CN1263818C - Water dispersible adhesive composition, adhesive sheet and rubber foam adhesive sheet employing the same - Google Patents
Water dispersible adhesive composition, adhesive sheet and rubber foam adhesive sheet employing the same Download PDFInfo
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- CN1263818C CN1263818C CN 03141127 CN03141127A CN1263818C CN 1263818 C CN1263818 C CN 1263818C CN 03141127 CN03141127 CN 03141127 CN 03141127 A CN03141127 A CN 03141127A CN 1263818 C CN1263818 C CN 1263818C
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- aqueous dispersion
- dispersion type
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Abstract
The present invention aims to provide a water dispersible adhesive composition which has superior adhesiveness and end stripping properties to foam, and stable adhesive force for a long time; the present invention also aims to provide an adhesive sheet for arranging the adhesive layer composed of the water dispersible adhesive composition onto base material, and an adhesive sheet of rubber foam for arranging the adhesive sheet on a single side or both sides of the rubber foam. The adhesive sheet and the adhesive sheet of the rubber foam are composed of the water dispersible adhesive composition, and the water dispersible adhesive composition is prepared by adding an adhesive containing phenol skeletons to the copolymerization composition of (methyl) acrylic acid alkylester as a main component, and a monomer composition containing silane series monomer.
Description
Technical field
The present invention relates to the aqueous dispersion type binder composition and it is arranged on adhesive sheet on the base material (comprising band shape, sheet, form such as membranaceous) and these are arranged on the single face of rubbery foam body or the rubbery foam body adhesive sheet on the two sides.
Background technology
Before this, the rubbery foam body with dustproof, heat insulation, sound insulation, vibrationproof, buffering, watertight and gastight material as purpose, for example, at parts of civil construction, electronic machine, residential equipment machine and boats and ships, vehicle, automobile etc. etc., in various Industrial products, as widely adopting for the sealing material of filling the space.Yet, in recent years, also extensively adopted in information machine fields such as Personal Computer, Cell phone or PDA.
This rubbery foam body is to add to mix vulcanizing agent and whipping agent in good rubber based polymer such as EPDM weathering resistance, winter hardiness, thermotolerance, chemical proofings etc. such as (propylene diene rubber), make the product of sulfur foam, and be provided with the binder layer that is easy to construct.
In the past, as the binder composition in this purposes, the solvent type binder composition of dissolving acrylic acid series or rubber based polymer is a main flow in organic solvent.Yet, in recent years, considered from the hygienic issues of environmental problem or operating environment, wish to be transformed into no-solvent type.
Employing is as the adhesive sheet of the binder composition of a kind of aqueous dispersion type of no-solvent type, owing to do not adopt organic solvent, considers it is preferred from environmental health, and its advantage is, even consider it also is good etc. from solvent resistance.Yet this aqueous dispersion type adhesive sheet is compared with solvent type adhesive sheet, the binding property of clung body (particularly uneven surface such as foams) and retentivity is difficult to all good, has the bad shortcomings of practicality such as terminal separability.
The inventor concentrates on studies in order to address the above problem, discovery is in the monomer mixture of aqueous dispersion type (methyl) alkyl acrylate as principal constituent, add silane and be monomer and add chain-transfer agent as required when carrying out polymerization, can obtain the binding property and the retentivity of clung body are all reached high-caliber and same with Solvent Adhesive practical characteristic (terminal separability etc.) (spy opens the 2001-163655 communique).
Yet, as above-mentioned tackiness agent the rubbery foam body also is difficult to the bounding force that attains full and complete satisfaction, and, because of the kind difference of rubbery foam body, descend during adhesiveness sometimes.Fusible this through the time descend, not only with foams during, and also being the phenomenon that can see in the foams adhesive sheet of foams as base material as clung body.
The problem that invention will solve
The purpose of this invention is to provide and a kind of foams are had good binding property and terminal stripping performance, and, bounding force through the time stable aqueous dispersion type binder composition.Another purpose of the present invention provides a kind of, and the binder layer that is made of this aqueous dispersion type binder composition is arranged on adhesive sheet on the base material, and these are arranged on face of rubbery foam body or the rubbery foam body adhesive sheet on two faces.
Solve the means of problem
The inventor is to found that above-mentioned problem concentrates one's attention on to inquire into, descend during adhesiveness, be because the nonpolarity element (paraffin oil of rubbery foam body, pitch etc.) shift to due to the binder layer, making silane in the monomer mixture of (methyl) acrylate as principal constituent with aqueous dispersion type is to add the bonding imparting agent that contains the phenol skeleton in the polymkeric substance that forms of monomer copolymerization, whereby, can prevent the nonpolarity element migration of rubbery foam body, thereby obtaining rubber is that foams have good binding property and terminal stripping performance, and, through the time the good tackiness agent of adhesion stability, so finished the present invention.
Not clear by the reason that the bonding imparting agent that contains the phenol skeleton is added into the excellent results of bringing into play in the binder composition, but can think, when the polarity of tackiness agent is hanged down, rubber is that the nonpolarity element of foams easily moves to binder layer, cause through the time bounding force descend, and when polarity is high, can suppress the migration of composition, do not cause that bounding force reduces.Concrete, when the low polymerized rosin ester of polarity adds as bonding imparting agent, find that binding property reduces, otherwise, when adding high rosin phenol of polarity or terpene phenolic, can suppress binding property and descend, therefore, can infer it is because in the bonding imparting agent molecule due to the useful effect of phenol skeleton.
Promptly, the present invention relates to a kind of aqueous dispersion type binder composition (inventive point 1), it is characterized in that, said composition is toward making with (methyl) alkyl acrylate as principal constituent, and contain in the aqueous dispersions that silane is the polymkeric substance that obtains of monomeric monomer mixture copolymerization, add contain the phenol skeleton bonding imparting agent constituted, particularly, the invention still further relates to a kind of aqueous dispersion type binder composition (inventive point 2), it is characterized in that, polymkeric substance is to make with (methyl) alkyl acrylate as principal constituent, and obtaining the insoluble composition of solvent when adopting the monomeric composition of not siliceous methane series to carry out polymerization is the monomer mixture of the resin combination below 5%, with the silane that is 0.005～l weight part with respect to these monomer mixture 100 weight parts be monomer, with above-mentioned similarity condition under carry out the resulting polymkeric substance of copolymerization.
In addition, the invention still further relates to aqueous dispersion type binder composition (inventive point 3), said composition is above-mentioned aqueous dispersion type binder composition, said composition is by with respect to making with (methyl) alkyl acrylate as principal constituent, and the monomeric monomer mixture of siliceous methane series carries out copolymer 1 00 weight part that copolymerization obtains, and interpolation can be that monomer bonded organic compound 0.005～1 weight part constitutes with silane; The aqueous dispersion type binder composition that The present invention be more particularly directed to (inventive point 4) wherein, can be that monomer bonded organic compound is a silane compound with above-mentioned silane.
In addition, the present invention relates to a kind of dispersed adhesive composition, (inventive point 5), said composition is above-mentioned aqueous dispersion type binder composition, wherein, silane is that monomer is that methoxy silane is a monomer; The invention still further relates to a kind of aqueous dispersion type binder composition (inventive point 6), it is characterized in that copolymerization has methacrylic acid in above-mentioned polymkeric substance.
In addition, the invention still further relates to a kind of aqueous dispersion type binder composition (inventive point 7), wherein, above-mentioned bonding imparting agent for rosin phenol is or terpene phenolic is bonding imparting agent.
