CN1141642A - Coextrusion process for ethylene based polymers and compositions thereof - Google Patents
Coextrusion process for ethylene based polymers and compositions thereof Download PDFInfo
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- CN1141642A CN1141642A CN 95191778 CN95191778A CN1141642A CN 1141642 A CN1141642 A CN 1141642A CN 95191778 CN95191778 CN 95191778 CN 95191778 A CN95191778 A CN 95191778A CN 1141642 A CN1141642 A CN 1141642A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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Abstract
The invention relates to a process for extruding an ethylene based polymer into a layer, which comprises (1) extruding an ethylene derived polymer, having a density of less than 0.94 and containing (A) from 25 to 5000 ppm of a phosphorus containing anti-oxidant, and (B) from 0 to 150 ppm of a phosphorus-free, phenolic anti-oxidant; and (2) applying and adhering the film or layer onto a substrate.
Description
Invention field
The present invention relates to extrude coating composition, method and in these compositions and method Application of Additives, and relate to the coated articles of extruding.The present invention has the purposes of uniqueness in packing, particularly liquid as the packing of beverage.
Background of invention
New LDPE (film grade) (LDPE) is made by high-pressure process with radical initiator.It has side chain and wide molecular weight distribution makes it to carry out high speed and extrudes, as extrude or coating process in.LDPE is used for providing a sealing ply in the Foods or drinks packing.LDPE is in rigor condition (for example high temperature) coating down, and is bonding to help.To this purposes, LDPE is traditionally without additives such as antioxidants, because these additives are considered to have a disadvantageous effect to bonding.More rigor condition can be improved bondingly, but has worsened the organ sensation performance.
In the present invention, the composition of special additive or additive can conditionally be used to provide on a small quantity and have improved adhesive effect and organ sensation performance concurrently under harsh extrusion condition.In extruding coating, have at least during one deck gets between folder between matrix (extruded layer is wanted adherent) and the cooling roller downwards.At high temperature carry out bonding.
When not being crucial, antioxidant has been used for preventing that polyolefine from worsening bonding, for example is exposed in the thermal environment when melt-processed etc.Hindered phenol is as main anti-oxidant (AO).It is used as the antioxidant of LDPE alone.Main anti-oxidant is with less important antioxidant, and as P contained compound, particularly phosphorous acid ester cooperates and has been used for LLDPE (LLDPE).
Because bounding force reduces, so the general LDPE that extrudes the coating grade does not contain AO; The AO unit is used for LDPE, LLDPE and PP (polypropylene) grade that blown film is extruded, and requirement is not important because these are to adherent.
Extruding the unitary technology formerly of grade material additive therefor for the coating except that LDPE or casting film comprises: GB.2156358; GB 2156359; GB 2156360; EP551062; US5026592.What GB 803557 related to is linear polyethylene.
LDPE is discussed but is not to be used to apply or the technology formerly about additive that casting film is extruded application comprises US4863938 and US5219600.
US 4863983 relates generally to extruding of LLDPE material, and purpose is to improve melt fracture rather than the bonding and balance organ sensation performance.Fluorocarbon polymer is necessary composition, as organophosphite or organophosphate or their mixture.Hindered phenol not necessarily but should not have yet, and (the 2nd hurdle, the 34th row) antioxidant can randomly add.In an embodiment, the add-on of antioxidant is 300ppm (the 6th hurdle the 16th row).The hydrocarbon polymer definition is extensive, and new LDPE (film grade) is open as mixing element (the 3rd hurdle the 40th row).Yet US4863983 does not speak of under harsh extrusion condition to helping bonding and excessively not worsening the special antioxidant prescription of the same special polyethylene material mixing of organ sensation performance.It does not speak of the utilization that consumption is at least the P contained compound of 25ppm yet, and the phenol antioxidant consumption is 0-150ppm.
US 5219600 discloses a kind of moulding compound, and LDPE (the 2nd hurdle eighth row) is one of long a series of polyolefine option.Hindered amine as light stabilizer (HALS) is necessary composition.In fact need not use phenol type master AO.Should use the aromatic phosphite or the phosphinate AO additive of 0.01-0.5 part.The purpose of this invention is to reduce variable color.The extrusion and the bonding and organ sensation impact of performance are not discussed.
