CN105219313B - Adhesive composition and surface-protective adhesive film - Google Patents
Adhesive composition and surface-protective adhesive film Download PDFInfo
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- CN105219313B CN105219313B CN201510671721.XA CN201510671721A CN105219313B CN 105219313 B CN105219313 B CN 105219313B CN 201510671721 A CN201510671721 A CN 201510671721A CN 105219313 B CN105219313 B CN 105219313B
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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
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides an adhesive composition and a surface-protective adhesive film, which is excellent in the balance of adhesive force when being stripped at low and high speeds, and is thus also excellent in durability and reworking performance. The invention is characterized by being composed of an acrylic acid polymer comprising a copolymer of: (A) a (meth)acrylate monomer having a C4-C10 alkyl group, (B) a copolymeriable monomer having a hydroxyl group, (C) a copolymeriable monomer having a carboxyl group, (D) a polyalkylene glycol mono(meth)acrylate monomer, and (E) a nitrogen-containing vinyl monomer having no hydroxyl group or an alkoxy group-containing (meth)acrylate monomer, and further comprising (F) an isocyanate compound having 3 or more functional groups, (G) a cross-linking retardant agent, (H) a cross-linking catalyst, and (I) a polyether-modified siloxane compound, wherein the acrylic acid polymer has an acid value of 0.01-8.0.
Description
The application is the applying date to be on April 3rd, 2013, Application No. 201310114472.5, the artificial rattan lumber industry of application
Co., Ltd., the divisional application of the application for a patent for invention of entitled " adhesive composition and surface protection film ".
Technical field
The present invention relates to the surface protection film used in the manufacturing process of liquid crystal display.More particularly it relates to
It is fitted on the surface of the opticses of Polarizer, the polarizer of composition liquid crystal display etc., protects Polarizer, polarizer
Deng opticses surface surface protection film adhesive composition, and using its surface protection film.
Background technology
All the time, to constitute the manufacture of the opticses of Polarizer, the polarizer of part etc. of liquid crystal display
In operation, in the temporary transient coating surface protecting film in the surface of opticses.When opticses are assembled into into liquid crystal display, by table
Surface protective film is peeled off from opticses and removed.In order to the surface protection film for protecting optical component surfaces only makes in manufacturing process
With, therefore, also referred to as operation film.
Surface protection film used in the operation of manufacture opticses, in the poly terephthalic acid with optical transparence
Adhesive phase is formed in the one side of glycol ester (PET) resin film.Additionally, until fit in before opticses, will be in order to protect
The stripping film for being stripped process for protecting the adhesive phase is fitted in above adhesive phase.
The opticses of Polarizer, polarizer etc. are additionally, since, in the state of surface protection film is fitted with, are carried out
The examination and test of products of the optical assessment being mixed into etc. with the display capabilities of LCD panel, colourity, contrast, impurity.Therefore, for
The necessary performance of surface protection film is, within the adhesive layer non-cohesive bubble or impurity.
And, when making surface protection film fit in the opticses of Polarizer, polarizer etc., due to a variety of causes,
Having temporarily peel off surface protection film, then the situation for re-pasting surface protection film.At this moment require easily from the optical section of adherend
The stripping (have doing over again property (リ ワ ー Network) of part) surface protection film.
And, when peeling off surface protection film from the opticses of Polarizer, polarizer etc., it is desirable to can rapidly shell
From.That is, also can rapidly peel off to pass through to peel off at a high speed, it is desirable to which it is few that bonding force is affected by peeling rate.
So, in recent years, as the requirement performance of the adhesive phase for constituting surface protection film, it is desirable to (1) obtain low
The balance of the bonding force in fast peeling rate and high speed peeling rate, (2) are prevented from the generation of adhesive residue, and (3)
With performance of doing over again.
But, although the requirement performance individually of these (1)～(3) is disclosure satisfy that, but is very difficult to tool simultaneously
Performance is required for (1) required in the adhesive phase of surface protection film～(3).
For example, the balance of the bonding force during low speed is peeled off and peeled off at a high speed is obtained with regard to (1)；(2) prevent binding agent residual
The generation stayed, it is known to motion below.
With (methyl) alkyl acrylate of the alkyl with carbon number below 7 and the copolymerizable chemical combination containing carboxyl
The copolymer of thing be main component, with cross-linking agent to acrylic adhesives made by its crosslinking Treatment, after laminating if
Through long-time, then with binding agent to the side shifting of adherend one, and the problem risen during to the bonding force Jing of adherend.For
Prevent the problem from producing, it is known that following binding agent (contact adhesive)：Described adhesive is 8～10 using having carbon number
Alkyl (methyl) alkyl acrylate with have alcohol hydroxyl group copolymerizable compound copolymer, it is handed over cross-linking agent
Connection is processed and obtained (patent documentation 1).
And propose following binding agent etc.：Described adhesive by mixing (methyl) on a small quantity in above-mentioned same copolymer
Alkyl acrylate and the copolymer of the copolymerizable compound containing carboxyl, are obtained with the process of cross-linking agent cross-linking.But,
When in the surface protection for using it for the smooth plastic plate in the low surface of surface tension etc., have due to adding when adding man-hour or preserving
Delivery in hot weather capture acts the problem of the peeling for waiting or manually peels off the problem of releasable difference when peeling off at a high speed.
In order to solve these problems, adhesive composition is proposed, described adhesive compositionss are by (a) 100 weight portion
(methyl) acrylic acid alkyl with (methyl) alkyl acrylate with the alkyl that carbon number is 8～10 as main component
In ester, add the copolymerizable compound containing carboxyl of (b) 1～15 weight portion and (c) carbon number of 3～100 weight portions is
The vinyl esters of 1～5 aliphatic carboxylic acid obtains the copolymer of monomer mixture, is mixed into relative to above-mentioned in the copolymer
B the carboxyl of () composition is obtained (patent documentation 2) for cross-linking agent more than equivalent.
Adhesive composition described in patent documentation 2, without produce plus man-hour or when preserving etc. in float etc.
Peeling, and rising is also little during the Jing of bonding force, and releasable is outstanding, even long-term preserve, be particularly high-temperature atmosphere
Under long-term preservation, it is also possible to peeled off again with little power, at this moment, adhesive residue do not produced on adherend, also, entered
Row also can again be peeled off when peeling off at a high speed with little power.
And, with regard to (3) with performance of doing over again, for example, propose adhesive composition, described adhesive compositionss by with
For the weight portion of acrylic resin 100 is 0.0001～10 weight portion, isocyanates are mixed in acrylic resin
The sclerosing agent of compound and specific silicate oligomer are obtained (patent documentation 3).
In patent documentation 3, the carbon number with alkyl is for about 2～12 alkyl acrylate, the carbon number of alkyl
For about 4～12 alkyl methacrylate etc. is main monomer component, for example, can be comprising the monomer containing carboxyl etc.,
Monomer component containing other functional groups.It is generally preferable that containing above-mentioned principal monomers more than 50 weight %, and, it is desirable to
The content of the monomer component containing functional group be 0.001～50 weight %, preferably 0.001～25 weight %, more preferably 0.01～
25 weight %.Even if due to the adhesive composition described in such patent documentation 3 at high temperature or it is hot and humid under, coagulate
The rheological parameters' change with time of poly- power and bonding force is also little, also, to displaying that outstanding effect in the bonding force of curved surface, therefore have
Doing over again property.
Usually, if adhesive phase is made into flexible character, adhesive residue becomes to be susceptible to, and doing over again property is also held
Easily reduce.I.e. it is easy to peel off difficult, difficulty of fitting again when becoming mistakenly to fit.Accordingly, it would be desirable to by the official with carboxyl etc.
