CN109233725A - Surface protection sticker and adhesive sheet - Google Patents

Surface protection sticker and adhesive sheet Download PDF

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Publication number
CN109233725A
CN109233725A CN201710675311.1A CN201710675311A CN109233725A CN 109233725 A CN109233725 A CN 109233725A CN 201710675311 A CN201710675311 A CN 201710675311A CN 109233725 A CN109233725 A CN 109233725A
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China
Prior art keywords
acid
carbamate
surface protection
mass parts
carbamide resin
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Granted
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CN201710675311.1A
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Chinese (zh)
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CN109233725B (en
Inventor
田邉慎吾
斋藤秀平
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Toyochem Co Ltd
Artience Co Ltd
Original Assignee
Toyo Ink SC Holdings Co Ltd
Toyochem Co Ltd
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Priority to CN202110613192.3A priority Critical patent/CN113337236B/en
Publication of CN109233725A publication Critical patent/CN109233725A/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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)

Abstract

The purpose of the present invention is to provide it is a kind of for make it is good to the wetability for being attached to body, be attached at curved face part when be not likely to produce and float and peel off, can remove again and the surface protection sticker and adhesive sheet of the good adhesive sheet of productivity.Reactant, that is, carbamate carbamide resin (A) 100 mass parts of the surface protection sticker relative to carbamate prepolymer (a) and amine compounds (b) containing isocyanate group; 3 mass parts and 20 isocyanate hardener (B) below the mass are comprised more than, and the molecular weight dispersity of the carbamate carbamide resin (A) is 1.5~6.

Description

Surface protection sticker and adhesive sheet
Technical field
The present invention relates to a kind of surface protection sticker and adhesive sheets.
Background technique
All the time, in order to prevent various components impaired equal and use surface protective plate.In the adhesion of surface protective plate Layer uses the sticker comprising acrylic resin or carbamate (urethane) resin in being formed more.It include ammonia in the two The sticker (hereinafter referred to as carbamate sticker) of carbamate resin has the adhesion strength of appropriateness and removes again to glass Property, thus it is used for the surface protection purposes of the displays such as liquid crystal display.
For example, disclosing in patent document 1 has one kind comprising carbamate resins, isocyanate hardener and is selected from The sticker of at least one of poly- alkane glycol based compound, epoxy compound and phosphate based compound compound.
Also, as the high sticker using carbamate carbamide resin of adhesion strength, disclose has one in patent document 2 Kind comprising make ternary or more the resulting carbamate carbamide resin of polyalcohol, polyisocyanate and mono amino polyol reaction, And the sticker of isocyanate hardener.
In addition, disclose has one kind comprising making chain elongation agent, end stopping agent and making polyalcohol and gather different in patent document 3 Cyanate esters react resulting isocyanate group end prepolymer and react resulting carbamate carbamide resin and isocyanide The sticker of acid esters curing agent.
[existing technical literature]
[patent document]
[patent document 1] Japanese Patent Laid-Open 2015-7226 bulletin
[patent document 2] Japanese Patent Laid-Open 2007-023117 bulletin
[patent document 3] Japanese Patent Laid-Open 2006-124692 bulletin
Summary of the invention
[problem to be solved by the invention]
But for the sticker of patent document 1, adhesion strength is low, therefore in protection for example with the display of curved face part In the case where the surface of device, there are problems that adhesive sheet floats or peels off from curved face part.
In addition, the branch of carbamate carbamide resin is more for the sticker of patent document 2, it is three-dimensional structure, therefore The cohesiveness of adhesion coating is superfluous if this sticker is processed as surface protective plate.If accordingly, there exist by the surface protective plate It is attached at curved face part and then leads to the problem of and float.
In addition, for the sticker of patent document 3, institute is reacted by isocyanate group end prepolymer and chain elongation agent The hydroxyl of formation has secondary hydroxyl groups, therefore there is the firm time spent with isocyanate hardener, is used for by adhesive sheet Time taking productive problem is spent before surface protection purposes.
The purpose of the present invention is to provide it is a kind of for make it is good to the wetability for being attached to body, be attached at curved face part when It is not likely to produce and floats and peel off, can remove again and the surface protection sticker and adhesive sheet of the good adhesive sheet of productivity.
[technical means to solve problem]
Surface protection sticker of the invention relative to containing isocyanate group carbamate prepolymer (a) and amination Reactant, that is, 100 mass parts of carbamate carbamide resin (A) for closing object (b) comprise more than 3 mass parts and 20 below the mass Isocyanate hardener (B), and the molecular weight dispersity of the carbamate carbamide resin (A) is 1.5~6.
[The effect of invention]
According to the present invention, it is possible to provide it is a kind of for make it is good to the wetability for being attached to body, be attached at curved face part when not It is also easy to produce and floats and peel off, can remove again and the surface protection sticker and adhesive sheet of the good adhesive sheet of productivity.
Specific embodiment
Term is defined before the present invention will be described.The so-called body that is attached to refers to attaching adhesive tape in present specification Object.So-called molecular weight dispersity refers to weight average molecular weight divided by the resulting number of number average molecular weight in this specification Value, is the standard of molecular weight distribution.
So-called productivity, which refers to, in this specification shows rapidly the cohesiveness of adhesion coating when applying sticker (with few Heat is crosslinked), therefore coating speed can be accelerated, the productivity of adhesive sheet is promoted.
So-called adhesive sheet in this specification, the adhesion coating of the hardening thing comprising substrate and containing sticker of the invention.
In this specification, " band ", " film " and " piece " meaning is identical.
Principal component refers to the ingredient for deploying that blending amount is most in a variety of ingredients in this specification.
In this specification, as long as no special instructions, then " molecular weight " refers to number average molecular weight (Mn).In addition, " Mn " It is that the polystyrene for being measured and being found out by gel permeation chromatography (gel permeation chromatographV, GPC) changes The number average molecular weight of calculation.
Sticker of the invention is relative to carbamate prepolymer (a) and amine compounds (b) containing isocyanate group Reactant, that is, 100 mass parts of carbamate carbamide resin (A), comprises more than 3 mass parts and 20 isocyanates below the mass Curing agent (B), and the molecular weight dispersity of the carbamate carbamide resin (A) is 1.5~6, is preferred for surface protection use On the way.
Surface protection sticker of the invention is relative to the carbamate urea tree with relatively narrow molecular weight dispersity Rouge (A), comprising suitable isocyanate hardener (B).Had using the surface protective plate of the surface protection sticker suitable The adhesion strength and cohesiveness of degree, therefore flat part is needless to say, also fully touches to curved face part, float therefore, it is difficult to generating or It peels off, can optionally remove and (also referred to as remove again).
The liquid crystal display that surface protection sticker of the invention for example can be used for having flat part or curved face part (liquid crystal display, LCD), display of organic electroluminescence (electroluminescent display, ELD) displays, the touch screen (touch panel) using these displays such as.In addition, can be widely used in equipped with such The mobile phone of display or touch screen, smart phone, input board (tablet) terminal the electronics such as portable terminal, computer set Standby surface protection purposes.
In addition, surface protection is not limited to glass, if enumerating raw material, it can be used for such as polyolefin (polyolefin), gold, silver, copper, tin indium oxide (indium tin oxide, ITO) etc. are easy the protection of impaired raw material.
In addition, surface protection purposes is not limited to display, it can be used for such as glass pane, light emitting diode (light Emitting diode, LED), the protection of vehicle, all surfaces such as wiring.In addition, surface protection can be used for the manufacture step of component The surface protection after protection and manufacture in rapid.It is protected in addition, surface protection of the invention may of course be used for surface with sticker Protect the purposes other than purposes.
(carbamate carbamide resin (A))
Carbamate carbamide resin (A) is the carbamate prepolymer and one kind containing isocyanate group for making more than one Above amine compounds carry out urea reaction (forming urea bond) resulting reactant.Urea reaction optionally can in the presence of a catalyst into Row.Solvent optionally can be used in copolyreaction.In addition, carbamate carbamide resin (A) can be used alone or using two kinds with On.
