CN1481428A - Removable adhesive compsns and process for producing same - Google Patents

Removable adhesive compsns and process for producing same Download PDF

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Publication number
CN1481428A
CN1481428A CNA018206905A CN01820690A CN1481428A CN 1481428 A CN1481428 A CN 1481428A CN A018206905 A CNA018206905 A CN A018206905A CN 01820690 A CN01820690 A CN 01820690A CN 1481428 A CN1481428 A CN 1481428A
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Prior art keywords
water
weight unit
base resin
adhesive compositions
resin
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CNA018206905A
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CN1269930C (en
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堀薰夫
幸
宇都伸幸
明
佐藤千明
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Kaken Tech Co Ltd
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Kaken Tech Co Ltd
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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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/412—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of microspheres

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Removable adhesive compositions which upon water absorption undergo a decrease in adhesive strength (an adhesive composition removable with water and an adhesive composition removable with water in combination with heat). The removable adhesive compositions comprise 100 parts by weight of a base adhesive resin such as a hot-melt resin or thermosetting resin, 1 to 200 parts by weight of a water-absorbing crosslinked polymer, 1 to 300 parts by weight of heat-expandable particles, and 0.001 to 20 parts by weight of a surfactant.

Description

Removable adhesive compositions and manufacture method thereof
Technical field
What the present invention relates to is about after absorb water back or the suction/heating, the removable adhesive compositions that clinging power can descend (containing seal gum), particularly about the employed removable adhesive compositions of the structure that is bonded by plural component parts, though it brought into play certain adhesion strength before suction is handled, but after suction or suction/heating back clinging power can reduce rapidly, and can be at an easy rate and isolating removable adhesive compositions of original component parts and manufacture method thereof.
Background technology
In recent years, owing to formulated the method for utilizing again,, when requiring every component parts can separate, reclaim, can also distinguish again and utilize for the tectosome that engages by adhesive compositions.Wish that also adhesive compositions after finishing the label that is attached on the body material, indicating the application target of film or shielded film etc., can easily peel off.
But the bonding basic constituent of prior art is a purpose with adhere each component parts, powerful adhesive label of brute force only, give the separation of each component parts and under the situation of not damaging body material peeling label etc. bring difficulty.
At this, the spy opens to have invented among the flat 5-173487 and formed the adhesive label that the propylene of being furnished with water absorbent polymer is a binder layer on the heat-shrinkable thin slice.But disclosed adhesive label must use the heat-shrinkable plate as body material, its constitute not only complexity and also cost very high.In addition, water-absorbing polymer is using the high tackiness agent of cohesive force separately, and for example, during tackiness agents such as segmented copolymer or Resins, epoxy, its separability then can be insufficient.
In addition, open the spy and disclosedly among the flat 11-217548 peel off possible adhesion thin slice again.Specifically be made of body material and the binder layer that forms on this body material, this binder layer is a tackiness agent with respect to the propylene of 100 weight unit, is furnished with the polyolefine saccharoid in the value range of 1～25 weight unit.But this type of is peeled off possible adhesion again and signs through after between longer-term, still has the difficulty that can not simply easily peel off with body material.
In addition, because the polyolefine saccharoid is that to be difficult to blending dispersion in the tackiness agent even at propylene, thus when adding the polyolefine saccharoid, must the strict addition of controlling the polyolefine saccharoid, the bad problem of its initial stage clinging power also can appear simultaneously.
The disclosed method of peeling off from the matrix of binding, paste or paint thing with sheet of peeling off that is to use of Te Kaiping 7-118580 communique.Say that this peels off with thin slice is to be made of body material and the binder layer that is formed by anaerobies tackiness agent or anaerobies tackiness agent that forms on this body material matrix.After this peels off and is affixed on the surface of binding, paste or paint thing with thin slice,, peel off from binding etc. by the curing of binder layer.But, after between longer-term, also have and be difficult to the problem peeled off from matrix equably.In addition, in stripping process, owing to needing attaching to peel off and making it the solidified operation, so need long time with thin slice.
Therefore, the spy opens in the flat 11-92728 communique and to propose to use the removable adhesive compositions that adds the water-soluble filler in 0.1～200 weight unit value range in the matrix resin of the tackiness agent of 100 weight unit.This removable adhesive compositions can easily be peeled off at short notice, and, when the Hotmelt Adhesive that uses as the matrix resin of tackiness agent, because its viscosity height if do not add the water-soluble filler of more amount, then is difficult to make its homodisperse.
On the other hand, the spy open clear 56-61467 number, spy open clear 56-61468 number, spy open clear 60-252681 number, spy open clear 63-17981 number, spy open flat 6-33025 number, spy open flat 6-184504 number, spy open flat 11-228921 number, the spy opens 2000-868994 number and the spy opens in the 2000-239620 communique, discloses the heat-releasable tackiness agent that adds the thermal expansivity particle of institute in quantitative in tackiness agent that is formed by acrylic resin etc. or light-cured resin.But these heat-releasable tackiness agents only consider that heating peels off, and reckon without and utilize the combination of water-absorbent crosslinked polymer and thermal expansivity particle to quicken the problem of peeling rate.
At this, the present invention is quantitative water-absorbent crosslinked polymer and even thermal expansivity particle by adding, even invented and used as the Hotmelt Adhesive of the base resin of tackiness agent etc., it is uniformly dispersed, and the adhesive compositions that can peel off at short notice.
Even promptly the object of the present invention is to provide a kind of water-absorbent crosslinked polymer of interpolation more amount, also can make its blending dispersion in the base resin of various tackiness agents even, and before suction, has very strong clinging power, the adhesive compositions that can peel off at short notice after the suction and manufacture method thereof.
Another object of the present invention is to provide a kind of, make removable adhesive compositions and the manufacture method thereof that to peel off (natural separation) after its suction/heating naturally by thermal expansivity particle and water-absorbent crosslinked high molecular being used in combination.
Summary of the invention
The removable adhesive compositions that provides a kind of back clinging power that absorbs water to reduce, also can address the above problem, it contains the interior water-absorbent crosslinked polymer of scope of 1～200 weight unit with respect to the base resin of the tackiness agent of 100 weight unit.
That is to say, the base resin of tackiness agent and institute be the interior water-absorbent crosslinked high molecular combination of scope and the removable adhesive compositions that generates quantitatively, under the condition of structural member (component parts and another structural member) that is used to adhere, the water-absorbent crosslinked polymer in back that is soaked in water suitably expands, make the clinging power between each component parts descend rapidly, and can carry out Separation and Recovery with each component parts.
In addition, be added on the water-absorbent crosslinked high molecular words in this value range, can guarantee that it can mix by homodisperse in the base resin of tackiness agent.
Said " the suction back " that clinging power is reduced is meant, in water (also containing ethanol or tensio-active agent etc. sometimes, as follows), warm water (40 ℃～below 70 ℃) or hot water (also comprise pressurized conditions 70～150 ℃) etc., soak and make the state of the mandatory suction of water-absorbent crosslinked polymer.But, do not comprise the state after water-absorbent crosslinked polymer absorbs airborne moisture.
In addition, in the formation of removable adhesive compositions of the present invention, when water-absorbent crosslinked polymer was the particle shape, its median size was in the value range of 1～300 μ m; When above-mentioned water-absorbent crosslinked polymer was fibrous, its average fiber length was good in the value range of 2～60mm.
Long by the water-absorbent crosslinked high molecular median size or the average fiber that limit in this value range, can be so that water-absorbent crosslinked polymer disperses in the base resin of tackiness agent more uniformly.And, have the long water-absorbent crosslinked high molecular words of such median size or average fiber, the generation of problems such as the skewness of the clinging power before can preventing from effectively to absorb water or reduction.
In addition, in the formation of removable adhesive compositions of the present invention, above-mentioned water-absorbent crosslinked high molecular water absorbent rate is to be good in 5～1,000 times the value range.
Limited the water-absorbent crosslinked polymer of water absorbent rate like this,, also can reach the effect that suction back clinging power descends even add on a small quantity.
In addition, in the formation of removable adhesive compositions of the present invention, above-mentioned water-absorbent crosslinked polymer is the crosslinked body of the hydrolyzed solution of starch-acrylonitrile grafting polymkeric substance, the crosslinked body of the corrective of starch-acrylic acid-grafted polymkeric substance, the saponified crosslinked body of vinyl-acetic ester-acrylate copolymer, the crosslinked body of the hydrolyzed solution of propylene shin multipolymer, the crosslinked body of the hydrolyzed solution of allylamine multipolymer, the crosslinked body of polyacrylic part corrective, the cross-linking polyvinyl alcohol sex change thing that contains carboxyl, iso-butylene-Maleic Acid, Anhydrous multipolymer, the polyoxyethylene cross-linking agent, at least a in the cross-linked polyurethane sex change thing is good.
