[go: up one dir, main page]

CN1246879A - Primer for plastic films - Google Patents

Primer for plastic films Download PDF

Info

Publication number
CN1246879A
CN1246879A CN98802385A CN98802385A CN1246879A CN 1246879 A CN1246879 A CN 1246879A CN 98802385 A CN98802385 A CN 98802385A CN 98802385 A CN98802385 A CN 98802385A CN 1246879 A CN1246879 A CN 1246879A
Authority
CN
China
Prior art keywords
film
coating
primer
poly
base paint
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
CN98802385A
Other languages
Chinese (zh)
Inventor
D·E·麦吉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Oil Corp
Original Assignee
Mobil Oil Corp
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 Mobil Oil Corp filed Critical Mobil Oil Corp
Publication of CN1246879A publication Critical patent/CN1246879A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

本发明涉及用于塑料薄膜的底涂料,该底涂料包含聚(乙烯醇)和增粘剂,特别是聚(乙烯亚胺)和/或硬化环氧树脂的共混物。本发明对提高塑料薄膜的氧阻隔性能有用。The present invention relates to primers for plastic films comprising blends of poly(vinyl alcohol) and tackifiers, especially poly(ethyleneimine) and/or hardened epoxy resins. The present invention is useful for improving the oxygen barrier performance of plastic films.

Description

The base paint that is used for plastics film
Invention field
The present invention relates to the base paint that plastics film is used, it comprises poly-(vinyl alcohol) and tackifier, specifically is the blend of poly-(ethyleneimine) and/or hardening epoxy resin.The invention provides plastics film with good oxygen barrier properties.
Background of invention
The plastics film of orientation, particularly poly-(vinyl alcohol) has been widely used in especially food of wrapped product.Poly-(vinyl alcohol) is the water-soluble synthetic polymer that makes by the alcoholysis polyvinyl acetate.One of its known application is as laminating adhesive.When being used for packaging film, poly-(vinyl alcohol) can provide oil-tight, fat and wax, and has the film of good oxygen barrier performance.Owing to this reason, poly-(vinyl alcohol) is through being commonly used for the masking paste (barrier coating) on the thermoplastic film.Yet, do not have a kind of single unmodified polymer film to have packing required gas-barrier characteristic and anti-moisture performance and bond properties.
In the past, people attempt to provide the film with high oxygen, oily barrier and moisture resistance.And some polymeric film can have good bond metal level in the above.United States Patent (USP) 5,330,831 (Knoerzer etc.) disclose a kind of multilayer film.The multilayer film of Knoerzer etc. comprise that one deck has the polymeric substrates of undercoat, the one deck on this coating crosslinked poly-(vinyl alcohol) and a strata (vinyl alcohol) homopolymer on cross-linked layer or the blend of multipolymer and ethylene acrylic acid co polymer on its at least one surface.This patent also disclose one deck optional be coated in metal level on this blend layer.In addition, United States Patent (USP) 4,214,039 (Steiner etc.) are devoted to study thermoplastic film, and this film comprises the film substrate that applied undercoat on it and is applied in vinylidene chloride polymer on the undercoat as finishing coat.Yet, these films need two kinds different, base paint and polymer layer are to obtain chemical barrier and bond properties.Many coating machines only have two places, are used for simultaneously applying coating at film simultaneously.
Therefore, the wrapping material field need provide and have good oxygen barrier performance and to the fusible precoated layer of plastics film.
Therefore the objective of the invention is to provide undercoat with good oxygen barrier performance for wrapping material.By barrier and bond properties are combined in one deck, can remove coating place from, and should coating place can be used for applying other obstruct and/or other performance, as stopping property.
Summary of the invention
The present invention relates to base paint that a kind of plastics film uses and the purposes in wrapping material thereof.Base paint comprises poly-(vinyl alcohol) and tackifier, the particularly blend of poly-(ethyleneimine) and/or hardening epoxy resin.The present invention is useful to the oxygen barrier properties that improves plastics film.
The hardening epoxy resin amount is about 15-35 part to per 100 parts poly-(vinyl alcohols).Base paint also comprises about 10-20 part oxalic dialdehyde of per 100 parts poly-(vinyl alcohols).In addition, base paint also comprises Lipotril.Tackifier are polymines preferably.
Wrapping material of the present invention comprise the package base that (a) has first top layer and second top layer; (b) precoated layer has the base paint at least one top layer of the substrate of being coated on, and wherein base paint is the blend of poly-(vinyl alcohol), tackifier and/or Resins, epoxy; (c) optional finishing coat and/or the metal level that is coated on the precoated layer.
Useful is, because result of the present invention can make the packaging film with unique undercoat.The unique blend of undercoat of the present invention provides good oxygen barrier properties.
Undercoat of the present invention can have one deck to be coated in coating and/or metal level on the undercoat, therefore can provide bigger barrier property and sealing agent intensity.For example, the undercoat of not expected and the synergy of finishing coat provide extra obstruct to strengthen.
For understanding the present invention better, and other and further purpose, can be with reference to following specification sheets and accompanying drawing, scope of the present invention will be pointed out in claims.
Accompanying drawing
Fig. 1 is the graphic representation of the oxygen barrier properties relation of base paint concentration of component and uncoated thin film;
Fig. 2 is the graphic representation of the oxygen barrier properties relation of base paint concentration of component and coating rear film.
Fig. 3 is the graphic representation of the oxygen barrier properties relation of base paint concentration of component and metal spraying film.
Fig. 4 is the base paint concentration of component and the graphic representation that is used for the strength relationship that 127 ℃ of ripples that form the coated thin film of sealing seal.
Fig. 5 is the base paint concentration of component and the another graphic representation that is used for the strength relationship that about 104 ℃ of ripples that form the coated thin film of sealing seal.
Invention is described
The present invention includes for the primer of plastic sheeting and in the purposes of packaging material. Primer is the blend of poly-(vinyl alcohol) and tackifier and/or hardening epoxy resin.
Primer of the present invention can be used as priming coat and is used for substrate, such as the polypropylene of orientation or coating and/or the metal spraying of other plastic sheeting. Film primary coat and coating or primary coat and metal spraying has strengthened oxygen barrier properties. Have been found that collaborative oxygen barrier properties is better than the predicted value of the oxygen barrier properties that provides based on each layer aspect barrier property.
Poly-(vinyl alcohol) in the blend of the present invention refers to any poly-(vinyl alcohol) of buying, such as EVANOL 71-30, E.I.Dupont product.
The example of tackifier includes but not limited to, United States Patent (USP) 4,214, the described hardening epoxy resin of 039 (Steiner) (being incorporated herein by reference) and polymine, preferably polyethylene imines.
For per 100 parts poly-(vinyl alcohols), amount of epoxy is about 15-35 part. Find that amount of epoxy is high can to reduce barrier property, per 100 parts of poly-(vinyl alcohol) 25 parts of epoxy resin can obtain good oxygen barrier properties.
Primer can also contain crosslinking agent, and for per 100 parts poly-(vinyl alcohols), its amount is about 10-20 part. Cross-linked dosage is high to promoting the crosslinked useful of PVOH priming coat. The suitable example of the crosslinking agent that the present invention uses includes but not limited to, glyoxal, melamino-for maldehyde, glutaraldehyde, preferred glyoxal.
