CN101280159B - Preparation of high-weather-resistance high-adherence high-transparency polyolefin adhesive film - Google Patents
Preparation of high-weather-resistance high-adherence high-transparency polyolefin adhesive film Download PDFInfo
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Abstract
The invention relates to a preparation method of polyolefin adhesive film which has the advantages of high weatherability, high adhesive force and high transparency; silane coupling agent and additive are mixed to obtain complex solution according to the weight ratio of 20:1-1:1, and then the complex solution is coated on the surface of the cast film through the methods of spraying and doctor coating; the redundant solution is dried finally; the polyolefin adhesive film prepared by the method has the advantages of high transparency, high weatherability and high adhesive force; the self-adhered situation under the normal temperature is avoided; the humidity conditioning is not needed before being used; the laminated glass prepared by the adhesive film not only has good transparency, good impact resistance performance and strong initial adhesive force with the glass, but also has good weatherability and long term storage property.
Description
Technical field
The present invention relates to a kind of preparation method of polyolefin adhesive film, relate in particular to a kind of method of in preparing the polyolefin adhesive film process, adding silane coupling agent, initiator and linking agent.
Background technology
Laminated glass is a kind of very ideal multi-usage glass kind, not only can protect the person and property safety but also is keeping the attractive in appearance transparent of glass, also can reduce noise simultaneously, control sunlight and the harmful ultraviolet ray that masks at least 99%.In addition, the double glazing of being processed by laminated glass can increase thermal insulation.Therefore, laminated glass is as a kind of excellent scheme that solves the safety precaution problem.On Highrise buildings, automobile and communal facility, be widely used in recent years.
Laminated glass is bonded through intermediate coat by two-layer or multilayer unorganic glass (wherein one or more layers available organic resin plate replaces).Its security comes from and is bonded in intermediate coat on glass: when glass is impacted and can not splash when broken, still keep global shape, thereby reduce the injury that glass fragment causes personal property, play a protective role.
As the intermediate coat of laminated glass, how to prepare on the market with plastifying PVB (polyvinyl butyral acetal) at present.This intermediate coat and glass have good bonding force, and have very high tensile strength transparent with well, use very extensively.But have following shortcoming when using above-mentioned glued membrane: facility investment is big; Tint permanence is poor; Poor with PET (polyethylene terephthalate) resin bonding power; Water-intake rate is big; Softening agent is prone to separate out, and influences bounding force and outward appearance.
In order to overcome above-mentioned shortcoming, the special public clear 47-2103 communique of Japan discloses a kind of intermediate coat, and it adopts partly-hydrolysed EVA (ethene-vinyl acetate interpolymer) to make as material forming.But its shortcoming is poor with the cementability of glass, and the transparency, weathering resistance and wet fastness are also poor.In addition, disclose a kind of laminated glass-use intermediate coat in the japanese kokai publication hei 7-2551 number bulletin, it is through the composition molding that adds the such acquisitions such as transparent properties-correcting agent of condensation reaction resultant in the Injecatable EVA Copolymer is made with a kind of.Its advantage is that the transparency is good, wet fastness is good, shock-resistance is good, and self-adhesion not under the normal temperature does not need damping before the use.But plasticizer-resistant not, and there is the problem of prolonged preservation property.
The method of use of silane coupling agent has very big influence to the bounding force of glued membrane.Usually adopt two kinds of methods: direct addition method and surface pretreatment methods.Direct addition method: promptly directly silane coupling agent is joined in the resin, move to the surface when bonding again, play a role; Surface pretreatment methods: be about to silane and be made into suitable solution, be coated on by maxxaedium.The former addition is few, and silane possibly be fixed in inside in the preservation process, and transition process needs the time when bonding, so its prolonged preservation performance possibly be affected.Latter's prolonged preservation property is good, but operation bothers.
In order to improve film and the bonding force and the prolonged preservation property of being glued material; Simplify production process; Mention among the Chinese patent document CN-1038658A and contain amino silane in the polyester film surface-coated and can improve itself and PVB (polyvinyl butyral acetal) bounding force, and be prepared into two-sided laminated glass and single face abrasion-resistance glass thus.But this method exists following shortcoming: contain amino silane hydrolyzate often relatively rapidly, viscosity changes very fast, the inconvenience of filming, and xanthochromia is serious.
All there is the danger because of outdoor thermo-oxidative ageing and ultraviolet light and aging flavescence in above-mentioned all intermediate coat products.
