CN104650779A - Adhesive composition and surface protection film - Google Patents

Adhesive composition and surface protection film Download PDF

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Publication number
CN104650779A
CN104650779A CN201410588424.4A CN201410588424A CN104650779A CN 104650779 A CN104650779 A CN 104650779A CN 201410588424 A CN201410588424 A CN 201410588424A CN 104650779 A CN104650779 A CN 104650779A
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China
Prior art keywords
methyl
compound
monomer
acrylate
adhesive composition
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CN201410588424.4A
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CN104650779B (en
Inventor
长仓毅
岛口龙介
长谷川良
新见洋人
吉田弘幸
菱沼昌世
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Fujimori Kogyo Co Ltd
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Fujimori Kogyo Co Ltd
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Priority to CN201810171056.1A priority Critical patent/CN108300343A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09J155/00—Adhesives based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09J123/00 - C09J153/00
    • 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
    • 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]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides an adhesive composition which has excellent antistatic performance, ideal binding power balance at low stripping speed and high stripping speed, and good durability and reprocessability, and a surface protection film. The adhesive composition comprises at least one copolymer acrylic polymer selected from the group of (A) a (methyl) acrylate monomer with C4-C18 alkyl carbon number; (B) a copolymerizable monomer including hydroxy; (C) a copolymerizable monomer including hydroxy; (D)a poly alkylene glycol single (methyl) acrylate monomer, and (E) a vinyl monomer not including hydroxy but including nitrogen or a (methyl) alkyl acrylate monomer including alkoxy, and also comprises (F) a trifunctional isocyanate compound, (G) a difunctional noncyclic aliphatic series isocyanate compound, and (H) an antistatic agent.

Description

Adhesive composition and surface protection film
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 employ 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 assembled into 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; and; this adhesive layer is fitted with the stripping film through lift-off processing, to protect this adhesive layer until fit on 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 again again to be there is after temporary transient stripper surface protective membrane, now requires easily to peel off (re-workability) from the optics as adherend.
In addition, time finally from the optics such as Polarizer, polarizer stripper surface protective membrane, 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; namely allow to meet the performance requriements to the adhesive layer forming surface protection film respectively; namely; namely allow to meet the indivedual performance requriementss in above-mentioned (1) ~ (4) 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 problem 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., there is the problem of releasable difference when the problem, the high speed in field hand-manipulated that produce the peelings such as separation because of heating when adding man-hour or preserve are peeled off.
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 static resistance 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 (a) quaternary ammonium salt, pyridinium salt, there are the various cationic antistatic agents of the cation radicals such as primary ~ uncle is amino; B () has the anionic antistatic agents of the anion-radicals of sulphonate-base, sulfuric ester alkali, phosphoric acid ester alkali, phosphonic acids alkali etc.; The both sexes static inhibitor of (c) amino acids, amidosulphuric acid ester class etc.; The non-ionic antistatic agent of (d) alkamine, glycerols, polyethylene glycols etc.; E () makes static inhibitor as above carry out polymer to 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, instead of be 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, be difficult to again peel off after mistake laminating, 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.
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
In the prior art, as the performance requriements of the adhesive layer to formation surface protection film, require that it can obtain the balance of cohesive force and have excellent antistatic property and cycling processability etc. under low peeling rate and high peeling rate 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.
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, wherein,
This adhesive composition comprises: containing at least one in the carbonatoms of (A) alkyl (methyl) acrylate monomer that is C4 ~ C18 and be selected from by the acrylic polymers of the multipolymer of at least one in the copolymerisable monomer of (B) hydroxyl, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) not hydroxyl and nitrogenous vinyl monomer or the copolymerisable monomer group that forms containing (methyl) alkyl acrylate monomer of alkoxyl group
Further, also containing isocyanate compound more than (F) trifunctional, (G) two sense non-ring type aliphatic isocyanates compound and (H) static inhibitor.
In addition, when the total amount of the acrylic polymers setting aforementioned copolymer is 100 weight part, preferably:
The carbonatoms of aforementioned (A) alkyl is the content of (methyl) acrylate monomer of C4 ~ C18 is 50 ~ 91 weight parts,
The content of the copolymerisable monomer of aforementioned (B) hydroxyl is 0.1 ~ 10 weight part,
The content of aforementioned (C) carboxylic copolymerisable monomer is 0 ~ 1.0 weight part,
The content of aforementioned (D) polyalkylene glycol mono (methyl) acrylate monomer is 0 ~ 50 weight part,
Aforementioned (E) not hydroxyl and nitrogenous vinyl monomer or the content containing (methyl) alkyl acrylate monomer of alkoxyl group is 0 ~ 20 weight part.
