CN1098892C - Adhesive sheet for sandwiched glass - Google Patents
Adhesive sheet for sandwiched glass Download PDFInfo
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- CN1098892C CN1098892C CN99121275A CN99121275A CN1098892C CN 1098892 C CN1098892 C CN 1098892C CN 99121275 A CN99121275 A CN 99121275A CN 99121275 A CN99121275 A CN 99121275A CN 1098892 C CN1098892 C CN 1098892C
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- Prior art keywords
- vinyl acetate
- described film
- ethylene
- film
- acetate copolymer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
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- Joining Of Glass To Other Materials (AREA)
Abstract
The present invention introduces an adhesive sheet for sandwich glass, which is formed by processing a mixture composed of 100 parts by weight of ethylene-vinyl acetate copolymer, 1 to 50 parts by weight of polyvinyl butyral, 0.05 to 5 parts by weight of silane coupling agents and 0.02 to 2 parts by weight of nucleating agents by the plasticization at 100 to 200 DEG C. The adhesive sheet has the advantages of low temperature of sheet combination, no need of using an autoclave, greater adhesive performance with an organic resin plate and no autohesion phenomenon for storage at a normal temperature. Sandwich glass manufactured by using the adhesive sheet has the advantages of favorable adhesion strength, transparency, impact resistance, weather resistance, moisture resistance, etc. The adhesive sheet is used for manufacturing ordinary sandwich glass, and is also suitable for manufacturing decorative sandwich glass, non-sputtering bulletproof glass, etc.
Description
The present invention relates to ethylene-vinyl acetate copolymer and polyvinyl butyral acetal is the adhesive sheet for sandwiched glass of main component.
Laminated glass is a kind of present optimal shatter proof glass, is widely used on automobile, buildings and communal facility.It is by two-layer or two-layer above unorganic glass plate (wherein one deck or two-layer also can be synthetic resin board), processes with film is bonding.
Add softening agent and be processed into film in polyvinyl butyral acetal, it is well-known being used to manufacture laminated glass, and this class film has very strong from bonding tendency, generally takes following measure from adhesion in order to prevent it in storing.The first, under the cryogenic refrigeration condition, deposit.The film surface forms water droplet after from low temperature to the room temperature, handles so will carry out damping to film before use.The second, spray antiseized powder.Film will be through cleaning and drying before using.The 3rd, the lining resin sheet removes before the use again between film.These have all increased work difficulty and laminated glass cost.And lamination process must be carried out under High Temperature High Pressure with autoclave, the facility investment height of lamination process, and working process is loaded down with trivial details.
In addition, the synthetic resins transparent panel is being carried out under the situation of lamination process, softening agent can ooze out from the interface between film and the synthetic resin board, cohesiveness is reduced, also corrode synthetic resin board simultaneously, make the synthetic resin board albefaction, these all are the shortcomings of this technology.
In order to oligomer polyol, isocyanic ester and chainextender is that to manufacture laminated glass also be known for the polyurethane pellicle of main raw material.Polyurethane pellicle is plasticizer-containing not, and it is low and corrode the technological deficiency that synthetic resin board makes the synthetic resin board albefaction to have solved film and synthetic resin board cementability well.But other deficiency of polyvinyl butyral acetal (PVB) film still exists in urethane (PU) film.
In order to overcome the deficiency of PVB film and PU film, Japanese Patent 90-53381 discloses a kind of heat cross-linking film, and it is in ethylene-vinyl acetate copolymer (EVA), adds organo-peroxide and silane coupling agent moulding and makes.This film is deposited no self-adhesion tendency at normal temperatures, does not use autoclave just can process and closes sheet.Yet, produce the thermofixation reaction that free radical is participated in order to realize that organo-peroxide decomposes, require to use 140～150 ℃ lamination process temperature, like this, when making polychromy laminated glass, must use heat color, Jia Gong operation simultaneously is poor, thereby causes cost up, and this is its shortcoming.In addition, this intermediate coat and synthetic resin board are being carried out under the situation of lamination process, having the problem that causes the synthetic resin board thermal distortion owing to high temperature.
European patent EP 0602644A1 discloses a kind of manufacture method of adhesive sheet for sandwiched glass.It is that the resin combination that is made of ethylene-vinyl acetate copolymer or ethene-(methyl) acrylate copolymer, transparent modifying agent, silane coupling agent is formed.Chinese patent CN 1142437A discloses a kind of and the manufacture method essentially identical adhesive sheet for sandwiched glass of European patent.It is by ethylene-vinyl acetate copolymer or ethene-(methyl) Acrylate copolymer, and the resin combination that transparent modifying agent, silane coupling agent, rosin based resin or hydrocarbon resin constitute is formed.With the film that above-mentioned two kinds of methods are made, under normal temperature condition, deposit no self-adhesion phenomenon, needn't use autoclave, can under lower processing temperature and tonnage, carry out lamination process.Simultaneously, with synthetic resin boards such as polycarbonate (PC) plate, polyacrylic ester (PMMA) plates very strong cementability is arranged, can not ooze out softening agent from film cementability is reduced, synthetic resin board also can not be etched.But these two kinds of film tensile strength are low, can not be used for the place that automobile front windshield etc. needs safety interlayer glass with the laminated glass of its manufacturing.In addition, the bonding strength of the laminated glass made from these two kinds of films, the transparencys etc. are also not ideal.
The invention provides a kind of like this adhesive sheet for sandwiched glass, it stores no self-adhesion phenomenon at normal temperatures, with the organic resin plate very strong cementability is arranged, and does not corrode the organic resin plate.Processing is closed sheet and can be carried out under lower temperature, also need not use autoclave.With its laminated glass of manufacturing the good transparency, wet fastness, weathering resistance, shock-resistance, cementability etc. are arranged simultaneously.
With the polyvinyl butyral acetal is the film of main component, must use a large amount of softening agent, and must use autoclave under High Temperature High Pressure, to close sheet, softening agent can ooze out from the interface between film and the synthetic resin board, cementability is reduced, but also the erosion synthetic resin board makes the synthetic resin board albefaction.Cancellation or minimizing plasticizer dosage are the effective ways that solves film and synthetic resin adhesive.Discover that ethylene-vinyl acetate copolymer has good plastification to polyvinyl butyral acetal, and the two there is good consistency.Just can be when in polyvinyl butyral acetal, adding ethylene-vinyl acetate copolymer manufacturing film less with even not using softening agent, it is low to organic resin plate cementability so just can to solve polyvinyl butyral film, and corrodes the problem of organic resin plate plate.
