CN103448334A - Ultraviolet-resistant big-breadth low-temperature pre-coated film and preparation method thereof - Google Patents
Ultraviolet-resistant big-breadth low-temperature pre-coated film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an ultraviolet-resistant big-breadth low-temperature pre-coated film and a preparation method thereof. The pre-coated film comprises an external layer, a functional layer and a middle layer positioned between the external layer and the functional layer, wherein the external layer is a biaxially-oriented polyethylene terephthalate film; the middle layer is a polyethyleneimine water solution layer; and the functional layer is a film composed of a mixture of ethylene-vinyl acetate copolymers, ultraviolet absorbent master batches and anti-adhesion agent master batches. The pre-coated film has the functional layer composed of the mixture of ethylene-vinyl acetate copolymers, ultraviolet absorbent master batches and anti-adhesion agent master batches, so that a better ultraviolet absorption function is achieved, more than 80% of UVA and 100% of UVB can be absorbed, and the problem that a printed matter is aged, yellowed and degraded due to irradiation of sunlight is effectively avoided. Meanwhile, the pre-coated film can be covered at low temperature, thus reducing the extent of damage to the printed matter and saving energy.
Description
Technical field
The present invention relates to the pre-coating film technical field, relate in particular to a kind of UV resistant large format low temperature pre-coating film and preparation method thereof.
Background technology
Overlay film refers to that the plastic sheeting that will scribble adhesive covers the surface of printed matter, then, through heating, pressurized treatments, plastic sheeting and printed matter is bonded together, and becomes the process technology of paper unification finished product.The pre-coating film technology is current domestic state-of-the-art overlay film processing technology, is an environmental protection, clean technology.The pre-coating film technology refers to the plastic sheeting of coated PUR in advance, under certain temperature and pressure condition, directly pre-coating film and printing is carried out to the compound technology of hot pressing.Through the printed matter of overlay film, due to surface how thin the and transparent plastic sheeting of one deck, the more level and smooth light in surface, glossiness and the fastness of printed matter have been improved, the picture and text color is more bright-coloured, is rich in third dimension, also plays the effects such as waterproof, antifouling, wear-resisting, folding, resistance to chemical attack simultaneously.Be widely used in the incrustations such as books and periodicals, picture album, front cover, certificate, at present towards the more outdoor billboard development of large format.
The main component of paper printed matter is cellulose, hemicellulose and lignin, and ultraviolet ray can make C-C key and C-O key fracture wherein, the paper mechanical performance is reduced, thereby become fragile.Produce new coloured group and color development system, the original whiteness of paper will inevitably descend and the yellowing variable color simultaneously.Moreover, ultraviolet ray also can cause light degradation, photooxidative degradation to the organic dyestuff of printed layers, make it destructurized, and color change also can cause yellow to the binder in ink system simultaneously, affects vividness.
Pre-coating film of the prior art be take the individual layer overlay film of small breadth as main, is mainly used in the small articles such as books, periodical, and how in indoor use, although it can play effect attractive in appearance and protection books outward appearance.But because pre existing is filmed and can not produced absorption to ultraviolet ray, can be aging gradually under ultraviolet ray is irradiated, the damage that can't avoid ultraviolet ray to cause printed matter and paper, therefore can not be in outdoor long-term use.
For the problems referred to above, those skilled in the art have made some improvement to existing pre-coating film, as Chinese patent application 201110134029.5 provides a kind of pre-coating film with anti-ultraviolet function, this pre-coating film is comprised of subfunction layer, sandwich layer, coating function layer, and sandwich layer is between subfunction layer and coating function layer; The material of subfunction layer is served as reasons and is comprised that polypropylene and ultraviolet screener form, ultraviolet screener be incorporated as 0.1-3% of polypropylene quality; The material of sandwich layer is modified poly ethylene, and the material of coating function layer is bonding agent; Subfunction layer, sandwich layer, coating function layer thermal synthesis one.Although above-mentioned pre-coating film has certain absorption to ultraviolet ray, in above-mentioned patent, ultraviolet screener is selected nano titanium oxide or hexichol first copper, and above-mentioned material is difficult for acquisition and production cost, manufacturing cost is higher.
Summary of the invention
The object of the present invention is to provide a kind of UV resistant large format low temperature pre-coating film, it is applicable to the two-sided overlay film of outdoor large format billboard, and can prevent that printed matter from aging, xanthochromia, degraded occurring because of ultraviolet radiation;
Another object of the present invention is to provide a kind of UV resistant large format low temperature pre-coating film, and it can carry out overlay film at lower temperature, can reduce damage and the saving energy to printed matter;
Another object of the present invention is to provide a kind of UV resistant large format low temperature pre-coating film, can be to the absorptivity of the U vinyl acetate in ultraviolet ray more than 80%, the UVB in ultraviolet ray is absorbed in to 100%;
Another object of the present invention is the preparation method who proposes a kind of UV resistant large format low temperature pre-coating film.
