CN113956826A - Bonding composition, protective film and application thereof - Google Patents
Bonding composition, protective film and application thereof Download PDFInfo
- Publication number
- CN113956826A CN113956826A CN202111271916.7A CN202111271916A CN113956826A CN 113956826 A CN113956826 A CN 113956826A CN 202111271916 A CN202111271916 A CN 202111271916A CN 113956826 A CN113956826 A CN 113956826A
- Authority
- CN
- China
- Prior art keywords
- styrene
- block copolymer
- butadiene block
- silane
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 230000001681 protective effect Effects 0.000 title claims abstract description 41
- 230000001070 adhesive effect Effects 0.000 claims abstract description 52
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 50
- 239000000853 adhesive Substances 0.000 claims abstract description 44
- 229910000077 silane Inorganic materials 0.000 claims abstract description 36
- -1 silane modified styrene-butadiene Chemical class 0.000 claims abstract description 35
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003292 glue Substances 0.000 claims abstract description 13
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims description 28
- 239000004593 Epoxy Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000012790 adhesive layer Substances 0.000 claims description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229910052990 silicon hydride Inorganic materials 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000005060 rubber Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- SGKDAFJDYSMACD-UHFFFAOYSA-N dimethoxy(propyl)silane Chemical compound CCC[SiH](OC)OC SGKDAFJDYSMACD-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- CIQDYIQMZXESRD-UHFFFAOYSA-N dimethoxy(phenyl)silane Chemical compound CO[SiH](OC)C1=CC=CC=C1 CIQDYIQMZXESRD-UHFFFAOYSA-N 0.000 description 1
- NFCHYERDRQUCGJ-UHFFFAOYSA-N dimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[SiH](OC)CCCOCC1CO1 NFCHYERDRQUCGJ-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- MDLRQEHNDJOFQN-UHFFFAOYSA-N methoxy(dimethyl)silicon Chemical compound CO[Si](C)C MDLRQEHNDJOFQN-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
-
- 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
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J123/06—Polyethene
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the field of adhesives, in particular to an adhesive composition, a protective film and application thereof, wherein the composition at least comprises a silane modified styrene-butadiene block copolymer; the silane-modified styrene-butadiene block copolymer is prepared by carrying out hydrosilylation reaction on a silane compound containing an active group and a styrene-butadiene block copolymer. The adhesive composition disclosed by the invention does not have the defects of hollowing and poor adhesion on the surface of a protected object after being adhered to the surface of the protected object, and can not generate residual glue and shadows after being stripped, so that the problem that the surface of the protected object is polluted by an adhesive for a protective film in the prior art when being stripped is solved.
Description
Technical Field
The invention relates to the field of adhesives, in particular to an adhesive composition, a protective film and application thereof.
Background
In the processing and transportation processes in the fields of synthetic resin boards, metal boards, coated steel plates, LEDs, wafer dicing, and the like, in order to prevent stains from adhering to or scratching the surfaces of these products, surface protective films are often applied for protection.
The protective film can be attached to the surface of an adherend through an adhesive layer provided on the protective film when used, and can be peeled and removed when not needed. Therefore, the protective film used is required to have appropriate adhesive properties, to be easily peeled off at the time of peeling, and not to stain the surface of an adherend or the like.
The protective film is generally composed of a base film material and an adhesive layer attached to the surface of the base film material, and after a part of the existing protective film is torn off from the surface of a protected object, an adhesive in the adhesive layer is easily attached to the surface of the protected object, so that residual adhesive and image retention are caused.
For example, patent application No. CN202011226115.4 provides a protective film with an adhesive layer and a preparation method thereof, the protective film comprises a surface layer, an intermediate layer and a self-adhesive layer, wherein the self-adhesive layer comprises the following components in parts by weight: 10-25 parts of EVA material, 40-60 parts of PE material, 5-10 parts of tackifying resin and 10-20 parts of SEBS material, wherein the surface layer comprises 70-90 parts of polypropylene resin composition and 10-30 parts of polyethylene resin according to parts by weight, the polyethylene resin is low-density polyethylene resin, and the polypropylene resin composition comprises ethylene-propylene block copolymer, fluorine-containing compound and release resin. The invention effectively improves the product quality, does not need additional coating and is convenient to use. However, through tests, the researchers of the invention find that the adhesive composition has tackifying resin in the self-adhesive layer, and the defects of adhesive residue and image retention are easy to appear in the using process, thereby influencing the practical use.
Disclosure of Invention
The present invention is directed to overcome the problems of the adhesive used for the protective film in the prior art that the adhesive is prone to have the defects of adhesive residue and image retention during the use process, and therefore, the first object of the present invention is to provide an adhesive composition capable of avoiding the defects of adhesive residue and image retention; a second object of the present invention is to provide a protective film comprising the above adhesive composition; the third object of the present invention is to provide the use of the above adhesive composition and a protective film comprising the above composition.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a bonding composition is provided, which comprises a binder,
the composition at least comprises a silane modified styrene-butadiene block copolymer;
the silane-modified styrene-butadiene block copolymer is prepared by carrying out hydrosilylation reaction on a silane compound containing an active group and a styrene-butadiene block copolymer.
Many prior art bonding compositions are primarily prepared from rubber elastomers, examples of which include SBS and SEBS. However, such rubber elastomers have a relatively general adhesive effect, and are likely to have insufficient adhesive force in a use environment where strong adhesive force is required, and are likely to have a phenomenon of hollowing or poor adhesion after being adhered to the surface of an adherend.
The invention modifies the traditional styrene-butadiene block copolymer (SBS) to improve the adhesive property. The residual double bonds generated by polymerization of butadiene chain segments in SBS are utilized, and the silane compound containing active groups is grafted to the SBS main chain in a silicon-hydrogen addition mode, and the active groups have good adhesion, so that the adhesion between the adhesive composition and an adherend can be effectively improved.
Meanwhile, as the silane compound is connected with the SBS main chain through a chemical bond, the silane compound cannot fall off from the styrene-butadiene block copolymer main chain in the process of bonding with an adherend, and when the silane compound is peeled off, residual glue and shadows cannot be generated on the surface of the adherend, so that the practical use effect of the bonding composition is greatly improved.
In addition, the double bonds of the styrene-butadiene block copolymer (SBS) in the invention are subjected to addition reaction with the silicon-hydrogen bonds, so that the originally existing double bonds are eliminated and become saturated bonds, and therefore, the styrene-butadiene block copolymer has good weather resistance, heat resistance, compression deformation resistance and excellent mechanical properties. And, with the addition of the silane group in the side chain, it is possible to introduce good weather resistance and high and low temperature resistance peculiar to the silane compound into the styrene-butadiene block copolymer.
Preferably, the reactive group of the reactive group-containing silane compound includes at least silicon hydride;
also comprises at least one of hydroxyl, alkoxy, epoxy, acryloxy and vinyl.
The silane compound in the invention at least comprises a hydrosilation structure, and the hydrosilation structure can perform addition reaction with alkenyl under the action of a platinum catalyst so as to be connected with the SBS main chain, namely, the hydrosilation group is used as a bridging group. In addition, at least one of hydroxyl, alkoxy, epoxy, acryloxy, vinyl and the like is also included, which can effectively enhance the polarity of SBS, thereby improving the bonding effect between the bonding composition and the adherend.
More preferably, the silane compound includes a hydroxyl group, an alkoxy group, and an epoxy group in addition to the hydrosilane.
Further preferably, examples of the silane compound include: one of trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, phenyldimethoxysilane, hydrosilyl-containing hydroxysilicone oil, hydrosilyl-containing polyether-modified silicone oil, 3- (2, 3-glycidoxy) propyldimethoxysilane, 3- [ (2,3) -glycidoxy ] propyldimethoxysilane, and 3-glycidyloxypropyldimethoxysilane, or a hydrolysate or mixed hydrolysate thereof.
Preferably, the styrene-butadiene block copolymer is a styrene-terminated styrene-butadiene-styrene block copolymer; and the content ratio of the styrene chain segment to the butadiene in the styrene-butadiene-styrene block copolymer is (30-70): (70:30).
The content ratio of the styrene segment to the butadiene in the styrene-butadiene-styrene block copolymer in the invention affects the adhesive property of the final silane-modified styrene-butadiene block copolymer, and the higher the butadiene content is, the more the points of attachment of the butadiene segment to the silane compound are, and the stronger the adhesive property of the finally prepared silane-modified styrene-butadiene block copolymer is.
Preferably, the silane-modified styrene-butadiene block copolymer is prepared by the following method:
dissolving the styrene-butadiene block copolymer in an organic solvent to form a uniform glue solution, adding a silane compound and a platinum catalyst into the glue solution, heating to perform hydrosilylation reaction, and removing the solvent after the reaction is finished to obtain the silane modified styrene-butadiene block copolymer.
Preferably, the bonding composition also comprises an epoxy cross-linking agent, an inorganic filler and an epoxy curing agent;
the mass ratio of the silane modified styrene-butadiene block copolymer to the epoxy cross-linking agent to the inorganic filler to the epoxy curing agent is 100: (10-20): (5-10): (0.5 to 1).
In order to provide the proper adhesive and mechanical properties of the adhesive composition, the present invention requires mixing the silane-modified styrene-butadiene block copolymer with a polymer matrix material and pelletizing the mixture. In order to improve the compatibility between the silane modified styrene-butadiene block copolymer and the polymer matrix material in the mixing process, a certain amount of epoxy crosslinking agent and epoxy curing agent are added into the bonding composition, and epoxy groups in the epoxy crosslinking agent can generate ring-opening polymerization reaction under the catalysis of the epoxy curing agent, so that the silane modified styrene-butadiene block copolymer can be stably and uniformly dispersed in the polymer matrix material. The physical properties of the adhesive composition can be adjusted by controlling the amount of the epoxy crosslinking agent added, and when the amount of the epoxy crosslinking agent added is less than 10% of the silane-modified styrene-butadiene block copolymer, the adhesive composition is too flexible and easily deformed, but when the amount of the epoxy crosslinking agent added is more than 20% of the silane-modified styrene-butadiene block copolymer, the adhesive composition is too hard and is not suitable for use as a protective film. The inorganic filler is added to improve the overall mechanical properties of the adhesive composition, and when the amount of the inorganic filler is less than 5% of the silane-modified styrene-butadiene block copolymer, the improvement of the mechanical properties is not significant, and when the amount of the inorganic filler is greater than 10% of the silane-modified styrene-butadiene block copolymer, the problem of excessively high hardness is also caused.
In addition, the invention has no excessive requirements on the types of epoxy curing agents, and the traditional amine or acid anhydride curing agents can be applied to the technical scheme of the invention.
Preferably, the epoxy crosslinking agent is an epoxy resin containing two or more epoxy groups;
the epoxy resin comprises one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and alicyclic epoxy resin.
Preferably, the inorganic filler is selected from any one of silica, titanium dioxide, talc, light calcium carbonate and montmorillonite.
A protective film characterized in that,
comprises a polymer base film layer and a bonding layer arranged on one side of the polymer base film layer;
the adhesive layer contains the adhesive composition.
The protective film comprises a polymer-based film layer and an adhesive layer containing the adhesive composition, and can be adhered to the surface of an object to be protected through the adhesive layer to play a good surface protection role.
A method for preparing a protective film,
and mixing the bonding composition with a polymer base material, extruding and granulating to obtain bonding layer granulation materials, and then melting and multi-layer co-extruding the bonding layer granulation materials with a polymer base film layer material to obtain the protective film.
In order to improve the adhesion between the polymer base film layer and the adhesive layer, it is preferable that the polymer base film layer is made of the same material as the polymer base material. The epoxy curing agent contained in the protective film bonding layer can tightly bond the silane modified styrene-butadiene block copolymer on the surface of the polymer base film layer obtained by co-extrusion of the polymer base material, so that the bonding layer and the polymer base film layer are compounded into an integrated structure, and delamination cannot occur. In the co-extrusion process, the epoxy group of the epoxy cross-linking agent can generate ring-opening reaction under the action of the epoxy curing agent to form a cross-linked polymer with other components, so that the bonding performance of the cured bonding layer is mainly provided by the silane compound on the modified styrene-butadiene block copolymer, the defects of hollowing and poor adhesion cannot be formed on the surface of a protected object after the protective film is adhered to the surface of the protected object, and the residual glue and the residual shadow cannot be generated after the protective film is peeled off.
The application of the bonding composition or the protective film containing the bonding composition in surface protection.
Therefore, the invention has the following beneficial effects:
(1) the adhesive composition of the present invention has good adhesion, and does not form hollowing on the surface of an adherend and cause poor adhesion;
(2) after being peeled off, the bonding composition can not generate the defects of residual glue and image retention on the surface of a protected object, thereby greatly improving the actual use effect of the invention;
(3) the silane modified styrene-butadiene block copolymer has good weather resistance and high and low temperature resistance.
Detailed Description
The invention is further described with reference to specific examples. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
The preparation method of the silane-modified styrene-butadiene block copolymer used in the examples of the present invention is as follows.
The silane-modified styrene-butadiene block copolymer (a 1) was prepared as follows: 10g of SBS (styrene/butadiene = 30/70) (synthetic rubber factory, Baling petrochemical company) was dissolved in 100ml of toluene, 1g of methylhydrodimethoxysilane and 100ppm of platinum catalyst were added thereto, heating was carried out at 100 ℃ for 1.5 hours to carry out hydrosilylation reaction, after the reaction was completed, 1g of activated carbon was added to the solution, stirring and adsorption was carried out for 10min, the filtrate was obtained by filtration, the solvent was evaporated, and then, a small molecular compound was removed by vacuum pumping to obtain a silane-modified styrene-butadiene block copolymer (A1).
The silane-modified styrene-butadiene block copolymer (a 2) was prepared as follows: 10g of SBS (styrene/butadiene = 70/30) (synthetic rubber factory, Baling petrochemical company) was dissolved in 100ml of toluene, 1g of methylhydrogendimethoxysilane and 100ppm of platinum catalyst were added thereto, heating was carried out at 100 ℃ for 1.5 hours to carry out hydrosilylation reaction, after the reaction was completed, 1g of activated carbon was added to the solution, stirring and adsorption was carried out for 10min, the filtrate was obtained by filtration, the solvent was evaporated, and then, the small molecular compound was removed by vacuum pumping to obtain a silane-modified styrene-butadiene block copolymer (A2).
The silane-modified styrene-butadiene block copolymer (a 3) was prepared as follows: 10g of SBS (styrene/butadiene = 50/50) (synthetic rubber factory, Baling petrochemical company) was dissolved in 100ml of toluene, 1g of methylhydrogendimethoxysilane and 100ppm of platinum catalyst were added thereto, heating was carried out at 100 ℃ for 1.5 hours to carry out hydrosilylation reaction, after the reaction was completed, 1g of activated carbon was added to the solution, stirring and adsorption was carried out for 10min, the filtrate was obtained by filtration, the solvent was evaporated, and then, the small molecular compound was removed by vacuum pumping to obtain a silane-modified styrene-butadiene block copolymer (A3).
The formulation of the specific examples 1-10 is shown in table 1 below:
TABLE 1
EXAMPLES 1 to 10 Material tables
Note: the unit of the addition of the materials in the above table is parts.
The formulation tables for comparative examples 1-2 are shown in Table 2 below.
Of these, comparative example 1 used SBS without silane modification as the bonding composition host, and comparative example 2 used SEBS without silane modification as the bonding material host.
TABLE 2
Comparative examples 1-2 Material tables
Note: the unit of the addition of the materials in the above table is parts.
The formulation table for comparative example 3 is shown in table 3 below.
The main material of the bonding composition adopts SBS rubber which is not modified by silane, and a certain amount of methyl hydrogen dimethoxy silane is additionally added.
TABLE 3
Material Table of comparative example 3
Note: the unit of the addition of the materials in the above table is parts.
The adhesive compositions prepared in examples 1 to 10 and comparative examples 1 to 3 were prepared as follows to obtain protective films.
A kind of protective film is provided,
comprises a polymer base film layer and a bonding layer arranged on one side of the polymer base film layer,
the adhesive layer contains the adhesive composition;
the preparation method of the protective film comprises the following steps:
mixing the bonding composition with the low-density polyethylene master batch according to the mass ratio of 30:70, extruding and granulating, obtaining bonding layer granulation particles through extrusion granulation, and then performing melt multilayer coextrusion with the polymer master batch to obtain the protective film.
The protective films prepared by the above methods were each tested for their performance in the following manner.
[ Performance test method and evaluation method ]
(1) Prism structure adhesion force:
the protective films obtained in the above examples and comparative examples were cut into 25mm long strips, attached to prism sheets and pressed back and forth 3 times at a speed of 300 mm/min using a 2kg rubber roller, left at room temperature-10 ℃, 25 ℃ and 80 ℃ for 20min, and tested for 180-degree peel strength at 300 mm/min using a peel tester (KJ-1065A, Kejian tester) in accordance with GB/T2792-1998, to thereby obtain prism structure adhesive force.
(2) Adhesion Property
The protective films obtained in the examples and comparative examples were cut into a 25mm long strip, and the protective films were attached to a prism sheet and pressed 3 times back and forth at a speed of 300 mm/min by a 2kg rubber press roll, and after storage at 23 ℃ and 50 ℃ for a certain period of time, the adhesion state of the prism sheet and the various protective films to the sample was visually observed, and the following determinations were made.
A: completely sealing;
b: only a small part of the film was poorly adhered to the film, and a part of the film (within 30% of the area) was lifted;
c: part of the sample film is poorly sealed and part of the sample film (with an area ratio of 30-70%) floats;
d: in the portion where the area ratio is 70% or more, the film floats from the prism sheet.
(3) Residual adhesive property
The peeling of the prism sheet surface in the adhesion test (2) was determined as follows.
A: no residual glue and no shadow are left;
b: only a small part of the film is in a dot shape or a linear shape (within 30 percent of the area ratio), and the residual glue and the residual shadow are remained;
c: part of the photoresist is left floating with the remained photoresist and the remained shadow (the area ratio is 30-70%);
d: in the portion having an area ratio of 70% or more, there are residual glue and a residual shadow.
The test results are shown in table 5 below:
TABLE 5
Summary of test results
From the above test results, it can be seen that:
by comparing comparative examples 1-2 with examples 1-10, researchers found that after the styrene-butadiene block copolymer was silane-modified, the adhesion effect of the adhesive composition was greatly improved, specifically, the adhesion and the sealing property of the prism structure of examples 1-10 of the present invention were significantly improved compared to the comparative examples, indicating that the adhesion property of the styrene-butadiene block copolymer can be effectively improved after the silane containing an active group was grafted to the main chain of the styrene-butadiene block copolymer.
Meanwhile, as can be seen from the analysis of comparative example 3, the addition of a certain amount of silane monomer containing active group in the adhesive composition can improve the adhesive effect of the composition to a certain extent, specifically, the adhesion is improved from the original D level of comparative example 1 to the C level of comparative example 3, but the improvement degree is limited. Moreover, the residual glue property is poor, and the defects of residual glue and image retention are easily generated on the surface of the protected object, so that the method is not suitable for practical use.
It was found by comparing examples 1 to 3 that as the content of butadiene units in the styrene-butadiene block copolymer increases, the number of double bonds reacted with silane increases, so that the content of active groups in the silane-modified styrene-butadiene block copolymer increases, improving the adhesion in the prism structure adhesion test, which is consistent with the theory in the above description.
In addition, the result of the prism structure adhesion test under different temperature conditions shows that the high and low temperature resistance of the composition can be effectively improved by grafting the silane compound in the styrene-butadiene block copolymer. Specifically, the adhesive force was reduced to a small extent under high and low temperature conditions in examples 1 to 10 of the present invention, while the adhesive force was reduced to a large extent in the adhesive compositions of comparative examples 1 to 3. The silane modified styrene-butadiene block copolymer has better weather resistance and high and low temperature resistance compared with the traditional SBS and SEBS.
As described above, the adhesive composition of the present invention has suitable adhesive properties and can stably adhere a protective film to the surface of an object to be protected. Meanwhile, the adhesive force of the paint can not be greatly reduced in high and low temperature environments, and the paint has better weather resistance and high and low temperature resistance.
In addition, after the protective film is stripped, the surface of the protected object does not have adhesive residue or image retention, so that the normal use of the protected object is not disturbed, and the protective film can be applied to surface protection in the processing and transportation processes in the fields of synthetic resin plates, metal plates, coating and coating steel plates, LEDs, wafer cutting and the like.
Claims (10)
1. A bonding composition characterized in that,
the composition at least comprises a silane modified styrene-butadiene block copolymer;
the silane-modified styrene-butadiene block copolymer is prepared by carrying out hydrosilylation reaction on a silane compound containing an active group and a styrene-butadiene block copolymer.
2. The bonding composition of claim 1,
the active group of the silane compound containing the active group at least comprises silicon hydride;
and at least one of hydroxyl, alkoxy, epoxy, acryloxy, epoxy and vinyl.
3. The bonding composition of claim 1,
the styrene-butadiene block copolymer is a styrene-terminated styrene-butadiene-styrene block copolymer;
and the content ratio of the styrene chain segment to the butadiene in the styrene-butadiene-styrene block copolymer is (30-70): (70:30).
4. A bonding composition according to any one of claims 1 to 3,
the preparation method of the silane modified styrene-butadiene block copolymer comprises the following steps:
dissolving the styrene-butadiene block copolymer in an organic solvent to form a uniform glue solution, adding a silane compound and a platinum catalyst into the glue solution, heating to perform hydrosilylation reaction, and removing the solvent after the reaction is finished to obtain the modified styrene-butadiene block copolymer.
5. A bonding composition according to any one of claims 1 to 3,
the adhesive composition also comprises an epoxy cross-linking agent, an inorganic filler and an epoxy curing agent;
wherein the mass ratio of the silane modified styrene-butadiene block copolymer to the epoxy cross-linking agent to the inorganic filler to the epoxy curing agent is 100: (10-20): (5-10): (0.5 to 1).
6. A bonding composition according to claim 5,
the epoxy cross-linking agent is epoxy resin containing two or more epoxy groups;
the epoxy resin comprises one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and alicyclic epoxy resin.
7. A bonding layer, characterized in that,
the adhesive layer contains the adhesive composition according to any one of claims 1 to 6.
8. A protective film characterized in that,
comprises a polymer base film layer and a bonding layer arranged on one side of the polymer base film layer;
the adhesive layer contains the adhesive composition according to any one of claims 1 to 6.
9. A method for producing the protective film according to claim 8,
and mixing the bonding composition with a polymer base material, extruding and granulating to obtain bonding layer granulation materials, and then melting and multi-layer co-extruding the bonding layer granulation materials with a polymer base film layer material to obtain the protective film.
10. Use of the adhesive composition according to any one of claims 1 to 7 or the protective film according to any one of claims 8 to 9 for surface protection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111271916.7A CN113956826B (en) | 2021-10-29 | 2021-10-29 | Bonding composition, protective film and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111271916.7A CN113956826B (en) | 2021-10-29 | 2021-10-29 | Bonding composition, protective film and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113956826A true CN113956826A (en) | 2022-01-21 |
| CN113956826B CN113956826B (en) | 2023-04-07 |
Family
ID=79468327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111271916.7A Active CN113956826B (en) | 2021-10-29 | 2021-10-29 | Bonding composition, protective film and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113956826B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101675115A (en) * | 2007-04-16 | 2010-03-17 | 陶氏康宁公司 | hydrosilylation curable compositions |
| CN103764682A (en) * | 2011-08-26 | 2014-04-30 | 旭化成化学株式会社 | Method for producing denatured conjugated diene polymer, denatured conjugated diene polymer, denatured conjugated diene polymer composition, rubber composition, and tire |
| CN104159927A (en) * | 2012-02-29 | 2014-11-19 | 戴纳索尔弹性体有限公司 | Hydrogenated aromatic alkenyl and diene copolymers containing comonomers that have silyl hydride units and functionalized analogues thereof |
| CN105273643A (en) * | 2014-06-10 | 2016-01-27 | 信越化学工业株式会社 | Temporary adhesive material for wafer processing, wafer processing lamination, and method for manufacturing thin wafer using the same |
-
2021
- 2021-10-29 CN CN202111271916.7A patent/CN113956826B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101675115A (en) * | 2007-04-16 | 2010-03-17 | 陶氏康宁公司 | hydrosilylation curable compositions |
| CN103764682A (en) * | 2011-08-26 | 2014-04-30 | 旭化成化学株式会社 | Method for producing denatured conjugated diene polymer, denatured conjugated diene polymer, denatured conjugated diene polymer composition, rubber composition, and tire |
| CN104159927A (en) * | 2012-02-29 | 2014-11-19 | 戴纳索尔弹性体有限公司 | Hydrogenated aromatic alkenyl and diene copolymers containing comonomers that have silyl hydride units and functionalized analogues thereof |
| CN105273643A (en) * | 2014-06-10 | 2016-01-27 | 信越化学工业株式会社 | Temporary adhesive material for wafer processing, wafer processing lamination, and method for manufacturing thin wafer using the same |
Non-Patent Citations (1)
| Title |
|---|
| 杨幸: ""PDMS改性苯乙烯三嵌段聚合物膜的制备及其在CH4/N2分离中的应用"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113956826B (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1126790C (en) | Acrylate-containing polymer blends and methods of using | |
| CN1105761C (en) | Base for masking tape for coating and masking tape for coating | |
| JP2832565B2 (en) | Automotive coating protection sheet | |
| CA2224237C (en) | Acrylate-containing polymer blends | |
| JP5960273B2 (en) | Automotive adhesive tape | |
| CN102549098B (en) | Process for production of pressure-sensitive adhesive composition, process for production of pressure-sensitive adhesive film, raw material composition for pressure-sensitive adhesive, and pressure-sensitive adhesive film | |
| CN104099046B (en) | Silane primer for improving the adhesiveness of adhesive tape on hydrophilic surfaces, especially on the glass surface | |
| KR100730680B1 (en) | Adhesive / Sealer Compositions and Bonded Structures Using the Same | |
| AU5638996A (en) | Methods of using acrylate-containing polymer blends | |
| JP2016529358A (en) | Pressure sensitive adhesive foam | |
| RU2652254C2 (en) | Reactive hot melt adhesive | |
| JP2018502176A (en) | Rubber based multilayer pressure sensitive adhesive assembly | |
| CN1168544C (en) | Method for tackifying surface of soft layer | |
| EP3904411B1 (en) | Photocurable resin composition and method for producing image display device | |
| JP2004176028A (en) | Reactive hot melt adhesive composition | |
| CN113956826B (en) | Bonding composition, protective film and application thereof | |
| JPH1143658A (en) | Surface protective film | |
| CN1188500A (en) | Method of using acrylate-containing polymer blends | |
| JPS6121174A (en) | Tacky tape or sheet for surface protection | |
| JP4394757B2 (en) | Pressure sensitive adhesive and surface protective material | |
| CN110283543B (en) | Silicone pressure-sensitive adhesive for masking tape and preparation method thereof | |
| CN114685709A (en) | Acrylic resin for high-temperature-resistant UV (ultraviolet) adhesive reducing agent and preparation method and application thereof | |
| JP2616027B2 (en) | Surface protection film | |
| JP4156242B2 (en) | Double-sided pressure-sensitive adhesive sheet and method for producing the same | |
| CN110724479A (en) | Special hot-melt pressure-sensitive adhesive for high-molecular self-adhesive waterproof adhesive tape and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |