TW434144B - Biaxially oriented film to be laminated on a metal - Google Patents

Abstract

A biaxially oriented film to be laminated on a metal, which is a laminate film comprising (A) a first layer of a polyester comprising ethylene terephthalate as a main recurring unit; and (B) a second layer formed from a composition of a polycarbonate and polyesters, the polycarbonate and the polyesters being each contained in amounts of 20 to 50% by weight and 50 to 80% by weight based on the total thereof; the polyesters consisting essentially of a first polyester comprising ethylene terephthalate as a main recurring unit and having a terminal carboxyl group concentration of more than 5 eq./10<SP>6</SP> g and a second polyester comprising butylene terephthalate as a main recurring unit and having a terminal carboxyl group concentration of less than 20 eq./10<SP>6</SP> g; and the first and second polyesters being each contained in an amount of 10 to 90% by weight based on the total thereof; and in which (C) the plane orientation coefficients of the first layer and second layer are both in the range of 0.05 to 0.10.

Description

434 彳 44 A7 B7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (〆) 1 1 This invention is based on a biaxially stretched thin layer of gold laminated on a gold frame. f The present invention is a double-layer stretch film 1 | film t laminated on a metal frame, and this thin layer is laminated on a metal plate before canning and adding X. Please make 1 1 1 (such as stretching) In the case of gold tin cans »It has excellent molding and I. Read 1: | Sex 1 because it not only has excellent adhesion to the gold intestine plate 1 odor retention (read back 1 I retention) and low temperature resistance The impact properties are also extremely excellent and also have a good note. 1 i. I. Good forming properties (such as extrusion processability and stretchability) »Therefore, item 1 1 is suitable for metal cans such as beverage males and food cans. 01 The inner and outer surfaces of the maggot I ’m writing to prevent corrosion on this page. I. 1 Etching. To simplify the process »and improve the operating conditions and prevent pollution, etc. &gt; Recently 1 1 Has developed a metal can with anti-embroidery resistance without using organic solvents. 1 I Method 0 The most widely used method is to coat a thermoplastic resin film on the surface of a gold-plated plate such as a tin-plated pin plate without a tungsten pin plate or an aluminum plate. Resin film * 1 1 1 is often used polyester film Q 1 i Japanese Patent Laid-Open No. Sho 56 -J 0 4 5 1 and B Japanese Patent No. 1- 1 I 132546 shows- The laminated metal sheet obtained by laminating a low-melt polyester adhesive layer 1 A biaxially stretched polyethylene terephthalate on a gold hurdle sheet 1 is used as a can material. Biaxially stretched i 1 poly Ethylene terephthalate film has good heat resistance and heat retention% 1 1 but its forming processability is not enough »Therefore, during the process of adding X to the can, f * film is easily broken due to cyanide formation or cracking. Deformation caused by breaking t causes a relatively large I Λ * 〇 1 1 Used in B Japanese Patent Laid-Open No. 1-192545-3-Gazette and Japanese Bento Lit Kaiping 1 I 1 1 1 1 Applicable to the public 97 2 434 彳 4 4 A7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs _._ B7_ V. Description of the Invention (&gt;) No. 2-57339 shows a method to reduce the amorphousness or crystallinity to extremely low The aromatic polyfluorene material is laminated on a metal plate, and the obtained laminated metal plate is used as a can-making material. Although the amorphous or extremely low-crystalline aromatic polyester film has excellent formability, it has poor fragrance retention, and is used in post-processing processes, such as printing after canning or high-temperature sterilization, or It is easy to become brittle during long-term storage, because when it is subjected to external force, it is easy to deteriorate and crack. European patent EP-A-0653455 A1 shows a multilayer film laminated on a metal. The first layer (A1) is a polyester resin with a melting point higher than 20ITC, and the second layer (A2) is a polynitrate or melt-bonded. A resin composition of more than 20 ° C of a polyester resin and a polyacrylate, and the content of the polysulfonate resin in the resin composition is relative to the total weight of the polyester resin and the polysulfonate resin. 1% by weight or more; when this multilayer film is laminated on a metal plate, it is impacted and energized (酎 impact test), showing that its current value is less than fl.laA; the total thickness is in the range of 5-100 // 11 However, the European patent EP-A-0653455 A1 does not mention whether two different polyesters are used in the resin composition of the second layer at the same time. One of the objects of the present invention is to provide a new layer of laminated metal sheet The other object of the present invention is to provide a multilayer film laminated on a metal plate. This multilayer film, which is not colored and does not contain any bubbles, has excellent forming processability, and therefore is extruded. "Neltswing" never happened &quot; phenomenon, and it will not break during the stretching process. * —. n I 'n ϋ East (Notes on the back of the poem before reading 孑 k write this page) This paper scale applies to China National Standards (CNS) 4 specifications (210X297 mm) A7 434 14 4 B7 ____ 5. Description of the invention (々) Another object of the present invention is to provide a multilayer film laminated on a metal plate, which not only has excellent low temperature impact resistance and gold resistance. The fascia is also excellent in adhesiveness, odor retention, or aroma retention (hereinafter referred to as aroma retention), and also has good film-forming properties (such as extrusion molding processability and stretchability). Other objects and advantages of the invention will become more apparent through the following description. According to the present invention, the objects and advantages of the above-mentioned laminated biaxially stretched film on the gold foil can be obtained. The composition of the laminated film is as follows: (A) The polyester layer composed of ethylene terephthalate as the main repeating unit forms the first layer, (B) the resin layer composed of polyester and polysulfonate forms the second layer, and the resin composition substantially contains The repeating unit shown in the following chemical formula ⑴: ( Please read the notes on the back-Γΐκ-Write this page) Ruler-Paper |

Consolidate 5-5- to contain the base, also the base 2 鐽 ^ Ξ Its son R1 child original, the original 硪 out of a large alkane, the son of the Rong ring ^ ^ 00 ^ ^ 硪 璟 0 in the ring teeth containing 0 and stand 0 Out of each η, the primary element of the group and the quasi-standard home group-the basis of the selected group is the external base value and the base ο benzene table, substituted oxane, Ziduyuan has its own 0 η -5 and