Estimate sealable coating (as acrylic coating) but and fine being bonded on the base paint of the present invention of the coating of low temperature seal energy.
The coating weight of base paint of the present invention can be controlled by solid content at an easy rate.Should use the base paint of about 6% solid content, adopt coating process of the present invention, this class base paint can provide/1000 inches of about 0.4 grams 2(g/msi) undercoat weight.But less solid content helps and other binders for coatings, but this point must be taken all factors into consideration with barrier property.Higher solids content can have disadvantageous effect to operability, because base paint can become too sticking.
The coating coating weight that is applied on the base paint of the present invention is the amount that adopts usually in the film coating industry.Among the embodiment in this specification sheets, according to the coating that is coated with, its scope is about the 0.6-1.3% solid content, and the coating weight of about 0.6-1.3g/msi can be provided.Yet this scope should not be considered to a kind of restriction.
Can also add Lipotril in the base paint prescription, its amount is about per 100 parts of poly-(vinyl alcohol) 0.25 part of Lipotrils.
The evaluation of static content shows, uses base paint of the present invention, and acrylic coating shows that the tendency that produces static charge is lower, meets the requirements.
Wrapping material of the present invention comprise the package base that (a) has first top layer and second top layer; (b) precoated layer has the base paint at least one top layer coating of substrate, and wherein base paint is poly-(vinyl alcohol), tackifier and/or epoxy resin blend; (c) optional finishing coat and/or the metal level that is coated on the precoated layer.The blend of base paint can also comprise linking agent and/or Lipotril.
Package base of the present invention comprises any polymeric film substrate that allow to see through oxygen and steam itself, uses this class film that is used to pack purpose to require such transmitance to be minimum.The suitable example of polymer materials includes but not limited to, nylon, polyethylene terephthalate, polycarbonate and polyolefine.Substrate preferably is a polyolefine, includes but not limited to polyethylene, polypropylene, polybutene, terpolymer, multipolymer and their blend.Better substrate is the polypropylene of orientation.
The example of package base of the present invention also comprises cardboard and fiberboard.The suitable example of cardboard and fiberboard includes but not limited to, the paper of glassine paper and delaminated clay.
Package base of the present invention can have the thickness of any requirement.For guaranteeing the good mechanical processing characteristics on high-speed packaging device, substrate thickness generally is about the 10-50 micron, is about the 10-35 micron preferably, and better about 12-25 micron is better.
By any coating process known in the art,, be coated with precoated layer at least one surface of package base of the present invention as the grooved roll coating.Can adopt any pretreatment process known in the art, the pre-treatment polymeric substrates is to strengthen the bounding force of precoated layer and polymeric substrates.Pretreatment process well-known in the art includes but not limited to, flame treating, Cement Composite Treated by Plasma, chemical treatment and Corona discharge Treatment.Preferred flame treating and Corona discharge Treatment, preferred especially Corona discharge Treatment.
As previously mentioned, base paint of the present invention is the blend of poly-(vinyl alcohol), tackifier and/or Resins, epoxy.The base paint blend also comprises linking agent and/or Lipotril.
The thickness of precoated layer is about the 0.5-2.0 micron, and about 0.7-1.5 micron is advisable, and about 1.0-1.5 micron is better.
The weight ratio of tackifier and/or Resins, epoxy and polyvinyl alcohol is about 0.15-0.35, better is about 0.20-0.30, and about 0.22-0.28 is better.
The weight ratio of linking agent and polyvinyl alcohol is about 0.05-0.4, better is about 0.10-0.30, and about 0.11-0.12 is better.
Precoated layer of the present invention can randomly have finishing coat and/or the metal level that applies on it.Can adopt any way known in the art,, finishing coat is coated on the surface of precoated layer as the grooved roll coating.The effect of finishing coat provides extra obstruct and/or stopping property and/or machinability and/or impressionability.
At United States Patent (USP) 4,214, the example (doing this quotes as a reference) that can be used as finishing coat coating has been described among 039 (Steiner).The preferred example of coating includes but not limited to, comprises the emulsion or the solution of polyvinylidene chloride, polyvinyl chloride, polyvinyl alcohol, ethylene acrylic acid co polymer and acrylic acid or the like.Coat-thickness can reach 5.0 microns.
Can pass through manner known in the art, as vacuum plating or plasma deposition, with layer metal deposition on surface layer.Metal level provides extra barrier and sealing agent performance for wrapping material.
The example that is used for the suitable metal of metal level includes but not limited to aluminium and aluminum oxide.
Embodiment
Following non-limiting example has illustrated the chemical barrier and the binder performance of Traditional Packing film and packaging film of the present invention.
Embodiment 1
Packaging film of the present invention
This embodiment has illustrated the chemical barrier and the bond properties of packaging film of the present invention.Carry out chemical barrier and adhesion test having on eight kinds of film substrate of different coating blend compositions.
Eight kinds of film substrate scribble the precoated layer of eight kinds of different base paint blends separately.Adopt oppositely direct grooved roll coating coating base paint blend.Film after the coating is with the dry air baking oven of about 125 feet per minute clock rate degree by 200.The base paint blend comprises PVOH, Resins, epoxy base paint and oxalic dialdehyde.The base paint blend is listed in table 1.
Table 1
Sample number into spectrum Film volume numbering ????PVOH ????phr The Resins, epoxy phr of 12% solid content Oxalic dialdehyde phr Coating wt g/msi
?1 PC-06186-01 ????100 ????15 ????10 ????0.2
?2 PC-06186-02 (also comprising the 0.25phr Lipotril) ????100 ????25 ????10 ????0.2
?3 PC-06186-03 ????100 ????15 ????15 ????0.2
?4 PC-06186-04 ????100 ????25 ????15 ????0.2
?5 PC-06186-0 ????100 ????15 ????10 ????0.4
?6 PC-06186-06 ????100 ????25 ????10 ????0.4
?7 PC-06186-07 ????100 ????15 ????15 ????0.4
?8 PC-06186-08 ????100 ????25 ????15 ????0.4
Eight kinds of precoated layers are coated with the finishing coat of EAA preparation separately then.Use oppositely direct grooved roll coating machine to use the EAA preparation.Film after the coating passes through 200 dry air baking oven.The EAA prescription comprises 100phrM4983 (Michemprime that Michelman produces), 1.5phr NaOH; 4phr carnauba wax emulsion (can obtain) from Michelman, 0.3phr (amorphous) synthetic silica matting agent (Silloid) and 0.4phr talcum.
