CN110494527A

CN110494527A - The manufacturing method of sticker, adhesive sheet and C-terminal carbamate prepolymer

Info

Publication number: CN110494527A
Application number: CN201980001763.9A
Authority: CN
Inventors: 斋藤秀平; 户根嘉孝
Original assignee: Toyochem Co Ltd; Toyo Corp
Current assignee: Toyochem Co Ltd; Toyo Corp
Priority date: 2018-04-12
Filing date: 2019-03-26
Publication date: 2019-11-22
Anticipated expiration: 2039-03-26
Also published as: CN110494527B; TW201943824A; JP6519687B1; WO2019198488A1; KR102587039B1; TWI803614B; KR20200140795A; JP2019183037A

Abstract

The present invention provides a kind of working life and initial hardening property is good, even and if being capable of forming wetability and substrate adhesion well and being placed under hot and humid environment the also sticker of the adhesion coating with good releasable.Sticker of the invention includes C-terminal carbamate prepolymer (UPH) and polyfunctional isocyanate compound (I), and the C-terminal carbamate prepolymer (UPH) is that the number average molecular weight of polyether polyol (HA) and every 1 functional group that the number average molecular weight comprising every 1 functional group is 1650 or more be 300 or less and a variety of compounds (HX) containing active hydrogen-based of a compound (HB) containing active hydrogen-based with multiple active hydrogen-baseds in molecule and the reaction product of more than one polyisocyanate (N).Compound (HB) containing active hydrogen-based includes the compound containing active hydrogen-based for only including primary OH as active hydrogen-based.

Description

The manufacturing method of sticker, adhesive sheet and C-terminal carbamate prepolymer

Technical field

The present invention relates to the manufacturing methods of a kind of sticker, adhesive sheet and C-terminal carbamate prepolymer.

Background technique

Since before, as the surface protective plate of various components, it has been widely used in substrate sheets and has been formed with adhesion coating Adhesive sheet.As sticker, there are acrylic acid series sticker, silicone-based sticker and carbamate system sticker etc..Acrylic acid Be sticker adhesion strength it is excellent, but because adhesion strength is strong, therefore it is not good enough to be attached at the releasable after being attached to body.Especially in height Under warm high humidity environment through when after, releasable further decreases due to the rising of adhesion strength, be easy to produce after removing again glue Agent remain on the tendency for being attached to body pollution on the surface for being attached to body.About silicone-based sticker, also there is following worry: In Be attached to body be easy to produce pollution, and then the relatively low silicone resin of molecular weight volatilize and be adsorbed in the table of the equipment such as electronic component Face and cause undesirable condition.In contrast, carbamate system sticker has good adhesion relative to body is attached to, together When releasable it is also more excellent and also not volatile.

In the present specification, " sticker " is the sticker (exfoliated sticker again) with releasable, " adhesive sheet " For the adhesive sheet (releasable adhesive sheet) with releasable.

Liquid crystal display (Liquid Crystal Display, LCD) and display of organic electroluminescence (Organic Electroluminescence Display, OELD) etc. flat-panel monitors and by the flat-panel monitor and touch screen combination Made of touch-screen display be widely used in TV (Television, TV), personal computer (Personal Computer, PC), in the electronic equipments such as mobile phone and portable-type information terminal.

Carbamate system adhesive sheet is preferably used as flat-panel monitor and touch-screen display and these manufacture Substrate that is manufactured or using (glass substrate and is formed with tin indium oxide (Indium Tin on the glass substrate in process Oxide, ITO) film ITO/ glass substrate etc.) and optical component etc. surface protective plate.

As the manufacturing method of carbamate system sticker, there are as below methods: containing reactive hydrogen used as polyalcohol etc. The C-terminal carbamate prepolymer and polyfunctional isocyanateization of the reaction product of the compound and polyisocyanate of base The method for closing object；And make polyalcohol and polyfunctional isocyanate compound one without using C-terminal carbamate prepolymer The method (single method (one shot method)) of secondary property reaction.

The manufacturing method of common adhesive sheet includes: working procedure of coating, by sticker coated in substrate sheets；Heating process, To be formed by overlay be thermally dried processing and formed comprising sticker hardening thing adhesion coating；Rolling step, will Adhesive sheet obtained is wound in core and forms the form of adhesive sheet roller；And maintenance process, adhesive sheet roller is conserved.

Existing technical literature

Patent document

Patent document 1: No. 5501489 bulletins of Japanese Patent No.

Patent document 2: Japanese Patent Laid-Open 2016-138237 bulletin

Patent document 3: Japanese Patent Laid-Open 2016-204468 bulletin

Summary of the invention

Problem to be solved by the invention

Carbamate system sticker is hardened immediately after just manufacturing, if but initial hardening property it is excessively high, just like Lower worry: working life, (pot life) shortened, and during until sticker is coated in substrate sheets, sticker glues Degree becomes to be too high to carry out even application.If the initial hardening property of carbamate system sticker is too low, there is following load Sorrow: adhesive sheet obtained after the hot wind or heat drying when heat drying by overlay of overlay or adhesion coating The influence of suffered mechanical stress when winding and when conserving and generate core scale trace, orange peel defect and curling etc. in adhesion coating Appearance is bad.Carbamate system sticker preferably has good working life, while having good initial hardening Property.

Adhesive sheet is preferably that adhesion coating is good relative to the adhesion (also referred to as substrate adhesion) of substrate sheets.Adhesive sheet is excellent Be selected as that there is good substrate adhesion, at the same have from be attached to when body is removed can be easy from be attached to body remove again it is good Releasable.Even if adhesive sheet is preferably in the case where being exposed in hot and humid environment, also there is no glue after removing again Agent component residue be attached to body pollution in the surface for being attached to body.

Adhesion coating is preferably attached to body relative to glass etc. and has good wetability, adhesive sheet is attached at attached Body when bubble will not be involved in attach interface.In carbamate system sticker, in order to improve wetability, addition plasticizing sometimes Agent.However, especially in the case where being exposed in hot and humid environment, there is production in the case where more than the additive amount of plasticiser Sticker component residue is in the worry for being attached to body pollution on the surface for being attached to body after the removing again of raw adhesive sheet.Therefore, it moulds The additive amount of agent is preferably few, does not add plasticiser more preferably.Even if carbamate system sticker is preferably plasticizing The additive amount of agent is few/do not add the allotment composition of plasticiser preferably, it may have good wetability.

As association document of the invention, 1~patent document of patent document 3 can be enumerated.

A kind of carbamate system sticker is disclosed in patent document 1, comprising making containing there are many polyalcohol (A) and more officials The composition of energy isocyanate compound (B) hardens and the polyurethanes system resin of acquisition, a variety of polyalcohols (A) packets Containing tool there are three the number average molecular weight (Mn) of OH base be 8000~20000 polyalcohol (A1) and tool there are three above OH The number average molecular weight (Mn) of base is 5000 polyalcohols (A2) (technical solution 1) below.

A kind of sticker glycol composition is disclosed in patent document 2, include following polyalcohols (A1), and to Polyisocyanate compounds (B) react to obtain sticker (technical solution 1).

Polyalcohol (A1): function radix is 3 or more, the number average molecular weight (Mn) of every 1 functional group be 500~ 2500, the polyoxy sub alkyl polylol that oxygen ethylidene is 16 moles of % or more relative to the content of the total amount of oxyalkylene.

A kind of sticker set group is disclosed in patent document 2, and there is host agent composition and the receiving for being contained in the 1st container In the hardener composition of the 2nd container,

The host agent composition is the sticker glycol composition,

The hardener composition includes polyisocyanate compounds (B),

The one or both of them of the host agent composition and the hardener composition contains catalyst (C) (technical side Case 5).

A kind of carbamate system sticker is disclosed in patent document 3, includes carbamate prepolymer, the amino It is 0.07meq/g or less that urethane prepolymer, which is using degree of unsaturation, and number average molecular weight (Mn) is 3000~30000 Polyetherdiol A and polyisocyanate C and obtain, and OH possessed by NCO base possessed by polyisocyanate C and polyetherdiol A The ratio of base total amount is the range (technical solution 9) of 0.85~1.15 (molar ratio).

Furthermore the symbol for each ingredient recorded in 1~patent document of patent document 3 is the symbol recorded in these documents, And with symbol used in each ingredient of the invention without any relationship.

The carbamate system sticker recorded in patent document 1, patent document 2 is to utilize single method amino obtained Formic acid esters system sticker.Typically, used the adhesion coating of the carbamate system sticker obtained using single method hard Firmly, have the tendency that the surface smoothness of adhesion coating due to curing shrinkage is also easy deterioration.

In the carbamate system sticker recorded in patent document 3, the raw material as carbamate prepolymer is polynary Alcohol, the polyetherdiol A that the number average molecular weight (Mn) using every 1 functional group is 1500~15000.Using such long Chain raw polyol of the polyalcohol as carbamate prepolymer in the case where, have following tendency: adhesion coating can be improved Wetability, but sticker initial hardening property reduce and adhesion coating releasable reduce.

The present invention is formed in view of the situation, its purpose is to provide a kind of working life and initial hardening property are good, and Even and if being capable of forming wetability and substrate adhesion well and being placed under hot and humid environment also with good releasable Adhesion coating sticker, and use its adhesive sheet.

Technical means to solve problem

Sticker of the invention includes:

C-terminal carbamate prepolymer (UPH), the C-terminal carbamate prepolymer (UPH) be comprising The quantity mean molecule of polyether polyol (HA) and every 1 functional group that the number average molecular weight of every 1 functional group is 1650 or more Amount for 300 or less and a compound (HB) containing active hydrogen-based with multiple active hydrogen-baseds in molecule it is a variety of containing active hydrogen-baseds Compound (HX), the reaction product with more than one polyisocyanate (N)；And

Polyfunctional isocyanate compound (I), and

Compound (HB) containing active hydrogen-based includes the only change containing active hydrogen-based comprising primary OH as active hydrogen-based Close object.

Adhesive sheet of the invention includes the adhesion coating of substrate sheets and the hardening thing comprising the sticker of the invention.

The manufacturing method of C-terminal carbamate prepolymer of the invention includes: to keep the quantity of every 1 functional group average More than one polyether polyol (HA) that molecular weight (Mn) is 1650 or more, with more than one polyisocyanate (N) with different The ratio of cyanic acid ester group surplus is reacted and the process that generates isocyanate group terminal carbamate ester prepolymer (UPN)；And

Make isocyanate group terminal carbamate ester prepolymer (UPN) obtained and the quantity average mark of every 1 functional group Son amount (Mn) is 300 or less and more than one a compound (HB) containing active hydrogen-based with multiple active hydrogen-baseds in molecule The process of reaction.

In the present specification, " Mw " be by gel permeation chromatography (Gel Permeation Chromatography, GPC) measure and find out polystyrene conversion weight average molecular weight." Mn " is to measure the polyphenyl second found out by GPC The number average molecular weight of alkene conversion.These are measured using the method recorded in [embodiments] one.

The effect of invention

According to the present invention, it is possible to provide a kind of working life and initial hardening property are good, and are capable of forming wetability and substrate Even if adhesion is good and is placed under hot and humid environment the also sticker of the adhesion coating with good releasable, and makes With its adhesive sheet.

Detailed description of the invention

Fig. 1 is the constructed profile of the adhesive sheet of the 1st embodiment of the invention.

Fig. 2 is the constructed profile of the adhesive sheet of the 2nd embodiment of the invention.

Specific embodiment

Sticker of the invention is to include C-terminal carbamate prepolymer (UPH) and polyfunctional isocyanate's chemical combination The carbamate system sticker of object (I), the C-terminal carbamate prepolymer (UPH) are a variety of containing active hydrogen-based The reaction product of compound (HX) and more than one polyisocyanate (N).

In the present invention, a variety of compounds (HX) containing active hydrogen-based include the number average molecular weight (Mn) of every 1 functional group It is 300 or less for 1650 or more more than one polyether polyol (HA) and the number average molecular weight (Mn) of every 1 functional group And more than one a compound (HB) containing active hydrogen-based with multiple active hydrogen-baseds in molecule.

