CN1153195A - Adhesive sheet with foamed substrate - Google Patents
Adhesive sheet with foamed substrate Download PDFInfo
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- CN1153195A CN1153195A CN 96121125 CN96121125A CN1153195A CN 1153195 A CN1153195 A CN 1153195A CN 96121125 CN96121125 CN 96121125 CN 96121125 A CN96121125 A CN 96121125A CN 1153195 A CN1153195 A CN 1153195A
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Abstract
An adhesive sheet with a foamed substrate, comprising a substrate comprising a foamed elastomer having specific properties, and a layer of a pressure-sensitive adhesive formed on the substrate. Due to use of the substrate having specific properties, the adhesive sheet has excellent adhesive properties to rough surfaces and also has excellent oil resistant adhesive properties.
Description
The present invention relates to sheet shape, the band shape, or the like adhesive sheet, it has foamed substrate, has one deck pressure sensitive adhesive on foam substrate.
Every kind of sheet shape with foamed substrate, band shape, etc. adhesive sheet form by on base material, forming one deck pressure sensitive adhesive, and base material is by for example foaming such as the polyethylene preparation of isoprene-isobutylene rubber, chloroprene rubber, synthetic resins, and said adhesive sheet is widely used in wall, brick, top ceiling etc. that mirror, hook, famous brand etc. are fixed on buildings are for example gone up or instrument surperficial first-class.Said adhesive sheet also be used to decoration for example ornament, sign, spolier etc. be fixed to body of a motor car, for example as said in No. the 5334447th, United States Patent (USP).
According to the difference of adhesive sheet,, can obtain strong bounding force and cement strength by disperseing or loose being applied to by external stress or vibration on the adhesive sheet fixed object by foam substrate with foam substrate.Resiliency by said base material can also press sticking expansion down to having the not advantage of the bonding zone of the adherend of plane surface.
In recent years, with regard to the wall of buildings, more glad use has a non-planar surface the material of construction of shape and wallpaper (cloth) and is unwilling to use material of construction and the wallpaper (cloth) with smooth-flat-surface.Also have,, becoming main trend because the glossiness mirror board of the improvement of levelling technology is modified, but depending on the circumstances, may relate to foreign material and on coated surface, need to form protuberance at coating step with regard to body of a motor car.
Yet, use isoprene-isobutylene rubber, chloroprene rubber or synthetic rubber insensitive to compressive set as the general adhesive sheet of base material, thus when compression or even when adhesive sheet is vulnerable to compressive set, also can not get sufficient bond area and guarantee the bond area that reaches initial, the stress relaxation effect of the foam substrate of these adhesive sheets is very poor, therefore since the event of unrelieved stress they the part can occur and get loose.So, can be fallen by these adhesive sheet fixed objects sometimes for above-mentioned reasons.
So, an object of the present invention is under above-mentioned habitual situation, to provide a kind of uneven surface had the improved fusible sheet adhesive that has foamed substrate.
Every kind of adhesive sheet with foamed substrate often is exposed in the harsh environment for use, particularly is exposed in the oil.For example in following situation: object is being sticked with glue after sheet adheres on the equipment, gluing segment is that coating applies by machine oil bespatter or this part by solvent.Also have; when the sheet adhesive with foamed substrate is used to the side ornament of fixed car; following situation occurs: when refueling, the gasoline that overflows can be attached to kerosene that the place of being fixed and degreasing fluid for example be used to remove the protection wax of protecting the new cars coating plate can following and be attached to the place that is fixed.
Yet, in the sheet adhesive of this class, because the side of the event foam layer of its structure is easy to be seen through by oil.When the automobile that has fixed sidepiece ornament was exposed in such environment over a long time, usually the liquid that can penetrate was transferred to adhesive layer and is reduced the force of cohesion of tackiness agent, and the binding property of adhesive layer is reduced widely.Also have, because the stress concentration that swelling produced by the foams oil suction is in the edge section of adhesive layer, adhesive layer is partly thrown off and the falling of the object that is fixed suddenly sometimes in some cases.
Therefore, yes is restricted for the environment for use of this class sheet adhesive.
Another object of the present invention provides a kind of sheet adhesive of using that has foamed substrate under such environment, it has improved oil resistant binding property and by the structure of improving foam substrate user's mask is had less resistance system.
Because result to the various researchs of first above-mentioned purpose, have now found that: the foaming elastomer that has specific compression load value and stress relaxation rate by use forms one deck pressure sensitive adhesive as base material and on this base material, can obtain uneven surface is had the sheet adhesive that has foamed substrate of remarkable tackiness.Find to have finished the present invention based on this.
First kind of embodiment of the present invention be sheet shape, band shape, or the like the sheet adhesive of band foamed substrate, it comprise one deck by have 23 ℃ down 25% stress under compressiones be 0.6-3.0kgf/cm
2Be formed on pressure sensitive adhesive on this base material keeping stress relaxation rate after static to be at least base material that 20% elastomerics forms and one deck in one minute.
In the present invention, 25% compression and 23 ℃ down the elastomeric stress of foaming with keeping one minute static after the stress relaxation rate measure by the method for following (1) to (3) and calculating.
(1) be that the foaming elastomer of 0.5-2.0mm is cut into 25mm * 25 mm size and is that 10mm ± 0.5mm makes sample with the synthetic total thickness of slicing layer with thickness.