What is can rolled into a ball is monomer crosslinked in host, adhesive phase is made into certain hardness so as to doing over again property.
[prior art literature]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open No. Sho 63-225677 publication
[patent documentation 2] Japanese Patent Laid-Open 11-256111 publication
[patent documentation 3] Japanese Patent Laid-Open 8-199130 publication
The content of the invention
[the invention problem to be solved]
In the prior art, as the requirement performance of the adhesive phase for constituting surface protection film, it is desirable to：Obtain low speed
Balance and doing over again property of bonding force in peeling off and peeling off at a high speed etc., but, although disclosure satisfy that each, the requirement of each
Performance, but the whole required in the adhesive phase of surface protection film can not be met and require performance.
The present invention makes in view of the foregoing.The problem of the present invention is to provide a kind of adhesive composition and surface
The balancing good of the bonding force of protecting film, described adhesive compositionss and surface protection film in low speed is peeled off and peeled off at a high speed,
And durability and doing over again property are also excellent.
[method for solving problem]
In order to solve above-mentioned problem, the present invention provides a kind of adhesive composition, and it is by the carbon number containing (A) alkyl
(methyl) acrylate monomer and the copolymerisable monomer of (B) containing hydroxyl and (C) for C4～C10 is containing the copolymerizable of carboxyl
Monomer and (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) not the nitrogenous vinyl monomer of hydroxyl or
The acrylic polymer of at least one copolymer in (methyl) alkyl acrylate monomer containing alkoxyl is constituted, its
Further change containing isocyanate compound more than (F) 3 sense, (G) cross-linked inhibitor, (H) crosslinking catalyst, (I) polyethers
Property silicone compounds, the acid number of aforesaid propylene acids polymers is 0.01～8.0.
It is preferred that the above-mentioned copolymerisable monomer of (B) containing hydroxyl is selected from (methyl) acrylic acid 8- hydroxyl monooctyl esters, (methyl)
The own ester of acrylic acid 6- hydroxyls, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxy methacrylates, N- hydroxyls (methyl) third
In acrylamide, N- methylols (methyl) acrylamide, the compound group of N- ethoxys (methyl) acrylamide composition at least one
More than kind；It is (methyl) acrylate monomer of C4～C10 relative to the carbon number of above-mentioned (A) alkyl of 100 weight portions, contains
There are the above-mentioned copolymerisable monomer of (B) containing hydroxyl of 0.1～5.0 weight portion, also, the copolymerizable list of above-mentioned (B) containing hydroxyl
In body, (methyl) acrylic acid 8- hydroxyl monooctyl esters, the own ester of (methyl) acrylic acid 6- hydroxyls and (methyl) acrylic acid 4- hydroxybutyls
Total amount is 0～0.9 weight portion.
It is preferred that the above-mentioned copolymerisable monomer of (C) containing carboxyl is selected from (methyl) acrylic acid, carboxyethyl (methyl) propylene
Acid esters, carboxylic amyl group (methyl) acrylate, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2- (methyl) acryloyl
Epoxide propyl group hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl phthalic acid, 2- (methyl) acryloxy second
Base succinic acid, 2- (methyl) acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) third
It is more than at least one in the compound group of alkene trimethylammonium tetrahydrophthalic acid composition；Relative to the upper of 100 weight portions
State (methyl) acrylate monomer of carbon number for C4～C10 of (A) alkyl, above-mentioned (C) containing 0.35～1.0 weight portion
Copolymerisable monomer containing carboxyl.
It is preferred that above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer is selected from polyalkylene glycol mono (methyl)
In acrylate, methoxypolyalkylene glycol (methyl) acrylate, ethyoxyl poly alkylene glycol (methyl) acrylate
At least one more than；Relative to 100 weight portions above-mentioned (A) alkyl carbon number for C4～C10 (methyl) acrylic acid
Ester monomer, containing above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer of 1～20 weight portion.
Preferably with respect to 100 weight portions above-mentioned (A) alkyl carbon number for C4～C10 (methyl) acrylate list
Body, containing 1～20 weight portion above-mentioned (E) the not nitrogenous vinyl monomer of hydroxyl or (methyl) acrylic acid containing alkoxyl
Alkyl ester monomer.
It is preferred that isocyanate compound more than above-mentioned (F) 3 sense is selected from hexamethylene diisocyanate compound
Isocyanuric acid ester body, the isocyanuric acid ester body of isophorone diisocyanate compound, hexamethylene diisocyanate chemical combination
The adduction object of thing, the adduction object of isophorone diisocyanate compound, the contracting of hexamethylene diisocyanate compound
It is more than at least one in two urea bodies, the compound group of the biuret body composition of isophorone diisocyanate compound；Relatively
Isocyanate compound more than the above-mentioned copolymer of 100 weight portions, above-mentioned (F) 3 sense containing 0.4～5.0 weight portion.
Above-mentioned (I) polyether-modified silicone compounds are the polyether-modified silicone compounds that HLB value is 7～12,
Preferably with respect to the above-mentioned copolymer of 100 weight portions, above-mentioned (I) containing 0.01～0.5 weight portion polyether-modified siloxanes
Compound.
Above-mentioned (G) cross-linked inhibitor is keto-enol tautomerism compound, preferably with respect to the above-mentioned copolymerization of 100 weight portions
Thing, above-mentioned (G) cross-linked inhibitor containing 1.0～5.0 weight portions.
Above-mentioned (H) crosslinking catalyst is organo-tin compound, preferably with respect to the above-mentioned copolymer of 100 weight portions, is contained
Above-mentioned (H) crosslinking catalyst of 0.01～0.5 weight portion.
It is preferred that, make the adhesive phase of above-mentioned binder composition cross-links viscous under low speed peeling rate 0.3m/min
It is with joint efforts 0.05～0.1N/25mm, the bonding force under high speed peeling rate 30m/min is below 1.0N/25mm.
Additionally, the present invention provides a kind of bonding film, it is to be formed with to make above-mentioned binding agent on one or two sides of resin film
Bonding film obtained from the adhesive phase of compositionss crosslinking.
Additionally, the present invention provides a kind of surface protection film, it is characterised in that it is that bonding is formed in the one side of resin film
Surface protection film obtained from oxidant layer, described adhesive layer is obtained by making above-mentioned binder composition cross-links, uses ball pen
It is no to transfer the pollution to adherend after describing on surface protection film via described adhesive layer.
Above-mentioned surface protection film, it can be used as the purposes of the surface protection film of Polarizer.
It is preferred that being formed carry out antistatic and anti-pollution place on the contrary face in side in above-mentioned resin film and above-mentioned adhesive phase
Reason.
[invention effect]
According to the present invention, disclosure satisfy that needed for the indeterminable adhesive phase in surface protection film in the prior art
The over-all properties wanted.In addition it is possible to obtain the excellent performance for preventing adhesive residue.In particular it is possible to enter one
Step improves the performance for preventing adhesive residue.
Specific embodiment
Below, based on the preferred embodiment explanation present invention.
The adhesive composition of the present invention, its host is by (methyl) that the carbon number containing (A) alkyl is C4～C10
Acrylate monomer and the copolymerisable monomer of (B) containing hydroxyl and the copolymerisable monomer of (C) containing carboxyl and (D) poly- alkylene
The nitrogenous vinyl monomer or the (first containing alkoxyl of base glycol list (methyl) acrylate monomer and (E) not hydroxyl
Base) acrylic polymer of at least one copolymer in alkyl acrylate monomer constitutes, and it further contains (F) 3
More than sense isocyanate compound, (G) cross-linked inhibitor, (H) crosslinking catalyst, (I) polyether-modified silicone compound
Thing, the acid number of aforesaid propylene acids polymers is 0.01～8.0.