Even it is a small amount of that the water-absorbent crosslinked polymer of these kinds adds, also can reach the effect that suction back clinging power descends.
Even it is a small amount of that the water-absorbent crosslinked polymer of these kinds adds, it is uniformly dispersed in the base resin of tackiness agent.
In addition, in the formation of removable adhesive compositions of the present invention,, be good with the tensio-active agent that contains 0.001～20 weight unit with respect to the base resin of the tackiness agent of above-mentioned 100 weight unit.
The addition of the tensio-active agent in this value range not only can make the clinging power after the suction descend more effectively, and can it be peeled off naturally according to its addition.
In addition, in the formation of removable adhesive compositions of the present invention, the base resin of above-mentioned tackiness agent is a rubber resin, and with respect to the base resin of this tackiness agent of 100 weight unit, is good with the adhesion additives of the value range that contains 1～800 weight unit.
Use the base resin and the adhesion additives of tackiness agent like this, initial stage adhesion strength height and the significantly reduced removable adhesive compositions of suction back clinging power can be provided.
In addition, in the formation of removable adhesive compositions of the present invention, the base resin of above-mentioned tackiness agent is good with hot-melt resin.
Use hot-melt resin like this as the base resin of tackiness agent, for example, SBS segmented copolymer or SIS segmented copolymer etc., the base resin of tackiness agent and water-absorbent crosslinked high molecular blending dispersion then can be more even.
That is to say,, just can adjust its viscosity by heating because hot-melt resin do not use solvent, thus can the water-absorbent crosslinked polymer of deterioration, it is uniformly dispersed.
In addition, in the formation of removable adhesive compositions of the present invention, the base resin of above-mentioned tackiness agent is good with heat-curing resin.
Use heat-curing resin like this, because the intensity of force of can adhering at the raising initial stage, and can bring into play its good mechanical characteristics or thermotolerance, use with tackiness agent so can be used as structure.
In addition, in the formation of removable adhesive compositions of the present invention,, be good with the thermal expansivity particle of the value range that contains 1～300 weight unit again with respect to the base resin of the tackiness agent of 100 weight unit.
The combination of water-absorbent crosslinked like this polymer and thermal expansivity particle, when using hot water or steam, when can make water-absorbent crosslinked macromolecule water uptake, the thermal expansivity particle also expands, so can peel off from bur at short notice.And,, it is peeled off naturally according to the change of its addition.
Another kind of sample attitude of the present invention, i.e. the manufacture method of the removable adhesive compositions that descends for suction back clinging power is to contain
The operation of the base resin of the tackiness agent under the modulation molten state,
With median size in the value range that with respect to the base resin of this tackiness agent of 100 weight unit, adds 1～200 weight unit be that water-absorbent crosslinked polymer in 1～800 mu m range or average fiber length are water-absorbent crosslinked polymer or the water-absorbent crosslinked high molecular dry blending operation of the blended of the two in 2～60mm scope
Manufacture method for the removable adhesive compositions of feature.
Use like this to be the removable adhesive compositions that the tackiness agent under the molten state is made, in the base resin of tackiness agent, also can make the water-absorbent crosslinked polymer can homodisperse even without solvent.Therefore, can obtain before the suction strong clinging power being arranged, the water-absorbent crosslinked polymer appropriateness in suction back expands the effective removable adhesive compositions that clinging power descends rapidly simultaneously.
In addition, another kind of sample attitude of the present invention, i.e. the manufacture method of the removable adhesive compositions that descends for suction back clinging power is to contain
Preparation is as the operation of the heat-curing resin of the base resin of tackiness agent,
With the water-absorbent crosslinked high molecular operation in the value range that with respect to the base resin of this tackiness agent of 100 weight unit, adds 1～200 weight unit be the manufacture method of the removable adhesive compositions of feature.
Use heat-curing resin to make removable adhesive compositions like this, in the base resin of tackiness agent, also can be even without solvent so that water-absorbent crosslinked polymer can homodisperse.Therefore, can obtain before the suction extremely strong clinging power being arranged, the water-absorbent crosslinked polymer appropriateness in suction back expands the effective exfoliated bonding utmost point constituent that clinging power descends rapidly simultaneously.
In addition, when implementing the manufacture method of exfoliated bonding utmost point constituent of the present invention,, be good with the operation of the thermal expansivity particle in the value range that adds 1～300 weight unit again with respect to the base resin of the above-mentioned bonding utmost point of 100 weight unit.
Such enforcement can obtain under the situation of using hot water or steam etc., the effective removable adhesive compositions that just can peel off from adherend in the extremely short time.
Description of drawings
Shown in Figure 1 is the example that influences that is caused by water-absorbent crosslinked high molecular addition.
The variation example of the clinging power that shown in Figure 2 is causes with respect to the difference of suction condition.
Shown in Figure 3 is the example that influences that is caused by the addition of thermal expansion particle.
Shown in Figure 4 is the sectional drawing of forming heat of the present invention and using the film like tackiness agent of removable adhesive compositions.
Embodiment
[the 1st example]
The 1st example of the present invention is the removable adhesive compositions that contains following (A)～(D) composition (following also have claim water removable adhesive compositions in).Wherein, composition (A) and (B) is essential, (C) and composition (D) be optional one.(A) basic resin of tackiness agent: the water-absorbent crosslinked polymer of 100 weight unit (B): 1～200 weight unit (C) adhesion additives: 1～800 weight unit (D) tensio-active agent: the base resin of 0.001～20 weight unit 1, tackiness agent
The base resin of tackiness agent used in the present invention can use Hotmelt Adhesive, solvent based tackiness agent, light solidified tackiness agent, a liquid type Thermocurable tackiness agent, binary liquid shape Thermocurable tackiness agent, pressure-sensitive adhesive etc.
For example, Hotmelt Adhesive, agent solvent based tackiness agent is arranged, perhaps pressure-sensitive adhesive can be following various resin: (methyl) acrylic polymer, polyvinyl chloride (PVC) RESINS, polyurethane, the rhodia resin, ethylene vinyl acetate copolymer, vinylite, olefine kind resin, polyvinyl acetal resin, the polyvinyl alcohol inductor, silicone resin, natural rubber, acrylic rubber, neoprene (diene) rubber, paracril, divinyl rubber, isoprene-isobutylene rubber, vinyl cyanide one divinyl rubber (NBR), ethylene vinyl acetate copolymer (EVA) resin, styrene-butadiene-styrene (SBS) block polymer, styrene-isoprene-phenylethene (SIS) block polymer, styrene-ethylene-butylene-styrene (SEBS) block polymer, vibrin, phenoxy resin, thio resin etc.
In addition, light solidified tackiness agent or hot setting adhesive can have following various tackiness agent: Resins, epoxy, oxetane resin, active acrylic resin (SGA), silicone resin, polyurethanes resin, polyester resin, cyano-acrylate binder, phenolic tackiness agent, trimeric cyanamide one aldehydes tackiness agent, urine aldehydes tackiness agent etc.
Particularly when using Resins, epoxy, with as the bisphenol A type epoxy resin of host or alicyclic epoxy resin etc. with as common uses such as the polyamine of solidifying agent or imidazoles to good.
In addition, when using active acrylic resin, be good with the mixture of use Acrylic Acid Monomer and free radical generating agent and as solidifying agent with the mixture that uses Acrylic Acid Monomer and reductive agent as host.2. water-absorbent crosslinked polymer (1) kind
If water-absorbent crosslinked polymer is to make particle or the fiber etc. of absorbent resin by linking agent reaction gained, though its kind is not defined, but as the basic resin of absorbent resin, it is good also being to use following resin: starch based resin, polyacrylic acid resinoid, polyvinyl alcohol resin, polyacrylamide resinoid, polyoxymethylene resinoid.
Therefore, as said water-absorbent crosslinked resin is from unsaturated charcoal acid---for example, choose at least a monomer composition in vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, fumaric acid, butenoic acid, methylene-succinic acid, beta-hydroxy vinylformic acid, beta-hydroxy propylene propionic acid and the corrective thereof, and make this monomer composition and linking agent polymerization and.
Said linking agent is preferably the following a kind of or combination more than two kinds: i) diacrylate ethylene glycol (methyl) ester, two sense spring acrylate (dimethacrylates
Binaryglycol ester), triglycol two (methyl) acrylate, N, the two (first of N '-methylene
Base) contains vinyl unsaturated group more than 2 in the molecule of acrylamide etc.
Compound; Ii) ethylene glycol, glycol ether, glycerol, propylene glycol, 1,4-butyleneglycol, polypropylene glycol etc.
Multivalence ethanol; Iii) ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, glycerine three epoxies third
The polyglycidyl ether of ether etc.; The iv) halogen epoxide of epichlorohydrin, α-ethyl glycol etc.; The v) polyacetals of glutaraldehyde, oxalic dialdehyde etc.; Vi) polyamine class such as 1; Vii) polyvalent isocyanate compound, multivalence epoxy compounds, multivalence aziridine cpd.
