CN103102865B - Silane coupling agent for bonding addition type silicon rubber and leather material - Google Patents
Silane coupling agent for bonding addition type silicon rubber and leather material Download PDFInfo
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- CN103102865B CN103102865B CN201210591679.7A CN201210591679A CN103102865B CN 103102865 B CN103102865 B CN 103102865B CN 201210591679 A CN201210591679 A CN 201210591679A CN 103102865 B CN103102865 B CN 103102865B
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- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 63
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 44
- 239000010985 leather Substances 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- TVYLLQBPAACXHJ-UHFFFAOYSA-N diethyl benzene-1,2-dicarboxylate hydrochloride Chemical compound Cl.CCOC(=O)C1=CC=CC=C1C(=O)OCC TVYLLQBPAACXHJ-UHFFFAOYSA-N 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000007639 printing Methods 0.000 abstract description 6
- 239000004753 textile Substances 0.000 abstract description 5
- 150000002148 esters Chemical class 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 10
- -1 polysiloxane Polymers 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 238000005987 sulfurization reaction Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 238000012356 Product development Methods 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920000260 silastic Polymers 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical group 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a silane coupling agent for bonding an addition type silicon rubber and a leather material. The silane coupling agent comprises the following ingredients: 100 parts of ether acetate, 8-12 parts of butyl titanate, 10-15 parts of tetraethoxysilane, 9-12 parts of silane coupling agent, 20-30 parts of a catalyst and 0.1-0.6 part of 5wt% of oxalic acid water solution, wherein the catalyst is a chloroplatinic acid-phthalic acid diethyl ester complex solution with 0.15wt% of chloroplatinic acid. According to the silane coupling agent, the hydrolysis of ester and alkoxy and the open loop of epoxyl are utilized to prompt the chemical bonding of surfaces of the addition type silicon rubber and the leather material; and meanwhile by adding the catalyst into the silane coupling agent, the deep curing of the silicon rubber at the bonding interface is improved. Therefore, a bonding interface with good bonding property is formed on the surface of the leather material without physical embedding, so that the silane coupling agent has a better application prospect in the field of silicon rubber textile printing.
Description
(1) technical field
The present invention relates to a kind of silane coupling agent for bond addition-type silicon rubber and material, be mainly used in the fields such as printing in textiles.
(2) background technology
Addition-type silicon rubber is take the liquid silastic containing vinyl as matrix, with the polysiloxane containing Si-H key, be commonly called as containing hydrogen silicone oil, as linking agent (solidifying agent), under catalyst action, liquid silastic and containing hydrogen silicone oil generation addition reaction of silicon with hydrogen, thus be cross-linked into the solid elastomer of tridimensional network.Before addition-type silicon rubber sulfuration, the viscosity of sizing material is lower, is convenient to printing and pouring, and not low molecule by product is emitted when sulfuration, and shrinking percentage is little, can deep sulfuration.After sulfuration, become soft and transparent or translucent elastomerics, this elastomerics has good high temperature performance, can in-65 ~ 200 ℃ of temperature ranges, keep elasticity for a long time.Meanwhile, addition-type silicon rubber has good electric property and chemical stability, and it is water-fast, resistance to ozone, resistance to irradiation, weather-resistant, hydrophobic protection against the tide, shockproof, nonflammable, has physiology inertia, nontoxic, tasteless.Due to these advantages, addition-type silicon rubber, except being applied to the industries such as Electronic Packaging, in recent years, has also obtained in printing in textiles field paying close attention to widely.Especially its good hand touch, the speciality such as environmental protection, make it become high-end symbol in stamp field.
But, the inactive surfaces of add-on type liquid silicon rubber makes the bonding of itself and textile material become difficulty, especially at the material for the nonwoven such as leather, nitrile rubber silking road, liquid addition-type silicon rubber is difficult to penetrate into the inner pattern structure that forms of spinning, therefore, it is a difficult problem for industry to the bonding of these materials always.
In order to improve the adhesive property of addition-type silicon rubber, using silane coupling agent or tackifier is conventional methods.
Conventionally, tackifier add in silicon rubber, can change the character of silicon rubber, such as making silicon rubber hardening, lose flexibility and elasticity; Make silicon rubber albefaction, light transmission declines, and is difficult to be suitable for the various requirement of Printing Industry color; Make silicon rubber stability decreases, be difficult to standing storage.Therefore,, in order to keep the character of silicon rubber itself, adopt the method for silane coupling agent to there is more significant advantage.According to current achievement in research, common silane coupling agent mainly contains following a few class:
(1) silane coupling agent take polymethyl hydrogen siloxane as membrane-forming agent; (2) silane coupling agent take silicone resin as membrane-forming agent; (3) silane coupling agent take Silicone-Modified Acrylate Resin as membrane-forming agent; (4) silane coupling agent take epoxy resin as membrane-forming agent; (5) silane coupling agent take the disilane containing acryloyl-oxy-oxyl and alkoxyl group or sily oxide as membrane-forming agent.