Can enumerate for (methyl) acrylate monomer of C4～C10 as the carbon number of (A) alkyl：(methyl) acrylic acid
Butyl ester, (methyl) Isobutyl 2-propenoate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate,
(methyl) 1-Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) acrylic acid nonyl ester,
The different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate etc..
Can enumerate as the copolymerisable monomer of (B) containing hydroxyl：(methyl) acrylic acid 8- hydroxyl monooctyl esters, (methyl) acrylic acid
(methyl) dihydroxypropyl of the own ester of 6- hydroxyls, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxy methacrylates etc.
Alkyl esters, N- hydroxyls (methyl) acrylamide, N- methylols (methyl) acrylamide, N- ethoxys (methyl) acrylamide etc.
(methyl) acrylic amide containing hydroxyl etc..
It is preferred that, selected from (methyl) acrylic acid 8- hydroxyl monooctyl esters, the own ester of (methyl) acrylic acid 6- hydroxyls, (methyl) acrylic acid 4-
Hydroxybutyl, (methyl) acrylic acid 2- hydroxy methacrylates, N- hydroxyls (methyl) acrylamide, N- methylols (methyl) acrylamide,
It is more than at least one in the compound group of N- ethoxys (methyl) acrylamide composition.
Relative to 100 weight portions above-mentioned (A) alkyl carbon number for C4～C10 (methyl) acrylate monomer,
Preferably comprise the above-mentioned copolymerisable monomer of (B) containing hydroxyl of 0.1～5.0 weight portion.
Also, in the copolymerisable monomer of (B) containing hydroxyl, (methyl) acrylic acid 8- hydroxyl monooctyl esters, (methyl) acrylic acid
The total amount of the own ester of 6- hydroxyls and (methyl) acrylic acid 4- hydroxybutyls is preferably less than 1 weight portion (allowing situation about not containing),
It is preferred that 0～0.9 weight portion.
It is preferred that the copolymerisable monomer of (C) containing carboxyl is selected from (methyl) acrylic acid, carboxyethyl (methyl) acrylate, carboxylic
Amyl group (methyl) acrylate, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2- (methyl) acryloxy third
Base hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl phthalic acid, 2- (methyl) acryloyl-oxyethyl succinum
Acid, 2- (methyl) acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) acryloyl-oxy
It is more than at least one in the compound group of base ethyl tetrahydrochysene phthalic acid composition.
Relative to 100 weight portions (A) alkyl carbon number for C4～C10 (methyl) acrylate monomer, preferably
The copolymerisable monomer of (C) containing carboxyl containing 0.35～1.0 weight portion, further preferably 0.35～0.6 weight portion.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, can be poly alkylene glycol have it is many
In individual hydroxyl, a hydroxyl is used as the esterified compound of (methyl) acrylate.Become because (methyl) is acrylate-based
Polymerizable group, therefore, it is possible to be copolymerized to host polymer.Other hydroxyls can both keep OH constant, it is also possible to become methyl ether
Or the alkyl ether such as ether, or the saturated carboxylic acid ester such as acetass etc..
As the alkylidene that poly alkylene glycol has, ethylidene, propylidene, butylidene etc. can be enumerated, this is non-limiting
's.Poly alkylene glycol is alternatively the of more than two kinds poly- Asia of poly- ethylidene glycol, polytrimethylene glycol, polybutylene glycol etc.
The copolymer of alkyl diol.As the copolymer of poly alkylene glycol, poly- ethylidene glycol-polytrimethylene glycol can be enumerated, gathered
Ethylidene glycol-polybutylene glycol, polytrimethylene glycol-polybutylene glycol, poly- ethylidene glycol-polytrimethylene glycol-
Polybutylene glycol etc., the copolymer can be block copolymer, random copolymer.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, polyalkylene glycol mono (first is preferably selected from
Base) acrylate, methoxypolyalkylene glycol (methyl) acrylate, ethyoxyl poly alkylene glycol (methyl) acrylate
In at least one more than.
More specifically, poly- ethylidene glycol-mono- (methyl) acrylate, polytrimethylene glycol-mono- (methyl) third can be enumerated
Olefin(e) acid ester, polybutylene glycol-mono- (methyl) acrylate, poly- ethylidene glycol-polytrimethylene glycol-mono- (methyl) acrylic acid
Ester, poly- ethylidene glycol-polybutylene glycol-mono- (methyl) acrylate, polytrimethylene glycol-polybutylene glycol-mono- (first
Base) acrylate, poly- ethylidene glycol-polytrimethylene glycol-polybutylene glycol-mono- (methyl) acrylate；Methoxyl group gathers
Ethylidene glycol-(methyl) acrylate, methoxyl group polytrimethylene glycol-(methyl) acrylate, methoxyl group polybutylene two
Alcohol-(methyl) acrylate, methoxyl group-poly- ethylidene glycol-polytrimethylene glycol-(methyl) acrylate, methoxyl group-poly- Asia
Glycol-polybutylene glycol-(methyl) acrylate, methoxyl group-polytrimethylene glycol-polybutylene glycol-(methyl)
Acrylate, methoxyl group-poly- ethylidene glycol-polytrimethylene glycol-polybutylene glycol-(methyl) acrylate；Ethyoxyl
Poly- ethylidene glycol-(methyl) acrylate, ethyoxyl polytrimethylene glycol-(methyl) acrylate, ethyoxyl polybutylene
Glycol-(methyl) acrylate, ethyoxyl-poly- ethylidene glycol-polytrimethylene glycol-(methyl) acrylate, ethyoxyl-poly-
Ethylidene glycol-polybutylene glycol-(methyl) acrylate, ethyoxyl-polytrimethylene glycol-polybutylene glycol-(first
Base) acrylate, ethyoxyl-poly- ethylidene glycol-polytrimethylene glycol-polybutylene glycol-(methyl) acrylate etc..
Preferably with respect to 100 weight portions above-mentioned (A) alkyl carbon number for C4～C10 (methyl) acrylate list
Body, above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer containing 1～20 weight portion.
(E) in, as (E-1) nitrogenous vinyl monomer, the vinyl monomer containing amido link can be enumerated, contains ammonia
The vinyl monomer of base, the vinyl monomer with nitrogenous heterocycle structure etc..More specifically, N- vinyl -2- can be enumerated
Ketopyrrolidine, NVP, methyl ethylene ketopyrrolidine, N- vinylpyridines, N- vinylpiperidones, N- second
Alkenyl pyrimidine, N- vinyl piperazines, N- vinylpyrazines, N- vinyl pyrroles, N- vinyl imidazoles, N- Yi Xi Ji oxazoles, N-
The heterocycle structure with N- vinyl substituted of polyvinyl morpholinone, N- caprolactams, N- vinyl lauric lactams etc.