Ethylene-vinyl acetate copolymer has good flexibility, and the elasticity as the rubber still has pliability preferably at subzero 50 ℃.The transparency is good, and tackiness is good, and chemical stability is good, and is ageing-resistant, anti-ozone, and intensity is better, nontoxicity.It is the ideal material of making film.With the ethylene-vinyl acetate copolymer is that the film that main component cooperates other auxiliary agent to make is deposited no self-adhesion phenomenon at normal temperatures, with the organic resin plate stronger cementability is arranged, processing is closed sheet and need do not used autoclave, just can process under lower temperature, pressure and close sheet.But poor with the laminated glass resistance to impact shock that this film is manufactured, the bonding strength and the transparency are also desirable not to the utmost.
Purpose of the present invention is exactly will be by adjusting polyvinyl butyral acetal and ethylene-vinyl acetate copolymer physicochemical property separately, determine scientific and reasonable proportioning, select to add comparatively ideal auxiliary agent, develop a kind of novel film, can greatly keep the advantage of above-mentioned two kinds of films, and overcome deficiency separately.
This novel film provided by the invention is by ethylene-vinyl acetate copolymer 100 weight parts, polyvinyl butyral acetal 1～50 weight part, and the polymer blended material that silane coupling agent 0.05～5 weight part, nucleator 0.02～2 weight part constitute forms.
Below the present invention is made detailed explanation.
Used in the present invention ethylene-vinyl acetate copolymer, its transparency and mechanical property be difference to some extent with the different of vinyl acetate content.Vinyl acetate content is 10～60% in this multipolymer, and suitable scope is 20～40%, and in ethylene-vinyl acetate copolymer, vinyl acetate content is too high, and the transparency that makes film can improve, but physical strengths such as tensile strength then will descend.On the contrary, if vinyl acetate content is low excessively, it is enough good making and handing over the tensile strength of sheet, yet its transparency reduces the starting temperature that flows rising, its degassing property, lamination process variation such as process period.
The melt index of ethylene-vinyl acetate copolymer (MI) is 0.1～500g/10 minute, is preferably 2～150g/10 minute, if the MI value is too small, then the flowability of the film that obtains reduces, thereby makes the lamination process reduction.If opposite MI value is excessive, then the viscosity of the film that obtains reduces, thereby makes and extrude from the edge section at the lamination process film, therefore the thickness of intermediate coat is reduced, and the shock-resistance of the laminated glass that obtains also so reduction.
Ethylene-vinyl acetate copolymer can be according to high-pressure process, and known technologies such as emulsion process are made.
Ethylene-vinyl acetate copolymer can be plasticized, and is partly-hydrolysed, sour modification, the crosslinked modifier that waits modification.
Below the polyvinyl butyral acetal that uses in the invention is illustrated.
Polyvinyl butyral acetal has the good transparency, temperature tolerance, photostabilization, tensile strength height, cohesiveness, is the ideal material of making film.
Used polyvinyl butyral acetal can be by known two-step process production.
Use polyvinyl butyral acetal among the present invention, weight-average molecular weight is 3～270,000, and preferable range is 5～150,000.
Polyvinyl butyral acetal mean polymerisation degree scope is 500～3500, and preferable range is 750～2000.
The consumption of polyvinyl butyral acetal is 1～500 weight part with respect to ethylene-vinyl acetate copolymer 100 weight parts, and preferable range is 3～30 weight parts
Polyvinyl butyral acetal content is low excessively; Then melt viscosity is little, and the tensile strength of film is low, and the bonding strength of manufacturing laminated glass is poor.Too high levels, then melt viscosity is too big, and processibility is low.
Below the silane coupling agent that uses among the present invention is illustrated.
Silane coupling agent is a big class organosilicon micromolecular compound that has two kinds of different in kinds in the molecule simultaneously, acts on different functional groups.General available general formula YSiR
nX
3-nExpression, n=1 or 0 in the formula; R is an alkylene; Y is an organo-functional group, can be amino, glycidyl, sulfydryl, vinyl, isobutenyl etc., and it was both aliphatic, and was also aromatic, they easily with organic compound in the functional group react; X is the group that a class hydrolyzable generates the silicon alkyl, as halogen, and methoxyl group, oxyethyl group, alkoxyl group, functional groups such as acetoxyl group, the silicon alkyl of generation can be had an effect with the alkyl of inorganic material surface, improves the cementability between organic materials and inorganic materials.And make the water tolerance of goods, and electrical insulating property, resistance to deterioration and mechanical property etc. is improved.
As containing amino silane coupling agent, can be: 3-aminopropyl dimethylethoxysilane silicon, 3-aminopropyl methyldiethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-aminoethyl)-3-aminopropyl three or four TMOSs.
Silane coupling agent as having glycidyl can be: 3-Racemic glycidol propoxy-dimethylethoxysilane, 3-Racemic glycidol propoxy-methyldiethoxysilane, 3-glycidoxypropyltrime,hoxysilane, 2-(3.4-epoxycyclohexyl) ethyl trimethoxy silane.
As silane coupling agent with sulfydryl, can be thiopurine methyltransferase dimethylethoxysilane, its dimethyl methyl diethoxy silane of mercapto first, 3-mercapto propyl group methyldiethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercapto propyl-dimethyl Ethoxysilane, 3-thiopropyl methyldiethoxysilane.
As having the silane coupling agent that vinyl is arranged, can be: vinyltriethoxysilane.
As silane coupling agent, can be γ-isobutenyl ethyl oxygen propyl trimethoxy silicane with isobutenyl.
Above-mentioned silane coupling agent can use separately, also can two or morely be used.
Silane coupling agent with respect to ethylene-vinyl acetate copolymer 100 weight parts, can cooperate 0.05～5 weight part, preferred 0.1～2 weight part, if silane coupled agent content is low excessively, be not enough to improve the adhesiveproperties of film, if too high levels, resin combination can not absorb fully, in the intermediate coat course of processing, silane coupling agent is separated out phenomenon, influences the quality of film, and film has yellowing phenomenon, influences the transparency of film and laminated glass.
