CN105419684A - Hot melt adhesive film for rubber and metal adhesion and preparation method of hot melt adhesive film - Google Patents
Hot melt adhesive film for rubber and metal adhesion and preparation method of hot melt adhesive film Download PDFInfo
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- CN105419684A CN105419684A CN201510924923.0A CN201510924923A CN105419684A CN 105419684 A CN105419684 A CN 105419684A CN 201510924923 A CN201510924923 A CN 201510924923A CN 105419684 A CN105419684 A CN 105419684A
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- melt adhesive
- hot melt
- adhesive film
- rubber
- bonding
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/048—Presence of homo or copolymers of ethene in the pretreated surface to be joined
Abstract
The invention relates to a hot melt adhesive film for rubber and metal adhesion. The hot melt adhesive film is used for rubber and metal adhesion, causes no release of a solvent in the production process, is simple in preparation technology and can replace a frequently-used liquid adhesive or complicated metal surface pretreatment process. The production process of the hot melt adhesive film for rubber and metal adhesion comprises the following two steps: (1) taking EVA or POE resin as a matrix, melt-grafting maleic anhydride modified polybutadiene, and carrying out pelleting and drying to obtain hot melt adhesive particles; (2) uniformly mixing the hot melt adhesive particles with a sulfur carrier, and preparing the hot melt adhesive film of appropriate thickness. By grafting maleic anhydride, the hot melt adhesive film has an excellent adhesive force with metals; meanwhile, the sulfur carrier releases sulfur at high temperature to co-vulcanize added butadiene segments and rubber, so that the hot melt adhesive film also maintains a favorable adhesive force with rubber.
Description
Technical field
The invention belongs to hot melt adhesive technical field, be specifically related to a kind of bonding of rubber to metal hot melt adhesive film.
Background technology
Metal to rubber is bonded in a lot of industrial circle all has demand, as tracked armored vehicle bogie wheel in mechanical engineering, building, boats and ships, war industry, grip-pad land the bonding of glue and track bushings.Because rubber and metal-polar differ greatly, need one deck caking agent could be bonding preferably.Traditional method has vulcanite method, brass or brass-plating method, resorcinol formaldehyde system, resol method, polyisocyanic acid ester process, halogenated rubber method and contains extraordinary vulcanizing agent halogenated polymer method and water accack method etc.The large Alternative of these traditional methods is comparatively complicated, needs the pretreatment procedures such as polishing, and liquid sizing agent often also has the problem of solvent evaporates toxicity.
Hot melt adhesive film technique is simple, nontoxic, but is not a kind of new theory, just due to adhesive technology reason, uses in some traditional field always, and bonding being difficult to all the time of certain material is broken through, and such as rubber is bonding with metal.In view of rubber and the current existing problem of metal sticking, we are necessary the hot melt adhesive film developing a kind of bonding of rubber to metal, make rubber-metal have good adhesiveproperties.
Summary of the invention
The object of this invention is to provide a kind of hot melt adhesive film that rubber and metal can be made to have good bonding performance, and described hot melt adhesive film is nontoxic, odorlessness, complete processing is simple, can substitute traditional bonding of rubber to metal technique.
The present invention, by carrying out modification to EVA or POE resin, obtains a kind of hot melt adhesive film making rubber and metal have good bonding performance.
Bonding of rubber to metal hot melt adhesive film prepared by the present invention, is characterized in that, is prepared from by following raw material by weight:
Hot-melt adhesive granules 100 parts
Sulfur-donor 0.5-5 part;
Wherein, hot-melt adhesive granules is prepared from by following raw material by weight:
EVA resin or POE resin 100 parts
Peroxide initiator 0.01-0.2 part
Maleic anhydride modified polyhutadiene 0.5-10 part.
Preferably, the fusing point of described EVA resin or POE resin is within the scope of 50 ~ 105 DEG C, and melting index is 1 ~ 40g/10min.