For reaching this purpose, the present invention by the following technical solutions:
A kind of UV resistant large format low temperature pre-coating film, comprise extexine, functional layer, and the intermediate layer between described extexine and functional layer, and wherein, described extexine is biaxial tension polyethylene terephthalate film;
Described intermediate layer is the polymine aqueous layer;
The film that the mixture that described functional layer is ethylene-vinyl acetate copolymer, ultra-violet absorber master batch and anti-blocking agent master batch forms.
As a kind of preferred version of above-mentioned UV resistant large format low temperature pre-coating film, the thickness of described extexine is the 20-75 micron.
As a kind of preferred version of above-mentioned UV resistant large format low temperature pre-coating film, the molecular formula of described polymine is [CH
2cH
2nH-]
n, its mean molecule quantity is 1000-10000;
The solid content of described polyethylene ammonia spirit is 0.4%-2.5%, and the coating dry weight is 0.007-0.03g/m
2, thickness is 0.01-0.03 micron.
A kind of preferred version as above-mentioned UV resistant large format low temperature pre-coating film, in described functional layer, the vinyl acetate content of ethylene-vinyl acetate copolymer is 25%-40%, fusing point is 65 ℃-75 ℃, and thickness is 25-250 microns, and melt index is 25-70g/10min.
A kind of preferred version as above-mentioned UV resistant large format low temperature pre-coating film, described ultra-violet absorber master batch is UV-531, 2-(2-hydroxyl-3, 5 couples of (a, the a-dimethyl benzyl) phenyl) benzene a pair of horses going side by side triazole, 2-(2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-bis-tertiary phenyl)-5-chlorination BTA, 2-(2-hydroxyl-3, 5-bis-tertiary amyl phenyl) benzene a pair of horses going side by side triazole, a kind of or the combination of at least two kinds and the mixing thing of ethylene-vinyl acetate copolymer composition in UV-531, the ratio of both weight is (1-3): (7-5).
A kind of preferred version as above-mentioned UV resistant large format low temperature pre-coating film, contain ultra-violet stabilizer in described ultra-violet absorber master batch, and the weight of described ultra-violet stabilizer accounts for 3%-5% of ultraviolet absorber master batch gross weight; Described ultra-violet stabilizer is 4-benzoyloxy-2,2,6, the combination of a kind of in 6-tetramethyl piperidine, three (1,2,2,6,6-pempidine base) phosphite ester, HMPA or at least two kinds.
A kind of preferred version as above-mentioned UV resistant large format low temperature pre-coating film, described anti-blocking agent master batch is a kind of or the combination of at least two kinds and the mixing thing of ethylene-vinyl acetate copolymer composition in mica, kieselguhr, kaolin, calcium carbonate, synthetic silica, and the ratio of both weight is (1-3): (7-5).
As a kind of preferred version of above-mentioned UV resistant large format low temperature pre-coating film, described ultra-violet absorber master batch accounts for 1%-5% of functional layer gross weight; Described anti-blocking agent master batch accounts for 0.1%-0.5% of functional layer gross weight.
A kind of preparation method of UV resistant large format low temperature pre-coating film as previously discussed, it comprises the following steps:
Steps A: the extexine that preparation is formed by the biaxial tension pet film;
Step B: the painting polyethylene imines aqueous solution oven dry on the inner face of extexine, to form intermediate layer;
Step C: prepare ethylene-vinyl acetate copolymer, ultraviolet radiation absorption master batch, anti-blocking agent master batch, and described ethylene-vinyl acetate copolymer, ultraviolet radiation absorption master batch, anti-blocking agent master batch are mixed according to required percentage by weight, deliver to extruder and be heated to molten condition, through the extrusion coated functional layer that forms on intermediate layer of extruder;
Step D: finally by chill roll and the compression roller of 20-30 ℃, form laminated film.
