CA1040520A - Heat-adhesive laminated film - Google Patents
Heat-adhesive laminated filmInfo
- Publication number
- CA1040520A CA1040520A CA191,607A CA191607A CA1040520A CA 1040520 A CA1040520 A CA 1040520A CA 191607 A CA191607 A CA 191607A CA 1040520 A CA1040520 A CA 1040520A
- Authority
- CA
- Canada
- Prior art keywords
- film
- heat
- block copolymer
- terephthalate
- adhesive laminated
- 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
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
- B32B15/09—Layered products comprising a layer of metal comprising metal 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 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
-
- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/516—Oriented mono-axially
-
- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
-
- 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
- B32B2307/70—Other properties
- B32B2307/718—Weight, e.g. weight per square meter
-
- 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
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/08—Dimensions, e.g. volume
- B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
- B32B2309/105—Thickness
-
- 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
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/12—Copper
-
- 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
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/24—Aluminium
-
- 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
- B32B2405/00—Adhesive articles, e.g. adhesive tapes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
HEAT-ADHESIVE LAMINATED FILM
ABSTRACT OF THE DISCLOSURE
A heat-adhesive laminated film comprising a base film formed of plastic material having excellent heat resistance, such as a polyester, polyamide or polycarbonate, or formed of metal foil, such as aluminum or copper foil, and a film of a resin laiminated on at least one side of said base film. The resin comprises predominently a block copolyester having a melting point higher than 180°C but lower then the temperature at which the characteristics of the base film deteriorate and having a Young's modulus c (dyne/cm2) and a breaking elongation (.DELTA.?/?o) X 100 (%) when measured at 20°C and 130°C which satisfy, respectively, the following relationships:
107 (dyne/cm2) <.epsilon.<1010 (dyne/cm2) (.DELTA.?/?o) X 100 > 40 (%). These laminated films possess improved heat resistance and heat-seal strength and are useful in the packaging of food intended for extended storage, for packaging sterilized medical instruments and in the electrical field.
ABSTRACT OF THE DISCLOSURE
A heat-adhesive laminated film comprising a base film formed of plastic material having excellent heat resistance, such as a polyester, polyamide or polycarbonate, or formed of metal foil, such as aluminum or copper foil, and a film of a resin laiminated on at least one side of said base film. The resin comprises predominently a block copolyester having a melting point higher than 180°C but lower then the temperature at which the characteristics of the base film deteriorate and having a Young's modulus c (dyne/cm2) and a breaking elongation (.DELTA.?/?o) X 100 (%) when measured at 20°C and 130°C which satisfy, respectively, the following relationships:
107 (dyne/cm2) <.epsilon.<1010 (dyne/cm2) (.DELTA.?/?o) X 100 > 40 (%). These laminated films possess improved heat resistance and heat-seal strength and are useful in the packaging of food intended for extended storage, for packaging sterilized medical instruments and in the electrical field.
Description
r`\ ~
~1~)4~)5~
The present invention relates to a heat-adhesive laminated film having excellent heat resistance. ~lore particularly, it relates to a heat-adhesive laminated film produced by laminating a film of plastic material having excellent heat resistance, such as a polyester, polyamide or polycarbonate film or a metal foil, such as aluminum or copper foil, with a film of a resin `
comprising predominantly a block copolyester.
The subject matter of this specification is closely related to that of copending Canadian patent application Serial No. 191,606 filed on February 1, 1974, by the applicants of this application.
Hitherto, heat resistant film such as polyester film, polyamide film or polycarbonate film and metal foil such as a]uminum foil or copper foil have been variously used for food packaging? insulating material, tape or the like due to their ~ ;
excellent mechanical,electrical and chemical properties (e.g. ~;
chemical proofing, oil resistance and water proofing), heat j,, resistance and coldproofing. Usually, they have been used in the form of laminates partially or wholly with each other or with 20 other plastic film or metal foil. ~owever, such plastic film `~
j or metal foil per se has no heat-adhesive property and therefore there have been proposed methods for giving them such property. Among these methods laminating a thermoplastic ;
resin on the surface of the film has been preferred because such resin can be adhered by heating under pressure for short time and does not give rise to the problem of pot life. Due to this poor heat resistance of the thermoplastic resin, however, when the thermoplastic resin is laminated, the inherent heat resistance of polyester film, polyamide film or polycarbonate film can not be effectively utilized.
"
sz~ ~
Accordingly, there has been a need for a film (laminate) having both of excellent heat resistance and excellent heat adhe-sion for use in the packaging and electrical fields.
In the packaging field for medical instruments and foods, the packaged material is usually sterilized by heating at above 100C, usually at 110 to 120C. For complete sterilization-it is necessary to heat at about 120C for 15 or more minutes in - la -!~, ,,J
, ~ ' . . " '' 1C14~5;~
- a retort pouch (pressure vessel for sterilization). In addition to the steriliza~lon step a further treatment in the retort pouch is required for about same time before and after the sterilization.
It would therefore be desirable if the sterilization time could be shortened in order to rationalize the retort treatment and for reducing the cost. The heat sterilizatic.~ procedure should be carried out at sufficiently high temperature and for enough time to kill the spores of bacteria which have high heat - resistance, and the relation between the temperature and time sufficient for killing the spores is shown by the "longarithmic rule". That is, the number of killed spores varies longarithmically in accordance with change of temperature and the tlme. Accordingly, when the sterillzation temperature ls raised, the sterilization time can be largely reduced.
Conventionally, the film used for forming a retort pouch has been a laminated (two layer) film comprising polyethylene film and polyester film, polyamide film or polycarbonate film, ` `~
or a three layer film having aluminum foil between the two layers of the above laminated film. In these laminated films, the polyester film, polyamide film and polycarbonate film has been used for the purpose of affording mechanical strength and providing heat resistance and coldproofing of the laminate, ~he metal foil such as aluminum foil has been used as a barrier mainly from oxygen, steam, light and ultraviolet rays, and the polyethylene film has been used mainly for the purpose of giving heat-sealing characteristics to the laminate. A container made from these laminating materials must withstand the high temperature and high pressure in the retort sterilization step, but in fact may barely tolerate the conventional retort sterilization temperature of about 120C as far as the polyethylene film is concerned. However, for rationalization of the retort treatment, a still higher sterilization temperature is desirable, and therefore, there has been a need to develop an improved heat
~1~)4~)5~
The present invention relates to a heat-adhesive laminated film having excellent heat resistance. ~lore particularly, it relates to a heat-adhesive laminated film produced by laminating a film of plastic material having excellent heat resistance, such as a polyester, polyamide or polycarbonate film or a metal foil, such as aluminum or copper foil, with a film of a resin `
comprising predominantly a block copolyester.
The subject matter of this specification is closely related to that of copending Canadian patent application Serial No. 191,606 filed on February 1, 1974, by the applicants of this application.
Hitherto, heat resistant film such as polyester film, polyamide film or polycarbonate film and metal foil such as a]uminum foil or copper foil have been variously used for food packaging? insulating material, tape or the like due to their ~ ;
excellent mechanical,electrical and chemical properties (e.g. ~;
chemical proofing, oil resistance and water proofing), heat j,, resistance and coldproofing. Usually, they have been used in the form of laminates partially or wholly with each other or with 20 other plastic film or metal foil. ~owever, such plastic film `~
j or metal foil per se has no heat-adhesive property and therefore there have been proposed methods for giving them such property. Among these methods laminating a thermoplastic ;
resin on the surface of the film has been preferred because such resin can be adhered by heating under pressure for short time and does not give rise to the problem of pot life. Due to this poor heat resistance of the thermoplastic resin, however, when the thermoplastic resin is laminated, the inherent heat resistance of polyester film, polyamide film or polycarbonate film can not be effectively utilized.
"
sz~ ~
Accordingly, there has been a need for a film (laminate) having both of excellent heat resistance and excellent heat adhe-sion for use in the packaging and electrical fields.
In the packaging field for medical instruments and foods, the packaged material is usually sterilized by heating at above 100C, usually at 110 to 120C. For complete sterilization-it is necessary to heat at about 120C for 15 or more minutes in - la -!~, ,,J
, ~ ' . . " '' 1C14~5;~
- a retort pouch (pressure vessel for sterilization). In addition to the steriliza~lon step a further treatment in the retort pouch is required for about same time before and after the sterilization.
It would therefore be desirable if the sterilization time could be shortened in order to rationalize the retort treatment and for reducing the cost. The heat sterilizatic.~ procedure should be carried out at sufficiently high temperature and for enough time to kill the spores of bacteria which have high heat - resistance, and the relation between the temperature and time sufficient for killing the spores is shown by the "longarithmic rule". That is, the number of killed spores varies longarithmically in accordance with change of temperature and the tlme. Accordingly, when the sterillzation temperature ls raised, the sterilization time can be largely reduced.
Conventionally, the film used for forming a retort pouch has been a laminated (two layer) film comprising polyethylene film and polyester film, polyamide film or polycarbonate film, ` `~
or a three layer film having aluminum foil between the two layers of the above laminated film. In these laminated films, the polyester film, polyamide film and polycarbonate film has been used for the purpose of affording mechanical strength and providing heat resistance and coldproofing of the laminate, ~he metal foil such as aluminum foil has been used as a barrier mainly from oxygen, steam, light and ultraviolet rays, and the polyethylene film has been used mainly for the purpose of giving heat-sealing characteristics to the laminate. A container made from these laminating materials must withstand the high temperature and high pressure in the retort sterilization step, but in fact may barely tolerate the conventional retort sterilization temperature of about 120C as far as the polyethylene film is concerned. However, for rationalization of the retort treatment, a still higher sterilization temperature is desirable, and therefore, there has been a need to develop an improved heat
- 2 -104~5Z0 ~
adhesive laminate capable of tolerating higher sterilization temperatures, such as 130~C or more.