<carbamate prepolymer (a) containing isocyanate group>
Carbamate prepolymer (a) containing isocyanate group preferably make polyisocyanate (x) and polyalcohol (y) into Row urethane reaction (formed urethane bond) and the compound synthesized.In addition, polyisocyanate (x) preferably molecule There are two two functional isocyanates (x1) of isocyanate group for middle tool.In addition, there are two hydroxyls for tool in polyalcohol (y) preferably molecule Two function polyalcohols (y1) of base.The isocyanate group of polyisocyanate (x) is to be more than rubbing for the amount of the hydroxyl of polyalcohol (y) That ratio is to use.
In urethane reaction, in order to promote reaction and it is preferable to use catalyst.
<polyisocyanate (x)>
Polyisocyanate (x) for example can be used aromatic poly-isocyanate, aliphatic polymeric isocyanate, aromatic-aliphatic poly- Compound well known to isocyanates and alicyclic polymeric isocyanate etc..
Aromatic poly-isocyanate can for example be enumerated: 1,3- phenylene vulcabond, 4,4 '-diphenyl diisocyanates Ester, Isosorbide-5-Nitrae-phenylene vulcabond, 4,4 '-methyl diphenylene diisocyanates, 2,4- toluene di-isocyanate(TDI), 2,6- toluene Diisocyanate, 4,4 '-toluidine diisocyanates, 2,4,6- triisocyanate toluene, 1,3,5- triisocyanate benzene, diformazan Oxygroup aniline diisocyanate (dianisidinediisocyanate), 4,4 '-diphenyl ether diisocyanates and 4,4 ', 4 "-triphenylmethane triisocyanates etc..
Aliphatic polymeric isocyanate can for example be enumerated: trimethylene diisocyanate, tetramethylene diisocyanate, six Asias Methyl diisocyanate, pentamethylene diisocyanate, 1,2- trimethylene diisocyanate, 2,3- tetramethylene diisocyanate, 1,3- tetramethylene diisocyanate, ten dimethylene diisocyanates and 2,4,4- trimethyl hexamethylene diisocyanates etc..
Aromatic-aliphatic polyisocyanate can for example be enumerated: ω, ω '-diisocyanate -1,3- dimethyl benzene, ω, ω ' - Diisocyanate-Isosorbide-5-Nitrae-dimethyl benzene, ω, ω '-diisocyanate-Isosorbide-5-Nitrae-diethylbenzene, Isosorbide-5-Nitrae-tetramethyl xylylen two Isocyanates and 1,3- tetramethyl xylylen diisocyanate etc..
Alicyclic polymeric isocyanate can for example be enumerated: 3- isocyanatomethyl -3,3,5- trimethylcyclohexylisocyanate, 1,3- pentamethylene diisocyanate, 1,3- cyclohexane diisocyanate, Isosorbide-5-Nitrae-cyclohexane diisocyanate, methyl -2,4- hexamethylene Alkane diisocyanate, methyl -2,6- cyclohexane diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxides (cyclohexyl isocyanate) and Isosorbide-5-Nitrae-are bis- (isocyanatomethyl) hexamethylene etc..
The polyisocyanate is diisocyanate, also be can be used ester modified resulting three isocyanic acid of the diisocyanate Ester.Triisocyanate can for example be enumerated: trimethylolpropane adduct body, the biuret (biuret) of the diisocyanate Body and tripolymer (tripolymer includes isocyanurate ring) etc..
Polyisocyanate (x) preferably 4,4 '-methyl diphenylene diisocyanates, hexamethylene diisocyanate and 3- are different Cyanic acid ester methyl -3,5,5- trimethylcyclohexylisocyanate (isophorone diisocyanate) etc..
Polyisocyanate (x) can be used alone or using two or more.
<polyalcohol (y)>
Polyalcohol (y) is the compound with more than two hydroxyls.Polyalcohol (y) preferred, polyethers polyalcohol, polyester are more Compound well known to first alcohol, polycarbonate polyol etc..
In order to realize the appropriate cohesiveness and adhesion strength of adhesion coating, polyalcohol (y) used in the present invention preferably will tool There are two the polyalcohols of hydroxyl as principal component.In addition, and apparatus there are three above hydroxyl polyalcohol in the case where, it is excellent Choosing with less than tool there are two hydroxyl polyalcohol quality come using.
Polyether polyol can for example enumerate the compound containing reactive hydrogen that will have more than two reactive hydrogens in a molecule As initiator, addition polymerization more than one oxirane (oxirane) compound and the reactant that obtains.
Compound and amine of the preferred hydroxyl of compound containing reactive hydrogen etc..
The compound of hydroxyl can for example be enumerated: ethylene glycol (ethylene glycol, EG), propylene glycol (propylene Glycol, PG), 1,4-butanediol, neopentyl glycol, the compound of two functions containing reactive hydrogen such as butyl ethyl pentanediol；Glycerol, three Compound of the trifunctionals such as hydroxymethyl-propane containing reactive hydrogen；Compound etc. of the tetrafunctionals such as pentaerythrite containing reactive hydrogen.
Amine can for example be enumerated: two function such as N- amino ethyl ethanolamine, isophorone diamine and xylylene amine contains The compound of reactive hydrogen；Compound of the trifunctionals such as triethanolamine containing reactive hydrogen；The tetrafunctionals such as ethylenediamine and aromatic diamine contain The compound of reactive hydrogen；Compound etc. of five function such as Diethylenetriamine containing reactive hydrogen.
Oxirane compound can for example enumerate ethylene oxide (ethylene oxide, EO), propylene oxide The alkylene oxides such as (propylene oxide, PO) and epoxy butane (butylene oxide, BO) (alkVlene oxide, AO)；Tetrahydrofuran (tetrahydrofuran, THF) etc..
Polyether polyol preferably has the alkylidene oxygroup from the compound containing reactive hydrogen in the molecule The polyether polyol (is also known as " polyoxy sub alkyl polylol ") by (alkVleneoxy group).Polyoxy alkylidene is polynary The two functional polyethers polyalcohol such as the preferred polyethylene glycol of alcohol, polypropylene glycol and polytetramethylene glycol, particularly preferred crystallinity is low, The polypropylene glycol of flexibility can be assigned.Two functional polyethers polyalcohols have two-dimentional bridging property, therefore adhesion coating can get appropriateness Adhesion strength and cohesiveness.
There is no particular restriction for the number average molecular weight (Mn) of polyether polyol, just effectively shows the transparency or flexibility For, preferably 200~6,000, more preferable 400~4,000, and then preferably 600~4,000.By the way that Mn is set as 200 or more, It is easy to carry out reaction controlling when synthesizing the carbamate prepolymer containing isocyanate group.In addition, by the way that Mn is set as 6,000 Hereinafter, being easy cohesiveness being adjusted to appropriate range for carbamate carbamide resin.
Polyester polyol for example preferably makes more than one polyol component and more than one sour component be esterified instead Answer resulting compound (carboxylate) or the compound (ring-opening polymerization polymer) for synthesizing lactone ring opening polymerization etc..
Lactone can for example enumerate polycaprolactone, poly- (Beta-methyl-gamma-valerolactone) and poly- valerolactone etc..
The polyol component can for example be enumerated: ethylene glycol (ethylene glycol, EG), propylene glycol (propylene Glycol, PG), diethylene glycol, 1,3-BDO, 1,4-butanediol, neopentyl glycol, 3- methyl-1,5- pentanediol, 2- butyl- 2- ethyl -1,3-PD, 2,4- diethyl -1,5-PD, 1,2- hexylene glycol, 1,6- hexylene glycol, 2- ethyl -1,3- oneself two Alcohol, 1,8- ethohexadiol, 1,9- nonanediol, 2- methyl-1,8- ethohexadiol, 1,8- decanediol, octacosanol, glycerol, three hydroxyl first Base propane, pentaerythrite and hexanetriol etc..
The sour component can for example be enumerated: succinic acid, dimethyl succinic acid, adipic acid, pyromellitic acid (pyromellitic Acid), azelaic acid, decanedioic acid, 1,12- dodecanedioic acid, 1,14- tetracosandioic acid, dimeric dibasic acid, 2- methyl-1,4- hexamethylene Dicarboxylic acids, 2- ethyl-Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, terephthalic acid (TPA), M-phthalic acid, phthalic acid, Isosorbide-5-Nitrae-naphthalene dicarboxylic acids, And 4,4 '-diphenyl dicarboxylic acids and these acid anhydrides etc..