Ring-type nitrogen vinyl compound；N- (methyl) acryloyl morpholine, N- (methyl) acryloylpiperazines, N- (methyl) acryloyl
Base aziridine, N- (methyl) acryloyl group azetidine, N- (methyl) acryloyl group pyrrolidine, N- (methyl) acryloyl
Phenylpiperidines, N- (methyl) acryloyl group azepine (N- (メ タ) ア Network リ ロ イ Le ア ゼ パ Application), N- (methyl) acryloyl group a word used for translation
The ring-type nitrogen vinyl compound of the heterocycle structure replaced with N- (methyl) acryloyl group of Xin Yin etc.；N- cyclohexyl maleoyl
Imines, N-phenylmaleimide etc., the ring with the heterocycle structure in ring with nitrogen-atoms and vinyl unsaturated bond
Shape nitrogen vinyl compound；(methyl) acrylamide, N- methyl (methyl) acrylamide, N- isopropyls (methyl) acrylamide,
(methyl) acrylamide that the unsubstituted or monoalkyl of the N- tert-butyl groups (methyl) acrylamide etc. replaces；N, N- dimethyl (methyl)
Acrylamide, N, N- diethyl (methyl) acrylamide, N, N- dipropyl acrylamides, N, N- diisopropyls (methyl) acryloyl
Amine, N, N- dibutyl (methyl) acrylamide, N- ethyl-N-methyls (methyl) acrylamide, N- Methyl-N-propyls (methyl) third
(methyl) acrylamide that the dialkyl group of acrylamide, N- methyl-N-isopropyls (methyl) acrylamide etc. replaces；(methyl) propylene
Sour N, N- dimethylaminomethyl ester, (methyl) acrylic acid N, N- dimethyl aminoethyl esters, (methyl) acrylic acid N, N- diformazans
Base aminopropan base ester, (methyl) acrylic acid N, N- dimethylamino isopropyl esters, (methyl) acrylic acid N, N- dimethylamino fourths
Base ester, (methyl) acrylic acid N, N- diethylamino methyl ester, (methyl) acrylic acid N, N- diethylamino ethyl esters, (methyl)
Acrylic acid N- ethyl-N-methylamino ethyl esters, (methyl) acrylic acid N- methyl-N-propylamino ethyl esters, (methyl) propylene
Sour N- methyl-N-isoproylaminos ethyl ester, (methyl) acrylic acid N, N- Dibutylaminoethyl esters, the tertiary fourth of (methyl) acrylic acid
(methyl) propenoic acid dialkyl amino ester of base amino-ethyl ester etc.；N, N- dimethylaminopropyl (methyl) acrylamide, N,
N- diethyl amino propyls (methyl) acrylamide, N, N- dipropylamino propyl group (methyl) acrylamides, N, N- diisopropyls
Aminopropyl (methyl) acrylamide, N- ethyl-N-methylamino propyl group (methyl) acrylamides, N- methyl-N-propylaminos
The N of propyl group (methyl) acrylamide, N- methyl-N-isoproylamino propyl group (methyl) acrylamides etc., what N- dialkyl group replaced
Aminopropyl (methyl) acrylamide；N- vinyl formamides, N- vinyl acetamides, N- vinyl-N-methylacetaniides etc.
N- vinylcarboxylic acid amide types；N- methoxies (methyl) acrylamide, N- ethoxyethyl groups (methyl) acrylamide, N-
(methyl) of butoxymethyl (methyl) acrylamide, N-[2-(2-methyl-4-oxopentyl), N, N- di-2-ethylhexylphosphine oxides (methyl) acrylamide etc.
Acrylic amide；Unsaturated carboxylic acid nitrile of (methyl) acrylonitrile etc. etc..
As (E-1) nitrogenous vinyl monomer, the material of hydroxyl is not preferably contained, more preferably do not contain hydroxyl and carboxylic
The material of base.It is monomer as implied above as such monomer, preferably for example, containing N, amino or N that N- dialkyl group replaces,
The acrylic monomer of the amide groups that N- dialkyl group replaces；NVP, N- caprolactams, N- second
The lactams of the N- vinyl substituted of thiazolinyl -2- piperidones etc.；N- (methyl) acryloyl morpholines or N- (methyl) acryloyl pyrrole
Cough up the cyclic amine that N- (methyl) acryloyl group of alkane etc. replaces.
(E) in, as (E-2), (methyl) alkyl acrylate monomer containing alkoxyl, can enumerate (methyl) acrylic acid
2- methoxy ethyl esters, (methyl) acrylic acid 2- ethoxyethyl group esters, (methyl) acrylic acid 2- Among esters, (methyl) third
Olefin(e) acid 2- isopropoxy ethyl esters, (methyl) acrylic acid 2- butoxy ethyl esters, (methyl) acrylic acid 2- methoxy propyl base esters,
(methyl) acrylic acid 2- ethoxy-c base esters, (methyl) acrylic acid 2- propoxypropyl esters, (methyl) acrylic acid 2- isopropoxies
Propyl diester, (methyl) acrylic acid 2- butoxypropyl esters, (methyl) acrylic acid 3- methoxy propyl base esters, (methyl) acrylic acid 3- second
Epoxide propyl diester, (methyl) acrylic acid 3- propoxypropyl esters, (methyl) acrylic acid 3- isopropoxide propyl esters, (methyl) propylene
Sour 3- butoxypropyls ester, (methyl) acrylic acid 4- methoxy butyl acrylates, (methyl) acrylic acid 4- ethoxybutyl esters, (methyl)
Acrylic acid 4- propyloxybutyl esters, (methyl) acrylic acid 4- isopropoxy butyl esters, (methyl) acrylic acid 4- butoxybutyl esters
Deng.
These (methyl) alkyl acrylate monomers for containing alkoxyl have the alkane in (methyl) alkyl acrylate
The structure that base is replaced by alkoxyl.
Preferably with respect to 100 weight portions (A) alkyl carbon number for C4～C10 (methyl) acrylate monomer,
(methyl) propylene of nitrogenous vinyl monomer or (E-2) containing alkoxyl of (E-1) containing 1～20 weight portion not hydroxyl
Acid alkyl ester monomer.(E-1) the not nitrogenous vinyl monomer of the hydroxyl, (first of (E-2) containing alkoxyl can respectively be used
Base) a kind in alkyl acrylate monomer or two or more merging use.
As isocyanate compound more than (F) 3 sense, there are at least more than 3 isocyanates (NCO) in 1 molecule
The polyisocyanate compound of base, can enumerate：Hexamethylene diisocyanate, isophorone diisocyanate, hexichol
(1 point of the diisocyanates of dicyclohexylmethane diisocyanate, toluylene diisocya-nate, xylylene diisocyanate etc.
There is the compound of 2 NCO bases in son) biuret modified body or isocyanurate-modified body, trimethylolpropane or glycerol
Deng trivalent more than polyhydric alcohol (in 1 molecule have at least more than 3 OH bases compound) adduction object (polyhydric alcohol changes
Gonosome) etc..
(F) isocyanate compounds more than 3 senses is at least with isocyanates (NCO) base of more than 3 in 1 molecule
Polyisocyanate compound, isocyanuric acid ester body, the different Buddhist selected from hexamethylene diisocyanate compound is particularly preferred
Isocyanuric acid ester body, the adduction object of hexamethylene diisocyanate compound, the different Fo Er of your ketone diisocyanate cpd
The adduction object of ketone diisocyanate cpd, the biuret body of hexamethylene diisocyanate compound, isophorone two are different
It is more than at least one in the compound group of the biuret body composition of cyanate esters.Relative to the copolymer of 100 weight portions,
Preferably comprise isocyanate compound more than (F) 3 sense of 0.4～5.0 weight portion.
As (G) cross-linked inhibitor, can enumerate：Methyl acetoacetate, ethyl acetoacetate, acetoacetic acid monooctyl ester, second
The 'beta '-ketoester of ethyl acetoacetic acid oil base ester, lauryl acetoacetate, acetoacetic acid stearoyl ester etc., acetylacetone,2,4-pentanedione, 2,4- acetyl butyryls, benzene
The beta-diketon of formyl acetone etc..These are keto-enol tautomerism compounds, with polyisocyanate compound as cross-linking agent
In adhesive composition, by the NCO closing for having cross-linking agent, binding agent group after cross-linking agent mixing can be suppressed
The excessive viscosity of compound rises or gelation, extends the storage period of adhesive composition.
