CN102746722B - 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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- CN102746722B CN102746722B CN201110097422.1A CN201110097422A CN102746722B CN 102746722 B CN102746722 B CN 102746722B CN 201110097422 A CN201110097422 A CN 201110097422A CN 102746722 B CN102746722 B CN 102746722B
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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, relate to especially a kind of can medium chemical bonded refractory polyethylene film surface and the polyethylene film surface treatment constituent of ultraviolet curing ink and label thereof.
Background technology
After the processing process such as labels class (1abe1) product is printed by printing house, stamp, torn edges, can be made into label finished product is supplied to End-Customer to use, wherein the plane materiel of label is printed with various patterns or word, and therefore the press quality of plane materiel is extremely important.Common label plane materiel can be divided into paper and film class, and wherein general paper plane materiel printing is easier to, and the ink after printing also not easily drops; Moreover the press quality of film class plane materiel then needs more technical control, such as, with regard to the higher thin-film material of the surface tension such as PET (PET) film, its surface printing ink comparatively easily adheres to; But, with regard to the thin-film material that the surface tension such as polyethylene (PE) film are lower, the more difficult attachment of its surface printing ink.Therefore, in order to obtain the printed patterns of better quality on thin-film material, surface treatment must be carried out to thin-film material (as PE film).
Such as, the chamber of commerce of many PE label factories makes PE film surface by physics sided corona treatment in advance, to make its surface tension be increased to more than 38dyne/cm, to improve the tack of ink on PE film surface.On the other hand, Ye You manufacturer is at PE film surface coating one deck chemical treatments, because chemical treatments is good to the adhesive force of PE film, and ink is also good to the adhesive force of inorganic agent, so reach medium in conjunction with PE film and ink, to improve the object of ink adhesion (fastness).
Moreover in recent years in order to meet the trend of environmental protection, more and more multi-vendor use gradually does not have the ultraviolet curing ink (UV-curing ink) of environmental toxicity.Only, when UV curing printing ink print is on PE film or other thin-film material, the problem that ink comes off from local, PE film surface or large area in fact still easily occurs, therefore the printing tack (fastness) how solving the UV cured printing ink on PE film surface becomes the important topic manufacturing PE film label.
Therefore, be necessary polyethylene film surface treatment constituent and label thereof that a kind of improvement is provided, to solve the problem existing for prior art.
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, first surface treatment constituent is coated polyethylene (PE) film surface and form chemical treatment top layer, surface treatment constituent and PE film surface is allowed to form firmly bond by chemical reaction, then when on the chemical treatment top layer that ultraviolet (UV) curing printing ink print coats PE film and irradiate UV be cured time, multiple functional radical oligomer in chemical treatment top layer or multiple functional radical acrylic monomer can with the composition generation chemical bonded refractory of UV cured printing ink, so UV cured printing ink formed ink logo by chemical treatment top layer strong be attached to PE film surface, no longer there is the phenomenon that ink logo comes off, thus the press quality improving polyethylene film label is conducive to.
For reaching aforementioned object of the present invention, the invention provides a kind of polyethylene film surface treatment constituent, wherein said surface treatment constituent comprises:
A () acid number, between acrylic system (acrylic) macromolecule of 40-150, accounts for 70.0-90.0 weight portion;
The oligomer (oligomer) of (b) many acrylics functional group, acrylic monomer or its both, account for 29.9-5.0 weight portion;
C () bridging agent (crosslinker), accounts for 0.1-5.0 weight portion; And
D () retarder thinner, adds 70-1400 weight portion, make final total curable type part of described (a) and (b) composition account for the 3-20wt% scope of described surface treatment constituent;
Wherein said surface treatment constituent, in order to coat on the surface of a polyethylene (PE) film, forms a chemical treatment top layer, to print an ink logo further.
Moreover the invention provides a kind of label of polyethylene film, wherein said label comprises:
One polyethylene film, has a front and a back side;
One chemical treatment top layer, coating is formed on the front of described polyethylene film;
One ink logo, printing is formed on described chemical treatment top layer;
One pressure-sensitive adhesive layer, is affixed on the back side of described polyethylene film; And
One release layer, has one release adjacent described pressure-sensitive adhesive layer;
Wherein said chemical treatment top layer is coated with by above-mentioned surface treatment constituent and is formed.
In one embodiment of this invention, described ink logo uses a ultraviolet (UV) cured printing ink.