(2) with the speed of foam compression trier (making) sample is compressed to 25% thickness, measures instantaneous (keeping static in 0 minute) load (25% compression load) and the compression load after maintenance one minute is static with 10 millimeters/minute under 23 ℃ envrionment temperature by Toyo Poldwin Co..
(3) by the following stress relaxation rate that calculates:
Stress relaxation rate (%)=[1-(A-B)/A] * 100
A: the compression load after maintenance in 0 minute is static.
B: the compression load after maintenance in 1 minute is static.
Because the result to the other various researchs of second above-mentioned purpose has now found that: add that by chloride elastomerics the foams of the elastomer blends that the oil absorbency elastomerics is formed obtain a kind of sheet adhesive with foamed substrate as base material by using.In this sheet adhesive, when oil when the side of foaming layer penetrates, lather volume does not almost change and oil is held in the foam layer to contain that oil shifts to the adhesive layer side.Find now to have finished the present invention based on this.
Second kind of embodiment of the present invention is a kind of sheet adhesive that has foamed substrate, and it comprises that a base material of being made up of the foams of chloride elastomerics and the elastomeric mixture of oil absorbency and one deck are formed on the pressure sensitive adhesive on this base material.
In first kind of embodiment of the present invention, foaming elastomer obtains by mediating a kind of composition, and said composition is to obtain by elastomerics and rubber stiffener, vulcanizing agent, whipping agent, the oxidation inhibitor of mediating as each basal component, then the mixture of mediating is molded as sheet, moulded parts is vulcanized and foaming.
In the present invention, this elastomerics can be at room temperature to have rubber like elastic elastomerics, and the kind of used in the present invention elastomerics is had no particular limits.Elastomeric example is natural rubber, divinyl rubber, styrene-butadiene rubber(SBR), isoprene-isobutylene rubber, chloroprene rubber, EPM (ethylene-propylene copolymer), EPDM (ethylene-propylene-diene-polymkeric substance), ethylene-acrylate copolymer, chlorosulfonated polyethylene, chlorinatedpolyethylene, paracril, urethanes, thiorubber, epichloro hydrin rubber, silicone rubber, viton, hydrogenated nitrile-butadiene rubber, ethylene-vinyl acetate copolymer.They can be used alone or as a mixture.
Because the sheet adhesive of band foamed substrate is used under various envrionment conditionss widely, so sheet adhesive preferably has well balanced at aspects such as various weather resistance such as ozone resistance, ultraviolet resistance, thermotolerance, winter hardiness, oil-proofness, water tolerance, acid resistance, alkali resistances.According to this viewpoint, in above-mentioned elastomerics, isoprene-isobutylene rubber, chloroprene rubber, EPM, EPDM, ethylene-acrylate copolymer, urethanes, epichloro hydrin rubber, silicone rubber, hydrogenated nitrile-butadiene rubber are by preferred, and epichloro hydrin rubber is more by Cheng Xuan.
The example of epichloro hydrin rubber is Epicholorohydrin homopolymer, Epicholorohydrin-ethylene oxide copolymer, Epicholorohydrin-glycidyl allyl ether multipolymer and Epicholorohydrin-ring monochloroethane-glycidyl allyl ether terpolymer.Consider that from ozone resistance and winter hardiness Epicholorohydrin-oxyethane-glycidyl allyl ether terpolymer is by preferred.Can also use the mixture of the epichloro hydrin rubber of Epicholorohydrin-oxyethane-glycidyl allyl ether terpolymer as main ingredient and other classes.
The example of rubber stiffener is for example for example high-phenylethylene village fat, thermoprene, coumarone-indene resin, resol, modified cyanurotriamide resin, vinyl-toluene multipolymer, lignin, phenol resins fiber, alicyclic series petroleum resin of carbon black, white carbon black (silica), magnesium basic carbonate, treated carbonates or ultra-fine ground Magnesium Silicate q-agent and organic toughener of inorganic strengthening agent.
The example of vulcanizing agent is for example sulphur, sulfur monochloride, sulfur dichloride, morpholine disulfide or a curing alkylphenol of sulphur compound; The inorganic sulphide agent is selenium, ruthenium, magnesium oxide, an aluminum oxide or zinc white for example; Oximes is for example to quinolone dioxime, P, P '-dibenzoyl quinolone dioxime, tetrachloro-P-phenyl ester or poly--P-dinitrobenzene; Nitroso compound; Polyamine is hexamethylene-diamine, Triethylenetetramine (TETA), tetren, hexamethylene-diamine carbonate, N for example, osmanthus-1 in the N '-two, 6-hexanediamine (N, N '-dicinnaminen-1,6-hexanediamine), 4,4 '-methylene-bis (hexahydroaniline) carbonate or 4,4 '-methylene-bis (2-chloroaniline); Organo-peroxide is dicumyl peroxide, tert-butyl peroxide isopropyl benzene, 2 for example, 5-dimethyl-2,5-two (tert-butyl peroxide) hexane, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexin-3,1, two (t-butyl peroxy sec.-propyl) benzene, 1 of 3-, two (t-butyl peroxy)-3 of 1-, 3,5-trimethyl-cyclohexane or benzoyl peroxide; Resin curing agent is alkyl resinox, alkyl monosulfide phenol resins or hexamethylol methyl melamine resin for example; Multifunctional (methyl) acrylate monomer is ethylene glycol dimethacrylate or trimethylolpropane trimethacrylate for example; The cyamelide triallyl; And 2,4,6-tri-thiol-S-dioxane (tridiane).Compounds suitable for use can be selected from these compounds according to elastomeric kind.
In order to shorten curing time and to reduce curing temperature and can also use suitable vulcanization accelerator for example guanidine acclerators, aldehyde-amine promoter, aldehyde-ammonia promotor, thiazole promotor, sulfinyl amine promotor, thiocarbamide promotor, thiuram accelerator, dithiocar-bamate promotor or Zanthate promotor with vulcanizing agent according to the vulcanizing agent kind.
Zinc white, magnesium oxide or the like can be used as vulcanization accelerator additive and use with vulcanization accelerator.
The example of whipping agent is for example sodium bicarbonate, bicarbonate of ammonia or a volatile salt of inorganic foaming agent; Nitroso compound is N for example, N '-dinitrosopentamethylene tetramine; Azo-compound is azodicarbonamide or Diisopropyl azodicarboxylate for example; And sulfonyl hydrazide compound for example benzol sulfohydrazide, P, P '-disulfonyl hydrazide phenylate (P, P '-oxybis (benzenesul fonylhydrazide) or toluene sulfonyl hydrazide.Whipping agent suitable in above-mentioned compound can be selected for use according to the kind of above-mentioned vulcanizing agent.In order to improve expansion rate and to reduce blowing temperature and can also select suitable habitual frothing aid for use according to the kind of whipping agent.
Oxidation inhibitor is preferably the compound that is difficult for bloom and can not hinders vulcanization reaction.The example of oxidation inhibitor is α-nonox, 4,4 '-(α, the alpha-alpha-dimethyl phenyl) pentanoic, octylated diphenylamine, N-sec.-propyl-N '-phenyl P-pHENYLENE dI AMINE, N-phenyl-N '-(3-methacryloxy-2-hydroxypropyl)-P-pHENYLENE dI AMINE, and 2,2,4-trimethylammonium-1, the 2-dihydroquinoline, 2,5 di tert butylhydroquinone, 2, the 6-di-tert-butyl-4-methy phenol, 2,2 '-methylene radical-two (4-methyl-6-tert butyl phenol), 4,4 '-sulphur two (the 6-tertiary butyl-3-methylphenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), the polymerisate of tricresyl phosphite nonylbenzene ester.
Except above-mentioned basal component, usually by the various additives of compounding in the rubber mold products, such as scorch retarder, uv-absorbing agent, mastication promotor, processing aid, softening agent, Rubber Softener, filler, stablizer, lubricant, fire retardant, static inhibitor, tinting material, anti-mycotic agent all can with elastomerics compounding mutually.
The kneading of elastomerics and these compounding components can be used and mediate the conventional equipment that the rubber compounding component is used, and for example mixing roller, Banbury mixer, pressure kneader, single screw extrusion machine, twin screw extruder wait and carry out.
Elastomer sheet can form by a rolling press roll extrusion or a mouthful mould extrusion molding.
Forming sheet material postcure and foaming can be by passing baking zone with sheet material or rotocure realizes.
Thickness to the foaming flexure strip that obtains does not like this have special restriction.Thickness is preferably 0.4-5mm.If the thickness of sheet material is too thin, when film is adhered to uneven surface by pressure, can not get sufficient profiling and the tackiness of uneven surface is reduced.If the thickness of sheet material greater than essential thickness, just can not get additional features and improves.
The compressibility that the invention is characterized in foam elastomer is such so that when 23 ℃ compression testing, 25% compression load (stress) down is 0.6-3.0kgf/cm
2Be at least 20% with the stress relaxation rate after maintenance in 1 minute is static.That is, the load during by aforesaid reduction by 25% compression can be enough to guarantee the gluing area to uneven surface, and by aforesaid increase stress relaxation, and the sheet adhesive that caused by unrelieved stress is thrown off to be subjected to meeting and made.Therefore, sheet adhesive becomes the cement strength that the object on the uneven surface is had brilliance.
Now this point is done more detailed the explanation.Concerning the mutual relationship of the gluing area of uneven surface, for example, the load when used thickness is 1mm and 25% compression is 3.0kgf/cm about compression load
2The foaming elastomer sheet adhesive of making base material planned to need 3.0kgf/cm at least when being glued on the adherend that the plane difference is 0.25mm fully
2Pressure, and when pressure was lower than above-mentioned value, sheet adhesive will inevitably be swelled.In other words, when compression load is low, applies same pressure and can guarantee the gluing area bigger uneven surface.
On the other hand, if 25% when compression load greater than 3.0kgf/cm
2, just can not fully guarantee gluing area to uneven surface; If yet the load in 25% when compression is less than 0.6kgf/cm
2, sheet adhesive is subject to the compression of sheet adhesive rolling power, and causes the product size stability problem.Also have, kept the elastic stress relaxation rate of static post-foaming to be at least 20% in the present invention at one minute, and preferably be at least 30%.This is because be less than 20% when the stress relaxation rate, that is, unrelieved stress surpasses at 80% o'clock, worked to being glued the interface by the breakaway force of the foamed substrate of profiling distortion that uneven surface causes, thereby gluing with the passage of time area constantly reduces.Therefore, the fixation problem that comes off may take place.In addition, the upper limit to the stress relaxation rate of the foaming elastomer that kept 25% compression after static in one minute does not add special restriction.Yet in theory, this higher limit can be 100%, is generally 60%.
For the compressibility that makes foaming elastomer is in the above-mentioned scope of the present invention, for example, should reasonably selects the kind and compounding ratio of elastomerics and compounding component, and can control the size and sum of the abscess after the sulfuration.The controlling party rule is not added special restriction.
The example of the chloride elastomerics in second kind of embodiment of the present invention is epichloro hydrin rubber, chloroprene rubber, chlorinatedpolyethylene and chlorosulfonated polyethylene.Because these chloride elastomericss have big polarity, so they are not lipophilic, and they are considered to be difficult to the oil resisting rubber with oil swell usually.
The foamed substrate that requirement is used for sheet adhesive has suitable caoutchouc elasticity and suitable stress relaxation rate.In view of this, epichloro hydrin rubber and chloroprene rubber be by preferred, and epichloro hydrin rubber owing to show less oil suction swelling more by preferably.
Epicholorohydrin is that the example of rubber is Epicholorohydrin homopolymer, Epicholorohydrin-ethylene oxide copolymer, Epicholorohydrin-allyl group shrink base oil ether copolymer, Epicholorohydrin-oxyethane-glycidyl allyl ether terpolymer.Consider that from ozone resistance and winter hardiness Epicholorohydrin-oxyethane-class propyl glycidyl ether terpolymer is by preferred.Can also use as this terpolymer of basal component and the system that mixes of other class epichloro hydrin rubbers.
The used elastomeric example of oil absorbency is polypropylene, silicone rubber, EPDM (ethylene-propylene-diene (diethane) polymkeric substance), EPM (ethylene-propylene copolymer) among the present invention.Can also use polymkeric substance for example acryl bead or cross-linked polystyrene beads grain with high oil absorbency.In these elastomericss, from showing and the good blend processibility of chlorination elastomer, remarkable even foaming and the viewpoint that reaches suitable elasticity and suitable elongation, silicone rubber, EPM, EPDM are by preferably.EPM that the charge is small and EPDM are more by preferably.In addition, the diene component of EPDM both can be that DCPD (Dicyclopentadiene (DCPD)) also can be ENB (an inferior vinyl norbornene).
In the present invention, use chloride elastomerics and the elastomeric mixture of oil absorbency.Two kinds of used elastomeric ratios are by the elastomeric weight ratio of the elastomerics/oil absorbency of chlorine, and it is 50/50 to 95/5, and is preferably 60/40 to 85/15.
If the content of chloride elastomerics very little, the swelling when oil suction is just big, and stress is concentrated in the edge section of adhesive layer, and adhesive layer becomes and is easy to throw off.Otherwise if the elastomeric content of oil absorbency very little, it is just not enough and along with the disappearance in time to keep the ability of oil in the foam layer, shifts to lipophilic adhesive layer between the never lipophilic foam layer of oil, has reduced the force of cohesion of tackiness agent, thereby has reduced tackiness.
In second kind of embodiment of the present invention, foams (foaming elastomer) be by mediate the elastomeric mixture of chloride elastomerics and oil absorbency with as rubber stiffener, vulcanizing agent, whipping agent, the oxidation inhibitor of each compounding component, with the mixture molding shape in blocks of this kneading, sulfuration obtains with this moulded parts of foaming then.
Thickness and porosity to foam sheet do not limit especially.Usually, the thickness of sheet material is that 0.3mm to 5mm and its porosity are 20% to 80%.
In this implementation, rubber dose, vulcanizing agent, whipping agent, oxidation inhibitor and other components and kneading method when needing can be as the Compounds and methods in first kind of embodiment of the present invention.
When selected vulcanizing agent, both can use and vulcanize chloride elastomerics and the elastomeric vulcanizing agent of oil absorbency simultaneously and also can use and only vulcanize chloride elastomeric vulcanizing agent.
Sheet adhesive of the present invention is by using such foams (foaming elastomer) as base material, form the pressure sensitive adhesive layer of desired thickness on the one or both sides of base material, it being shaped to sheet shape or being with shape to prepare.
Kind for pressure sensitive adhesive used among the present invention has no particular limits.Can use rubber is that tackiness agent, acryloyl are tackiness agent or silicone-based adhesive.Thickness to pressure sensitive adhesive layer also has no particular limits.Can use the thickness that is applied to habitual sheet adhesive usually, thickness can be from about 10-2000 μ m.When pressure sensitive adhesive layer is formed on the two sides of base material, can be identical or different in kind, thickness and the various performance of the layer on two sides.
In the method that forms pressure sensitive adhesive layer on the base material is direct coating pressure sensitive adhesive method on base material, is laminated in method on the base material forming (the having separate sheet) pressure sensitive adhesive layer that has the pressure sensitive adhesive layer of definite thickness and will form thus on the separate sheet.In these methods, for the cementation that improves pressure sensitive adhesive layer can be in advance to substrate surface impose primary coat processing, Corona discharge Treatment, electron rays handle, or the like.
By doing more detailed introduction to the present invention with reference to each embodiment and each reference example.In these embodiment and reference example, unless have in addition outside the person of pointing out, all umbers are parts by weight.
Reference example 1-1
Use Epicholorohydrin-oxyethane-glycidyl allyl ether terpolymer (trade(brand)name Epichlomer CG is made by DAISO CO.LTD.), prepare following compounding composition 1-A.After mediating this composition by mixing roller, kneaded composition is formed the sheet stock that thickness is 0.6mm by rolling.Then sheet stock is heated to 150 ℃, time and is 30 minutes with sulfuration and this sheet stock that foams.As a result, make the foaming elastomer 1-A that thickness is 0.75mm.
Compounding composition 1-A
100 parts of Epichlomer CG
20 parts of carbon blacks
50 parts in lime carbonate
5 parts of dioctyl phthalate (DOP)s
5 parts in magnesium oxide
1.5 parts of ethylene thioureas
N, 4 parts of N '-dinitrosopentamethylene tetramine
3 parts of urea frothing aids
2,2,4-trimethylammonium-1,3 parts in the polymkeric substance of 2-quinol
1 part of stearic acid
Reference example 1-2
By as the same way as among the reference example 1-1, change into the 0.85mm except using the following compounding composition 1-B replacement compounding composition 1-A and the thickness of rolling sheet stock, make and have the foaming elastomer 1-B that thickness is 2mm.
Compounding composition 1-B
100 parts of Epichlomer CG
30 parts of carbon blacks
50 parts in lime carbonate
5 parts of dioctyl phthalate (DOP)s
5 parts of zinc white
1.5 parts of ethylene thioureas
N, 5 parts of N '-dinitrosopentamethylene tetramine
3 parts of urea frothing aids
2,2,4-trimethylammonium-1,3 parts in the polymkeric substance of 2-quinol
1 part of stearic acid
Reference example 1-3
By as the same way as among the reference example 1-1, change into the 0.7mm except using the following compounding composition 1-C replacement compounding composition 1-A and the thickness of rolling sheet, make and have the foaming elastomer 1-C that thickness is 0.8mm.
Compounding composition 1-C
100 parts of Epichlomer CG
10 parts of carbon blacks
50 parts in lime carbonate
5 parts of dioctyl phthalate (DOP)s
5 parts of zinc white
2 parts of ethylene thioureas
N, 2 parts of N '-dinitrosopentamethylene tetramine
1 part of urea frothing aid
2,2,4-trimethylammonium-1,3 parts in the polymkeric substance of 2-quinol
1 part of stearic acid
Reference example 1-4
Press as the same way as among the reference example 1-1, has the foaming elastomer 1-D that thickness is 0.8mm except replacing compounding composition 1-A by the following compounding composition 1-D that uses isoprene-isobutylene rubber 365 (making) preparation and the thickness of rolling sheet stock is changed into the 0.65mm, making by EssoCo..
Compounding composition 1-D
365 100 parts of isoprene-isobutylene rubbers
35 parts of carbon blacks
40 parts in lime carbonate
Paraffin oil (P-200, trade(brand)name, by
NipponPetroleum Co. manufacturing) 10 part
5 parts in magnesium oxide
5 parts of zinc white
1 part of paraquinonedioxime
N, 5 parts of N '-dinitrosopentamethylene tetramine
4 parts of urea frothing aids
2,2,4-trimethylammonium-1,3 parts in the polymkeric substance of 2-dihydro silicon quinoline
1 part of stearic acid
Reference example 1-5
By as the same way as among the reference example 1-1, has the foaming elastomer 1-E that thickness is 0.8mm except using following compounding composition 1-E to replace compounding composition 1-A and the thickness of rolling sheet stock is changed into the 0.75mm, making.
Compounding composition 1-E
100 parts of Epichlomer CG
10 parts of carbon blacks
50 parts in lime carbonate
5 parts of dioctyl phthalate (DOP)s
5 parts of zinc white
1 part of ethylene thiourea
N, 1 part of N '-dinitrosopentamethylene tetramine
0.5 part of urea frothing aid
2,2,4-trimethylammonium-1,3 parts in the polymkeric substance of 2-dihydro silicon quinoline
1 part of stearic acid
Embodiment 1-6
Press as the same way as among the reference example 1-1, has the foaming elastomer 1-F that thickness is 0.8mm except replacing compounding composition 1-A by the compounding composition 1-F that uses isoprene-isobutylene rubber 365 (making) preparation and the thickness of sheet stock is changed into the 0.65mm, making by EssoCo..
Compounding composition 1-F
365 100 parts of isoprene-isobutylene rubbers
35 parts of carbon blacks
40 parts in lime carbonate
Paraffin oil (P-200, trade(brand)name, by
Nippon Petroleum Co. manufacturing) 10 part
5 parts in magnesium oxide
5 parts of zinc white
3 parts of paraquinonedioximes
N, 5 parts of N '-dinitrosopentamethylene tetramine
4 parts of urea frothing aids
2,2,4-trimethylammonium-1,3 parts of 2-dihydro silicon quinolines
1 part of stearic acid
Reference example 1-7
Use have thickness as polyethylene (vinyl acetate content is about 17% weight) foam sheet 1.1mm, that can buy on the market as foaming elastomer 1-G.
Each elastomerics 1-A to 1-G among the above-described reference example 1-1 to 1-7 is cut into 25mm * 25mm size, and laminated by this way each section to make the total thickness of the per sample (p.s.) that obtains be 10mm ± 0.5mm.When with compression testing machine with the speed of 10 mm/min with per sample (p.s.) be compressed to original depth 25% the time, be determined at the compression load that kept in 0 minute after static and at the compression load that kept in 1 minute after static.In addition, obtain in the stress relaxation rate that kept in 1 minute after static by these measured values.
The thickness of the measured value of gained and calculation result and foaming elastomer 1-A to 1-G is shown among the following table 1-1.
Table 1-1
Foaming elastomer 25%
Compression load (kgf/cm2)
0 minute stress relaxation rate after after keeping static reference example kind thickness maintenance static in 1 minute, keeping static back in 1 minute
(mm) (％)1-1 1-A 0.75 1.34 0.88 341-2 1-B 1.2 0.83 0.57 311-3 1-C 0.8 2.54 1.85 271-4 1-D 0.8 0.69 0.54 221-5 1-E 0.8 4.5 3.51 221-6 1-F 0.8 0.69 0.59 151-7 1-G 1.1 1.00 0.9 10
Embodiment 1-1
The foaming elastomer that uses gained among the reference example 1-1 is as base material.By method shown below two surfaces of base material are imposed primary coat and handle, the layer thickness that has of method preparation that will be by the following stated is that two surfaces that the sheet stock of the pressure sensitive adhesive of 70 μ m is laminated to base material make the sealing tape that has foamed substrate.Primary coat is handled:
Use Adeka Bontightes (merchant's name is made by ASAHIDENKA KOGYO K.K.) the following primary coat treatment solution of preparation.With about 1 μ m/m
2Dry-coated amount this treatment solution is coated on two surfaces of base material, and 120 ℃ of dryings 5 minutes.
100 parts of Adeka Bontighter HUX-290H
(aqueous urethane resin)
3 parts of Adeka Bontighter HUX-11W
5 parts of Adeka Bontighter HUX-XW
500 parts of preparations of water with sheet stock of pressure sensitive adhesive layer:
In flask, place 92 parts of 2-EHAs, 8 parts of vinylformic acid, 0.2 part of Diisopropyl azodicarboxylate and 200 parts of vinyl acetic monomers.Behind atmosphere, the mixture that is produced is stirred 20 hours to carry out polyreaction down at 50 ℃ with nitrogen replacement inside.With the tolylene diisocyanate adduct of the TriMethylolPropane(TMP) of 1% weight behind the polymers soln that obtains thus, be coated on the mixture of gained on the interleaving paper and stand 5 hours 130 ℃ drying treatment, obtain having the sheet material that thickness is the pressure sensitive adhesive layer of 70 μ m.
Embodiment 1-2
Press as the same manner among the embodiment 1-1, the foaming elastomer 1-B that obtains in using reference example 1-2 does the base material, obtains having the sealing tape of foamed substrate.
Embodiment 1-3
Press as the same manner among the embodiment 1-1, the foaming elastomer 1-C that obtains in using reference example 1-3 does the base material, obtains having the sealing tape of foamed substrate.
Embodiment 1-4
Press as the same manner among the embodiment 1-1, the foaming elastomer 1-D that obtains in using reference example 1-4 does the base material, obtains having the sealing tape of foamed substrate.
Comparative example 1-1
Press as the same way as among the embodiment 1-1, the foaming elastomer 1-E that obtains in using reference example 1-5 does the base material, obtains having the sealing tape of foamed substrate.
Comparative example 1-2
Press as the same way as among the embodiment 1-1, the foaming elastomer 1-F that obtains in using reference example 1-6 does the base material, obtains having the sealing tape of foamed substrate.
Comparative example 1-3
Press as the same way as among the embodiment 1-1, the foaming elastomer 1-G that obtains in using reference example 1-7 does the base material, obtains having the sealing tape of foamed substrate.
By the following method the every kind of sealing tape that has foamed substrate that obtains among embodiment 1-1 to 1-4 and the comparative example 1-1 to 1-3 is carried out the uneven surface adhesive test.The uneven surface adhesive test:
The one side that will be cut into the every kind of sealing tape that has foamed substrate of 25mm * 100mm size under 23 ℃ atmosphere is adhered to the surface of the stainless steel plate (200g) of 4mm * 50mm * 130mm size, and the unidirectional pressurization of the another side of sealing tape by the heavy roller of 1kg adhered to by pressure and has the not sheet glass of plane surface (" Kasumi ", trade(brand)name, by Nippon Sheet Glass Company, Limited makes).Measure the area ratio of sealing tape actual adhesion from the opposed surface of sheet glass in the sticking back of pressure to sheet glass at once.Place and be in this state always glass is vertical then, detect after 7 days and the variation of the gluing area after 14 days.
The test-results of gained is shown among the following table 1-2:
Table 1-2
Gluing area is than (%)
Be right after press sticking after after 7 days after 14 days
Embodiment 1 85 85 85
Embodiment 2 95 95 95
Embodiment 3 80 76 72
Embodiment 4 95 86 81
Comparative example 1 70 65 is thrown off
Comparative example 2 95 78 64
Comparative example 3 90 65 is thrown off
From the result shown in the above table 1-2 as seen, the sealing tape that has foamed substrate that obtains in embodiment 1-1 to 1-4 is being pressed when sticking, can obtain big gluing area and as time goes by demonstrate the minimizing of less gluing area the adherend with uneven surface.Therefore, these sealing tapes have unsurpassed on uneven surface the ability of cementation object.
Reference example 2-1
(trade(brand)name Gechron 3100 as chloride elastomeric epichloro hydrin rubber in use, by Nippon Zeon Co., Ltd. make) and EPDM (trade(brand)name EPT-4021 is made by Mitsui PetrochemicalIndustsies Ltd.) the following compounding composition 2-A of preparation.After mediating said composition, kneaded composition is rolled into has the sheet stock that thickness is 0.6mm by mixing roller.By being heated to 150 ℃, this sheet stock being vulcanized and foaming during 30 minutes time, obtain having the foaming elastomer 2-A that thickness is 0.75mm then.
Compounding composition 2-A
3,100 80 parts of Gechron
20 parts of EPT-4021
20 parts of carbon blacks
50 parts in lime carbonate
5 parts of dioctyl phthalate (DOP)s
5 parts in magnesium oxide
1.5 parts of vinyl thiocarbamides
N, 4 parts of N '-dinitrosopentamethylene tetramine
3 parts of urea frothing aids
2,2,4-trimethylammonium-1,3 parts in the polymkeric substance of 2-dihydro silicon quinoline
1 part of stearic acid
Reference example 2-2
By as the same way as among the reference example 2-1,, obtain having the foaming elastomer 2-B that thickness is 0.75mm except will be 65 parts/35 especially instead with reference to the ratio of the Gechrom 3100/EPT-4021 in the compounding composition of 2-1.
Reference example 2-3
Use isoprene-isobutylene rubber 365 (trade(brand)names, make by Esso Co.) the following compounding composition 2-C of preparation, again by as the same way as among the reference example 2-1 by mediate, in flakes, sulfuration and the said composition that foams, make and have the foaming elastomer 2-C that thickness is 0.75mm.
Compounding composition 2-C:
365 100 parts of isoprene-isobutylene rubbers
35 parts of carbon blacks
40 parts in lime carbonate
Paraffin oil (P-200, trade(brand)name, by
Nippon Oil Company, Ltd. makes)
10 parts
5 parts in magnesium oxide
5 parts of zinc white
1 part of paraquinonedioxime
N, 5 parts of N '-dinitrosopentamethylene tetramine
4 parts of urea frothing aids
2,2,4-trimethylammonium-1,3 parts in the polymkeric substance of 2-dihydro silicon quinoline
1 part of stearic acid
Reference example 2-4
(vinyl acetate content: about 17% weight) the foaming sheet is as foaming elastomer 2-D as the polyethylene of 0.8mm to use the thickness of buying on the market that has.
Embodiment 2-1
The foaming elastomer 2-A that obtains among the reference example 2-1 is used as base material.By the method described in the above embodiment 1-1 two surfaces of base material being imposed primary coat handles.The sheet layer of the pressure sensitive adhesive layer with 70 μ m thickness that will make by the method described in the above embodiment 1-1 is incorporated on the base material, obtains having the sealing tape of foamed substrate.
Embodiment 2-2
Press as the same way as among the embodiment 2-1, the foaming elastomer 2-C that obtains in using reference example 2-3 obtains having the sealing tape of foamed substrate as the base material.
Comparative example 2-2
Press as the same way as among the embodiment 2-1, the foaming elastomer 2-D that obtains in using reference example 2-4 obtains having the sealing tape of foamed substrate as the base material.
The following method that is used as one of oil resistant test is checked oil absorbency and swelling property that every kind of sealing tape that has the foamed substrate that obtains in embodiment 2-1 and 2-2 and reference example 2-1 and 2-2 floods in oil.
Oil absorbency is measured with swelling property and is observed:
The thickness that has that will live through under 23 ℃ atmosphere that primary coat handles is that the polyester film of 50 μ m is laminated to every sealing tape with foamed substrate (two surfaces of 10mm * 10mm) are placed 24 hours to obtain sample with subassembly then.
To under 23 ℃ atmosphere, one hour sample of dipping in kerosene (dipping back) and at spontaneous dry one day sample (after 1 day) behind the dipping is measured oil absorbency according to the variation of sample weight.Also have,, obtain difference with the preceding thickness of dipping in kerosene with the sidepiece variation in thickness of microscope as the observation sealing tape of swelling property.
The result of gained is shown among the following table 2-1.
Table 2-1
Swelling property (variable quantity of thickness)
Oil absorbency (mg) (mm)
Flood after preceding 1 day and flood after back 1 day
Embodiment 2-1 72 45 0.08 0.07
Embodiment 2-2 80 48 0.09 0.07
Comparative example 2-1 95 57 0.25 0.12
Comparative example 2-2 40 22 0.05 0.02
With regard to every kind of sealing tape that has the foamed substrate that in embodiment 2-1 and 2-2 and comparative example 2-1 and 2-2, obtains,, be determined at the variation of the bounding force before and after the dipping in the oil by following method as other oil resistant test.The mensuration of bounding force:
To live through the primary coat thickness that has at last under 23 ℃ atmosphere is that the polyester film of 50 μ m is adhered to every kind of sealing tape having foamed substrate (surface of 10mm * 100mm).By adhering on the surface of stainless steel plate with the unidirectional pressurization of the heavy roller of 2kg anti-phase pressure with sealing tape.Allow this subassembly place 24 hours and obtained sample.
One hour sample of dipping in sample (dipping before) before dipping in kerosene, the kerosene under 23 ℃ of atmosphere (dipping back) and spontaneous dry one day sample (after 1 day) behind the dipping is to measure the bounding force of peeling off under 50 millimeters/minute 180 ℃ the condition at peeling rate using the general-purpose tensile testing machine under 23 ℃ the environment.
The result of gained is shown among the following table 2-2.
Table 2-2
Bounding force (g/10mm is wide)
Dipping is after back 1 day before the dipping
Embodiment 2-1 1,300 1, and 150 1,080
Embodiment 2-2 1,400 1, and 300 1,250
Comparative example 2-1 980 450 400
Comparative example 2-2 800 800 250
Can find out from above table 2-1 and the result shown in the table 2-2, in every kind of sealing tape with the foamed substrate that in embodiment 2-1 and 2-2, obtains, even when oil when the foam layer side surface penetrates, the volume change of foam layer is very little, because sealing tape penetrates oil and transfers to function in the binder layer by keep oil to have containment with foam layer, it is very little passing and reduce bounding force in time, and demonstrating sealing tape of the present invention is being unsurpassed aspect the grease-proof binding property.
As described above, because using to have, the sheet adhesive that has foamed substrate of the present invention is in the interior constrictive foaming elastomer of specified range as base material, therefore, sheet adhesive is easy to according to the uneven surface of adherend and is easy to guarantee by sticking area.Also have, can not take place owing to high stress relaxation to cause the release problem of throwing off adherend, so these sheet adhesive demonstrate improved object cement strength by unrelieved stress.
In addition, owing in the present invention chloride elastomerics and the elastomeric mixture foams of oil absorbency are used as base material, therefore can provide to have improved oil resistant cementation and use the less sheet adhesive that has foamed substrate that is restricted.
Although the present invention has been done in detail and, concerning those skilled in the art, under the prerequisite that does not deviate from spirit of the present invention and scope, can make various changes and improvements therein certainly with reference to the introduction of its specific implementations.
Claims (6)
1 one kinds of sheet adhesive that have foamed substrate, it comprises one deck by having 25% boil down to 0.6-3.0kgf/cm under 23 ℃
2Be formed on pressure sensitive adhesive on the said base material keeping stress relaxation rate after static to be at least base material that 20% foaming elastomer forms and one deck in 1 minute.
2 as the desired sheet adhesive that has foamed substrate in the claim 1, and wherein foaming elastomer comprises epichloro hydrin rubber.
3 one kinds of sheet adhesive that have foamed substrate, it comprises base material that one deck is made up of chloride elastomerics and the elastomeric mixture foams of oil absorbency and one deck and is formed on pressure sensitive adhesive on the said base material.
4 as the desired sheet adhesive that has foamed substrate in the claim 3, and wherein chloride elastomerics is an epichloro hydrin rubber.
5 as the desired sheet adhesive that has foamed substrate in the claim 3, and wherein the oil absorbency elastomerics is a kind of material that is selected from polypropylene, silicone rubber, EPDM, EPM at least.
6 as the desired sheet adhesive that has foamed substrate in the claim 3, and the elastomeric important ratio of wherein chloride elastomerics oil absorbency is 50/50 to 95/5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96121125 CN1153195A (en) | 1995-09-15 | 1996-09-14 | Adhesive sheet with foamed substrate |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP262274/95 | 1995-09-15 | ||
| JP118854/96 | 1996-05-14 | ||
| CN 96121125 CN1153195A (en) | 1995-09-15 | 1996-09-14 | Adhesive sheet with foamed substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1153195A true CN1153195A (en) | 1997-07-02 |
Family
ID=5126764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96121125 Pending CN1153195A (en) | 1995-09-15 | 1996-09-14 | Adhesive sheet with foamed substrate |
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| Country | Link |
|---|---|
| CN (1) | CN1153195A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106053341A (en) * | 2016-08-18 | 2016-10-26 | 博耐尔汽车电气系统有限公司 | Detection method and detection tool for foaming glue-coated material used for vehicle air conditioner |
| CN106198381A (en) * | 2016-08-18 | 2016-12-07 | 博耐尔汽车电气系统有限公司 | The detection method of a kind of air conditioning for automobiles parts foaming rubberized material and detection instrument |
| CN106226232A (en) * | 2016-08-18 | 2016-12-14 | 博耐尔汽车电气系统有限公司 | Air conditioning for automobiles adhesive tape detection method and the detection instrument of foaming rubberized material |
| CN106226231A (en) * | 2016-08-18 | 2016-12-14 | 博耐尔汽车电气系统有限公司 | For air conditioning for automobiles adhesive tape foaming rubberized material detection method and detection instrument |
-
1996
- 1996-09-14 CN CN 96121125 patent/CN1153195A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106053341A (en) * | 2016-08-18 | 2016-10-26 | 博耐尔汽车电气系统有限公司 | Detection method and detection tool for foaming glue-coated material used for vehicle air conditioner |
| CN106198381A (en) * | 2016-08-18 | 2016-12-07 | 博耐尔汽车电气系统有限公司 | The detection method of a kind of air conditioning for automobiles parts foaming rubberized material and detection instrument |
| CN106226232A (en) * | 2016-08-18 | 2016-12-14 | 博耐尔汽车电气系统有限公司 | Air conditioning for automobiles adhesive tape detection method and the detection instrument of foaming rubberized material |
| CN106226231A (en) * | 2016-08-18 | 2016-12-14 | 博耐尔汽车电气系统有限公司 | For air conditioning for automobiles adhesive tape foaming rubberized material detection method and detection instrument |
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