Summary of the invention
The object of the invention will comprehensively overcome above-mentioned various shortcomings of the prior art exactly; The preparation method of a kind of high weather-proof, high adhesion, high transparency polyolefin adhesive film is provided; The polyolefin adhesive film that this method is prepared has high transparent, high weatherable characteristics; Self-adhesion not at normal temperatures; Do not need damping before the use, and make with the laminated glass of this glued membrane preparation not only transparent good, impact resistance is good, strong with bonding force at the beginning of the glass, the more important thing is to have extraordinary weathering resistance and prolonged preservation property.
In order to achieve the above object, the present invention adopts following technical scheme:
Earlier with silane coupling agent with have the initiator that produces the radical ability or can be made into composite solution by weight 20: 1～1: 1 with the linking agent that matrix and silane coupling agent form hydrogen bond simultaneously; Then composite solution is overlying on the casting films surface through the spraying or the mode of blade coating, at last excessive solution is dried.
Wherein, with the silane coupling agent preferred vinyl or the methacryloxy of initiator wiring solution-forming, with the preferred epoxy silane coupling of the silane coupling agent of linking agent wiring solution-forming.
Silane coupling agent comes down to one type of silane with organo-functional group, in its molecule, has ability and the chemically combined reactive group of inanimate matter material (like glass, silica sand, metal etc.) and and the chemically combined reactive group of organic material (synthetic resins etc.) simultaneously.Available general formula Y (CH
2) nSiX
3Expression, here, n=0～3; The hydrolyzable group of X-; Y one organo-functional group can react with resin.X is chloro, methoxyl group, oxyethyl group, methoxy ethoxy, acetoxyl group etc. normally, generates silanol (Si (OH) during these group hydrolysis
3), and combine with inorganic substance, form siloxanes.Y is vinyl, amino, epoxy group(ing), methacryloxy, sulfydryl or urea groups.These reactive groups can combine with the organic substance reaction.Therefore,, can between the interface of inorganic substance and organic substance, erect " molecule bridge ", link together the material of two kinds of character great disparities, work to improve performance of composites and increase bonding strength through using silane coupling agent.
From form processing of the present invention; The silane coupling agent that is made into mixing solutions with initiator can be from following selection: vinyltrimethoxy silane (KH171); Vinyltriethoxysilane (KH151); Vinyltriacetoxy silane (SH6075), methyl allyl acyloxypropyl trimethoxysilane (KH570).The silane coupling agent that is made into mixing solutions with linking agent can be selected from: γ Racemic glycidol oxygen propyl trimethoxy silicane (A187); β (3; The 4-epoxycyclohexyl) ethyl trimethoxy silane (A-186), β (3, the 4-epoxycyclohexyl) ethyl triethoxysilane (coatosil1770); γ Racemic glycidol oxygen propyl-triethoxysilicane (A1871), γ Racemic glycidol oxygen propyl group methyldiethoxysilane (W-78).
Initiator is the compound that one type of easy decomposes becomes radical (being elementary radical), can be used for causing alkene class, the monomeric radical polymerization of diene class and copolymerization, also can be used for the crosslinking curing and the polymer crosslinking reaction of unsaturated polyester.Action of evocating is when being heated, to decompose to produce radical in the present invention, and the silane that radical will contain unsaturated link(age) grafts on the POE matrix.The operable initiator of the present invention has two types: azo cpd and superoxide.Azo cpd can be from following selection: 2, and the two isovaleronitriles of 2 '-azo, 2,2 '-Diisopropyl azodicarboxylate, 2-tertiary butyl azo-2-cyanogen-pentane, 2-tertiary butyl azo-isobutyronitrile.Superoxide can be from following selection: 2, and 5-dimethyl--(peroxo--2,5-di-t-butyl) hexane, Di Cumyl Peroxide 99, Lucidol, 1,1-two (t-butylperoxy) 3,3,5-trimethyl-cyclohexane, cyclohexanone peroxide, methylethyl ketone peroxide.
Amino has very strong reactivity, it can with epoxy reaction, can form hydrogen bond with carbonyl, can with anhydride reaction.Utilize amino reactivity in the present invention, the silane that will contain epoxy group(ing) is grafted on the POE matrix.Can be selected from the linking agent that matrix and silane coupling agent form hydrogen bond simultaneously: second diamino, divinyl triammonium, triethylene four ammonia.
Above-mentioned each initiator can use separately, also can compoundly use.Equally, above-mentioned each linking agent can use separately, also can compoundly use.
