CN104710947B - A kind of metal surface pre-coating film and preparation method thereof - Google Patents
A kind of metal surface pre-coating film and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of metal surface pre-coating film and preparation method thereof.Metal surface of the present invention pre-coating film, includes the most successively: substrate layer, intermediate layer and hot melt adhesive layer, and described substrate layer, intermediate layer and hot melt adhesive layer are mutually combined closely；Described substrate layer includes the most successively: hardening coat, substrate layer and printing layer, and described substrate layer, hardening coat and printing layer are mutually combined closely.Compared with the pre-coating film of existing metal surface, the pre-coating film that the present invention provides not only has wear-resisting anti-zoned performance, and the adhesion between pre-coating film and monolithic metal can be strengthened, meet water boiling resistance in post processing, the requirement of resistance to bending, reach the requirement that film-covered iron is tested by subsequent processing operations, and its preparation method makes full use of existing pre-coating film production line, effectively reduce cost prepared by pre-coating film, and compare for dry type covers iron thin film goods, significantly reduce the cost covering iron thin film He covering iron process.
Description
Technical field
The present invention relates to film coating technique field, metal surface, particularly relate to the preparation method of a kind of metal surface pre-coating film and this pre-coating film.
Background technology
It is applied to the film coated plate of tank industry processed, is commonly called as film-covered iron (Laminated Steel), be to use PET, PVC, VCM or PP thin film and sheet metal (galvanized sheet, cold-reduced sheet, aluminium sheet, corrosion resistant plate) carry out laminating forming, interior painting, outer painting technology can be replaced.Concrete preparation method is by covered rearing with plastic film on iron plate, middle uses binding agent, after heating pressurized treatments, makes together with two kinds of binding substances of different nature of plastic sheeting and iron plate, forms the incrustation process technology of ferrum/mould unification.Monolithic metal is played protection and decorative effect by it, can be widely applied to mental package field, such as chemical barrel, food cans, foreign material tank etc., it is possible to be applied to furnishing fields, such as home appliance panel, door-plate etc..
Traditional canister/bucket resist technology mainly uses the method for inner-wall spraying epoxy resin to process, but contains the harmful substance of bisphenol-A class (Bis-phenol A) in this coating, is a kind of internationally recognized environmental hormone, to human body infringement greatly.
Present commonly used dry type film coating technique comes metallic plate overlay film, and this technique uses dry type composite production line, by solvent-borne type glue application on metallic plate, with film bond after oven for drying.But in the application of this technology, drying course having solvent volatilization, environment can be worked the mischief by the volatilization of solvent, and the iron plate after overlay film the most easily has dissolvent residual, dries and entirely also can not produce bubble and bonding hypodynamic problem；And after overlay film, needing film-covered iron is carried out high-temperature maturing guarantee cohesive force, this technique both consumed energy, and production efficiency is the lowest.
It addition, along with the development of technology, metal film coated plate is more and more higher to the requirement of film product, thin film is not only needed to possess the high strength bonding performance between metallic plate, also require film coated plate surface abrasion resistance, be difficult to scratch, additionally, some also requires that film coated plate has the performance of water boiling resistance.
Based on drawbacks described above and demand; the invention provides and a kind of directly can cover pre-coating film in metal surface by hot pressing; and the method providing overlay film; the omnidistance solvent-free volatilization of the method; precoated metal is without chemical residual; production process energy-saving and environmental protection, safe efficient, can realize protecting environment simultaneously, keep the safety in production, use purpose safely.
Summary of the invention
It is an object of the invention to propose a kind of metallic plate pre-coating film and preparation method thereof.There is between described pre-coating film and monolithic metal good bonding force, there is excellent anti-wear performance and possess water boiling resistance performance.
Metallic plate pre-coating film of the present invention, includes the most successively: substrate layer, intermediate layer and hot melt adhesive layer, and described substrate layer, intermediate layer and hot melt adhesive layer are mutually combined closely；
Wherein, described intermediate layer is formed by the mixture including polyurethane or acrylic acid ester emulsion and firming agent；Intermediate layer is as substrate layer and the binder couse of hot melt adhesive layer, the adhesive force (adhesive force is up to 3N/15mm) not only can being greatly enhanced between two-layer, and the pre-coating film using this intermediate layer to be formed also can meet the requirement of resistance to 100 DEG C of more than decocting in water 30min.
Wherein said polyurethane is polyaminoester emulsion commonly used in the art, and polyaminoester emulsion generally refers to oligomer polyol, chain extender, diisocyanate as raw material, the emulsion that the they prepared with usual method is formed in water.Commercially available formula has a variety of, substantially can meet the needs in intermediate layer of the present invention.
Described acrylic acid ester emulsion can be selected for acrylic acid ester emulsion commonly used in the art, typically can be selected for acrylic acid methyl ester. etc..
Described hot melt adhesive layer is formed by modified EVA (ethylene-vinyl acetate copolymer), PE (polyethylene), EEA (ethylene-ethylacrylate resin), EAA (ethylene acrylic acid co polymer) or EMA (ethylene-methyl acrylate copolymer)；Modified hot melt adhesive layer is as the compound surface of pre-coating film and the metal surface hot pressing of the present invention, it is possible to strengthens the cohesive force between pre-coating film and iron plate, also is able to meet the requirement of subsequent processing operations simultaneously.
In hot melt adhesive layer, described modified EVA (ethylene-vinyl acetate copolymer), PE (polyethylene), EEA (ethylene-ethylacrylate resin), EAA (ethylene acrylic acid co polymer) or EMA (ethylene-methyl acrylate copolymer) can select the type of suitable film forming commonly used in the art, particularly, typically select EVA more.
Described substrate layer includes the most successively: hardening coat, substrate layer, and described substrate layer, hardening coat are mutually combined closely；Described hardening coat is formed by the mixture including aqueous pu dispersions and firming agent.
Described substrate layer also includes printing layer, and described substrate layer includes the most successively: hardening coat, substrate layer and printing layer, and described substrate layer, hardening coat and printing layer are mutually combined closely.
The thickness of each composition layer of heretofore described metal pre-coat film can select according to the thickness of the various products required for this area, particularly, it is 8-50 μm that the present invention proposes the thickness of described substrate layer, the thickness of described hardening coat is 2-10 μm, the thickness of printing layer is 0.5-4 μm, the thickness in intermediate layer is 0.5-3 μm, and the thickness of hot melt adhesive layer is 8-30 μm.
The thickness of substrate layer is preferably 9～15 μm.
The thickness of hardening coat is preferably 2.5-4 μm.
The thickness of printing layer is preferably 2-3 μm.
The thickness of hot melt adhesive layer is preferably 12-19 μm.
In described hardening coat, the percentage by weight of aqueous pu dispersions is 15%-50%；And the percentage by weight of described firming agent is less than 15%, remaining composition includes levelling agent, film former, thickening agent and deionized water diluent.
Described levelling agent is silicone levelling agent, and described film former is gylcol ether, glycol ether ester or ester alcohols, and described thickening agent includes that acrylate and/or methacrylate copolymer, described diluent are deionized water.
Wherein, the firming agent in described hardening coat is aliphatic isocyanates class, such as hexamethylene diisocyanate or isophorone diisocyanate etc., by arranging hardening coat so that the surface of pre-coating film has anti-wear performance (hardness is up to more than H).
It addition, the percentage by weight of polyurethane or acrylic acid ester emulsion is 30%-60% in described intermediate layer, the percentage by weight of described firming agent is less than 10%, and remaining composition includes defoamer, levelling agent and diluent；Described defoamer is organosilicon emulsion defoaming agents, and described levelling agent is silicone levelling agent；Described diluent is deionized water.
Wherein, the firming agent in described intermediate layer is isocyanates, such as hexamethylene diisocyanate or isophorone diisocyanate etc..
The coating dry weight in described intermediate layer is 0.2-3g/m2。
The coating dry weight in intermediate layer is preferably 1.0-2.5g/m2。
Described substrate layer is biaxial stretching polyester layer；
Described printing layer is exactly that pattern uses method commonly used in the art be printed on substrate layer upper surface, and the printing-ink of printing layer of the present invention is preferably Japan (Tianjin Toyo Ink Co., Ltd.) or the intaglio plate composite inks for plastics of DIC (Shanghai DiC Ink Co., Ltd)；By arranging printing layer, the market demand to different colours overlay film product can be met.
Preferably, when described hot melt adhesive layer is formed by EVA, wherein the VA percentage by weight in hot melt adhesive layer is 10%-30% and melt index is 10-25g/10min；Preferably, the VA percentage by weight in PUR resin is 15%-20%, and melt index is 10-20g/10min.
When described PUR is made up of LDPE, melt index is 5-25g/10min, it is preferable that melt index is 6-20g/10min.
When described hot melt adhesive layer is formed by PE, its melt index is 5-25g/10min.
The metal pre-coat film of the present invention has excellent anti-wear performance and possesses water boiling resistance performance, except relevant to arranging of above layers, it is most important that relevant to its preparation method.
Therefore the present invention also provides for the preparation method of above-mentioned metal pre-coat film.
The preparation method of metal pre-coat film of the present invention, comprises the following steps:
(1) lower surface being coated on described substrate layer of the mixture of dispersions of polyurethanes and firming agent will be included, form hardening coat；
(2) use printing-ink to print at substrate layer upper surface, form printing layer, described substrate layer, described hardened layer and described printing layer constitute substrate layer；
(3) upper surface at described printing layer is coated with the mixture formed by polyurethane or acrylic acid ester emulsion and firming agent and dries, and forms intermediate layer；
(4) coat modified EVA at described intermediate layer upper surface, PE, EEA, EAA or EMA are to form hot melt adhesive layer, thus obtain pre-coating film.
Further, described preparation method also includes, in step (3), first the upper surface of described printing layer is carried out sided corona treatment, the surface dynes value making described printing layer reaches more than 36, being coated with the mixture formed by polyurethane or acrylic acid ester emulsion and firming agent at the described printing layer upper surface through sided corona treatment and dry the most again, described drying temperature is 65-95 DEG C.
Or further, polarity in view of hot melt adhesive layer is more weak, in order to make product (i.e. the pre-coating film of the embodiment of the present invention with leaflet recombination process in) in the application have good cohesive force, preferably, the surface of hot melt adhesive layer is also carried out sided corona treatment, to obtain a certain amount of polar group.Represent sided corona treatment degree with wetting tension (i.e. dyne value), then after sided corona treatment the surface dynes value of hot melt adhesive layer between 46-54.
Specifically, the base material 1 being loaded with the intermediate layer 2 of solidification is sent to recombination site by the deflector roll of extrusion composite production line, extruder extruding and hot melting glue-line 3 simultaneously.It is provided with ozonator at the recombination site of neighbouring extrusion composite production line, the ozone produced by ozonator is jetted in the EVA casting films of extruder extrusion, the concentration of ozone is 40%, power 800W, gas flow is 3.5SCXFM, and ozone makes the cast surface of resin produce some polar groups, forms firm interface binding power with intermediate layer, then base material is combined by the extruding of the nip roller of extrusion composite production line recombination site with curtain coating, forms composite membrane.
Wherein, before the coating, the mixture to described polyurethane or acrylic emulsion with firming agent carry out 40-1000 turn/the low speed dispersion of min processes.
The time that described low speed dispersion processes is 6-15 minute.
In described step (1), before the coating, first mixture to described dispersions of polyurethanes Yu firming agent carry out 2000-5000 turn/high speed dispersion of min processes.
The time that described high speed dispersion processes is 10-20 minute.
Compared with the pre-coating film of existing metal surface, the pre-coating film that the present invention provides not only has wear-resisting anti-zoned performance, and the adhesion between pre-coating film and monolithic metal can be strengthened, meet water boiling resistance in post processing, the requirement of resistance to bending, reach the requirement that film-covered iron is tested by subsequent processing operations, and its preparation method makes full use of existing pre-coating film production line, effectively reduce cost prepared by pre-coating film, and compare for dry type covers iron thin film goods, significantly reduce the cost covering iron thin film He covering iron process.
Accompanying drawing explanation
Fig. 1 is the structural representation of pre-coating film according to embodiments of the present invention；
Fig. 2 is the structural representation of the substrate layer of pre-coating film according to embodiments of the present invention；
Wherein, 1 is substrate layer；2 is intermediate layer；3 is hot melt adhesive layer；11 is substrate layer；12 is hardening coat；13 is printing layer；111 is the faying face between printing layer 13 and substrate layer 11；112 is the faying face between hardening coat 12 and substrate layer 11.
Detailed description of the invention
For further illustrating the present invention, special offer specific examples below, the example of described embodiment is shown in the drawings.Following embodiment is intended to for explaining the present invention, rather than limits the scope of the invention.
In the present invention, unless otherwise clearly defined and limited, fisrt feature second feature it " on " or D score can include that the first and second features directly contact, it is also possible to include that the first and second features are not directly contact but by the other characterisation contact between them.And, fisrt feature second feature " on ", " top " and " above " include that fisrt feature directly over second feature and oblique upper, or is merely representative of fisrt feature level height higher than second feature.Fisrt feature second feature " under ", " lower section " and " below " include that fisrt feature directly over second feature and oblique upper, or is merely representative of fisrt feature level height less than second feature.
As being not specifically stated, equipment conventional in the equipment of employing is all this area in the present embodiment, the main ingredient of employing is all main ingredient commonly used in the art.
Embodiment 1
As depicted in figs. 1 and 2, pre-coating film according to embodiments of the present invention, including substrate layer 1, intermediate layer 2 and hot melt adhesive layer 3.
Specifically, substrate layer 1 includes substrate layer 11, hardening coat 12 and printing layer 13.
Wherein, substrate layer 11 is biaxial stretching polyester (BOPET) layer.The thickness of substrate layer 11 can be 8-50 μm, and thickness is preferably 9～15 μm.
Following steps prepare metal surface of the present invention precoated shet.
Step one: provide biaxial stretching polyester layer as substrate layer 11.
Step 2: utilize coating apparatus to be coated on the first face 112 of substrate layer 11 hardening coat 12 including the mixture of dispersions of polyurethanes and firming agent.
Step 3: utilize printer to be coated on the second face 111 of substrate layer 11, to form base material 1 on the printing layer 13 including Japan's composite inks for plastics.
Step 4: be coated with the mixed liquor of polyurethane and the firming agent prepared by said ratio on printing layer 13, and utilize drying plant to carry out drying and processing, makes urethane cures print on layer 13 to form intermediate layer 2.
Before step 4 is implemented, first printing layer 13 surface of base material 1 is carried out sided corona treatment, a certain amount of such as the polar group of carbonyl class to obtain.The surface dynes value printing layer 13 after sided corona treatment can reach more than 36.Drying temperature and may be provided in 85 DEG C, the thickness in the intermediate layer 2 after drying is about 2 μm.
Step 5: EVA thermosol glue-line 3 hot pressing is compound on intermediate layer 2 by extrusion equipment complex.
Specifically, the base material 1 being loaded with the intermediate layer 2 of solidification is sent to recombination site by the deflector roll of extrusion composite production line, extruder extruding and hot melting glue-line 3 simultaneously.It is provided with ozonator at the recombination site of neighbouring extrusion composite production line, the ozone produced by ozonator is jetted in the EVA casting films of extruder extrusion, the concentration of ozone is 40%, power 800W, gas flow is 3.5SCXFM, ozone makes the cast surface of resin produce some polar groups, and then base material 1 is combined by the extruding of the nip roller of extrusion composite production line recombination site with curtain coating, forms composite membrane.
The most stretched, cooling, the thickness of hot melt adhesive layer is 15 μm after deburring.Thus obtain preparation film.
Additionally, polarity in view of hot melt adhesive layer 3 is more weak, in order to make product (i.e. the pre-coating film of the embodiment of the present invention with leaflet recombination process in) in the application have good cohesive force, preferably, the surface of hot melt adhesive layer 3 is carried out sided corona treatment, to obtain a certain amount of polar group.Represent sided corona treatment degree with wetting tension (i.e. dyne value), then after sided corona treatment the surface dynes value of hot melt adhesive layer 3 between 46-54.
The performance of the pre-coating film of preparation meets national standard and industry standard.Metal surface water boiling resistance PET pre-coating film technical requirement was shown in Table for 1 (wherein MD is for longitudinally, and TD is horizontal).
Table 1 metal surface water boiling resistance PET pre-coating film technical requirement
Embodiment 2
The embodiment of the present invention 2 and the difference of embodiment 1 are that hot melt adhesive layer 3 uses modified LDPE.Owing to the melt index of PE is higher, its required processing temperature is the highest.In extruder device temperature controls, the temperature that extruder is cast is set to the processing temperature of modified PE.
In embodiment 2, other steps are all identical with corresponding steps in embodiment 1, do not repeat them here.The performance of the pre-coating film of preparation meets national standard and industry standard.Metal surface water boiling resistance PET pre-coating film technical requirement was shown in Table for 1 (wherein MD is for longitudinally, and TD is horizontal).
Embodiment 3
It is not print layer 13 with embodiment 2 difference.The performance of the pre-coating film of preparation meets national standard and industry standard.Metal surface water boiling resistance PET pre-coating film technical requirement was shown in Table for 1 (wherein MD is for longitudinally, and TD is horizontal).
Although above it has been shown and described that embodiments of the invention, it is understandable that, above-described embodiment is exemplary, being not considered as limiting the invention, above-described embodiment can be changed in the case of without departing from the principle of the present invention and objective, revises, replace and modification by those of ordinary skill in the art within the scope of the invention.
Claims (11)
1. a metal surface pre-coating film, it is characterised in that include the most successively: substrate layer,
Intermediate layer and hot melt adhesive layer, described substrate layer, intermediate layer and hot melt adhesive layer are mutually combined closely；Wherein,
Described intermediate layer is formed by the mixture including polyurethane or acrylic acid ester emulsion and firming agent；Described hot melt
Glue-line is formed by modified EVA, PE, EEA, EAA or EMA；
Described substrate layer includes the most successively: hardening coat, substrate layer, described substrate layer, hard
Change coating mutually to combine closely；Described hardening coat is by including the mixed of aqueous pu dispersions and firming agent
Compound is formed.
Metal surface the most according to claim 1 pre-coating film, it is characterised in that described base material
Layer also includes printing layer, and described substrate layer includes the most successively: hardening coat, substrate layer and print
Brush layer, described substrate layer, hardening coat and printing layer are mutually combined closely.
3. metal surface as claimed in claim 2 pre-coating film, it is characterised in that described substrate layer
Thickness be 8-50 μm, the thickness of described hardening coat is 2-10 μm, printing layer thickness be 0.5-4 μm.
4. metal surface as claimed in claim 2 pre-coating film, it is characterised in that described substrate layer
Thickness be 9～15 μm；The thickness of hardening coat is 2.5-4 μm；The thickness of printing layer is 0.5-3 μm.
5. metal surface as claimed in claim 1 pre-coating film, it is characterised in that described intermediate layer
Thickness be 0.5-3 μm, the thickness of hot melt adhesive layer is 8-30 μm.
6. the metal surface pre-coating film as described in claim 1 or 5, it is characterised in that described heat
The thickness of melten gel layer is 12-19 μm.
7. the preparation method of the metal surface pre-coating film as described in claim 1-6 is arbitrary, including with
Lower step:
(1) being coated under described substrate layer of the mixture of dispersions of polyurethanes and firming agent will be included
Surface, forms hardening coat；
(2) use printing-ink substrate layer upper surface print, formed printing layer, by described substrate layer,
Described hardening coat and described printing layer constitute substrate layer；
(3) upper surface at described printing layer is coated with by polyurethane or acrylic acid ester emulsion and firming agent shape
Become mixture and dry, formed intermediate layer；
(4) modified EVA, PE, EEA, EAA or EMA are coated at described intermediate layer upper surface
To form hot melt adhesive layer, thus obtain pre-coating film.
8. preparation method as claimed in claim 7, it is characterised in that in step (3), the most right
The upper surface of described printing layer carries out sided corona treatment, make the surface dynes value of described printing layer reach 36 with
On, it is coated with by polyurethane or acrylate breast at the described printing layer upper surface through sided corona treatment the most again
Mixture that liquid and firming agent are formed also is dried, and described drying temperature is 65-95 DEG C.
9. preparation method as claimed in claim 7 or 8, it is characterised in that at the table of hot melt adhesive layer
Face is also carried out sided corona treatment, makes after sided corona treatment the surface dynes value of hot melt adhesive layer between 46-54.
10. preparation method as claimed in claim 7, it is characterised in that in step (3), is being coated with
Before cloth, the mixture of described acrylic acid ester emulsion Yu firming agent is carried out 40-1000 and turns/the low speed of min
Dispersion processes；The time that described low speed dispersion processes is 6-15 minute.
11. preparation methoies as claimed in claim 7, it is characterised in that in described step (1),
Before the coating, first mixture to described dispersions of polyurethanes with firming agent carries out 2000-5000 and turns
The high speed dispersion of/min processes；The time that described high speed dispersion processes is 10-20 minute.
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| CN106957608A (en) * | 2016-01-08 | 2017-07-18 | 北京康得新功能材料有限公司 | Film-covered iron pre-coating film and preparation method thereof |
| CN107474268B (en) * | 2017-07-25 | 2021-01-26 | 深圳市联星服装辅料有限公司 | High-temperature-resistant waterproof film and manufacturing method thereof |
| CN108624245A (en) * | 2018-05-10 | 2018-10-09 | 重庆新康意安得达尔新材料有限公司 | A kind of environmental protection pre-coating film and preparation method thereof |
| CN108641621A (en) * | 2018-05-10 | 2018-10-12 | 重庆新康意安得达尔新材料有限公司 | A kind of metal surface pre-coating film and preparation method thereof |
| 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 |
| CN109694660A (en) * | 2018-10-11 | 2019-04-30 | 福建鸿利印刷材料工贸有限公司 | A kind of environmental protection pre-coating film and preparation method thereof |
| CN112063319A (en) * | 2020-09-14 | 2020-12-11 | 福建泰安预涂膜有限公司 | High-temperature-resistant and water-resistant pre-coating film and preparation process and application thereof |
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| CN202671486U (en) * | 2012-07-04 | 2013-01-16 | 北京康得新复合材料股份有限公司 | BOPP (Biaxially-Oriented Polypropylene) lamination film |
| CN202912881U (en) * | 2012-07-04 | 2013-05-01 | 北京康得新复合材料股份有限公司 | Two-way stretch tackifying precoating film |
| CN103555216B (en) * | 2013-10-28 | 2015-09-30 | 中国印刷科学技术研究所 | One can complete biolytic pre-coating film |
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