US5026592 discloses a kind of multilayered structure that is added with the polymkeric substance that ethene makes at the 2nd hurdle the 18th row.The 3rd hurdle the 17th row has been discussed the phosphite ester stabilizer (by 2000-8000ppm) that adds 0.2-0.8 weight %.The not open phosphorous antioxidant that utilizes less than 1500 of this specification sheets.Polymkeric substance contains the ethene derivatives unit that is lower than 50 weight %.The layer that is added with antioxidant or stablizer contains the above hydrocarbon resin tackifier of 5 weight %; And this invention is talked basically is the tackifier of less than 4 weight % or the composition of essentially no tackifier.This US Patent specification relates to is to extrude back film diaxial orientation and that contain opalizer, at this moment this invention field be in non-diaxial orientation coextrusion on matrix, matrix is stiff or non-stretchable (elasticity is lower than 10%).The anti-oxidant relatively poor layer of extruding in this invention is preferably upper layer or at least enough approaching surface, and the surface is the principal element of decision bond properties and organ sensation performance.
Have been found that based on the polyethylene selection use AO that is used for extruding the material that applies type method, can improve the over-all properties of bounding force/organ sensation performance.
Can also reach higher process velocity (owing to having improved bonding) and without recourse to the improvement adherent blend composition of costliness, as ethylene-acrylic acid copolymer with the present invention.Therefore, it is bonding that the present composition of discussing does not later preferably have the enhancing of the polymkeric substance that acid or ester group monomer obtain basically, and basically by ethene with contain the multipolymer that the non-polar group comonomer obtains and form.
Have been found that based on the polyethylene selection use AO that is used for extruding the material that applies type method, can improve bounding force/organ sensation performance synthesis balance.
Summary of the invention
It is the method that polymer based is extruded into one deck that the present invention generally provides ethene, and this method comprises:
(1) density is lower than 0.94, and contains (A) at least 25, preferably be lower than the phosphorous antioxidant of 5000ppm and (B) ethylene derivative polymer-extruded of the without phosphorus phenolic antioxidant of 0-150ppm; With
(2) this layer is applied and is bonded on the matrix.
As rule, can add except that (A) and the additive the composition (B) that uses in case of necessity, but only be bonding or the organ sensation performance does not run under the situation of interference influence and just uses.Preferably, polymkeric substance only contains antioxidant (A).When being lower than 25ppm, AO just is difficult to uniform distribution; And be higher than 5000ppm, be difficult to check out additive effect.
Because be film or thin layer to be extruded on matrix and thereon bonding, so the present invention is different from US.4863983.Between matrix and film or thin layer, can use extra play, to improve or to optimize adhesive effect, as ethylene acrylic.In US4863983, film is extruded, but after extruding, be not bonded on the matrix.
Ppm in this specification sheets (part/1,000,000) is meant the umber in per 1,000,000 parts of composition total weight.
In extruding coating method, thin layer is put on the matrix.In some method, this thin layer forms the outside surface that is coated with product, and still, extruding layer can be added between other layer (for forming outside surface) and the matrix, the so-called lamination of extruding, and this is a kind of special shape of extruding coating.In other method, can extrude simultaneously more than one deck and be coated on the matrix.
Matrix is preferably the non-thermal plasticity surface, is main paper or card or cardboard as Mierocrystalline cellulose, or the metallic surface, as aluminium foil.Yet the present invention also can be added in thermoplastic material, on the matrix as polyester, polypropylene and polymeric amide etc.
The polymkeric substance of ethylene derivative can be single polymers component or blend.The unit that preferably should contain the ethylene derivative of at least 50 weight %.Density polymer is lower than 0.94.Preferably when requiring melt strength (for example for self-supporting film), the molecular weight of polymkeric substance should be enough to satisfy this purpose.The density of polymkeric substance is at least 0.88.Particularly 0.89 or 0.90.
If the use comonomer can be used C
3-C
12Non-polar monomer, particularly monoolefine, as propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene or 1-octene, or preferably have the monomer of 4-12 carbon atom, this monomer has polar group, as ethylenic unsaturated ester; As vinyl acetate, methyl acrylate, ethyl propenoate, propyl acrylate equivalent or ethylenically unsaturated carboxylic acids or acid anhydrides are as acrylic or methacrylic acid.