(G) cross-linked inhibitor is preferably keto-enol tautomerism compound, especially preferably selected from acetylacetone,2,4-pentanedione, acetyl
It is more than at least one in the compound group of ethyl acetate composition.
Relative to the copolymer of 100 weight portions, (G) cross-linked inhibitor of 1.0～5.0 weight portions is preferably comprised.
In the case of with polyisocyanate compound as cross-linking agent, (H) crosslinking catalyst be for above-mentioned copolymer and
The material of reaction (cross-linking reaction) function as catalyst of cross-linking agent, can enumerate：The amine of tertiary amine etc.
Organo-metallic compound of compound, organo-tin compound, organo-lead compound, organic zinc compound etc. etc..
Can enumerate as tertiary amine：Trialkylamine, N, N, N ', N '-tetra, N, N- dialkyl amido alcohol, Sanya
Ethyldiamine, morpholine derivative, bridged piperazine derivatives etc..
As organo-tin compound, can enumerate：Dialkyl tin oxide, the soap of dialkyl tin, the fat of stannous
Fat hydrochlorate etc..
(H) the preferred organo-tin compound of crosslinking catalyst, especially preferably selected from di-n-octyltin oxide, tin dilaurate two
It is more than at least one in the compound group of tin octylate composition.
Relative to the copolymer of 100 weight portions, (H) crosslinking catalyst of 0.01～0.5 weight portion is preferably comprised.
(I) polyether-modified silicone compounds are the silicone compounds with polyether-based, except conventional siloxanes
Unit (- SiR1 2- O-), also with the siloxane unit (- SiR with polyether-based1(R2O(R3O)nR4)-O-〕.Herein, R1Represent a kind
Or alkyl or aryl of more than two kinds, R2And R3Represent one kind or two or more alkylidene, R4The one kind or two or more alkyl of expression,
Acyl group etc. (terminal groups).Can enumerate as polyether-based：Polyethylene oxide base ((C2H4O)n) or polypropylene oxide base
〔(C3H6O)n) etc. polyoxyalkylene.
(I) polyether-modified silicone compounds are preferably the polyether-modified silicone compounds that HLB value is 7～12.
Also, relative to the copolymer of 100 weight portions, preferably comprise (I) of 0.01～0.5 weight portion polyether-modified silicone compound
Thing.More preferably 0.1～0.5 weight portion.
So-called HLB is, such as hydrophile-lipophile balance (hydrophilic specified in JIS K3211 (surfactant term) etc.
With oil loving ratio).
Polyether-modified silicone compounds are, for example, for the polysiloxane main chain with silylation, Neng Goutong
Over hydrogenation Silanization reaction obtains the grafting of the organic compound with unsaturated bond and polyoxyalkylene.Specifically can lift
Go out：Dimethylsiloxane methyl (polyethylene glycol oxide) silicone copolymers, dimethylsiloxane methyl (polyethylene glycol oxide)
Siloxanes methyl (polypropylene oxide) silicone copolymers, dimethylsiloxane methyl (polypropylene oxide) copolymeric siloxane
Thing etc..
By the way that (I) polyether-modified silicone compounds are mixed into into adhesive composition, the viscous of binding agent can be improved
With joint efforts and performance of doing over again.
Furthermore, as other compositions, can suitably mix copolymerizable (methyl) acrylic compounds containing oxyalkylene
Acrylamide monomer, surfactant, hardening accelerator, plasticising that monomer, (methyl) acrylamide monomer, dialkyl group replace
The known additive of agent, filler, cure inhibitors, processing aid, age resister, antioxidant, antistatic additive etc..These
Can individually or two or more merging is used.
As antistatic additive, ionic compound can be enumerated.Also, by making ionic acrylic monomer copolymerization in master
The copolymer of agent can give antistatic property.
The copolymer of the host used in the adhesive composition of the present invention can pass through the carbon number of polymerization (A) alkyl
(methyl) acrylate monomer and the copolymerisable monomer of (B) containing hydroxyl and (C) for C4～C10 is containing the copolymerizable of carboxyl
Monomer and (D) polyalkylene glycol mono (methyl) acrylate monomer synthesize.The polymerization of copolymer is without special limit
It is fixed, it is possible to use the appropriate polymerization such as polymerisation in solution, emulsion polymerization.
By mixing more than (F) 3 sense isocyanate compound, (G) cross-linked inhibitor, (H) in above-mentioned copolymer
Crosslinking catalyst, (I) polyether-modified silicone compounds, further appropriate arbitrary additive can prepare the present invention's
Adhesive composition.
Above-mentioned copolymer, preferably acrylic polymer, preferably comprise (methyl) acrylate of 50～100 weight %
The acrylic monomer of monomer, (methyl) acrylic acid, (methyl) acrylic amide etc..
In addition, the acid number of acrylic polymer is preferably 0.01～8.0.By the acid number, contaminative can be improved, carried
Height prevents the performance that adhesive residue occurs.
Herein, " acid number " refers to represent one of index of sour amount, represents neutralization 1g and contains the poly- of carboxyl
The mg numbers of the potassium hydroxide needed for compound.
Preferably so that the adhesive phase of above-mentioned binder composition cross-links is under low speed peeling rate 0.3m/min
Bonding force is 0.05～0.1N/25mm, and the bonding force under high speed peeling rate 30m/min is below 1.0N/25mm.Thus,
Bonding force can be obtained with peeling rate performance with low uncertainty, even Jing is peeled off at a high speed, promptly peeled off and be also possibly realized.
Also, in order to fit again, when temporarily peeling off surface protection film, it is not necessary to excessive power, it is easy to peel off from adherend.
So that the gel fraction of the adhesive phase (binding agent after crosslinking) of the binder composition cross-links of the present invention
It is preferred that 95～100%.So, because gel fraction is high, the bonding force in peeling off can low speed does not become too much, reduce from
The unconverted monomer of copolymer or the dissolution of oligomer, improve doing over again property, it is hot and humid in durability, suppress adherend
Pollution.
The bonding film of the present invention is so that the adhesive phase of the binder composition cross-links of the present invention in resin film
One or two sides on be formed with.Additionally, the surface protection film of the present invention is the binder composition cross-links for making the present invention
The surface protection film that adhesive phase is formed in the one side of resin film.The adhesive composition of the present invention is due to causing above-mentioned (A)
Each composition of～(I) balances well mixing, the balancing good with bonding force under peeling off and peel off at a high speed in low speed, and resistance to
Long property and doing over again property (after being described on surface protection film via adhesive phase with ball pen, no to transfer the pollution to adherend)
Also it is excellent.Therefore, it is possible to be suitably used as the purposes of Polarizer surface protection film.
The stripping film (partition) of base material film, protection adhesive surface as adhesive phase can use the resin film of polyester film etc.
Deng.
In base material film, on the face contrary with adhesive phase side is formed of resin film, can implement by silicone, fluorine
The antifouling process of releasing agent or coating agent, the silicon dioxide microparticle of class etc.；By the anti-quiet of the coating or kneading of antistatic agent etc.
Electric treatment.
In stripping film, on the face with adhesive surface adhesive side of adhesive phase, implement to pass through silicone, the demoulding of fluorine class
The demoulding of agent etc. is processed.
Embodiment
Below, based on embodiment, the present invention is illustrated.
The preparation ＞ of ＜ acrylic copolymers
[embodiment 1]
Nitrogen is imported in the reaction unit equipped with agitator, thermometer, reflux condenser and nitrogen ingress pipe, will be reacted
Air nitrogen displacement in device.Then, the weight portion of 2-EHA 100, acrylic acid are added in reaction unit
The weight portion of 8- hydroxyls monooctyl ester 0.9, the weight portion of acrylic acid 0.5, the poly- weight portion of ethylidene glycol mono acrylic ester 3, N- vinylpyridines
The weight portion of pyrrolidone 5 and the weight portion of solvent (ethyl acetate) 60.Then, the azo for instilling as polymerization initiator through 2 hours
The weight portion of bis-isobutyronitrile 0.1, its reaction 6 hours is made in 65 DEG C, obtains third used in the embodiment 1 that weight average molecular weight is 500,000
Olefin(e) acid analog copolymer solution 1.Extract a part for acrylic copolymer, the sample as following acid value measuring.