In addition, for electrical parts there have been used laminates of a metal foil such as alumlnum foil or copper foil with polyester film, polyamide film or polycarbonate film for electrical heating elements and printed circuit, and the films and ; foils are required to have heat adhesion and heat resistance properties.
These requirements are explained in detail below.
Generally, for providing excellent heat adhesion proper~ies in a film, the heat adhesive resin layer of the Pilm should:
(1) be able to be liquefied by heating and thereby flowed every nook and corner of the surface of the ob~ect to which it is to be adhered, (2) have good affinity with the object to which it is to be adhered, exhibit good thermodynamic wetting, and stimulate the intermolecular forces between the resin and the object,
adhesive laminate capable of tolerating higher sterilization temperatures, such as 130~C or more.
In addition, for electrical parts there have been used laminates of a metal foil such as alumlnum foil or copper foil with polyester film, polyamide film or polycarbonate film for electrical heating elements and printed circuit, and the films and ; foils are required to have heat adhesion and heat resistance properties.
These requirements are explained in detail below.
Generally, for providing excellent heat adhesion proper~ies in a film, the heat adhesive resin layer of the Pilm should:
(1) be able to be liquefied by heating and thereby flowed every nook and corner of the surface of the ob~ect to which it is to be adhered, (2) have good affinity with the object to which it is to be adhered, exhibit good thermodynamic wetting, and stimulate the intermolecular forces between the resin and the object,
(3) capable of being solidified rapidly,
(4) have a small residual stress, and
(5) have such good flexibility that stress concentration does not occur when the layer is destroyed, and simultaneously exhibit a good enough cohesive force to resist to destruction. ;
The property to resist to desctruction means that after the laminated film is adhered or heat-sealed, the film must satisfy the condition mentioned in item t5) at high temperature when it is treated at high temperature. Moreover, the laminated film is generally used over a wide range of temperature from high temperatures to room temperature, and therefore the resin must have such good dynamlc property as to satisfy the condition mentioned in item (5) over a wide range of temperatures from high temperatures such as 130C or more to low temperatures such as room or lower temperature.
Thus, among the above-mentioned conditions (1) to (5), the condition (5), 104~)~Z(~
i.e. the dynamic property, plays a most important role in giving to the laminated film excellen~ adhesion strength and heat-seal ;: .:., strength over a wide range of temperature and the dynamic property is effected largely by the thermic property of the adhesive resin.
That is, the adhesive resin layer preferably has a glass transition ~: .: .:
point of less than room temperature and also a melting point of more than 130C as thermic properties, for affording the laminated ilm such excellent adhesion strength or heat-seal strength over a wide range of temperature. ~ -It has now been found that for obtaining a film having the desired excellent adhesion strength and heat-seal strength `
over the indicated temperature range, the dynamic properties of the adhesive resln layer must satisfy the fol1owing conditlons -at 20C and 130C. That is, when measured at a crosshead speed of 30 cm/minute, it has a Young's modulus ~ satisfying the -relationship: ~
. .
107 (dyne/cm2) < ~ < 101 (dyne/cm2) and a breaking elongation (~/Qo) X 100 (a rate of elongation to the initial length):
(~/Qo) X 100 > 40 (%) When the adhesive resin layer has a Young's modulus :
of 10 dyne/cm2 or more, the adhesive resin layer becomes hard and glass-like, and thereby surface stress concentration can occur to give a product having poor adhesion strength or heat- -seal strength. On the other hand, when the adhesive resin layer has a Young's modulus of 107 dyne/cm2 or less, the layer becomes soft and can not retain sufficiently good cohesive force to resist to destruction and does not show excellent adhesion strength or heat-seal strength even if the breaking elongation is more than 40 %. In addition, when the adhesive resin layer has a breaking elongation of 40 % or less, the layer is not tough enough to resist ~o destruction and does not have excellent ~-adhesion strength or heat-seal strength either, even if the Young~s .
~i4~15ZO ~
modulus is in a range of 10 (dyne/cm ) ~ ~ ~ 10 (dyne/cm2).
It is preferable that the adhesive resin layer should show a Young's modulus and breaking elongation in the above range even at temperatures above 130C.
Accordingly, the invention provides a heat-adhesive laminated film comprising a base film formed of a plastic film formed of a polyester, polyamide, or polycarbonate or a metal foil selected from aluminum and copper foils, and a film of a resin laminated to one or both sides thereof said resin com-prising predominantly a block copolyester comprising (1) acrystalline polyester segment having a melting point of at least 200C. and a molecular weight of from 400 to 10,000, and (2) a polymer segment of either a polyether or a polyester, having a low melting point, a molecular weight of from 400 to 6,000 and present in a proportion of 5 to 80 percent by weight of the block copolymer, said resin having a melting point higher than 180C but lower than the temperature at which the characteristics of the base film deteriorate and having a Young's modulus ~(dyne/cm2) and a breaking elongation (~Q/Qo) X 100 (%) when measured at 20C and 130C which satisfy, respectively, the Eollowing relationships:
107 (dyne/cm2) ~ ~ < 101 (dyne/cm2) and (~Q/Qo) X 100 > 40 (%).
The laminated film of the invention can be produced by laminating a block copolyester film on a base film comprising a plastic film or a metal foil.
The plastic film used as the base film may be formed of polyester (e.g. polyethylene terephthalate, poly(ethylene terephthalate/ethylene isophthalate), polytetramethylene tere- ;
phthalate, or polyethylene-1,?-diphenoxyethane~4,4'-dicarboxylate), a polyamide (e.g. nylon 6, nylon 66, nylon 6/10, or polyxylylene ~ - 5 -104052~
.
adipamide), a polycarbonate (e.g. 4~4'-dihydroxydiphenyl-2,2-propane, i.e. bisphenol A), a copolymer formed predominantly from the monomers of any of the above polymers, or a mixture of any of these polymers or copolymers with another polymer having similarly excellent or superior heat resistance. The plastic film may be non-oriented film, uniaxially oriented film, or biaxially oriented film, but biaxially oriented film is particularly preferred. The plastic film may include one or more other additives such as an antistatic agent, a lubricant, : ' ' ' "' ':.
, - 5a -' . '.
:.
104~S2~
a haze preventing agent, a plasticizer, a stabi~izer, an anti-blocking agent, or a colorant. Suitable metal foils include aluminum and copper foils. The base film used in the present invention preferably has a melting point of 200C or more.
The block copolyester to be laminated on the base film comprises a crystalline polyest~r segment having a high melting point and a polymer segment having a low melting point and a molecular weight of 400 or more. As mentioned above, the block copolyester has a melting point higher than 180C but lower than the temperature at which the characteristics of the base film deteriorate, and further has the dynamic properties (when it is distorted at 20C and 130C at a crosshead speed of 30 cm/minute) of Young's modulus E (dyne/cm2) and a breaking elongatlon (~Q/Qo) X 100 (%) whlch satisfy the following relationships:
(dyne/cm ) < E < 10 (dyne/cm ) and (QQ/Qo) X 100 > 40 (%) The temperature at which the characteristlcs of the base fllm deteriorate means the temperature at which the dynamic properties of the base film deteriorate, when the base film comprises a polymer havlng excellent heat reslstance such as a polyester, polyamide or polycarbonate, and this temperature will usually be about 20C lower than the meltlng point of the polymer (base film). When the base film comprises a metal foil, the temperature will be about 300C, since the characteristics of metal foil only change at higher temperature.
The component of the crystalline polyester segment may be one which would have a melting point of 200C or more if a --~
polymer having fiber-forming properties were to be produced from the component alone. An example of such a crystalline polyester segment is one comprising an aromatic polyester unit -having a bond in the para position, such as an ethylene tere-, ~. . .
phthalate unit, tetramethyle~e terephthalate unit or the like as "~ ~
,' .
~4~52 [) the main compo`nent, preferably 70 or more % by weight of ethylene terephthalate unit or tetramethylene tetraphthalate unit. It may partially contain a dibasic acid component, such as isophthalic acid, adipic acid, sebacic acid, or dodecanoic acid. The crystalline polyester segment having a high melting point has a molecular weight of 400 to 10,000.
The polymer segment having a low melting poin~ may be substantially amorphous in the block copolyester. Examples of polymer segments having a low melting point include polyethers, aliphatic polyesters and polylactones. The polymer segment usually has a molecular weight of 400 to 6,000, preferably 700 to 3,000. The ratio of the amount of polymer segment having a low melting point in the block copolyester is preferably in the range of 5 to 30 % by weight, more preferably from 10 to 60 % by weight, and most preferably from 20 to 50 % by weight.
Examples of suitable polymer segments having a low melting point include polyethylene oxide glycol, polytetramethylene oxide glycol, polyethylene adipate, polyethylene dodecanoate, polyneopentyl adipate, polyneopentyl sebacate, polyneopentyl dodecanoate, poly(e-caprolactone) and polypivalolactone.
Examples of the block copolyester include polyethylene terephthalate/polyethylene oxide block copolymer, polytetramethylene terephthalate/polyethylene oxide block copolymer, polyethylene terephthalate/polytetramethylene oxide block copolymer, polytetramethylene terephthalate/polytetramethylene oxide block copolymer, polyethylene terephthalate/poly--caprolactone block copolymer, polytetramethylene terephthalate/poly-~-caprolactone block copolymer polyethylene terephthalate/polypivalolactone block copolymer, polyethylene terephthalate/polyethylene adipate block copolymer, polyethylene terephthalate/polyneopentyl sebacate block copolymer, polytetramethylene terephthalate/polyethylene dodecanoate block copolymer, polytetramethylene terephthalatet polyneopentyl dodecanoate block copolymer polyethylene terephthalate~
, , ~ . ..
104~52~
isophthalate/polytetramethylene oxide block copolymer and polytetramethylene terephthalate-isophthalate/polytetramethylene oxide block copolymer.
The laminated film of the in~entlon may be produced by an extrusion lamination method, i.e. by melt-extruding the block copolyester and laminating it on the base Eilm, or by a dry lamination method, i.e. by applying an adhesive to either the base film or the block copolyester film, drying it and then laminating the two together. When the extrusion lamination method is used, the block copolyester film may be directly extruded and laminated on the base film, or optionally an adhesive may be applied to the base film and dried before the extrusion and lamination of the block copolyester fil~m. The laminated film may be also produced by applying a block copoly-ester solution on the base film by gravure roll coating, reverse~roll coating, rod coating or spray coating, and drying to remove the solvent.
The base film and the block copolyester may each have various thicknesses. The suitable thickness of each thereof ~ay be chosen according to the intended utility of the laminated Pilm and the conditions of use thereof. However, the thickness of the base film is preferably 10 ~ or more, particularly 10 to ,;~
500 ~, more particularly 10 to 30 ~ and that of the block -: .
copolyester film is preferably 30 ~ or more, particularly 30 . .
to 500 ~, more particularly 30 to 100 ~.
In the laminated film of the invention, other plastic `~
; film or metal foil may be optionally laminated on the outside of the base film or between the base film and the block copoly-ester film, or any other resin may be optionally coated thereon, or further there may be printed thereon.
The laminated film of the present invention can be heat-sealed without losing its dynamic properties. It presents ' ', . .:
., .. , . ~ .. . . . . .... . . . . . .
an attractive appearance and has excellent heat-seal strength over a wide range of temperature from below room temperature to high temperature such as more than 130C.
Moreover, the laminated film of the invention has excellent tear strength, pinhole resistance, impact strength, wear resistance, blocking resistance and oil resistance, and is furthermore nontoxic.
The present inveniton is illustrated by the following Examples in which parts are by weight, and the tests were carried out as follows:
~1) Young's modulus and breaking elongation The text material was melted, made into film and allowed to cool. The test film thus produced was cut into strips 1 cm in width and then allowed to stand at a prescribed temperature J~ r~
for 5 minutes using Tensilon (UTM-III type, made by Toyo Seiki K.K.). The load-elongation diagram was drawn at a gauge length of 1.5 cm and at a rate to pulling of 30 cm/minute, and thereby the Young's modulus (dyne/cm2) and the breaking elongation (~Q/Qo) X 100 (%) were calculated.
(2) Melting point ~y using a micromelting point apparatus (made by Yanagimoto Seisakusho), the temperature was raised at a rate of 1C/minute and the point was checked when the film became dark when observed by a polarmicroscope.
(3) Heat-seal strength of hhe laminated film Tensilon (UTM-III type, made by Toyo Seiki K.K.) was used. The heat-sealed laminated film was allowed to stand at a prescribed temperature for 5 minutes and then subjected to T-peel at a crosshead speed of 30 cm/minute.
Example 1 A stainless steel reactor was charged with dlmethyl terephthalate (10,000 parts), 1,4-butanediol (5,~00 parts) and titanlum tetrabutoxide (6 parts) and the mixture was subjected 9 ~
.... . ...
.. .
1(~4~5ZO
to ester exchange reaction at 140 to 230C in nitrogen gas.
The reaction mixture was added to a mixture of polytetramethylene oxide h,aving molecular weight of 1,000 (3,800 parts) and Irganox V 'I )'d l ~ hl D ~
: A . lolo (antioxidant, made by Ciba-Geigy; 30 parts) which was preheated at 230C. The pressure in the reactor was gradually reduced with increasing temperature, and then the mixture was subjected to polycondensatlon reaction at 245C, at reduced -~
pressure of about 0.1 mmHg for 2 hours with agitation. The polytetramethylene terephthalate/polytetramethylene oxide block ~- 10 copolymer thus obtained was cooled with water and then pelleti~ed to give a cylindrical pellet having 3 mm in diameter and 3 mm in length which was dried at 80C, at about 0.1 mmHg for 5 hours.
The reduced viscosity of the copolymer thus obtalned was 1.7~ dl/g, which was measured at a concentration of 0.2 g/dl in phenol/
tetrachloroethane: 6/4 by weight and at 30C. The melting point thereof was 215C.
The block copolyester was heat-pressed at 230C, 4 kg/cm2 for 30 seconds using a iron plate coated with poly-! tetrafluoroethylene and then allowed to cool to give a film.
', 20 The dynamic properties of the film thus obtained were measured ` - ;~
at room temperature (20C), 130C and 160C.
~ s a base film there was used a biaxially oriented polyethylene terephthalats film of 19 ~ in thickness, and as an ad~esive there was used a 15 % (solids) solution of Vylon ,~
300 (made by Toyo Boseki K.K.)/Collonate L (made by Nippon Polyurethane K.K.): 95/5 by weight solids in ethyl acetate``.
The adhesive was applied to the base film by gravure coater , (100 mesh X 40 ~), and the resultant product was passed through a 2 m dryer at a rate of 30 m/mlnute, and a non-oriented block copolyester film of 40 ~ in thickness was laminated thereon at a nip temperature of 90 to 95C and a nip pressure of 5 kg/cm by the dry lamination method. Two sheets of the lamlnatecl film thus obtained were put togatller with the non-oriented block ...
. . , : .: .
4¢)52(;~
copolyester sides of both films facing each other, and then lt was heat-sealed at 250C, 2 kg/cm for one second. The dynamic properties of the block copolyester resin layer are shown in Table 1, and the heat-seal strength of the laminated film are shown in Table 2. For comparison, the dynamic properties and heat-seal strength of polyethylene and random copolyester which had similar melting point to-that of the present block copolyester were measured. The results are also shown in Table 1 and Table 2, respectively.
Comparative Examp].e 1 Example 1 was repeated except that the following random copolyester was used instead of block copolyester.
The random copolyester was polyethylene terephthalate/
dodecane dicarboxylate: 80/20 by molar ratio produced by a conventional ester exchange method from dimethyl terephthalate, ethylene glycol and dodecanedicarboxylic acid. It has an intrinsic viscosity of 0.695 dl/g which was measured in phenol/
1,1,2,2-tetrachloroethane: 6/4 by weight at 30C.
Comparative Example 2 -, Example 1 was repeated except that a high viscosity 'rrdde ~
A~ polyethylene (Hizex # 5600F, made by Mitsui Toatsu Chemicals Inc.) lnstead of block copolyester.
Comparative Example 3 Example 1 was repeated except that a low viscosity "~r~ "~
polyethylene (Sumikasen #F 702-2, made by Sumitomo Chemical Co., Ltd.) instead of block copolyester.
The heat-sealing of the random copolyester of Comparative Example 1 was carried out in the same manner as that of the present block copolyester. The polyethylenes of Comparative Examples 2 and 3 were heat-sealed as follows: Polyethylene was melt-extruded and laminated in the thickness of 40 ~ on biaxially oriented polyetllylene terephthalate film of 12 ~l in thickness. Two sheets of the laminated film thus obtainecl werc ~O~S2~
put together with the polyethylene layer sides of both films facing each other, and t.hen heat-sealed at 250C, 2 kg/cm2 for one second.
. Example _ _ ~ reak~.n~
nu~ber of Melting Young's ~odulus E ~dyne/cm ) ~longatlon adhesive point . (~ o)X 100 (~) . resin (C) I .
la~yer 20C 130C 160C 20C1130CI160C
Ex. 1 215 2.0 X 109 5.0 X 10~ ~,0 X 10~ 400 400 300 Ex. i 215 7,6 X 10~' ~.0 X 10~ 2.7 X 10~5o 20 10 Comp. 132 2.7 X 109 2.0 X 10~ * 200 100 * ~ :
Comp 110 3.3 X 109 . * 3 * i '~ .
.*~ Impossible to me~sure because the material had melted, :
Table 2 ~ :
,:
. . _ . ,:
Heat-seal streneth (~/cm) Example number o~ . ..
la~inated film 20C 160C
. _ ' " ~, ~xample 1 4000 500 Comp. ~xample 1 . 1000 50 Comp. ~xample 2 2400 0 . .
Comp, Example ~ 1500 _ _ ;
. ..
As will be clear from the above results, the laminated film having the block copolyester resin layer of the present .-~
invention showed excellent heat-seal strength not only at room .
temperature but also at the high temperature of 160C, while on the other hand, the laminated film of the Comparative Examples did not show such excellent heat-seal strength at high temperature. ~ 2 :
~ 1~4~35ZO
_xample 2 ;;
To biaxially oriented polyethylene terephthalate film of 12 ~ in thickness was applied isocyanate anchoring agent (EL 250, made by Toyo Ink K.K.; concentration: 4 %) by miller roll method, and the resultant was passed through 2 m dryer wherein it was dried by hot-air of 110C. On the coating layer the block copolyester of Example 1 was melt-extruded at resin temperature of 230C and laminated in thickness of 40 ~ at a :- rate of 40 m/minute. The laminated film thus obtained was heat-sealed, of which the heat-seal strength was measured in the same manner as described in Example 1. The heat-seal strength was 3600 g/cm at room temperature and 550 g/cm at 160C.