These polymkeric substance can prepare with various polymerization processs, for example gas phase or solution polymerization, but preferably under high pressure use radical initiator, obtain the wide material of hyperbranched molecular weight distribution.
The ethylene derivative density polymer is preferably 0.900-0.940, and melt index is preferably 1-100, especially is 2-20.
Formed by blend if ethene is polymer based, then the LDPE preferable amount is at least 10 weight %, is preferably 20 weight %, is at least 50 weight % especially, and this LDPE preferably uses for example LLDPE mixing use of non-branching polymkeric substance of more multi-thread type.
For total composition, promptly ethene is polymer based and any mixture of following polymeric constituent, and suitable Mw/Mn is at least 5, especially is 6 or higher.
The general formula of phosphorated antioxidant is:
A is 0 or 1 in the formula, and b is the integer of 1-4 and equals R
1Valence mumber.R
1Be the organic group of monovalence or multivalence (for example 2-4), preferably derived from phenol, alcohol, xenol, glycol, polyvalent alcohol (for example dibasic alcohol), 2,4-di-tert-butylphenol, tetramethylolmethane, 4-nonyl phenol, benzylalcohol, 4-chlorinated phenol; 1,1, the 1-TriMethylolPropane(TMP); R
2Can be identical or different, be the univalent perssad with 1-30 carbon atom, can be selected from aryl replacement or non-replacement, alkyl or their mixture, as aralkyl, and group of naphthene base.R
1And R
2Heteroatoms be can contain,, can these non-interfering substituent such as chlorine, fluorine, cyano group, alkyl (side chain or straight chain) be replaced with non-interfering substituent as O and N; Alkoxyl group, acyl group and amido carbonyl.
Being used for many organophosphites of the present invention and organophosphite is the compound of knowing, and each is the ester of phoshorous and Phoshoric acid naturally.Can synthesize by same phosphorus trichloride of desired organic hydroxy compounds (manufacturing phosphorous acid ester) or same Phosphorus Oxychloride (manufacturing phosphoric acid ester) reaction.The numerous species of organophosphite and organophosphate can be buied by market, and the mixture of these compounds also can use.The representative of organophosphite and organophosphate comprises: tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, two (the 2-of diphosphorous acid, the 4-di-tert-butyl-phenyl) pentaerythritol ester, tricresyl phosphite (4-nonyl phenyl) ester, tricresyl phosphite (4-(1-phenylethyl) phenyl) ester, diphosphorous acid four (2, the 4-di-tert-butyl-phenyl)-4,4 '-two phenylene esters, tricresyl phosphite (4-aminomethyl phenyl) ester, tricresyl phosphite (4-chlorophenyl) ester, phosphorous acid decyl diphenyl, tricresyl phosphate (2, the 4-di-tert-butyl-phenyl) ester, tricresyl phosphate (4-aminomethyl phenyl) ester, tricresyl phosphate (4-nonyl phenyl) ester, phosphoric acid 2-ethylhexyl diphenyl ester, and their mixture.Can use the following tricresyl phosphite aromatic ester of general formula:
R in the formula
1Represent the tertiary butyl, 1,1-dimethyl propyl, cyclohexyl or phenyl, R
2And R
3One of be hydrogen, another is hydrogen, methyl, the tertiary butyl, 1,1-dimethyl, propyl group, cyclohexyl or phenyl.
Suitable compounds can be buied on market.
" antioxidant " speech is used for illustrating traditional main effect of P contained compound, yet, this do not get rid of this compound processing or in final the application to other Effect on Performance.By inference, antioxidant (A) is effectively main removing on the hydroperoxide functionality.
Other composition can be used as additive and exists, (or/also be called organ sensation degree of performance) and bond properties but consumption can not exert an influence owing to peculiar smell.In the food product pack situation, preferred compositions contains minimum other such additive.
The polymkeric substance of ethylene derivative and composition (A) preferably mix in the forcing machine downstream that monomer carries out the polymeric reactor.Help to reduce any like this, and guarantee that antioxidant (A) exists and be active in polymkeric substance to prevent thermolysis etc. as far as possible to bonding and detrimentally affect sense of taste performance.
About existing in case of necessity but preferred no composition HALS, preferable amount is lower than consumption among the US5219600, for example is lower than 0.01pph.The fluoroelastomer preferable amount is lower than among the US4863983 disclosed, and the ratio that makes phosphorous antioxidant and fluoroelastomer is greater than 5.Perhaps, the amount of P contained compound is lower than 100ppm.The consumption of HALS and fluoroelastomer is high can to produce detrimentally affect to bonding and/or sense of taste performance.
Preferably without main anti-oxidant, as hindered phenol compound, the feature of hindered phenol is the phenols that exists the ortho position to replace.The phenolic compound that can use on a small quantity comprises if desired:
1. single 2, the 6-dialkyl phenol, as 2,6-di-t-butyl-4-aminomethyl phenyl, 2,6-di-t-butyl 4-methoxymethyl phenol or 2,6-di-t-butyl-4-p-methoxy-phenyl.
2。Bisphenols, as 2,2 '-methylene radical-two-(the 6-tertiary butyl-4-methylphenol), 2,2 '-methylene radical-two-(the 6-tertiary butyl-4-ethylphenol), 2,2 '-methylene radical-two-(4-methyl-6-(Alpha-Methyl cyclohexyl)-phenol), 1,1-pair-(5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl)-butane, 2,2-two-(3,5-two-tert-butyl-hydroxy phenyl)-propane, 1,1,3-three-(5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl)-butane, 2,2-pair-(5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl)-4-dodecyl sulfydryl-butane, 1,1,5,5-four-(5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl)-pentane, ethylene glycol-two (3,3-pair-(3 '-tertiary butyl-4 '-hydroxy phenyl)-butyric ester), 1,1-pair-(3,5-dimethyl-2-hydroxy phenyl)-3-(dodecyl sulphur)-butane, or 4,4 '-sulfo--two (the 6-tertiary butyl-3-methylphenol).
3. hydroxybenzyl compound is as 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,4,6-Three methyl Benzene, 2,2-pair-(3, the 5-di-tert-butyl-4-hydroxyl benzyl) propanedioic acid two (octadecyl) ester, 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) chlorinated isocyanurates, or 3,5-di-tert-butyl-4-hydroxyl benzyl di(2-ethylhexyl)phosphate ethyl.
4. the acid amides of β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid, as 1,3,5-three (3,5-di-tert-butyl-hydroxy phenyl-propionyl)-hexamethylenedine.
5. β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid is with the ester of monobasic or polyvalent alcohol, and these are pure as methyl alcohol, stearyl alcohol, 1,6-hexylene glycol, ethylene glycol, sulfo-glycol ether, neopentyl glycol, tetramethylolmethane, tricarbimide three hydroxyl ethyl esters.
6. spirocyclic compound, as spiral shell-two acetal or spiral shell two ketals of diphenol, as have in 3-and 9-position that phenolic group replaces 2,4,8,10-four oxygen spiral shells-(5,5)-undecane are as 3, two (3, the 5-di-tert-butyl-hydroxy phenyl)-2,4,8 of 9-, 10-four oxygen spiral shell (5,5)-undecanes, 3,9-two-(1,1-dimethyl-2-(3, the 5-di-tert-butyl-hydroxy phenyl)-ethyl)-2,4,8,10-four oxygen spiral shells-(5,5)-undecane.
In a preferred specific embodiments, used 0-100ppm, especially be less than the phenolic stabilizer of 50ppm.Equally preferably utilize the P contained compound of low amount, sufficient quantity is 50-1000ppm, is preferably 60-500, especially is 75-200ppm.Consumption is low can to make binding property better.
Extrusion process is suitable for carrying out similar in appearance to implementing traditionally to extrude under the condition that applies a certain given polymkeric substance.For non-polar polymer, suggestion uses comparatively high temps bonding to help, for example at 295-330 ℃ and linear velocity 10-600, be preferably 300-550 rice/minute.Polymkeric substance for polar functionalities can advise using low temperature, for example 265-300 ℃.
