CN102822293A - Adhesive sheet - Google Patents
Adhesive sheet Download PDFInfo
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- CN102822293A CN102822293A CN2011800164970A CN201180016497A CN102822293A CN 102822293 A CN102822293 A CN 102822293A CN 2011800164970 A CN2011800164970 A CN 2011800164970A CN 201180016497 A CN201180016497 A CN 201180016497A CN 102822293 A CN102822293 A CN 102822293A
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- pressure sensitive
- resin
- surface substrate
- sensitive adhesive
- sensitive adhesion
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2425/00—Presence of styrenic polymer
- C09J2425/006—Presence of styrenic polymer in the substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2455/00—Presence of ABS
- C09J2455/006—Presence of ABS in the substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2469/00—Presence of polycarbonate
- C09J2469/006—Presence of polycarbonate in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
Disclosed is an adhesive sheet comprising a front base material and an adhesive layer provided on the back surface of the front base material, said adhesive sheet being characterized in that the adhesive layer is formed by applying an aqueous dispersion adhesive prepared by adding, as a plasticizer, a nonionic surfactant containing an amino group to an aqueous dispersion adhesive composition that contains 2-ethylhexyl acrylate, ethylenically unsaturated carboxylic acid and, as necessary, an acrylic copolymer obtained by emulsion polymerization of other polymerizable unsaturated monomers. The adhesive sheet has superior adherence between the front base material and adhesive layer, and the adhesion to adherends is superior. Furthermore, the adhesive sheet does not leave an adhesive residue on the adherend, even when peeled off after being adhered for a long period of time.
Description
Technical field
The present invention relates to pressure sensitive adhesion sheet, at length say, relate to after pasting on the resin system housing of household electrical appliances and electronics and can peel off, and can paste the sheet of releasing pressure sensitive adhesive again on this housing once more in an as original ground as required.
Background technology
Up to now, the pressure sensitive adhesion sheet that on adhesive surface on the resin system housing of household electrical appliances and electronics, records this trade(brand)name and description of commodity, method of use etc. is to show, to sell.
In recent years, consider the recycling of utilization again after the resin system housing of used household electrical appliances and electronics is reclaimed, pulverizes from the viewpoint of saving resource.
Will be the time with the resin system housing recycling of household electrical appliances and electronics; On this resin system housing, be pasted with under the situation of pressure sensitive adhesion sheet; The situation of this pressure sensitive adhesion sheet being peeled off back recycling is arranged, also have in the situation of pasting recycling under original state of this pressure sensitive adhesion sheet.
When with pressure sensitive adhesion sheet when this resin system housing strips down recycling; Require enough bounding forces so that in the time that pastes this resin system housing, firmly fix, but also require pressure sensitive adhesion sheet to have the releasable that when this resin system housing is peeled off, can peel off easily.In addition, during the direct recycling of original state when stick on this resin system housing with pressure sensitive adhesion sheet on, require the surface substrate of pressure sensitive adhesion sheet identical with the material of this resin system housing.
That is, require pressure sensitive adhesion sheet to have and the bounding force of bonded body such as resin system housing and the character that can peel off again from the bonded body, and then require its surface substrate to process, hope that these conditions can both satisfy by the material identical with bonded body.
On the other hand, as the pressure sensitive adhesive of releasable pressure sensitive adhesion sheet, considering from the viewpoint of environmental problem, is being that pressure sensitive adhesive changes to the water system pressure sensitive adhesive from solvent.When being the water system pressure sensitive adhesive, if can strip down from bonded body easily, then the closing force with the surface substrate that belongs to same material also reduces, and remains in the problem on the bonded body with regard to producing pressure sensitive adhesive layer like this.
Past; For bonded bodies such as paper, metal, plastics classes; Require pressure sensitive adhesion sheet to have good cementability and pressure sensitive adhesion label pressure sensitive adhesive composition when bonded body is peeled off can not remained on the bonded body and can peel off again; As the pressure sensitive adhesion sheet that meets this target, there have the people once to propose at lamination on the surface of surface substrate to be a kind of through (with reference to patent documentation 1: the spy opens the 2000-281989 communique to containing binding property micropartical (A) and also containing the pressure sensitive adhesion sheet that adds the contact adhesive composition layer as the surfactant-based softening agent such as T 46155 nonylplenyl ether of softening agent in the aqueous pressure-sensitive adhesive composition of pressure sensitive adhesive (B) and form as required.）。
In the patent documentation 1; As surfactant-based softening agent; Only use the T 46155 nonylplenyl ether in an embodiment; As another concrete example, polyoxygenated alkyl phenyl ethers such as polyoxyalkylene alkyl such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, T 46155 two (stearyl) ether or thiazolinyl ethers, polyoxyethylene octyl phenyl ether, T 46155 two (nonyl) phenyl ether, T 46155 two (nonyl phenyl) ether in paragraph ［ 0058 ］, have only been put down in writing.
Yet; Use has cooperated the pressure sensitive adhesion sheet of pressure sensitive adhesive of these surfactant-based softening agent when bonded body is peeled off; The bounding force of surface substrate and pressure sensitive adhesive layer is abundant inadequately; The pressure sensitive adhesive composition taking place sometimes remain in bonding residual on the bonded body, exists the enough good problem of not talkative releasable.