;~ Example 3 ; A stninless steel reactor was charged with dimethyl terephthalate (6,200 parts), 1,4-butanediol (4,000 parts) and tltanium tetrabutoxide (5.5 parts) and the mixture was subjected to ester exchange reaction at 140 to 230C in nitrogen gas. The reaction mixture was added to a mixture of polytetramethylene ` oxide having a molecular weight of 1,000 (5,000 parts) and d ~r/~ " ~
O Sumilizer BHT (antioxidant, made by Sumitomo Chemical Co., Ltd.;23 parts) which was preheated at 230C. The pressure in the reactor was gradually reduced while raising the temperature, and then the mixture was subjected top~ycondensation reaction at 245C, at reduced pressure of about 0.1 mmHg for 2 hours ~
with agitation to give polytetramethylene terephthalate/poly- r tetramethylene oxide block copolymer. The block copolymer thus obtained was dried at 80C, at reduced pressure of about 0.1 mmHg for 5 hours. The reduced viscosity (nsp/C) of the copolymer was 1.99 dl/g, which was measured at a concentration of 0.2 g/dl in phenol/tetrachloroethane: 6/4 by weight and at 30~C. The melting point thereof was 205C.
Tlle block copolyester was heat~p~essed at 230C, 4 kg/cm2 for 30 seconds by using an iron plate coated with ~3 ~:~
sz~
polytetrafluoroethylene and the allowed to cool to give a film.
The dynamic properties of the film thus obtained were measured at room temperature (20C), 130C and 150C. The results are shown in Table 3.
. ~.- .
: .:
Tabl e ~ ~ .
- , 2~reak~n~ elon~ation Young~s modullls E (dyne/cm ) (~leO)x 100 (~o) - - - - ~ ~ ~
20C 130C 150C 2~C 130~ 1 150C
_ _ _ .- ~:
1.0 X 109 3.5 X 10~ 2.0 X 108 500 400 300 ~
_ _ _ _ `, :' '.
As a base film there was used a biaxially oriented ~ ;
polyethylene terephthalate film of 19 ~ in thickness, nylon 66 .: . .
film of 20 ~ in thickness or polycarbonate film of 20 ~ in thickness, and as an ad,hesive there was used a 15 % (solids) , ~ r~
solution of Vylon 300 (made by Toyo Boseki K.K.)/Collonate L
"~d"~ar~' (made by Nippon Polyurethane K.K.): 95/5 by weight solids in ethyl acetate. The adhesive was applied to the base film by - gravure coater (100 mesh X 40 ~), the resultant was passed through 2 m dryer at a rate of 30 m/minute, and thereon a non-oriented block copolyester film of 40 ~ in thickness was laminated at nip temperature of 90 to 95C and at nip pressure of 5 kg/cm2 by dry lamination method. Two sheets of the ~
laminated film thus obtained were put together with the non- -oriented block copolyester sides of both films facing each other~
and then it was heat-sealed under the following conditions:
When polyethylene terephthalate film was used as the ,' base film: ;~
Temperature: 250C, Pressure: 2 kg/cm2/second ~
When nylon 66 film was used as the base film: ,~, Temperature: 240C, Pressure: 2 kg/cm2/second When polycarbonate obtained from bisphenol A was used ' 34~5;~0 as the base film: ~-Temperature: 220C, Pressure: 2 kg/cm2/second - The heat seal strength in each case are shown in Table 4.
~L `! ; ;
_ _ _'. .
Temperature :
Base f ilm 20~C j 150C
_ ~' ' iolyethylene terephthalate ~000 (,~/cm) 500 (g/cm) Nylon 66 2000 ~00 Polyc~rh onat e 2 800 '300 . . _ . ' .
Example 4 A stainless steel reactor was charged with dimethyl terephthalate (6,200 parts), ethylene glycol (5,000 parts), zinc acetate (5 parts) and antimony trioxide (3 parts) and the mixture was subjected to ester exchange reaction at 140 to 230C in nitrogen gas. The reaction mixture was added to a mixture of polytetramethylene oxide having molecular weight of 1,000 ` ~/ra~J~ "
(5,000 parts) and Irganox 1010 (antioxidant, made by Ciba-Geigy;
23 parts) which was preheated at 230C. The pressure in the reactor was gradually reduced while raising the temperature, -~
and then the mixture was subjected to polycondensation reaction at 245C, at reduced pressure of about 0.1 mmHg for 2 hours with agltation. The reaction product was dried at 80C, at reduced ;`
pressure of about 0.1 mmHg for 2 hours. The reduced viscosity ;
(nsp/C) of the copolymer thus obtained was 1.59 dl/g, which was measured at concentration of 0.2 g/dl in phenol/tetrachloroethane:
The property to resist to desctruction means that after the laminated film is adhered or heat-sealed, the film must satisfy the condition mentioned in item t5) at high temperature when it is treated at high temperature. Moreover, the laminated film is generally used over a wide range of temperature from high temperatures to room temperature, and therefore the resin must have such good dynamlc property as to satisfy the condition mentioned in item (5) over a wide range of temperatures from high temperatures such as 130C or more to low temperatures such as room or lower temperature.
Thus, among the above-mentioned conditions (1) to (5), the condition (5), 104~)~Z(~
i.e. the dynamic property, plays a most important role in giving to the laminated film excellen~ adhesion strength and heat-seal ;: .:., strength over a wide range of temperature and the dynamic property is effected largely by the thermic property of the adhesive resin.
That is, the adhesive resin layer preferably has a glass transition ~: .: .:
point of less than room temperature and also a melting point of more than 130C as thermic properties, for affording the laminated ilm such excellent adhesion strength or heat-seal strength over a wide range of temperature. ~ -It has now been found that for obtaining a film having the desired excellent adhesion strength and heat-seal strength `
over the indicated temperature range, the dynamic properties of the adhesive resln layer must satisfy the fol1owing conditlons -at 20C and 130C. That is, when measured at a crosshead speed of 30 cm/minute, it has a Young's modulus ~ satisfying the -relationship: ~
. .
107 (dyne/cm2) < ~ < 101 (dyne/cm2) and a breaking elongation (~/Qo) X 100 (a rate of elongation to the initial length):
(~/Qo) X 100 > 40 (%) When the adhesive resin layer has a Young's modulus :
of 10 dyne/cm2 or more, the adhesive resin layer becomes hard and glass-like, and thereby surface stress concentration can occur to give a product having poor adhesion strength or heat- -seal strength. On the other hand, when the adhesive resin layer has a Young's modulus of 107 dyne/cm2 or less, the layer becomes soft and can not retain sufficiently good cohesive force to resist to destruction and does not show excellent adhesion strength or heat-seal strength even if the breaking elongation is more than 40 %. In addition, when the adhesive resin layer has a breaking elongation of 40 % or less, the layer is not tough enough to resist ~o destruction and does not have excellent ~-adhesion strength or heat-seal strength either, even if the Young~s .
~i4~15ZO ~
modulus is in a range of 10 (dyne/cm ) ~ ~ ~ 10 (dyne/cm2).
It is preferable that the adhesive resin layer should show a Young's modulus and breaking elongation in the above range even at temperatures above 130C.
Accordingly, the invention provides a heat-adhesive laminated film comprising a base film formed of a plastic film formed of a polyester, polyamide, or polycarbonate or a metal foil selected from aluminum and copper foils, and a film of a resin laminated to one or both sides thereof said resin com-prising predominantly a block copolyester comprising (1) acrystalline polyester segment having a melting point of at least 200C. and a molecular weight of from 400 to 10,000, and (2) a polymer segment of either a polyether or a polyester, having a low melting point, a molecular weight of from 400 to 6,000 and present in a proportion of 5 to 80 percent by weight of the block copolymer, said resin having a melting point higher than 180C but lower than the temperature at which the characteristics of the base film deteriorate and having a Young's modulus ~(dyne/cm2) and a breaking elongation (~Q/Qo) X 100 (%) when measured at 20C and 130C which satisfy, respectively, the Eollowing relationships:
107 (dyne/cm2) ~ ~ < 101 (dyne/cm2) and (~Q/Qo) X 100 > 40 (%).
The laminated film of the invention can be produced by laminating a block copolyester film on a base film comprising a plastic film or a metal foil.
The plastic film used as the base film may be formed of polyester (e.g. polyethylene terephthalate, poly(ethylene terephthalate/ethylene isophthalate), polytetramethylene tere- ;
phthalate, or polyethylene-1,?-diphenoxyethane~4,4'-dicarboxylate), a polyamide (e.g. nylon 6, nylon 66, nylon 6/10, or polyxylylene ~ - 5 -104052~
.
adipamide), a polycarbonate (e.g. 4~4'-dihydroxydiphenyl-2,2-propane, i.e. bisphenol A), a copolymer formed predominantly from the monomers of any of the above polymers, or a mixture of any of these polymers or copolymers with another polymer having similarly excellent or superior heat resistance. The plastic film may be non-oriented film, uniaxially oriented film, or biaxially oriented film, but biaxially oriented film is particularly preferred. The plastic film may include one or more other additives such as an antistatic agent, a lubricant, : ' ' ' "' ':.
, - 5a -' . '.
:.
104~S2~
a haze preventing agent, a plasticizer, a stabi~izer, an anti-blocking agent, or a colorant. Suitable metal foils include aluminum and copper foils. The base film used in the present invention preferably has a melting point of 200C or more.
The block copolyester to be laminated on the base film comprises a crystalline polyest~r segment having a high melting point and a polymer segment having a low melting point and a molecular weight of 400 or more. As mentioned above, the block copolyester has a melting point higher than 180C but lower than the temperature at which the characteristics of the base film deteriorate, and further has the dynamic properties (when it is distorted at 20C and 130C at a crosshead speed of 30 cm/minute) of Young's modulus E (dyne/cm2) and a breaking elongatlon (~Q/Qo) X 100 (%) whlch satisfy the following relationships:
(dyne/cm ) < E < 10 (dyne/cm ) and (QQ/Qo) X 100 > 40 (%) The temperature at which the characteristlcs of the base fllm deteriorate means the temperature at which the dynamic properties of the base film deteriorate, when the base film comprises a polymer havlng excellent heat reslstance such as a polyester, polyamide or polycarbonate, and this temperature will usually be about 20C lower than the meltlng point of the polymer (base film). When the base film comprises a metal foil, the temperature will be about 300C, since the characteristics of metal foil only change at higher temperature.
