CA1247315A - Laminate films of polycarbonates and polyalkylene terephthalates - Google Patents
Laminate films of polycarbonates and polyalkylene terephthalatesInfo
- Publication number
- CA1247315A CA1247315A CA000472212A CA472212A CA1247315A CA 1247315 A CA1247315 A CA 1247315A CA 000472212 A CA000472212 A CA 000472212A CA 472212 A CA472212 A CA 472212A CA 1247315 A CA1247315 A CA 1247315A
- Authority
- CA
- Canada
- Prior art keywords
- diol
- film
- acid
- polyalkylene terephthalate
- laminate film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2429/00—Carriers for sound or information
- B32B2429/02—Records or discs
Landscapes
- Laminated Bodies (AREA)
Abstract
Laminate films of polycarbonates and polyalkylene terephthalates Abstract The present invention relates to transparent laminate films, consisting of a polycarbonate film and a polyester film, to their preparation and to their use for the manufacture of switch panels, nameplates and foil switches.
Description
~L2~3~5 -- 1 ~
Laminate films of polycarbonates and polyalkylene tere~hthal tes For the manufacture of sw;tch panels, nameplates and foil switches, films of both polycarbonate and poly-ethylene terephthalate are employed. ~hen selecting the films, a polycarbonate film is generally preferred, since this can easily be produced hith a surface wh;ch has a matt structure and is therefore insens;t;ve to scratch;ng, and can, moreover, very read;ly be pr;nted by screen-print;ng methods.
Films of polyethylene terephthalate, ~h;ch can be produced only with high-gloss, reflect;ng and hence scratch-sensitive surfaces, are d;ff;cult to imprint and are e~-ployed only if the film has to meet stringent demands w;th respect to solvent res;stance, for example ;n order to en-able d;rt accumulated ;n use to be cleaned off the surface ~ith solvents.
There has therefore been no lack of attempts to develop transparent films ~h;ch can be produced analogously to polycarbonate e;ther ~ith pol;shed surfaces or w;th sur-faces of ~att structure, are readily pr;ntable and at the same t~me are res;stant to solvents~
The obv;ous use of known films of polycarbonate/
polyester mlxtures tsee, for example, JA-49-080162, JA-49-113 a49, JA-S1-~64 561, US Patent Spec;f;cat;ons 3,956,229 and 3,975,355, DE-OS tGerman Publ;shed Specification) Z,647,565, US Patent Spec;f;cat;ons 4,155,898 and 4,157,997 and JA 56-034 428) does not succeed, s;nce such films are difficult to imprint, ;f there is a high proportion of polyalkylene terephthalate, and are not sufficiently sol-vent-resistant, if there is a high proportion of polycar-bonate.
~ he present invention relates to transparent !am-inate films, consisting of A) a transparent, thermoplastic polycarbonate film of a thickness of about 50 ~m to 350 ~m, preferably 100 ~m to Le A 22 596-US
. _ ~L2~73~5 200 ~m, and B) a transparent, thermoplastic polyalkylene tereph-thalate film of a thickness from 10 ,um to 100 Jum, prefer-ably 25 ~m to 50 ym.
Transparency in the sense of the present invention means that the light transmission is >, 50X, measured by means of an Ulbricht sphere9 so that the proportion of scattered light is also included~ since a considerable pro-portion of the light is diffusely scattered in the case of structured filmsr Printability in the sense of the present invent;on means that the film can be printed with commerciaLly avail able lacquers, preferably screen-printing inks, without pretreatment and that the printing ink is intimately bonded to the film surface. When examining the adhesive strength by the cross-cut test according to DIN 53,151, the ink on the cutting edge must not come off when a self-adhesive film is stuck across the cut and then drawn off.
Solvent resistance in the sense of the present in-2n vention means that the surface is not attacked by aliphatic, cycloaliphatic or aromatic solvents, such as acetone, methylene chloride, cyclohexanon~, benzyl alcohol, toluene and the like~
Surface structur~ng in the sense of the present in-vention means that the ~ilm surface has a rou~hness R3zfrom 3 to 5û ym tmeasured according to DIN 4,768).
The laminate films according to the invention are, in our view, novel and possess the desired combination of properties, namely transparency, solvent resistance and printability, so that they are suitable for the intended use outlined at the start.
According to US Patent Specification 3,730,767, magnetic media are known which, on a polyester base, con-tain an interlayer which serves as an adhesion promoter and in each case consists of a polyestertpolycarbonate mixture, the polycarbonate content being 1 to 25% by weight, Le A ZZ 596 -US
_ 3 _ ~4~3~5 relative to the weight of the polyester. The interlayer serves to improve the adhesion of the magnetic layer.
Accord;ng to Japanese Patent Appl;cat;on No. 43,191 of 1971, publ;shed on 3~2.1973 under No. 8,880, b;axially stretched f;lms are known ~hich are bu;lt up from poly-ester films, wherein one of the polyester films must con-ta;n quant;t;es of 0.01 to 2X by ~eight, relat;ve to the we;ght of polyester, of another thermoplastic resin ~hich is incompatible with the polyester. For example, poly-1G carbonate can be used as the other thermoplastic resin.This procedure aims for clear-transparent~ biaxially stret-ched polyester f;lm lam;nates having good slip properties.
According to Japanese Patent Appl;cat;on No. 159,149 of 1976, published on 20.7.1978 under No. 8~,413~ combina-tions of dielectric f;lms and carbon black-filled poly-carbonate films are known. The d;electric films, can, inter alia, consist of polyester resins. The lam;nates are used as an electrostatic recording material.
In our view, the polyester/polycarbonate laminate ~ilms according to the invent;on are neither anticipated nor suggested by these three last-ment;oned Literature references.
For the preparation of the polycarbonate f;lm com-ponent, ~he polycondensatlon products obta;nable by react-ing d~phenols~ in part~cular dihydroxydiarylalkanes, w;thphosgene or d~esters of carbonic ac~d are suitable, and, 1n add;tion to the unsubstituted d;hydroxyd;arylalkales, those whose aryl rad;cals carry methyl groups or halogen atoms ;n the o-pos;tion andtor m-pos;t;on relat;ve to the 3û hydroxyl yroup are also su;table. Branched polycarbonates are l;kew;se su;table.
The su;table polycarbonates have weight-average molecular we;ghts Mw of between 10,000 and 100,000, preferably between 20,000 and 40,000, determined by measure-ments of the relat;ve v;scosity ;n CH2Cl2 at 25C and ata concentrat1on of 0.5 9 per 100 ml.
Le A 22 596-UB
~2~731S
Examples of su;table diphenols are hydroquinone, resorc;nol, 4,4'-d;hydroxyd;phenyl, b;s-(hydroxy-phenyl)-alkanes, such as, for example, C1~C8-alkylene-b;sphenols or c2-c8-alkyl;dene-b;sphenols, b;s-(hydroxy-phenyl)-5 cycloalkanes, such as, for example, C5-C15-cycloalkylene-bisphenols or C5-C15-cycloalkylidene-bisphenols and bis-(hydroxy-phenyl) sulphides, ethers, ketones, sulph-oxides or sulphones, ani~ also a,~ '-bis-(hydroxy-phenyl)-diisopropylbenzene and the corresponding compounds alky-10 lated in the nucleus or halogenated in the nucleus. Poly-carbonates based on 2,2-bis-(4-hydroxy-phenyl)-propane (bis-phenol A), 2,2-bis-(4-hydroxy-3,5-dichloro-phenyl)-propane (tetrachlorobisphenol A), 2,2-bis-(4-hydroxy-3,5-dibromo-phenyl)-propane (tetrabromobisphenol A), 2,2-bis-(4-hydroxy-15 3,5-dimethyl-phenyl)-propane (tetramethylbisphenol A) and 1,1-bis-(4-hydroxy-phenyl)-cyclohexane and those based on trinuclear bisphenols such as c~, a'-bis-(4-hydroxyphenyl)-p-diisopropylbenzene are preferred.
Further diphenols suitable for the preparat;on of 20 the polycarbonates are described, for example, in US Patent Specifications 3,028,365, 3~06Z,781, 3,148,172 and 3,271,367.
Polyalkylene terephthalates which are su;table according to the lnvention for the preparation of the poly-alkylene terephthalate film component ~) are reaction pro-25 ducts of aromatic d~carboxylic acids or their reactivederivatives tfor example dimethyl esters) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reactlon products~ They can be prepared by known methods. tIn this connect;on, see, for example, Kunststoff 30 Handbuch CPlastics Handbook], Volume VIII, pages 695 et seq., Carl Hanser Yerlag, Munich 1973).
Preferred polyalkylene terephthalates contain at least 8û mol X, in particular at least 90 mol X, relative to the d;carboxylic acid conponent, of terephthalic acid radi-35 cals and at least 80 mol X, in particular at least 90 mol X,relative to the diol component, of ethylene glycol and/or Le A 22 596-US
3~
butane-1,4-diole radicals, particularly preferably butane-1,4-diol radicals.
In addit;on to terephthalic acid radicals~ these preferred polyalkylene terephthalates can contain up to 2û mol % of radicals of other aromatic or cycloaliphatic dicarboxylic acids having 8-14 C atoms or al;phatic di~
carboxylic acids hav;ng 4-12 C atoms, such as, for example, rad;cals of phthalic ac;d, ;sophthal;c ac;d, naphthalene-Z,6-dicarboxylic ac;d, 4,4'-d;phenyld;carboxyl;c ac;d, succinic acid~ adipic acid, sebacic acid, azelaic acid and cyclohexanediacet;c ac;d.
In add;t;on to ethanediol or butane-1,4-diol radi-cals, these preferred polyalkylene terephthalates can con~
tain up to 20 mol % of other aliphatic diols having 3-12 C atoms or cycloaliphat;c d;ols having 6-21 C atoms, for example radicals of propane~1,3-diol, 2-ethylpropane-1,3-diol, neopentyl glycol, pentane-1,5-d;ol, hexane-1,6-diol, cyclohexane-1,4-d;methanol, 3-methylpentane-2,4-d1ol, 2-methyl-pentane-2,4-diol, Z,2,4-trimethylpentane-1,3-d;ol and -1,6-dioll 2~ethylh~ -1,3-diol, 2,2 ~iethylpropane-1,3~ iol, heKane-2,5 dlol, 2,2-bis-~-h~droxycyclohexyl)-propane and 2,~-dihydroxy-1,1,3,3-tetrc~m~thy.~clobutane, and such with arcm~tic residues l.Uke ~ di-(B-h~drox~ethox~).-Y~nzen~, 2,2-bi~-(3-~-hydroxy-ethoxy-phenyl)~propane and 2,2 bis-~4-hydroxypropoxy-phenyl)-propane ~DE-OS ~German Publlshed Specif~cation) 2,407,674, DE-OS ~German Publ~shed Specif~cation) 2,407,776 and DE-OS
~German Published Specif;cation) 2,715,932).
The polyalkylene terephthalates can be branched by incorporation of relatively small quantities of trihydric or tetrahydric alcohols or 3-basic or 4-basic carboxylic acids, such as are described, for example, in DE-OS (German Published Specification) 1,900,270 and US Patent Specifi-cation 3,692,744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane and pentaerythritol.
It is advisable to use not more than 1 mol X of the Le A 22 596-US
-branching agent, relative to the acid component.
Polyalkylene terephthalates which are particularly preferred are those which have been prepared solely from ~erephthalic acid or its reactive derivatives (for example its dialkyl esters) and ethylene glycol and/or butane-1,4-diol~ and very particularly from butane-1,4-diol~
The polyalkylene terephthalates used have in gene-ral an intrinsic viscosity of 0.4 to 1.5 dl/g, preferably 0.5 - 1.3 dltg, and in particular 0.6 - 1.2 dl/g, each measured in phenol/o-d;chlorobenzen~ 1 ;n parts by we;ght) at 25C.
The preparat;on of the laminate films according to the ;nvent;on is carried out by a co-extrusion process, the melt of the two components A) and ~) be;ng fed v;a a two~
layer adaptor at temperatures of about 260C to about 290C to a slot d;e, and the melt web be;ng stretched over a chill-roll take-off. The f;rst take-off roll must here be strongly cooled ttemperature 10C to 50C) and can be prov;ded, as required, w;th a pol;shed surface or structured surface~
The important point here is that the cooling of the melt web takes place w;th;n a~s to 3 seconds.
The present ;nvention thus also relates to a pro-cess for prepar;ng the laminate f;lms according to the in-vention, ~hich process i3 characterised in that the melts ofthe two components A~ and B) are fed via a two-layer adap-tor at temperatures of 200C to 290C to a slot die, and that the melt web ;s stretched over a chill-roll take-off, ;t being necessary for the f;rst take-off roll to be cooled to temperatures of about 10C to 50C, and the surface of this take-off roll being provided, as required, with a polished surface or a structured surface.
The films according to the invent;on can, on one s;de, have the surface wh;ch ;s requ;red ;n practice and 3S has a matt structure and is solvent-resistant, as a result of the polyalkylene terephthalate component, and, on the Le A 22 596-us 73~.~
other s;de, the required easy printability on the back, as a result of the polycarbonate component. Furthermore, these films are highly transparent, so that the inks printed on the back are cLearly visible ~;th a good effect of depth, when ~iewed from the front.
The fact that such high-grade films can be obtained by co-extrusion of polycarbonate and polyalkylene tereph-thalate is surprising, inasmuch as, on the one hand, poly-alkylene terephthalates are partiaLly crystalline poly-mers, the melts of which must be cooled very rapidly totemperatures below their particular glass transition point TG, which is between 80C and 40C, in order to obtain transparency of polyalkylene terephthalate films, and, on the other hand, polycarbonate melts must be cooled rela-tively slowly, in order to obtain polycarbonate films oflow strain and having the necessary surface qual;ty. In spite of the rapid cooling in the co-extrusion process according to the invention, the surface quality of the poly-carbonate fllm component A) is good and comparable to that of pol`ycarbonate films obtained by extrusion and slow cooling.
When a take-off roll with a structured surface is used, the poly~len~ terephthalate surface of the laminate film correspondingly has a matt structure, if the poly-ZS alkylene terephthalate layer faces the structured roll sur-~ace during the co-extrusion~
A further preparation variant for the laminate films accordin~ to the invention consists in coating an unstretched polyalkylene terephthalate film, which is bright on both s;des, on one side with a melt of polycarbo~
nate, the polyalkylene terephthalate film running ontG a cooling roll with a structured surface, and the melt web of the polycarbonate melt being pressed by means of a fur-ther roll, preferably coated with heat-resistant rubber~
against the polyalkylene terephthalate film. Due to the heat capacity of the polycarbonate melt, the polyalkylene Le A 22 596-US
~2~73~.S
terephthalate f;lm is softened to such an extent that ;t assumes the surface structure of the cooling roll~ By con-trast, attempts to laminate films of polyalkylene tereph-thalate with films of polycarbonate did not lead to the laminate films according to the invention, with the de-sired pattern of properties, above all because ctreaks in the laminating adhesive become visible during the subse-quent printing on the polycarbonate side, and s;nce only the variant with a glossy, that is to say polished viewing side, is available.
The present invention therefore also relates to a process for preparing the laminate films according to the invention from the components A) and ~), which process is characterised in that a transparent, unstretched thermo-plastic polyalkylene terephthalate film, according to com-ponent ~ hich is bright on both sides and has a thick-ness of 10 ,um to 100 ,um, is coated on one side with a hot melt, at a temperature between 270 and 330C, of thermo-plastic, transparent polycarbonate, the polyalkylene tereph-thalate film running onto a cooling roll wi~h a structuredsurface and at a tempera~ure of 10C to 50C, and the melt web of the polycarbonate melt being pressed by means of a further roll, preferably coated with heat-resistant rubber, a~alnst the polyalkylene terephthalate film under a pre~sure of 0.1 to 10 kp/cm of roll length.
Example A homopolycarbonate of Z,2-bis-(4-hydroxyphenyl)-propane having a relative viscosity of 1.4Z tmeasured at 25C in CHzCl2 and at a concentration of 0.5 g/100 ml by means of an Ubbelohde viscometer) is melted in a single-screw extruder at barrel temperatures of 300C, and the melt is fed via a two-layer adaptor to a slot die.
A polybutylene terephthalate having an ;ntrinsic viscosity of 1.25 (measured in phenol~o-dichlorobenzene at 25C) is melted in a single-screw extruder, and the melt is likewise fed via the t~o-layer adaptor to the common Le A 22 596-U~
~2~7315 _ 9 _ slot die. The channel cross-section of the adaptor for the polycarbonate melt is greater than that for the polybuty-Lene terephthalate melt by a factor of 3.
The melt of the polymers, layered above one ano~
ther, is forced out of the d;e gap of the slot d;e onto a cool;ng roll which has a structured surface and a sur-face temperature of 23C. The f;lm obta;ned by cooling of the melt is h;ghly transparent, and the polybutylene terephthalate layer has a structured surface wh;ch ;s in-sens;t;ve to scratch;ng.
Le A 22 596-US
., ,
Laminate films of polycarbonates and polyalkylene tere~hthal tes For the manufacture of sw;tch panels, nameplates and foil switches, films of both polycarbonate and poly-ethylene terephthalate are employed. ~hen selecting the films, a polycarbonate film is generally preferred, since this can easily be produced hith a surface wh;ch has a matt structure and is therefore insens;t;ve to scratch;ng, and can, moreover, very read;ly be pr;nted by screen-print;ng methods.
Films of polyethylene terephthalate, ~h;ch can be produced only with high-gloss, reflect;ng and hence scratch-sensitive surfaces, are d;ff;cult to imprint and are e~-ployed only if the film has to meet stringent demands w;th respect to solvent res;stance, for example ;n order to en-able d;rt accumulated ;n use to be cleaned off the surface ~ith solvents.
There has therefore been no lack of attempts to develop transparent films ~h;ch can be produced analogously to polycarbonate e;ther ~ith pol;shed surfaces or w;th sur-faces of ~att structure, are readily pr;ntable and at the same t~me are res;stant to solvents~
The obv;ous use of known films of polycarbonate/
polyester mlxtures tsee, for example, JA-49-080162, JA-49-113 a49, JA-S1-~64 561, US Patent Spec;f;cat;ons 3,956,229 and 3,975,355, DE-OS tGerman Publ;shed Specification) Z,647,565, US Patent Spec;f;cat;ons 4,155,898 and 4,157,997 and JA 56-034 428) does not succeed, s;nce such films are difficult to imprint, ;f there is a high proportion of polyalkylene terephthalate, and are not sufficiently sol-vent-resistant, if there is a high proportion of polycar-bonate.
~ he present invention relates to transparent !am-inate films, consisting of A) a transparent, thermoplastic polycarbonate film of a thickness of about 50 ~m to 350 ~m, preferably 100 ~m to Le A 22 596-US
. _ ~L2~73~5 200 ~m, and B) a transparent, thermoplastic polyalkylene tereph-thalate film of a thickness from 10 ,um to 100 Jum, prefer-ably 25 ~m to 50 ym.
Transparency in the sense of the present invention means that the light transmission is >, 50X, measured by means of an Ulbricht sphere9 so that the proportion of scattered light is also included~ since a considerable pro-portion of the light is diffusely scattered in the case of structured filmsr Printability in the sense of the present invent;on means that the film can be printed with commerciaLly avail able lacquers, preferably screen-printing inks, without pretreatment and that the printing ink is intimately bonded to the film surface. When examining the adhesive strength by the cross-cut test according to DIN 53,151, the ink on the cutting edge must not come off when a self-adhesive film is stuck across the cut and then drawn off.
Solvent resistance in the sense of the present in-2n vention means that the surface is not attacked by aliphatic, cycloaliphatic or aromatic solvents, such as acetone, methylene chloride, cyclohexanon~, benzyl alcohol, toluene and the like~
Surface structur~ng in the sense of the present in-vention means that the ~ilm surface has a rou~hness R3zfrom 3 to 5û ym tmeasured according to DIN 4,768).
The laminate films according to the invention are, in our view, novel and possess the desired combination of properties, namely transparency, solvent resistance and printability, so that they are suitable for the intended use outlined at the start.
According to US Patent Specification 3,730,767, magnetic media are known which, on a polyester base, con-tain an interlayer which serves as an adhesion promoter and in each case consists of a polyestertpolycarbonate mixture, the polycarbonate content being 1 to 25% by weight, Le A ZZ 596 -US
_ 3 _ ~4~3~5 relative to the weight of the polyester. The interlayer serves to improve the adhesion of the magnetic layer.
Accord;ng to Japanese Patent Appl;cat;on No. 43,191 of 1971, publ;shed on 3~2.1973 under No. 8,880, b;axially stretched f;lms are known ~hich are bu;lt up from poly-ester films, wherein one of the polyester films must con-ta;n quant;t;es of 0.01 to 2X by ~eight, relat;ve to the we;ght of polyester, of another thermoplastic resin ~hich is incompatible with the polyester. For example, poly-1G carbonate can be used as the other thermoplastic resin.This procedure aims for clear-transparent~ biaxially stret-ched polyester f;lm lam;nates having good slip properties.
According to Japanese Patent Appl;cat;on No. 159,149 of 1976, published on 20.7.1978 under No. 8~,413~ combina-tions of dielectric f;lms and carbon black-filled poly-carbonate films are known. The d;electric films, can, inter alia, consist of polyester resins. The lam;nates are used as an electrostatic recording material.
In our view, the polyester/polycarbonate laminate ~ilms according to the invent;on are neither anticipated nor suggested by these three last-ment;oned Literature references.
For the preparation of the polycarbonate f;lm com-ponent, ~he polycondensatlon products obta;nable by react-ing d~phenols~ in part~cular dihydroxydiarylalkanes, w;thphosgene or d~esters of carbonic ac~d are suitable, and, 1n add;tion to the unsubstituted d;hydroxyd;arylalkales, those whose aryl rad;cals carry methyl groups or halogen atoms ;n the o-pos;tion andtor m-pos;t;on relat;ve to the 3û hydroxyl yroup are also su;table. Branched polycarbonates are l;kew;se su;table.
The su;table polycarbonates have weight-average molecular we;ghts Mw of between 10,000 and 100,000, preferably between 20,000 and 40,000, determined by measure-ments of the relat;ve v;scosity ;n CH2Cl2 at 25C and ata concentrat1on of 0.5 9 per 100 ml.
Le A 22 596-UB
~2~731S
Examples of su;table diphenols are hydroquinone, resorc;nol, 4,4'-d;hydroxyd;phenyl, b;s-(hydroxy-phenyl)-alkanes, such as, for example, C1~C8-alkylene-b;sphenols or c2-c8-alkyl;dene-b;sphenols, b;s-(hydroxy-phenyl)-5 cycloalkanes, such as, for example, C5-C15-cycloalkylene-bisphenols or C5-C15-cycloalkylidene-bisphenols and bis-(hydroxy-phenyl) sulphides, ethers, ketones, sulph-oxides or sulphones, ani~ also a,~ '-bis-(hydroxy-phenyl)-diisopropylbenzene and the corresponding compounds alky-10 lated in the nucleus or halogenated in the nucleus. Poly-carbonates based on 2,2-bis-(4-hydroxy-phenyl)-propane (bis-phenol A), 2,2-bis-(4-hydroxy-3,5-dichloro-phenyl)-propane (tetrachlorobisphenol A), 2,2-bis-(4-hydroxy-3,5-dibromo-phenyl)-propane (tetrabromobisphenol A), 2,2-bis-(4-hydroxy-15 3,5-dimethyl-phenyl)-propane (tetramethylbisphenol A) and 1,1-bis-(4-hydroxy-phenyl)-cyclohexane and those based on trinuclear bisphenols such as c~, a'-bis-(4-hydroxyphenyl)-p-diisopropylbenzene are preferred.
Further diphenols suitable for the preparat;on of 20 the polycarbonates are described, for example, in US Patent Specifications 3,028,365, 3~06Z,781, 3,148,172 and 3,271,367.
Polyalkylene terephthalates which are su;table according to the lnvention for the preparation of the poly-alkylene terephthalate film component ~) are reaction pro-25 ducts of aromatic d~carboxylic acids or their reactivederivatives tfor example dimethyl esters) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reactlon products~ They can be prepared by known methods. tIn this connect;on, see, for example, Kunststoff 30 Handbuch CPlastics Handbook], Volume VIII, pages 695 et seq., Carl Hanser Yerlag, Munich 1973).
Preferred polyalkylene terephthalates contain at least 8û mol X, in particular at least 90 mol X, relative to the d;carboxylic acid conponent, of terephthalic acid radi-35 cals and at least 80 mol X, in particular at least 90 mol X,relative to the diol component, of ethylene glycol and/or Le A 22 596-US
3~
butane-1,4-diole radicals, particularly preferably butane-1,4-diol radicals.
In addit;on to terephthalic acid radicals~ these preferred polyalkylene terephthalates can contain up to 2û mol % of radicals of other aromatic or cycloaliphatic dicarboxylic acids having 8-14 C atoms or al;phatic di~
carboxylic acids hav;ng 4-12 C atoms, such as, for example, rad;cals of phthalic ac;d, ;sophthal;c ac;d, naphthalene-Z,6-dicarboxylic ac;d, 4,4'-d;phenyld;carboxyl;c ac;d, succinic acid~ adipic acid, sebacic acid, azelaic acid and cyclohexanediacet;c ac;d.
In add;t;on to ethanediol or butane-1,4-diol radi-cals, these preferred polyalkylene terephthalates can con~
tain up to 20 mol % of other aliphatic diols having 3-12 C atoms or cycloaliphat;c d;ols having 6-21 C atoms, for example radicals of propane~1,3-diol, 2-ethylpropane-1,3-diol, neopentyl glycol, pentane-1,5-d;ol, hexane-1,6-diol, cyclohexane-1,4-d;methanol, 3-methylpentane-2,4-d1ol, 2-methyl-pentane-2,4-diol, Z,2,4-trimethylpentane-1,3-d;ol and -1,6-dioll 2~ethylh~ -1,3-diol, 2,2 ~iethylpropane-1,3~ iol, heKane-2,5 dlol, 2,2-bis-~-h~droxycyclohexyl)-propane and 2,~-dihydroxy-1,1,3,3-tetrc~m~thy.~clobutane, and such with arcm~tic residues l.Uke ~ di-(B-h~drox~ethox~).-Y~nzen~, 2,2-bi~-(3-~-hydroxy-ethoxy-phenyl)~propane and 2,2 bis-~4-hydroxypropoxy-phenyl)-propane ~DE-OS ~German Publlshed Specif~cation) 2,407,674, DE-OS ~German Publ~shed Specif~cation) 2,407,776 and DE-OS
~German Published Specif;cation) 2,715,932).
The polyalkylene terephthalates can be branched by incorporation of relatively small quantities of trihydric or tetrahydric alcohols or 3-basic or 4-basic carboxylic acids, such as are described, for example, in DE-OS (German Published Specification) 1,900,270 and US Patent Specifi-cation 3,692,744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane and pentaerythritol.
It is advisable to use not more than 1 mol X of the Le A 22 596-US
-branching agent, relative to the acid component.
Polyalkylene terephthalates which are particularly preferred are those which have been prepared solely from ~erephthalic acid or its reactive derivatives (for example its dialkyl esters) and ethylene glycol and/or butane-1,4-diol~ and very particularly from butane-1,4-diol~
The polyalkylene terephthalates used have in gene-ral an intrinsic viscosity of 0.4 to 1.5 dl/g, preferably 0.5 - 1.3 dltg, and in particular 0.6 - 1.2 dl/g, each measured in phenol/o-d;chlorobenzen~ 1 ;n parts by we;ght) at 25C.
The preparat;on of the laminate films according to the ;nvent;on is carried out by a co-extrusion process, the melt of the two components A) and ~) be;ng fed v;a a two~
layer adaptor at temperatures of about 260C to about 290C to a slot d;e, and the melt web be;ng stretched over a chill-roll take-off. The f;rst take-off roll must here be strongly cooled ttemperature 10C to 50C) and can be prov;ded, as required, w;th a pol;shed surface or structured surface~
The important point here is that the cooling of the melt web takes place w;th;n a~s to 3 seconds.
The present ;nvention thus also relates to a pro-cess for prepar;ng the laminate f;lms according to the in-vention, ~hich process i3 characterised in that the melts ofthe two components A~ and B) are fed via a two-layer adap-tor at temperatures of 200C to 290C to a slot die, and that the melt web ;s stretched over a chill-roll take-off, ;t being necessary for the f;rst take-off roll to be cooled to temperatures of about 10C to 50C, and the surface of this take-off roll being provided, as required, with a polished surface or a structured surface.
The films according to the invent;on can, on one s;de, have the surface wh;ch ;s requ;red ;n practice and 3S has a matt structure and is solvent-resistant, as a result of the polyalkylene terephthalate component, and, on the Le A 22 596-us 73~.~
other s;de, the required easy printability on the back, as a result of the polycarbonate component. Furthermore, these films are highly transparent, so that the inks printed on the back are cLearly visible ~;th a good effect of depth, when ~iewed from the front.
The fact that such high-grade films can be obtained by co-extrusion of polycarbonate and polyalkylene tereph-thalate is surprising, inasmuch as, on the one hand, poly-alkylene terephthalates are partiaLly crystalline poly-mers, the melts of which must be cooled very rapidly totemperatures below their particular glass transition point TG, which is between 80C and 40C, in order to obtain transparency of polyalkylene terephthalate films, and, on the other hand, polycarbonate melts must be cooled rela-tively slowly, in order to obtain polycarbonate films oflow strain and having the necessary surface qual;ty. In spite of the rapid cooling in the co-extrusion process according to the invention, the surface quality of the poly-carbonate fllm component A) is good and comparable to that of pol`ycarbonate films obtained by extrusion and slow cooling.
When a take-off roll with a structured surface is used, the poly~len~ terephthalate surface of the laminate film correspondingly has a matt structure, if the poly-ZS alkylene terephthalate layer faces the structured roll sur-~ace during the co-extrusion~
A further preparation variant for the laminate films accordin~ to the invention consists in coating an unstretched polyalkylene terephthalate film, which is bright on both s;des, on one side with a melt of polycarbo~
nate, the polyalkylene terephthalate film running ontG a cooling roll with a structured surface, and the melt web of the polycarbonate melt being pressed by means of a fur-ther roll, preferably coated with heat-resistant rubber~
against the polyalkylene terephthalate film. Due to the heat capacity of the polycarbonate melt, the polyalkylene Le A 22 596-US
~2~73~.S
terephthalate f;lm is softened to such an extent that ;t assumes the surface structure of the cooling roll~ By con-trast, attempts to laminate films of polyalkylene tereph-thalate with films of polycarbonate did not lead to the laminate films according to the invention, with the de-sired pattern of properties, above all because ctreaks in the laminating adhesive become visible during the subse-quent printing on the polycarbonate side, and s;nce only the variant with a glossy, that is to say polished viewing side, is available.
The present invention therefore also relates to a process for preparing the laminate films according to the invention from the components A) and ~), which process is characterised in that a transparent, unstretched thermo-plastic polyalkylene terephthalate film, according to com-ponent ~ hich is bright on both sides and has a thick-ness of 10 ,um to 100 ,um, is coated on one side with a hot melt, at a temperature between 270 and 330C, of thermo-plastic, transparent polycarbonate, the polyalkylene tereph-thalate film running onto a cooling roll wi~h a structuredsurface and at a tempera~ure of 10C to 50C, and the melt web of the polycarbonate melt being pressed by means of a further roll, preferably coated with heat-resistant rubber, a~alnst the polyalkylene terephthalate film under a pre~sure of 0.1 to 10 kp/cm of roll length.
Example A homopolycarbonate of Z,2-bis-(4-hydroxyphenyl)-propane having a relative viscosity of 1.4Z tmeasured at 25C in CHzCl2 and at a concentration of 0.5 g/100 ml by means of an Ubbelohde viscometer) is melted in a single-screw extruder at barrel temperatures of 300C, and the melt is fed via a two-layer adaptor to a slot die.
A polybutylene terephthalate having an ;ntrinsic viscosity of 1.25 (measured in phenol~o-dichlorobenzene at 25C) is melted in a single-screw extruder, and the melt is likewise fed via the t~o-layer adaptor to the common Le A 22 596-U~
~2~7315 _ 9 _ slot die. The channel cross-section of the adaptor for the polycarbonate melt is greater than that for the polybuty-Lene terephthalate melt by a factor of 3.
The melt of the polymers, layered above one ano~
ther, is forced out of the d;e gap of the slot d;e onto a cool;ng roll which has a structured surface and a sur-face temperature of 23C. The f;lm obta;ned by cooling of the melt is h;ghly transparent, and the polybutylene terephthalate layer has a structured surface wh;ch ;s in-sens;t;ve to scratch;ng.
Le A 22 596-US
., ,
Claims (12)
1. A transparent laminate film, consisting of A) a transparent, thermoplastic polycarbonate film of a thickness from 50 µm to 350 µm and B) a transparent, thermoplastic polyalkylene terephthalate film of a thickness from 10 µm to 100 µm.
2. A laminate film according to Claim 1, in which the thickness of the polycarbonate film is 100 µm to 200 µm.
3. A laminate film according to Claim 1 or 2, in which the thickness of the polyalkylene terephthalate film is 23 µm to 50 µm.
4. A laminate film according to Claim 1 wherein the polycarbonate film of component A) is formed from a polycarbonate based on bisphenol A, tetrachloro-bisphenol A, tetrabromobisphenol A, tetramethy-bisphenol A, 1,1-bis-(4-hydroxy-phenyl)-cyclohexane or .alpha.,.alpha.'-bis-(4-hydroxyphenyl)-p-diisopropylbenzene.
5. A laminate film according to Claim 1 in which the polyalkylene terephthalate film of component B) is formed from a polyalkylene terephthalate which contains at least 80 mol %, relative to the dicarboxylic acid component, of terephthalic acid radicals, at least 80 mol %, relative to the diol component, of ethylene glycol and/or butane-1,4-diol radicals, 0 to 20 mol % of radicals of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyl-dicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid or cyclohexanediacetic acid, and 0 to 20 mol % of radicals selected from propane-1,3-diol, 2-ethylpropane-1,3-diol, neopentyl glycol, pentane-1,5-diol, hexane-1,6-diol, cyclohexane-1,4-dimethanol, 3-methylpentane-2,4-diol, 2-methylpentane-2,4-diol, 2,2,4-trimethylpentane-1,3-diol and -1,6-diol, 2-ethylhexane-1,3-diol, 2,2-diethylpropane-1,3-diol, hexane-2,5-diol, 1,4-di-(.beta.-hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexane)-propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis-(3-.beta.-hydroxyethoxy-phenyl)-propane and 2,2-bis-(4-hydroxy-propoxy-phenyl)-propane.
6. A laminate film according to Claim 1 in which the polyalkylene terephthalate film of component B) is formed from a polyalkylene terephthalate which has been prepared solely from terephthalic acid or its dialkyl ester, and ethylene glycol and/or butane-1,4-diol.
7. A laminate film according to Claim 6 in which the polyalkylene terephthalate has been prepared solely from terephthalic acid or its dialkyl ester and butane-1,4-diol.
8. A process for the production of a laminate film which film consists of a transparent thermoplastic polycarbonate film having a thickness of 50 to 350 microns and a transparent thermoplastic polyalkylene terephthalate film having a thickness of from 10 to 100 microns comprising:
(i) feeding the melts of a thermoplastic polycarbonate and of a thermoplastic polyalkylene terephthalate via a two layer adaptor at a temperature of 260°C to 290°C to a slot die and stretching the melt web over a chill-roll take-off with the proviso that the first take-off roll is to be cooled to a temperature of about 10 to 50°C and that the surface of the take-off roll is either polished or structured.
(i) feeding the melts of a thermoplastic polycarbonate and of a thermoplastic polyalkylene terephthalate via a two layer adaptor at a temperature of 260°C to 290°C to a slot die and stretching the melt web over a chill-roll take-off with the proviso that the first take-off roll is to be cooled to a temperature of about 10 to 50°C and that the surface of the take-off roll is either polished or structured.
9. A laminate film consisting of (a) a transparent thermoplastic polycarbonate film having a thickness of 50 to 350 microns and (b) a transparent thermoplastic polyalkylene terephthalate film having a thickness of 10 to 100 microns produced by the process of Claim 8.
10. A switch panel fabricated from a laminate film as defined in Claim 1.
11. Name plates fabricated from a laminate film as defined in Claim 1.
12. A foil switch fabricated from a laminate film as defined in Claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843401480 DE3401480A1 (en) | 1984-01-18 | 1984-01-18 | COMPOSITE FILMS OF POLYCARBONATES AND POLYALKYLENE TEREPHTHALATES |
| DEP3401480.2 | 1984-01-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1247315A true CA1247315A (en) | 1988-12-28 |
Family
ID=6225182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000472212A Expired CA1247315A (en) | 1984-01-18 | 1985-01-16 | Laminate films of polycarbonates and polyalkylene terephthalates |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0150004B1 (en) |
| JP (1) | JPS60162646A (en) |
| CA (1) | CA1247315A (en) |
| DE (2) | DE3401480A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2032187A1 (en) * | 1990-01-03 | 1991-07-04 | Harold Frazee Giles, Jr. | Polycarbonate/copolyetherester composites |
| DE4202975A1 (en) * | 1992-02-03 | 1993-08-05 | Bayer Ag | Decorative laminate - comprises thermoplastic synthetic foil, decorative colour or adhesive layer, thermoplastic synthetic layer, and opt. top lacquer layer |
| GB2276347B (en) * | 1993-03-26 | 1997-01-29 | Toyo Kohan Co Ltd | Double layered thermoplastic resin laminated metal sheet |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54142271A (en) * | 1978-04-28 | 1979-11-06 | Kureha Chem Ind Co Ltd | Multi-layer blow molded article |
-
1984
- 1984-01-18 DE DE19843401480 patent/DE3401480A1/en not_active Withdrawn
-
1985
- 1985-01-07 EP EP85100118A patent/EP0150004B1/en not_active Expired
- 1985-01-07 DE DE8585100118T patent/DE3563928D1/en not_active Expired
- 1985-01-14 JP JP60003447A patent/JPS60162646A/en active Granted
- 1985-01-16 CA CA000472212A patent/CA1247315A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3401480A1 (en) | 1985-10-24 |
| EP0150004A3 (en) | 1986-11-20 |
| DE3563928D1 (en) | 1988-09-01 |
| EP0150004A2 (en) | 1985-07-31 |
| JPS60162646A (en) | 1985-08-24 |
| EP0150004B1 (en) | 1988-07-27 |
| JPH0327021B2 (en) | 1991-04-12 |
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