment 1]
Nitrogen is imported in the reaction unit being furnished with agitator, thermometer, reflux exchanger and nitrogen ingress pipe, thus the air with nitrogen replacement in reaction unit.Then, in reaction unit, add the 2-EHA of 100 weight parts, the own ester of vinylformic acid 6-hydroxyl of 0.9 weight part, the vinylformic acid of 0.4 weight part, and add the solvent (ethyl acetate) of 60 weight parts simultaneously.Then, through the Diisopropyl azodicarboxylate as polymerization starter of 2 hours instillation 0.1 weight parts, at 65 DEG C, make it react 6 hours, obtain weight-average molecular weight be 500,000, for the acrylic acid copolymer soln 1 of embodiment 1.Get a part for acrylic copolymer, use as determination of acid value sample described later.
[embodiment 2 ~ 9 and comparative example 1 ~ 4]
Except have adjusted the composition of each monomer respectively as described in (A) in table 1 ~ (C) except, operate in the same manner as the above-mentioned acrylic acid copolymer soln 1 for embodiment 1, obtain for the acrylic acid copolymer soln in embodiment 2 ~ 9 and comparative example 1 ~ 4.
The manufacture > of < adhesive composition and surface protection film
[embodiment 1]
To the acrylic acid copolymer soln 1 according to the embodiment 1 manufactured as mentioned above, add 1.5 weight part 1-octylpyridinium hexafluorophosphates and after stirring, add 0.5 weight part CoronateHX(コ ロ ネ ー ト HX, the isocyanuric acid ester of hexamethylene diisocyanate compound), 0.5 weight part CoronateL(コ ロ ネ ー ト L, the affixture of tolunediisocyanate compound and TriMethylolPropane(TMP)) after be uniformly mixed, obtain the adhesive composition of embodiment 1.This adhesive composition is coated on the stripping film be made up of the polyethylene terephthalate scribbling silicone resin (PET) film, then at 90 DEG C, carries out drying and remove solvent, obtain the bonding sheet that adhesive layer thickness is 25 μm.
Then; prepare polyethylene terephthalate (PET) film face implementing antistatic treatment and antifouling process; and bonding sheet is transferred to this polyethylene terephthalate (PET) film with implement on the opposing face in face of antistatic treatment and antifouling process, obtain the surface protection film of the embodiment 1 of the stacked formation with " PET film/adhesive layer/stripping film (scribbling the PET film of silicone resin) implementing antistatic treatment and antifouling process ".
[embodiment 2 ~ 9 and comparative example 1 ~ 4]
Except have adjusted the composition of each additive respectively as described in (D) ~ (E) of table 1 except, carry out operating in the same manner as the surface protection film of above-described embodiment 1 and obtain embodiment 2 ~ 9 and the surface protection film comparing 1 ~ 4.
Table 1
In table 1, the numerical value in bracket all represents that the total weight organized with (A) is set to 100 weight parts and the numerical value of each Parts by Ingredients obtained.In addition, the compound title of the abbreviation correspondence of each composition used in table 1 is shown in Table 2.In addition, Coronate(コ ロ ネ ー ト, registered trademark) HX, CoronateHL and CoronateL be Nippon Polyurethane Industry Co., Ltd. (NipponPolyurethaneIndustryCo., Ltd.) trade name, Takenate(タ ケ ネ ー ト, registered trademark) D-140N, D-127N, D-110N, D-120N be the trade name of Mitsui Chemicals, Inc.
Table 2
< test method and evaluation >
23 DEG C, under the environment of 50%RH, the surface protection film of embodiment 1 ~ 9 and comparative example 1 ~ 4, after aging 7 days, is peeled off stripping film (scribbling the PET film of silicone resin), thus adhesive layer is exposed, and as the sample of chart surface resistivity.
And then; by the surface protection film that this adhesive layer exposes; the Polarizer surface of pasting on liquid crystal cell is fitted in by adhesive layer; place and under 50 DEG C, 5 normal atmosphere, carry out pressure kettle process 20 minutes after 1 day; at room temperature place 12 hours further, using the surface protection film obtained thus as measuring cohesive force, peeling off the sample of static voltage, re-workability and weather resistance.
< acid number >
The acid number of acrylic polymers: by sample dissolution in solvent (diethyl ether and ethanol being carried out the solvent mixed with volume ratio 2:1), adopt potential difference automatic titration device (AT-610, capital of a country electronic industry Co., Ltd. manufactures), the potassium hydroxide-ethanol solution being about 0.1mol/L by concentration carries out potential difference titration, determine in and the amount of potassium hydroxide-ethanol solution needed for sample.Then, acid number is obtained according to following formula.
Acid number=(B × f × 5.611)/S
The amount (mL) of the 0.1mol/L potassium hydroxide-ethanol solution used in B=titration
The coefficient of f=0.1mol/L potassium hydroxide-ethanol solution
The quality (g) of the solids component of S=sample
< cohesive force >
Adopt tensile testing machine; with low peeling rate (0.3m/min) and high peeling rate (30m/min); above-mentioned obtained mensuration sample (surface protection film wide for 25mm being fitted in the sample on Polarizer surface) is peeled off to 180 ° of directions; determine stripping strength, and using this stripping strength as cohesive force.
< surface resistivity >
After weathering, before laminating Polarizer, peel stripping film (scribbling the PET film of silicone resin) off and adhesive layer is exposed, adopt resistivity meter HirestaUP-HT450(Ha イ レ ス タ UP-HT450, Mitsubishi of Co., Ltd. chemical analysis technology (MitsubishiChemicalAnalytechCo., Ltd.) manufacture), determine the surface resistivity of adhesive layer.
< peels off static voltage >
Adopt high precision electrostatic transducer SK-035, SK-200(Co., Ltd.'s Keyemce (KeyenceCorporation) manufacture), measure when carrying out 180 ° of strippings to above-mentioned obtained mensuration sample with the draw speed of 30m/min, the voltage (static voltage) that Polarizer is charged and produce, using the maximum value of measured value as stripping static voltage.
< re-workability >
After carrying out describing (load be 500g, 3 times back and forth) with ballpoint pen on the surface protection film of mensuration sample obtained above, from Polarizer stripper surface protective membrane, observe the surface of Polarizer, confirm not transfer the pollution to Polarizer.Evaluation objective benchmark: be evaluated as "○" when not transferring the pollution to Polarizer; Be evaluated as " △ " when confirming that the track described along ballpoint pen at least displaced pollution to local; "×" is evaluated as when confirming that the track described along ballpoint pen has pollution transportation and also confirms from adhesive surface the disengaging having binding agent.
< weather resistance >
60 DEG C, 90%RH environment transfers to be set up and states obtained mensuration sample after 250 hours, taken out under being placed in room temperature and places 12 hours further, then measure cohesive force, confirm significantly not increase compared with initial stage cohesive force.Evaluation objective benchmark: is "○" when the cohesive force after test is the average evaluation of less than 1.5 times of initial stage cohesive force, average evaluation more than 1.5 times is "×".
Evaluation result is shown in Table 3.In addition, in surface resistivity, represent " m × 10 by " mE+n "
+ n" (wherein, m is arbitrary real number, and n is positive integer).
Table 3
For the surface protection film of embodiment 1 ~ 9, the cohesive force under low peeling rate 0.3m/min is 0.05 ~ 0.1N/25mm, and the cohesive force under high peeling rate 30m/min is below 1.0N/25mm; Surface resistivity is 5.0 × 10
+ 11Ω/below, stripping static voltage is ± 0 ~ 0.3kV; Further, use ballpoint pen across adhesive layer after surface protection film is described, do not transfer the pollution to adherend, and 60 DEG C, place 250 hours under the environment of 90%RH after weather resistance be also excellent.
That is, meet performance requriementss whole as follows: (1) obtains the balance of cohesive force under low peeling rate and high peeling rate simultaneously; (2) generation of glue residue is prevented; (3) excellent antistatic property; And (4) cycling processability.
In addition, by and be selected from (E-1) first in aliphatic category isocyanate compound group more than one and be selected from more than one in aromatic series kind isocyanate compound group of (E-2) second, the balance of the cohesive force of low speed stripping area and high speed stripping area can be improved.
For the surface protection film of comparative example 1, due to do not comprise (C) containing carboxyl can the monomer of copolymerization, its acid number is 0; In addition, may be the cause owing to not comprising (E) isocyanate compound, the cohesive force under its low peeling rate 0.3m/min and high peeling rate 30m/min be excessive, re-workability and poor durability.
For the surface protection film of comparative example 2; may be because (B) monomer containing hydroxyl is very few, in (E) isocyanate compound and by the cause of (E-1) and (E-2), its cohesive force under low peeling rate 0.3m/min and the cohesive force under high peeling rate 30m/min is excessive, surface resistivity and stripping static voltage is high, re-workability and poor durability.
For the surface protection film of comparative example 3, its storage period is too short, owing to being cross-linked before coating, therefore, cannot be coated with, and this may be because of the too much cause of (E) isocyanate compound.
For the surface protection film of comparative example 4, its storage period is too short, owing to being cross-linked before coating, therefore, cannot be coated with, and this may be because of the too much cause of (E) isocyanate compound.
As mentioned above, in the surface protection film of comparative example 1 ~ 4, performance requriementss whole as follows cannot be met: (1) obtains the balance of the cohesive force under low peeling rate and high peeling rate simultaneously; (2) generation of glue residue is prevented; (3) excellent antistatic property; And (4) cycling processability.
Claims (11)
1. an adhesive composition, wherein,
This adhesive composition is made up of the acrylic polymers of multipolymer, the carbonatoms that the acrylic polymers of described multipolymer contains (A) alkyl be (methyl) acrylate monomer of C4 ~ C10, (B) containing hydroxyl can the monomer of copolymerization and (C) containing carboxyl can the monomer of copolymerization
And, be also 30 ~ 49 DEG C containing (D) fusing point and be the static inhibitor as ionic compound of solid at 30 DEG C of temperature, also containing isocyanate compound more than (E) trifunctional,
Be (methyl) acrylate monomer of C4 ~ C10 relative to the carbonatoms of (A) alkyl described in 100 weight parts, containing (B) described in 0.1 ~ 8.0 weight part containing hydroxyl can the monomer of copolymerization, containing (C) described in 0.35 ~ 1.0 weight part containing carboxyl can the monomer of copolymerization
Isocyanate compound more than described (E) trifunctional comprises and is selected from more than at least one of (E-1) first in aliphatic category isocyanate compound group and is selected from more than at least one of (E-2) second in aromatic series kind isocyanate compound group
Relative to the described multipolymer of 100 weight parts, the total content of isocyanate compound more than described (E) trifunctional is 0.5 ~ 5.0 weight part.
2. adhesive composition as claimed in claim 1, wherein,
Described (B) containing hydroxyl can in the monomer of copolymerization, the total amount of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, (methyl) vinylformic acid own ester of 6-hydroxyl and (methyl) vinylformic acid 4-hydroxybutyl is 0 ~ 0.9 weight part.
3. adhesive composition as claimed in claim 1 or 2, wherein,
The acid number of described multipolymer is 0.01 ~ 9.0.
4. adhesive composition as claimed in claim 1 or 2, wherein,
In described adhesive composition, relative to the described multipolymer of 100 weight parts, containing the keto-enol tautomerism compound of 1.0 ~ 5.0 weight parts as cross-linked inhibitor,
Relative to the described multipolymer of 100 weight parts, containing the organo-tin compound of 0.01 ~ 0.5 weight part as crosslinking catalyst.
5. adhesive composition as claimed in claim 1 or 2, wherein,
The cohesive force of the adhesive layer that described adhesive composition is cross-linked under low peeling rate 0.3m/min is 0.05 ~ 0.1N/25mm, and the cohesive force under high peeling rate 30m/min is below 1.0N/25mm.
6. adhesive composition as claimed in claim 1 or 2, wherein,
The surface resistivity of the adhesive layer that described adhesive composition is cross-linked is 5.0 × 10
+ 11Ω/below, stripping static voltage is ± 0 ~ 0.3kV.
7. adhesive composition as claimed in claim 1 or 2, wherein,
Relative to the described multipolymer of 100 weight parts, described (D) is 0.1 ~ 5.0 weight part as the static inhibitor content of ionic compound.
8. an adhesive film, its single or double at resin molding forms adhesive layer and forms, and described adhesive layer the adhesive composition according to any one of claim 1 ~ 7 is cross-linked form.
9. a surface protection film, its one side at resin molding forms adhesive layer and forms, and described adhesive layer the adhesive composition according to any one of claim 1 ~ 7 is cross-linked form.
10. surface protection film as claimed in claim 9, its surface protection film purposes as Polarizer is used.
11. surface protection films as claimed in claim 9, wherein,
On the face contrary with the side being formed with described adhesive layer of described resin molding, implement antistatic and antifouling process.
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| JP6221091B2 (en) * | 2012-11-16 | 2017-11-01 | 藤森工業株式会社 | Surface protection film |
| JP6187896B2 (en) * | 2012-11-16 | 2017-08-30 | 藤森工業株式会社 | Adhesive layer, adhesive film and surface protective film |
| JP6222698B2 (en) | 2014-02-21 | 2017-11-01 | 藤森工業株式会社 | Adhesive film and surface protective film |
| JP6248312B2 (en) * | 2014-04-24 | 2017-12-20 | 藤森工業株式会社 | Adhesive composition and surface protective film |
| JP6198275B2 (en) * | 2014-08-29 | 2017-09-20 | 藤森工業株式会社 | Antistatic surface protection film |
| JP6206969B2 (en) * | 2014-09-10 | 2017-10-04 | 藤森工業株式会社 | Adhesive composition and surface protective film |
| JP6228146B2 (en) * | 2015-01-09 | 2017-11-08 | 藤森工業株式会社 | Adhesive composition and adhesive film |
| JP6483519B2 (en) * | 2015-05-11 | 2019-03-13 | 藤森工業株式会社 | Adhesive composition and surface protective film |
| KR102024260B1 (en) * | 2015-09-04 | 2019-09-23 | 주식회사 엘지화학 | Pressure sensitive adhesive composition |
| KR102056591B1 (en) * | 2015-12-07 | 2019-12-17 | 주식회사 엘지화학 | Pressure sensitive adhesive composition |
| JP6566568B2 (en) * | 2016-02-29 | 2019-08-28 | 藤森工業株式会社 | Method for producing antistatic surface protective film |
| JP6580540B2 (en) * | 2016-09-28 | 2019-09-25 | 藤森工業株式会社 | Adhesive composition and adhesive film |
| JP6597727B2 (en) * | 2017-05-11 | 2019-10-30 | 東洋インキＳｃホールディングス株式会社 | Surface protective adhesive and adhesive sheet |
| JP6677673B2 (en) * | 2017-05-15 | 2020-04-08 | 藤森工業株式会社 | Pressure-sensitive adhesive composition and surface protective film |
| JP6370976B2 (en) * | 2017-08-31 | 2018-08-08 | 藤森工業株式会社 | Adhesive composition and surface protective film |
| JP6386152B2 (en) * | 2017-10-11 | 2018-09-05 | 藤森工業株式会社 | Adhesive composition and adhesive film |
| JP6843041B2 (en) * | 2017-12-27 | 2021-03-17 | 藤森工業株式会社 | Adhesive composition and adhesive film |
| JP6691177B2 (en) * | 2018-07-10 | 2020-04-28 | 藤森工業株式会社 | Surface protection film |
| JP6936840B2 (en) * | 2018-08-07 | 2021-09-22 | 藤森工業株式会社 | Adhesive composition and adhesive film |
| JP6585248B2 (en) * | 2018-08-07 | 2019-10-02 | 藤森工業株式会社 | Adhesive composition and adhesive film |
| KR102125020B1 (en) * | 2018-09-05 | 2020-06-19 | (주)이녹스첨단소재 | Adhesive sheet for display and display comprising the same |
| JP7207961B2 (en) * | 2018-11-12 | 2023-01-18 | 藤森工業株式会社 | Adhesive composition, and adhesive film and surface protective film using the same |
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| JP7333852B2 (en) | 2019-09-03 | 2023-08-25 | 藤森工業株式会社 | adhesive film |
| JP6871456B2 (en) * | 2020-04-08 | 2021-05-12 | 藤森工業株式会社 | Surface protective film |
| KR102398470B1 (en) * | 2020-05-08 | 2022-05-17 | 율촌화학 주식회사 | Pressure sensitive adhesive composition, protective film using the same, and production method of protective film using the same |
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| Publication number | Publication date |
|---|---|
| KR101554861B1 (en) | 2015-09-22 |
| JP6268407B2 (en) | 2018-01-31 |
| KR101578380B1 (en) | 2015-12-17 |
| JP2014025006A (en) | 2014-02-06 |
| CN104893624A (en) | 2015-09-09 |
| CN103571400A (en) | 2014-02-12 |
| KR20150113941A (en) | 2015-10-08 |
| TWI550048B (en) | 2016-09-21 |
| TW201404846A (en) | 2014-02-01 |
| KR20140013916A (en) | 2014-02-05 |
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