Such as the silane coupling agent that the polymethyl hydrogen siloxane with methyl blocking and vinyltrimethoxy silane, heptane and Platinic chloride are made into, can have a better role to base materials such as metal, glass, pottery, PMMA synthetic glass, ABS plastic; And the silane coupling agent that adopts the polymethyl hydrogen siloxane of silicone resin, tetraethoxy, gamma-methyl allyl acyloxypropyl trimethoxysilane, butyl (tetra) titanate and methyl blocking to be made into has good cohesiveness to base materials such as aluminium, stainless steel, steel.In the time adopting bisphenol A-type or bisphenol f type epoxy resin to make silane coupling agent as principal constituent, be applicable to the processing of epoxy laminate, PC, PPS, PBT, ABS, PET and metal base.Adopt 1-methyl-bis-(2-methacryloyl oxyethyl group) the silica-based ethane of silicon-2-trimethoxy, butyl (tetra) titanate, tetraethoxy, heptane preparation silane coupling agent, some difficult sticky materials are had a better role as material surfaces such as fluoro-resin, urethane, acrylate.Can find out from silane coupling agent formula above, common silane coupling agent is mainly to introduce si-h bond or unsaturated link(age) (carbon-carbon double bond) to form and the bonding of addition-type silicon rubber, and, the Main System that is applicable to bonding macromolecule polymer material has epoxy systems and contains acryloyl-oxy-oxyl system, but, prepare silane coupling agent using epoxy resin as body material, the bottom coating hardness obtaining is larger, more crisp, be not suitable for the bonding of flexible materials.And adopt acryloyl-oxy-oxyl system, and complicated process of preparation, productive rate is low, and the variation of silane coupling agent composition is large.
(3) summary of the invention
Applicant of the present invention carries out the applied research of addition-type silicon rubber for a long time, from a large amount of experiments, analyze and find, addition-type silicon rubber is under the mechanism that does not have physics to inlay, can only pass through the good bonding interface of the incompatible formation of chemical bond, wherein, the chemical bonding of Si-O base and body material is the most incidental form, but, in addition-type silicon rubber, but lack this group, but, because can being hydrolyzed under proper condition, linking agent containing hydrogen silicone oil in addition-type silicon rubber forms silicon hydroxyl, therefore, in silane coupling agent introduce can with the group of silicon hydroxyl bonding in the group of leather substance generation bonding and silicon rubber, can increase both bonding forces.In addition, in leather substance, often contain the composition that easily makes poisoning of catalyst in addition-type silicon rubber, also make silicon rubber be difficult to solidify at leather substance case depth, thereby affect cohesive strength.Therefore, introducing portion catalyzer in silane coupling agent, can improve both bonding interface places silica gel solidify.According to this thinking, the title complex that the present invention introduces ester group, alkoxy grp, epoxide group and Platinic chloride and diethyl phthalate in silane coupling agent makees catalyzer, utilize the synergy between these groups, addition-type silicon rubber and leather substance effectively can be combined.This is also the present invention program's thinking source.
The object of the invention is to provide a kind of silane coupling agent that can effectively improve addition-type silicon rubber and leather substance cohesive force.
The technical solution used in the present invention is:
For a silane coupling agent for bond addition-type silicon rubber and leather substance, described silane coupling agent is made up of the component of following mass parts:
100 parts of ethyl acetate, 8 ~ 12 parts of butyl (tetra) titanates, 10 ~ 15 parts of tetraethoxys, silane coupling agent 9-12 part, catalyzer 20-30 part, oxalic acid aqueous solution 0.1-0.6 part of 5wt%;
Described catalyzer is Platinic chloride-diethyl phthalate complex solution that the massfraction of platinum is 0.15wt%, and the massfraction of described platinum refers to the massfraction of the platinum element wherein containing.。
Further, silane coupling agent of the present invention is preferably made up of the component of following mass parts:
100 parts of ethyl acetate, 9 parts of butyl (tetra) titanates, 12 parts of tetraethoxys, 10 parts of silane coupling agents, 25 parts of catalyzer, 0.3 part of the oxalic acid aqueous solution of 5wt%.
Silane coupling agent of the present invention is the silane coupling agent that simultaneously comprises epoxy group(ing) and alkoxyl group, as γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidyl ether oxygen base propyl group methyl dimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, be preferably γ-glycidyl ether oxygen propyl trimethoxy silicane, conventional model is KH560.