The number average molecular weight (Mn) preferably 200~8,000, more preferable 500~6,000, Jin Eryou of polyester polyol Select 500~4,000, particularly preferred 500~3,000.By the way that Mn is set as 200 or more, in amino of the synthesis containing isocyanate group It is easy to carry out reaction controlling when urethane prepolymer.In addition, by the way that Mn is set as 8,000 hereinafter, for carbamate urea tree It is easy cohesiveness being adjusted to appropriate range for rouge.
Other polyhydric alcohols other than described can such as be enumerated: polycarbonate polyol, butadiene-based polyalcohol, castor oil are more First alcohol etc..Other polyalcohols are preferably with polyether polyol or polyester polyol and for using.
The number average molecular weight (Mn) preferably 200~8,000 or so of other polyalcohols.
Polyalcohol (y) preferred, polyethers polyalcohol.
If in addition, there is the case where corrosion is attached to body containing acid functional groups such as carboxyl, sulfonic groups in polyalcohol (y). Therefore, by the surface protection sticker of the application be applied to easily corrode in the case where being attached to body, it is preferable to use not Polyalcohol with acid functional groups.
Polyalcohol (y) can be used alone or using two or more.
<catalyst>
For example preferred three-level amine compound of catalyst and organic metal based compound etc..
Three-level amine compound can for example be enumerated: triethylamine, triethylenediamine and 1,8- diazabicyclo (5.4.0)-ten one Alkene -7 (1,8-diazabicyclo (5.4.0)-undecene-7, DBU) etc..
The preferred tin based compound of organic metal based compound and non-tin based compound etc..
Tin based compound can for example be enumerated: dibutyl tin dichloride, Dibutyltin oxide, dibutyl tin bibromide, two fourths Two maleic acid tin of base, dibutyl tin dilaurate (dibutyltin dilaurate, DBTDL), dibutyl tin acetate, two fourths Base artificial gold, tributyl artificial gold, tributyltin oxide, tributyltin acetate, triethyl group ethyoxyl tin (triethyltin Ethoxide), tributyl ethyoxyl tin (tributyltin ethoxide), dioctyl tin oxide, tributyltin chloride, three fourths Base trichloroacetic acid tin and 2 ethyl hexanoic acid tin etc..
Non- tin based compound can for example be enumerated: the titaniums such as dibutyl titanium chloride, butyl titanate and butoxy titanium trichloride Based compound；The lead based compounds such as plumbi oleas, 2 ethyl hexanoic acid lead, lead benzoate and lead naphthenate；2 ethyl hexanoic acid iron and second The iron series compounds such as acyl acetone iron；The cobalts based compound such as cobalt benzoate and 2 ethyl hexanoic acid cobalt；Zinc naphthenate and 2 ethyl hexanoic acid The zinc based compound such as zinc；The zirconium compounds such as zirconium naphthenate.
Catalyst can be used alone or using two or more.
Catalyst uses 0.01 mass preferably with respect to polyisocyanate (x) and total 100 mass parts of polyalcohol (y) Part~1.0 mass parts.
When in the synthesis in the carbamate prepolymer (a) containing isocyanate group use a variety of polyalcohols (y) and respectively Reactivity it is different when, if, in the presence of that can not carry out reaction controlling, each polyalcohol is individually synthesized using a kind of catalyst And the situation of reaction solution muddiness.At this point, if being easy to control reaction (such as reaction speed etc.) using two kinds of catalyst, can solving Certainly described problem.That is, in the present invention, it is preferable to use two or more catalyst when using a variety of polyalcohols (y).Two kinds are urged There is no particular restriction for the combination of agent, can enumerate tertiary amine/organic metal system, tin system/non-tin system and tin system/tin system etc..These In combination, preferred tin system/tin system, more preferable dibutyl tin dilaurate and 2 ethyl hexanoic acid tin.
The mass ratio (2 ethyl hexanoic acid tin/dibutyl tin dilaurate) of 2 ethyl hexanoic acid tin and dibutyl tin dilaurate There is no particular restriction, and preferably greater than 0 and less than 1, more preferably 0.2~0.6.If utilizing the mass ratio with range appropriate, Then reaction controlling becomes easy.
<solvent>
In the synthesis of the carbamate prepolymer (a) containing isocyanate group, the molten of more than one optionally can be used Agent.Solvent can for example be enumerated: methyl ethyl ketone, ethyl acetate, toluene, dimethylbenzene and acetone etc..In these solvents, just contain isocyanide For boiling point of the dissolubility of the carbamate prepolymer (a) of perester radical and solvent etc., ethyl acetate and toluene Deng.
<polymerization>
There is no particular restriction for the polymerization of carbamate prepolymer (a) containing isocyanate group, can be used blocky poly- Polymerization well known to legal and solution polymerization process etc..
Polymerization sequence can for example be enumerated:
Sequentially 1) by more than one polyisocyanate (x), more than one polyalcohol (y), optionally more than one Catalyst and optionally more than one solvent is filled to the sequence of flask together；
Sequentially 2) by more than one polyalcohol (y), optionally more than one catalyst and optionally more than one Solvent is filled to flask, and the sequence for adding more than one polyisocyanate (x) is wherein being added dropwise.
In these sequences, in order to preferentially react the low molecular composition in raw material, and molecular weight dispersity is reduced, and just For reaction controlling is easy, preferred sequence 2).
Using catalyst, reaction temperature is preferably smaller than 100 DEG C, more preferable 85 DEG C~95 DEG C.If making to react Temperature then can inhibit the side reaction other than urethane reaction less than 100 DEG C, therefore be easy to get desired resin.
In the case where not using catalyst, preferably 100 DEG C or more of reaction temperature, more preferable 110 DEG C or more.
Using catalyst, the mostly time of urethane reaction substantially needs 1 hour or more situation.Separately Outside, in the case where not using catalyst, 3 hours or more situations are mostly substantially needed.
The isocyanate group of polyisocyanate (x) when synthesizing carbamate prepolymer (a) containing isocyanate group (NCO) and the hydroxyl of polyalcohol (y) (OH) is preferably 1.1~2, more preferable 1.1~1.8 if the molar ratio computing with NCO/OH, into And it is preferred that 1.2~1.6.By making NCO/OH ratio range appropriate, the carbamate pre-polymerization of appropriate strand can be formed Object, therefore wetability and productivity are further promoted.
<amine compounds (b)>
Carbamate carbamide resin (A) be make more than one carbamate prepolymer (a) containing isocyanate group and More than one amine compounds (b) carry out urea and react resulting reactant.
Amine compounds (b) preferably monoamine, diamines, amine more than trifunctional, amine more than more preferable diamines or trifunctional, into And it is preferred that the diamines with hydroxyl or amine more than trifunctional, particularly preferably have more than two amino or more than one ammonia The compound of base and more than one hydroxyl.By using amine compounds (b), carbamate carbamide resin (A) can not be depended on Molecular weight and cohesiveness is promoted by urea bond.Especially in the case where carbamate carbamide resin (A) has primary OH, instead Answer speed fast, therefore the required time until hardening terminates is short, productivity is further promoted.
Amine compounds (b) can for example enumerate ethylenediamine, trimethylene diamine, tetra-methylenedimine, five methylene diamine, six Methylene diamine, three second tetramines, Diethylenetriamine, triaminopropane, 2,2,4- trimethylhexamethylenediamines, 2- hydroxyethyl second Diamines, diethanol amine, diisopropanolamine (DIPA), methylamino -2 1-, 3-propanediol, N- (2- hydroxyethyl) propane diamine, N- (3- hydroxyl Propyl) ethylenediamine, (2- hydroxyethyl propylidene) diamines, (two -2- hydroxyethyl ethylidene) diamines, (two -2- hydroxyethyls Asias Propyl) the aliphatic amines chemical combination such as diamines, (2- hydroxypropyl ethylidene) diamines, (two -2- hydroxypropyl ethylidene) diamines, piperazine Object；The ester ring types amine compounds such as isophorone diamine, 4,4 '-diamines of dicyclohexyl methyl hydride-；Phenylenediamine, xylylene amine, 2,4- toluenediamines, 2,6- toluenediamine, diethyl toluene diamine, 3,3 '-two chloro- 4,4 '-diaminodiphenyl-methanes, 4, The aromatic diamines such as 4 '-bis--(sec-butyl) diphenyl methanes；And by the converting carboxylate groups of dimeric dibasic acid be amino dimer diamine (dimer diamine)；End has level-one or the dendrimer, dendritic polymer (dendrimer) of second level amino etc..