Preferably, described peroxide initiator is one or more mixture in dicumyl peroxide, two (tert-butyl peroxide) hexanes of 2,5-dimethyl-2,5-, benzoyl peroxide, tert-butyl hydroperoxide carbonic acid-2-ethylhexyl.
Preferably, described dicumyl peroxide is as best results during peroxide initiator.
Preferably, described maleic anhydride modified polyhutadiene number-average molecular weight is within the scope of 2500-9900, and maleic anhydride content is in 3 ~ 20% scopes.
Preferably, described sulfur-donor is one or more mixture following: 4,4`-dimorpholinyl disulfide (DTDM), tetramethyl-thiuram disulfide (TMTD), tetramethylthiuram tetrasulfide (TMTT), 2-(4-morpholine base dithio) benzothiazole (MDB).
Preferably, described 4,4`-dimorpholinyl disulfides (DTDM), tetramethyl-thiuram disulfide (TMTD) mixing are as best results during sulfur-donor.
The preparation method of bonding of rubber to metal hot melt adhesive film of the present invention, is characterized in that: be prepared from by following two steps:
1) with the EVA of formula ratio or POE resin for matrix, add the peroxide initiator of formula ratio and maleic anhydride modified polyhutadiene, with twin screw extruder fusion-grafting and granulation at 190 DEG C, obtain hot-melt adhesive granules;
2) in the hot-melt adhesive granules of formula ratio, add the sulfur-donor of formula ratio, mix, prepare by casting method the hot melt adhesive film that thickness is 0.3mm.
Advantageous Effects of the present invention is as follows:
1, the preparation technology of hot melt adhesive film is simple, make metal and rubber firmly bonding, solve metal-rubber in prior art and be difficult to bonding problem.
2, prepare the material environmental protection that hot melt adhesive film uses, smell or release toxic substance in the course of processing, can not be produced, and solvent-free volatilization, be conducive to the technical renovation of material.
3, hot melt adhesive film laminating of the present invention evenly, and in sulfidation, bubble-free produces, and makes rubber and metal have good bonding strength.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1
Step one, get the EVA resin of 100 mass parts, wherein the fusing point of EVA resin is 50 DEG C, melting index is 40g/10min, add 2 of 0.01 mass parts, the maleic anhydride modified polyhutadiene that two (tert-butyl peroxide) hexane of 5-dimethyl-2,5-and 5 mass fraction average molecular weights are 4500, maleic anhydride content is 3%, uses twin-screw extrusion grafting at 190 DEG C and granulation is dried; Step 2, take 100 mass parts step one granulation, the DTDM adding 0.5 mass parts mixes, and adopts casting method, prepares the film that thickness is 0.3mm.Concrete test result is in table 1.
Embodiment 2
Step one, get the POE resin of 100 mass parts, wherein the fusing point of POE resin is 60 DEG C, melting index is 15g/10min, add 2 of 0.2 mass parts, the maleic anhydride modified polyhutadiene that two (tert-butyl peroxide) hexane of 5-dimethyl-2,5-and 5 mass fraction average molecular weights are 7500, maleic anhydride content is 20%, uses twin-screw extrusion grafting at 190 DEG C and granulation is dried; Step 2, take 100 mass parts step one granulation, the TMTD adding 5 mass parts mixes, and adopts casting method, prepares the film that thickness is 0.3mm.Concrete test result is in table 1.
Embodiment 3
Step one, get the EVA resin of 100 mass parts, wherein the fusing point of EVA resin is 105 DEG C, melting index is 2g/10min, the maleic anhydride modified polyhutadiene that the dicumyl peroxide and the 0.5 mass fraction average molecular weight that add 0.05 mass parts are 9900, maleic anhydride content is 6%, uses twin-screw extrusion grafting at 190 DEG C and granulation is dried; Step 2, take 100 mass parts step one granulation, the DTDM adding 0.5 mass parts mixes, and adopts casting method, prepares the film that thickness is 0.3mm.Concrete test result is in table 1.