One centimeter 7 29 X Printed by the Central Procurement Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 434 彳 4 4 A7 B7 V. Description of the invention (4) The content of the polyester and polyester relative to their total weight base is 20, respectively -50 reset and 50-80 weight X; polychisel essentially consists of ethylene terephthalate as the main repeating unit and the terminal carboxyl group concentration is 5 when fi / l0e grams (eq./106 g ) The first polyester above and the second polyester composed mainly of butyl terephthalate and repeating units, and the terminal carboxyl group content is less than 20 μg / 10 g; the first polyester and the second Relative to the total weight of the base, the content of this polyester is between 10-30 weights X; and (C) the plane tensile pseudo numbers of the first and second layers are in the range of 0.05-0.10. Inner β As described above, the biaxially stretched sheet of the present invention includes two layers. The first layer is formed of a polyester composed of ethylene terephthalate as the main repeating unit. The content of ethylene terephthalate in polyester relative to the substrate of the repeating unit is at least 5 G Mol 5 £, and 8 G Mol 5; the above is better, and 85 Mo 3 3t is more preferred , 90 Moore X and better. In the present invention, a polyester containing 80 to 100 moles of ethylene terephthalate can be easily produced with respect to the total repeating unit substrate, and is convenient to use. Examples of dicarboxylic acids that can be copolymerized with such polyesters include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid and 2,6- or 2,7-naphthalenedicarboxylic acid; aliphatic dicarboxylic acids such as Adipic acid, adipic acid, sebacic acid, and sebacic acid: alicyclic dicarboxylic acids, such as 1,4-hexanehexanedicarboxylic acid. Examples of glycol components that can be copolymerized with such polyesters include aliphatic diols, such as diethylene glycol, butanediol, and hexanediol; and alicyclic diols, such as 1,4-hexanehexanedimethanol β which Military independence or mixed use. (Please read the note on the back. V write this page) This paper size is applicable to China National Standard (CNS) Α4 size (210 × 29? Mm) Printed by the Central Consumers ’Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 434144 A7 _. ._B7. V. Description of the invention (r) The melt adhesion of these polyesters is above 20 (TC, and more preferably 210 · 0 or more. If low-melt polyester is used, the heat resistance of the resulting film is The impact resistance and impact resistance will be relatively poor. The intrinsic viscosity of the above polyester (retained in the gaseous phenol of 35 «C) is preferably 0.5-0.9, and particularly preferably 0_6-〇_8. Ester can be prepared by the traditional melt polymerization method. The side-germanium (Ge) compound catalyst or the gadolinium (Ti) compound catalyst used in the preparation of poly_ is better. From the viewpoint of reducing the content of oligomers, The preferred polymerization method is a solid-phase polymerization method. Especially after the polymer acid is mixed and melted, the polymerization reaction of the polyester in the presence of an antimony (Sb> compound catalyst) will help the ribs to decarboxylate. The second gaseous 硪 β which is formed by the formation of air bubbles is therefore not suitable for the antimony catalyst. The second layer of fluorene is composed of polyester and polyester. The polyacid contains essentially the repeating unit shown in the above chemical formula (1). In the above chemical formula (1), R1 and R2 represent 1-5 The alkyl group of the main atom can be a straight or branched chain alkyl group, such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, etc. (Please read the note on the back first. Fork to write on this page) Hexane and pentyl rings include the examples of the children of the alkanes, the original master ring 0 6 I 5 containing radicals and 1 gas containing, the fluorine table from the substitution of your son 4 original halogen halogen 0 as described above For example, the basic alkyl group of the original group is 0, 0 is the middle group and the bromine is better than the median single complex. Γ: 3 is shown. Of ο equal to η and η and f base paper is based on the Chinese paper standard (CNS) Λ4 * MM 210X297 mm) 434144 Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention ( The polyacrylates suitable for use in the present invention may have a heavy unit that is based on the above formula (1). The same, or it may be at least two different types of repeating units as shown in chemical formula (1). Polyesters usually use phase-opened dihydric phenol to dissolve in the presence of known acid acceptors or molecular weight regulators. Prepared by the reaction of a precursor of an acetic acid ester in a solvent (such as dichloromethane) (such as light &lt; (Melt polymerization method) β produced by transesterification reaction of ester) β The polyphosphonate used in the present invention can be prepared by the following methods: 0) In the interfacial polymerization method, excess dihydric phenol and nitrate precursors are reacted. Method; ¢) the method of carrying out the end-capping reaction in the interfacial polymerization method; ⑶ the method of adjusting the ratio of the binary and the precursors in the interfacial polymerization method; ⑷ in the melt polymerization method, the polyhydric hydroxy compound is A method for adding after the polymerization reaction is completed; and a method in which a polycarbonate having a terminal hydroxyl content of less than 20 mols per 10 e g is melt-mixed with an appropriate amount of a dihydric phenol, and a contact is added if necessary Mediator Phenols react with each other to increase the content of terminal hydroxyl groups. "The average molecular weight of polyether ester is preferably 100 Go-4 GO () (), and more preferably 100 G-3 50 G 0. good. The polyester constituting the second layer essentially includes ethylene terephthalate as -8-(Please read the note on the back first ν4 'to write this page) This paper size applies to China National Standards (CNS) Α4 specifications ( 2 ΙΟχ297 mm) Printed by the Central Procurement Bureau of the Ministry of Economic Affairs, Consumer Work Cooperative, 434 M 4 Α7 Β7 V. Description of the invention (7) The first polyester consisting of a main repeating unit and a terminal carboxyl group degree of 5 equivalent / 10e or more And a second polyester with butylene terephthalate as the main repeating unit and a terminal carboxyl group concentration of 20 equivalents / 10e or less. The first polyester must have a terminal carboxyl group concentration of 5 to 10/10 g. If the concentration of the terminal carboxyl group is less than 5 equivalents / 1G6 g, the dispersion &gt; properties of the polyacrylate in the poly curtain will be poor, so that the film will be difficult to stretch, and even in a worse case, it cannot be stretched. The terminal carboxyl group concentration is preferably 7 equivalents / 1G6 g or more, and more preferably 12 equivalents / 1G6 g or more, and 15 equivalents / 106 g is particularly preferable. The β terminal carboxyl group concentration is preferably 20 equivalents / 10e g or less β As far as the first polyester composed of ethylene terephthalate as the main repeating unit is concerned, the above-mentioned examples for the first polyester are all compatible, so I will not repeat them here. In the first polyester, the content of ethylene terephthalate relative to the total repeating unit substrate is preferably 80-100 Molar X. In the second polyester, the content of The content is at least 50 weight X or more relative to the total repeating unit base. This content is preferably at least 80 deciles X, more preferably at least 85 moles X, and at least 85 moles X is even better. At least 95 moles is preferred as the second polyester Examples of the dicarboxylic acids of the copolymerized third layer include: aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, 2, 6- or 2,7-dicarboxylic acid; aliphatic dicarboxylic acids such as Adipic acid, azelaic acid, sebacic acid, and sebacic acid; fatty acids such as 1,4-cyclohexanedi-9- (please read the notes on the back first / write this page) Zhang scale is applicable to China National Standard for Standards (CNS) Α4 (210 &gt; &lt; 297 mm) Printed by the Central Labor Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 1 1 4 4434 1 4 4ti a7 _B7_____ 5. Description of the invention (f) Formic acid · Examples of glycols which are another third layer component copolymerized with the second polyester include: aliphatic secondary enzymes such as diglycol, butanediol, and hexanediol; and aliphatic diols such as丨, 4-Chen Dimethonate. They can be used alone or in combination. The concentration of the terminal carboxyl group of the second poly_ must be less than 20 equivalents / 1Ge g, preferably less than 17 equivalents / 10βg, and more preferably 5-17 equivalents / 106 g. The particularly preferred ν is 5- 15 equivalents / 10 gram. The second type of polyfluorene composed of butadiene dibenzoate as the main repeating unit is to enhance the dispersion of the polyester in the polyester phase in order to suppress the melt-fluid Uelt during extrusion. swing) &quot; phenomenon and the rupture phenomenon during the stretching process, which can improve the film-forming property "If the terminal carboxyl group concentration of this polyester is higher than 20 equivalents / lfls gram *, it will no longer have improved polyacid The effect of dispersibility and film-forming properties "The melt adhesion of the second polyester is preferably 20 ° C or more. 210 · Ό is more preferred. If this melting point is too low, the heat resistance of the resulting film and Impact resistance will be less than β. The intrinsic degree of the second poly (determined in phenol at 35 ° C) is preferably from 0.6 to 1.6, and particularly from 0.7 to 1.5. As mentioned above with p-benzene Ethylene diformate is the same as polyester with main repeating unit. It is better to use the germanium compound catalyst or titanium compound catalyst and use solid phase polymerization to prepare the second polyester. The preferred examples of germanium compounds include: ⑴Amorphous gasification thread, ⑵ 撖 Crystal gasification thread, © in age metals, age earth metals or mixtures thereof Under normal circumstances, it is dissolved in glycol, and it is dissolved in diol. The preferred examples of titanium compounds include -I 0-(Please read the notes on the back to write this page) This paper is applicable to China National Ladder Standard (CNS) A4 specification (210X297 cm) 434 1 4 4 ^ A7 B7 Printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, V. Description of the invention (9) Tetrabutyl titanium, titanium acetate, etc. The content of the polyester and polyester in the second layer is 20-50 wt% X and 50-80 wt X, respectively. During the forming process, the phenomenon of “box melting and strong shooting” and the rupture phenomenon in the stretching process will frequently occur, making the film formation worse. Β If the ratio of polyacrylate is less than 20 weight X, the low temperature resistance The balance will not be improved. The content of the first polyester and the second polyester in the polymer is 10-90 weight relative to the weight of the first polyester and the second polyester. In the range of ft X, "If the ratio of the second polyester is higher than 90 weight X, or the tb ratio of the first polyester is less than 10 weight X , The resulting film will be blackened, and it will also form hafnium dioxide due to the decarboxylation of polycarboxylate, resulting in the inclusion of air bubbles, which will make it difficult to form a thin film. Conversely, if the second If the ratio of this kind of polyester is higher than 90%, the dispersion of polysulfonate in the polyester phase cannot be improved. Therefore, the phenomenon of "melt vibration" during extrusion and the stretching process The cracking phenomenon cannot be suppressed. The blending ratio (weight X) of the first polyester to the second polyester is preferably 20-85 / 80-15, and 4 0 -8 0 / 6 0- 2 0 is better. The polyester contained in the second layer has terminal hydroxyl groups. The purpose of this terminal hydroxyl group is to make the second layer (B) adhere to the gold plate. The terminal hydroxyl hydrazone concentration of the ester is preferably at least 25 equivalents / ioe gram • and more preferably at least 30 equivalents / 10 gram, -11- .----------- ------ 、 1Τ ------ ^ (Please read the note on the back first: write this page) This paper is in use ® National Standard (CNS) A4 Specification & 2I0X297 mm) Printed by the Consumer Cooperatives of the China Economic and Trade Bureau of the Ministry of Economic Affairs A? 4 1 4 4Λ3 A7 B7 &quot;. II V. Description of the invention (l °) 40-200 equivalent / 10βg is the best. The second layer is formed by the composition of Polyuronic Acid® and Poly Brew. The composition preferably contains a phosphorus compound. Phosphorus compounds can inhibit the reaction between polyesters and polyesters, thus preventing the coloration of the resulting films due to decarboxylation and osmium dioxide. However, if the dish contains too much halo, the effect of the improved polydispersity of the second poly® will be reduced, so its film-forming properties are also deteriorated. The content of the phosphorus compound is 2 G-1 0 0 ρ ρ is preferred, and 40 _ 1 〇〇ΡΡ »is more preferred, and 40-50 PP * is most preferred. Phosphorous compounds can be either inorganic or organic, such as hypophosphoric acid, phosphoric acid, pyrophosphoric acid, phosphonium phosphate, and salts thereof, dialkyl and trialkylphosphonium, diaryl and triarylphosphonium, phosphonium alkyl, and diphosphonium Alkyl hypo-acid, monoaryl and diaryllinamic acid, phosphites, phosphates, polyphosphoric acid, etc. Among them, phosphorous acid, phosphoric acid, phosphorous acid® and phosphate are preferred. Examples of vinegars include lower grades Alkyl (such as methyl and ethyl) fluorene, phenyl esters, glycols (such as ethylene glycol), etc. Beta phosphorus compounds can be added during the manufacture of polyesters and / or polyesters, It can also be added during melt extrusion. The composition containing polynitrate and polymerase in the second layer has sea / island crystals, in which the polyacrylate is dispersed in an island-like form (dispersed 柙) in a sea-like polyester (continuous mosaic phase). Polyurethane islands appear to be one-round particles. If you cut the length and width of the double-stretched film, the average length of the particles on the cut surface is between 0.1-20 #. If such particles with an average major diameter are dispersed into independent phases (islands), then they are extruded into a shape. 1 2- (Please read the precautions on the back first. Write this page) This paper is applicable to the Chinese standard (CNS) A4 specification (210 × 297 gong) 434144- The printing of A7 B7 by the Consumer Cooperatives of the Ministry of Economic Affairs, Bureau of Labor and Social Security, China 5. The phenomenon of "melt vibration" in the process of &quot; &quot;, and the stretching process The cracking phenomenon can be suppressed, so the impact resistance ® excellent double sedan stretch film is obtained. The size of the polyacrylic bird on the above cut surface is preferably between 0.1-10; «, and 〇 1-5 #B is more preferred. In the biaxially stretched film of the present invention, the polyester constituting the first layer thereof and the composition of polyethylene terephthalate and polyester constituting the second layer may be dispersed or dispersed as necessary. Incorporates additives such as anti-gasification_, thermal stability_, UV absorber, plasticizer, Particles, organic particles, antistatic agents, etc. β The centerline average surface roughness Ua) of the biaxially stretched film of the present invention is preferably at least 5-150πβ, and more preferably 10-6fln. E Ra if If it is within the above range, it is easy to make a thin film. "For finishing the surface roughness (Ra) of the biaxially stretched film can be within the above 5-150η · range. • You can add Zhao Huaerga to the first layer. Polyester, and / or added to the second layer of polysulfonic acid and polyester composition, or moderate phase separation of polysulfonate phase and polysaccharide phase "added lubricant, whether inorganic or Both organic and inorganic lubricants are preferred. Examples of inorganic lubricants include: silica, aluminum gas, titanium dioxide, calcium acetate, calcium acid bait, etc. Examples of organic lubricants include: Polystyrene particles, cross-linked silicone resin particles, etc. The average particle size of the lubricant is better than 2.5, and 0 · 01-2 _ 0 is better. When the average particle size of the lubricant is greater than 2.5 # «When the pinhole has changed during the forming phase -1 3- I ------------ Refer to ---- ir ------ East {Please read the back Attention Xiang Luo wrote this page) This paper size is in accordance with Chinese National Standard (CNS). A4 is now standard (2I0X297mm) 434 M4 A7 ______B7 V. Description of the invention (&gt; &gt; From the point of view of anti-pinhole resistance, the average grain size is less than 2.5 // b, and the average grain size ratio (longer diameter / shorter diameter) ) Is a monodisperse lubricant of j 〇-12, for example, spherical silica, spherical digassed titanium spherical knots, spherical interstitial silica resin particles, and the like. The surface roughness of the film is measured according to JIS B (1601-1982). The average surface roughness of the centerline is expressed as (Ra: n ·). The formula is as follows, where L image is rough in the centerline direction. The length of the degree curve captures a fixed value. • The center line of the extracted part represents X and the direction of vertical magnification of this part represents the threshold value. The surface roughness curve is represented by Y = f (x).

Printed by the Consumer Cooperative of the Central Standard Bureau of the Ministry of Economic Affairs. The guaranteed package value is as good as one touch. * 0) The structure of the connection layer is divided: the second is the second, the second is the second. The shape and mutual taste of the five-value ester plate, but the aroma method is to homogenize the two genus of contact with some square Ka Ping Yi, the gold connection of the middle and lower, and the first layer of the middle to the M to The second structure is a straight object containing 25. The first layer contains the internal benefit of 0. The second layer is composed of two containing two internal adducts. It is also thin and long, and the poly film male security deposit is stretched to obtain the thin layer. It is used to make the ester gold deposits used to pull the shaft and pull the acid, and it has the double-median axis. The difference between this film's bright and large agglomeration layer is the most obvious because of the thin structure. After the hair loss of the result, the tb sexual attachment will be double-sexed in addition to the original. 1-111— —1 Pack — — Order — I — I i ^ {Please read and read the note f% on the back to write this page) This paper size is applicable to China National Standard (CNS) A4 Washing (210X297mm) ) 434 1 44 A7 ____B7____ Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (Η) Includes melting and co-extrusion of the polyester and the composition of polysulfonate and polyester respectively , Laminated and fused together, biaxially stretched and The method of curing and other steps includes the steps of melting and extruding the composition of polyacetate and polysulfonic acid® and polyester to form a separate film, stretching, laminating, and fusing the thin sheets together. . Biaxial stretching methods include particle sequence biaxial stretching method, simultaneous biaxial stretching method, inflation bethod, etc. * The thickness of the film of the present invention thus prepared is between 5-100 # ·, 10-75 # is preferred. The thickness ratio (A / B) of the first layer (A) to the second layer (B / gt) is preferably 1 / 99-5G / 50, and 5 / 95-40. / 60 is more preferable, and 1 G / 9 0-3 0/7 0 is still to be selected. The biaxially stretched film of the present invention has the first layer (Α) and the second layer (B &gt;) of which the plane stretching ratio must be Between G. 0 5-0. 1 0. f = l (nx + ny) / 2 b ηζ where nx, ny and the refractive indices in the longitudinal, propagation, and thickness directions, respectively, are examples of refraction in the above equation: According to the following method, set up a Fukun M analyzer on the eyepiece side of the Abbe refractometer, and then use the color light (NaD rays) to measure the refractive index of the film in each direction. The fixing solution used is Diiodomethane, the measurement temperature is 25 edges. If the number of plane stretch nickel is too small, when the stretch ratio of deep drawing is too high, cracks will occur. If the number of plane stretch is too large, then Deep drawn The cracking phenomenon will easily occur in the process. The thermal recovery rate of 15 0eC of the double-stretched film of the present invention is preferably less than 10X, which is a thin film. 0-15- 1 ^ 1 i ^ i ^ nk. ^ ——F ^^^ 1 f-. In 1 ^ 1 ml ^ eJ (Please read the precautions on the back before writing this page) This paper size is applicable to China National Standard (CNS) A4 size (210X297mm) 434144 * A7 B7 Yin Jia, Central Kneading Bureau, Ministry of Economic Affairs, Shellfish Consumer Cooperative, V. Explanation of the invention (&lt; 4) The heat shrinkage rate is determined by the following method: two thin sticks are injected on the thin sample at room temperature (interval ID ») Then place it in an oven with 15ITC hot air circulation for 30 minutes, then cool to room temperature, mark the interval before and after heating, and divide the difference between the interval before and after heating by the interval before heating to represent the thermal shrinkage. If the film If the thermal shrinkage rate (150 ° C) is too large, when the thin layer is laminated on the metal plate, the dimension dimension will be small> and the defects such as «shrinkage» will easily occur on the film β. The peak temperature of the loss modulus α &quot;) located in the biaxially stretched film of the present invention is 1D0-16 (TC The loss modulus of elasticity. You use a dynamic viscoelasticity measuring device to measure the peak temperature of β at the highest temperature of the loss modulus of elasticity (ΕΗ) at a frequency of 10 Hz and a dynamic displacement of 2 5 X 1 0-4. The composition of polynitrate and poly_ and the degree of melt mixing are moderately tempered. If the highest peak temperature is higher than 160 eC, the film will become difficult to stretch, which will worsen the moldability of the continuous film. If the highest peak temperature is lower than lf10 &quot; C, the impact resistance of the film after canning will be poor. In addition, the biaxially stretched thin film of the present invention is best to have the following elongation at 10 (TC elongation at break (em) in TC) and the elongation at break (Eτ) in transverse direction of 10 ITC: (EM + ET) / 2 &gt; 150, and -50 ^ Em-Ετ £ 250 The tensile test was performed on a 10 mir wide rectangular sample using a tensile test Jg machine equipped with a heated probe, the test temperature was 10 ° C, the chuck spacing IDcb, Pressurizing-1 6- ---- ΙΓ, ------ install-(Please read the precautions on the back first and write this page)