Surface oxidation through a gap, at this moment, can take place in extruding layer under not supporting, pass through between matrix and cooling roller with bonding and cooling then.
It is that extruding of polymer based utilizes consumption to be the phosphorous antioxidant of the 25ppm hindered phenol type antioxidant with 0-150ppm in the coating process that the present invention also is provided at ethene, be adhered to high adhesion is provided on the matrix and peculiar smell seldom.This utilization can cause or relate to the identical characteristics of pointing out above in the method.
The present invention also provides a composition, and said composition contains:
(A) have density and be lower than 0.95, contain at least 25 and preferably be lower than the phosphorous antioxidant of 5000ppm, and 0-150ppm
(B) without phosphorus phenolic antioxidant, preferably have be lower than 0.01pph, hindered amine type light stabilizer, and the ratio of P contained compound and fluoroelastomer processing aid is higher than 5.
US4863983 requires the fluoroelastomer consumption to surpass the amount that provides above.US5219600 requires HALS excessive.
The present invention also provides a composition, and said composition contains:
(A) LDPE of at least 50 weight %, the density of this LDPE is for being lower than 0.95, and contains 25 and preferably be lower than the P contained compound of 5000ppm and 0-150ppm
(B) without phosphorus phenol antioxidant, said composition contain the hindered amine type stablizer that is lower than 0.01pph.US4865983 does not discuss the mixture of LDPE with special additive.US5219600 requires the HALS consumption to surpass described amount.
Accompanying drawing
Fig. 1 illustrates that bounding force among the embodiment is with the relation of antioxidant amounting;
Fig. 2 illustrates that bounding force is with another figure of antioxidant magnitude relation among the embodiment;
Fig. 3 indicates among the embodiment photostabilizer or fluoroelastomer processing aid that adherent is influenced;
Fig. 4 illustrates the casting extrusion equipment that uses in an embodiment.
Embodiment
Prepare blend in an embodiment, tested bounding force and sense of taste performance.
Method according to ASTM-D1505 and D 2839 is measured density.According to ASTM D1238 condition E; 2.16 kilogram is measured melt index at 190 ℃.
Use the determine with dsc method fusing point.
Tested bounding force in the T-lift-off structure, unit is newton/15 millimeter, is illustrated in to produce on the bar of one 15 mm wides to separate required power.
With purpose is to have tested sense of taste performance with respect to the manual control panel of standard comparison sense of taste performance.Positive value specifies sense of taste performance is than standard deviation, and the negative value explanation is better than standard.
Embodiment 1
In autoclave, prepared polymkeric substance with peroxide initiator.This kind material can be buied in market as the Escorene grade by ExxonChemical company, and it has following properties:
Table 1
| Density melt index Mw/Mn fusing point | 0.9185 7.9 6 106℃ |
| Comonomer type | Do not have |
| Additive | Do not have |
With pulverous polyethylene antioxidant is sneaked in the masterbatch, powder polyethylene is the MP652.35 grade, is buied by Exxon Chemical, has following characteristics:
Table 2
| The density melt index | 0.923 6 |
| Comonomer | Do not have |
| Additive | Do not have |
Obtain containing in the various masterbatch antioxidant of suitable high-content (as 1%) with the different additive of listing in the table 3.
Table 3
| Masterbatch | Antioxidant |
| Contrast 1 | Do not have |
| Contrast 2 | Irganox?1010 |
| The present invention 3 | Irgafos?P-EPQ |
Irganox and Irgafos are registered trademarks.Chemical composition is listed in the table 6 of back.These masterbatch are added in the above-mentioned Escorene grade (table 1) obtain
Table 4
| Test piece number (Test pc No.) | Female item number | AO?ppm |
| 1 | 1 | (contrast) 0 |
| 2 | 2 and 3 | 500 Irganox, 1,010 1000 Irgafos P-EPQ (contrast) |
| 3 | 2 | 500 Irganox 1010 (contrast) |
| 4 | 3 | 1000 Irgafos P-EPQ (the present invention) |
With sample under 295 ℃ mold outlet 4 in extrusion coating on the equipment on aluminium foil 6 as matrix.With ambient air in the space 8 make matrix through corona treatment to improve binding property.The polymkeric substance coiled material extruded orientation stretches and pulls to roll gap 10 between pressure roll 12 and the cooling roller 14.
