CN102746722A - Composition for treating polyethylene (PE) film surface and PE film label - Google Patents
Composition for treating polyethylene (PE) film surface and PE film label Download PDFInfo
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- CN102746722A CN102746722A CN2011100974221A CN201110097422A CN102746722A CN 102746722 A CN102746722 A CN 102746722A CN 2011100974221 A CN2011100974221 A CN 2011100974221A CN 201110097422 A CN201110097422 A CN 201110097422A CN 102746722 A CN102746722 A CN 102746722A
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Abstract
The invention discloses a composition for treating a polyethylene (PE) film surface and a PE film label. The composition for treating a PE film surface comprises acrylic polymers having acid values of 40 to 150, multifunctional oligomers and/or acrylic monomers, bridging agents and diluting solvents. The composition for treating a PE film surface can be coated on a PE film so that a chemically treated surface layer is formed. The composition for treating a PE film surface and a PE film surface can undergo a chemical reaction so that firm chemical bonds are formed; and simultaneously, the multifunctional oligomers or the acrylic monomers of the composition for treating a PE film surface can chemically bond with components of UV ink. Therefore, ink patterns prepared from the UV ink can be firmly attached to the PE film surface by surface chemical treatment so that falling-off of the ink patterns is avoided and printing quality of a PE film label is improved.
Description
Technical field
The invention relates to a kind of polyethylene film surface treatment constituent and label thereof, but particularly relevant for the polyethylene film surface treatment constituent and the label thereof of a kind of media chemical bonded refractory polyethylene film surface and ultraviolet curing ink.
Background technology
After labels class (label) product passes through processing treatment such as printing house printing, stamp, torn edges, can be made into the label finished product and be supplied to End-Customer to use, wherein the plane materiel of label is printed with various pattern or literal, so the press quality of plane materiel is extremely important.Common label plane materiel can be divided into paper class and film class, and wherein general paper class plane materiel printing is easier to, and the printing ink after the printing also is difficult for dropping; Moreover the press quality of film class plane materiel then needs more technical control, and for example with regard to the higher thin-film material of surface tension such as polyethyleneterephthalate (PET) film, surface printing printing ink is more or less freely adheres to for it; Yet with regard to the lower thin-film material of surface tension such as Vilaterm (PE) film, its surface printing printing ink difficulty adheres to.Therefore, in order on thin-film material, to obtain the printed patterns of better quality, must carry out surface treatment to thin-film material (like the PE film).
For example, the many PE labels factory chamber of commerce makes PE film surface through the physics corona treatment in advance, so that its surface tension increases to more than the 38dyne/cm, so that improve printing ink in the lip-deep tack of PE film.On the other hand; Manufacturer is also arranged at PE film surface coated one deck chemical processing agent, because chemical processing agent is good to the sticking power of PE film, and printing ink is also good to the sticking power of treatment agent; Combine PE film and printing ink so reach media, to improve the purpose of ink adhesion (fastness).
Moreover in recent years in order to meet the trend of environmental protection, more and more multi-vendor the use gradually do not had the ultraviolet curing ink (UV-curing ink) of environmental toxicity.Only; When the UV curing printing ink print is on PE film or other thin-film material; The problem that printing ink comes off from PE film surface local or big area in fact still takes place easily, becomes the important topic of making the PE film label so how to solve the printing tack (fastness) of the UV curing inks on PE film surface.
Die, be necessary to provide a kind of polyethylene film surface treatment constituent and label thereof of improvement, to solve the existing in prior technology problem.
Summary of the invention
Main purpose of the present invention is to provide a kind of polyethylene film surface treatment constituent and label thereof; It adopts chemically treated method; Earlier the surface treatment constituent is coated Vilaterm (PE) film surface and form the chemical treatment top layer; Let surface treatment constituent and PE film surface form firm key knot through chemical reaction; Then when ultraviolet ray (UV) curing printing ink print is coated on the chemical treatment top layer of PE film and is shone UV and be cured, multiple functional radical oligomer in the chemical treatment top layer or multiple functional radical acryl monomer can with the composition generation chemical bonded refractory of UV curing inks, so the ink logo that the UV curing inks forms can through the chemical treatment top layer strong to be attached to the PE film surperficial; The phenomenon that ink logo comes off no longer takes place, thereby helps improving the press quality of polyethylene film label.
For reaching aforementioned purpose of the present invention, the present invention provides a kind of polyethylene film surface treatment constituent, and wherein said surface treatment constituent comprises:
(a) acid number accounts for the 70.0-90.0 weight part between acryl system (acrylic) polymer of 40-150;
(b) multiple pressure gram force functional group's oligomer (oligomer), acryl monomer or its both, account for the 29.9-5.0 weight part;
(c) bridging agent (crosslinker) accounts for the 0.1-5.0 weight part; And
(d) solvent use in dilution, adds the 70-1400 weight part, make said (a) and (b) composition final always consolidate the 3-20wt% scope that type part accounts for said surface treatment constituent;
Wherein said surface treatment constituent forms a chemical treatment top layer in order on the surface of coating a Vilaterm (PE) film, with further printing one ink logo.