In addition, amine compounds (b) may be used at molecule two ends have propoxyl group amine by the following general formula [2] represented by Polyoxyalkylene glycols diamines etc..
General formula [2]:
H2N-CH2-CH2-CH2-O-(CmH2m-O)n-CH2-CH2-CH2-NH2
(in formula, m indicates that 2~4 arbitrary integer, n indicate 2~50 arbitrary integer)
In these amine compounds (b), for the aspect of the control of urea reaction, preferably there are more than two second level amino And the compound with a primary OH.The compound can unlimitedly use well known compound.
If enumerating the synthetic method of the compound with more than two second level amino and with a primary OH An example then preferably makes the compound at least one hydroxyl and (methyl) acryloyl group and has more than two level-one amino Compound carry out Michael addition reaction (Michael addition reaction) resulting compound.The compound The possessed preferred primary OH of hydroxyl.As a result, to carbamate carbamide resin and isocyanate hardener hardening terminate be Only the required time shortens, and can make coating speed high speed, therefore productivity is further promoted.
The compound with more than two level-one amino can enumerate the compound illustrated in amine compounds (b).This In a little compounds, isophorone diamine, 2,2,4- trimethylhexamethylenediamines, hexamethylene diamine are because of Michael addition reaction Control be easy, therefore preferably.
There is no particular restriction for the polymerization of carbamate carbamide resin (A), so that it may the feelings of the well known polymerization of application For the aspect for the reaction controlling that urea reacts under condition, make when synthesizing the carbamate prepolymer (a) containing isocyanate group When with catalyst, preferably make the catalyst deactivation.As long as acetylacetone,2,4-pentanedione etc. is for example deployed in the deactivation.
The polymerization sequence of carbamate carbamide resin (A) is preferably by the carbamate prepolymer (a) containing isocyanate group And more than one solvent optionally is filled to flask, under cryogenic conditions in comparison, spends the time by amine compounds Object (b) is added dropwise to sequence therein.Make low molecular composition preferential reaction as a result, molecular weight dispersity can be reduced, therefore to curved surface Each adaptive in portion is further promoted.
In addition, anti-by making after reacting amine compounds (b) with the carbamate prepolymer (a) containing isocyanate group It answers terminator to be reacted, unreacted isocyanate group can be made to disappear.It is viscous before deploying isocyanate hardener (B) as a result, The ageing stability of the host agent of agent further promoted.In addition, so-called host agent, refers to the combination for eliminating curing agent from sticker Object.
The preferred monoamine of reaction terminating agent.In addition, monoamine, which preferably has, to be become and the crosslinking points of isocyanate hardener (B) Hydroxyl.
Monoamine can for example enumerate 2-amino-2-methyl-1-propanol.
Reaction terminating agent can be used alone or using two or more.
The weight average molecular weight (Mw) preferably 30 of carbamate carbamide resin (A), 000~250,000, more preferable 30, 000~200,000, and then preferably 50,000~200,000.By the way that weight average molecular weight (Mw) is set as in the range, Each adaptive of curved face part is further promoted.
The molecular weight dispersity preferably 1.5~6 of carbamate carbamide resin (A), more preferable 2~5, and then preferably 2.5~ 4.The difficulty that molecular weight dispersity is synthesized less than 1.5 is high.In addition, by making molecular weight dispersity 6 hereinafter, can inhibit low Molecular weight constituent, therefore each adaptive of curved face part is further promoted.
(isocyanate hardener (B))
Isocyanate hardener (B) is the well known compound with multiple isocyanate group.Isocyanate hardener (B) It is preferred that it is stated that polyisocyanate (x), wherein more preferable aromatic poly-isocyanate, aliphatic polymeric isocyanate, fragrant rouge Fat adoption isocyanates and alicyclic polymeric isocyanate and these trimethylolpropane adduct body and these contracting two The trifunctional isocyanates etc. of urea body and the tripolymer as these.
Isocyanate hardener (B) can be used alone or using two or more.
Relative to 100 mass parts of carbamate carbamide resin (A), the blending amount of isocyanate hardener (B) is preferably greater than 3 Mass parts and for 20 below the mass, more preferable 5 mass parts~15 mass parts.If deploying suitable isocyanate hardener (B), Then it is easy to get appropriate adhesion strength and cohesiveness.
(plasticiser (C))
Surface protection sticker of the invention can also include plasticiser (C).If comprising plasticiser (C), adhesion coating pair The wetability for being attached to body is further promoted.For the viewpoints such as compatibility with other compositions, plasticiser (C) preferably carbon number 8 ~30 aliphatic ester or phosphate etc..
The aliphatic ester of carbon number 8~30 can for example be enumerated: the monoacid or polyacid and carbon number 18 of carbon number 6~18 are below The one of the ester and carbon number 6~18 of the ester of branch's alcohol, the unsaturated fatty acid of carbon number 14~18 or chorismic acid and tetravalence alcohol below The ester of first acid or polyacid and poly- alkane glycol, using peroxide etc. by aliphatic ester obtained by unsaturated position epoxidation etc..
The monoacid or polyacid of carbon number 6~18 and the ester of the branch's alcohol below of carbon number 18 can for example be enumerated: lauric acid is different The different cetyl of stearyl, isopropyl myristate, myristic acid, myristic acid octyldodecyl, the different tristearin of palmitinic acid Base ester, Standamul 7061, octyldodecyl oleate, two iso stearyl ester of adipic acid, the different cetyl of decanedioic acid two, partially Three oleyl ester of benzenetricarboxylic acid and the different cetyl of trimellitic acid three etc..
The unsaturated fatty acid or chorismic acid of carbon number 14~18 can for example be enumerated: nutmeg oleic acid, oleic acid, linolenic acid, Linolenic acid, different palmitinic acid and isostearic acid etc..As tetravalence alcohol below, can enumerate: ethylene glycol, propylene glycol, glycerol, Trimethylolpropane, pentaerythrite and sorbitan (sorbitan) etc..
As the monoacid or polyacid of carbon number 6~18 and the ester of poly- alkane glycol, can enumerate: two caproic acid polyethylene glycol, two- 2 ethyl hexanoic acid polyethylene glycol, two polyethylene glycol monomethyl ether of tin dilaurate polyethylene glycol, two oleic acid polyethylene glycol and adipic acid Deng.
Aliphatic ester obtained by unsaturated position epoxidation can for example be enumerated using peroxide etc.: epoxidation soybean The epoxidations grease such as oil, epoxy linseed oil, epoxidized cotton seed oil, or by the unsaturated fatty acid epoxidation of carbon number 8~18 Obtained by compound and carbon number 1~6 straight chain or the carboxylate of branch's alcohol etc..
Phosphate can for example enumerate phosphorous acid or phosphoric acid and the straight chain of carbon number 2~18 or the ester compounds of branch's alcohol.
Plasticiser (C) can be used alone or using two or more.
For the viewpoints such as wetting speed promotion, the number average molecular weight (Mn) preferably 300~1000 of plasticiser (C), More preferable 300~900, and then preferably 350~850.
Relative to 100 mass parts of carbamate carbamide resin (A), the blending amount of plasticiser (C) preferably 0.1 mass parts~ 100 mass parts, more preferable 1 mass parts~80 mass parts, and then preferably 10 mass parts~50 mass parts.If deploying suitable plasticizing Agent (C), then wetability is further promoted.
(antioxidant (D))
Surface protection sticker of the invention can also include antioxidant (D).If can press down comprising antioxidant (D) The heat deterioration of carbamate carbamide resin (A) processed.
The free radical chains inhibitor such as the preferred phenolic antioxidant of antioxidant and amine antioxidant and sulphur system are anti-oxidant Agent or phosphorous antioxidant etc..
Phenolic antioxidant can for example be enumerated: 2,6- di-t-butyl-paracresol, butylated hydroxyanisol, 2,6- bis-- The list phenolic antioxidant such as tert-butyl -4- ethyl -phenol and β-(3,5- di-t-butyl -4- hydroxy phenyl) propionic acid stearyl ester；
2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol), 2,2 '-di-2-ethylhexylphosphine oxides (4- ethyl -6- tert-butyl benzene Phenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol)s and 3, 9- bis- [1,1- dimethyl -2- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionyloxy] ethyls] 2,4,8,10- tetra- oxygen Double phenolic antioxidants such as miscellaneous spiral shell [5,5] hendecane；
1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane, 1,3,5- trimethyls -2,4,6- tri- (3,5- Di-t-butyl -4- hydroxybenzyl) benzene, four-[methylene -3- (3 ', 5 ' -4 '-hydroxy phenyl of di-t-butyl -) propionic ester] first Alkane, bis- [3,3 '-bis--(4 '-hydroxyls -3 '-tert-butyl-phenyl) butyric acid] glycol esters and 1,3,5- tri- (3 ', 5 '-two-tertiary fourths Base -4 '-hydroxybenzyl)-S- triazine -2,4, polymer electrolytes phenolic antioxidants such as 6- (1H, 3H, 5H) triketone, tocopherol etc..
Sulfur antioxidant can for example be enumerated: 3,3 '-thiodipropionate dilauryls, 3,3 '-thio-2 acids two-ten Tetraalkyl ester and 3,3 '-thio-2 acid distearyl base esters etc..
Phosphorous antioxidant can for example be enumerated: triphenyl, diphenylisodecyl base ester and phosphorous acid benzene Base diiso decyl ester etc..
Antioxidant (D) can be used alone or using two or more.
Relative to 100 mass parts of carbamate carbamide resin (A), the blending amount of antioxidant (D) preferably 0.01 mass parts ~10 mass parts, more preferable 0.1 mass parts~5 mass parts.
(antistatic agent (E))
Surface protection sticker of the invention can also include antistatic agent (E).If inhibiting comprising antistatic agent (E) The breakage removed static discharge when adhesive sheet, such as be easy to prevent from being fitted into part in display etc. etc..
Antistatic agent can for example enumerate inorganic salts, polyol compound, ionic liquid, surfactant etc..These are anti- Preferred ion liquid in electrostatic agent.In addition, " ionic liquid " is also referred to as room temperature fuse salt, the property of liquid at 25 DEG C is indicated Shape.
Inorganic salt can such as be enumerated: sodium chloride, potassium chloride, lithium chloride, lithium perchlorate, ammonium chloride, potassium chlorate, aluminium chloride, Copper chloride, frerrous chloride, iron chloride, ammonium sulfate, potassium nitrate, sodium nitrate, sodium carbonate and sodium sulfocyanate etc..
Polyol compound can for example be enumerated: propylene glycol, butanediol, hexylene glycol, polyethylene glycol, trimethylolpropane and Pentaerythrite etc..
Ionic liquid is the salt of cation with anion, for example preferred imidazol ion of cation, pyridinium ion, ammonium Ion etc..
Ionic liquid comprising imidazol ion can for example be enumerated: the bis- (trimethyl fluoride sulfonyls of 1- ethyl-3-methylimidazole Base) acid imide, bis- (trifluoromethyl sulfonyl) acid imides of 1,3- methylimidazole and 1- butyl -3- methylimidazole bis- (three Methyl fluoride sulfonyl) acid imide etc..
Ionic liquid comprising pyridinium ion can for example be enumerated: bis- (trifluoromethyl sulfonyl) acyls of 1- picoline are sub- Bis- (trifluoromethyl sulfonyl) acid imides of amine, 1- butyl-pyridinium, bis- (trifluoromethyl sulfonyl) acid imides of 1- hexyl pyridine, Bis- (trifluoromethyl sulfonyl) acid imides of 1- octylpyridinium, bis- (trifluoromethyl sulfonyl) acyls of 1- hexyl -4- picoline Bis- (trifluoromethyl sulfonyl) acyls of imines, 1- hexyl -4- picoline hexafluorophosphate, 1- octyl -4- picoline are sub- Bis- (perfluoroethyl sulfonyl base) acyls of bis- (fluorosulfonyl) acid imides of amine, 1- octyl -4- picoline, 1- picoline are sub- Amine and bis- (perfluoro butyl sulfonyl) acid imides of 1- picoline etc..
Ionic liquid comprising ammonium ion can for example be enumerated: bis- (trifyl) acid imides of tri-methyl-amyl ammonium, N, Bis- (trifyl) acid imides of N- diethyl-N- Methyl-N-propyl ammonium, N, N- diethyl-N- methyl -- V-pentyl ammonium are double (trifyl) acid imide, N, bis- (trifyl) acid imides of N- diethyl-N- methyl -- V-pentyl ammonium and three-are just Butyl methyl ammonium bis-trifluoromethylsulfoandimide etc..
It in addition to this, can be suitable for using the cationic well known ionic liquid for Pyrrolizidine Yan, phosphonium salt and sulfonium salt etc..
Surfactant can be classified as nonionic, anionic property, cationic and the type of both sexes.
The type of nonionic can for example be enumerated: fatty acid glyceride, polyoxyalkylene alkyl ether, polyoxyethylene Phenyl ether, polyoxyethylene amine, polyoxyethylene amine aliphatic ester, fatty diglycollic amide, polyether ester amides Type, ethylene oxide-epichlorohydrin type and polyether ester type etc..
The type of anionic property can for example be enumerated: alkylsulfonate, alkylbenzene sulfonate, alkyl phosphate and polyphenyl second Alkene sulfonic acid type etc..
The type of cationic can for example enumerate third containing tetraalkylammonium salt, triakyl benzyl ammonium salt and quarternary ammonium salt base Olefine acid ester polymer type etc..
The type of both sexes can for example be enumerated: alkyl betaine and alkyl imidazole glycine betaine, senior alkyl aminopropionate The sweet teas such as equal amino acid type amphoterics surfactant, senior alkyl dimethyl betaine and senior alkyl dihydroxy ethyl glycine betaine Dish alkaline amphoteric surfactant etc..
Antistatic agent (E) can be used alone or using two or more.
Relative to 100 mass parts of carbamate carbamide resin (A), the blending amount of antistatic agent (E) preferably 0.01 mass parts ~10 mass parts, more preferable 0.03 mass parts~5 mass parts.
(solvent)
Surface protection sticker of the invention optionally may include solvent.Solvent can for example be enumerated: methyl ethyl ketone, second Compound well known to acetoacetic ester, toluene, dimethylbenzene and acetone etc..In these solvents, just with the phase of carbamate carbamide resin (A) For the viewpoints such as the boiling point of capacitive and solvent, ethyl acetate and toluene.
Solvent can be used alone or using two or more.
(any ingredient)
As long as surface protection sticker of the invention can include optionally any for it can solve project in the range of Ingredient.Any ingredient can be enumerated: other resins, filler, metal powder, pigment, foil-like object other than carbamate system resin, Softening agent, ultraviolet absorbing agent, light stabilizer, surface lubricant, levelling agent, anticorrosive, heat-resisting stabilizing agent, Inhibition of polymerization Agent, defoaming agent and lubricant etc..
Filler can for example be enumerated: talcum, calcium carbonate, titanium oxide etc..
Ultraviolet absorbing agent can for example be enumerated: benzophenone series ultraviolet absorbing agent, enumerate BTA system ultraviolet absorbing agent, Salicylic acid system ultraviolet absorbing agent, oxalic acid aniline system ultraviolet absorbing agent, cyanoacrylate system ultraviolet absorbing agent and triazine It is ultraviolet absorbing agent etc..