Coated material is assessed.
Table 5
| Test piece number (Test pc No.) | Bounding force newton/15 millimeter | Comment examination sensation (sense of taste performance) with manual control panel |
| ????1 | ????1.23 | The sense of taste strong (3.2) |
| ????2 | (0.04 low) | The sense of taste low (can not survey) |
| ????3 | (0.04 low) | The sense of taste low (1.3) |
| ????4 | ????1.53 | The sense of taste low (1.1) |
Use the present invention, can obtain strong bounding force and also have good sense of taste performance simultaneously.Just when no Irganox1010, just obtain strong bounding force.The IrganofosP-EPQ of 1000ppm has improved sense of taste performance, and does not reduce, and in fact is to have increased bounding force.
Embodiment 2
Made mixture with similar method, with the relative effect of the low levels antioxidant that show to add and the effect of small amount of H ALS and fluoroelastomer.
Table 6
| Test number | Irganox 1010(1) | PEPQ (2)ppm | Tinuvin?662 (3)ppm | B900 (4)ppm | Fluoroelastomer (5) ppm |
| 1 does not add | 0 | 0 | 0 | 0 | 0 |
| 2 add masterbatch 1 | 0 | 0 | 0 | 0 | 0 |
| 3 | 100 | 0 | 0 | 0 | 0 |
| 4 | 200 | 0 | 0 | 0 | 0 |
| 5 | 100 | 200 | 0 | 0 | 0 |
| 6 | 200 | 200 | 0 | 0 | 0 |
| 7 | 0 | 200 | 0 | 0 | 0 |
| 8 | 100 | 200 | 0 | 0 | 0 |
| 9 | 200 | 400 | 0 | 0 | 0 |
| 10 | 0 | 400 | 0 | 0 | 0 |
| 11 | 100 | 400 | 0 | 0 | 0 |
| 12 | 100 | 200 | 0 | 0 | 0 |
| 13 | 0 | 400 | 200 | 0 | 0 |
| 14 | 0 | 400 | 500 | 0 | 0 |
| 15 | 0 | 0 | 0 | 1000 | 0 |
| 16 | 0 | 400 | 0 | 0 | 200 |
| 17 | 0 | 400 | 0 | 0 | 500 |
(1) registered trademark; Main component
Phenylpropionic acid, 3, two (1, the 1-the dimethyl ethyl)-4-hydroxyls of 5--, 2,2-pair-((3-(3,5-couple-(1, the 1-dimethyl ethyl)-4-hydroxy phenyl)-1-oxygen propoxy-) methyl)-1,3-glyceryl ester (general formula I)
(2) Irgafos P-EPQ, registered trademark; The main component phosphonous acid, (1,1 '-xenyl)-4,4 '-two base is two-, four (2, two (1, the 1-dimethyl ethyl) phenyl of 4-) ester (general formula I I)
(3) registered trademark
Succinic Acid is with 4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines alcoholic acid polymkeric substance (general formula III)
(4)20％Irganox?1076＋80％Irgafos168
Irganox1076; Phenylpropionic acid, 3, two (1, the 1-dimethyl ethyl) the 4-hydroxyls of 5--, stearyl (general formula I V)
Irgafos168: phenol 2, two (1, the 1-the dimethyl ethyl)-phosphorous acid esters (3: 1) (general formula V) of 4-
(5) polymer processing aids: obtain fluoroelastomer by Du Pont or 3M company, or the AMF702 that is obtained by Schulman company is as masterbatch (used herein)
The results are shown in table 7:
Table 7
| Test number | Bounding force newton/15 millimeter | Sense of taste performance (with respect to comparison) | Sense of taste performance (with respect to test 10) |
| ????1 | ????0.92 | ????0 | |
| ????2 | ????0.85 | ????0.9 | |
| ????3 | ????0.71 | ????-2.6 | |
| ????4 | ????0.12 | ||
| ????5 | ????0.88 | ||
| ????6 | ????0.18 | ||
| ????7 | ????1.63 | -1.3 and-1.2 | |
| ????8 | ????1.14 | ????-1.6 | |
| ????9 | ????0.23 | ||
| ????10 | ????1.43 | ????-1.6 | ????0 |
| ????11 | ????0.82 | ||
| ????12 | ????0.89 | ||
| ????13 | ????0.98 | ||
| ????14 | ????0.91 | ????0.6 | |
| ????15 | ????0.85 | ????-1.9 | |
| ????16 | ????1.09 | ||
| ????17 | ????0.96 | ????-0.3 |
Some the results are shown in each figure
Fig. 1-3.
