CN1044069A - High-sensitivity thermosensitive multilayer film and the method for producing plate-making stencil shet - Google Patents

Abstract

The present invention relates to high-sensitivity thermosensitive multilayer film and with the method for this film production plate-making with paper.In the present invention, high-sensitivity thermosensitive multilayer film is made up of at least one functional layer and at least one peel ply.This functional layer thickness be 0.1 to 12 μ m, percent thermal shrinkage be at least 30% and the thermal shrinkage stress value be at least 50g/mm ²Thermoplastic resin make.Peel ply is made up of the thermoplastic resin that is different from functional layer, and is the special plural layers that can be easy to peel off and can apply a compression stress to functional layer.When making template paper with above-mentioned plural layers, operating efficiency during lamination and contractility can improve by behind lamination described peel ply and porous supporting body being peeled off.

Description

High-sensitivity thermosensitive multilayer film and the method for producing plate-making stencil shet

The present invention relates to a kind of new type of high sensitivity thermosensitive multilayer film and a kind of method of using this film production template paper.More particularly, the present invention relates to a kind of high-sensitivity thermosensitive multilayer film that is suitable for the type of production paperboard, can be by using laser beam, especially semiconductor low energy laser bundle or LED bundle carries out the direct heating of pulsed exposure, by heat the indirect that a given original copy also passes to this heat steps such as film because of the instantaneous irradiation of flashing type of using flash lamp or xenon-krypton lamp, or by transmission of heat by contact with hot pin, on the precalculated position, bore a hole and the information on the given original copy is recorded in this template paper according to image on the data or literal, and relate to a kind of method that is used to produce above-mentioned template paper.

Recently, developed prepare a kind of can be by means of hot pin, discharge equipment or electrochemical recording equipment by the template paper of the information of given original copy perforation and use the technology of the template paper of this perforation as galley, and come into operation.About relying on the research of using such as the new method for platemaking of led array, laser array and laser head, also underway at present.

With regard to the method for platemaking of the above-mentioned type, there is a kind of method well-known technically.This method is included in and closely stacks one page on the film surface of this template paper and have therein with can light-absorbing printing ink or the toner literal of expressing or the original copy of image, make literal on the original copy or image when the method for punching that adopts by means of infrared ray or xenon lamp flash of light carrying out high energy district, produce heat, and this heat is conducted to film surface, thereby make the film melts that needs perforation, the actual required plate-making of final acquisition.

As the template paper that will under this plate-making situation, use, a kind of laminated product also is well-known technically, the preparation of this laminated product is to stretch with an extremely expensive high accuracy stenter to exist with absolute version, the thick pet film of about 2 μ m, simultaneously film is carried out abundant heat treatment at this stenter rear portion, thereby the resin crystallization that makes film is (when measuring with densimetry, degree of crystallinity reaches about 45%), with adhesive formed oriented film is superimposed upon a kind of supporter as on onion skin or the sheet material (web form) with an independent step again.

Though this laminated product has sufficient hear resistance, and demonstrate very gratifying dimensional stability, but it is bearing inevitably and is scratching, fold, curl, strain (inhomogeneous tension force) and breaking, because above-mentioned during this medium is added in film stack on the supporter by adhesive, when supporter and film are bonding, the surface irregularity of supporter still exists, and make it to display by film surface, reach the degree of harm film surface microcosmic smoothness, and, destroyed the thickness evenness of film because adhesive is used along the inhomogeneous of interface.In addition, such pet film is added under extended state, carefully carries out on the supporter.Although elaborate, but be difficult to obtain to have the inhomogeneity laminated product that is entirely satisfactory.Therefore, the template paper of at present available this laminating acquisition has incomplete gratifying quality.

When the template paper that has a low bad quality by this performance because of laminating method when galley constituted, its was inevitable with such as the phenomenon of the layering that takes place along adhesive interface to curl and sensitivity or the serious local deteriorated of resolution ratio some shortcomings like this.When using high energy district method for punching, this problem does not need very conscientious consideration.Yet when adopting low energy district method for punching, this problem just must be considered very in earnest.

Hot pin provides very little heating unit (for example, 10 to 16 points/mm), and be widely used in various types of printers, word processor, and be tending towards digitized facsimile machine at present, to they carrying out with miniaturization, improve service speed and energy-conservation be the special research of target.Therefore, when using a kind of so hot pin to make a plate, the template paper that be used to produce this version just need present high sensitivity and high-resolution especially, and has homogeneous quality.

With regard to the production method of template paper as described herein, a kind of like this method has for example been proposed, promptly comprise a kind of very thin single thin film of preparation, closely be pressed on the mirror roller this film, and this film stack is added in (the clear 60(1985 of Japanese Patent Application)-89,396 on the supporter).It is careful to need when its shortcoming of the method for this character is to dispose film, complicated operation, the essential expensive laminating apparatus and the device atmosphere of cleaning used, and the protection that needs to consider harmful electrostatic effect.In this method, when the material of film by breakable material or weak nerve (low elastic modulus) constitutes, when perhaps this film had very little thickness less than 2 μ m, the quality that the template paper of being produced can not obtain to be entirely satisfactory was because film must be easy to take place various troubles.

Also there are some research work exploring a kind of film that finally will be used for boring a hole that can make itself and obtain more highly sensitive method.For example, a kind of like this method has been proposed, comprise and make a kind of flexible polymer be easy to hot melt relatively, so that adopt nature solution casting method to be superimposed upon on the porous supporting body, form extremely thin one deck of the about 1.0 μ m of thickness, and make the polymeric layer rapid draing of this stack, thereby induce the cast of this polymer to be orientated, a kind of template paper (the clear 63(1988 of Japanese Patent Application)-209,996 that improves perforation sensitivity owing to less thick of final generation).Yet, by the template paper of preparation as mentioned above, with regard to solvent recovering rate and based on regard to the rate of drying of preparation process, be unsafty, in addition, its shortcoming also is the thickness evenness of local losses film inevitably, thereby restricts the lower limit in film thickness.And then this method is had no option except the film that uses low softening point, because it must improve sensitivity under low state of orientation.When the template paper of being produced is kept at (for example) about 50 ℃ high temperature, cause curling phenomenon easily, under opposite extreme situations, also can cause lamination.When using hot pin to make a plate, this template paper adheres on the hot pin easily.The shortcoming of this template paper also is to tolerate the impact of printing, and resolution ratio is not enough, because its intensity significantly is lower than biaxially oriented film.

Some known methods are arranged, they separate destination layer then by the multilayer that comprises supporting layer is stretched together altogether with other layer, obtain desirable layer (a clear 57(1982 of Japanese Patent Application)-176,125 and clear 57(1982)-176,126).Why these methods can not be satisfactory, are film deficiency aspect tensile property and stripping performance of being produced.These inventions can not separate easily and mention in the same breath at the high-sensitivity thermosensitive multilayer film of excellent performance aspect the anti-curling phenomenon with the present invention.There is a kind of method well-known technically, it comprises carries out common stretching to plural layers that merged pet resin and acrylic resin, for example under 100 ℃ to 240 ℃ the high temperature this oriented film is altogether being heat-treated then, thereby make PETG layer sufficient crystallising and make this layer have higher stripping performance, then peel off and (for example obtain a kind of heat-pesistant thin film, the thin-walled film that can be used as capacitor) (the clear 60(1985 of Japanese Patent Application)-178,031).Known have a kind of method, it comprises carries out successively biaxial stretch-formed to the film with similar layer combination, it is biaxial stretch-formed to carry out the while then, this oriented film is heat-treated being higher than the crystalling propylene fusing point and being lower than under the temperature of crystallizing polyester fusing point subsequently, thereby fully promote the crystallization of polyester, after this peel off (the clear 61(1986 of Japanese Patent Application)-31,236).These methods one are established a capital based on following notion: because peeling off of carrying out in drawing process causes the film fragmentation or cause the uniformity of film loss, so must fully carry out the mainly heat treatment after stretching, thereby promote the crystallization of polyester, what guarantee to peel off carries out smoothly.These methods have been used to following method, a kind of method is at first with film and support unit lamination, peel off (the clear 63(1988 of Japanese Patent Application)-53 subsequently, 097), another kind method is that a kind of plural layers and supporter are carried out similar lamination, peel off subsequently, thereby produce a kind of template paper (the clear 64-14 of Japanese Patent Application, 092) of the usefulness of making a plate.All these methods all belong to a kind of technical merit that can not mention in the same breath with technical merit of the present invention, the present invention relates to have the efficient production method of highly peeling off convenient and high-quality high sensitivity thin-film and plate-making stencil shet, and aspect anti-curling phenomenon the production method of the plate-making stencil shet of excellent performance.

The present inventor has related to it basic invention of high-sensitivity thermosensitive film to Japan Patent office (the clear 62(1987 of Japanese Patent Application)-282,983) and United States Patent (USP) and trademark office (United States Patent (USP) 4,766,033) applied for patent.The present invention be directed to thermosensitive film itself, and invention itself is efficiently.When the plural layers of peeling off stretching to obtain destination layer and this one deck and porous supporting body when laminated together, this lamination often is difficult to carry out, and the laminated product of being produced is easy to curl.

Owing to recognize and be badly in need of eliminating the existing shortcoming of heat-sensitive plate-making using stencil paper commonly used, the present invention aims to provide a kind of high-sensitivity thermosensitive multilayer film, this film has smooth surface, do not have to produce such as scuffing, fold, curl, strain, float and the possibility of mass defect such as fragmentation, also do not produce such as curling and delamination some harmful phenomenons like this, and the present invention also provides a kind of and can produce the template paper with high sensitivity and high-resolution galley.

The present inventor is for exploring a kind of novel thermosensitive type paperboard with plate-making quality, various researchs have constantly been carried out, find that the object type paperboard obtains like this: the functional layer (M) with special nature that discovery needs in plate-making and desirable printing process is overlayed on any one surface on the positive and negative surface of a special peel ply (P), further a plate-making is overlayed on the formed composite bed as the outermost layer that is connected with this functional layer with supporting layer (S), and by heating with add pressure handle this which floor and combine.Based on this understanding, the present invention improves.

Specifically, The present invention be directed to a kind of multi-layer film structure, it comprises a kind of plural layers of following acquisition, one by coextrusion with on stacked each surface that is placed on a positive and negative surface of special peel ply of the specific function that forms of stretching altogether, and a plate-making overlayed on any one surface or two surfaces on this positive and negative surface of plural layers with supporting layer, make it to be connected with this functional layer; The present invention also peels off the method for producing plate-making stencil shet at a kind of by the functional layer and the supporting layer that make laminated product from peel ply.

More particularly, the invention provides a kind of high-sensitivity thermosensitive multilayer film with plate-making quality; A kind of by this film production and the template paper that is used to make a plate and a kind of method that is used to produce this template paper.These plural layers are characterised in that, functional layer by a kind of its hot contraction ratio at least 30%, the thermal contraction value is 50g/mm at least ²And the thermoplastic resin with 0.1 to 12 μ m thickness forms, and peel ply is to be formed by a kind of thermoplastic resin that contains at least a interleaving agent and be different from the functional layer resin.

Have been found that, by porous supporting body being attached on the common stretch multi-layer film of forming by functional layer and peel ply, peeling off the temperature-sensitive perforate paperboard that this peel ply obtains subsequently, curl with regard to the performance of phenomenon with regard to the lamination efficient of this film and plate-making stencil shet tolerance, be significantly improved compared with the same based article that obtains by independent functional layer lamination.In general, when when film, especially the film with high perforation sensitivity left standstill (particularly under higher relatively temperature) for a long time, it tended to curl, and causes functional layer to be separated by delamination under extreme case.This mainly is owing to impose on the tension force of film in air drying process, makes functional layer just be easy to curl immediately after the lamination, keeps the porous supporting body of contact fast then can not follow this tendency with it.

In general, in order to prevent this trouble, the dimensional stability of improving film to prevent because (for example) film heat setting and the way of aging adverse effect is very popular.Yet this way can not be prevented the phenomenon of curling fully, because size is to be caused by the spontaneous variation of volume and the crystallization of polymer itself over time.

The present inventor has done various researchs to this point, discovery makes the overlapping complex of the multilayer of the functional layer that comprises that general thickness is big with the supporter lamination and special peel ply is peeled off from the film that is produced, generally obtain result preferably, and find, the plural layers of a kind of layer of structure carry out common stretching under following stretching condition to being in like this, can also obtain better result, this stretching condition makes the special peel ply that combines with functional layer to produce a compression stress that is suitable for this functional layer to this functional layer.Find further that also in fact can prevent above-mentioned trouble fully, method is to make the common oriented film of this stretching stand a kind of suitable heat-set treatment, thus give with the enough compression of this functional layer to compensate the contraction that this functional layer must take place after stretching.

At one preferably in the embodiment of the present invention, this common stretch multi-layer film that contains at least one functional layer and at least one peel ply is characterised in that, functional layer by a kind of its hot contraction ratio at least 30%, thermal shrinkage stress is 50g/mm at least ²And the thermoplastic resin with thickness of 0.1 to 12 μ m forms, and peel ply can make the compression strain of generation 0.05 to 10% on an one direction at least of this functional layer.Therefore, make plate-making stencil shet have the performance of the curling phenomenon of tolerance behind itself and supporter lamination by high-sensitivity thermosensitive multilayer film provided by the invention.

Employed in the present invention " functional layer " this term is meant that the temperature-sensitive character of utilizing resin carries out the perforation of relevant literal or image, thereby at a kind of resin bed of its above-noted information.For example, under the situation of template printing, functional layer itself is exactly a kind of resin bed, and this resin bed is to be used for being formed on masterplate required in the printing process, to produce needed literal, symbol, photo or figure on given surface to be printed.In general, preferably unbodied thermoplastic resin forms this one deck by being essentially.Itself just have relative higher crystallinity and in the final plural layers that form the relatively low thermoplastic resin of degree of crystallinity, the resin of the functional layer that all belongs to the present invention and expected.Therefore, the material that is used for this functional layer can be the thermoplastic resin of unbodied or crystallization.Resin so that the form that is included in the final film exists must be in amorphous state basically, and when measuring with densimetry, its degree of crystallinity is not more than 30%, is preferably and is not more than 20%, is more preferably and is not more than 10%.Good especially is that the material of this functional layer is a kind of synthetic resin that is above-mentioned degree of crystallinity under abundant annealing and poised state when measuring with the DSC method.Best is, this material is a kind ofly constantly under common working condition to be unbodied resin.

The thermoplastic resin that is applicable to above-mentioned explanation comprises, the polyester resin of copolymerization for example, the polyamides amine type resin, ethylene-vinyl alcohol type copolymer, polycarbonate type resin, the polystyrene type resin of copolymerization, acrylate type resin, vinyl chloride resin, vinylidene chloride type copolymer resin and polypropylene type resin.These resins both can use separately, also can two yuan or the form of polynary composition use (as mixture or multilayer composite).These thermoplastic resins can mix use with other polymer, oligomer, plasticizer etc.Employed in the present invention " polyester resin of copolymerization " this term is meant the dicarboxylic acids part that comprises two or more different polyester and/or the resin of glycol moiety.Under the situation of using dicarboxylic acids part not of the same race, terephthalic acid (TPA) and other dicarboxylic acids are for example, with M-phthalic acid, phthalic acid and 2, the 6-naphthalene dicarboxylic acids is the aromatic dicarboxylic acid of representative, on its aromatic ring, contain the substituent aromatic dicarboxylic acid that esterification is not had contribution, and be that the composition of the aliphatic dicarboxylic acid of representative is possible with succinic acid and adipic acid.Two or more dicarboxylic acids of selecting from this group dicarboxylic acids of just having mentioned can be used as two or more (dicarboxylic acids) of being discussed.Using under the situation of glycol moiety of the same race not, two or more compositions that are selected from following glycol also are possible, and these glycol are ethylene glycol, propane diols, 1, the 4-butanediol, 1,5-pentanediol, 1, the 6-hexylene glycol, neopentyl glycol, polyethylene glycol, polytetramethylene glycol and cyclohexanedimethanol, the glycol with an aromatic substituent be as 1,4-naphthalene glycol, glycol with a bis-phenol ring, and other known glycol.A kind of polyester resin of copolymerization preferably, be by prepare a kind of mainly form and contain in addition by ethylene glycol be not more than the 40%(mole), better be 20 to 40%(moles), be more preferably 25 to 36%(moles) 1, the glycol moiety of 4-cyclohexanedimethanol, and allow this glycol moiety and the dicarboxylic acids of mainly forming partly carry out polycondensation reaction and the product that obtains by terephthalic acid (TPA).Preferably, preparation, that be in abundant annealing and poised state like this raw material, its degree of crystallinity is not more than 20% when measuring with the DSC method.Wish that degree of crystallinity is not more than 20%.Wish that this material is in amorphous state (degree of crystallinity is not more than 10%) basically, preferably is in complete amorphous state.

Not the polyester of copolymer, can be used as functional layer (M) by it being made film with the degree of crystallinity that is controlled at above-mentioned scope.

By prepare mainly the dicarboxylic acids part formed by terephthalic acid (TPA) and by about 70%(mole) ethylene glycol and about 30%(mole) 1, the glycol moiety that the 4-cyclohexanedimethanol is formed, and make these part copolymerization, obtained to be fit to the polyester resin of a kind of typical copolymerization of this description.

Available in the present invention polyamides amine type resin comprises that for example nylon 6,66,6-10, and 11 and 12, and nylon 6-66,6-66-610 and the 6-66-612 of copolymerization.In the middle of above-mentioned other polyamides amine type resin, it is desirable especially that the nylon of copolymerization proves.In addition, with a spot of a kind of aromatic dicarboxylic acid, for example terephthalic acid (TPA), M-phthalic acid or phthalic acid, or a kind ofly contain these polyamides amine type resins that polymerisation do not had the substituent aromatic dicarboxylic acid copolymerization of contribution, also be available.

In these copolymers, prove desirable by making above-mentioned aromatic dicarboxylic acid carry out those copolymers that suitable copolymerization obtains, because have rigid element (can suitably improve glass transition point effectively) in their molecular structure; They also prove desirable by those copolymers that hydrocarbon part that has a lot of side chains or the part copolymerization with a saturated rings or a polar group are obtained, because can reduce degree of crystallinity effectively and increase elastic modelling quantity.About degree of crystallinity, the rule that polyester had been determined already is equally applicable to these copolymers.The toatl proportion of these comonomers generally is not more than the 30%(mole), preferably be not more than the 20%(mole).

Ethylene-vinyl alcohol copolymer wishes that its acetate unit content is 20 to 50%(moles), be preferably 30 to 45%(moles).Be not more than 40%(weight by mixing therein) at least a resin that is selected from nylon type resin, polyester resin and the ion of bonding resin composition that comes this copolymer of modification to obtain also be available.

Polycarbonate type resin wishes to use the monomer that is easier to reduce softening point than monomer commonly used, perhaps by copolymerisation in conjunction with such monomer.They can be randomly to contain 5 to 40%(weight) the form of other film forming polymer produce.

Polypropylene type polymer often exists with the little form of film of thickness.

The polystyrene type resin of available in the present invention copolymerization comprises that for example those use acrylonitrile, acrylate and the diene type monomer resin as comonomer.In the polystyrene type resin of above-mentioned other copolymerization, those combine the resin of acrylate therein by copolymerisation, prove desirable especially aspect sensitivity.In above-mentioned all thermoplastic resins, the polyester of copolymerization has sensitivity, intensity, anti-printing impact and anti-solvent borne at equilibrium, proves that in this sense they are desirable especially.

Above-mentioned each the group thermoplastic resin, each all can randomly mix therein based on the resin total amount and be not more than 50%(weight) other polymer or oligomer.

They also allow to mix various additives therein according to accidental requirement, for example the filler of the fine powder of macromolecular compound, antioxidant, heat stabilizer, plasticizer, big molecule plasticizer, surfactant, slip additive, auxiliary agent, colouring agent, light absorption material, little specific heat filler, the good heat conductor of conduct mixes with the quantity that can not damage the functional layer desired properties separately.The instantiation of additive is the powdered oxide of polysiloxanes (liquid or granulated polymer), fluorine type polymer powder, silica, talcum powder, calcium carbonate, carbon, graphite, aluminium oxide, various metal and these metals, and its average grain diameter is 0.01 to 8 μ m.Known monomers with these functions can be grafted on the resin of functional layer (M), or is grafted on the surface region of functional layer.

For example, when using the plate-making of semiconductor laser or led array, mix the thermoplastic resin of a kind of light absorption material such as carbon, graphite, metal oxide or the colouring agent in above-mentioned other additive therein, can present not obtainable before this excellent effect and as with the desirable punching quality of height of the cooperative effect of this particular polymers.

The thermoplastic resin that has added above-mentioned additive has and the relevant same excellent properties of ultrahigh speed plate-making that uses solid-state laser, gas laser and other method.

In addition, be used for making the thermoplastic resin of functional layer, to utilize high-performance aspect the perforation with situation about therefrom benefiting under, wish to have the programming rate with 2 ℃/minute, under the 1Kg load according to ASTM D-1525() measure, scope is 30 ℃ to 150 ℃, is preferably 40 ℃ to 130 ℃, is more preferably 50 ℃ to 120 ℃ Vicat softening point.

Above-mentioned thermoplastic film not only can be used for heat-sensitive plate-making using stencil paper, and can be used as the numerical data record-paper and as the material of dish, plate and band or recording-member.Perforated material can be used as for example filter material, breathing penetrable material or hygienic material etc.

Functional layer of the present invention must have 20Kg/mm at least ², better be to be not less than 30Kg/mm ², be more preferably and be not less than 50Kg/mm ², also will be good be to be not less than 70Kg/mm ², best is to be not less than 100Kg/mm ²Tensile modulus of elasticity.If the functional layer of using has the tensile modulus of elasticity of not enough above-mentioned lower limit, a lot of shortcomings will take place in the thing followed, film seems weak can't bear, the processing characteristics deficiency of template paper, to such an extent as to elongation or fragmentation etc. can take place in it between the separation period of functional layer and peel ply, the template paper of storing takes place along with the disappearance of time to curl or delamination, in the plate-making step process because institute's applied pressure, deterioration of film generation dimensional stability or distortion or adhesion, template paper have the harmful phenomenon as elongation and fragmentation in printing process.

Tensile modulus of elasticity adopts the method for stipulating among the ASTM D882-67 to measure, and comes report data according to the modulus that the stress of 2% percentage elongation is taken as 100%.

Functional layer further need have 50g/mm at least ², be preferably 75 to 1,200g/mm ², be more preferably 100 to 1,000g/mm ²The thermal shrinkage stress value.

The thermal shrinkage stress value is following to be measured, downcut wide 10mm from the sample thin film that contains functional layer one, this film is contained in the appropriate location, promptly its two ends are clipped in and keep tension on the anchor clamps of respectively adorning a strain gauge outfit and the 50mm distance that is separated from each other, this sample thin film is immersed in the silicone oil that is heated to different temperatures, then the stress that therefore produces in the test sample film.Submergence in 10 seconds finishes in silicone oil when oily temperature is no more than 100 ℃, and finishes in submergence in 5 seconds when the oil temperature surpasses 100 ℃, gets stress value respectively.For the film of uniaxial tension, on draw direction, get stress value.For biaxial stretch-formed film, be recorded in the mean value of two stress values getting on the vertical and horizontal.(this method of reporting the result will be suitable for hereinafter always.) with regard to performance, this film wishes it is biaxial stretch-formed.This film is so far put under the row that conform to the present invention, because some (if not all) shrinkage stress values of getting in different temperatures fall into the scope of above-mentioned definition.Shrinkage stress value in above-mentioned scope wishes to appear at 60 to 150 ℃, be preferably 60 to 140 ℃, be more preferably 70 to 120 ℃, best be under 70 to 110 ℃ the temperature.The lower limit 50g/mm definite to the thermal shrinkage stress value ², the necessary key property of effective perforation that formation own will be done on this paper.If the thermal shrinkage stress value is less than this lower limit, effectively perforation just is not easy to obtain with (for example) hot skill of handling needles.If this value surpasses 1,200g/mm ², perforation tends to produce excessively wide hole, film generation strain, and curl, resolution ratio is easy to degradation.If the shrinkage stress value appeared at low temperature, will produce shortcomings such as resolution ratio degradation and paper take place to curl, because dimensional stability degradation and perforation produce excessively wide hole.If this value appears at too high temperature, the thing followed just has the shortcoming of perforation sensitivity degradation.