Below the nucleator that uses among the present invention is illustrated.
The opaque of resin material is because the crystallization that polymkeric substance produces in the resin causes scattering of light.If the crystalline size is much smaller than wavelength of visible light in the resin, then scattering does not take place to light in crystallization, just can not influence the transparency of resin yet.Introduce nucleator in film, purpose is to increase crystalline quantity and the size that reduces crystallization, increases the transparency of film.
Nucleator can be selected from carboxylic-acid, metallic salt and a kind of have polyvalent alcohol (or derivative) more than five yuan with phenyl aldehyde (or derivative) condensation reaction and product.
The carboxylic-acid nucleator can be: phenylformic acid, hexanodioic acid, phenylbenzene acetic acid etc.
The metallic salt nucleator can be: sodium stearate, sodium-acetate, sodium phenylate etc.
Condensation reaction products can be: dibenzylidene sorbitol compound, dibenzylidene xyllitol compound, dibenzylidene galactitol compound, dibenzylidene mannitol compound.
As above-mentioned dibenzylidene sorbitol compound, can be: dibenzylidene sorbitol, two (methyl benzylidene) Sorbitol Powder, two (ethyl benzylidene) Sorbitol Powder, two (propyl group benzylidene) Sorbitol Powder, two (butyl benzylidene) Sorbitol Powder, two (amyl group benzylidene) Sorbitol Powder, two (hexyl benzylidene) Sorbitol Powder, two (chloro benzylidene) Sorbitol Powder.
As other nucleators, can also use: tribenzylidene sorbitol, two (4-tert-butyl-phenyl) sodium of phosphoric acid, phosphoric acid 2,2 '-methylene-bis (4.6-di-tert-butyl-phenyl) sodium, hydroxyl-two (p t butylbenzoic acid) aluminium etc.
Above-mentioned nucleator can be used alone, but also two or more is used.
The consumption of above-mentioned nucleator with respect to ethylene-vinyl acetate copolymer 100 weight parts, is 0.02～2 weight part, and preferably the scope of getting is 0.05～1 weight part.
Use to anti-aging agent in the film is illustrated below.
In film of the present invention, the aging of resin is inevitably, impels the extraneous factor of ageing of plastics to comprise physics, chemistry and biological effect, and the chemical process of ageing of plastics and changes of microstructure are very complicated.Comprise molecular rupture, the variation of crosslinked side group, that the principal reaction course of weathering process comprises is chain initiation, chainpropagation and chain termination reaction.
The anti-aging measure of plastics can be divided into physical method and chemical process, and physical method mainly is that frosting is carried out applying coating, makes it enclose one deck protective layer or film, and shielding ultraviolet rays and extraneous factor reach age inhibiting purpose to the influence of material.This method obviously is unconformable in the anti-aging of film.Chemical process mainly is to select corresponding anti-aging agent such as oxidation inhibitor, UV light absorber, photomask agent, quencher, free radical scavenger, thermo-stabilizer etc. according to the performance characteristics of material and aging reaction mechanism, is added to and goes to reach age inhibiting purpose in the plastics.It is the optimum method of film anti-aging.
Above-mentioned oxidation inhibitor can be divided into arylamine class, phenols, ester class and other classification, and product has tens kinds of antioxidant 1010s, antioxidant 1076, antioxidant CA, oxidation inhibitor DLTDP, DSTDP etc.
Above-mentioned oxidation inhibitor can one or more be used, and its amount is 0.01～2.5 weight part with respect to ethylene-vinyl acetate copolymer 100 weight parts, and preferable range is 0.05～1 weight part.
Above-mentioned UV light absorber, photomask agent, quencher, free radical scavenger may be interpreted as photostabilizer.
Photostabilizer mainly is selected from: uV-p, uv-9, uV-21, chlorination uv-9, chlorination salol, tens kinds of light stabilizer 2002, GW508, TMP, PMP etc.
The content of above-mentioned photostabilizer: with respect to ethylene-vinyl acetate copolymer 100 weight parts is 0.01～5 weight part, and preferable range is 0.05～2 weight part.
But one or more are used above-mentioned photostabilizer according to different needs.
It is to prevent that polymkeric substance is heated and the degraded that takes place and crosslinked in processing and use that above-mentioned thermo-stabilizer mainly acts on, with the work-ing life of prolongation material.
Above-mentioned thermo-stabilizer mainly contains: lead compound, metallic soap, organotin, composite fluid, organic stabilizer, epoxy compounds, phosphorous acid ester and polyvalent alcohol etc.
Above-mentioned thermo-stabilizer can one or more be used, and its usage quantity is 0.01～5 weight part with respect to ethylene-vinyl acetate copolymer 100 weight parts, and preferably the scope of getting is 0.1～3 weight part.
The anti-aging auxiliary agent of film can be selected from above-mentioned oxidation inhibitor, photostabilizer, thermo-stabilizer, but the interpolation total amount of anti-aging auxiliary agent can not influence the physical properties of film.
In the present invention, the blending and modifying of ethylene-vinyl acetate copolymer and polyvinyl butyral acetal is absolutely necessary.It is with ethylene-vinyl acetate copolymer 100 weight parts, polyvinyl butyral acetal 1～50 weight part, silane coupling agent 0.05～5 weight part, nucleator 0.02～2 weight part, various anti-aging auxiliary agent 0.05～5 weight parts are plasticated through 100 ℃～200 ℃ and to be realized.Must be through the hot mastication blending and modifying except that ethylene-vinyl acetate copolymer and polyvinyl butyral acetal, other auxiliary agent can participate in hot mastication, also can not participate in hot mastication and adds before making film.But guarantee that each analog assistant can sneak in the resin equably.
Hot mastication can adopt any one equipment such as twin rollers, Banbury mixer, forcing machine to finish.
The manufacturing of film can be adopted extrusion process, rolling process, casting method, blow moulding or other suitable suitable method manufacturing.
In order to make in laminated glass is made, the gas between glass and film is discharged easily, and film need be made the pitted skin of certain roughness.
About the thickness of film, can decide according to purposes, but the general thickness scope is 0.1～2mm.If the thickness of film is too thin, then the shock-resistance of the laminated glass that obtains reduces, if the thickness of film is blocked up, then the transparency of the laminated glass that obtains reduces.