In addition, the present invention relates to a kind of adhesive sheet, it is that the binder layer that is made of above-mentioned aqueous dispersion type binder composition is arranged on the single face (inventive point 8) of base material or the adhesive sheet of 2 (inventive points 9).
In addition, the present invention relates to a kind of rubbery foam body adhesive sheet (inventive point 10), it is characterized in that, the binder layer that is made of above-mentioned aqueous dispersion type binder composition is arranged on the single face of rubbery foam body or 2, and, also relate to a kind of rubbery foam body adhesive sheet (inventive point 11), it is characterized in that, above-mentioned adhesive sheet is arranged on the single face of rubbery foam body or 2.
Also have, in this manual, so-called " the insoluble composition of solvent " is that (wherein, the weight of nonvolatile component is as W for accurate weighing specified amount (about 500mg) sample
1Mg), it in room temperature is flooded 3 days in ethyl acetate after, is taken out insolubles, with this insolubles in 100 ℃ of dryings 2 hours, gravimetry (W
2Mg), calculate according to following formula:
The insoluble composition of solvent (weight %)=(W
2/ W
1) * 100
The simple declaration of accompanying drawing
Fig. 1 is the sectional drawing of one of pattern ground expression adhesive sheet of the present invention example.
Fig. 2 is the sectional drawing of the another example of pattern ground expression adhesive sheet of the present invention.
Fig. 3 is the sectional drawing of the another example of pattern ground expression adhesive sheet of the present invention.
Fig. 4 is the sectional drawing of the another example of pattern ground expression adhesive sheet of the present invention.
Fig. 5 is the sectional drawing of one of pattern ground expression rubbery foam adhesive sheet of the present invention example.
Fig. 6 is the sectional drawing of the another example of pattern ground expression rubbery foam adhesive sheet of the present invention.
Fig. 7 is the sectional drawing of the another example of pattern ground expression rubbery foam adhesive sheet of the present invention.
Fig. 8 is the sectional drawing of pattern ground expression to the bounding force measuring method of rubbery foam body in the embodiment of the invention.
Fig. 9 is the sectional drawing of the measuring method of terminal separability test in pattern ground this expression of expression inventive embodiments.
Figure 10 is the sectional drawing of the bounding force measuring method of the rubbery foam body adhesive sheet in the pattern ground expression embodiment of the invention.
The simple declaration of symbol
1. binder layer, 2. base material, 3. release liner, 4. binder layer, 5. adhesive sheet, 6. adhesive sheet, 7. back side processing layer, 8. foams.
The working of an invention scheme
The invention provides a kind of toward with (methyl) alkyl acrylate as principal constituent, and, contain silane and be in the aqueous polymer dispersion that monomeric monomer mixture copolymerization obtains, add the aqueous dispersion type binder composition that bonding imparting agent constituted that contains the phenol skeleton.
As used (methyl) alkyl acrylate of main composition monomer, can enumerate compound in the present invention with general formula (1) expression:
CH
2＝C(R
1)COOR
2 (1)
(in the formula, R
1Expression hydrogen atom or methyl, R
2The alkyl of expression carbonatoms 2～14).
As described R
2, can enumerate, for example, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, isopentyl, hexyl, heptyl, 2-ethylhexyl, iso-octyl, different nonyl, isodecyl etc.Wherein, as R
2, the alkyl of carbonatomss 2～10 such as butyl, 2-ethylhexyl is preferred.Above-mentioned (methyl) alkyl acrylate can separately or mix more than 2 kinds and use.For example,, butyl acrylate be can use separately, butyl acrylate and 2-EHA perhaps are used in combination as alkyl acrylate.At this moment, the ratio of 2-EHA and butyl acrylate, the former/latter=0/100～55/45 (for example, 5/95～60/40) about.
With (methyl) alkyl acrylate be in the monomer mixture of principal constituent should (methyl) alkyl acrylate [for example, above-mentioned (methyl) vinylformic acid C2-14 alkyl ester] ratio, generally more than 80 weight % (for example, about 80～99.8 weight %), preferably more than 85 weight % (for example, about 85～99.5 weight %), more preferably at (for example, about 90～99 weight %) more than the 90 weight %.
Above-mentioned monomer mixture in order to import the cross-linking set that is used for heat cross-linking, contains functional group's monomer (monomer that contains the heat cross-linking functional group) usually.This monomer that contains the functional group as the comonomer composition, also can be improved the bounding force to clung body whereby.
As the above-mentioned monomer that contains the functional group, can enumerate, for example vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, Ba Dousuan, maleic anhydride etc. contain the monomer or the acid anhydrides of carboxyl; Hydroxyl monomers such as (methyl) vinylformic acid 2-hydroxyl second fat, (methyl) vinylformic acid 2-hydroxypropyl fat, (methyl) vinylformic acid 2-hydroxyl fourth fat; (methyl) acrylamide, N, amide-containing monomers such as N-dimethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-methoxymethyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide; (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid tert-butyl amino ethyl ester etc. contain amino monomers; (methyl) glycidyl acrylate etc. contains the glycidyl monomer; (methyl) vinyl cyanide, N-(methyl) acryloyl morpholine, N-vinyl-2-Pyrrolidone etc.Wherein, to contain the monomer of carboxyl or its acid anhydrides etc. be preferred to vinylformic acid etc.The above-mentioned functional group monomer of containing can use more than a kind or 2 kinds.
The above-mentioned consumption that contains the functional group monomer with respect to above-mentioned (methyl) alkyl acrylate 100 weight parts, for example reaches 0.5～12 weight part, about preferred 1～8 weight part.
In addition, in above-mentioned monomer mixture,, as required, also can contain other co-polymerized monomer in order to improve characteristics such as cohesive force.As this co-polymerized monomer, can enumerate, for example, vinyl esters such as (methyl) methyl acrylate, vinyl-acetic ester; Aromatic ethenyl compound such as vinylbenzene, Vinyl toluene; (methyl) esters of acrylic acid of cycloalcohols such as cyclopentyl two (methyl) acrylate, isobornyl (methyl) acrylate; (methyl) esters of acrylic acid of polyvalent alcohols such as neopentyl glycol two (methyl) acrylate, hexylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylol methane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate etc.These copolymerization monomers both can use a kind also can use more than 2 kinds.
In the present invention; as the silane with above-mentioned (methyl) alkyl acrylate copolymer is monomer; can be not particularly limited so long as have the former polymerizable compound that gives of silicon; but; from to the good consideration of above-mentioned (methyl) alkyl acrylate copolymer, the silane compound with (methyl) acryl of (methyl) acryloxyalkyl silane derivative etc. is preferred.As silane is monomer, can enumerate, for example 3-methacryloxypropyl trimethoxy silane, 3-acryloxy propyl trimethoxy silicane, 3-methacryloxypropyl triethoxyl silane, 3-acryloxy propyl-triethoxysilicane, 3-methacryloxypropyl methyl dimethoxysilane, 3-acryloxy propyl group methyl dimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-acryloxy propyl group methyldiethoxysilane etc.These silane are that monomer can be used singly or two or more kinds in combination.
Except that above-mentioned, silane as the possibility copolymerization is monomer, for example, can enumerate vinyltrimethoxy silane, vinyltriethoxysilane, 4-vinyl butyl Trimethoxy silane, 4-vinyl butyl triethoxyl silane, 8-vinyl octyl group Trimethoxy silane, 8-vinyl octyltri-ethoxysilane, 10-methacryloxy decyl Trimethoxy silane, 10-acryloxy decyl Trimethoxy silane, 10-methacryloxy decyl triethoxyl silane, 10-acryloxy decyl triethoxyl silane etc.