In addition, isocyanate compound more than aforementioned (F) trifunctional is 1 ~ 90 with the weight ratio (F/G) of (G) two sense non-ring type aliphatic isocyanates compound, relative to 100 weight part foregoing acrylic polymkeric substance, the total amount of the isocyanate compound preferably more than aforementioned (F) trifunctional and (G) two sense non-ring type aliphatic isocyanates compound is 0.1 ~ 5.0 weight part.
In addition, aforementioned (G) two sense non-ring type aliphatic isocyanates compound is the compound making diisocyanate cpd and diol compound react and generate.As aforementioned diisocyanates compound, be aliphatic diisocyanate, form preferably by the one be selected from the compound group that is made up of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysinediisocyanate.In addition, as foregoing glycols compound, preferably by being selected from by 2-methyl 1,3-PD, 2,2-dimethyl-1, ammediol, 2-methyl-2-propyl-1, ammediol, 2-ethyl-2-butyl-1,3-PD, 3-methyl isophthalic acid, 5-pentanediol, 2, one in the compound group that 2-dimethyl-1,3-propylene glycol monohydroxy pivalate, polyoxyethylene glycol, polypropylene glycol form is formed.
In addition, preferably the copolymerisable monomer of aforementioned (B) hydroxyl is 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.
In addition, preferably aforementioned (C) carboxylic copolymerisable monomer is selected from by (methyl) vinylformic acid, (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, more than at least one in the compound group that 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid forms.
In addition, preferred (D) polyalkylene glycol mono (methyl) acrylate monomer is for being selected from more than at least one in polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate.
Isocyanate compound more than aforementioned (F) trifunctional, preferably be selected from 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, 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, in the compound group that the affixture of hydrogenated xylylene diisocyanate cpd forms more than at least one.
In addition, preferred foregoing acrylic polymkeric substance aforementioned (E) not hydroxyl and nitrogenous vinyl monomer or containing more than at least one in (methyl) alkyl acrylate monomer of alkoxyl group of containing aforementioned copolymerisable monomer group.
In addition, preferably aforementioned (H) static inhibitor contains 0.01 ~ 5.0 weight part relative to the aforementioned copolymer of 100 weight parts and the ionic compound of fusing point 30 ~ 50 DEG C or the copolymerization amount in aforementioned copolymer are 0.1 ~ 5.0 % by weight and containing the ionic compound of acryl.
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 + 10Ω/below, stripping static voltage is ± 0 ~ 1kV.
Further, the invention provides a kind of surface protection film, it is characterized in that, the single or double of resin molding forms adhesive layer and forms, 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 foregoing adhesives layer of aforementioned resin film, implement antistatic treatment 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, and excellent antistatic property can be obtained, the generation of glue residue phenomenon can be prevented.Specifically, excellent antistatic property can not only be kept, but also the addition of static inhibitor can be reduced, also can improve the performance preventing glue residue.
In addition, by by isocyanate compound more than (F) trifunctional and (G) two sense non-ring type aliphatic isocyanates compound using, can make that bridging property is excellent, stain resistance also becomes good, and then the balance of cohesive force under low peeling rate and high peeling rate is excellent.
Embodiment
Below, based on preferred embodiment the present invention being described.
Adhesive composition of the present invention, is characterized in that,
Its host is by least one in (methyl) acrylate monomer being C4 ~ C18 containing the carbonatoms of (A) alkyl and be selected from being made up of the acrylic polymers of the multipolymer of at least one in the copolymerisable monomer of (B) hydroxyl, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) not hydroxyl and nitrogenous vinyl monomer or the copolymerisable monomer group that forms containing (methyl) alkyl acrylate monomer of alkoxyl group as copolymerisable monomer group
Further, described adhesive composition is also containing isocyanate compound more than (F) trifunctional, (G) two sense non-ring type aliphatic isocyanates compound and (H) static inhibitor.