In order to prepare the laminated glass that uses film among the present invention, film can be assembled between two or multi-disc sheet glass or the synthetic resin board, assembly is put into rubber bag, behind degassing certain hour under the vacuum tightness of 3～25pa, under the condition that keeps this degassing phase, put into a temperature and be 80～120 ℃ baking oven, be incubated after 10～30 minutes, just make laminated glass.The preparation method of laminated glass can also adopt other to satisfy the method for processing requirement.
The laminate structure of laminated glass is the structure of a kind of sheet glass/film/glass basically, but in addition, also can list following laminate structure.
Sheet glass/film/synthetic resin board
Sheet glass/film/ornament/film/sheet glass
Synthetic resin board/film/ornament/film/synthetic resin board
Sheet glass/film/metal sheet/film/synthetic resin board
Synthetic resin board/film/metal sheet/film/synthetic resin board
Below be embodiment and the comparative example among the present invention, also listed in addition the fundamental characteristics of the film that obtains and laminated glass.All " parts " all are meant weight part.
Embodiment 1
(1) manufacturing of film
With a kind of vinyl acetate content is 25%, melting index is 2g/10 minute ethylene-vinyl acetate copolymer (EVA, 360, mitsui chemical polymerization company) 100 parts, 10 parts of polyvinyl butyral acetals (B-76, U.S. Monsanto Company), 1.0 parts of dibenzylidene sorbitols, the 3-aminopropyl trimethoxysilane cooperates, mixes the back together for 1.0 parts and supplies with forcing machine, and fusion is plasticated under 170 ℃ temperature, obtains a kind of polymer blended material.
Directly supply with three roll squeezers from the polymer blended material that forcing machine is extruded, regulate the spacing between mould and three rollers, make the film of thickness 0.4mm.
(2) manufacturing of laminated glass
At two block length 300mm, wide 300mm between the transparent float glass plate of thick 3mm, thereby obtains a kind of interlayer assembly with this plateholder.In the rubber bag of then assembly being packed into, taking out the degassing under the vacuum tightness of 15Pa after 15 minutes, under keeping this degassing phase, it is transferred to temperature and is in 110 ℃ the baking oven, insulation is 20 minutes under this temperature, sheet glass and film are bonded together, thereby make a kind of by laminated glass that sheet glass/film/the sheet glass lamination constitutes.
Embodiment 2-12 comparative example 1-6
Except the consumption according to regulation in the table 1 cooperates ethylene-vinyl acetate copolymer, outside polyvinyl butyral acetal, nucleator, the silane coupling agent, other all makes film according to method similarly to Example 1, makes laminated glass with this film according to implementing 1 same method then.
Embodiment 13-18 comparative example 7-17
Except the consumption according to regulation in the table 2 cooperates ethylene-vinyl acetate copolymer, polyvinyl butyral acetal, nucleator, the silane coupling agent, outside under 200 ℃ of temperature, plasticating, other all according to implement 1 same method and make film.
Embodiment 13-18 except that adopting sheet glass/film/synthetic resins plate structure, all makes laminated glass according to method similarly to Example 1, and comparative example 7～17 is all made laminated glass according to method similarly to Example 1.
Embodiment 19-35
Except the consumption according to regulation in the table 3 cooperated ethylene-vinyl acetate copolymer, polyvinyl butyral acetal, nucleator, silane coupling agent, other all made film according to the 1 same method of enforcement.
Remove assembly when laminated glass is manufactured the 20Pa vacuum tightness degassing 30 minutes, in baking oven outside 25 minutes these 2 differences of insulation under 100 ℃ of temperature, other all according to similarly to Example 1 method with this film manufacturing laminated glass.
Embodiment 36～42
The consumption that removes according to regulation in the table 4 cooperates ethylene-vinyl acetate copolymer, outside polyvinyl butyral acetal, nucleator, the silane coupling agent, also have mixture to plasticate under 145 ℃ of temperature and be polymer blended material, other all makes film according to method similarly to Example 1.
Adopt with the same method of embodiment 19～35 with this film and to make laminated glass.
In embodiment and comparative example, the composition of each sample (film) sees Table 1～table 4.
Ethylene-vinyl acetate copolymer in the following his-and-hers watches, the symbol of polyvinyl butyral acetal is made explanations.
The composition information slip weight part of table 1 film
| The name of an article | Embodiment | Comparative example | |||||||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | ||||||||
| EVA | 360 | 100 | 100 | 100 | |||||||||||||||
| 420 | 100 | 100 | 100 | ||||||||||||||||
| 40 | 100 | 100 | 100 | ||||||||||||||||
| 460 | 100 | 100 | 100 | ||||||||||||||||
| P2807 | 100 | 100 | 100 | ||||||||||||||||
| P2805 | 100 | 100 | 100 | ||||||||||||||||
| PVB | Butvar B-76 | 10 | 30 | 4 | 7 | 5 | |||||||||||||
| Butvar B-73 | 5 | 15 | 20 | 25 | 5 | ||||||||||||||
| Butvar B74 | 3 | 10 | |||||||||||||||||
| Nucleator | Dibenzylidene sorbitol | 1.0 | 0.3 | 2.0 | 0.5 | 1.0 | 1.0 | 1.0 | |||||||||||
| Two (methyl benzylidene) sorbyl alcohol | 0.5 | 0.2 | 1.0 | 0.3 | 0.8 | 0.5 | |||||||||||||
| Two (ethyl benzylidene) sorbyl alcohol | 0.2 | 0.2 | 0.2 | 0.3 | 0.3 | ||||||||||||||
| Silane coupling agent | 3-aminopropyl trimethyl silane | 1.0 | 2.0 | 0.5 | 1.0 | 0.5 | |||||||||||||
| N (2 hydrogen ethyl) 3 aminopropyl methyl dimethoxysilanes | 0.5 | 2 | 0.5 | 0.5 | 0.3 | ||||||||||||||
