CN101548235B - Process for producing a non-transparent microvoided self-supporting film - Google Patents
Process for producing a non-transparent microvoided self-supporting film Download PDFInfo
- Publication number
- CN101548235B CN101548235B CN2007800446839A CN200780044683A CN101548235B CN 101548235 B CN101548235 B CN 101548235B CN 2007800446839 A CN2007800446839 A CN 2007800446839A CN 200780044683 A CN200780044683 A CN 200780044683A CN 101548235 B CN101548235 B CN 101548235B
- Authority
- CN
- China
- Prior art keywords
- film
- monomeric unit
- linear polyesters
- transparent
- glass transition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/10—Watermarks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44F—SPECIAL DESIGNS OR PICTURES
- B44F1/00—Designs or pictures characterised by special or unusual light effects
- B44F1/06—Designs or pictures characterised by special or unusual light effects produced by transmitted light, e.g. transparencies, imitations of glass paintings
Abstract
The present invention discloses a film consisting essentially of a continuous phase linear polyester matrix having dispersed therein a non-crosslinked random SAN-polymer and dispersed or dissolved therein at least one ingredient from the group of ingredients consisting of inorganic opacifying pigments, whitening agents, colorants, UV-absorbers, light stabilizers, antioxidants and flame retardants, wherein the film is white, microvoided, non-transparent and axially stretched; the linear polyester matrix has monomer units consisting essentially of at least one aromatic dicarboxylic acid, at least one aliphatic diol and optionally at least one aliphatic dicarboxylic acid; the weight ratio of the linear polyester to the non-crosslinked SAN-polymer is in the range of 2.0:1 to 19.0:1; and one of said at least one aromatic dicarboxyate monomer units is isophthalate and said isophthalate is present in said polyester matrix in a concentration of 15 mole % or less of all the dicarboxylate monomer units in said linear polyester matrix; the use of the non-transparent microvoided axially stretched film as a synthetic paper; an image recording element comprising the non-transparent microvoided axially stretched film; a process for the preparing of the non-transparent microvoided axially stretched film; and a process for obtaining a transparent pattern therewith.
Description
Invention field
The present invention relates to prepare the method for non-transparent microvoided self-supporting film.
Background of invention
US 3; 755; 499 disclose the synthetic sheet material that is used to write purposes; It is made up of the linear polyesters and the superpolymer that glass transition point is higher than said linear polyesters that are selected from polyethylene terephthalate, gather the multipolymer of ethylene m-phthalate and ethylene glycol terephthalate and ethylene m-phthalate basically; The mixture ratio of this superpolymer is 7 to 35 weight % of this polymeric blends; This superpolymer is selected from polymethylmethacrylate, vinyl cyanide and cinnamic multipolymer, vinyl cyanide, butadiene and cinnamic multipolymer, owing to be dispersed in the said linear polyesters the said superpolymer with the nuclear that constitutes its irregular surface, said synthetic sheet material has the surface of very fine alligatoring.In the time of these blended polymer materials and in succession stretch and all under 85 to 95 ℃, carry out usually according to open, draw ratio is 2 to 3.5 times of original length, regulates the writability and the opacity of sheet material according to its final use.US 3,755,499 goal of the invention it is said provide have improved surface condition, opacity and other essential attributes be used to write and the similar synthetic sheet material of other purposes.US3; 755; 499 is further open, and the thermoplastic resin that sneak into can have or not have the compatibility with this linear polyesters, as long as it can basically evenly mix with this linear polyesters when moulding and be dispersed in this linear polyesters; No matter transparent whether the film that forms can produce even frosting after stretching; But and thus obtained film thermal shrinkage, have and acceptablely write character and have sufficient opacity, and in order further to improve high temperature film dimensional stability down, it can and be lower than thermal treatment under the temperature of fusing point of mixed thermoplastic resin and linear polyesters at the draft temperature that is higher than this linear polyesters.Embodiment 2 glass transition temperature of having given an example is that 100 to 105 ℃ vinyl cyanide and cinnamic multipolymer and concentration is the mixing of polyethylene terephthalate of 7 to 35 weight %, and extrudes to form the membrane sample of 150 micron thick through T-die head melt.These diaphragms vertically and transversely stretch with the big draw ratio of pleurodiaphragmatic in terspace beginning length twice at it under 85 ℃ with biaxial stretch-formed machine subsequently simultaneously, and also under 85 ℃ with vertical three times biaxial stretch-formed with horizontal three times of whiles.The gained film it is reported to have following character:
| Acrylonitritrile-styrene resin (weight %) | 7 | 7 | 35 | 35 |
| Polyethylene terephthalate (weight %) | 93 | 93 | 65 | 65 |
| Draw ratio (LxW) multiple | 2x2 | 3x3 | 2x2 | 3X3 |
| Thickness after the stretching (μ m) | 48 | 26 | 45 | 25 |
| Fracture strength (kg/cm) | 880 | 1210 | 650 | 730 |
| Breaking extension (%) | 110 | 45 | 55 | 23 |
| Light-transmission coefficient (%) | 80.8 | 84.2 | 72.3 | 77.6 |
| Turbidity value (%) | 92.5 | 90.6 | 94.3 | 96.6 |
| Writability [pencil hardness] | ≤4H | ≤3H | ≤4H | ≤3H |
US 3,755,499 the interpolation of inorganic opacification pigment (opacifying pigment) is not disclosed or according to image heating to the wherein influence of disclosed opaque microporous barrier.
The open preparation of EP-A 0 606 663 is used to comprise the method for opaque polyester copolymer carrier of the reflectivity photographic material of inorganic inert pigment; Said polyester comprises that the ethylene glycol terephthalate unit is as main repetitive; Said method comprises the following steps according to give order: perhaps supply terephthalic acid (TPA) and monoethylene glycol to two (beta-hydroxy-ethyl) terephthalate or its oligomer so that carry out esterif iotacation step; Or supply terephthalic acid (TPA) dimethyl esters and monoethylene glycol is so that the execution transesterification; Polycondensation under the condition of the vacuum that little by little reduces, the polymkeric substance that perhaps granulation obtained, subsequent drying particle and charging they to extruder; Or the direct multipolymer that is obtained with the melt form charging is to extruder; With the sheet-form extruded polymer, quenching and solidify the sheet material of gained, biaxial stretch-formed this sheet material on the quenching member; The annealing biaxially-stretched film; It is characterized in that terephthalic acid (TPA) or terephthalic acid (TPA) dimethyl esters are substituted by the dimethyl esters of another kind of aromatic dicarboxylic acid or another kind of aromatic dicarboxylic acid respectively, and/or monoethylene glycol is alternative by another kind of glycol, respectively about the maximum 20 moles of % of the said alternative total of monoethylene glycol and terephthalic acid (TPA) or DMT.EP-A 0,606 663 is a monoethylene glycol and the polycondensation product of terephthalic acid (TPA) (m-phthalic acid substitutes amount and is the maximal value of 20mol% at the most) or DMT (it is the maximal value of 20mol% at the most that DMIP substitutes amount) as the open polyester copolymer of embodiment preferred.
EP-A 0 654 503 discloses by 50 to 97 weight % linear polyesters and 3 to 50 weight % and has contained the moulded products that the polymer blend of cinnamic polymkeric substance is processed, and wherein this number percent is with respect to this polyester and the summation that contains cinnamic polymkeric substance.EP-A 0 654 503 is also open; This polyester contains at least 80 weight % polyethylene terephthalates and can contain the ethylene m-phthalate that gathers of 20 weight % at the most; In embodiment 7 illustrated the potpourri of 85 weight % polyester and 15 weight %ABS 2, this polyester is made up of the potpourri that 94 weight % polyethylene terephthalates and 6 weight % gather ethylene m-phthalate.
But EP-A 1 291 155 open embossing, the polyethylene terephthalate of coating (PET) film comprises: the PET basilar memebrane of uniaxial orientation; With the coating that puts on the PET basilar memebrane, by cross directional stretch, said coating resin floods the surface portion of PET basilar memebrane when said cross directional stretch as complex for its floating coat and PET basilar memebrane, causes the surface portion of film responsive to embossing thus.EP-A 1 291 155 discloses the PET basilar memebrane in addition by coextrusion; And the copolyester layer such as the embodiment 4 and 5 that form two-layer at least and coextrusion are said; Be made up of m-phthalic acid copolymerization terephthalic acid (TPA) random copolymerization ester copolymer, mol ratio is about 18% m-phthalic acid and 82% terephthalic acid (TPA).
The non-transparent microvoided axially stretched film of prior art is limited by inadequate opacity together with lacking dimensional stability or sufficient dimensional stability and inadequate opacity.In addition, for special application, the whiteness of non-transparent microvoided axially stretched film is insufficient.
Prior art:
So far, following prior art file is known by the applicant:
US 3,755,499, are disclosed on August 28th, 1973,
EP-A 0 606 663, is disclosed on July 20th, 1994,
EP-A 0 654 503, is disclosed in May 24 nineteen ninety-five
EP-A 1 291 155, is disclosed on March 12nd, 2003
WO 94/04961A is disclosed on March 3rd, 1994
US 5,156,709, are disclosed on October 20th, 1992,
Inventive aspect
Therefore one aspect of the present invention provides improved non-transparent microvoided axially stretched film.
Therefore another aspect of the present invention provides the method for making improved non-transparent microvoided axially stretched film.
Therefore one aspect of the present invention also comprises the method that obtains transparent pattern in the non-transparent microvoided axially stretched film that is provided at.
It is obvious that others of the present invention and advantage become from the description of hereinafter.
Summary of the invention
Have been found that; Can produce surprisingly and have higher optical density (OD); It is the opacity of higher degree; White, microporeization, opaque, self-supporting and biaxially-stretched film; It has the external phase linear polyesters matrix of being made up of the monomeric unit of terephthalate, isophthalic acid ester and aliphatic dimethylene basically; And have at least a amorphous high polymer and/or at least a crystallization superpolymer that are dispersed in wherein; The glass transition temperature of amorphous high polymer is higher than the glass transition temperature of said linear polyesters matrix, and the fusing point of crystallization superpolymer is higher than the glass transition temperature of said linear polyesters matrix, and this is to be at least 0.02 linear polymer matrix and at the tensile force longitudinal stretching extrudate of＞4N/ square millimeter through the mol ratio of using isophthalic acid ester monomeric unit and terephthalate monomeric unit in the linear polyesters matrix.
Aspect of the present invention is through being used to prepare the method realization of non-transparent microvoided self-supporting film; Comprise step: i) in kneading machine or extruder, mix at least a linear polyesters; It has basically altogether is made up of terephthalate, isophthalic acid ester and aliphatic dimethylene; Wherein the mol ratio of isophthalic acid ester monomeric unit and terephthalate monomeric unit is at least 0.02, monomeric unit so that linear polyesters matrix to be provided; At least a amorphous high polymer and/or the fusing point at least a crystallization superpolymer higher that glass transition temperature is higher than the glass transition temperature of said linear polyesters matrix than the glass transition temperature of said linear polyesters matrix; Randomly be selected from least a composition of inorganic opacification pigment, whitening agent, ultraviolet light absorber, light stabilizer, anti-oxidant, fire retardant and colorant; Ii) form step I with thick film) the middle potpourri that produces, quenching subsequently; Iii) with longitudinally the stretch twice at least of this thick film to initial length of the tensile force of＞4N/ square millimeter; Iv) laterally stretch from the twice at least of step longitudinal stretching film to original width (iii).
Aspect of the present invention is also through being used to obtain the method realization of transparent pattern; Comprise step: apply heat and the optional non-transparent microvoided biaxial stretch-formed self-supported membrane that applies pressure to through the method generation that comprises the steps that is aided with according to image: i) in kneading machine or extruder, mix at least a linear polyesters; It has basically altogether is made up of terephthalate, isophthalic acid ester and aliphatic dimethylene; Wherein the mol ratio of isophthalic acid ester monomeric unit and terephthalate monomeric unit is at least 0.02, monomeric unit so that linear polyesters matrix to be provided; At least a amorphous high polymer and/or the fusing point at least a crystallization superpolymer higher that glass transition temperature is higher than the glass transition temperature of said linear polyesters matrix than the glass transition temperature of said linear polyesters matrix; Randomly be selected from least a composition of inorganic opacification pigment, whitening agent, ultraviolet light absorber, light stabilizer, anti-oxidant, fire retardant and colorant; Ii) form step I with thick film) the middle potpourri that produces, quenching subsequently; Iii) with longitudinally the stretch twice at least of this thick film to initial length of the tensile force of＞4N/ square millimeter; Iv) laterally stretch from the twice at least of step longitudinal stretching film to original width (iii).
The non-transparent microvoided self-supporting film that aspect of the present invention also produces through above-described method is realized as the purposes of synthetic paper.
Aspect of the present invention also realizes through the purposes of non-transparent microvoided self-supporting film in image recording element that above-described method produces.
Open the preferred embodiments of the invention in detailed Description Of The Invention.
