CN1237131C - Polyester mulching film - Google Patents
Polyester mulching film Download PDFInfo
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- CN1237131C CN1237131C CN 01140189 CN01140189A CN1237131C CN 1237131 C CN1237131 C CN 1237131C CN 01140189 CN01140189 CN 01140189 CN 01140189 A CN01140189 A CN 01140189A CN 1237131 C CN1237131 C CN 1237131C
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Abstract
The present invention relates to a polyester coating film. At least one surface of a polyester film with the opacity represented by the optical concentration of higher than 0.3 is provided with a polyester coating film of the coating layer. The present invention is characterized in that the 60-degree mirror face glossiness G1 and the 75-degree mirror face glossiness G2 of the coating layer respectively conform to the formula (1) (G1<=20...) and the formula (2)(1<G2/G1<=4...).
Description
Technical field
The present invention relates to printing ink adherence, printing and the good polyester mulching film of anti-powder deciduous, particularly be suitable as the base material that label is used.
Background technology
Ployester series film has the crystallinity of height, the good transparency, gloss, mechanical property and resistance, so can be used for purposes widely.And then, in order to pay the purpose of printing, anti-adhesive, static resistance etc., generally be to form coating on the ployester series film surface.In addition, for the transparency and the operability (anti-adhesive, sliding, wearability etc.) that make film and deposit,, form concavo-convex at film surface so generally be in the coating of ployester series film, to contain particle.
In press, particularly as in the frequent heat seal printing of using and lithography of the method for label printing, exist when the roller that is printed face and printing press produces slip, film and roller friction, particle are cut from coating, the problem that pulverize falls from the coating surface.In the past, particle fell from such coating and was not caused attention, but particle comes off and not only lose above-mentioned characteristic, and the powder that falls pollutes roller.In addition, generation printing ink comes off and causes commodity value to reduce.
Summary of the invention
The objective of the invention is to address the above problem, provide to keep the printing ink adherence, and anti-powder deciduous and the good polyester mulching film of printing.
The present inventor has carried out result of study with keen determination in order to achieve the above object, finds to make specified range by the mirror surface luster with the lining aspect of ployester series film, can be met the ployester series film of printing ink adherence and printing and anti-powder deciduous.
That is, finish problem of the present invention by following method.
1) polyester mulching film, be the polyester mulching film that coating is set at least one face of the ployester series film with opaqueness of representing more than 0.3 with optical concentration, it is characterized in that 60 degree mirror surface luster G1 of above-mentioned lining aspect and 75 degree mirror surface luster G2 satisfy following formula (1) and (2).
G1≤20 …(1)
1＜G2/G1≤4 …(2)
2) above-mentioned 1) described polyester mulching film it is characterized in that ployester series film contains the cavity in this film inside, and its apparent density is 0.3～1.3g/cm
3
3) above-mentioned 1) described polyester mulching film is characterized in that at least a kind resin that above-mentioned coating is selected by polyester system, polyurethane series, acrylic acid polymer and/or their multipolymer and is that the composition of main composition composition constitutes with the inert particle more than a kind.
4) above-mentioned 1) described polyester mulching film, the resin that it is characterized in that above-mentioned coating are to be that resin constitutes by the vibrin of water-insoluble and water dispersible and at the aqurous ployurethane that intramolecularly has 1 blocked isocyanate at least.
5) above-mentioned 1) described polyester mulching film is characterized in that the surperficial intrinsic impedance value of above-mentioned lining aspect is 1 * 10
13Ω/cm
2Below.
6) above-mentioned 1) described polyester mulching film it is characterized in that ployester series film contains the cavity in this film inside, and its empty lamination number density is more than the 0.20/μ m.
The vibrin of the main composition composition of the ployester series film that uses as base material among the present invention is to make the aromatic dicarboxylic acid of phthalic acid, m-phthalic acid, naphthalene dicarboxylic acids etc. or its ester and ethylene glycol, glycol ether, 1,4-butyleneglycol, 1, the polyester that the glycol polycondensation of 6-hexylene glycol, neopentyl glycol etc. obtains are as main body.
In addition, as the composition of vibrin, but also can contain aromatic series, aliphatics, alicyclic omega-dicarboxylic acids or aromatic series, aliphatics, the alicyclic glycols of copolymerization.
These vibrin can be made by following known method, are about to method that aromatic dicarboxylic acid and glycol carry out the esterification aftercondensated, the alkyl ester of aromatic dicarboxylic acid and glycol are carried out the method for transesterification reaction aftercondensated or make the diol ester of aromatic dicarboxylic acid carry out the method etc. of polycondensation.
As the typical example of such vibrin, can enumerate polyethylene terephthalate, polybutylene terephthalate or gather-2, the thermoplastic polyester of 6-naphthoic acid glycol ester etc.These polyester can be homopolymer, also can mix vibrin not of the same race, also can be and the 3rd composition copolymerization.Wherein, preferably ethylene glycol terephthalate, mutual-phenenyl two acid bromide two alcohol ester, 2,6-naphthoic acid glycol ester unit is above, above, the 90 moles of polyester that % is above more preferably of 80 moles of % preferably of 70 moles of %.Wherein, polyethylene terephthalate most preferably.
Consider that from the aspect of practicality such as intensity, toughness the ployester series film of Shi Yonging particularly preferably is the biaxial oriented stretch film in the present invention.
In the present invention the ployester series film of Shi Yonging can be single layer structure, also can be multilayered structure, but preferably one part layer or all part layers are opaque.The optical concentration of opaqueness of expression ployester series film is more than 0.3, preferably 0.3～4.0, particularly preferably be 0.5～3.0.If during optical concentration less than 0.3, when printing on the surface of the polyester mulching film that obtains, printing effect is not obvious, is unfavorable.In addition, if optical concentration is 4.0 when following, can expect better printing effect.
Be not particularly limited for the method that obtains the optical concentration in the above-mentioned scope, but can be by in vibrin, containing inorganic particulate or obtaining with the non-hot plasticity resin that mixes of this vibrin.These content is not particularly limited, but when using inorganic particulate, for generating polyester, preferably 5～35 weight %, particularly preferably be 8～25 weight %.On the other hand, when containing the non-hot plasticity resin that mixes, for polyester, preferably 5～35 weight %, particularly preferably be 8～28 weight %.In addition, and with inorganic particulate and with vibrin in during the non-hot plasticity resin that mixes, for ployester series film, its total amount sees it is ideal from film strength, toughness, system membrane stability when 40 weight % are following.
Be not particularly limited for the inorganic particulate that uses, but preferably median size be 0.1～4.0 μ m particle, particularly preferably be the particle of 0.3～1.5 μ m.Particularly, preferably the white pigment of titanium oxide, barium sulfate, lime carbonate, zinc sulphide etc. also can be these mixing.And then, also can and use the inorganic particulate that generally in film, contains, for example silicon oxide, aluminum oxide, talcum, kaolin, clay, calcium phosphate, mica, hectorite, zirconium white, Tungsten oxide 99.999, lithium fluoride, Calcium Fluoride (Fluorspan), calcium phosphate etc.
In addition, as with the non-hot plasticity resin that mixes of vibrin, be not particularly limited, but for example, when mixing, can enumerate polyolefin-based resins, acrylic resin, phenoxy resin, polyphenylene oxide resin, polycarbonate resin of polystyrene resin, polyvinyl resin, acrylic resin, polymethylpentene resin etc. etc. with polyethylene terephthalate.In addition, also can be with these hot plasticity mixed with resin, also can be modification.Certainly, also can and use with above-mentioned inorganic particulate.In addition, as required, also can add various whitening agent.
And then, the ployester series film that the present invention uses, preferably containing its apparent density is 0.3～1.3g/cm
3The ployester series film of micro-cavity.
In addition, its empty lamination number density from require resiliency and sur-face peeling intensity two aspects to see to be more than the 0.20/μ m, preferably more than the 0.25/μ m, the ployester series film that contains micro-cavity more than the 0.30/μ m most preferably.Its result, the processing characteristics when the printing palpability of the polyester mulching film that obtains and printing is good.At this, empty lamination number density (individual/μ m) defines with following formula:
Empty number (the individual)/film thickness (μ m) of film thickness direction
The upper limit of this cavity lamination number density, from empty expression efficiency, preferably 0.80/μ m, 0.55/μ m more preferably.As with this Auto-regulating System of Density of Heavy Medium in above-mentioned scope institute method, except the addition of regulating the non-hot plasticity resin that mixes or kind, viscosity, the screw rod shape of variable forcing machine or the method for static(al) mixing tank etc. is set to the molten resin stream, but not limited by these.
Scattering of light takes place by on the micro-cavity in being contained in film and the interface as the polyester of matrix in the ployester series film that contains these micro-cavities, can further improve opaqueness, reduces the interpolation of above-mentioned inorganic particulate, so be useful especially.And then, by containing micro-cavity, base material film self lightweight can being easy to simultaneously so handle, economic benefits such as raw materials cost reduction and transportation cost reduction also increase.
Method as the ployester series film that obtains containing such micro-cavity, can use disclosed known method, promptly pass through for hot plasticity vibrin as matrix, as the non-hot plasticity resin that mixes that mixes in the above-mentioned vibrin, to in vibrin, disperse the sheet of the non-resin that mixes to stretch at a direction of principal axis at least by finely particulate, around the above-mentioned non-resin microparticle that mixes, produce the method in cavity etc.
In addition, the thickness of the ployester series film that contains micro-cavity that obtains, preferably 5～300 μ m.Particularly contain its empty lamination number density and be the thickness of the ployester series film of the above micro-cavity of 0.20/μ m, preferably 20～300 μ m, 40～250 μ m most preferably.
And then polyester mulching film of the present invention must be provided with coating at least one face as the ployester series film of base material.Above-mentioned coating, the adherence upgrading layer that preferably has following function, promptly in the evaluation method of printing ink adherence described later, the ink residue rate that has by cross-section method is more than 90%.
As the method that coating is set, can enumerate that the coating liquid that will contain adherence upgrading resin combination is coated in the lip-deep side of ployester series film of base material or by coextrusion adherence upgrading resin method in method of the ployester series film superimposed layer of base material etc.And then, also can in advance this film surface be carried out surface treatment in order further to improve the ployester series film of base material and the adherence of coating.As the surface-treated method, for example can enumerate method, flame treating by the active energy beam irradiation of Corona discharge Treatment, plasma discharge treatment, ultraviolet ray (UV) radiation treatment, radioactive rays (EB) radiation treatment etc., and then the vapor deposition method of PVD, CVD etc.
Particularly as the method that coating is set, the coating liquid that will contain adherence upgrading resin combination is coated in the method on this ployester series film surface, from coating of the present invention and printing ink layer, with other the adherence of Liniment, be effective means.
As the resin combination that constitutes such coating, preferably the resin of at least a kind of formation selecting with polyester system, polyurethane series, acrylic acid polymer and/or these multipolymer and the inert particle more than a kind are as the composition of main composition.
In above-mentioned adherence upgrading resin, by the polyester based resin that contains sulfonic water-insoluble and water dispersible in molecule with at the water-soluble poly carbonic acid that intramolecularly has 1 blocked isocyanate at least is the coating that the adherence upgrading resin of mixed with resin constitutes, not only can improve adherence with the ployester series film of base material, and can improve adherence with the printing-ink of general ultraviolet ray (UV) solidified nature printing ink and oxypolymerization printing ink etc. greatly, so be special ideal.
At this moment, polyester based resin of above-mentioned water-insoluble and water dispersible (A) and aqurous ployurethane are the content of resin (B), and preferred weight ratio is that (A)/(B)=90/10～10/90, particularly preferred weight ratio are (A)/(B)=80/20～20/80.
Polyester mulching film of the present invention, 60 degree mirror surface luster G1 of lining aspect and 75 degree mirror surface luster G2 must satisfy following formula (1) and (2).
G1≤20 …(1)
1＜G2/G1≤4 …(2)
60 degree mirror surface luster G1 of lining aspect must be below 20, preferably below 18, particularly preferably be below 15.In addition, the ratio G2/G1 of 75 degree mirror surface luster G2 and 60 degree mirror surface luster G1 must be greater than 1 less than 4, preferably greater than 1 less than 3.5, particularly preferably is greater than 1 less than 3.
If 60 degree mirror surface luster G1 of lining aspect surpass 20, then anti-powder deciduous is insufficient.In addition, the ratio (G2/G1) of 75 degree mirror surface luster G2 and 60 degree mirror surface luster G1 is 1 when following, and anti-powder deciduous is insufficient, and then printing also reduces.On the other hand, if G2/G1 surpasses 4, tail off owing to absorb the concavo-convex of coating surface of printing ink, so printing degenerates.
At 60 degree mirror surface luster G1 of lining aspect and 75 degree mirror surface luster G2 when satisfying above-mentioned formula (1) and (2), the standard deviation of the preferably suitable median size of adjusting the inert particle that is contained in coating, particle diameter, form (particle diameter ratio, major diameter/minor axis), particle content, coating thickness etc.
Particularly, be contained in the ratio (d/t) preferably 1.0～5.0, more preferably 1.2～4.0, most preferably 1.5～2.5 of the thickness t (μ m) of the median size d (μ m) of the inert particle of coating and coating.If during d/t less than 1.0, can not get sufficient printing ink and thick property, printing paper feeding and anti-adhesive.On the other hand, if surpass 5.0, particle comes off from the coating of polyester mulching film when printing, becomes the reason that powder comes off easily.Above-mentioned d and the fractographic photo of t available electron are obtained.
The thickness t of coating, preferably 0.01～5.0 μ m, more preferably 0.05～1.5 μ m, 0.1～1.0 μ m most preferably.If during the thickness less than 0.01 μ m of coating, insufficient with the adherence of the ployester series film of base material, in addition, particle can not be fixed in the coating fully the tendency that exists particle to come off from coating.On the contrary, if when surpassing 5.0 μ m, then particle is embedded in the resin of coating, exists in the tendency that indispensable concave-convex surface and anti-adhesive will be difficult to obtain in the use of polyester mulching film.
As the inert particle that contains in the coating, can enumerate titanium oxide, barium sulfate, salt of wormwood, calcium sulfate, silicon oxide, aluminum oxide, talcum, kaolin, carclazyte, calcium phosphate, mica, hectorite, zirconium white, Tungsten oxide 99.999, lithium fluoride, Calcium Fluoride (Fluorspan) etc. inorganic particulate and, the organic polymer system particle of polyethylene-based, polyacrylic, melamine system, benzoguanamine system, silicone resin system etc. etc.Use wherein a kind of, but also can two kinds and use.
The median size d of inert particle 0.04～1.5 μ m preferably in the above-mentioned coating, more preferably 0.06～1.0 μ m particularly preferably is 0.1～0.8 μ m.The median size of inert particle was less than 0.04 o'clock, and what form on the polyester mulching film surface is concavo-convex insufficient, had the inadequate tendency of printing ink adherence.If opposite during greater than 1.5 μ m, particle then comes off from the coating of polyester mulching film, becomes the reason of the powder that falls.
In the above-mentioned particle, consider that from anti-particle deciduous aspect preferably particle diameter ratio (major diameter/minor axis) is 1.0～1.5, the standard deviation of particle diameter is the inert particle below 1.0.Particularly preferably be, particle diameter ratio (major diameter/minor axis) is 1.0～1.2, and the standard deviation of particle diameter is the inert particle below 0.5.The inert particle of above-mentioned condition can be satisfied, spherical silicon oxide particle, spherical organic silicone resin particle, spherical crosslinked polyethylene particle, spherical cross linked acrylic particle, spherical or cubic calcium carbonate particles or calcium phosphate particle can be enumerated.
The median size of the inert particle in the above-mentioned coating, particle diameter be the standard deviation of particle diameter when, can calculate according to the method that Japanese Patent discloses No. 284534/1989 communique is put down in writing.
In the above-mentioned coating, the weight ratio of resin/particle preferably 30/70～70/30, more preferably 35/65～60/40, most preferably 40/60～50/50.The weight ratio of resin was less than 30 o'clock, and then particle can not be fixed in the coating fully, and particle comes off from coating, becomes the reason of shedding.On the contrary, the ratio of resin then was difficult to obtain abundant printing ink and thick property, paper feeding and anti-adhesive greater than 70 o'clock.
And then, polyester mulching film of the present invention, the surperficial intrinsic impedance value of lining aspect, preferably 1 * 10
13Ω/cm
2Below, more preferably 1 * 10
12Ω/cm
2Below.If surperficial intrinsic impedance value is than 1 * 10
13Ω/cm
2When big, this polyester mulching film is being made in the various operations of labelization, for example coating of binding agent, printing, severing, die-cut etc. in, electrostatic problem takes place easily.When making surperficial intrinsic impedance value in the above-mentioned scope, for example can adopt the method for interpolation static inhibitor in above-mentioned adherence upgrading resin combination shown below etc.
In addition, constituting the composition of above-mentioned coating, and then when containing static inhibitor, can prevent the various operations in the film labelization that will obtain, for example coating of binding agent, printing, severing, die-cut etc. produces the electrostatic problem, so desirable especially.As static inhibitor, the static inhibitor of coating-type, can use generally employed (for example, quaternary ammonium salt is a static inhibitor), the electric conductive polymer of electroconductive stuffing of metal coat fiber of metal oxide of metal powder of emboliform carbon black, nickel, copper etc., stannic oxide, zinc oxide etc., fibrous brass, stainless steel, aluminium etc., flaky graphite, aluminium foil, Copper Foil etc., sulfonated polyaniline, polypyrrole etc., in the scope that does not hinder effect of the present invention, can use above-mentioned static inhibitor arbitrarily.
As the method that coating is set, as mentioned above, preferably will contain adherence upgrading resin and reach the method that is coated in the ployester series film surface with inert particle as the coating liquid of the adherence upgrading resin combination of main composition.At this moment, the liquid temperature of coating liquid preferably is set in 10 ℃～20 ℃, most preferably is set in 12 ℃～18 ℃.In addition, the pH of coating liquid preferably is set in 5.5～7.5, most preferably 6.0～7.0.If the inert particle that the liquid temperature of coating liquid or pH beyond above-mentioned scope, then apply in the liquid condenses easily, produces owing to the filter stoppage in the coating liquid circulatory system makes the anti-shedding reduction of productivity reduction, coating, the problems such as ageing stability reduction of coating liquid.In addition, before the above-mentioned coating liquid of coating, preferably use the strainer of wire netting, deep bed filter, spiral formula strainer, cartridge filter etc. to filter this coating liquid and remove big inert particle above above-mentioned preferred average particle size range.Be set in the above-mentioned scope by the liquid temperature and the pH that will apply liquid, and/or using above-mentioned strainer to filter coating liquid, the 60 degree mirror surface luster G1 and the 75 degree mirror surface luster G2 that can easily obtain the lining aspect satisfy the polyester mulching film of above-mentioned formula (1) and (2).
In addition, as above-mentioned coating method, can suit to use normally used methods such as gravure coating, counter-rotating coating, suitable extrusion apply, the suitable extrusion of counter-rotating applies etc. roller coat application mode, brushing mode, air knife mode, blade application pattern or spot printing (roller cutter) application pattern, curtain formula application pattern, spray pattern, impregnation method.
Step as coating, can be on stretched polyester based film surface not in advance the method for coating, on the ployester series film surface of single shaft direction orientation, apply, and then with its method, any means of method etc. of ployester series film surface applied after biaxially oriented processing in the vertical direction orientation, but after coating on the ployester series film surface of uniaxial orientation, at the vertical direction stretch orientation, finishing the method for crystallization, is most preferred method from adherence, economy, degree of purification etc.
Below, specifically describe the present invention with embodiment, but the present invention is not limited by the following examples.In addition, various rerum naturas, performance measurement, the evaluation method of following embodiment employing are as follows.
(1) printing
After the coating of polyester mulching film surface is with terylene screen cloth (#300 order) printing UV curable ink (Seiko Ah the getting of Co., Ltd. Bath system, UVA710 black), with 500mJ/cm
2Carry out the uviolizing processing and obtain printing sample.The sample that obtains is as follows with visual judgement.
◎: Printing Department is very obviously judged easily
Zero: Printing Department is obviously judged easily
△: Printing Department is inhomogeneous a little
*: Printing Department is inhomogeneous
(2) printing ink adherence
When using oxypolymerization (or solvent) type printing ink, after print with terylene screen cloth (250 order) on the coating surface of polyester mulching film, air-dry one day.In addition, when using the UV curable ink, after print with terylene screen cloth (300 order) on the coating surface of polyester mulching film, give 500mJ/cm with the UV exposure apparatus
2UV exposure, the UV curable ink is solidified.
The oxypolymerization type printing ink that uses is to use oxypolymerization type printing ink (Jujo Chemical Co, Ltd.'s system, black) is diluted to volume ratio 4: 1 with diluting solvent (ten process Co., Ltd.'s system, wash Telon).In addition, the UV curable ink is to use Co., Ltd. to make the printing ink (UVA710, black) of Seiko Ah getting Bath system.
To the solidified ink lay, with the intersection facet that cutting knife is cut into 100 grids of 2mm * 2mm, will match the fragrant adhesive tape of fine jade (Ri Wan Co., Ltd. system, CT-24,25mm wide) bubble be attached to above it with entering, and then thereon fully friction make its abundant driving fit.Then, press the rear and front end portion of the fragrant not driving fit of adhesive tape of match fine jade of above-mentioned printing ink with hand, from intersect facet will match the fragrant adhesive tape of fine jade upward (90 spend direction) peel off rapidly.
Printing ink face after observation is peeled off, the ink residue rate by 100 square holes (treating as the number of peeling off) even the part of square hole is stripped from also, with the standard evaluation printing ink adherence in following 4 stages, with ◎ and zero as qualified.
◎: residual rate 100% (not peeling off fully)
Zero: residual rate greater than more than 90% less than 100% (no problem in the practicality, as can to use)
△: residual rate greater than more than 70% less than 90% (adherence slightly a little less than, problem might take place on practical)
*: residual rate greater than more than 50% less than 70% (problem is arranged on adherence)
(3) anti-powder deciduous
Use black paper with the formula friction tester (mountain pass science industry society system) that shakes at the contact surface of load drive head unit and polyester mulching film, with the load of drive head unit with 200gf/25mm
2(5mm * 5mm), make this film reciprocal 10 times with the friction of load drive head unit after, with visual, deceive the state of paper according to following judgement.
◎: complete non-cohesive powder on black paper
Zero: on black paper, have 1～10 place to adhere to powder below the 0.5mm
*: on black paper, the powder that adheres to more than 11 places below the 0.5mm is arranged, or adhere to the powder bigger than 0.5mm
(4) static resistance
After placing 24 hours under 23 ℃, the atmosphere of 65%RH, (Mitsubishi's oiling (strain) system, Hai Yilaisita-IP) are determined at the surperficial intrinsic resistance value (Ω/cm that imposes coating under the voltage 500V using the high resistivity meter under its atmosphere with the polyester mulching film
2).
(5) median size of inert particle
Disclose the record of No. 284534/1989 communique according to Japanese Patent, use scanning electron microscope and image processing apparatus to measure particle more than at least 100, obtain median size (μ m).
(6) thickness of coating
With the section photo of scanning electron microscope production polyester mulching film, on its photo, measure the thickness of coating.Change the position and carry out 100 same measurements, with the mean value of its observed value thickness (μ m) as coating.
(7) opaqueness of ployester series film
Use Macbeth densitometer TR-927 type, measure transmitance, from the light penetration calculating optical concentration that obtains, as the index of opaqueness by the light of G strainer.Optical concentration light penetration (scope: the logarithm (Log of inverse 0～100%)
10) expression.Shown that the light concentration value is big more, opaqueness is high more.
(8) apparent density of ployester series film
Ployester series film is correctly cut out the square of 10cm * 10cm, obtain mean thickness t (μ m) after measuring 50 dot thickness.And then the weight of working sample is accurate to 0.1mg as W (g), and the value of calculating with following formula is as apparent density.
Apparent density (g/cm
3)=(W/t) * 100
(9) mirror surface luster of the lining aspect of polyester mulching film
Method 2 (75 degree specular gloss), method 3 (60 degree specular gloss) according to the JIS-Z8741 record are measured.
(10) intrinsic viscosity of the vibrin of formation ployester series film
Dissolved polyester resin in the mixed solvent of phenol 60 weight % and sym.-tetrachloroethane 40 weight %, cross the filter solid composition with glass filter after, measure down at 30 ℃.
(11) the empty lamination number density of ployester series film
At first, film is embedded in the Resins, epoxy, use slicing machine along with the sample that vertical draw direction is parallel and the vertical thin face is cut off of film, make 5 samples.In same sample, scanning electron microscope is used in 5 places at different positions, and with 300～3, face is cut off in 000 times the multiplying power microscopic examination that suits, and production can be confirmed the photo of distribution in the cavity of film full thickness.The straight line on the arbitrary site vertical thin-film surface on photograph image, count the crossing empty number (lamination number) of straight line therewith, in addition, the full thickness (μ m) along this straight line mensuration film removes the lamination number in cavity and obtains empty lamination number density (individual/μ m) with it.In addition, measure at 5 places, obtain the mean value that amounts to 25 places, as the empty lamination number density (individual/μ m) of sample for each photo.
(12) temperature of coating liquid
Use the temperature survey of mercury formula apply surely liquid the liquid temperature (℃).
(13) pH of coating liquid
Use pH meter (that the hole field makes is made, block this it Buddhist nun-ACT D-22) to measure.
Embodiment 1
The resin combination that contains the Titanium Dioxide (Rutile) Top grade 5 weight % of the polystyrene 15 weight % of the pet resin 80 weight % of intrinsic viscosity 0.62dl/g and melting index 5.5g/10 minute and median size 0.3 μ m 285 ℃ of following fusions, on the roller of 40 ℃ of surface temperatures, squeeze out, then, the not drawing sheet that obtains 3.5 times of 90 ℃ of following longitudinal stretchings, is obtained the single axle drawn membrane of ployester series film.
Modulation coating liquid, this coating liquid contains, and the solid composition is that copolymer polyester resin ((strain) system, crust are twisted flax fibers and woven according to Jules Renard by Japan), the solid composition of 3.15 weight % be the terminal isocyanate group of 5.85 weight % with the water soluble polyurethane resin of wetting ability base block (the first industrial pharmacy (strain) system, like the Lars is special swell), for above-mentioned resin composition is that the quaternary amine as static inhibitor of 6.20 weight % is the silicon oxide particle of the median size 0.45 μ m of static inhibitor, 12.4 weight %.
It is 6.5 that the coating liquid that will obtain with pH regulator liquid is adjusted to pH, then, filters with deep bed filter (Sumitomo three M society systems, the special filter bag of niche), stirs 2 hours down at 15 ℃ in coating liquid circulatory system blank storage tank then.
On the face of the single axle drawn membrane that obtains with aforesaid way with suitable this coating liquid of coating such as coating process of pressing of counter-rotating so that the thickness of the preceding resin solid composition that stretches becomes 0.9 μ m, then carry out drying and behind 3.5 times of 120 ℃ of following cross directional stretchs, heat-treat with 4% lax one side on one side down at 230 ℃, obtaining in apparent density is 1.10g/cm
3And empty lamination number density is 0.31/μ m, contain the polyester mulching film that forms coating on the single face of ployester series film of thickness 50 μ m of micro-cavity.The characteristic and the evaluation result of the film that obtains are illustrated in table 1 and the table 2.
Embodiment 2
Except the copolymer polyester resin that will be contained in coating make 2.5 weight %, with aqurous ployurethane make 4.6 weight %, as inert particle, the silicon oxide particle of median size 0.45 μ m is made 6.0 weight %, the calcium carbonate particles of median size 0.8 μ m is made outside the 2.0 weight %, and other and embodiment 1 obtain the polyester mulching film identically.The characteristic and the evaluation result of the film that obtains are illustrated in table 1 and the table 2.
Comparative example 1
Except the inert particle that will be contained in coating use median size 2.0 μ m benzo amine formaldehyde condenses particle 9.0 weight %, other and embodiment 1 obtain the polyester mulching film identically.The characteristic and the evaluation result of the film that obtains are illustrated in table 1 and the table 2.
Comparative example 2
Except the copolymer polyester resin that will be contained in coating make 9.1 weight %, with water-soluble carbamate make 3.9 weight %, as inert particle, with the silicon oxide particle of median size 5.5 μ m make 2.9 weight %, with the silicon oxide particle of median size 2.7 μ m make 2.9 weight %, with the silicon oxide particle of median size 0.15 μ m make 7.3 weight %, resin solid composition thickness before will stretching makes outside the 1.8 μ m, other and embodiment 1 obtain the polyester mulching film identically.The characteristic and the evaluation result of the film that obtains are illustrated in table 1 and the table 2.
Comparative example 3
Except the temperature with the coating liquid in the blank storage tank makes 40 ℃, other and embodiment 1 obtain the polyester mulching film identically.The characteristic and the evaluation result of the film that obtains are illustrated in table 1 and the table 2.
Comparative example 4
Except the pH that will apply liquid makes 9.5, other and embodiment 1 obtain the polyester mulching film identically.The characteristic and the evaluation result of the film that obtains are illustrated in table 1 and the table 2.
Table 1
| G1 | G2 | Opaqueness (optical concentration) | Apparent density (g/cm 3) | Median size (μ m) | Cavity lamination number density (individual/μ m) | |
| Embodiment 1 | 8.9 | 32.7 | 0.80 | 1.10 | 0.45 | 0.31 |
| Embodiment 2 | 16.1 | 22.5 | 0.81 | 1.10 | 0.54 | 0.31 |
| Comparative example 1 | 14.8 | 7.3 | 0.79 | 1.10 | 2.0 | 0.31 |
| Comparative example 2 | 6.1 | 2.5 | 0.82 | 1.10 | 1.9 | 0.31 |
| Comparative example 3 | 12.3 | 10.2 | 0.80 | 1.10 | 0.45 | 0.31 |
| Comparative example 4 | 15.4 | 12.8 | 0.79 | 1.10 | 0.45 | 0.31 |
Table 2
| Printing | The printing ink adherence | Anti-powder deciduous | Static resistance (surperficial intrinsic impedance value, Ω/cm 2) | |
| Embodiment 1 | ◎ | ◎ | ○ | 3×10 11 |
| Embodiment 2 | ◎ | ◎ | ○ | 4×10 11 |
| Comparative example 1 | ○ | ◎ | × | 1×10 12 |
| Comparative example 2 | ○ | ◎ | × | 2×10 12 |
| Comparative example 3 | ○ | ◎ | △ | 5×10 11 |
| Comparative example 4 | ○ | ◎ | △ | 7×10 11 |
Polyester mulching film of the present invention, owing to can keep the printing ink adherence, and prevent that powder from coming off, improved printing, so be useful as the label base material especially.
Claims (10)
1. polyester mulching film, it is the polyester mulching film that coating is set at least one face of the ployester series film with opaqueness of representing more than 0.3 with optical concentration, it is characterized in that above-mentioned coating is to be by polyester, polyurethane series, at least a resin of selecting in acrylic acid polymer and/or their multipolymer and at least a inert particle constitute as the resin combination of main composition composition, the median size of the inert particle that contains in the above-mentioned coating is 0.04～1.5 μ m, and the weight ratio of resin/particle is 30/70～70/30, and 60 degree mirror surface luster G1 of above-mentioned lining aspect and 75 degree mirror surface luster G2 satisfy following formula (1) and (2)
G1≤20 …(1)
1＜G2/G1≤4 …(2)
2. polyester mulching film according to claim 1 it is characterized in that ployester series film contains the cavity in this film inside, and its apparent density is 0.3～1.3g/cm
3
3. polyester mulching film according to claim 1, the resin that it is characterized in that above-mentioned coating are to be that resin constitutes by the vibrin of water-insoluble and water dispersible and at the aqurous ployurethane that intramolecularly has a blocked isocyanate at least.
4. polyester mulching film according to claim 1 is characterized in that the surperficial intrinsic impedance value of above-mentioned lining aspect is 1 * 10
13Ω/cm
2Below.
5. polyester mulching film according to claim 1 it is characterized in that ployester series film contains the cavity in this film inside, and its empty lamination number density is more than the 0.20/μ m.
6. polyester mulching film according to claim 1 is characterized in that the weight ratio of the resin/particle in the above-mentioned coating is 35/65～60/40.
7. polyester according to claim 1 is carried out film, it is characterized in that the median size d of the inert particle that contains in the above-mentioned coating and the ratio d/t of the thickness t of coating are 1.0～5.0.
8. polyester mulching film according to claim 1 is characterized in that, the median size d of the inert particle that contains in the above-mentioned coating is 0.06～1.0 μ m.
9. polyester mulching film according to claim 1 is characterized in that, the thickness t of above-mentioned coating is 0.01～5.0 μ m.
10. polyester mulching film according to claim 1, it is characterized in that the inert particle in the above-mentioned coating is the inorganic particulate of selecting, the organic polymer particle of selecting from polyethylene-based, polyacrylic, melamine system, silicone resin system from titanium oxide, barium sulfate, salt of wormwood, calcium sulfate, silicon oxide, aluminum oxide, talcum, kaolin, carclazyte, calcium phosphate, mica, hectorite, zirconium white, Tungsten oxide 99.999, lithium fluoride, Calcium Fluoride (Fluorspan).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01140189 CN1237131C (en) | 2001-11-29 | 2001-11-29 | Polyester mulching film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01140189 CN1237131C (en) | 2001-11-29 | 2001-11-29 | Polyester mulching film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1421497A CN1421497A (en) | 2003-06-04 |
| CN1237131C true CN1237131C (en) | 2006-01-18 |
Family
ID=4675717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01140189 Expired - Lifetime CN1237131C (en) | 2001-11-29 | 2001-11-29 | Polyester mulching film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1237131C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4831552B1 (en) * | 2011-03-28 | 2011-12-07 | Ｊｘ日鉱日石金属株式会社 | Co-Si copper alloy sheet |
-
2001
- 2001-11-29 CN CN 01140189 patent/CN1237131C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1421497A (en) | 2003-06-04 |
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