Benzophenone series ultraviolet absorbing agent can for example be enumerated: 2,4-DihydroxyBenzophenone, 2- hydroxyl -4- methoxyl group two Benzophenone, 2- hydroxyl -4- octyloxybenzophenone, 2- hydroxyl -4- dodecyl oxygroup benzophenone, 2,2 '-dihydroxy -4- two Methoxy benzophenone, 2,2 '-dihydroxy -4,4 '-dimethoxy-benzophenones, 2- hydroxyl -4- methoxyl group -5- sulfonic group hexichol Ketone and bis- (2- methoxyl group -4- hydroxyl -5- benzoylphenyl) methane etc..
Enumerate BTA system ultraviolet absorbing agent can for example be enumerated: 2- (2 '-hydroxyls -5 '-aminomethyl phenyl) benzotriazole, 2- (2 '-hydroxyls -5 '-tert-butyl-phenyl) benzotriazole, 2- (2 '-hydroxyls -3 ', 5 '-di-t-butyl phenyl) benzotriazole, 2- (2 '-hydroxyls -3 '-tert-butyl -5 '-aminomethyl phenyl) -5- chlorobenzotriazole, 2- (2 '-hydroxyls -3 ', 5 '-di-t-butyl phenyl) - 5- chlorobenzotriazole, 2- (2 '-hydroxyls -3 ', 5 '-two-tertiary pentyl phenyl) benzotriazole, 2- (2 '-hydroxyls -4 '-octyloxy benzene Base) benzotriazole, 2- [2 '-hydroxyls -3 '-(3 ", 4 ", 5 ", 6 "-tetrahydric phthalimide methyl) -5 '-aminomethyl phenyls] benzene And triazole, 2,2 '-di-2-ethylhexylphosphine oxides [4 '-(1,1,3,3 '-tetramethyl butyl) -6- (2H- benzotriazole -2- base) phenol] and 2- (2 '-hydroxyls -5 '-methacryl-oxyphenyl) -2H- benzotriazole etc..
Salicylic acid system ultraviolet absorbing agent can for example be enumerated: phenyl salicylic acid esters, p- tert-butylphenyl salicylate acid esters and P- octylphenyl salicylate etc..
Cyanoacrylate system ultraviolet absorbing agent can for example be enumerated: cyano -3 2- ethylhexyl -2-, 3 '-diphenylprops Olefin(e) acid ester and cyano -3 ethyl -2-, 3 '-diphenylacrylate esters etc..
Light stabilizer can for example enumerate be obstructed amine system light stabilizer, ultra-violet stabilizer etc..
Amine system of being obstructed light stabilizer can for example be enumerated: [bis- (2,2,6,6- tetramethyl -4- piperidyl) sebacates], double (1,2,2,6,6- pentamethyl -4- piperidyl) sebacate and 1,2,2,6,6- pentamethyl -4- piperidyl decanedioic acid methyl esters etc..
Ultra-violet stabilizer can for example be enumerated: bis- (octyl phenyl) thioether nickel, [2,2 '-thiobis (4- t-octyl phenol Salt)]-n-butylamine nickel, nickel complex -3,5- di-t-butyl -4- hydroxybenzyl-phosphonic ethyl ester, benzoic ether type it is sudden Go out agent and nickel dibutyl dithiocarbamate etc..
Levelling agent can enumerate acrylic acid series levelling agent, fluorine system levelling agent, silicon systems levelling agent etc..If enumerating the commercially available of levelling agent Product, then acrylic acid series levelling agent can for example be enumerated: Po Lifuluo (Polyflow) No.36, Polyflow No.56, Polyflow No.85HF, Polyflow No.99C (being the manufacture of chemical company of common prosperity society) etc..Fluorine system levelling agent can for example be enumerated: Mei Jiafa (Megafac) F470N, Megafac F556 (being the manufacture of DIC (DIC) company) etc..Silicon systems levelling agent can for example enumerate lattice Blue Dick (Grandic) PC4100 (manufacture of DIC (DIC) company) etc..
[adhesive sheet]
Adhesive sheet of the invention has substrate and adhesion coating, and the adhesion coating is the hardening thing of surface protection sticker. Adhesion coating can be formed in the one or two sides of substrate.In addition, the attachment of foreign matter in order to prevent, adhesion coating is not contacted with substrate Face is usually protected using stripping film before the use.
Substrate can be with no particular limitation using soft piece and plate.Substrate can enumerate plastics, paper and metal foil and These laminated body etc..
For the face of substrate contacted with adhesion coating, in order to promote adhesion, such as corona discharge can be carried out in advance The wet processeds such as the dry process such as processing or thickening smears (anchor coat agent) coating etc are easily then handled.
Plastics as substrate can for example be enumerated: polyethylene terephthalate (polyethylene Terephthalate, PET), the esters system resin such as polyethylene naphthalate (polyethylene naphthalate, PEN)； Polyethylene (polyethylene, PE), polypropylene (polypropylene, PP) and cyclic olefin polymer (cycloolefin Polymer, COP) etc. olefin-based resins；The vinyl resins such as polyvinyl chloride；The amides such as nylon66 fiber system resin；Carbamate It is resin (comprising foaming body) etc..
In addition to polyurethane sheet, the thickness of substrate is usually 10 μm~300 μm or so.Gather in addition, substrate uses Thickness when carbamate piece (including foaming body) is usually 20 μm~50,000 μm or so.
Paper can for example enumerate plain paper, coating paper and art paper etc..
Metal foil can such as enumerate aluminium foil, copper foil.
The usable well known lift-off processing that silicone series stripping agent etc. is implemented to the surface of plastics or paper etc. of stripping film Well known stripping film.
The manufacturing method of adhesive sheet can for example enumerate the surface that sticker is coated on to substrate, form overlay, then will Overlay is dry and hardens, the method for forming adhesion coating.Heating and drying temperature are usually 60 DEG C~150 DEG C or so.Adhesion coating Thickness be usually 0.1 μm~200 μm or so.
Coating method can for example enumerate roll coater (roll coater) method, chipping wheel coater (comma coater) method, Die coating machine (die coater) method, reversed coating machine (reverse coater) method, silk screen printing (silk screen) method and Method well known to gravure coater (gravure coater) method etc..
In addition, can enumerate with the method on the contrary, applying sticker on the surface of stripping film and forming overlay, then The adhesion coating that overlay drying and hardening are formed to the hardening thing containing sticker of the invention, finally in the exposing of adhesion coating The method of face paste conjunction substrate sheets.If replacing substrate using the method fitting stripping film, available stripping film/adhesion coating/ The casting adhesive sheet of stripping film.
[embodiment]
Hereinafter, using embodiment come embodiments of the present invention will be described.In addition, embodiments of the present invention are certain It is not limited to embodiment.Hereinafter, " part " refers to " mass parts ", " % " refers to " quality % ".
[measurement of weight average molecular weight (Mw) and number average molecular weight (Mn)]
Weight average molecular weight (Mw) and number average molecular weight (Mn) are surveyed by gel permeation chromatography (GPC) method It is fixed.Determination condition is as follows.In addition, Mw and Mn are polystyrene scaled value.
<determination condition>
Device: Shimadzu brilliance (SHIMADZU Prominence) (manufacture of company of Shimadzu Seisakusho Ltd.),
Tubing string: 3 Gen Suo get Ke Si (SHODEX) LF-804 (manufacture of Showa electrician company) is connected in series,
Detector: differential refractive index detector,
Solvent: tetrahydrofuran (THF),
Flow velocity: 0.5mL/min,
Solvent temperature: 40 DEG C,
Sample solution concentration: 0.1%,
Sample injection rate: 100 μ L.
[material]
Used material is as follows.