Summary of the invention
The present invention develops in view of the situation of above-mentioned prior art; Its purpose is; A kind of like this pressure sensitive adhesion sheet is provided, and its surface substrate and pressure sensitive adhesive layer have good adaptation, and good to the binding property of bonded body; And, even after sticking on bonded body for a long time, peel off can on bonded body, not produce yet bonding residual.
The inventor etc. study in order to solve above-mentioned problem; The result finds; One deck is set through being coated with the pressure sensitive adhesive layer that amino non-ionics comes synthetic aqueous dispersion type pressure sensitive adhesive to obtain that contains that adds in a kind of aqueous dispersion type pressure-sensitive-adhesive compsn that is containing specific acrylic copolymer as softening agent through the back side at surface substrate; Just can solve above-mentioned problem, thereby accomplish the present invention based on this opinion.
Promptly; The present invention provides a kind of pressure sensitive adhesion sheet; It comprises surface substrate and the pressure sensitive adhesive layer that is arranged on this surface substrate back side; It is characterized in that; This pressure sensitive adhesive layer coating aqueous dispersion type pressure sensitive adhesive and forming, said aqueous dispersion type pressure sensitive adhesive are to come syntheticly through the amino non-ionics that contains that in the aqueous dispersion type pressure-sensitive-adhesive compsn that contains acrylic copolymer, adds as softening agent, and said acrylic copolymer obtains through 2-EHA and ethene property unsaturated carboxylic acid are carried out letex polymerization.
In addition, the present invention provides a kind of like this pressure sensitive adhesion sheet, and wherein, said surface substrate is made up of the material identical materials with the bonded body of pasting pressure sensitive adhesion sheet.
In addition, the present invention provides a kind of like this pressure sensitive adhesion sheet, and wherein, surface substrate is made up of the mixture more than 2 kinds in polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin, polycarbonate resin or the above-mentioned resin.
In addition; The present invention provides a kind of like this pressure sensitive adhesion sheet; Wherein, but acrylic copolymer be 2-EHA and ethene property unsaturated carboxylic acid and then carry out the acrylic copolymer that letex polymerization obtains with other unsaturated monomers of copolymerization as required.
Pressure sensitive adhesion sheet of the present invention, its surface substrate and pressure sensitive adhesive layer have good adaptation, and also good to the binding property of bonded body, and then, can not occur in bonding residual on the bonded body even after pasting bonded body for a long time, peel off yet.
Embodiment
Among the present invention; The aqueous dispersion type pressure sensitive adhesive that is used to form pressure sensitive adhesive layer is to come syntheticly through the amino non-ionics that contains that in the aqueous dispersion type pressure-sensitive-adhesive compsn that contains acrylic copolymer, adds as softening agent, and said acrylic copolymer obtains through 2-EHA and ethene property unsaturated carboxylic acid are carried out letex polymerization.
Acrylic copolymer can be to be formed by the monomer copolymerization that contains 2-EHA and ethene property unsaturated carboxylic acid basically, and then, also can with can form with other unsaturated monomer copolymerization of these monomer copolymerizations.Preferably form by the monomer copolymerization that contains 2-EHA and ethene property unsaturated carboxylic acid basically.
As ethene property unsaturated carboxylic acid, can enumerate (methyl) vinylformic acid such as vinylformic acid, methylacrylic acid; Methylene-succinic acid, toxilic acid, maleic anhydride, fumaric acid, fumaric acid anhydride etc. are preferably (methyl) vinylformic acid.As ethene property unsaturated carboxylic acid, can use a kind separately, also can combination more than 2 kinds be used.As ethene property unsaturated carboxylic acid, especially preferably vinylformic acid and methylacrylic acid are merged use.When vinylformic acid and methylacrylic acid being merged when using, the polymerization ratio of the two by mass ratio, is preferably 1/10～10/1, and more preferably 1/5～5/1, further be preferably 1/3～3/1.
As other unsaturated monomer, the carbon number that can enumerate alkyl such as methyl acrylate, ethyl propenoate, propyl acrylate, Bing Xisuandingzhi, NSC 11786, vinylformic acid Lauryl Ester, TEB 3K, Jia Jibingxisuanyizhi, propyl methacrylate, NSC 20956, N-Hexyl methacrylate, methylacrylic acid Lauryl Ester is that 1～20 (methyl) alkyl acrylate, 2-Hydroxy ethyl acrylate, vinylformic acid-2-hydroxy propyl ester, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-3-hydroxyl butyl ester, vinylformic acid-4-hydroxyl butyl ester, methylacrylic acid-2-hydroxy methacrylate, methylacrylic acid-2-hydroxy propyl ester, methylacrylic acid-3-hydroxy propyl ester, methylacrylic acid-3-hydroxyl butyl ester, methylacrylic acid-4-hydroxyl butyl ester etc. contain (methyl) alkyl acrylate of hydroxyl etc.Other unsaturated monomer can use a kind separately, also can combination more than 2 kinds be used.
Contain proportionally in the acrylic copolymer from ethene property unsaturated carboxylic acid unitary, unitary amount 100 mass parts with respect to from 2-EHA are preferably 0.1～10 mass parts, more preferably 0.3～5 mass parts.In addition, contain proportionally in the acrylic copolymer from other unsaturated monomer unitary, unitary amount 100 mass parts with respect to from 2-EHA are preferably 0～20 mass parts, more preferably 0～15 mass parts.