| The 3-mercaptopropyl trimethoxysilane | 1.0 | 0.8 | 0.5 | 0.3 | 1.0 | ||||||||||||||
| The 3-aminopropyl triethoxysilane | 0.3 | 2.0 | 0.5 | ||||||||||||||||
The composition information slip weight part of table 2 film
| The name of an article | Embodiment | Comparative example | ||||||||||||||||
| EVA | 13 | 14 | 15 | 16 | 17 | 18 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | |
| RB-11 | 100 | |||||||||||||||||
| MB 11 | 100 | |||||||||||||||||
| P1450 | 100 | |||||||||||||||||
| KA-20 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | ||||||
| HA-20 | 100 | |||||||||||||||||
| 625 | 100 | |||||||||||||||||
| PVB | SD-1 | 30 | ||||||||||||||||
| SD-2 | 25 | |||||||||||||||||
| SD-3 | 5 | 15 | ||||||||||||||||
| SD-4 | 7 | 50 | 7 | 7 | 7 | 7 | 40 | 7 | 7 | 7 | 7 | |||||||
| SD-5 | 10 | |||||||||||||||||
| Nucleator | Dibenzylidene sorbitol | 0.3 | 0.2 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | ||||
| Dibenzylidene xyllitol | 1.0 | |||||||||||||||||
| The dibenzylidene mannitol | 1.5 | |||||||||||||||||
| Tribenzylidene sorbitol | 0.3 | 0.1 | ||||||||||||||||
| Silane coupling agent | The 3-glycidoxypropyltrime,hoxysilane | 0.5 | 0.3 | 0.05 | 0.05 | 0.005 | 0.3 | 0.3 | ||||||||||
| The 3-mercaptopropyltriethoxysilane | 0.3 | 0.3 | 0.3 | |||||||||||||||
| 3-aminopropyl methyldiethoxysilane | 0.1 | 0.2 | 0.3 | |||||||||||||||
| The 3-aminopropyl trimethoxysilane | 0.1 | 0.2 | 0.5 | 0.3 | ||||||||||||||
The composition information slip weight part of table 3 film
| The name of an article | Embodiment | |||||||||||||||||
| 19 | 20 | 21 | 22 | 23 | 24 | 25 | 26 | 27 | 28 | 29 | 30 | 31 | 32 | 33 | 34 | 35 | ||
| EVA | P2807 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |||
| P2805 | 100 | |||||||||||||||||
| 450 | 100 | |||||||||||||||||
| 460 | 100 | |||||||||||||||||
| Nucleator | Dibenzylidene sorbitol | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | ||||||||
| Two (methyl benzylidene) Sorbitol Powder | 0.2 | 0.3 | ||||||||||||||||
| The dibenzylidene sorbitol of senior fat parcel | 1.2 | 0.3 | ||||||||||||||||
| Two (butyl benzylidene) Sorbitol Powder | 0.2 | 0.3 | ||||||||||||||||
| Dibenzylidene xyllitol | 0.3 | |||||||||||||||||
| The dibenzylidene mannitol | 0.3 | |||||||||||||||||
| Silane coupling agent | The 3-aminopropyl trimethoxysilane | 0.3 | ||||||||||||||||
| The 3-mercaptopropyl trimethoxysilane | 0.3 | |||||||||||||||||
| The 3-glycidoxypropyltrime,hoxysilane | 1.0 | |||||||||||||||||
| N-(2-aminoethyl)-3-aminopropyl methyltrimethoxy silane | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | ||||
| PVB | Butvar B-73 | 2 | 7 | 15 | 0.5 | 3 | 5 | |||||||||||
| Butvar B-74 | 3 | 7 | ||||||||||||||||
| Butvar B-76 | 7 | 7 | 7 | 7 | 7 | |||||||||||||
| SD-3 | 7 | |||||||||||||||||
| SD-4 | 7 | |||||||||||||||||
| SD-5 | 7 | 7 | ||||||||||||||||
The composition information slip weight part of table 4 film
| The name of an article | Embodiment | |||||||
| 36 | 37 | 38 | 39 | 40 | 41 | 42 | ||
| EVA | P2805 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| P2807 | ||||||||
| PVB | Butvar B-73 | |||||||
| Butvar B-74 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | |
| Butvar B-76 | ||||||||
| Nucleator | Dibenzylidene sorbitol | 0.5 | 0.3 | 0.1 | 0.05 | 0.01 | 1.0 | 1.5 |
| Two (methyl benzylidene) Sorbitol Powder | ||||||||
| The dibenzylidene galactitol | ||||||||
| Coupling agent | The 3-aminopropyl trimethoxysilane | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| The 3-mercaptopropyl trimethoxysilane | ||||||||
| The 3-glycidoxypropyltrime,hoxysilane | ||||||||
Ethene-acetate ethylene copolymer (EVA)
| Vinyl acetate content (wt%) | MI (g/10 branch) | Manufactory | |
| 360 | 25％ | 2 | Mitsui chemical polymerization company |
| 420 | 19％ | 150 | Mitsui chemical polymerization company |
| 40 | 40％ | 55 | Mitsui chemical polymerization company |
| 460 | 19％ | 2.5 | Mitsui chemical polymerization company |
| P2807 | 28％ | 15 | Mitsui chemical polymerization company |
| P2805 | 28％ | 6 | Mitsui chemical polymerization company |
| RB-11 | 41％ | 60 | Sumitomo Chemical company limited |
| MB-11 | 32％ | 60 | Sumitomo Chemical company limited |
| P1455 | 14％ | 3.5 | Mitsui chemical polymerization company |
| KA-20 | 25％ | 3.0 | Sumitomo Chemical company limited |
| HA-20 | 20％ | 20 | Sumitomo Chemical company limited |
| 625 | 15％ | 14 | Japan Cao Da Industrial Co., Ltd |
| 450 | 19％ | 15 | Mitsui chemical polymerization company |
Polyvinyl butyral acetal
Film performance test item and method are as follows: 1. the moisture content test adopts GB 1034-86 plastics water absorption test method 2. tensile strength tests to adopt GB 13022-91 plastics-film stretching method for testing performance 3. elongation at break rates test
| Molecular-weight average | Mean polymerisation degree | Butyral content | Factory | |
| Butvar B-76 | 45000 ～ 55000 | 750 | 87.5％ | U.S. Monsanto Company |
| Butvar B-73 | 50000 ～ 80000 | 1000 | 79.5％ | U.S. Monsanto Company |
| Butvar B-74 | 100000 ～ 150000 | 2000 | 80％ | U.S. Monsanto Company |
| SD-1 | 68～78％ | Organic chemical industry demonstration plant, Tianjin | ||
| SD-2 | 68～78％ | Organic chemical industry demonstration plant, Tianjin | ||
| SD-3 | 69～78％ | Organic chemical industry demonstration plant, Tianjin | ||
| SD-4 | 70～78％ | Organic chemical industry demonstration plant, Tianjin | ||
| SD-5 | 70～78％ | Organic chemical industry demonstration plant, Tianjin |
Adopt GB 13022-91 plastics-film stretching method for testing performance
4. weathering test
Adopt GB 9344-88 plastics xenon source exposure test method, after irradiation 1500 hours, detect tensile strength with method same in the above-mentioned tensile strength test, this tensile strength is the evaluation foundation with respect to the retention rate of initial value.