[embodiment 2～9 and comparative example 1～9]
The composition of monomer each according to table 1 (A)～(E) it is described as set, in addition, according to it is above-mentioned
Acrylic copolymer solution 1 used in embodiment 1 similarly, obtains third used in embodiment 2～9 and comparative example 1～9
Olefin(e) acid analog copolymer solution.
[table 1]
The preparation ＞ of ＜ adhesive compositions and surface protection film
[embodiment 1]
For the acrylic copolymer solution 1 of embodiment 1 prepared as described above, addition KF-351A be (HLB=12's
Polyether-modified silicone compounds) 0.2 weight portion, the weight portion of acetylacetone,2,4-pentanedione 2.5 and after stirring, add U ロ ネ ー ト HX (six
The isocyanuric acid ester body of methylene diisocyanate compound) 1.5 weight portions, stir after the weight portion of tin dilaurate dioctyl tin 0.02
Mixing is mixed, the adhesive composition of embodiment 1 is obtained.The adhesive composition is coated into the poly- to benzene two of silicone coating
After on the stripping film that formic acid glycol ester (PET) film is constituted, by removing solvent in 90 DEG C be dried, the thickness of adhesive phase is obtained
Spend the bonding sheet for 25 μm.
Then, bonding sheet is transferred to the polyethylene terephthalate of the upper Jing antistatics of one side and antifouling process
(PET) reverse side in the Jing antistatics of film and antifouling process face, is had " PET film/the binding agent of Jing antistatics and antifouling process
The surface protection film of the embodiment 1 of the laminar structure of layer/stripping film (PET film of silicone coating) ".
[embodiment 2～9 and comparative example 1～9]
Additive composition each set as described in (F)～(I) of table 2, in addition, according to it is above-mentioned
The surface protection film of embodiment 1 similarly, obtains embodiment 2～9 with the surface protection film for comparing 1～9.
[table 2]
The overall table for showing the mixed proportion of each composition is divided into two tables by Tables 1 and 2, with the summation that arbitrary (A) is organized
The numerical value bracket of the weight portion required by 100 weight portions is enclosed and represented.Also, each composition used in by Tables 1 and 2
The compound name of abbreviation is shown in table 3 and table 4.In addition, U ロ ネ ー ト (registered trade mark) HX and same HL are Japanese Port リ
The trade name of ウ レ タ Application Industrial Co., Ltd, タ ケ ネ ー ト (registered trade mark) D-140N are the business of Mitsui Chemicals, Inc
The name of an article, KF-351A, KF-352A, KF-353, KF-640 and X-22-6191 are the trade names of KCC of SHIN-ETSU HANTOTAI.
[table 3]
[table 4]
＜ test methods and evaluation ＞
By the surface protection film in embodiment 1～9 and comparative example 1～9 aging 7 days under 23 DEG C, the atmosphere of 50%RH after,
Peel off stripping film (PET film of silicone coating), the test sample to expose the material of adhesive phase as gel fraction.
Further, the surface protection film for exposing adhesive phase is fitted in via adhesive phase and is pasted onto on liquid crystal cell
The surface of Polarizer, after placing 1 day, Jing 50 DEG C, 5 atmospheric pressure, the autoclave process of 20 minutes, further places 12 in room temperature
Hour, using material Jing derived above as bonding force and the test sample of durability.
<Acid number>
The acid number of acrylic polymer, sample is dissolved in into solvent, and (diethyl ether and ethanol are with volume ratio 2:1 is mixed to get
Material) in, using potential difference automatic titration device (capital of a country electronics industry system, AT-610), using 0.1 above-mentioned potential difference titration
Device, potential difference titration is carried out with the potassium hydroxide-ethanol solution that concentration is for about 0.1mol/l, is determined needed in order to neutralize sample
Potassium hydroxide-ethanol solution amount.Then, acid number is tried to achieve by following formula.
Acid number=(B × f × 5.611)/S
The amount (ml) of the 0.1mol/l potassium hydroxide-ethanol solutions used in B=titration
The factor of f=0.1mol/l potassium hydroxide-ethanol solutions
The quality (g) of the solid constituent of S=samples
＜ gel fraction ＞
After aging end, the quality for fitting in the test sample before Polarizer is correctly determined, immersion 24 is little in toluene
Shi Hou, by the metal mesh filter of 200 mesh.Then, after 100 DEG C of dried screenings 1 hour, the matter of residue is correctly determined
Amount, from following formula the gel fraction of adhesive phase (binding agent after crosslinking) is calculated.
Gel fraction (%)=insoluble matter quality (g)/binding agent quality (g) × 100
＜ bonding force ＞
Using following peel strengths as bonding force：Using tensile testing machine low speed peeling rate (0.3m/min) and height
Under the peeling rate (30m/min) of speed test sample obtained above is peeled through (in the laminating of polarisation plate surface to 180 ° of directions
The material of 25mm wide surface protection film) determine peel strength.
＜ doing over again property ＞
Described on the surface protection film by test sample obtained above with ball pen (load 500g, reciprocal 3 times)
Afterwards, surface protection film observation polarisation plate surface is peeled off from Polarizer, confirmation is no to transfer the pollution to Polarizer.Evaluation objective benchmark
It is not to be evaluated as "○" to the situation that Polarizer is transferred the pollution, confirms that the track described along ball pen turns at least a portion
The situation for moving pollution is evaluated as " Δ ", confirms that the track described along ball pen transfers the pollution, also has bonding from adhesive surface
The situation that agent departs from is evaluated as "×".
＜ durability ＞
After being placed through test sample obtained above 250 hours under 60 DEG C, 90%RH atmosphere, taken in room temperature
Go out, after further placing 12 hours, determine bonding force, confirm compared with initial bonding force relatively without significantly increase.Comment
Valency target fiducials be the bonding force after test be less than 1.5 times of initial bonding force of situation be evaluated as "○", more than 1.5 times
Situation is evaluated as "×".
Evaluation result is shown in Table 5.
[table 5]
Bonding force of the surface protection film of embodiment 1～9 under low speed peeling rate 0.3m/min is 0.05～0.1N/
25mm, the bonding force under high speed peeling rate 30m/min is below 1.0N/25mm, with ball pen via adhesive phase in table
There is no the pollution transportation to adherend after describing on surface protective film, 60 DEG C, the atmosphere of 90%RH it is durable when placing within lower 250 hours
Property is also outstanding.
That is, the balance of the bonding force in low speed peeling rate and high speed peeling rate is obtained with regard to (1)；(2) bonding is prevented
The generation of agent residual；(3) do over again performance, simultaneously meet whole requirement performances.
The surface protection film of comparative example 1 because of without (D) polyalkylene glycol mono (methyl) acrylate monomer and
(E) nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl, low speed peeling rate 0.3m/min
Under bonding force it is low, doing over again property is also slightly poor.
The surface protection film of comparative example 2, because of the monomer of (B) containing hydroxyl is very few, (D) polyalkylene glycol mono
(methyl) acrylate monomer is very few, do not contain (E) nitrogenous vinyl monomer or (methyl) alkyl acrylate containing alkoxyl
Base ester monomer, (F) isocyanate compound are excessive, the HLB value of the silicone compounds that (I) is polyether-modified is too small, therefore low speed
Bonding force under bonding force and high speed peeling rate 30m/min under peeling rate 0.3m/min becomes too much, doing over again property and resistance to
Long property is deteriorated, gel fraction step-down.