Among the present invention, acrylic copolymer can obtain through letex polymerization.Letex polymerization can adopt various emulsion polymerizations to carry out, but as long as general emulsion polymerization.Specifically; For example can enumerate; In reactor drum, drop into 2-EHA and ethene property unsaturated carboxylic acid and the monomers such as other unsaturated monomers that use as required, emulsifying agent, polymerization starter etc.; Behind inert gas replacement inside such as nitrogen, under refluxing, heat up while stir as dispersion medium with water; At suitable polymerization temperature, for example in the TR about 40～100 ℃, carry out suitable polymerization time, the method for emulsion polymerization about 1～8 hour for example.
The emulsifying agent that uses during as letex polymerization does not have particular determination, for example can enumerate anionic emulsifier, nonionic emulsifier, reactive emulsifier etc.But, add after the emulsifying agent that uses during letex polymerization and the letex polymerization as softening agent to contain amino non-ionics be different.
As anionic emulsifier; For example can enumerate potassium oleate, Sodium Lauryl Sulphate BP/USP, X 2073, sodium alkyl naphthalene sulfonate, dialkyl sodium sulfosuccinate, Voranol EP 2001 sodium sulfate, polyxyethylated allyl ethers sodium sulfate, polyxyethylated allyl ethers ammonium sulfate, Voranol EP 2001 SULPHOSUCCINIC ACID ESTER, polyxyethylated allyl ethers SULPHOSUCCINIC ACID ESTER etc.
As nonionic emulsifier; For example can enumerate Voranol EP 2001, polyxyethylated allyl ethers, polyoxyethylene oxypropylene segmented copolymer, cithrol, W 166 cresols ether, polyoxyethylene sorbitan fatty acid esters etc.
As reactive emulsifier; For example can enumerate single maleic acid ester and verivate, (methyl) acryl polyoxyalkylene alkyl SULPHOSUCCINIC ACID ESTER etc. of polyethyleneglycol (methyl) propenoate of various molecular weight (oxyethane addition mole number is different), polyethenoxy alkylphenols (methyl) propenoate, 2-(methyl) acryloxy ethylsulfonic acid ammonium, polyoxyethylene glycol.The aspect that from the environmental health aspect, particularly never can produce the environmental hormone problem considers, preferred solvent be above-mentioned in the middle of the emulsifying agent of higher alcohols analog derivative.
Emulsifying agent can use a kind separately, also can combination more than 2 kinds be used.
The consumption of emulsifying agent with respect to acrylic copolymer 100 mass parts, is preferably 0.2～10 mass parts usually, more preferably 0.5～5 mass parts.Be in the above-mentioned scope through the consumption that makes emulsifying agent, can obtain can not produce the emulsion of coagulative appropriate particle diameter.
The acrylic copolymer that obtains through letex polymerization obtains with the form of emulsion.The median size of dispersive acrylic copolymer is preferably 100～500nm in emulsion, and more preferably 150～400nm further is preferably 200～350nm.
The weight-average molecular weight of acrylic copolymer is preferably 30,000～1, and 500,000, more preferably 50,000～1,000,000, be preferably 100,000～500,000 especially.Explain that in this specification sheets, weight-average molecular weight is meant the value by polystyrene standard conversion acquisition that adopts the solvable composition of gel permeation chromatography THF.
Among the present invention, adopt the above-mentioned emulsion polymerization, obtain containing the aqueous dispersion type pressure-sensitive-adhesive compsn of acrylic copolymer.
Aqueous dispersion type pressure sensitive adhesive among the present invention obtains through non-ionics that contains amino and the mixing of in the aqueous dispersion type pressure-sensitive-adhesive compsn that contains the aforesaid propylene acid copolymer, adding as softening agent.
As containing amino non-ionics; So long as amino bonded is to non-ionics; Use various non-ionics all can, amino number, preferred below 6 in non-ionics 1 molecule; More preferably below 3, preferred especially below 2.
As the suitable concrete example that contains amino non-ionics, can enumerate the polyoxygenated enamine, more preferably the polyoxyalkylene alkylamine.As the concrete example of polyoxygenated enamine, for example can enumerate, by the polyoxygenated enamine of formula (1) expression.
(in the formula, R is alkyl, thiazolinyl or the acyl group of carbon number 3～30, A
1And A
2Be the alkylidene group of carbon number 2～4, x and y are 0 or positive integer, and x+y is 2～40, when x is 2 when above, and a plurality of A
1Can be the same or different; When y is 2 when above, a plurality of A
2Can be the same or different.）
The carbon number of R is preferably 4～24 in the formula (1), and more preferably 6～20, be preferably 10～20 especially.In addition, as A
1And A
2, can enumerate ethylidene, propylidene, butylidene, but preferred ethylidene, propylidene, more preferably ethylidene.X and y are 2 (A when above
1O) x and (A
2O) y can be the segment of a kind of oxyalkylene group such as polyoxyethylene groups, polyoxypropylene base, polyoxy crotonyl, also can be the polyoxyalkylenes that makes up more than 2 kinds that contains the oxyalkylene group of carbon number 2～4.As the polyoxyalkylenes that makes up more than 2 kinds of the oxyalkylene group that contains carbon number 2～4, can be random structure, also can be block structure.In addition, x+y is 2～40, is preferably 3～20, is preferably 4～17 especially.