In one embodiment of this invention, the acid number of mentioned component (a) refers between the acrylic system macromolecule of 40-150 the acrylic system macromolecule that acid number is relatively high, and wherein these acrylic system macromolecules spendable monomer when polymerisation at least comprises: (a1) C
1-C
4the ester group acrylate monomer of (i.e. carbon number 1-4) or C
1-C
6ester group methacrylate monomers, and (a2) is containing the mixture of carboxyl acrylic monomer, and select to comprise (a3) other vinyl monomer, (a4) be different from (a1) or (a2) other acrylic acid functional group monomer, or the mixing of (a3) and (a4).The monomer of above-mentioned (a1) and (a2) is the composition that must use, and the monomer of (a3) and (a4) then can choice for use or do not use on demand.After the monomer constituents of aforementioned at least (a1) and (a2) is mixed, add appropriate solvent (such as toluene, ethyl acetate or its mixing etc.) and initiator (such as dibenzoyl peroxide, lauroyl peroxide, azodiisobutyronitrile or its mixing etc.), and under the temperature conditions of 80 to 95 DEG C, react 5 to 8 hours, namely obtain solid 35-50wt%, weight molecular weight between 20 ten thousand to 80 ten thousand and acid number between the acrylic system macromolecule of 40-150.
In one embodiment of this invention, the C of mentioned component (a1)
1-C
4ester group acrylate monomer be such as selected from methyl acrylate, ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate or its mixing.
In one embodiment of this invention, the C of mentioned component (a1)
1-C
6ester group methacrylate monomers be such as selected from methyl methacrylate, EMA, n propyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, Tert-butyl Methacrylate or its mixing.
In one embodiment of this invention, the carboxyl acrylic monomer that contains of mentioned component (a2) refers to the monomer comprising more than one carboxyl, such as, be selected from acrylic acid, methacrylic acid, 2-butenoic acid, maleic acid, fumaric acid, itaconic acid or its mixing.
In one embodiment of this invention, other vinyl monomer of mentioned component (a3) is such as selected from vinyl acetate, styrene or its mixing.
In one embodiment of this invention, other acrylic acid functional group monomer of mentioned component (a4) is such as selected from hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, hydroxyethyl methacrylate, hydroxy propyl methacrylate, acrylamide, Methacrylamide, epihydric alcohol acrylic ester, epihydric alcohol methylpropenoic acid ester or its mixing.
It should be noted that, the acid number of the acrylic system macromolecule indication of mentioned component (a) is defined as: when testing sample (i.e. the acrylic system macromolecule) of titration 1 g, required potassium hydroxide quality (in units of milligram): (56.1) AN/W, wherein A is the titer of potassium hydroxide, and unit is ml; N is the equivalent concentration of potassium hydroxide; 56.1 is molecular weight of potassium hydroxide; W is the quality of determinand, and unit is g.In the present invention, the high molecular acid number of acrylic system of mentioned component (a) need between 40-150, such as 40,50,60,70,80,90,100,110,120,130,140,150 or its any two numbers between number range.The high acid value acrylic system macromolecule of mentioned component (a) uses 70.0-90.0 weight portion, such as 70,75,80,85,90 or its any two numbers between number range.
In one embodiment of this invention, at least one in the oligomer of choice for use many acrylics functional group of the present invention and the acrylic monomer of many acrylics functional group, the oligomer of many acrylics functional group of its mentioned component (b) and/or acrylic monomer use 29.9-5.0 weight portion, such as 29.9,25,20,15,10,5 or its any two numbers between number range.
In one embodiment of this invention, the oligomer of many acrylics functional group of mentioned component (b) refers to and comprises several oligomer to hundreds of acrylic functional groups, such as be selected from polyurethane (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 the oligomer of many acrylics functional group approximately between thousands of between tens thousand of, and range of viscosities is between 100 to 300, between 000cps.
In one embodiment of this invention, the acrylic monomer of many acrylics functional group of mentioned component (b), be often referred to the acrylic monomer comprising 3 to 6 acrylic functional groups, such as, be selected from trimethylolpropane triacrylate (TMPTA), trimethylol-propane trimethacrylate (TMPTMA), ethyoxyl trimethylolpropane triacrylate (EOTMPTA), tetramethylol methane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, double pentaerythritol C5 methacrylate, double pentaerythritol methacrylate or its mixing.
In one embodiment of this invention, the bridging agent of mentioned component (c) refer to can with the compound of carboxyl reaction, be such as selected from metallo-chelate (metal chelate), isocyanic acid oligomer (polyisocyanate), epoxides (epoxy), nitrogen heterocycle propane compound (polyaziridine), melmac (melamine resin) or its mixing.The bridging agent of mentioned component (c) uses 0.1-5.0 weight portion, such as 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 number range.
In one embodiment of this invention, the retarder thinner of mentioned component (d) is in order to meet the demand providing applicable application viscosity, the overall viscosity of described surface treatment constituent can be reduced by adding appropriate retarder thinner, make its more easily carry out coating operations obtain expect coating dry measure scope.Described retarder thinner can be selected from: low boiling point solvent, such as methyl acetate, ethyl acetate, acetone, butanone, isopropyl alcohol, n-hexane, cyclohexane, normal heptane or its mixing; And/or medium-boiling solvent, such as toluene, dimethylbenzene, butyl acetate, cyclohexanone, glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether (EGMBE) or its mixing.The retarder thinner of mentioned component (d) uses 70-1400 weight portion, make final total curable type part of described (a) and (b) composition account for the 3-20wt% scope of described surface treatment constituent, such as 70,85,100,200,400,600,800,1000,1400 or its any two numbers between number range.
In one embodiment of this invention, before the described UV cured printing ink of printing, the surface of described PE film, preferably in advance by a sided corona treatment, makes the surface tension of described PE film be increased to more than 38 dyne/centimetre (dyne/cm), to improve described UV cured printing ink to the tack of PE.Above-mentioned sided corona treatment belongs to physical surface treatment method.Moreover the present invention further adopts chemically treated method, first described surface treatment constituent is coated described PE film surface, allow the surface of described surface treatment constituent and PE film form firmly bond by chemical reaction.Then, when UV curing printing ink print coat PE film chemically treating surface and irradiate again UV be cured time, many acrylics functional group oligomer in described surface treatment constituent and/or acrylic monomer separately can with the composition generation chemical bonded refractory of described UV cured printing ink, so make described UV cured printing ink just by chemical treatment top layer strong be attached to described PE film surface, no longer there is the phenomenon that ink logo comes off, be thus conducive to the press quality improving PE film label.
In the present invention, curable type part of described surface treatment constituent is deployed into occupies between overall 3 to 20wt%, and select to adopt intaglio plate, oppositely intaglio plate, heliogravure, five roller coating cloth, coiling rod or its equivalent way to be in the same way coated on the front of PE film, the average coat dry measure of described chemical treatment top layer on the front of described polyethylene film is about between 0.1 to 5.0 g/square centimeter, wherein being preferably between 0.5 to 2.0 g/square centimeter, such as, is 0.5,1.0,1.5 or 2.0.After being coated with described surface treatment constituent, different according to bridging agent kind, under normal temperature (23 ± 2 DEG C), place 24 littlely allowed described surface treatment constituent after mature up to 168 hours, itself and the chemical bonded refractory of PE film reacts just complete, just can have good firm attachment degree.So, can utilize described surface treatment constituent on the front of PE film, be coated with formation one chemical treatment top layer.
Then, choice for use one release layer, and on release of release layer, be coated with applicable pressure sensitive adhesive (pressure-sensitive adhesive), after oven drying, form a pressure-sensitive adhesive layer.Subsequently, fitting in the pressure-sensitive adhesive layer of release and the above-mentioned back side with the PE film on chemical treatment top layer of release layer, becomes semi-finished product with center rewinding, then through the width of itemize rewinding needed for printing client and the label finished product of length.Such as, please refer to shown in Fig. 1, in a preferred embodiment of the present invention, a label finished product of the present invention roughly comprises: a polyethylene (PE) film 10, there is a front and a back side; One chemical treatment top layer 11, coating is formed on the front of described polyethylene film 10; One ink logo 12, printing is formed on described chemical treatment top layer 11; One pressure-sensitive adhesive layer 13, contact the back side of described polyethylene film 10 at described pressure-sensitive adhesive layer 13 after, described pressure-sensitive adhesive layer 13 can be posted on the back side of described polyethylene film 10; And a release layer 14, have one release, described release adjacent described pressure-sensitive adhesive layer 13, wherein said chemical treatment top layer 11 is coated with by above-mentioned surface treatment constituent and is formed.Described release layer 14 can be selected from various mould release membrance or release liners, such as polyester (PET) mould release membrance, polyethylene (PE) mould release membrance, Ge Laxin (glassine) release liners or plastic-coated brown paper (PEK) release liners.
Accompanying drawing explanation
Fig. 1 is the generalized section of the label of present pre-ferred embodiments polyethylene film.
Detailed description of the invention
The explanation of following embodiment be illustrate the present invention can in order to implement specific embodiment, as used herein dialect be in order to illustrate and understand the present invention, and be not used to limit the present invention.
When preparing polyethylene film surface treatment constituent of the present invention, first prepare the acrylic system macromolecule of high acid value (acid number is between 40-150), its preparation process is as follows:
(1) reaction system is set, comprises the equipment such as the glass reaction groove of 1 liter, variable-ratio agitator, temperature indicator, reflux condensing tube, charge pipe, constant temperature water bath;
(2) various monomer (a1) ~ (a4) is added reactive tank respectively according to formulation content, with beaker weighing starting agent and after adding dissolution with solvents, add in reactive tank, remaining solvent adds reactive tank respectively;
(3) agitator speed is set as 100rpm, starts to stir, and constant temperature water bath temperature is set as that 90 DEG C start to heat up;
(4), after condenser pipe backflow occurs, timing 1 hour is started;
(5), after interpolation solution mixes, pour charge pipe into, add gradually in reactive tank in certain hour; And
(6), after continuing heating a period of time, add the solvent of dilution, be cooled to room temperature and namely obtain product.
The method of testing of polyethylene film surface treatment constituent:
Viscosity: with Brookfield DV-I prime viscometer viscosimeter, #2 rotating shaft, rotating speed 30rpm, under room temperature, (23 ± 2 DEG C) survey its viscosity number, in units of cps.
Solid: its measurement is by scale pan weighing (W
0), scale pan weighing (W inserted by the sample that takes a morsel
1) after, put into 150 DEG C of baking ovens through 60 points of bells, remove wherein moisture content, after returning back to room temperature, then survey its weight (W
2), solid is (W
2-W
0)/(W
1-W
0) × 100%.
The adherence test procedure of polyethylene film surface treatment constituent:
(1) configuration for the treatment of agent formula (i.e. surface treatment constituent):
(1-1) the appropriate high molecular solution of (a) high acid value acrylic system is got, add the oligomer (oligomer) of (b) many acrylics functional groups, acrylic monomer or its both, then be diluted to the concentration of curable type part about 10% with solvent; And
(1-2) (c) bridging agent is added in the above-mentioned solution of curable type part 10%, stirs for subsequent use.
(2) coating for the treatment of agent formula:
(2-1) inorganic agent of above-mentioned configuration is coated on the PE film front that sided 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 DEG C of baking ovens, takes out after 5 minutes; And
(2-3) PE film specimen page is under the environment of constant temperature and humidity (23 DEG C, 50%RH), places appropriate time after mature, then carries out next step.
(3) coating of UV cured printing ink:
(3-1) UV cured printing ink hand is applied on the chemical treatment top layer of PE film specimen page, to form ink logo by the coiling rod getting #1;
(3-2) by the specimen page of tool ink logo through UV drying machine drying program; And
(3-3) specimen page to be positioned under constant temperature and humidity condition more than at least one hour.
(4) adherence experiment:
(4-1) after test tape (3M#600) takes one end in hand fixing, directly pull open fit in PE film specimen page to be tested ink logo on the surface, and remove bubble ten times with finger joint place of exerting pressure back and forth;
(4-2) adhesive tape one end is torn up, make to be enough to hold by finger clamp, draw rapidly except adhesive tape (a minute must be less than from the time of sticking tearing-off adhesive tape) with the angle of about 90 ° immediately; And
(4-3) whether visual examination adhesive tape is totally transparent, confirms the area that comes off of ink logo.
The preparation of high acid value acrylic system macromolecule A of the present invention:
(1) after glass reaction groove, reflux condensing tube, charge pipe clean respectively, device reaction system.
(2) by methyl methacrylate 90 grams, n-butyl acrylate 72 grams, 12 grams, acrylic acid, hydroxyethyl methacrylate 4 grams, add reactive tank respectively, after being dissolved in 20 grams of toluene with beaker weighing dibenzoyl peroxide 0.4 gram, add in reactive tank, toluene 50 grams, 200 grams, ethyl acetate add reactive tank respectively.
(3) agitator speed is set as that 100rpm starts to stir, and constant temperature water bath temperature is set as that 90 DEG C start to heat up.
(4), after condenser pipe backflow occurs, timing 1 hour is started.
(5) methyl methacrylate 30 grams, n-butyl acrylate 24 grams, 4 grams, acrylic acid, hydroxyethyl methacrylate 2 grams are added glass beaker respectively and mix, after being dissolved in 12 grams of toluene with another beaker weighing dibenzoyl peroxide 0.8 gram again, add in preceding paragraph monomer mixed solution, charge pipe poured into by whole mixed liquor, adds gradually in reactive tank in 1 hour.
(6) continue heating after 4 hours, add 80 grams of dilution with toluene, namely the room temperature that is water-cooled to constant temperature water bath being changed room temperature obtains product A.
The preparation of high acid value acrylic system macromolecule B of the present invention:
(1) after glass reaction groove, reflux condensing tube, charge pipe clean respectively, device reaction system.
(2) by Tert-butyl Methacrylate 48 grams, ethyl acrylate 96 grams, 16 grams, acrylic acid, styrene 18 grams, add reactive tank respectively, after being dissolved in 20 grams of toluene with beaker weighing laurylperoxide 0.4 gram, add in reactive tank, toluene 40 grams, 200 grams, ethyl acetate, isopropyl alcohol 20 grams add reactive tank respectively.
(3) agitator speed is set as that 100rpm starts to stir, and constant temperature water bath temperature is set as that 90 DEG C start to heat up.
(4), after condenser pipe backflow occurs, timing 1 hour is started.
(5) Tert-butyl Methacrylate 16 grams, ethyl acrylate 32 grams, 6 grams, acrylic acid, styrene 6 grams are added glass beaker respectively and mixes, after being dissolved in 32 grams of toluene with another beaker weighing laurylperoxide 0.8 gram again, add in preceding paragraph monomer mixed solution, charge pipe poured into by whole mixed liquor, adds gradually in reactive tank in 1 hour.
(6) continue heating after 4 hours, add 80 grams of dilution with toluene, namely the room temperature that is water-cooled to constant temperature water bath being changed room temperature obtains product B.
The preparation of prior art (comparative example) acrylic system macromolecule C:
(1) after glass reaction groove, reflux condensing tube, charge pipe clean respectively, device reaction system.
(2) by methyl methacrylate 103 grams, n-butyl acrylate 72 grams, 2 grams, acrylic acid, hydroxyethyl methacrylate 1 gram, add reactive tank respectively, after being dissolved in 20 grams of toluene with beaker weighing dibenzoyl peroxide 0.4 gram, add in reactive tank, toluene 50 grams, 200 grams, ethyl acetate add reactive tank respectively.
(3) agitator speed is set as that 100rpm starts to stir, and constant temperature water bath temperature is set as that 90 DEG C start to heat up.
(4), after condenser pipe backflow occurs, timing 1 hour is started.
(5) methyl methacrylate 34 grams, n-butyl acrylate 24 grams, 1 gram, acrylic acid, hydroxyethyl methacrylate 1 gram are added glass beaker respectively and mix, after being dissolved in 12 grams of toluene with another beaker weighing dibenzoyl peroxide 0.8 gram again, add in preceding paragraph monomer mixed solution, charge pipe poured into by whole mixed liquor, adds gradually in reactive tank in 1 hour.
(6) continue heating after 4 hours, add 80 grams of dilution with toluene, namely the room temperature that is water-cooled to constant temperature water bath being changed room temperature obtains product C.
The embodiment of the present invention one
(1) inorganic agent test recipe one:
Table one:
611A-85: polyurethane oligomer, Changxing chemical products.
Desmodur L75: multiple functional radical isocyanic acid oligomer, Bayer product.
(2) coating of inorganic agent test recipe one:
(2-1) with #1 coiling rod, inorganic agent test recipe one is coated on the sided corona treatment front of low density polyethylene (LDPE) (LDPE) film specimen page one of 85 μm, to form a chemical treatment top layer.
(2-2) specimen page one being put into temperature is 60 DEG C of baking ovens, takes out after 5 minutes.
(2-3) by the condition of specimen page one in constant temperature and humidity condition (23 DEG C, 50%RH relative humidity), place and carry out next step again in 168 hours.
(3) the UV cured printing ink coating of specimen page one:
(3-1) yellow UV cured printing ink hand is applied on the chemical treatment top layer of PE film specimen page one, to form ink logo by the coiling rod getting #1.
(3-2) by the specimen page of tool ink logo once UV drying machine drying program.
(3-3) specimen page one to be positioned under constant temperature and humidity condition more than at least one hour.
(4) the adherence experiment of specimen page one:
(4-1) after test tape (3M#600) takes one end in hand fixing, directly pull open fit in PE film specimen page one to be tested ink logo on the surface, and remove bubble ten times with finger joint place of exerting pressure back and forth.
(4-2) test tape one end being torn up, make to be enough to hold by finger clamp, drawing rapidly except adhesive tape (a minute must be less than from sticking to the time removing test tape) with the angle of about 90 ° immediately.
(4-3) whether the face of pasting of visual examination test tape is totally transparent, confirms the area that comes off of ink logo.
The embodiment of the present invention two
(1) inorganic agent test recipe two:
Table two:
SR454: ethyoxyl trimethylolpropane triacrylate (EOTMPTA), Sartomer's product
PFAZ321: multiple functional radical aziridine bridging agent, Bayer product.
(2) coating of inorganic agent test recipe two:
(2-1) with #1 coiling rod, inorganic agent test recipe two is coated on the sided corona treatment front of low density polyethylene (LDPE) (LDPE) film specimen page two of 85 μm, to form a chemical treatment top layer.
(2-2) specimen page two being put into temperature is 60 DEG C of baking ovens, takes out after 5 minutes.
(2-3) by the condition of specimen page two in constant temperature and humidity condition (23 DEG C, 50%RH), place and carry out next step again in 24 hours.
(3) the UV cured printing ink coating of specimen page two:
(3-1) yellow UV cured printing ink hand is applied on the chemical treatment top layer of low density polyethylene (LDPE) (LDPE) film specimen page two, to form ink logo by the coiling rod getting #1.
(3-2) by the specimen page two of tool ink logo through UV drying machine drying program.
(3-3) specimen page two to be positioned under constant temperature and humidity condition more than at least one hour.
(4) the adherence experiment of specimen page two:
(4-1) after test tape (3M#600) takes one end in hand fixing, directly pull open fit in LDPE film specimen page two to be tested ink logo on the surface, and remove bubble ten times with finger joint place of exerting pressure back and forth.
(4-2) test tape one end being torn up, make to be enough to hold by finger clamp, drawing rapidly except adhesive tape (a minute must be less than from sticking to the time removing test tape) with the angle of about 90 ° immediately.
(4-3) whether the face of pasting of visual examination test tape is totally transparent, confirms the area that comes off of ink logo.
The embodiment of the present invention three
(1) inorganic agent test recipe three:
Table three:
| Composition | Use amount |
| Acrylic system macromolecule 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: ethyoxyl trimethylolpropane triacrylate (EOTMPTA), Sartomer product.
Desmodur L75: multiple functional radical isocyanic acid oligomer, Bayer product.
(2) coating of inorganic agent test recipe three:
(2-1) with #1 coiling rod, inorganic agent test recipe three is coated on the sided corona treatment front of low density polyethylene (LDPE) (LDPE) film specimen page three of 85 μm, to form a chemical treatment top layer.
(2-2) specimen page three being put into temperature is 60 DEG C of baking ovens, takes out after 5 minutes.
(2-3) by the condition of specimen page three in constant temperature and humidity condition (23 DEG C, 50%RH), place and carry out next step again in 168 hours.
(3) the UV cured printing ink coating of specimen page three:
(3-1) yellow UV cured printing ink hand is applied on the chemical treatment top layer of low density polyethylene (LDPE) (LDPE) film specimen page three, to form ink logo by the coiling rod getting #1.
(3-2) by the specimen page three of tool ink logo through UV drying machine drying program.
(3-3) specimen page three to be positioned under constant temperature and humidity condition more than at least one hour.
(4) the adherence experiment of specimen page three:
(4-1) after test tape (3M#600) takes one end in hand fixing, directly pull open fit in LDPE film specimen page three to be tested ink logo on the surface, and remove bubble ten times with finger joint place of exerting pressure back and forth.
(4-2) test tape one end being torn up, make to be enough to hold by finger clamp, drawing rapidly except adhesive tape (a minute must be less than from sticking to the time removing test tape) with the angle of about 90 ° immediately.
(4-3) whether the face of pasting of visual examination test tape is totally transparent, confirms the area that comes off of ink logo.
The comparative example one of prior art
(1) inorganic agent test recipe four:
Table four:
| Composition | Use amount |
| Acrylic system macromolecule 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 test recipe four is processed:
(2-1) with #1 coiling rod, inorganic agent test recipe four is coated on the sided corona treatment front of low density polyethylene (LDPE) (LDPE) film specimen page four of 85 μm, to form a chemical treatment top layer.
(2-2) specimen page four being put into temperature is 60 DEG C of baking ovens, takes out after 5 minutes.
(2-3) by the condition of specimen page four in constant temperature and humidity condition (23 DEG C, 50%RH), place and carry out next step again in 168 hours.
(3) the UV cured printing ink coating of specimen page four:
(3-1) yellow UV cured printing ink hand is applied on the chemical treatment top layer of low density polyethylene (LDPE) (LDPE) film specimen page four, to form ink logo by the coiling rod getting #1.
(3-2) by the specimen page four of tool ink logo through UV drying machine drying program.
(3-3) specimen page to be positioned under constant temperature and humidity condition more than at least one hour.
(4) the adherence experiment of specimen page four:
(4-1) after test tape (3M#600) takes one end in hand fixing, directly pull open fit in LDPE film specimen page four to be tested ink logo on the surface, and remove bubble ten times with finger joint place of exerting pressure back and forth.
(4-2) test tape one end being torn up, make to be enough to hold by finger clamp, drawing rapidly except adhesive tape (a minute must be less than from sticking to the time removing test tape) with the angle of about 90 ° immediately.
(4-3) whether the face of pasting of visual examination test tape is totally transparent, confirms the area that comes off of ink logo.
The comparative example two of prior art
(1) inorganic agent test recipe five:
Table five:
| Composition | Use amount |
| Acrylic system macromolecule C | 100.0 |
| Toluene | 300.0 |
| Add up to | 400.0 |
| Solid (%) | 11.47 |
| Viscosity (cps) | 95 |
(2) coating of test recipe five is processed:
(2-1) with #1 coiling rod, inorganic agent test recipe five is coated on the sided corona treatment front of low density polyethylene (LDPE) (LDPE) film specimen page five of 85 μm, to form a chemical treatment top layer.
(2-2) specimen page five being put into temperature is 60 DEG C of baking ovens, takes out after 5 minutes.
(2-3) by the condition of specimen page five in constant temperature and humidity condition (23 DEG C, 50%RH), place and carry out next step again in 24 hours.
(3) the UV cured printing ink coating of specimen page five:
(3-1) yellow UV cured printing ink hand is applied on the chemical treatment top layer of low density polyethylene (LDPE) (LDPE) film specimen page five, to form ink logo by the coiling rod getting #1.
(3-2) by the specimen page Five Classics UV drying machine drying program of tool ink logo.
(3-3) specimen page to be positioned under constant temperature and humidity condition more than at least one hour.
(4) the adherence experiment of specimen page five:
(4-1) after test tape (3M#600) takes one end in hand fixing, directly pull open fit in LDPE film specimen page five to be tested ink logo on the surface, and remove bubble ten times with finger joint place of exerting pressure back and forth.
(4-2) test tape one end being torn up, make to be enough to hold by finger clamp, drawing rapidly except adhesive tape (a minute must be less than from sticking to the time removing test tape) with the angle of about 90 ° immediately.
(4-3) whether the face of pasting of visual examination test tape is totally transparent, confirms the area that comes off of ink logo.
The tack experimental result after tearing up test is carried out on the chemical treatment top layer of each PE film specimen page:
Table six:
Please refer to shown in table six, in existing polyethylene (PE) film (being such as LDPE film etc.), be coated on by the surface treatment constituent of comparative example one or two the chemical treatment top layer that PE film is formed utilizes test tape to carry out tearing up test after printing-ink pattern, the ink logo that wherein test result shows existing PE film comes off area about 60 to 80%, chemical treatment top layer namely on its PE film cannot firmly in conjunction with ink logo, and large-area coming off leaves PE film because of external active force impact to make ink logo very easily.In comparison, in polyethylene of the present invention (PE) film, be coated on by the surface treatment constituent of embodiment one, two or three the chemical treatment top layer that PE film is formed utilizes test tape to carry out tearing up test after printing-ink pattern, the ink logo that wherein test result shows PE film of the present invention does not observe any obvious dropping situations sticked by adhesive tape, chemical treatment top layer namely on PE film of the present invention can firmly in conjunction with ink logo, makes ink logo not easily because external active force impact to come off to leave PE film.
In more detail, the present invention adopts chemically treated method, first surface treatment constituent is coated polyethylene (PE) film surface and form chemical treatment top layer, surface treatment constituent and PE film surface is allowed to form firmly bond by chemical reaction, then when ultraviolet (UV) curing printing ink print coat PE film chemical treatment top layer and irradiate UV be cured time, multiple functional radical oligomer in chemical treatment top layer or multiple functional radical acrylic monomer can with the composition generation chemical bonded refractory of UV cured printing ink, so UV cured printing ink formed ink logo by chemical treatment top layer strong be attached to PE film surface, no longer there is the phenomenon that ink logo comes off, thus the press quality improving polyethylene film label is conducive to.
The present invention is described by above-mentioned related embodiment, but above-described embodiment is only enforcement example of the present invention.Must it is noted that published embodiment limit the scope of the invention.On the contrary, be contained in the spirit of claims and the amendment of scope and impartial setting to be included in scope of the present invention.
Claims (9)
1. a polyethylene film surface treatment constituent, is characterized in that: the formula of described surface treatment constituent is:
A () acid number, between the acrylic system macromolecule of 40-150, accounts for 70.0-90.0 weight portion;
The oligomer of (b) many acrylics functional group, acrylic monomer or its both, account for 29.9-5.0 weight portion;
C () bridging agent, accounts for 0.1-5.0 weight portion; And
D () retarder thinner, adds 70-1400 weight portion, make final total curable type part of described (a) and (b) composition account for the 3-20wt% scope of described surface treatment constituent;
Wherein said surface treatment constituent in order to coat a polyethylene (PE) film surface on formation one chemical treatment top layer, to print an ink logo further;
The acid number of wherein said composition (a) between the acrylic system macromolecule of 40-150 in polymerisation time the monomer selected at least comprise: (a1) C
1-C
4ester group acrylate monomer or C
1-C
6ester group methacrylate monomers, and (a2) is containing carboxyl acrylic monomer; The acid number of described composition (a) between the acrylic system macromolecule of 40-150 in polymerisation time the monomer selected separately comprise: (a3) vinyl monomer, (a4) are different from the acrylic acid functional group monomer of (a1) or (a2), or the mixing of (a3) and (a4); The oligomer of many acrylics functional group of described composition (b) comprises several to hundreds of acrylic functional groups, and the oligomer of described many acrylics functional group is selected from urethane acrylate class, polyester acrylate class, polyether acrylate class, Epoxy Acrylates or its mixing; The acrylic monomer of many acrylics functional group of described composition (b) comprises 3 to 6 acrylic functional groups, and the acrylic monomer of described many acrylics functional group is selected from trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, ethyoxyl trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, double pentaerythritol C5 methacrylate, double pentaerythritol methacrylate or its mixing; The bridging agent of described composition (c) is selected from metallo-chelate, isocyanic acid oligomer, epoxides, nitrogen heterocycle propane compound, melmac or its mixing; The retarder thinner of described composition (d) is selected from: methyl acetate, ethyl acetate, acetone, butanone, isopropyl alcohol, n-hexane, cyclohexane, normal heptane, toluene, dimethylbenzene, butyl acetate, cyclohexanone, glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether (EGMBE) or its mixing.
2. polyethylene film surface treatment constituent as claimed in claim 1, is characterized in that: described ink logo uses a ultraviolet curing ink.
3. polyethylene film surface treatment constituent as claimed in claim 1, is characterized in that: the C of described composition (a1)
1-C
4ester group acrylate monomer be selected from methyl acrylate, ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate or its mixing.
4. polyethylene film surface treatment constituent as claimed in claim 1, is characterized in that: the C of described composition (a1)
1-C
6ester group methacrylate monomers be selected from methyl methacrylate, EMA, n propyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, Tert-butyl Methacrylate or its mixing.
5. polyethylene film surface treatment constituent as claimed in claim 1, it is characterized in that: the monomer comprising more than one carboxyl containing carboxyl acrylic monomer of described composition (a2), and be selected from acrylic acid, methacrylic acid, 2-butenoic acid, maleic acid, fumaric acid, itaconic acid or its mixing.
6. polyethylene film surface treatment constituent as claimed in claim 1, is characterized in that: the vinyl monomer of described composition (a3) is selected from vinyl acetate, styrene or its mixing.
7. polyethylene film surface treatment constituent as claimed in claim 1, is characterized in that: the acrylic acid functional group monomer of described composition (a4) is selected from hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, hydroxyethyl methacrylate, hydroxy propyl methacrylate, acrylamide, Methacrylamide, epihydric alcohol acrylic ester, epihydric alcohol methylpropenoic acid ester or its mixing.
8. a label for polyethylene film, is characterized in that: described label comprises:
One polyethylene film, has a front and a back side;
One chemical treatment top layer, coating is formed on the front of described polyethylene film;
One ink logo, printing is formed on described chemical treatment top layer;
One pressure-sensitive adhesive layer, is affixed on the back side of described polyethylene film; And
One release layer, has one release adjacent described pressure-sensitive adhesive layer;
Wherein said chemical treatment top layer is coated with by polyethylene film surface treatment constituent as claimed in claim 1 and is formed.
9. the label of polyethylene film as claimed in claim 8, is characterized in that: the average coat dry measure of described chemical treatment top layer on the front of described polyethylene film is between 0.1 to 5.0 g/square centimeter.
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| 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 |
| JP7159547B2 (en) * | 2017-11-10 | 2022-10-25 | 東洋紡株式会社 | release film |
| 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 |
| JPWO2022163547A1 (en) * | 2021-01-29 | 2022-08-04 |
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