In addition, when the total amount of the acrylic polymers setting aforementioned copolymer is 100 weight part, preferably contain: the carbonatoms of 50 ~ 91 weight parts aforementioned (A) alkyl is (methyl) acrylate monomer of C4 ~ C18, the copolymerisable monomer of 0.1 ~ 10 weight part aforementioned (B) hydroxyl, 0 ~ 1.0 weight part aforementioned (C) carboxylic copolymerisable monomer, 0 ~ 50 weight part aforementioned (D) polyalkylene glycol mono (methyl) acrylate monomer, and 0 ~ 20 weight part aforementioned (E) not hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl group.
Carbonatoms as (A) alkyl is (methyl) acrylate monomer of C4 ~ C18, 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, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid pentadecyl ester, (methyl) aliphatic acrylate, (methyl) vinylformic acid heptadecyl ester, (methyl) octadecyl acrylate, (methyl) myristyl ester, the different tetradecyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid cetyl, (methyl) vinylformic acid isocetyl ester, (methyl) stearyl acrylate acyl ester, (methyl) vinylformic acid isooctadecane base ester etc.
When the total amount of the acrylic polymers setting multipolymer is 100 weight part, preferably the carbonatoms of (A) alkyl is the content of (methyl) acrylate monomer of C4 ~ C18 is 50 ~ 91 weight parts.
As the copolymerisable monomer of (B) hydroxyl, 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.
The copolymerisable monomer of preferred above-mentioned hydroxyl is 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.
When the total amount of the acrylic polymers setting multipolymer is 100 weight part, preferably the content of the copolymerisable monomer of aforementioned (B) hydroxyl is 0.1 ~ 10 weight part.
Preferably (C) carboxylic copolymerisable monomer is selected from by (methyl) vinylformic acid, (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, more than at least one in the compound group that 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid forms.
When the total amount of the acrylic polymers setting multipolymer is 100 weight part, preferably the content of aforementioned (C) carboxylic copolymerisable monomer is 0 ~ 1.0 weight part.Adhesive composition in adhesive layer of the present invention also can not contain (C) carboxylic copolymerisable monomer.
As (D) 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 can become the saturated carboxylic acid esters 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.
The averaged repeating numbers preferably forming the alkylene oxide of polyalkylene glycol chain in (D) polyalkylene glycol mono (methyl) acrylate monomer is 3 ~ 14.So-called " averaged repeating numbers of alkylene oxide ", refers to the mean number that in " polyalkylene glycol chain " part contained in the molecular structure of (D) polyalkylene glycol mono (methyl) acrylate monomer, alkylene oxide unit repeats.
As (D) 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.
When the total amount of the acrylic polymers setting multipolymer is 100 weight part, preferably the content of aforementioned (D) polyalkylene glycol mono (methyl) acrylate monomer is 0 ~ 50 weight part.Adhesive composition in adhesive layer of the present invention also can not comprise (D) polyalkylene glycol mono (methyl) acrylate monomer.
In (E), as the vinyl monomer that (E-1) is nitrogenous, 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., the ring-type nitrogen vinyl compound with the heterocycle structure that N-(methyl) acryl replaces of N-(methyl) acryloyl morpholine, N-(methyl) acryloylpiperazines, the rare acyl group aziridine of N-(methyl) third, N-(methyl) acryl azetidine, N-(methyl) acryl tetramethyleneimine, N-(methyl) acryloylpiperidine, N-(methyl) acryl azepan, N-(methyl) acryl Azacyclooctane etc., 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 the vinyl monomer that (E-1) is nitrogenous, 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 lactams such as NVP, N-caprolactam, N-vinyl-2-piperidone; N-(methyl) the acryl substituted cyclic amines such as N-(methyl) acryloyl morpholine, N-(methyl) acryl tetramethyleneimine.
In (E), as (E-2) (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 are containing (methyl) alkyl acrylate monomer of alkoxyl group, the structure that the atom alkoxy with the alkyl in (methyl) alkyl acrylate replaces.
When the total amount of acrylic polymers setting multipolymer is 100 weight part, preferably (E-1) hydroxyl and nitrogenous vinyl monomer or (E-2) are not 0 ~ 20 weight part containing the content of (methyl) alkyl acrylate monomer of alkoxyl group.To (E-1), hydroxyl and nitrogenous vinyl monomer and (E-2), containing (methyl) alkyl acrylate monomer of alkoxyl group, both can not use one to can be used together two or more respectively yet.In the adhesive composition of adhesive layer of the present invention, also can not comprise (E) not hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl group.
As isocyanate compound more than (F) trifunctional, as long as be selected from a part more than at least one or two in the polyisocyanate compounds of isocyanic ester (NCO) base at least with more than three.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.Relative to the aforementioned copolymer of 100 weight parts, preferably containing isocyanate compound more than aforementioned (F) trifunctional of 0.5 ~ 5.0 weight part.
And, as isocyanate compound more than (F) trifunctional used in the present invention, preferably include and be selected from more than at least one of (F-1) first in aliphatic category isocyanate compound group and be selected from more than at least one of (F-2) second in aromatic series kind isocyanate compound group, wherein, described (F-1) first aliphatic category isocyanate compound group be 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, described (F-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 (F-1) first aliphatic category isocyanate compound group and (F-2) the second aromatic series kind isocyanate compound group.In the present invention, as isocyanate compound more than (F) trifunctional, by and with being selected from more than at least one of (F-1) first in aliphatic category isocyanate compound group and being selected from more than at least one of (F-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, isocyanate compound preferably more than (F) trifunctional comprises and is selected from more than at least one of aforementioned (F-1) first in aliphatic category isocyanate compound group and is selected from more than at least one of aforementioned (F-2) second in 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 (F) trifunctional is 0.5 ~ 5.0 weight part.In addition, as being selected from more than at least one of (F-1) first in aliphatic category isocyanate compound group and the mixture ratio being selected from more than at least one of (F-2) second in aromatic series kind isocyanate compound group, calculating with weight ratio and being preferably (F-1): (F-2) is in the scope of 10%:90% ~ 90%:10%.
Further, (G) the two sense non-ring type aliphatic isocyanates compound used in the present invention, be the non-ring type in two functional isocyanate compounds and belong to aliphatic compound.As (G) two sense non-ring type aliphatic isocyanates compound, the compound that preferred diisocyanate cpd and diol compound react and generate.
Such as, when with general formula " O=C=N-X-N=C=O " (wherein, X is divalent group) represent diisocyanate cpd, with general formula " HO-Y-OH " (wherein, Y is divalent group) when representing diol compound, to react generated compound as diisocyanate cpd and diol compound, such as, the compound that general formula Z below represents can be enumerated.
[general formula Z]
O＝C＝N-X-(NH-CO-O-Y-O-CO-NH-X) n-N＝C＝O
At this, n is the integer of more than 0.When n is 0, general formula Z is expressed as " O=C=N-X-N=C=O ".Also can comprise as (G) two sense non-ring type aliphatic isocyanates compound the compound (relative to the unreacted diisocyanate cpd of diol compound) that n in general formula Z is 0, preferably contain as neccessary composition the compound that n is more than 1 integer.(G) the two senses non-ring type aliphatic isocyanates compound mixture that also can be made up of multiple compounds that the n in general formula Z is not identical.
The diisocyanate cpd that general formula " O=C=N-X-N=C=O " represents is aliphatic diisocyanate.Preferred X is the aliphatic divalent group of non-ring type.As aforementioned aliphatic diisocyanate, form preferably by one or more being selected from the compound group that is made up of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysinediisocyanate.
The diol compound that general formula " HO-Y-OH " represents is aliphatic diol.Preferred Y is the aliphatic divalent group of non-ring type.As foregoing glycols compound, preferably by being selected from by 2-methyl 1, ammediol, 2,2-dimethyl-1,3-propylene glycol, 2-methyl-2-propyl-1,3-PD, 2-ethyl-2-butyl-1, ammediol, 3-methyl isophthalic acid, one or more in the compound group that 5-pentanediol, 2，2-dimethyl-1，3-propanediol monohydroxy pivalate, polyoxyethylene glycol, polypropylene glycol form are formed.
Isocyanate compound more than aforementioned (F) trifunctional is 1 ~ 90 with the weight ratio (F/G) of (G) two sense non-ring type aliphatic isocyanates compound.
Relative to 100 weight part foregoing acrylic polymkeric substance, the total amount of the isocyanate compound preferably more than aforementioned (F) trifunctional and (G) two sense non-ring type aliphatic isocyanates compound is 0.1 ~ 5.0 weight part.
Preferably (H) static inhibitor to be (H-1) fusing point be ionic compound or (H-2) ionic compound containing acryl of 30 ~ 50 DEG C.
In the present invention, as (H) static inhibitor, the ionic compound being 30 ~ 50 DEG C by (H-1) fusing point makes an addition in multipolymer, or by (H-2) ionic compound copolymerization containing acryl in multipolymer.Infer because the fusing point of these (H) static inhibitor is low and have chain alkyl, therefore, high with the affinity of acrylic copolymer.
As the ionic compound that (H-1) fusing point is 30 ~ 50 DEG C, it is the ionic compound with positively charged ion and negatively charged ion, can enumerate: positively charged ion is the cationic nitrogenous Huo person phosphonium cation, sulfonium cation 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 hexafluoro-phosphate radical (PF 6 -), thiocyanate ion (SCN -), benzene sulfonamide acid group (RC 6h 4sO 3 -), perchlorate (ClO 4 -), tetrafluoroborate (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 ~ 50 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, preferably (H-1) fusing point is the content of the ionic compound of 30 ~ 50 DEG C is 0.01 ~ 5.0 weight part.
As (H-2) 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 positively charged ion of (methyl) acryl; Negatively charged ion is hexafluoro-phosphate radical (PF 6 -), thiocyanate ion (SCN -), organic sulfonic acid root (RSO 3 -), perchlorate (ClO 4 -), tetrafluoroborate (BF 4 -), imide root (R containing F f 2n -) etc. the compound of inorganic or organic anion.As the imide root (R containing F f 2n -) R f, perfluoroalkyl group sulfonyl, the fluorosulfonyl of trifyl, five fluorine ethylsulfonyls etc. can be enumerated.As the imide root containing F, 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.
Preferably (H-2) ionic compound containing acryl copolymerization amount is in the copolymer 0.1 ~ 5.0 % by weight.
As the object lesson of (H) static inhibitor, be not particularly limited, but as the object lesson that (H-1) fusing point is the ionic compound of 30 ~ 50 DEG C, 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 (H-2) 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 can contain polyether modified siloxane compound arbitrarily.Polyether-modified silicone compounds 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, 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 preferred, polyethers modified silicone com is 0.01 ~ 0.5 weight part, is more preferably 0.1 ~ 0.5 weight part.
HLB refers to the hydrophilic-lipophilic balance (wetting ability and oil loving ratio) of the regulations such as such as JIS K3211 (tensio-active agent term).
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 polyether modified siloxane compound is matched with adhesive composition, cohesive force and the cycling processability of binding agent can be improved.When adhesive composition is not containing polyether modified siloxane compound, cost can be made lower.
And, as other composition, can suitably coordinate containing alkylene oxide (alkylene oxide) 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 adhesive composition of the present invention host used, can by by the carbonatoms of (A) alkyl be C4 ~ C18 (methyl) acrylate monomer at least one, with be selected from as copolymerisable monomer group by the copolymerisable monomer of (B) hydroxyl, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) at least one not in hydroxyl and nitrogenous vinyl monomer or the copolymerisable monomer group that forms containing (methyl) alkyl acrylate monomer of alkoxyl group carries out copolymerization to synthesize.To the polymerization process of multipolymer, there is no particular limitation, can use the polymerization process that solution polymerization, letex polymerization etc. are suitable.
When the ionic compound using (H-2) containing acryl as (H) static inhibitor, as the multipolymer of adhesive composition of the present invention host used, by by the carbonatoms of (A) alkyl be C4 ~ C18 (methyl) acrylate monomer at least one, with be selected from as copolymerisable monomer group by the copolymerisable monomer of (B) hydroxyl, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) at least one not in hydroxyl and nitrogenous vinyl monomer or the copolymerisable monomer group that forms containing (methyl) alkyl acrylate monomer of alkoxyl group, and (H-2) carries out copolymerization to synthesize containing the ionic compound of acryl.
Adhesive composition of the present invention by coordinating the isocyanate compound of more than (F) trifunctional, (G) two sense non-ring type aliphatic isocyanates compound, (H) static inhibitor, also having suitable any additive to prepare in above-mentioned multipolymer.In addition; if when (H-2) ionic compound containing acryl being polymerized in host multipolymer; both can add (H) static inhibitor further to this multipolymer, also can not add (H) static inhibitor.
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 of preferred acrylic polymers is 0.01 ~ 8.0.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.
