CN107400474A - A kind of novel environment friendly pre-coating film and its manufacture method - Google Patents
A kind of novel environment friendly pre-coating film and its manufacture method Download PDFInfo
- Publication number
- CN107400474A CN107400474A CN201710801894.8A CN201710801894A CN107400474A CN 107400474 A CN107400474 A CN 107400474A CN 201710801894 A CN201710801894 A CN 201710801894A CN 107400474 A CN107400474 A CN 107400474A
- Authority
- CN
- China
- Prior art keywords
- tack coat
- layer
- coating film
- film
- environment friendly
- 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
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 53
- 238000000576 coating method Methods 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000010410 layer Substances 0.000 claims abstract description 124
- -1 polypropylenes Polymers 0.000 claims abstract description 45
- 239000004743 Polypropylene Substances 0.000 claims abstract description 39
- 229920001155 polypropylene Polymers 0.000 claims abstract description 37
- 239000004831 Hot glue Substances 0.000 claims abstract description 28
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 23
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 23
- 238000005266 casting Methods 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000007493 shaping process Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 238000001125 extrusion Methods 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 239000003351 stiffener Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 7
- 238000009987 spinning Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 238000003851 corona treatment Methods 0.000 claims description 4
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 239000004005 microsphere Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 3
- UGFMBZYKVQSQFX-UHFFFAOYSA-N para-methoxy-n-methylamphetamine Chemical compound CNC(C)CC1=CC=C(OC)C=C1 UGFMBZYKVQSQFX-UHFFFAOYSA-N 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 241000219198 Brassica Species 0.000 claims 1
- 235000003351 Brassica cretica Nutrition 0.000 claims 1
- 235000003343 Brassica rupestris Nutrition 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 claims 1
- 235000010460 mustard Nutrition 0.000 claims 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 abstract description 25
- 229920006378 biaxially oriented polypropylene Polymers 0.000 abstract description 25
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 12
- 238000007731 hot pressing Methods 0.000 abstract description 6
- 239000012528 membrane Substances 0.000 abstract description 5
- 238000010345 tape casting Methods 0.000 abstract description 5
- 229920005606 polypropylene copolymer Polymers 0.000 abstract 1
- 230000008569 process Effects 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 4
- 239000005025 cast polypropylene Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical compound C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000003000 extruded plastic Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920005630 polypropylene random copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/10—Presence of homo or copolymers of propene
- C09J2423/106—Presence of homo or copolymers of propene in the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a kind of novel environment friendly pre-coating film and its manufacture method.The novel environment friendly pre-coating film includes, top layer, the first tack coat, intermediate layer, the second tack coat and the hot melt adhesive layer set gradually from top to bottom；The top layer, the first tack coat, intermediate layer, the second tack coat and hot melt adhesive layer are by polypropylene and ethylene-vinyl acetate copolymer coextrusion casting film forming.The present invention uses the tape casting film processed, four layer polypropylenes and one layer of ethylene-vinyl acetate copolymer are disposably coextruded to generation polypropylene pre-membrane by casting technique, without applying hot melt adhesives layer, more it is not required to silane coupling agent, can be compound with printed matter hot pressing, reduce production cost, production efficiency improves, applied to printed matter overlay film field, common BOPP pre-coating films on the market can be replaced to a certain extent.Meanwhile casting technique can improve the elongation at break of film, avoid the printed matter after common BOPP products overlay film when being die cut machine-shaping, be also easy to produce skinning even chip the problem of.
Description
Technical field
The present invention relates to technical field of material chemistry, more particularly to a kind of novel environment friendly pre-coating film and its manufacture method.
Background technology
Overlay film refers to a kind of paper unification formed in the laminating layer of plastic film of paper printed matter surface laminating machine
The process technology of product.Precoating membrane process refers to that surface is coated with the plastic sheeting of PUR, is directly used by way of hot pressing
Processed in the overlay film of printed matter.Compared with traditional i.e. painting type film, pre-coating film has that technique is simple, solvent-free pollution, does not produce
The advantages that raw harmful VOC emission, it is widely used on the paper printing matters such as all kinds of packing boxes, packaging bag, book cover.