The surface protection film of comparative example 3, because of the monomer of (B) containing hydroxyl it is excessive, (C) acidiferous monomer is excessive, (D)
Polyalkylene glycol mono (methyl) acrylate monomer is excessive and (E) is nitrogenous vinyl monomer or the (first containing alkoxyl
Base) alkyl acrylate monomer is excessive, (I) is polyether-modified silicone compounds HLB value it is excessive, therefore acrylic
The bonding force under bonding force and high speed peeling rate 30m/min under the acid number high, low speed peeling rate 0.3m/min of thing becomes
Excessive, doing over again property and poor durability.
The surface protection film of comparative example 4, because of (C) containing acid monomer it is very few, without (D) polyalkylene glycol mono
(methyl) acrylate monomer, (E) nitrogenous vinyl monomer or (methyl) the alkyl acrylate monomer mistake containing alkoxyl
It is few, therefore the bonding force under low speed peeling rate 0.3m/min is low, doing over again property and poor durability.
The surface protection film of comparative example 5, because of the monomer of (B) containing hydroxyl it is excessive, the monomer of (C) containing acid is excessive,
(D) polyalkylene glycol mono (methyl) acrylate monomer it is very few, without (E) nitrogenous vinyl monomer or containing alkoxyl
(methyl) alkyl acrylate monomer, (F) isocyanate compound are very few, therefore the acid number of acrylic polymer becomes high and low
Bonding force under bonding force and high speed peeling rate 30m/min under fast peeling rate 0.3m/min become too much, doing over again property and
Durability is deteriorated, gel fraction step-down.
The surface protection film of comparative example 6 is likely due to not mix (G) cross-linked inhibitor, therefore storage period excessively becomes
It is short, it is unable to be coated due to carrying out crosslinking before coating.
The surface protection film of comparative example 7, it may be possible to contain in due to there is (methyl) acrylate monomer of alkyl at (A)
MA with C1 alkyl, the monomer of (B) containing hydroxyl be excessive, without (D) polyalkylene glycol mono (methyl) acrylate monomer
(E) nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl, no mixing (H) cross-linking catalyst
The bonding force under bonding force and high speed peeling rate 30m/min under agent, therefore low speed peeling rate 0.3m/min is excessive, do over again
Property and poor durability.
The surface protection film of comparative example 8, because of (D) polyalkylene glycol mono (methyl) acrylate monomer it is excessive,
(methyl) alkyl acrylate monomer without (E) nitrogenous vinyl monomer or containing alkoxyl, change without mixing (I) polyethers
The silicone compounds of property, therefore under the bonding force under low speed peeling rate 0.3m/min and high speed peeling rate 30m/min
Bonding force is excessive, doing over again property is slightly poor.
The surface protection film of comparative example 9, because of without (D) polyalkylene glycol mono (methyl) acrylate monomer and
(E) nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl, (I) polyether-modified siliconization
Compound is excessive, therefore the bonding force under low speed peeling rate 0.3m/min is low, doing over again property is slightly poor, poor durability.
So, in the surface protection film of comparative example 1～9, it is impossible to while meeting (1) obtains low speed peeling rate and high speed
The balance of the bonding force in peeling rate；(2) generation of adhesive residue is prevented；(3) whole with performance of doing over again will
Seek performance.
Claims (11)
1. a kind of adhesive composition, it is the adhesive composition containing acrylic polymer and cross-linking agent, wherein,
The acrylic polymer by by the carbon number of (A) alkyl for C4～C10 (methyl) acrylate monomer and
(B) copolymerisable monomer containing hydroxyl and the copolymerisable monomer of (C) containing carboxyl and (D) polyalkylene glycol mono (methyl) third
Olefin(e) acid ester monomer and (E) the not nitrogenous vinyl monomer of hydroxyl or (methyl) the alkyl acrylate list containing alkoxyl
At least one copolymer for carrying out copolymerization in body is constituted,
Relative to 100 weight portions above-mentioned (A) alkyl carbon number for C4～C10 (methyl) acrylate monomer, with 1 weight
Contain above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer more than amount part and less than the ratio of 10 weight portions.
The acid number of aforesaid propylene acids polymers is 0.01～8.0,
In being (methyl) acrylate monomer of C4～C10 in the carbon number of above-mentioned (A) alkyl of 100 weight portions, contain 50
(methyl) acrylic acid-2-ethyl caproite or (methyl) Isooctyl acrylate monomer more than weight portion,
And, containing isocyanate compound more than (F) 3 sense, (G) cross-linked inhibitor, (H) crosslinking catalyst, (I) HLB
Value is 7～12 polyether-modified silicone compounds.
2. adhesive composition according to claim 1, wherein,
The above-mentioned copolymerisable monomer of (B) containing hydroxyl is selected from (methyl) acrylic acid 8- hydroxyl monooctyl esters, (methyl) acrylic acid 6-
The own ester of hydroxyl, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxy methacrylates, N- hydroxyls (methyl) acrylamide,
It is more than at least one in N- methylols (methyl) acrylamide, the compound group of N- ethoxys (methyl) acrylamide composition；
It is (methyl) acrylate monomer of C4～C10 relative to the carbon number of above-mentioned (A) alkyl of 100 weight portions, contains
The above-mentioned copolymerisable monomer of (B) containing hydroxyl of 0.1～5.0 weight portion, also, the above-mentioned copolymerisable monomer of (B) containing hydroxyl
In, (methyl) acrylic acid 8- hydroxyl monooctyl esters, the own ester of (methyl) acrylic acid 6- hydroxyls and (methyl) acrylic acid 4- hydroxybutyls it is total
Measure as 0～0.9 weight portion.
3. adhesive composition according to claim 1 and 2, wherein,
The above-mentioned copolymerisable monomer of (C) containing carboxyl is selected from (methyl) acrylic acid, carboxyethyl (methyl) acrylate, carboxylic penta
Base (methyl) acrylate, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2- (methyl) acryloxypropyl
Hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl phthalic acid, 2- (methyl) acryloyl-oxyethyl succinic acid,
2- (methyl) acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) acryloxy
It is more than at least one in the compound group of ethyl tetrahydrophthalic acid composition；
It is (methyl) acrylate monomer of C4～C10 relative to the carbon number of above-mentioned (A) alkyl of 100 weight portions, contains
The above-mentioned copolymerisable monomer of (C) containing carboxyl of 0.35～1.0 weight portion.
4. adhesive composition according to claim 1 and 2, wherein, above-mentioned (D) polyalkylene glycol mono (methyl) propylene
Acid ester monomer be selected from polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate,
It is more than at least one in ethyoxyl poly alkylene glycol (methyl) acrylate.
5. adhesive composition according to claim 1 and 2, wherein, relative to above-mentioned (A) alkyl of 100 weight portions
Carbon number for C4～C10 (methyl) acrylate monomer, containing the nitrogenous of 1～20 weight portion above-mentioned (E) not hydroxyl
Vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl.
6. adhesive composition according to claim 1 and 2, wherein,
Isocyanate compound more than above-mentioned (F) 3 sense is the isocyanide urea selected from hexamethylene diisocyanate compound
Acid esters body, the isocyanuric acid ester body of isophorone diisocyanate compound, the adduction of hexamethylene diisocyanate compound
It is object, the adduction object of isophorone diisocyanate compound, the biuret body of hexamethylene diisocyanate compound, different
It is more than at least one in the compound group of the biuret body composition of isophorone diisocyanate compound；
Relative to the above-mentioned copolymer of 100 weight portions, Carbimide. more than above-mentioned (F) 3 sense containing 0.4～5.0 weight portion
Ester compounds.