This film need have and is not less than 30%, is preferably 30 to 90%, is more preferably 40 to 80% hot contraction ratio.This hot contraction ratio is following to be measured, downcut the sample that 50mm is square from a given film, this piece sample thin film is put into a thermostat that is set in predetermined temperature, under the state that allows free shrink, it was handled 10 minutes in this thermostat, measure the amount of contraction of this sample, calculate its percentage according to original size.

Hot contraction ratio in above-mentioned scope is wished to appear at 60 to 170 ℃, is preferably 60 to 160 ℃, is more preferably 60 to 150 ℃, preferably under 65 to 140 ℃ temperature.If hot contraction ratio is less than 50%, effectively perforation just is not easy to obtain, and sensitivity descends, and dimensional stability and resolution ratio are easy to reduce.Otherwise if hot contraction ratio surpasses 90%, resolution ratio and dimensional stability can be undermined, and template paper can curl, because perforation produces excessively wide hole and film generation strain.If this hot contraction ratio appeared at low temperature, film just produces inferior dimensional stability, and template paper tends to curl.If this ratio appears at too high temperature, will produce the injured shortcoming of perforation sensitivity.

Functional layer in template paper of the present invention, its thickness range are 0.1 to 12 μ m, are preferably 0.3 to 8 μ m, are more preferably 1 to 6 μ m.If this thickness is less than 0.1 μ m, the paper of being produced just is not suitable for actual use, because it is difficult to dispose, undercapacity is easy to during perforation produce wide hole, is easy to fragmentation takes place in perforation procedure, and presents lack of resolution.Otherwise if thickness surpasses 12 μ m, the convenience degree of perforation just reduces, and processing characteristics worsens.When method with the hot skill of handling needles, the low semiconductor laser of exporting of utilization, or as a kind of better use means when utilization has the low-yield especially led array method under high-speed and makes a plate operation, functional layer wishes to have 0.3 to 5 μ m, be preferably 0.5 to 4 μ m, be more preferably 0.6 to 3 μ m, best is the thickness of 0.7 to 2 μ m.

Functional layer can be not with overlay on the porous supporting body state and with by on the peelable substrate that overlays a random surface, perforation peels off the form of the self supporting structure that obtains then or uses with the form at the enterprising eleven punch 11 of platen roller of irregular surface.Heat internally under the situation of film in this case or at laser beam or led array with high output, the thickness of wishing functional layer is 5 to 12 μ m, though do not need it is defined especially.

In general, the functional layer among the present invention forms with single layer structure.It also can randomly form with a kind of double-layer structure at least, is about to it and overlays on the one deck that is selected from sensitizer layer, sensitivity regulating course, lubricant layer, hot melt layer, anti-sticking layer, enhancement layer, dimensionally stable agent layer and optics perforated layer.

Peel ply in the template paper of the present invention mainly needs with the height perfect performance in order to give this template paper in the stretching step process.It is used for further guaranteeing that additive transfers on the functional layer effectively, and be used for the defencive function layer the surface and strengthen this template paper to disposing and make the tolerance that impacts.Before step was about to begin, it was destined to be stripped from after the lamination of this film and supporter is finished or in plate-making.Therefore, this peel ply need be made with the material that can be easy to from functional layer strips down.This peel strength between peel ply and the functional layer should not make peeling off of peel ply taken place in the process of stretching, lamination or other disposing task.

Better is, peel ply is given full play to following effect: film can successfully be stretched under the condition that the functional layer that exists with absolute version can not easily stretch, and invest that functional layer that film offsets stretching with bearing capacity (Pressive force) passs in time and the compression stress that produces.

When using single peel ply, the material of peel ply is that a kind of its Vicat softening point is not more than 120 ℃, preferably is not more than 110 ℃, and crystalline melt point is not more than 160 ℃ and the degree of crystallinity (measuring with the DSC method) that is in abundant annealed condition and is not more than 60% polyolefin-type resin.Polyolefin-type resin available in this patent comprises, vinyl-type polymer for example, the copolymer that constitutes by ethene and a kind of monomer with polar group, ethene-alpha-olefin copolymer, the propylene type copolymer that degree of crystallinity is relatively low, PB Polybutene-1 type copolymer and various polyolefinic copolymers etc.When two or more these polyolefin-type resins used with the form of mixture, degree of crystallinity was expressed as the summation of calculating based on the mixing ratio of this each component resin of mixture.

The Vicat softening point of mixture is meant the value of measuring under mixture conditions.

Mainly the mixture of being made up of the polyolefin-type resin can be used as the material of peel ply, contains 50%(weight at the most) the polyolefin-type resin of other thermoplastic resin can be used as the peel ply material ideally.For example, can use mainly by ethylene copolymer and form and mix 5 to 50%(weight therein) the mixture of ethene-alpha-olefin elastomer copolymer, and mixture and 5 to 100 parts of mixtures that (weight) polypropylene type polymer is formed of mentioning just now by 100 parts (weight).Can be used for ethylene copolymer of the present invention comprises, for example contain 5 to 25%(weight) vinyl-vinyl acetate copolymer (EVA) of vinyl acetate unit, ethene and the copolymer that is selected from the monomer of unsaturated aliphatic monocarboxylic acid and ester class thereof, their ionomer resin, linear low density polyethylene (LLDPE) (LLDPE), very low density polyethylene (LDPE) (VLDPE), and their mixture.Better is that ethylene copolymer is LLDPE and VLDPE.Yet, condition is, the commercially available high-crystallinity (surpass 60%) and the polypropylene type polymer of high Vicat softening point (being higher than 120 ℃) or the ethene of this polypropylene type polymer and minor amounts of comonomers (for example, being not more than 7%(weight)) copolymer be used as an independent stratum and directly overlay the row that situation on the functional layer does not belong to the present invention.This is because this polymer or copolymer do not have enough compatibilities, and the ratio of (for example with 0.3 to 3.5%(weight) of can oozing out is mixed) liquid or paste additive, and tend to the interlayer structure of breakable layer stampings in extrusion.Because the amount of admissible additive is less, so, unless fully heat-treat, otherwise can damage the uniformity of bleed and endanger stripping performance.When so that two steps, the bubbler tube pulling method used this polymer or copolymer, before stretching in the folder edge of film and the drawing process interface between each layer strain takes place easily, may also can cause between other layer, separating.When by external force, when for example forcing to stretch by the stenter method, this trend is especially remarkable.Particularly in the successively biaxial-oriented method of order, separation between each layer and uneven pulling occur in the part of being clamped by tenter clip easily.

The former is better, because this phenomenon of the picture latter is rare.The above-mentioned better Vicat softening point (assay method is identical with functional layer material, and the value of measuring under mixture conditions is represented the situation of this mixture) that is used as the thermoplastic resin of peel ply is 30 to 120 ℃.If Vicat softening point is lower than 30 ℃, resin itself can obtain binding effect and make to peel off difficulty.If this temperature surpasses 120 ℃, resin will run into the trouble of the problem relevant with the behavior of additive bleed.

Functional layer may easily partly be peeled off and be damaged, because it becomes too hard, can not absorb the part strain of various operating periods, and in addition, the whole polylayer forest of functional layer and peel ply becomes easier and is torn.

Thermoplastic resin itself has gratifying tensile property, and helps the stretching of other resin bed of adjacency with it, thereby prevents because the phenomenon that the result who stretches and may occurring tangles with other resin bed.Carrying out laminated product altogether in the drawing process, interlayer adhesion itself shows with the effect of additive synchronously closely, prevents that each component layers is disconnected from each other.This cooperative effect has been widened the scope of optimum stretch condition, and helps the stable of film.As a result, the tensile property of the film of being produced, for example the intensity of combination layer improves, and the tensile property of functional layer improves equally.

In order to thermoplastic resin or the composition that forms this peel ply, just the performance of the compression performance by the overlapping tensile property that combines the plural layers of peel ply, peel ply, the peel ply relevant with the additive bleed and resin or composition be for the affinity of other resin, hope be a kind of when measuring with the DSC method its degree of crystallinity be not more than 60% raw material.When the optimum stretch condition of the resin of peel ply or composition when similar condition in order to the resin that forms functional layer differs widely, stretch altogether and just can't carry out smoothly.Therefore, as the raw material of peel ply, preferably use the Vicat softening point of a kind of its Vicat softening point and functional layer resin to be more or less the same in 100 ℃ resin.

Best is to wish that this peel ply can apply a compression stress that can produce 0.05 to 10% compression ratio to functional layer on its at least one direction.This compression stress can the amount of choosing wantonly be produced by the resin bed that exists with absolute version, promptly by single layer structure, perhaps by the combination layer of two or more resin beds, be that any one deck in the composite construction is produced.

Now lift a better embodiment, when a kind of unbodied basically resin is used for the peel ply (P) of single structure, with a kind of its Vicat softening point than draft temperature low be not less than 10 ℃, preferably than draft temperature height and especially be not less than the resin that the form of 10 ℃ amorphous polymer or copolymer exists at least and form a continuous phase than draft temperature height.In the time will using a kind of crystalline polymer, hope to be having than draft temperature high 2～40 ℃ and the crystalline polymer of especially high 5 to 30 ℃ than draft temperature fusing point or the form of copolymer, or forms the thermoplastic resin composition of continuous phase with the resin that the form of the mixture of two or more these base polymers or copolymer exists.The ratio of resin of wishing continuous phase is for being not less than the 50%(volume), preferably be not less than the 60%(volume).According to oozing out with additive and the relation of compression stress is calculated, the thickness of peel ply (P) is generally 2 to 20 μ m, is preferably 3 to 12 μ m.The particularly important is, additive should mix in the resin effectively, and allows valuably from wherein oozing out.The tensile modulus of elasticity of individual layer wishes to be 5 to 60Kg/mm ²If modulus is less than the lower limit of this scope, the peel ply of being produced is just soft excessively, and in compression stress and the aspects such as facility peeled off shortcoming is arranged all.If modulus surpasses the upper limit, then all there is remarkable defective aspect such as peel ply peeling off in compression stress and decrement, the facility of peeling off and drawing process.

When peel ply will be by general desirable when forming with composite construction like that, hope is to stack at least two resin beds with some difference in functionalitys on peel ply (P), for example, resin bed is used for the purpose that prevents that the stripping process of peel ply after stretching step is damaged, a resin bed is used for making the additive that oozes out to transfer in the functional layer, and a resin bed is used for functional layer is applied suitable compression stress.Owing to stack the result of these resin beds, have the ratio that is beneficial to the additive that is oozed out, the uniformity of peeling off, and better be the control of compression stress.As an example of such combination layer, can enumerate and mainly have both pliability, comprise the ability of additive and impel the P of the ability that additive oozes out _BLayer.Above-mentioned thermoplastic resin that will in above-mentioned single layer structure, use or composition layer (P _B1Layer: be used to refer to " main peel ply " hereinafter) and have the olefin type polymer of the fusing point lower or copolymer layer or a main composition layer (P that forms by this polymer or copolymer than draft temperature _B2Layer), belong to above-mentioned P _BThe row of class.P _BBetter instantiation comprise for example above-mentioned EVA, alkene class unsaturated monocarboxylic and derivative thereof, soft ethene-alpha-olefin copolymer etc.Its Vicat softening point (is classified above-mentioned P as than the low composition layer that is not less than 10 ℃ amorphous polymer or copolymer layer or mainly is made up of this polymer or copolymer of draft temperature _BP in the class _B3) be another example.P _BLayer wishes to have the 50Kg/mm of being not more than ², be preferably 5 to 40Kg/mm ²Tensile modulus of elasticity.If tensile modulus of elasticity surpasses the upper limit of this scope, then the peel ply produced of proof the adaptability of functional layer (M), unusual delamination, compression stress, decrement, additive in the manufacturing process are oozed out behavior and thin functional layer (M) peel off aspect such as facility all can not be satisfactory.When forming P _BLayer will prevent the interlayer interference to functional layer (M) when making it in abutting connection with functional layer (M), makes to peel off on whole surface at full speed that (100 to 200m/ branch) carries out reposefully, and prevention P _ALayer corrodes functional layer (M) and makes the P that combines with functional layer (M) _ABroken possibility takes place in layer.

Then, use its crystalline melt point generally than draft temperature high and its Vicat softening point be not less than 120 ℃ polypropylene type polymer or copolymer layer or the composition layer mainly formed by this polymer or copolymer as up-stripping layer (P _A).

(I) group combination layer in this multilayer peel ply comprises from above-mentioned P _B1, P _B2And P _B3The one deck at least and at least one P that select in the layer _ALayer.As for each component layers putting in order in this combination layer, from P _B1, P _B2And P _B3Middle each layer of selecting is configured in P _AAt least on any one surface on the positive and negative surface of layer, best two surfaces.

The better example alignment of each layer is will be having than (P in this case _A) (5 to 50Kg/mm for the soft tensile modulus of elasticity of layer ²) above-mentioned resin or resin combination be arranged at least and have the hereinafter (P of tensile modulus of elasticity that will mention, harder _A) layer a side on, the reason of doing like this is described below.For guaranteeing to be convenient to peel off, wish that functional layer (M) combination is from P _B1, P _B2And P _B3The middle layer of selecting.(II) group combination layer comprises at least one P similarly _B1The layer and from P _B2And P _B3Between one deck at least of selecting.Putting in order of each component layers is arbitrarily in this combination layer.In a kind of desirable arrangement, can easily contain a kind of resin bed that promotes additive and can easily ooze out contained additive of isolating and be configured to combine with functional layer.The instantiation of the combination layer of (I) group comprises P _B1/ P _A, P _B2/ P _A, P _B3/ PA, P _B1/ P _A/ P _B1, P _B2/ P _A/ PB2, P _B3/ P _A/ P _B3, P _B1/ PA/P _B2/ P _B1/ P _A/ P _B3And P _B2/ P _A/ P _B3

Other layer can randomly freely be attached in the combinations thereof layer.The instantiation of the combination layer of (II) group comprises P _B2/ P _B1/ P _B3/ P _B1, P _B1/ P _B2/ P _B1And P _B1/ PB3/P _B1, that best is P _B2/ P _B1/ P _B2, P _B3/ P _B1/ P _B3And P _B2/ P _B1/ P _B3Other layer can randomly freely be attached in the combinations thereof layer.Be intended to the up-stripping layer (P of humidification in order to formation _A) thermoplastic resin wish to have and be higher than 120 ℃, be preferably and be not less than 130 ℃ and be more preferably the Vicat softening point that is not less than 135 ℃, and be not less than 50Kg/mm ², be preferably and be not less than 70kg/mm ²Tensile modulus of elasticity.For example, propylene based polymer can be advantageously used for and be such thermoplastic resin.This propylene based polymer can be homopolymers or copolymer, or they and be not more than 40%(weight) other polymer mixture of PB Polybutene-1 for example.Also have other thermoplastic resin, comprise PB Polybutene-1 type polymer and copolymer, methylpentene type polymer and copolymer and composition thereof, and other similar optional aggregation thing, copolymer and composition thereof.In a kind of Ideal Match, these thermoplastic resins are and 40 to 5%(weight) flexible polymer or copolymer mix and use.This combination can invest functional layer (M) especially effectively with suitable decrement.In flexible polymer that can be used for said mixture and copolymer, it is desirable especially that elastomer resin and rubber resin prove.For example, they comprise the known resin as the ethene-alpha-olefin copolymer.Importantly, a kind of like this layer of barras should stretch altogether with other component layers that comprises functional layer (M), and can obtain effectively above-mentioned give with decrement.

Forming in the peel ply process with combining of other layer by the layer that is intended to humidification, the bonding strength between these layers should be greater than the bonding strength between functional layer and above-mentioned in two-layer arbitrary layer.

The thickness of each component layers is not particularly limited in the peel ply of sandwich construction.In general, P _AThe thickness range of layer is 0.5 to 20 μ m, and that best is 1 to 10 μ m.P _B1The layer thickness or from P _B2And P _B3Between the thickness of the layer selected, when these layers use independently of one another, represent or when they use with multilayered state, represent with the thickness of combination with thickness in monolayer, ooze out and invest with regard to the relation of required compression stress with regard to itself and additive, be generally 1 to 20 μ m, best be 2 to 10 μ m.

The peel ply that the present invention expected, no matter exist or exist with sandwich construction with single layer structure, all must mix a kind of suitable interleaving agent therein, to guarantee the smooth disengaging of this peel ply and functional layer, prevent that this peel ply breaks away from functional layer by accident during any step except that strip step, and whole process can be carried out smoothly.The interleaving agent that meets this description comprises, the ester of higher fatty acids and polyalcohol for example, the ester of higher fatty acids and polyoxyethylene-type alcohol, nonionic surface active agent such as polyoxyethylene alkyl ether, higher alcohol and ester thereof, higher fatty acid amides, wax, oligomer, silicone oil, fluorine type oil, fluosilicate type macromolecular compound etc.In above-mentioned interleaving agent, those are in a liquid state under normal room temperature and at 50 ℃ of interleaving agents with the viscosity that is not less than 100 centipoises, prove to the purpose that invests suitable stripping performance it is desirable especially.They can be paste under normal room temperature, preferably have not to be higher than 50 ℃ fusing point.Viscosity can be single viscosity of planting interleaving agent of using separately, or unites the viscosity of mixture of two or more interleaving agents of use.In above-mentioned interleaving agent, can be independently of one another or add a kind of antistatic additive, antiplastering aid etc. with combining with one another.

The amount of the interleaving agent that adds, the gross weight in the thermoplastic resin that is used for forming peel ply is generally 0.2 to 5%(weight) scope.Under the situation of the peel ply of sandwich construction, that component layers that combines with functional layer must be mixed the interleaving agent of afore mentioned rules amount therein at least.Mix the interleaving agent in the predetermined peel ply, this peel ply overlay on the functional layer and this two-layer stretch altogether after, be seeped into this peel ply surface rapidly, help separating between functional layer and the peel ply.Therefore, in addition when this separation be after supporter is overlayed on the functional layer during with High-Speed Automatic carrying out, also can take out the film that breaks away from from this strip step and can not cause any trouble.Because peel ply has suitable bonding force, therefore, it can prevent effectively that in production process the accidental of other possible component layers taking place separates.

Peeling strength test between peel ply and the functional layer is being fixed on the draw speed that 200mm/ divides, and peels off (K of Japanese Industrial Standards (JIS) 6854) that the sample test piece of a T shape apperance is carried out with above-mentioned tension test method.Peel strength generally is not more than the 2g/cm width, preferably is not more than the 1g/cm width.Under the situation of the peel ply of sandwich construction, the peel strength between functional layer and the whole compound peel ply is same as described above.At peel ply inside, P _BLayer and P _APeel strength between the layer must be greater than functional layer and P _BPeel strength between the layer could suppress P _BLayer and P _ASeparation between the layer.Wish to be not less than the 5g/cm width, preferably be not less than the 10g/cm width in the peel strength of this discussion.Carry out in hope under the situation of high-speed separation, in peel ply in peel ply gross weight 0.5 to 3.0%(weight) ratio mix monoolein and poly-glycerine monoleate mixture (with the former/latter is 1: 4 to 4: 1 mixing ratio preparation), be of value to the acceleration that obtains separating rate.

Peel ply of the present invention also can mix variously in order to improve the additive of remover physical property except that mixing above-mentioned interleaving agent in case of necessity therein, also can further incorporate a layer that combines and can improve the functional layer surface property with peel ply into.For example, mix a small amount of (as 0.1 to 3%(weight)) amino modified siloxanes, sulfhydryl modified siloxanes or epoxide modified siloxanes as antiplastering aid, prove favourable.

In addition, the functional layer in the plural layers of the present invention need apply one to peel ply and can produce suitable compression strain and little compression stress to the flatness that can damage this peel ply on its at least one direction.Best is that this compression stress puts on vertical and horizontal simultaneously.Here the functional layer that employed " not damaging flatness " this saying is meant this film itself is not folded into a kind of zigzag and the blushing phenomenon takes place because of the compressing of this compression stress makes.The amount of the compression strain of measuring with the method that also will narrate specially hereinafter need be for 0.05 to 10%, be preferably 0.1 to 5%, be more preferably 0.2 to 3%.If this compression ratio less than 0.05%, then overlays on the porous supporting body at these plural layers, then peel ply is peeled off after contingent curling phenomenon just can not prevent fully.If compression ratio surpasses 10%, then these plural layers itself are yielded to and are undesiredly peeled off phenomenon and the blushing phenomenon takes place, functional layer suffers damage its flatness after will breaking away from peel ply then on it is stacked in support membrane, in addition, the version of final production can produce that a quality uniformity is endangered, the version body is to the bent such shortcoming of supporter one lateral bending.This reduction volume of compression strain is not always to equal to stack the reduction volume that the back takes place.Stack the elongation and the stretching of film side in the process, support the elongation and the shrinkage degree on side, the water yield of absorption, hysteresis creep and bond condition all produce delicate influence to it.The mensuration of decrement is performed as follows, the given plural layers that under predetermined condition, stretch, and remove layer on the film of the method that employing will illustrate hereinafter after stretch, and the functional layer that is removed suitably measured.Functional layer is returning to original size after film removes, the peel ply that has its source in imposes on the compression stress of functional layer after stretching.Since this compression stress mainly because of the thickness of peel ply, stretching condition, and the amount of the elastic shrinkage that in each component layers, exists of the back that stretches different, so the compression ratio of functional layer can be for example waits and is controlled by the thickness of each component layers in the peel ply of peel ply thickness that changes single layer structure or sandwich construction or by regulating stretching condition and heat-setting condition.The best magnitude of decrement changes along with the purpose of utilizing these plural layers or along with the kind of functional layer (M).For example, under the situation of material with relatively low tensile modulus of elasticity or soft material, it is easily that this magnitude is fixed on the big slightly level.Yet in general, this magnitude is fixed in the above-mentioned scope.The stretching condition of plural layers has a direct impact the performance of functional layer, and can be controlled by the heat-setting condition after stretching.In this case, use fixed value and to adopt to reach a fixing loose amount be easily as the temperature of the heat setting of target as a factor.

Relation between functional layer and the peel ply aspect thermal contraction, the temperature dependency of elongation-shrinkage that can be by determining them, promptly this dependence of shrinkage ratio and shrinkage stress is estimated.Preferably, the shrinkage ratio of peel ply under heat-treat condition must be greater than the shrinkage ratio of functional layer.If this relation conversely, then functional layer (if always being not) meeting sometimes apply compression to peel ply.In this case, not equal to the ability of coiling-resistant phenomenon is enhanced undermined.

Therefore, suggestion is controlled at predetermined scope to compression ratio, and the amount of contraction in two-layer gives appropriate consideration to heat-setting condition and this simultaneously.

For the preparation of plural layers of the present invention, the method that adopt is not particularly limited.This preparation can be undertaken by preparing the general any known method that adopts of any common plural layers.For example, this is prepared as follows and carries out, fusing functional layer and the required raw material of peel ply on the extruder of sub-material, the raw material of fusion is gone out by ring-type or T type multilayer film coextrusion head, the extruded film of fused raw material is cooled off suddenly, and adopt the stretch film of this cooling of stenter method or bubble method.For the stretching condition that will use in this case, draft temperature to be selected (promptly begin stretch this a part of temperature) should make the functional layer that is formed by specific resin reach predetermined orientation, and the peel ply of single layer structure is formed by above-mentioned resin, and makes it to mix therein necessary additive.Under the situation of the peel ply of sandwich construction, as long as select aforesaid resin and layer combination, and for that the specific component layers in each component layers that combines with functional layer, as long as it is just much of that to be chosen in the resin that has wherein mixed necessary additive.

Draft temperature is generally 60 ° to 150 ℃, is preferably 70 ° to 130 ℃, is more preferably 80 ° to 120 ℃.Hope is carried out biaxial stretch-formed, and its draw ratio is approximately 4 to 49 times, preferably 8 to 36 times of original table area.In this case, the material and the thickness of design peel ply is also controlled stretching condition and heat-setting condition, thereby makes peel ply apply predetermined compression stress to functional layer.In the whole bag of tricks that can be used for this production fully, the bubble method proof is applicable to this production fully, it is useful especially that bubble method proves on following meaning, and it can adopt biaxial stretch-formed operation simultaneously, change at a high speed effectively with large volume, easily produces a kind of high sensitivity thin-film.Under the situation of stenter method, external force carries out owing to stretch to be to apply by the terminal part to each layer of stacking, thus the easy genetic horizon of this stretching with layer between depart from mutually with undesired and peel off.These abnormalities take place significantly especially in the successively biaxial-oriented operation of order, and the film of being produced can not reach the patient level of the present invention.Therefore, the allowable range of stretching condition (temperature, speed and draw ratio) narrows down, and brings difficulty for the production of the film with desired properties.It also becomes and is difficult to guarantee to invest effectively stripping performance, compression stress and decrement.Bubble method can be not worried because of these harmful phenomenons, acted on equably on the whole surface by the tensile force that interior pressure produced because allow.

Plural layers of the present invention comprise at least one functional layer and at least one peel ply.This peel ply can be a single layer structure, or sandwich construction.

For the plural layers of being made up of the peel ply (abbreviating P as) of functional layer (abbreviating M as) and single layer structure, following typical layer combination is possible:

M/P，M/P/M，M/P/M/P，M/P/M/P/M，M/P/M/P/M/P/M，……

In above-mentioned these layer combinations, on positive and negative two outer surfaces those combination identities of a M layer being arranged all is preferably, and those combination identities with symmetrical configurations are better.

Take a kind of by main peel ply (P with difference in functionality for its peel ply (P) _B1, P _B2And P _B3) and an auxilliary peel ply (P _A) plural layers of the sandwich construction formed, following typical layer combination is possible: have a M layer be connected to above-mentioned peel ply (I) group the positive and negative superficial layer of layer combination at least one, best be two lip-deep combinations, there is a M layer to be inserted in two combinations between the adjacent inner layer, and has each ground, surface of several M layers to be connected on the positive and negative superficial layer and have a M layer to be inserted in two combinations between the adjacent inner layer.For the layer combination of above-mentioned (II) group, same combination also is possible.

This plural layers wish to have a kind of its outermost one deck at least arbitrarily, preferably two-layer all be the layer combination of functional layer.For the curling phenomenon in the whole film is minimized, wish to have a kind of layer structure of symmetry by the film that positive and negative superficial layer and intermediate layer are formed.

Using plural layers of the present invention to produce the high-sensitivity thermosensitive plate-making stencil shet is to realize like this, supporter with plate-making quality is overlayed at least one functional layer of this plural layers, along this film of interfacial separation between its functional layer and the peel ply, thereby obtain target basis.It is desirable to, this production is performed as follows, so that peel ply can prepare plural layers to a kind of like this method that functional layer applies the compression of scheduled volume, carries out stacking of aforesaid supporter, carry out then above-mentioned divided thin film from, thereby make functional layer (M) remove compression stress.

As the supporting layer of plate-making stencil shet of the present invention, can use be suitable for reaching this paper intended purposes, can see through the porous membrane or the paper of printing ink, or have the body paper of rough surface.Last class supporting layer comprises, for example the original weight scope is 3 to 15g/m ²Japan paper and the glossy paper of onion skin form, and the similar paper of synthetic fibers, natural fiber, regenerated fiber and composition thereof.The screen cloth type weaving cloth of being made by long fibre is another example.Be preferably, the order number of this screen cloth type weaving cloth is approximately 50 to 500 orders, 70 to 300 orders preferably.Body paper with rough surface of being convenient to bore a hole can be used as special supporter, for example, be used for and have relatively large thickness, greatly be combined to form a kind of laminated product (being used for perforation) about 6 to 18 mu m ranges and the functional layer that has a peel ply, then body paper that has functional layer and peel ply are peeled off, functional layer is bored a hole, make it to have the discontinuous hole of point-like of arranging, and be used for printing with the state that is loaded with given information by preset pattern.

The minute protrusions and the depression of the regular arrangement of body paper of Shi Yonging are particularly protruding by this way.The shape of cross section of these bossings is circle, rectangle, ellipse, line or continuous sieve aperture.These bossings can random layout.Best is that they are regular arrangements.In general, the height of these bossings is not less than 15 μ m, is preferably and is not less than 25 μ m, is more preferably and is not less than 30 μ m.Under the situation of discontinuous projection, the size range of single boss is 2.5 * 10 ^-5To 1.44 * 10 ^-2Mm ²The ratio of bossing effective surface area is greatly about 1 to 35% scope.These bossings itself constituted in the body paper will by lamination be in the part that the functional layer of released state easily combines.These bossings can employing and film or film in the body paper identical materials, for example be processed to form by embossing.In addition, they also can form by the method for printing or pattern-making against corrosion on the surface of film, film, paper or fiber.

Above-mentioned supporter is by using adhesive or adopting hot melt or some other method combines with functional layer.The adhesive that is used for this lamination is not particularly limited.Can use any adhesive commonly used.The present invention can with adhesive comprise, be dissolved in the adhesive of ability usefulness in the solvent, the adhesive of latex form, the adhesive of hot melt form, powdery adhesive, effect by means of water, the mixture of two components, the reaction constrictive type adhesive of ultraviolet light or electron beam irradiation, and the adhesive that relies on the combination of these functions, the hot melt build adhesive that for example has the emulsion denseness, adhesive with emulsion function, have the emulsion function and have both the adhesive of curing agent function, and by merging the adhesive that the solution of adhesive in certain solvent and reaction constrictive type adhesive form.Monobasic or two yuan or polynary mixture from above-mentioned adhesive is selected can be used to reach this purpose.

The amount of the adhesive that uses, the solids content when amounting to into after bonding is generally 0.1 to 8g/m ², be preferably 0.2 to 5g/m ², be more preferably 0.3 to 3g/m ²The method of this lamination is not particularly limited.Any method that can select generally to be used for lamination is fit to the kind of the adhesive that will use.This lamination only needs desirable supporter is attached on the thermoplastic resin membrane, as the outermost layer of these plural layers.For applied adhesives, for example can use the applicator roll that scraper is housed.

In the present invention, plural layers are overlayed on the predetermined supporting layer.The necessary connecting function layer of this supporting layer makes the outermost layer that itself constitutes these plural layers.When plural layers are made into to comprise two or more functional layer, just can obtain many plate-making stencil shets from plural layers.When plural layers have a kind of functional layer (M) and peel ply (P) with M/P/M/P/M ... this mode alternately arrange and positive and negative outermost layer in one deck is the layer structure of functional layer (M) at least arbitrarily the time, can once obtain many paper through the following steps, supporting layer (S) is attached on the functional layer (M) with plate-making quality.Make and itself constitute outermost layer, the overlapping complex (plate-making stencil shet) that separation is made up of supporting layer and functional layer, remove this peel ply (P), on the functional layer with an exposed surface (M), carry out above-mentioned steps, and repeat to peel off the step of the overlapping complex of forming by supporting layer and functional layer (plate-making stencil shet) in order.

To plate-making stencil shet of the present invention, following six kinds of cross section structures are arranged:

S/M/P/M

S/M/P/M/S

(the defined P in P=such as front wherein _B1, P _B2And P _B3, P preferably _B1) the peel ply here has single layer structure,

S/M/P _X/P _Y/M

S/M/P _X/P _Y/M/S

(X ≠ Y wherein, X is selected from B1, B2 and B3, Y also is selected from B1, B2 and B3) and

S/M/P _X/P _Y/P _Z/M

S/M/P _X/P _Y/P _Z/M/S

(wherein Y ≠ X or Z, X is selected from B1, B2 and B3, Y is selected from A, B1, B2 and B3, Z is selected from B1, B2 and B3) peel ply here has sandwich construction.At this, S represents porous support layer.The incomplete structure of more than enumerating any one functional layer (M) situation about existing as internal layer.

According to the present invention, at first preparation comprises the plural layers of functional layer and peel ply, be superimposed upon on the one side on positive and negative surface by lamination then or be superimposed upon positive and negative two lip-deep supporting layers successively or simultaneously and peel peel ply off, produce the object type paperboard of plate-making usefulness.

The heat-sensitive plate-making using stencil paper that will obtain with method of the present invention has level and smooth film surface, with comparing of obtaining with commonsense method with based article, be difficult for scuffing, fold, bending, strain and fragmentation, and have high sensitivity, high-resolution and homogeneous quality.It can be advantageously used in bore a hole the at a high speed forme-producing system of information of the low energy.

In addition, method of the present invention is favourable, its be (1) it make support physical efficiency by lamination overlay equably approximately be in commonsense method on the film of the little thickness in the inaccessiable scope, (2) can be to the lubricated and the antistatic treatment of the film surface of this paper with plate-making quality by carrying out automatically from the peel ply bleed, (3) originally can be in this paper with plate-making quality owing to improved the result of sensitivity the buckling phenomenon that takes place of process in time, can prevent fully basically, (4) can obtain many paper from plural layers with plate-making quality, (5) respectively on the positive and negative surface of supporter, respectively stack the plural layers of a functional layer by the peel ply medium, can its unaltered form use as final products, and only need before facing use, to separate, therefore, the fully curling phenomenon of the paper with plate-making quality from this plural layers acquisition, scratch and pollution, (6) the laminating operation expense is cheap, and (7) remove from plural layers that the peel ply that gets off is recyclable to be used again.

Details of the present invention will be as follows by instance interpretation, but the present invention will be limited by these examples never.

The mensuration of physical property is all carried out with following method in each example.

(1) degree of crystallinity

1. the degree of crystallinity that constitutes the polymer raw material of film is measured by the melting heat method, wherein simple method is to use the fusing point of DSC method with 10 ℃/minute determination of heating rate specific sample, from this sample and have area between the indium standard sample of known melting heat, calculate degree of crystallinity as follows than obtaining melting heat (Δ H).

Degree of crystallinity=100 * Δ H/ Δ Hm

Δ Hm is the melting heat of the crystallographic component of sample itself in the following formula, and is that (Kagaku Binran second edition-application, Japanese chemical association publishes literature value, P.336-841).

2. there is, makes the following mensuration of degree of crystallinity of good film with the form after stretching, obtain not each degree of crystallinity of the raw material that exists with form of film with densimetry, draw calibration curve,, ignore by the error that the difference of crystal structure causes with this calibration curve calculating.About the master data of the relation between density and the degree of crystallinity still according to above-mentioned document, the homogeneous data of copolymer is then based on as the numerical value of suitably regulating when making it non-crystallizable.

(2) perforation sensitivity

Perforation sensitivity, be when the hot pin of line of the plate-making parts that given plate-making stencil shet adopted the Type 007 DPF plate-making type automatic stamper of being made by Riso Kagaku Sha can be bored a hole with the force of impression of adjusting, determine with the force of impression energy (milli is burnt) of each point.Full blackboard branch is (under standard conditions, the mid point of former density range when promptly making a plate with former word selection type, the steady component that the square full blackboard of 5mm divides in the original copy of printing) optical density (OD), be to use to make the DM-800 portable density instrument that limited company makes by big Japanese screen and measure, and when standard black sample (optical density (OD) 1.72, DIN16536, the 47B/P type) when being blank, its numerical value is not less than 1.0.

(3) crimpness

One given film sample is placed on the plate glass plate, Japan paper (the METSUKE 12g/m of an onion skin form of making by polyester with good dimensional stability ²) use 10%(weight) methanol solution of vinyl acetate type glue adheres on this film, after the drying, is of a size of this sample of frame fixation of 10cm * 10cm with an inside casing.Mark two lines in this film upper edge diagonal, make these two lines with right angle intersection, this sample was placed one month to fixed temperature one, in 23 ℃ of constant temperature, humidity are the room of 50%RH, make it adjust about 2 hours, by measuring the crimp radius r(mm of vertical and horizontal) and with following formula calculating crimpness R.

R＝ 100/(r)

Though this crimpness should be 0 in the ideal case, the actual permissible limit is about 7 to 8, and the value greater than 15 will make this product not have practical value.If crimpness surpasses 20, will find delamination later on.

(4) compression volume

The compression volume of functional layer is determined by following: when in the room that given plural layers that are cut into 1000mm * 50mm is placed on 23 ℃ of constant temperature, relative humidity 50%RH aging 24 hours and when measuring functional layer after peeling off with peel ply, the length of the film of stretching was the percentage of the length of former plural layers.

It below is the resin that in each example, is used for functional layer and peel ply.

Functional layer (M1): by terephthalic acid (TPA) with by 1,4-cyclohexanedimethanol 30%(mole) and ethylene glycol 70%(mole) the mixing glycol of composition obtain, Vicat softening point is that 82 ℃, density are 1.27g/cm ³, limiting viscosity is that 0.75 amorphous basically copolymer polyester and particle size range are not more than 8.0 μ m, average grain diameter is that 4.5 μ m, concentration are the mixture of the silica of 3000ppm.

Functional layer (M2): from by terephthalic acid (TPA) 80%(mole) and M-phthalic acid 20%(mole) mixed dicarboxylic acid formed with by ethylene glycol 90%(mole) and 1,4-cyclohexanedimethanol 10%(mole) the noncrystalline copolymer polyester that obtains of the mixing glycol formed.

Functional layer (M3): limiting viscosity be 0.68 and when material is fully annealed watery fusion can be the copolymer polyester of 11 card/grams (measuring) with the DSC method.

Functional layer (M4): with known method by epsilon-caprolactams, hexamethylene diamine and with terephthaldehyde's acid substitution adipic acid the part nylon 6 and nylon 66 components of copolymer content as a supplement, promptly make earlier the 65%(mole) nylon 6 and 35%(mole) nylon 66 components replace 40%(mole in these nylon 66 components with terephthalic acid (TPA) then) adipic acid, and the degree of crystallinity that obtains is 8%, fusing point is 170 ℃ copolymer nylon.

Functional layer (M5): by acetate unit content is the 45%(mole) ethylene-vinyl alcohol type copolymer (125 ℃ of Vicat softening points, 70%(weight) and ion of bonding resin (MMA content 18%(weight) 61 ℃ of glass transition points), neutralization number 35%, 70 ℃ of Vicat softening points) the 30%(weight) composition of forming.

Peel ply (P _B1-1): melt index is 3.3, density is 0.906g/cm ³, fusing point is 122 ℃, use Perkin-Elmer Co., Ltd, DSC-2DSC type analyzer with 10 ℃ of/minute intensification velocity determinations the very low density polyethylene (LDPE) 90%(weight of crystallization melting heat (Δ Hu)) and vinyl acetate unit content be 10%(weight), melt index is 1.0, Vicat softening point is that 81 ℃, fusing point are 95 ℃ vinyl-vinyl acetate copolymer 10%(weight) mixture.

Peel ply (P _B2-1): by vinyl acetate unit content is 10%(weight), melt index is 1.0, Vicat softening point is that 81 ℃, fusing point are 95 ℃ vinyl-vinyl acetate copolymer 70%(weight), density is 0.88g/cm ³, melt index is 0.44, Vicat softening point is 40 ℃ noncrystalline ethene-alpha-olefin copolymer elastomer 15%(weight) and ethene 4%(weight) random copolymerization and density is 0.90g/cm ³, molten floating value is 7, Vicat softening point is that 138 ℃, the modulus of elasticity in static bending are 110Kg/mm ², fusing point is 143 ℃ ethylene-propylene copolymer 15%(weight) form, Vicat softening point is 82 ℃ combination resin mixture, 2: 1 mixtures of monoolein 3%(weight) and two glycerin mono-fatty acid esters are as interleaving agent, 1.5%(weight) amino-modified silicone oil as antiplastering aid.

Peel ply (P _B1-2): by melt index be 1.0, density is 0.890g/cm ³, fusing point is that 117 ℃, watery fusion heat (Δ Hu) are that 4.0 card/grams, Vicat softening point are 60 ℃ very low density polyethylene (LDPE) and 3%(weight) monoolein and two glycerin mono-fatty acid esters 2: the 1(weight ratio) composition formed as interleaving agent of mixture.

Peel ply (P _B1-3): by being used for above-mentioned peel ply (P _B1-2) the very low density polyethylene (LDPE) in be used for above-mentioned peel ply (P _B1-1) vinyl-vinyl acetate copolymer in is with 8: the 2(weight ratio) mix the composition of forming, and at peel ply (P _B2-1) same amount interleaving agent that uses in and bonding inhibitor.

Auxilliary peel ply (P _A-1): its density 80%(weight) is 0.90g/cm ³, molten floating value is 7, Vicat softening point is that 138 ℃, the elasticity of flexure are 110kg/mm ², fusing point is 143 ℃ and 4%(weight) the ethylene-propylene copolymer and the 20%(weight of ethylene random copolymerization) the ethene-alpha-olefin elastomer (density is 0.88g/cm ², the Vicat softening point maximum is 40 ℃) mixture.

Auxilliary peel ply (P _A-2): be used for aforementioned auxilliary peel ply (P _A-1) ethylene-propylene copolymer in and melt index are 1.0, density is 0.890g/cm ³, fusing point is that 117 ℃, watery fusion heat (Δ Hu) are that 4.0 card/grams, Vicat softening point are the composition that 60 ℃ very low density polyethylene (LDPE) mixes with 8: 2 weight ratios.

Example 1

Functional layer (M1), peel ply (P _B2-1) and auxilliary peel ply (P _A-1) respectively with extruder fusing, and after extruding, finish, thereby every layer structure can be M1/P when annular multilayer die head comes out _B2-1/P _A-1/P _B2-1/M1 makes these layers quenching hardening by refrigerant.So obtain tubular reel.

Next step, stretching simultaneously on the both direction under the draft temperature of atmospheric pressure and 102 ℃ make final draw speed can be vertically be 5.0 and laterally also be 5.0 after, this reel stretched becomes bubble shape, then 20 ℃ of following air coolings.The both sides of the film of above acquisition are cut, the result, two films can roll with two coiling machines.Level and smooth stretching is so steadily carried out, and does not produce vibration or pore, and the film that obtains is uniform.In addition, do not peel off (on nip rolls) between each layer before stretching, perhaps can't see part at all and peel off phenomenon.Every layer thickness is 2/8/2/8/2 μ m in this plural layers.The compression volume of functional layer is vertically with horizontal average out to 1.1%.M1/P _A-3/M1, the i.e. P that only forms with layer M1 by co-polymer polypropylene _A-3 combination layer presents a lot of bubble oscillations and hole, and can not evenly stretch.Part before stretching is peeled off especially and can be occurred in the part that is held, and the slip between each layer often takes place during stretching and peels off.Because layer M1 and P _ALayer border disturbance between-1, one deck can be cut another layer, and also can see later this phenomenon that the M1 layer is torn when peeling off.Example as a comparison is to M1/P _A-3/P _B2-1/P _AThe layer structure of-3/M1 done similar research.The result has the quality lower than each example, and as in last comparison example, see peel off phenomenon before stretching and during stretching all clearly, also get muddled between layer M1 and other layer and a layer M1 has much when peeling off and tear.

As supporter, at first use 150 purpose polyester fibers (fibre diameter 45 μ m), the Metsuke 8.7g/m that next uses abaca to make ²Japan paper, and as adhesive, then use the vinyl-vinyl acetate copolymer type resin that is dissolved in methyl alcohol, this support body layer is pressed onto the two sides of described plural layers.The amount of adhesive used herein is counted 3.0g/m with solids content ³

Being laminated to all is level and smooth in any case, and in the time carrying out uniform treatment dry, do not have fold, otch or curl.The layered product that is obtained is easy to dispose, and firmly, simultaneously, its M1 layer is protected, and fault or otch can not take place, the phenomenon of also not curling after peeling off.

This lamination physical efficiency is easily peeled off, and can become two template paper.

Separate above-mentioned M1 layer, and analyze its performance.The result is tensile break strength 18.2kg/mm ², the tensile elongation 110% during fracture, tensile modulus of elasticity 220kg/mm ², shrinkage stress value 430g/mm ²(at 85 ℃ peak value), 80 ℃ hot contraction ratio 78%.All The above results all are the mean value of vertical and horizontal, also are the results shown in hereinafter.

Layer M1 and P _B2Peeling off easily between-1, its suitable peeling force is the 0.8g/cm width.Layer P _B2-1 and the layer P _ABonding strength between-1 reaches is enough to the level that do not take place to peel off.

Interleaving agent oozing out on the interface that forms with layer M1 is just right, and good effect and layer M1 and the P of peeling off is provided _B2Suitable bonding between-1 makes and delamination, fold do not take place or floats.In order to compare, done the test of no interleaving agent, in this case, a layer M1 is torn, and peels off carry out not smooth, and in this comparison example, because electrostatic interaction, each layer all run into dust, tear and fold that spark causes.The use of interleaving agent not only makes stable effect and other the above-mentioned effect peeled off between each layer, and this phenomenon (when taking place in the problem that is clamminess that has solved the hot pin of printer line, the film hot pin of adhering is torn or is presented fold, makes by the formed image distortion of perforation).Though common commercially available high-crystallinity polyester film (2 μ m) recoat one deck antitack agent also can be used, production of the present invention still has the advantage that does not need additionally to apply antitack agent.In addition, the P that peels off _B2-1/P _A-2 all is callable, might recycle.

Next step is made 0.5 μ m with the thickness of layer M1, and carries out same test, shows that it has the film character much at one with described layer M1.Compression ratio is vertical and horizontal average out to 2.1%.How to carry out lamination with porous supporting body, all no problem.This makes might be with not thinking in the past that the functional layer M1 as thin as a wafer that does not cause fold, otch or tear made template paper smoothly.When the thickness of layer M1 was made into 10 μ m and 12 μ m, this film just can carry out than more uniform stretching of single M1 layer film and lamination.When being not more than 8 μ m, the thickness of single thin film because porose or thickness is extremely inhomogeneous, can not evenly stretch.

Next step, the Metsuke that uses as supporter with the film of being made up of above-mentioned functions layer (M1) (2 μ m and 0.5 μ m are thick), prepare with polyester fiber is 9.5g/m ²Nonwoven, the methanol solution that adopts vinyl-vinyl acetate copolymer type resin is configured in the both sides of above-mentioned plural layers as adhesive.The amount of used adhesive is 3.5g/cm by solid content meter ³

This laminate layers operation is very smoothly, does not take place when drying such as fold, otch or such trouble of curling.The multi-layered product that is obtained is easy to dispose and have enough intensity.Do not observe that dust adheres to or otch, because its functional plane is capped fully.The phenomenon of curling does not take place in this stage.

After aforesaid operations, with the low stretching of 2g/cm width and 200m/ divide high-speed, partly (P of peel ply is peelled off in the both sides of this laminate _B2-1/P _A-1/P _B2-1).Carry out this peeling off and have no difficulty, and obtain required template paper.

Measure the perforation sensitivity of this template paper, reach the hypersensitive level, the thick M1 of 0.5 μ m is that 0.03 milli is burnt, the M of 1.0 μ m thickness ₁Be that (product that obtains with Same Way has all properties that is in optimized scope to 0.04 milli Jiao, compression volume is 1.5%) crimpness also measures under the aging temperature of 40 ℃ and 50 ℃, for all products under 40 ℃ is 0, is respectively 0,0 and 2 for the product at 50 ℃ all thickness.In order to compare, when each above-mentioned layer M1 is stripped from into an independently film and be laminated to the nonwoven that does not cause fold (the Metsuke 12.0g/m that is made by above-mentioned polyester-type fiber ²) when going up, measured crimpness.The result is: 40 ℃ aging be 8,10 and 12,50 ℃ aging be 25,30 and 35, and, delamination takes place when using the template paper made from the film of 1.0 μ m and 2.0 μ m.

In order further to compare, use a crystallization pet film (degree of crystallinity of surveying with densimetry is about 32%) as functional layer and be similar to above-mentioned supporter lamination, made a kind of template paper.Measure the perforation sensitivity of this template paper, for thickness be 1.0 μ m be that 0.12 milli is burnt, and be that 2.0 μ m are that 0.13 milli is burnt for thickness.Crimpness in this example, for 40 ℃ aging be 8, for 50 ℃ aging be 16.Can reach a conclusion from this result, present much higher perforation sensitivity than template paper and much better coiling-resistant performance behind high temperature ageing with the commodity film production with the template paper of plural layers production of the present invention.

Example 2

With with example 1 in identical method manufacturing be respectively the M of 2/8/2/8/2 μ m by thickness ₁/ P _B2-1/P _A-1/P _B2-1/M ₁The laminated film of forming, different is that the resin that constitutes layer M1 in example 1 comprises 1%(weight now) average grain diameter is the carbon black of 0.03 μ m.The all properties of this M layer film is all within OK range.

Next step, the template paper being made up of M layer and supporter strips down from former roll of material, and this former roll of material is as passing through of being carried out in example 1 support body layer of being made up of 200 order cardboards to be pressed onto on the above-mentioned plural layers to obtain.Lamination is level and smooth, and the M layer of template paper has evenly smooth face.50 ℃ aging after, crimpness is 3.

When carrying out drifting test, allow semiconductor laser (the peak power 30mw that is focused into 10 μ m hot spots by collimation lens, wavelength 780nm) bundle can be bored a hole with the 5mw energy to this template paper effect 1/100 second, and has reached and have clear and high-resolution height and accurately print.

In order to compare, degree of crystallinity is 45% and comprises 1%(weight when measuring with densimetry) average grain diameter be that the pet film (thickness is 2 μ m) of 0.03 μ m carbon black is laminated to supporter to make template paper, the eleven punch 11 of going forward side by side test, in this case, can not bore a hole with the energy of same amount.

Example 3

Use is used for layer M and P in example 1 _B2-1 identical film is made under the same conditions by thickness and is respectively 2/15/2(μ m) M ₁/ P _B2-1/M ₁The plural layers of forming, different is, and draft temperature is set in 77 ℃, and environment temperature is 75 ℃, and draw speed vertically is being 4.0, laterally is being 3.7, having only a kind of in addition is to make under the draft temperature identical with example 1.This example is realized steadily stretching, and the phenomenon of peeling off between hole or each layer do not occur.The all properties of M layer all is in only scope of the present invention.

Next step is by using 200 order paper to make multi-layered product as supporter, UV-cured dose as adhesive and the both sides that this supporter is laminated to described plural layers simultaneously.The consumption of curing agent is 0.4g/m ²Lamination is level and smooth, has obtained uniform reel.Measuring the compression volume of each plural layers, the former is-the 0.8%(elongation), the latter is 1.5%, measures the perforation sensitivity as the template paper that is used to print that strips down from multi-layered product carrying out in the example 1 then, proves overdelicate.Measure crimpness, for-40 ℃ aging be respectively 14 and 2, and for 50 ℃ aging be respectively 27 and 4.

In order to compare, laminated together crystallization (degree of crystallinity of measuring with densimetry the is 45%) pet film that described supporter and commercially available 2 μ m are thick.Yet fold can take place in this product, and only applies more to hale to stretch just on vertical and horizontal and might carry out lamination, and resulting film quality is inferior, fold, uneven adhesive coating are arranged, break and distortion.In addition, the concave of supporter and convexity are copied on the surface of film, though and this surface may more or less be flat at first, room temperature (23 ℃) down after aging 24 hours crimpness be 8, for 40 ℃ aging be 12, for 50 ℃ aging be 15.

Example 4

Obtain reel as follows: make a plate-shaped pattern, the height that wherein useful method against corrosion forms at interval with 150 orders is that 40 μ m, diameter are the bossing of 20 μ m, bottom thickness is 50 μ m, with this pattern as buck plate, after being coated onto UV-cured dose on the bossing, place by use with above-mentioned example 3 in the M that obtains of same procedure ₁/ P _B1-3/M ₁The plural layers that (thickness 8/8/8 μ m) forms also make it sclerosis.Then, by layer M ₁The template paper of forming with buck plate strips down from above-mentioned reel, finds that film surface has excellent uniformity.Layer M ₁Film performance within optimized scope of the present invention.

In order to compare, the layer M1 thick 8 μ m strips down from the plural layers with structure same as described above, is placed on the above-mentioned buck plate, makes template paper after being similar to above-mentioned sclerosis.This product surface is inhomogeneous, and fold is arranged, and the coated weight of adhesive is inhomogeneous.

Next step does drifting test (peeling off buck plate after the perforation) to these template paper, and template paper wherein of the present invention shows enough high sensitivity perforation uniformly, and provides high resolution image with the burnt energy level of 0.12 milli.On the other hand, the template paper in the comparison example then can not fully be bored a hole, and image is not too even, and blooming takes place in print procedure, makes resolution deteriorates.Microscopic examination further discloses, image perforation not enough (film insufficient sensitivity) on the medium-sized paperboard of comparison example, because the ground square punch of needs perforation too a little less than, bridge is cut off, the hole is extended, and the bridge that the image on the template paper of the present invention is then formed with approximate homogeneous polymer provides a shape perforation.

Have high-resolution definition printing and realize, when with about 1000 pages of the automatic press printing of drum type Automatic inking, do not have the literal defective at all by the present invention.On the contrary, comparison example can not fully be printed, because a little less than the resolution ratio, but except that this problem, at some partial loss literal and hollow phenomenon takes place, because there is not printing ink (not perforation) in the place of needs printing.

Example 5

Functional layer (M ₁), peel ply (P _B1-1) and peel ply (P _B2-1) respectively with the extruder fusing, which floor is extruded together with this by annular multilayer die head, becomes to have M ₁/ P _B2-1/P _B1-1/P _B2-1/M ₁The multilayer pipe shape of structure makes its quenching hardening with refrigerant then, obtains tubular reel.Then this reel is heated to 105 ℃, the speed of dividing with 50m/ is drawn into bubble shape simultaneously to both direction, and 103 ℃ of heating, thereby make this volume can be 5.0 times of longitudinal stretchings, laterally also stretching 5.0 times, then this product is cooled to 20 ℃, obtains with the folding 1100mm folding width film of negative booster.

Under 75 ℃ of environment, further this film is carried out 5 seconds of heat-set treatment, make it,, exerted pressure for 0.5 second with the roller that is heated to 70 ℃ then, after this both sides of film are cut, be rolled into two films in cross-direction shrinkage 5% vertically shrinking 3%.Therefore, obtain thickness and be followed successively by 1.0/4/3/4/1.0(μ m) plural layers.

The plural layers that obtain with said method have little peel strength, at functional layer part (M ₁) and peel ply part (P _B2-1) be the 0.8g/cm width between, it allows easily to peel off with the 200m/ component velocity.After peeling off as above, the compression ratio of functional layer part be vertically with horizontal average out to 1.2%.

When not having heat setting when carrying out similar processing, functional layer partly is stretched 0.4%.

Above-mentioned functions layer segment (M ₁) tensile break strength be 16Kg/mm ², the tensile elongation during fracture is 100%, tensile modulus of elasticity is 220Kg/mm ², the shrinkage stress value of peak value is 480g/mm at 85 ℃ ², be 350g/mm at 100 ℃ ², hot contraction ratio is 5% at 70 ℃, is 30% at 80 ℃, is 58% at 90 ℃, is 70% at 100 ℃.The hot contraction ratio of peel ply part is 15% at 70 ℃, is 43% at 80 ℃, is 71% at 90 ℃, is 76% at 100 ℃.These values all are the mean value of vertical and horizontal.

Next step, as in the example 1, above-mentioned plural layers and the nonwoven layer of being made by the polyester-type fiber are forced together, peel ply is partly peeled off, measure the perforation sensitivity of the template paper that is obtained, do not lose any sensitivity as in the example 1, reaching the hypersensitive level.The crimpness of the template paper that is obtained is 0 when 30 ℃ and 40 ℃, is about 2 at 50 ℃.

On the other hand, the peel ply that separates with these template paper partly is callable, and allows by forming functional layer as its forward position layer and recycling once more.

Example 6

With example 5 in make plural layers under the identical condition, different is the thickness of functional layer to be made 0.5 μ m, 2 μ m or 6 μ m.This example also can be placed supporter equably.The compression volume of the functional layer that strips down from these plural layers, and the crimpness of the template paper of being made by these plural layers is shown in table 1.

In order to compare, when stretching separately, 8 μ m functional layers can not stretch uniformly, because bubble breaks.

Table 1

Comparative example 1

For the plural layers of in example 6, making with the thick functional layer of 2 μ m, measure its perforation sensitivity and crimpness, wherein, functional layer is peeled off to remove compression (sample A), same film is attached on the fixing framework after peeling off and heat setting 2 minutes (sample B) in 90 ℃ baking oven, vertically shrink 3%, under the condition of cross-direction shrinkage 5% in 80 ℃ of heat settings 2 minutes (sample C), and under similarity condition in 90 ℃ of heat settings 2 minutes (sample D).The results are shown in Table 2.

Table 2

*, delamination takes place

As conspicuous in this table, peel off the film that then is placed on the supporter earlier, when the coiling-resistant performance is improved, the trend of remarkable reduction perforation sensitivity is arranged.This is because the cause that characteristic orientation reduces, and the coiling-resistant performance is difficult to improve, unless above-mentioned performance reduces.

Example 7

Under the stretching condition identical, stretch altogether with bubble method with example 1, subsequently 70 ℃ of 0.5 seconds of roll process, these operational applications in: by function of use layer (M ₁) and peel ply (P _B1-2) M of Zhi Zuoing ₁/ P _B1-2/M ₁The plural layers of forming (sample 1) are by function of use layer (M ₁), peel ply (P _B1-2) and auxilliary peel ply (P _A-2) M of Zhi Zuoing ₁/ P _B1-2/P _A-2/P _B1-2/M ₁The plural layers of forming (sample 2) are by function of use layer (M ₂), contain 3%(weight) monoolein and 2: 1 mixture of two glycerin mono-fatty acid esters as the vinyl-vinyl acetate copolymer (vinyl acetate unit content 10%(weight) of interleaving agent, melt index 1.0,81 ℃ of Vicat softening points, 95 ℃ of fusing points) and auxilliary peel ply (P _A-1) M of Zhi Zuoing ₂/ P _B2-2/P _A-1/P _B2The plural layers (sample 3) that-2/M2 forms, and by function of use layer (M1) and peel ply (P _B1-3) M of Zhi Zuoing ₁/ P _B1-3/M1/P _B1-3/M ₁The plural layers of forming (sample 4).

Yet the stretching in the material 3 is to be to carry out under 87 ℃ of such conditions at draft temperature due to 90 ℃ and environment temperature.

For the mensuration of each functional layer, M ₁Shown the value roughly the same, with its layer structure-irrelevant, M with example 1 ₂Shown that its tensile break strength is 14kg/mm ², the tensile elongation during fracture is 70%, tensile modulus of elasticity is 250kg/mm ², the peak value of shrinkage stress value is 600g/mm at 110 ℃ ², be 260g/mm at 100 ℃ ², hot contraction ratio is 10% at 80 ℃, is 35% and be 55% at 140 ℃ at 100 ℃.

Template paper be to use above-mentioned plural layers with example 1 in identical method make.Table 3 is listed the compression volume and the crimpness of the functional layer of these samples, and the perforation sensitivity when making body paper.

Material 3 has also been done another experiment, and wherein, stretching is to carry out under the condition identical with example 1.Compression volume in this case is-the 0.2%(elongation) and, for the condition determination of 30 ℃, 40 ℃ and 50 ℃, crimpness is respectively 7,15 and 30.Peel ply is easy to stretch, fracture when peel ply divests behind lamination.

Table 3

Comparative example 2

With with example 1 in identical method make: have a layer structure M ₁/ PP/M ₁And function of use layer (M1) and as P only _AThe crystalline polypropylene of-1 component (abbreviating PP as) is as the plural layers (sample G) of remover, and has a layer structure M ₃/ PP/M ₃And function of use layer (M ₃) and above-mentioned PP as the plural layers (sample H) of peel ply.These films have the trend of peeling off between each layer causing during the stretched operation.

Though the stretching of these samples is to carry out with vertical amount of tension of 3.2, horizontal 3.2 with the draft temperature of bubble method at 110 ℃, unsettled stretching condition causes bubble oscillation and inhomogeneous cross section.

This trend is more obvious in sample H.These samples occur breaking being not more than under 105 ℃ the draft temperature, also occur breaking under 115 ℃ or higher temperature and such as the scrambling of local deliquescing.Under each situation, all carried out level and smooth stretching.

By thickness is 1.0/5/1.0(μ m) each layer form and the peeling force of the functional layer of the sample that obtains under 110 ℃ draft temperature is 4 to 5g/cm width, it can not be peeled off smoothly, because occur splitting and otch.Once attempted in manufacturing process, interleaving agent to be mixed in this peel ply, but caused released state, can not form homogeneous mixture with injection system.

Table 4 is listed the shrinkage factor (opposite with compression ratio) of functional layer among sample G and the H and the test result of the crimpness when peeling off.

Table 4

For obtaining further information, the watery fusion of sample H can be 8 card/grams, and to calculate degree of crystallinity (can be that 30 card/grams calculate with the watery fusion of crystallization PETG) in view of the above be about 26%.The percent thermal shrinkage of this film is 7% at 100 ℃, is 20% at 140 ℃, and is 40% at 160 ℃.

Comparative example 3

The reel of quenching is heated to 80 ℃, then the functional layer (M of sample H in the comparative example 2 ₃) in the stenter of this subsequent step in 90 ℃ 3.0 times of longitudinal stretchings, laterally also stretching 3.0 times, make by M after 150 ℃ of 5 seconds of heat setting at this sample ₃/ PP/M ₃-1.0/5/1.0(μ m) plural layers of Zu Chenging.

This plural layers split on stenter, misplace between each thin layer, and are in uneven thickness.Functional layer can not be carried out smoothly with separating of peel ply, and observed fracture.

The change in size of the functional layer after peeling off shows very big anisotropy, and its longitudinal shrinkage is 0.2%, and the cross-direction shrinkage amount is 0.05%.Crimpness vertically is 5 in the time of 30 ℃, vertically be 14 when laterally being 3,40 ℃, when laterally being 8,50 ℃ vertically be 25, laterally be 20.The perforation sensitivity of using the template paper of this film is that 0.10 milli is burnt.

Example 8

Functional layer (M4), peel ply (P _B1-3) and auxilliary peel ply (P _A-1) respectively with extruder fusing, and by annular multilayer die head which floor is extruded together to become and has M with this ₄/ P _B1-3/P _A-1/P _B1-3/M ₄The multilayer pipe shape of structure makes it hardening suddenly with refrigerant then, obtains the tubulose reel.It is biaxial stretch-formed to be under 100 ℃ to carry out the while with bubble shape, makes this volume cool off this reel with 20 ℃ air 3.0 times of longitudinal stretchings laterally also stretching after 3.0 times.The both sides of this film are scratched, be rolled into two films with coiling machine.Every layer thickness is 1/8/2/8/1(μ m in this laminated film).Functional layer part (M in the plural layers that obtain with said method ₄) and peel ply part (P _B1-3) peeling force between is little of the 1.0g/cm width, thereby this plural layers can separate easily.

The compressibility of the functional layer after peeling off counts 2.7% by the mean value of length/width.Layer (M ₄) be 43% at 100 ℃ percent thermal shrinkages, layer (M ₄) the thermal shrinkage stress value be 460g/mm ²These two mean values that value all is a length/width.

Use with example 1 in the perforation sensitivity of the template paper peeling peel ply off after the nonwoven of identical method lamination polyester fiber and obtained, reach the burnt high sensitivity level of 0.08 milli.The crimpness of the template paper of Huo Deing is 0 in the time of 30 ℃ in this way, is 2 in the time of 40 ℃, is 5 in the time of 50 ℃.Work as M ₄Layer is stripped from into individual layer when making comparisons, and crimpness is respectively 8,30,40, and delamination takes place.

Example 9

Functional layer (M5), peel ply (P _B1-3) and peel ply (P _A-1) extrudes to become by annular multilayer die head and have M5/P _B1-3/P _A-1/P _B1-3/M ₅Structure tubular makes it the quenching hardening with refrigerant then, obtains tubular reel.Then, be that 90 ℃ are carried out biaxial stretch-formed this volume that makes of while with bubble shape and can laterally also stretch after 3.0 times 3.0 times of longitudinal stretchings, cool off this reel with 20 ℃ air.The both sides of film are scratched and be rolled into two films with coiling machine.Every layer thickness is 1/6/2/6/1(μ m in this laminated film).

Peeling force in the plural layers that obtain with said method between functional layer (M5) and the peel ply is little of the 1.0g/cm width, and this plural layers can easily separate.Peel off the shrinkage factor of back functional layer and count 0.3% by the mean value of length/width.Functional layer (M ₅) be 63% 100 ℃ shrinkage factors, be 210g/mm at 70 ℃ shrinkage stresses ²These two mean values that value all is a length/width.After nonwoven with the method lamination polyester fiber identical with example 1, peel peel ply off and the perforation sensitivity of the template paper that obtains, reach the burnt high sensitivity of 0.07 milli.The crimpness of the template paper of Huo Deing is 0 at 30 ℃ in this way, is 5 at 40 ℃, is 8 at 50 ℃.

Comparative example 4

After obtaining the tubular reel the same with example 1, first to carry out the while at 130 ℃ with bubble shape biaxial stretch-formed, make this volume can be 1.5 times of longitudinal stretchings, laterally also stretching 1.5 times, cool off this reel with 20 ℃ of air then.Laminated film (the M that is being obtained ₁/ P _B2-1/P _A-1/P _B2-1/M ₁) in every layer thickness be 3/3/6/3/3(μ m).Functional layer (M in the plural layers that obtained ₁) and peel ply between peeling force be the 5.5g/cm width, this plural layers are difficult to a little peel off, and are easy to tear.Functional layer (M ₁) be 23% 100 ℃ shrinkage factors, the equilibrium valve of it and 110 ℃ of temperature is 28%.(equaling peak value) is 45g/mm at 100 ℃ shrinkage stresses ²These values all are the mean value of length/width.

The template paper that obtains for peel peel ply off after the nonwoven with the method lamination polyester fiber identical with example 1 even measuring perforation sensitivity is that 0.13 milli is burnt, also can't obtain enough perforation.

Comparative example 5

Comparative example 5 carries out with the method identical with example 1, and the final thickness of functional layer that different is is 15 μ m.Even the perforation sensitivity of the template paper that is obtained is determined is that 0.13 milli is burnt, also can't obtain enough perforation.

Claims (19)

1, in the common stretch multi-layer film that comprises at least one functional layer (M) and at least one peel ply (P), a kind of high-sensitivity thermosensitive multilayer film, it is characterized in that described functional layer by a kind of hot contraction ratio at least 30%, the thermal shrinkage stress value is 50g/mm at least ²And thickness is that the thermoplastic resin of 0.1 to 12 μ m is formed, have 30 to 120 ℃ Vicat softening point, contain at least a interleaving agent and form with the described peel ply of described functional layer combination by the different thermoplastic resin of a kind of and described functional layer resin, and above-mentioned two-layerly all can easily peel off.

2, according to the high-sensitivity thermosensitive multilayer film of claim 1, wherein the described thermoplastic resin that exists with the state of the film that forms described functional layer (M) has 0 to 30% degree of crystallinity.

3, according to the high-sensitivity thermosensitive multilayer film of claim 1, film its hot contraction ratio under 60 to 170 ℃ temperature that wherein forms described functional layer (M) is at least 30%, and its thermal shrinkage stress value is 50g/mm at least under 60 to 150 ℃ temperature ²

4, according to the high-sensitivity thermosensitive multilayer film of claim 1, wherein the degree of crystallinity of described peel ply (P) material of measuring with DSC be not more than the whole resin that forms this layer the average crystallite degree 60%, and at least one peel ply contains a kind of interleaving agent.

5, according to the high-sensitivity thermosensitive multilayer film of claim 1, wherein said peel ply (P) applies a compression stress to described functional layer (M) at least one direction, and its compression strain is 0.05 to 10%.

6, according to the high-sensitivity thermosensitive multilayer film of claim 1, wherein said peel ply (P) is a kind of by at least one auxilliary peel ply (P _A) and at least one contain the main peel ply (P of interleaving agent _B) the multilayer peel ply formed, and described auxilliary peel ply is to be formed by a kind of thermoplastic resin that has the crystalline melt point that is higher than described functional layer draft temperature and be higher than 120 ℃ Vicat softening point.

7, according to any one high-sensitivity thermosensitive multilayer film in the claim 1,4 and 5, wherein said peel ply (P) is by at least one auxilliary peel ply (P _A) and at least one and described auxilliary peel ply (P _A) any one surface in conjunction with and the main peel ply (P that can easily peel off, contain interleaving agent with described functional layer (M) _B), and described these peel plies are so stacked, so that P _BAnd P _ABetween separation can not take place or only than M and P _BBetween just can take place under the big peeling force effect of the power of separating.

8, according to any one high-sensitivity thermosensitive multilayer film in the claim 1,5 and 7, wherein on the positive and negative surface of described peel ply (P), respectively stack a described functional layer (M).

9, according to any one high-sensitivity thermosensitive multilayer film in the claim 1,5 and 8, wherein at least two functional layers (M) are configured on the positive and negative surface, and dispose at least one peel ply as internal layer.

10, according to the high-sensitivity thermosensitive multilayer film of claim 1 or claim 2, wherein said functional layer (M) is mainly formed by at least a resin that is selected from polyester-type copolymer, nylon type copolymer, polycarbonate type copolymer and ethylene-vinyl alcohol type copolymer, each all is unbodied basically structure under filminess, and has 40 to 150 ℃ Vicat softening point.

11, the method for producing high-sensitivity thermosensitive template paper by a kind of common stretch multi-layer film that comprises at least one functional layer (M) and at least one peel ply (P), described functional layer by a kind of hot contraction ratio at least 30%, the thermal shrinkage stress value is 50g/mm at least ²And thickness range is that the thermoplastic resin of 0.1 to 12 μ m is formed, have 30 to 120 ℃ Vicat softening point, contain a kind of interleaving agent and form with the described peel ply of described functional layer combination by the different thermoplastic resin of a kind of resin of and described functional layer, and above-mentioned two-layerly all can peel off easily, this method is characterised in that: a kind of porous supporting body (S) is overlayed on one deck at least of described functional layer, subsequently along the described plural layers of interfacial separation between described functional layer (M) and the described peel ply (P).

12, according to the method for claim 11, wherein said plural layers have the functional layer (M) that respectively stacks on the positive and negative surface of described peel ply (P).

13, according to the method for claim 11 or 12, wherein said peel ply (P) comprises an auxilliary peel ply (P by a kind of _A) and one overlay this auxilliary peel ply (P _A) any one lip-deep, as to contain interleaving agent main peel ply (P _B) the multilayer peel ply form, and described auxilliary peel ply is to have than the draft temperature of functional layer high crystallization temperature and be higher than the thermoplastic resin formation of 120 ℃ Vicat softening point with a kind of.

14, according to claim 11, the method of any one in 12 and 13, wherein, described peel ply (P) applies a compression stress to described functional layer (M) on its at least one direction, making its generation scope is 0.05 to 10% compression strain, on at least one described functional layer (M), stack a porous supporting body (S), subsequently, the functional layer that stacks described porous supporting body (S) thereon (M) is separated with described peel ply (P), thereby make described functional layer (M) remove the described compression stress that applies by described peel ply (P), improve the coiling-resistant ability of template paper.

15, according to the method for claim 11, wherein said functional layer (M) is mainly formed by at least a resin that is selected from polyester-type copolymer, nylon type copolymer, polycarbonate type copolymer and ethylene-vinyl alcohol type copolymer, and each all is unbodied basically structure and has 40 ℃ to 150 ℃ Vicat softening point under filminess.

16, a kind of laminated product, it has a porous supporting body (S) at least one functional layer (M) that overlays in a kind of altogether stretch multi-layer film that comprises at least one functional layer (M) and at least one peel ply (P), described functional layer by a kind of hot contraction ratio at least 30%, the thermal shrinkage stress value is 50g/mm at least ², thickness range is that the thermoplastic resin of 0.1 to 12 μ m is formed, have 30 ℃ to 120 ℃ Vicat softening point, contain a kind of interleaving agent and form with the described peel ply of described functional layer combination by the thermoplastic resin different with the resin of described functional layer, and above-mentioned two-layer can peeling off easily.

17, according to the laminated product of claim 16, wherein said peel ply (P) applies a compression stress to described functional layer (M) at least one direction, and making its generation scope is 0.05 to 10% compression strain.

18, according to the laminated product of claim 16 or 17, wherein functional layer (M) is configured on the positive and negative surface of described peel ply (P), and installs porous supporting body (S) layer on its outer surface.

19, according to any one laminated product in the claim 16,17 and 18, wherein, described peel ply (P) comprises an auxilliary peel ply (P _A) and be configured in described auxilliary peel ply (P _A) any one lip-deep, as to contain interleaving agent main peel ply (P _B).