HALS and fluoroelastomer have been offset the positive influence of P contained compound to bounding force, so should not use or only just using (Fig. 3) at a puss.Only in the amount of fluoroelastomer when being lower than 80ppm (P contained compound consumption (400ppm) 1/5), could obtain good adhesive strength.HALS causes the limit deterioration of sense of taste performance.
When hindered phenol AO surpassed 150ppm, P contained compound was difficult to detect to the influence of bounding force.Be lower than 150ppm, especially be lower than the 10ppm (see figure 1), the existence of a small amount of P contained compound can obviously improve bounding force, and maximum improvement appears at P contained compound and is lower than 400ppm, especially during 200ppm.
Can see identical effect at Fig. 2.
The mixture of phenolic antioxidant (Irganox1076) and P contained compound (Irgafos168) can increase the consumption of phenolic antioxidant and quite low bounding force.
Have been found that by utilizing antioxidant of the present invention, can improve the drawing-off performance.
Coating material of the present invention can be used for sheathing foodstuff and solid or liquid drink.Therefore the invention still further relates to the coating material that obtains with the inventive method packs.
Use the present invention, with traditional do not contain any antioxidant but select to use phosphorous antioxidant and do not have or on a small quantity the LDPE of other additive compare, sense of taste performance and bounding force all have improvement.
For observing U.S.'s law, All Files comprises all test methods and hot file, at this with for referencial use.
Claims (12)
1. be that polymer based is extruded stratified method with ethene, comprise:
(1) extrude the polymkeric substance of ethylene derivative, its density is lower than 0.94, and contains (A) at least 25, preferably is lower than the phosphorous antioxidant of 5000ppm, and (B) the without phosphorus phenolic antioxidant of 0-150ppm, and
(2) apply with adhesive film or the layer on matrix.
2. the process of claim 1 wherein that this method is coating or coextrusion method, is preferably the coating process on the non-thermal plasticity matrix.
3. the method for claim 1 or claim 2, wherein, the ethylene derivative polymkeric substance contains the ethene of at least 50 weight % and the polymerisable comonomer that contains polarity or non-polar group of a kind of in case of necessity olefinic, and the melt index of polymkeric substance is preferably 2-20.
4. the method for claim 3, the therein ethylene derived polymer contains the LDPE of at least 10% weight, and its Mw/Mn is at least 5, preferably contains 50% weight at least.
5. each method in the aforementioned claim, wherein, the ethylene derivative polymkeric substance is gone up substantially and is not contained hindered amine as light stabilizer and/or fluoroelastomer.
6. each method in the aforementioned claim, wherein, the ethylene derivative polymkeric substance contains and is lower than 0.01; Preferably be lower than the hindered amine type light stabilizer of 0.48pph (per hundred parts of weight parts) and/or be lower than 1/5, preferably be lower than P contained compound, the fluoroelastomer of 1/6 weight.
7. each method in the aforementioned claim, wherein, application temperature is 265 °-330 ℃, linear velocity be 10-600 rice/minute.
8. be extruding in the coating method of polymer based at ethene, use the consumption phosphorous antioxidant of 25ppm and the hindered phenol type antioxidant of 0-150ppm at least,, provide the application of high adhesion and low bad sense of taste performance to be adhered on the matrix.
9. composition contains:
Density is lower than 0.95 ethylene derivative polymkeric substance, and this polymkeric substance contains:
(A) at least 25, preferably be lower than 5000ppm phosphorous antioxidant and
(B) 0-150ppm is without phosphorus phenolic antioxidant, preferably contains the hindered amine type light stabilizer that is lower than 0.01ppm, and the ratio of P contained compound and fluoroelastomer processing aid is higher than 5.
10. composition contains:
The density of at least 50 weight % is lower than 0.95 LDPE, contains than polymkeric substance:
(A) 25 and preferably be lower than the P contained compound of 5000ppm, and
(B) the without phosphorus phenolic antioxidant of 0-150ppm, said composition contain the hindered amine type stablizer that is lower than 0.01pph.
11. the composition of claim 8 or 9 is used for the multi-layer packaging structure, said structure is used to pack solid, semiliquid or liquid food or
12. the method for the composition of claim 9 or 10 or claim 1-7 is used for making the application of the multi-layer packaging structure that comprises solid or liquid foodstuff or beverage
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9423562A GB9423562D0 (en) | 1994-11-22 | 1994-11-22 | Coextrusion process for ethylene based polymers and compositions therefore |
| GB9423562.9 | 1994-11-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1141642A true CN1141642A (en) | 1997-01-29 |
Family
ID=10764794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95191778 Pending CN1141642A (en) | 1994-11-22 | 1995-11-21 | Coextrusion process for ethylene based polymers and compositions thereof |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0749458A1 (en) |
| JP (1) | JPH09510668A (en) |
| CN (1) | CN1141642A (en) |
| AU (1) | AU704255B2 (en) |
| CA (1) | CA2181739A1 (en) |
| GB (1) | GB9423562D0 (en) |
| TW (1) | TW402618B (en) |
| WO (1) | WO1996016115A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107921767A (en) * | 2015-08-31 | 2018-04-17 | 普瑞曼聚合物株式会社 | Laminated body and its manufacture method and diaphragm seal |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60313160T2 (en) * | 2002-05-27 | 2007-12-13 | Great Lakes Chemical (Europe) Gmbh | STABILIZED POLYPROPYLENE |
| EP2631268A1 (en) * | 2012-02-22 | 2013-08-28 | Borealis AG | Extrusion coating polyethylene with improved drawdown |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS581736A (en) * | 1981-06-25 | 1983-01-07 | Adeka Argus Chem Co Ltd | Polyolefin resin composition |
| JPH032239A (en) * | 1989-05-31 | 1991-01-08 | Mitsubishi Petrochem Co Ltd | Molded product for colored food |
| JP3285935B2 (en) * | 1992-07-02 | 2002-05-27 | 三菱化学株式会社 | Ethylene resin composition with suppressed off-flavor and odor |
| WO1994015786A1 (en) * | 1993-01-12 | 1994-07-21 | The Dow Chemical Company | An organoleptically improved laminated packaging structure |
| US5587247A (en) * | 1993-11-29 | 1996-12-24 | Sumitomo Chemical Company, Limited | Resin composition for extrusion molding |
-
1994
- 1994-11-22 GB GB9423562A patent/GB9423562D0/en active Pending
-
1995
- 1995-11-21 JP JP8516583A patent/JPH09510668A/en active Pending
- 1995-11-21 EP EP95941001A patent/EP0749458A1/en not_active Ceased
- 1995-11-21 AU AU42552/96A patent/AU704255B2/en not_active Ceased
- 1995-11-21 CA CA 2181739 patent/CA2181739A1/en not_active Abandoned
- 1995-11-21 CN CN 95191778 patent/CN1141642A/en active Pending
- 1995-11-21 WO PCT/EP1995/004608 patent/WO1996016115A1/en not_active Application Discontinuation
-
1996
- 1996-01-19 TW TW84112513A patent/TW402618B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107921767A (en) * | 2015-08-31 | 2018-04-17 | 普瑞曼聚合物株式会社 | Laminated body and its manufacture method and diaphragm seal |
Also Published As
| Publication number | Publication date |
|---|---|
| TW402618B (en) | 2000-08-21 |
| JPH09510668A (en) | 1997-10-28 |
| EP0749458A1 (en) | 1996-12-27 |
| AU704255B2 (en) | 1999-04-15 |
| AU4255296A (en) | 1996-06-17 |
| CA2181739A1 (en) | 1996-05-30 |
| WO1996016115A1 (en) | 1996-05-30 |
| GB9423562D0 (en) | 1995-01-11 |
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