The film performance detected result is listed in table 5, table 6, table 7.
Laminated glass test item and detection method are as follows:
1. boiling test
Adopt GB 5137.3-96, the anti-irradiation of automotive safety glass, high temperature, humidity and flame resistance test method.Requirement surpasses 13mm place apart from limit portion or crack, do not allow the bubble or other defective that exert an influence and use, and whether observation has produced film and peel off in this experiment.
2. impact test
Adopt GB 9962-88 laminated glass, the 1040g steel ball highly freely falls from 1200mm, and 6 samples only allow 1 intermediate coat fracture or expose because of glass peels off, as fracture or expose because of peeling off in the middle of producing, with " * " expression, otherwise, represent with " zero ".
3. Penetration resistance test
Adopt GB 9962-88 laminated glass, laminated glass destroys the freely through opening of ball that part can not produce diameter 75mm after highly impacting, can be as producing for the freely through opening of ball of diameter 75mm, with " * " expression, the opening as not producing, with " zero " expression.
4. radiation resistance test
Adopt GB 5137.3-96, the anti-irradiation of automotive safety glass, high temperature, humidity and flame resistance test method, transmittance minimizing relatively are not more than 10%, can not produce remarkable variable color, bubble and turbid phenomenon, in this experiment with what of the relative decrement of transmittance as estimating foundation.
5. transmitance test
Adopt GB/T 2680-94, visible light transmissivity is penetrated ratio, the direct transmittance of sunlight, and total solar energy transmittance, ultraviolet (uv) transmission is the mensuration of relevant window glass parameter when.
Table 5 film performance detected result
| The sample number into spectrum test item | Embodiment | ||||||||||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | |
| Water-intake rate (%) | 0.56 | 0.37 | 0.28 | 0.76 | 0.35 | 0.58 | 0.63 | 0.38 | 0.86 | 0.43 | 0.23 | 0.22 | 0.81 | 0.79 | 0.21 | 0.24 | 0.38 | 0.35 | 0.24 | 0.23 | 0.18 |
| Tensile strength (MPa) | 23.4 | 20.8 | 20.3 | 25.6 | 21.3 | 24.7 | 25.1 | 21.4 | 27.3 | 22.3 | 20.1 | 20.4 | 23.4 | 22.8 | 21.8 | 20.9 | 22.4 | 22.1 | 22.4 | 22.4 | 20.3 |
| Elongation at break (%) | 430 | 450 | 510.7 | 410.3 | 445 | 448 | 438 | 460 | 410 | 420 | 470 | 465 | 408 | 413 | 465 | 470 | 430 | 435 | 460 | 465 | 470 |
| Weathering resistance (tensile strength retention rate %) | 51 | 47 | 55.3 | 47.1 | 45.2 | 54.1 | 44.4 | 47 | 48 | 42 | 49.1 | 48.4 | 42 | 49 | 50 | 51 | 45 | 46.1 | 46.1 | 46.3 | 45.9 |
Table 6 film performance detected result
| The sample number into spectrum test item | Embodiment | ||||||||||||||||||||
| 22 | 23 | 24 | 25 | 26 | 27 | 28 | 29 | 30 | 31 | 32 | 33 | 34 | 35 | 36 | 37 | 38 | 39 | 40 | 41 | 42 | |
| Water-intake rate (%) | 0.17 | 0.20 | 0.21 | 0.19 | 0.18 | 0.17 | 0.20 | 0.19 | 0.18 | 0.17 | 0.38 | 0.14 | 0.23 | 0.43 | 0.24 | 0.44 | 0.38 | 0.43 | 0.41 | 0.39 | 0.40 |
| Tensile strength (MPa) | 20.1 | 22.4 | 22.3 | 21.9 | 20.3 | 20.8 | 21.3 | 21.4 | 21.3 | 22.4 | 24.8 | 20.08 | 21.4 | 23.4 | 22.3 | 23.5 | 22.7 | 22.8 | 22.8 | 21.9 | 22.7 |
| Elongation at break (%) | 480 | 450 | 455 | 470 | 480 | 465 | 470 | 473 | 465 | 460 | 410.7 | 600 | 510 | 440 | 495 | 430 | 450 | 445 | 445 | 460 | 455 |
| Weathering resistance (tensile strength retention rate %) | 48.7 | 44 | 43 | 49.4 | 44 | 43 | 46 | 45.8 | 45.3 | 45.4 | 46.2 | 46.3 | 46.9 | 44.3 | 44.9 | 44.1 | 35.2 | 20.8 | 10.3 | 47.6 | 48.3 |
Table 7 film performance detected result
| The sample number into spectrum test item | Comparative example | ||||||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | |
| Water-intake rate (%) | 0.14 | 0.13 | 0.15 | 0.16 | 0.14 | 0.13 | 2.0 | 0.55 | 0.50 | 0.38 | 0.18 | 0.38 | 1.86 | 0.38 | 0.37 | 0.39 | 0.40 |
| Tensile strength (MPa) | 16.8 | 14.3 | 14.8 | 17.8 | 15.7 | 14.8 | 30.9 | 23.4 | 23.1 | 22.7 | 14.1 | 21.9 | 29.8 | 21.9 | 22.3 | 22.4 | 23.1 |
| Elongation at break (%) | 650.4 | 870 | 750 | 670 | 710 | 702 | 2503 | 440 | 440 | 510 | 780 | 500 | 290 | 495 | 485 | 490 | 470 |
| Weathering resistance (tensile strength retention rate %) | 44.7 | 41.4 | 47.5 | 47.6 | 47.3 | 45.3 | 40.3 | 39.8 | 39.7 | 38.2 | 37.7 | 38.5 | 36.9 | 37.1 | 38.4 | 39.3 | 40.1 |
6. humidity test
Adopt GB 5137.3-96, whether the anti-irradiation of automotive safety glass, high temperature, humidity and flame resistance test method are observed to have produced and are peeled off phenomenon.