As a kind of preferred version of the preparation method of above-mentioned UV resistant large format low temperature pre-coating film,
In step B, the preparation process in intermediate layer comprises the following steps:
Step b1: described extexine inner face is carried out to sided corona treatment, the surperficial dyne value of described extexine inner face is reached more than 42;
Step b2: through the painting polyethylene imines aqueous solution on the described extexine inner face of sided corona treatment, also drying, bake out temperature is 70-100 ℃;
In step C, the preparation process of functional layer comprises the following steps:
Step c1: ultra-violet absorber, light stabilizer are mixed with ethene-acetate copolymer and make the ultra-violet absorber master batch, ultra-violet absorber is 30% by weight percentage, light stabilizer is 3% by weight percentage, and all the other are ethylene-vinyl acetate copolymer;
Wherein the ultra-violet absorber of ultra-violet absorber master batch is UV-531,2-(2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2-hydroxyl-3,5-bis-tertiary amyl phenyl) mixture that benzene a pair of horses going side by side triazole or UV-531 and ethene-acetate copolymer form by weight 1:1, light stabilizer is HMPA;
Step c2: anti-blocking agent ethene-acetate copolymer is mixed and makes the anti-blocking agent master batch, and wherein anti-blocking agent is synthetic silica, is wherein 25% by weight percentage, and all the other are ethylene-vinyl acetate copolymer;
Step c3: the ultraviolet radiation absorption master batch that above-mentioned steps c1, c2 are made, anti-blocking agent master batch and ethene-acetate copolymer are according to ultra-violet absorber master batch percentage by weight 3%, anti-blocking agent master batch percentage by weight 0.1%, all the other mix for the percentage by weight of ethylene-vinyl acetate copolymer, deliver to extruder and be heated to molten condition, extrusion coated on intermediate layer through extruder, by the chill rolls of 20-30 ℃ and compression roller, form laminated film.
Beneficial effect of the present invention is: the application is by providing a kind of UV resistant large format low temperature pre-coating film, it has by tool by ethylene-vinyl acetate copolymer, the functional layer of the compositions of mixtures of ultra-violet absorber master batch and anti-blocking agent master batch, make it there is the ultraviolet function of better absorption, can absorb the UVA more than 80%, 100% UVB, effectively avoided printed matter due to the irradiation of sunshine cause aging, xanthochromia, the problem of degraded, this pre-coating film can carry out overlay film at a lower temperature simultaneously, the damage angle of minimizing to printed matter, can save the energy again simultaneously.
The accompanying drawing explanation
Fig. 1 is the structural representation of the UV resistant large format low temperature pre-coating film that provides of the specific embodiment of the invention 1;
Fig. 2 is the preparation flow figure of the UV resistant large format low temperature pre-coating film that provides of the specific embodiment of the invention one;
Fig. 3 is the curve map of the UV resistant large format low temperature pre-coating film that provides of the specific embodiment of the invention one to ultraviolet absorption ability;
Wherein:
1: functional layer; 2: intermediate layer; 3: extexine.
The specific embodiment
Further illustrate technical scheme of the present invention below in conjunction with accompanying drawing and by the specific embodiment.
Embodiment one
As shown in Figure 1, in this embodiment, a kind of UV resistant large format low temperature pre-coating film that the application provides, it comprises extexine 3, functional layer 1 and the intermediate layer 2 between extexine 3 and functional layer 1, above-mentioned functions layer 1 is the PUR functional layer; And extexine 3 is biaxial tension polyethylene terephthalate film, and intermediate layer 2 is the polymine aqueous layer, the film that the mixture that functional layer 1 is ethylene-vinyl acetate copolymer, ultra-violet absorber master batch and anti-blocking agent master batch forms.
The thickness of above-mentioned extexine 3 is the 20-75 micron, and preferred, the thickness of extexine 3 is 25 microns.
The molecular formula of polymine is [CH2CH2NH-] n, and its mean molecule quantity is 1000-10000, and in this embodiment, its mean molecule quantity preferably 10000; And the solid content of polyethylene ammonia spirit is 0.4%-2.5%, the coating dry weight is 0.007-0.03g/m2, and thickness is 0.01-0.03 micron, and as preferably, the solid content of polyethylene ammonia spirit is 0.8, and the coating dry weight is 0.03g/m2, and thickness is 0.03 micron.
In the mixture of above-mentioned composition function layer 1, the vinyl acetate content of ethylene-vinyl acetate copolymer is 25%-40%, and fusing point is 65 ℃-75 ℃, and thickness is 25-250 microns, and melt index is 25-70g/10min.
The ultra-violet absorber master batch is UV-531,2-(2-hydroxyl-3,5 couples of (a, the a-dimethyl benzyl) phenyl) benzene a pair of horses going side by side triazole, 2-(2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-bis-tertiary phenyl)-5-chlorination BTA, 2-(2-hydroxyl-3,5-bis-tertiary amyl phenyl) a kind of or the combination of at least two kinds and the mixing thing of ethylene-vinyl acetate copolymer composition in benzene a pair of horses going side by side triazole, UV-531, the ratio of both weight is (1-3): (7-5).
Also contain ultra-violet stabilizer in above-mentioned ultra-violet absorber master batch, the weight of this ultra-violet stabilizer accounts for 3%-5% of ultraviolet absorber master batch gross weight; Described ultra-violet stabilizer is 4-benzoyloxy-2,2,6, the combination of a kind of in 6-tetramethyl piperidine, three (1,2,2,6,6-pempidine base) phosphite ester, HMPA or at least two kinds.
Above-mentioned anti-blocking agent master batch is a kind of or the combination of at least two kinds and the mixing thing of ethylene-vinyl acetate copolymer composition in mica, kieselguhr, kaolin, calcium carbonate, synthetic silica, and the ratio of both weight is (1-3): (7-5).
And above-mentioned ultra-violet absorber master batch accounts for 1%-5% of functional layer gross weight; Described anti-blocking agent master batch accounts for 0.1%-0.5% of functional layer gross weight.
The preferred version as the application, the mixture that functional layer 1 is ethylene-vinyl acetate copolymer, ultra-violet absorber master batch and anti-blocking agent master batch, its thickness is 25 microns, wherein the ultra-violet absorber master batch accounts for gross weight than 1%, the anti-blocking agent master batch accounts for weight ratio 0.1%, and all the other are ethylene-vinyl acetate copolymer.
The UV resistant large format low temperature pre-coating film that the application provides; ultraviolet ray is had to good absorption function; as shown in Figure 3; have in this figure and can find out the ultraviolet ray of UVB(medium wave erythemal effect) section transmissivity be 0; the ultraviolet ray of UVA(long wave blackspot effect) the section transmissivity is lower than 15%; the pre-coating film that visible the application provides has good UV resistant function, can the article by overlay film be played a very good protection.
As shown in Figure 2, the application also provides a kind of preparation method of above-mentioned UV resistant large format low temperature pre-coating film, and it comprises the following steps:
Steps A: the extexine that preparation is formed by the biaxial tension pet film;
Step B: the painting polyethylene imines aqueous solution oven dry on the inner face of extexine, to form intermediate layer;
Step C: prepare ethylene-vinyl acetate copolymer, ultraviolet radiation absorption master batch, anti-blocking agent master batch, and described ethylene-vinyl acetate copolymer, ultraviolet radiation absorption master batch, anti-blocking agent master batch are mixed according to required percentage by weight, deliver to extruder and be heated to molten condition, through the extrusion coated functional layer that forms on intermediate layer of extruder;
Step D: finally by chill roll and the compression roller of 20-30 ℃, form laminated film.
In step B, the preparation process in intermediate layer comprises the following steps:
Step b1: described extexine inner face is carried out to sided corona treatment, the surperficial dyne value of described extexine inner face is reached more than 42;
Step b2: through the painting polyethylene imines aqueous solution on the described extexine inner face of sided corona treatment, also drying, bake out temperature is 70-100 ℃;
In step C, the preparation process of functional layer comprises the following steps:
Step c1: ultra-violet absorber, light stabilizer are mixed with ethene-acetate copolymer and make the ultra-violet absorber master batch, ultra-violet absorber is 30% by weight percentage, light stabilizer is 3% by weight percentage, and all the other are ethylene-vinyl acetate copolymer;
Wherein the ultra-violet absorber of ultra-violet absorber master batch is UV-531,2-(2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2-hydroxyl-3,5-bis-tertiary amyl phenyl) mixture that benzene a pair of horses going side by side triazole or UV-531 and ethene-acetate copolymer form by weight 1:1, light stabilizer is HMPA;
Step c2: anti-blocking agent ethene-acetate copolymer is mixed and makes the anti-blocking agent master batch, and wherein anti-blocking agent is synthetic silica, is wherein 25% by weight percentage, and all the other are ethylene-vinyl acetate copolymer;
Step c3: the ultraviolet radiation absorption master batch that above-mentioned steps c1, c2 are made, anti-blocking agent master batch and ethene-acetate copolymer are according to ultra-violet absorber master batch percentage by weight 3%, anti-blocking agent master batch percentage by weight 0.1%, all the other mix for the percentage by weight of ethylene-vinyl acetate copolymer, deliver to extruder and be heated to molten condition, extrusion coated on intermediate layer through extruder, by the chill rolls of 20-30 ℃ and compression roller, form laminated film.
In step C, the extruder that this step is mentioned is equipped with 3-10 layer screen pack, and the aperture of screen pack is the 30-200 order.
For above-mentioned UV resistant large format low temperature pre-coating film and preparation method are described, present embodiment provides more specifically preparation method of above-mentioned large format low temperature pre-coating film: it comprises the following steps:
Steps A: be prepared with the extexine that the biaxial tension pet film forms, the thickness of this extexine is 25 microns, and fabric width 1340 is millimeter;
Step B: by the extexine inner face through the row sided corona treatment, corona machine intensity is chosen to be the 5.5K vinyl acetate, dyne value after corona is more than 42, by the smooth roll coating machine, the aqueous solution of polymine is coated to above-mentioned treated side and form intermediate layer, through oven drying, bake out temperature is set as 90 ℃, and wherein the solid content of polymine is 0.8%, and the coating dry weight is 0.03g/m2, thickness is 0.01 micron;
Step C: preparation ultraviolet radiation absorption master batch, anti-blocking agent master batch, and described ethylene-vinyl acetate copolymer, ultraviolet radiation absorption master batch, anti-blocking agent master batch are mixed according to required percentage by weight, deliver to extruder and be heated to molten condition, extrusion coated on intermediate layer through extruder, by the chill rolls of 20-30 ℃ and compression roller, form laminated film.
Wherein, in step C, concrete preparation process comprises the steps:
Step c1: ultra-violet absorber, light stabilizer are mixed with ethene-acetate copolymer and make the ultra-violet absorber master batch;
Wherein the ultra-violet absorber of ultra-violet absorber master batch is UV-531, light stabilizer is HMPA, wherein ultra-violet absorber is 30% by weight percentage, light stabilizer is 3% by weight percentage, all the other are ethylene-vinyl acetate copolymer, wherein the content of vinyl acetate is 30%, and melt index is 35g/10min;
Step c2: anti-blocking agent ethene-acetate copolymer is mixed and makes the anti-blocking agent master batch, wherein anti-blocking agent is synthetic silica, is wherein 25% by weight percentage, and all the other are ethylene-vinyl acetate copolymer, wherein vinyl acetate content is 30%, and melt index is 35g/10min;
Step c3: the ultra-violet absorber master batch that step c1, c2 are made, anti-blocking agent master batch and ethene-acetate copolymer count 3% according to ultra-violet absorber master batch percentage by weight, the anti-blocking agent master batch is 0.1% by weight percentage, all the other deliver to the extruder hopper for the ratio of ethylene-vinyl acetate copolymer mixes, the extexine with intermediate layer 21 that above-mentioned steps B is made is delivered to recombination site by the deflector roll of extruding composite production line, extruder curtain coating PUR, form functional layer, thickness is 50 microns.The extruding of extexine and the curtain coating nip roller by extruding the composite production line recombination site combines, and forms composite membrane.Wherein extruder temperature is set in 215 ℃, and 7 metafiltration nets are housed, and aperture is ground floor 40 orders, the second layer 80 orders, and the 3rd layer of 120 order, the 4th layer of 200 order, layer 5 120 orders, layer 6 80 orders, layer 7 40 orders, extruded velocity is 50MPM.After stretched, cooling, deburring, this pre-coating film coiled material fabric width is 1320 millimeters, through cutting packing, makes finished product, and wherein extrusion molding is prior art.
Embodiment bis-
In this embodiment, UV resistant large format low temperature pre-coating film is identical with the structure of embodiment mono-, but the applied material difference of concrete preparation process, in this embodiment, the concrete preparation process of above-mentioned UV resistant large format low temperature pre-coating film comprises the steps:
Steps A: previously prepared extexine material, extexine is the biaxial tension pet film, 50 microns of thickness, 1340 millimeters of fabric widths;
Step B: by the extexine inner face through the row sided corona treatment, corona machine intensity is chosen to be the 5.5K vinyl acetate, dyne value after corona is more than 42, by bachelor's coating machine, the aqueous solution of polymine is coated to above-mentioned treated side and form intermediate layer, through oven drying, bake out temperature is set as 90 ℃, and wherein the solid content of polymine is 0.8%, and the coating dry weight is 0.03g/m2, thickness is 0.01 micron;
Step C: ultra-violet absorber, light stabilizer are mixed with ethene-acetate copolymer and make the ultra-violet absorber master batch, wherein the ultra-violet absorber of ultra-violet absorber master batch is 2-(2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, light stabilizer is HMPA, wherein ultra-violet absorber is 30% by weight percentage, light stabilizer is 3% by weight percentage, all the other are ethylene-vinyl acetate copolymer, wherein vinyl acetate content is 30%, and melt index is 35g/10min;
Step D: make the anti-blocking agent master batch, the anti-blocking agent of this master batch is synthetic silica, is wherein 25% by weight percentage, and all the other are ethylene-vinyl acetate copolymer, and wherein vinyl acetate content is 30%, and melt index is 35g/10min;
Step e: ethylene-vinyl acetate copolymer, ultra-violet absorber master batch, anti-blocking agent master batch three are mixed and deliver to extruder, wherein the ultra-violet absorber master batch is 3% by weight percentage, the anti-blocking agent master batch is 0.1% by weight percentage, all the other are ethylene-vinyl acetate copolymer, wherein vinyl acetate content is 30%, and melt index is 35g/10min.
Wherein the step e concrete steps are as follows: the extexine that will be loaded with intermediate layer is sent to recombination site by the deflector roll of extruding composite production line, and extruder curtain coating PUR forms functional layer, and thickness is 200 microns.Be provided with ozone generator at the contiguous recombination site place that extrudes composite production line, on the ozone winding-up PUR casting films produced by ozone generator, the concentration of ozone is 75%, power 750W, gas flow is 3.5SCXFM, make the curtain coating surface of resin produce some polar groups, then the extruding of extexine 1 and the curtain coating nip roller by extruding the composite production line recombination site combines, the formation composite membrane.Wherein extruder temperature is set in 215 ℃, 7 metafiltration nets are housed, aperture is for being respectively for ground floor 40 orders, for the second layer 80 orders, being the 3rd layer of 120 order, being the 4th layer of 200 order, being layer 5 120 orders, being layer 6 80 orders, being layer 7 40 orders, and extruded velocity is 50MPM.After stretched, cooling, deburring, this pre-coating film coiled material fabric width is 1320 millimeters, through cutting packing, makes finished product.
Embodiment tri-
In this embodiment, UV resistant large format low temperature pre-coating film is identical with the structure of embodiment mono-, but the applied material difference of concrete preparation process, in this embodiment, the concrete preparation process of above-mentioned UV resistant large format low temperature pre-coating film comprises the steps:
Steps A: previously prepared extexine material, extexine is the biaxial tension pet film, 75 microns of thickness, 1340 millimeters of fabric widths;
Step B: by the extexine inner face through the row sided corona treatment, corona machine intensity is chosen to be the 5.5K vinyl acetate, dyne value after corona is more than 42, by bachelor's coating machine, the aqueous solution of polymine is coated to above-mentioned treated side and form intermediate layer, through oven drying, bake out temperature can be located at 90 ℃, and wherein the solid content of polymine is 0.8%, and the coating dry weight is 0.03g/m2, thickness is 0.01 micron;
Step C: make in advance the ultra-violet absorber master batch, the ultra-violet absorber 2-(2-hydroxyl-3 of this master batch, 5-bis-tertiary amyl phenyl) benzene a pair of horses going side by side triazole, UV-531 are by weight the 1:1 mixture, light stabilizer is HMPA, wherein ultra-violet absorber is 30% by weight percentage, and light stabilizer is 3% by weight percentage.All the other are ethylene-vinyl acetate copolymer, and wherein vinyl acetate content is 25%, and melt index is 30g/10min;
Step D: make in advance the anti-blocking agent master batch, the anti-blocking agent of this master batch is synthetic silica, is wherein 25% by weight percentage, and all the other are ethylene-vinyl acetate copolymer, and wherein vinyl acetate content is 25%, and melt index is 30g/10min;
Step e: ethylene-vinyl acetate copolymer, ultra-violet absorber master batch, anti-blocking agent master batch three are mixed and deliver to extruder, wherein the ultra-violet absorber master batch is 3% by weight percentage, the anti-blocking agent master batch is 0.1% by weight percentage, all the other are ethylene-vinyl acetate copolymer, wherein vinyl acetate content is 25%, and melt index is 30g/10min.
Wherein step e specifically comprises the steps: the extexine that is loaded with intermediate layer is sent to recombination site by the deflector roll of extruding composite production line, and extruder curtain coating PUR forms functional layer, and thickness is 75 microns.Be provided with ozone generator at the contiguous recombination site place that extrudes composite production line, on the ozone winding-up PUR casting films produced by ozone generator, the concentration of ozone is 75%, power 750W, gas flow is 3.5SCXFM, make the curtain coating surface of resin produce some polar groups, then the extruding of extexine 1 and the curtain coating nip roller by extruding the composite production line recombination site combines, the formation composite membrane.Wherein extruder temperature is set in 215 ℃, and 7 metafiltration nets are housed, and aperture is for being respectively: ground floor is 40 orders, and the second layer is 80 orders, the 3rd layer is 120 orders, and the 4th layer is 200 orders, and layer 5 is 120 orders, layer 6 is 80 orders, and layer 7 is 40 orders, and extruded velocity is 50MPM.After stretched, cooling, deburring, this pre-coating film coiled material fabric width is 1320 millimeters, through cutting packing, makes finished product.
Embodiment tetra-
In this embodiment, UV resistant large format low temperature pre-coating film is identical with the structure of embodiment mono-, but the applied material difference of concrete preparation process, in this embodiment, the concrete preparation process of above-mentioned UV resistant large format low temperature pre-coating film comprises the steps:
Steps A: previously prepared extexine material, appearance 1 is the biaxial tension pet film, 25 microns of thickness, 1340 millimeters of fabric widths;
Step B: by the extexine inner face, through the row sided corona treatment, corona machine intensity is chosen to be the 5.5K vinyl acetate, and the dyne value after corona is more than 42.By bachelor's coating machine, the aqueous solution of polymine is coated to above-mentioned treated side and form intermediate layer, through oven drying, bake out temperature is set to 90 ℃, and wherein the solid content of polymine is 0.8%, and the coating dry weight is 0.03g/m2, and thickness is 0.01 micron;
Step C: make in advance the ultra-violet absorber master batch, the ultra-violet absorber 2-of this master batch (2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-bis-tertiary phenyl)-5-chlorination BTA mixes by weight 1:1, light stabilizer is 4-benzoyloxy-2,2,6,6-tetramethyl piperidine, HMPA mix by weight 1:2, wherein ultra-violet absorber is 30% by weight percentage, and light stabilizer is 3% by weight percentage.All the other are ethylene-vinyl acetate copolymer, and wherein vinyl acetate content is 35%, and melt index is 45g/10min.
Step D: make the anti-blocking agent master batch, the anti-blocking agent of this master batch is synthetic silica, is wherein 25% by weight percentage, and all the other are ethylene-vinyl acetate copolymer, and wherein vinyl acetate content is 35%, and melt index is 45g/10min.
Step e: ethylene-vinyl acetate copolymer, ultra-violet absorber master batch, anti-blocking agent master batch three are mixed and deliver to extruder, wherein the ultra-violet absorber master batch is 3% by weight percentage, the anti-blocking agent master batch is 0.1% by weight percentage, all the other are ethylene-vinyl acetate copolymer, wherein vinyl acetate content is 35%, and melt index is 45g/10min.
In step e, specifically comprise the steps: the extexine that is loaded with intermediate layer is sent to recombination site by the deflector roll of extruding composite production line, extruder curtain coating PUR, form functional layer, and thickness is 100 microns.Be provided with ozone generator at the contiguous recombination site place that extrudes composite production line, on the ozone winding-up PUR casting films produced by ozone generator, the concentration of ozone is 75%, power 750W, gas flow is 3.5SCXFM, make the curtain coating surface of resin produce some polar groups, then the extruding of extexine 1 and the curtain coating nip roller by extruding the composite production line recombination site combines, the formation composite membrane.Wherein extruder temperature is set in 215 ℃, and 7 metafiltration nets are housed, and aperture is for being respectively, and ground floor is 40 orders, the second layer is 80 orders, and the 3rd layer is 120 orders, and the 4th layer is 200 orders, and layer 5 is 120 orders, layer 6 is 80 orders, and layer 7 is 40 orders, and extruded velocity is 50MPM.After stretched, cooling, deburring, this pre-coating film coiled material fabric width is 1320 millimeters, through cutting packing, makes finished product.
Know-why of the present invention has below been described in conjunction with specific embodiments.These are described is in order to explain principle of the present invention, and can not be interpreted as by any way limiting the scope of the invention.Explanation based on herein, those skilled in the art does not need to pay performing creative labour can associate other specific embodiment of the present invention, within these modes all will fall into protection scope of the present invention.
Claims (10)
1. a UV resistant large format low temperature pre-coating film, comprise extexine, functional layer, and the intermediate layer between described extexine and functional layer, it is characterized in that, described extexine is biaxial tension polyethylene terephthalate film;
Described intermediate layer is the polymine aqueous layer;
The film that the mixture that described functional layer is ethylene-vinyl acetate copolymer, ultra-violet absorber master batch and anti-blocking agent master batch forms.
2. UV resistant large format low temperature pre-coating film according to claim 1, is characterized in that, the thickness of described extexine is the 20-75 micron.
3. UV resistant large format low temperature pre-coating film according to claim 1, is characterized in that, the molecular formula of described polymine is [CH
2cH
2nH-]
n, its mean molecule quantity is 1000-10000;
The solid content of described polyethylene ammonia spirit is 0.4%-2.5%, and the coating dry weight is 0.007-0.03g/m
2, thickness is 0.01-0.03 micron.
4. UV resistant large format low temperature pre-coating film according to claim 1, it is characterized in that, in described functional layer, the vinyl acetate content of ethylene-vinyl acetate copolymer is 25%-40%, and fusing point is 65 ℃-75 ℃, thickness is 25-250 microns, and melt index is 25-70g/10min.
5. UV resistant large format low temperature pre-coating film according to claim 1, it is characterized in that, described ultra-violet absorber master batch is UV-531, 2-(2-hydroxyl-3, 5 couples of (a, the a-dimethyl benzyl) phenyl) benzene a pair of horses going side by side triazole, 2-(2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-bis-tertiary phenyl)-5-chlorination BTA, 2-(2-hydroxyl-3, 5-bis-tertiary amyl phenyl) benzene a pair of horses going side by side triazole, a kind of or the combination of at least two kinds and the mixing thing of ethylene-vinyl acetate copolymer composition in UV-531, the ratio of both weight is (1-3): (7-5).
6. UV resistant large format low temperature pre-coating film according to claim 5, is characterized in that, contain ultra-violet stabilizer in described ultra-violet absorber master batch, the weight of described ultra-violet stabilizer accounts for 3%-5% of ultraviolet absorber master batch gross weight; Described ultra-violet stabilizer is 4-benzoyloxy-2,2,6, the combination of a kind of in 6-tetramethyl piperidine, three (1,2,2,6,6-pempidine base) phosphite ester, HMPA or at least two kinds.
7. UV resistant large format low temperature pre-coating film according to claim 1, it is characterized in that, described anti-blocking agent master batch is a kind of or the combination of at least two kinds and the mixing thing of ethylene-vinyl acetate copolymer composition in mica, kieselguhr, kaolin, calcium carbonate, synthetic silica, and the ratio of both weight is (1-3): (7-5).
8. UV resistant large format low temperature pre-coating film according to claim 1, is characterized in that, described ultra-violet absorber master batch accounts for 1%-5% of functional layer gross weight; Described anti-blocking agent master batch accounts for 0.1%-0.5% of functional layer gross weight.
9. the preparation method of a UV resistant large format low temperature pre-coating film as claimed in claim 1, is characterized in that, comprises the following steps:
Steps A: the extexine that preparation is formed by the biaxial tension pet film;
Step B: the painting polyethylene imines aqueous solution oven dry on the inner face of extexine, to form intermediate layer;
Step C: prepare ethylene-vinyl acetate copolymer, ultraviolet radiation absorption master batch, anti-blocking agent master batch, and described ethylene-vinyl acetate copolymer, ultraviolet radiation absorption master batch, anti-blocking agent master batch are mixed according to required percentage by weight, deliver to extruder and be heated to molten condition, through the extrusion coated functional layer that forms on intermediate layer of extruder;
Step D: finally by chill roll and the compression roller of 20-30 ℃, form laminated film.
10. the preparation method of UV resistant large format low temperature pre-coating film according to claim 9, is characterized in that,
In step B, the preparation process in intermediate layer comprises the following steps:
Step b1: described extexine inner face is carried out to sided corona treatment, the surperficial dyne value of described extexine inner face is reached more than 42;
Step b2: through the painting polyethylene imines aqueous solution on the described extexine inner face of sided corona treatment, also drying, bake out temperature is 70-100 ℃;
In step C, the preparation process of functional layer comprises the following steps:
Step c1: ultra-violet absorber, light stabilizer are mixed with ethene-acetate copolymer and make the ultra-violet absorber master batch, ultra-violet absorber is 30% by weight percentage, light stabilizer is 3% by weight percentage, and all the other are ethylene-vinyl acetate copolymer;
Wherein the ultra-violet absorber of ultra-violet absorber master batch is UV-531,2-(2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2-hydroxyl-3,5-bis-tertiary amyl phenyl) mixture that benzene a pair of horses going side by side triazole or UV-531 and ethene-acetate copolymer form by weight 1:1, light stabilizer is HMPA;
Step c2: anti-blocking agent ethene-acetate copolymer is mixed and makes the anti-blocking agent master batch, and wherein anti-blocking agent is synthetic silica, is wherein 25% by weight percentage, and all the other are ethylene-vinyl acetate copolymer;
Step c3: the ultraviolet radiation absorption master batch that above-mentioned steps c1, c2 are made, anti-blocking agent master batch and ethene-acetate copolymer are according to ultra-violet absorber master batch percentage by weight 3%, anti-blocking agent master batch percentage by weight 0.1%, all the other mix for the percentage by weight of ethylene-vinyl acetate copolymer, deliver to extruder and be heated to molten condition, extrusion coated on intermediate layer through extruder, by the chill rolls of 20-30 ℃ and compression roller, form laminated film.
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| CN115710471B (en) * | 2023-01-09 | 2023-04-28 | 苏州奥美材料科技有限公司 | Functional plastic film and preparation method and application thereof |
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