Silane is that amount of monomer can suitably be selected according to the kind of above-mentioned (methyl) alkyl acrylate and purposes etc., and silane is monomeric copolymerization resultant, with respect to monomer mixture (silica removal methane series monomer beyond) 100 weight parts of above-mentioned (methyl) alkyl acrylate as principal constituent, when surpassing 1 weight part, sometimes be reduced to can not the adherent degree for bounding force, in addition, and during less than 0.005 weight part, because the polymer strength deficiency, cohesive force easily reduces.Therefore, in the present invention, with respect to the silane of above-mentioned monomer mixture (silane be monomer except) 100 weight parts be amount of monomer to reach 0.005～1 weight part be preferred, 0.01～0.5 weight part more preferably.
Constitute the polymkeric substance of aqueous dispersion type binder composition of the present invention, for example, with above-mentioned (methyl) alkyl acrylate as principal constituent, and the monomeric monomer mixture of siliceous methane series, adopts common emulsion polymerization, the aqueous dispersions of manufacturing (methyl) acrylate copolymer.
In aqueous dispersion type pressure-sensitive adhesive composition of the present invention, obtain the monomer mixture of the insoluble composition of solvent when particularly making (methyl) alkyl acrylate carry out polymerization at the resin combination below 5% as principal constituent and the monomeric composition of not siliceous methane series, with the silane that reaches 0.005～1 weight part with respect to these monomer mixture 100 weight parts be monomer, with adopt that not contain above-mentioned silane be under the similarity condition of monomeric composition when carrying out polymerization, carry out polymerization, the aqueous dispersion type pressure-sensitive adhesive composition that contains resulting polymkeric substance, be not only aqueous dispersion type, and, can have good terminal separability and high retentivity.
So-called " similarity condition ", meaning except that having or not silane is other conditions the monomer, for example, the kind of the kind of temperature of reaction, reaction times, polymerization starter and consumption, chain-transfer agent and consumption etc. are same.
Also have, obtaining the insoluble composition of solvent when making the monomeric composition of the not siliceous methane series of employing carry out polymerization, to surpass the monomer mixture of 5% resin combination and silane be monomer when carrying out polymerization, reduces terminal separability easily.
As available emulsion polymerization way among the present invention, generally can adopt polymerization in batch, drip polymerization, the polymerization etc. of dripping in batches continuously, polymerization temperature is for example about 20～100 ℃.
As the used polymerization starter of polymerization, for example, can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2, two (the 2-methyl propionyl amidine) dithionates, 2 of 2 '-azo, two (the 2-amidine propane) dihydrochlorides, 2 of 2 '-azo, two [2-(5-methyl-2-tetrahydroglyoxaline-2-yl) propane] dihydrochlorides, 2 of 2 '-azo, the two azo series initiators such as (N, N '-dimethylene isobutyl amidine) of 2 '-azo; Persulphate such as Potassium Persulphate, ammonium persulphate; Superoxide series initiators such as benzoyl peroxide, tertbutyl peroxide, hydrogen peroxide; Phenyl replaces replacement ethane series initiators such as ethane; Aromatic carbonyl; Redox system initiators such as the composition of the composition of persulphate and sodium bisulfite, superoxide and sodium ascorbate etc., but be not limited to these.The consumption of polymerization starter with respect to monomer mixture total amount 100 weight parts, for example is about 0.005～1 weight part.
In addition, when polymerization, also can adopt chain-transfer agent.As chain-transfer agent, can enumerate chain-transfer agent commonly used, for example thio-alcohol such as lauryl mercaptan.The consumption of chain-transfer agent with respect to monomer mixture total amount 100 weight parts, for example is about 0.001～0.5 weight part.
In addition, as emulsifying agent, can adopt negatively charged ion such as Sodium Lauryl Sulphate BP/USP, Texapon Special, Sodium dodecylbenzene sulfonate, Voranol EP 2001 sodium sulfate, polyoxyethylene alkyl phenyl ether ammonium sulfate, polyoxyethylene alkyl phenyl ether sodium sulfate is emulsifying agent; Nonionic such as Voranol EP 2001, polyoxyethylene alkyl phenyl ether is an emulsifying agent etc.These emulsifying agents both can use separately, also can more than 2 kinds and use.The consumption of emulsifying agent with respect to monomer mixture total amount 100 weight parts, for example is about 0.2～10 weight part, preferred 0.5～5 weight part.
Also have, aqueous dispersion type binder composition of the present invention, except adopting above-mentioned emulsion polymeric manufacture method, can also after adopt letex polymerization method in addition to make above-mentioned (methyl) acrylate copolymer, adopt emulsifying agent that it is dispersed in and make dispersion liquid in the water.
Aqueous dispersion type binder composition of the present invention, for prevent to the release liner that has been coated with the silicone-based stripper or back side processing layer through the time heavy peeling off, in containing the aqueous dispersions that above-mentioned silane is monomeric (methyl) acrylate copolymer, also can add to be monomer bonded organic compound with silane.Can be monomer bonded organic compound with silane, so long as have can be that Si-OH radical reaction bonded active group (for example hydroxyl or the carboxyl) person that monomeric Si-OR base (R is alkyl such as methyl, ethyl) hydrolysis generates can be not particularly limited with silane, with silane be that the good silane compound of reactwity of monomer is preferred.
As above-mentioned silane compound, be that intramolecularly has Si-H or Si-OH base and Si-OR base (R is a methyl, alkyl such as ethyl) compound, for example, can enumerate methyltrimethoxy silane, butyl trimethoxy silane, the dodecyl Trimethoxy silane, the hexadecyl Trimethoxy silane, octadecyl dimethyl methyl TMOS, the dimethoxy dimethylsilane, methoxytrimethylsilane, di ethoxy di methyl-monosilane, Union carbide A-162, phenyl-trimethylsilicane, phenyl triethoxysilane, the dimethoxy diphenyl silane, phenylbenzene (ethoxymethyl) base silane, the dimethoxy-methyl phenyl silane, triethyl silicane, tripropyl silane, the trimethyl silicane alkanol, triethyl silicane alcohol etc.
It can be preferred with the functional group person of polymer reaction that above-mentioned silane compound does not have, but so long as that the functional group of significantly reaction do not take place is also harmless.As silane compound with this functional group, for example, can enumerate (methyl) acrylic acid series silane compounds such as 3-methacryloxypropyl trimethoxy silane, 3-acryloxy propyl trimethoxy silicane, or dimethoxy-3-sulfydryl propyl group methyl-monosilane, 3-sulfydryl propyl trimethoxy silicane etc.These silane compounds both can use separately, also can more than 2 kinds and use.
As being monomer bonded organic compound amount,, for less than 0.005 weight part the time, can not prevent heavily peeling off sometimes with respect to polymkeric substance 100 weight parts of above-mentioned (methyl) alkyl acrylate as principal constituent with silane.And when surpassing 1 weight part, cohesive force reduces, or sometimes clung body is produced and pollute, and in addition, when adopting can be with the siloxane-based monomer bonded of multiple functional radical organic compound the time, makes sometimes to peel off on the contrary and increases the weight of.Can infer that this is because unreacted organic compound has when existing as due to the function of linking agent.Therefore, in the present invention,, can be that monomer bonded organic compound amount is that 0.005～1 weight part is preferred with silane to above-mentioned polymer 100 weight parts, 0.01～0.5 weight part more preferably.