, tT This paper size is applicable to the Chinese national standard (CNS &gt; A4 size (210X297 mm) 434144 Printed by the Ministry of Economic Affairs + Central Standards Bureau Beige Consumer Cooperative A7 _B7 V. Description of the invention (β) rate is 10c * / * in, when the sample breaks, the elongation (3t) represents its 100 W breaking elongation. "Set to represent the film extrusion direction perpendicular to the transverse direction. The breaking elongation at 100 ° C can be determined according to polyiodic acid and Make some adjustments to the composition of polyester, the degree of melt mixing, and the stretching conditions of the film. If the value of (εμ + ετ) / 2 is less than 150, the film will be difficult to stretch, and the shape of the arsenic film will be significantly reduced. ) / 2 is less than -50, the film will become so easy to rupture during the conveying phase. If this value is higher than 250, the anisotropy of the film will reach the end value, and the film will have low temperature impact resistance after lamination. The properties of the biaxially stretched film of the present invention are melted and quenched. The peak temperature (Tec 丨) of the low temperature crystallization of DSC and the melting and quenching of the above-mentioned samples are repeated three times. Four cycles) of thin film crystallization at DSC The temperature difference (Tcc4-Tccl) of Tcc4) is preferably between 1G and 60 ° C. The measurement methods of Tcc1 and Tcc4 are as follows: β Take a 20b g sample and heat it from the chamber at a heating rate of 2QeC per minute. To 90-C, keep at 90 * C for 3 minutes, then take out the sample box on an aluminum foil placed on ice for quenching and heat curing. The obtained sample is heated at a temperature of 20 ° C per minute in DSC. Heat and read the sample's low-temperature crystallization spike temperature (T cc 1). Similarly, take 2 卩 g sample and heat from room temperature to 290 ° C at a heating rate of 20 * C for 毎 minutes and keep at 290 ° C Leave it for 3 minutes, then take out the sample box on an aluminum foil placed on ice for quenching and heat curing. This-1 7----------- ^ install ------ order- ----- ▲ (Please read the precautions on the back / 4-, write this page) This paper size is applicable to China National Standards (CNS) A4 now (2 丨 0X297 public) Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by a consumer cooperative 4 3 4 1 4 4 A7 B7 V. Description of the invention (4) After the procedure is repeated four times, the sample obtained is heated in DSC at a rate of 毎 minutes 2 (liters of TC®), and the sample is read at a low end. Peak temperature (Tcc4) β The peak temperature Tccl and Tcc4 for low temperature crystallization can be adjusted according to the composition of polysulfonic acid and polyester, the degree of melt mixing and the amount of phosphorus compounds added. Β When this peak temperature difference (Tcc4-Tccl When the temperature is less than 10 ° 〇, the film will be difficult to stretch, and the flail film &gt; formability will decrease rapidly. If the peak temperature difference is greater than 60 ° C, the impact resistance after canning will be deteriorated. None is what we want. To prepare the biaxially stretched film of the present invention, an unstretched film is first stretched and then thermally cured. The selected stretching ratio and thermal curing conditions are as follows: the longitudinal stretching ratio is 2.5-3.6 times and the transverse stretching ratio It is 2.7-3.6 times, and the heat curing temperature is 15G-220 ° C (160-200 eC is preferred). As described above, the biaxially stretched film of the present invention is composed of a first layer and a second layer, but the third layer may further include a third layer adjacent to the second layer. The third layer is formed of polyester with ethylene terephthalate as the main repeating unit. Examples of such polyesters are the same as the first fluorene. Therefore, the description of the first layer of polyester is also valid for the third layer. As far as the biaxially stretched film of the present invention having the third layer is concerned, it is necessary to understand that the plane stretch number and Ra of the third layer are the same as the second layer of the biaxially stretched film of the present invention having a two-layer structure of the upper layer. . The thickness of the third layer is preferably between 0.5-lfl #. As far as the gold slabs to be laminated of the biaxially stretched film according to the present invention (to be other than those used for can-making) are concerned, tin-plated vehicle boards, tin-free pin plates, aluminum plates, and other steels are used. ----------- 1T ------ β (Please read the precautions on the back V &quot; write this page) This paper size is applicable to Chinese family members (CNS) Α4 is now U10X297 (Mm) 434 14 4 A7 B7 Impressions of the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () 1 The plates are suitable for throwing 0 The method of laminating thin films on metal plates is as follows: 1 1 0) The board is heated to a temperature higher than the softening point of the film, so that the thin 1 I film is laminated with the 9 cold section * to bond the two together. Please 1! (?) The film is coated with an undercoat layer in advance to form an adhesive layer.靥 9 Then read this adhesive 1 | Laminated on top of the gold plate adjacent to it 〇 Any known adhesive is back ft 1 I Applicable »For example epoxy based adhesive, radon / -Based adhesive, alkyd Note 1 I means I resin based adhesive, etc. Item 1 1 It is better to laminate the m-axis stretched film of the present invention on a metal plate. The second layer or writing sheet made of polyester composition 1 The third layer made of polyester is connected to the metal plate m &gt; and the first layer made of polyester 1 | is connected to the metal can The inclusions 9 are contacted to improve the m impact properties, the cobalt properties of the metal sheet, and the fragrance retention properties. For example, the biaxially stretched film of the present invention containing the first-* layer and the second layer of 1 1 is laminated on the metal. Inside the tank and the second layer is ordered | Must be directly connected to the metal tank 〇1 I The following will further explain the present invention 〇 However, these examples 1 are not limited to the invention 〇 Polyester and polysulfonate properties M fixed and thin 1! The evaluation criteria are as follows: Λ 本质 Intrinsic viscosity of the polyester [V] 1 1 M is determined in o-chlorophenol at 35 ° C 〇1 I Melting point of the polyester π B) and glass transition temperature Π g) 1 1 Scanning card meter (DSC) measurement. 1 © Polyester terminal carboxyl group concentration 1 I Tetrabromophenol blue is used as an indicator. 9 Hydrogenated benzyl alcohol solution is titrated in 1 1 phenol and tetrakisethane mixed solvent (2: ί 1). . 1 I -1 9- 1 1 1 1 This paper size is applicable to China National Standards (CNS) A4 (2 丨 OX297 mm) 434144 A7 B7 Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () (4) Viscosity average molecule (MV) 1 of polyacetate 1 Calculated according to the following formula Sc hn el 1 and obtained in the digas methane solution 1 I mass viscosity UV]) Calculated 0 1 1 Please 1 1 IV ] Read 1 1 Log Mv = 1-log — read t IC .83 1.23 X 10 -4 on the back 1 I (5) terminal hydroxyl concentration tone of poly (ester) 1 1 using the bb color method (D ie Μ r ο ίο 1. C he 1. 88 (1965) PP • 2 15) 1 1 1 Based on the interaction reaction between T i C1 4 and the terminal hydroxyl group m to obtain 〇im. 1 Observe the extruded state of the molten polymer * and then evaluate according to the following criteria. 1 | © "Melting" does not occur during extrusion molding% Extrusion 1 Forming is extremely stable 〇1 1 〇: "Melting undulation" phenomenon rarely occurs during extrusion molding | Extrusion can be regarded as stable 1 1 A; occasionally during the extrusion process &quot; melting swing H phenomenon t extrusion 1 1 instability of the formation 〇1 1 X frequently occurs during extrusion &quot;; Phenomenon * Extrusion of m A is virtually impossible. 0 (7) The stretchability of thin film! 1 Observe the stretched state of the film 9 and then evaluate it according to the following criteria. Ⅰ: It does not occur during the stretching process. Breaking phenomenon, the stretching m is stable! 〇 * There is almost no breaking phenomenon during the stretching process, and the stretching can be regarded as stable 1 1 set 0 I 1 △ * 4 During the stretching process However, the cracking phenomenon will occur and the stretching will be unstable. 0 1 1 -2 0-1 1 i 1 The size of this paper is in accordance with Chinese Standard (CNS) A4 (2 丨 OX 297 mm) 434144 Α7 Β7 Central Ministry of Economic Affairs Printed by the Zhuhai Bureau Shellfish Cooperative Cooperative V. Description of the Invention (π) X: Frequent breakage occurs during stretching, and stretching is virtually impossible. ⑻The processing properties of the film (rolling property) After forming a release layer and a retaining layer on a 5Q0iB wide and 2Q00II long film, roll the film. Check the appearance of the roll in detail. The number of the above lumps was then evaluated according to the following criteria. λ ❾: The number of block protrusions with a length of 1 m or more is 0: The number of block protrusions with a length of 1 «1 or more is between 1-5. X: The number of block-like protrusions with a length of 1 m or more is 6 mm or more. (9) Surface roughness (R a) is determined using a needle contact type surface roughness meter (SURFCORDER SE-30C, manufactured by Kosaka Laboratories Ltd.), provided that the needle radius is 2 μU * and the contact pressure. 〇3g, cut-off value ΰ · 2 5 β β-continuous film formability 48-hour continuous film formation, and then evaluated according to the following criteria: ®: During the 48-hour continuous mineral film formation, the number of film cracking occurred in The following β once: 2-3 times during the formation of continuous mineral ore during 4δ hours, thin film rupture occurred 2-3 times. Λ: 4-5 times during the formation of continuous mineral ore film formation. X: continuous 48 hours During the formation of the mineral film, the cracking of the thin cymbal occurred more than 6 times. ((Η) The average major diameter of the polyacrylate-2 1- (Please read the precautions on the back side r ^. Write this page). China National Standards &lt; CNS) A4 size (210X297 mm) Printed by the Consumers ’Cooperative of the Central Government Bureau of the Ministry of Economic Affairs«. 434144, A7 B7 ______ V. Description of the invention (/) Ultra-thin cutting machine for film samples (/) Including the thickness of the film (parallel and vertical directions) to make a film cut. Use 8 «1〇4 to stain the polysterate portion of this section sample, and then use a transmission electron microscope to take a photograph (acceleration voltage of 100 KV), and take a photo from the photograph (magnification: 5000-10000 times) Obtain at least 20 长 long diameter of polyetherate, and calculate its average value β (12> loss elastic modulus (maximum peak temperature loss elastic modulus of Ε 4 &lt; Ε &quot;) 葆 using dynamic viscous viscous Under the conditions of 10 位 Z frequency and ± 25X10-4 dynamic displacement, the peak temperature of the β position at the highest temperature of the loss elastic modulus is the highest peak temperature of the loss elastic modulus (£ &quot;) "(1 3) 1 0 tr C Elongation at break Using a tensile tester (manufactured by Tensilon Universal Tensile Tester of Toyo Baldwin Co., Ltd.) equipped with a heated probe, a tensile test was performed on a 10 * «wide rectangular sample. The temperature is 10 (TC, the chuck distance is 10 cia, and the compression rate is 10 ce / nin. When the sample is broken, the elongation (X) represents its 100 * 0 elongation at break. &Lt; 1 4) Low temperature crystallization spike Temperature (T cc 1 and T cc 4 &gt; Using DSC, take a 20 · g sample at 20Ό The temperature rate was heated from room temperature to 29 ° C, held at 29 ° C for 3 minutes, and then quenched. The low-temperature crystallization spike temperature of this sample represents the Tccle sample. The film was heated, maintained at high temperature, and quenched as described above. After four cycles of heating, the muddy fire sample was heated at a heating rate of 20 ° C. (The low-temperature crystallization peak temperature obtained by T represents Tcc4e -22- ---------- predicated- ----- Order ------ β (Please read the precautions on the back ... write this page first) This paper size is easy to use China® furniture standard (CNS) Α4 is now (210 × 297 mm) "4 3 4 1 4 4 j A7 _B7_" printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, V. Description of the invention (W) (1 S) Peel strength Place two thin sheets of the same type on two pieces of 210 # · In the middle of the thick supply plate, this pin plate has been electrolytically treated with chromic acid. The layer to evaluate the peel strength is placed on the outside (connected with the metal plate). The pressure of kg / cn2 was heated at 285 ° C for 30 seconds. The obtained laminated board was cut into a sample specimen of 10m width and 50 SB length. The end of this sample was pre-coated with 201 · faint peel. It can be separated by using a concrete laminate. The two laminates are separated from each other in the opposite direction from the mold release agent coated with 20 »« 寛 to form a T-shape. Both ends of the separated part are tested by a tensile tester. Fix and measure the peeling degree at 20β · / «ΰη pressure rate (according to JIS K6854 method). U6) Low-temperature impact resistance The same method as described above was used to prepare a composite sheet composed of a single film and a single pin plate. After the laminated board was made, it was stored in 5QT: water for 5 days, and then the laminated board was subjected to an impact deformation resistance test according to the JIS K54QD method. In other words, a die with a radius of curvature of 5 B »is fixed on the film without a cymbal layer, and then it is dropped from the height of 2flc« to the punch with a static weight of 3G0g. At the same time, a 5-foot-thick oak cymbal board was placed under the cymbal board. After this impact deformation test, an electrode was fixed on the film without lamination, and another electrode was fixed on the cotton cloth impregnated with IX saline solution. The cotton was placed on the surface of the other film of the laminate. (That is, the position where the static weight is accepted) ^ Measure the current value by applying a voltage of 6V • The smaller the current value (A), the better the low temperature balance resistance ^ (17) fragrance retention -23- I ---- ------ ^ ------ 1T ------ 2 (Please read the notes on the back first. Γ_This page) This paper size is applicable to China® home kneading rate (CNS) Α4 specification (210X297 mm) Printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, 4 3 4 Μ 4, Α7 ________B7 ___ Five 'Invention Description (") Cut the laminated board into a 150 MW diameter dial, and use a drawing die And deep-drawing with four scales and a weighing bed to form a sideless container with a diameter of 5 5 »« (hereinafter referred to as a golden canister). The inner side is a gold scraper can with a built-up film. 2 0 PP »d- The aqueous solution of the string was left to stand for 5 days. Then the film was peeled off, and the peeled film was cut into 15 caX15cia test pieces, and then heated at 80 ° C for 30 minutes. Then the gas phase layer was used. The amount of d-Ning adsorbed by 毎 克 胜 膜 was determined by surgery. The smaller the amount of rubbish attached, the better the fragrance retention. The fragrance retention is estimated according to the following criteria: 〇: The adsorption Dong is equal to or less than polyethylene terephthalate. △: The amount of adsorption is slightly larger than polyethylene terephthalate β X: The amount of refuse attached is larger than polyethylene terephthalate β Examples 1 to 8 and Comparative Examples 1 to 4 Preparation of a layer of polymer (A))] Copolymerization of polyethylene terephthalate with 12 isophthalic acid X isophthalic acid by solid-phase polymerization method, the intrinsic degree of isobenzoic acid is 0.64, 楱It is prepared in the presence of germanium dioxide catalyst, which contains B.3 reunion. The average particle size ratio is 1.1 and the average particle size is 0.3. U bis gasification titanium β melting point of this polyester It is 22 9T :, the glass transition temperature is 73 * 0 β [preparation of polyacetate] 216 parts by weight of diphenyl ether, 228 parts by weight of bisphenol A and 0.05 parts by weight of bisphenol A are sold In the reactor, the reactor is equipped with a stirrer and a vacuum steaming system with a nitrogen inlet. The reaction strip is first degassed under vacuum at room temperature and then replaced with nitrogen. The nitrogen gas step is repeated three times. Then, the 30 minute mirror is heated at normal pressure and 19Q ° C for -2 4- (Please read the precautions on the back first to write this page) The paper size is applicable to the Chinese national standard (CNS) Α4 specifications (210 × 297 mm) ^ 3414 4 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ A7 B7 V. Description of the invention (&gt; 〇 Anti-grinding, make the mill &gt; force slowly drop to 5D within 60 minutes ** Hg &lt; &gt; The reaction temperature was then heated to 290 in about 60 minutes. (: Here, the heating vacuum was changed from 50 ilHg to less than 1 eBHg. During this reaction, phenol is distilled off due to the reaction. After carrying out incubation under the same conditions for 40 minutes, a polyphosphonic acid having a terminal hydroxyl group degree of 73 equivalents / 10 g and a viscosity average molecular weight (Mv) of 2 6, 0 0 0 was obtained. Polyester / Polyfluorene Composition Film (Polymer (Second Layer (B)) Polymer and Preparation of Film)] Blend polyethylene terephthalate and polybutylene terephthalate in the proportions shown in Table 1. A mixture of the above-mentioned polybasic acid ester and polyester was prepared, and then β-OPP (indicated by phosphorus concentration) phosphoric acid was added as a phosphorus compound. The resulting mixture, together with the first layer &lt; A), was co-extruded with a double-layer spade die to form a double-layer unstretched film. In this extrusion process, after drying, the polyester polymer of the first mill (A) is melt extruded using an extruder at a polymerization temperature of about 280 eC, and the second layer (B) is also Melt extrusion at a polymerization temperature of about 29 ° C. The laminated film prepared by this double-roller mold is cooled and rolled on a cast stick to obtain an unstretched film. Then, it is unstretched at a temperature of 130 ° C. The film is stretched to 3.0 times in the transverse direction, and then stretched to 3.0 times in the direction of 130 4C. Finally, it is thermally cured at 18fl ° C to obtain a biaxially stretched film. -25- This paper size Applicable to China's impoverished family (CMS) Α4 specification (210 × 2ίΐ7 mm) (Please read the precautions on the back / write this page first) Pack_ * 1T * 434144

7 7 AB V. Description of the invention (μ) Table 1 Polycarbonate (wt.%) Polyester (wt.%) Polyethylene terephthalate (% by weight) Polybutylene terephthalate (wt.%) Comparison Example 1 18 82 60 40 Example 1 22 78 60 40 Example 2 40 60 60 40 Comparative Example 2 62 &gt; 38 60 40 Comparative Example 3 40 60 8 92 Example 3 40 60 12 88 Example 4 40 60 20 80 Example 5 40 60 40 60 Example 6 40 60 80 20 Example 7 40 60 85 15 Example 8 40 60 88 12 Comparative Example 4 40 60 92 8 f K --------------------- --ST--1 ---- ^ (Please read the precautions on the back first and fill in this page) The biaxially stretched film thus prepared has a first layer (A) with a plane stretching factor of 0.06, The plane elongation coefficient of the second layer (B) is 0-5, the thickness of the first layer (A) is 6 # 1, and the thickness of the second layer (B) is 24 // *. The thermal shrinkage of l5GeC of this film is 5-75; The above-mentioned polyethylene terephthalate and polybutylene terephthalate were printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, both of which were prepared by solid-phase polymerization. When the former is used, the intrinsic viscosity is 0.64, melting point is 255 ° C, glass transition temperature is T8eC, and -2 6-This paper size uses China National Standards (CNS) A4 specifications (210X297 mm) 434144

Printed by the Central Government Bureau of the Ministry of Economic Affairs and the Industrial Cooperative Cooperative. V. Description of the invention (&lt;) The terminal carboxyl group concentration is 15 equivalents / 1 () 6 grams. When using tetrabutyl titanate® medium, the intrinsic viscosity is 1.1, The melting point is 223 ° C, the glass transition temperature is 32eC, and the terminal carboxyl group concentration is 10 tango / 106 g. The evaluation results are shown in Table 2. K can be seen from the table that the biaxially stretched film of the present invention has Excellent extrusion processability, stretchability, metal sheet adhesion, low temperature impact resistance and fragrance retention. Table 2 Extrusion processability stretchability peel strength (kg / cm) low temperature resistance Impact (mA) Fragrance retention Comparative Example 1 〇06 0.5 〇 Example 1 ◎ ◎ 6 0.2 〇 Example 2 ◎ ◎ 3 0.1 〇 Comparative Example 2 XX Comparative Example 3 Δ Δ 3 0.5 〇 Example 3 0 〇2.5 0.1 〇 Example 4 〇 2.5 2.5 〇 Example 5 ◎ ◎ 3 0.1 〇 Example 6 ◎ ◎ 3 0.1 〇 Example 7 〇 03 0.1 〇 Example 8 〇 03 0.1 〇 Comparative Example 4 XX -27 The size of this paper is applicable to the standard of China National Family Standard (CNS) 8-4 (210XW mm) • -Il · --------, installed ------ order- ----- A (Please read the precautions on the back of this page, and write this page) 434144 Printed by the Ministry of Economic Affairs, Consumers Cooperative, A7 _B7___ 5. Explanation of the invention (Comparative Example 5 in Example 2 In the use, only the second employment (B) (thickness 3Q # b>) was used, and the first layer (A) was not used. It was found that its fragrance retention decreased to the level of X β 贲 Examples 9-16 and Comparative Example 6 -7 Put 216 parts of diphenyl heavy acid, 2.8 parts by weight of bisphenol A, and 0.05 parts by weight of bisphenol A sodium salt into a reactor, which is equipped with a stirrer And a vacuum steamed preserved meat system with a radon inlet, this reaction system is first degassed at room temperature, then replaced by radon gas, the step of introducing radon gas is repeated three times. Then at normal pressure and 190T The reaction is heated for 3D minutes, and the pressure is gradually reduced to 50 * BHge within 60 minutes, and then the reaction temperature is heated to 29Q-C within about 60 minutes. At the same time, the vacuum is changed from 5t) BnHg Below 1 * BHg. During this reaction, phenol will be steamed out due to the reaction. After carrying out the reaction under the same conditions for 40 minutes, the terminal hydroxyl group is 48 Polyester with equivalent weight / I0e grams and a degree average molecular weight U v) of 28,000. The thus-obtained polyacrylate is 4 5 PPB (expressed in pounds) as a phosphorus compound. ADK STAB 2 112 (manufactured by Asahi Denka Eogyo Co., Ltd.) is mixed and then melt-extruded. [Preparation of laminated film] Polyethylene terephthalate (its intrinsic viscosity is 0.64, Pseudo-prepared in the presence of germanium dioxide catalyst. It contains 0.2% by weight x average particle size ratio of 1.1 and average particle size of 0.3 &gt; The melting point of this polyethylene terephthalate is 2 5 5 ° C • The glass transition temperature is 78 * C (for the polymer of the first layer (A)). -2 8-— — 1 — ^ 装 IΪΤ_ ^ (Please read the precautions on the back rih-write this page first) This paper size applies to China National Standard (CNS) A4 (210X297 mm) Central Bureau of Standards, Ministry of Economic Affairs Printed by a consumer co-operative cooperative 434144 ^ A7 B7 V. Description of the invention (") As shown in Table 3, 40% by weight or more of the polyacrylate was prepared, and 60% by weight of polyethylene terephthalate-based poly- &lt; 70 Chongtong! Π Polyester terephthalate-based polyester (30 weight X) dry blend of polyester >> This polyethylene terephthalate-based polycool and polyterephthalate The succinate-based polyesters are all prepared by solid-phase polymerization. The former uses a digassed germanium catalyst, and the latter uses a tetrabutyl titanate catalyst. As shown in Table 3, the intrinsic viscosity of the prepolymer is changed. Phase &gt; Solid-phase polymerization time and terminal carboxyl group concentration in the polymerization reaction. Table 3 PET-based polyester mm intrinsic viscosity melting point CC) glass calendar CC) terminal pen group concentration (equivalent / 106 g) Comparative Example 6 PET 0.75 255 78 4 Example 9 PET 0.75 255 78 12 Example 10 PET 0.75 255 78 20 Example 11 PET 0.75 255 78 30 Example 12 PET 0.75 255 78 30 Example 13 PET 0.75 255 78 30 Comparative Example 7 PET 0.75 255 78 30 Example 14 PETI12 0.75 229 74 25 Example 15 PETI12 0.75 229 74 12 Example 16 PETI12 0.75 229 74 30 -2 9 -This paper size is applicable to the Chinese Girl Standard (CNS) Α4 (2 丨 0X297mm) 1.1-Γ ------ .. Attack ------ 袭 τ ------ J- (Please read the precautions on the back first to fill in this page) 434 14 4 ^ A7 B7