Adhesive sheet of the invention is the adhesion coating for including substrate sheets and the hardening thing comprising the sticker of the invention Carbamate system adhesive sheet.

[sticker]

(C-terminal carbamate prepolymer (UPH))

C-terminal carbamate prepolymer (UPH) is to make a variety of compounds (HX) containing active hydrogen-based and more than one Polyisocyanate (N) copolyreaction and the reaction product that obtains.Copolyreaction can optionally be deposited in more than one catalyst In lower progress.More than one solvent optionally can be used in copolyreaction.

C-terminal carbamate prepolymer (UPH) is preferably isocyanate group terminal carbamate ester prepolymer (UPN) with the reaction product of the compound (HB) containing active hydrogen-based, the isocyanate group terminal carbamate ester prepolymer It (UPN) is the reaction product of polyether polyol (HA) and polyisocyanate (N).

In the present invention, a variety of compounds (HX) containing active hydrogen-based include long chain polyether polyol (HA) with than The compound (HB) containing active hydrogen-based of shorter chain.

Polyether polyol (HA) is 1650 or more for the number average molecular weight (Mn) of every 1 functional group, and every 1 functional group Number average molecular weight (Mn) is greater than the compound containing active hydrogen-based for being typically used as the raw material of carbamate (pre-) polymer Long chain polyether polyol.

As polyether polyol (HA), well known can be used.As polyether polyol (HA), can enumerate will have in a molecule There is the compound containing active hydrogen-based of multiple active hydrogen-baseds to be used as initiator, and adds more than one oxirane compound The compound (addition polymer) obtained at polymerization.

As initiator, compound and amine of hydroxyl etc. can be enumerated.Specifically, can enumerate: ethylene glycol (Ethylene Glycol, EG), propylene glycol (Propylene Glycol, PG), 1,4-butanediol, neopentyl glycol, butyl ethyl Two functional initiators such as pentanediol, N- amino ethyl ethanolamine, isophorone diamine and xylylene diamine；Glycerol, three hydroxyl first The trifunctional initiators such as base propane and triethanolamine；The tetrafunctionals initiator such as pentaerythrite, ethylenediamine and aromatic diamine；Diethyl Five functional initiator such as triamine etc..

It as oxirane compound, can enumerate: ethylene oxide (Ethylene Oxide, EO), propylene oxide The alkylene oxides such as (Propylene Oxide, PO) and epoxy butane (Butylene Oxide, BO) (Alkylene Oxide, AO)； Tetrahydrofuran (Tetrahydrofuran, THF) etc..

As polyether polyol (HA), the alkylene oxide adduct (also referred to as " polyoxy of the compound preferably containing active hydrogen-based Alkylidene polyol ").Wherein, preferably polyethylene glycol (Polyethylene Glycol, PEG), polypropylene glycol (Polypropylene Glycol, PPG), terminal addition have the PPG (PPG-EO) and polytetramethylene two of ethylene oxide (EO) The two functional polyethers polyalcohols such as the poly- alkane glycol such as alcohol；Trifunctionals polyether polyol such as alkylene oxide adduct of glycerol etc..

The degree of unsaturation of polyether polyol (HA) is preferably low.Degree of unsaturation refers to contained in the every 1g of polyether polyol not It is saturated the total amount of base, and corresponding with impurity single methanol amount.By using the low high-purity material of degree of unsaturation, sticker it is initial hard The property changed becomes good, in addition, especially in the case where being exposed in hot and humid environment, after can inhibit the removing again of adhesive sheet Sticker component residue is attached to body pollution in the surface for being attached to body.The degree of unsaturation of polyether polyol (HA) is preferably 0.07meq/g hereinafter, more preferably 0.04meq/g hereinafter, particularly preferably 0.01meq/g or less.

In the present specification, as long as not indicating especially, the degree of unsaturation of polyalcohol is according to Japanese Industrial Standards (Japanese Industrial Standards, JIS) K1557 6.7 and measure resulting value.

Compound (HB) containing active hydrogen-based is that the number average molecular weight (Mn) of every 1 functional group is 300 hereinafter, and every 1 The number average molecular weight (Mn) of functional group is less than the hydrogen-based containing activity for the raw material for being typically used as carbamate (pre-) polymer Compound shorter chain the compound containing active hydrogen-based.

As active hydrogen-based, can enumerate: hydroxyl, sulfydryl and amino are (in the present specification, as long as not indicating especially, ammonia Base includes imino group) etc..It as the compound (HB) containing active hydrogen-based, can enumerate: polynary with multiple hydroxyls in a molecule Have in amino alcohol, a molecule in polyamines, a molecule in alcohol, a molecule with multiple amino with amino and hydroxyl multiple The polymercaptan etc. of sulfydryl.One or more can be used in these.Compound (HB) containing active hydrogen-based can be non-polymer, It can be condensate.

Wherein, preferably polyalcohol.The reactivity of polyamines and polymercaptan is high and working life is short, therefore in the feelings using these Under condition, preferably it is used in combination with polyalcohol.In addition, in the case where polyalcohol includes secondary hydroxyl groups, carbamate system sticker Initial hardening property do not improve, therefore for the viewpoint of working life and initial hardening property, the compound (HB) containing active hydrogen-based Preferably comprising the reactive primary OH with appropriateness.

As the polyalcohol of non-polymer, can enumerate: ethylene glycol (EG), propylene glycol (PG), diethylene glycol, triethylene glycol, 1,3-BDO, 1,4-butanediol, neopentyl glycol, 1,5-PD, 3- methyl-1,5- pentanediol, ethyl -1 2- butyl -2-, 3-propanediol, 2,4- diethyl -1,5-PD, 1,2- hexylene glycol, 1,6- hexylene glycol, 2- ethyl -1,3- hexylene glycol are (also referred to as " 1,3- ethohexadiol "), 1,8- ethohexadiol, 1,9- nonanediol, 2- methyl-1,8- ethohexadiol, 1,8- decanediol, octacosanol, Glycerol, trimethylolpropane (Trimethylolpropane, TMP), pentaerythrite and hexanetriol etc..

As the polymeric polyalcohol for the compound (HB) that can be used as containing active hydrogen-based, can enumerate: polyester polyol is gathered Ethoxylated polyhydric alcohol, polyacrylic polyols, polycaprolactone polyol, polycarbonate polyol and castor oil system polyalcohol etc..Wherein, Preferably polyester polyol, polyether polyol and these combination.

As the polyester polyol for the compound (HB) that can be used as containing active hydrogen-based, well known can be used.It is more as polyester First alcohol, such as the change obtained by more than one polyol component and the esterification of more than one sour component can be enumerated It closes object (carboxylate).

It as the polyol component of raw material, can enumerate: ethylene glycol (EG), propylene glycol (PG), diethylene glycol, 1,3- fourth two Alcohol, 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- hexylene glycol (1,3- ethohexadiol), 1,8- ethohexadiol, 1, 9- nonanediol, 2- methyl-1,8- ethohexadiol, 1,8- decanediol, octacosanol, glycerol, trimethylolpropane, pentaerythrite and Hexanetriol etc..

It as the sour component of raw material, can enumerate: succinic acid, dimethyl succinic acid, adipic acid, pimelic acid, azelaic acid, the last of the ten Heavenly stems two Acid, 1,12- dodecanedioic acid, 1,14- tetracosandioic acid, dimer acid, 2- methyl-1,4- cyclohexane dicarboxylic acid, ethyl -1 2-, 4- cyclohexane dicarboxylic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), Isosorbide-5-Nitrae-naphthalene dicarboxylic acids, 4,4 '-diphenyl dicarboxylic acids And these acid anhydrides etc..

As the polyether polyol for the compound (HB) that can be used as containing active hydrogen-based, well known can be used.It is more as polyethers First alcohol can be enumerated the compound containing active hydrogen-based with multiple active hydrogen-baseds in a molecule being used as initiator, and make one kind Above oxirane compound addition polymerization and the compound (addition polymer) obtained.As initiator and oxa- cyclopropyl Person identical as person illustrated in polyether polyol (HA) can be used in hydride compounds.

It is excellent as the polyether polyol that can be used as the compound (HB) containing active hydrogen-based in the same manner as polyether polyol (HA) It is selected as the alkylene oxide adduct (polyoxy sub alkyl polylol) of the compound containing active hydrogen-based.Wherein, preferably polyethylene glycol (PEG), polypropylene glycol (PPG), terminal addition have the poly- alkane such as PPG (PPG-EO) and the polytetramethylene glycol of ethylene oxide (EO) The two functional polyethers polyalcohol such as glycol；Trifunctionals polyether polyol such as alkylene oxide adduct of glycerol etc..

It as the polyamines for the compound (HB) that can be used as containing active hydrogen-based, can enumerate: ethylenediamine, 1,2- propane diamine, 1,3- Propane diamine, Putriscine, 1,5- pentanediamine, 1,6- hexamethylene diamine, 1,7- heptamethylene diamine, 1,8- octamethylenediamine, 1,9- nonamethylene diamine, 1, 10- decamethylene diamine, 1,12- dodecamethylene diamine, 1,14- tetradecane diamines, 1,16- hexadecane diamines, hexamethylene diamine, trimethyl Hexamethylene diamine, iminobispropylamine, methyl-imino double propylamine, 1,5- diamino -2- methylpentane, isophorone two The bis- aminomethyl cyclohexanes of amine, 1,3-, 1- Cyclohexylamino -3- aminopropane, 3- amino methyl -3,3,5- trimethyl cyclohex Base amine, the dimethylene amine of norbornane skeleton, m-xylene diamine (meta-xylylene diamine, MXDA), hexa-methylene The aliphatic polyamines such as diamine carbamates, Diethylenetriamine, three second tetramines, tetren and five second hexamines；3,3 '-two chloro- 4, 4 '-diaminodiphenyl-methanes (3,3 '-dichloro-4,4 '-diaminodiphenylmethane, MOCA), 4,4 '-diaminos Base diphenyl methane, 2,4 '-diaminodiphenyl-methanes, 3,3 '-diaminodiphenyl-methanes, 3,4 '-diamino-diphenyl first Alkane, 2,2 '-benzidines, 3,3 '-benzidines, 2,4- diaminophenol, 2,5- diaminophenol, o-phenylenediamine, Phenylenediamine, p-phenylenediamine, 2,3- toluenediamine, 2,4- toluenediamine, 2,5- toluenediamine, 2,6- toluenediamine, 3,4- toluene Aromatic polyamines such as diamines and diethyl toluene diamine etc..

It as the amino alcohol for the compound (HB) that can be used as containing active hydrogen-based, can enumerate: monoethanolamine, diethanol amine, 2- Amino-2-methyl -1- propyl alcohol, three (hydroxymethyl) aminomethanes and 2-amino-2-ethyl-1,3-propanediol etc. have hydroxyl Monoamine；N- (2- hydroxypropyl) ethanol amine etc. has the diamines etc. of hydroxyl.

It as the polymercaptan for the compound (HB) that can be used as containing active hydrogen-based, can enumerate: two mercaptan of methane, 1,3- butane two Mercaptan, Isosorbide-5-Nitrae-butanediethiol, 2,3- butanediethiol, 1,2- dimercaptobenzene, 1,3- dimercaptobenzene, Isosorbide-5-Nitrae-dimercaptobenzene, 1, 10- decanedithiol, 1,2- dimercaptoethylsulfide, 1,6- hexanedithiol, 1,9- nonane, two mercaptan, 1,8- octanedithiol, 1, 5- pentanedithiol, 1,2- propanedithiol, 1,3- propanedithiol, Toluene-3,4-dithiol, bis- mercaptan of 4-, chloro- 1, the 2- benzene two of 3,6- bis- Mercaptan, 1,5- naphthyl disulfide alcohol, 1,2- benzene diformazan alkanethiol, 1,3- benzene diformazan alkanethiol, Isosorbide-5-Nitrae-benzene diformazan alkanethiol, 4,4 '-sulphur Generation double benzenethiol, 2,5- dimercapto-1,3,4-thiadiazole, 1,8- dimercapto -3,6- dioxaoctane, 1,5- dimercapto -3- sulphur Miscellaneous pentane, 2- di-n-butyl amino -4,6- dimercapto-s-triazine and mercapto end polymer (polysulfide polymers etc.) etc..

Typically, in carbamate system sticker, in order to improve wetability, plasticiser is added sometimes.However, In In the case that the additive amount of plasticiser is more, especially in the case where being exposed in hot and humid environment, has and generate adhesive sheet Sticker component residue is in the worry for being attached to body pollution on the surface for being attached to body after removing again.

In the present invention, by using every 1 functional group number average molecular weight (Mn) be 1650 or more long chain Polyether polyol (HA), preferably comprising alkylene oxide (Alkylene oxy, AO) base long chain polyether polyol (HA) as compound of the raw material containing active hydrogen-based of C-terminal carbamate prepolymer (UPH), even if for plasticiser Additive amount is few/do not add the allotment composition of plasticiser preferably, it is also capable of forming good relative to the wetability for being attached to body Adhesion coating.It is not easy to roll up for example, can be formed adhesive sheet being attached at bubble when glass substrate and ITO/ glass substrate etc. are attached to body Enter to attach the adhesion coating at interface.Think the quantity ratio because of the organic group being bonded with oxygen atom, preferably alkylidene that constitute ehter bond It is more and show function and effect identical with plasticiser.

In original of the polyether polyol (HA) for using long chain as C-terminal carbamate prepolymer (UPH) In the case where material, have following tendency: the wetability of adhesion coating is improved, and on the other hand, the initial hardening property of sticker is reduced and glued Layer releasable reduce.The number average molecular weight (Mn) of every 1 functional group of polyether polyol (HA) is higher, the tendency It is bigger.

For improving the viewpoint of wetability of adhesion coating, the quantity average mark of every 1 functional group of polyether polyol (HA) Son amount (Mn) is preferably 2000 or more, and more preferably 3000 or more.

In the present invention, by and use the compound (HB) containing active hydrogen-based of shorter chain as C-terminal amino first The raw material of acid esters prepolymer (UPH) can improve the first of the sticker as caused by the polyether polyol (HA) for using long chain Begin the reduction of indurative reduction and the releasable of adhesion coating.

With regard to the wetability raising of adhesion coating, the viewpoint of the balance of the releasable of the initial hardening property of sticker, adhesion coating For, the number average molecular weight (Mn) of every 1 functional group of polyether polyol (HA) is preferably 2000~10000, more preferably 3000~9000.

The initial hardening of the sticker as caused by the polyether polyol (HA) for using long chain can be effectively improved For the reduced aspect of the releasable of the reduction and adhesion coating of property, every 1 functional group of the compound (HB) containing active hydrogen-based Number average molecular weight (Mn) be preferably 30~300, more preferably 30~100.

The polyether polyol and/or polyethers more than trifunctional that more than one polyether polyol (HA) may include two functions Polyalcohol.Similarly, more than one the compound (HB) containing active hydrogen-based may include the chemical combination containing active hydrogen-based of two functions The compound containing active hydrogen-based more than object and/or trifunctional.

Typically, the compound containing active hydrogen-based of two functions has two-dimentional bridging property, can assign appropriateness to adhesion coating Flexibility.The compound containing active hydrogen-based more than trifunctional has three-dimensional cross-linked property, can assign the hard of appropriateness to adhesion coating Degree.

It is each by the polyether polyol (HA) and more than one the compound (HB) containing active hydrogen-based that select more than one From function radix (quantity of active hydrogen-based), the adhesion strength of adjustable carbamate system sticker, cohesiveness and remove again The characteristics such as property.The function radix that can select a variety of materials depending on the application etc., so that the spies such as adhesion strength, cohesiveness and releasable Property become preferred scope.For being easy for making adhesion strength and releasable and the aspect deposited, more than one polyether polyol (HA) preferably comprising polyether polyol more than trifunctional.Be easy for making reaction stability and cohesiveness and the aspect deposited and Speech, more than one the compound (HB) containing active hydrogen-based are preferably the compound containing active hydrogen-based comprising two functions.

A variety of compounds (HX) containing active hydrogen-based of raw material as C-terminal carbamate prepolymer (UPH) It may include known containing activity other than more than one the polyether polyol (HA) and the compound (HB) containing active hydrogen-based The compound of hydrogen-based.

As association document of the invention, there is 1~patent document of patent document 3 cited in " background technique " one. In these documents, the polyalcohol for the long chain that the number average molecular weight (Mn) for every 1 functional group is 1650 or more has It records, but is the change containing active hydrogen-based of 300 shorter chains below for the number average molecular weight (Mn) of every 1 functional group Close object (HB) and with without record and imply.In addition, the carbamate system sticker recorded in patent document 1, patent document 2 It is to be obtained using single method, C-terminal carbamate prepolymer is not used.

As polyisocyanate (N), well known can be used, can enumerate: aromatic poly-isocyanate, aliphatic poly isocyanic acid Ester and alicyclic polymeric isocyanate etc..

It as aromatic poly-isocyanate, can enumerate: 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, the United Nations General Assembly Anisidine diisocyanate, 4,4 '-diphenyl ether diisocyanates and 4,4 ', 4 "-triphenylmethane triisocyanate, 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 xylylene diisocyanate and 1,3- tetramethyl xylylene diisocyanate etc..

It as aliphatic polymeric isocyanate, can enumerate: trimethylene diisocyanate, tetramethylene diisocyanate, six Methylene diisocyanate (Hexamethylene Diisocyanate, HDI), pentamethylene diisocyanate, the Asia 1,2- third Group diisocyanate, 2,3- tetramethylene diisocyanate, 1,3- tetramethylene diisocyanate, ten dimethylene diisocyanates and 2,4,4- trimethyl hexamethylene diisocyanates etc..

It as alicyclic polymeric isocyanate, can enumerate: isophorone diisocyanate (Isophorone Diisocyanate, IPDI), 1,3- pentamethylene diisocyanate, 1,3- cyclohexane diisocyanate, two isocyanide of Isosorbide-5-Nitrae-hexamethylene Acid esters, methyl -2,4- cyclohexane diisocyanate, methyl -2,6- cyclohexane diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl Isocyanates) and bis- (isocyanatomethyl) hexamethylenes of Isosorbide-5-Nitrae-etc..

In addition, can be enumerated as polyisocyanate: the trimethylolpropane adduct body of the polyisocyanate, double contractings Urea (biuret) body, allophanate (allophanate) body and tripolymer (tripolymer includes isocyanurate ring) etc..

As polyisocyanate (N), preferably 4,4 '-methyl diphenylene diisocyanates, hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) etc..Details will be in rear narration, more than one polyisocyanate (N) Preferably include isophorone diisocyanate (IPDI).

The preferred material allocation of C-terminal carbamate prepolymer (UPH) is than as described below.

Activity is preferably contained relative to a variety of with the molal quantity of isocyanate group (NCO) possessed by polyisocyanate (N) The ratio (NCO/H) of the total mole number of activity hydrogen-based (H) possessed by the compound (HX) of hydrogen-based becomes 0.20~0.84, more preferably Material allocation ratio is determined for 0.40~0.80 mode.Have following tendency: NCO/H is closer to 1, in synthesis of hydroxy terminal amino group Easier gelation when urethane prepolymer (UPH).If NCO/H be 0.84 hereinafter, if can effectively inhibit synthesis of hydroxy end Gelation when carbamate prepolymer (UPH).

Just by using the wetability improvement effect of polyether polyol (HA) bring adhesion coating, by using containing active hydrogen-based The improvement of the releasable of the initial hardening property and adhesion coating of compound (HB) bring sticker, desired hydroxyl end For the viewpoint for stablizing synthesis of Amino End Group urethane prepolymer (UPH),

It is preferred that are as follows: relative to more than one 100 mass parts of polyether polyol (HA), more than one containing active hydrogen-based The amount of compound (HB) is 0.5 mass parts~40 mass parts, the amount of more than one polyisocyanate (N) be 1.0 mass parts~ 20 mass parts.

More preferably: relative to more than one 100 mass parts of polyether polyol (HA), more than one the hydrogen-based containing activity The amount of compound (HB) be 1.0 mass parts~20 mass parts, the amount of more than one polyisocyanate (N) is 3.0 mass parts ~10 mass parts.

More than one catalyst optionally can be used in the polymerization of C-terminal carbamate prepolymer (UPH).Make For catalyst, well known can be used, three-level amine compound and organic metal based compound etc. can be enumerated.

It as three-level amine compound, can enumerate: triethylamine, triethylenediamine and 1,8- diazabicyclo (5,4,0)-ten one Carbene -7 (1,8-Diazabicyclo (5,4,0)-undecene-7, DBU) etc..

As organic metal based compound, tin based compound and non-tin based compound etc. can be enumerated.

It as tin based compound, can enumerate: dibutyl tin dichloride, Dibutyltin oxide, dibutyl tin bibromide, two horses Come sour dibutyl tin (dibutyltin dimaleate), dibutyl tin dilaurate (Dibutyltin Dilaurate, DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyl artificial gold, tributyltin oxide, tributyltin acetate, three Ethyl hexanol tin (triethyltin ethoxide), tributyl ethyl alcohol tin (tributyltin ethoxide), dioctyl oxygen Change tin, tributyltin chloride, trichloroacetic acid tributyl tin and 2 ethyl hexanoic acid tin etc..

It as non-tin based compound, can enumerate: the titaniums such as dibutyl titanium chloride, butyl titanate and butoxy titanium trichloride System；The lead systems such as plumbi oleas, 2 ethyl hexanoic acid lead, lead benzoate and lead naphthenate；The iron such as 2 ethyl hexanoic acid iron and ferric acetyl acetonade System；The cobalts such as cobalt benzoate and 2 ethyl hexanoic acid cobalt system；The zinc such as zinc naphthenate and 2 ethyl hexanoic acid zinc system；The zirconiums such as zirconium naphthenate.

The type and additive amount of catalyst can in the range of being reacted well suitable design.

Because of the reactive difference of a variety of compounds (HX) containing active hydrogen-based, it is easy to produce in single catalyst system The worry of the gonorrhoea of gelation or reaction solution.In said case, by using two kinds of catalyst, it is easy to control reaction (example Such as reaction speed), so as to solve described problem.There is no particular restriction for the combination of two kinds of catalyst, can enumerate: tertiary amine/ Organic metal system, tin system/non-tin system and tin system/tin system etc..Preferably tin system/tin system, more preferably dibutyl tin dilaurate With 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 more than 0, less than 1, more preferably 0.2~0.6.If the mass ratio less than 1, catalyst is living The balance of property is good, effectively inhibits the gelation and gonorrhoea of reaction solution, polymerization stability further increases.

More than one solvent optionally can be used in the polymerization of C-terminal carbamate prepolymer (UPH).As Solvent can be used well known, can enumerate: methyl ethyl ketone, ethyl acetate, toluene, dimethylbenzene and acetone etc..With regard to C-terminal ammonia For boiling point of the dissolubility of carbamate prepolymer (UPH) and solvent etc., particularly preferably ethyl acetate and toluene etc..

As the polymerization of C-terminal carbamate prepolymer (UPH), there is no particular restriction, can be using blocky poly- The known polymerization methods such as legal and solution polymerization process.

As the polymerization sequence of C-terminal carbamate prepolymer (UPH), can enumerate:

Sequentially 1) by more than one polyether polyol (HA), more than one the compound (HB) containing active hydrogen-based, one Kind or more polyisocyanate (N), more than one catalyst optionally and more than one solvent optionally fill together Enter the sequence into flask；

Sequentially 2) by more than one polyether polyol (HA), more than one the compound (HB) containing active hydrogen-based, view More than one the catalyst that needs and more than one solvent optionally are fitted into flask, and addition one is added dropwise thereto Kind or more polyisocyanate (N) sequence；

Sequentially 3) by more than one polyether polyol (HA), more than one polyisocyanate (N), one kind optionally Above catalyst and more than one solvent optionally are fitted into flask together, keep polyisocyanate (N) and polyethers more First alcohol (HA) generates isocyanate group terminal carbamate ester prepolymer (UPN) with the ratio reaction of isocyanate group surplus Afterwards, the sequence etc. of more than one the compound (HB) containing active hydrogen-based is added.