In addition, contain amino non-ionics, its HLB value is preferably 8～20, is preferably 10～16 especially.
Contain amino non-ionics and can use a kind, also can combination more than 2 kinds be used.When combination more than 2 kinds is used, especially preferably will above-mentioned preferred especially combination use more than 2 kinds.
The addition that contains amino non-ionics as softening agent with respect to acrylic copolymer 100 mass parts, is preferably 0.1～2.0 mass parts, and more preferably 0.15～1.5 mass parts further is preferably 0.2～1.2 mass parts.
For acrylic copolymer is linked in the aqueous dispersion type pressure sensitive adhesive of the present invention through the effect of linking agent, preferably cooperate linking agent.
As being applicable to the linking agent that makes acrylic copolymer crosslinked, preferred epoxy is a linking agent.As epoxy is linking agent; For example can use; NSC 6366 diglycidyl ether, polyoxyethylene glycol diglycidyl ether, dihydroxyphenyl propane diglycidyl ether, Bisphenol F diglycidyl ether, phthalic acid diglycidyl ester, dimeracid diglycidyl ether, triglycidyl group isocyanuric acid ester, Glycerol dimer triglycidyl group ether, the many glycidyl ethers of TriMethylolPropane(TMP), Sorbitol Powder four glycidyl group ether, N, N, N '; N '-four glycidyl group-m-xylylenediamine, 1; Two (N, the N-diglycidyl amino methyl) hexanaphthenes of 3-, N, N; N ', N '-epoxies such as four glycidyl group diaminodiphenyl-methane are linking agent.
Linking agent can use a kind separately, also can combination more than 2 kinds be used.The consumption of linking agent with respect to acrylic copolymer 100 mass parts, is preferably 0.01～10 mass parts, more preferably 0.1～5 mass parts.
In the aqueous dispersion type pressure sensitive adhesive of the present invention, can cooperate various additives such as tackifier, bonding imparting agent, stablizer.
As tackifier, can enumerate ROHM based polymer, polymethyl acrylic acid based polymer, gather (methyl) acrylic ester polymer, polyolefin polymkeric substance etc.The cooperation ratio of tackifier; As long as its consumption can make the viscosity of coating aqueous dispersion type pressure sensitive adhesive become the viscosity that is suitable for being coated with, as long as its consumption can make the viscosity of aqueous dispersion type pressure sensitive adhesive be in the scope of 100～10000mPas (BM type viscometer, 25 ℃, 60rpm).Generally, with respect to acrylic copolymer 100 mass parts, be preferably 0.1～10 mass parts, more preferably 1～5 mass parts.
As bonding imparting agent, can enumerate rosin esters such as rosin, rosin ester, hydrogenated wood rosin glycerol ester is the bonding imparting agents of terpenic series such as bonding imparting agent, terpene phenol resin.Bonding imparting agent can be when letex polymerization and the acrylic monomer coexistence, also can make the bonding resin emulsion of giving of emulsive carry out adding after the letex polymerization by known method, also can the two be merged and use.The cooperation ratio of bonding imparting agent generally, with respect to acrylic copolymer 100 mass parts, is preferably 0.1～20 mass parts, more preferably 5～15 mass parts.Through the cooperation ratio that makes bonding imparting agent is more than 0.1 mass parts; Can not can cause in stickup, using with peeling off; Through the cooperation ratio that makes bonding imparting agent is below 20 mass parts, can easily peel off from bonded body under the bonding residual condition not taking place.
Aqueous dispersion type pressure-sensitive-adhesive compsn among the present invention as long as the amount of resin solid state component is 30～70 quality % usually, is preferably 40～60 quality %.
Pressure sensitive adhesion sheet of the present invention is the pressure sensitive adhesion sheet that comprises the surface substrate and the pressure sensitive adhesive layer at the back side that is arranged on this surface substrate.
As surface substrate, can use various plastics sheets, film.Concrete example as surface substrate; Can enumerate vibrin such as polyolefin resin such as polyvinyl resin, acrylic resin, pet resin, PEN resin, polybutylene terephthalate resin for example, PVC RESINS, polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate resin, polyamide resin, polyimide resin, fluoro-resin and sheet material, the film of the various synthetic resins such as mixture more than 2 kinds in them; Especially; Consider preferred the use and the resin material identical materials that is used for the resin-case of tame electrical article and electronics from HS and cheap angle.As these surface substrates, the sheet material, the film that preferably constitute by the mixture more than 2 kinds in polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate resin or the above-mentioned resin.Surface substrate can be an individual layer, also can be identical type or different types of multilayer more than 2 layers.
The thickness of surface substrate does not have particular restriction, is preferably 10～350 μ m usually, and more preferably 15～300 μ m are preferably 20～250 μ m especially.
Printing also can be set on the surface of surface substrate receive to hold layer.If the surface of surface substrate is provided with printing and receives to hold layer, then after pressure sensitive adhesive layer is arranged on the back side of surface substrate, just can print.
Printing receives to hold layer and can be provided with the coating agent through being coated with various letterings., preferably can enumerate vinyl resin or vibrin, perhaps use the lettering that forms with applying agent with applying agent as lettering by their merging.
For the closing force of further raising with pressure sensitive adhesive layer, the back side of surface substrate also can apply and be prone to bonding processing.Do not have particular restriction as easy bonding processing, for example can enumerate Corona discharge Treatment etc.
In the pressure sensitive adhesion sheet of the present invention, on the back side of surface substrate, form the pressure sensitive adhesive layer that contains above-mentioned contact adhesive composition.
The thickness of pressure sensitive adhesive layer does not have particular restriction, and common dried thickness is preferably 3～150 μ m, and more preferably 5～100 μ m further are preferably 10～60 μ m.
As the method that on the back side of surface substrate, forms the pressure sensitive adhesive layer contain above-mentioned contact adhesive composition, can enumerate the above-mentioned aqueous dispersion type pressure sensitive adhesive of coating on above-mentioned aqueous dispersion type pressure sensitive adhesive of coating and exsiccant method on the back side of substrate sheet, the lift-off processing face at releasing sheet in advance and dry, formed pressure sensitive adhesive layer is fitted to method on the back side of surface substrate etc. then.
As to the surface substrate of above-mentioned aqueous dispersion type pressure sensitive adhesive or the coating process of releasing sheet; For example can enumerate, scraping article coating method, scraper coating method, rolling method, scraper plate coating method, mouthful pattern coating method, grooved roll coating method, curtain stream coating method etc. are known method in the past.
Drying is preferably carried out under 60～130 ℃ usually, more preferably under 80～120 ℃, carries out.Do not have particular restriction time of drying, common 10 seconds～5 minutes just enough.
There is not particular determination as releasing sheet.As the base material of releasing sheet, for example can enumerate paper, synthetic paper, synthetic resin film etc.As paper; For example can enumerate, paper base materials such as good quality paper, zellglas, White Board, close the paper base material of paper and usefulness Mierocrystalline cellulose, starch, Z 150PH, vinylformic acid-styrons etc. such as good quality paper, zellglas, White Board have been carried out paper base material that the filler processing forms etc. through the layer that resembles that closes on these paper base material upper stratas that thermoplastic resins such as Vilaterm, Vestolen PP 7052 form.As the plastic synthetic resin film; For example can enumerate; Contain the film of vibrin such as polyolefin resines such as polyvinyl resin, acrylic resin, polybutylene terephthalate resin, pet resin and these synthetic resin film are applied and be prone to film that bonding processing forms etc., the base material that preferably forms through coating stripper on these base materials.
As stripper, can enumerate fluorine resin, siloxane-based resin, contain the carbamate of chain alkyl etc.
Pressure sensitive adhesion sheet of the present invention can be used as the pressure sensitive adhesion sheet that pastes bonded body and uses; Paste on the bonded body and use; Its purposes is unqualified, especially preferably pastes on the bonded body that forms through the situation of bonded body being carried out recycling to use.
Pressure sensitive adhesion sheet of the present invention can preferably be applicable to the material and the identical occasion of material that constitutes bonded body of the surface substrate of pressure sensitive adhesion sheet.
As the material that constitutes bonded body,, can enumerate the bonded body that constitutes by the mixture more than 2 kinds in polystyrene resin, ABS resin, polycarbonate resin or the above-mentioned resin as concrete example.
The shape of bonded body does not have particular restriction, can process different shape.
Embodiment
Below, with embodiment the present invention is described more specifically.Explain that the present invention does not receive any qualification of these examples.
(embodiment 1)
(1) modulation of aqueous dispersion type pressure-sensitive-adhesive compsn
In the reaction vessel that is equipped with stirrer, reflux cooler, TM, nitrogen ingress pipe and tap funnel, add 2-EHA 100 mass parts, vinylformic acid 0.2 mass parts, methylacrylic acid 0.4 mass parts; Adding Voranol EP 2001 sodium sulfate (tensio-active agent, Kao Corp's system, trade(brand)name " ラ テ system Le E-118B ") 0.5 mass parts, polyxyethylated allyl ethers ammonium sulfate (tensio-active agent, the first industrial pharmacy system, trade(brand)name " ア Network ア ロ Application KH-05 ") 0.1 mass parts, Voranol EP 2001 (tensio-active agent, Kao Corp's system, trade(brand)name " エ マ Le ゲ Application 103 ") 1.0 mass parts, hydrogenated wood rosin glycerol ester again is that bonding imparting agent (physics and chemistry Off ァ イ Application テ Network system, trade(brand)name " リ カ タ ッ Network F-105 ") 2.0 mass parts, terpenes phenol are bonding imparting agent (ヤ ス Ha ラ ケ ミ カ Le Co., Ltd. system, trade(brand)name " YS Port リ エ ス タ ー N-125 ") 0.5 mass parts and deionized water 80 mass parts; At room temperature stir, modulate the emulsification of the mixture of unsaturated monomer in advance.
In addition; In the reaction vessel that is equipped with stirrer, reflux cooler, TM, nitrogen ingress pipe and tap funnel, add deionized water 28 mass parts; Enclose nitrogen, internal temperature is risen to 80 ℃, while keep this temperature to add ammonium persulfate aqueous solution 0.5 mass parts of 10 quality %.