7. bonding strength test
Adopt GJB 1258-91, the polyvinyl butyral acetal intermediate coat.
8. caloric test
With sample under the temperature 70 ℃ place 2 hours after, with 2 hours it is cooled to-20 ℃ from 70 ℃, placing 2 hours in temperature-20 ℃ again, spend 2 hours then it ℃ is heated to 70 ℃ from temperature-20,, carry out altogether observing whether phenomenon has taken place to peel off after 10 circulations as 1 circulation with this process.
9. mist degree
Adopt transmittance, mist degree tester to measure haze value.
Above-mentioned laminated glass performance test results is listed in table 8, table 9, table 10.
Table 8 laminated glass performance test results
| The sample number into spectrum test item | Embodiment | ||||||||||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | |
| But light transmission rate % | 84.5 | 83.4 | 85.6 | 86.7 | 85.3 | 84.7 | 87.1 | 84.7 | 86.3 | 85.6 | 88 | 83.4 | 81.3 | 82.4 | 85.6 | 86.7 | 84.9 | 80.3 | 81.4 | 82.1 | 86.9 |
| Mist degree % | 0.87 | 0.89 | 0.81 | 0.56 | 0.92 | 0.37 | 0.35 | 0.45 | 0.83 | 0.77 | 0.30 | 0.67 | 0.68 | 0.93 | 0.74 | 0.63 | 0.78 | 0.98 | 0.88 | 0.85 | 0.43 |
| Cohesive strength MPa | 7.1 | 7.2 | 7.0 | 7.9 | 7.2 | 7.5 | 8.0 | 7.4 | 7.6 | 7.3 | 7.9 | 7.5 | 8.8 | 9.4 | 9.3 | 10.4 | 9.1 | 9.03 | 7.14 | 7.2 | 7.5 |
| Shock resistance (zero *) | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Penetration-resistant (zero *) | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Boiling test (that peels off has or not) | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have |
| Humidity test (that peels off has or not) | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have |
| Radiation resistance (transmittance decrement %) | 2.3 | 2.4 | 2.2 | 1.0 | 2.5 | 0.8 | 1.3 | 2.0 | 2.4 | 2.7 | 0.7 | 1.4 | 2.3 | 2.1 | 1.8 | 1.3 | 1.5 | 2.7 | 2.0 | 1.9 | 0.5 |
| Oven test (that peels off has or not) | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have |
Table 9 laminated glass performance test results
| The sample number into spectrum test item | Embodiment | ||||||||||||||||||||
| 22 | 23 | 24 | 25 | 26 | 27 | 28 | 29 | 30 | 31 | 32 | 33 | 34 | 35 | 36 | 37 | 38 | 39 | 40 | 41 | 42 | |
| Visible light transmissivity % | 88.5 | 86.3 | 84.5 | 89.1 | 85.4 | 84.2 | 84 | 84.1 | 84.1 | 84.2 | 84.3 | 84.2 | 84.3 | 84.2 | 85.5 | 84.3 | 78 | 75 | 74 | 86.3 | 87.6 |
| Mist degree % | 0.43 | 0.87 | 0.89 | 0.43 | 0.64 | 0.73 | 0.74 | 0.75 | 0.74 | 0.73 | 0.70 | 0.72 | 0.72 | 0.71 | 0.66 | 0.70 | 1.4 | 2.0 | 3.4 | 0.66 | 0.37 |
| Bonding strength MPa | 7.1 | 7.2 | 7.1 | 7.2 | 7.1 | 7.2 | 7.1 | 7.2 | 7.1 | 7.1 | 7.2 | 1.7 | 7.0 | 7.1 | 7.5 | 7.4 | 7.4 | 7.4 | 7.5 | 7.4 | 7.5 |
| Shock resistance (zero *) | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Penetration-resistant (zero *) | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Boiling test (that peels off has or not) | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have |
| Humidity test (that peels off has or not) | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have |
| Radiation resistance (transmittance decrement %) | 1.0 | 2.7 | 2.9 | 1.0 | 2.0 | 1.8 | 2.3 | 2.0 | 1.9 | 1.8 | 1.7 | 1.8 | 1.9 | 2.0 | 1.6 | 1.8 | 3.4 | 6.0 | 9.6 | 1.9 | 1.5 |
| Oven test (that peels off has or not) | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have | Do not have |
Table 10 laminated glass performance test results
| The sample number into spectrum test item | Comparative example | ||||||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | |
| Visible light transmissivity % | 84.3 | 81.2 | 89.4 | 89.5 | 84.6 | 84.5 | 81.3 | 81.4 | 81.5 | 81.5 | 81.6 | 81.3 | 81.4 | 81.4 | 81.6 | 82 | 81.9 |
| Mist degree % | 0.72 | 0.89 | 0.37 | 0.36 | 0.69 | 0.70 | 0.88 | 0.88 | 0.86 | 0.86 | 0.84 | 0.89 | 0.83 | 0.83 | 0.79 | 0.67 | 0.68 |
| Bonding strength MPa | 3.1 | 2.7 | 1.8 | 1.7 | 2.8 | 1.9 | 4.3 | 3.0 | 7.0 | 1.0 | 1.5 | 1.1 | 5.6 | 7.1 | 7.1 | 7.2 | 7.1 |
| Shock resistance (zero *) | × | × | × | × | × | × | × | × | ○ | × | × | × | × | ○ | ○ | ○ | ○ |
| Penetration-resistant (zero *) | × | × | × | × | × | × | × | × | ○ | × | × | × | × | ○ | ○ | ○ | ○ |
| Boiling test (that peels off has or not) | Have | Have | Have | Have | Have | Have | Do not have | Have | Do not have | Have | Have | Have | Do not have | Do not have | Do not have | Do not have | Do not have |
| Humidity test (that peels off has or not) | Have | Have | Have | Have | Have | Have | Do not have | Have | Do not have | Have | Have | Have | Do not have | Do not have | Do not have | Do not have | Do not have |
| Radiation resistance (transmittance decrement %) | 2.3 | 2.7 | 0.7 | 0.6 | 2.0 | 2.1 | 2.5 | 2.6 | 2.4 | 2.4 | 2.3 | 2.2 | 2.1 | 2.0 | 1.9 | 2.0 | 2.1 |
| Oven test (that peels off has or not) | Have | Have | Have | Have | Have | Have | Have | Have | Do not have | Have | Have | Have | Have | Do not have | Do not have | Do not have | Do not have |
Claims (20)
1, a kind of adhesive sheet for sandwiched glass is characterized in that by ethylene-vinyl acetate copolymer 100 weight parts, polyvinyl butyral acetal 1～50 weight part, and silane coupling agent 0.05～5 weight part, nucleator 0.02～2 weight part constitutes.