In addition, in the present invention, for prevent to the release liner that has been coated with the silicone-based stripper or back side processing layer through the time heavy peeling off, carry out as principal constituent and the monomeric monomer mixture of siliceous methane series with (methyl) alkyl acrylate in the polymkeric substance that copolymerization obtains making, as the silane with above-mentioned (methyl) alkyl acrylate copolymer is monomer, and adopting silane is that the R of monomeric Si-OR base is that the methoxy silane of methyl is that monomer is preferred.As methoxy silane is monomer, for example, can enumerate 3-methacryloxypropyl trimethoxy silane, 3-acryloxy propyl trimethoxy silicane, 3-methacryloxypropyl methyl dimethoxysilane, 3-acryloxy propyl group methyl dimethoxysilane, vinyltrimethoxy silane, 4-vinyl butyl Trimethoxy silane, 8-vinyl octyl group Trimethoxy silane, 10-methacryloxy decyl Trimethoxy silane, 10-acryloxy decyl Trimethoxy silane etc.
Can infer, when using methoxy silane to be monomer, because methoxy silane is that monomeric hydrolysis rate is fast, most of methoxyl group is hydrolyzed into silanol in polymerization, when drying, the silane that enters polymkeric substance is that monomeric major part consumes in crosslinked, so, through the time can be that monomer reduces in the preservation process with the silane of peel ply reaction.
In addition, in order to reach same purpose, carry out as principal constituent and the monomeric monomer mixture of siliceous methane series with (methyl) alkyl acrylate in the polymkeric substance that copolymerization obtains making, using methacrylic acid is preferred as the monomer that contains the above-mentioned functional group of containing.People infer, when adopting the polymkeric substance of methacrylic acid copolymerization, the rising that can prevent peeling force is because methacrylic acid can be in the inner distribution of particulate, the siloxane-based monomeric hydrolysis that enters polymkeric substance inside than acrylic acid hydrophobicity height in aqueous dispersions.
In the present invention, can use linking agent according to the purposes of tackiness agent.As above-mentioned linking agent, can adopt normally used linking agent, for example isocyanate-based linking agent, epoxy are that linking agent, oxazoline are that linking agent, ethylenimine are linking agent, metal-chelating system linking agent etc.Linking agent is oil soluble and water misciblely all can.
Aqueous dispersion type binder composition of the present invention adds the bonding imparting agent with phenol skeleton and constitutes in containing the aqueous dispersions that above-mentioned silane is monomeric (methyl) acrylic ester polymer.
The bonding imparting agent that uses among the present invention is the compound that intramolecularly contains the phenol skeleton, for example, can enumerate rosin phenol resins, terpene phenolic resin, alkyl phenol resin etc.
Here, as the rosin phenol resins, " the マ ノ Le " that can adopt waste river chemical industry (strain) to make, " Si Mileite resin (the resinoid trade(brand)name of alkylphenol) (the ス ミ ラ イ ト レ ジ Application) " that Sumitomo デ ユ レ ズ (strain) makes etc., as the terpene phenolic resin, " the Na ノ レ Star ト " that can adopt ヤ ス Ha ラ ケ ミ カ Le (strain) to make, " YS Port リ ス -; " マ イ テ イ エ-ス " etc.; as alkyl phenol resin, can adopt Hitachi to change into " ヒ ノ-Le " that industry (strain) is made; " the Star キ ロ-Le " that Sumitomo Chemical (strain) is made; the product of the market sales such as " PP シ リ-ズ " that group Rong Huaxue (strain) makes.These bonding imparting agents both can use separately, also can more than 2 kinds and use.
The amount of bonding imparting agent, with respect to polymkeric substance 100 weight parts of above-mentioned (methyl) alkyl acrylate, when being lower than 5 weight parts and being higher than 50 weight parts, can't obtain using upward sufficient adhesion characteristic sometimes as principal constituent, for example, sometimes to the binding property deficiency of rubbery foam body.Therefore, with respect to the amount of the bonding imparting agent of above-mentioned polymkeric substance 100 weight parts 5～50 weight parts preferably, be more preferably 10～40 weight parts among the present invention.
In addition, in aqueous dispersion type binder composition of the present invention, in addition, can also add normally used additive in the tackiness agent as required, for example, antiager, weighting agent, pigment, tinting material etc.
In addition, aqueous dispersion type binder composition of the present invention in order to make particle-stabilisedization, can adopt common alkaline matters such as ammonia that its pH is transferred to 7～9.At this moment, when residual ammonia for a long time, for make the release liner that has been coated with the silicone-based stripper or back side processing layer carry out through the time heavy peeling off, its addition is fewer better, and is better about pH7～8.
Secondly, the example of adhesive sheet of the present invention is illustrated with reference to accompanying drawing, but the present invention is not limited to these.
Adhesive sheet of the present invention is the binder layer that is made of above-mentioned aqueous dispersion type binder composition to be arranged on the single face of base material or the two sides constitute.The sectional drawing of one of adhesive sheet of having binder layer on base material film two sides example is shown to Fig. 1 pattern.
In Fig. 1, illustrate respectively, 5 is adhesive sheet, and 1 is the binder layer that above-mentioned aqueous dispersion type binder composition constitutes, and 2 is base material, and 3 is release liner.Adhesive sheet 5, be by the aqueous dispersion type binder composition is coated with on base material 2, carry out heat cross-linking, forming binder layer 1 makes, said aqueous dispersion type binder composition is at siliceous methane series monomer and add the bonding imparting agent contain the phenol skeleton with (methyl) alkyl acrylate in as the multipolymer of the monomer mixture of principal constituent is constituted.Then, in order to protect adhesive face and release liner 3 to fit.Preferably it is reeled like that by diagram, also can be preserved with former state.In addition, after forming binder layer 1 on the release liner 3, also can be bonding with base material 2.
As the base material among the present invention 2, for example, can adopt plastic film classes such as polypropylene screen, ethylene-propylene copolymer film, polyester film, polyvinyl chloride; Stationery such as Japan paper and kraft paper; Dry goods such as cotton and chemical fabric; Non-woven dry goods such as polyester non-woven fabric and vinylon non-woven; Tinsel etc.Above-mentioned plastic film, unstretching film and stretching (unilateral stretching or two-way stretch) any of film all can.In addition, can also adopt normally used priming paint or corona discharge mode etc. to carry out surface treatment in the base material on the face of coating adhesive.The thickness of base material can suitably be selected according to purpose, is generally 10～500 μ m.
The above-mentioned aqueous dispersion type binder composition of coating carries out heat cross-linking by heating and forms binder layer 1.Heat cross-linking can adopt method commonly used, is that the kind of monomer and linking agent is heated to the temperature that crosslinking reaction carries out and carries out heat cross-linking according to silane for example.The insoluble composition of the solvent of the binder layer after crosslinked for example is 15～70 weight %.In addition, the molecular weight (weight-average molecular weight is converted into polystyrene standard) of the solvable composition of solvent of the binder layer after crosslinked, for example about 100,000～600,000, preferred about 200,000～450,000.The molecular weight of insoluble composition of the solvent of the binder layer after crosslinked and the solvable composition of solvent, for example, with respect to the above-mentioned silane of monomer mixture total amount be the kind of monomer or the monomer ratio that contains the functional group, chain-transfer agent and linking agent and amount that amount, particularly silane are monomer and chain-transfer agent by suitably adjusting, can set arbitrarily.