V. Description of the invention () PET: polyethylene terephthalate PETI12: PET copolymerized with 12 mol X isophthalic acid Table 3 (continued) PBT-based polyester intrinsic viscosity melting point CC) glass transfer brewing (° C) Terminal carboxyl group concentration (equivalents / 106 g) Comparative Example 6 PBTI5 0.9 218 28 8 Example 9 PBTI5 0.9 2 18 28 8 Example 10 PBTI5 0.9 218 28 8 Example 11 PBTI5 0.9 218 28 8 Example 12 PBTI5 0.9 218 28 12 Example Π ΒΒΤΪ5 0.9 218 28 18 Comparative Example 7 PBTI5 0.9 218 28 22 Example 14 PBT 0.9 223 32 10 Example 15 PBT 0.9 223 32 18 Example 16 PBTI5 0.9 218 28 8 {Please read the back page first Attention item V--Fill in this page). Packing-Order the Ministry of Economic Affairs, Central Bureau of Standards, Shellfish Consumer Cooperation, Du Yin 袈 PET: Polybutylene terephthalate PETI5: Copolymerized with 5 mol 5 liters of isophthalic acid PBT The above polyethylene terephthalate and polysulfonate-polycopolymer blends are all dried according to commonly used methods, and then fed to their respective extrusion machines to form double-layer co-extruded laminated films. Blended polymer melt extruded from co-extrusion slit, polyethylene terephthalate Polymerization temperature is 280 -3 0-This paper size applies Chinese National Standard (CNS) A4 specification (2tOx297 mm) 434144 A7 B7 5. Description of the invention (β) ° C, and the polymerization temperature of the blended polymer is 2 8 0 -2 90 ° Ce co-extruded film is cooled and rolled into an unstretched film on a casting rod after cooling. The unstretched thin film was then stretched to 3.0 times in the transverse direction at a temperature of 135 ° C, and then 3.0 times in the longitudinal direction at a temperature of 135 ° C, and finally heat cured at a temperature of 180 &quot; C. Preparation of biaxially stretched film In the biaxially stretched film thus prepared, the thickness of the polyethylene terephthalate layer was 5 # ·, and the plane ^ stretch coefficient was 0.0 7, and the polymer layer was blended with The thickness is 20 # *, and the plane drawing pseudo-number is 0.06. The film's 150 &quot; C thermal shrinkage is 5-73 :. The evaluation results are shown in Table 4. When the terminal carboxyl group concentration of the poly (terephthalene) ethylene-based polyester is more than 5 equivalents / lfl6 g, and the terminal carboxyl group concentration of the polybutylene terephthalate-based polyester is less than 20 equivalents / 10e g The obtained film has excellent adhesion to the gold plate, and the film-forming properties (extrusion processability and stretchability) of the film can also be assured. l · ---- = ----- j outfit ------ order ------ i (please read the precautions on the back vv first to write this page) The Central Consumers' Bureau of the Ministry of Economic Affairs, the Consumer Cooperatives Imprint-3 1- This paper size applies to China National Standards (CNS &gt; A4 size (210X297 mm) 434144 A7 B7 Printed by the Consumer Cooperatives of the Central Ladder Standard Bureau of the Ministry of Economic Affairs 5. Description of the invention (Table 4 Extrusion) Processability Stretchability Peel Strength (kg / cm) 冲击 Impact Resistance (mA) Fragrance Retaining Comparative Example 6 Δ X Example 9 ◎ 〇 2.5 0.1 〇 Example 10 ◎ ◎ 2.5 0.1 〇 Example 11 ◎ ◎ 2.5 0.1 ○ Example 12 ◎ 3.0 3.0 〇 Example 1 3 〇 3.5 3.5 〇 Comparative Example 7 XX Example 14 ◎ ◎ 2.0 0.1 〇 Example 15 〇 2.0 2.0 〇 Example 16 ◎ ◎ 2.5 0.1 〇 Example 17 -20 at 40 weight 5; Polyacrylic acid used in Example 1-8 "and 60 weights of Tongren, which are composed of polyethylene terephthalate and polybutylene terephthalate and 5 used in Example 11. Polyester dry blend blended with Mohr X isophthalic acid as ADK STAB 2112 (Asahi Denka Kogyo Co., Ltd. The addition amount (expressed as phosphate) is shown in Table 5. The laminated film was prepared under the same conditions as in Example 11. The results are shown in Table 5. We found that when the phosphorus compound was added at 20-10 0 PP. * In between, you can get good results. -32- Zhang scale general Chinese national 搮 隼 (CNS &gt; Α4 grid (210X297 mm) ---. L · --------- Install ------ order ------ i (please read the precautions on the back Η% write this page) 434 1 44 Α7 Β7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (~) Sell 5 Example 17 Phosphate addition amount (PPm) Extrusion molding processability Stretchability Peel strength (kg / cm) Lin Impact resistance (mA) Fragrance retention 22 〇2.5 0.1 〇 Example 18 40 ◎ ◎ 2.5 0.1 〇Example 19 50 ◎ ◎ 2.5 0.1 〇Example 20 95 ◎ 3.0 0.1 〇 Examples 21-27 and Comparative Examples 8-11 [for polyester film layer (first layer (A)) Preparation of polymers] Copolymerization of polyethylene terephthalate and 12 mol X isophthalic acid by solid-phase polymerization. The intrinsic viscosity of isophthalic acid is 0.64. Existence It was prepared as follows, which contained 3 weight X average particle size ratio of 1.1 and average particle size of G.3jub. Titanium vaporized · The melting point of this polyester was 229 ° C, and the glass transition temperature was 73 ° C. The nitrate was the same as in Examples 1-8. [Preparation of Polymer for Polyester-Polyester Composition Film Layer (Secondary (B)), and Preparation of Polyester Film] Blend polyethylene terephthalate in the proportion shown in Table 6 » Polybutylene terephthalate was used to prepare the above-mentioned polyphosphonate and polyester mixture, and then 4PP · (expressed as phosphoric acid degree> phosphoric acid as a phosphorus compound was added. The resulting mixture together with the first layer (A) was doubled. Co-extrusion of a thin layer die to make a double-stretched unstretched film. In this extrusion process, the polyester polymer of the first (A) is dried and melt-knocked using an extruder at a polymerization temperature of about 28 JTC. Extrusion -33- 'The paper size is applicable to China Gujia Standard (CNS) Α4 size (210 × 297 mm) Packing --- ----------- J- (Please read the precautions on the back / ¾ K) 434144 Printed PET: Polyethylene terephthalate PBT: Polybutylene terephthalate-34- A7 B7 Printed in the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The layer (B) is also melt-extruded at a polymerization temperature of about 29G ° C. The laminated film polymer obtained by this double-mould molding is cooled and wound on the inlay stick That is to obtain an unstretched film, then this unstretched film was stretched to 3.0 times in the transverse direction at a temperature of 130 &quot; C, and then stretched to 3.4 times in the longitudinal direction at a temperature of 14 ETC, and finally at a temperature of 180 ° C. Biaxially stretched product is obtained by heat curing. Table 6 Polycarbonate (Weight, 0Λ) Polyester (% by weight, PET (% by weight), PBT (% by weight)) Long diameter (μηι) of polycarbonate dispersed particles Comparative Example 8 18 82 40 60 0.9 Example 21 22 78 40 60 0.7 Example 22 40 60 40 60 1.7 Comparative Example 9 62 38 40 60 Unstretchable Comparative Example 10 40 60 8 92 0.3 Example 23 40 60 12 88 0.8 Example 24 40 60 20 80 1.0 Example 25 40 60 60 40 3.1 Example 26 40 60 80 20 4.3 Example 27 40 60 88 12 15.0 Comparative Example Π 40 60 92 8 Cannot be stretched 夂 Paper dimensions are applicable to Chinese national standards ( CNS) A4 specification (210X297mm) I ---- P ------ ^ copy ------ 1T ------ 2 (please read the precautions on the back first H ^ write copy (Page) 434144 A7 __B7_ V. Description of the invention (W)

The biaxially stretched film thus prepared has a plane stretch pseudo-number of the first layer &lt; A) of 0.06, a plane stretch pseudo-number of the second layer (B) of 0.05, and a thickness of the first layer (A). The thickness is 6 # ·, the thickness of the second layer (B) is 24 # · β, the thermal shrinkage of the thin film at 150 ° C is 5-7U, and the above polyethylene terephthalate and polybutylene terephthalate All were prepared by solid-phase polymerization. For the former, if the medium is used, the intrinsic viscosity is 0.64, the melting point is 2 &amp; 5eC, the glass transition temperature is 78 ° C, and the terminal carboxyl group concentration is 15 equivalents / 10e g. In the medium, the intrinsic viscosity is 1.1, the melting point is 223 ° C, the glass transition temperature is 32 ° C, and the terminal carboxyl group concentration is 10 equivalents / 106 g. The evaluation results are shown in Table 7. It can be seen from the table that the biaxially stretched film of the present invention has excellent extrusion processability, stretchability, adhesion to metal plates, low temperature impact resistance, and heat retention. -, Binding J (Please read the note on the back V4 first to write this page) The Central Standards Bureau of the Ministry of Economic Affairs, Peigong Consumer Cooperative Co., Ltd.-3 5- This paper size is applicable to China National Standard (CNS) A4 specification (2 丨 〇 X 297 mm) 434144 A7 B7 V. Description of the invention (material) Table 7 Extrusion molding processability Tensile peeling strength (kg / cm) Low temperature impact resistance (mA) Comparative example of fragrance retention 8 〇〇0.8 0.8 〇Example 21 ◎ ◎ 6 0.2 〇Example 22 ◎ ◎ 3 0.1 〇Comparative Example 9 XX Comparative Example I 〇Δ Δ 3 0.5 〇Example 23 〇2.5 2.5 〇Example 24 〇2.5 0.1 〇Example 25 ◎ ◎ 3 0.1 〇 Example 26 ◎ ◎ 3 0.1 〇 Example 27 〇 03 0.1 〇 Comparative Example 11 XX Example 28-3 4 and Comparative Example 12_13 According to the same method of Example 9-16 and Comparative Example 6-T The film was stretched axially, but the terminal carboxyl group concentrations of the PET-based polyester and the PBT-based polyester therein were changed as shown in Table 8. The results are shown in Tables 8 and 9. ---- η ------ Ί 装 ------ 订 ------ i (Please read the precautions on the back / write this page) The Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives Printing -36- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 4 34 4 4

A V. Description of the invention (V) Table 8 Concentration of long-term terminal carboxyl group (equivalent A 06 g) of PET PBT polycarbonate dispersed particles Terminal carboxyl group concentration (equivalent / 106 g) (μπι) Comparative Example 12 4 6 Unstretchable implementation Example 28 15 '6 6.7 Example 29 25 6 4.3 Example 30 35 6 2.8 Example 3 1 35 10 3.7 Comparative Example 13 35 25 Unstretchable Example 32 30 8 3.0 Example 33 15 16 4.1 Example 34 35 6 3.5 I --- η ----- 'attack—— (Please read the precautions on the back-if you fill out this page)

'Printed by the Central Consumers' Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives-37- This paper size 14 uses the Chinese National Standard (CNS) A4 specification (210X297 mm) 434144 A7 B7 V. Description of the invention (bucket) Table 9 Extrusion Chengtong processability, stretchability, peeling strength (kg / cm), low temperature impact resistance (mA), county-level comparative example 12 ΔX Example 28 ◎ 3.0 3.0 0.1 Example 29 ◎. ◎ 2.5 0.1 〇 Example 30 ◎ ◎ 2.5 0.1 〇 Example 3 1 ◎ ◎ 2.5 0.1 〇 Comparative Example 13 XX Example 32 ◎ ◎ 2.5 0.1 〇 Example 33 〇 2.5 2.5 〇 Example 34 ◎ ◎ 2.5 0.1 〇 (Please read the notes on the back first% (4 write this page). Packaging. The Ministry of Economic Affairs of the Ministry of Economic Affairs, Bureau of Shellfish Consumer Cooperatives printed Examples 35-43 and Comparative Example 14-U. Polymers and Applications for Polyester Film (First 1 (A)) The polymer applied to the polycarbonate-polyacetate composition film layer (second step (B)) is the same as that in Example 8 and Comparative Examples 1-4. [Preparation of polymer for polyester film layer (third layer (0)] Copolymerization of 15 mol X isophthalic acid with polyethylene terephthalate and isophthalic acid by solid phase polymerization method, isophthalic acid The intrinsic viscosity is 0.60, which is prepared in the presence of a dioxin catalyst. The melting point of this polyester is 218 ° C and the glass transition temperature is 72 ° 0. [Preparation of laminated film] -3 8 ^ Λ This paper size is in accordance with the Chinese Standard (CNS) A4 specification (2) 0 × 297 mm. 1 λ / 1 1 4 4 ^ Α7 Β7 Printed by the Consumer Cooperative of the Central Ladder Bureau of the Ministry of Economic Affairs. 5. Description of Invention (β) is used for The polyester of the first layer (A &gt;, a polyester-polyester composition for the second layer (B &gt;), and the polyester for the third layer (C), as described above, have a three-layer wedge. Three layers of unstretched laminated film were prepared by sequential co-extrusion. After the polyester polymers of the first layer (A) and the third layer (C) were dried, the extruder was used at a polymerization temperature of about 28 (TC). Melt extrusion is performed, and the second layer (B) is also melt extruded at a polymerization temperature of about 29 G &quot; C. The 稹 layer film obtained through the three-shot molding is cooled &lt; The unstretched film was sown above. Then the unstretched film was stretched to 3.0 times in the transverse direction at a temperature of 130 ° C, then stretched to 3.G times in the longitudinal direction at a temperature of 135 ° C, and finally at 180 ° C. The biaxially stretched film is prepared by thermal curing at a temperature of ° C. The biaxially stretched film thus prepared has a plane stretched image number of 0.06 for the first layer (A), and a second layer (B &gt; The plane tensile coefficient is 0.05, the plane tensile coefficient of the third layer (C) is Q.06, the thickness of the first layer (A) is 3 # η, and the thickness of the second layer (B) is 24 / iB. The thickness of the three layers (C) is. The 150DC thermal shrinkage ratio of this film is 5-7 ×. The evaluation results are shown in Table 10. The three-layer biaxially stretched film of the present invention has excellent extrusion molding processability, can be Tensile properties, low temperature impact resistance and fragrance retention, and the adhesion to metal plates have also been greatly improved. Table 10 also shows the polyesters and polymers used in the composition of the second layer (B). The melting point of gallate. -39- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) ί 1 ^ — ^ 1--ll · j. ^^^ 1 ^ lfl ^^^ 1 eJ (Please read the note on the back # (Written on this page) 434144, A7 B7 V. Description of the invention (4) Table 10 Melting point (° C) of the composition Extrusion processability Stretchability Peel strength (kg / cm) Miscellaneous impact resistance (mA) Guarantee Fragrance Comparative Example 14 * 251/220 〇07 0.5 〇 Example 35 250/220 ◎ ◎ 7 0.2 〇 Example 36 251/221 ◎ ◎ 7 0.1 〇 Example 37 251 /-◎ ◎ 7 0.1 〇 Comparative Example 15 25 1 /-XX Comparative Example 16-/ 224 Δ Δ 7 0.5 〇 Example 38-/ 224 〇07 0.1 〇 Example 39-/ 223 〇07 0.1 〇 Example 40 251/221 ◎ ◎ 7 0.1 〇 Implementation Example 41 252 /-◎ ◎ 7 0.1 〇 Example 42 252 /-〇07 0.1 〇 Example 43 253 /-〇07 0.1 〇 Comparative Example Π 253 /-XX * Melting point of polyethylene terephthalate / The fit of polybutylene terephthalate · m itt rtt it rn n I tit j 1 \ J. HJ ^ i flf .¾. .1 ^ (Please read the precautions on the back first V% write this page) Melting point printed by Zhongli Bureau Shellfish Consumer Cooperative of the Ministry of Economic Affairs Example 4 4-5 1 and Comparative Examples 1 8-1 9 Polymer used in the first layer (A) and polymer used in the second layer (B) Polyester-polyester composition The polymer film layer Yu Example 9-16 and Comparative Examples 6-7 are the same. [Preparation of polymer for polyester film 第三 (third layer (C &gt;)]-4 0-This paper is scaled to China Standards (CNS) A4 (210X297 mm) 434144 A 7 B7 5 Description of the invention (shirt) Copolymerization of poly (ethylene terephthalate) and 7 mol X isophthalic acid by solid phase polymerization method, the intrinsic viscosity of isophthalic acid is 0 · β0, and nickel In the presence of plum media, β is obtained. The melting point of this polyester is 2 38 eC, and the glass transition S degree is 76 ° Ce. [Preparation of laminated mold] The above polyethylene terephthalate, polyacetate-polya The composition and polyethylene terephthalate are cool, and the copolymers are dried according to commonly used methods, and then fed to their respective extrusion machines to form three-layer co-extruded laminated films. Polyethylene terephthalate , Polysulfonate-polyester composition and polyethylene terephthalate copolymer are melt-extruded from co-extrusion slits, and their polymerization temperatures are 2 8 (TC, 2 8 0-2 9 QC And about 2 8 (TC.) The co-extruded film is cooled and wound on an inlaid stick to make an unstretched laminated film laminated in the above order. The unstretched film was stretched to 3.fl times in the transverse direction at a temperature of 5 90, and then 3.0 times in the longitudinal direction at a temperature of 135 eC. Finally, it was thermally cured at a temperature of 180 ° C to obtain a biaxially drawn film. Extruded layer film "The biaxially stretched film thus prepared had a first layer (A) (polyethylene terephthalate layer) having a plane stretch number of 0 · M and a second layer (B) ( Polyester-polyester layer) has a plane tensile coefficient of 0.06, and the first layer (nmi tn 1 ^ 1 ^^^ 1 I. 1 ^ 1 i I i in ^ 'J (Please read the Please fill in this page again.) Printed by the Ministry of Economic Affairs of the Ministry of Economic Affairs of the Sample Cooperative Consumer Cooperatives Co., Ltd. * Αί 5 1 is the thickness of the thick &gt; thin (C this layer. Three) Articles * Poly Co-Ester Diacetic acid (B two-layer benzene di-para-poly ο 2 is the degree of thickness and the rate of heat shrinkage ρ is shown in the evaluation of the evaluation of the film 15% 7 esters of poly (diphenylene) benzene diacetic acid p-poly (p-phenylene) in the 0- 4 畺 当 5 at the concentration. The carboxyl-terminated methylbenzene is p-polymerized and the Chinese paper standard (CNS) A4 (2! 0X297 mm) is applied on the scale of the paper. 434144 A7 B7 V. Description of the invention ( 〇) Butyric acid When the terminal carboxyl group concentration of the ester-based polyester is less than 20 equivalents / 106 g, the obtained film has the adhesiveness of Lujiayujin, and the film forming property (formability and stretchability) is also good. Can be intriguing .: ---, h ------. Install -------- order I .------ meaning (please read the note f on the back / ¾ write this page) ) Printed by the Central Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, Example 5 2-5 5 at 40% by weight! Polynitrate used in Examples 35-43 and 60% by weight of polymer pair used in Example 46 A dry blend of a polyester composed of ethylene phthalate and polybutylene terephthalate copolymerized with 5 mol X isophthalic acid as a dish compound. ADK STAB 2 112. {Asahi Denka Kogyo Co., Ltd.) is shown in Table-4 2-

Table II Extrusion processability, stretchability, peeling strength (kg / cm), low temperature impact resistance (mA), aroma retention, comparative example 18 ΔX Example 44 ◎ 〇6 0.1 〇 Example 45 ◎ ◎ 6 0.1 〇 Implementation Example 46 ◎ ◎ 6 0.1 〇 Example 47 ◎ ◎ 6 0.1 〇 Example 48 〇 〇 6 0.1 〇 Comparative Example 18 XX Example 49 ◎ ◎ 6 0.1 〇 Example 50 〇 5.5 5.5 〇 Example 5 1 ◎ ◎ 6 0.1 〇 This paper size is based on Chinese solid sample (CNS &gt; A4 grid (210X297 mm) 434144 A7 B7_ 5. In the description of the invention (4f) 12, the laminated film was prepared under the same conditions as in Example 48. The results are shown. In Table 12. We found that when the phosphorus compound is added in the amount of 20 -1 0 0 PPβ, good results can be obtained. (Please read the precautions on the back-if% write this page), install Examples 56-62 In Example 36, the copolymerization of isophthalic acid used in the third layer (C) polyester was changed as shown in Table 13. The melt adhesion of each polyester is also shown in Table 1. 3 中 β, tr Λ. Printed by the Central Consumers' Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives -43- Table 12 Addition of Phosphorus Compounds ( ppm) Extrusion processability Stretchability Peel strength (kg / cm) Longitudinal impact resistance (mA) Fragrance retention Example 52 22 〇〇0.1 0.1 〇Example 53 40 ◎ ◎ 6 0.1 〇Example 54 50 ◎ ◎ 6 0.1 〇 Example 55 95 ◎ ◎ 6 0.1 〇 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 434144 V. Description of the invention Table 13 Amount of copolymerized isophthalic acid (Mole %) Melting point (° C) Example 56 0 (polyethylene terephthalate) 255 Example 57 2 250 Example 58 &quot; 4 245 Example 59 10 230 Example 60 15 218 Example 61 20 205 Example 62 The results of 25 193 are shown in Table 14. When the amount of isophthalic acid is between 3 and 20 Moore X (Examples 5 8-6 1), good results can be obtained β (Please read the (Note 74 written on this page) • Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -44- This paper size is applicable to the Chinese National Standard (CNS) Α4 grid (2 丨 0X297 mm) Δ Δ 1— 4 3 4

AB 5. Description of the invention (40 Table 14 Extrusion processability Stretchability Peel strength (kg / cm) Low temperature impact resistance (mA) Fragrance retention Example 56 ◎ ◎ 5 Ol 〇 Example 57 ◎ ◎ 5.5 0.1 I 〇 Example 58 ◎ &lt; ◎ 6 Ol 〇 Example 59 ◎ ◎ 6.5 Ol 〇 Example 60 ◎ ◎ 7 Ol 〇 Example 6 I ◎ 7.5 Ol 〇 Example 62 〇 0 0 0 〇- --U ------ '^-(Please read the precautions on the back and fill out this page first.) The Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, printed examples 63-68. In Example 46, The thickness of the isophthalic acid used in the copolymerization of the third layer (C) of polyethylene terephthalate is shown in Table 15 to ensure that the total thickness of the second layer (B) and the third layer (C) is 21 // 祖. The results obtained are shown in Table 15. When the thickness of the third layer (C) is between 0.5-10 (Examples 64-67), particularly good results can be obtained. Especially when the thickness of the third layer (C) When the thickness is I-5 / ub (Examples 65 and 66), the results are better. 0-4 5- This paper is a universal standard for ten bacteria (CNS) Α4 size (2! 0X297 cm). Printed with A7 B7 by the Central Bureau of the Ministry of Plastics and Rubber Cooperatives. Description of the invention (44) Table 15 Thickness of the third layer (C) (㈣ Extrusion processability Stretchable peeling flap (kg / cm) Lin impact resistance (mA) Example 63 0.1 ◎ ◎ 4.5 0.2 〇Example 64 0.5 ◎ ◎ 5 0.1 〇Example 65 2 ◎ 6 0.1 〇Example 66 5 ◎ ◎ 6.5 0.1 〇Example 67 8 ◎ ◎ 7 0.1 〇Example 68 12 ◎ ◎ 7.5 0.3 〇 Example 6 9- 7 5 and Comparative Examples 20-23 Except ADK STAB 2112 (manufactured by Asahi Denka Kogyo Co., Ltd.) in the ratio shown in Table 16 in place of 6〇ΡΡιι phosphoric acid And the composition of the second (B) is changed as shown in Table 16. The unstretched film was prepared in the same manner as in Examples 1-8 and tb compared with Examples 1-4. Central China National Kneading Rate (CNS) A4 (210X297 mm) nn n I-mi -ill n \ I-In 1 (Please read the note on the back to fill out this page first) 434144 A7

B. Description of the invention (Table 6) Polycarbonate (wt.%) Polyester (wt.%) PET (wt. PBT (wt.%) Phosphorus-based stabilizer (ppm) Comparative Example 20 18 82 40 60 40 Example 69 22 78 40 60 40 Example 70 40 60 40 60 40 Comparative Example 21 62 38 40 60 40 Comparative Example 22 40 60 8 92 40 Example 71 40 60 12 88 40 Example 72 40 60 20 80 40 Example 73 40 60 60 40 40 Example 74 40 60 80 20 40 Example 75 40 60 88 12 40 Comparative Example 23 40 60 92 8 40

The results of the evaluation by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives II PET: Polyethylene terephthalate PBT. · Polybutylene terephthalate are shown in Table 17. It can be seen from the table that the biaxially stretched laminated film of the present invention has excellent extrusion processability, stretchability, adhesion to the gold plate, low-temperature impact resistance, and fragrance retention "-47- This paper uses Chinese National Standard (CNS) A4 (2 丨 0X297 mm)

Il ·, ---------- install ------ order ------ A (谙 read the precautions on the back first, write this page) 434 1 4 4

AB 5. Description of the invention (4 each) Table 17 Maximum peak temperature (ETC) Extrusion molding processability Stretchability Peel strength (kg / cm) Impact resistance (mA) Comparative example 20 130 ◎ ◎ 6 0.5 〇Example 69 142 ◎ ◎ 6 0.2 〇Example 70 144 ◎ ◎ 3 0.1 〇Comparative Example 21 &gt; XX Comparative Example 22 108 Δ △ 3 0.5 〇Example 71 112 〇2.5 0.1 〇Example 72 120 〇 2.5 0.1 〇Example 73 148 ◎ ◎ 3 0.1 〇Example 74 156 ◎ ◎ 3 0.1 〇Example 75 157 〇〇3 0.1 〇Comparative Example 23 „Π XX. Printed and implemented by Shellfish Consumer Cooperatives, Central Bureau of the Ministry of Economic Affairs Examples 7 6-8 4 and Comparative Example 2 4 · 2 7 The polymers used in the first layer (A) and the polysulfonic acid esters used were the same as in Examples 1-8 and Comparative Examples 1-4. Polyurethane-Polyfluorene Composition Film (Polymer (Second Layer (B)) Polymer and Preparation of Laminated Film)] Mix the above-mentioned poly-ester and polyester mixture in the proportion shown in Table 18 The ratios shown in Table 18 make poly (p-phenylene) used as the first polymer after copolymerization with 12Mear X isophthalic acid. Ethylene formate and polypara 4 8 —— | &lt; ----- i ------ tr ------ A (Please read the precautions on the back first-f.4: Write this page ) This paper size applies to China National Standards (CNS) A4 «L (2 丨 OX297 mm) 434144 A7 B7 V. Description of the invention (47) The mixture obtained by mixing butyl phthalate), and then according to Table 18 The amount shown is added with "I acid as a phosphorus compound. The resulting mixture is co-extruded with a first layer (A) into a double-layered unstretched thin film β in a double-layer cast chess. In this extrusion process, the first layer ( The polyester polymer of A) is melt-extruded using an extruder at a polymerization temperature of about 28 G • C, and the second layer (B) &amp; is melt-extruded at a polymerization temperature of about 2 3 (TC). After the double-layered molded polymer is cooled, it is wound on a casting roll to obtain an unstretched film. The unstretched film is then stretched in the longitudinal direction and according to the stretching ratio and temperature shown in Table 19. Horizontal stretching is also thermally cured at the temperature shown in Table 19. In this way, a biaxially stretched laminated film is prepared. (Please read the notes on the back first to write this page) Central Standards Bureau of the Ministry of Economic Affairs-Industrial Consumption • 49- cooperatives printed in this paper scale applicable Chinese national standard Mu (CNS) Α4 said grid (210Χ297 public shame) 434 144

7 7 AB V. Description of the invention (4) Table 18 Polycarbonate (wt ° / 〇 polyester (wt.%) PET (wt. PBT (wt.%) Phosphorus-based stabilizer (ppm) Comparative Example 24 18 82 40 60 60 Implementation Example 76 22 78 40 60 60 Example T7 40 60 40 60 50 Comparative Example 25 62 Λ. 38 40 60 40 Comparative Example 26 40 60 S 92 80 Example 78 40 60 12 88 80 Example 79 40 60 20 80 60 Implementation Example 80 40 60 60 40 40 Example 81 40 60 80 20 20 Example 82 40 60 88 12 20 Comparative Example 27 40 60 92 8 20 Example 83 40 60 40 60 50 Example 84 40 60 40 60 50 (Please first Those who read the notes on the back fill in this page) The biaxially stretched film made of PET: polyethylene terephthalate PBT: polybutylene terephthalate, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, The number of plane tensile injuries of the first layer (A) is 0.06, the number of plane tensile injuries of the second layer (B) 6 is 0.05, and the thickness of the first layer (A) is 6 / a. The thickness of the second layer (B) is 2 4 #. The 150eC thermal shrinkage of this film is 5-7X. -50- This paper size is applicable to China National Standard (CNS) A4 (2) 0 × 297 mm 434144 A7 B? V. Description of the invention (49) Table 19 Longitudinal stretching temperature (° C) Longitudinal stretching ratio Lateral stretching temperature (° C) Lateral stretching ratio heat curing temperature (° C) Comparative Example 24 120 2.9 140 3.0 180 Example 76 120 2.9 140 3.0 180 Example 77 120 2.9 140 3.0 180 Comparative Example 25 120 2.9 140 3.0 180 Comparative Example 26 120 2.9 140 3.0 180 Example 78 120 2.9 140 3.0 180 Example 79 120 2.9 140 3.0 180 Implementation Example 80 120 2.9 140 3.0 180 Example 81 120 2.9 140 3.0 180 Example 82 120 2.9 140 3.0 180 Comparative Example 27 120 2.9 140 3.0 180 Example 83 120 2.5 135 3.4 180 Example 84 120 3.2 140 2.8 180 (Please first (Please read the note on the back of this page and write this page.) The evaluation results printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives are shown in Table 20. It can be seen from the table that the biaxially stretched laminated film of the present invention has excellent extrusion. Formability, stretchability, adhesion to gold-plated sheet, low-temperature impact resistance, and fragrance retention. -5 1- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 434144 A7 B7 V. Description of invention (ί-) Table 20 (Em + Et) / 2 Em-Et Extrusion processability Continuous film properties Peel strength (kg / cm) 冲击 Impact resistance (mA) Fragrance retention Comparative Example 24 230 -20 ◎ 7.0 0.6 〇 Example 76 230 20 ◎ ◎ 6.0 0.2 〇 Example 77 210 100 ◎ 3.0 0.1 〇 Comparative Example 25 160 120 XX. Comparative Example 26 250 140 Δ 〇2.0 0.5 〇Example 78 250 120 〇 ◎ 2.5 0.1 〇Example 79 245 130 〇 ◎ 3.0 0.1 〇Example 80 180 80 ◎ 〇3.5 0.1 〇Example 81 160 80 ◎ 〇3.0 0.1 〇 Example 82 160 60 〇3.0 3.0 〇 Comparative Example 27 155 30 XX Example 83 170 240 〇3.0 3.0 〇 Example 84 160 -40 〇3.0 3.0 -------- ------ Equipment-(Please read the precautions on the back 孑 ¾write this page)-Order the printing of Examples 85-92 and Comparative Examples 28-29 of the Central Beef Consumer Cooperative of the Ministry of Economic Affairs Polyester and polyethylene terephthalate on the first layer (A) are the same as those of Examples 1-8 and Comparative Example 4. AM STAB PEP-8 is used as a phosphorus-based stabilized plutonium of a polybasic acid ester. As shown in Table 21, 40 weight U of this polysulfonate and 60 weight χ by poly-52-this paper size applies Chinese National Standard (CNS) A4 specifications (2 丨 0X297 mm) 434144 A7

7 B V. Description of the invention (θ) Polyethylene terephthalate-based polyester (polyester composed of 40 weights of Dong and polybutylene terephthalate (6U heavy boy J!) Dry blended together " Both polyethylene terephthalate-based polyester and polybutylene terephthalate-based polyester are made by a solid-phase polymer method. The former uses a dioxin catalyst and the latter uses a tetrabutyl titanate catalyst. Medium, the pre-polymer's intrinsic degree, the solid polymerization time in the solid phase polymerization reaction, and the terminal carboxyl group concentration are changed as shown in Table 21 Table 21 PET-based polyester surface intrinsic viscosity melting point CC) glass transition temperature (° C) Concentration of terminal carboxyl groups (equivalents / 106 g) Comparative Example 28 PETI12 0.75 229 74 4 Example 85 PETI12 0.75 229 74 12 Example 86 PETI12 0.75 229 74 20 Example 87 PETI12 0.75 229 74 30 Example 88 PETI12 0.75 229 74 30 Example 89 PETI12 0.75 229 74 30 Comparative Example 2 9 PETI12 0.75 229 74 30 Example 90 PETI12 0.75 225 78 25 Example 91 PETI12 0.75 225 78 12 Example 92 PETI12 0.75 225 78 30 Central Ministry of Economy Associate Bureau Staff Consumer Cooperative Printing PET: Poly Ethyl terephthalate PETI12: with 12 moles! ΪIsophthalic acid copolymerized PET -53- (Please read the precautions on the back before filling out this page) This paper size applies Chinese National Standard (CNS) A4 (2 丨 0X29 &quot;? Mm) 4 4 4

A

7 B V. Description of the invention () Table 21 (continued) PBT-based polyester mm intrinsic viscosity melting point CC) glass transition chick (° C) terminal carboxyl group concentration (equivalent / 106 g) Comparative Example 2S PBTI5 0,9 218 28 8 Implementation Example 85 PBS 5 0.9 218 28 8 Example 86 PBTI5 0.9 218 28 8 Example 87 PBTI5 0.9 218 28 8 Example 88 PBTI5 0.9 218 28 12 Example 89 PBTI5 0.9 218 28 20 Comparative Example 29 PBTI5 0.9 218 28 22 Example 90 PBT 0.9 223 32 10 Example 9 1 PBT 0.9 223 32 18 Example 92 PBTI5 0.9 223 28 8 ---------- install-(Notes on the back of the poem before reading 孑% write this page) Economy Ministry of Central Standards Bureau, Shellfish, Consumer Cooperation, DuPont PBT: Polybutylene terephthalate PETI5: PBT copolymerized with 5 mol 5: Isophthalic acid. Manufactured according to Examples 1-8 and Comparative Examples 1-4. A biaxially stretched film was obtained. The lateral stretching is performed at 140 ° C. The evaluation results are shown in Table 22. -54- This paper size is applicable to the national standard (CNS) A4 specification (210X297 mm) 434144 A7 B7 V. Description of the invention (Η) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives. 22 Forming processability Tensile peeling strength (kg / cm) Low temperature impact resistance (mA) Fragrance retention Comparative Example 28 Δ X Example 85 ◎ 〇2.5 0.1 〇Example 86 ◎ ◎ 2.5 0.1 〇Example 87 ◎ -¼ ◎ 3.0 0.1 〇Example 88 ◎ ◎ 3.0 0.1 〇Example 89 〇〇3.5 0.1 〇Comparative Example 29 XX Example 90 ◎ ◎ 2.0 0.2 〇Example 9 1 / 〇2.0 2.0 〇Example 92 ◎ ◎ 3.0 0.1 〇Example 93-9 &amp; and Comparative Examples 30-33 Examples 6 9-7 5 and Comparative Examples 20-23 The biaxially stretched films have low-temperature crystallization peak temperatures (Tccl and Tcc4), extrusion processability, and drawability The extensibility is shown in Table 2. 3. ----------- Installation-(锖 Please read the notes on the back first% to fill out this page) Order-55- This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) 4 3 4 彳 4 4 A7 B7 V. Description of the invention (M)

Table 23 Tccl Tcc4 Tcc4-Tcc 1 Extrusion processability stretchability ° c ° c ° c Comparative Example 30 95 132 37 ◎ ◎ Example 93 95 134 39 ◎ ◎ Example 94 92 137 45 ◎ ◎ Comparative Example 3 1 91 138 47 XX Comparative Example 3 2 60 104 44 Δ 0 Example 95 66 108 42 〇 ◎ Example 96 75 110 35 〇 ◎ Example 97 115 145 30 ◎ 〇 Example 98 152 170 18 ◎ 〇 Example 99 156 172 16 〇Comparative Example 3 3 157 170 13 XX Examples 100-107 and bb Comparative Examples 34-37 Examples 1-8 and Comparative Examples 1-4 The biaxially stretched films, each centerline surface Roughness (Ra) is shown in Table 24 * 0 (please read the precautions on the back to fill in this page first) (CNS &gt; A4 size (210X297 mm) 434144

AB 5. Description of the invention (β) Table 24 Ra (nm) Comparative Example 34 23 Example 100 25 Example 101 27 Comparative Example 35 Comparative Example 36 13 Example 102 15 Example 103 17 Example 104 20 Example 105 37 Implementation Example 106 54 Example 107 110 Comparative Example 37 • ---------- Installation-(Please read the precautions on the back before writing this page) The standard of the Ministry of Economic Affairs is printed for employee consumer cooperatives -57- This paper size applies to China National Standards (CNS) 4 grid (2I0X297 mm)

Claims (1)

434144 Λ8 B8 C8 D8 _ I IM _ _ ##. — —- · —.--. — · __ *!-Six 'Application Special Policy 111 &quot; —- No. 85 108 7 82 r is laminated on the metal "Biaxially stretched film" patent (revised on January 31, 1990) 6. Scope of patent application: 1. A biaxially stretched film laminated on metal, the composition is as follows: (Please read the precautions on the back first (Fill in this page again) (A) The first layer is formed by a polyester layer composed mainly of ethylene terephthalate repeating units, and (B) The second layer is formed by a resin composition composed of polyester and polycarbonate The resin composition substantially contains a repeating unit represented by the following chemical formula ⑴: R3m R1 R4n In the formula, R1 and R2 are independent, and they are extracted from the group of 氲 atom, alkyl group containing 1-5 1-5 atom, and cycloalkyl group containing 5-6 値 ring 硪 atom. R1 and R2 can also be combined in Together, a cycloalkenyl group containing a 5-6 fluorene ring fluorene atom to which a plutonium atom is bonded; R3 and R4 are independent of each other, and you have a Selected from the group, and η are each a stand-alone, pseudo-representative 〇, 1 or 2, Ministry of Economic Affairs wisdom 574/0: The content of polysterate and polyester printed by the consumer cooperative is relative to the basis weight of the knot. 20 -50 weight X and 5g-8 () weight; I; polyester is essentially composed of ethylene terephthalate as the main repeating unit and the terminal carboxyl group concentration is 5 equivalents / 106g (eq / 1〇sg ) The first polyester above and the second polyester composed mainly of butyl terephthalate and repeating units, and the terminal carboxyl group concentration is less than 20 equivalents / 106 g; the first polyester and the second polyester The content of each kind of polyester relative to its total weight base is between 10-90. Chongyong Paper is suitable for Chinese National Standard (CNS) Λ4 specification (21〇χ 297 mm) 434 1 44 A8 B8 C8 D8 Printed by Shellfish Consumer Cooperative of Central Standards Bureau of the Ministry of Economic Affairs 6. Application for patent scope 1 Quantity 5: between • and 1 of them »(C &gt; plane stretch of the first and second layer The coefficients are all within the range of 0. 0-5-0. 10 1 1 0 1 I Please [I 2. Please refer to the biaxially stretched film of the first item of the patent range * Among them the first layer it read 1 | polyester It is composed of poly terephthalate reading back 1 1 side I acid ethylene ester which accounts for the total repetition bo early bit 8 0 -1 0 0. Note 1 I means I 3. If the scope of patent application is the first, The biaxially stretched film of the item wherein the second layer of item 1 of the polyester is substantially% is composed of the repeating unit shown in the chemical formula (1) and then filled with 1 1 write 嗖 1 »but where R] L and R 2 Both are methyl * ED and η are 0. Page 4 The biaxially stretched film 1 of item 1 in which the first polyester constituting the second layer polyester is composed of polyethylene terephthalate which accounts for 80-1 00 mole 1 I 5! . 1 1 5 · If the biaxially stretched film of item 1 of the patent scope is claimed, wherein the terminal carboxyl group concentration of the first polyester constituting the second polyester of the order I is 7-2 0 equivalents / 1 1 10 6 Between 0 1 1 6. If the biaxially stretched film of item 1 of the patent application scope, wherein the second polyester constituting the first I two-layer polyester, you repeat the unit by iJs knot 80 -1 0 0 mol 1 It is composed of 1 X polybutylene terephthalate. 1 1 7. For example, please request the biaxially stretched film of item 1 of the patent 9 in which the terminal carboxyl group Mα of the second polyester constituting the first I second-layer polyester is 5-17 equivalents / 1 f 10 6 g. Time 01 I 8. The biaxially stretched film according to item 1 of the scope of patent application> wherein the second layer composed of a composition of poly m 1 | acid ester and polyester contains 2 0 -1 0 0 1 1 PP® (expressed as a phosphorus atom) phosphorus compound. 1 1-2-1 1 1 1 This paper uses China National Standards (CNS) A4 gauge (2I0X297 mm) 434144 Α8 Β8 C8 DS Printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives 6. Application for Patent Consumption Circumference 9. The biaxially stretched film of item 1 of the scope of patent application, wherein the peak thickness at the highest temperature of the relationship between the loss of elastic modulus and temperature is between 100-160 eC. 10. If the biaxially stretched film of item 1 of the scope of patent application, its elongation at 100 eC in the longitudinal direction (E M) and elongation at 1 G 0 eC in the transverse direction (ET) is sufficient to play the two equations. · (Em + ET) / 2 &gt; 150, and -50 S EM-E £ 250 Μ Τ 11. For example, the biaxially stretched film of item 1 of the patent application scope. The second layer has a sea / island structure, Polyesters are island-like in the sea-like polyester. 12. If the biaxially stretched film according to item 11 of the scope of patent application, wherein the cut surface obtained by cutting the biaxially stretched film parallel to the transverse direction and the thickness direction, the second layer has an average major diameter of Q · 1- 20 / ia island. 13. For example, the biaxially stretched film of item 1 of the patent scope, wherein the low temperature crystallization peak temperature (Tccl) of the sample prepared by melting and quenching the film in DSC and the melting of the film through three further cycles The low temperature crystallization peak temperature (Tcc4) in DSC of the sample prepared by quenching and quenching, and the temperature difference (Tcc4-Tccl) between the two is between 10-60 ° C. 14. The biaxially stretched film of item 1 of the patent application, wherein the average surface roughness (Ra) of the centerline of the first layer is in the range of 5-150 nB. 15. If the biaxially stretched film of item 1 of the patent application has a thermal shrinkage of 150 ° C or lower of 10 ° C or lower. 16. For example, the biaxially stretched film of item 1 of the patent scope, which has -3- (please read the notes on the back before filling in this card) This paper size is applicable to China's national standard C CNS &gt; Α4 &lt; 210X297 mm) 434144 8 8 8 8 ABCD 6. The third layer adjacent to the second layer of the patent application scope, and the third layer is a polyester composed of polyethylene terephthalate as the main repeating unit Formed. 17. The biaxially stretched film as claimed in item 1 or item 16 of the patent scope, wherein the thickness is between 5-100 &gt; ua. 18. For the biaxially stretched film according to item 1 of the patent application, wherein the thickness ratio of the first layer to the second layer is between 1:99 and 50:50. 13. The biaxially stretched film according to item 16 of the application, whose thickness is between G.5-10 &gt; u IB. In In ^^^ 1 I------ If ·---^ —- . ^^^ 1 ^ 1—. I (Please read the notes on the back before filling out this page) Ministry of Economic Affairs, Smart Money-^ 9 工 &quot; Feed Cooperation 钍 Printing -4- Applicable Paper Standard Applies to Chinese National Standards 嗥(CNS) A4 specifications (210X 2W) Λ8 B8 C8 D8 _ I IM _ _ ##. — —- · —.--. — · __ *!-Six 'Application Special Policy 111 &quot; —- No. 85 108 7 82 r is laminated on the metal "Biaxially stretched film" patent (revised on January 31, 1990) 6. Scope of patent application: 1. A biaxially stretched film laminated on metal, the composition is as follows: (Please read the precautions on the back first (Fill in this page again) (A) The first layer is formed by a polyester layer composed mainly of ethylene terephthalate repeating units, and (B) The second layer is formed by a resin composition composed of polyester and polycarbonate The resin composition substantially contains a repeating unit represented by the following chemical formula ⑴: R3m R1 R4n In the formula, R1 and R2 are independent, and they are extracted from the group of 氲 atom, alkyl group containing 1-5 1-5 atom, and cycloalkyl group containing 5-6 値 ring 硪 atom. R1 and R2 can also be combined in Together, a cycloalkenyl group containing a 5-6 fluorene ring fluorene atom to which a plutonium atom is bonded; R3 and R4 are independent of each other, and you have a Selected from the group, and η are each a stand-alone, pseudo-representative 〇, 1 or 2, Ministry of Economic Affairs wisdom 574/0: The content of polysterate and polyester printed by the consumer cooperative is relative to the basis weight of the knot. 20 -50 weight X and 5g-8 () weight; I; polyester is essentially composed of ethylene terephthalate as the main repeating unit and the terminal carboxyl group concentration is 5 equivalents / 106g (eq / 1〇sg ) The first polyester above and the second polyester composed mainly of butyl terephthalate and repeating units, and the terminal carboxyl group concentration is less than 20 equivalents / 106 g; the first polyester and the second polyester The content of each kind of polyester relative to its total weight base is between 10-90. Chongyong Paper is suitable for Chinese National Standard (CNS) Λ4 specification (21〇χ 297 mm)