<polyisocyanate (x)>
(x1): HDI (live to change Cohan and create carbamate (Sumika Covestro by hexamethylene diisocyanate Urethane) " De Shimo all (Desmodur) H " of company's manufacture),
(x2): IPDI (isophorone diisocyanate, live change Cohan wound carbamate company manufacture " De Shimo is (Desmodur)I”)、
(x3): XDI (" the resistance to moral of Plutarch (Takenate) that eylylene diisocyanate, Mitsui Chemicals, Inc.'s system are made 500”)。
<polyalcohol (y)>
(y1): (" this (Sannix) PP-600 of Sani library ", polyoxypropylene glycol, Mn600, hydroxyl value 2, three foreignize PPG600 It is manufactured at industrial group)
(y2): PPG1000 (" this (Sannix) PP-1000 of Sani library ", polyoxypropylene glycol, Mn1000, hydroxyl value 2, Sanyo Chemical conversion industry company manufacture)
(y3): PPG2000 (" this (Sannix) PP-2000 of Sani library ", polyoxypropylene glycol, Mn2000, hydroxyl value 2, Sanyo Chemical conversion industry company manufacture)
(y4): PPG4000 (" this (Sannix) PP-4000 of Sani library ", polyoxypropylene glycol, Mn4000, hydroxyl value 2, Sanyo Chemical conversion industry company manufacture)
(y5): PX1000 (the modified polyoxypropylene glycol of " Pu Limubo (Primepol) PX-1000 ", terminal primary, Mn1000, hydroxyl value 2, the manufacture of chemical conversion industry company of Sanyo)
(y6): P1010 (" Kuraray polyalcohol (Kuraray Polyol) P-1010 ", polyester polyol, Mn1000, hydroxyl Radix 2, Kuraray Corporation manufacture)
(y7): GI1000 (" Ni Suo (NISSO)-PB GI-1000 ", two terminal hydroxyl hydrogenated butadiene polymers, Mn1000, hydroxyl Radix 2, the manufacture of Cao Da company of Japan)
(y8): C1090 (" Kuraray polyalcohol (Kuraray Polyol) C-1090 ", polycarbonate polyol, Mn1000, hydroxyl value 2, Kuraray Corporation manufacture)
(y9): AM302 (" Ai Dike polyalcohol (ADEKA Polyol) AM-302 ", glycerol PO/EO polyalcohol, Mn3000, Hydroxyl value 3, the manufacture of Ai Dike (ADEKA) company)
(y10): T-500 (" more Li Ha get Na (Polyhardner) T-500 ", polypropylene glycerol aether (polyoxypropylene glyceryl ether), Mn5000, hydroxyl value 3, the manufacture of the first industrial pharmaceutical company)
(y11): D-660 (" happiness road cloth (Hilube) D-660 ", polypropylene glycol, Mn3000, hydroxyl value the 2, first industry system Medicine company manufacture)
(y12): BPEF (" double phenoxetol fluorenes (bisphenoxy ethanol fluorene) ", the bis- [4- (2- of 9,9- Hydroxyl-oxethyl) phenyl] fluorenes, formula weight 438.5, hydroxyl value 2, the manufacture of JFE chemical company)
<synthesis of amine compounds (b)>
(b1): have blender, reflux cooling tube, nitrogen ingress pipe, thermometer, addition funnel four-hole boiling flask in fill 25.0 parts, 25.0 parts of toluene of isophorone diamine (isophorone diamine, IPDA) is filled out, is dripped at room temperature from addition funnel Add the mixture of 21.1 parts of 4- hydroxybutyl acrylate with 18.8 parts of butyl propyleneglycol acid esters.After completion of dropwise addition, slowly by interior temperature 80 DEG C are warming up to, after reaction in 2 hours is carried out while maintaining 80 DEG C, is added 39.9 parts of toluene, there are two two to obtain tool Grade amino and compound (1) solution with a primary OH.
(b2): have blender, reflux cooling tube, nitrogen ingress pipe, thermometer, addition funnel four-hole boiling flask in fill 40.0 parts of isophorone diamine (IPDA), 40.0 parts of toluene are filled out, 4- hydroxybutyl acrylic acid is added dropwise from addition funnel at room temperature 67.7 parts of ester.After completion of dropwise addition, interior temperature is slowly warming up to 80v, exists on one side maintain 80 DEG C while and react within 2 hours at 80 DEG C Afterwards, 67.7 parts of toluene are added, to obtain tool there are two second level amino and with compound (2) solution of a primary OH.
(b3): HPEA；N- (3- hydroxypropyl) ethylenediamine (manufacture of Tokyo chemical conversion industry company)
(b4): DEA；Diethanol amine (manufacture of Tokyo chemical conversion industry company)
(b5): DIPA；Diisopropanolamine (DIPA) (manufacture of Tokyo chemical conversion industry company)
(b6): MAPD；Methylamino -2 1-, 3-propanediol (manufacture of Daicel (Daicel) company)
(b7): AMP；2-amino-2-methyl-1-propanol (manufacture of DOW Chemical (Dow Chemical) company)
<isocyanate hardener (B)>
(B1): (trimethylolpropane of " Su meter Dou (Sumidur) HT ", hexamethylene diisocyanate adds HDI adduct It closes object, live to change the manufacture of Cohan wound carbamate company)
(B2): HDI isocyanuric acid ester (the isocyanide urea of " Su meter Dou (Sumidur) N3300 ", hexamethylene diisocyanate Acid esters body lives to change the manufacture of Cohan wound carbamate company)
(B3): HDI biuret (live by the biuret body of " Su meter Dou (Sumidur) N3200 ", hexamethylene diisocyanate Change the manufacture of Cohan wound carbamate company)
<plasticiser (C)>
(C1): M182A (" You Nisita (Unister) M182A ", methyl oleate, the manufacture of You company)
(C2): W262 (" Mo Saize (Monocizer) W262 ", ether-ether system plasticiser, the manufacture of DIC (DIC) company)
(C3): E-6000 (" Sang Saze (Sansocizer) E-6000 ", epoxidized fatty acid 2- ethylhexyl, new Japan Physical and chemical company's manufacture)
(C4): TOP (" TOP ", three (2- ethylhexyl) phosphates, the manufacture of big eight industrial chemistry company)
<antioxidant (D)>
(D1): Irg1010 (" Yi Jialesi (IRGANOX) 1010 ", pentaerythrite four [3- (3,5- di-t-butyl -4- hydroxyls Base phenyl) propionic ester], BASF (BASF) company manufacture)
<antistatic agent (E)>
(E1): FSI- ammonium salt (3- normal-butyl methyl ammonium bis-trifluoromethylsulfoandimide)
(E2): FSI- lithium salts (lithium bis-trifluoromethylsulfoandimide)
[synthesis example of carbamate carbamide resin (A)]
(synthesis example 1)
Have blender, reflux cooling tube, nitrogen ingress pipe, thermometer, addition funnel four-hole boiling flask in load mulberry 628 parts of Ni Kusi (Sannix) PPG600 (two function polypropylene glycols, the manufacture of chemical conversion industry company of Sanyo), two isocyanide of isophorone 372 parts of acid esters, 250 parts of toluene, 0.1 part of the dioctyl tin cinnamic acid tin as catalyst are slowly warming up to 100 DEG C, and it is small to carry out 2 Shi Fanying.It is cooled to 25 DEG C, 750 parts of ethyl acetate is added, after 3 parts of acetylacetone,2,4-pentanedione, with 2 hours (1) 220 part of dropwise addition compounds, 25 DEG C are maintained, and then continues to react for 1 hour.After confirming isocyanate group residual by titration, 2- amino -2- first is added 23 parts of base-propyl alcohol, confirm the NCO characteristic absorption (2,270cm of infrared (IR) figure (infrared chart)-1) disappear, and terminate Reaction.The weight average molecular weight Mw of this carbamate carbamide resin (A1) is 143,000, molecular weight dispersity 5.8.
By the Mw of the type of used raw material and their allotment ratio and carbamate carbamide resin obtained (A1) It is shown in Table 1 with molecular weight dispersity.In addition, the blending amount of the raw material in table is nonvolatile component scaled value, unit is [part].
(2~synthesis example of synthesis example 16)
As shown in table 1 change embodiment 1 material and allotment ratio, in addition to this, come in a manner of identical with synthesis example 1 into Row obtains the resin of 2~synthesis example of synthesis example 16 respectively therefrom.