Reaction temperature when using catalyst is preferably less than 100 DEG C, more preferably 50 DEG C~95 DEG C, particularly preferably 60 DEG C~85 DEG C.If reaction temperature is 100 DEG C or more, there is following worry: being difficult to control reaction speed and polymerization stability etc., and It is difficult to generate the C-terminal carbamate prepolymer (UPH) with desired molecular weight.It is anti-when without using catalyst Answering temperature is preferably 100 DEG C or more, and more preferably 110 DEG C or more.

Sequentially 1) and sequence 2) in, the polyether polyol (HA) of long chain chain short compared with containing active hydrogen-based Compound (HB) is mixed with polyisocyanate (N) simultaneously.In the method, there is following tendency: shorter chain with high reactivity The compound (HB) containing active hydrogen-based compared with the polyether polyol (HA) of the low long chain of reactivity, preferentially with gather it is different Cyanate (N) reaction.In said case, have a following worry: the polyether polyol (HA) of the low long chain of reactivity with Unreacted state remains and leads to reaction solution gonorrhoea.In order to eliminate with the poly- of the remaining long chain of unreacted state Ethoxylated polyhydric alcohol (HA), and the case where be set as condition of the molal quantity of isocyanate group relative to the total mole number surplus of active hydrogen-based Under, there is following worry: the compound (HB) containing active hydrogen-based of shorter chain being caused first to react and give birth to polyisocyanate (N) At isocyanate group terminal carbamate ester prepolymer and shorter chain with high reactivity the compound containing active hydrogen-based (HB) undesirable reaction, so as to cause reaction pension gelation.

It is easy for for the aspect of control reaction, preferably sequentially 3).Polymerization using the sequence include: make it is a kind of with On polyether polyol (HA) reacted and generated different with the ratio of isocyanate group surplus with more than one polyisocyanate (N) The process of cyanic acid ester group terminal carbamate ester prepolymer (UPN)；And make isocyanate group terminal carbamate obtained The process that ester prepolymer (UPN) is reacted with more than one the compound (HB) containing active hydrogen-based.

Sequentially 3) in, in the state that the compound (HB) containing active hydrogen-based of shorter chain does not coexist, first only make anti- The polyether polyol (HA) of the low long chain of answering property is reacted with polyisocyanate (N), then makes isocyanates obtained Base terminal carbamate ester prepolymer (UPN) is reacted with the compound (HB) containing active hydrogen-based.In the method, reaction can inhibit The gelation of liquid and gonorrhoea simultaneously stably synthesize desired C-terminal carbamate prepolymer (UPH).

Therefore, C-terminal carbamate prepolymer (UPH) is preferably isocyanate group terminal carbamate ester pre-polymerization The reaction product of object (UPN) and the compound (HB) containing active hydrogen-based, the isocyanate group terminal carbamate ester prepolymer It (UPN) is the reaction product of polyether polyol (HA) and polyisocyanate (N).

In sequentially 3), more than one polyisocyanate (N) preferably includes isophorone diisocyanate (IPDI). In said case, it is easy to control reaction and desired C-terminal carbamate prepolymer (UPH) can be stably synthesized.

(polyfunctional isocyanate compound (I))

As polyfunctional isocyanate compound (I), well known can be used, can be used using as C-terminal carbamic acid Compound (the specifically aromatic series polyisocyanate that the form of the polyisocyanate (N) of the raw material of ester prepolymer (UPH) illustrates Ester, aliphatic polymeric isocyanate, aromatic-aliphatic polyisocyanate, alicyclic polymeric isocyanate and these trimethylolpropane Adduction object/biuret body/allophanate body/tripolymer).

(plasticiser (P))

As described above, in the present invention, even if additive amount for plasticiser (P) it is few/do not add the tune of plasticiser (P) preferably With composition, the sticker with good wetability also can provide.Therefore, in sticker of the invention, plasticiser (P) is not used To improve the essential component of wetability, but sticker of the invention optionally may include more than one plasticiser (P).Wherein, In the case where adding plasticiser (P), amount can also be suppressed to low-level.Plasticiser (P) is relative to C-terminal amino The amount of 100 mass parts of urethane prepolymer (UPH) may be, for example, 50 below the mass (0 mass parts~50 mass parts), preferably 40 below the mass (0 mass parts~40 mass parts), and more preferably 30 below the mass (0 mass parts~30 mass parts), in turn Preferably 20 below the mass (0 mass parts~20 mass parts), particularly preferably 10 below the mass (0 mass parts~10 mass Part), most preferably 5 below the mass (0 mass parts~5 mass parts).

As plasticiser (P), there is no particular restriction, for the viewpoints such as compatibility with other compositions, preferably molecule The organic acid esters of amount 250~1,000.

It as monoacid or the ester of polyacid and alcohol, such as can enumerate: lauric acid iso stearyl ester, myristic acid isopropyl The different cetyl of ester, myristic acid, myristic acid octyldodecyl, palmitinic acid iso stearyl ester, Standamul 7061, oil Sour octyldodecyl, dibutyl phthalate, dioctyl phthalate, dibutyl phthalate (DHP), O-phthalic Sour dibenzyl ester, butyl benzyl phthalate, diisodecyl adipate (DIDA), two iso stearyl ester of adipic acid, dibutyl sebacate, the last of the ten Heavenly stems The different cetyl of diacid two, citroflex A-4, trimellitic acid tributyl, three monooctyl ester of trimellitic acid, inclined benzene front three Sour three own esters, three oleyl ester of trimellitic acid and the different cetyl of trimellitic acid three etc..

It as the ester of other acid and alcohol, such as can enumerate: nutmeg oleic acid, oleic acid, linoleic acid, linolenic acid, different palmitinic acid And the unsaturated fatty acids such as isostearic acid or chorismic acid and ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythrite and The ester of the alcohol such as sorbitol anhydride.

It as monoacid or the ester of polyacid and poly- alkane glycol, such as can enumerate: two caproic acid polyethylene glycol, two -2- ethyls Caproic acid polyethylene glycol, two methoxypolyethylene glycol of tin dilaurate polyethylene glycol, two oleic acid polyethylene glycol and adipic acid etc..

For improving the viewpoints such as wetability, the molecular weight (formula weight or Mn) of organic acid esters is preferably 250~1,000, more Preferably 400~900, particularly preferably 500~850.If molecular weight is 250 or more, the heat resistance of adhesion coating becomes well, If molecular weight is 1,000 hereinafter, the wetability of sticker becomes good.

(solvent)

Sticker of the invention optionally may include more than one solvent.As solvent, well known can be used, can arrange It lifts: methyl ethyl ketone, ethyl acetate, toluene, dimethylbenzene and acetone etc..With regard to C-terminal carbamate prepolymer (UPH) For the viewpoints such as the boiling point of dissolubility and solvent, particularly preferably ethyl acetate and toluene etc..

(antideteriorant)

Sticker of the invention optionally may include more than one antideteriorant.It can inhibit the length by adhesion coating as a result, Phase uses the reduction of caused various characteristics.It as antideteriorant, can enumerate: hydrolysis agent, antioxidant, ultraviolet absorbing agent And light stabilizer etc..

In the case where the inferior adhesion coating of hot and humid environment generates hydrolysis and generates carboxyl, in order to block the carboxylic Hydrolysis agent can be used in base.It as hydrolysis agent, can enumerate: carbon imidodicarbonic diamide system, isocyanates system, oxazoline system and epoxy System etc..Wherein, for hydrolyzing the viewpoint of inhibitory effect, preferably carbon imidodicarbonic diamide system.

Carbon imidodicarbonic diamide system hydrolysis inhibitor is the compound in a molecule with more than one carbon imidodicarbonic diamide base.

As single carbon imide compound, such as can enumerate: dicyclohexylcarbodiimide, two acyl of diisopropyl carbon are sub- Amine, dimethyl carbon imidodicarbonic diamide, diisobutyl carbon imidodicarbonic diamide, dioctyl carbon imidodicarbonic diamide, diphenyl carbon imidodicarbonic diamide and naphthalene Base carbon imidodicarbonic diamide etc..

Poly- carbon imidodicarbonic diamide compound can make diisocyanate carry out decarburization in the presence of carbon imidodicarbonic diamide catalyst Sour condensation reaction and generate.Herein, it as diisocyanate, such as can enumerate: 4,4 '-methyl diphenylene diisocyanates, 3, 3 '-dimethoxy-4 's, 4 '-methyl diphenylene diisocyanates, 3,3 '-dimethyl -4,4 '-methyl diphenylene diisocyanates, 4,4 '-diphenyl ether diisocyanates, 3,3 '-dimethyl -4,4 '-diphenyl ether diisocyanates, 2,4- toluene diisocynate Ester, 2,6- toluene di-isocyanate(TDI), 1- methoxyphenyl -2,4- diisocyanate, isophorone diisocyanate, 4,4 '-two Diphenylmethane diisocyanate and tetramethyl xylylene diisocyanate etc..As carbon imidodicarbonic diamide catalyst, can arrange It lifts: 1- phenyl -2- Phospholes -1- oxide, 3- methyl -2- Phospholes -1- oxide, 1- ethyl -3- methyl -2- Phospholes -1- oxide, 1- ethyl -2- Phospholes -1- oxide and these 3- phospholene isomers etc. Phospholes oxide etc..

It as isocyanates system hydrolysis inhibitor, such as can enumerate: 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene diisocyanate Acid esters, m-benzene diisocyanate, paraphenylene diisocyanate, 4,4 '-methyl diphenylene diisocyanates, 2,4 '-diphenyl methanes Diisocyanate, 2,2 '-methyl diphenylene diisocyanates, 3,3 '-dimethyl -4,4 '-biphenyl diisocyanates, 3,3 '-two 4,4 '-biphenyl diisocyanate of methoxyl group-, 3,3 '-two chloro- 4,4 '-biphenyl diisocyanates, 1,5- naphthalene diisocyanate, 1, 5- tetrahydro naphthalene diisocyanate, tetramethylene diisocyanate, 1,6- hexamethylene diisocyanate, ten dimethylenes, two isocyanide Acid esters, trimethyl hexamethylene diisocyanate, 1,3- cyclohexylene diisocyanate, 1 or 4 cyclohexylidene diisocyanate, Xylylene diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine two are different Cyanate, isophorone diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanates and 3,3 '-dimethyl -4,4 '-two rings Hexyl methane diisocyanate etc..

As oxazoline system hydrolysis inhibitor, such as can enumerate: 2,2 '-adjacent benzene bis- (2- oxazolines), 2,2 '-isophthalic are double (2- oxazoline), 2,2 '-(2- oxazolines) bis- to benzene, 2,2 '-(4- methyl -2- oxazolines) bis- to benzene, 2, the 2 '-bis- (4- of isophthalic Methyl -2- oxazoline), bis- (4,4 '-dimethyl -2- are disliked for 2,2 '-(4,4 '-dimethyl -2- oxazolines) bis- to benzene, 2,2 '-isophthalic Oxazoline), 2,2 '-ethylenebis (2- oxazoline), 2,2 '-tetramethylenes bis- (2- oxazolines), 2,2 '-hexamethylene bis (2- dislike Oxazoline), 2,2 '-eight di-2-ethylhexylphosphine oxides (2- oxazoline), 2,2 '-ethylenebis (4- methyl -2- oxazoline) and 2,2 '-diphenylenes Bis- (2- oxazolines) etc..

It as epoxy hydrolysis inhibitor, such as can enumerate: the aliphatic such as 1,6- hexylene glycol, neopentyl glycol and poly- alkane glycol The diglycidyl ether of glycol；D-sorbite, sorbitol anhydride, polyglycerol, pentaerythrite, two glycerine, glycerine and three hydroxyls The polyglycidyl ether of the aliphatic polyols such as methylpropane；The poly epihydric alcohol of the ester ring types polyalcohol such as cyclohexanedimethanol Ether；The aliphatic such as terephthalic acid (TPA), M-phthalic acid, naphthalene dicarboxylic acids, trimellitic acid, adipic acid and decanedioic acid are aromatic The 2-glycidyl ester or poly glycidyl ester of polybasic carboxylic acid；Resorcinol, double-(p-hydroxybenzene) methane, 2,2- are bis--(right Hydroxy phenyl) propane, three-(p-hydroxybenzene) methane and 1, two shrinks of the polyphenol such as 1,2,2- tetra- (p-hydroxybenzene) ethane Glycerin ether or polyglycidyl ether；N, N- diglycidylaniline, N, N- diglycidyl toluidines and N, N, N ', N '- Four glycidyl group-is bis--the N- glycidyl derivatives of the amine such as (p-aminophenyl) methane；The three-glycidyl of amino-phenol Radical derivative；(2- hydroxyethyl) isocyanuric acid ester of triglycidyl group three and triglycidyl group isocyanuric acid ester；O-cresol Epoxy resin such as type epoxy resin and phenol novolak type epoxy resin etc..

There is no particular restriction for the additive amount of hydrolysis agent, relative to 100 matter of C-terminal carbamate prepolymer (UPH) Measure part, preferably 0.1 mass parts~5 mass parts, more preferably 0.2 mass parts~4.5 mass parts, particularly preferably 0.5 mass Part~3 mass parts.

As antioxidant, free radical scavenger and peroxide decomposer etc. can be enumerated.It, can as free radical scavenger Enumerate phenol system compound and amine compound etc..As peroxide decomposer, chalcogenide compound and phosphorus series compound can be enumerated Deng.

It as phenol system compound, such as can enumerate: 2,6- di-t-butyl-paracresol, butylated hydroxyanisol, 2,6- Di-t-butyl -4- ethyl -phenol, β-(3,5- di-t-butyl -4- hydroxy phenyl) propionic acid stearyl ester, 2,2 '-di-2-ethylhexylphosphine oxide (4- Methyl-6-tert-butylphenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol)s, 4,4 '-thiobis (3- methyl-6-terts Butylphenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol)s, bis- [1,1- dimethyl -2- [β-(the tertiary fourths of 3- of 3,9- Base -4- hydroxy-5-methyl base phenyl) propionyloxy] ethyl] 2,4,8,10- tetra- oxaspiro [5,5] hendecanes, benzenpropanoic acid, 3,5- is bis- (1,1- dimethyl ethyl) -4- hydroxyl -, C7-C9 pendant alkyl group ester, 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 ' - Di-t-butyl -4 '-hydroxy phenyl) propionic ester] methane, bis- [3,3 '-bis--(4 '--3 '-tert-butyl-phenyl of hydroxyl) butyric acid] glycol Ester, 1,3,5- tri- (3 ', 5 ' -4 '-hydroxybenzyl of di-t-butyl -)-S- triazines -2,4,6- (1H, 3H, 5H) triketone and tocopherol Deng.

It as sulfur antioxidant, can enumerate: 3,3 '-thiodipropionate dilauryls, 3,3 '-thio-2 acid, two meat Cardamom base ester and 3,3 '-thio-2 acid distearyl base esters etc..

It as phosphorus series compound, such as can enumerate: triphenyl phosphite, diphenylisodecyl ester, 4,4 '-Aden Bis- (two-tridecyl of the 3- methyl-6-tert butyl phenyl) phosphite esters of base-, bis- (the octadecyl phosphorous acid of cyclic annular four base of neopentane Ester), three (nonyl phenyl) phosphite esters, three (Dan Renji phenyl) phosphite esters, three (dinonylphenyl) phosphite esters, two isodecyls Base pentaerythritol diphosphites, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5- di-t-butyl -s 4- hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- decyloxy -9,10- dihydro-9-oxy be miscellaneous - 10- phospho hetero phenanthrene, three (2,4- di-t-butyl phenyl) phosphite esters, cyclic annular four base of neopentane bis- (2,4- di-t-butyl phenyl) are sub- Phosphate, bis- (2, the 6- di-t-butyl -4- aminomethyl phenyl) phosphite esters and 2 of cyclic annular four base of neopentane, 2- di-2-ethylhexylphosphine oxide (4,6- Di-t-butyl phenyl) phosphorous acid monooctyl ester etc..

The heat deterioration of C-terminal carbamate prepolymer (UPH) is prevented by using antioxidant.In addition, can have Effect ground inhibits exudation of the plasticiser (P) when using plasticiser (P) from adhesion coating.

There is no particular restriction for the additive amount of antioxidant, relative to 100 matter of C-terminal carbamate prepolymer (UPH) Measure part, preferably 0.01 mass parts~5 mass parts, more preferably 0.1 mass parts~3 mass parts, particularly preferably 0.2 mass parts ~2 mass parts.

As antioxidant, for stability and the viewpoint of antioxidant effect, it is preferable to use more than one conduct The phenol system compound of free radical scavenger, more preferably and be used as more than one phenol system compound of free radical scavenger with More than one phosphorus series compound as peroxide decomposer.In addition, particularly preferably and being used as antioxidant The phenol system compound of free radical scavenger and phosphorus series compound as peroxide decomposer, and and with these antioxidants and The hydrolysis agent.

It as ultraviolet absorbing agent, such as can enumerate: benzophenone based compound, benzotriazole based compound, salicylic acid Based compound, oxanilide based compound, cyanoacrylate based compound and triazine based compound etc..

There is no particular restriction for the additive amount of ultraviolet absorbing agent, relative to C-terminal carbamate prepolymer (UPH) 100 mass parts, preferably 0.01 mass parts~3 mass parts, more preferably 0.1 mass parts~2.5 mass parts, particularly preferably 0.2 mass parts~2 mass parts.

As light stabilizer, be obstructed amine compound and hindered piperidine based compound etc. can be enumerated.The addition of light stabilizer There is no particular restriction for amount, relative to 100 mass parts of C-terminal carbamate prepolymer (UPH), preferably 0.01 mass parts ~2 mass parts, more preferably 0.1 mass parts~1.5 mass parts, particularly preferably 0.2 mass parts~1 mass parts.

(antistatic agent)

Sticker of the invention optionally may include more than one antistatic agent (AS agent).As antistatic agent, can arrange Lift inorganic salts, polyol compound, ionic liquid and surfactant etc., wherein preferably ionic liquid.Furthermore " from Sub- property liquid " is also referred to as room temperature fuse salt, and the salt to have mobility at 25 DEG C.

It as inorganic salts, such as can enumerate: sodium chloride, potassium chloride, lithium chloride, lithium perchlorate, ammonium chloride, potassium chlorate, chlorine Change aluminium, copper chloride, frerrous chloride, iron chloride, ammonium sulfate, potassium nitrate, sodium nitrate, sodium carbonate and sodium sulfocyanate etc..

It as polyol compound, such as can enumerate: propylene glycol, butanediol, hexylene glycol, polyethylene glycol, trihydroxy methyl third Alkane and pentaerythrite etc..

It as the ionic liquid comprising imidazol ion, such as can enumerate: the bis- (fluoroforms of 1- ethyl-3-methylimidazole Base sulfonyl) acid imide, bis- (trifluoromethyl sulfonyl) acid imides of 1,3- methylimidazole and 1- butyl -3- methylimidazole Bis- (trifluoromethyl sulfonyl) acid imides etc..

It as the ionic liquid comprising pyridinium ion, such as can enumerate: the bis- (trimethyl fluoride sulfonyls of 1- picoline Base) acid imide, bis- (trifluoromethyl sulfonyl) acid imides of 1- butyl-pyridinium, 1- hexyl pyridine be bis- (trifluoromethyl sulfonyl) Bis- (trifluoromethyl sulfonyl) acid imides of acid imide, 1- octylpyridinium, bis- (the trifluoromethyl sulphurs of 1- hexyl -4- picoline Acyl group) acid imide, 1- hexyl -4- picoline hexafluorophosphate, the bis- (trimethyl fluoride sulfonyls of 1- octyl -4- picoline Base) acid imide, bis- (fluorosulfonyl) acid imides of 1- octyl -4- picoline, the bis- (perfluoroethyl sulfonyls of 1- picoline Base) acid imide and bis- (perfluoro butyl sulfonyl) acid imides of 1- picoline etc..

It as the ionic liquid comprising ammonium ion, such as can enumerate: bis- (trifluoromethane sulfonyl group) acyls of trimethyl heptyl ammonium Imines, N, bis- (trifluoromethane sulfonyl group) acid imides of N- diethyl-N- Methyl-N-propyl ammonium, N, N- diethyl-N- methyl-N- Bis- (trifluoromethane sulfonyl group) acid imides of amyl ammonium, N, bis- (trifluoromethane sulfonyl group) acyls of N- diethyl-N- methyl-N- heptyl ammonium Imines and the double trifluoromethanesulfonimides of three normal-butyl methyl ammoniums etc..

In addition, the commercially available ionic liquid of Pyrrolizidine Yan, phosphonium salt and sulfonium salt etc. can be properly used.

Surfactant is classified as low-molecular-weight surfactant and high molecular surfactant.Any kind have it is non-from Sub- property, anionic property, cationic and amphoteric type.

As the low-molecular-weight surfactant of nonionic, can enumerate: fatty acid glyceride, polyoxyalkylene alkyl ether, Polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl amine, polyoxyethylene alkyl amine aliphatic ester and fatty diglycollic amide etc..

It as the low-molecular-weight surfactant of anionic property, can enumerate: alkylsulfonate, alkylbenzene sulfonate and phosphoric acid alkane Base ester etc..

It as the low-molecular-weight surfactant of cationic, can enumerate: tetraalkylammonium salt, triakyl benzyl ammonium salt etc..

As the low-molecular-weight surfactant of both sexes, alkyl betaine and alkyl imidazole glycine betaine etc. can be enumerated.

It as the high molecular surfactant of nonionic, can enumerate: polyether ester amides type, ethylene oxide-epichlorohydrin type And polyether ester type etc..

As the high molecular surfactant of anionic property, polystyrene sulfonic acid type etc. can be enumerated.

As the high molecular surfactant of cationic, the acrylic polymer type of the base containing quarternary ammonium salt can be enumerated Deng.

It as the high molecular surfactant of both sexes, can enumerate: the amino acid type amphoterics table such as senior alkyl aminopropionate The betaine type amphoterics surface-actives such as face activating agent, senior alkyl dimethyl betaine and senior alkyl dihydroxy ethyl glycine betaine Agent etc..

Relative to 100 mass parts of C-terminal carbamate prepolymer (UPH), the additive amount of antistatic agent is preferably 0.01 mass parts~10 mass parts, more preferably 0.03 mass parts~5 mass parts.

(levelling agent)

Sticker of the invention optionally may include levelling agent.By adding levelling agent, the levelability of adhesion coating can be improved. As levelling agent, acrylic acid series levelling agent, fluorine system levelling agent and silicone-based levelling agent etc. can be enumerated, adhesive sheet is may refrain from and removes again Being attached to for the viewpoint of body pollution afterwards, preferably acrylic acid series levelling agent etc..

There is no particular restriction for the weight average molecular weight (Mw) of levelling agent, and preferably 500~20,000, more preferably 1, 000~15,000, particularly preferably 2,000~10,000.If Mw is 500 or more, from applying when the heat drying of overlay The amount of vaporization of coating can obtain the Pollution restraint of surrounding sufficiently few.If Mw is 20,000 hereinafter, effectively showing adhesion coating The improvement effect of levelability.

There is no particular restriction for the additive amount of levelling agent, may refrain from being attached to body pollution and improving after adhesive sheet is removed again and glues For the viewpoint of the levelability of layer, relative to 100 mass parts of C-terminal carbamate prepolymer (UPH), preferably 0.001 mass parts~2 mass parts, more preferably 0.01 mass parts~1.5 mass parts, particularly preferably 0.1 mass parts~1 mass Part.

(any other ingredient)

Sticker of the invention can optionally include any other ingredient in the range of not undermining effect of the invention.Make It for any other ingredient, can enumerate: other resins, filler (talcum, carbonic acid other than catalyst, carbamate system resin Calcium and titanium oxide etc.), it is metal powder, colorant (pigment etc.), foil-like object, softening agent, conductive agent, silane coupling agent, lubricant, anti- Corrosive agent, heat-resisting stabilizing agent, weathering stabilizers, polymerization inhibitor and defoaming agent etc..

(allotment ratio)

Sticker of the invention include more than one C-terminal carbamate prepolymer (UPH) and more than one Polyfunctional isocyanate compound (I) as an essential component, and then optionally includes more than one any ingredient.These tune There is no particular restriction for proportion, and preferred allotment is than as described below.

More than one polyfunctional isocyanate compound (I) relative to more than one C-terminal carbamate it is pre- The amount of 100 mass parts of polymers (UPH) is preferably 1 mass parts~30 mass parts, more preferably 3 mass parts~20 mass parts.It is a kind of The amount of above polyfunctional isocyanate compound (I) if 3 mass parts more than, then the cohesive strength of adhesion coating becomes well, if Below the mass for 20, then working life becomes good.

(manufacturing method of sticker)

There is no particular restriction for the manufacturing method of sticker of the invention.

The C-terminal carbamate prepolymer synthesized and relative to utilization the method (preferably sequence 3) (UPH) more than one polyfunctional isocyanate compound (I) and more than one any ingredient optionally of addition mixing, can Manufacture sticker of the invention.

[adhesive sheet]

Adhesive sheet of the invention includes the adhesion coating of substrate sheets and the hardening thing comprising the sticker of the invention.Adhesion Layer can be formed in the one or two sides of substrate sheets.The exposed surface of adhesion coating can be optionally coated using stripping film.Furthermore it is inciting somebody to action Adhesive sheet is attached at when being attached to body, can remove stripping film.

Fig. 1 shows the constructed profiles of the adhesive sheet of the 1st embodiment of the invention.In Fig. 1, symbol 10 is adhesive sheet, Symbol 11 is substrate sheets, and symbol 12 is adhesion coating, and symbol 13 is stripping film.Adhesive sheet 10 is formed with viscous for the single side in substrate sheets The single side adhesive sheet of layer.

Fig. 2 indicates the constructed profile of the adhesive sheet of the 2nd embodiment of the invention.In Fig. 2, symbol 20 is adhesive sheet, Symbol 21 is substrate sheets, and symbol 22A, symbol 22B are adhesion coating, and symbol 23A, symbol 23B are stripping film.

As substrate sheets, there is no particular restriction, can enumerate resin sheet, paper and metal foil etc..Substrate sheets can also be at these At least one surface layer of substrate sheets folds laminates made of layer of any one or more.For the formation adhesion coating of substrate sheets The face of side, it is optionally also implementable to there is Corona discharge Treatment and anchor coating agent (anchor coating agent) coating etc. easily to connect Processing.

As the composition resin of resin sheet, there is no particular restriction, can enumerate: polyethylene terephthalate Esters system resins such as (Polyethylene Terephthalate, PET)；Polyethylene (Polyethylene, PE) and polypropylene Olefin-based resins such as (Polypropylene, PP)；The vinylites such as polyvinyl chloride；The amides such as nylon66 fiber system resin；Amino first Acid esters system resin (including foaming body)；These combination etc..

There is no particular restriction for the thickness of resin sheet except polyurethane sheet, and preferably 15 μm~300 μm.Poly- amino There is no particular restriction for the thickness of formic acid esters piece (including foaming body), and preferably 20 μm~50,000 μm.

As paper, there is no particular restriction, can enumerate: plain paper, coating paper and art paper etc..

As the composition metal of metal foil, there is no particular restriction, can enumerate: aluminium, copper and these combination etc..

As stripping film, there is no particular restriction, can be used and implements remover to the surface of the substrate sheets such as resin sheet or paper The known stripping film of lift-off processing known to coating etc..

Adhesive sheet can be manufactured using known method.

Firstly, sticker of the invention is coated on the surface of substrate sheets and forms the coating comprising sticker of the invention Layer.Coating method can apply known method, can enumerate: roll coater method, chipping wheel coater method, die coating machine method, reversed coating machine Method, silk screen printing and gravure coater method etc..

Secondly, being dried and hardening and formed the adhesion coating of the hardening thing comprising sticker of the invention to overlay. There is no particular restriction for heat drying temperature, and preferably 60 DEG C~150 DEG C or so.Thickness (thickness after dry) basis of adhesion coating Purposes and it is different, but preferably 0.1 μm~200 μm.

Secondly, optionally, stripping film to be attached to the exposed surface of adhesion coating by known method.

Single side adhesive sheet can be manufactured in this way.

By carrying out the operation to two sides, two sides adhesive sheet can be manufactured.

It can also be with the method on the contrary, sticker of the invention is coated on the surface of stripping film and is formed comprising this hair The overlay of bright sticker is then dried overlay and hardens and form the hardening comprising sticker of the invention Substrate sheets are laminated in the exposed surface of adhesion coating by the adhesion coating of object.

The manufacturing method of adhesive sheet preferably comprises: working procedure of coating, by sticker coated in substrate sheets；Heating process, To be formed by overlay be thermally dried processing and formed comprising sticker hardening thing adhesion coating；Rolling step, will Adhesive sheet obtained is wound in core and forms the form of adhesive sheet roller；And maintenance process, adhesive sheet roller is conserved.

In sticker of the invention, C-terminal amino first is used as by using the polyether polyol (HA) of long chain Compound of the raw material containing active hydrogen-based of acid esters prepolymer (UPH), even if additive amount for plasticiser it is few/preferably do not add modeling The allotment of agent forms, and can also form the adhesion coating with good wetability.

In the present invention, by and use the compound (HB) containing active hydrogen-based of shorter chain as C-terminal amino first Compound of the raw material containing active hydrogen-based of acid esters prepolymer (UPH), can improve the polyether polyol by using long chain (HA) reduction of the releasable of the reduction and adhesion coating of the initial hardening property of sticker caused by.

Sticker of the invention can have good working life, while have good initial hardening property.Of the invention is viscous Agent working life it is good, therefore until by sticker coated in substrate sheets until during, the viscosity of sticker will not Become even application that is excessively high and can be realized sticker.The initial hardening property of sticker of the invention is good, therefore overlay Or after hot wind or heat drying of the adhesion coating when being not easily susceptible to the heat drying of overlay when the winding of adhesive sheet obtained And when maintenance the influence of suffered mechanical stress and can inhibit and generate core scale trace, orange peel defect and curling etc. in adhesion coating Appearance is bad.

In sticker of the invention, the addition of plasticiser can be lowered or do not use plasticiser, in addition, using shorter chain Raw material change containing active hydrogen-based of the compound (HB) containing active hydrogen-based as C-terminal carbamate prepolymer (UPH) Object is closed, thus especially in the case where being exposed in hot and humid environment, is glued after the removing again of adhesive sheet can be effectively inhibited Agent component residue be attached to body pollution in the surface for being attached to body.

The substrate adhesion of sticker of the invention is also good.

As described above, according to the present invention, it is possible to provide a kind of working life and initial hardening property are good, and can Even if forming wetability and substrate adhesion well and being placed under hot and humid environment also with the adhesion of good releasable The sticker of layer, and the adhesive sheet using it.

[purposes]

Adhesive sheet of the invention can come with, the form of label, piece and two sides band etc. using.Adhesive sheet of the invention can be excellent Selection of land is used as surface protective plate, cosmetic piece and Anti-skid sheet etc..

Flat-panel monitors such as liquid crystal display (LCD) and display of organic electroluminescence (OELD) and by the plate Touch-screen display made of display and touch screen combination is widely used in TV (TV), personal computer (PC), mobile phone and can It takes in the electronic equipments such as formula information terminal.

Adhesive sheet of the invention is preferably used as flat-panel monitor and touch-screen display (also referred to as by these general designations For " display ") and these manufacturing process in substrate that is manufactured or using (glass substrate and formed on the glass substrate Have the ITO/ glass substrate etc. of tin indium oxide (ITO) film) and optical component etc. surface protective plate.

Embodiment

Hereinafter, being illustrated to synthesis example, the embodiment of the present invention and comparative example.Furthermore in the following record, as long as It does not indicate especially, then " part " refers to mass parts, and " % " refers to quality %, and " RH " refers to relative humidity.

[measurement of Mn, Mw]

Number average molecular weight (Mn) and weight average molecular weight (Mw) are surveyed by gel permeation chromatography (GPC) method It is fixed.Determination condition is as described below.Furthermore Mn, Mw are polystyrene scaled value.

< determination condition >

Device: Shimadzu brilliance (SHIMADZU Prominence) (manufacture of limited liability company, Shimadzu Seisakusho Ltd.),

Tubing string；The TSKgel GMH of two Tosoh (TOSOH) manufactures is connected in series,

Detector: differential refractive index detector (RID-10A),

Solvent: tetrahydrofuran (THF),

Flow velocity: 1mL/min,

Solvent temperature: 40 DEG C,

Sample solution concentration: 0.1%,

Sample injection rate: 100 μ L.

[material]

Used material is as described below.

(HA-1): general Lay minot (Preminol) 5001F (abbreviation in table: PREM 5001F), Asahi Glass company manufacture, Two functional polyethers polyalcohols, Mn4000, hydroxyl value 2, hydroxyl value 28, degree of unsaturation 0.02,

(HA-2): general Lay minot (Preminol) S4013F (abbreviation in table: PREM S4013F), Asahi Glass corporation Make, two functional polyethers polyalcohols, Mn12000, hydroxyl value 2, hydroxyl value 9, degree of unsaturation 0.007,

(HA-3): general Lay minot (Preminol) S4318F (abbreviation in table: PREM S4318F), Asahi Glass corporation Make, two functional polyethers polyalcohols, Mn18000, hydroxyl value 2, hydroxyl value 6, degree of unsaturation 0.007,

(HA-4): Powerware promise (Excenol) 828 (abbreviation in table: EXCE 828), the manufacture of Asahi Glass company, three officials Can polyether polyol, Mn5000, hydroxyl value 3, hydroxyl value 34, degree of unsaturation 0.07,

(HA-5): general Lay minot (Preminol) S3011 (abbreviation in table: PREM S3011), Asahi Glass company manufacture, Trifunctional polyether polyol, Mn10000, hydroxyl value 3, hydroxyl value 17, degree of unsaturation 0.006,

(HA-6): general Lay minot (Preminol) 3012 (abbreviation in table: PREM 3012), the manufacture of Asahi Glass company, three Functional polyethers polyalcohol, Mn12000, hydroxyl value 3, hydroxyl value 14, degree of unsaturation 0.020,

(HA-7): Powerware promise (Excenol) 838 (abbreviation in table: EXCE 838), the manufacture of Asahi Glass company, four officials It can polyether polyol, Mn8000, hydroxyl value 4, hydroxyl value 28, degree of unsaturation 0.07.

The unit of degree of unsaturation is meq/g.

The function radix of each polyether polyol (HA), Mn, the Mn of every 1 functional group and degree of unsaturation are shown in Table 1 in advance.

The number average molecular weight (Mn) of < every 1 functional group is the general polyether polyol more than 300, less than 1650 (HM)>

(HM-1): PP-2000, Sanyo are melted into company's manufacture, two functional polyethers polyalcohols, Mn2000, hydroxyl value 2, hydroxyl value 56、

(HM-2): the manufacture of G-1500, Ai Dike (ADEKA) company, trifunctional polyether polyol, Mn1500, hydroxyl value 3, Hydroxyl value 112,

(HM-3): the manufacture of G-3000B, Ai Dike (ADEKA) company, trifunctional polyether polyol, Mn3000, hydroxyl value 3, Hydroxyl value 56.

The Mn of the function radix of each polyether polyol (HM), Mn and every 1 functional group is shown in Table 1 in advance.

(HB-1): ethylene glycol (EG), only comprising primary OH,

(HB-2): 1,5-PD, only comprising primary OH,

(HB-3): 2- ethyl -1,3- hexylene glycol (1,3- ethohexadiol), comprising primary OH and secondary hydroxyl groups,

(HB-4): PPG600 (digital representation Mn, also identical about PEG), polypropylene glycol, chemical conversion company, Sanyo manufacture, only Comprising secondary hydroxyl groups,

(HB-5): PEG300, polyethylene glycol, Sanyo chemical conversion company manufacture, only comprising primary OH,

(HB-6): PEG600, polyethylene glycol, Sanyo chemical conversion company manufacture, only comprising primary OH,

(HB-7): glycerol, comprising primary OH and secondary hydroxyl groups,

(HB-8): trimethylolpropane (TMP), only comprising primary OH,

(HB-9): SP-750, Sanyo's chemical conversion company's manufacture, six functional polyethers polyalcohols, Mn700, hydroxyl value 6, only including Secondary hydroxyl groups,

(HB-10): isophorone diamine.

The function radix, Mn and the Mn of every 1 functional group of the compound (HB) respectively containing active hydrogen-based are shown in Table 1 in advance.

(N-1): isophorone diisocyanate (IPDI), Tokyo chemical conversion industry company manufacture,

(N-2): hexamethylene diisocyanate (HDI), Tokyo chemical conversion industry company manufacture,

(N-3): toluene di-isocyanate(TDI) (2,4- toluene di-isocyanate(TDI)s (80 mass %) and 2,6- toluene di-isocyanate(TDI) The mixture of (20 mass %)) (TDI), the manufacture of Tosoh company.

The Mn of the function radix of each polyisocyanate (N), Mn and every 1 functional group is shown in Table 1 in advance.

(I-1) Crow Knight (Coronate) HL, the manufacture of Tosoh company, hexamethylene diisocyanate (HDI)/tri- hydroxyl first Base propane (TMP) adduct,

(I-2) Su meter Dou (Sumidur) N-3300, firmly change Bayer carbamate (Sumika Bayer Urethane) Company's manufacture, hexamethylene diisocyanate (HDI)/isocyanuric acid ester,

(I-3) Su meter Dou (Sumidur) N-75, firmly change Bayer carbamate (Sumika Bayer Urethane) public affairs Take charge of manufacture, hexamethylene diisocyanate (HDI)/isocyanic acid biuret (Isocyan biuret),

(I-4) De Shimo all (Desmodur) Z4470BA, live in change Bayer carbamate (Sumika Bayer Urethane) company's manufacture, isophorone diisocyanate (IPDI)/isocyanuric acid ester.

(C-1): easy fine jade Northey (IRGANOX) 1135 (manufacture of BASF (BASF) company).

(E-1): Ai Laike Sai Er (Elexcel) AS-804 (manufacture of the first industrial pharmaceutical company).

< plasticiser (P) >

(P-1): ATBC (Mitsubishi Chemical Ind's manufacture), citroflex A-4.

[synthesis example of C-terminal carbamate prepolymer (UPH)]

(synthesis example 1) (two-step polymerization method)

It is packed into the four-hole boiling flask for having blender, reflux cooling tube, nitrogen ingress pipe, thermometer and addition funnel The toluene and 0.01 matter of the polyether polyol (HA-1) of 100 mass parts, the polyisocyanate (N-1) of 10 mass parts, 47 mass parts The tin dilaurate dioctyl tin as catalyst of part is measured, and is mixed.Content liquid is slowly warming up to 80 DEG C and progress 2 is small Shi Fanying, to obtain isocyanate group terminal carbamate ester prepolymer (reaction of first stage).Then, by content liquid cooling But it to 60 DEG C, after the ethyl acetate for adding 28 mass parts, adds the compound (HB-2) containing active hydrogen-based of 4 mass parts and makes it It reacts (reaction of second stage).In the first stage and in the reaction entirety of second stage, polyisocyanate used in reaction The molal quantity of isocyanate group (NCO) is relative to the chemical combination used in reaction all containing active hydrogen-based possessed by ester (N) Object (HX) (is for the ratio (NCO/H) of (HA-1) and the total mole number of activity hydrogen-based (H) possessed by (HB-1)) in the example 0.71。

Remaining is being confirmed using infrared spectroscopic analysis (infrared radiation (Infrared Radiation, IR) analysis) After isocyanate group disappears, by content liquid cooling, but simultaneously reaction was completed, so that nonvolatile component 60%, viscosity 2 are obtained, 100cps, The solution of colorless and transparent C-terminal carbamate prepolymer (UPA-1).C-terminal carbamate obtained is pre- Polymers is Mn=16,500, Mw=43,000.

By the molal quantity of isocyanate group (NCO) possessed by polyisocyanate (N) used in allotment composition, reaction Total mole number relative to activity hydrogen-based (H) possessed by the compound (HX) used in reaction all containing active hydrogen-based Mn, Mw than (NCO/H) and C-terminal carbamate prepolymer obtained are shown in table 2-1.The unit of blending amount is " mass parts " (also identical in other tables).

(2~synthesis example of synthesis example 42) (two-step polymerization method)

In 2~synthesis example of synthesis example 42, used polyether polyol (HA), the compound containing active hydrogen-based are changed (HB) and the allotment ratio of the type of polyisocyanate (N) and these is gathered in the same manner as synthesis example 1 using two stages in addition to this It is legal to obtain colorless and transparent C-terminal carbamate prepolymer (UPA-2)~C-terminal carbamate prepolymer (UPA-42) solution.

In each synthesis example, by isocyanate group possessed by polyisocyanate (N) used in allotment composition, reaction (NCO) molal quantity is relative to activity hydrogen-based possessed by the compound (HX) used in reaction all containing active hydrogen-based (H) ratio (NCO/H) of total mole number and Mn, Mw of C-terminal carbamate prepolymer obtained be shown in table 2-1~ In table 2-5.

(synthesis example 43) (a stage polymerization)

It is packed into the four-hole boiling flask for having blender, reflux cooling tube, nitrogen ingress pipe, thermometer and addition funnel The polyether polyol (HA-6) of 100 mass parts, the compound (HB-2) containing active hydrogen-based of 4 mass parts, 47 mass parts toluene And 0.01 mass parts the tin dilaurate dioctyl tin as catalyst, carry out mix and be slowly warming up to 80 DEG C.To content liquid The polyisocyanate (N-1) of 9 mass parts of middle addition, the ethyl acetate of 28 mass parts simultaneously react within 2 hours.Used in reaction Polyisocyanate (N) possessed by isocyanate group (NCO) molal quantity relative to used in reaction all containing activity The compound (HX) of hydrogen-based (is the ratio of the total mole number of activity hydrogen-based (H) possessed by (HA-6) and (HB-2)) in the example It (NCO/H) is 0.58.

After confirming remaining isocyanate group using infrared spectroscopic analysis (IR analysis) and disappearing, but simultaneously by content liquid cooling Reaction was completed, to obtain nonvolatile component 60%, viscosity 3,300cps, the C-terminal carbamate of White-opalescent are pre- The solution of polymers (UPA-43).C-terminal carbamate prepolymer obtained is Mn=26,500, Mw=73,000.

By the molal quantity of isocyanate group (NCO) possessed by polyisocyanate (N) used in allotment composition, reaction Total mole number relative to activity hydrogen-based (H) possessed by the compound (HX) used in reaction all containing active hydrogen-based Mn, Mw than (NCO/H) and C-terminal carbamate prepolymer obtained are shown in table 2-5.

(synthesis example C-1~synthesis example C-6) (a stage polymerization)

In synthesis example C-1~synthesis example C-6, change is selected from polyether polyol (HA), polyether polyol (HM) and contains work The types of a variety of compounds (HX) containing active hydrogen-based in the compound (HB) of property hydrogen-based, the type of polyisocyanate (N) with And these allotment ratio obtains colorless and transparent comparison using a stage polymerization in the same manner as synthesis example 43 in addition to this C-terminal carbamate prepolymer (UPB-1)~C-terminal carbamate prepolymer (UPB-6) solution.

In each synthesis example, by isocyanate group possessed by polyisocyanate (N) used in allotment composition, reaction (NCO) molal quantity is relative to activity hydrogen-based possessed by the compound (HX) used in reaction all containing active hydrogen-based (H) ratio (NCO/H) of total mole number and Mn, Mw of C-terminal carbamate prepolymer obtained are shown in table 2-6.

(synthesis example C-7) (two-step polymerization method)

In synthesis example C-7, polyether polyol (HM-3) is used instead of polyether polyol (HA-1), and change containing activity The compound (HB) of hydrogen-based and the type of polyisocyanate (N) and material allocation ratio, in addition to this, with the same land productivity of synthesis example 1 The solution of the C-terminal carbamate prepolymer (UPB-7) of colorless and transparent comparison is obtained with two-step polymerization method.

By the molal quantity of isocyanate group (NCO) possessed by polyisocyanate (N) used in allotment composition, reaction Total mole number relative to activity hydrogen-based (H) possessed by the compound (HX) used in reaction all containing active hydrogen-based Mn, Mw than (NCO/H) and C-terminal carbamate prepolymer obtained are shown in table 2-6.

(allotment example D-1)

In allotment example D-1, it is packed into polyether polyol (HA-6), the compound (HB-3) containing active hydrogen-based, 47 mass parts Toluene, 28 mass parts ethyl acetate and 0.01 mass parts as catalyst tin dilaurate dioctyl tin and mixed It closes, thus to obtain the solution (polynary mixed alkoxide solution) of the polyalcohol (PO-1) of colorless and transparent comparison.Allotment composition is shown In table 2-6.

[manufacture of carbamate system sticker and adhesive sheet]

(embodiment 1)

Deploy the molten of C-terminal carbamate prepolymer (UPA-1) obtained in the synthesis example 1 of 100 mass parts Liquid, the polyfunctional isocyanate compound (I-1) of 10 mass parts, the antioxidant (C-1) of 1 mass parts and the work of 100 mass parts It for the ethyl acetate of solvent, and is stirred using dispersion machine, thus to obtain carbamate system sticker.Furthermore solvent with The usage amount of outer each material indicates nonvolatile component scaled value (also identical in other embodiments and comparative example).Group will be deployed At being shown in table 3-1.For sticker obtained, implement the evaluation of working life.

Prepare polyethylene terephthalate (PET) film (dew Miller (Lumirror) T-60, the Toray system of 50 μ m-thicks Make) as substrate sheets.It will be obtained in such a way that the thickness after drying becomes 12 μm using chipping wheel coater (registered trademark) Carbamate system sticker be coated on the substrate sheets single side.Then, it is dry at 100 DEG C that overlay will be formed by Two minutes and form adhesion coating.38 μm of thickness of stripping film (super Staeger (Super Stik) is attached on the adhesion coating The manufacture of SP-PET38, Lin get Ke (Lintec) company), to obtain adhesive sheet.About the evaluation of initial hardening property, 23 DEG C- After being conserved 3 hours under conditions of 50%RH, implementation evaluation.About other evaluations, conserved one week under conditions of 23 DEG C of -50%RH Afterwards, implementation evaluation.

(2~embodiment of embodiment 55,1~comparative example of comparative example 8)

In 2~embodiment of embodiment 55, each example of 1~comparative example of comparative example 8, become as shown in table 3-1~table 3-2 The type of more used material and allotment ratio, in addition to this, implement similarly to Example 1 carbamate system sticker and The evaluation of the manufacture of adhesive sheet and these.Furthermore comparative example 8 is the example that sticker is manufactured by single method.

[assessment item and evaluation method]

The assessment item of sticker and adhesive sheet and evaluation method is as follows described.

(working life)

For sticker obtained, it is immediately placed in the vial with lid after fabrication, the vial is put into Into 40 DEG C of thermostatic water baths, the viscosity of the sticker since investment after 1 hour and after 6 hours is measured respectively.It is small to find out 6 When after relative to the rate of viscosity increase (viscosity [again] behind viscosity/1 hour after 6 hours) after 1 hour.The following institute of evaluation criteria It states.

Zero: less than 3 times of viscosity climbing, well.

△: viscosity climbing is 3 times or more, 5 times hereinafter, can be practical.

×: viscosity climbing is more than 5 times, can not be practical.

[initial hardening property]

Adhesive sheet after conserving 3 hours in the environment of 23 DEG C of -50%RH of leisure cuts out the test of width 30mm length 100mm Piece.After the test film is attached at stainless steel (SUS) net (aperture: 0.077mm, line footpath: 0.05mm), it is impregnated in ethyl acetate In.It is 30 minutes dry at 100 DEG C after being extracted 24 hours at 50 DEG C, gel fraction (matter is calculated based on following formula (1) Measure %).

Gel fraction (quality %)=(G2/G1) × 100 ... (1)

In the formula, each symbol indicates parameter below.

G1: the quality of the adhesion coating before being extracted using ethyl acetate,

G2: the quality of the adhesion coating after the extraction and drying of ethyl acetate is utilized.

Evaluation criteria is as described below.

◎: gel fraction is 80 mass % or more, excellent.

Zero: gel fraction be 50 mass % or more, less than 80 mass %, well.

△: gel fraction be 20 mass % or more, less than 50 mass %, can be practical.

×: the less than 20 mass % of gel fraction, it can not be practical.

(wetability)

The test that adhesive sheet after a week cuts out width 50mm length 100mm is conserved in the environment of 23 DEG C of -50%RH of leisure After placing 30 minutes in the environment of 23 DEG C of -50%RH, stripping film is removed from test film for piece.The institute of stripping film will have been removed The end of glass plate is fixed in the wherein end for stating the longitudinal direction of test film, will not be subject to fixed another end using hand The position of height 5cm is raised up to from the surface of glass plate.Hand is unclamped in this condition, and measurement is until adhesion coating is integrally close contact in Time until the surface of glass plate.Evaluation criteria is as described below.

Zero: less than 4 seconds until contiguity, well.

△: until contiguity until for 4 seconds or more, it is 8 seconds less than, can be practical.

×: it is 8 seconds or more until contiguity, it can not be practical.

(substrate adhesion)

It is orthogonal relative to each other for the adhesion coating for conserving adhesive sheet after a week in the environment of 23 DEG C of -50%RH Two rectilinear directions are respectively with 11 times half incisions of the interval 1mm implementation, to form the block of 100 1mm square.Using finger to institute After stating 100 pieces of whole frictions 1 minute, the block number remained in substrate sheets is visually counted.Evaluation criteria is as described below.

◎: the remaining block number of institute is 81~100, excellent.

Zero: the remaining block number of institute is 61~80, well.

△: the remaining block number of institute is 41~60, can be practical.

×: the remaining block number of institute is 0~40, can not be practical.

(releasable)

Three pieces that adhesive sheet after a week cuts out width 70mm length 100mm are conserved in the environment of 23 DEG C of -50%RH of leisure Test film.For three pieces of test films, stripping film is removed in the environment of 23 DEG C of -50%RH respectively, by sodium hydroxide glass plate It is attached at the surface of the adhesion coating of exposing, is crimped using make-up machine.By three pieces of laminated bodies obtained be set as 85 DEG C- It is placed respectively in the baking oven of 85%RH 72 hours (condition 1), 120 hours (condition 2), 240 hours (condition 3).Three pieces are laminated Body takes out from baking oven respectively, after air is 3 hours cooling in the environment of 23 DEG C of -50%RH, adhesive sheet is removed from glass plate, is led to Visually observation is crossed to evaluate releasable.Evaluation criteria is as described below.

◎: at all conditions, absolutely not adhesion composition of layer is attached to glass surface, excellent.

Zero: under condition 1, condition 2, absolutely not adhesion composition of layer is attached to glass surface, but under condition 3, generates Adhesion composition of layer is attached to glass surface, well.

△: under condition 1, absolutely not adhesion composition of layer is attached to glass surface, but under condition 2, condition 3, generates Adhesion composition of layer is attached to glass surface, can be practical.

×: at all conditions, generates adhesion composition of layer and be attached to glass surface, it can not be practical.

(being attached to body pollution inhibition)

The test that adhesive sheet after a week cuts out width 70mm length 100mm is conserved in the environment of 23 DEG C of -50%RH of leisure Piece removes stripping film in the environment of 23 DEG C of -50%RH.Sodium hydroxide glass plate is attached to the table of the adhesion coating of exposing Face is crimped using make-up machine.Laminated body obtained is placed 72 hours in the baking oven for being set as 85 DEG C of -85%RH. Laminated body is taken out from baking oven, after air is 3 hours cooling in the environment of 23 DEG C of -50%RH, adhesive sheet is removed from glass plate, And it evaluates and is attached to body pollution.In darkroom, to the irradiation luminous diode in the surface of the glass plate for the side for posting adhesive sheet (Light Emitting Diode, LED) light, observation is by visual observation to be evaluated.Evaluation criteria is as described below.

◎: not observing the attachment of adhesion composition of layer in glass surface completely, excellent.

Zero: the attachment of thin adhesion composition of layer is observed at 1 position of glass surface~2 positions, well.

△: observing the attachment of thin adhesion composition of layer at 3 positions of glass surface, can be practical.

×: the attachment/of thin adhesion composition of layer is observed more than 4 positions of glass surface or at 1 of glass surface The attachment of dense adhesion composition of layer is observed at position~2 positions, can not be practical.

[evaluation result]

It shows the results of the evaluation in table 4-1~table 4-2.

In 1~embodiment of embodiment 55, manufacture includes C-terminal carbamate prepolymer (UPH) and multifunctional isocyanide The carbamate system sticker of ester compound (I), the C-terminal carbamate prepolymer (UPH) are every 1 function Polyether polyol (HA), the quantity of every 1 functional group for the long chain that the number average molecular weight (Mn) of base is 1650 or more Average molecular weight (Mn) is the compound (HB) and polyisocyanate (N) containing active hydrogen-based of 300 shorter chains below Reaction product.

In these embodiments, working life and the initial hardening good sticker of property can be manufactured, even if not adding plasticiser Or lower the addition of plasticiser, even if can also manufacture, wetability is good, substrate adhesion is good and is exposed to hot and humid environment Under, it may have good releasable is attached to the adhesive sheet of body pollution inhibition.

Utilize the poly- of many general of the number average molecular weight (Mn) more than 300, less than 1650 that every 1 functional group is used only The comparative example 2 for the C-terminal carbamate prepolymer that ethoxylated polyhydric alcohol (HM) is obtained as the compound containing active hydrogen-based In, due to being not added with plasticiser, the wetability of adhesive sheet obtained is bad.

Using use every 1 functional group number average molecular weight (Mn) be 1650 or more long chain polyether polyols General polyether polyol (HM) of the number average molecular weight (Mn) of alcohol (HA) and every 1 functional group more than 300, less than 1650 is made Comparative example 1, the comparative example 3~ratio of the C-terminal carbamate prepolymer obtained for the compound (HX) containing active hydrogen-based Compared in example 5, even if not adding plasticiser, the good adhesive sheet of wetability can also be manufactured.However, in these comparative examples, due to not Number average molecular weight (Mn) using every 1 functional group is the compound containing active hydrogen-based of 300 shorter chains below (HB) raw material as C-terminal carbamate prepolymer, therefore the working life of sticker and initial hardening property are bad, and It is bad that the releasable of adhesive sheet is attached to body pollution inhibition.The substrate of adhesive sheet obtained in these comparative examples touches Property is also bad.

Utilize general polyether polyols of the number average molecular weight (Mn) more than 300, less than 1650 for using every 1 functional group The chemical combination containing active hydrogen-based of alcohol (HM) chain short compared with the number average molecular weight (Mn) of every 1 functional group is 300 below Comparative example 6, the ratio for the C-terminal carbamate prepolymer that object (HB) is obtained as the compound (HX) containing active hydrogen-based Compared in example 7, under conditions of not adding plasticiser, the number average molecular weight (Mn) without using every 1 functional group is 1650 or more Long chain polyether polyol (HA), therefore the wetability of adhesive sheet obtained is bad.In comparative example 6, pass through one Stage polymerization method and the terminal hydroxyl of carbamate prepolymer obtained are being mixed for level-one and second level, therefore are obtained Sticker initial hardening property it is also bad.In comparative example 7, the carbamate prepolymer that is obtained by two-step polymerization method Terminal hydroxyl be only level-one, therefore initial hardening property is improved.

In comparative example 8, the quantity of every 1 functional group is averaged without using C-terminal carbamate prepolymer (UPH) Polyether polyol (HA), the number average molecular weight of every 1 functional group for the long chain that molecular weight (Mn) is 1650 or more (Mn) compound (HB) and polyfunctional isocyanate compound (I) that are 300 shorter chains below containing active hydrogen-based plus With mixing, and carbamate system sticker is manufactured by single method.The initial hardening property of sticker obtained is bad, makes It is bad that body pollution inhibition is attached to the releasable of its adhesive sheet.

[table 1]

[table 2-5]

The present invention is not limited to the embodiment and embodiments, without departing from purport of the invention, then can fit Suitable design alteration.

The Japanese patent application Japan Patent Patent 2018- that this application claims filed an application on April 12nd, 2018 Its entire disclosure is incorporated in this specification by the priority based on No. 077040.

The explanation of symbol

10,20: adhesive sheet

11,21: substrate sheets

12,22A, 22B: adhesion coating

13,23A, 23B: stripping film

Claims

1. a kind of sticker, includes:

C-terminal carbamate prepolymer (UPH), the C-terminal carbamate prepolymer (UPH) are to include every 1 The polyether polyol (HA) and the number average molecular weight of every 1 functional group that the number average molecular weight of functional group is 1650 or more be 300 or less and a compound (HB) containing active hydrogen-based with multiple active hydrogen-baseds in molecule a variety of changes containing active hydrogen-based Close object (HX), the reaction product with more than one polyisocyanate (N)；And

Polyfunctional isocyanate compound (I), and

Compound (HB) containing active hydrogen-based includes the compound containing active hydrogen-based for only including primary OH as active hydrogen-based.

2. sticker according to claim 1, wherein isocyanate group (NCO's) rubs possessed by polyisocyanate (N) The ratio of the total mole number of activity hydrogen-based (H) possessed by your compound (HX) containing active hydrogen-based of the number relative to more than one It (NCO/H) is 0.20~0.84.

3. sticker according to claim 1 or 2, wherein more than one polyether polyol (HA) include trifunctional with On polyether polyol.

4. sticker according to any one of claim 1 to 3, wherein relative to C-terminal carbamate pre-polymerization 100 mass parts of object (UPH), the additive amount (P) of plasticiser are 0 mass parts~10 mass parts.

5. sticker according to any one of claim 1 to 4, wherein C-terminal carbamate prepolymer (UPH) It is described for the reaction product of isocyanate group terminal carbamate ester prepolymer (UPN) and the compound (HB) containing active hydrogen-based Isocyanate group terminal carbamate ester prepolymer (UPN) is the reaction product of polyether polyol (HA) and polyisocyanate (N).

6. sticker according to any one of claim 1 to 5, wherein more than one polyisocyanate (N) includes different Isophorone diisocyanate.

7. sticker according to any one of claim 1 to 6 also includes selected from by antioxidant, hydrolysis agent, purple The antideteriorant of one or more of group composed by ultraviolet absorbers and light stabilizer.

8. sticker according to any one of claim 1 to 7 also includes antistatic agent.

9. a kind of adhesive sheet, including substrate sheets and comprising such as the hardening thing of sticker described in any item of the claim 1 to 8 Adhesion coating.

10. a kind of manufacturing method of C-terminal carbamate prepolymer, comprising:

Make 1650 or more the number average molecular weight of every 1 functional group more than one polyether polyol (HA), with it is a kind of with On polyisocyanate (N) isocyanate group terminal carbamate ester pre-polymerization is generated with the reaction of the ratio of isocyanate group surplus The process of object (UPN)；And

Make isocyanate group terminal carbamate ester prepolymer (UPN) obtained and the number average molecular weight of every 1 functional group For 300 or less and the work of more than one compound (HB) reaction containing active hydrogen-based in molecule with multiple active hydrogen-baseds Sequence, and