Fig. 2 is another routine sectional drawing of pattern ground expression adhesive sheet of the present invention, on 1 face of base material 2 above-mentioned binder layer 1 is set, and the binder layer 4 that is made of the binder composition that is different from binder layer 1 is set on other 1 face, forms adhesive sheet 6.And, fit in order to protect adhesive face and release liner 3.Here be not particularly limited as binder layer 4, can adopt binder compositions such as the original acrylic acid series that oneself knows, rubber system, silicone-based according to the kind of its purposes and clung body.Preferably it is reeled by diagram, but also can be preserved by its former state.Also have, in Fig. 2, release liner 3 connects and composes with binder layer 4, also can but connect and compose with binder layer 1.In this case, also can determine its formation according to the kind of the clung body of initial stickup adhesive sheet.
Fig. 3 is the sectional drawing of the another example of pattern ground expression adhesive sheet of the present invention, and is illustrated on 1 face of base material 2 binder layer 1 is set, applying release liner 3 on this layer and constituting.Preferably it is reeled by diagram, but also can be preserved by its former state.
Fig. 4 is the sectional drawing of the another example of pattern ground expression adhesive sheet of the present invention, and is illustrated in the formation that binder layer 1 is set on the base material 2 that back side processing layer 7 is set.It is reeled like that by diagram, binder layer 1 contact back side processing layer 4 is preserved.
The back side of the present invention processing layer 7 can adopt the previous method that oneself knows of employings such as silicone-based stripper, chain alkyl series stripping agent, fluorine series stripping agent is arranged on layer on the base material 1.
Adhesive sheet of the present invention is the adhesive sheet that the rubbery foam body is had good bounding force, is generally more than the 3N/20mm, more than the preferred 4N/20mm, and more preferably 5N/20mm above (180 degree strip ofves, peeling rate 300mm/ branch is 23 ℃, in the 60%RH atmosphere).
In addition, rubbery foam body adhesive sheet provided by the invention, it is characterized in that the binder layer that above-mentioned aqueous dispersion type binder composition constitutes is arranged on the single face or two sides of rubbery foam body, and the rubbery foam body adhesive sheet that provides, it is characterized in that above-mentioned adhesive sheet is arranged on the single face or two sides of rubbery foam body.
Fig. 5 be pattern be illustrated in the sectional drawing of one of rubbery foam body adhesive sheet that adhesive sheet shown in Figure 15 is set on rubbery foam body single face example.In Fig. 5,8 expression rubbery foam bodies, other are with above-mentioned.In addition, adhesive sheet 5 also can be arranged on the two sides of rubbery foam body 8.
Fig. 6 is the sectional drawing that the another example of foams adhesive sheet of the present invention is shown, and on the single face of rubbery foam body 8 adhesive sheet shown in Figure 26 is set and constitutes.At this moment, the formation of adhesive sheet 6 is to be adhered on the foams 8 by binder layer 1.In addition, adhesive sheet 6 also can be arranged on the two sides of rubbery foam body 8.
In addition, to form binder layer 1 be not to be contained in the two sides adhesive sheet that what is called on the base material does not have base material so the present invention also can be formed on the release liner 3.Like that,, can make the rubbery foam body adhesive sheet that the binder layer of aqueous dispersion type binder composition formation is arranged on (or on two sides) on the single face of rubbery foam body shown in its sectional drawing as shown in Figure 7 by fitting with foams 8.
Rubber among the present invention is foams 8, is the mixture that contains rubber based polymer, vulcanizing agent, whipping agent, vulcanization accelerator, frothing aid etc., by heating, carries out sulfur foam and makes.
As the rubber based polymer, be not particularly limited, can adopt original those that are suitable for, for example, can enumerate propylene diene rubber (EPDM) and ethylene propylene rubber, ethylene, propylene tar polymer and silicone-based rubber, fluorine is rubber and acrylic rubber, polyurethane series rubber and polyamide-based rubber, natural rubber and polyisobutene, polyisoprene and neoprene, isobutylene-isoprene copolymer and isopropyl cyanide rubber, styrene butadiene ribber and styrene butadiene styrene rubber, styrene isoprene styrenerubber and styrene ethylene divinyl rubber, styrene ethylene butylene styrene rubber and styrene isoprene acrylonitrile-styrol rubber, alpha-olefin such as chlorosulfonated polyethylene and butene-1 Dicyclopentadiene (DCPD) and ethylidene norbornene etc. have the ring-type of unconjugated double bond or non-annularity polyenoid as rubber based copolymer of composition etc.From viewpoints such as practicality, EPDM is preferred.
Vulcanizing agent also is not particularly limited; can adopt those of original use; for example; (for example can enumerate sulphur, sulphur compound, selenium, magnesium oxide, plumbous oxide, zinc oxide, organo-peroxide class, polyamines, oximes; p-benzoquinones dioxime, p, p '-dibenzoyl benzoquinones dioximes etc.), nitroso compound class (for example, p-dinitrosobenzene), resene are (for example; alkylbenzene resinox, melamine-formaldehyde condensation products etc.), ammonium salt class (for example, ammonium benzoate) etc.
These vulcanizing agents can suitably be selected to use more than a kind or 2 kinds, and from resulting from the sulfuration of resulting rubbery foam body and the considerations such as physical properties such as weather resistance of foaminess, sulphur and sulphur compound class, particularly sulphur are preferred.In addition, the consumption of vulcanizing agent can suitably determine according to the sulfuration efficient that depends on its kind, for example, using Sulfur and sulphur compound time-like, usually rubber based polymer 100 weight parts is reached 0.1～10 weight part, preferred 0.5～5 weight part.
In addition, as whipping agent, be not particularly limited, for example, can adopt inorganic is whipping agent or organic system whipping agent.
As inorganic be whipping agent, for example, can adopt volatile salt, bicarbonate of ammonia, sodium bicarbonate, ammonium nitrite, sodium borohydride, nitrine class etc.And as the organic system whipping agent, for example, (for example can adopt the azo based compound, Diisopropyl azodicarboxylate, Cellmic C 121 (ADCA), barium azodicarboxylate etc.), fluoric ether (for example, Trichloromonofluoromethane, Dichloromonofluoromethane etc.), the hydrazine based compound (for example, p-toluene sulfonyl hydrazide, phenylbenzene sulfo group-3,3 '-disulfonyl hydrazide, 4,4 '-oxo two (benzol sulfohydrazide) etc.), the Urea,amino-based compound (for example, p-toluylene sulfonylsemicarbazide, 4,4 '-oxo two (phenylsulfonamido urea) etc.), three azole compounds (for example, 5-morpholinyl-1,2,3, the 4-thiatriazole), N-nitroso-group based compound (N, N '-dinitrosopentamethylene tetramine, N, N '-dimethyl-N, N '-dinitrosoterephthalamine) etc.
These whipping agents can suitably be selected more than a kind or 2 kinds to use, but consider organic system whipping agents such as preferred azo based compound and N-nitroso-group based compound from resulting from the viewpoints such as physical properties of foaminess of resulting rubbery foam body.In addition, the cooperation ratio of whipping agent can be according to as suitably decisions such as the foam physical propertiess of purpose, but generally is to be 0.1～100 weight part with respect to rubber based polymer 100 weight parts, preferred 0.5～50 weight part, more preferably 1～30 weight part.