The usage quantity of linking agent should be taken into account that water-absorbent crosslinked high molecular water regain decides, for example, with respect to monomer composition 100 molecular fractions, the usage quantity of this linking agent is preferably in the value range of 0.005～2 molecular fraction, but is preferably in the scope of 0.01～1 molecular fraction.
In addition, if do not use linking agent, should obtain water-absorbent crosslinked polymer by adding linking agent and making it reaction then earlier with uncrosslinked absorbent resin polymerization.
Therefore, suitable cross-linked polymer is as follows: the linking agent of the hydrolyzed solution of the linking agent of the linking agent of the hydrolyzed solution of starch-acrylonitrile grafting polymkeric substance, the corrective of starch-acrylic acid-grafted polymkeric substance, the saponified linking agent of vinyl-acetic ester-acrylate copolymer, propylene shin multipolymer, the linking agent of the hydrolyzed solution of allylamine multipolymer, polyacrylic part corrective linking agent, the cross-linking polyvinyl alcohol sex change thing that contains carboxyl, iso-butylene-Maleic Acid, Anhydrous multipolymer, polyoxyethylene cross-linking agent, cross-linked polyurethane sex change thing etc.
These water-absorbent crosslinked polymers, because its good water-absorbent, so can prevent the reduction of initial stage clinging power effectively adding under more a spot of situation.(2) water absorbent rate
The water absorbent rate of water-absorbing resin is advisable in 000 times the value range 5～1.Reason is, when 5 times of water absorbent rate less thaies, the reduction of the back clinging power that just may absorb water is insufficient, or needs to add a large amount of absorbent resin; But the water absorbent rate of absorbent resin is excessive, just may make adhesive compositions before suction moisture on every side be blotted, and adds in the base resin that advances tackiness agent, just may cause the reduction of initial stage clinging power.Therefore, the water absorbent rate of absorbent resin is good to enclose in 10～500 times value range, but is preferably in 50～300 times the value range.
In addition, the mensuration of the water absorbent rate of absorbent resin is that water-absorbing resin be impregnated in the competent water, measures according to the volume increase ratio of gained behind the 24 Xiao Time.(3) median size and average fiber are long
Water-absorbent crosslinked high molecular median size is in the value range of 0.1～800 μ m.Reason is, if water-absorbent crosslinked high molecular median size then is difficult to it is uniformly dispersed less than 0.1 μ m, perhaps causes clinging power after the suction inadequate problem that descends easily; And water-absorbent crosslinked high molecular median size also is difficult to make it to be uniformly dispersed in the base resin of tackiness agent greater than 800 μ m, perhaps causes the decline of initial stage clinging power.Therefore, water-absorbent crosslinked high molecular median size is to be good in the value range of 0.5～500 μ m, and its optimum value is in the scope of 10～100 μ m.
In addition, water-absorbent crosslinked high molecular average fiber length should be in the value range of 2～60mm.Reason is, if water-absorbent crosslinked high molecular average fiber is long just to be difficult to it is uniformly dispersed less than 2mm, perhaps causes the clinging power after the suction to descend insufficient easily; And the long 60mm that surpasses of water-absorbent crosslinked high molecular average fiber also is difficult to make it to be uniformly dispersed in the base resin of tackiness agent, perhaps causes the decline of initial stage clinging power.Therefore, water-absorbent crosslinked high molecular average fiber length is to be good in the value range of 3～50mm, and its optimum value is in the scope of 5～40mm.
In addition, water-absorbent crosslinked high molecular median size or average fiber length are the numerical value according to the photograph actual measurement of electron microscope, calculate its mean value and.
But water-absorbent crosslinked high molecular shape is not limited to particle shape or fibrous, and polygon, mixing irregularly shaped and different shape all can.(4) addition
Water-absorbent crosslinked high molecular addition is in weight unit, promptly with respect to the base resin of the adhesive meter of 100 weight unit, should add the water-absorbent crosslinked polymer of 1～200 weight unit value range.
Its reason is, water-absorbent crosslinked high molecular addition less than 1 weight unit just causes the clinging power after the suction to descend insufficient easily; And water-absorbent crosslinked high molecular addition surpasses 200 weight unit, just easily causes the decline of initial stage clinging power, and is difficult to make it to be uniformly dispersed in the base resin of tackiness agent.
Therefore, water-absorbent crosslinked high molecular addition, with respect to the base resin of the tackiness agent of 100 weight unit, with in the value range that adds 10～100 weight unit for good, its optimum value is in the scope of 20～80 weight unit.
With reference to Fig. 1 the influence of water-absorbent crosslinked high molecular addition to clinging power is described at this.Among Fig. 1, shown in the transverse axis is that shown in the longitudinal axis is the value of clinging power (MPa) with respect to water-absorbent crosslinked high molecular addition (weight unit) value of the base resin of the tackiness agent of 100 weight unit.Shown in the line A is not contain among the embodiment 1 under the situation of prescription of tensio-active agent, the initial stage clinging power of measuring along with the variation of water-absorbent crosslinked high molecular addition, and shown in the line A ' is the clinging power of soaking in warm water (60 ℃) after 6 hours.Shown in the line B is to contain among the embodiment 1 under the situation of prescription of a certain amount of tensio-active agent, the initial stage clinging power of measuring along with the variation of water-absorbent crosslinked high molecular addition, and shown in the line B ' is the clinging power of soaking in hot water (60 ℃) after 6 hours.
Change curve by Fig. 1 can be clear and definite, water-absorbent crosslinked high molecular addition is not influence (line A and B) basically concerning the initial stage clinging power, and when water-absorbent crosslinked high molecular addition surpasses 25 weight unit, the clinging power of dipping after the 6 hours tangible reduction of having compared with the initial stage clinging power in warm water (60 ℃) respectively, the degree of its reduction is more obvious with the line B ' that contains tensio-active agent.
Therefore, form for containing to some extent quantitatively the tackiness agent of tensio-active agent, water-absorbent crosslinked high molecular addition just can make the clinging power after the suction fully reduce when the value of 10 weight unit is above.Form for the tackiness agent that does not contain tensio-active agent, water-absorbent crosslinked high molecular addition can make the clinging power after the suction fully reduce when the value of 30 weight unit is above.
The change curve of clinging power shown in Figure 1 except the kind of the base resin of tackiness agent, also can change according to the kind difference of water-absorbent crosslinked polymer or adhesion additives etc.(5) surface treatment
When in the base resin of tackiness agent, adding water-absorbent crosslinked polymer, earlier with the base resin heat fused for well.But, easily cause water-absorbent crosslinked high molecular thermolysis and aggegation during heat fused, and make water-absorbent crosslinked polymer be difficult to disperse equably.At this, should earlier water-absorbent crosslinked polymer be carried out surface treatment, to improve its thermotolerance and blending dispersion.
Specifically,, carry out that coupler is handled or add inorganic particles, metal plating, metal-plated gas, inorganics plating gas, also or use than the high polymer open covering of water-absorbent crosslinked high molecular glass transition point on water-absorbent crosslinked high molecular surface.(6) other
In the water-absorbent crosslinked polymer, only otherwise break away from purpose scope of the present invention, also can add one or two or more kinds combination of following each agent, for example, thixotropic agent, viscosity adjustment agent, plasticizer, tinting material, pigment, anti-marquis's agent, UV light absorber, variable color prevent agent, antioxidant, inorganic particulate, carbon granule, carbon fiber bar, electroconductive particle, extender, sanitas, antiseptic-germicide, sterilant etc.
Particularly, can improve water-absorbent crosslinked high molecular thermotolerance by adding antioxidant, inorganic particulate, carbon granule, carbon fiber bar, electroconductive particle etc.That is to say,, also can prevent the water-absorbent crosslinked high molecular thermolysis and the aggegation that cause because of heating effectively even in the heated base resin that is under the melted state, add.3. adhesion additives (1) kind
The interpolation of adhesion additives is in order to improve the initial stage clinging power, and reduces the clinging power after the suction effectively.In addition, the interpolation by the adhesion additives can make when water-absorbent crosslinked polymer is added in the base resin, brings into play the effect of its dispersion agent.
The kind of said adhesion additives should be taken into account that the characteristic that is descended by the clinging power after the suction decides, specifically can be by a kind of of following each resin or the combination more than two kinds: aliphatics through-stone oleo-resinous, aromatic series through-stone oleo-resinous, aliphatics aromatic series copolymerization through-stone oleo-resinous, alicyclic ring family hydrogenated petroleum resin, alkyl phenol resin, xylene resin, coumarone-benzene fused ring acrylic resin, the card olefine resin, card alkene resol, aromatic series sex change card olefine resin, hydrogenation card olefine resin, the rosin series resin, hydrogenation rosin series resin, disproportionation rosin is a resin, dimerisation rosin series resin, esterified rosin is a resin etc.
In these adhesion additives, be good particularly to use aliphatics through-stone oleo-resinous or aromatic series through-stone oleo-resinous.Its reason is, by using the adhesion additives, reduces effectively even add the clinging power that can also make on a small quantity after the suction, and because its cost is lower, so economy comparatively.(2) addition
The addition of adhesion additives is in weight unit, in the base resin of the adhesion meter of promptly per 100 weight unit, should add the value range of 1～800 weight unit.
Its reason is, addition less than 1 weight unit of adhesion additives then causes the decline of the clinging power after the suction insufficient easily; And the addition of adhesion additives surpasses 800 weight unit, then is difficult to make it to be uniformly dispersed in the base resin of tackiness agent, and the creep resistance of the tackiness agent of gained is descended.
Therefore, the addition of adhesion additives, with respect to the base resin of the tackiness agent of 100 weight unit, with in the value range that adds 5～500 weight unit for good, its optimum value is in the scope of 30～300 weight unit.4. tensio-active agent (1) kind
Tensio-active agent is applicable to and can absorbs water rapidly so that the situation that clinging power descends, the not special restriction of its kind, for example, aniorfic surfactant, cationic surfactant, non-corpuscular type tensio-active agent, polymeric surface active agent all can.
It specifically can be the combination of following one or two or more kinds, for example, lipid acid, fatty acid ester, polyoxyethylene fatty acid ester, sorbitan fatty acid esters, Sorbitol Powder fatty acid ester, sorbitan lipid acid ether-ether, Sorbitol Powder lipid acid ether-ether, glycerol fatty acid ester, sucrose fatty ester etc.
Particularly when various ester below the use, also can impel the clinging power after the suction to reduce rapidly even add amount seldom, also can prevent simultaneously the reduction of initial stage clinging power effectively, for example, polyethylene glycol glycerol monostearate, ten tristearins, Sorbitol Powder monostearin, Sorbitol Powder monolaurin, sorbitan monostearin, sorbitan monolaurin, sucrose distearate, sucrose Stearic diglyceride etc.(2) addition
The addition of tensio-active agent is in weight unit, promptly in the base resin with respect to the adhesion meter of 100 weight unit, should add the value range of 0.001～20 weight unit.
Its reason is that addition less than 0.001 weight range of surfactivity meter then can't be found its additive effect, even after the adhesive compositions suction, the decline of its clinging power can be inabundant yet; And the addition of tensio-active agent surpasses 20 weight unit, then is difficult to make it to be uniformly dispersed in the base resin of tackiness agent, perhaps can cause the initial stage clinging power to descend.
Therefore, the addition of tensio-active agent, with respect to the base resin of the tackiness agent of 100 weight unit, with in the value range that adds 0.5～10 weight unit for good, its optimum value is in the scope of 1～5 weight unit.5. additive (1) water soluble filler
In the base resin of tackiness agent, with above-mentioned water-absorbent crosslinked polymer, it is good adding water soluble filler.Like this, the clinging power after the suction then can more effectively reduce.
This type of water soluble filler can be one or two or more kinds combination of inorganic salts, chelating class, polyose, urea numerical value, sodium bicarbonate etc.In addition, when adding this water soluble filler, its addition is with the tackiness agent basis resin of per 100 weight unit, and the value range that adds 5～50 weight unit is good.(2) coupler
In the base resin of tackiness agent, from the group who forms by silane coupling agent, aluminium coupler, titanium coupling agent, to select at least a coupler to be added to suitable.Its reason is, if added this coupler, in impregnated in water before, for airborne moisture, can prevent the decline of its clinging power; And after in being immersed in water, also do not hinder the rapid reduction of clinging power.
This coupler specifically can be γ-An Bingjisanyiyangjiguiwan, γ-Huan Yangbingyangbingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane, gamma-aminopropyl-triethoxy-aluminium, γ-aminopropyl trimethoxy titanium etc.
When adding coupler, the addition of this coupler is in the base resin of the tackiness agent of per 100 weight unit, should add the value range of 0.1～20 weight unit, but be good with the value range of 0.5～10 weight unit, its optimum value is in the scope of 1～5 weight unit.(3) organic solvent
When using fluid binder, should suitably add organic solvent.
Such organic solvent can be the combination of following one or two or more kinds, and for example, methyl-ethyl ketone, methyl-isobutyl ketone, first are stupid, ether, ethyl acetate, tetrahydrofuran (THF), N, N '-N,N-DIMETHYLACETAMIDE, methyl alcohol, 1-butanols etc.(4) other
In the base resin of tackiness agent, under the situation that does not break away from purpose of the present invention, can add with make an addition to water-absorbent crosslinked polymer in identical following one or two or more kinds the additive of combination of additive, for example, thixotropic agent, viscosity adjustment agent, plasticizer, tinting material, pigment, anti-marquis's agent, variable color prevent agent, solidifying agent, antioxidant, inorganic particulate, carbon granule, carbon fiber bar, electroconductive particle etc.6. manufacture method
Do not limit though the manufacture method of water removable adhesive compositions is special,, be good to comprise following operation.
(A) the base resin operation of the tackiness agent of modulation melted state
(B) for the base resin of the tackiness agent of 100 weight unit, with add 1～
The median size of 200 weight unit value ranges is the water-absorbent crosslinked of 1～800 μ m
Polymer and average fiber length be 2～60mm water-absorbent crosslinked polymer or
Any one water-absorbent crosslinked high molecular dry blending operation of person.(1) the base resin operation of the tackiness agent of modulation melted state
This operation is the base resin of heated adhesive and the operation that makes it to be melted state.Therefore, as the base resin of tackiness agent,, be good with the thermoplastic resin that uses SIS segmented copolymer or SBS segmented copolymer etc. in order can more easily to handle.
But, even when using heat-curing resin, or use the potentiality curing adhesive or use the binary liquid shape tackiness agent that forms by host and solidifying agent, all can easily modulate the base resin of the tackiness agent of melted state.
For example, using when being the epoxy adhesive of the Thermocurable that forms of solidifying agent, only heat bisphenol a resin and make it thawing, for dry blending operation described later is prepared by bisphenol a resin and amine, for amine is solidifying agent, with in the middle of the dry blending operation or be added to good afterwards.(2) dry blending operation mixture ratio
Tackiness agent basis resin with respect to per 100 weight unit melted states, water-absorbent crosslinked high molecular mixture ratio is advisable in the value range of 1～200 weight unit, if the words in the value range of 10～100 weight unit then can be better, its optimum value is in the scope of 20～80 weight unit.
Its reason is, if water-absorbent crosslinked high molecular mixture ratio is discontented 1 weight unit, though its blending dispersion ratio is easier to, the water removable adhesive compositions of gained is after suction, and the reduction meeting of its clinging power is insufficient; And water-absorbent crosslinked high molecular addition surpasses 200 weight unit, then causes the uneven state of blending dispersion easily.Mixing temperature
Temperature when water-absorbent crosslinked polymer is mixed in the base resin of tackiness agent is good in 100～250 ℃ value range with the base resin temperature of tackiness agent.Its reason is, its mixing temperature is not under 100 ℃ situation, and water-absorbent crosslinked high molecular blending dispersion is not easy evenly; And mixing temperature is when surpassing 250 ℃, and water-absorbent crosslinked polymer is easier to be decomposed and aggegation takes place.
Therefore, if the words of water-absorbent crosslinked high molecular mixing temperature in 120～200 ℃ value range can be better, its optimum value is in 150～180 ℃ value range.Hybrid machine
Water-absorbent crosslinked polymer is in sneaking into the base resin of tackiness agent the time, for employed machine, there is no particular limitation, for example, round tube type mixing machine, two double wall pyramid type mixing machines, high-speed stirring formula mixing machine, V-shape mixing machine, ribbon blender, spirrillum mixing machine, flow rotary bench-type mixing machine, air-flowing type mixing machine, twayblade mixing machine, internal mixer, crushing type blade mixing machine, rotary type mixing machine, spirrillum extrusion machine etc. all can.Organic solvent
When water-absorbent crosslinked polymer mixes in the base resin of bonder, do not expand, do not use aqueous solvent, be advisable with dry blending in order to make water-absorbent crosslinked polymer.But, in the inexcessive expansible scope of water-absorbent crosslinked polymer, be good to use organic solvent.7. using method (1) coating method
When using water removable adhesive compositions of the present invention to adhere component parts, with known tackiness agent coating method, for example, roller coating machine, shaft-like coating machine, bristle are smeared, scraper is smeared etc. all can.
When the exfoliated bonder constituent of water is a solution class tackiness agent or a liquid type tackiness agent, use divider to be advisable; Be the occasion of hot-melt adhesive, use applicator to be advisable.
In order to make the water removable adhesive compositions that its clinging power is descended, and when its clinging power was not reduced, promptly the initial stage clinging power strengthened, should be at the applicator surface place of tackiness agent, give earlier with the coupler processing that feels secure.(2) form
For water removable adhesive compositions of the present invention, there is no particular limitation for its form, for example can be hot melt build tackiness agent, film like tackiness agent, Solvent Adhesive, spray-type tackiness agent etc.In addition, can also layers on substrates folded use adhesive tape, shielding tape (being coated with the application adhesive tape), shielded film, locating adhesive tape, coating with adhesive tape, engineering with adhesive tape etc.At this moment, should use polyester film, polyvinyl chloride film, polypropylene film, fluorine resin film etc. as base material, and form the bonding coat that thickness is 10～500 μ m thereon.(3) stripping conditions 1
The stripping conditions of water removable adhesive compositions when peeling off, as long as the words of the condition of suction back clinging power decline are arranged, and other particular determination arranged, for example, 10～150 ℃ water (also comprises the hot water under the pressurized conditions, as follows) the middle immersion 10 minutes～24 hours, perhaps took a shower 10 minutes～24 hours with 10～150 ℃ water.Its reason is, fixed suction conditioned disjunction shower condition, water, warm water or hot water are got final product, and fixed absorbent time or shower time can be decomposed effectively with adherend and be as the criterion.But, descend in order to make clinging power more apace, in water, should add ethanol class or tensio-active agent (also comprising dispersion agent or clean-out system etc.), its ratio is that to add 0.1～20 weight unit in the water with per 100 weight unit be good.On the other hand, use liquid as peeling off, except that using above-mentioned water, warm water or hot water, the words that add the inert liq of fluorine class or silicone more also can.
Illustrate that with reference to Fig. 2 the asynchronous clinging power of suction condition changes at this.As tackiness agent, to prepare according to the composition shown in the embodiment 3, shown curve is respectively places after institute fixes time the variation of its clinging power under the situation of according to condition 25 ℃ * 80%RH, water (25 ℃), 60 ℃ of warm water, 90 ℃ of hot water.As we can see from the figure, when not absorbing water basically (25 ℃ * 80%RH), along with the variation of time, the variation of its clinging power does not have substantially; And after soaking in pyritous warm water or hot water, the decline of clinging power is more remarkable.Therefore, by the adjusting of water temperature, can set required splitting time.(4) stripping conditions 2
When the water removable adhesive compositions is peeled off, be suitable for pressurization.Reason is can reduce clinging power rapidly so that the water-absorbent crosslinked polymer in the water removable adhesive compositions absorbs water more hastily by pressurization.Therefore, specifically, pressure on every side should be at 0～1MPa (in about 1～10atm) the value range, if (words in about 1～5atm) the value range are then better, and its optimum value is enclosed 0.1～0.3MPa (in about 1～3atm) the value range at 0～0.5MPa.[second example]
Removable adhesive compositions in second example of the present invention (below be also referred to as heat and use removable adhesive compositions) contains the composition of following (A)～(E), its feature is enclosed the base resin for (A) tackiness agent, has added (B) water-absorbent crosslinked polymer and (E) thermal expansivity particle.Therefore, the heat of second example and with in the removable adhesive compositions, (A), (B) and (E) composition be essential, (C) enclose any composition with (D) composition.
In addition, the same for the composition content of (A)～(D) with the content of first example, omit in this explanation.(A) base resin of tackiness agent: the water-absorbent crosslinked polymer of 100 weight unit (B): 1～200 weight unit (C) adhesion additives: 1～800 weight unit (D) tensio-active agent: 0.001～20 weight unit (E) thermal expansivity particle: the kind of 1～300 weight unit, 1. thermal expansivity particles
The thermal expansivity particle is good to use by heating the particle shape that can increase volume, for example, by inferior Ethylene Dichloride-acrylonitrile compolymer resin, vinyl-acetic ester-acrylonitrile compolymer resin, methyl methacrylate-acrylonitrile compolymer resin, acrylonitrile resin, resol, Resins, epoxy etc. one or two or more kinds constitute shell, portion is surrounded by the gas or the liquid of foamable within it.
The median size of thermal expansivity particle should be in the value range of 1～300 μ m.Reason is if that the median size of said thermal expansivity particle just might reduce the separability of bonding agent less than 1 μ m; And if the median size of said thermal expansivity particle is that it is difficult to mix in the base resin of bonding agent just greater than 300 μ m easily.Therefore, the median size of thermal expansivity particle with in the value range of 3～200 μ m for better, its optimum value is in the value range of 5～150 μ m.The median size of the such a small ball of hollow can use the portrait treatment unit to calculate according to the photo of opticmicroscope.2. the addition of thermal expansivity particle
The addition of thermal expansivity particle is in weight unit, promptly in the base resin with respect to the tackiness agent of 100 weight unit, should add the value range of 1～300 weight unit, its reason is, if the addition of thermal expansivity particle is the words of less than 1 weight unit, then can't bring into play its additive effect, make the separability of tackiness agent reduce; And the addition of thermal expansivity particle surpasses 300 weight unit, and the separability of tackiness agent is reduced, and it is inhomogeneous simultaneously it to be disperseed in the base resin of tackiness agent.Therefore, the addition of thermal expansivity particle, with respect to the base resin of the tackiness agent of 100 weight unit, with in the value range that adds 10～150 weight unit for better, its optimum value is in the scope of 30～100 weight unit.
The addition of thermal expansivity particle should consider that stripping conditions described later decides.For example, in order to be adjusted to when the heat treated of carrying out more than 105 ℃, the also state that can not peel off naturally, its addition in the value range of 1～40 weight unit, be advisable (with respect to the base resin of the tackiness agent of 100 weight unit); And require to be adjusted to when the heat treated of carrying out more than 120 ℃ the also state that can not peel off naturally, its addition in the value range of 1～30 weight unit, be advisable (with respect to the base resin of the tackiness agent of 100 weight unit).
On the one hand, if want the words under the state of temperature more than the 105 ℃ heat treated 15～30 minutes, the addition of thermal expansivity particle it peeled off naturally, so should be adjusted in the value range of 45～100 weight unit and be advisable (with respect to the base resin of the tackiness agent of 100 weight unit); If want in heat treated under the state of temperature more than 105 ℃ 15 minutes, it is peeled off naturally, and the addition of thermal expansivity particle should be adjusted in the value range of 100～300 weight unit and be advisable (with respect to the base resin of the tackiness agent of 100 weight unit).
With reference to Fig. 3 the influence of the addition of thermal expansivity particle to clinging power is described at this.Among Fig. 3, transverse axis is the addition of the thermal expansivity particle with respect to the base resin of the tackiness agent of 100 weight unit, shown in the left side axle of the longitudinal axis is for the adhesive compositions among the embodiment 14, along with the variation of the addition of thermal expansivity particle and the natural splitting time of measuring (impregnated under the situation in 90 ℃ the warm water), shown in the right figure is initial stage clinging power (MPa).As can be seen from Figure 3, the addition of thermal expansivity particle is that the initial stage clinging power does not have influence substantially, and the addition of thermal expansivity particle surpasses 20 weight unit, and the time of peeling off naturally then can significantly shorten.Therefore, as an example, the addition of thermal expansivity particle is above if surpass 25 weight unit, and natural splitting time (when impregnated in 90 ℃ the hot water) just can foreshorten in 10 hours.
The change curve of the natural splitting time among Fig. 3, except the kind of the base resin of tackiness agent changed, the kind of water-absorbent crosslinked polymer etc. changes leaf can be influenced.3. using method (1) coating method and influence thereof
For the heat of second example and with the coating method or shape of removable adhesive compositions for, also can be identical in the content of first example, also can change heat as shown in Figure 4 and use the form of removable adhesive compositions in the fixed scope.
At this, shown in Fig. 4 (a) is to comprise film to form the heat of resin and use removable adhesive compositions, simultaneously should heat and with the thickness of adhesive compositions in the scope of 10～200 a μ m interior example extremely.Shown in Fig. 4 (b) is on the heat and single side face (the B side among the figure) with removable adhesive compositions (following first adhesive coating that also claims) of film like, is provided with by not containing organic class thermal expansivity particle and water-absorbent crosslinked polymer or comparing with first adhesive coating to contain the adhesive coating (following second adhesive coating that also claims) that a spot of organic class thermal expansivity particle and water-absorbent crosslinked high molecular Thermocurable tackiness agent composition form.
Shown in Fig. 4 (c) is two pieces of heat and between with removable adhesive compositions (first adhesive coating), is provided with by not containing organic class thermal expansivity particle and water-absorbent crosslinked polymer or comparing with first adhesive coating to contain the adhesive coating (following the 3rd adhesive coating that also claims) that a spot of organic class thermal expansivity particle and water-absorbent crosslinked high molecular Thermocurable tackiness agent composition form.(2) stripping conditions
Said stripping conditions can be identical with the content of form shown in first, still, with additional heating condition---use hot water to compare, this example has used the thermal expansivity particle, and its peeling rate then can be rapider.Therefore, base resin with respect to the tackiness agent of 100 weight unit, for example, when having added the thermal expansivity particle of 1～40 weight unit, single words with the heating of the temperature more than 105 ℃ can prevent that then nature from peeling off, and by heating and use the immersion of 70～150 ℃ hot water, just can peel off naturally with interior in 12 hours.In addition, if when adding the quantitative tensio-active agent of institute again, single words with the heating of the temperature more than 105 ℃ also can not peeled off naturally, and by using the immersion of 70～150 ℃ hot water, just can peel off naturally with interior in 5 hours.4. manufacture method
Heat does not also have special qualification with the manufacture method of removable adhesive compositions, is good but comprise following operation.(A) prepare as the operation (B) of the heat-curing resin of the base resin of tackiness agent base resin, add water-absorbent crosslinked high molecular operation (C) in 1～200 weight unit scope and add the operation that the operation (1) of the thermal expansivity particle in 1～300 weight unit scope is prepared heat-curing resin with respect to the tackiness agent of 100 weight unit
Preparing heat-curing resin, for example at random in the operation of Resins, epoxy in order not make clinging power, the suitable fully degassing.In addition, in order to adjust the viscosity of heat-curing resin, should add reactive thinner or solvent, at this moment, the viscosity of heat-curing resin is adapted at 100～100, in the value range of 000mPas (measuring temperature at 25 ℃).In the stage of preparing heat-curing resin, should add various particles or additives such as fiber or antioxidant, tinting material.(2) add water-absorbent crosslinked high molecular operation
This operation is in the heat-curing resin as the base resin of tackiness agent, evenly adds quantitative water-absorbent crosslinked high molecular operation.When using heat-curing resin, because viscosity ratio is lower, the base resin of heated adhesive and make it to be molten state after, water-absorbent crosslinked polymer needn't carry out dry blending, is added to afterwards but in advance water-absorbent crosslinked polymer is diluted to the solvent state.(3) operation of interpolation thermal expansivity particle
This operation is in the heat-curing resin as the base resin of tackiness agent, evenly add the operation of quantitative thermal expansivity particle.When adding the thermal expansivity particle, can not foam in adding the way in order to make the thermal expansivity particle, so should make the envrionment temperature when adding be lower than blowing temperature, be good more than 10 ℃ to be lower than blowing temperature.
Embodiment
Followingly describe the present invention more in detail with reference to embodiment.But said embodiment not delimit the scope of the invention.The making of [embodiment 1] (1) water removable adhesive compositions
In temperature remains on 180 ℃ molten-bath, fill 100 weight unit as the SIS segmented copolymer of base resin and the phenolic antioxidant of 0.2 weight unit, stirred 3 hours with planetary stirring machine, make it uniform fusion.Then, be KI gel 201K-F2 (KURARE Co., Ltd. system that the cross-linked isobutylene-Maleic Acid, Anhydrous multipolymer of hydrogenated petroleum resin, 35 weight unit forms according to the C5 of 30 weight unit respectively, its averaged particles directly is 15 μ m, water absorbent rate is 200 times), 7 weight unit as the polyethylene glycol glycerol monostearate (HLB:15.7) of tensio-active agent, the whiteruss as plasticizer of 5 weight unit (burning-point: 256 ℃, density: 0.865g/cm 3) ratio contain in the molten-bath.Stirred 1 hour with planetary stirring machine again, behind the various compositions of affirmation uniform mixing fusion, just become the water removable adhesive compositions of embodiment 1.A1 shown in the table 1 is the SIS segmented copolymer that uses in embodiment 1, and what B1 represented is water-absorbent crosslinked polymer, and (C5 is a hydrogenated petroleum resin, softening temperature: 100 ℃, molecular-weight average: 650), what D1 represented is tensio-active agent to C1 for the adhesion additives.(2) the initial stage clinging power evaluation i of water removable adhesive compositions)
Use hot melt to use applicator at 180 ℃, 0.98MPa (10kgf/cm 2) condition under, go up the adhesive compositions of applied thickness at aluminium sheet (thick 1.5mm, long 100mm, wide 25mm) for about 1mm.And another piece aluminium sheet (overlapping area: 12.5 * 25mm of stacked thereon placement 2), kept 24 hours down in the normal temperature state, and make style (measuring number=5).Then, according to JISK6850 (test method of the tensile shear adhesion strength of tackiness agent), use tensile testing machine draw speed as 20mm/ minute condition under, measure initial stage clinging power (tensile shear adhesion strength).Clinging power 1 after ii) absorbing water
Flood sample (measure number=5) in the water at normal temperatures 6 hours, after 12 hours, with measure the identical method of initial stage clinging power, the clinging power of Ce Dinging respectively.Back clinging power 2 iii) absorbs water
In 60 ℃ warm water, flood sample (measure number=5) 3 hours, after 6 hours, with measure the identical method of initial stage clinging power, the clinging power of Ce Dinging respectively.[embodiment 2～5]
As shown in table 1, what embodiment 2 was discussed is the influence of the usage quantity of the tensio-active agent in reducing embodiment 1, embodiment 3 is discussed be with embodiment 1 in the influence of employed water-absorbent crosslinked polymer, the adhesion additives usage quantity different with tensio-active agent, what embodiment 4 was discussed is the influence of the kind of the tensio-active agent among the change embodiment 3, and what embodiment 5 was discussed is respectively the influence when not using adhesion additives or tensio-active agent of embodiment 1.
Can see among the embodiment 2, decline being arranged by table 1, so though the initial stage clinging power has had enhancing, the decline of the clinging power after suction tendency has then diminished owing to compare the usage quantity of employed tensio-active agent with embodiment 1.Among the embodiment 3, owing to compare with embodiment 1, increased water-absorbent crosslinked high molecular usage quantity, reduced the usage quantity of adhesion additives or tensio-active agent simultaneously, so when having strengthened the initial stage clinging power, the decline of the clinging power after suction tendency also becomes bigger.Among the embodiment 4, owing to changed the kind of the tensio-active agent among the embodiment 3, so compare with embodiment 3, though its initial stage clinging power has reduction slightly, the decline of the clinging power after the suction then can be more remarkable.In addition, owing to do not use the tensio-active agent of the prescription of embodiment 1, so its initial stage clinging power has increase slightly than embodiment 1, but the decline of the clinging power after the suction then can become not obvious among the embodiment 5.[comparative example 1]
As shown in table 1, discussed in the comparative example 1 for embodiment 1, when not using adhesion additives or tensio-active agent, also do not use under the situation of water-absorbent crosslinked polymer etc. the variation of the clinging power after its suction.From the result of table 1, owing to do not add water-absorbent crosslinked polymer etc., between the clinging power after its initial stage clinging power and the suction, there is not significant gap in the comparative example 1.[comparative example 2]
As shown in table 1, discussed in the comparative example 2 for embodiment 1, do not add water-absorbent crosslinked polymer, and when reducing the usage quantity of adhesion additives, the variation of the clinging power after its suction.From the result of table 1, owing to do not add suction type cross-linked polymer etc., between the clinging power after its initial stage clinging power and the suction, there is not significant difference in the comparative example 2.Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1 Comparative example 2
Prescription Base resin ??A1 ??100 ?A1 ?100 ??A1 ??100 ??A1 ??100 ??A1 ??100 ??A1 ??100 ??A1 ??100
Water-absorbent crosslinked polymer ??B1 ??35 ?B1 ?35 ??B1 ??50 ??B1 ??50 ??B1 ??25 ??0 ??0
The adhesion additives ??C1 ??30 ?C1 ?30 ??C1 ??20 ??C1 ??20 ??0 ??0 ??C1 ??13
Tensio-active agent ??D1 ??7 ?D1 ?5 ??D1 ??3 ??D2 ??3 ??0 ??0 ??D2 ??5
Liquid paraffin ??5 ?5 ??0 ??0 ??0 ??0 ??0
Antioxidant ??0.2 ?0.2 ??0.2 ??0.2 ??0.2 ??0.2 ??0.2
Estimate The initial stage clinging power ??0.41 ?0.66 ??0.70 ??0.63 ??0.54 ??0.38 ??0.49
Water logging bubble 6Hrs ??0.17 ?0.31 ??0.17 ??0.43 ??0.51 ??0.34 ??0.47
Water logging bubble 12Hrs Peel off ?0.12 ??0.23 ??0.09 ??0.45 ??0.28 ??0.54
Warm water soaking 3Hrs ??0.36 ?0.39 ??0.18 ??0.33 ??0.47 ??0.35 ??0.47
Warm water soaking 6Hrs ??0.23 ?0.17 ??0.11 ??0.33 ??0.43 ??0.33 ??0.43
* the water-absorbent crosslinked polymer of base resin: A1 (SIS segmented copolymer) *: B1 (cross-linked isobutylene-Maleic Acid, Anhydrous multipolymer) * additives: C1 (C5 is a hydrogenated petroleum resin) * tensio-active agent: the D1 (polyethylene glycol glycerol monostearate) that adheres
D2 (10-tristearin) the * unit of filling a prescription: weight unit * clinging power unit: MPa (=N/mm 2) structure of [embodiment 6] (1) water removable adhesive compositions
Present embodiment discuss the time water removable adhesive compositions in, under the condition of the adhesion additives that added more amount, to the influence of water-absorbent crosslinked high molecular median size.That is to say, in temperature remains on 180 ℃ molten-bath, after the phenolic aldehyde as the SIS segmented copolymer of base resin and 0.2 weight unit that fills 30 weight unit is antioxidant, stirred 3 hours, make its fusion equably with the planet stirrer.Then, be that (averaged particles directly is 30 μ m for the water-absorbent crosslinked high molecular K201-F2 of conduct of hydrogenated petroleum resin, 21 weight unit according to the C5 of 50 weight unit respectively, water absorbent rate is 200 times, represent with B2 in the table 2), the whiteruss as plasticizer of 5 weight unit (burning-point: 256 ℃, density: 0.865g/cm 3) ratio contain in the molten-bath.Right Hou was stirred 1 hour with planetary stirring machine again, behind each composition of affirmation uniform mixing fusion, just became the water removable adhesive compositions of embodiment 6.(2) evaluation of water removable adhesive compositions
Similarly to Example 1, measure and estimate the clinging power (suction back clinging power 1 and suction back clinging power 2) of dipping after 6 hours in water or warm water (60 ℃) respectively.Consequently, because the addition of adhesion additives is more, dipping is after 6 hours in water, and the decline of clinging power is not remarkable; Dipping is after 6 hours in warm water (60 ℃), and its clinging power is 1/3 of initial stage clinging power approximately.[embodiment 7～11]
As shown in table 2, size and addition except water-absorbent crosslinked high molecular kind, averaged particles among the embodiment 7～11 have the change, all equally with embodiment 6 make the water removable adhesive compositions and are estimated.
Consequently, in embodiment 7, dipping is after 6 hours in water, and the decline of its clinging power is not remarkable, and dipping is after 6 hours in warm water (60 ℃), and its clinging power disappears substantially.In addition, among the embodiment 8, dipping is after 6 hours in water, and the decline of its clinging power is not remarkable, and dipping is after 6 hours in hot water (60 ℃), and its clinging power also disappears substantially.Among the embodiment 9, dipping is after 6 hours in water, and the decline of its clinging power is not remarkable, and dipping is after 6 hours in hot water (60 ℃), and its clinging power disappears substantially.But, in embodiment 9,, follow the fashion so its initial stage clinging power also has to reduce owing to used the bigger water-absorbent crosslinked polymer of median size.Among embodiment 10 and the embodiment 11, dipping is after 6 hours in water respectively, and the decline of its clinging power is not remarkable, and dipping is after 6 hours in hot water (60 ℃), and its clinging power disappears substantially.[comparative example 3]
As shown in table 2, in comparative example 3, in embodiment 6, do not add the water-absorbent crosslinked polymer, other are made adhesive compositions similarly to Example 6 and are estimated.Its result is, owing to do not add water-absorbent crosslinked polymer etc. in the comparative example 3, so impregnated in water and the warm water after 6 hours the not obvious table 2 of the reduction of its clinging power
Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Comparative example 3
Prescription Base resin ??A1 ??30 ??A1 ??30 ??A1 ??30 ??A1 ??30 ??A1 ??30 ??A1 ??30 ??A1 ??30
Water-absorbent crosslinked polymer ??B2 ??21 ??B2 ??57 ??B3 ??57 ??B4 ??57 ??B5 ??57 ??B6 ??57 ??0
The agent of adhesion additives ??C1 ??50 ??C1 ??50 ??C1 ??50 ??C1 ??50 ??C1 ??50 ??C1 ??50 ??C1 ??50
Whiteruss ??5 ??5 ??5 ??5 ??5 ??5 ??5
The antioxidant drug ??0.2 ??0.2 ??0.2 ??0.2 ??0.2 ??0.2 ??0.2
Estimate The initial stage clinging power ??1.10 ??1.10 ??1.03 ??0.48 ??1.10 ??0.96 ??0.78
Water logging bubble 6Hrs ??1.10 ??1.10 ??1.06 ??0.45 ??1.10 ??0.91 ??1.04
Warm water soaking 6Hrs ??0.33 ??0.00 ??0.15 ??0.06 ??0.00 ??0.00 ??1.00
* the water-absorbent crosslinked polymer of base resin: A1 (SIS segmented copolymer) *:
B2: cross-linked isobutylene-Maleic Acid, Anhydrous multipolymer, median size 30 μ m
B3: cross-linked isobutylene-Maleic Acid, Anhydrous multipolymer, median size 150 μ m
B4: cross-linked isobutylene-Maleic Acid, Anhydrous multipolymer, median size 1400 μ m
B5: polyacrylate is polymer, median size 30 μ m
B6: polyacrylate is polymer, median size 150 μ m* adhesion additives: C1 (C5 is a hydrogenated petroleum resin) the * unit of filling a prescription: weight unit * clinging power unit: MPa (=N/mm 2) [embodiment 12]
With the water removable adhesive compositions of embodiment 1 gained from the hot melt applicator with 180 ℃, 0.98MPa (10kgf/cm 2) condition smear, and the sieve aperture of using in screen printing (polyamine system, 30cmm * 30cm) and gabion (aluminum) adhesion are fixing.Under this state,, do not find the phenomenon that sieve aperture is peeled off from gabion though screen printing has been implemented 5,000 times yet.Then, if soaked 10 minutes in 60 ℃ hot water, gabion then can separate in sieve aperture very naturally.Therefore, present embodiment so neither exist there is not combustion bad temper problem in health effects yet, and the overburden operation of the sieve aperture behind the screen printing is simply quick owing to use organic solvent.But under the situation of existing use hot-melt adhesive, need in methyl-ethyl ketone of 60 ℃, soak after 1 hour, scrape with scraper again, easily cause damage gabion.[embodiment 13]
With the water removable adhesive compositions of embodiment 1 gained from the hot melt applicator with 180 ℃, 0.98MPa (10kgf/cm 2) condition open and smear, and fixing with the thermal insulation material (hard polyurethane rubber) and metal basket (japanning aluminum) adhesion that are used on the refrigerator.Assemble refrigerator (surrounding temperature is under 60 ℃ the condition) with this understanding, though long run test 50,000 hours, do not find the phenomenon that thermal insulation material is peeled off from the metal basket yet.Then, after decomposing refrigerator and taking out the parts that are made of thermal insulation material and metal basket, with 95 ℃ hot water injection 10 minutes, the metal basket then can separate with metallic substance very naturally to the bonding part.Therefore, present embodiment can make insulating material separate from the metal basket quickly and easily.In addition, for the metal basket, owing to can not produce damage, so can directly utilize again.But under the situation of using existing tackiness agent, need scrape, can cause damage like this metal basket with scraper.[embodiment 14] (1) heat is also used the manufacturing of removable adhesive compositions
What the present invention's example was discussed is the kind of the base resin of tackiness agent.That is to say, after in container, adding this microsphere of pine F-30D (Matsumoto Yushi-Seiyaku Co., Ltd.'s system) of Resins, epoxy 828 (japan epoxy resin Co., Ltd. system), 75gKI gel 201K-F2 (KURARE of Co., Ltd. system) and 25g of 100g respectively as the thermal expansivity particle, stirred 1 hour with stirrer, each composition can be mixed.Then, add the Epomate B002 as solidifying agent (japan epoxy resin Co., Ltd. system) of 50g, and then stirred 5 minutes, just become the heat of present embodiment and use removable adhesive compositions.(2) heat is also used the evaluation of removable adhesive compositions
Similarly to Example 1, make measure test portion after, when measuring the initial stage clinging power, respectively the mensuration test portion of placement in hot water (90 ℃) and process furnace (105 ℃, 120 ℃) is measured its natural splitting time.Its result is as shown in table 3, has obtained high value---7.5MPa as the initial stage clinging power.On the other hand, it is carried out heat treated 12 hours with interior, peel off very difficult naturally; And use hot water, it is peeled off naturally.[embodiment 15～20]
As shown in table 3, embodiment 15～20 discussed the initial stage clinging power, concerning with hot water and process furnace in natural splitting time the influence of addition of thermal expansion particle, the influence of the kind of absorbent resin, the influence of the kind of thermohardening type resin (active acrylic resin), the additive effect of tensio-active agent and coupler etc.In the table 3, * symbol meaning suction/heating condition is placed the state that also can not peel off naturally after 12 hours down.Consequently, if the addition of thermal expansion type particle is 40 weight unit, it is strong and only in the heat of using hot-water soak 12 hours can peel off naturally under with interior condition and with exfoliated bonding agent constituent then can to obtain the initial stage clinging power.In addition, even the kind of change absorbent resin or heat-curing resin, and under the condition that above-mentioned heating is established, make it nature and peel off at need, only also can obtain in the heat of using hot-water soak 12 hours to peel off naturally under with interior condition also with exfoliated bonding agent constituent.Also have,, peel off at need, also can obtain using hot water and soaking the heat that just can peel off naturally under with interior condition in 3 hours also with exfoliated bonding agent constituent even under the condition of above-mentioned heat treated, make it nature owing to added tensio-active agent.Table 3
Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18 Embodiment 19 Embodiment 20
Prescription Base resin ??A2 ??100 ?A2 ?100 ??A2 ??100 ??A2 ??100 ??A2 ??100 ??A4 ??100 ??A4 ??100
Solidifying agent ??A3 ??50 ?A3 ?50 ??A3 ??50 ??A3 ??50 ??A3 ??50 ??A5 ??100 ??A5 ??100
Water-absorbent crosslinked polymer ??B2 ??75 ?B5 ?75 ??B5 ??75 ??B5 ??75 ??B5 ??75 ??B2 ??75 ??B5 ??75
The thermal expansivity particle ??C1 ??25 ?C1 ?25 ??C1 ??25 ??C1 ??25 ??C1 ??50 ??C1 ??25 ??C1 ??50
Tensio-active agent ??0 ?0 ??D1 ??6 ??0 ??0 ??0 ??0
Coupler ??0 ?0 ??0 ??5 ??0 ??0 ??0