Test makes the oxygen perviousness of film.Dry rear film is tested in the oxygen-permeable device, and in this device, dry oxygen stream is by infiltrating the pad of salt brine solution, with the moisture of pilot-gas, and then by film, the placement that meets at right angles of dry film and finishing coat gas stream upstream.The oxygen that mensuration sees through, the Units of Account time is by the oxygen amount of unit surface film.Oxygen intercepts test-results and lists in table 2.
Table 2
Sample number into spectrum TO 2(centimetre 3/ 100 inches 2/ day) Askco 230-260 (gram/inch) Keep Askco (gram/inch) Ripple seals 220 (gram/inches) Ripple seals 260 (gram/inches) Keep ripple and seal (gram/inch)
?1 ????5.02 ????169 ????166 ????100 ????140 ????145
?2 ????1.64 ????186 ????163 ????125 ????200 ????255
?3 ????2.41 ????134 ????129 ????105 ????150 ????170
?4 ????2.12 ????144 ????171 ????150 ????160 ????180
?5 ????0.33 ????373 ????168 ????160 ????190 ????190
?6 ????0.15 ????515 ????541 ????265 ????220 ????360
?7 ????0.20 ????261 ????230 ????260 ????220 ????215
?8 ????0.16 ????421 ????411 ????400 ????415 ????310
As shown in Table 2, packaging film of the present invention has lower gas-premeable and good bond properties.Therefore, the unique blend of precoated layer of the present invention not only provides chemical barrier but also provides the binding property that the Traditional Packing film is provided.Yet the blend of the precoated layer of packaging film of the present invention has been cancelled the needed undercoat of conventional films.
Embodiment 2
The packaging film of metal spraying
This embodiment illustrates the traditional metal spraying packaging film and the chemical barrier and the bond properties of metal spraying packaging film of the present invention.Carry out chemical barrier and adhesion test having on nine kinds of MC550 film substrate of different coating blend compositions (producing) by Mobil.
Nine kinds of film substrate have been coated with the precoated layer of nine kinds of different base paint blends separately.The base paint blend comprises PVOH, EAA, Resins, epoxy base paint and oxalic dialdehyde.The base paint blend is listed in table 3.
Table 3
Sample number into spectrum ??PVOH?phr Solid content % ?EAA?phr Resins, epoxy phr Oxalic dialdehyde phr
????1 ????100 ????1 ????100 ????0 ????0
????2 ????100 ????1 ????200 ????0 ????0
????3 ????100 ????4 ????100 ????0 ????0
????4 ????100 ????4 ????200 ????0 ????0
????5 ????100 ????1 ????0 ????100 ????20
????6 ????100 ????1 ????0 ????200 ????20
????7 ????100 ????4 ????0 ????100 ????20
????8 ????100 ????4 ????0 ????200 ????20
????9 ????100 ????4 ????0 ????100 ????20
Then with each precoated layer of metal spraying.
Its steam breathability of the Film test that makes, oxygen perviousness and bond properties.Test-results is listed in table 4.
Table 4
Sample number into spectrum ????TO 2 ????WVTR Wearing and tearing Binding property
????1 ????2.64 ????0.03 Difference Good
????2 ????3.09 ????0.03 Difference Good
????3 ????0.42 ????0.03 Difference Good
????4 ????1.03 ????0.02 Difference Good
????5 ????3.34 ????0.04 Difference Good
????6 ????2.01 ????0.05 Difference Good
????7 ????0.89 ????0.04 Medium Good
????8 ????1.22 ????0.04 Medium Good
????9 ????0.95 ????0.02 Difference Good
As shown in Table 4, sample 5-9, the packaging film of metallizing of the present invention had not only had chemical barrier but also had had the binding property that the Traditional Packing film of sample 1-4 is provided.Yet the packaging film of metal spraying of the present invention has good bond properties, so do not need the undercoat of extra conventional films.
Embodiment 4
Base paint preparation described in polypropylene film sample (sample 1-21) the primary coat following table of orientation.M4983 is the Michemprime that is produced by Michelman.M215 is the carnauba wax emulsion that obtains from Michelman.SR344 is the Tospearl 145 that obtains from Toshiba Silicone Co..ML71513 is the synthetic wax that obtains from Michelman.D8500 is the Daran 8500 that obtains from Hampshire Chemical.Test the oxygen barrier properties and the stopping property of each sample, the results are shown among table 5 and Fig. 1-5.
Table 5
Table A CN-81
The operation of LAB coating machine
50 220 130 60 ° of treatment capacities 2 of basement membrane=FPM O chill roll 92MC550 primary coat
Face is coated with 50 220 130 60 °
SYLOID42 disperseed 60 seconds in WARING blending machine
Be the label sample of " ACN8 XX ", for the physical test of R#1701
Only there is the sample of base paint to be denoted as " ACN8-XXA "
Preparation standard Resins, epoxy base paint, and be diluted to 20% solid content, be used for the total coating 10 20 40 11 less solid content LTX standard oxalic dialdehyde SYLD choline salt H of blending % % % % % 2O HE XYL HEX WO standard oxalic dialdehyde SYLD choline film volume latex LOT solid content latex talcum Resins, epoxy 42 hydrochlorate CELL P﹠amp; The total # % of H LTX talcum Resins, epoxy 42 hydrochlorides Ke Kekekekekekeke gram % phr phr phr phr phr phr phr
I：5010ACN8 1 ELVANOL 90/50 8.0 99.8 0.00 6.0 2.0 0.0 2.0 90.2 2.0 200 5 100 0 15 10 0 0.25 125.3ACN8 2 ELVANOL 90/50 8.0 107.0 0.00 10.7 3.2 0.0 2.1 77.0 2.0 200 6 100 0 25 15 0 0.25 140.3ACN8 3 ELVANOL 90/50 8.0 112.7 0.00 15.8 4.5 0.0 2.3 64.7 2.0 200 7 100 0 35 20 0 0.25 155.3ACN8 4 ELVANOL 90/50 8.0 119.8 0.00 7.2 2.4 0.0 2.4 68.3 2.0 200 6 100 0 15 10 0 0.25 125.3ACN8 5 ELVANOL 90/50 8.0 124.8 0.00 12.5 3.7 0.0 2.5 56.5 2.0 200 7 100 0 25 15 0 0.25 140.3ACN8 6 ELVANoL 90/50 8.0 80.5 0.00 11.3 3.2 0.0 1.6 103. 2.0 200 5 100 0 35 20 0 0.25 155.3
4ACN8??7?ELVANOL?90/50?8.0??96.0???0.00???5.8????2.9????0.0????1.9?????93.5????2.0????200??5????100??0??????15??????15????0????0.25??130.3ACN8??8?ELVANOL?90/50?8.0??103.3??0.00???10.3???4.1????0.0????2.1?????80.2????2.0????200??6????100??0??????25??????20????0????0.25??145.3ACN8??9?ELVANoL?90/50?8.0??120.5??0.00???16.9???2.4????0.0????24??????57.8????2.0????200??7????100??0??????35??????10????0????0.25??145.3ACN8?10?ELVANOL?90/50?8.0??129.4??0.00???7.8????5.2????0.0????2.6?????55.1????2.0????200??7????100??0??????15??????20????0????0.25??135.3ACN8?11?ELVANOL?90/50?8.0??92.4???0.00???9.2????1.8????0.0????1.8?????94.6????2?0????200??5????100??0??????25??????10????0????0.25??135.3ACN8?12?ELVANOL?90/50?8.0??99.8???0.00???14.0???3.0????0.0????2.0?????81.2????2.0????200??6????100??0??????35??????15????0????0.25??150.3ACN8?13?ELVANOL?90/50?8.0??134.4??0.00???8.1????4.0????0.0????2.7?????50.9????2.0????200??7????100??0??????15??????15????0????0.25??130.3ACN8?14?ELVANOL?90/50?8.0??86.1???0.00???8.6????3.4????0.0????1.7?????100.????2.0????200??5????100??0??????25??????20????0????0.25??145.3
2ACN8?15?ELVANOL?90/50?8.0??103.3??0.00???14.5???2.1????0.0????2.1?????78.1????2.0????200??6????100??0??????35??????10????0????0.25??145.3ACN8?16?ELVANOL?90/50?8.0??110.9??0.00???6.7????4.4????0.0????2.2?????75.8????2.0????200??6????100??0??????15??????20????0????0.25??135.3ACN8?17?ELVANOL?90/50?8.0??129.4??0.00???12.9???2.6????0.0????2.6?????52.5????2.0????200??7????100??0??????25??????10????0????0.25??135.3ACN8?18?ELVANOL?90/50?8.0??83.2???0.00???11.6???2.5????0.0????1.7?????101.????2.0????200??5????100??0??????35??????15????0????0.25??150.3
0A,CN8 19 STD PEIPRIMER[0.10% solid contents] ... finishing coat ACN8 20 STD PEIPRIMER[0.10% solid contents from the M4983 of masterbatch are arranged] ... finishing coat ACN8 21 STD PEIPRIMER[0.10% solid contents from the standard acrylic acid or the like of masterbatch are arranged] ... finishing coat from the DARAN 8500 of masterbatch is arranged
After the primary coat, use coating roller coat finishing coat from following masterbatch
M215??SiO 2???????????????????????????????????????M215?SiO 2
ACN8?1.3，10，12??M4983???CNTRL?25.0?611.3?6.11??30.6??0.0???45.8?0.0??306.2??0.0??1000??16??100??0.4???4???0???0.3???0??104.7
SR344??????????????????????????????????????????????SR344
ACN8 4.6,13,15 acrylic acid or the like CNTRL 22.0 497.1 2.73 32.8 109.4 5.5 0.0 352.5 0.0 1,000 16 100 0.25 6 40 0.05 0 146.7
ACN8?7.9，16，18??D8500???CNTRL?49.0?641.5?9.43??ML715 *13
23.6??0.0???0.0??0.0??325.5??0.0??1000??32??100??0.3??1.5??0???0?????0??101.8
Fig. 1 is the graphic representation of the oxygen barrier properties relation of base paint concentration of component and uncoated thin film.Fig. 1 shows, poly-(vinyl alcohol) of higher concentration corresponding to low concentration Resins, epoxy, provides as increasing the better oxygen barrier properties that coating wt provided.
Fig. 2 is the graphic representation of the oxygen barrier properties relation of base paint concentration of component and coated thin film.Fig. 2 shows that after the top layer coating, all samples all confirms the predicated value better oxygen barrier properties of beguine according to the barrier of each component contribution.Provide 117 centimetres when for example, the salable coating of low temperature is coated with on polymine 3/ 100 inches 2/ day oxygen barrier performance, be roughly (129 centimetres of the barriers that this thickness polypropylene of painting polyethylene imines provides 3/ 100 inches 2/ day).Shown in the curve of Fig. 1, the average barrier of the sample of coating low temperature seal coating is about 3.7 centimetres 3/ 100 inches 2/ day.The barrier that the low temperature seal coating is contributed is about 1300 centimetres 3/ 100 inches 2/ day.Therefore, estimate that the primary coat and the expectation oxygen perviousness of coating bonded film can be than 3.69 centimetres 3/ 100 inches 2/ it is better.Calculate predicated value by each stratified roughly barrier:
(1/1300)+(1/3.7)＝(1/3.69)
(1/3.7) value comprises the barrier of oriented polypropylene and base paint.(1/300) the value inverse (1/172) of obstruct value that can be deducted the oriented polypropylene of primary coat polymine by the inverse (1/129) of the obstruct value of the polymine that the salable coating of low temperature is arranged on the oriented polypropylene of same thickness obtains.
Yet the actual mean value of six samples is about 2.1 centimetres 3/ 100 inches 2/ day.This value is less than any one group of mean value that the base paint sample is only arranged.It is about the twice of desired value.
When acrylic coating is applied on the film, its result even better.The oxygen of supposing oriented polypropylene films is about 129 centimetres through value 3/ 100 inches 2/ day, then the barrier of the acrylate layer on the polymine should be able to provide about 610 centimetres 3/ 100 inches 2/ day (1/107-1/129 ≈ 1/610).Therefore, estimate, be coated with acrylic acid polymine and should have 2.99 centimetres by the mean value of Fig. 1 3/ 100 inches 2/ day (1/3+1/610 ≈ 1/2.99).Fig. 2 also shows averaged oxygen value of seeing through than predicated value good about six times (～0.5 centimetre 3/ 100 inches 2/ day).
When being applied in film primary coat after on lower coating weight the polyvinylidene chloride of coating, polyvinylidene chloride provides about 0.85 centimetre on the primary coat epoxy resin thin film 3/ 100 inches 2The oxygen obstruct value in/sky, the primary coat film of uncoated polyvinylidene chloride provides 124 centimetres 3/ 100 inches 2The oxygen obstruct value in/sky.Therefore, the polyvinylidene chloride layer provides 0.86 centimetre 3/ 100 inches 2The obstruct value in/sky.If this coating paint has 2.6 centimetres 3/ 100 inches 2On the substrate of/day obstruct value, the oxygen obstruct value of expectation should be about 0.81 centimetre 3/ 100 inches 2/ day.To six samples that are coated with polyvinylidene chloride, its mean value is 0.05 centimetre 3/ 100 inches 2/ day.Than 16 times of desired values.
These data show that when undercoat of the present invention used with any finishing coat, oxygen barrier properties had the collaborative raising of not anticipated.And the barrier property of finishing coat own is good more, and it is also good more to act synergistically.
Fig. 3 is the graphic representation of the oxygen barrier properties relation of base paint concentration of component and metallizing film.Different with the coated thin film sample, the film of metallize shows better barrier property at lower poly-(vinyl alcohol) coating weight.When the thin film cladding metal of polymine or Resins, epoxy primary coat, oxygen obstruct value is at 1.5 centimetres 3/ 100 inches 2/ day scope.Be changed to poly-(vinyl alcohol) base paint, averaged oxygen sees through value and is about 0.13 centimetre 3/ 100 inches 2/ day.Yet some sample (for example, the primary coat film among the embodiment A CN8-16) can provide 0.01 centimetre behind metallizing 3/ 100 inches 2The oxygen obstruct value in/sky.This is more or less the same with the oxygen obstruct value by the oriented polypropylene on ethylene-vinyl alcohol copolymer top layer is arranged, and this oriented polypropylene provides 0.03 centimetre behind metallizing 3/ 100 inches 2The oxygen in/sky sees through value.Because the film that has the ethylene-vinyl alcohol copolymer top layer to make is difficult to produce, so the invention provides tangible advantage.
Fig. 4 is the base paint concentration of component and is used for 127 ℃ of graphic representations that form the ripple sealing-strength relation of the coated thin film that seals.But can reach best effect with the low temperature seal coating, but the effect that can obtain with polyvinylidene chloride (Daran 8500), and its performance is better than the performance of acrylic acid or the like.It is relevant with the bounding force of base paint that its improvement be it seems.Amount of epoxy is higher in the base paint, can improve the bounding force to coating.
Fig. 5 is the base paint concentration of component and is used for about 104 ℃ of another graphic representations that form the ripple sealing-strength relation of the coated thin film that seals.When low temperature, can reach equifinality.Surprisingly the low temperature seal coating of Huo Deing has been improved low temperature seal.At 82 ℃, the low temperature seal coating still has＞sealing of 400 gram/inches.

Claims (10)

1.一种用于塑料薄膜的底涂料，它包含聚(乙烯醇)和增粘剂和/或硬化环氧树脂的共混物。CLAIMS 1. A primer for plastic films comprising a blend of poly(vinyl alcohol) and tackifier and/or hardened epoxy resin. 2.如权利要求1所述的底涂料，其特征在于，对每100份聚(乙烯醇)而言，所述环氧树脂的量约为15-35份。2. The primer of claim 1, wherein the epoxy resin is present in an amount of about 15-35 parts per 100 parts of poly(vinyl alcohol). 3.如权利要求1所述的底涂料，其特征在于，所述底涂料还包含乙二醛，对每100份聚(乙烯醇)而言其量约为10-20份。3. The primer of claim 1, further comprising glyoxal in an amount of about 10-20 parts per 100 parts poly(vinyl alcohol). 4.如权利要求1所述的底涂料，其特征在于，所述底涂料还包含胆碱盐酸盐。4. The primer of claim 1, further comprising choline hydrochloride. 5.如权利要求1所述的底涂料，其特征在于，所述增粘剂是聚乙烯亚胺。5. The primer of claim 1, wherein the tackifier is polyethyleneimine. 6.如权利要求1所述的底涂料，其特征在于，所述塑料薄膜上涂布聚合物涂层和/或喷镀金属层，基底有一在聚合物涂层或金属层下面的底涂料。6. primer as claimed in claim 1, is characterized in that, coating polymer coating and/or metallization layer are coated on the described plastic film, and substrate has a primer below polymer coating or metal layer. 7.如权利要求6所述的底涂料，其特征在于，对每100份聚(乙烯醇)而言，所述环氧树脂量约为15-35份。7. The primer of claim 6, wherein the amount of epoxy resin is about 15-35 parts per 100 parts poly(vinyl alcohol). 8.如权利要求6所述的底涂料，其特征在于，所述底涂料还包含乙二醛，对每100份聚(乙烯醇)而言其量约为10-20份。8. The primer of claim 6, further comprising glyoxal in an amount of about 10-20 parts per hundred parts poly(vinyl alcohol). 9.如权利要求6所述的底涂料，其特征在于，所述底涂料还包含胆碱盐酸盐。9. The primer of claim 6, further comprising choline hydrochloride. 10.如权利要求6所述的底涂料，其特征在于，所述增粘剂是聚乙烯亚胺。10. The primer of claim 6, wherein the tackifier is polyethyleneimine.
CN98802385A 1997-02-10 1998-02-06 Primer for plastic films Pending CN1246879A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US3758597P 1997-02-10 1997-02-10
US60/037,585 1997-02-10

Publications (1)

Publication Number Publication Date
CN1246879A true CN1246879A (en) 2000-03-08

Family

ID=21895138

Family Applications (1)

Application Number Title Priority Date Filing Date
CN98802385A Pending CN1246879A (en) 1997-02-10 1998-02-06 Primer for plastic films

Country Status (10)

Country Link
EP (1) EP0960159A4 (en)
JP (1) JP2001511211A (en)
KR (1) KR20000070911A (en)
CN (1) CN1246879A (en)
AR (1) AR011658A1 (en)
AU (1) AU735361B2 (en)
BR (1) BR9807569A (en)
CA (1) CA2280050A1 (en)
ID (1) ID23409A (en)
WO (1) WO1998034982A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104962146A (en) * 2015-07-03 2015-10-07 海南必凯水性涂料有限公司 High-oxygen-barrier self-adhesive polyvinyl alcohol coating and preparation method thereof
CN104961903A (en) * 2015-07-03 2015-10-07 海南赛诺实业有限公司 High-oxygen-barrier no-primer polyvinyl alcohol coated film and manufacturing method thereof
CN109689749A (en) * 2016-09-14 2019-04-26 巴斯夫欧洲公司 Prepare the method with the polymer film of gas barrier property
CN109747971A (en) * 2017-11-08 2019-05-14 林紫绮 Method for preventing ink contamination of packaging materials by cationic aqueous solution

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0200957D0 (en) 2002-01-17 2002-03-06 Secr Defence Novel polymer and uses thereof
GB0421706D0 (en) * 2004-09-30 2004-11-03 Univ Belfast "Polymer Material"
WO2012005288A1 (en) * 2010-07-09 2012-01-12 日本合成化学工業株式会社 Saponified ethylene/vinyl ester copolymer composition and multilayer structure using the composition
US9303179B2 (en) 2012-11-02 2016-04-05 Michelman, Inc. Primer coating for metallized gas barrier films
CN114080371B (en) * 2019-07-10 2024-01-02 Ａｇｃ株式会社 Glass substrate and method for producing same
CA3194949A1 (en) 2020-12-11 2022-06-16 Richard Schwarz Sustainable barrer containers and methods
US11884466B2 (en) 2020-12-11 2024-01-30 Sonoco Development, Inc. Sustainable barrer containers and methods
DE102021114174A1 (en) * 2021-06-01 2022-12-01 Mondi Ag Film composite, film packaging and method for producing a film composite
CN114854155B (en) * 2022-04-06 2023-08-22 杭州师范大学 High-strength, freeze-resistant and transparent conductive PVA/quaternary ammonium salt elastomer
GB2628562A (en) 2023-03-28 2024-10-02 Innovia Films Ltd Barrier film

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4214039A (en) * 1979-04-23 1980-07-22 Mobil Oil Corporation Polypropylene film with primer of a water dispersed epoxy resin coating
US5552212A (en) * 1990-12-13 1996-09-03 Mobil Oil Corporation High barrier film combination
US5192620A (en) * 1991-11-08 1993-03-09 Mobil Oil Corporation Metallized composite film structure and method
US5487940A (en) * 1991-12-23 1996-01-30 Mobil Oil Corp. Oxygen and moisture barrier metallized film structure
JPH06228347A (en) * 1993-01-29 1994-08-16 Teijin Ltd Easily bondable antistatic polyester film
US5496649A (en) * 1994-07-21 1996-03-05 Mobil Oil Corp. Cross-linked PVOH coatings having enhanced barrier characteristics
EP0794861A4 (en) * 1994-12-02 1998-08-12 Mobil Oil Corp A HOT-SEALABLE MULTILAYER FILM CONTAINING POLYVINYL ALCOHOL
US5547764A (en) * 1994-12-22 1996-08-20 Mobil Oil Corporation Method of producing PVOH coatings with enhanced properties

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104962146A (en) * 2015-07-03 2015-10-07 海南必凯水性涂料有限公司 High-oxygen-barrier self-adhesive polyvinyl alcohol coating and preparation method thereof
CN104961903A (en) * 2015-07-03 2015-10-07 海南赛诺实业有限公司 High-oxygen-barrier no-primer polyvinyl alcohol coated film and manufacturing method thereof
CN109689749A (en) * 2016-09-14 2019-04-26 巴斯夫欧洲公司 Prepare the method with the polymer film of gas barrier property
CN109747971A (en) * 2017-11-08 2019-05-14 林紫绮 Method for preventing ink contamination of packaging materials by cationic aqueous solution

Also Published As

Publication number Publication date
AU735361B2 (en) 2001-07-05
JP2001511211A (en) 2001-08-07
EP0960159A1 (en) 1999-12-01
AU6152898A (en) 1998-08-26
KR20000070911A (en) 2000-11-25
AR011658A1 (en) 2000-08-30
EP0960159A4 (en) 2001-04-04
BR9807569A (en) 2000-02-01
WO1998034982A1 (en) 1998-08-13
CA2280050A1 (en) 1998-08-13
ID23409A (en) 2000-04-20

Similar Documents

Publication Publication Date Title
CN1246879A (en) Primer for plastic films
JP2944192B2 (en) Stretched multilayer heat-sealing packaging film
CN101120069B (en) Adhesive compositions based on ethylene copolymers and their use for extrusion coating and extrusion lamination on various supports
CN1048026C (en) Composite sheet
EP2583834B1 (en) Modified polyvinyl alcohol coated film used for printing and preparation method thereof
JP6670472B2 (en) Moistureproof film for building materials
CN1040993A (en) But contain the polyester film of extrusion coating of amido functional group silane base paint and the laminate film of extrusion coating thereof
CN1059534A (en) Siloxane polymer and multipolymer barrier coating and barrier coat preparation method
CN1930234A (en) Polypropylene modification for improved adhesion of polypropylene-based multilayer packaging film structure to vacuum deposited aluminum
CN1411495A (en) Barrier coatings having bis-silanes
CN1112878A (en) Gas barrier laminated product and method for producing the same
CA1290122C (en) Reactive coextrusion of functionalized polymers
US6649235B2 (en) Process for producing coated polymeric articles and the articles produced thereby
JPH10510487A (en) Heat sealable multilayer film containing polyvinyl alcohol layer
CN1137949C (en) Coating agent for film, laminate and preparation method thereof
CN1268087A (en) Multi-layer films with syndiotactic barrier layer containing a wax
JPH03203641A (en) Heat-sealable opaque multi-layer oriented film
JP2020131676A (en) High interlaminar adhesive gas barrier vapor-deposited film
CN1599665A (en) Thermoformable multilayer film based on acrylic polymer for protecting substrates and resulting objects
JP5739684B2 (en) Gas barrier film and method for producing the same
JP2020131675A (en) High interlaminar adhesive gas barrier vapor-deposited film
CN111902482A (en) Resins for use as tie layers in multilayer structures with polyethylene terephthalate
US20020169253A1 (en) Primer for plastic films
CN1135408A (en) Packing material containing silicon dioxide layer and polyolefine layer
CN1224383A (en) Metallized multilayer packaging film

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication