CN1338485A - Resin composition containing ethylene-vinyl acetate copolymer saponin and its formed article - Google Patents
Resin composition containing ethylene-vinyl acetate copolymer saponin and its formed article Download PDFInfo
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- CN1338485A CN1338485A CN 01133197 CN01133197A CN1338485A CN 1338485 A CN1338485 A CN 1338485A CN 01133197 CN01133197 CN 01133197 CN 01133197 A CN01133197 A CN 01133197A CN 1338485 A CN1338485 A CN 1338485A
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- polymkeric substance
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Abstract
The components of the resin composition according to the invention are mixture of polymer (1) of 99.5-60 w% and polymer (2) of 0.5-40 w%, inwhich the total weight of polymer (1) and (2) is 100 w%. The polymer (1) is a saponified ethene-vinyl acetate copolymer with a 20-60 mol% of ethene units and a saponification value of 90-100%; the polymer (2) is a saponified ethene-vinyl acetate copolymer with a 85-95 mol% of ethene units and a saponification value of 40-100%.
Description
Technical field
The present invention relates to not only under drying conditions, even under high humidity, also can present the resin combination that contains ethylene-vinyl acetate copolymer saponin of excellent gas shielding, and with the molding of its processing.
Background technology
Ethylene-vinyl acetate copolymer saponin (following note is made EVOH) is the good thermoplastic resin of gas-barrier property, is widely used in food, medicine, electronic material etc., particularly oxygen demand is had in the field of gas-barrier property.
Yet the feature that EVOH has is that gas-barrier property is good under drying conditions, and gas-barrier property significantly reduces under high humidity.
The problem that invention will solve
In view of the problem in the above-mentioned old technology, the purpose of this invention is to provide a kind of not only under drying conditions, even under high humidity, also can present the EVOH based resin composition of excellent gas shielding.Solve the means of problem
Present inventors find, by comparing the specific ethylene-vinyl acetate copolymer saponin mixing formation resin combination that the unitary saponification deg of acetate unit content and vinyl acetate between to for plastic is different with specified quantitative, can achieve the above object, and so far finish the present invention.
That is, resin combination provided by the invention, feature is by following polymkeric substance of 99.5～60 weight parts (1) and the following polymkeric substance of 0.5～40 weight part (2) formed (the total amount of polymkeric substance (1) and polymkeric substance (2) is 100 weight parts).Molding with the layer that is formed by this resin combination is provided simultaneously.
Polymkeric substance (1): the ethylene-vinyl acetate copolymer saponin of 20～60 moles of % of acetate unit content, saponification deg 90～100%
Polymkeric substance (2): the ethylene-vinyl acetate copolymer saponin of 85～95 moles of % of acetate unit content, saponification deg 40～100%
The working of an invention scheme
For achieving the above object, the acetate unit content of contained polymkeric substance (1) is 20～60 moles of % in the resin combination of the present invention, best 25～50 moles of %, better 30～45 moles of %.
When the EVOH that uses acetate unit content to be lower than 20 moles of % replaced polymkeric substance (1), the gas-barrier property of resin combination under high humidity significantly degenerated.On the other hand, when using acetate unit content to surpass the EVOH of 60 moles of %, the gas-barrier property of resin combination is all insufficient under drying conditions and under high humidity.
The saponification deg of the polymkeric substance (1) that resin combination of the present invention is contained is preferably in more than 95% more than 90%, better more than 97%.
When the EVOH that is lower than 90% with saponification deg replaced polymkeric substance (1), the gas-barrier property of resin combination all became insufficient under drying conditions and under high humidity.
Resin combination of the present invention can only contain a kind of EVOH that is equivalent to polymkeric substance (1), in the scope of suitable polymkeric substance (1), also can contain the acetate unit content EVOH different with saponification deg more than 2 kinds.
The acetate unit content of contained polymkeric substance (2) is 85～95 moles of % in the resin combination of the present invention.
When being lower than the EVOH replacement polymkeric substance (2) of 85 moles of % with acetate unit content, resin combination gas-barrier property under high humidity becomes insufficient.On the other hand, acetate unit content surpasses the above EVOH of 95 moles of %, the intermiscibility of shortage and polymkeric substance (1), and therefore, when using its to replace polymkeric substance (2), the gas-barrier property of resin combination is all insufficient under drying conditions and under high humidity.Preferably ethylene content surpasses 90 moles of %.
The saponification deg of polymkeric substance (2) is 40～100%, best 50～80%.
Saponification deg is lower than 40% EVOH and polymkeric substance (1) shortage intermiscibility, and therefore, when replacing polymkeric substance (2) with it, the gas-barrier property of resin combination becomes insufficient.
Resin combination of the present invention can only contain a kind of EVOH that is equivalent to polymkeric substance (2), in the scope of suitable polymkeric substance (2), also can contain the acetate unit content EVOH different with saponification deg more than 2 kinds.
The amount of contained polymkeric substance (2) in the resin combination of the present invention, when polymkeric substance (1) and polymkeric substance (2) add up to 100 weight parts the time, be 0.5～40 weight part, its lower value is preferably 1 weight part, best 30 weight parts of higher limit, more preferably 20 weight parts.
When polymkeric substance (2) was less than 0.5 weight part, the gas-barrier property of resin combination under high humidity became insufficient.When polymkeric substance (2) during more than 40 weight parts, the gas-barrier property of resin combination all becomes insufficient under drying conditions and under high humidity.
The rigidity of (the total amount of polymkeric substance (1) and polymkeric substance (2) is 100 weight parts) this resin combination is any all higher than polymkeric substance (1) and polymkeric substance (2) when resin combination of the present invention contains the polymkeric substance (2) of 0.5～3 weight part.On the other hand, polymkeric substance in the resin combination of the present invention (2) is during more than 5 weight parts, and the rigidity of this resin combination is lower than polymkeric substance (1).So the amount of the polymkeric substance in the resin combination (2) is as long as be 0.5-40 weight part (the total amount of polymkeric substance (1) and polymkeric substance (2) is 100 weight parts), even under high humidity, also can obtain good gas-barrier property, therefore the suitable amount of selective polymer (2) in this scope, the gas-barrier property of resin combination under high humidity can be kept, and its rigidity can be regulated.
The total content of polymkeric substance in the resin combination of the present invention (1) and (2) may not be exactly critical, but normally resin combination overall 50～100%, best 70～100%, better 90～100%.
The manufacture method of contained polymkeric substance (1) and polymkeric substance (2) does not have particular determination in the resin combination of the present invention, as an example, carries out the saponified method by carrying out the ethylene-vinyl acetate copolymer that copolymerization forms by desired acetate unit content.Carry out the acetate unit content and the saponification condition of saponified ethylene-vinyl acetate copolymer by suitable adjusting, can obtain polymkeric substance (1) and polymkeric substance (2).
The method for saponification of ethylene-vinyl acetate copolymer does not have particular determination, following method is for example arranged, at organic solvent, concrete picture dimethylbenzene, toluene, dissolve ethylene-acetate ethylene copolymer in the aromatic hydrocarbon of benzene one class, carry out saponification with basic catalyst, interpolation precipitates the method for resultant respectively as the lean solvent of the ethylene-vinyl acetate copolymer of methyl alcohol one class in reaction system, with being dispersed in, granular or pulverous ethylene-vinyl acetate copolymer looks like methyl alcohol, ethanol, in the alcohol such as Virahol, carry out saponification with basic catalyst again, utilization removes by filter pure and mild catalyzer, uses the method for pure wash residual thing again.
As basic catalyst, can use alkali alcoholate, as the methylate of sodium and the ethylate and the alkali-metal oxyhydroxide of sodium, as sodium hydroxide and potassium hydroxide.
The saponification condition of ethylene-vinyl acetate copolymer, for example as described below.
Response matrix (ethylene-vinyl acetate copolymer) concentration: 10～50%
Temperature of reaction: 30～60 ℃
Reaction times: 1～6 hour
Catalyst levels: 0.02～0.6 equivalent (every acetate groups)
By reaction conditionss such as conditioned reaction substrate concn, temperature of reaction, reaction times, catalyst levelss, can regulate saponification deg.
Contained polymkeric substance (1) and/or polymkeric substance (2) in the resin combination of the present invention, under the characteristic of not obvious infringement resin combination of the present invention, but the monomer class of also available following copolymerization is carried out sex change, as alpha-olefin, unsaturated acid, unsaturated acid anhydride, unsaturated hydrochlorate, alkene sulfonic acid, alkene sulfonate, list or dialkyl esters, nitrile, amides, alkyl vinyl ether class, vinyl etc.
Resin combination of the present invention under the condition of not obvious its characteristic of infringement, also can suitably contain polymkeric substance (1) and (2) resin and additive in addition.
The polymkeric substance that resin combination of the present invention can contain (1) and (2) resin in addition for example have following thermoplastic resin.Resin combination of the present invention except that polymkeric substance (1) and (2), can contain a kind of resin, also can contain the resin more than 2 kinds.
Polyolefin-based resins
The ethylene-vinyl ester copolymer
Ethene-(methyl) acrylic copolymer
Ethene-(methyl) acrylate copolymer
Polyester based resin
Polyamide-based resin
Acrylic resin
The acrylic resin
Polyvinyl alcohol
Poly carboxylic acid (acid anhydride)
Polymkeric substance (1) and (2) ethylene-vinyl acetate copolymer saponin in addition
As the example additives that resin combination of the present invention can contain, oxidation inhibitor, photostabilizer, UV light absorber, anti-turbid dose, antifogging agent, plasticizer, antistatic agent, lubrication prescription, tinting material etc. are for example arranged.
The manufacture method of resin combination of the present invention, promptly, polymkeric substance (1), polymkeric substance (2) and the composition (resin and additive) that appends are as required carried out the blended method, be not limited in this respect, for example can give an example, normally used single shaft or double-shafted extruder carry out the method that fusion is mixed with raw material when using resin to mix.Method for extrusion machine that polymkeric substance (1) and polymkeric substance (2) and other any compositions are packed into; there is not particular restriction; for example; the material of particle or powder shaped is carried out dry blending in advance; again with the mixture that obtains with pack into method in the extrusion machine of devices such as feeder and compactor, use several feeders each material to be respectively charged into the method for extrusion machine.Also more than one material dissolution (mainly being organic solvent) in solvent can be sent in the extrusion machine with infusion pump again.
In the high density masterbatch of synthetic polymkeric substance (1) and/or polymkeric substance (2) in advance, with an amount of polymkeric substance (1) and/or polymkeric substance (2), and the desired composition that appends mixes, and also can obtain resin combination of the present invention by mixing.
Resin combination of the present invention, when under 23 ℃, the condition of relative humidity 0%RH, measuring, the oxygen air penetrability that presents, per 1 μ m thickness is probably at 10cc/m
2.day.atm below.Resin combination of the present invention, when under 23 ℃, the condition of relative humidity 90%RH, measuring, the oxygen air penetrability that presents, per 1 μ m thickness is probably at 50cc/m
2.day.atm below.That is, resin combination of the present invention and also can present good carrier of oxygen shielding not only under low humidity under high humidity.Therefore, the molding that will have the layer that is formed by resin combination of the present invention is when the wrapping material, even content is rotten on also preventing under high humidity.
Among the present invention, the oxygen air penetrability is measured with following method according to JIS K-7126 standard.
At first, under 210 ℃ to resin combination with hot pressing in 3 minutes, cold pressing with 5 minutes at 30 ℃ following pair again, make the thick thing test portion of 30 μ m film.Then this test portion film is installed on the determinator, METHOD FOR CONTINUOUS DETERMINATION oxygen air penetrability is obtained the oxygen oxygen transmission rate and is actually the oxygen oxygen transmission rate that reaches the constant moment (normally from measure beginning a few hours～3 day after).Measure the oxygen air penetrability determinator (trade(brand)name: OX-TRAN100) that the oxygen air penetrability can use U.S. MOCON society system.Perhaps use the device equal with it.
The saturating rate of oxygen by the aforesaid method actual measurement calculates the thick oxygen air penetrability of per 1 μ m, represents the oxygen air penetrability of resin combination with this calculated value.Thin-films Oxygen air penetrability (the cc/m that forms by same resin combination
2.day/atm) thickness with film is inversely proportional to.
Resin combination of the present invention can be processed into the molding such as film, sheet, pipe, tube, bottle with the layer that is formed by this resin combination.These molding can be the individual layers that is formed by resin combination of the present invention, also can be the multilayer body of the layer more than the one deck that is formed by resin combination layer of the present invention and other materials.In molding with the layer that forms by resin combination of the present invention, by resin combination of the present invention forms layer thickness, according to the desired gas-barrier property level of this molding and difference is generally 10～500 μ m, best 15～100 μ m.With the molding that resin combination of the present invention forms, preferably packaging material for food, drug packing material, electronics wrapping material, pneumatic thickener are wherein suitable to especially packaging material for food.
When resin combination of the present invention contains the polymkeric substance (2) (the total amount of polymkeric substance (1) and polymkeric substance (2) is 100 weight parts) of 0.5～3 weight part, the rigidity of this resin combination is all higher than polymkeric substance (1) and any one rigidity of polymkeric substance (2), so by this resin combination is shaped, can obtain having very high rigidity, the little molding of distortion during use.
Resin combination of the present invention contains more than 5 weight parts, when being less than 40 parts by weight polymer (2) (the total amount of polymkeric substance (1) and polymkeric substance (2) is 100 weight parts), this tree refers to the good-extensibility of composition than polymkeric substance (1), so optimum is as containing extension process such as stent extensions, atubular extension and utilizing the raw material of the molding manufacturing of hot formed figuration process.
In the multilevel shaping product with the layer that is formed by resin combination of the present invention, the layer beyond the resin combination layer of the present invention for example can be the layer that is formed by woven cloth, non-woven, woven cloth, sheet, film, reticulation etc.The raw material of the layer beyond the resin combination layer of the present invention can as its example, have mineral such as natural fibers such as thermoplastic resin, thermosetting resin, rubber, thermoplastic elastomer, fiber crops, Calucium Silicate powder according to the suitably selections such as purposes of molding, or the like.Also can use metal sheets such as the synthetic paper, foam, aluminium and the iron that form by timber, paper, polypropylene and polystyrene etc. or tinsel etc.
By resin combination layer of the present invention layer in addition is set in molding, it is functional to improve mechanical characteristics such as flexural rigidity, compressive strength, surperficial invulnerability, dimensional stability and thermotolerance, thermal insulation, plasticity, water vapor gas-barrier property etc., also can pay gloss and characteristics such as surface smoothing, beautiful appearance simultaneously.
Layer beyond the resin combination layer of the present invention can be a single layer structure, also can be the multilayered structure that forms more than two layers.
As the thermoplastic resin example that constitutes resin combination layer of the present invention layer in addition.New LDPE (film grade) is arranged, high density polyethylene(HDPE), ethylene-propylene copolymer, ethylene-butene copolymer, the alkene copolymer of ethene-, ethylene-octene copolymer, polyolefin-based resins such as polypropylene, the ethylene-vinyl ester copolymer, ethene-(methyl) acrylate copolymer, polyester based resin, polyamide-based resin, acrylic resin, the acrylic resin, the cellulose-based resin of hydrophobization, halogen-containing resin, polyvinyl alcohol, hydrogen bond resins such as derivatived cellulose, ionomer resin, polycarbonate resin, polysulfone resin, polyethersulfone resin, polyether-ether-ketone resin, the polyhenylene ether resin, polyhenylene oxidation resin, poly-propine sulfide resins, the celcon resin, polyacetal resin, liquid-crystal polyester resin, aromatic poly is that the engineering plastics of resin etc. are resin etc.Also available with these resins carry out the grafting sex change, crosslinked or molecule chain end is modified the so-called denatured resin that obtains.
To have when being used for food product pack by the cambial molding of resin combination of the present invention, this molding has preferably that extended polypropylene film (CPP), extended polypropylene film (OPP), thermoplastic resin foam layer etc. are not augmented layer.
In molding,, also can have bond layer or adhesive resin layer for layer is bonded to each other with the layer that forms by resin combination of the present invention.
As the adhesive resin example, there is (1) from unsaturated carboxylic acid or its acid anhydrides, the vinyl monomer that contains epoxy group(ing), esters of unsaturated carboxylic acids, vinyl acetate, to select more than one monomer and the sour sex change olefin polymer that grafting forms is carried out with unsaturated carboxylic acid or its acid anhydrides in multipolymer and (2) of olefinic monomer.
As the former specific examples, ethene-(methyl) acrylic copolymer, ethene-(methyl) acrylic copolymer metal corsslinking thing, ethene-epihydric alcohol methylpropenoic acid ester multipolymer, ethylene-methyl methacrylate glycidyl ester-acetate ethylene copolymer, ethylene-methyl methacrylate glycidyl ester-(methyl) methyl acrylate copolymer, ethene-(methyl) acrylate copolymer, ethene-(methyl) acrylate-copolymer-maleic anhydride and ethylene-vinyl acetate copolymer etc. are arranged.
As the latter's specific examples, the example as unsaturated carboxylic acid or its acid anhydrides being carried out grafted acid sex change olefin polymer has maleic anhydride graft sex change ethylene-based polymer, maleic anhydride graft denaturing acrylamide based polymer etc.
As molding manufacture method with the layer that forms by resin combination of the present invention, can use general thermoplastic resin to implement the manufacturing process that is shaped, for example use the extrusion molding, reaction-injection moulding, blowing method of board-like mould such as T mould or circular ring type mould etc.In these moulding methodes, can obtain the molding of individual layer, also available co-extruded shaping method and multilayer blowing method obtain the multilevel shaping product.
The molding that uses these moulding methodes to obtain also can utilize melt coating method, extruding lay-up method, dry laminate method etc. to obtain the multilevel shaping product.
And then, with film or the thin slice that these moulding methodes obtain, utilize stent to extend, various extension methods such as atubular extension extend, and also can utilize vacuum forming, press thermoformings such as sky is shaped, the empty shaping of vacuum/pressure to carry out secondary processing.
Resin combination of the present invention adds man-hour at it, and the moment of torsion that adds to device is very low, and torque vibration is also very little, so processing stability is good.For example, with the resin that uses in the following comparative example 1, utilize single shaft extrusion machine [screw diameter=40mm φ], with extruder temperature: 220 ℃, die temperature:: when 220 ℃, amount of compression: 20kg/ hour mixed, the load current (moment of torsion) that adds to extrusion machine was 26A.On the other hand, when the resin combination that following embodiment 1 is obtained mixed under identical condition, the load current (moment of torsion) that adds to extrusion machine was 20A, and is low during used resin in the comparative example 1 because torque ratio is mixed, so processing stability is good.
Embodiments of the invention below are shown, but the present invention is not limited by these embodiment.
About the measuring method in the present embodiment, evaluation method is as follows.
[oxygen air penetrability]
The oxygen air penetrability is measured according to JIS K-7126 (isopiestic method) standard.
The test portion film is installed in (trade(brand)name: OX-TRAN100, U.S. MOCON society system) on the commercially available oxygen air penetrability determinator, and METHOD FOR CONTINUOUS DETERMINATION oxygen permeability is obtained the oxygen air penetrability that in fact the oxygen air penetrability reaches the constant moment.
As the test portion film, use resin combination is paid hot pressing in 3 minutes at 210 ℃, pay the 30 μ m thick film of colding pressing in 5 minutes and obtaining at 30 ℃ again.Calculate the thick oxygen air penetrability of per 1 μ m by the oxygen air penetrability of surveying in the said determination, represent the oxygen air penetrability of resin combination with this calculated value.
[rigidity]
Rigidity is estimated in the following order.
Use omnipotent precise materials trier (Shimadzu Seisakusho Ltd.: AGS500D), under 23 ℃ condition,, detect the SS curve, obtain Young's modulus by this curve with 5mm/ minute speed stretching test portion sheet.The high more rigidity of Young's modulus is also high more.
The test portion sheet that uses in the said determination is the hot pressing of resin combination being paid 210 ℃/3 minutes, pay again 30 ℃/5 minutes cold pressing, be made into the thick film of 100 μ m, again it is cut into the rectangle of 2cm * 12.5cm.
[extensibility]
Extensibility is estimated in the following order.
(Shimadzu Seisakusho Ltd.'s system: AGS500D), at 60 ℃, the speed stretching test portion sheet with 100mm/ minute detects the SS curve, obtains yielding stress, Young's modulus and breaking elongation by this curve to use omnipotent precise materials trier.Yielding stress is more little, and Young's modulus is more little, and perhaps breaking elongation is big more, and the resin combination extensibility is good more.
Making the test portion sheet that uses in the said determination is the hot pressing of resin combination being paid 210 ℃/3 minutes, pay again 30 ℃/5 minutes cold pressing, be made into the thick film of 100 μ m, it is cut into No. 1 dumbbell shape again.
(embodiment 1)
Will be as 32 moles of % of 90 parts by weight of ethylene unit content of polymkeric substance (1); the ethylene-vinyl acetate copolymer saponin of saponification deg 99%; with 89 moles of % of 10 parts by weight of ethylene unit content as polymkeric substance (2); the ethylene-vinyl acetate copolymer saponin of saponification deg 60% (trade(brand)name: テ Network ノ リ Application Network K431; chemical industry Co., Ltd. system is deceived in the field) carry out particle and mix; with the mixture that obtains; with the equidirectional double-shafted extruder [BT-40-S2-60-L of response type; (strain) plastics engineering institute system; L/D=60; screw diameter=40mm φ]; with screw rod speed of rotation: 200rpm; die temperature: 200 ℃, mixed in amount of compression: 30kg/ hour.Estimate the performance of gained resin combination, the results are shown in table 1.
(embodiment 2)
Be taken as 2 weight parts mix except the polymkeric substance among the embodiment 1 (1) being taken as 98 weight parts, polymkeric substance (2), other and embodiment 1 the same resin composition modulation are estimated its performance, the results are shown in table 1.
(comparative example 1)
Estimate the performance of the ethylene-vinyl acetate copolymer saponin of 32 moles of % of acetate unit content, saponification deg 99%, the results are shown in table 1.
(comparative example 2)
The polymkeric substance (2) in the ethylene-vinyl acetate copolymer saponin replacement embodiment 1 that uses 82 moles of % of acetate unit content, saponification deg 90%, other and embodiment 2 the same resin composition modulations are estimated its performance, the results are shown in table 1.
(comparative example 3)
The polymkeric substance (2) in the ethylene-vinyl acetate copolymer saponin replacement embodiment 2 that uses 82 moles of % of acetate unit content, saponification deg 90%, other and embodiment 1 the same resin composition modulation are estimated its performance, the results are shown in table 1.
Table 1
| Embodiment | Comparative example | |||||
| ??1 | ???2 | ??1 | ????2 | ??3 | ||
| First composition | Kind | ??A | ???A | ??A | ??A | ??A |
| Weight portion | ??90 | ???98 | ??100 | ??90 | ??98 | |
| Second composition | Kind | ??B | ???B | ??- | ??C | ??C |
| Weight portion | ??10 | ???2 | ??0 | ??10 | ??2 | |
| Oxygen air penetrability (cc/m 2.day.atm) | 0％RH | ??9 | ???2 | ??13 | ??86 | ??35 |
| 90％RH | ??35 | ???43 | ??62 | ??245 | ??68 | |
| Rigidity | Young's modulus (kg/cm 2) | ??19000 | ???27000 | ??24000 | ??22000 | ??28000 |
| Extensibility | Young's modulus (kg/cm 2) | ??1900 | ???5800 | ??4300 | ??5000 | ??3500 |
| Yielding stress (kg/cm 2) | ??280 | ???340 | ??410 | ??320 | ??380 | |
| Breaking elongation (%) | ??520 | ???30 | ??420 | ??490 | ??480 | |
The meaning of mark number is as follows in the table.