2, by the described film of claim 1, the melt index that it is characterized in that described ethylene-vinyl acetate copolymer is 0.1～500g/10 branch.
3, by the described film of claim 2, the melt index that it is characterized in that ethylene-vinyl acetate copolymer is 2～150g/10 branch.
4, by the described film of claim 1, it is characterized in that vinyl acetate content is 10～60% in the described ethylene-vinyl acetate copolymer.
5, by the described film of claim 4, it is characterized in that vinyl acetate content is 20～40% in the ethylene-vinyl acetate copolymer
6, by the described film of claim 1, it is characterized in that described polyvinyl butyral acetal mean polymerisation degree is 500～3500.
7, by the described film of claim 6, it is characterized in that the polyvinyl butyral acetal mean polymerisation degree is 750～2000.
8, by the described film of claim 1, it is characterized in that described polyvinyl butyral acetal weight-average molecular weight is 3～270,000.
9, by the described film of claim 8, it is characterized in that the polyvinyl butyral acetal weight-average molecular weight is 5～150,000.
10, by the described film of claim 1, it is characterized in that described polyvinyl butyral acetal amount with respect to ethylene-vinyl acetate copolymer 100 weight parts, is 1～50 weight part.
11, by the described film of claim 10, it is characterized in that the polyvinyl butyral acetal amount with respect to ethylene-vinyl acetate copolymer 100 weight parts, is the 3-30 weight part.
12, by the described film of claim 1, it is characterized in that described silane coupling agent is the silane compound that contains a kind of functional group in amino, glycidyl, sulfydryl, vinyl, the isobutenyl.
13, by the described film of claim 12, it is characterized in that the silane coupling agent amount with respect to ethylene-vinyl acetate copolymer 100 weight parts, is 0.05～5 weight part.
14, by the described film of claim 13, it is characterized in that the silane coupling agent amount with respect to ethylene-vinyl acetate copolymer 100 weight parts, is the 0.1-2 weight part.
15,, it is characterized in that described nucleator can be selected from carboxylic-acid, metallic salt and a kind of product that is obtained with phenyl aldehyde (or derivative) condensation reaction by the polyvalent alcohol more than five yuan (or derivative) by the described film of claim 1.
16, by the described film of claim 15, it is characterized in that the carboxylic-acid nucleator can be selected from: phenylformic acid, hexanodioic acid, phenylbenzene acetic acid.
17, by the described film of claim 15, it is characterized in that the metallic salt nucleator can be selected from: sodium stearate, sodium-acetate, sodium phenylate.
18, by the described film of claim 15, it is characterized in that condensation reaction products can be selected from: dibenzylidene sorbitol compound, dibenzylidene xyllitol compound, dibenzylidene galactitol compound, dibenzylidene mannitol compound.
19, by the described film of claim 1, the amount that it is characterized in that described nucleator is 0.02～2 weight part with respect to ethylene-vinyl acetate copolymer 100 weight parts.
20, by the described film of claim 19, it is characterized in that the nucleator amount is 0.05～1 weight part with respect to ethylene-vinyl acetate copolymer 100 weight parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99121275A CN1098892C (en) | 1999-11-04 | 1999-11-04 | Adhesive sheet for sandwiched glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99121275A CN1098892C (en) | 1999-11-04 | 1999-11-04 | Adhesive sheet for sandwiched glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1284518A CN1284518A (en) | 2001-02-21 |
| CN1098892C true CN1098892C (en) | 2003-01-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99121275A Expired - Fee Related CN1098892C (en) | 1999-11-04 | 1999-11-04 | Adhesive sheet for sandwiched glass |
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| Country | Link |
|---|---|
| CN (1) | CN1098892C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2565838A1 (en) * | 2004-05-07 | 2005-11-17 | Asahi Glass Company, Limited | Single-sealed multilayer transparent unit |
| JP4789024B2 (en) * | 2009-12-25 | 2011-10-05 | 積水化学工業株式会社 | Laminated glass interlayer film, laminated glass multilayer interlayer film and laminated glass |
| CN105585805A (en) * | 2016-02-24 | 2016-05-18 | 苏州常德新科膜材料有限公司 | PVB (polyvinyl butyral) membrane capable of reducing ultraviolet harm and production process thereof |
| CN113771326B (en) * | 2021-09-16 | 2022-12-20 | 安徽省阳明达新材料科技有限公司 | Production process method of EVA (ethylene vinyl acetate) film for flame-retardant laminated glass |
| CN115352169B (en) * | 2022-08-08 | 2024-05-28 | 无锡市璞宏工程玻璃有限公司 | Integrated SGP laminated glass process and process system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5415909A (en) * | 1992-12-17 | 1995-05-16 | Sekisui Chemical Co., Ltd. | Interlayer film and laminated glass using the same |
| CN1142437A (en) * | 1995-06-08 | 1997-02-12 | 积水化学工业株式会社 | Middle film for laminated glass and the laminated glass products for the side windows of vehicles |
-
1999
- 1999-11-04 CN CN99121275A patent/CN1098892C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5415909A (en) * | 1992-12-17 | 1995-05-16 | Sekisui Chemical Co., Ltd. | Interlayer film and laminated glass using the same |
| CN1142437A (en) * | 1995-06-08 | 1997-02-12 | 积水化学工业株式会社 | Middle film for laminated glass and the laminated glass products for the side windows of vehicles |
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| CN1284518A (en) | 2001-02-21 |
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