(synthesis example 17)
It is loaded in the four-hole boiling flask for having blender, reflux cooling tube, nitrogen ingress pipe, thermometer and addition funnel 40 parts of P1010 and 160 part of AM302.In wherein 200 parts of toluene of addition, as the dibutyl tin dilaurate of catalyst 0.03 part and 0.01 part of 2 ethyl hexanoic acid tin, slowly it is warming up to 90 DEG C.It lasts 1 hour and is added dropwise 13 parts of HDI and 13 parts of toluene Gained person is mixed, carries out reacting for 1 hour after dropwise addition.It is sampled at any time, is confirming remaining using infrared absorption (IR) spectrum After the disappearance of isocyanate group, by reaction solution cooling, reaction was completed.The weight averaged molecular of this carbamate carbamide resin Measure Mw be 141,000, molecular weight dispersity 6.1.
(synthesis example 18)
Have blender, reflux cooling tube, nitrogen ingress pipe, thermometer, addition funnel four-hole boiling flask in load mulberry 799 parts of Ni Kusi (Sannix) PPG1000 (two function polypropylene glycols, the manufacture of chemical conversion industry company of Sanyo), hexa-methylene two are different 146 parts of cyanate, 250 parts of toluene, 0.1 part of the dioctyl tin cinnamic acid tin as catalyst are slowly warming up to 100 DEG C, carry out 2 Hour reaction.It is cooled to 70 DEG C, 750 parts of toluene is added, after 3 parts of acetylacetone,2,4-pentanedione, with 30 minutes (1) 27 part of dropwises addition compounds, ties up 70 DEG C are held, and then continues to react for 1 hour.After confirming isocyanate group residual by titration, 2- amino -2- first is added 0.8 part of base-propyl alcohol, confirm the NCO characteristic absorption (2,270cm of IR figure-1) disappear, and reaction was completed.This carbamate urea tree The weight average molecular weight Mw of rouge (A18) is 230,000, molecular weight dispersity 6.9.
[table 1]
Table 1
(embodiment 1)
Deploy 100 parts of carbamate carbamide resin (A1), isocyanate hardener (B1) 3.5 obtained in synthesis example 1 Part, 0.5 part of antioxidant (D1) and 100 parts of solvent ethyl acetate, are stirred using disperser, obtain sticker.In addition, The usage amount of each material in addition to solvent indicates nonvolatile component scaled value.
About substrate, prepare 25 μm of thickness polyethylene terephthalate (PET) (" dew Miller (Lumirror) T- 60 ", Toray manufactures).It, will be obtained viscous at coating speed 3m/min using chipping wheel coater (registered trademark) Agent in such a way that thickness after drying becomes 12 μm coated on the substrate, form overlay.
Secondly, will be formed by overlay drying using drying oven with the condition of 100 DEG C, 2 minutes, and form adhesion coating. On the adhesion coating, 38 μm of coating thickness of commercially available stripping film, and then support within one week under conditions of 23 DEG C of -50%RH Shield, obtains adhesive sheet therefrom.
(2~embodiment of embodiment 36,1~comparative example of comparative example 4)
As shown in table 2 change embodiment 1 material and allotment ratio, in addition to this, in the same manner as example 1 into Row obtains the sticker and adhesive sheet of 2~embodiment of embodiment 36,1~comparative example of comparative example 4 respectively therefrom.
[assessment item and evaluation method]
The assessment item of sticker and adhesive sheet obtained and evaluation method is as follows.
(releasable)
Adhesive sheet obtained is prepared to the size of wide 25mm. long 100mm, as measurement sample.Then, 23 DEG C- In the environment of 50%RH, by stripping film from measurement sample removing, and the adhesion coating of exposing is attached at sodium hydroxide glass plate, made The roller round trip of 2kg is crimped.Later, it is placed 24 hours under conditions of 60 DEG C of -90%RH.Then, 23 DEG C- After being gas-cooled 30 minutes in the environment of 50%RH, foundation Japanese Industrial Standards (Japanese Industrial Standards, JIS) Z0237, using cupping machine (edrophonium chloride (Tensilon): Ao Lian science and technology (Orientec) company manufactures), with stripping Adhesion strength is measured from speed 300mm/min, 180 ° of peel angle of condition.In addition, adhesion strength is low, it is easy to be removed again. Evaluation criteria is as follows.
◎: less than 200mN/25mm.It is excellent.
Zero: 200mN/25mm more than and less than 500mN/25mm.Well.
△: 500mN/25mm more than and less than 1000mN/25mm.It can be practical.
×: more than 1000mN/25mm.It can not be practical.
(wetability)
Adhesive tape obtained is prepared to the size of wide 50mm. long 100mm, as measurement sample.Then, 23 DEG C- After being placed 30 minutes in the environment of 50%RH, stripping film is removed from measurement sample.The both ends of adhesive tape are held with two hands and are made After the central part and contact glass sheet of the adhesion coating of exposing, two hands are unclamped.Make adhesion coating to by the self weight for measuring sample The required time is measured until the whole contiguity with glass plate, thus evaluates the wetability of sticker.Touch with glass plate Until needed for time it is more short then the better to the wetability of glass plate (compatibility), therefore using glass plate manufacturing step In can protect glass well.Evaluation criteria is as follows.
◎: less than 3 seconds until contiguity.It is excellent.
Zero: to contiguity until need 3 seconds more than and less than 5 seconds.Well.
△: to contiguity until need 5 seconds more than and less than 8 seconds.It can be practical.
×: it is needed 8 seconds or more until contiguity.It can not be practical.
(curved face part adaptive)
Adhesive tape obtained is prepared to the size of wide 25mm long 40mm, as measurement sample.Then, at 23 DEG C Release liner (liner) is torn in the environment of 50%RH, to the adhesion coating of exposing, along polypropylene rounding column (diameter 30mm) Circumference attaches adhesive tape sample.After 3 days, with visual Observe and measure sample to the contiguity degree of cylinder.Evaluation criteria is as follows.
◎: the end for measuring sample does not float.It is excellent.
Zero: the end for measuring sample floats 1mm or less.Well.
△: the end for measuring sample floats more than 1mm and is 3mm or less.It can be practical.
×: the end for measuring sample floats more than 3mm.It can not be practical.
(productivity)
The coating speed of embodiment 1 is changed to 30m/min, in addition to this, is carried out in the same manner as example 1 to make Make adhesive sheet, the hardenability under high speed coating is evaluated.Evaluation is the adhesion coating after touching drying steps with finger, Hardenability is evaluated with sticky feeling.
◎: it hardly feels tacky.It is excellent.
Zero: it is slightly tacky, even if but suppressing film with finger and will not lose shape.Well.
△: it is tacky, but slight variations are perceived if suppressing film with finger.It can be practical.
×: serious tacky, film loses shape if touching.It can not be practical.
[table 2]
Table 2
[table 3]
Table 3
According to the record of synthesis example, by delaying after spending the time that amine compounds are added dropwise under cryogenic conditions in comparison The slow temperature for improving reaction solution, can the narrow carbamate carbamide resin of synthetic molecular weight dispersion degree.According to table 2 and table 3 as a result, Using the surface protection sticker of the application of the carbamate carbamide resin can make with wetability and releasable, The adhesive sheet that curved face part adaptive is good and productivity is high.

Claims (7)

1. a kind of surface protection sticker, which is characterized in that relative to the carbamate prepolymer (a) containing isocyanate group And the reactant of amine compounds (b), that is, 100 mass parts of carbamate carbamide resin (A), comprise more than 3 mass parts and 20 mass parts Isocyanate hardener (B) below, and
The molecular weight dispersity of the carbamate carbamide resin (A) is 1.5~6.
2. surface protection sticker according to claim 1, which is characterized in that the carbamate carbamide resin (A) Weight average molecular weight be 30,000~250,000.
3. surface protection sticker according to claim 1 or 2, it is characterised in that also include plasticiser (C).
4. surface protection sticker according to claim 1 or 2, which is characterized in that relative to the carbamate 100 mass parts of carbamide resin (A), include 0.1 mass parts~100 mass parts plasticiser (C).
5. surface protection sticker according to claim 1 or 2, which is characterized in that also include antioxidant (D).
6. surface protection sticker according to claim 1 or 2, which is characterized in that also include antistatic agent (E).
7. a kind of adhesive sheet, it is characterised in that have: substrate and adhesion coating, the adhesion coating are to appoint according to claim 1 in 6 The hardening thing of surface protection sticker described in one.
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