In this rubbery foam body, cooperate for promoting the sulfurized vulcanization accelerator and guaranteeing that the frothing aid of good foaming is preferred.
As vulcanization accelerator, for example, (for example can adopt the dithiocarbamic acid class, Sodium dimethyldithiocarbamate 40min, Thiocarb, ziram, zinc diethyldithiocarbamate etc.), thiazoles (for example, 2-mercaptobenzothiazole, dibenzo sulphur pyrrole based bisulfide etc.), the guanidine class (for example, diphenylguanidine, two-neighbour-tolyl guanidine etc.), sulfamido (for example, benzo-aza cyclopentadienyl-2-diethyl sulfanilamide (SN), N-cyclohexyl-2-benzo-aza cyclopentadienyl sulfanilamide (SN) etc.), thiurams (for example, the tetra methylthiuram monosulphide, tetramethyl thiuram disulfide etc.), the xanthan acids (for example, Good-Rite Nix, zinc isopropyl xanthate etc.), the aldehyde ammonia class (for example, acetyl aldehyde ammonia ammonium, vulkacit H etc.), aldehyde amines (for example, normal-butyl aldehyde aniline, butyl aldehyde monobutylamine (MBA) etc.), Thiourea (for example, diethyl thiourea, trimethyl thiourea etc.).These vulcanization accelerators can suitably be selected more than a kind or 2 kinds to use, and for example, consider dithiocarbamic acid class and thiazoles and with being preferred from viewpoints such as vulcanization rates.
In addition, the cooperation ratio of vulcanization accelerator is considered from viewpoints such as anti-bloom, vulcanization rates, for example, is 0.1～10 weight part with respect to rubber based polymer 100 weight parts, preferred 0.5～5 weight part.
Also have, opposite with vulcanization accelerator, consider as purposes such as regulating the moulding processibility, also can suitably cooperate vulcanization retardant, for example organic acid (for example, anhydride phthalic acid, M-nitro benzoic acid, Whitfield's ointment etc.) and amine (for example, N-nitroso-group-pentanoic, N-nitroso-group-Phenyl beta naphthylamine etc.).
As frothing aid, for example, can adopt urea based compound, Whitfield's ointment based compound, M-nitro benzoic acid based compound etc.These frothing aids can suitably be selected more than a kind or 2 kinds to use, to the sulfurized influence less, cost is low etc., and viewpoint is considered, preferably adopts the urea based compound.In addition, the cooperation ratio of frothing aid for example, is 1～15 weight part with respect to rubber based polymer 100 weight parts, preferred 2～10 weight parts, more preferably 3～8 weight parts.
In addition, in this rubbery foam body, according to its purposes, fits best filler, treated oil, lubricant etc. in addition, can also suitably cooperate for example known additives such as softening agent, fire retardant, antiaging agent, oxidation inhibitor, pigment, tinting material, mould inhibitor.
As filler, for example, can adopt zinc white, carbon black, lime carbonate, magnesiumcarbonate, silicic acid and its esters, talcum, mica, wilkinite, silicon-dioxide, aluminum oxide, aluminosilicate, acetylene black, aluminium powder etc.These fillers can suitably be selected to use more than a kind or 2 kinds, and zinc white also has as function of stabilizer, and carbon black also can be used as strongthener, so, the preferred use.In the ordinary course of things, lime carbonate is to decorate to use.The cooperation ratio of filler for example, reaches 80～200 weight parts with respect to rubber based polymer 100 weight parts, preferred 10～180 weight parts.
As treated oil, can adopt paraffin series oil and oil is wet goods, preferred operations oil.The cooperation ratio of treated oil for example, is 10～60 weight parts with respect to rubber based polymer 100 weight parts, preferred 30～50 weight parts.By adding treated oil, the mixing of mixture becomes easily, and foaming also becomes easy.
As lubricant, for example, can adopt stearic acid and ester class thereof etc., its cooperation ratio for example, is 1～5 weight part with respect to rubber based polymer 100 weight parts, preferred 2～4 weight parts.By adding lubricant, for example, be difficult to when mixing can improve processibility attached on the roller.
As softening agent, for example, (for example can adopt paraffin class, clorafin), wax class, cycloalkane, aromatic hydrocarbons, pitch class, dry oils (for example, Semen Lini oil), animals and plants oils, low-molecular weight polymer class, phthalate, phosphoric acid ester, alkyl sulfonates, bonding imparting agent etc.By adding softening agent, mixture becomes soft and is easy to foaming.
As fire retardant, for example, can adopt aluminium hydroxide and magnesium hydroxide etc.
In this rubbery foam body, according to its purpose and purposes, can also suitably cooperate the nonrubber based polymer, for example, can adopt acrylic acid polymer (for example, poly-(methyl) alkyl acrylate), polyvinyl chloride, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyvinyl acetate (PVA), polymeric amide, polyester, chlorinatedpolyethylene, ammonia ester based polymer, styrenic, silicone-based polymkeric substance, epoxy is resin etc.
These nonrubber based polymers according to its purpose and purposes, can suitably be selected to use more than a kind or 2 kinds, and its cooperation ratio for example, is below the 50 weight % of rubber based polymer, below the preferred 30 weight %, more preferably below the 15 weight %.
The manufacturing of rubbery foam body mixture of the present invention, at first, rubber based polymer, vulcanization aid, filler, processing wet goods gradation composition, for example, by kneader or batch mixing with mixing roll modulating mixtures such as rolling machines.Also have, in this is mixing, also can suitably heat.Then, suitably select to cooperate vulcanizing agent, whipping agent and frothing aid in this mixture again, adopt batch mixing to heat after further mixing it and also can with rolling machine etc.
The formation of rubbery foam body of the present invention, but by what the processing of said mixture heating carrying out sulfur foam was formed, but when it forms, as required, also mixture for example can be shaped to the form of regulations such as sheet material, again this formed body be carried out heat treated and make the sulfuration foams.At this moment, formed body also can be shaped to form arbitrarily by rights, and there is no particular limitation about its form.
Therefore, formed body before sulfur foam is handled, can be with mixture, for example both can adopt batch mixing with the suitable mode of rolling machine or roll-type rolling press or extrusion moulding etc., be shaped to sheet or other forms, also can adopt suitably mode such as injection molding or compression moulding, be shaped to regulation form with concavo-convex grade etc. by the mould of regulation.
As mentioned above, when formation has the foams of concaveconvex shape, also can adopt, the formed body of sulfided state not is configured in to have on the concavo-convex mould heats, the mixture that forms formed body is flowed on this mould concavo-convex, carry out mode that sulfur foam handles etc.The advantage of this mode is, has the complexity of fold in employing and also can form its concaveconvex shape with good precision during the mould of dark concaveconvex structure.
Therefore, the size of formed body is arbitrarily, and can be according in addition suitably decision such as the form of purpose rubbery foam body.When being sheet material, generally its thickness below 100mm, preferred 1 μ m～80mm, preferred especially 10 μ m～50mm.
Above-mentioned sulfur foam is handled, and can begin temperature and blowing temperature etc. according to the sulfuration of vulcanizing agent that adopts and whipping agent etc., carries out under based on suitable condition in the past.General sulfur foam temperature is about below 200 ℃, preferred 120～180 ℃.When adopting this sulfur foam to handle, make mixture softening usually, whipping agent is decomposed, form foamy structure, vulcanize simultaneously, form the sulfuration foams of purpose.Sulfur foam is handled, and can also to be purpose with the adjusting of expansion ratio etc. carry out adding to depress.This pressurized conditions also can same prior art.
The expansion ratio of the rubbery foam body that forms (the density ratio before and after the foaming) can be according to suitably decisions such as application targets.Generally, set 0.5g/cm for based on density
3Below, preferred 0.20g/cm
3Below, more preferably 0.15g/cm
3Below.This density, use level that can be by adopting above-mentioned whipping agent and sulfur foam treatment time and temperature wait regulates expansion ratio etc. and controls.In addition, the adjusting by expansion ratio etc., it is independent or continuously that the foaming structure that can also control the sulfuration foams becomes, or independent, mix the foamy structure that exists etc. continuously.
According to rubbery foam body adhesive sheet of the present invention, because adopting water-dispersed acrylic is tackiness agent, so be preferred aspect environmental health, can present extremely good terminal separability and retentivity, can also obtain through the time bounding force stable rubbery foam body adhesive sheet.Therefore, can be as for example cushioning material and cushioning material, the sealing material of various purposes such as airtight and waterproof, lagging material, the existing various uses such as damping material of sound insulation and antivibration etc.
Embodiment
The invention will be further described below by embodiment, but the present invention is not subjected to their qualification.Also have, " part " reaches " % ", all is benchmark with weight except that being stipulated especially.
Cooling tube has been installed in employing, nitrogen ingress pipe, temperature is taken into account the reactor of stirrer, 70 parts of butyl acrylates, 30 parts of 2-EHAs, 3 parts in vinylformic acid, 3-methacryloxypropyl trimethoxy silane (silicone Co., Ltd. of SHIN-ETSU HANTOTAI system, " KBM-503 ") 0.05 part, 0.05 part of lauryl mercaptan (chain-transfer agent), 2,0.1 part of two [2-(5-methyl-2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride (initiator) of 2 '-azo, be added into oneself and added in 100 parts in the water of 1.5 parts of polyoxyethylene Sodium Lauryl Sulphate BP/USPs (emulsifying agent) and carry out letex polymerization, obtain polymkeric substance.Also have, adopting and not sneaking into silane is that the solvent indissolvable component of polymerization that monomeric composition the carries out the polymerization occasion equally polymkeric substance when stopping is 0%.
Toward wherein adding 10% ammonium water, be adjusted to pH8 after, add 0.06 part of positive decyl Trimethoxy silane as silane compound (" AY43-210MC " that eastern レ ダ ウ コ one ニ Application グ シ リ コ one Application Co., Ltd. makes), obtain aqueous dispersions.Press 30 parts of solid component meters toward wherein adding, obtain the aqueous dispersion type tackiness agent with respect to 100 parts of rosin phenol resins of solids component (" マ ノ Le E-100 " that Arakawa Chemical Industries, Ltd. makes) as bonding imparting agent.
With above-mentioned adhesive coated on the heavy release surface of oneself release liner through being coated with the silicone-based stripper (" SLB-80W5D " that カ イ ト chemical industry Co., Ltd. makes), in 120 ℃ of dryings 3 minutes, make the adhesive sheet that is provided with thickness 70 μ m binder layers.This adhesive sheet is sticked on the two sides of non-woven (the Japanese paperboard system PR-14 of Co., Ltd.), make adhesive sheet.
Except using rosin phenol resin (Sumitomo デ ユ レ ッ Star Co., Ltd. system, " ス ミ ラ イ ト レ ジ Application PR12603 ") aqueous dispersions presses 30 parts of solid component meters, the rosin phenol resin that adds as bonding imparting agent in replacement the foregoing description 1 (" マ ノ Le E-100 " that waste river chemical industry (strain) is made) in addition, adhesive sheet is made in operation similarly to Example 1.
Except using terpenes phenol resin (ヤ ス Ha ラ ケ ミ カ Le Co., Ltd. system, " Na ノ レ Star ト G1450 ") aqueous dispersions presses 30 parts of solid component meters, the rosin phenol resin that adds as bonding imparting agent in replacement the foregoing description 1 (" マ ノ Le E-100 " that waste river chemical industry (strain) is made) in addition, adhesive sheet is made in operation similarly to Example 1.
Comparative example 1
Except with the polymerized rosin ester being resin (waste river KCC system, " ス one パ one エ ス テ Le E-625 ") aqueous dispersions presses 30 parts of solid component meters, the rosin phenol resin that adds as bonding imparting agent in replacement the foregoing description 1 (" マ ノ Le E-100 " that waste river chemical industry (strain) is made) in addition, adhesive sheet is made in operation similarly to Example 1.
Comparative example 2
The bonding imparting agent in not adding the foregoing description 1, adhesive sheet is made in operation similarly to Example 1.
Comparative example 3
The reactor that cooling tube, nitrogen ingress pipe, temperature are taken into account stirrer has been installed in employing, 0.07 part of 70 parts of butyl acrylate, 30 parts of 2-EHAs, 3 parts in vinylformic acid, lauryl mercaptan (chain-transfer agent), 2,0.1 part of two [2-(5-methyl-2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride (initiator) of 2 '-azo, be added into oneself and added in 100 parts in the water of 1.5 parts in polyoxyethylene nonylplenyl ether sodium sulfate (emulsifying agent) and carry out letex polymerization, obtain polymkeric substance.
Add 10 weight % ammonium water inward, be adjusted to pH8.Add inward with respect to 100 parts of rosin phenol resins of solids component (" マ ノ Le E-100 " that waste river chemical industry (strain) is made) and press 30 parts of solid component meters as bonding imparting agent, add soluble epoxide type linking agent (TEPIC again, Mitsubishi Gas Chemical Co., Ltd's system) 0.14 part, obtains the aqueous dispersion type tackiness agent.
It is operated similarly to Example 1, make adhesive sheet.
To the adhesive sheet investigation following properties that obtains in above embodiment and the comparative example.The results are shown in table 1.Bounding force to the rubbery foam body
Paste the PET film of thickness 40 μ m on the adhesive sheet single face that in embodiment and comparative example, obtains, be cut into wide 20mm, long 100mm, make to estimate and use test piece.With this test piece, be that the rubbery foam body sticks on product on the metal sheet as clung body to contain paraffin series oil, pitch as the EPDM of softening agent, with the 2kg roller come and go 1 time method press sticking, in 23 ℃ place 30 minutes down after, measure the needed power of peeling off.Condition determination is, the universal tensile testing machine " TCM-1kNB " that adopts ミ ネ ベ ア Co., Ltd. to make, and 180 degree are peeled off, and carry out (with reference to Fig. 8) in the peeling rate 300mm/ branch, 23 ℃, 60%RH atmosphere.
Terminal separability test
The adhesive sheet of making in embodiment and the comparative example, sticking on the paraffin series oil, the bituminous EPDM that contain as softening agent is on the rubbery foam body (thick 5mm), is cut into wide 10mm, long 50mm, makes to estimate and uses test piece.One end of this test piece is pasted back (surface) in the end of ABS plate with the contact area of 10mm * 10mm, and (wide 10mm * 40mm) pastes at the surface of turning back to the ABS plate rest part.It is placed 2 hours in 70 ℃ of atmosphere after, whether estimate on the surface ABS plate and peel off (with reference to Fig. 9) from the rubbery foam body.
The bounding force of rubbery foam body adhesive sheet
The adhesive sheet of making in embodiment and the comparative example, sticking on the paraffin series oil, the bituminous EPDM that contain as softening agent is on the rubbery foam body (thick 5mm), is cut into wide 20mm, long 100mm, makes to estimate and uses test piece.With this test piece on SUS plate as clung body, with the 2kg roller come and go 1 time method press sticking, it is placed 7 days in (initial value) and the 60 ℃/90%RH atmosphere after 23 ℃ are placed 30 minutes after (through the time preserve the back), mensuration is peeled off needed power.Condition determination is, the universal tensile testing machine " TCM-1kNB " that adopts ミ ネ ベ ア Co., Ltd. to make, and 90 degree are peeled off, and carry out (with reference to Figure 10) in the peeling rate 300mm/ branch, 23 ℃, 60%RH atmosphere.
Table 1
| Binder composition | Rubbery foam body bounding force [N/20mm] | The terminal separability of rubbery foam body | Bounding force to the SUS plate | ||||
| Cross-linking method | The bonding resin of giving | Initial stage [N/20mm] | Through the time preserve after [N/20mm] | ||||
| | | Rosin phenol | 7 | ○ | 12 | 12 | |
| | | 6 | ○ | 12 | 12 | ||
| | | 5 | ○ | 10 | 10 | ||
| Comparative example 1 | Silanol | The polymerized | 8 | ○ | 12 | 6 | |
| Comparative example 2 | Do not have | 1 | × | 5 | 5 | ||
| Comparative example 3 | Resins, epoxy | Rosin phenol | 5 | × | 10 | 10 | |
As shown in table 1, aqueous dispersion type tackiness agent of the present invention (embodiment 1～3) shows, to the bounding force of rubbery foam body, terminal separability, through the time bounding force after preserving all have good performance.
Opposite with it, adopt not contain the comparative example 1 of the polymerized rosin ester of phenol skeleton as bonding imparting agent, the bounding force of rubbery foam body, terminal separability are shown the performance that fully satisfies, but through the time poor adhesion after preserving.In addition, do not add the comparative example 2 of bonding imparting agent, poor to the bounding force of rubbery foam body, terminal separability.In addition, not making silane is monomer copolymerization and to adopt epoxy be that linking agent carries out crosslinked aqueous dispersion type tackiness agent (comparative example 3), and terminal separability is poor.
The effect of invention
As mentioned above, water-dispersed pressure-sensitive adhesive composition of the present invention, owing to adopt the acrylic adhesive of water-dispersion type, so good on environmental sanitation, it is arranged on bonding sheet and rubbery foam bonding sheet on the base material, have good cohesive and terminal fissility to the rubbery foam body, and, brought into play through the time adhesion stability good adhesion characteristic.
Claims (17)
1. aqueous dispersion type binder composition, it is to make with (methyl) alkyl acrylate as principal constituent, and to contain silane be that monomeric monomer mixture carries out in the aqueous polymer dispersion that copolymerization obtains, adds that the bonding imparting agent that contains the phenol skeleton constitutes.
2. according to the aqueous dispersion type binder composition of putting down in writing in the claim 1, it is characterized in that, the polymkeric substance of this aqueous dispersion type binder composition is to make with (methyl) alkyl acrylate as principal constituent, and when adopting the monomeric composition polymerization of not siliceous methane series, obtain the monomer mixture of the insoluble composition of solvent at the resin combination below 5%, with the silane that is 0.005～1 weight part with respect to these monomer mixture 100 weight parts be monomer, with above-mentioned similarity condition under the polymkeric substance that obtains of copolymerization.
3. according to the aqueous dispersion type binder composition of record in the claim 1, this aqueous dispersion type binder composition is by with respect to polymkeric substance 100 weight parts, and interpolation can be that monomer bonded organic compound 0.005～1 weight part constitutes with silane.
4. according to the aqueous dispersion type binder composition of record in the claim 2, this aqueous dispersion type binder composition is by with respect to polymkeric substance 100 weight parts, and interpolation can be that monomer bonded organic compound 0.005～1 weight part constitutes with silane.
5. according to the aqueous dispersion type binder composition of record in the claim 3, wherein, can be that monomer bonded organic compound is a silane compound with silane.
6. according to the aqueous dispersion type binder composition of record in the claim 4, wherein, can be that monomer bonded organic compound is a silane compound with silane.
7. according to the aqueous dispersion type binder composition of each record in the claim 1～6, it is characterized in that silane is that monomer is that methoxy silane is a monomer.
8. according to the aqueous dispersion type binder composition of each record in the claim 1～6, it is characterized in that copolymerization has methacrylic acid in polymkeric substance.
9. according to the aqueous dispersion type binder composition of claim 7 record, it is characterized in that copolymerization has methacrylic acid in polymkeric substance.
10. the aqueous dispersion type binder composition of arbitrary record in 1～6 as requested, wherein, bonding imparting agent is that rosin phenol system or terpene phenolic are bonding imparting agent.
11. the aqueous dispersion type binder compositions of 7 records as requested, wherein, bonding imparting agent is that rosin phenol system or terpene phenolic are bonding imparting agent.
12. the aqueous dispersion type binder compositions of 8 records as requested, wherein, bonding imparting agent is that rosin phenol system or terpene phenolic are bonding imparting agent.
13. the aqueous dispersion type binder compositions of 9 records as requested, wherein, bonding imparting agent is that rosin phenol system or terpene phenolic are bonding imparting agent.
14. an adhesive sheet, it is that the binder layer that the aqueous dispersion type binder composition of each record in the claim 1～13 constitutes is arranged on the single face of base material.
15. an adhesive sheet, it is that the binder layer that the aqueous dispersion type binder composition of each record in the claim 1～13 constitutes is arranged on the two sides of base material.
16. a rubbery foam body adhesive sheet is characterized in that, the binder layer that the aqueous dispersion type binder composition of each record in the claim 1～13 is constituted is arranged on the single face or two sides of rubbery foam body.
17. a rubbery foam body adhesive sheet is characterized in that, the adhesive sheet of each record of claim 14 or 15 is arranged on the single face or two sides of rubbery foam body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141127 CN1263818C (en) | 2003-06-09 | 2003-06-09 | Water dispersible adhesive composition, adhesive sheet and rubber foam adhesive sheet employing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141127 CN1263818C (en) | 2003-06-09 | 2003-06-09 | Water dispersible adhesive composition, adhesive sheet and rubber foam adhesive sheet employing the same |
Publications (2)
| Publication Number | Publication Date |
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| CN1566245A CN1566245A (en) | 2005-01-19 |
| CN1263818C true CN1263818C (en) | 2006-07-12 |
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| TWI409313B (en) * | 2005-01-26 | 2013-09-21 | Nitto Denko Corp | Adhesive composition, adhesive optical film and image display device |
| US7892373B2 (en) * | 2005-08-19 | 2011-02-22 | Basf Aktiengesellschaft | Adhesive for nonceramic floor coverings |
| US7897683B2 (en) * | 2006-05-24 | 2011-03-01 | Nitto Denko Corporation | Medical adhesive and medical adhesive tape or sheet |
| JP5101919B2 (en) * | 2007-04-09 | 2012-12-19 | 日東電工株式会社 | Double-sided adhesive tape or sheet for printed circuit board and printed circuit board with double-sided adhesive tape |
| JP4780676B2 (en) * | 2007-11-22 | 2011-09-28 | 日東電工株式会社 | Aqueous pressure sensitive adhesive composition and use thereof |
| JP4766571B2 (en) * | 2007-11-22 | 2011-09-07 | 日東電工株式会社 | Aqueous pressure sensitive adhesive composition and use thereof |
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