The component of the crystalline polyester segment may be one which would have a melting point of 200C or more if a --~
polymer having fiber-forming properties were to be produced from the component alone. An example of such a crystalline polyester segment is one comprising an aromatic polyester unit -having a bond in the para position, such as an ethylene tere-, ~. . .
phthalate unit, tetramethyle~e terephthalate unit or the like as "~ ~
,' .
~4~52 [) the main compo`nent, preferably 70 or more % by weight of ethylene terephthalate unit or tetramethylene tetraphthalate unit. It may partially contain a dibasic acid component, such as isophthalic acid, adipic acid, sebacic acid, or dodecanoic acid. The crystalline polyester segment having a high melting point has a molecular weight of 400 to 10,000.
The polymer segment having a low melting poin~ may be substantially amorphous in the block copolyester. Examples of polymer segments having a low melting point include polyethers, aliphatic polyesters and polylactones. The polymer segment usually has a molecular weight of 400 to 6,000, preferably 700 to 3,000. The ratio of the amount of polymer segment having a low melting point in the block copolyester is preferably in the range of 5 to 30 % by weight, more preferably from 10 to 60 % by weight, and most preferably from 20 to 50 % by weight.
Examples of suitable polymer segments having a low melting point include polyethylene oxide glycol, polytetramethylene oxide glycol, polyethylene adipate, polyethylene dodecanoate, polyneopentyl adipate, polyneopentyl sebacate, polyneopentyl dodecanoate, poly(e-caprolactone) and polypivalolactone.
Examples of the block copolyester include polyethylene terephthalate/polyethylene oxide block copolymer, polytetramethylene terephthalate/polyethylene oxide block copolymer, polyethylene terephthalate/polytetramethylene oxide block copolymer, polytetramethylene terephthalate/polytetramethylene oxide block copolymer, polyethylene terephthalate/poly--caprolactone block copolymer, polytetramethylene terephthalate/poly-~-caprolactone block copolymer polyethylene terephthalate/polypivalolactone block copolymer, polyethylene terephthalate/polyethylene adipate block copolymer, polyethylene terephthalate/polyneopentyl sebacate block copolymer, polytetramethylene terephthalate/polyethylene dodecanoate block copolymer, polytetramethylene terephthalatet polyneopentyl dodecanoate block copolymer polyethylene terephthalate~
, , ~ . ..
104~52~
isophthalate/polytetramethylene oxide block copolymer and polytetramethylene terephthalate-isophthalate/polytetramethylene oxide block copolymer.
The laminated film of the in~entlon may be produced by an extrusion lamination method, i.e. by melt-extruding the block copolyester and laminating it on the base Eilm, or by a dry lamination method, i.e. by applying an adhesive to either the base film or the block copolyester film, drying it and then laminating the two together. When the extrusion lamination method is used, the block copolyester film may be directly extruded and laminated on the base film, or optionally an adhesive may be applied to the base film and dried before the extrusion and lamination of the block copolyester fil~m. The laminated film may be also produced by applying a block copoly-ester solution on the base film by gravure roll coating, reverse~roll coating, rod coating or spray coating, and drying to remove the solvent.
The base film and the block copolyester may each have various thicknesses. The suitable thickness of each thereof ~ay be chosen according to the intended utility of the laminated Pilm and the conditions of use thereof. However, the thickness of the base film is preferably 10 ~ or more, particularly 10 to ,;~
500 ~, more particularly 10 to 30 ~ and that of the block -: .
copolyester film is preferably 30 ~ or more, particularly 30 . .
to 500 ~, more particularly 30 to 100 ~.
In the laminated film of the invention, other plastic `~
; film or metal foil may be optionally laminated on the outside of the base film or between the base film and the block copoly-ester film, or any other resin may be optionally coated thereon, or further there may be printed thereon.
The laminated film of the present invention can be heat-sealed without losing its dynamic properties. It presents ' ', . .:
., .. , . ~ .. . . . . .... . . . . . .
an attractive appearance and has excellent heat-seal strength over a wide range of temperature from below room temperature to high temperature such as more than 130C.
Moreover, the laminated film of the invention has excellent tear strength, pinhole resistance, impact strength, wear resistance, blocking resistance and oil resistance, and is furthermore nontoxic.
The present inveniton is illustrated by the following Examples in which parts are by weight, and the tests were carried out as follows:
~1) Young's modulus and breaking elongation The text material was melted, made into film and allowed to cool. The test film thus produced was cut into strips 1 cm in width and then allowed to stand at a prescribed temperature J~ r~
for 5 minutes using Tensilon (UTM-III type, made by Toyo Seiki K.K.). The load-elongation diagram was drawn at a gauge length of 1.5 cm and at a rate to pulling of 30 cm/minute, and thereby the Young's modulus (dyne/cm2) and the breaking elongation (~Q/Qo) X 100 (%) were calculated.
(2) Melting point ~y using a micromelting point apparatus (made by Yanagimoto Seisakusho), the temperature was raised at a rate of 1C/minute and the point was checked when the film became dark when observed by a polarmicroscope.
(3) Heat-seal strength of hhe laminated film Tensilon (UTM-III type, made by Toyo Seiki K.K.) was used. The heat-sealed laminated film was allowed to stand at a prescribed temperature for 5 minutes and then subjected to T-peel at a crosshead speed of 30 cm/minute.
Example 1 A stainless steel reactor was charged with dlmethyl terephthalate (10,000 parts), 1,4-butanediol (5,~00 parts) and titanlum tetrabutoxide (6 parts) and the mixture was subjected 9 ~
.... . ...
.. .
1(~4~5ZO
to ester exchange reaction at 140 to 230C in nitrogen gas.
The reaction mixture was added to a mixture of polytetramethylene oxide h,aving molecular weight of 1,000 (3,800 parts) and Irganox V 'I )'d l ~ hl D ~
: A . lolo (antioxidant, made by Ciba-Geigy; 30 parts) which was preheated at 230C. The pressure in the reactor was gradually reduced with increasing temperature, and then the mixture was subjected to polycondensatlon reaction at 245C, at reduced -~
pressure of about 0.1 mmHg for 2 hours with agitation. The polytetramethylene terephthalate/polytetramethylene oxide block ~- 10 copolymer thus obtained was cooled with water and then pelleti~ed to give a cylindrical pellet having 3 mm in diameter and 3 mm in length which was dried at 80C, at about 0.1 mmHg for 5 hours.
The reduced viscosity of the copolymer thus obtalned was 1.7~ dl/g, which was measured at a concentration of 0.2 g/dl in phenol/
tetrachloroethane: 6/4 by weight and at 30C. The melting point thereof was 215C.
The block copolyester was heat-pressed at 230C, 4 kg/cm2 for 30 seconds using a iron plate coated with poly-! tetrafluoroethylene and then allowed to cool to give a film.
', 20 The dynamic properties of the film thus obtained were measured ` - ;~
at room temperature (20C), 130C and 160C.
~ s a base film there was used a biaxially oriented polyethylene terephthalats film of 19 ~ in thickness, and as an ad~esive there was used a 15 % (solids) solution of Vylon ,~
300 (made by Toyo Boseki K.K.)/Collonate L (made by Nippon Polyurethane K.K.): 95/5 by weight solids in ethyl acetate``.
The adhesive was applied to the base film by gravure coater , (100 mesh X 40 ~), and the resultant product was passed through a 2 m dryer at a rate of 30 m/mlnute, and a non-oriented block copolyester film of 40 ~ in thickness was laminated thereon at a nip temperature of 90 to 95C and a nip pressure of 5 kg/cm by the dry lamination method. Two sheets of the lamlnatecl film thus obtained were put togatller with the non-oriented block ...
. . , : .: .
4¢)52(;~
copolyester sides of both films facing each other, and then lt was heat-sealed at 250C, 2 kg/cm for one second. The dynamic properties of the block copolyester resin layer are shown in Table 1, and the heat-seal strength of the laminated film are shown in Table 2. For comparison, the dynamic properties and heat-seal strength of polyethylene and random copolyester which had similar melting point to-that of the present block copolyester were measured. The results are also shown in Table 1 and Table 2, respectively.
Comparative Examp].e 1 Example 1 was repeated except that the following random copolyester was used instead of block copolyester.
The random copolyester was polyethylene terephthalate/
dodecane dicarboxylate: 80/20 by molar ratio produced by a conventional ester exchange method from dimethyl terephthalate, ethylene glycol and dodecanedicarboxylic acid. It has an intrinsic viscosity of 0.695 dl/g which was measured in phenol/
1,1,2,2-tetrachloroethane: 6/4 by weight at 30C.
Comparative Example 2 -, Example 1 was repeated except that a high viscosity 'rrdde ~
A~ polyethylene (Hizex # 5600F, made by Mitsui Toatsu Chemicals Inc.) lnstead of block copolyester.
Comparative Example 3 Example 1 was repeated except that a low viscosity "~r~ "~
polyethylene (Sumikasen #F 702-2, made by Sumitomo Chemical Co., Ltd.) instead of block copolyester.
The heat-sealing of the random copolyester of Comparative Example 1 was carried out in the same manner as that of the present block copolyester. The polyethylenes of Comparative Examples 2 and 3 were heat-sealed as follows: Polyethylene was melt-extruded and laminated in the thickness of 40 ~ on biaxially oriented polyetllylene terephthalate film of 12 ~l in thickness. Two sheets of the laminated film thus obtainecl werc ~O~S2~
put together with the polyethylene layer sides of both films facing each other, and t.hen heat-sealed at 250C, 2 kg/cm2 for one second.
. Example _ _ ~ reak~.n~
nu~ber of Melting Young's ~odulus E ~dyne/cm ) ~longatlon adhesive point . (~ o)X 100 (~) . resin (C) I .
la~yer 20C 130C 160C 20C1130CI160C
Ex. 1 215 2.0 X 109 5.0 X 10~ ~,0 X 10~ 400 400 300 Ex. i 215 7,6 X 10~' ~.0 X 10~ 2.7 X 10~5o 20 10 Comp. 132 2.7 X 109 2.0 X 10~ * 200 100 * ~ :
Comp 110 3.3 X 109 . * 3 * i '~ .
.*~ Impossible to me~sure because the material had melted, :
Table 2 ~ :
,:
. . _ . ,:
Heat-seal streneth (~/cm) Example number o~ . ..
la~inated film 20C 160C
. _ ' " ~, ~xample 1 4000 500 Comp. ~xample 1 . 1000 50 Comp. ~xample 2 2400 0 . .
Comp, Example ~ 1500 _ _ ;
. ..
As will be clear from the above results, the laminated film having the block copolyester resin layer of the present .-~
invention showed excellent heat-seal strength not only at room .
temperature but also at the high temperature of 160C, while on the other hand, the laminated film of the Comparative Examples did not show such excellent heat-seal strength at high temperature. ~ 2 :
~ 1~4~35ZO
_xample 2 ;;
To biaxially oriented polyethylene terephthalate film of 12 ~ in thickness was applied isocyanate anchoring agent (EL 250, made by Toyo Ink K.K.; concentration: 4 %) by miller roll method, and the resultant was passed through 2 m dryer wherein it was dried by hot-air of 110C. On the coating layer the block copolyester of Example 1 was melt-extruded at resin temperature of 230C and laminated in thickness of 40 ~ at a :- rate of 40 m/minute. The laminated film thus obtained was heat-sealed, of which the heat-seal strength was measured in the same manner as described in Example 1. The heat-seal strength was 3600 g/cm at room temperature and 550 g/cm at 160C.
;~ Example 3 ; A stninless steel reactor was charged with dimethyl terephthalate (6,200 parts), 1,4-butanediol (4,000 parts) and tltanium tetrabutoxide (5.5 parts) and the mixture was subjected to ester exchange reaction at 140 to 230C in nitrogen gas. The reaction mixture was added to a mixture of polytetramethylene ` oxide having a molecular weight of 1,000 (5,000 parts) and d ~r/~ " ~
O Sumilizer BHT (antioxidant, made by Sumitomo Chemical Co., Ltd.;23 parts) which was preheated at 230C. The pressure in the reactor was gradually reduced while raising the temperature, and then the mixture was subjected top~ycondensation reaction at 245C, at reduced pressure of about 0.1 mmHg for 2 hours ~
with agitation to give polytetramethylene terephthalate/poly- r tetramethylene oxide block copolymer. The block copolymer thus obtained was dried at 80C, at reduced pressure of about 0.1 mmHg for 5 hours. The reduced viscosity (nsp/C) of the copolymer was 1.99 dl/g, which was measured at a concentration of 0.2 g/dl in phenol/tetrachloroethane: 6/4 by weight and at 30~C. The melting point thereof was 205C.
Tlle block copolyester was heat~p~essed at 230C, 4 kg/cm2 for 30 seconds by using an iron plate coated with ~3 ~:~
sz~
polytetrafluoroethylene and the allowed to cool to give a film.
The dynamic properties of the film thus obtained were measured at room temperature (20C), 130C and 150C. The results are shown in Table 3.
. ~.- .
: .:
Tabl e ~ ~ .
- , 2~reak~n~ elon~ation Young~s modullls E (dyne/cm ) (~leO)x 100 (~o) - - - - ~ ~ ~
20C 130C 150C 2~C 130~ 1 150C
_ _ _ .- ~:
1.0 X 109 3.5 X 10~ 2.0 X 108 500 400 300 ~
_ _ _ _ `, :' '.
As a base film there was used a biaxially oriented ~ ;
polyethylene terephthalate film of 19 ~ in thickness, nylon 66 .: . .
film of 20 ~ in thickness or polycarbonate film of 20 ~ in thickness, and as an ad,hesive there was used a 15 % (solids) , ~ r~
solution of Vylon 300 (made by Toyo Boseki K.K.)/Collonate L
"~d"~ar~' (made by Nippon Polyurethane K.K.): 95/5 by weight solids in ethyl acetate. The adhesive was applied to the base film by - gravure coater (100 mesh X 40 ~), the resultant was passed through 2 m dryer at a rate of 30 m/minute, and thereon a non-oriented block copolyester film of 40 ~ in thickness was laminated at nip temperature of 90 to 95C and at nip pressure of 5 kg/cm2 by dry lamination method. Two sheets of the ~
laminated film thus obtained were put together with the non- -oriented block copolyester sides of both films facing each other~
and then it was heat-sealed under the following conditions:
When polyethylene terephthalate film was used as the ,' base film: ;~
Temperature: 250C, Pressure: 2 kg/cm2/second ~
When nylon 66 film was used as the base film: ,~, Temperature: 240C, Pressure: 2 kg/cm2/second When polycarbonate obtained from bisphenol A was used ' 34~5;~0 as the base film: ~-Temperature: 220C, Pressure: 2 kg/cm2/second - The heat seal strength in each case are shown in Table 4.
~L `! ; ;
_ _ _'. .
Temperature :
Base f ilm 20~C j 150C
_ ~' ' iolyethylene terephthalate ~000 (,~/cm) 500 (g/cm) Nylon 66 2000 ~00 Polyc~rh onat e 2 800 '300 . . _ . ' .
Example 4 A stainless steel reactor was charged with dimethyl terephthalate (6,200 parts), ethylene glycol (5,000 parts), zinc acetate (5 parts) and antimony trioxide (3 parts) and the mixture was subjected to ester exchange reaction at 140 to 230C in nitrogen gas. The reaction mixture was added to a mixture of polytetramethylene oxide having molecular weight of 1,000 ` ~/ra~J~ "
(5,000 parts) and Irganox 1010 (antioxidant, made by Ciba-Geigy;
23 parts) which was preheated at 230C. The pressure in the reactor was gradually reduced while raising the temperature, -~
and then the mixture was subjected to polycondensation reaction at 245C, at reduced pressure of about 0.1 mmHg for 2 hours with agltation. The reaction product was dried at 80C, at reduced ;`
pressure of about 0.1 mmHg for 2 hours. The reduced viscosity ;
(nsp/C) of the copolymer thus obtained was 1.59 dl/g, which was measured at concentration of 0.2 g/dl in phenol/tetrachloroethane:
6/4 by weight and at 30C. The melting point thereof was 200C.
The block copolyester was heat-pressed at 230C, 4 kg/cm for 30 second by using an iron plate coated with polytetrafluoroethylene and then allowed to cool to give a film.
52~
The dynamic properties of the film thus obtained were measured at 20C, 130C and 150C. The results are shown in Table 5.
q~a~le ~ .
~:
_ . .
Young's modulus E (dyne/c~2) Break~ng elongatlon l _ i 20~C 130C I 150C 20C1~0C I 150C
:~ ~ . ..
6.0 X 108 l2.5 X 10~ 1l.O ~ 10~ 600 400 300 . .
~s a base film there was used a biaxially oriented -~polyethylene terephthalate f ilm of 19 ~ in thickness, and as an adhesive there was used a 15 % (solids) solution of Vylon 300 ~ rd C/~ r~
d~ ~made by Toyo Boseki K.K.)/Collonate L (made by Nippon Poly- I
urethane K.K.): 9S/5 by weight solids in ethyl acetate. The adhesive was applled to the base film by gravure coater (100 mesh X 40 ~), the resultant was passed through 2 m dryer at a rate of 30 m/minute, and a non-oriented block copolyester film of 40 ~ in thickness was laminated thereon at a nip temperature of 90 to 95C and nip pressure of 5 kg/cm by dry lamination method.
Two sheets of the laminated film thus obtained were put together with the non-oriented block copolyester sides of both f ilms facing each other, and then it was heat-sealed at 250C, 2 kg/cm2 for one second. The heat-seal strength of the film was 2,800 g/cm : -.,: .
at room temperature and 200 g/cm at 150C.
Example 5 ;
:~ ~, , .
A stainless steel reactor was charged with dimethyl terephthalate (6,000 parts), dimethyl isophthalate (2,000 parts), 1,4-butanediol (4,600 parts) and titanium tetrabutoxide (4.5 parts) and the mixture was subjected to ester exchange reaction , at 140 to 230C in nitrogen gas. The reaction mixture was added . .
to a mixture of polytetramethylene oxide having molecular weight of 1,000 (3,000 parts) and Irganox 1010 (antioxidant, made by Ciba-Geigy; 24 parts) whlch was p~reheated at 230C. The pressure ~ .
~146~5ZO
in the reactor was gradually reduced while raising the temperature, and then the mixture was subjected to polycondensation reaction at 245C, at reduced pressure of about 0.1 mmHg for 2 hours with agitation to give polytetramethylene terephthalate-isophthalate/
polytetramethylene oxide block copolymer. The reaction product was dried at 80C, at reduced pressure of about 0.1 mmHg for 2 hours. The reduced viscosity (~sp/C) of the copolymer thus obtained was 1.70 dl/g, which was measured at concentration of 0.2 g/dl in phenol/tetrachloroethane: 6/4 by weight and at 30C.
The melting point thereof was 185C.
The block copolyester was heat-pressed at 230C, 4 kg/cm for 30 seconds by using an iron plate coated with polytetrafluoroethylene and then allowed to cool to give a film. ~
The dynamic properties of the film thus obtalned were measured ;
at room temperature, 130C and 160C. The results are shown in Table 6.
Table 6 _ _ :~
2~eakin~ elonga-tion Youn~ls ~odulus E (dyne/cm ) (~/eo~Y~ 100 (~) _ .
20~ 130C 160C20C I 130C ~ 160~
_ .
2.0 X lo8 3,0 X 108 ~.0 X 107 600 3-oo 200 .
As a base film there was used a biaxially oriented polyetllylene terephthalate film of 19 ~ in thickness, and as an adhesive there was used a 15 % (solids) olution of Vylon 300 '`~r~d~l~a r~ " ~Sr~ "
(made by Toyo Boseki K.K.)/Collonate ~ (made by Nippon Poly-urethane K.K.): 95/5 by weight solids in ethyl acetate. The adhesive was applied to the base film by gravure coater (100 mesh X 40 ~), the resultant was passed through 2 m dryer at a rate of 30 m/minute, and a non-oriented block copolyester fllm having 40 ~ in thickness was laminated thereon at a nip temperature of 90 to 95C and at a nip pressure of 5 k~/cm by dry laminntion ~7 .~
. . .
: ~4~S2~) ~
method. Two sheets of the lamlnated film thus obtained were put together with the non-oriented block copolyester sides of both films facing each other, and then it was heat-sealed at 250C, 2 kg/cm2 for one second. The heat-seal strength of the film was 3,400 g/cm at room temperature and 200 g/cm at 160C.
Example 6 The block copolyester produced by Example 1 was melt-extruded and laminated to a thickness of 50 ~ at a resin tempera-ture of 235C and at a rate of 40 m~minute on a copper foil of ;
35 ~ thickness treated by electrolysis. Two sheets of the laminated film thus obtained were put together with the resin side of both films facing each other, and then it was heat-sealed at 250C, 4 kg/cm2 for one second. The heat-seal strength of the film was 3,500 g/cm at room temperature (20C) and 1,200 g/cm at 160C.
Example 7 ~ On both sides of a biaxially oriented polyethylene -~ terephthalate film of l9 ~ thickness was laminated the non-:, :
oriented block copolyester of 30 ~ thickness produced in Example l in the same manner as described in Example 1 by using the same -adheslve as in Example 1 to give a three layer laminated film comprising non-oriented block copolyester film (30 ~ in thickness), biaxially oriented polyethylene terephthalate film (l9 ~ in thickness) and non-oriented block copolyester film (30 ~ in thickness). Two sheets of the film thus obtained were put together and then heat-sealed at 250C, 4 kg/cm for one second. The heat-seal strength of the film was 3,200 g/cm at room temperature (20C) and 350 g/cm at 160C.
,"":
~8 `~:
:' ..
.; . .
.~. .- , .
The block copolyester was heat-pressed at 230C, 4 kg/cm for 30 second by using an iron plate coated with polytetrafluoroethylene and then allowed to cool to give a film.
52~
The dynamic properties of the film thus obtained were measured at 20C, 130C and 150C. The results are shown in Table 5.
q~a~le ~ .
~:
_ . .
Young's modulus E (dyne/c~2) Break~ng elongatlon l _ i 20~C 130C I 150C 20C1~0C I 150C
:~ ~ . ..
6.0 X 108 l2.5 X 10~ 1l.O ~ 10~ 600 400 300 . .
~s a base film there was used a biaxially oriented -~polyethylene terephthalate f ilm of 19 ~ in thickness, and as an adhesive there was used a 15 % (solids) solution of Vylon 300 ~ rd C/~ r~
d~ ~made by Toyo Boseki K.K.)/Collonate L (made by Nippon Poly- I
urethane K.K.): 9S/5 by weight solids in ethyl acetate. The adhesive was applled to the base film by gravure coater (100 mesh X 40 ~), the resultant was passed through 2 m dryer at a rate of 30 m/minute, and a non-oriented block copolyester film of 40 ~ in thickness was laminated thereon at a nip temperature of 90 to 95C and nip pressure of 5 kg/cm by dry lamination method.
Two sheets of the laminated film thus obtained were put together with the non-oriented block copolyester sides of both f ilms facing each other, and then it was heat-sealed at 250C, 2 kg/cm2 for one second. The heat-seal strength of the film was 2,800 g/cm : -.,: .
at room temperature and 200 g/cm at 150C.
Example 5 ;
:~ ~, , .
A stainless steel reactor was charged with dimethyl terephthalate (6,000 parts), dimethyl isophthalate (2,000 parts), 1,4-butanediol (4,600 parts) and titanium tetrabutoxide (4.5 parts) and the mixture was subjected to ester exchange reaction , at 140 to 230C in nitrogen gas. The reaction mixture was added . .
to a mixture of polytetramethylene oxide having molecular weight of 1,000 (3,000 parts) and Irganox 1010 (antioxidant, made by Ciba-Geigy; 24 parts) whlch was p~reheated at 230C. The pressure ~ .
~146~5ZO
in the reactor was gradually reduced while raising the temperature, and then the mixture was subjected to polycondensation reaction at 245C, at reduced pressure of about 0.1 mmHg for 2 hours with agitation to give polytetramethylene terephthalate-isophthalate/
polytetramethylene oxide block copolymer. The reaction product was dried at 80C, at reduced pressure of about 0.1 mmHg for 2 hours. The reduced viscosity (~sp/C) of the copolymer thus obtained was 1.70 dl/g, which was measured at concentration of 0.2 g/dl in phenol/tetrachloroethane: 6/4 by weight and at 30C.
The melting point thereof was 185C.
The block copolyester was heat-pressed at 230C, 4 kg/cm for 30 seconds by using an iron plate coated with polytetrafluoroethylene and then allowed to cool to give a film. ~
The dynamic properties of the film thus obtalned were measured ;
at room temperature, 130C and 160C. The results are shown in Table 6.
Table 6 _ _ :~
2~eakin~ elonga-tion Youn~ls ~odulus E (dyne/cm ) (~/eo~Y~ 100 (~) _ .
20~ 130C 160C20C I 130C ~ 160~
_ .
2.0 X lo8 3,0 X 108 ~.0 X 107 600 3-oo 200 .
As a base film there was used a biaxially oriented polyetllylene terephthalate film of 19 ~ in thickness, and as an adhesive there was used a 15 % (solids) olution of Vylon 300 '`~r~d~l~a r~ " ~Sr~ "
(made by Toyo Boseki K.K.)/Collonate ~ (made by Nippon Poly-urethane K.K.): 95/5 by weight solids in ethyl acetate. The adhesive was applied to the base film by gravure coater (100 mesh X 40 ~), the resultant was passed through 2 m dryer at a rate of 30 m/minute, and a non-oriented block copolyester fllm having 40 ~ in thickness was laminated thereon at a nip temperature of 90 to 95C and at a nip pressure of 5 k~/cm by dry laminntion ~7 .~
. . .
: ~4~S2~) ~
method. Two sheets of the lamlnated film thus obtained were put together with the non-oriented block copolyester sides of both films facing each other, and then it was heat-sealed at 250C, 2 kg/cm2 for one second. The heat-seal strength of the film was 3,400 g/cm at room temperature and 200 g/cm at 160C.
Example 6 The block copolyester produced by Example 1 was melt-extruded and laminated to a thickness of 50 ~ at a resin tempera-ture of 235C and at a rate of 40 m~minute on a copper foil of ;
35 ~ thickness treated by electrolysis. Two sheets of the laminated film thus obtained were put together with the resin side of both films facing each other, and then it was heat-sealed at 250C, 4 kg/cm2 for one second. The heat-seal strength of the film was 3,500 g/cm at room temperature (20C) and 1,200 g/cm at 160C.
Example 7 ~ On both sides of a biaxially oriented polyethylene -~ terephthalate film of l9 ~ thickness was laminated the non-:, :
oriented block copolyester of 30 ~ thickness produced in Example l in the same manner as described in Example 1 by using the same -adheslve as in Example 1 to give a three layer laminated film comprising non-oriented block copolyester film (30 ~ in thickness), biaxially oriented polyethylene terephthalate film (l9 ~ in thickness) and non-oriented block copolyester film (30 ~ in thickness). Two sheets of the film thus obtained were put together and then heat-sealed at 250C, 4 kg/cm for one second. The heat-seal strength of the film was 3,200 g/cm at room temperature (20C) and 350 g/cm at 160C.
,"":
~8 `~:
:' ..
.; . .
.~. .- , .
Claims (13)
1. A heat-adhesive laminated film comprising a base film formed of a plastic film formed of a polyester, poly-amide, or polycarbonate or a metal foil selected from al-uminum and copper foils, and a film of a resin laminated to one or both sides thereof said resin comprising predominantly a block copolyester comprising (1) a crystalline polyester segment having a melting point of at least 200°C. and a molecular weight of from 400 to 10,000, and (2) a polymer segment of either a polyether or a polyester, having a low melting point, a molecular weight of from 400 to 6,000 and present in a proportion of 5 to 80 percent by weight of the block copolymer, said resin having a melting point higher than 180°C but lower than the tem-perature at which the characteristics of the base film deteriorate and having a Young's modulus .epsilon.(dyne/cm2) and a breaking elongation (.DELTA.?/?o) X 100 (%) when measured at 20°C and 130°C which satisfy, respectively, the following relationships:
107 (dyne/cm2) <.epsilon.<1010 (dyne/cm2) and (.DELTA.?/?o) X 100 >40 (%).
107 (dyne/cm2) <.epsilon.<1010 (dyne/cm2) and (.DELTA.?/?o) X 100 >40 (%).
2. A heat-adhesive laminated film according to claim 1, wherein the block copolyester has a melting point at least about 20°C lower than the melting point of the base film.
3. A heat-adhesive laminated film according to claim 1, wherein the crystalline polyester segment having a high melting point comprises 70 or more % by weight of ethylene terephthalate units or tetramethylene terephthalate units, and would have a melting point of 200°C or more if a polymer having fiber-forming properties were produced therefrom, and has a molecular weight of 400 to 10,000.
4. A heat-adhesive laminated film according to claim 1, 2 or 3, wherein the polymer segment having a low melting point comprises 20 to 50% by weight of the block copolyester.
5. A heat-adhesive laminated film according to claim 1, wherein the base film is formed of a polyester, polyamide or poly-carbonate and is in the form of non-oriented film, uniaxially oriented film or biaxially oriented film.
6. A heat-adhesive laminated film according to claim 1, 2 or 3, wherein the base film has a thickness of 10 to 500 µ and the block copolyester film has a thickness of 30 to 500 µ.
7. A heat-adhesive laminated film according to claim 1, 2 or 3, wherein the base film has a thickness of 10 to 30 µ and the block copolyester film has a thickness of 30 to 100 µ.
8. A heat-adhesive laminated film according to claim 1, 2 or 3, wherein the resin is a polyethylene terephthalate/polyethylene oxide block copolymer, polytetramethylene terephthalate/poly-ethylene oxide block copolymer, polyethylene terephthalate/poly-tetramethylene oxide block copolymer, polytetramethylene tereph-thalate/polytetramethylene oxide block copolymer, polyethylene terephthalate/poly-.epsilon.-caprolactone block copolymer, polytetramethy-lene terephthalate/poly-.epsilon.-caprolactone block copolymer, polyethy-lene terephthalate/polypivalolactone block copolymer, polyethylene terephthalate/polyethylene adipate block copolymer, polyethylene terephthalate/polyneopentyl sebacate block copolymer, polytetra-methylene terephthalate/polyethylene dodecanoate block copolymer, polytetramethylene terephthalate/polyneopentyl dodecanoate block copolymer, polyethylene terephthalate?isophthalate/polytetra-methylene oxide block copolymer, or polytetramethylene tereph-thalate?isophthalate/polytetramethylene oxide block copolymer.
9. A heat-adhesive laminated film according to claim 1, wherein the base film is polyethylene terephthalate film having a thickness of 10 to 30 µ and the resin film has a thickness of 30 to 70 µ and is made from a tetramethylene terephthalate/tetra-methylene oxide block copolymer containing 20 to 50 % by weight of polytetramethylene oxide having a molecular weight of 400 to 3,000.
10. A heat-adhesive laminated film according to claim 1, wherein the base film is polyethylene terephthalate film having a thickness of 10 to 30 µ and the resin film has a thickness of 30 to 70 µ and is made from a polytetramethylene terephthalate-iso-phthalate/polytetramethylene oxide block copolymer containing 20 to 50 % by weight of polytetramethylene oxide having a molecular weight of 400 to 3,000.
11. A heat-adhesive laminated film according to claim 1, wherein the resin film is formed by melt-extruding and laminating a block copolyester on the base film.
12. A heat-adhesive laminated film according to claim 1, which is produced by applying an adhesive on either or both of the base film and the block copolyester film and contacting the films together.
13. A heat-adhesive laminated film according to claim 1, which is produced by applying a block copolyester solution on the base film by gravure roll coating, reverse-roll coating, rod coating or spray coating and drying the product to remove the solvent.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1395673A JPS543498B2 (en) | 1973-02-02 | 1973-02-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1040520A true CA1040520A (en) | 1978-10-17 |
Family
ID=11847648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA191,607A Expired CA1040520A (en) | 1973-02-02 | 1974-02-01 | Heat-adhesive laminated film |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS543498B2 (en) |
| BR (1) | BR7400757D0 (en) |
| CA (1) | CA1040520A (en) |
| DE (1) | DE2404747A1 (en) |
| FR (1) | FR2216108B1 (en) |
| GB (1) | GB1437046A (en) |
| IT (1) | IT1004842B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5039375A (en) * | 1973-08-13 | 1975-04-11 | ||
| JPS5053194A (en) * | 1973-09-11 | 1975-05-12 | ||
| JPS5416556B2 (en) * | 1973-09-13 | 1979-06-22 | ||
| JPS604058B2 (en) * | 1974-10-09 | 1985-02-01 | 吉崎 鴻造 | container lid |
| JPS51125513A (en) * | 1975-04-23 | 1976-11-02 | Toyo Boseki | Polyester printing film |
| JPS51125514A (en) * | 1975-04-23 | 1976-11-02 | Toyo Boseki | Polyester printing film |
| JPS5220112A (en) * | 1975-08-01 | 1977-02-15 | Toyo Boseki | Polyester composite printing film |
| JPS5247069A (en) * | 1975-10-11 | 1977-04-14 | Toyo Boseki | Polyester system films with superior processibilty |
| JPS5266087A (en) * | 1975-11-26 | 1977-06-01 | Toray Industries | Coated metallic container |
| JPS5287483A (en) * | 1976-01-14 | 1977-07-21 | Toyobo Co Ltd | Printed polyester films |
| JPS5288491A (en) * | 1976-01-19 | 1977-07-23 | Toyobo Co Ltd | Spacer for packing polyester film |
| JPS5381577A (en) * | 1976-12-24 | 1978-07-19 | Toyo Boseki | Polyester film with excellent workability |
| ES487112A1 (en) * | 1978-12-22 | 1980-10-01 | Monsanto Co | Metal-thermoplastic-metal laminates and a process for the preparation of such laminates. |
| DE3777247D1 (en) * | 1986-06-07 | 1992-04-16 | Hoechst Ag | DECORATIVE COVER FILM. |
| US4946743A (en) * | 1987-06-26 | 1990-08-07 | Reynolds Consumer Products, Inc. | Nonoriented polyester films for lidding stock with modified heat seal layer |
| GB8724237D0 (en) * | 1987-10-15 | 1987-11-18 | Metal Box Plc | Laminated metal sheet |
| GB8724241D0 (en) * | 1987-10-15 | 1987-11-18 | Metal Box Plc | Laminated metal sheet |
| GB8724239D0 (en) * | 1987-10-15 | 1987-11-18 | Metal Box Plc | Laminated metal sheet |
| GB8724238D0 (en) * | 1987-10-15 | 1987-11-18 | Metal Box Plc | Laminated metal sheet |
| GB8724242D0 (en) * | 1987-10-15 | 1987-11-18 | Metal Box Plc | Laminated metal sheet |
| DE602004016203D1 (en) * | 2003-10-14 | 2008-10-09 | Du Pont | MULTI-CHAMBER PACKAGING WITH TEMPERATURE-RELATED TORQUE SEALS |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1911034A1 (en) * | 1968-03-06 | 1969-09-11 | Eastman Kodak Co | Process for the production of linear block copolyesters |
-
1973
- 1973-02-02 JP JP1395673A patent/JPS543498B2/ja not_active Expired
-
1974
- 1974-01-30 GB GB428574A patent/GB1437046A/en not_active Expired
- 1974-01-31 IT IT67275/74A patent/IT1004842B/en active
- 1974-02-01 CA CA191,607A patent/CA1040520A/en not_active Expired
- 1974-02-01 FR FR7403511A patent/FR2216108B1/fr not_active Expired
- 1974-02-01 DE DE2404747A patent/DE2404747A1/en not_active Withdrawn
- 1974-02-01 BR BR74757A patent/BR7400757D0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB1437046A (en) | 1976-05-26 |
| BR7400757D0 (en) | 1974-09-10 |
| FR2216108B1 (en) | 1976-11-26 |
| JPS49103970A (en) | 1974-10-02 |
| DE2404747A1 (en) | 1974-08-15 |
| IT1004842B (en) | 1976-07-20 |
| JPS543498B2 (en) | 1979-02-23 |
| FR2216108A1 (en) | 1974-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1040520A (en) | Heat-adhesive laminated film | |
| CA1039171A (en) | Heat-adhesive film laminate | |
| US3914502A (en) | Heat-adhesive laminated film | |
| EP1193294B1 (en) | Aliphatic polyester compositions, films made thereof and laminates thereof | |
| CA2356674C (en) | Biodegradable bag | |
| US4725481A (en) | Vapor-permeable, waterproof bicomponent structure | |
| EP0408042B1 (en) | Heat-sealable laminated polyester film | |
| CA1314124C (en) | Non-oriented polyster films for lidding stock with modified heat seal layer | |
| US4070417A (en) | Stretched polyester film from a polymer blend | |
| JP3247053B2 (en) | Polyester film for metal plate lamination and method for producing the same | |
| EP1855881B1 (en) | Breathable, heat-sealable composite polymeric film | |
| EP1448679B1 (en) | Heat-shrinkable polyester film | |
| KR20060109623A (en) | Polyester film | |
| KR20020013731A (en) | Transparent Polyester Film having at least Three Layers, Its Use and Process for Its Production | |
| JPH035143A (en) | Heat-shrinkable film | |
| EP1176162A2 (en) | Biaxially oriented polyester film | |
| JP2004051959A (en) | Aliphatic polyester film and laminated product | |
| JP4418161B2 (en) | Heat-sealable polylactic acid-based biaxially stretched film | |
| JPH07316318A (en) | Highly shrinkable film | |
| JPH0425456A (en) | Coated polyester film and vapor deposition film using same | |
| WO2001048062A1 (en) | Oriented polymeric film comprising at least one copolyetherester | |
| JP4221987B2 (en) | Laminated film for packaging | |
| KR100225395B1 (en) | Multi-layered polyester film and method for manufacturing the same | |
| JPH06126917A (en) | Polyester laminate | |
| JP2002127337A (en) | Multi-layer stretched polyamide film |