Moreover the present invention provides a kind of label of polyethylene film, and wherein said label comprises:
One polyethylene film has a positive and back side;
One chemical treatment top layer, coating is formed on the front of said polyethylene film;
One ink logo, printing is formed on the said chemical treatment top layer;
One pressure-sensitive adhesive layer is affixed on the back side of said polyethylene film; And
One release layer has one release said pressure-sensitive adhesive layer of adjacency;
Wherein said chemical treatment top layer is to be coated with by above-mentioned surface treatment constituent to form.
In one embodiment of this invention, said ink logo uses a ultraviolet ray (UV) curing inks.
In one embodiment of this invention, the acid number of mentioned component (a) is that polymer is meant that the higher relatively acryl of acid number is a polymer between the acryl of 40-150, and wherein these acryl are that polymer spendable monomer when polyreaction comprises at least: (a1) C
1-C
4The ester group acrylate monomer or the C of (being carbon number 1-4)
1-C
6The ester group methacrylate monomers, and (a2) contain the monomeric mixture of carboxyl acryl, and select to comprise (a3) other vinyl monomer, (a4) and be different from (a1) or (a2) other vinylformic acid functional group monomer, or (a3) with the mixing of (a4).Above-mentioned (a1) and monomer (a2) are the compositions that must use, and the monomer that (a3) reaches (a4) then can be selected to use or do not use on demand.After aforementioned (a1) at least and (a2) monomer composition mixed; Add appropriate solvent (for example toluene, ETHYLE ACETATE or its mixing etc.) and initiator (for example BPO, lauroyl peroxide, Diisopropyl azodicarboxylate or its mixing etc.); And under 80 to 95 ℃ temperature condition; Reacted 5 to 8 hours, and promptly obtained solid 35-50wt%, weight molecular weight between 200,000 to 800,000 and acid number be polymer between the acryl of 40-150.
In one embodiment of this invention, the C of mentioned component (a1)
1-C
4The ester group acrylate monomer for example be selected from methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, NSC 20949, tert-butyl acrylate or its mixing.
In one embodiment of this invention, the C of mentioned component (a1)
1-C
6The ester group methacrylate monomers for example be selected from TEB 3K, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate or its mixing.
In one embodiment of this invention, the carboxyl acryl monomer that contains of mentioned component (a2) is meant the monomer that comprises an above carboxyl, for example is selected from vinylformic acid, methylacrylic acid, 2-butylene acid, maleic acid, FUMARIC ACID TECH GRADE, itaconicacid or its mixing.
In one embodiment of this invention, other vinyl monomer of mentioned component (a3) for example is selected from vinyl-acetic ester, vinylbenzene or its mixing.
In one embodiment of this invention, other vinylformic acid functional group monomer of mentioned component (a4) for example is selected from Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester, Rocryl 400, Rocryl 410, acrylic amide, USAF RH-1, epihydric alcohol acrylic ester, epihydric alcohol methylpropenoic acid ester or its mixing.
It should be noted that; The acryl of mentioned component (a) is being defined as of acid number of polymer indication: when the testing sample (being that acryl is a polymer) of 1 g of titration; Needed Pottasium Hydroxide quality (is unit with the milligram): (56.1) AN/W; Wherein A is the titer of Pottasium Hydroxide, and unit is ml; N is the equivalent concentration of Pottasium Hydroxide; 56.1 be the molecular weight of Pottasium Hydroxide; W is the quality of determinand, and unit is g.In the present invention, the acryl of mentioned component (a) is that high molecular acid number needs between 40-150, for example 40,50,60,70,80,90,100,110,120,130,140,150 or its any two numbers between numerical range.The high acid value acryl of mentioned component (a) is that polymer uses the 70.0-90.0 weight part, for example 70,75,80,85,90 or its any two numbers between numerical range.
In one embodiment of this invention; The present invention selects to use at least a in multiple pressure gram force functional group's oligomer and multiple pressure gram force functional group's the acryl monomer; The multiple pressure gram force functional group's of its mentioned component (b) oligomer and/or acryl monomer use the 29.9-5.0 weight part, for example 29.9,25,20,15,10,5 or its any two numbers between numerical range.
In one embodiment of this invention; The multiple pressure gram force functional group's of mentioned component (b) oligomer is meant and comprises several oligomers to hundreds of acryl functional group; For example be selected from urethane (polyurethane) esters of acrylic acid, polyester (polyester) esters of acrylic acid, polyethers (polyether) esters of acrylic acid, epoxy (epoxy) esters of acrylic acid or its mixing etc.; Its weight molecular weight of oligomer of multiple pressure gram force functional group approximately between thousands of between tens thousand of; And range of viscosities is between 100 to 300, between the 000cps.
In one embodiment of this invention; The multiple pressure gram force functional group's of mentioned component (b) acryl monomer; Be often referred to the acryl monomer that comprises 3 to 6 acryl functional group, for example be selected from Viscoat 295 (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), oxyethyl group Viscoat 295 (EOTMPTA), tetramethylol methane tetraacrylate, oxyethyl group tetramethylol methane tetraacrylate, double pentaerythritol C5 methacrylate, double pentaerythritol methacrylate or its mixing.
In one embodiment of this invention; The bridging agent of mentioned component (c) be meant can with the compound of carboxyl reaction, for example be selected from metallo-chelate (metal chelate), isocyanic acid oligomer (polyisocyanate), epoxide (epoxy), nitrogen heterocycle propane compound (polyaziridine), melamine resin (melamine resin) or its mixing.The bridging agent of mentioned component (c) uses the 0.1-5.0 weight part, for example 0.1,0.5,1.0,1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0 or its any two numbers between numerical range.
In one embodiment of this invention; The diluting solvent of mentioned component (d) is in order to satisfy the demand that is fit to coating viscosity that provides; Can reduce the overall viscosity of said surface treatment constituent through adding an amount of diluting solvent, make it be coated with the coating dry measure scope that operation obtains expecting more easily.Said diluting solvent can be selected from: low boiling point solvent, for example methyl acetate, ETHYLE ACETATE, acetone, butanone, Virahol, normal hexane, hexanaphthene, normal heptane or its mixing; And/or medium-boiling solvent, for example toluene, YLENE, butylacetate, pimelinketone, methyl glycol, glycol monoethyl ether, ethylene glycol monobutyl ether or its mixing.The diluting solvent of mentioned component (d) uses the 70-1400 weight part; Make said (a) and (b) final total type part admittedly of composition account for the 3-20wt% scope of said surface treatment constituent, for example 70,85,100,200,400,600,800,1000,1400 or its any two numbers between numerical range.
In one embodiment of this invention; Before the said UV curing inks of printing; The surface of said PE film preferably in advance through a corona treatment, increases to more than 38 dyne/centimetres (dyne/cm) surface tension of said PE film, to improve the tack of said UV curing inks to PE.Above-mentioned corona treatment belongs to the surface treatment method of physical property.Moreover the present invention further adopts chemically treated method, earlier said surface treatment constituent is coated said PE film surface, lets the surface of said surface treatment constituent and PE film form firm key knot through chemical reaction.Then; When the UV curing printing ink print is coated the chemically treating surface of PE film and is shone UV again and be cured; Multiple pressure gram force functional group's oligomer in the said surface treatment constituent and/or acryl monomer are understood the composition generation chemical bonded refractory with said UV curing inks in addition; So make said UV curing inks just can through the chemical treatment top layer strong be attached to said PE film surface, the phenomenon that ink logo comes off no longer takes place, thereby helps improving the press quality of PE film label.
In the present invention; Solid type part of said surface treatment constituent is deployed into occupies between whole 3 to 20wt%; And selection is adopted in the same way, and intaglio plate, reverse intaglio plate, photogravure, five roller coating cloth, coiling rod or its equivalent way are coated on the front of PE film; Said chemical treatment top layer in the average coating dry measure on the front of said polyethylene film approximately between 0.1 to 5.0 g/square centimeter; Wherein being preferably between 0.5 to 2.0 g/square centimeter, for example is 0.5,1.0,1.5 or 2.0.After being coated with said surface treatment constituent; Different according to the bridging agent kind; Let said surface treatment constituent after ripen in 24 hours to 168 hours in normal temperature (23 ± 2 ℃) held, the chemical bonded refractory reaction of itself and PE film just can be complete, and good firm attachment degree just can be arranged.Said surface treatment constituent so, promptly capable of using is coated with on the front of PE film and forms a chemical treatment top layer.
Then, select to use a release layer, and the pressure sensitive adhesive (pressure-sensitive adhesive) that coating is fit on release of release layer, through behind the oven drying, form a pressure-sensitive adhesive layer.Subsequently, fitting in release the pressure-sensitive adhesive layer of release layer and the above-mentioned back side with the PE film on chemical treatment top layer, becomes work in-process with the center rewinding, are the required width of printing client and the label finished product of length through the itemize rewinding again.For example, please with reference to shown in Figure 1, in a preferred embodiment of the present invention, roughly comprise on the label finished product of the present invention: a Vilaterm (PE) film 10 has a positive and back side; One chemical treatment top layer 11, coating is formed on the front of said polyethylene film 10; One ink logo 12, printing is formed on the said chemical treatment top layer 11; One pressure-sensitive adhesive layer 13, behind the back side of the said polyethylene film 10 of said pressure-sensitive adhesive layer 13 contacts, said pressure-sensitive adhesive layer 13 can be affixed on the back side of said polyethylene film 10 in commentaries on classics; And a release layer 14, have one release, the said pressure-sensitive adhesive layer 13 of said release adjacency, wherein said chemical treatment top layer 11 is to be coated with by above-mentioned surface treatment constituent to form.Said release layer 14 can be selected from various dicing films or separate-type paper, for example polyester (PET) dicing film, Vilaterm (PE) dicing film, Ge Laxin (glassine) separate-type paper or plastic-coated kraft paper (PEK) separate-type paper.
Description of drawings
Fig. 1 is the diagrammatic cross-section of the label of preferred embodiment polyethylene film of the present invention.
Embodiment
Below the explanation of each embodiment be can be in order to the specific embodiment of implementing in order to illustration the present invention, be in order to explanation and understand the present invention at the professional term of this use, but not in order to restriction the present invention.
When preparation polyethylene film surface treatment constituent of the present invention, the acryl of at first preparing high acid value (acid number is between 40-150) is a polymer, and its preparation process is following:
(1) reactive system is set, comprises 1 liter equipment such as glass reaction groove, variable-ratio whisking appliance, temperature indicator, reflux condensing tube, filling tube, constant temperature water bath;
(2) various monomers (a1)～(a4) are added reactive tank respectively according to formulation content, with beaker weighing starting agent and after adding dissolution with solvents, add in the reactive tank, remaining solvent adds reactive tank respectively;
(3) agitator speed is set at 100rpm, begins to stir, and the constant temperature water bath temperature is set at 90 ℃ and begins to heat up;
(4) after prolong refluxes and occurs, picked up counting 1 hour;
(5) after interpolation solution mixes, pour filling tube into, in certain hour, add in the reactive tank gradually; And
(6) after continuation heating for some time, add the solvent of dilution, be cooled to room temperature and promptly get product.
The testing method of polyethylene film surface treatment constituent:
Viscosity: with Brookfield DV-I prime viscometer viscosmeter, the #2 rotating shaft, rotating speed 30rpm, (23 ± 2 ℃) are surveyed its viscosity number under the room temperature, are unit with cps.
Solid: its measurement is with scale pan weighing (W
0), the sample that takes a morsel is inserted scale pan weighing (W
1) after, put into 150 ℃ of baking ovens through 60 fens bells, remove wherein moisture content, return back to room temperature after, survey its weight (W again
2), solid is (W
2-W
0)/(W
1-W
0) * 100%.
The adherence testing sequence of polyethylene film surface treatment constituent:
(1) configuration of treatment agent formula (being the surface treatment constituent):
(1-1) getting an amount of (a) high acid value acryl is high molecular solution, add (b) multiple pressure gram force functional group oligomer (oligomer), acryl monomer or its both, with solvent it is diluted to the concentration of solid type part about 10% again; And
(1-2) (c) bridging agent is added in the above-mentioned solution of solid type part 10%, it is subsequent use to stir.
(2) coating of treatment agent formula:
(2-1) treatment agent of above-mentioned configuration is coated on the PE film front that corona treatment is crossed in advance, to form a chemical treatment top layer with #1 coiling rod;
(2-2) above-mentioned PE film specimen page being put into temperature is 60 ℃ of baking ovens, takes out after 5 minutes; And
(2-3) (23 ℃, under environment 50%RH), placement appropriate time after ripen carries out next step to PE film specimen page again in fixed temperature and humidity.
(3) coating of UV curing inks:
The coiling rod of (3-1) getting #1 is applied to UV curing inks hand on the chemical treatment top layer of PE film specimen page, to form ink logo;
(3-2) with the specimen page of tool ink logo through UV drying machine drying program; And
(3-3) specimen page was positioned under the fixed temperature and humidity condition more than at least one hour.
(4) adherence experiment:
After (4-1) test tape (3M#600) is fixed by an end in hand, directly draw back on the ink logo surface that fits in PE film specimen page to be tested, and remove bubble ten times to point the joint place of exerting pressure back and forth;
(4-2) adhesive tape one end is torn up, making is enough to hold with banjo splint, draws rapidly except that adhesive tape (must be less than one minute from sticking to the time that removes adhesive tape) with about 90 ° angle immediately; And
(4-3) whether the visual inspection adhesive tape is totally transparent, confirms the area that comes off of ink logo.
High acid value acryl of the present invention is the preparation of polymer A:
(1) after glass reaction groove, reflux condensing tube, filling tube clean respectively, the device reaction system.
(2) TEB 3K 90 grams, n-butyl acrylate 72 grams, vinylformic acid 12 grams, Rocryl 400 4 are restrained, add respectively reactive tank; After being dissolved in 20 gram toluene with beaker weighing BPO 0.4 gram; Add in the reactive tank, toluene 50 grams, ETHYLE ACETATE 200 grams add reactive tank respectively.
(3) agitator speed is set at 100rpm and begins to stir, and the constant temperature water bath temperature is set at 90 ℃ and begins to heat up.
(4) after prolong refluxes and occurs, picked up counting 1 hour.
(5) TEB 3K 30 grams, n-butyl acrylate 24 grams, vinylformic acid 4 grams, Rocryl 400 2 grams are added glass beaker respectively and mix; After being dissolved in 12 gram toluene with another beaker weighing BPO 0.8 gram again; Add in the preceding paragraph monomer mixed solution; All mixed solution is poured filling tube into, in 1 hour, adds in the reactive tank gradually.
(6) continue heating after 4 hours, add 80 gram dilution with toluene, the room temperature that is water-cooled to of constant temperature water bath being changed room temperature promptly gets product A.
High acid value acryl of the present invention is the preparation of polymer B:
(1) after glass reaction groove, reflux condensing tube, filling tube clean respectively, the device reaction system.
(2) methacrylic tert-butyl acrylate 48 grams, ethyl propenoate 96 grams, vinylformic acid 16 grams, vinylbenzene 18 are restrained, add respectively reactive tank; After being dissolved in 20 gram toluene with beaker weighing laurylperoxide 0.4 gram; Add in the reactive tank, toluene 40 grams, ETHYLE ACETATE 200 grams, Virahol 20 grams add reactive tank respectively.
(3) agitator speed is set at 100rpm and begins to stir, and the constant temperature water bath temperature is set at 90 ℃ and begins to heat up.
(4) after prolong refluxes and occurs, picked up counting 1 hour.
(5) methacrylic tert-butyl acrylate 16 grams, ethyl propenoate 32 grams, vinylformic acid 6 grams, vinylbenzene 6 grams are added glass beaker respectively and mix; After being dissolved in 32 gram toluene with another beaker weighing laurylperoxide 0.8 gram again; Add in the preceding paragraph monomer mixed solution; All mixed solution is poured filling tube into, in 1 hour, adds in the reactive tank gradually.
(6) continue heating after 4 hours, adding 80 gram dilution with toluene, the room temperature that is water-cooled to of constant temperature water bath being changed room temperature promptly gets product B.
Prior art (comparative example) acryl is the preparation of polymer C:
(1) after glass reaction groove, reflux condensing tube, filling tube clean respectively, the device reaction system.
(2) TEB 3K 103 grams, n-butyl acrylate 72 grams, vinylformic acid 2 grams, Rocryl 400 1 are restrained, add respectively reactive tank; After being dissolved in 20 gram toluene with beaker weighing BPO 0.4 gram; Add in the reactive tank, toluene 50 grams, ETHYLE ACETATE 200 grams add reactive tank respectively.
(3) agitator speed is set at 100rpm and begins to stir, and the constant temperature water bath temperature is set at 90 ℃ and begins to heat up.
(4) after prolong refluxes and occurs, picked up counting 1 hour.
(5) TEB 3K 34 grams, n-butyl acrylate 24 grams, vinylformic acid 1 gram, Rocryl 400 1 gram are added glass beaker respectively and mix; After being dissolved in 12 gram toluene with another beaker weighing BPO 0.8 gram again; Add in the preceding paragraph monomer mixed solution; All mixed solution is poured filling tube into, in 1 hour, adds in the reactive tank gradually.
(6) continue heating after 4 hours, adding 80 gram dilution with toluene, the room temperature that is water-cooled to of constant temperature water bath being changed room temperature promptly gets product C.
The embodiment of the invention one
(1) the treatment agent test recipe one:
Table one:
611A-85: urethane oligomer, Changxing Chemicals.
Desmodur L75: multiple functional radical isocyanic acid oligomer, Bayer product.
(2) coating of treatment agent test recipe one:
(2-1) treatment agent test recipe one is coated on the corona treatment front of new LDPE (film grade) (LDPE) film specimen page one of 85 μ m, to form a chemical treatment top layer with #1 coiling rod.
(2-2) specimen page one being put into temperature is 60 ℃ of baking ovens, takes out after 5 minutes.
(2-3) with the condition of specimen page one, place and carried out next step in 168 hours again in fixed temperature and humidity condition (23 ℃, 50%RH relative humidity).
(3) the UV curing inks of specimen page one coating:
The coiling rod of (3-1) getting #1 is applied to yellow UV curing inks hand on the chemical treatment top layer of PE film specimen page one, to form ink logo.
(3-2) with the specimen page of tool ink logo once UV drying machine drying program.
(3-3) specimen page one was positioned under the fixed temperature and humidity condition more than at least one hour.
(4) adherence of specimen page one experiment:
After (4-1) test tape (3M#600) is fixed by an end in hand, directly draw back on the ink logo surface that fits in PE film specimen page one to be tested, and remove bubble ten times to point the joint place of exerting pressure back and forth.(4-2) test tape one end is torn up, making is enough to hold with banjo splint, draws rapidly except that adhesive tape (must be less than one minute from sticking to the time that removes test tape) with about 90 ° angle immediately.
Whether the face of pasting of (4-3) visual inspection test tape is totally transparent, confirms the area that comes off of ink logo.
The embodiment of the invention two
(1) the treatment agent test recipe two:
Table two:
SR454: oxyethyl group Viscoat 295 (EOTMPTA), Sartomer Company products PFAZ 321: multiple functional radical ethyleneimine bridging agent, Bayer product.
(2) coating of treatment agent test recipe two:
(2-1) treatment agent test recipe two is coated on the corona treatment front of new LDPE (film grade) (LDPE) film specimen page two of 85 μ m, to form a chemical treatment top layer with #1 coiling rod.
(2-2) specimen page two being put into temperature is 60 ℃ of baking ovens, takes out after 5 minutes.
(2-3) (23 ℃, condition 50%RH) is placed and was carried out next step in 24 hours again in the fixed temperature and humidity condition with specimen page two.
(3) the UV curing inks of specimen page two coating:
The coiling rod of (3-1) getting #1 is applied to yellow UV curing inks hand on the chemical treatment top layer of new LDPE (film grade) (LDPE) film specimen page two, to form ink logo.
(3-2) with the specimen page two of tool ink logo through UV drying machine drying program.
(3-3) specimen page two was positioned under the fixed temperature and humidity condition more than at least one hour.
(4) adherence of specimen page two experiment:
After (4-1) test tape (3M#600) is fixed by an end in hand, directly draw back on the ink logo surface that fits in LDPE film specimen page two to be tested, and remove bubble ten times to point the joint place of exerting pressure back and forth.
(4-2) test tape one end is torn up, making is enough to hold with banjo splint, draws rapidly except that adhesive tape (must be less than one minute from sticking to the time that removes test tape) with about 90 ° angle immediately.
Whether the face of pasting of (4-3) visual inspection test tape is totally transparent, confirms the area that comes off of ink logo.
The embodiment of the invention three
(1) the treatment agent test recipe three:
Table three:
| Composition | Usage quantity |
| Acryl is polymer B | 70.0 |
| CN296 (Polyester oligomer, Sartomer) | 15.0 |
| SR295 (four functional group monomers, Sartomer) | 15.0 |
| Desmodur L75 (bridging agent, Bayer) | 0.8 |
| Toluene | 420.0 |
| Add up to | 520.8 |
| Solid (%) | 11.93 |
| Viscosity (cps) | 68 |
SR454: oxyethyl group Viscoat 295 (EOTMPTA), Sartomer product.
Desmodur L75: multiple functional radical isocyanic acid oligomer, Bayer product.
(2) coating of treatment agent test recipe three:
(2-1) treatment agent test recipe three is coated on the corona treatment front of new LDPE (film grade) (LDPE) film specimen page three of 85 μ m, to form a chemical treatment top layer with #1 coiling rod.
(2-2) specimen page three being put into temperature is 60 ℃ of baking ovens, takes out after 5 minutes.
(2-3) (23 ℃, condition 50%RH) is placed and was carried out next step in 168 hours again in the fixed temperature and humidity condition with specimen page three.
(3) the UV curing inks of specimen page three coating:
The coiling rod of (3-1) getting #1 is applied to yellow UV curing inks hand on the chemical treatment top layer of new LDPE (film grade) (LDPE) film specimen page three, to form ink logo.
(3-2) with the specimen page three of tool ink logo through UV drying machine drying program.
(3-3) specimen page three was positioned under the fixed temperature and humidity condition more than at least one hour.
(4) adherence of specimen page three experiment:
After (4-1) test tape (3M#600) is fixed by an end in hand, directly draw back on the ink logo surface that fits in LDPE film specimen page three to be tested, and remove bubble ten times to point the joint place of exerting pressure back and forth.
(4-2) test tape one end is torn up, making is enough to hold with banjo splint, draws rapidly except that adhesive tape (must be less than one minute from sticking to the time that removes test tape) with about 90 ° angle immediately.
Whether the face of pasting of (4-3) visual inspection test tape is totally transparent, confirms the area that comes off of ink logo.
The comparative example one of prior art
(1) the treatment agent test recipe four:
Table four:
| Composition | Usage quantity |
| Acryl is polymer C | 100.0 |
| Desmodur L75 (bridging agent, Bayer) | 1.0 |
| Toluene | 300.0 |
| Add up to | 401.0 |
| Solid (%) | 11.63 |
| Viscosity (cps) | 120 |
Desmodur L75: multiple functional radical isocyanic acid oligomer, Bayer product.
(2) coating of Processing Test prescription four:
(2-1) treatment agent test recipe four is coated on the corona treatment front of new LDPE (film grade) (LDPE) film specimen page four of 85 μ m, to form a chemical treatment top layer with #1 coiling rod.
(2-2) specimen page four being put into temperature is 60 ℃ of baking ovens, takes out after 5 minutes.
(2-3) (23 ℃, condition 50%RH) is placed and was carried out next step in 168 hours again in the fixed temperature and humidity condition with specimen page four.
(3) the UV curing inks of specimen page four coating:
The coiling rod of (3-1) getting #1 is applied to yellow UV curing inks hand on the chemical treatment top layer of new LDPE (film grade) (LDPE) film specimen page four, to form ink logo.
(3-2) with the specimen page four of tool ink logo through UV drying machine drying program.
(3-3) specimen page was positioned under the fixed temperature and humidity condition more than at least one hour.
(4) adherence of specimen page four experiment:
After (4-1) test tape (3M#600) is fixed by an end in hand, directly draw back on the ink logo surface that fits in LDPE film specimen page four to be tested, and remove bubble ten times to point the joint place of exerting pressure back and forth.
(4-2) test tape one end is torn up, making is enough to hold with banjo splint, draws rapidly except that adhesive tape (must be less than one minute from sticking to the time that removes test tape) with about 90 ° angle immediately.
Whether the face of pasting of (4-3) visual inspection test tape is totally transparent, confirms the area that comes off of ink logo.
The comparative example two of prior art
(1) the treatment agent test recipe five:
Table five:
| Composition | Usage quantity |
| Acryl is polymer C | 100.0 |
| Toluene | 300.0 |
| Add up to | 400.0 |
| Solid (%) | 11.47 |
| Viscosity (cps) | 95 |
(2) coating of Processing Test prescription five:
(2-1) treatment agent test recipe five is coated on the corona treatment front of new LDPE (film grade) (LDPE) film specimen page five of 85 μ m, to form a chemical treatment top layer with #1 coiling rod.
(2-2) specimen page five being put into temperature is 60 ℃ of baking ovens, takes out after 5 minutes.
(2-3) (23 ℃, condition 50%RH) is placed and was carried out next step in 24 hours again in the fixed temperature and humidity condition with specimen page five.
(3) the UV curing inks of specimen page five coating:
The coiling rod of (3-1) getting #1 is applied to yellow UV curing inks hand on the chemical treatment top layer of new LDPE (film grade) (LDPE) film specimen page five, to form ink logo.
(3-2) with the specimen page Five Classics UV drying machine drying program of tool ink logo.
(3-3) specimen page was positioned under the fixed temperature and humidity condition more than at least one hour.
(4) adherence of specimen page five experiment:
After (4-1) test tape (3M#600) is fixed by an end in hand, directly draw back on the ink logo surface that fits in LDPE film specimen page five to be tested, and remove bubble ten times to point the joint place of exerting pressure back and forth.
(4-2) test tape one end is torn up, making is enough to hold with banjo splint, draws rapidly except that adhesive tape (must be less than one minute from sticking to the time that removes test tape) with about 90 ° angle immediately.
Whether the face of pasting of (4-3) visual inspection test tape is totally transparent, confirms the area that comes off of ink logo.
The chemical treatment top layer of each PE film specimen page tears up the tack experimental result after the test:
Table six:
Please with reference to shown in the table six; In existing Vilaterm (PE) film (for example being LDPE film etc.); Being coated on the chemical treatment top layer that forms on the PE film by comparative example one or two surface treatment constituent utilizes test tape to tear up test after the printing-ink pattern; Wherein test result shows that the ink logo of existing PE film comes off area about 60 to 80%; The combination ink logo that just the chemical treatment top layer on its PE film can't be firm makes ink logo very easily leave the PE film because of large-area the coming off of external reactive force influence.In comparison; In Vilaterm of the present invention (PE) film; Being coated on the chemical treatment top layer that forms on the PE film by embodiment one, two or three surface treatment constituent utilizes test tape to tear up test after the printing-ink pattern; Wherein the ink logo of test result demonstration PE film of the present invention is not observed any obvious dropping situations that has been sticked by adhesive tape; Chemical treatment top layer on the PE film just of the present invention can be firm the combination ink logo, make that ink logo is difficult for leaving the PE film because of external reactive force influence comes off.
More detailed; The present invention adopts chemically treated method; Earlier the surface treatment constituent is coated Vilaterm (PE) film surface and form the chemical treatment top layer; Let surface treatment constituent and PE film surface form firm key knot through chemical reaction; Then coat the chemical treatment top layer of PE film and shine UV when being cured when ultraviolet ray (UV) curing printing ink print, multiple functional radical oligomer in the chemical treatment top layer or multiple functional radical acryl monomer can with the composition generation chemical bonded refractory of UV curing inks, so the ink logo that the UV curing inks forms can through the chemical treatment top layer strong to be attached to the PE film surperficial; The phenomenon that ink logo comes off no longer takes place, thereby helps improving the press quality of polyethylene film label.
The present invention is described by above-mentioned related embodiment, yet the foregoing description is merely the example of embodiment of the present invention.Must be pointed out that disclosed embodiment does not limit scope of the present invention.On the contrary, being contained in the spirit of claims and the modification and impartial setting of scope includes in scope of the present invention.
Claims (15)
1. polyethylene film surface treatment constituent, it is characterized in that: said surface treatment constituent comprises:
(a) acid number is a polymer between the acryl of 40-150, accounts for the 70.0-90.0 weight part;
(b) multiple pressure gram force functional group's oligomer, acryl monomer or its both, account for the 29.9-5.0 weight part;
(c) bridging agent accounts for the 0.1-5.0 weight part; And
(d) solvent use in dilution, adds the 70-1400 weight part, make said (a) and (b) composition final always consolidate the 3-20wt% scope that type part accounts for said surface treatment constituent;
Wherein said surface treatment constituent is in order to form a chemical treatment top layer on the surface of coating a Vilaterm (PE) film, with further printing one ink logo.
2. polyethylene film surface treatment constituent as claimed in claim 1, it is characterized in that: said ink logo uses a ultraviolet curing ink.
3. polyethylene film surface treatment constituent as claimed in claim 1 is characterized in that: the acid number of said composition (a) is that the monomer that polymer is selected for use during in polyreaction comprises at least: (a1) C between the acryl of 40-150
1-C
4Ester group acrylate monomer or C
1-C
6The ester group methacrylate monomers, and (a2) contain carboxyl acryl monomer.
4. polyethylene film surface treatment constituent as claimed in claim 1; It is characterized in that: the acid number of said composition (a) is that polymer comprises in addition between the acryl of 40-150: (a3) vinyl monomer, (a4) are different from (a1) or vinylformic acid functional group monomer (a2), or (a3) with the mixing of (a4).
5. polyethylene film surface treatment constituent as claimed in claim 3 is characterized in that: the C of said composition (a1)
1-C
4The ester group acrylate monomer be selected from methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, NSC 20949, tert-butyl acrylate or its mixing.
6. polyethylene film surface treatment constituent as claimed in claim 3 is characterized in that: the C of said composition (a1)
1-C
6The ester group methacrylate monomers be selected from TEB 3K, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic tert-butyl acrylate or its mixing.
7. polyethylene film surface treatment constituent as claimed in claim 3; It is characterized in that: the carboxyl acryl monomer that contains of said composition (a2) comprises the monomer of an above carboxyl, and is selected from vinylformic acid, methylacrylic acid, 2-butylene acid, maleic acid, FUMARIC ACID TECH GRADE, itaconicacid or its mixing.
8. polyethylene film surface treatment constituent as claimed in claim 4 is characterized in that: the vinyl monomer of said composition (a3) is selected from vinyl-acetic ester, vinylbenzene or its mixing.
9. polyethylene film surface treatment constituent as claimed in claim 4 is characterized in that: the vinylformic acid functional group monomer of said composition (a4) is selected from Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester, Rocryl 400, Rocryl 410, acrylic amide, USAF RH-1, epihydric alcohol acrylic ester, epihydric alcohol methylpropenoic acid ester or its mixing.