A: the ethylene-vinyl acetate copolymer saponin of 32 moles of % of acetate unit content, saponification deg 99%
B: the ethylene-vinyl acetate copolymer saponin of 89 moles of % of acetate unit content, saponification deg 60% (trade(brand)name: chemical industry Co., Ltd. system is deceived in テ Network ノ リ Application Network K431, field)
C: the ethylene-vinyl acetate copolymer saponin of 82 moles of % of acetate unit content, saponification deg 90% (trade(brand)name: chemical industry Co., Ltd. system is deceived in テ Network ノ リ Application Network R100, field)
Claims (6)
1. a resin combination is characterized in that being made of following 99.5～60 parts by weight polymer (1) and 0.5～40 parts by weight polymer (2) (the total amount of polymkeric substance (1) and polymkeric substance (2) is 100 weight parts),
Polymkeric substance (1): the ethylene-vinyl acetate copolymer saponin of 20～60 moles of % of acetate unit content, saponification deg 90～100%,
Polymkeric substance (2): the ethylene-vinyl acetate copolymer saponin of 85～95 moles of % of acetate unit content, saponification deg 40～100%.
2. according to the resin combination of claim 1 record, it is characterized in that the acetate unit content of polymkeric substance (2) surpasses 90 moles of %.
3. according to the resin combination of claim 1 record, it is characterized in that polymkeric substance (2) surpasses 5 weight parts.
One kind have by resin combination form the layer molding, it is characterized in that this resin combination is formed by following polymkeric substance (1) 99.5～60 weight part and polymkeric substance (2) 0.5～40 weight parts (the total amount of polymkeric substance (1) and polymkeric substance (2) is 100 weight parts)
Polymkeric substance (1): the ethylene-vinyl acetate copolymer saponin of 20～60 moles of % of acetate unit content, saponification deg 90～100%,
Polymkeric substance (2): the ethylene-vinyl acetate copolymer saponin of 85～95 moles of % of acetate unit content, saponification deg 40～100%.
5. according to the molding of claim 4 record, it is characterized in that the acetate unit content of polymkeric substance (2) surpasses 90 moles of %.
6. according to the molding of claim 4 record, it is characterized in that polymkeric substance (2) surpasses 5 weight parts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP244281/2000 | 2000-08-11 | ||
| JP2000244281 | 2000-08-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1338485A true CN1338485A (en) | 2002-03-06 |
Family
ID=18734989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01133197 Withdrawn CN1338485A (en) | 2000-08-11 | 2001-08-11 | Resin composition containing ethylene-vinyl acetate copolymer saponin and its formed article |
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| CN (1) | CN1338485A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111918888A (en) * | 2019-01-22 | 2020-11-10 | Lg化学株式会社 | Vinyl alcohol-based copolymer, method for preparing the same, and gas barrier film comprising the same |
| CN112322164A (en) * | 2020-10-29 | 2021-02-05 | 立邦（上海）化工有限公司 | Surface treating agent for delaying frosting of aluminum fin of radiator and preparation method thereof |
-
2001
- 2001-08-11 CN CN 01133197 patent/CN1338485A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111918888A (en) * | 2019-01-22 | 2020-11-10 | Lg化学株式会社 | Vinyl alcohol-based copolymer, method for preparing the same, and gas barrier film comprising the same |
| CN111918888B (en) * | 2019-01-22 | 2023-08-15 | Lg化学株式会社 | Vinyl alcohol-based copolymer, method for preparing the same, and gas barrier film comprising the same |
| US11905403B2 (en) | 2019-01-22 | 2024-02-20 | Lg Chem, Ltd. | Vinyl alcohol based copolymer, method for preparing the same and gas barrier film comprising the same |
| CN112322164A (en) * | 2020-10-29 | 2021-02-05 | 立邦（上海）化工有限公司 | Surface treating agent for delaying frosting of aluminum fin of radiator and preparation method thereof |
| CN112322164B (en) * | 2020-10-29 | 2022-06-07 | 立邦（上海）化工有限公司 | Surface treating agent for delaying frosting of aluminum fin of radiator and preparation method thereof |
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