The surface resistivity of the adhesive layer preferably making foregoing adhesives composition be cross-linked is 5.0 × 10 + 10Ω/below, stripping static voltage is ± 0 ~ 1kV.In addition, in the present invention, the meaning of so-called " ± 0 ~ 1kV " refers to " 0 ~-1kV " and " 0 ~+1kV ", i.e. "-1 ~+1kV ".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 single or double 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) ~ (H) 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, can preferably be used as the surface protection film purposes of Polarizer.
As the base material film of adhesive layer, the stripping film (barrier film) of protection adhesive surface, 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 vinylformic acid 8-hydroxyl monooctyl ester of 3.0 weight parts, the polypropylene glycol mono acrylic ester (forming the averaged repeating numbers n=12 of the alkylene oxide of polyalkylene glycol chain) of 10 weight parts, and add the solvent (vinyl acetic monomer) 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, 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 ~ (E) and (H-2) 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.
Table 1
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, be uniformly mixed after adding the two senses non-ring type aliphatic isocyanates compound G-1 of 2.0 weight part Coronate HX (isocyanuric acid ester of コ ロ ネ ー ト HX, hexamethylene diisocyanate compound), 0.5 weight part synthesis example 1, 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 (F) ~ (H) of table 2 except, operate in the same manner as the surface protection film of above-described embodiment 1, obtain the surface protection film of embodiment 2 ~ 9 and comparative example 1 ~ 4.
Table 2
Table 1 and table 2 to represent that the whole table of each components matching ratio is divided into the table of two parts, and 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 corresponding with the abbreviation of each composition used in table 1 and table 2 is shown in table 3 and table 4.In addition, Coronate (コ ロ ネ ー ト, registered trademark) HX, Coronate HL and Coronate L is Nippon Polyurethane Industry Co., Ltd. (Nippon Polyurethane Industry Co., Ltd.) trade name, Takenate (タ ケ ネ ー ト, registered trademark) D-140N, D-127N, D-110N, D-120N are the trade names of Mitsui Chemicals, Inc.
In Table 1, by (H) static inhibitor, (H-2) that copolymerization is in multipolymer containing (H) static inhibitor added after quaternary ionic compound of acryl and polymerization, be recorded in respectively in different hurdles.
Table 3
Table 4
The synthesis > of < bis-sense non-ring type aliphatic isocyanates compound
The two senses non-ring type aliphatic isocyanates compound of synthesis example 1 ~ 3 adopts the synthesis of following method.As shown in table 5 and table 6, vulcabond is mixed with the ratio of mol ratio NCO/OH=16 with diol compound, react 3 hours at 120 DEG C, then, adopt thin film evaporation unit under reduced pressure to remove unreacted vulcabond, obtain desired two sense non-ring type aliphatic isocyanates compound.
Table 5
Synthesis example 1G-1 Synthesis example 2G-2 Synthesis example 3G-3
Diisocyanate cpd HDI HDI HDI
Diol compound K-1 K-2 K-3
Table 6
< 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 surface of the Polarizer pasted 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 after 12 hours further, the sample it can be used as and measure cohesive force, peeled off static voltage, re-workability and weather resistance.
< 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 (Mitsubishi Chemical Analytech Co., 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, be confirmed whether to 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, confirms whether there is obvious 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 7.In addition, in surface resistivity, represent " m × 10 by " mE+n " + n" (wherein, m is arbitrary real number, and n is positive integer).
Table 7
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 + 10Ω/below, stripping static voltage is ± 0 ~ 1kV; 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 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.
For the surface protection film of comparative example 1; may due to not containing the cause as isocyanate compound more than linking agent (F) trifunctional and (G) two sense non-ring type aliphatic isocyanates compound, its cohesive force under low peeling rate 0.3m/min and 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 2; it is not containing (G) two sense non-ring type aliphatic isocyanates compound; but containing the diisocyanate cpd containing urea diketone ring as two sense ring type isocyanate compounds; therefore, excessive, the poor durability of its cohesive force under high peeling rate 30m/min.
For the surface protection film of comparative example 3; may be due to (F) trifunctional more than the cause of isocyanate compound too much and not containing (G) two sense non-ring type aliphatic isocyanates compound; its storage period is too short; be cross-linked before coating; therefore, cannot be coated with.
For the surface protection film of comparative example 4; may be because (G) two sense non-ring type aliphatic isocyanates compound is more than the cause of isocyanate compound more than (F) trifunctional, its cohesive force under high peeling rate 30m/min is excessive, poor durability.