Embodiment 4
Step one, get the EVA resin of 100 mass parts, wherein the fusing point of EVA resin is 72 DEG C, melting index is 20g/10min, the maleic anhydride modified polyhutadiene that the dicumyl peroxide and the 5 mass fraction average molecular weights that add 0.1 mass parts are 5000, maleic anhydride content is 10%, uses twin-screw extrusion grafting at 190 DEG C and granulation is dried; Step 2, take 100 mass parts step one granulation, the TMTD adding 1 mass parts mixes, and adopts casting method, prepares the film that thickness is 0.3mm.Concrete test result is in table 1.
Embodiment 5
Step one, get the EVA resin of 100 mass parts, wherein the fusing point of EVA resin is 81 DEG C, melting index is 3g/10min, add two (tert-butyl peroxide) hexane of 2,5-dimethyl-2,5-of 0.05 mass parts and the dicumyl peroxide of 0.05 mass parts, the maleic anhydride modified polyhutadiene that 10 mass fraction average molecular weights are 2500, maleic anhydride content is 17%, uses twin-screw extrusion grafting at 190 DEG C and granulation is dried; Step 2, takes 100 mass parts step one granulation, and the DTDM of the TMTD and 0.5 mass parts that add 0.5 mass parts mixes, and adopts casting method, prepares the film that thickness is 0.3mm.Concrete test result is in table 1.
Embodiment 6
Step one, get the POE resin of 100 mass parts, wherein the fusing point of POE resin is 104 DEG C, melting index is 1g/10min, add two (tert-butyl peroxide) hexane of 2,5-dimethyl-2,5-of 0.05 mass parts and the dicumyl peroxide of 0.05 mass parts, the maleic anhydride modified polyhutadiene that 10 mass fraction average molecular weights are 3100, maleic anhydride content is 8%, uses twin-screw extrusion grafting at 190 DEG C and granulation is dried; Step 2, takes 100 mass parts step one granulation, and the DTDM of the TMTD and 0.5 mass parts that add 0.5 mass parts mixes, and adopts casting method, prepares the film that thickness is 0.3mm.Concrete test result is in table 1.
Hot melt adhesive film of the present invention adopts casting method to obtain, after the vacuum press laminating precompressed of 60-80 DEG C, under high voltage mercury lamp, radiation 1-10min completes curing cross-linked, concrete steps are: by ethylene-octene copolymer with other functional agent through pre-mixing, melt extrude, casting film-forming, last rolling obtains finished product.Wherein, the UV of casting machine solidifies polyolefin optical film thickness and can regulate by root Ju actual needs, and use more thickness to be 0.2mm at present, the thickness of hot melt adhesive film of the present invention is 0.3mm.
Performance test scheme:
1. bonding force test
Method for making sample: by EPDM (terpolymer EP rubber)/hot melt adhesive film/aluminium sheet structure sample preparation, wherein EPDM is of a size of width 2cm, thickness 2mm, length is 10cm, and aluminium sheet is of a size of width 2cm, thickness 2mm, length is 5cm, and at 160 degree of vulcanizing press pressurization 10min, pressure is 2MPa.
Testing method: peel off rubber and aluminium sheet bounding force for 180 degree, peeling rate is 100mm/min.
Table 1 hot melt adhesive film the performance test results
From test result, stripping strength size and selected substrate resin kind, the molecular weight of maleic anhydride modified polyhutadiene, maleic anhydride content, addition and carry the kind of sulphur body and addition all has larger contact, embodiment 1-6 all has better bonding force with EPDM rubber and metal aluminum sheet, wherein the best is embodiment 3 and embodiment 6, and stripping strength is more than 100N/cm.
In sum, product involved in the present invention all has good bonding force with rubber and metal, and solvent-free volatilization, operating procedure simply, can substitute traditional rubber and metal sticking method in some field.
The above; be only the specific embodiment of the present invention; but protection scope of the present invention is not limited thereto; any those of ordinary skill in the art are in the technical scope disclosed by the present invention; the change can expected without creative work or replacement, all should be encompassed within protection scope of the present invention.Therefore, the protection domain that protection scope of the present invention should limit with claims is as the criterion.