Then, the emulsifying mixture thing of above-mentioned synthetic unsaturated monomer in advance is transferred in the tap funnel, spent splash in 4 hours.Meanwhile splash into 5 quality % ammonium persulfate aqueous solutions, 4 mass parts, under 80 ℃ of internal temperatures, carry out letex polymerization.
After splashing into end,, obtain the acrylic copolymer emulsion 80 ℃ of following slakings 4 hours.Then, be cooled to room temperature, with in the ammoniacal liquor and after, add entry, obtain the aqueous dispersion type contact adhesive composition of solid state component 50 quality %, pH8.0.The median size of the acrylic copolymer in the aqueous dispersion type contact adhesive composition is 270nm.
(2) modulation of aqueous dispersion type pressure sensitive adhesive
With respect to aqueous dispersion type contact adhesive composition 100 mass parts that obtain in above-mentioned (1); Add the emulsion-type rosin ester and be bonding imparting agent (Ha リ マ changes into society's system, trade(brand)name " Ha リ エ ス タ ー SK-816 ") 3.0 mass parts, emulsion-type terpenes phenol and be bonding imparting agent (waste river KCC system, trade(brand)name " タ マ ノ ー Le E-100 ") 5.3 mass parts, and (R is 15 for alkyl, the x+y of the average carbon number 12 that obtains from Oleum Cocois in ラ イ オ Application ア Network ゾ Co., Ltd. system, trade(brand)name " エ ソ ミ Application C/25 ", the formula (1) as the polyoxyethylene alkyl amine of softening agent; HLB value 15.4) 0.6 mass parts; And then add polyacrylic tackifier ianthone ロ ー system ア Application ド ハ ー ス society system, trade(brand)name " ア Network リ ゾ ー Le ASE-60 ") 3.0 mass parts; Make viscosity increase to 8000mPas (BM type viscometer, 25 ℃, 60rpm), obtain the aqueous dispersion type pressure sensitive adhesive.
(3) making of pressure sensitive adhesion sheet
Adding epoxy in aqueous dispersion type pressure sensitive adhesive 100 mass parts that in above-mentioned (2), obtain is linking agent (Na ガ セ ケ system テ ッ Network ス society system, trade(brand)name " デ Na コ ー Le EX-313 ") 0.5 mass parts; With its mixing; With roller cutter coating machine ianthone ロ ー Le Na イ フ コ ー タ ー] be that the condition of 20 μ m is coated on the lift-off processing face of stripping film (リ Application テ ッ Network society system, zellglas, the trade(brand)name " SP-8K ア オ " crossed with the silicone resin lift-off processing) with obtaining mixture according to dried coating thickness; Drying is 2 minutes under 90 ℃, forms pressure sensitive adhesive layer.After the drying; With the polystyrene resin film! オ ー ジ ー Co., Ltd. system, trade(brand)name " Ha イ ス チ レ Application PS65 ", thickness 65 μ m) with releasing sheet on pressure sensitive adhesive layer fit together, process the pressure sensitive adhesion sheet that surface substrate is the releasable of polystyrene resin film.
Likewise; As surface substrate; Use ABS resin film (Port リ マ ー society of SHIN-ETSU HANTOTAI system, trade(brand)name " PSZ980 ", thickness 80 μ m), polycarbonate resin film (Supreme Being people society system, trade(brand)name " ピ ュ ア エ ー ス C-110-100 ", thickness 100 μ m) respectively, contain the hybrid resin of polycarbonate resin-ABS resin film (using the blowing film-making machine that Supreme Being people is changed into the thick film of 100 μ m that the polycarbonate resin-ABS resin based polymer alloy " マ Le チ ロ Application T2711 " of society's system obtains on one side under 240 ℃, make its fusion be extruded into shape on one side), contain the hybrid resin of polycarbonate resin-polystyrene resin film (with polycarbonate resin (" the ノ バ レ ッ Network ス 7027R " of the エ of Mitsubishi Application ジ ニ ア リ Application グ プ ラ ス チ ッ Network ス society system) and polystyrene resin (" G690N " of Japanese PS society system) balanced mix; The thick film of 100 μ m that uses the blowing film-making machine under 260 ℃, to make its fusion be extruded into shape on one side and obtain) replace the polystyrene resin film on one side, make surface substrate and be the releasable of ABS resin film pressure sensitive adhesion sheet, polycarbonate resin film releasable pressure sensitive adhesion sheet, contain polycarbonate resin-ABS resin hybrid resin film releasable pressure sensitive adhesion sheet, contain the pressure sensitive adhesion sheet of releasable of film of the hybrid resin of polycarbonate resin-polystyrene resin.So process 5 kinds of different pressure sensitive adhesion sheets of surface substrate.
(embodiment 2)
Except in (2) of embodiment 1, not adding the emulsion-type rosin ester is that bonding imparting agent and emulsion-type terpenes phenol are the bonding imparting agent, and all the other adopt the method same with embodiment 1, make 5 kinds of different pressure sensitive adhesion sheets of surface substrate.
(embodiment 3)
Except in (1) of embodiment 1, not adding hydrogenated wood rosin glycerol ester is that bonding imparting agent, terpenes phenol are bonding imparting agent and in (2) of embodiment 1, not add the emulsion-type hydrogenated wood rosin glycerol ester be that bonding imparting agent and emulsion-type terpenes phenol are the bonding imparting agent; All the other adopt the method same with embodiment 1, make 5 kinds of different pressure sensitive adhesion sheets of surface substrate.