Platinic chloride-diethyl phthalate solution of the present invention can make by the method providing with Publication about Document: Huang Wenrun, the market of organosilicon material and product development (continuous eight), organosilicon material and application, 1994, (1): 1, concrete, described method is: 1g Platinic chloride (H
2ptCl
66H
2o) and 200mL dehydrated alcohol,, in there-necked flask, under nitrogen protection, be heated to 80 ℃, backflow 2h; be cooled to 40 ℃, under reduced pressure steam except ethanol, obtain tawny dope, add 5 ~ 10mL chloroform; at 30 ~ 40 ℃, chloroform is removed under reduced pressure, reaction is carried out approximately 10 times, makes product become solid again.Finally add 245 grams of diethyl phthalates, it is dissolved, filter, obtaining platinum massfraction is the Platinic chloride diethyl phthalate complex solution of 0.15wt%.
The preparation method of the silane coupling agent described in the present invention also provides, described method is: get each raw material by ratio of component, ethyl acetate, butyl (tetra) titanate and tetraethoxy are mixed, then add the oxalic acid aqueous solution of silane coupling agent, catalyzer, 5wt%, under room temperature, mix, make the described silane coupling agent for bond addition-type silicon rubber and leather substance.
Silane coupling agent provided by the invention can be used for boning addition-type silicon rubber and leather substance, well known to a person skilled in the art as the application method of silane coupling agent, conventionally by silane coupling agent film and leather substance surface, dry, then addition-type silicon rubber is printed on the leather substance surface through silane coupling agent processing, again silicon rubber baking is become to resilient solid, leather substance and addition-type silicon rubber can have been bondd.
Beneficial effect of the present invention is mainly reflected in: adopt ethyl acetate, butyl (tetra) titanate, tetraethoxy to be mixed to get ester class mixed solvent, utilize ester class mixed solvent that ester group is provided, silane coupling agent provides alkoxyl group and epoxy group(ing), utilize the hydrolysis of ester group and alkoxyl group and the open loop of epoxy group(ing) to impel the chemical bonding on addition-type silicon rubber and leather substance surface, meanwhile, in silane coupling agent, add catalyzer to improve the deeply-curing of bonding interface place silicon rubber.Like this, there is no the chimeric leather substance surface of physics, forming the good bonding interface of bonding force.Silane coupling agent provided by the invention can improve the cohesive strength on add-on type silica gel and leather substance surface preferably, and cohesive strength is high, is difficult to peel off.In silicon rubber printing in textiles field, there is good application prospect.
(4) accompanying drawing explanation
Fig. 1 is the cross-section morphology that the embodiment of the present invention 1 obtains adhesive.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
In the embodiment of the present invention, used catalyst is Platinic chloride-diethyl phthalate complex solution of massfraction 0.15%, can be according to document [Huang Wenrun, the market of organosilicon material and product development (continuous eight) [J], organosilicon material and application, 1994, (1) method providing: 1] makes, and is specially: 1g Platinic chloride (H
2ptCl
66H
2o) and 200mL dehydrated alcohol,, in there-necked flask, under nitrogen protection, be heated to 80 ℃, backflow 2h; be cooled to 40 ℃, under reduced pressure steam except ethanol, obtain tawny dope, add 5 ~ 10mL chloroform; at 30 ~ 40 ℃, chloroform is removed under reduced pressure, reaction is carried out approximately 10 times, makes product become solid again.Finally add 245 grams of diethyl phthalates, it is dissolved, filter, obtain platinum massfraction at 0.15% Platinic chloride diethyl phthalate complex solution.
Embodiment 1 ~ 11:
First prepare ester class mixed solvent, this mixed solvent comprises ethyl acetate, butyl (tetra) titanate and tetraethoxy.According to the formula shown in table 1, three kinds of components are mixed, stir.Then, get the mixed solvent preparing, then add silane coupling agent (KH560), Platinic chloride-diethyl phthalate complex solution of platinum massfraction 0.15%, and 5% oxalic acid aqueous solution, each amounts of components is in table 1.Above material is mixed between 20-30 ° of C, and coolant seal, obtains needed silane coupling agent.
Using common corium cloth (ox-hide) as matrix, the silane coupling agent preparing is evenly coated on cladding, at lower than 60 ° of C temperature, toast 10min to dry, surface is tack-free, then choose business-like liquid addition-type silicon rubber (Dongguan Lianzhan Silicone Technology Co., Ltd., TG-1 stamp silica gel and B solidifying agent), the TG-1 that is 100:13 by mass ratio mixes with B solidifying agent, adopt silk-screen printing technique to be printed on the cladding through silane coupling agent processing, then at 120-150 ° of C, silicon rubber vulcanization is become to resilient solid.After completely cooling, tear layer of silica gel with hand, observe its situation of peeling off at leather surface, result is as shown in table 1.Effect in kind after embodiment 1 bonding as shown in Figure 1.