Claims (8)
1. a bonding of rubber to metal hot melt adhesive film, is characterized in that, is prepared from by following raw material by weight:
Hot-melt adhesive granules 100 parts
Sulfur-donor 0.5-5 part;
Wherein, hot-melt adhesive granules is prepared from by following raw material by weight:
EVA resin or POE resin 100 parts
Peroxide initiator 0.01-0.2 part
Maleic anhydride modified polyhutadiene 0.5-10 part.
2. the bonding of rubber to metal hot melt adhesive film piece described in Ju right 1, is characterized in that: the fusing point of described EVA resin or POE resin is within the scope of 50 ~ 105 DEG C, and melting index is 1 ~ 40g/10min.
3. the bonding of rubber to metal hot melt adhesive film piece described in Ju right 1, it is characterized in that: described peroxide initiator is dicumyl peroxide, 2, one or more mixture in two (tert-butyl peroxide) hexanes of 5-dimethyl-2,5-, benzoyl peroxide, tert-butyl hydroperoxide carbonic acid-2-ethylhexyl.
4. the bonding of rubber to metal hot melt adhesive film piece described in Ju right 3, is characterized in that: described dicumyl peroxide is as best results during peroxide initiator.
5. the bonding of rubber to metal hot melt adhesive film piece described in Ju right 1, is characterized in that: described maleic anhydride modified polyhutadiene number-average molecular weight is within the scope of 2500-9900, and maleic anhydride content is in 3 ~ 20% scopes.
6. the bonding of rubber to metal hot melt adhesive film piece described in Ju right 1, it is characterized in that: described sulfur-donor is one or more mixture following: 4,4`-dimorpholinyl disulfide, tetramethyl-thiuram disulfide, tetramethylthiuram tetrasulfide, 2-(4-morpholine base dithio) benzothiazole.
7. the bonding of rubber to metal hot melt adhesive film piece described in Ju right 6, is characterized in that: described 4,4`-dimorpholinyl disulfides (DTDM), tetramethyl-thiuram disulfide (TMTD) mixing are as best results during sulfur-donor.
8. the preparation method of the bonding of rubber to metal hot melt adhesive film piece described in Ju right 1-7 any one, is characterized in that: be prepared from by following two steps:
1) with the EVA of formula ratio or POE resin for matrix, add the peroxide initiator of formula ratio and maleic anhydride modified polyhutadiene, with twin screw extruder fusion-grafting and granulation at 190 DEG C, obtain hot-melt adhesive granules;
2) in the hot-melt adhesive granules of formula ratio, add the sulfur-donor of formula ratio, mix, prepare by casting method the hot melt adhesive film that thickness is 0.3mm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510924923.0A CN105419684B (en) | 2015-12-11 | 2015-12-11 | A kind of bonding of rubber to metal hot melt adhesive film and preparation method thereof |
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| CN201510924923.0A CN105419684B (en) | 2015-12-11 | 2015-12-11 | A kind of bonding of rubber to metal hot melt adhesive film and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108219692A (en) * | 2017-12-29 | 2018-06-29 | 江苏鹿山光电科技有限公司 | A kind of crosslinked EVA heat conduction packaging adhesive film and preparation method thereof |
| CN109066503A (en) * | 2018-07-02 | 2018-12-21 | 安徽坤和电气有限公司 | A kind of corrosion resistant high-strength plastic steel cable bridge |
| CN115287003A (en) * | 2022-08-04 | 2022-11-04 | 广东汇齐新材料有限公司 | Composite hot melt adhesive film for metal bonding and preparation method thereof |
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| CN108219692A (en) * | 2017-12-29 | 2018-06-29 | 江苏鹿山光电科技有限公司 | A kind of crosslinked EVA heat conduction packaging adhesive film and preparation method thereof |
| CN109066503A (en) * | 2018-07-02 | 2018-12-21 | 安徽坤和电气有限公司 | A kind of corrosion resistant high-strength plastic steel cable bridge |
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