10. polyethylene film surface treatment constituent as claimed in claim 1; It is characterized in that: the multiple pressure gram force functional group's of said composition (b) oligomer comprises several to hundreds of acryl functional group, and said multiple pressure gram force functional group's oligomer is selected from urethane acrylate class, polyester acrylate class, polyether acrylate class, epoxy acrylate class or its mixing.
11. polyethylene film surface treatment constituent as claimed in claim 1; It is characterized in that: the multiple pressure gram force functional group's of said composition (b) acryl monomer comprises 3 to 6 acryl functional group, and said multiple pressure gram force functional group's acryl monomer is selected from Viscoat 295, trimethylolpropane trimethacrylate, oxyethyl group Viscoat 295, tetramethylol methane tetraacrylate, oxyethyl group tetramethylol methane tetraacrylate, double pentaerythritol C5 methacrylate, double pentaerythritol methacrylate or its mixing.
12. polyethylene film surface treatment constituent as claimed in claim 1 is characterized in that: the bridging agent of said composition (c) is selected from metallo-chelate, isocyanic acid oligomer, epoxide, nitrogen heterocycle propane compound, melamine resin or its mixing.
13. polyethylene film surface treatment constituent as claimed in claim 1 is characterized in that: the diluting solvent of said composition (d) is selected from: methyl acetate, ETHYLE ACETATE, acetone, butanone, Virahol, normal hexane, hexanaphthene, normal heptane, toluene, YLENE, butylacetate, pimelinketone, methyl glycol, glycol monoethyl ether, ethylene glycol monobutyl ether or its mixing.
14. the label of a polyethylene film is characterized in that: said label comprises:
One polyethylene film has a positive and back side;
One chemical treatment top layer, coating is formed on the front of said polyethylene film;
One ink logo, printing is formed on the said chemical treatment top layer;
One pressure-sensitive adhesive layer is affixed on the back side of said polyethylene film; And
One release layer has one release said pressure-sensitive adhesive layer of adjacency;
Wherein said chemical treatment top layer is to be coated with by polyethylene film surface treatment constituent as claimed in claim 1 to form.
15. the label of polyethylene film as claimed in claim 14 is characterized in that: said chemical treatment top layer on average is coated with dry measure approximately between 0.1 to 5.0 g/square centimeter in one on the front of said polyethylene film.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103194104A (en) * | 2013-03-21 | 2013-07-10 | 中山金利宝胶粘制品有限公司 | Plastic film surface coating composition and labeled product thereof |
| CN103792604A (en) * | 2012-10-26 | 2014-05-14 | 3M创新有限公司 | Regression reflection product and ornament |
| JP2019084803A (en) * | 2017-11-10 | 2019-06-06 | 東洋紡株式会社 | Release film |
| CN110511641A (en) * | 2019-09-23 | 2019-11-29 | 厦门长塑实业有限公司 | A kind of BOPA pre-coating film and preparation method thereof enhancing UV ink adhesion |
| WO2022163547A1 (en) * | 2021-01-29 | 2022-08-04 | 日東電工株式会社 | Surface modification sheet, laminate, surface modification member, painted object, surface modification member manufacturing method, and painted object manufacturing method |
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| CN101429416A (en) * | 2007-11-07 | 2009-05-13 | 3M新设资产公司 | Adhesion agent composition for environment-friendly water transfer printing volume label |
| WO2010116814A1 (en) * | 2009-04-10 | 2010-10-14 | リンテック株式会社 | Pressure-sensitive adhesive sheet and pressure-sensitive adhesive label using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101429416A (en) * | 2007-11-07 | 2009-05-13 | 3M新设资产公司 | Adhesion agent composition for environment-friendly water transfer printing volume label |
| WO2010116814A1 (en) * | 2009-04-10 | 2010-10-14 | リンテック株式会社 | Pressure-sensitive adhesive sheet and pressure-sensitive adhesive label using same |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103792604A (en) * | 2012-10-26 | 2014-05-14 | 3M创新有限公司 | Regression reflection product and ornament |
| CN103792604B (en) * | 2012-10-26 | 2016-12-21 | 3M创新有限公司 | Retroreflecting goods and appligue |
| CN103194104A (en) * | 2013-03-21 | 2013-07-10 | 中山金利宝胶粘制品有限公司 | Plastic film surface coating composition and labeled product thereof |
| JP2019084803A (en) * | 2017-11-10 | 2019-06-06 | 東洋紡株式会社 | Release film |
| JP7159547B2 (en) | 2017-11-10 | 2022-10-25 | 東洋紡株式会社 | release film |
| CN110511641A (en) * | 2019-09-23 | 2019-11-29 | 厦门长塑实业有限公司 | A kind of BOPA pre-coating film and preparation method thereof enhancing UV ink adhesion |
| CN110511641B (en) * | 2019-09-23 | 2021-07-23 | 厦门长塑实业有限公司 | BOPA (biaxially-oriented polyamide) pre-coating film for enhancing adhesive force of UV (ultraviolet) ink and preparation method thereof |
| WO2022163547A1 (en) * | 2021-01-29 | 2022-08-04 | 日東電工株式会社 | Surface modification sheet, laminate, surface modification member, painted object, surface modification member manufacturing method, and painted object manufacturing method |
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|---|---|
| CN102746722B (en) | 2015-01-21 |
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