WO1989000500A1 - Sac et procede pour sa fabrication - Google Patents

Sac et procede pour sa fabrication Download PDF

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Publication number
WO1989000500A1
WO1989000500A1 PCT/SE1988/000247 SE8800247W WO8900500A1 WO 1989000500 A1 WO1989000500 A1 WO 1989000500A1 SE 8800247 W SE8800247 W SE 8800247W WO 8900500 A1 WO8900500 A1 WO 8900500A1
Authority
WO
WIPO (PCT)
Prior art keywords
bag
layer
silane
olefin copolymer
silanol condensation
Prior art date
Application number
PCT/SE1988/000247
Other languages
English (en)
Inventor
Christer BERGSTRÖM
Peter Nikko
Hans MÅRTENSSON
Original Assignee
Neste Oy
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Neste Oy filed Critical Neste Oy
Publication of WO1989000500A1 publication Critical patent/WO1989000500A1/fr

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Classifications

    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/72—Cured, e.g. vulcanised, cross-linked
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • 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
    • B32B2383/00—Polysiloxanes
    • 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
    • B32B2439/00—Containers; Receptacles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08J2300/108—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups

Definitions

  • the present invention relates to a bag and a method of making it.
  • Bags of various types and materials are previous ⁇ ly known. Bags were originally made mainly of woven textile material, such as jute, but are nowadays usual ⁇ ly made of paper or polymer material. Bags of polymer material usually consist of a single layer of poly ⁇ ethylene. Bags of polymer material are superior to bags made of paper, for example with regard to their resistance to water and other liquids, their impermea ⁇ bility to oxygen and other gases, etc. Even if the strength usually is adequate, there is need for fur ⁇ ther improvement.
  • the present invention aims at satisfying this need and providing a bag of improved strength.
  • the higher strength of the bag according to the invention brings the advantage that a stronger bag is obtained with the same wall thickness as for known bags.
  • the increased strength can also be utilised for providing a bag which is as strong as known bags, but has a reduced wall thickness, whereby material is saved.
  • the object of the invention is achieved by means of a bag which consists of a multilayered polymer material consisting of at least one polyolefin layer together with at least one layer of a crosslinked polymer obtained by crosslinking of an olefin copo ⁇ lymer with hydrolysable silane groups under the ac ⁇ tion of water and a silanol condensation catalyst.
  • the bag according to the invention is produced by coextruding a multilayered polymer material con ⁇ sisting of at least one layer of an olefin copolymer with hydrolysable silane groups and at least one poly ⁇ olefin layer, a silanol condensation catalyst for crosslinking of the silane group-containing olefin copolymer being provided in a layer which is separate from the silane group-containing olefin copolymer.
  • the bag according to the invention consists of a multilayered polymer material which includes at least one polyolefin layer and at least one layer of crosslinked polymer.
  • the polyolefin in the polyolefin layer can be selected among different olefin polymers, such as olefin homopolymers, for example polyethylene, poly ⁇ propylene, polybutene and the like, and olefin copo- lymers, for example poly(ethylene/vinyl acetate), poly(ethylene/butyl acrylate) and the like.
  • the polyolefin consists of poly ⁇ ethylene (PE) which can be selected among LD poly ⁇ ethylene (low-density polyethylene, LDPE) and HD poly ⁇ ethylene (high-density polyethylene, HDPE) , linear LD polyethylene, polyethylene of very low density (VLDPE), polyethylene of ultra-low density (ULDPE) and ethylene copolymers (for example EVA and EBA) .
  • PE poly ⁇ ethylene
  • LDPE low-density polyethylene
  • HDPE high-density polyethylene
  • VLDPE very low density
  • ULDPE ultra-low density
  • EVA and EBA ethylene copolymers
  • thin layer is here meant a thickness corresponding to film and foil, i.e. up to about 2 mm, preferably about 1 mm at most, and more preferred about 0.6 mm at most.
  • a further disadvantage is that any gel lumps not clogging the equipment will be discharged and show up in the product as disfiguring undesired lumps which, if they occur in thin layers, such as films and foils, are unacceptable and usually make the product useless.
  • precuring retarders Undesired precuring may be prevented by incorporat ⁇ ing in the polymer composition substances counteracting precuring, so-called precuring retarders.
  • precuring retarders may be in the form of drying agents.
  • the addi ⁇ tion of precuring retarders implies that there is intro ⁇ quizal into the polymer composition a further component, which makes the composition more expensive and, besides, may be undesirable, for example in packages in contact with food products. It therefore is an advantage if the addition of such further components as precuring retar ⁇ ders can be avoided.
  • the present invention obviates, the above-mentioned disadvantages by providing the silanol condensation catalyst in a layer separate from the silane group- containing olefin copolymer, i.e. either in the layer or layers consisting of polyolefin or in a different separate layer, such as a layer which is provided between the silane group-containing polymer and the polyolefin and which contains the silanol condensation catalyst.
  • the last-mentioned layer may consist of, for example, a so-called master batch layer of the silanol condensation catalyst.
  • the silane group-containing olefin copolymer is crosslinked by subjecting it to the action of water and by causing the silanol condensation catalyst to diffuse into the layer of the silane group-containing polymer.
  • the silane group-containing polymer is restricted to silane group-containing olefin copolymers.
  • the rea ⁇ son for this is that it was found, when the invention was in progress, that the aim of the invention cannot be achieved with all silane-containing olefin polymers.