7. adhesive composition according to claim 1 and 2, wherein,
Relative to the above-mentioned copolymer of 100 weight portions, above-mentioned (I) containing 0.01～0.5 weight portion polyether-modified siloxanes
Compound.
8. adhesive composition according to claim 1 and 2, wherein,
Above-mentioned (G) cross-linked inhibitor is keto-enol tautomerism compound；
Relative to the above-mentioned copolymer of 100 weight portions, above-mentioned (G) cross-linked inhibitor containing 1.0～5.0 weight portions；
Above-mentioned (H) crosslinking catalyst is organo-tin compound；
Relative to the above-mentioned copolymer of 100 weight portions, above-mentioned (H) crosslinking catalyst containing 0.01～0.5 weight portion.
9. a kind of bonding film, it is to be formed with to make binding agent according to claim 1 and 2 on one or two sides of resin film
The bonding film of the adhesive phase of compositionss crosslinking.
10. a kind of surface protection film, it is to be formed with to make bonding according to claim 1 and 2 in the one side of resin film
The surface protection film of the adhesive phase of agent compositionss crosslinking.
11. surface protection films according to claim 10, it is used as the purposes of the surface protection film of Polarizer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-086439 | 2012-04-05 | ||
| JP2012086439A JP5901399B2 (en) | 2012-04-05 | 2012-04-05 | Adhesive composition and surface protective film |
| CN201310114472.5A CN103361001B (en) | 2012-04-05 | 2013-04-03 | Binder composition and surface protection film |
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| CN201310114472.5A Division CN103361001B (en) | 2012-04-05 | 2013-04-03 | Binder composition and surface protection film |
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| CN105219313B true CN105219313B (en) | 2017-05-03 |
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| CN201310114472.5A Active CN103361001B (en) | 2012-04-05 | 2013-04-03 | Binder composition and surface protection film |
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| CN201310114472.5A Active CN103361001B (en) | 2012-04-05 | 2013-04-03 | Binder composition and surface protection film |
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| JP (1) | JP5901399B2 (en) |
| KR (1) | KR101526222B1 (en) |
| CN (2) | CN105219313B (en) |
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| JP6393921B2 (en) * | 2013-11-20 | 2018-09-26 | 藤森工業株式会社 | Adhesive composition 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 |
| KR101687478B1 (en) | 2014-03-05 | 2016-12-16 | 주식회사 엘지화학 | Adhesive composition, a comprising anti-scattering film and decor film |
| TWI645010B (en) * | 2014-03-17 | 2018-12-21 | 日商住友化學股份有限公司 | Resin film with adhesive and optical laminate using the same |
| JP6333596B2 (en) * | 2014-03-26 | 2018-05-30 | リンテック株式会社 | Manufacturing method of workpiece fixing sheet with resin layer |
| JP6934443B2 (en) * | 2014-03-28 | 2021-09-15 | リンテック株式会社 | Adhesives and adhesive sheets |
| JP6220481B2 (en) * | 2015-09-01 | 2017-10-25 | リンテック株式会社 | Adhesive sheet |
| JP6108023B1 (en) * | 2016-02-02 | 2017-04-05 | 東洋インキＳｃホールディングス株式会社 | Adhesive and adhesive sheet |
| JP2017144608A (en) * | 2016-02-16 | 2017-08-24 | 藤森工業株式会社 | Surface protective film and optical component laminated with the same |
| JP6521906B2 (en) * | 2016-06-16 | 2019-05-29 | 藤森工業株式会社 | Pressure sensitive adhesive composition and antistatic surface protective film |
| JP6677673B2 (en) * | 2017-05-15 | 2020-04-08 | 藤森工業株式会社 | Pressure-sensitive adhesive composition and surface protective film |
| JP6378401B2 (en) * | 2017-06-12 | 2018-08-22 | 藤森工業株式会社 | Surface protection film |
| JP6530540B2 (en) * | 2018-07-25 | 2019-06-12 | 藤森工業株式会社 | Surface protection film |
| JP6725725B2 (en) * | 2019-05-15 | 2020-07-22 | 藤森工業株式会社 | Surface protection film |
| JP7263974B2 (en) * | 2019-08-09 | 2023-04-25 | 東洋インキＳｃホールディングス株式会社 | Adhesives and adhesive sheets |
| JP7375451B2 (en) * | 2019-10-17 | 2023-11-08 | Dic株式会社 | adhesive composition |
| JP6871456B2 (en) * | 2020-04-08 | 2021-05-12 | 藤森工業株式会社 | Surface protective film |
| JP7041199B2 (en) | 2020-06-24 | 2022-03-23 | 藤森工業株式会社 | Surface protection film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006002140A (en) * | 2004-05-20 | 2006-01-05 | Saiden Chemical Industry Co Ltd | Polymer composition for pressure-sensitive adhesive, pressure-sensitive adhesive composition for surface protective film, and the surface protective film |
| CN101553548A (en) * | 2006-09-14 | 2009-10-07 | 综研化学株式会社 | Adhesive composition and adhesive sheet |
| CN102076802A (en) * | 2009-04-30 | 2011-05-25 | 日东电工株式会社 | Adhesive composition for optical film, adhesive layer for optical film, and adhesive optical film, and image display device |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080200587A1 (en) * | 2007-02-16 | 2008-08-21 | 3M Innovative Properties Company | Pressure-sensitive adhesive containing acicular silica particles crosslinked with polyfunctional aziridines |
| US8188194B2 (en) * | 2007-07-11 | 2012-05-29 | Soken Chemical & Engineering Co., Ltd. | Adhesive for polarizing plate and polarizing plate having adhesive layer |
| JP2009091406A (en) * | 2007-10-04 | 2009-04-30 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition and surface protection film |
| EP2053109A1 (en) * | 2007-10-22 | 2009-04-29 | Nitto Denko Corporation | Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive layer for optical film, production method thereof, pressure-sensitive adhesive optical film and image display |
| EP2072552A3 (en) * | 2007-12-20 | 2009-07-29 | Nitto Denko Corporation | Pressure-sensitive adhesive composition for optical films, pressure-sensitive adhesive optical film and image display |
| JP5580069B2 (en) * | 2009-02-26 | 2014-08-27 | 日東電工株式会社 | Adhesive composition for surface protective film and use thereof |
| JP5623020B2 (en) * | 2009-02-27 | 2014-11-12 | 日東電工株式会社 | Adhesive composition, adhesive layer, and adhesive sheet |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006002140A (en) * | 2004-05-20 | 2006-01-05 | Saiden Chemical Industry Co Ltd | Polymer composition for pressure-sensitive adhesive, pressure-sensitive adhesive composition for surface protective film, and the surface protective film |
| CN101553548A (en) * | 2006-09-14 | 2009-10-07 | 综研化学株式会社 | Adhesive composition and adhesive sheet |
| CN102076802A (en) * | 2009-04-30 | 2011-05-25 | 日东电工株式会社 | Adhesive composition for optical film, adhesive layer for optical film, and adhesive optical film, and image display device |
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| KR101526222B1 (en) | 2015-06-05 |
| CN103361001B (en) | 2015-11-18 |
| TWI495698B (en) | 2015-08-11 |
| KR20130113373A (en) | 2013-10-15 |
| CN105219313A (en) | 2016-01-06 |
| CN103361001A (en) | 2013-10-23 |
| TW201343833A (en) | 2013-11-01 |
| JP2013216739A (en) | 2013-10-24 |
| JP5901399B2 (en) | 2016-04-06 |
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