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 (14)

1. an adhesive composition, it comprises:
Containing at least one in the carbonatoms of (A) alkyl (methyl) acrylate monomer that is C4 ~ C18 and be selected from as copolymerisable monomer group by the acrylic polymers of the multipolymer of at least one in the copolymerisable monomer of (B) hydroxyl, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) not hydroxyl and nitrogenous vinyl monomer or the copolymerisable monomer group that forms containing (methyl) alkyl acrylate monomer of alkoxyl group
Further, the isocyanate compound of more than (F) trifunctional, (G) two sense non-ring type aliphatic isocyanates compound and (H) static inhibitor is also comprised.
2. adhesive composition as claimed in claim 1, wherein,
When the total amount of the acrylic polymers setting described multipolymer is 100 weight part,
The carbonatoms of described (A) alkyl is the content of (methyl) acrylate monomer of C4 ~ C18 is 50 ~ 91 weight parts,
The content of the copolymerisable monomer of described (B) hydroxyl is 0.1 ~ 10 weight part,
The content of described (C) carboxylic copolymerisable monomer is 0 ~ 1.0 weight part,
The content of described (D) polyalkylene glycol mono (methyl) acrylate monomer is 0 ~ 50 weight part,
Described (E) not hydroxyl and nitrogenous vinyl monomer or the content containing (methyl) alkyl acrylate monomer of alkoxyl group is 0 ~ 20 weight part.
3. adhesive composition as claimed in claim 1 or 2, wherein, isocyanate compound more than described (F) trifunctional is 1 ~ 90 with the weight ratio F/G of (G) two sense non-ring type aliphatic isocyanates compound,
Relative to acrylic polymers described in 100 weight parts, the total amount of isocyanate compound more than described (F) trifunctional and (G) two sense non-ring type aliphatic isocyanates compound is 0.1 ~ 5.0 weight part.
4. adhesive composition as claimed in claim 1 or 2, wherein,
Described (G) two sense non-ring type aliphatic isocyanates compound is the compound that diisocyanate cpd and diol compound react and generate,
Described diisocyanate cpd is aliphatic diisocyanate and consists of the one be selected from the compound group that is made up of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysinediisocyanate
Described diol compound is by being selected from by 2-methyl 1, ammediol, 2,2-dimethyl-1, ammediol, 2-methyl-2-propyl-1, ammediol, 2-ethyl-2-butyl-1,3-PD, 3-methyl isophthalic acid, 5-pentanediol, 2, one in the compound group that 2-dimethyl-1,3-propylene glycol monohydroxy pivalate, polyoxyethylene glycol, polypropylene glycol form is formed.
5. adhesive composition as claimed in claim 1 or 2, wherein,
The copolymerisable monomer of described (B) hydroxyl is 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
Described (C) carboxylic copolymerisable monomer is selected from by (methyl) vinylformic acid, (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, more than at least one in the compound group that 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid forms.
6. adhesive composition as claimed in claim 1 or 2, wherein, described (D) polyalkylene glycol mono (methyl) acrylate monomer is selected from more than at least one in polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate.
7. adhesive composition as claimed in claim 1 or 2, wherein, isocyanate compound more than described (F) trifunctional, be selected from the isocyanuric acid ester by 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, 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, in the compound group that the affixture of hydrogenated xylylene diisocyanate cpd forms more than at least one.
8. adhesive composition as claimed in claim 1 or 2, wherein, described acrylic polymers contains described (E) not hydroxyl and nitrogenous vinyl monomer or containing more than at least one in (methyl) alkyl acrylate monomer of alkoxyl group as described copolymerisable monomer group.
9. adhesive composition as claimed in claim 1 or 2, wherein,
Described (H) static inhibitor contains 0.01 ~ 5.0 weight part relative to the described multipolymer of 100 weight parts and fusing point is the ionic compound of 30 ~ 50 DEG C or the copolymerization amount in described multipolymer is 0.1 ~ 5.0 % by weight and containing the ionic compound of acryl.
10. 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.
11. adhesive compositions 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 + 10Ω/below, stripping static voltage are ± 0 ~ 1kV.
12. 1 kinds of surface protection films, it forms adhesive layer at the single or double of resin molding to form, and described adhesive layer the adhesive composition according to any one of claim 1 ~ 11 is cross-linked form.
13. surface protection films as claimed in claim 12, its surface protection film purposes as Polarizer is used.
14. surface protection films as claimed in claim 13, 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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