Estimate The initial stage clinging power ??7.5 ?7.5 ??5.8 ??7.5 ??7.3 ??26.1 ??26.5
Hot water (90 ℃) soaks ??10Hrs ?9Hrs ??3Hrs ??9Hrs ??3min ??9Hrs ??3min
105 ℃ of heating ??× ?× ??× ??× ??30min ??× ??30min
120 ℃ of heating ??× ?× ??× ??× ??15min ??× ??15min
* base resin: A1 (SIS segmented copolymer), A2 (epikote828), A3 (epometeB002), A4 (Hard LockC-320-K-03A), the water-absorbent crosslinked polymer of A5 (HardLockC-320-K-03B) *
B2: cross-linked isobutylene-Maleic Acid, Anhydrous multipolymer, median size 30 μ m
B5: polyacrylic acid hydrogen is polymer, the median size 30 μ m* unit of filling a prescription: weight unit * clinging power unit: MPa (=N/mm 2)
Utilization on the industry
As mentioned above, the exfoliated bonding agent constituent of water of the present invention, because it contains the water-absorbent crosslinked macromolecule of deciding to some extent in the value range in the base resin of adhesive, and contain the surfactant of deciding to some extent in the value range, thus its initial stage adhesion intensity of force in same as the prior art, and even after in water or warm water hot water, soaking, make water-absorbent crosslinked polymer water uptake expansion, just separate from adherend at an easy rate, for example, glass and appurtenances thereof etc.
In addition, heat of the present invention is also with in the exfoliated bonding agent constituent, owing to be to contain respectively hydroscopicity cross-linked polymer and the thermal expansion type particle of deciding to some extent in the value range in the bonding agent in heat cure, so it has stronger initial stage adhesion strength, on the other hand, even in the situation that the heat treated of carrying out about 120 ℃ also can not peeled off naturally, as long as use hot water so that water-absorbent crosslinked macromolecule water uptake, the thermal expansion of thermal expansion type particle, then can naturally peel off with interior in 12 hours.
Each component parts of the container of the cosmetics containers that exfoliated bonding agent constituent of the present invention is applicable to reclaim, drug container, fragrant container, beverage product container, flavoring container, accommodating articles, air container, liquid crystal storage receptacle (comprising the LCD plate), circuit board storage receptacle (basket that comprises electronic unit) etc. is bonded into required clad vessel.
Removable adhesive compositions of the present invention, because its adhesion strength of expectation can reduce, thus the suitable adhesive of using as the fixed grit of screen printing, the tentative position in the semiconductor device carrying with adhesive, shielding tape with adhesive, prevent loosened screw with adhesive, wallpaper with adhesive, decorating film (shielded film) with adhesive, fixing glass with adhesive, fixing metal with adhesive, fixedly magnetite with adhesive, ceramic tile with adhesive, fixedly timber uses with adhesive etc. with adhesive, the toy of adhering with adhesive, connection fiber optics with adhesive, bound book.
For removable adhesive compositions of the present invention, consider to lead the interpolation of the kind of base resin and inorganic particulate etc., can also use as moulding resin, for example, semiconductor sealing resin, electronic isolation type resin, circuit board form with resin etc.
In addition, the manufacture method of exfoliated bonding agent constituent of the present invention, owing to be in the base resin of bonding agent, to contain hydroscopicity cross-linked polymer and the thermal expansivity particle of deciding to some extent in the value range, and so that water-absorbent crosslinked macromolecule and thermal expansivity particle can Uniform Dispersion mixes, so the reduction of the adhesion strength after its suction is very remarkable effectively.

Claims (12)

1. exfoliated bonding agent constituent that the back clinging power that absorbs water reduces, it is with respect to the base resin of the bonding agent of 100 weight unit, and the water-absorbent crosslinked polymer that contains in the scope of 1～200 weight unit is the separability bonding agent constituent of feature.
2. separability adhesive compositions according to claim 1 is characterized in that, when above-mentioned water-absorbent crosslinked polymer was the particle shape, its median size was in the value range of 1～800 μ m; When above-mentioned water-absorbent crosslinked polymer was fibrous, its average fiber length was in the value range of 2～60mm.
3. according to claim 1 or 2 described removable adhesive compositions, it is characterized in that above-mentioned water-absorbent crosslinked high molecular water absorbent rate is in 5～1,000 times the value range.
4. according to any described glass adhesive compositions of claim 1～3, it is characterized in that above-mentioned water-absorbent crosslinked polymer is the crosslinked body of the hydrolyzed solution of starch-acrylonitrile grafting polymkeric substance, the crosslinked body of the corrective of starch-acrylic acid-grafted polymkeric substance, the saponified crosslinked body of vinyl-acetic ester-acrylate copolymer, the crosslinked body of the hydrolyzed solution of propylene shin multipolymer, the crosslinked body of the hydrolyzed solution of allylamine multipolymer, the crosslinked body of polyacrylic part corrective, the cross-linking polyvinyl alcohol sex change thing that contains carboxyl, iso-butylene-Maleic Acid, Anhydrous multipolymer, the polyoxyethylene cross-linking agent, at least a in the cross-linked polyurethane sex change thing.
5. according to any described glass adhesive compositions of claim 1～4, it is characterized in that,, contain the tensio-active agent of 0.001～20 weight unit with respect to the base resin of the tackiness agent of above-mentioned 100 weight unit.
6. according to any described glass adhesive compositions of claim 1～5, it is characterized in that, the base resin of above-mentioned tackiness agent is a rubber resin, and, contain the adhesion additives of the value range of 1～800 weight unit with respect to the base resin of this tackiness agent of 100 weight unit.
7. according to any described glass adhesive compositions of claim 1～6, it is characterized in that the base resin of above-mentioned tackiness agent is a hot-melt resin.
8. according to any described glass adhesive compositions of claim 1～5, it is characterized in that the base resin of above-mentioned tackiness agent is a heat-curing resin.
9. according to any described glass adhesive compositions of claim 1～8, it is characterized in that,, contain the thermal expansivity particle of the value range of 1～300 weight unit with respect to the base resin of the tackiness agent of 100 weight unit.
10. the manufacture method of a separability adhesive compositions is the manufacture method of the removable adhesive compositions that clinging power can descend after the suction, contains
The operation of the base resin of the tackiness agent under the modulation molten state,
With base resin, add median size in the value range of 1～200 weight unit and be suction type cross-linked polymer in 1～800 mu m range or average fiber length and be water-absorbent crosslinked polymer or the water-absorbent crosslinked high molecular dry blending operation of the blended of the two in 2～60mm scope with respect to the heat adhesive of 100 weight unit.
11. the manufacture method of a removable adhesive compositions is the manufacture method of the separability adhesive compositions that clinging power can descend after the suction, contains
Preparation is as the operation of the heat-curing resin of the base resin of tackiness agent,
With base resin, add the water-absorbent crosslinked high molecular operation in the value range of 1～200 weight unit with respect to the heat adhesive of 100 weight unit.
12. manufacture method according to claim 10 or 11 described removable adhesive compositions, it is characterized in that, with respect to the base resin of the above-mentioned tackiness agent of 100 weight unit, the operation of adding the thermal expansion type particle in the value range of 1～300 weight unit again is.
CNB018206905A 2001-01-10 2001-09-28 Removable adhesive compsns and process for producing same Expired - Fee Related CN1269930C (en)

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