  • the desired result is not obtained with silane- containing graft polymers, even if the silanol conden ⁇ sation catalyst is incorporated in another layer free from crosslinkable silane.
  • the silanol con ⁇ densation catalyst is originally provided in another layer, and undesired precuring thus should be precluded, such precuring still occurs and imparts to the film a grainy, unacceptable appearance.
  • silane-containing graft polymers also leads to free monomer residues in the final product, which result in an obnoxious smell and may constitute a health hazard, for example if the ma ⁇ terial is used in food packagings. It was therefore found necessary, in the context of this invention, to utilise for the crosslinkable polymer a silane group- containing olefin copolymer and to provide the silanol condensation -catalyst in a layer separate from this polymer.
  • the present invention thus is characterised by the combination of these two requirements.
  • the crosslinkable polymer material according to the invention is a silane-con- taining copolymer by which is meant an olefin copolymer, preferably an ethylene bipolymer or terpolymer contain ⁇ ing crosslinkable silane groups provided in the polymer by copolymerisation.
  • crosslink- able silane groups are attached to the polymer chain thus is critical; according to the invention, for example unsaturated silane compounds can be copoly- merised with olefins, or amino silane compounds can react with acrylate esters, whereas the invention does not include graft polymers in which peroxides are de ⁇ composed and graft unsaturated silane compounds on the finished polymer by direct reaction with the polymer chain.
  • the silane-containing polymer has preferably been obtained by copolymerisation of an olefin, preferably ethylene, and an unsaturated silane compound which is represented by the formula
  • R is an ethylenically unsaturated hydrocarbyl or hydrocarbyloxy group
  • R' is an aliphatic saturated hydrocarbyl group
  • Y is a hydrolysable group
  • n is 0, 1 or 2. If there is more than one Y group, these need not be identical.
  • unsaturated silane com- pound examples include those in which R is vinyl, allyl, isopropenyl, butenyl, cyclohexenyl, or gamma-(meth)aeryloxy propyl,
  • Y is methoxy, ethoxy, methoxyethoxy, formyloxy, acetoxy, propionyloxy, chloride or an alkyl or arylamino group
  • R' is a methyl, ethyl, propyl, decyl or phenyl group.
  • CH 2 CHSi(OA) in which each A which is the same or different, is a hydrocarbyl group having 1-8 carbon atoms, preferably 1-4 carbon atoms.
  • the most preferred compounds are vinyl trimethoxy silane, vinyl trismethoxyethoxy silane, vinyl triethoxy silane, gamma-(meth)aeryloxypropyltrimethoxy silane, gamma-(meth)acryloxypropyltriethoxy silane and vinyl triacetoxy silane.
  • copolymerisation of the olefin (ethylene) and the unsaturated silane compound may be carried out under any suitable conditions causing copolymeri ⁇ sation of the two monomers. Furthermore, polymerisation may be carried out in the presence of one or more further comonomers copo- lymerisable with the two monomers.
  • Examples of such comonomers are: (a) vinyl carboxylate esters, such as vinyl acetate and vinyl pivalate; (b) (meth)acry- lates, such as methyl(meth)acr late, ethyl(meth)acrylate, and butyl(meth)acrylate; (c) olefinically unsaturated carboxylic acids, such as (meth)acrylic acid, maleic acid and fumaric acid; (d) (meth)acrylic acid deriva ⁇ tives, such as (meth)acrylonitrile and (meth)aer 1amide; and (e) vinyl ethers, such as vinyl methyl ether and vinyl phenyl ether.
  • vinyl carboxylate esters such as vinyl acetate and vinyl pivalate
  • (b) (meth)acry- lates such as methyl(meth)acr late, ethyl(meth)acrylate, and butyl(meth)acrylate
  • vinyl esters of monocarboxylic acids having 1-4 carbon atoms are preferred, such as vinyl acetate, and (meth)acrylates of alcohols having 1-4 carbon atoms, such as methyl(meth)- acrylate.
  • An especially preferred comonomer is butyl acrylate. Two or more such olefinically unsaturated compounds may be used in combination.
  • (meth)acrylic acid is here intended to comprise both acrylic acid and methacrylic acid.
  • the comonomer content in the copolymer may amount to about 40% by weight, preferably about 0.5-35% by weight, and most preferred about 1-25% by weight of the copolymer.
  • the silane-containing polymer of the present invention contains the silane compound in a content of 0.001-15% by weight, preferably 0.01-5% by weight, and most preferred 0.1-3% by weight.
  • Crosslinking of the polymer is carried out by so-called moisture hardening which means that the silane group, under the action of water, is hydrolysed and splits off alcohol to form silanol.
  • the silanol groups are then crosslinked under the action of a so-called silanol condensation catalyst by a conden ⁇ sation reaction during which water is split off.
  • silanol condensation catalysts may be used for the present invention. More particu- larly, they are selected among carboxylates of metals, such as tin, zinc, iron, lead and cobalt, organic bases, inorganic acids and organic acids.
  • silanol condensation catalysts are dibutyl tin dilaurate, dibutyl tin diacetate, dioctyl tin dilaurate, stannoacetate, stannocaprylate, lead naph ⁇ thenate, zinc caprylate, cobalt naphthenate, ethyl amines, dibutyl amine, hexyl amines, pyridine, inorganic acids, such as sulphuric acid and hydrochloric acid, and orga ⁇ nic acids, such as toluene sulphonic acid, acetic acid, stearic acid, and maleic acid.
  • Especially preferred catalyst compounds are the tin carboxylates.
  • the amount of silanol condensation catalyst employed usually is of the order 0.001-10% by weight, preferably 0.01-5% by weight, especially 0.03-3% by weight, relative to the amount of silane-containing polymer in the com ⁇ position.
  • the crosslinkable polymer may contain different addi ⁇ tives, as is usually the case in polymer compositions.
  • additives are miscible thermoplastics, stabilisers, lubricants, fillers, colourants and foaming agents.
  • miscible thermo ⁇ plastics such as polyethylene of low density, medium density and high density, polypropylene, chlorinated polyethy ⁇ lene, and various copoly ers including ethylene and one or more other monomers (such as vinyl acetate, methyl acrylate, propylene, butene, hexene and the like).
  • the above-mentioned polyolefin may be used alone or as a mixture of several polyolefins.
  • fillers examples include inorganic fillers, such as silicates, for example kaolin, talc, montmorillonite, zeolite, mica, silica, calcium silicate, asbestos, glass powder, glass fiber, calcium carbonate, gypsum, magnesium carbonate, magne ⁇ sium hydroxide, carbon black, titanium oxide and the like.
  • silicates for example kaolin, talc, montmorillonite, zeolite, mica, silica, calcium silicate, asbestos, glass powder, glass fiber, calcium carbonate, gypsum, magnesium carbonate, magne ⁇ sium hydroxide, carbon black, titanium oxide and the like.
  • the sheet material is unwound from the supply roll, and bags are manufactured in per se known manner from the sheet material. After manufacture, the finished bags are stored so that the silane group-containing olefin copolymer in the sheet material is crosslinked under the action of ambient moisture.
  • This moisture may be the natural moisture of the ambient atmosphere, or the moisture content can be increased intentionally, for example by supplying water or water vapour.
  • the bag can be formed in known manner, and bags of the so-called valve type are especially preferred in the context of this invention.
  • the multilayered polymer material from which the bag is manufactured may in principle have an unlimited number of layers, but it is preferred that the multilayered polymer material has two or three layers.
  • one layer consists of poly ⁇ olefin, such as polyethylene, and the other layer of crosslinked silane group-containing olefin copolymer, such as poly(ethylene/vinyl trimethoxy silane).
  • poly ⁇ olefin such as polyethylene
  • crosslinked silane group-containing olefin copolymer such as poly(ethylene/vinyl trimethoxy silane).
  • any one of these layers may be facing the bag inside or outside, but when the polyolefin layer consists of polyethylene, especially HD polyethylene, it is preferred to make the HD polyethylene layer face the inside of the bag to facilitate opening of the bag.
  • these layers may optionally consist of two polyolefin layers and one crosslinked layer of silane group-containing olefin copolymer, or of two layers of crosslinked silane group-containing olefin copolymer and one polyolefin layer.
  • the two layers comprising the same type of polymer need not be identical, and their composition can be varied within the scope of the above-mentioned definitions.
  • the multilayered polymer material may consist of an outer layer of LD polyethylene, followed by an intermediate layer of crosslinked silane group-contain- ing olefin copolymer, such as pol (ethylene/vinyl tri ⁇ methoxy silane), and finally a layer of HD polyethylene.
  • the HD polyethylene layer is preferably arranged to face the inside of the bag to facilitate opening of the bag, as mentioned above, while the LD polyethylene layer is arranged to face the outside of the bag to prevent stacked bags from sliding off.
  • Drop test of ba The bags were dropped from a drop table according to ISO/TC 122/SC 2/W3 N10. The bags were dropped from the following heights: 1.00, 1.25, 1.50, 1.75, 2.00, 2.25, 2.50, 3.00, 3.50, 4.00 5.00 to a miximum of 6.00 meters unless the bag had previously been damaged. The bags are dropped in three different po ⁇ sitions. On the flat side and the side edge, the bag being turned over on the other side after each drop, and on its end.
  • the bag is always placed on the same edge.
  • the bag is filled wit 50 kg of a mixture of polyethy ⁇ lene and titanium dioxide master batch having a bulk density of 950 kg/m3. in the Examples, the bag filling degree was 90%.
  • the drop height is calculated as the mean value of 6 drop heights without damage to the bag.
  • FILM BLOWING The extruder temperature for layers containing SILANE and HDPE from the feeding zone to the filter during the tests had been set at: for SILANE 130°C, 160°C, 170°C, and for HDPE 180°C, 190°C, 190°C.
  • the filter temperature was maintained at 200 C, as was the temperature in the adapter.
  • the corresponding temperatures were: for SILANE 130°C, 160°C, 170°C, and for LDPE 2 170°C,
  • the temperature in the filter, the adapter and the die was 200 C.
  • the film was run with a blowing ratio of 1.6 and with a frost line of 950 mm.
  • FILM BLOWING The extruder and die temperatures were set with LDPE 1 in the film blowing line. When constant conditions had been established, the selected layer or layers were charged with the silane polymer and polyolefin. When the silane polymer and the poly ⁇ olefin had displaced LDPE 1 , the catalyst was charged into the polyolefin layer. In this manner, a film free from defects and without gel formation can be produced.
  • CROSSLINKING Crosslinking of the bag film begins after the bag film has been unwound and the bags have been welded or glued, and the film comes into contact with the humidity of the air. In the Example, cross ⁇ linking was measured two weeks after the valve bag had been glued and stored at 20°C and 30% air humidity.
  • the essential bag production characteristics are that the bag has a good dart drop value, high yield point and stiffness, good tear strength, and good drop strength. It appears from the above Table that it is possible in Exam ⁇ ple 2 to obtain with a coextruded film of vinyl silane/ LDPE which is thinner than the film material of a con ⁇ ventional bag, a strength which is the same or higher than in the conventional bag. This can be utilised to make a bag which is as strong as the conventional bag, but thinner, or one can make a bag which has the same thickness but is stronger than the conven ⁇ tional bag. Production of a thinner bag means not only a saving of material, but also a saving of the costs for storing and transporting bags and granules. Furthermore, the bag according to the invention has a far higher temperature resistance than conventional bags so that it is possible to package far warmer products in the bag according to the invention than in a conventional bag.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

La présente invention se rapporte à un sac, tel que de préférence un sac à clapet, et à un procédé de fabrication d'un tel sac. Ledit sac se compose d'un matériau polymère multicouche, de préférence à deux ou trois couches. Les couches se composent de polyoléfine, de préférence du polyéthylène, et de copolymère oléfinique réticulé obtenu par réticulation d'un copolymère oléfinique avec des groupes silane hydrolysables tels que du poly-(éthylène/vinyl triméthoxy silane), sous l'action d'eau et d'un catalyseur de condensation au silanol. Pour produire le matériau multicouche, on place le catalyseur de condensation au silanol dans une couche séparée de la couche réticulable, par exemple dans la couche de polyoléfine ou dans une couche séparée, telle qu'une couche de mélange-maître contenant le catalyseur de condensation au silanol. Le matériau multicouche est produit par co-extrusion et utilisé pour la fabrication de sacs selon un procédé traditionnel. On effectue ensuite la réticulation du polymère réticulable en soumettant le sac à l'action de l'humidité et en provoquant le migration du catalyseur de condensation au silanol dans la couche ou les couches réticulable(s).
PCT/SE1988/000247 1987-07-20 1988-05-17 Sac et procede pour sa fabrication WO1989000500A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE8702914-6 1987-07-20
SE8702914A SE457960B (sv) 1987-07-20 1987-07-20 Saett vid framstaellning av ett flerskiktat polymermaterial av silan innehaallande olefinsampolymer

Publications (1)

Publication Number Publication Date
WO1989000500A1 true WO1989000500A1 (fr) 1989-01-26

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ID=20369157

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1988/000247 WO1989000500A1 (fr) 1987-07-20 1988-05-17 Sac et procede pour sa fabrication

Country Status (6)

Country Link
EP (1) EP0415918A1 (fr)
JP (1) JPH03500784A (fr)
DK (1) DK16590A (fr)
FI (2) FI900319A0 (fr)
SE (1) SE457960B (fr)
WO (1) WO1989000500A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5884625A (en) * 1996-07-09 1999-03-23 Hart; William T. Oral appliance for delivering gas to the retroglossal area
US5957133A (en) * 1997-07-21 1999-09-28 Hart; William T. Oral appliance with negative air supply for reducing sleep apnea and snoring
NL1033306C2 (nl) * 2007-01-30 2008-07-31 Kick Off Ltd Folielaminaat.
WO2010009017A1 (fr) * 2008-07-15 2010-01-21 Dow Global Technologies Inc. Procédé de fabrication d'une structure laminée verre/film de polyoléfine
WO2012087441A1 (fr) * 2010-12-21 2012-06-28 Dow Global Technologies Llc Film de laminage en copolymère polyoléfine thermoplastique, structures laminées et procédés pour leur préparation
US8609231B2 (en) 2009-12-17 2013-12-17 Dow Global Technologies Llc Composite laminates and uses thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3302702A (en) * 1965-06-14 1967-02-07 Schutte & Koerting Co Steam jet vacuum pump
JPH08336939A (ja) * 1995-06-14 1996-12-24 Nippon Unicar Co Ltd 積層フィルム
JP2014139008A (ja) * 2012-12-20 2014-07-31 Mitsubishi Chemicals Corp 接着性積層フィルム

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4069368A (en) * 1976-10-01 1978-01-17 Minnesota Mining And Manufacturing Company Workable and curable epoxy-terminated silane films
US4351876A (en) * 1979-12-27 1982-09-28 Mitsubishi Petrochemical Company Limited Laminate films and sheets of crosslinked polyethylene resins

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4069368A (en) * 1976-10-01 1978-01-17 Minnesota Mining And Manufacturing Company Workable and curable epoxy-terminated silane films
US4351876A (en) * 1979-12-27 1982-09-28 Mitsubishi Petrochemical Company Limited Laminate films and sheets of crosslinked polyethylene resins

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5884625A (en) * 1996-07-09 1999-03-23 Hart; William T. Oral appliance for delivering gas to the retroglossal area
US5950624A (en) * 1996-07-09 1999-09-14 Hart; William T. Oral appliance having hollow body
US5957133A (en) * 1997-07-21 1999-09-28 Hart; William T. Oral appliance with negative air supply for reducing sleep apnea and snoring
NL1033306C2 (nl) * 2007-01-30 2008-07-31 Kick Off Ltd Folielaminaat.
WO2010009017A1 (fr) * 2008-07-15 2010-01-21 Dow Global Technologies Inc. Procédé de fabrication d'une structure laminée verre/film de polyoléfine
US8609231B2 (en) 2009-12-17 2013-12-17 Dow Global Technologies Llc Composite laminates and uses thereof
WO2012087441A1 (fr) * 2010-12-21 2012-06-28 Dow Global Technologies Llc Film de laminage en copolymère polyoléfine thermoplastique, structures laminées et procédés pour leur préparation

Also Published As

Publication number Publication date
DK16590D0 (da) 1990-01-19
FI900319A0 (fi) 1990-01-19
EP0415918A1 (fr) 1991-03-13
SE457960B (sv) 1989-02-13
SE8702914D0 (sv) 1987-07-20
FI900320A0 (fi) 1990-01-19
DK16590A (da) 1990-01-19
JPH03500784A (ja) 1991-02-21

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