Table 1
+: powerful peelable leaving; ++: powerful local peelable; +++: brute force can not be peeled off, and leather surface is torn.
Embodiment result can find out, silane coupling agent provided by the invention can bond preferably leather substance and silicon rubber, and bond effect is good, is difficult to peel off.
Claims (4)
1. for a silane coupling agent for bond addition-type silicon rubber and leather substance, it is characterized in that described silane coupling agent is made up of the component of following mass parts:
100 parts of ethyl acetate, 8～12 parts of butyl (tetra) titanates, 10～15 parts of tetraethoxys, silane coupling agent 9-12 part, catalyzer 20-30 part, oxalic acid aqueous solution 0.1-0.6 part of 5wt%;
Described catalyzer is Platinic chloride-diethyl phthalate complex solution that the massfraction of platinum is 0.15wt%;
Described silane coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidyl ether oxygen base propyl group methyl dimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane.
2. silane coupling agent as claimed in claim 1, is characterized in that described silane coupling agent is made up of the component of following mass parts:
100 parts of ethyl acetate, 9 parts of butyl (tetra) titanates, 12 parts of tetraethoxys, 10 parts of silane coupling agents, 25 parts of catalyzer, 0.3 part of the oxalic acid aqueous solution of 5wt%.
3. silane coupling agent as claimed in claim 1, is characterized in that described silane coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane.
4. the preparation method of the silane coupling agent as described in one of claim 1～3, it is characterized in that described method is: get each raw material by ratio of component, ethyl acetate, butyl (tetra) titanate and tetraethoxy are mixed, then add the oxalic acid aqueous solution of silane coupling agent, catalyzer, 5wt%, under room temperature, mix, make the described silane coupling agent for bond addition-type silicon rubber and leather substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210591679.7A CN103102865B (en) | 2012-12-30 | 2012-12-30 | Silane coupling agent for bonding addition type silicon rubber and leather material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210591679.7A CN103102865B (en) | 2012-12-30 | 2012-12-30 | Silane coupling agent for bonding addition type silicon rubber and leather material |
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| CN104673179A (en) * | 2013-12-03 | 2015-06-03 | 上海新力动力设备研究所 | Epoxy-acryloyloxy primer for silicon rubber heat insulating layers and preparation method thereof |
| CN103865473B (en) * | 2014-01-26 | 2016-10-12 | 深圳市康利邦科技有限公司 | A kind of macromolecular material silica gel adhesive |
| CN105505084B (en) * | 2014-09-24 | 2018-05-11 | 比亚迪股份有限公司 | A kind of addition-type silicon rubber silane coupling agent and preparation method thereof |
| CN104830225B (en) * | 2015-01-27 | 2017-10-10 | 杭州师范大学 | It is a kind of to improve silane coupling agent of adhesive strength and preparation method thereof between silicon rubber and polypropylene material |
| CN104974662B (en) * | 2015-04-16 | 2017-07-28 | 杭州师范大学 | A kind of organosilicon film forming agent and preparation method and application |
| CN105062378A (en) * | 2015-08-13 | 2015-11-18 | 岳胜武 | Treating agent capable of realizing autohension of two-component addition type room temperature vulcanized silicone rubber and preparation method of treating agent |
| CN105505294B (en) * | 2015-12-22 | 2018-08-07 | 广东标美硅氟新材料有限公司 | A kind of silane coupling agent Nian Jie with dry-type transformer material for addition-type silicon rubber |
| JP2018162800A (en) * | 2017-03-24 | 2018-10-18 | セイコーエプソン株式会社 | Valve unit, liquid injection head, liquid injection device, manufacturing method for valve unit, manufacturing method for liquid injection head, and manufacturing method for liquid injection device |
| CN107336537A (en) * | 2017-07-01 | 2017-11-10 | 东莞市良展有机硅科技有限公司 | A kind of preparation method of mold membrane and mold membrane obtained by this method |
| CN108517121A (en) * | 2018-04-16 | 2018-09-11 | 吉林大学 | A kind of production method that slush mold silica gel reprints mould |
| CN112680023A (en) * | 2021-01-11 | 2021-04-20 | 东莞市迪奥顺水性涂料有限公司 | Silica gel ink capable of being printed on cloth easy to poison and preparation method thereof |
| CN113462284B (en) * | 2021-07-16 | 2022-10-14 | 广州回天新材料有限公司 | Primer for microwave oven coating adhesion and preparation method thereof |
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