But most pre-coating films, it is that one layer of second is applied by expressing technique on the basis of BOPP original films such as BOPP pre-coating films
Alkene-acetate ethylene copolymer (EVA) raw material and formed.Because the bonding intensity between BOPP and EVA is poor, pre-coating film produced
Need to apply one layer of silane coupling agent containing organic solvent on BOPP surfaces in journey to improve the fastness between EVA and BOPP.In pre-coating film
With printed matter heating it is compound after, silane coupling agent can separate out to be polluted to film surface, and influences the brightness of pre-coating film.Coat silane coupling agent
Pre-coating film process energy consumption can also be increased, be difficult to control processing technology.
In addition, BOPP originals film causes its elongation at break low in process of production due to stretch processes, therefore right
When printed matter after overlay film carries out cross cutting machine-shaping, be also easy to produce skinning even chip the problem of.And the present invention will be related to one kind
The processing technology and product of novel environment friendly pre-coating film.The environmentally friendly pre-coating film will be applied to printed matter overlay film field, can be to a certain degree
The upper common BOPP pre-coating films replaced on the market.
The Chinese patent of Application No. 201210340018.7 discloses the BOPP pre-coating films and its system of a kind of no silane coupling agent
Method is made, the directly hot pressing of its described hot melt adhesive layer (1.5-4 μm of thickness) is combined to the bidirectional stretching polypropylene film (thickness
12-18 μm) functional layer on.Form BOPP pre-coating films and without silane coupling agent, but need follow-up hot pressing combination process.
The Chinese patent of Application No. 201511008801.3 disclose a kind of biaxial tension polypropylene precoating film base material and
Its preparation method.Its base material is by top layer polypropylene layer, and sandwich layer polypropylene layer and lower floor's ethene-vinyl acetate resin layer are through co-extrusion
Go out and be prepared with biaxial tension.If wanting to produce pre-coating film, this base material still needs to be coated with EVA hot-melt adhesive, simply no longer needed
Silane coupling agent.
Application No. 200910179981.X Chinese patent, which discloses a kind of packaging field that is used for, has barrier property
Multi-layer co-extruded plastics film, its EVA layer on multi-layer co-extruded film original olefin layer below 5 μm of film one layer so that film has
There is heat sealability.
The Chinese patent of Application No. 200910062917.3 discloses a kind of ultra-low temperature heat sealing polypropylene casting film, its heat
The important materials of sealing are polypropylene random copolymer and polyolefin elastomer, and its sandwich layer and corona layer are mainly polypropylene.
Need to apply one layer of silane coupling agent containing organic solvent on BOPP surfaces in current BOPP pre-coating film production processes to carry
Fastness between high EVA and BOPP.After pre-coating film and printed matter heating are compound, silane coupling agent can separate out causes dirt to film surface
Dye, and influence the brightness of pre-coating film.Coating silane coupling agent can also increase pre-coating film process energy consumption, be difficult to control processing technology.
Polypropylene film is using double stretching technique, and its product film uneven thickness, elongation at break is low, follow-up painting
Cloth technique can increase production cost.Current cast polypropylene film main application fields are the packaging such as laminating film internal layer material
Field, it is not applied in printed matter overlay film field.
Therefore, the prior art is defective, it is necessary to improve.
The content of the invention
The technical problems to be solved by the invention are：There is provided one kind without priming coat, film thickness evenly, extension at break
Rate is higher, production cost is lower, can be applied to printed matter overlay film field, is precoated to a certain extent instead of common BOPP on the market
The novel environment friendly pre-coating film and its manufacture method of film.
Technical scheme is as follows：A kind of novel environment friendly pre-coating film, it is characterised in that：Sequentially include from top to bottom：
Top layer, the first tack coat, intermediate layer, the second tack coat and hot melt adhesive layer；Wherein, the top layer, the first tack coat, intermediate layer,
Second tack coat and hot melt adhesive layer are respectively by die head integrally extrusion stretching, and glued by first tack coat and described second
Connecing layer, bonding forms respectively by the top layer, the intermediate layer, the hot melt adhesive layer.
Applied to each above-mentioned technical proposal, the skin depth is 3-6 μm；First tack coat, the second tack coat
Thickness be 1.5-3 μm；The thickness in the intermediate layer is 6-12 μm；The thickness of the hot melt adhesive layer is 3-6 μm.
Applied to each above-mentioned technical proposal, the surface on the top layer is provided with some projections or different the recessed of shape that relax
It is convex；Also, the surface on the top layer is additionally provided with a smooth layer.
Applied to each above-mentioned technical proposal, the top layer is made up of extrusion grade polypropylene, slipping agent and antiblocking agent；
Wherein, the polyacrylic mass content of extrusion grade is 95-97wt%, and the mass content of slipping agent is 0.1-0.2wt%, and surplus is anti-
Adhesion agent.
Applied to each above-mentioned technical proposal, first tack coat and second tack coat are material structure identical
Adhesive linkage, wherein, first tack coat, the second tack coat are by extrusion grade polypropylene, spinning grade polypropylene and antistatic additive
Composition；Wherein, the polyacrylic mass content of extrusion grade is 83-89wt%, and the polyacrylic mass content of spinning-grade is 10-
15wt%, surplus are antistatic additive；
Applied to each above-mentioned technical proposal, the intermediate layer is made up of extrusion grade polypropylene and Stiffening agent；Wherein, squeeze
The mass content for going out grade polypropylene is 98-99wt%, and surplus is Stiffening agent；
Applied to each above-mentioned technical proposal, the hot melt adhesive layer is by ethylene-vinyl acetate mixture and ethylene propylene
Olefin(e) acid copolymer mixes；Wherein, the mass content of ethylene-vinyl acetate mixture is 92%-95%, and surplus is ethene
Acrylic copolymer.
Applied to each above-mentioned technical proposal, the slipping agent can be oleamide or erucyl amide；It is also, described anti-stick
Even agent is combined by one or more kinds of arbitrary proportions of silica, calcium carbonate or PMMA microsphere.
Applied to each above-mentioned technical proposal, the antistatic additive can be by ethoxylated fatty amine, quarternary ammonium salt compound, fat
One or both of fat acid fat, curing carbaminate any of the above ratio combines.
Applied to each above-mentioned technical proposal, the quality of contained vinyl acetate in the ethylene-vinyl acetate mixture
Content is 25-28wt%, melt index 3.0-5.0g/min.
A kind of manufacture method of novel environment friendly pre-coating film pre-coating film, it is characterised in that comprise the following steps： S1：Will composition
The top layer, the first tack coat and the second tack coat, intermediate layer, the raw material of hot melt adhesive layer are respectively fed to four from top to bottom arranged
Plasticizing makes plasticizing be respectively fed into the melt feed of melt in casting machine die head, and make the first bonding into melt in platform single screw rod
The distributor that the melt feed of layer and the second tack coat enters in casting machine die head is divided into two, and makes the bonding after distribution
Layer melt feed is located at the both sides up and down of the intermediate layer melt feed respectively；S2：The casting machine die head is to each melt feed
Carry out compound, and be extruded into film body；S3：The film body being extruded into is stretched, cooling and shaping, and to extexine corona at
Reason, deburring, obtains the novel environment friendly pre-coating film.
Applied to each above-mentioned technical proposal, the diameter of four single screw rods from top to bottom arranged is respectively：It is a diameter of
70mm, a diameter of 90mm, a diameter of 150mm and a diameter of 90mm single screw rod, wherein, what the raw material on the top layer was correspondingly placed into
A diameter of 70mm of single screw rod；The single screw rod that first tack coat, the raw material of the second tack coat are correspondingly placed into it is a diameter of
90mm；The a diameter of 150mm for the single screw rod that the raw material in the intermediate layer is correspondingly placed into；The raw material of the hot melt adhesive layer is correspondingly put
A diameter of 90mm of the single screw rod entered.
Applied to each above-mentioned technical proposal, the casting head is T-shaped mould head.
Using such scheme, the present invention uses the tape casting film processed, by four layer polypropylenes and one layer of ethene-vinyl acetate
Copolymer is disposably coextruded the polypropylene pre-membrane that generation thickness is 15-25 μm by casting technique, without being coated heating
Glue-line, silane coupling agent is not needed more, so that it may it is directly compound with printed matter progress hot pressing, production cost is greatly reduced, improves life
Produce efficiency.The tape casting is relative to double stretching method, and its equipment investment is few, and floor space is small, and film product thickness is uniform, extension at break
Rate is high.Because its film production is using casting technique, the elongation at break of film is high, therefore avoids common BOPP products
Printed matter after overlay film when being die cut machine-shaping, easily produce skinning even chip the problem of.
Brief description of the drawings
Fig. 1 is the structural representation of pre-coating film in the present invention；
Fig. 2 is the schematic diagram of the preparation method of pre-coating film in the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Present embodiments provide a kind of manufacture method of novel environment friendly pre-coating film and using pre- made from the manufacture method
Film.
See Fig. 1, the novel environment friendly pre-coating film of the embodiment of the present invention goes out casting films for five-layer co-squeezing, including from top to bottom successively
The top layer 1 of setting, the first tack coat 2, intermediate layer 3, the second tack coat 4 and hot melt adhesive layer 5；Wherein, top layer 1, the first tack coat
2nd, intermediate layer 3, the second tack coat 4 and hot melt adhesive layer 5 pass through die head integrally extrusion stretching, and pass through first tack coat respectively
2 and second adhesive linkage 4 by the top layer 1, the intermediate layer 3, the hot melt adhesive layer 5 respectively bonding form.
Specifically, top layer 1 is made up of extrusion grade polypropylene, slipping agent and antiblocking agent；Wherein, grade polypropylene is extruded
Mass fraction be 95-97wt%, the mass fraction of antiblocking agent is 3-5wt%, and the mass fraction of slipping agent is 0.1-
0.2wt%.Wherein, antiblocking agent is combined by one or more kinds of arbitrary proportions of silica, calcium carbonate or PMMA microballoons
Form.The effect of anti-blocking agent is the bumps for the projection or different relaxation shapes that many is formed on finished films surface so that film
There is certain roughness on surface, when film, which is stacked or rolled up, to be put together, can allow between film layer and retain a certain amount of air, from
And effective contact area between film is reduced, so as to have the function that to prevent film blocking.And slipping agent can be oleic acid acyl
Amine or erucyl amide.The effect of slipping agent is to be dispersed in by melting extrusion in film, is finally producing and using process
In move to film surface, form smooth layer, lower the coefficient of friction of film surface, be allowed to not mutual adhesion, separately unreel and divide
Cut more smoothly, and there is good opening performance.
First tack coat 2, the second tack coat 4 are made up of extrusion grade polypropylene, spinning grade polypropylene and antistatic additive；Its
In, the polyacrylic mass fraction of extrusion grade is 83-89wt%, and the polyacrylic mass fraction of spinning-grade is 10-15%, and surplus is anti-
Electrostatic agent.Antistatic additive is by one in ethoxylated fatty amine, quarternary ammonium salt compound, fatty acid ester, curing carbaminate
Kind or two or more arbitrary proportions combine.Antistatic additive can eliminate film in the production and use process because of the institute that rubs
Caused electrostatic.Antistatic additive is the stronger surfactant of migration, can be moved in film top layer over time；
Spinning grade polypropylene can increase the first tack coat, the bond effect of the second tack coat and other layers.
Intermediate layer 3 is made up of extrusion grade polypropylene and Stiffening agent；Wherein, the polyacrylic mass fraction of extrusion grade is 98-
99wt%, surplus are Stiffening agent.Stiffening agent can improve the deflection and rigidity of film.
Finally, hot melt adhesive layer 5 be by ethylene-vinyl acetate EVA mixtures and ethylene acrylic acid co polymer EAA mixing and
Into；Wherein, the mass fraction of ethylene-vinyl acetate EVA mixtures is 92%-95%, and surplus is ethylene acrylic acid co polymer
EAA.The content of vinyl acetate is 25-28wt%, melt index 3.0-5.0g/min in EVA.Hot melt adhesive layer is being heated and added
In the state of pressure, film can be made to be adjacent to bonding with printed matter surface.
Preferably, the thickness of top layer 1 is 3-6 μm；First tack coat 2, the thickness of the second tack coat 4 are
1.5-3μm；The thickness in the intermediate layer 3 is 6-12 μm；The thickness of the hot melt adhesive layer 5 is 3-6 μm.
The novel environment friendly pre-coating film of the embodiment of the present invention is using polypropylene PP and ethylene-vinyl acetate copolymer EVA mono-
The method of secondary property coextrusion curtain coating forms five-layer structure.Specifically the manufacture method comprises the following steps：
First by above-mentioned top layer 1, i.e. A layers, the first tack coat 2, i.e. B layers, intermediate layer 3, i.e. C layers, the second tack coat 4, i.e.,
D layers and hot melt adhesive layer 5, the i.e. raw material of E layers are put into four single screw rods respectively, 1. the diameter of four single screw rods is respectively
70mm、②90mm、③150mm、④90mm.Wherein the first tack coat (B layers) and the second tack coat (D layers) use same original
Material, same screw rod, by the distribution of the distributor in casting machine die head, the both sides up and down for being located at intermediate layer (C layers) respectively are allowed to,
See Fig. 2.Wherein, casting head is T-shaped mould head, and A to E layers passes through T-shaped mould head simultaneously, then fixed by extrusion, stretching, cooling
Type, extexine sided corona treatment, deburring, you can obtain upper surface tension force and be not less than 38mN/m, lower surface has hot melt adhesive layer
Novel environment friendly pre-coating film.
Thus, the present invention uses the tape casting film processed, and four layer polypropylenes and one layer of ethylene-vinyl acetate copolymer are led to
Cross casting technique and be disposably coextruded the polypropylene pre-membrane that generation thickness is (15-25) μm, without being coated hot melt adhesive layer, more
Do not need silane coupling agent, so that it may it is directly compound with printed matter progress hot pressing, production cost is greatly reduced, improves production efficiency,
Printed matter overlay film field will be applied to, common BOPP pre-coating films on the market can be replaced to a certain extent.In addition, the tape casting is relative
In double stretching method, its equipment investment is few, and floor space is small, and film product thickness is uniform, and elongation at break is high.Because its film is given birth to
Production is using casting technique, and the elongation at break of film is high, therefore the printed matter avoided after common BOPP products overlay film exists
Be die cut machine-shaping when, be also easy to produce skinning even chip the problem of.
It is specific embodiment below：
Example 1：
According to parts by weight：97 parts of grade polypropylene (RP320N Basels), antiblocking agent (silicon dioxide microsphere, 1-2 will be extruded
μm) 3 parts, it is 1. interior that 0.1 part of mixing of slipping agent (oleamide) is put into single screw rod；Will extrusion grade polypropylene (RP320N Basels) 88
2. part, 10 parts of spinning grade polypropylene (HM562N Basels) and 2 parts of mixing of antistatic additive (quarternary ammonium salt compound) are put into single screw rod
It is interior；Extrusion grade polypropylene 99 parts of (RP320N Basels) mixes to be put into single screw rod 3. interior with Stiffening agent (NA11 Asahi Chemical Industries)；Will
7 parts of 93 parts of EVA (28-03 Ahs Kerma (unit of kinetic energy)) and EAA (6100 Tao Shi) mixes that to be put into single screw rod 4. interior.
Wherein, single screw rod 1., single screw rod 2., each area's temperature in one to seven area of single screw rod 3. be respectively： 180/190/
195/200/210/215/220℃.Each area's temperature in one to seven area of single screw rod 4. is respectively： 170/175/180/190/
200/205/210℃.Temperature at T-shaped mould head is 220 DEG C.Five layer films are compound at T pattern heads, and drawn, cooling are fixed
Type, the process such as extexine sided corona treatment, deburring, it is the cast polypropylene pre-coating film that 15 μm of width are 3.4m to finally obtain thickness
(light film), the thickness of wherein A to E layers are respectively：3 μm, 1.5 μm, 6 μm, 1.5 μm and 3 μm.Film upper surface tension force is
38mN/m。
Example 2：
According to parts by weight：93 parts of grade polypropylene (4342C3 Exxons), organic matting agent polystyrene (AT-100 will be extruded
Louis) 4 parts, 3 parts of antiblocking agent (calcium carbonate microspheres, 0.5-2 μm), 0.1 part of mixing of slipping agent (erucyl amide) is put into single spiral shell
Bar is 1. interior；83 parts of grade polypropylene (4342C3 Exxons), 15 parts of spinning grade polypropylene (H19G-01 Ineos) will be extruded and resisted
It is 2. interior that 2 parts of mixing of electrostatic agent (ethoxylated fatty amine) are put into single screw rod；Will 99 parts of extrusion grade polypropylene (4342C3 Exxons)
Mix that to be put into single screw rod 3. interior with Stiffening agent (the high Son of 3262A)；By 95 parts of EVA (28-03 Ahs Kerma (unit of kinetic energy)) and EAA (5050 Tao Shi) 5
It is 4. interior that part mixing is put into single screw rod.
Wherein, single screw rod 1., single screw rod 2., each area's temperature in one to seven area of single screw rod 3. be respectively： 185/195/
200/205/210/215/220℃.Each area's temperature in single screw rod 4. one to seven area is respectively： 175/180/185/190/200/
205/210℃.Temperature at T-shaped mould head is 215 DEG C.Five layer films are compound at T pattern heads, drawn, cooling and shaping, outer
The processes such as top layer sided corona treatment, deburring, it is the cast polypropylene pre-coating film (mute film) that 20 μm of width are 3.4m to finally obtain thickness,
The thickness of wherein A to E layers is respectively：4 μm, 2 μm, 8 μm, 2 μm and 4 μm.Film upper surface tension force is 40mN/m.
By example 1, example 2 is compared with conventional common BOPP light film pre-coating films, the performance of the mute film pre-coating films of BOPP, such as
Shown in table 1.
Table 1：
As it can be seen from table 1 example 1 and 2 and commercially available common BOPP light film pre-coating films, BOPP is mute, and film pre-coating film compares,
The elongation at break of vertical and horizontal, which has, significantly to be lifted, therefore overcomes common BOPP film, due to elongation at break
During low and printed matter after overlay film cross cutting machine-shaping, be also easy to produce skinning even chip the problem of.
On the other hand, the commercially available common BOPP light film pre-coating films of the tensile strength ratio of example 1 and 2, the mute film pre-coating films of BOPP
Low, this is due to caused by being cast processing technology in itself.But in actual continuous paper film covering production process, example 1 and 2
Film do not have because the drafting force of equipment produces uncontrollable plastic deformation, therefore after its satisfaction the processing of road overlay film quality
It is required that.
After example 1 and 2 and printed matter are compound, through burn-in test (condition 1：54 DEG C of temperature, relative humidity 88%, 48 hours；
Condition 2：- 20 DEG C of temperature, 24 hours), foaming and paper membrane aliquation phenomenon do not occur for product after its overlay film, and post-press finishing technique is as scalded
Gold, local UV etc., it can be carried out on the surface after overlay film, meet common process requirement.
These are only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
All any modification, equivalent and improvement made within principle etc., should be included in the scope of the protection.
Claims (10)
- A kind of 1. novel environment friendly pre-coating film, it is characterised in that：Sequentially include from top to bottom：Top layer, the first tack coat, intermediate layer, Second tack coat and hot melt adhesive layer；Wherein, the top layer, the first tack coat, intermediate layer, the second tack coat and hot melt adhesive layer are integrally extruded by die head respectively Stretching, and divided the top layer, the intermediate layer, the hot melt adhesive layer by first tack coat and second adhesive linkage It Nian Jie not form.
- 2. novel environment friendly pre-coating film according to claim 1, it is characterised in that：The skin depth is 3-6 μm；Described One tack coat, the thickness of the second tack coat are 1.5-3 μm；The thickness in the intermediate layer is 6-12 μm；The hot melt adhesive layer Thickness is 3-6 μm.
- 3. novel environment friendly pre-coating film according to claim 1, it is characterised in that：The surface on the top layer is provided with some dash forward Rise or the bumps of different relaxation shape；Also, the surface on the top layer is additionally provided with a smooth layer.
- 4. novel environment friendly pre-coating film according to claim 4, it is characterised in that：The top layer be by extrusion grade polypropylene, Slipping agent and antiblocking agent composition；Wherein, the polyacrylic mass content of extrusion grade is 95-97wt%, the mass content of slipping agent For 0.1-0.2wt%, surplus is antiblocking agent；First tack coat and second tack coat are material structure identical adhesive linkage, wherein, first tack coat, Second tack coat is made up of extrusion grade polypropylene, spinning grade polypropylene and antistatic additive；Wherein, the polyacrylic quality of extrusion grade Content is 83-89wt%, and the polyacrylic mass content of spinning-grade is 10-15wt%, and surplus is antistatic additive；The intermediate layer is made up of extrusion grade polypropylene and Stiffening agent；Wherein, the polyacrylic mass content of extrusion grade is 98- 99wt%, surplus are Stiffening agent；The hot melt adhesive layer is mixed by ethylene-vinyl acetate mixture and ethylene acrylic acid co polymer；Wherein, second The mass content of alkene-vinyl acetate ester admixture is 92%-95%, and surplus is ethylene acrylic acid co polymer.
- 5. novel environment friendly pre-coating film according to claim 4, it is characterised in that：The slipping agent can be oleamide or mustard Sour acid amides；Also, the antiblocking agent is by one or more kinds of arbitrary proportion groups of silica, calcium carbonate or PMMA microsphere Conjunction forms.
- 6. according to the novel environment friendly pre-coating film described in claim 4, it is characterised in that：The antistatic additive can be by ethoxylated fatty The combination of any of the above ratio of one or both of amine, quarternary ammonium salt compound, fatty acid ester, curing carbaminate and Into.
- 7. according to the novel environment friendly pre-coating film described in claim 4, it is characterised in that：In the ethylene-vinyl acetate mixture The mass content of contained vinyl acetate is 25-28wt%, melt index 3.0-5.0g/min.
- 8. the manufacture method of the novel environment friendly pre-coating film any one of a kind of claim 1-7, it is characterised in that including such as Lower step：S1：By form the top layer, the first tack coat and the second tack coat, intermediate layer, hot melt adhesive layer raw material be respectively fed to by Plasticizing makes plasticizing be respectively fed to casting machine die head into the melt feed of melt into melt in four single screw rods of up to lower arrangement In, and the distributor for making the melt feed of the first tack coat and the second tack coat enter in casting machine die head is divided into two, And make up and down both sides of the tack coat melt feed after distribution respectively positioned at the intermediate layer melt feed；S2：The casting machine die head is compound to the progress of each melt feed, and is extruded into film body；S3：The film body being extruded into is stretched, cooling and shaping, and to extexine sided corona treatment, deburring, obtained described new Environmentally friendly pre-coating film.
- 9. manufacture method according to claim 8, it is characterised in that：The diameter of four single screw rods from top to bottom arranged point It is not：A diameter of 70mm, a diameter of 90mm, a diameter of 150mm and a diameter of 90mm single screw rod, wherein, the original on the top layer Expect a diameter of 70mm of single screw rod being correspondingly placed into；Single spiral shell that first tack coat, the raw material of the second tack coat are correspondingly placed into A diameter of 90mm of bar；The a diameter of 150mm for the single screw rod that the raw material in the intermediate layer is correspondingly placed into；The hot melt adhesive layer The a diameter of 90mm for the single screw rod that raw material is correspondingly placed into.
- 10. manufacture method according to claim 8 or claim 9, it is characterised in that：The casting head is T-shaped mould head.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710801894.8A CN107400474A (en) | 2017-09-07 | 2017-09-07 | A kind of novel environment friendly pre-coating film and its manufacture method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710801894.8A CN107400474A (en) | 2017-09-07 | 2017-09-07 | A kind of novel environment friendly pre-coating film and its manufacture method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107400474A true CN107400474A (en) | 2017-11-28 |
Family
ID=60397597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710801894.8A Pending CN107400474A (en) | 2017-09-07 | 2017-09-07 | A kind of novel environment friendly pre-coating film and its manufacture method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107400474A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108546523A (en) * | 2018-05-10 | 2018-09-18 | 重庆新康意安得达尔新材料有限公司 | A kind of metal surface pre-coating film |
| CN110699000A (en) * | 2019-10-11 | 2020-01-17 | 上海固柯胶带科技有限公司 | Film material for grinding and packaging semiconductor |
| CN113683979A (en) * | 2020-09-19 | 2021-11-23 | 江苏惠沣环保科技有限公司 | Preparation facilities of hot melt adhesive membrane of bonding PP material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003062957A (en) * | 2001-08-29 | 2003-03-05 | Japan Polychem Corp | Film for print laminate |
| CN102794966A (en) * | 2012-08-06 | 2012-11-28 | 北京康得新复合材料股份有限公司 | Glue-free bidirectional stretching polypropylene film used for paper-plastic composite and preparation method thereof |
| CN105172300A (en) * | 2015-09-17 | 2015-12-23 | 杭州中塑包装材料有限公司 | Multi-layer coextrusion cast film |
-
2017
- 2017-09-07 CN CN201710801894.8A patent/CN107400474A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003062957A (en) * | 2001-08-29 | 2003-03-05 | Japan Polychem Corp | Film for print laminate |
| CN102794966A (en) * | 2012-08-06 | 2012-11-28 | 北京康得新复合材料股份有限公司 | Glue-free bidirectional stretching polypropylene film used for paper-plastic composite and preparation method thereof |
| CN105172300A (en) * | 2015-09-17 | 2015-12-23 | 杭州中塑包装材料有限公司 | Multi-layer coextrusion cast film |
Non-Patent Citations (1)
| Title |
|---|
| 黎勇等: "防粘连剂在BOPP薄膜中的应用技术", 《塑料包装》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108546523A (en) * | 2018-05-10 | 2018-09-18 | 重庆新康意安得达尔新材料有限公司 | A kind of metal surface pre-coating film |
| CN110699000A (en) * | 2019-10-11 | 2020-01-17 | 上海固柯胶带科技有限公司 | Film material for grinding and packaging semiconductor |
| CN113683979A (en) * | 2020-09-19 | 2021-11-23 | 江苏惠沣环保科技有限公司 | Preparation facilities of hot melt adhesive membrane of bonding PP material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102732174B (en) | Pre-coating film and preparation method for same | |
| DE69909521T2 (en) | EXTRUSION COATING METHOD FOR MANUFACTURING HIGHLY PROXIMITY PROTECTIVE AND DECORATIVE COATINGS | |
| CN107351497A (en) | A kind of sense of touch type is without silane coupling agent BOPP precoating basement membranes and preparation method thereof | |
| CN102333652B (en) | Method for making multi-layer print media by extrusion coating | |
| CN107400474A (en) | A kind of novel environment friendly pre-coating film and its manufacture method | |
| CN102173156A (en) | Biaxial tension polyethylene film and preparation method thereof | |
| CN101096421A (en) | Method for producing polyolefin elastomer false skin and product thereof | |
| CN109278387A (en) | A kind of high-barrier heat-sealing type BOPP matt film and preparation method thereof | |
| US20150044434A1 (en) | Systems and Methods for Generating Surface Patterns on Composite Building Materials | |
| CN101175630A (en) | Transverse-direction, elastomeric, breathable film | |
| CN107849399A (en) | Adhesive film and adhesive film cylinder | |
| CN101451004A (en) | Film for producing composite paper-like film and paper-like film and method for producing the same | |
| CN101125933B (en) | Plastic film and preparation method thereof | |
| DE4423883A1 (en) | Thermoformable film, process for its production and use of the same | |
| CN207375990U (en) | A kind of novel environment friendly pre-coating film | |
| CN101633262B (en) | Non-adhesive biaxially-oriented polypropylene film for hot lamination and preparation method thereof | |
| KR101265551B1 (en) | Oriented Polypropylene Film and Composition for Adhesive Layer | |
| CN107177242A (en) | TPO automotive interior material of resistance to alcohol and preparation method thereof | |
| CN101885218B (en) | A kind of non-PVC series is through the calendering polyolefin adhesive plaster made of machining and method for making thereof | |
| CN110696458A (en) | Isolating membrane for self-adhesive waterproof roll and preparation method thereof | |
| US20110305896A1 (en) | Multi-Layer Sheet Structure Including An Acrylic Outer Layer | |
| CN101633259B (en) | Non-adhesive hot-laminating polyethylene film and preparation method thereof | |
| KR102705426B1 (en) | Manufacturing method of multilayer adhesive film having polarity for composite panel and steel sheet | |
| CN1532042A (en) | Method for producing laminated foam sheet | |
| CN114889283B (en) | BOPET film with high adhesive strength and used for primer-free precoating film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171128 |
|
| RJ01 | Rejection of invention patent application after publication |