In the present invention, earlier silane coupling agent and initiator or linking agent being made into composite solution by a certain percentage, ratio is preferably 20: 1～and 1: 1, more preferably 18: 1～2: 1.Again with casting films through the solvent trough of composite solution is housed, the casting films here can be firm curtain coating after the film that forms after the quenching also can be the film of complete moulding, preferably the former both saved time like this, had reduced human cost again.At last the baking of excessive solution heat is removed, the temperature of drying tunnel is very crucial here.If the temperature of drying tunnel is too high, can cause casting films softening, certain autohension is arranged, unfavorable to follow-up rolling; If temperature is low excessively, then can cause solution not exclusively dry, make the glued membrane surface leave silicane hydrolysate, influence the outward appearance and the transmittance of glued membrane.Be preferably 28-40 ℃.The bounding force and the prolonged preservation property of film so just in the Production Flow Chart of simplifying, have been improved.
In order to guarantee the weather resisteant and the transparency, casting films is processed by following resin combination: polyolefine 100 weight parts, transparent modified dose 0.01～1 weight part.
Contain tertiary carbon atom seldom in the molecule of the elastomerics that the ethylene-alpha-olefin copolymerization forms (POE), the molecular chain height is saturated, thus have more excellent ageing-resistant, weathering resistance.The relation with contents of alhpa olefin is to the tensile strength of intermediate coat among the POE, and this is known.The content of alhpa olefin is preferably 10-42% in this casting films, is preferably 12-40% especially.If the content of alhpa olefin is high, then the transmittance of intermediate coat and bond properties improve, but tensile strength decline, the erosion-resisting characteristics of the laminated glass of processing descends, and is unfavorable for safety; If the content of alhpa olefin is low, ageing-resistant performance and tensile strength improve, but the transparency and bond properties descend.
The POE melting index is related to the thickness of intermediate coat behind degassing performance and the lamination.The melting index of this intermediate coat is preferably 0.5g/10min～25g/10min, is preferably 2g/10min～15g/10min especially.If melting index is big, degassing performance is better, but the reduction of the viscosity of the intermediate coat that obtains, thereby make the intermediate coat behind the lamination ooze out from the edge section, the thickness of intermediate coat reduces, and the impact resistance of laminated glass descends; On the contrary, if melting index is little, the flowability of intermediate coat descends, and degassing performance descends during lamination.
Do not have unsaturated link(age) in Vilaterm (PE) molecule, and structure is more regular, so that it has is very excellent ageing-resistant, weathering resistance.PE is divided into LDPE (new LDPE (film grade)), HDPE (high density polyethylene(HDPE)), LLDPE (linear low density polyethylene) etc. again according to its molecular weight and molecular structure, because the LDPE crystallinity is the poorest, the transparency is best, so preferred LDPE.Melting index is related to the thickness of the glued membrane behind the lamination, so melting index is preferably 1g/10min～50g/10min, is preferably 2g/10min～18g/10min especially.
Therefore, select suitable POE or PE, most important for the performance of intermediate coat.
POE or PE are crystalline polymer, and its crystal formation speed is slower in temperature-fall period, and the crystalline particle of generation is bigger.This xln sphere diameter is greater than visible wavelength, and spherocrystal is different with on every side unformed body particulate specific refractory power, has produced scattering of light, and the transparency is descended, and it is big that mist degree becomes.Therefore, in order to improve the transparency of intermediate coat, reduce its mist degree, the diameter that must make its crystal grain is less than visible wavelength.In polymkeric substance, add transparent modified dose,, under the constant situation of spherulitic growth speed, accelerated crystallization velocity, reduced spherulite size, thereby improved the transparency, reduced mist degree for crystallization provides more nucleus.
Transparency properties-correcting agent can be selected from transparent modified dose of inorganic powder class, transparent modified dose of carboxylic-acid, transparent modified dose of metallic salt, a kind of product by the polyvalent alcohol more than five yuan or verivate and phenyl aldehyde or derivatives thereof condensation reaction generation.Select in the powders such as transparent modified dose of inorganic powder class can mica, talcum powder, white titanium pigment, lime carbonate, white carbon black; Transparent modified dose of carboxylic-acid can be selected from transparent modified dose of carboxylic-acids such as phenylformic acid, hexanodioic acid, phenylbenzene acetic acid; Metallic salt can be selected from octadecoic acid natrium, sodium-acetate, sodium phenylate and methylene bis (2, the 4-tert-butyl-phenyl) sodium phosphate etc. for transparent modified dose; The product that preferably generates by polyvalent alcohol more than five yuan (or verivate) and phenyl aldehyde (or derivatives thereof) condensation reaction; Like transparent bases such as dibenzylidene sorbitol, dibenzylidene xyllitol mannitol, dibenzylidene galactitols, more preferably in dibenzylidene sorbitol.The dibenzylidene sorbitol transparent base can be selected from: two (to the methyl dibenzylidene) pears sugar alcohol (TM-3, Shanxi chemical research institute), two (3; 4-dimethyl-dibenzylidene) Sorbitol Powder (3988; Milliken Co.), two (to the ethyl dibenzylidene) pears sugar alcohol (NC-4, Japan new physics and chemistry Co., Ltd.) etc.
Though the heat-resisting oxygen of POE resin itself, have excellent weather resistance; But owing to can receive high temperature, intensive ultraviolet in the course of processing and the use; So should add oxidation inhibitor, UV light absorber and UV stabilizer etc. as required, its addition can not damage the intermediate coat rerum natura.
As above-mentioned oxidation inhibitor, can enumerate: tertiary butyl hydroxytoluene (BHT), four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010), β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester (1076).
As above-mentioned UV light absorber; Can enumerate: UV-531 (UV531), 2-hydroxyl-4-methoxy benzophenone (UV325), 2-hydroxyl-4-acryloxy oxethyl-diphenyl-ketone (UV-416); 2-(2-hydroxyl-3; The 5-di-tert-butyl-phenyl)-and 5-chlorinated benzotriazole (UV327), 2-(2-hydroxyl-3 tertiary butyls-5-aminomethyl phenyl)-5-chlorinated benzotriazole (UV327), 2-(2-hydroxy-5-methyl base phenyl) benzotriazole (UVP) etc.
As above-mentioned UV stabilizer, can enumerate: two (2,2,6,6-tetramethyl--4-piperidyl) sebate (UV770); The polycondensate (UV622) of Succinic Acid and (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines alcohol), two (1; 2,2,6,6-pentamethyl--4-piperidyl) sebate (UV765); Two (1-octyloxy-2,2,6,6-tetramethyl--4-piperidyl) sebate (UV123) etc.
Through technique scheme, made high transparent, the high weather-proof polyolefin film of the inventive method has reached goal of the invention, and self-adhesion not under its normal temperature need not damping before use, has guaranteed result of use in the time of easy to operate.And the preparation method of this polyolefin film is more simple, economic, practical in terms of existing technologies, and industrialization degree is high, has good market outlook.With the laminated glass of this glued membrane preparation not only transparent good, impact resistance is good, just bonding force is strong with glass, the more important thing is to have extraordinary weathering resistance and prolonged preservation property, has embodied its economical and practical characteristics well.Except as the laminated glass intermediate coat, the made polyolefin film of the inventive method also can be used for other occasion that the weathering resistance and the transparency are had relatively high expectations, bonding such as solar cell package, outdoor composite building material; The occasion that bounding forces such as metal, timber, stone material, PC, PVC, PET are had relatively high expectations is such as house ornament, composite building material etc.
Embodiment
Embodiment 1
1. the preparation of glued membrane
With a kind of octene VA content is 38%, and melting index is the POE (model: ENGAGE of 5.0g/10min
TM8200), oxidation inhibitor (1010, the vapour crust) is 0.3 part; Dibenzylidene sorbitol (TM-3; Shanxi chemical research institute) 0.3 part cooperates together, and the compsn that is obtained through 200 ℃ of twin screw extruders back curtain coating (0.4mm) in flakes from the slit mould of plasticating, is passed through silane coupling agent (KH151 again; Homemade) with initiator (Di Cumyl Peroxide 99 DCP) weight ratio be 10: 1 solution tank, with 30 ℃ hot drying tunnel excessive solution is removed at last.
2. the preparation of laminated glass
This intermediate coat is clipped in two block length 30cm, and wide 30cm between the transparent float glass of thick 5mm, obtains a kind of sandwich molectron.Then this sandwich of layers body is put into rubber bag; The degassing is 5 minutes under 0.1Mpa vacuum tightness; Under keeping this degassing phase, it is moved in the baking oven; Rise to 110 ℃ from room temperature and kept 30 minutes down, glass and intermediate coat are bonded together, thereby make a kind of laminated glass that constitutes by glass/intermediate coat/glass.
Embodiment 2
Except with the POE (ENGAGE among the embodiment 1
TM8200) change high-pressure polyethylene (1F7B) in addition, other all prepare intermediate coat and laminated glass by embodiment 1 same method.
Embodiment 3
Except KH151 among the embodiment 1 and DCP weight ratio are changed 15: 1 at 10: 1, other all prepare intermediate coat and laminated glass by embodiment 1 same method.
Embodiment 4
Except KH151 among the embodiment 1 and DCP weight ratio are changed 5: 1 at 10: 1, other all prepare intermediate coat and laminated glass by embodiment 1 same method.
Embodiment 5
Except the amount with TM-3 among the embodiment 1 changes into 0.5%, other all prepare intermediate coat and laminated glass by embodiment 1 same method.
Embodiment 6
Except the amount with TM-3 among the embodiment 1 changes into 0.1%, other all prepare intermediate coat and laminated glass by embodiment 1 same method.
Embodiment 7
Except with TM-3 removes among the embodiment 1, other all prepare intermediate coat and laminated glass by embodiment 1 same method.
Comparative example 1
Except the POE among the embodiment 1 being changed into VA content is 28%, and melting index is that in addition, other all prepare intermediate coat and laminated glass by embodiment 1 same method to 7g/10min (KA-31, Sumitomo company produces).
Comparative example 2
Do not adopt the mixing solutions soaking method and adopt direct addition method: wherein DCP content is 0.03%, and KH151 content is 0.3%, and in addition, other all prepare intermediate coat and laminated glass by embodiment 1 same method.
The laminated glass Performance Detection
Carry out following experiment to laminated glass that obtains among embodiment 1-7 and the comparative example 1-2 and bounding force test sample, its result is shown in table 1.
1) transparency detects
The WGT-S type " transmittance/mist degree determinator " that uses Shanghai Precision Scientific Apparatus Co., Ltd to produce measure the laminated glass sample 23 ℃ with humidity 50% condition under transmittance and mist degree.
2) detection of bonding strength
Intermediate coat (newly formed) is clipped between a transparent float glass and the pet film, carries out bonding according to the preparation condition of above-mentioned laminated glass.This product is cut into wide 2.5cm, and long 10cm's is rectangular as sample.Carry out 180 ° with a tension testing machine then and peel off experiment.Speed is 50cm/min.
3) prolonged preservation property
With intermediate coat 40 ℃ of held of temperature 40 days, then according to measuring the stripping strength of this intermediate coat with the same method of above-mentioned bonding strength testing experiment.
4) aging resistance
The laminated glass appearance for preparing is carried out xenon lamp aging experiment 3000h, the variation of test yellowness index.
Table 1 (performance of laminated glass)
The application of the polyolefin adhesive film that the inventive method provides is not limited only to the described laminated glass intermediate coat of the foregoing description; Also can be used for other to weathering resistance and the transparency occasion of having relatively high expectations, bonding such as solar cell package, outdoor composite building material; To the occasion that bounding forces such as metal, timber, stone material, PC, PVC, PET are had relatively high expectations, such as house ornament, composite building material etc., its preparation method and principle are identical, and performance is similar, does not enumerate one by one at this.
Claims (4)
1. the preparation method of one kind high weather-proof, high adhesion, high transparency polyolefin adhesive film; It is characterized in that: earlier with silane coupling agent with have the initiator that produces the radical ability or can be made into composite solution by weight 20: 1～1: 1 with the linking agent that matrix and silane coupling agent form hydrogen bond simultaneously; Then composite solution is overlying on the casting films surface through the spraying or the mode of blade coating, at last excessive solution is dried; Wherein,
Described casting films is formed by the mixture that polyolefine 100 weight parts, transparent modified dose 0.01～1 weight part constitute, for just curtain coating after the film that forms after the quenching or the film of moulding fully;
Said initiator is azo-initiator or organic peroxide initiator, and the silane coupling agent that is made into mixing solutions with initiator is vinyltrimethoxy silane or vinyltriethoxysilane or vinyltriacetoxy silane or methyl allyl acyloxypropyl trimethoxysilane;
Said linking agent is quadrol, diethylenetriamine, triethylene tetramine or their at least two kinds of mixtures; The silane coupling agent that is made into mixing solutions with linking agent is: γ-Racemic glycidol oxygen propyl trimethoxy silicane or β-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane or β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane or γ-Racemic glycidol oxygen propyl-triethoxysilicane or γ-Racemic glycidol oxygen propyl group methyldiethoxysilane.
2. according to the described preparation method of claim; It is characterized in that; When said initiator was azo-initiator, said azo-initiator was 2,2 '-Diisopropyl azodicarboxylate, 2-tertiary butyl azo-2-cyanogen pentane, 2-tertiary butyl azo isobutyronitrile or they appoint at least two kinds mixture; When said initiator is organic peroxide initiator; Said organic peroxide initiator is 2; 5-dimethyl--(peroxo--2,5-di-t-butyl) hexane, Di Cumyl Peroxide 99, Lucidol, 1,1-two (t-butylperoxy)-3; 3,5-trimethyl-cyclohexane, cyclohexanone peroxide, methylethyl ketone peroxide or they appoint at least two kinds mixture.
3. preparation method according to claim 1 is characterized in that: the elastomerics POE that described polyolefine forms for the ethene-alpha-olefin copolymerization, or polythene PE.
4. preparation method according to claim 1; It is characterized in that: described transparent modified dose is transparent modified dose of inorganic powder class; Transparent modified dose of carboxylic-acid; Transparent modified dose of metallic salt, or a kind of product that generates by polyvalent alcohol or verivate more than five yuan and the condensation reaction of phenyl aldehyde or derivatives thereof.
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Families Citing this family (12)
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| US20120184061A1 (en) * | 2009-09-29 | 2012-07-19 | Toppan Printing Co., Ltd | Sealing material sheet for solar cell module and a method of manufacturing solar cell module |
| CN102115311A (en) * | 2010-12-23 | 2011-07-06 | 宾丽萍 | Environmentally-friendly sandwich sunscreen thermal-insulation glass |
| CN102709365A (en) * | 2012-06-12 | 2012-10-03 | 苏州阿特斯阳光电力科技有限公司 | Solar module and preparation method thereof |
| CN102863916B (en) * | 2012-09-14 | 2013-12-18 | 宁波威克丽特功能塑料有限公司 | POE (ethylene-octene copolymer) spectrum conversion solar cell packaging rubber film and preparation method thereof |
| CN104263285A (en) * | 2014-09-19 | 2015-01-07 | 乐凯胶片股份有限公司 | Polyolefin packaging adhesive film for photovoltaic module |
| CN104327439A (en) * | 2014-09-26 | 2015-02-04 | 宁波威克丽特功能塑料有限公司 | Middle membrane in sandwich glass and preparation method thereof |
| CN104479573A (en) * | 2014-12-12 | 2015-04-01 | 常州六合新能源有限公司 | Packaging material polyolefin adhesive film for photovoltaic modules and preparation process thereof |
| CN107915889A (en) * | 2017-12-21 | 2018-04-17 | 福建泓宝信塑胶科技有限公司 | Intermediate film for laminated glasses and the laminated glass containing it |
| CN111892878B (en) * | 2019-05-06 | 2022-03-04 | 3M创新有限公司 | Method for preparing surface pre-crosslinked adhesive film and surface pre-crosslinked adhesive film prepared by method |
| CN111253875B (en) * | 2020-03-24 | 2021-12-28 | 南京金永发塑胶加工制品有限公司 | EVA (ethylene-vinyl acetate) intermediate film for electric control dimming glass and preparation method thereof |
| CN111635558B (en) * | 2020-06-15 | 2022-03-22 | 南京淳达科技发展有限公司 | Polypropylene composite additive with nucleating effect and preparation method thereof |
| CN114231196A (en) * | 2020-09-07 | 2022-03-25 | 盐城百佳年代薄膜科技有限公司 | Impact-resistant EVA (ethylene-vinyl acetate copolymer) packaging adhesive film with three-layer structure, and preparation method and application thereof |
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| US4822828A (en) * | 1987-11-23 | 1989-04-18 | Hoechst Celanese Corporation | Radiation curable coating composition based on a silica/vinyl-functional silanol dispersion |
| CN1038658A (en) * | 1988-06-15 | 1990-01-10 | 赫希斯特人造丝公司 | Bottom scribbles the polyester film and the film laminate thereof of amido functional group silane |
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- 2008-03-19 CN CN2008100268753A patent/CN101280159B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4822828A (en) * | 1987-11-23 | 1989-04-18 | Hoechst Celanese Corporation | Radiation curable coating composition based on a silica/vinyl-functional silanol dispersion |
| CN1038658A (en) * | 1988-06-15 | 1990-01-10 | 赫希斯特人造丝公司 | Bottom scribbles the polyester film and the film laminate thereof of amido functional group silane |
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