(embodiment 4)
Except in (1) of embodiment 1, not adding terpenes phenol is bonding imparting agent and in (2) of embodiment 1, not add the emulsion-type rosin ester be that bonding imparting agent and emulsion-type terpenes phenol are the bonding imparting agent; All the other adopt the method same with embodiment 1, make 5 kinds of different pressure sensitive adhesion sheets of surface substrate.
(embodiment 5)
Except in (2) of embodiment 1, not adding emulsion-type terpenes phenol is the bonding imparting agent, and all the other adopt the method same with embodiment 1, make 5 kinds of different pressure sensitive adhesion sheets of surface substrate.
(embodiment 6)
Except in (2) of embodiment 1, not adding the emulsion-type rosin ester is the bonding imparting agent, and all the other adopt the method same with embodiment 1, make 5 kinds of different pressure sensitive adhesion sheets of surface substrate.
(embodiment 7)
Except the use level that in embodiment 1, makes the polyoxyethylene alkyl amine (ラ イ オ Application ア Network ゾ Co., Ltd. system, trade(brand)name " エ ソ ミ Application C/25 ") as softening agent is 0.4 mass parts; All the other adopt the method same with embodiment 1, make 5 kinds of different pressure sensitive adhesion sheets of surface substrate.
(embodiment 8)
Except in embodiment 1; Making the use level of the polyoxyethylene alkyl amine (ラ イ オ Application ア Network ゾ Co., Ltd. system, trade(brand)name " エ ソ ミ Application C/25 ") as softening agent is beyond 0.2 mass parts; All the other adopt the method same with embodiment 1, make 5 kinds of different pressure sensitive adhesion sheets of surface substrate.
(embodiment 9)
(R in ラ イ オ Application ア Network ゾ Co., Ltd. system, trade(brand)name " エ ソ ミ Application O/20 ", the formula (1) is an oil base, and x+y is 10 as the polyoxyethylene alkyl amine of softening agent except in embodiment 1, cooperating 0.6 mass parts.HLB value 12.5) in addition, all the other adopt the method same with embodiment 1, make 5 kinds of different pressure sensitive adhesion sheets of surface substrate.
(embodiment 10)
Except in embodiment 1, will respectively cooperating 0.3 mass parts as polyoxyethylene alkyl amine (ラ イ オ Application ア Network ゾ Co., Ltd. system, trade(brand)name " エ ソ ミ Application C/25 "), the polyoxyethylene alkyl amine (ラ イ オ Application ア Network ゾ Co., Ltd. system, trade(brand)name " エ ソ ミ Application O/20 ") of softening agent; Add up to beyond 0.6 mass parts; All the other adopt the method same with embodiment 1, make 5 kinds of different pressure sensitive adhesion sheets of surface substrate.
(comparative example 1)
In (1) of embodiment 1; Cooperate oxygen vinyl alkyl ether sodium sulfate (tensio-active agent, Kao Corp's system, trade(brand)name " ラ テ system Le E-118B ") 0.9 mass parts, W 166 cresols ether (tensio-active agent, Japanese emulsifying agent society system, trade(brand)name " ニ ュ ー コ ー Le CF-6 ") 0.5 mass parts, Voranol EP 2001 (tensio-active agent, Kao Corp's system, trade(brand)name " エ マ Le ゲ Application 103 ") 0.5 mass parts; Making staybelite is that the use level of bonding imparting agent is 2.5 mass parts; Not adding terpenes phenol is bonding imparting agent; And in (2) of embodiment 1; Mismatch polyoxyethylene alkyl amine, but cooperate Glycerol dimer (Tokyo changes into industry (strain) system, trade(brand)name " ジ グ リ セ ロ ー Le ") 2.0 mass parts and trolamine (Japanese catalyst (strain)) system as softening agent) 2.5 mass parts, in addition; Adopt the method identical, 5 kinds of different pressure sensitive adhesion sheets of making surface substrate with embodiment 1.
The composition of the aqueous dispersion type pressure sensitive adhesive that the pressure sensitive adhesion sheet of embodiment and comparative example uses in its pressure sensitive adhesive layer and the stripping test result of pressure sensitive adhesion sheet are shown in table 1 and table 2.Explain, in table 1 and the table 2, the numerical value of the use level of the gradation composition of expression aqueous dispersion type pressure sensitive adhesive, its unit is a mass parts.
The stripping test of pressure sensitive adhesion sheet is carried out according to the method shown in following and is estimated.
(1) stripping test
As bonded body; Prepare the polystyrene resin film! オ ー ジ ー Co., Ltd. system, trade(brand)name " Ha イ ス チ レ Application PS65 ", thickness 65 μ m), ABS resin film (Port リ マ ー society of SHIN-ETSU HANTOTAI system, trade(brand)name " PSZ980 ", thickness 80 μ m), polycarbonate resin film (Supreme Being people society system, trade(brand)name " ピ ュ ア エ ー ス C-110-100 ", thickness 100 μ m), contain the hybrid resin (PC-ABS resin) of polycarbonate resin-ABS resin film (using the blowing film-making machine that Supreme Being people is changed into the thick film of 100 μ m that the polycarbonate resin-ABS resin based polymer alloy " マ Le チ ロ Application T2711 " of society's system obtains on one side under 240 ℃, make its fusion be extruded into shape on one side), contain these 5 kinds of films of film (with polycarbonate resin (" the ノ バ レ ッ Network ス 7027R " of the エ of Mitsubishi Application ジ ニ ア リ Application グ プ ラ ス チ ッ Network ス society system) and polystyrene resin (" G690N " of Japanese PS society system) balanced mix, the thick film of 100 μ m that obtains on one side use blowing film-making machine one side under 260 ℃, to make its fusion be extruded into shape) of the hybrid resin (PC-PS resin) of polycarbonate resin-polystyrene resin.This film is fixing onboard, process bonded body.
With a kind of resin of surface substrate of its pressure sensitive adhesion sheet and the resin that constitutes bonded body is that the two the combination of identical pressure sensitive adhesion sheet and bonded body is at room temperature fitted; Then; 60 ℃, the environment held of 95%RH 7 days; Return to room temperature then, at room temperature pressure sensitive adhesion sheet is stripped down from bonded body.It is bonding residual whether visual observation has on the surface of the bonded body that pressure sensitive adhesion sheet is stripped from, and estimates according to following benchmark.
◎: on the surface of bonded body, do not have bonding residual.
*: on the surface of bonded body, have bonding residual.
[table 1]
[table 2]
Pressure sensitive adhesion sheet of the present invention can paste on the various bonded bodies such as resin system housing of tame electrical article and electronics.
Claims (4)
1. pressure sensitive adhesion sheet; It comprises surface substrate and the pressure sensitive adhesive layer that is arranged on this surface substrate back side; It is characterized in that; This pressure sensitive adhesive layer is coated with aqueous dispersion type pressure sensitive adhesive and forms; Said aqueous dispersion type pressure sensitive adhesive is to come syntheticly through the amino non-ionics that contains that in the aqueous dispersion type pressure-sensitive-adhesive compsn that contains acrylic copolymer, adds as softening agent, and said acrylic copolymer obtains through 2-EHA and ethene property unsaturated carboxylic acid are carried out letex polymerization.
2. the described pressure sensitive adhesion sheet of claim 1, wherein, surface substrate is made up of the material identical materials with the bonded body of pasting pressure sensitive adhesion sheet.
3. claim 1 or 2 described pressure sensitive adhesion sheets, wherein, surface substrate by polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin, polycarbonate resin, or above-mentioned resin in the mixture more than 2 kinds constitute.
4. each described pressure sensitive adhesion sheet of claim 1～3; Wherein, but acrylic copolymer be 2-EHA and ethene property unsaturated carboxylic acid and then carry out the acrylic copolymer that letex polymerization obtains with other unsaturated monomers of copolymerization as required.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-081410 | 2010-03-31 | ||
| JP2010081410 | 2010-03-31 | ||
| PCT/JP2011/058372 WO2011125918A1 (en) | 2010-03-31 | 2011-03-25 | Adhesive sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102822293A true CN102822293A (en) | 2012-12-12 |
| CN102822293B CN102822293B (en) | 2014-06-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180016497.0A Active CN102822293B (en) | 2010-03-31 | 2011-03-25 | Adhesive sheet |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5925676B2 (en) |
| CN (1) | CN102822293B (en) |
| MY (1) | MY174479A (en) |
| WO (1) | WO2011125918A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104099045A (en) * | 2013-04-09 | 2014-10-15 | 日东电工株式会社 | Adhesive composition and adhesive sheet |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6172502B2 (en) * | 2013-03-15 | 2017-08-02 | Dic株式会社 | Adhesive tape |
| JP6343364B2 (en) * | 2017-04-19 | 2018-06-13 | 日東電工株式会社 | Adhesive composition and adhesive sheet |
| ES2931335T3 (en) * | 2018-04-20 | 2022-12-28 | Basf Se | Gel-containing adhesive composition based on crosslinking by keto or aldehyde groups |
| JP7318408B2 (en) * | 2019-08-09 | 2023-08-01 | 三菱瓦斯化学株式会社 | Adhesive sheet for lamination, multi-layer body, and method for producing multi-layer body |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002221906A (en) * | 2001-01-24 | 2002-08-09 | Lintec Corp | Adhesive label |
-
2011
- 2011-03-25 MY MYPI2012004341A patent/MY174479A/en unknown
- 2011-03-25 JP JP2012509622A patent/JP5925676B2/en active Active
- 2011-03-25 CN CN201180016497.0A patent/CN102822293B/en active Active
- 2011-03-25 WO PCT/JP2011/058372 patent/WO2011125918A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002221906A (en) * | 2001-01-24 | 2002-08-09 | Lintec Corp | Adhesive label |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104099045A (en) * | 2013-04-09 | 2014-10-15 | 日东电工株式会社 | Adhesive composition and adhesive sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2011125918A1 (en) | 2011-10-13 |
| JPWO2011125918A1 (en) | 2013-07-11 |
| CN102822293B (en) | 2014-06-11 |
| JP5925676B2 (en) | 2016-05-25 |
| MY174479A (en) | 2020-04-22 |
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