Detailed Description Of The Invention
Definition
Being used for disclosing term of the present invention space or micropore for example is meant owing to cause particle, the microporosity that in drawing process, can in the oriented polymerization film, form, small closed pore, cavity, bubble or hole or holeization (cellulation) with the space of the immiscible particle initiation of polyester matrix.This space or micropore can be unfilled or filled by air or certain type of steam.Even fill at the beginning, this space or micropore also possibly pass through in time and filled by air or certain type of steam.
Term " opaque " is meant according to ASTM D589-97 or according to TAPPI, 360Lexington Avenue, the opacity test T425m-60 that New York, USA publish record greater than 90% visible light do not passed through percent.
Be used for disclosing term film of the present invention and be extrusion sheet with specific composition or by through have the identical or different liquid of forming be made by co-extrusion to have a sheet material that identical or different a plurality of films of forming contact with each other and constitute.Term film and paper tinsel be interchangeable use in the disclosure.
Be used for disclosing term linear polyesters of the present invention and be meant the polyester that comprises hydrocarbon dimethylene and dicarboxylic ester monomeric unit.
Being used for disclosing term foam of the present invention is meant through numerous air-bubble being trapped in the material that liquid or solid forms.
Be used for disclosing term of the present invention " the dimethylene aliphatic monomers unit of linear polyesters " and be meant the monomeric unit derived from dimethylene aliphatic diol or its ether, wherein this term aliphatic series comprises alicyclic.
Be used for disclosing that term density of the present invention is meant 100 millimeters * 100 millimeters, the have certain thickness weight of diaphragm of (with the inducing probes contact measurement of the ball point with 3 millimeters of diameters) is divided by its volume.The surface of this value supposition diaphragm is that put down and parallel.This value is corresponding to the apparent density value of reporting among EP-A 0 496323 and the WO 2005/105903A.
The term inorganic opacification pigment that is used for open the application be meant can opacification (promptly causing opaquer) pigment; It comprises refraction index at least 1.4 basic white inorganic pigment and can be when stretching when being dispersed in the polymkeric substance cause the pigment of opacity owing to microporeization.
Be used for disclosing term whitening agent of the present invention and be meant the white/colourless organic compound that under the ultraviolet influence of environment, shows blue light.
Be used for disclosing term of the present invention " carrier " be meant " self-supporting material " with its with can be used as the coating of solution or dispersion, evaporate or sputter on the carrier but itself not " layer " of self-supporting distinguish mutually.It also comprises optional conductive surface layer and bonding necessary any processing or the layer that apply in order to help sticking.
Be used for disclosing the polymer chain that term of the present invention " block of chain type-polymerization " does not comprise condensation polymer and is meant such chain type-polymerization: it can only be the polymer chain of chain type-polymerization perhaps at the block of segmented copolymer or graft copolymer.
But being used for disclosing term chromatography of the present invention is meant and can impacts the print process chromatography through conventional impact type and/or non-.
Being used for disclosing the conventional print process of term of the present invention comprises; But be not limited to ink jet printing, intaglio printing, serigraphy, aniline printing, offset printing, impression (stamp printing), photogravure, dye transfer, heat sublimation printing and heat and laser induced method.
Be used for disclosing terms pattern of the present invention and be meant any type of lipostrat that can have line, square, circle or any random structure.
Be used for disclosing term layer of the present invention and be meant that covering is known as for example (continuously) coating in the whole zone of the entity of carrier.
Be used for disclosing term of the present invention " opaque coating " and be meant that enough contrasts that can provide with transparent image are so that the visible film of this clear picture.Opaque coating can be " light tight (opaque) film ", but needn't be light tight fully so that do not have residual translucence, does not promptly have the light transmission film.See through the measurement that optical density that the visible light light filter records with transmission mode can provide the film opacity with MacBeth TR924 densitometer.ISO 2471 relates to the opacity of paper backing and when relating to this character of paper, is suitable for; This character is controlled the degree of printed matter on the similar scraps of paper that a sheet material visually covers the below, and opacity is defined as is " luminous reflectivity of the sheet-fed of representing with percent that has black and the ratio of the intrinsic luminous reflectivity of the same sample that has the white reflecting backing.80 gram/square meter copy papers for example be White-opalescent and have according to ISO 5-2 and record 0.5 optical density (OD) through yellow filter with MacBeth TR924 densitometer, metalized film has 2.0 to 3.0 optical density (OD) usually.
Be used for disclosing term transparent of the present invention and be meant to have transmission at least 50% incident visible light and do not make its diffuse reflection, preferred transmission at least 70% incident visible light and do not make its irreflexive character.
Be used for disclosing flexible being meant of term of the present invention and can under not damaged situation, follow the curvature of curved face object (like drum).
Be used for disclosing term of the present invention " colorant " and be meant dyestuff and pigment.
Be used for disclosing term of the present invention " dyestuff " and be meant the colorant that has 10 mg/litre or bigger solubleness at its applicating medium with under the relevant environment temperature.
Therefore to be defined as among the DIN 55943 that incorporates this paper into be under the relevant environment condition, to be dissolved in dispersion medium hardly to have inorganic or organic, colour or achromatic colour agent less than 10 mg/litre solubleness therein to term " pigment " quoting through this.
Produce the method for non-transparent microvoided film
Aspect of the present invention realizes through the method that produces non-transparent microvoided self-supporting film; It comprises step: i) in kneading machine or extruder, mix at least a linear polyesters; It has basically altogether is made up of terephthalate, isophthalic acid ester and aliphatic dimethylene; Wherein the mol ratio of isophthalic acid ester monomeric unit and terephthalate monomeric unit is at least 0.02, monomeric unit so that linear polyesters matrix to be provided; At least a amorphous high polymer and/or the fusing point at least a crystallization superpolymer higher that glass transition temperature is higher than the glass transition temperature of said linear polyesters matrix than the glass transition temperature of said linear polyesters matrix; Randomly be selected from least a composition of inorganic opacification pigment, whitening agent, ultraviolet light absorber, light stabilizer, anti-oxidant, fire retardant and colorant; Ii) form step I with thick film) the middle potpourri that produces, quenching subsequently; Iii) with longitudinally the stretch twice at least of this thick film to initial length of the tensile force of＞4N/ square millimeter; Iv) laterally stretch from the twice at least of step longitudinal stretching film to original width (iii).
First embodiment according to the method for the invention, homodisperse at least a amorphous high polymer and/or at least a crystallization superpolymer concentration are 5 to 35wt% in the polymer film, preferably 9 to 25wt%.
Second embodiment according to the method for the invention; Linear polyesters is 1.85: 1 to 19.0: 1 with disperseing wherein at least a amorphous polymer and/or the weight ratio of at least a crystallization superpolymer; Preferred 2.7: 1 to 13: 1, preferred especially 3.0: 1 to 10: 1.
The 3rd embodiment according to the method for the invention; The amorphous high polymer particle or the crystallization superpolymer particle that are dispersed in this external phase have the diameter less than 10 microns; Preferred particle has number average particle size 0.5-5 micron, and special preferred particle has 1 to 2 micron of particle mean size.Granularity is more little, and opacity is high more.
The 4th embodiment according to the method for the invention, this film do not comprise that polyethers is such as polyoxyethylene.Such polyethers reduces density and possibly decompose the space that produces other non-uniform Distribution.
The 5th embodiment according to the method for the invention, this film has alphanumeric, embossed pattern, randomly at least a in the hologram of embossing and continuous shadow tone or the digital picture.
The 6th embodiment according to the method for the invention, but film promptly is fit to impact or nonimpact printing providing transparent chromatography layer on the one side at least.But this transparent chromatography layer can be provided in the lip-deep alphanumeric of self-supported membrane of non-transparent microvoided axial tension, and embossed pattern is randomly on the hologram of embossing and continuous shadow tone or digital picture at least a.
The 7th embodiment according to the method for the invention, but film provides the chromatography layer of transparent porous on one side at least, promptly be fit to impact or for example ink jet printing of nonimpact printing.Disclosed among the transparent porous layer of transparence such as EP-A 1 362 710 and the EP-A 1 398 175 through applying liquid (it also can apply according to image) with suitable refraction index.Can be in the lip-deep alphanumeric of the self-supported membrane of the non-transparent microvoided axial tension that has transparent pattern, embossed pattern, but randomly on the hologram of embossing and continuous shadow tone or digital picture at least a this transparent chromatography layer is provided.
The transparence of this transparent porous receiving layer of a part can produce image alone, or the not transparence zone of opaque porous receiving layer composing images alone.Transparent pattern can for example be the part of bank note, stock, ticket, credit card, identity document or luggage and packaging label.
The 8th embodiment according to the method for the invention, polymeric membrane have about 10 microns-Yue 500 microns of thickness, preferred about 50 microns-Yue 300 microns.
The 9th embodiment according to the method for the invention, polymeric membrane has glue-line.This glue-line makes its wettability that can improve polymeric membrane and adhesive property, preferably includes vibrin, and urethane resin gathers (ester urethanes) resin or acryl resin.
The thick film of extruding of quenching has thickness about 10 to about 6000 microns, about 100 microns to 5000 microns of preferred thickness.
Through at first (for example vertically=MD) going up and stretch, go up stretching in second direction [for example perpendicular to vertically=TD (laterally)] then, realize thus according to biaxial stretch-formed polymeric membrane of the present invention in a direction.This makes the polymer chain orientation, improves density and crystallinity thus.Can be by two rollers with the friction speed operation that meets required draw ratio, through the superficial velocity that will rotate roller be made as V2 and linear extruded velocity be V1 so that draw ratio is V2/V1, carry out extruding machine-direction oriented on the direction.The longitudinal stretching ratio should be enough to make the space.
Can use the longitudinal stretching operation that is used to make axial and double axial orientated polyester film known in the art.For example; The rete of merging is passed through between a pair of infrared heater, its in the zone that take place to stretch with these layers be heated above the polyester glass transition temperature (for polyethylene terephthalate be about 80 ℃ and for gathering about 60 ℃ of ethylene m-phthalate) temperature.Said temperature should be near the glass transition temperature of continuous phase polymer to improve opacity.Under the situation of polyethylene terephthalate, under about 140 ℃, carry out longitudinal stretching about 80 usually.In the longitudinal stretching process, because opacity is realized in the space that in the film of longitudinal extension, is produced by each particle of dispersed polymeres.
Basically at an angle of 90 carry out cross directional stretch with the direction of longitudinal stretching, this angle is typically about between 70 ° and 90 °.For horizontal orientation, use suitable tenter frame usually, two edges of film are all clamped then heated the amalgamation layer that has prime coat on it through for example passing hot air heater (it is heated above glass transition temperature with film), pull to two limits thus.Under the situation of polyethylene terephthalate and multipolymer thereof,, preferably approximately carry out cross directional stretch under 85 to about 150 ℃ at about 80 to about 170 ℃.The cross directional stretch of film causes the space horizontal expansion.
Generation according to biaxial stretch-formed polymeric membrane of the present invention; Through twice at least with this thick film of tensile stress longitudinal stretching to the initial length of＞4.0N/ square millimeter; After middle quenching; Longitudinal stretching is succeeded by being at least three times of basic 90 ° angle cross directional stretch to original width with this first drawing process; Tensile stress is preferred＞the 4.0N/ square millimeter, and draft temperature is preferably on the glass transition temperature of external phase maximum 30 ℃ and particularly preferably on the glass transition temperature in external phase maximum 20 ℃.
The tenth embodiment according to the method for the invention, longitudinal stretching power＞5N/ square millimeter, longitudinal stretching power＞6.0N/ square millimeter is preferred, longitudinal stretching power＞7.0N/ square millimeter is preferred especially.
The 11 embodiment according to the method for the invention; Cross directional stretch carries out with the power of＞4.0N/ square millimeter; Cross directional stretch power＞5N/ square millimeter is preferred, and cross directional stretch power＞6.0N/ square millimeter is preferred especially, and cross directional stretch power＞7.0N/ square millimeter is especially preferred.
The 12 embodiment according to the method for the invention; The longitudinal stretching temperature is no more than on the glass transition temperature of linear polyesters matrix 40 ℃; The longitudinal stretching temperature that is no more than on the glass transition temperature of linear polyesters matrix 30 ℃ is preferred, and the longitudinal stretching temperature that is no more than on the glass transition temperature of linear polyesters matrix 20 ℃ is especially preferred.
The 13 embodiment according to the method for the invention; The cross directional stretch temperature is no more than on the glass transition temperature of linear polyesters matrix 40 ℃; Preferably be no more than on the glass transition temperature of linear polyesters matrix 30 ℃ cross directional stretch temperature, the cross directional stretch temperature that is no more than on the glass transition temperature of linear polyesters matrix 20 ℃ is especially preferred.
The device execution that vertical and horizontal stretch and can side by side produce with for example Br ü ckner.
The draw ratio that is used for longitudinal stretching is preferably between about 2 and about 6, preferably between about 2.5 and about 5, between preferred especially 3 and 4.Draw ratio is high more, and opacity is high more.
The 14 embodiment according to the method for the invention, longitudinal stretching be than at least 2.5, and preferably at least 3.0.
Cross directional stretch is than preferably in about 6 scopes of about 2-, preferably 2.5-about 5 and especially preferably about 3-about 4.Opacity higher rate of extension (in %/minute) and increase in lower cross directional stretch temperature.
The 15 embodiment according to the method for the invention, cross directional stretch be than at least 2.5, and preferably at least 3.0.
Production run may further include, and as further step, the thermal fixation step is resisted contraction.For example, this biaxially-stretched film passes second group of hot air heater, and its hot-air with 140 to 240 ℃ of temperature blows on the rete with heat setting or thermal fixation rete.Heat-set temperature must be enough to obtain the crystallization of polyester, does not make this layer overheated but take every caution against error, because the space can cave in.On the other hand, improve the dimensional stability that heat-set temperature has been improved film.Through changing heat-set temperature, suitable mixing that can obtained performance.Under the situation of polyethylene terephthalate or PEN, preferred heat setting or thermal fixation temperature are more than or equal to 140 ℃.
With afterwards, can pass through apparatus for coating before the longitudinal stretching, with first glue-line, so-called prime coat is applied to not on the pore-forming polyester layer like the airblade coating system.This first glue-line is for example formed by (methyl) acrylate copolymer of the latex form that spreads as aqueous dispersion, the multipolymer such as the vinylidene chloride copolymer that gather (methyl) acrylic ester, polyurethane, sulfonated polyester, styrene-(methyl) acrylate copolymer or chloride, and it is owing to the unsaturated carboxylic acid that has copolymerization has certain hydrophilic functional property.
The 16 embodiment according to the method for the invention, polymeric membrane do not contain foam.
The 17 embodiment according to the method for the invention, polymeric membrane do not contain gas-development agent and/or gas-development agent decomposition product.
Film optical density (OD) owing to micropore
The optical density (OD) of the film through measuring no pore-forming composition with film thickness is to provide correlative value, the film optical density (OD) owing to micropore that acquisition records with the transmission of visible light light filter.Following subsequently the film optical density (OD) that records with the transmission of visible light light filter of obtaining: biaxial stretch-formedly added the composition that composition is brought out in the space, and from the tight with the film thickness that predicts according to the vertical and horizontal draw ratio brings out the optical density (OD) that records with the transmission of visible light light filter of film composition of composition, deducted the optical density (OD) that this usefulness visible light light filter transmission records owing to the space.
Linear polyesters
The 18 embodiment according to the method for the invention; The mol ratio of isophthalic acid ester monomeric unit and terephthalate monomeric unit is at least 0.04; Mol ratio is preferred at least 0.05; Mol ratio is preferred especially at least 0.065 and mol ratio is especially preferred at least 0.075.
The 19 embodiment according to the method for the invention, the mol ratio of isophthalic acid ester monomeric unit and terephthalate monomeric unit is at least 0.11, mol ratio is preferred at least 0.13 and mol ratio is preferred especially at least 0.15.
The 20 embodiment according to the method for the invention, the mol ratio of isophthalic acid ester monomeric unit and terephthalate monomeric unit is at least 0.17, and mol ratio at least 0.20 is preferred, and mol ratio at least 0.25 is preferred especially.
The 21 embodiment according to the method for the invention, the mol ratio of isophthalic acid ester monomeric unit and terephthalate monomeric unit are 0.50 or still less, mol ratio 0.45 or still less be preferred and mol ratio 0.30 or still less be preferred especially.
The 22 embodiment according to the method for the invention, the number-average molecular weight of linear polyesters are 10,000 to 30,000.
The instance of suitable aliphatic dimethylene comprises ethylidene, propylidene, methyl propylidene, tetramethylene, pentamethylene, hexa-methylene, new pentylidene [CH
2C (CH
3)
2-CH
2], 1,4-cyclohexane-dimethylene, 1,3-cyclohexane-dimethylene, 1,3-cyclopentane-dimethylene, norbornane-dimethylene ,-CH
2CH
2(OCH
2CH
2)
n-(wherein n is an integer, and 1 to 5 is preferred) and composition thereof.
The 23 embodiment according to the method for the invention, aliphatic dimethylene monomeric unit is selected from ethylidene, tetramethylene, new pentylidene, norbornane-dimethylene and 1,4-cyclohexane-dimethylene.
The 24 embodiment according to the method for the invention; This aliphatic monomers unit is by ethylidene unit and new pentylidene and/or 1; 4-cyclohexanedimethyleterephthalate unit is formed, and new pentylidene and/or 1, the mol ratio at least 0.02 of 4-cyclohexanedimethyleterephthalate monomeric unit and ethylidene monomeric unit; Preferred molar ratio at least 0.04, special preferred molar ratio 0.065.
The 25 embodiment according to the method for the invention, linear polyesters comprise at least two kinds of linear polyester resins.When heating, for example during sneaking into extruder, the not synteny aromatic polyester resin of existence will experience double decomposition, condensation and depolymerization (decondensing) after sufficiently long heating, to be evolved into single resin.
Such polyester is well-known and can be through well-known technology preparation that for example US 2,465 in the art, 319 with US 2,901, those described in 466.
According to the 26 embodiment of polymeric membrane of the present invention, polymeric membrane further comprises the electric conductivity enhancement additive, and the slaine of the electric conductivity that for example ionization produce to strengthen in melt is such as magnesium acetate, manganese salt and cobaltous sulphate.Suitable salinity is about 3.5 * 10
-4The moles/mole polyester.The polyester melt viscosity that improves can realize that melt fixes (pinning) with the pin formula of the enhancing on the chill roll of cooling extruded thing remaining on 5 to 25 ℃ (preferred 15 to 30 ℃), can realize higher tensile force thus and realize that therefore the space of improving forms and higher opacification degree.
The linear polyesters that utilizes in the present invention should have 40 ℃-150 ℃ glass transition temperature, and preferably 50 to 120 ℃, and should be orientable.
The 27 embodiment according to the method for the invention; This linear polyesters has in the 0.5g/dL solution of 60 weight % phenol and 40 weight % o-dichlorobenzenes the limiting viscosity at 25 ℃ of 0.45dl/g at least that record; 0.48 the limiting viscosity to 0.9dl/g is preferred, 0.5 to 0.8dl/g limiting viscosity is especially preferred.
Amorphous high polymer
Being used for glass transition temperature that the amorphous high polymer of polymeric membrane of the present invention has is higher than it and is dispersed in the external phase glass transition temperature of linear polyesters for example wherein.Gather (ethylene glycol terephthalate), for example, have about 80 ℃ glass transition temperature.
The glass transition temperature and the refraction index of various amorphous high polymers provide in following table:
| T g[℃] | Sodium wire refraction index [ASTM D642] at 589.3nm | |
| Polystyrene | 100 | 1.57-1.60 |
| Gather-Alpha-Methyl-styrene | 168 | 1.610 |
| Gather-4-methyl-styrene | 93 | - |
| Gather-α-vinyl-naphthalene | 159 | 1.6818 |
| Polyacrylonitrile | 85 | 1.514，1.5187 |
| Polymethacrylonitrile | 120 | 1.520 |
| Polymethylmethacrylate | 105 | 1.49，1.4893 |
| Polyacrylamide | 165 | - |
| Vinyl cyanide and cinnamic multipolymer | 112 | 1.56?-1.57，1.57 |
| The cinnamic multipolymer of 28.5wt% vinyl cyanide and 71.5wt% | 108 | 1.56?-1.57，1.57 |
| ABS | 110 | 1.53?-1.54 |
The 28 embodiment according to the method for the invention, homodisperse amorphous high polymer are crosslinked or noncrosslinking.
The 29 embodiment according to the method for the invention, amorphous high polymer comprise the block of at least one chain type-polymerization.
The 30 embodiment according to the method for the invention; Amorphous high polymer comprises that the block of at least one chain type-polymerization and the block of this at least one chain type-polymerization are selected from polystyrene; Styrol copolymer, SAN-polymkeric substance, polyacrylate; Acrylic ester-multipolymer, polymethacrylate and methacrylate-multipolymer.
The 31 embodiment according to the method for the invention, amorphous high polymer comprise and are selected from the SAN-polymkeric substance, the styrol copolymer block of at least one chain type-polymerization of ABS-polymkeric substance and SBS-polymkeric substance.
The 32 embodiment according to the method for the invention, amorphous high polymer comprise the SAN-polymer blocks of at least one chain type-polymerization, and wherein the concentration of AN-monomeric unit is 15 to 35wt% in the SAN-polymkeric substance.
The 33 embodiment according to the method for the invention, amorphous high polymer do not comprise cellulose esters.
The 34 embodiment according to the method for the invention, amorphous high polymer is partial cross-linked at least for example partial cross-linked at least (methyl methacrylate) or partial cross-linked at least vinyl cyanide and the cinnamic multipolymer of gathering.
The 35 embodiment according to the method for the invention, film have linear polyesters as external phase and wherein disperse to have degree of crosslinking and be at least 10% superpolymer.
The 36 embodiment according to the method for the invention, amorphous high polymer are the SAN polymkeric substance, and the SAN polymer concentration is preferably at least 5% of film weight, at least 10% of special preferred film weight.
The SAN polymeric additive of this composition is the polymkeric substance of the known generic that is made up of the random copolymers of styrene monomer component (comprising the substituted styrene of styrene and α-low-carbon alkyl or its potpourri) and vinyl cyanide monomer component (comprising the substituted vinyl cyanide of vinyl cyanide and α-low-carbon alkyl or its potpourri) basically.Low-carbon alkyl is meant the straight or branched alkyl with 1 to 4 carbon atom, for example methyl, ethyl, isopropyl and the tert-butyl group.In the SAN polymkeric substance that is easy to get, the styrene component is styrene, the substituted styrene of α-straight chained alkyl normally, Alpha-Methyl-styrene, or its potpourri usually, and wherein styrene is preferred.Similarly, in the SAN polymkeric substance that is easy to get, the vinyl cyanide component is vinyl cyanide, Alpha-Methyl-vinyl cyanide or its potpourri normally, and wherein vinyl cyanide is preferred.
In the SAN polymkeric substance, the styrene component is with main part by weight, promptly with styrene component and vinyl cyanide component general assembly (TW) be higher than 50%, about 65% exists to about part by weight of 90%, especially about 70% to about 80% usually.The vinyl cyanide component is with minor proportions, promptly with styrene monomer component and acrylonitrile monemer component general assembly (TW) less than 50%, about 10% to about 35% usually, especially about part by weight of 20% to 30% exists.Styrene-acrylonitrile copolymer is present commercially available getting, and acrylonitrile content 15 is to 35wt%, preferred 18 to 32% weight and preferred especially 21 to 30% weight.
In following document, more particularly confirm and described SAN polymer type: R.E.Gallagher, US patent No.3,988,393; Issued on October 26th, 1976 (especially on the 9th hurdle, 14-16 capable with claim 8 in), " Whittington ' s Dictionary of Plastics ", Technomic Publishing Co.; First published, 1968, the 231 pages, title is in the part of " styrene-acrylonitrile copolymer (SAN) "; And R.B.Seymour, " Introduction to PolymerChemistry ", McGraw-Hill; Inc., 1971, the 200 pages (last two row) are to the 201st page (first row).At " Encyclopedia of Polymer Science and Technology ", JohnWiley and Sons, Inc., the 1st volume, the more special copolymerization SAN polymkeric substance of describing through styrene and vinyl cyanide in 1964, the 425-435 pages or leaves.
The 37 embodiment according to the method for the invention, amorphous high polymer are the SAN polymkeric substance of non-crosslinked, and its number-average molecular weight that has is 30,000 to 100,000,40,000 to 80,000th, and preferred.Typical SAN-polymkeric substance has 45,000 to 60,000 number-average molecular weight and 1.2 to 2.5 polymer dispersed degree (M
w/ M
n).
The 38 embodiment according to the method for the invention, amorphous high polymer are the SAN polymkeric substance of non-crosslinked, have weight-average molecular weight 50,000 to 200,000, preferably 75,000 to 150,000.The SAN polymer molecular weight is high more, and the size of the SAN polymer particle of dispersion is big more.
The crystallization superpolymer
Be used for the crystallization superpolymer according to polymeric membrane of the present invention, the fusing point that has is higher than it and is scattered in the continuous phase polymer glass transition temperature of linear polyesters for example wherein.Have abundant dystectic crystallization superpolymer and comprise tygon, polypropylene with gather (4-methyl-1-pentene).
The 39 embodiment according to the method for the invention, this film have linear polyesters as external phase and disperse wherein be to have 0.5 to 5 micron of number average particle size, preferred 1 to 2 micron crystallization superpolymer particle.
Provide in following table for various tygon and polyacrylic fusing point and refraction index:
| T m[℃] | Sodium wire refraction index [ASTM D642] at 589.3nm | |
| Tygon | 95 | 1.51-1.54 |
| High density polyethylene | 141 | 1.51-1.54 |
| Isotactic polyprophlene | 165 | 1.49 |
| Syndiotactic polypropylene | 189 | 1.49 |
| Polypropylene (atactic) | 1.4735 | |
| Gather (4-methyl-amylene) | 235 | 1.4630 |
Inorganic opacification pigment
The 40 embodiment according to the method for the invention, this film further comprise at least a inorganic opacification pigment that is selected from silicon dioxide, zinc paste, zinc sulphide, lithopone, barium sulphate, lime carbonate, titania, aluminum phosphate and clay.This titania can have anatase or rutile form and can use aluminium oxide and/or the silicon dioxide stabilization.Aluminum phosphate can be amorphous hollow pigment, for example from the Biphor of BUNGE
TMPigment.
The refraction index of these pigment is listed in the following table.
| Inorganic opacification pigment | Sodium wire refraction index in 589.3 nanometers |
| Smalite | 1.53-1.57 |
| Bentonitic clay | 1.557 |
| Potter's clay | 1.56 |
| Silicon dioxide-silica gel | 1.55 |
| Silicon dioxide-cristobalite | 1.487，1.484 |
| Silicon dioxide-quartz | 1.544，1.553 |
| Lime carbonate | 1.59，1.6，1.58 |
| Lime carbonate-kalzit | 1.486，1.64-1.66 |
| Barium sulphate-schohartite | 1.637，1.638，1.649，1.64 |
| Lithopone 30% (zinc sulphide/barium sulphate) | 1.84 |
| Zinc paste (ultra-fine) | 1.9 |
| Zinc paste (zincite) | 2.008，2.029 |
| Zinc sulphide | 2.37 |
| Titania-anatase | 2.554，2.493，2.55 |
| Titania-rutile | 2.616，2.903，2.76 |
According to the 41 embodiment of this method, this film comprises≤the inorganic opacification pigment of 5% weight, the total amount of the inorganic opacification pigment that promptly exists, and no matter its type is≤5% weight the inorganic opacification pigment of preferred≤3% weight.
The 42 embodiment according to the method for the invention, this film further comprise having number average particle size between the 0.1-10 micron, the inorganic opacification pigment of preferred 0.2-2 micron.
The interpolation of inorganic opacification pigment has the advantage of the orientation stabilization that makes polyester, thereby can under the situation of the opacity that does not influence this non-transparent microvoided axial tension self-supported membrane basically, under 175 ℃, make this non-transparent microvoided axial tension self-supported membrane stabilization.There not being inorganic opacification pigment, like BaSO
4Or TiO
2Situation under, the thermal fixation of polyester is that cost could realize with some opacities of non-transparent microvoided axial tension self-supported membrane only.In addition, refraction index is lower than 2.0 pigment, because the little difference in refractive index between this pigment and the polymer substrate can not provide remarkable opacity alone.
Have been found that the TiO 2 particles that is dispersed in the polymer film can not induce microporeization when stretched film.
Whitening agent
The 43 embodiment according to the method for the invention, the concentration of whitening agent are≤0.5 weight %, and≤0.1 weight % is preferred, and≤0.05 weight % is preferred especially, and≤0.035 weight % is especially preferred.
The 44 embodiment according to the method for the invention, this film further comprise and are selected from two-benzoxazoles, for example two-benzoxazolyls-stilbene and two-benzoxazolyls-thiophene; Benzotriazole-phenyl cumarin; Aphthotriazoles-phenyl cumarin; The whitening agent of triazine-phenyl cumarin and two (styryl) biphenyl.
Suitable whitening agent is:
Fire retardant
The 45 embodiment according to the method for the invention, this film further comprise and are selected from: brominated compound; Organic phosphorus compound; Melamine; Melamine-derivant (for example with organic or inorganic acid, like the melamine salt of boric acid, cyanuric acid, phosphoric acid or Jiao/polyphosphoric acid) and melamine homolog (like melam, melem and melon); Metal hydroxides (for example ammonium hydroxide and magnesium hydroxide); Ammonium polyphosphate and Firebrake ZB (for example consist of xZnO.yB
2O
3.zH
2O is like 2ZnO.3B
2O
3.3.5H
2O) fire retardant.
Suitable fire retardant comprises:
Anti-oxidant
46 embodiments according to the method for the invention, this film further comprise the anti-oxidant that is selected from organic tin derivates, sterically hindered phenol, sterically hindered phenol derivant and phosphite ester.
Suitable fire retardant comprises:
Light stabilizer
The 47 embodiment according to the method for the invention, this film further comprises hindered amine as light stabilizer.
Suitable light stabilizer comprises:
Ultraviolet light absorber
The 48 embodiment according to the method for the invention, this film further comprises the ultraviolet light absorber that is selected from benzotriazole derivatives and pyrrolotriazine derivatives.
Suitable ultraviolet light absorber comprises:
Image recording element
Also through the purposes of opaque self-supported membrane prepared in accordance with the present invention in image recording element realize of the present invention aspect.
According to the present invention, first embodiment of the purposes of opaque self-supported membrane prepared in accordance with the present invention in image recording element, but this film promptly is used for impact type and nonimpact printing having transparent chromatography layer on the one side at least.
According to the present invention, second embodiment of the purposes of opaque self-supported membrane prepared in accordance with the present invention in image recording element, but this film is having opaque chromatography layer on the one side at least, promptly is applicable at least a impact type and nonimpact printing technology.
According to the present invention; The 3rd embodiment of the purposes of opaque self-supported membrane prepared in accordance with the present invention in image recording element; But this film is having opaque transparent chromatography layer on the one side at least, promptly is applicable at least a impact type and nonimpact printing technology.
According to the present invention, the 4th embodiment of the purposes of opaque self-supported membrane prepared in accordance with the present invention in image recording element, this film is having the ink-jet receiving layer on the one side at least.Typical receiving layer is that touching rapidly with realization of porous is dry under the situation of water-based or solvent ink or thickener, or at phase change ink or curable ink, is atresia under the situation of radiation curable ink for example.The porous receiving layer comprises at least a pigment usually, like silicon dioxide or aluminium oxide; At least a bonding agent is like the ammonium salt of cinnamic acrylic ester-acrylic ternary copolymer; Surfactant, anionic surface active agent for example is like aliphatic sulfonate; Optional levelling agent is like dimethyl silicone polymer and optional mordant.
According to the present invention, the 5th embodiment of the purposes of opaque self-supported membrane prepared in accordance with the present invention in image recording element, this film is having imaging layer on the one side at least, for example photography layer, for example silver halide emulsion layer; Photothermographic element and photostable basically thermal imaging element; Dyestuff receiving layer with the thermal dye transfer system.
According to the present invention, the 6th embodiment of the purposes of opaque self-supported membrane prepared in accordance with the present invention in image recording element, this film has at least simultaneously can write layer, and for example available pencil, ball pen and fountain pen are write.
Obtain the method for transparent pattern
Aspect of the present invention is through being used to obtain the method realization of transparent pattern; Comprise step: apply heat and the optional non-transparent microvoided biaxial stretch-formed self-supported membrane that applies pressure to through the method acquisition that comprises the steps that is aided with according to image: i) in kneading machine or extruder, mix at least a linear polyesters; It has basically altogether is made up of terephthalate, isophthalic acid ester and aliphatic dimethylene; Wherein the mol ratio of isophthalic acid ester monomeric unit and terephthalate monomeric unit is at least 0.02, monomeric unit so that linear polyesters matrix to be provided; At least a amorphous high polymer and/or the fusing point at least a crystallization superpolymer higher that glass transition temperature is higher than the glass transition temperature of said linear polyesters matrix than the glass transition temperature of said linear polyesters matrix; Randomly be selected from least a composition of inorganic opacification pigment, whitening agent, ultraviolet light absorber, light stabilizer, anti-oxidant, fire retardant and colorant; Ii) form step I with thick film) the middle potpourri that obtains, quenching subsequently; Iii) with longitudinally the stretch twice at least of this thick film to initial length of the tensile force of＞4N/ square millimeter; Iv) laterally stretch from the twice at least of step longitudinal stretching film to initial length (iii).
According to first embodiment of the method for acquisition transparent pattern of the present invention, apply heat through pressing mold heating or heat, heat head, bar or laser heating or heat.Heating can be carried out from the one or both sides of this film.Can realize easily under the situation that film thickness does not have significantly to change that at least 0.4 or maximum 40% optical density (OD) changes.In addition, the hyalinization that realizes of the method through acquisition transparent pattern of the present invention is from the combination of the pressure between heat, thermal source and the film of thermal source supply and thermal source service time.Must be continuously or intermittently execute at least 1 millisecond of heat.Can use the heating of heat head with the single thermal pulse, but repeatedly short heating pulse is preferred to avoid the overheated of heating element.When using hot, can in heating process, between heat head and non-transparent microvoided biaxial stretch-formed self-supported membrane, use paper tinsel, for example can between non-transparent microvoided film and heat head, sandwich 6 micron thick PET films to prevent possibly polluting of hot head.A heat printing machine be can use, transparent pattern of the present invention, for example personalized watermark made like the DRYSTAR-printing machine of AGFA-GEVAERT N.V. supply.
Realize this transparence effect through embossing pattern, this pattern can stereognosis, promptly with tactile manner perception and the variation perception through glossiness.The temperature of thermal source is high more, and this embossing pattern is obvious more, and for example under the situation of SAN-polymkeric substance as disperse phase, this ecrase improves along with the temperature between 110 ℃ to 190 ℃.Much more obvious through hot-die being applied to the stereognosis embossment that obtains on the non-transparent microvoided biaxial stretch-formed self-supported membrane than what use the heat head to obtain.
The transparency that is realized depends on pressing mold/hot heading brush condition: time, temperature and pressure.The thermal fixation history of material also is important.The thermoinducible transparence of non-transparent microvoided biaxial stretch-formed self-supported membrane can and be carried out before or after transparence before or after choosing the layer that applies ink-jet receiving layer and so on wantonly.The relative position and the transparency in the carrier in transparence zone can be valuably as additional security measures.
According to second embodiment of the method for acquisition transparent pattern of the present invention, intermittently execute heat.
According to the 3rd embodiment of the method for acquisition transparent pattern of the present invention, but transparent chromatography layer was provided on this film executing heat according to image before.
According to the 4th embodiment of the method for acquisition transparent pattern of the present invention, but execute heat according to image after, transparent chromatography layer is provided on this film.
Commercial Application
Non-transparent microvoided axially stretched film of the present invention can be used as and is used for printing with the synthetic paper of other purposes, as the relector of LCD display and photoelectric device, as the carrier of image forming material (for example impact type and non-impact type (for example electrophotography, electrography and ink-jet) receive material, photothermographic recording materials, photostable basically thermal imaging recording materials, dye sublimation printing, hot transfer printing etc.); Be used in safety and the security purposes; For example in ticket, label, label, I.D., bank card, legal documents, bank note and packing, and also can be incorporated in the packing.
Below through Comparative Examples and the present invention of embodiment illustration.Only if indicate separately, number percent that provides among these embodiment and ratio are by weight.
Glue-line Nr.01 on the emulsion side of carrier:
Used composition among the embodiment:
Polyester:
| PET-nr | MFI?270℃/ 1.20kg [cm 3/10min] | Limiting viscosity ** [η][dl/g] | T g [℃] | ||
| 01 | T03 * | Polyethylene terephthalate | 34.8 | 0.60 | 80.5 |
| 02 | T04 * | Polyethylene terephthalate | 34.8 | 0.60 | 80.5 |
| 03 | WP75# | 98.5 the polyester of mole % terephthalate, 1.5 moles of % isophthalic acid esters and 100 moles of % ethylene unit | 0.77 | 80 |
| PET-nr | MFI?270℃/ 1.20kg [cm 3/10min] | Limiting viscosity ** [η][dl/g] | T g [℃] | ||
| 04 | DP9990# | The polyester of 90 moles of % terephthalate, 10 moles of % isophthalic acid esters and 100 moles of % ethylene unit | 0.60 | ||
| 05 | DP9730# | The polyester of 70 moles of % terephthalate, 30 moles of % isophthalic acid esters and 100 moles of % ethylene unit |
*AGFA-GEVAERT?N.V.
#La?Seda
*Limiting viscosity is measured down at 25 ℃ in the 0.5g/dL solution of 60 weight % phenol and 40 weight % o-dichlorobenzenes in the Ubbelohde viscosity meter
Styrene-acrylonitrile copolymer:
| SAN-nr | The Wt% vinyl cyanide | Wt% styrene | MFI?270℃/ 1.20kg [mL/10min] | Mn | Mw | T g [℃] | |
| 01 | TYRIL?905 * | 20 | 80 | 7.1 | 105.2 | ||
| 02 | TYRIL?867E * | 25 | 75 | 5.8 | 106.5 | ||
| 03 | SAN?140 * | 27.5 | 72.5 | 53.2 | 47,640 | 99,820 | 108.8 |
| 04 | LURAN 368R# | 28 | 72 | 3.9 | 107.3 | ||
| 05 | TYRIL?790 * | 29 | 71 | 12.1 | 106.3 | ||
| 06 | SAN?124 * | 28.5 | 71.5 | 37.9 | 53,940 | 109,350 | 108.1 |
| 07 | LURAN 388S# | 33 | 67 | 3.6 | 108.7 |
*DOW?CHEMICAL
#BASF
The MFI=melt flow index
MAGNUM 8391:ABS resin; 95 ℃ of Vicat softening temperatures; From DOW CHEMICALTPX
DX820: high rigidity is gathered (4-methylpentene), from MITSUI CHEMICAL
Titania: Renol-white/PTX 506 from the masterbatch of CLARIANT GmbH, contains 65 weight %TiO
2With 35 weight % polyester
Comparative Examples 1 to 3
The PET type and the SAN type that are used for producing the used extrudate of the film of Comparative Examples 1 to 3 provide in table 3.PET, SAN, TiO
2Mix with the percent by weight that provides in the table 1 with UVITEX OB-one; Then under vacuum condition (＜100 millibars) 150 ℃ of dryings 4 hours, potpourri be melted in the PET-extruder then and be extruded through the sheet material die head and cooling with the extrudate of production Comparative Examples 1 to 3.
Table 1:
| Comparative Examples nr | PET01 [wt％] | PET02 [wt％] | PET03 [wt％] | The SAN type | TiO 2 [wt％] | OB-one [ppm] |
| 1 | 98 | - | - | - | 2 | 150 |
| 2 | 47 | - | 47 | - | 6 | - |
| 3 | 44 | - | 44 | - | 12 | - |
The extrudate of Comparative Examples 1 to 3 wherein heats to produce Comparative Examples 1/LS1 respectively, the axially stretched film of 2/LS1 and 3/LS1 with the condition that provides in the table 2 in the stove of extrudate on being installed in this device then with INSTRON device longitudinal stretching.
Table 2:
| Comparative Examples nr. | Draw ratio | Tensile force [N/mm 2] | Thickness [micron] | OD?TR924 |
| 1/LS1 | 3.3 | 6.0 | 319 | 0.81 |
| 2/LS1 | 3.3 | 5.0 | 340 | 1.26 |
| 3/LS1 | 3.3 | 5.0 | 335 | 1.59 |
Then the longitudinal stretching film is carried out cross directional stretch with the condition that provides in the table 3, stretching time 30s, draw speed 1000%/minute.175 ℃ of thermal fixation films 1 minute, produce opaque basically Comparative Examples 1/LS1, the film of 2/LS2 and 3/LS3 at last.
Comparative Examples 1/LS1/BS1, the optical density (OD) of the film of 2/LS1/BS1 and 3/LS1/BS1 is measured with transmission mode with the MACBETH TR924 densitometer with visible light light filter, and the result provides in table 3.
Table 3:
| Comparative Examples nr. | Draw ratio | Draft temperature [℃] | Thickness [micron] | OD after the thermal fixation (TR924) |
| 1/LS1/BS1 | 3.3 | 135 | 120 | 0.45 |
| 2/LS1/BS1 | 3.3 | 135 | 140 | 0.90 |
| 3/LS1/BS1 | 3.3 | 135 | 135 | 1.12 |
*Tensile stress is high more, and draft temperature is low more
With the film 1/LS/BS of Comparative Examples, 2/LS/BS and 3/LS/BS are installed in Instron 4411 devices separately and under 120 to 190 ℃ all temps, heated 5 seconds, and the flatiron in the clamp of top contacts with this film with the pressure of 0.5N/ square millimeter.With the optical density (OD) of the MacBethTR924 densitometer transmission measurement test caudacoria that has the visible light light filter, also measured film thickness.The result is summarized in following table 4 and 5 respectively.
Table 4:
Table 5:
In the experimental error scope, do not observe film 1/LS/BS, the transparence of 2/LS/BS and 3/LS/BS in the heating Comparative Examples.This shows to lack the SAN-polymer beads period of the day from 11 p.m. to 1 a.m that disperses, the film that comprises titania does not have transparence, does not promptly have micropore to form.
Comparative Examples 4
As to Comparative Examples 1 to 3 said manufacturing consist of 2 weight % titania, 100ppmUVITEX OB-one and 98 weight %PET02 Comparative Examples 4 1083 micron thick extrudate and have 1.35 the optical density (OD) that records with transmission mode with the MacBeth TR924 densitometer that has a visible light light filter.Under the condition that extrudate provides in table 6 in length direction such as Comparative Examples 1 to 3 said stretching.The measurement of one-tenth-value thickness 1/10 be through average 16 different positions, uses resolution with 1 micron, 2 microns precision and diameter under the 0.8N ergometry, to contact the measured value of upper surface acquisition as the SONYU30A thickness meter that contacts ball of 3mm.
Table 6:
| Comparative Examples nr | Draw ratio | Tensile force [N/ square millimeter] | Thickness [micron] | OD (TR924) | OD [X-rite] |
| 4/LS1 | 3.3 | 6 | 323 | 0.805 | 0.55 |
| 4/LS2 | 3.3 | 4 | 328 | 0.84 | - |
On the film of longitudinal stretching, carry out cross directional stretch under the condition that in table 7, provides then, stretching time 30s, draw speed 1000%/minute.Also in table 7, provide with the optical density (OD) of the MacBeth TR924 densitometer that has the visible light light filter with transmission mode measured thickness and measurement.
Table 7:
| Comparative Examples nr. | Draw ratio | Draft temperature [℃] | Thickness [micron] | OD TR924 | OD [X-rite] |
| 4/LS1/BS1 | 3.3 | 135 | 120 | 0.47 | 0.30 |
| 4/LS2/BS1 | 3.3 | 135 | 124 | 0.53 | 0.33 |
Because as from can finding out the Comparative Examples 1 to 3; Composition for Comparative Examples 4; When biaxial stretch-formed, there be not the contribution of pore-forming to optical density (OD); Can utilize optical density (OD) baseline to be provided, for interstitial those compositions that contain the identical TiO 2 pigment of 2 weight % when biaxial stretch-formed, with of the contribution of this baseline estimate pore-forming to optical density (OD) based on aromatic polyester to the dependence of film thickness.
Beer-Lambert relation is not suitable for and contains light scattering pigment, like the painted film of titania.If film thickness is less than the mean free path length of scattered light, light can be overflowed after scattering, otherwise light can not overflowed and in fact disturbed further scattered light, thereby the accurate exponential dependency of optical density (OD) to film thickness is provided.This situation is too complicated consequently can not be described in theory, and therefore unique possible approach is to measure observed actual optical density (OD) under certain films thickness.Above-mentioned optical density (OD) seems and quite approaches the logarithm that linearity relies on the film thickness in 1084 to 120 microns of the layer thickness scopes, draws the following relationship formula:
OD=0.891log [thickness, micron meter]-1.3727
This relational expression provides the optical density (OD) that is attributable to used 2 weight % concentration TiO 2 pigments as the function of film thickness.
Comparative Examples 5 and embodiments of the invention 1 to 17
Following manufacturing all contains the extrudate of about 1100 micron thick of Comparative Examples 5 and the embodiments of the invention 1 to 17 of 2 weight % titania and 15 weight % SAN 06: with the mixed of the composition in the table 8 to provide in the table 8; Then this potpourri was descended dry 4 hours in vacuum (＜100 millibars) under 150 ℃; Fusion in the PET-extruder again pushes through the sheet material die head and cooling has density and isophthalic acid ester (IPA) like about 1.3 grams per milliliters of summarizing in the table 8 with manufacturing: the Comparative Examples 5 of terephthalate (TPA) ratio and the extrudate of embodiments of the invention 1 to 17.
Table 8:
| Comparative Examples nr. | PET02 [wt％] | PET04 [wt％] | PET05 [wt％] | IPA: TPA ratio | The SAN type | SAN [wt％] | UVITEX OB-one [ppm] | TiO 2 [wt％] | Density [g/mL] |
| 5 | 83 | 0 | - | 0 | 06 | 15 | - | 2.0 | 1.294 |
| Embodiment of the invention nr. | |||||||||
| 1 | 58 | 25 | - | 0.0310 | 06 | 15 | - | 2.0 | 1.289 |
| 2 | 41.5 | 41.5 | - | 0.0526 | 06 | 15 | 100 | 2.0 | 1.284 |
| 3 | 33.35 | 49.7 | - | 0.0636 | 06 | 15 | - | 1.95 |
| Comparative Examples nr. | PET02 [wt％] | PET04 [wt％] | PET05 [wt％] | IPA: TPA ratio | The SAN type | SAN [wt％] | UVITEX OB-one [ppm] | TiO 2 [wt％] | Density [g/mL] |
| 4 | 33.3 | 49.7 | - | 0.0637 | 06 | 15 | 100 | 2.0 | |
| 5 | 32.3 | 50.7 | - | 0.0650 | 06 | 15 | 100 | 2.0 | |
| 6 | 32.3 | 50.7 | - | 0.0650 | 06 | 15 | 100 | 2.0 | |
| 7 | 26.29 | 56.71 | - | 0.0733 | 06 | 15 | 100 | 2.0 | |
| 8 | 25.25 | 57.75 | - | 0.0748 | 06 | 15 | 100 | 2.0 | |
| 9 | 25 | 58 | - | 0.0751 | 06 | 15 | 100 | 2.0 | 1.304 |
| 10 | 24.3 | 58.7 | - | 0.0761 | 06 | 15 | 100 | 2.0 | |
| 11 | 1.05 | 82.0 | - | 0.109 | 06 | 15 | - | 1.95 | |
| 12 | - | 83 | - | 0.111 | 06 | 15 | - | 2.0 | 1.299 |
| 13 | - | 83 | - | 0.111 | 06 | 15 | 100 | 20 | |
| 14 | 28.25 | 22.3 | 32.5 | 0.168 | 06 | 15 | 100 | 1.95 | |
| 15 | 14.85 | 22.3 | 45.9 | 0.239 | 06 | 15 | - | 1.95 | |
| 16 | 1.05 | 22.3 | 59.7 | 0.320 | 06 | 15 | - | 1.95 | |
| 17 | 1.05 | - | 82.0 | 0.421 | 06 | 15 | - | 1.95 |
Described in Comparative Examples 1 to 3, each extrudate is carried out longitudinal stretching under the condition that in table 11, provides.Expection thickness be based on the thickness of extrudate thickness and be vertically (as to do not become pore membrane observed).
Longitudinal stretching is accompanied by the density that is caused by pore-forming to be reduced, and this density reduces obviously with IPA: the TPA ratio improves, and shows IPA surprisingly: the pore-forming that the raising of TPA ratio helps improving in the film.
Table 11:
Table 10 provides and records thickness; Expection thickness, if promptly based on the thickness of the not pore-forming of extrudate thickness, longitudinal stretching than and the cross directional stretch ratio; The optical density (OD) that records with transmission mode with the MacBethTR924 densitometer that has a visible light light filter; The expection optical density (OD) is promptly used the optical density (OD) that disclosed relational expression uses theoretical layer thickness value to calculate in the Comparative Examples 4; With observed optical density (OD) poor with owing to the expection optical density (OD) of the used specific TiO 2 pigment of 2 weight % concentration, Δ OD.
Table 10:
| Comparative Examples nr | IPA: TPA ratio | Thickness [μ m] | V1 speed [m/min] | Expection thickness [μ m] | OD TR924 | Expection OD | ΔOD | ΔOD/ OD | OD [X-rite] |
| 5/LS1 | 0 | 320 | 4.0 | 286 | 1.00 | 0.81 | 0.19 | 0.19 | 0.76 |
| Embodiment of the invention nr. | |||||||||
| 1/LS1 | 0.0310 | 325 | 4.0 | 286 | 1.05 | 0.81 | 0.24 | 0.23 | 0.82 |
| 1/LS2 | 0.0310 | 323 | 4.0 | 301 | 1.00 | 0.83 | 0.17 | 0.17 | 0.78 |
| 2/LS1 | 0.0526 | 318 | 4.0 | 286 | 1.06 | 0.81 | 0.25 | 0.23 | 0.85 |
| 3/LS1 | 0.0636 | 380 | 4.0 | 333 | 1.17 | 0.87 | 0.30 | 0.26 | 0.96 |
| 3/LS2 | 0.0636 | 380 | 4.0 | 333 | 1.15 | 0.87 | 0.28 | 0.24 | 0.97 |
| 3/LS3 | 0.0636 | 375 | 8.0 | 333 | 1.12 | 0.87 | 0.25 | 0.22 | 0.92 |
| 4/LS1 | 0.0637 | 350 | 4.0 | 333 | 1.21 | 0.87 | 0.34 | 0.28 | 0.98 |
| 4/LS2 | 0.0637 | 330 | 4.0 | 333 | 1.02 | 0.87 | 0.15 | 0.15 | 0.80 |
| 5/LS1 | 0.0650 | 365 | 4.0 | 333 | 0.87 | ||||
| 6/LS1 | 0.0650 | 300 | 4.0 | 290 |
| Comparative Examples nr | IPA: TPA ratio | Thickness [μ m] | V1 speed [m/min] | Expection thickness [μ m] | OD TR924 | Expection OD | ΔOD | ΔOD/ OD | OD [X-rite] |
| 6/LS2 | 0.0650 | 335 | 4.0 | 305 | |||||
| 6/LS3 | 0.0650 | 350 | 4.0 | 319 | |||||
| 7/LS1 | 0.0733 | 360 | 4.0 | 333 | 1.17 | 0.87 | 0.30 | 0.26 | 0.97 |
| 8/LS1 | 0.0748 | 330 | 4.0 | 333 | 1.08 | 0.87 | 0.21 | 0.19 | 0.90 |
| 9/LS1 | 0.0751 | 330 | 4.0 | 286 | 1.13 | 0.81 | 0.32 | 0.28 | 0.92 |
| 10/LS1 | 0.0761 | 350 | 4.0 | 333 | 1.18 | 0.87 | 0.31 | 0.26 | 1.00 |
| 10/LS2 | 0.0761 | 333 | 4.0 | 333 | 1.10 | 0.87 | 0.23 | 0.21 | 0.89 |
| 11/LS1 | 0.109 | 370 | 4.0 | 333 | 1.15 | 0.87 | 0.28 | 0.24 | 0.93 |
| 11/LS2 | 0.109 | 385 | 4.0 | 333 | 1.28 | 0.87 | 0.41 | 0.32 | 1.01 |
| 12/LS1 | 0.1111 | 345 | 4.0 | 286 | 1.20 | 0.81 | 0.39 | 0.32 | 1.02 |
| 12/LS2 | 0.1111 | 380 | 4.0 | 301 | 1.23 | 0.83 | 0.40 | 0.32 | 1.00 |
| 13/LS1 | 0.1111 | 320 | 4.0 | 286 | 1.24 | 0.81 | 0.43 | 0.35 | 1.00 |
| 13/LS2 | 0.1111 | 4.0 | 286 | 1.02 | 0.81 | 0.21 | 0.20 | 0.83 | |
| 13/LS3 | 0.1111 | 4.0 | 286 | 1.10 | 0.81 | 0.29 | 0.26 | 0.83 | |
| 14/LS1 | 0.168 | 393 | 4.0 | 333 | 1.15 | 0.87 | 0.28 | 0.24 | 0.97 |
| 15/LS1 | 0.239 | 390 | 4.0 | 333 | 1.12 | 0.87 | 0.25 | 0.22 | 0.91 |
| 16/LS1 | 0.320 | 392 | 4.0 | 327 | 1.37 | 0.87 | 0.50 | 0.36 | 1.10 |
| 16/LS2 | 0.320 | 400 | 4.0 | 327 | 1.10 | 0.87 | 0.23 | 0.21 | 0.89 |
| 17/LS1 | 0.421 | 375 | 4.0 | 333 | 1.13 | 0.87 | 0.26 | 0.23 | 0.76 |
| 17/LS2 | 0.421 | 380 | 4.0 | 333 | 0.97 | 0.87 | 0.10 | 0.10 | 0.89 |
Because the optical density (OD) of pore-forming increases to 17-36%.In addition, for embodiment of the invention 13/LS1, the optical density (OD) value of 13/LS2 and 13/LS3 has clearly show the influence of longitudinal stretching power, for having the highest longitudinal stretching power 8N/mm
2The film of embodiment of the invention 13/LS1, obtained the highest optical density (OD) value 1.24, by contrast, have longitudinal stretching power 5N/mm respectively
2And 6N/mm
2Embodiment of the invention 13/LS2 and the film of 13/LS3, obtained 1.02 and 1.10 respectively.
Under the condition that in table 11, provides on the film of longitudinal stretching, carry out cross directional stretch then with 30 seconds stretching times and 1000%/minute draw speed.Density, the thickness that records and expection thickness (if promptly based on thickness of the not pore-forming of extrudate thickness), longitudinal stretching than and cross directional stretch than also being listed in the table 11.
Cross directional stretch further reduces film density, and when PET04 and the raising of PET05 ratio, it is bigger that density reduces degree.This shows once more surprisingly, IPA: the pore-forming that the raising of TPA ratio helps improving in the film.
Surprisingly, the IPA 0.0650: under the TPA ratio, cross directional stretch be higher than 113 ℃ infeasible, but feasible down in the temperature (its than the glass transition temperature height of linear polyesters matrix less than 10 ℃) that is low to moderate 85 ℃.This can be through the much higher optical density (OD) of biaxial stretch-formed realization.
Table 11:
Table 12 provides and records thickness; Expection thickness; The optical density (OD) that records with transmission mode with the MacBethTR924 densitometer that has a visible light light filter; The expection optical density (OD) is promptly used the optical density (OD) that disclosed relational expression uses theoretical layer thickness value to calculate in the Comparative Examples 4; With observed optical density (OD) poor with owing to the expection optical density (OD) of the used specific TiO 2 pigment of 2 weight % concentration, Δ OD.
Table 12:
| Comparative Examples nr. | IPA: TPA ratio | V1 (LS) speed [m/min] | Thickness [μ m] | Expection thickness [μ m] | OD TR924 | Expection OD | ΔOD | ΔOD/ OD | OD [X-rite] |
| 5/LS1/BS1 | 0 | 4.0 | 101 | 87 | 1.00 | 0.35 | 0.65 | 0.65 | 0.78 |
| Embodiment of the invention nr | |||||||||
| 1/LS1/BS1 | 0.0310 | 4.0 | 95 | 87 | 1.01 | 0.35 | 0.66 | 0.65 | 0.78 |
| 1/LS2/BS1 | 0.0310 | 4.0 | 102 | 91 | 0.99 | 0.37 | 0.62 | 0.63 | 0.75 |
| 2/LS1/BS1 | 0.0526 | 4.0 | 100 | 87 | 1.04 | 0.35 | 0.69 | 0.66 | 0.80 |
| 2/LS?1/BS2 | 0.0526 | 4.0 | 97 | 87 | (1.04) | (0.35) | (0.69) | 0.66 | (0.80) |
| 3/LS1/BS1 | 0.0636 | 4.0 | 145 | 95 | 1.02 | 0.39 | 0.63 | 0.62 | 0.85 |
| 3/LS2/BS1 | 0.0636 | 4.0 | 150 | 95 | 1.11 | 0.39 | 0.72 | 0.65 | 0.90 |
| 3/LS3/BS1 | 0.0636 | 8.0 | 126 | 95 | 1.03 | 0.39 | 0.64 | 0.62 | 0.77 |
| 4/LS1/BS1 | 0.0637 | 4.0 | 140 | 95 | 1.20 | 0.39 | 0.81 | 0.67 | 0.97 |
| 4/LS1/BS2 | 0.0637 | 4.0 | 135 | 95 | 1.25 | 0.39 | 0.86 | 0.69 | 1.00 |
| 4/LS2/BS1 | 0.0637 | 4.0 | 116 | 95 | 1.10 | 0.39 | 0.71 | 0.64 | 0.86 |
| 5/LS1/BS1 | 0.0650 | 4.0 | 140 | 101 | 1.10 | 0.41 | 0.69 | 0.63 | 0.85 |
| 6/LS1/BS1 | 0.0650 | 4.0 | 110 | 88 | 1.06 | 0.36 | 0.70 | 0.66 | 0.84 |
| 6/LS2/BS1 | 0.0650 | 4.0 | 135 | 93 | 1.18 | 0.38 | 0.80 | 0.68 | 0.94 |
| 6/LS3/BS1 | 0.0650 | 4.0 | 150 | 97 | 1.11 | 0.40 | 0.71 | 0.64 | 0.88 |
| 7/LS1/BS1 | 0.0733 | 4.0 | 145 | 95 | 1.21 | 0.39 | 0.82 | 0.68 | 0.94 |
| 8/LS1/BS1 | 0.0748 | 4.0 | 138 | 95 | 1.20 | 0.39 | 0.81 | 0.67 | 0.97 |
| 9/LS1/BS1 | 0.0751 | 4.0 | 105 | 87 | 1.10 | 0.35 | 0.75 | 0.68 | 0.90 |
| Comparative Examples nr. | IPA: TPA ratio | V1 (LS) speed [m/min] | Thickness [μ m] | Expection thickness [μ m] | OD TR924 | Expection OD | ΔOD | ΔOD/ OD | OD [X-rite] |
| 10/LS1/BS1 | 0.0761 | 4.0 | 147 | 95 | 1.20 | 0.39 | 0.81 | 0.67 | 0.97 |
| 10/LS2/BS1 | 0.0761 | 4.0 | 112 | 95 | 1.05 | 0.39 | 0.66 | 0.63 | 0.82 |
| 11/LS1/BS1 | 0.109 | 4.0 | 207 | 95 | 1.26 | 0.39 | 0.87 | 0.69 | 1.04 |
| 11/LS1/BS2 | 0.109 | 4.0 | 199 | 95 | 1.28 | 0.39 | 0.89 | 0.69 | 1.04 |
| 11/LS1/BS3 | 0.109 | 4.0 | 198 | 95 | 1.27 | 0.39 | 0.88 | 0.69 | 1.03 |
| 11/LS2/BS1 | 0.109 | 4.0 | 205 | 95 | 1.34 | 0.39 | 0.95 | 0.71 | 1.12 |
| 11/LS2/BS2 | 0.109 | 4.0 | 210 | 95 | 1.34 | 0.39 | 0.95 | 0.71 | 1.08 |
| 11/LS2/BS3 | 0.109 | 4.0 | 214 | 95 | 1.35 | 0.39 | 0.96 | 0.71 | 1.11 |
| 12/LS1/BS1 | 0.111 | 4.0 | 169 | 87 | 1.32 | 0.35 | 0.97 | 0.73 | 1.06 |
| 12/LS2/BS1 | 0.111 | 4.0 | 185 156 | 91 | 1.26 | 0.37 | 0.89 | 0.71 | 1.00 |
| 12/LS1/BS1 | 0.111 | 4.0 | 130 | 86 | 1.24 | 0.35 | 0.89 | 0.72 | 1.00 |
| 13/LS2/BS1 | 0.111 | 4.0 | 125 | 86 | 0.95 | 0.35 | 0.60 | 0.63 | 0.74 |
| 13/LS3/BS1 | 0.111 | 4.0 | 120 | 86 | 0.98 | 0.35 | 0.63 | 0.64 | 0.74 |
| 14/LS1/BS1 | 0.168 | 4.0 | 198 | 95 | 1.30 | 0.39 | 0.91 | 0.70 | 1.05 |
| 14/LS1/BS2 | 0.168 | 4.0 | 201 | 95 | 1.28 | 0.39 | 0.89 | 0.69 | 1.04 |
| 14/LS1/BS3 | 0.168 | 4.0 | 204 | 95 | 1.30 | 0.39 | 0.91 | 0.70 | 1.08 |
| 15/LS1/BS1 | 0.239 | 4.0 | 191 | 95 | 1.20 | 0.39 | 0.81 | 0.67 | 0.99 |
| 15/LS1/BS2 | 0.239 | 4.0 | 186 | 95 | 1.19 | 0.39 | 0.80 | 0.67 | 0.97 |
| 16/LS1/BS1 | 0.320 | 4.0 | 211 | 95 | 1.26 | 0.39 | 0.87 | 0.69 | 1.00 |
| 16/LS1/BS2 | 0.320 | 4.0 | 210 | 95 | 1.30 | 0.39 | 0.91 | 0.70 | 1.08 |
| 16/LS2/BS1 | 0.320 | 4.0 | 190 | 95 | 1.19 | 0.39 | 0.80 | 0.67 | 0.95 |
| 16/LS2/BS2 | 0.320 | 4.0 | 200 | 95 | 1.21 | 0.39 | 0.82 | 0.68 | 0.98 |
| 17/LS1/BS1 | 0.421 | 4.0 | 190 | 95 | 1.14 | 0.39 | 0.75 | 0.66 | 0.91 |
| 17/LS1/BS2 | 0.421 | 4.0 | 170 | 95 | 1.14 | 0.39 | 0.75 | 0.66 | 0.90 |
| 17/LS1/BS3 | 0.421 | 4.0 | 170 | 95 | 1.16 | 0.39 | 0.77 | 0.66 | 0.91 |
| 17/LS2/BS1 | 0.421 | 4.0 | 150 | 95 | 1.03 | 0.39 | 0.64 | 0.62 | 0.81 |
| 17/LS2/BS2 | 0.421 | 4.0 | 150 | 95 | 1.07 | 0.39 | 0.68 | 0.63 | 0.83 |
For embodiment of the invention 13/LS1/BS1, the optical density (OD) value of 13/LS2/BS1 and 13/LS3/BS1 has also clearly show the influence of longitudinal stretching power, for having the highest longitudinal stretching power 8N/mm
2The film of embodiment of the invention 13/LS1/BS1, obtained the highest optical density (OD) value 1.24, by contrast, have longitudinal stretching power 5N/mm respectively
2And 6N/mm
2Embodiment of the invention 13/LS2/BS1 and the film of 13/LS3/BS1, obtained 0.95 and 0.98 respectively.
The result of table 12 shows, under roughly the same draft temperature, along with IPA: the TPA ratio rises to 0.132, and microporeization is increased to the contribution of the optical density (OD) of biaxially-stretched film and surpasses 70%.IPA 0.132: more than the TPA ratio, it is stable reduces to the IPA 0.421: TPA ratio (being equivalent to 30 moles of % isophthalic acid esters) is 0.66 still significant contribution portion down.
After contacting 5 seconds under 150 ℃, observe the variation of film thickness and optical density (OD) through film being clipped in Instron 4411 devices and with flatiron, confirm that there is pore-forming in several biaxially-stretched films at film.These result of experiment are listed in the table 13.
Table 13:
Embodiment 18
As 1 to 3 said manufacturing consists of 2 weight % titania, 100ppmUVITEX OB-one [ppm], 15 weight % SAN 06 and 83 weight % PET04, produces 0.0650 IPA to Comparative Examples: the extrudate of 1100 micron thick of the embodiment 18 of TPA ratio.Described in Comparative Examples 1-3, under like four groups of different conditions that provide in the table 14, extrudate is carried out the stretching of length direction.Expection thickness be based on the thickness of extrudate thickness and be vertically (as to do not become pore membrane observed).
Table 14:
Under the condition that in table 15, provides on the film of longitudinal stretching, described in Comparative Examples 1-3, carry out cross directional stretch then.Density, the thickness that records and expection thickness (if promptly based on thickness of the not pore-forming of extrudate thickness) and longitudinal stretching than and cross directional stretch than also being listed in the table 15.
Biaxial stretch-formed reduction film density, wherein the cross directional stretch temperature is low more, and density reduces manyly more.But; The reduction of density less than the simple degree of estimating according to the thickness (comparing) that records, longitudinal stretching with expection thickness based on extrudate thickness than and cross directional stretch than (observed) as be directed against into pore membrane, this can partial interpretation be the combination of two kinds of effects: the density that is caused by pore-forming on the one hand is reduced in to a certain extent owing to being obtained to compensate by the raising of the crystallinity of the biaxial stretch-formed polyester matrix that causes on the other hand.
Table 15:
Table 16 provide the thickness that records, expection thickness (if promptly based on thickness of the not pore-forming of extrudate thickness) and longitudinal stretching and cross directional stretch than, the optical density (OD) that records with transmission mode with the MacBethTR924 densitometer that has the visible light light filter, expect optical density (OD) (promptly using the optical density (OD) that disclosed relational expression uses theoretical layer thickness value to calculate in the Comparative Examples 4) and observed optical density (OD) and poor owing to the expection optical density (OD) of the used specific TiO 2 pigment of 2 weight % concentration, Δ OD and the temperature when carrying out cross directional stretch.
Table 16:
| Embodiment nr. | Draft temperature [℃] | Thickness [μ m] | Expection thickness [μ m] | OD (TR924) | Expection OD | ΔOD | ΔOD/ OD | OD (X-rite) |
| 18/LS3/BS1 | 86 | 199 | 101 | 1.35 | 0.41 | 0.95 | 0.70 | 1.10 |
| 18/LS3/BS2 | 91 | 185 | 101 | 1.32 | 0.41 | 0.91 | 0.69 | 1.07 |
| 18/LS3/BS3 | 98 | 180 190 | 101 | 1.28 1.36 | 0.41 | 0.87 0.95 | 0.68 0.70 | 1.03 |
| 18/LS3/BS4 | 100 | 165 | 101 | 1.20 | 0.41 | 0.79 | 0.66 | 0.96 |
| 18/LS3/BS5 | 100 | 150 | 101 | 1.22 | 0.41 | 0.81 | 0.66 | 1.00 |
| 18/LS3/BS6 | 100 * | 175 | 95 | 1.22 | 0.39 | 0.83 | 0.68 | 0.98 |
| 18/LS3/BS7 | 101 | 105 | 101 | 1.15 | 0.41 | 0.75 | 0.65 | 0.90 |
| 18/LS3/BS8 | 102 | 135 | 101 | 1.08 | 0.41 | 0.67 | 0.62 | 0.81 |
| 18/LS2/BS1 | 106 | 135 | 93 | 0.38 | 1.005 | |||
| 18/LS3/BS9 | 110 | 150 | 101 | 0.41 | 0.94 | |||
| 18/LS4/BS1 | 110 | 165 | 108 | 1.18 | 0.44 | 0.74 | 0.63 | 0.91 |
| 18/LS2/BS2 | 113 | 135 | 93 | 1.17 | 0.38 | 0.79 | 0.67 | 0.905 |
| 18/LS1/BS1 | 114 | 110 | 88 | 1.01 | 0.36 | 0.65 | 0.64 | 0.805 |
| 18/LS3/BS10 | 121 | 150 | 101 | 1.14 | 0.41 | 0.73 | 0.64 | 0.89 |
| 18/LS2/BS3 | 123 | 120 | 93 | 0.38 | 0.88 | |||
| 18/LS3/BS11 | 128 | 140 | 101 | 1.10 | 0.41 | 0.69 | 0.63 | 0.86 |
| 18/LS3/BS12 | 132 | 140 | 101 | 1.10 | 0.41 | 0.69 | 0.63 | 0.85 |
| 18/LS3/BS13 | 142 | 140 | 101 | 1.10 | 0.41 | 0.69 | 0.63 | 0.83 |
| 18/LS4/BS2 | 150 | 162 | 108 | 0.44 | 0.85 | |||
| 18/LS3/BS17 | 153 | 140 | 101 | 1.10 | 0.41 | 0.69 | 63 | 0.86 |
*Draw ratio=3.5
Result from table 16 is clear to be found out, as not owing to shown in the optical density (OD) of existing 2 weight % titania, the pore-forming degree brings up to 70% with the reduction of cross directional stretch temperature, regardless of other correlated condition in the cross directional stretch process.
Table 17 has been summarized for the different films that under about 110 ℃ of draft temperatures, obtain, stretching condition, thickness, based on the expection thickness of extrudate thickness, longitudinal stretching than and the optical density (OD) raising of cross directional stretch ratio, optical density (OD), expection optical density (OD) and the non-contribution property (non-attibutable) that causes by pore-forming.
Table 17:
*Draw ratio=3.5
Data in the table 17 show, stretching time was reduced to 10 seconds from 30 seconds and draw speed is increased to 2000%/min from 1000%/min and also helps pore-forming.
After contacting 5 seconds under all temps, observe the variation of film thickness and optical density (OD) through film being clipped in Instron 4411 devices and with flatiron, confirm that there is pore-forming in the biaxially-stretched film of embodiment 18/LS1/BS1 at film.These result of experiment are listed in the table 18 and 19.
For the film of embodiment 18/LS1/BS1, the optical density (OD) of observing at 150 ℃ is reduced to 0.42, and corresponding to 25%, the layer thickness with 26% reduces.
Table 18:
Table 19:
Comparative Examples 6 and embodiment of the invention 19-22
Comparative Examples 6 and the extrudate of embodiment of the invention 19-22 of about 1100 micron thick of SAN that all has titania and 15% weight of 2% weight like said preparation to Comparative Examples 1-3; Have the SAN of 15% weight or the ABS of 15% weight (MAGNUM 8391) and different PET02 and PET04 weight ratios, such as in the table 20 summary.
Table 20:
| Comparative Examples nr. | IPA: TPA ratio | PET02 [wt％] | PET04 [wt％] | MAGNUM 8391 [% weight] | SAN?06 [wt％] | UVITEX OB-one [ppm] | TiO 2 [wt％] |
| 6 | 0 | 83 | 0 | 15 | - | - | 2.0 |
| Embodiment of the invention nr. | |||||||
| 19 | 0.0401 | 32 | 51 | - | 15 | 100 | 2.0 |
| 20 | 0.0530 | 41.2 | 41.8 | - | 15 | 100 | 2.0 |
| 21 | 0.0650 | 32.3 | 50.7 | - | 15 | 100 | 2.0 |
| 22 | 0.1111 | - | 83 | - | 15 | 100 | 2.0 |
Described in Comparative Examples 1-3, under like the condition that provides in the table 21, each extrudate carried out the stretching of length direction.Expection thickness be based on the thickness of extrudate thickness and be vertically (as to do not become pore membrane observed).
Table 21:
*Draw speed 4.0m/min
Under the condition that in table 22, provides on the film of longitudinal stretching, carry out cross directional stretch then with 30 seconds stretching times and 1000%/minute draw speed.The thickness that records, expection thickness (if promptly based on thickness of the not pore-forming of extrudate thickness), longitudinal stretching than and cross directional stretch than, the optical density (OD), expection optical density (OD) (promptly using the optical density (OD) that disclosed relational expression uses theoretical layer thickness value to calculate in the Comparative Examples 4) and the observed optical density (OD) that record with transmission mode with the MacBeth TR924 densitometer that has the visible light light filter and poor owing to the expection optical density (OD) of the used specific TiO 2 pigment of 2 weight % concentration; Δ OD also provides in table 22.
Table 22:
*Draw speed 2000%/min
Optical density (OD) owing to pore-forming increases the obviously increase along with IPA: TPA ratio in the linear polyesters external phase; IPA among the Comparative Examples 6/LS1/BS1: TPA is than being 0, being 50% to the contribution of optical density (OD), and the IPA of embodiment of the invention 22/LS1/BS1: TPA is than being 0.111, being 71% to the contribution of optical density (OD).Measure embodiment of the invention 20/LS1/BS1, the elasticity of the biaxial stretch-formed extrudate of 20/LS1/BS2 and 20/LS2/BS1 (Young ' s) modulus and yield stress, the result is summarised in following table 23:
Table 23:
After contacting 5 seconds under 150 ℃, observe the variation of film thickness and optical density (OD) through film being clipped in Instron 4411 devices and with flatiron, confirm that there is pore-forming in the biaxially-stretched film of Comparative Examples 6/LS1/BS1 at film.These result of experiment are listed in the table 24.
Table 24:
After contacting 5 seconds under all temps, observe the variation of film thickness and optical density (OD) through film being clipped in Instron 4411 devices and with flatiron, confirm that there is pore-forming in the biaxially-stretched film of embodiment of the invention 19/LS1/BS1 and 22/LS1/BS1 at film.These result of experiment are listed in the table 25 and 26.
To the film of Comparative Examples 6/LS1/BS1 and embodiment of the invention 19/LS1/BS1 and 22/LS1/BS1 observe respectively 150 ℃ 0.19; 0.42 reduce with 0.60 optical density (OD), corresponding to 26,38 and 50%; Reflected IPA once more: the influence of TPA ratio is respectively 0,0.0401 and 0.111.
Table 25:
Table 26:
Embodiment of the invention 23-25
Extrudate like about 1100 micron thick of the embodiments of the invention 23-25 that the said variable concentrations with the SAN 06, TO4 and the PET04 that summarize in the table 27 of Comparative Examples 1-3 made the not painted dispersion of SAN06 in aromatic polyester.
Table 27:
| Embodiment of the invention nr | IPA: TPA ratio | PET02 [wt％] | PET04 [wt％] | SAN?06 [wt％] | Magnesium acetate [ppm] | UVITEX?OB-one [ppm] |
| 23 | 0.0314 | 57.7 | 25.3 | 17 | - | 100 |
| 24 | 0.0747 | 25.3 | 57.7 | 17 | - | 100 |
| 25 | 0.111 | - | 85.0 | 15 | 33 | - |
Described in Comparative Examples 1 to 3, under like the condition that provides in the table 28, each extrudate carried out the stretching of length direction.Expection thickness is to not becoming the observed thickness of pore membrane.
Table 28:
For embodiment of the invention 24/LS1, the optical density (OD) value of 24/LS2 and 24/LS3 has clearly show the influence of longitudinal stretching power, for having the highest longitudinal stretching power 8.65N/mm
2The film of embodiment of the invention 24/LS2, obtained the highest optical density (OD) value 1.06, by contrast, have longitudinal stretching power 8.44N/mm respectively
2And 6.36N/mm
2Embodiment of the invention 24/LS1 and the film of 24/LS3, obtained 0.97 and 0.78 respectively.
Also shown the influence of longitudinal stretching power for the optical density (OD) value of embodiment of the invention 25/LS1 and 25/LS2, for having higher longitudinal stretching power 9.5N/mm
2The film of embodiment of the invention 25/LS2, obtained the highest optical density (OD) value 1.14, by contrast, have longitudinal stretching power 8.0N/mm
2The film of embodiment of the invention 25/LS2, obtained 1.00.
Under the condition that in table 29, provides on the film of longitudinal stretching, carry out cross directional stretch then with 30 seconds stretching times and 1000%/minute draw speed.Table 29 give the thickness that records, expection thickness (if promptly based on thickness of the not pore-forming of extrudate thickness), longitudinal stretching than and cross directional stretch than, the optical density (OD) that records with transmission mode with the MacBeth TR924 densitometer that has the visible light light filter, expection optical density (OD) (promptly 0.05; The optical density (OD) of the polyethylene terephthalate that almost completely records through the refraction effect on the film two sides) and observed optical density (OD) poor with owing to the expection optical density (OD) of aromatic polyester, Δ OD.
Table 29:
Result in the table 29 shows; Compare with 0.78 the opacification optical density (OD) owing to pore-forming of the film of embodiments of the invention 23/LS2/BS1 (wherein linear polyesters matrix contain 0.0314 IPA: TPA than); The opacification optical density (OD) owing to pore-forming of the film of embodiments of the invention 25/LS2/BS4 and 25/LS2/BS5 (wherein linear polyesters matrix contains 0.111 IPA: TPA ratio) significantly improves, and is 1.28 and 1.29.
After contacting 5 seconds under all temps, observe the variation of film thickness and optical density (OD) through film being clipped in Instron 4411 devices and with flatiron, confirm that there is pore-forming in the biaxially-stretched film of embodiment of the invention 23/LS2/BS1,24/LS1/BS1 and 24/LS2/BS1 and embodiments of the invention 25 series at film.These result of experiment are listed in the table 30 and 31.
Table 30:
Table 31:
Film for embodiments of the invention 23/LS2/BS1; Observe 190 ℃ of optical density (OD) reductions of 0.67 down; Be equivalent to 81% (and to the film of embodiment of the invention 24/LS1/BS1 and 24/LS2/BS1, observe 0.85 and 0.88 optical density (OD) and reduce, be equivalent to 86% and 85% respectively).In the embodiment of the invention 24 series, change is equivalent to 64 to 84% between the optical density (OD) under 190 ℃ is reduced in 0.84 and 1.01.
These optical density (OD)s reduce by 13% reduction of the layer thickness of the film that is accompanied by embodiments of the invention 23/LS2/BS1; Film for embodiments of the invention 24/LS1/BS1 and 24/LS2/BS1; Layer thickness reduces 16% and 19%; For embodiments of the invention 25 series, observe 25 to 36% thickness reduction.These results show that when making the polyester layer transparence that contains 15 or 17 weight %SAN 06, optical density (OD) greatly reduces, and are at most 1.01.
Embodiment 26
As 1 to 58 said manufacturing contains 2 weight % titania, 15 weight %TPX
DX820 to embodiment, gather the extrudate (IPA: TPA mol ratio 0.0636) of about 1100 micron thick of the embodiment 26 of (4-methylpentene), 33.3 weight %PET02 and 49.7 weight %PET04.Described in embodiment 1 to 58, under like the condition that provides in the table 32, each extrudate carried out the stretching of length direction.Expection thickness is based on not becoming the observed extrudate thickness of pore membrane.
Table 32:
Under the condition that in table 33, provides on the film of longitudinal stretching, carry out cross directional stretch then with 30 seconds stretching times and 1000%/minute draw speed.Also provided in the table 33 thickness that records, expection thickness (if promptly based on thickness of the not pore-forming of extrudate thickness), longitudinal stretching than and cross directional stretch than, poor with owing to the expection optical density (OD) of aromatic polyester of the optical density (OD), expection optical density (OD) and the observed optical density (OD) that record with transmission mode with the MacBeth TR924 densitometer that has the visible light light filter, Δ OD.
Table 33:
Result in the table 33 clearlys show, owing to use the pore-forming when containing TPX as the PET04 matrix of the about 10 microns crystallization disperse phase of granularity, realizes 64% very big opacification of optical density (OD).But, at 1258N/mm
2Under longitudinal elasticity (Young ' s) modulus and at 26.4N/mm
2Under vertical yield stress be starkly lower than and use SAN to produce the material of reagent as opacification, referring to the result of embodiments of the invention 20/LS1/BS1,20/LS1/BS2 and 20/LS2/BS1.
The present invention can comprise and show clearly among this paper or hint that disclosed any characteristic or combination of features or its are any extensive.Consider foregoing description, it should be apparent to those skilled in the art that and to make various modifications within the scope of the invention.
Claims (21)
1. produce the method for non-transparent microvoided self-supporting film; It comprises step: i) in kneading machine or extruder, mix at least a linear polyesters; It has the monomeric unit of being made up of terephthalate, isophthalic acid ester and aliphatic dimethylene basically altogether; Wherein the mol ratio of isophthalic acid ester monomeric unit and terephthalate monomeric unit is at least 0.02, so that linear polyesters matrix to be provided; At least a amorphous high polymer and/or the fusing point at least a crystallization superpolymer higher that glass transition temperature is higher than the glass transition temperature of said linear polyesters matrix than the glass transition temperature of said linear polyesters matrix; The randomly at least a composition that is selected from inorganic opacification pigment, whitening agent, ultraviolet light absorber, light stabilizer, anti-oxidant and fire retardant; Ii) form step I with the thick film form) the middle potpourri that produces, quenching subsequently; Iii) with longitudinally the stretch twice at least of this thick film to initial length of the tensile force of＞4N/ square millimeter; Iv) laterally stretch from the twice at least of step longitudinal stretching film to original width (iii).
2. according to the process of claim 1 wherein said longitudinal stretching power＞5N/ square metre.
3. according to the method for claim 1 or 2, wherein said cross directional stretch carries out through＞4N/ square metre power.
4. according to each method of claim 1-2, wherein said cross directional stretch temperature is no more than on the glass transition temperature of this linear polyesters matrix 40 ℃.
5. according to each method of claim 1-2, wherein the said mol ratio of isophthalic acid ester monomeric unit and terephthalate monomeric unit is at least 0.065.
6. according to each method of claim 1-2, wherein the said mol ratio of isophthalic acid ester monomeric unit and terephthalate monomeric unit is at least 0.11.
7. according to each method of claim 1-2, wherein the said mol ratio of isophthalic acid ester monomeric unit and terephthalate monomeric unit is 0.50 or lower.
8. according to each method of claim 1-2, wherein said homodisperse amorphous high polymer or the concentration of said crystallization superpolymer in said film are 5 to 35wt%.
9. according to each method of claim 1-2, wherein said homodisperse amorphous high polymer is crosslinked or noncrosslinking.
10. according to each method of claim 1-2, wherein said amorphous high polymer comprises the block of at least one chain type-polymerization.
11. according to the method for claim 10, the block of wherein said at least one chain type-polymerization is selected from polystyrene, styrol copolymer, SAN-polymkeric substance, polyacrylate, acrylic ester-multipolymer, polymethacrylate and methacrylate-multipolymer.
12. according to the method for claim 11, wherein said styrol copolymer is selected from SAN-polymkeric substance and ABS-polymkeric substance.
13. according to the method for claim 12, wherein the concentration of AN-monomeric unit in said SAN-polymkeric substance is 15 to 35wt%.
14. according to the method for claim 12 or 13, the weight ratio of wherein said linear polyesters and said SAN-polymkeric substance was 2.0: 1 to 9.0: 1 scope.
15. according to each method in the claim 1 to 2, wherein said amorphous high polymer is cellulose ester not.
16. according to each method in the claim 1 to 2, wherein said at least a inorganic opacification pigment is selected from silicon dioxide, zinc paste, zinc sulphide, lithopone, barium sulphate, lime carbonate, titania, aluminum phosphate and clay.
17. according to each method in the claim 1 to 2, wherein said film comprises≤the inorganic opacification pigment of 5% weight.
18. according to each method in the claim 1 to 2, wherein said linear polyesters matrix comprises at least two kinds of linear polyester resins.
19. be used to obtain the method for transparent pattern; Comprise step: apply heat and the optional non-transparent microvoided biaxial stretch-formed self-supported membrane that applies pressure to through the method generation that comprises the steps that is aided with according to image: i) in kneading machine or extruder, mix at least a linear polyesters; It has the monomeric unit of being made up of terephthalate, isophthalic acid ester and aliphatic dimethylene basically altogether; Wherein the mol ratio of isophthalic acid ester monomeric unit and terephthalate monomeric unit is at least 0.02, so that linear polyesters matrix to be provided; At least a amorphous high polymer and/or the fusing point at least a crystallization superpolymer higher that glass transition temperature is higher than the glass transition temperature of said linear polyesters matrix than the glass transition temperature of said linear polyesters matrix; The randomly at least a composition that is selected from inorganic opacification pigment, whitening agent, ultraviolet light absorber, light stabilizer, anti-oxidant and fire retardant; Ii) form step I with the thick film form) the middle potpourri that obtains, quenching subsequently; Iii) with longitudinally the stretch twice at least of this thick film to initial length of the tensile force of＞4N/ square millimeter; Iv) laterally stretch from the twice at least of step longitudinal stretching film to original width (iii).
20. according to the non-transparent microvoided self-supporting film of each generation in the claim 1 to 18 purposes as synthetic paper.
21. the purposes of non-transparent microvoided self-supporting film in image recording element according to each generation in the claim 1 to 18.
Applications Claiming Priority (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06121665 | 2006-10-03 | ||
| EP06121665.1 | 2006-10-03 | ||
| EP06121669.3 | 2006-10-03 | ||
| EP06121669 | 2006-10-03 | ||
| EP07104953 | 2007-03-27 | ||
| EP07104953.0 | 2007-03-27 | ||
| EP07104948 | 2007-03-27 | ||
| EP07104948.0 | 2007-03-27 | ||
| EP07104947 | 2007-03-27 | ||
| EP07104947.2 | 2007-03-27 | ||
| EP07104950.6 | 2007-03-27 | ||
| EP07104950 | 2007-03-27 | ||
| PCT/EP2007/060373 WO2008040699A1 (en) | 2006-10-03 | 2007-10-01 | Process for producing a non-transparent microvoided self-supporting film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101548235A CN101548235A (en) | 2009-09-30 |
| CN101548235B true CN101548235B (en) | 2012-09-05 |
Family
ID=37733745
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800446839A Active CN101548235B (en) | 2006-10-03 | 2007-10-01 | Process for producing a non-transparent microvoided self-supporting film |
| CN2007800446896A Expired - Fee Related CN101548236B (en) | 2006-10-03 | 2007-10-01 | Non-transparent microvoided biaxially stretched film, production process therefor and process for obtaining a transparent pattern therewith |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800446896A Expired - Fee Related CN101548236B (en) | 2006-10-03 | 2007-10-01 | Non-transparent microvoided biaxially stretched film, production process therefor and process for obtaining a transparent pattern therewith |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN101548235B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101220225B1 (en) * | 2011-09-02 | 2013-01-09 | 에스케이씨 주식회사 | White porous polyester film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5457018A (en) * | 1993-11-24 | 1995-10-10 | Agfa Gevaert Ag | Shaped plastic article |
| CN1416451A (en) * | 2000-02-15 | 2003-05-07 | 拜尔公司 | Compsns. contg polycarbonate and pigments |
| JP2004196951A (en) * | 2002-12-18 | 2004-07-15 | Mitsubishi Engineering Plastics Corp | Easily torn polyester film and its use |
| CN1524109A (en) * | 2001-06-07 | 2004-08-25 | ����ɭ���ڻ�ѧר����˾ | Halogenated isobutylene-based copolymers having enhanced viscosity and thermoplastic compositions thereof |
-
2007
- 2007-10-01 CN CN2007800446839A patent/CN101548235B/en active Active
- 2007-10-01 CN CN2007800446896A patent/CN101548236B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5457018A (en) * | 1993-11-24 | 1995-10-10 | Agfa Gevaert Ag | Shaped plastic article |
| CN1416451A (en) * | 2000-02-15 | 2003-05-07 | 拜尔公司 | Compsns. contg polycarbonate and pigments |
| CN1524109A (en) * | 2001-06-07 | 2004-08-25 | ����ɭ���ڻ�ѧר����˾ | Halogenated isobutylene-based copolymers having enhanced viscosity and thermoplastic compositions thereof |
| JP2004196951A (en) * | 2002-12-18 | 2004-07-15 | Mitsubishi Engineering Plastics Corp | Easily torn polyester film and its use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101548235A (en) | 2009-09-30 |
| CN101548236A (en) | 2009-09-30 |
| CN101548236B (en) | 2012-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101681089B (en) | Non-transparent microvoided axially stretched film, production process therefor and process for obtaining a transparent pattern therewith | |
| JP5424884B2 (en) | Method for producing non-transparent microvoided self-supporting film | |
| CN101548235B (en) | Process for producing a non-transparent microvoided self-supporting film | |
| CN101548237B (en) | Non-transparent microvoided axially stretched film, production process therefor and process for obtaining a transparent pattern therewith | |
| JP2010522784A (en) | Non-transparent microporous biaxially stretched film, its use in synthetic paper and image recording element comprising it |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |