TWI251005B - Biaxially oriented polyester film and laminates thereof with copper - Google Patents

Abstract

Disclosed are biaxially oriented polyester film produced from a polyester comprising: (1) diacid residues comprising at least 90 mole percent of terephthalic acid residues, naphthalenedicarboylic acid residues or combinations thereof; and (2) diol residues comprising at least 90 mole percent of 1,4-cyclohexanedimethanol residues; wherein the polyester comprises a total of 100 mole percent diacid residues and a total of 100 mole percent diol residues; wherein a film of the polyester is stretched or oriented at stretch ratios and stretch temperatures that satisfy the equation (27*R)-(1.3*(T-Tg)) >= 27, where T is the average of the machine and transverse direction stretch temperatures in degrees Celsius, Tg is the glass transition temperature of the polymer film in degrees Celsius and R is the average of the machine and transverse direction stretch ratios and the stretched film is subsequently heat-set at an actual film temperature of from 260 DEG C to Tm, wherein Tm is the melting point of the polyester as measured by differential scanning calorimetry (DSC), while maintaining the dimensions of the stretched film.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel heat-stable polyester film; and to a polyester laminate and a copper-polyester laminate using the heat-stable polyester film. These films preferably have the desired combination of heat resistance (solder and dimensional stability) and low coefficient of thermal expansion required for flexible circuit applications. More particularly, the present invention relates to a poly(p-quinic ruthenate, 4-cyclohexamethylene dimethane-ethylene glycol) or poly(1,4-naphthalene dicarboxylic acid cycloheximide). A thermally stable polyester film made of the same or copolyester or a mixture thereof which can be biaxially oriented or stretched and heat set under certain conditions. [Prior Art] Poly(ethylene terephthalate) (PET) films have been widely used in a variety of packaging, packaging and lamination applications. PET films are sometimes used in shrink wrap applications where they are applied to a target and heated to shrink the film around the target. In other applications, such as flexible electronic circuits, heat-resistant packaging, and cooking bags, biaxially oriented and heat-set PET films that have good dimensional stability and shrink resistance at elevated temperatures can be used. However, the biaxially oriented PET film has a temperature exceeding 250. (:Useless because its inherent melting temperature (Tm) is 250 ° C. Some applications (such as some flexible boards) need to be at 26 〇. Thermal stability under the ( (ie, with good size) Films of stability. In particular, when the films are immersed in a solder bath that has been preheated to 26 〇t:, it must not blister or wrinkle. More specifically, when these films are immersed Preheating to 26 〇 1 of the solder bath i 0 seconds, it must pass 3% or less shrinkage. It will meet 86584.doc 1251005, it is important to have the lowest possible dielectric constant. Some derived from The polyester of 1,4-cyclohexanedimethanol (CHDM) has a melting point greater than 250 ° C. The following reference is made to discuss films made from polyesters prepared from CHDM. However, it is not known that these patent references are not available. In particular, the manufacture of films stabilized at 260 ° C is disclosed. Defensive Publication T876, 001 (1970) describes poly(p-1,4-cyclohexamethylene diacetate) (PCT) a film made with polyester and copolyester (which contains up to 20 mole percent of isodecanoic acid residues) The published patent application WO 96/06125 (1996) describes a biaxially oriented film made from a PCT polymer. The published patent application WO 92/14771 (1992) describes having an intrinsic viscosity (IV) of less than 0.80. Liters per gram of PCT polymer wherein the CHDM residue consists of from 75 to 100% of the cis isomer.

JP 1-299019 A (1989) describes the preparation of a PCT polymer comprising residues up to 15 mole percent derived from other dicarboxylic acids or other glycols and having an IV of at least 0.5 deciliter per gram. Biaxially stretched PCT film. JP 2-301419 (1989) describes how the biaxially stretched PCT film discussed in JP 1-299019 does not have an anti-260 ° C solder bath property, and describes how to irradiate the film as discussed in JP 1-299019 The solder bath properties are obtained by crosslinking the films. JP 2-196833 A (1990) describes an electrically insulating material based on a metallized biaxially oriented PCT film. CTE, temperature of use and flexible board applications are not discussed in this document. US 4,557,982 (1985), JP 60-069133 A (1985), JP 91-000215 B (1991), JP 60-085437 A (1985) and JP 90-063256 B (1990) 86584.doc 1251005 Description contains at least 80 Mo Percent steric acid residues and PCT polymers of at least 90 mole percent CHDM (60 to 100% trans isomer) residues. Biaxially oriented films with high biaxial orientation are useful in the manufacture of magnetic tape. JP 5 8-214208 A (1983) describes films made from PET, PCT and copolyesters which can be usefully used as electrically insulating and flexible printed circuit base films. US Patent Nos. 5,153,302 (1992) and JP 4-214757 A (1992) describe PCT and PCT copolyesters comprising at least 97 mole percent CHDM residues and at least 90 mole percent para-acid residues, and the use of These polymers are used to make capacitor films. U.S. Pat. SUMMARY OF THE INVENTION While many specific embodiments are contemplated in the scope of the present invention, some examples of the specific embodiments are specifically described herein. In a first embodiment of the invention, there is provided a biaxially oriented polyester film made from a polyester comprising: (1) a diacid residue comprising at least 90 mole percent of a phthalic acid residue a base, a hydrazine dicarboxylic acid residue or a combination thereof; and (2) a diol residue comprising at least 90 mole percent of a 1,4-cyclohexanedimethanol residue; wherein the polyester comprises a total of 100 moles a percentage of diacid residues and a total of 100 mole percent of diol residues; wherein the polyester film satisfies the draw ratio and draw temperature of the equation (27*R)-(1.3*(T-Tg)) 27 To stretch or orient, where T is the average stretching temperature (degrees Celsius) in the machine direction and the transverse axis direction, Tg is the glass transition temperature (degrees Celsius) of the polymer film, and R is the average stretching ratio in the machine direction and the transverse axis direction; The film stretched by 86584.doc 1251005 is measured from 26 ° C to TnU 〇 actual film temperature (where Tm is the melting point of the nozzle as measured by differential scanning calorimetry (1) sc). Type & 1 to 12 sec (preferably 丨 to (6) sec) while maintaining the I stretched film . Preferably, when the biaxially stretched and heat set (4) film is immersed in a solder bath which has been preheated to 26 Gt for 1Q seconds, its history I lags at 3% shrinkage, and when it is at 12 〇 to 15〇. It has a coefficient of thermal expansion of 10 85 ppm/C for daytime measurements. This low shrinkage value is preferably produced in combination with the adhesive (iv) and the electrical material to form a reddish laminate which can accept 26 generation waves or /tr: tr. The base film of this laminated circuit is fortunately soldered during the soldering process without blistering or I-patterning, as this will affect the privacy of the final application. The name "actual film temperature" refers to the actual temperature of the film, rather than the heated air temperature. The second embodiment of the present invention is a biaxially oriented polyester film made of polyester. And comprising: (1) a diacid residue comprising at least 90 mole percent of a phthalic acid residue, a nacreoic acid residue or a combination thereof; and (2) a diol residue comprising at least a % molar percentage μ. Cyclohexanized dimethanol residue; the oxime contains a total of (10) mole percentage of diacid residues and a total of 100 mole percent of diol residues; wherein when the polyester film is immersed Preheating to 26 (the rc ping bath for 10 seconds, it experienced no more than 3% shrinkage; and when measured between 12 〇 mc, its thermal expansion coefficient value, when it is between 25 and 9 〇 The value of the coefficient of thermal expansion is preferably 10 - 42 ppmrc when measured in the dead. The third embodiment of the invention is preferably greater than about 270 ° C by means of one or more layers 86584.doc -10- 1251005 (e.g. , from about 270 to 330 ° C) and more preferably from about 280 to 3 ° C. These polyesters can be easily It is prepared by conventional methods well known in the art. For example, a molten phase or a molten phase may be used in combination with a solid phase polycondensation technique if necessary. The polyesters typically have a ratio of from about 4 to about 1.2. Preferably, it is from about 0.5 to 1.1 and more preferably from 〇.7 to 1. 〇. When used herein, Ιν· refers to the use of each 1 ml of solvent at 25 ° C (which is from 6 〇 by weight of phenol) And 4% by weight of tetrachloroethane consisting of a viscosity measurement of a polymer containing 5 gram of gram. In this paper, the basic method for measuring vinegar Ι ν is proposed in ASTM method D2857_95. Any of the quinone dicarboxylic acid isomers, but 1,4-, 1,5-, 2,7- and especially the 2,6-isomers are preferred. From a dicarboxylic acid or a derivative of the diacid, such as a lower alkyl vinegar (for example, dimethyl phthalate), an acid complex (for example, a dimercapto gas) or in some instances For the traitor. If necessary, the polyester may contain a smaller amount of residues of other dicarboxylic acids or other diols' but the amount of such modified materials should be (e.g., no more than about 10 mole percent) to maintain a high degree of crystallinity and high melting point in the polymer. Useful modified monomers include other dicarboxylic acids containing from about 4 to about 14 carbon atoms. And other diols comprising from about 2 to about 12 carbon atoms. Preferred modified acids include isodecanoic acid and i.4-cyclohexanedicarboxylic acid. Some preferred modified glycols include B. Glycol, mercappropanediol, W hexanediol: neopentyl glycol. The catalyst materials used are 4, hop, > 5 and wrong. This difference can be used in the polyester synthesis of the present invention. Examples include ruthenium, manganese, zinc, cobalt, ruthenium, and gallium. 86584.doc -13-1251005 Catalyst systems are described in U.S. Patents 3,907,754, 3,962,189, 4,010,145, 4,356,299, 5,017,680, 5,668,243, and 5,681,918. These are hereby incorporated by reference in their entirety. Preferred catalyst metals include titanium and clocks, which are preferably titanium. The amount of catalyst metal used can range from about 5 to about 1 ppm, but it is preferred to use a titanium catalyst having a concentration of from about 5 to about 35 ρρηη to provide a polymer having good color, thermal stability, and electrical properties. Esters. Phosphorus compounds are often used in combination with the catalyst metals, and any of the normal use can be used to produce polyester-based phosphorus compounds. Phosphorus up to about 1 〇〇 ppm can typically be used. Although not essential, other additives typically present in the polyester may be used if necessary, as long as they do not hinder the properties of the polyester used to prepare the film. Such additives may include, but are not limited to, antioxidants, ultraviolet light and heat stabilizers, metal deactivators, colorants, pigments, impact modifiers, nucleating agents, branching agents, resistance Fuels and their analogues. The branching agent useful in the manufacture of the brewer in the context of the present invention may be one which can provide a knife branch in the acid unit portion of the polyester or in the ethylene glycol unit portion, or it may be one Hybrid. Some of these branching agents are described herein. However, examples of such branching agents are polyfunctional acids, polyfunctional anhydrides, polyfunctional diols, and acid/ethylene glycol hybrids. Examples thereof include mono- or tetradecanoic acids and their equivalent anhydrides, such as trimesic acid, pyromellitic acid, and lower calcined sugars thereof and the like; and tetraols such as isovalerol: Similarly, triols useful in the context of the present invention are: trimethyl hydrazin; or di(tetra) carboxylic acids and several groups: lysines and derivatives, such as samaric acid: methyl sulphate; And its analogs, barium trimellitate, are preferred branching agents. 86584.doc -14- 1251005 In a first step of the method of making the polyester film or sheet material, the polyester melt described above is extruded into a substantially amorphous phase film at any temperature well known in the art. For example, typical temperatures range from about 27 to 31 generations. The thickness of the unpeaked (or 纟 oriented) film ranges from (10) to 1000 microns, more typically from about 200 to 6 microns. The initial film extrusion can be carried out by any conventional method including, but not limited to, extrusion on a single propeller extruder or extrusion on a twin propeller extruder. Then, the film is used to satisfy the equation (27*R)_(13*(T_T gamma 27 stretching ratio and stretching temperature for stretching or orientation, where τ is the average stretching temperature of the machine and the horizontal axis (degree Celsius) The glass transition temperature of the polymer film is again (degrees Celsius) and R is the average stretch ratio of the machine and the transverse axis direction. The label, the buckle is a stretch ratio, which is the stretch of the film relative to the original size of the film. For example, 2 means that the size of the film has been stretched to twice its original size. The stretch ratio of the film is preferably 2·5 Χ to 3 勺 in the machine direction (MD) spoon, and Approximately 2.5Χ to 3Χ in the axial direction (TD), and the pull

The degree is between 90 and 110C. After stretching, the film is heat set at a temperature greater than about 260 ° C to Tm of the actual film temperature (where Tm is the melting point of the polymer, as measured by the differential scanning calorimetry (Dsc)). 5 second spoonful of Japanese temple pHj. ^ ^ 4> Wang Yi, according to the heating source of the oven (ie, convection, radiation, etc.), the film will need to be heated up to a maximum of 260 ° C, the time between the temples up to 30 seconds . This extra time is not included in this article... It does not take time. It refers only to the time when the sample is actually in the range from 260 ° C to Tm. The initial film extrusion can be carried out immediately prior to stretching (i.e., tandem) or can be carried out separately. During heat setting, the tenter frame 86858.doc -15-1251005 or other mechanical equipment (which can prevent the stretched film from over-relaxing during heat setting) can be utilized, the stretched film Maintain the stretched size of the film. The film can be stretched or relaxed up to 1% during heat setting, i.e., the overall size of the film can be increased or decreased by up to 10%. Any of the films of the present invention can be stretched or oriented using any conventional method. For example, the extruded polyester film can be stretched by roll stretching, long pitch stretching, tenter stretching, tubular stretching, or a combination thereof. In any of these methods, continuous biaxial stretching, simultaneous biaxial stretching, uniaxial stretching, or a combination thereof can be made. Synchronous biaxial stretching involves the simultaneous stretching of the film and the transverse axis direction. In the synchronous biaxial pull, the stretch ratio is not necessarily the same in the horizontal axis direction and in the machine direction. Continuous biaxial stretching involves first stretching in the machine direction (eg, stretching on a drum against a drum) and then stretching in the direction of the horizontal axis (eg, using a tenter frame in a continuous stretching process) The two types of stretching may be performed immediately after one of the other species (i.e., string 歹 or may be performed separately. The machine direction is defined as the long direction of the film (when the = horizontal axis direction is defined as the width of the film) 'that is, the universal direction with the machine direction. If continuous biaxial stretching is performed, the stretching ratio and temperature in the direction of the horizontal axis and the stretching in the poems are not necessarily the same. /, , = stretching or orientation The polyester film can be determined according to a well-known method to determine the filming/occurrence, for example, 'the stretched thin 栗 — — - times the batch method, for example, the film is placed in a heat-set structure and 1 %丨,彳€ A 1 time. (4)^ Set in the type of oven towel - section fixed coffin, 疋 可 can be carried out immediately after stretching. ^U kiosk) or can be each - can be Relax or stretch up to 1% during heat setting. 86584.doc •16- 1251005 Stretching and The number of hot-type steps can be different. The polyester film can be subjected to single stretching and single heat setting or treatment, single stretching and multiple heat setting, multiple stretching and single heat setting, or multiple times. Stretching and multiple hot foot type pass. If multiple stretching and/or heat setting is carried out, the father can use the stretching and heat setting at the right time, but it can also be heat set by one time. The type passes through without inserting through. The conditions for each pass need not be the same as the previous pass. For example, the polyester film can be heat set using a two-stage heat setting method by any actual temperature greater than the stretching temperature. The first heat setting is carried out at film temperature. Subsequently, the film is subjected to a continuous film temperature range from 26 (rc to Tm (where Tm is the melting point of the polymer, which can be by DSC (differential scanning calorimetry) To measure) the internal heat setting for a second period of time. The polyester film component of the laminate of the present invention normally has a final thickness value of about 〇·(10) to Ο.] halo (about 0.8 to 8 mils) (ie, After stretching and heat setting)约·· 04 to 〇·13 mm (about 1.25 to 5 mils). The biaxially oriented polyester film of the present invention can be produced from a polyester as defined herein; wherein the polyester film satisfies the equation ( 27*RH1 ·3*(T_Tg)p27 stretching ratio and stretching temperature for stretching or orientation, where τ is the average stretching temperature (degrees Celsius) in the machine direction and the transverse axis direction, and Tg is the glass transition of the polymer film Temperature (degrees Celsius) and R are the average stretch ratios in the machine and transverse directions; subsequently, the stretched film is at a true film temperature from 26 〇 (: to Tm (where Tm is the melting point of the polyester, such as The heat setting can be performed by differential scanning calorimetry (DSC) while maintaining the size of the stretched film. When the polyester film as described in the preceding paragraph is a preferred embodiment of the present invention, The film does not need to satisfy the equation as defined above. Further, 86584.doc -17- 1251005 provides a biaxially oriented polyester film manufactured from polyester as defined herein (which does not necessarily satisfy the equations described in the preceding paragraph), wherein when the polyester film is When it is preheated to 260 C in a solder bath for 1 sec, it undergoes no more than 3% shrinkage, and when it is between 120 and 15 (measured between TCs, it has 1 〇 _85 ppm/t: Thermal expansion coefficient value. For the specific embodiment of the present invention, when the polyester film of the present invention is further incorporated into a solder bath that has been preheated to 260 C for 1 sec, it preferably has Less than 3% shrinkage, and preferably has a CTE of 10-42 ppm/°c when measured between 25 and 9 ,, and/or when measured between 12 〇 and 15 (^c) It is 10-85 Ppm/° C. Further, when the polyester film is immersed in a solder bath which has been preheated to 26 ° C &gt; c for 10 seconds, it is preferable that it does not foam or wrinkle. Polyfluorene films also have improved hydrolysis resistance (as compared to similar films prepared from pET) and improved dielectric constant (compared to films prepared from ρ Ε τ and poly liminimine). thin Membranes can be usefully used in any application requiring a film and requiring dimensional stability at elevated temperatures. Special end uses (as exemplified herein) have flexible circuit boards; Conductors, liquid crystal displays, electrochromic displays, photovoltaic devices (ie, solar cells), OLEDs (organic light-emitting diodes), microfluidic devices (replaceable medical test kits), and other conductive layers Films. The particularly preferred end use of the film of the present invention is that a film having dimensional stability at 26 (rc and greater) is required. Some novel laminate structures may use any of the films or polyesters provided by the present invention, and Optionally, it may comprise at least one layer of a heat or UV hardened or hardened adhesive layer and at least one layer of biaxially stretched and heat set polyester. The invention also provides a steel/polyester laminate, 86584.doc -18 - 1251005, It comprises at least one layer of copper, at least one layer of heat or uv hardened or hardened adhesive layer and at least one layer of biaxially oriented and hot foot polyester. The copper layer is typically from about 17 to 140 thick. a metal copper foil of preferably rice (preferably about 3 to 7 micrometers). The copper foil may be a forged or rolled or electrolytically deposited copper foil. The heat-curable adhesive layer may be selected from the group Adhesive compositions such as propylene glycol, flame retardant (FR) acrylic acid, butyral phenol, acrylic epoxies, polyesters, epoxy polyesters, modified bismuth oxide resins Analogs. These adhesives typically can apply heat to the adhesive or expose it to heat at a pressure of from about 700 to 3500 kPa (1 to 5 pounds per square inch). It is hardened by heating to a temperature of about 12 Torr to 180 C for about 30 minutes to 1 hour. The hardened adhesive layer typically has a thickness in the range of about 15 to 1 micron. The present invention also provides a method of making a thermoplastic article comprising these laminate structures, including lamination; structural heat and pressure. The laminate structure of the present invention can be used in any of the art which is well known in the art or has been described herein, but is preferably used in a replaceable electronic circuit board. The laminates of the present invention can be used in single layer electronic circuits, two layer electronic circuits, and/or multilayer electronic circuits, such as described in FIG. The thermoplastic article can also be obtained by applying heat and pressure to several layers of the layer or "sandwich" as described above. The adhesive layer such as described above may also be applied between the laminates in the multilayer laminate I: body embodiment and/or &quot;sandwich, gentleman's broadcast. _, „, h. In Fig. 1-3, the polyimide film of the present invention can be used as an outer layer and/or as an inner layer for a replaceable electronic circuit, whether or not it is referred to as a brewed substrate, a mulched cover or another name. The present invention is not intended to be limited by the name "substrate,", "substrate," or "cover," as described in Figure 86584.doc -19-1251005. The coefficient of linear thermal expansion (CTE) of a film sample can be The measurement is performed according to ipc_tm_65〇2·4·41·3 using a Rhe〇metrics RSA state mechanical thermal separator (DMTA) device, and is further exemplified by the following examples. The present invention can be preferably embodied by the present invention. The following examples are further clarified, but it is to be understood that the examples are included for purposes of illustration only and are not intended to limit the scope of the invention unless otherwise indicated, unless otherwise indicated The total weight of the polymer composition is based on the total weight of the polymer composition, and all molecular weights are weight average molecular weights. Likewise, all percentages are by weight unless otherwise indicated. EXAMPLES The following examples further illustrate the polyesters according to the present invention. Film and its preparation. The solder resistance as defined by the present invention can be measured in accordance with Ipc_TM_65〇24131, with a welding bath set at 260 C in /. The samples tested in the following examples were not made into laminates, unetched and bare (ie, uncoated or laminated). The film shrinkage can be achieved by MD (machine direction) The film is measured at a position and at a two position in the TD (horizontal axis direction) at a size of 5. centimeters x 5.1 cm (2 x 2 inches). Then, as described herein, the film is as described herein. The sample was immersed in a solder bath that had been preheated to 26 (rc for 10 seconds. The foaming and wrinkles of the film were observed. Then, the dimensions were measured again. The original size was subtracted from the size after each impregnation and then divided by the original size. To obtain % shrinkage. Average four shrinkage % values together (2)^1]〇 and 2 butyl 1)) to obtain the overall shrinkage %. 86584.doc -20- 1251005 Glass transition temperature as defined by the present invention And the melting temperature can be measured using differential π-scan 1 thermal method (DSC) according to ASTM D 3418. 15.0 mg of each sample is sealed in an aluminum pan and heated to 290 C at a rate of 2 (rc / min. Cool the sample below its glass transition at a rate of about 32 (rc/* clock) Degree to produce an amorphous phase sample. During the scanning, the melting temperature (Tm) is consistent with the observed endothermic peak. The film sample has a linear thermal expansion coefficient (CTE) as defined by the present invention according to IPC- TM-650 2·4·41·3 is measured using a rheometer RSA ^ Dynamic Mechanical Thermometer (DMTA) device. This procedure is to place a nominal 2 mm wide χ 22 mm long film sample in the DMTA device clamp. Medium. The DMTA force is fixed at 2 grams. The sample is cooled to -1 Torr. 〇, heated to 15 〇. Helium, cooled to _ 丨〇 it, then heated to 15 CTC, all at a heating/cooling rate of lot:/min. During the second thermal scan, the length of the sample (as a function of temperature) is measured. The length of the sample was measured at 25-90 ° C and 12 (50 ° C temperature range / / sister slope). Two corrections were made. One was used to establish the baseline for DMTA and one was used to calibrate the machine to different standards. Sensitivity of the object. Copper, aluminum and some amorphous phase plastics with well-known CTE values were used as calibration standards. Then, using this correction, the measured length and temperature slope were at 25_9 (rc and 120-150 C). The cte of the unknown sample was calculated over the temperature range. Example 1 Comparative Example Example 1 and Comparative Example C-1-C-3 illustrate the effect of the heat setting temperature on the shrinkage of the film prepared from PcT. PCT polyester pellets (Lv. 〇74, Tm 293 ° C, Tg 94 ° C) were prepared using a ruthenium Ti catalyst (such as titanium isobutoxide). The pellets were at 135 ° C. Drying for 6 hours 86584.doc -21 - 1251005, then extruding it into 2 〇 32 mm (8 mils) on a Davis ((10)(4) standard sJMao ying pair) wiper equipped with a g-blocking type propeller Ear) Thick flakes. Maintain the tempering temperature and die temperature at 293t. <2 on the drum, and the temperature of the t-roller is set at 6 generations (150 °F). Then the films are stretched biaxially on a TM•long film stretching machine with the same stretch ratio and At the same rate of 35.56 cm (14 in pairs) per second, the two axes are simultaneously stretched under the conditions indicated in Table I, and then the two films are clamped into an aluminum frame and then inserted into the oven (the setting temperature and The time is not shown in Table I). The two films are placed in the + frame, and the temperature is sandwiched between the two films to measure the actual film temperature. This is also shown in the table. The licking type temperature is higher than the actual film temperature, and the listed hot foot 5L time includes the time required to add the g to the real film temperature (large, ''spoon 30 seconds). Thereafter, the % shrinkage produced by immersing the film in a solder bath which had been preheated to 26 Torr for 10 seconds is shown in Table 1. Examples are comparative examples which were produced under different stretching conditions, which are described below 26〇The heat setting at its actual film temperature produces a film with high shrinkage at 2 6 Q t. Between the formation of the comparative film, the formation of the laminate of the present invention, when the film is used to make a U-private connector or a flexible circuit film, this high degree of shrinkage and It is noted that the film of the comparative example was developed under the same conditions as those reported in Example 3 of ^¥〇/〇6125. Example i is an example of a film according to the present invention, It has been heat set to allow the film to have an acceptable shrinkage. The film is also acceptable for the film. In Table I, the i II I stretch ratio is stretched in both the machine and the transverse axis. The temperature is. c mention 86584.doc -22· 1251005 for y# in seconds, shrinkage % refers to the shrinkage percentage of the sample film after the dip has been preheated to 2 y y in the connection / valley 1 , CTE value refers to ppm / t and The film thickness is provided in microns.

Al -___ Example 2.5 130 250 120 236 8.0% 31 Tensile ratio Tensile temperature Heat setting temperature Heat setting time Actual film temperature shrinkage % CTE (23-90 ° C ) CTE (120-150 〇 C ) Film thickness f Example 2 -4 and Comparative Examples C-4 and C-2 C-3 1 2 2 2 100 100 100 250 270 290 60 60 60 235 246 274 14.2% 9.0% 1.7% - - 34 - - 65 51 51 51 Examples 2-4 In the case of the film of the film according to the present invention, the effects of the stretching ratio and the stretching temperature on the film &lt; shrinkage and CTE manufactured from pcT are explained together with Comparative Examples C_4 and C-5. As described in the previous examples, pct was aggregated into av. 0.74, Tm 293t, Tg94t) MM_. Then, the children's film was stretched biaxially on a τ. Μ. long film stretching machine at the same rate of stretching, 35.56 cm per second, 4 inches, at the same rate, using the conditions indicated in Table II. The axis is stretched synchronously. Money, the film was clamped into an aluminum frame and placed in an oven for heat setting. The alumina μ and time at the heat setting area 86584.doc -23- 1251005 are shown in Table η. Two sheets of film were placed in the ninth frame, and the gauge was sandwiched between the two films to measure the actual film temperature. It is desirable that the setting temperature is higher than the actual film temperature and that the heat setting time listed includes the time (about 30 seconds) required to heat the sample to the actual film temperature. The warp-type film was immersed in a splicing bath of 26 CTC, and the % shrinkage produced was shown in Table η. The examples contained in Table II are for reference. Example 1 _4 all have acceptable shrinkage and CTE, and are stretched under the condition that the equation (27*RML3*(T_Tg)^27 is satisfied, where T is the average stretching temperature (degrees Celsius) in the machine and the horizontal axis direction, Tg The glass transition temperature (degrees Celsius) of the polymer film and the average stretch ratio of the ruler in the machine direction and the transverse axis direction. These films were heat set at 26 〇t: or a larger actual film temperature. Comparative Example C-4 and C-5 does not conform to the equation (27*Ι^(1,3*(Τ-Τ^ρ27) and has an unacceptable CTE value. It should be noted that in Example 2 with WO/〇6125 The films of Comparative Example C-5 were stretched and heat set under the same conditions as reported. It is also worth noting that Examples 3 and 4 are acceptable, as w〇/〇6125 clearly describes "PCT behavior is different from PET. Once the film has been stretched more than 2.5 χ, there is no heat setting (time or temperature) to anneal the internal stress generated during the drawing process. In Table II, the stretch ratio is referred to in the machine and The stretching in the two directions of the horizontal axis, the temperature is given by C, the time is in seconds, and the shrinkage is referred to as the sample. The film is immersed in a solder bath preheated to 260 ° C for 10 seconds after shrinkage percentage, CTE value is expressed in ppm / ° C and film thickness is provided in microns. 86584.doc -24- 1251005

Table II Example 1 2 C-4 C-5 3 4 Stretch ratio 2 2.5 2 2.5 3 3.5 Stretching temperature 100 100 130 130 130 130 Heat setting temperature 290 290 290 280 290 290 Heat setting time 60 60 120 120 60 60 Actual Film temperature 274 272 279 260 276 269 Shrinkage % 1.7% 2.5% 1.7% 1.4% 1.5% 2.7% CTE (23-90〇C) 34 29 57 47 42 33 CTE (120-150°C) 65 51 146 100 80 61 Film thickness 51 31 51 31 23 15

Example 5_8 舆 Comparative Example C_6-r_Q Examples 5-8 and Comparative Examples C-6_c_9 illustrate the effects of heat setting temperature and time on shrinkage and CTE on a film made from Pct using a continuous stretching and tenter method. In the melt phase polycondensation process, 1 〇〇 of butadiene catalyst (e.g., titanium isobutoxide) was used to prepare PCT polyester pellets (1. From 〇74, Tm 293〇c, Tg94 °C). The pellet was dried at 120 ° C for 16 hours and then extruded into a 〇 460 mm (18 mil) on a Davis standard 6.4 cm (2.5 liter pair) extruder equipped with a polyester barrier type propeller. Ear) thick sheet. Maintain the melting temperature and die temperature at 3 〇〇 °C. The sheets are cast onto 3 rolls stacked downwards. The temperatures from the top to the bottom of the rolls are set to 49/57 ° C / 66 ° C (l2 〇 ° F / l 35 ° F / l 5 〇 T). Then, the film is stretched and stretched on a commercial tenter apparatus, and the machine direction of the apparatus is shown on the drum stack at a ratio of 86584.doc -25 - 1251005 shown in Table III and temperature stretching. After thinking about it, under the condition of showing the watch, the k-axis is stretched between the jaws of the frame frame of the tenter frame. The films are immediately passed through an annealing zone that provides a first heat setting of the virtual soil &amp; This annealing zone sets the heat setting zone with the setting temperature and time indicated in the detail. The uniform film temperature of the ruthenium in the annealed region can be obtained by placing a temperature indicating tape on the film. This tape changes color under the well-known temperature series to indicate the maximum temperature the film is subjected to. In Example 7 and Comparative Example C_m9, the second heat setting process can be carried out by setting the thinner---box, and then setting the temperature to the oven and indicating the temperature and time of the area. In table m). For these examples, two sheets of film were placed in the duck frame, and a thermometer was placed between the two films to measure the actual film, the four sputum, the ^, the spleen, and the pan. In Example 8, the second heat setting process can be performed by passing the film of the tenter duck frame a second time through the annealing zone at the heat setting zone (the setting temperature and time are indicated in the watch). . The actual film temperatures listed are the highest temperatures reached during the first and second heat set bonding. It should be noted that the set temperature is higher than the actual film temperature&apos; and the listed light time includes the time required to add the sample to the actual film temperature. Since it takes time to heat the film, the actual film temperature considered is a function of both temperature and time. The heat-set film was immersed in a splicing bath which had been pre-twisted to 26 n° r μ ϊ·曰η ν 丄, C, and the resulting shrinkage % is shown in Table m. Comparative example c_6_c_9 shows less than ·. The actual film temperature of c does not provide sufficient shrinkage at 26 (rc). The film of Example η has acceptable shrinkage and CTE. In Table m, the md stretch ratio is referred to as the machine-wide stretched 'TD The stretching ratio refers to stretching in the horizontal axis direction, and the temperature is 86584.doc -26 - 1251005 is provided by c. The time is in seconds, n/a means that the second heat setting treatment is not performed, and the shrinkage % means that The percent shrinkage after immersion of the film samples in a solder bath preheated to 260 ° C for 10 seconds, the CTE value is indicated in ppm/t: and the film thickness is provided in microns.

Table III Examples

Czi. C-7 5 6 C-8 C-9 7 8 MD stretch ratio 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 MD temperature 91 91 91 91 91 91 91 91 TD stretch ratio 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 TD Temperature 99 99 99 99 99 99 99 99 1st heat setting temperature 288 304 304 304 288 288 288 288 1st heat setting time 9 13 35 106 9 9 9 9 2nd heat setting temperature n/an/an/an/a 270 290 290 299 2nd heat setting time n/an/an/an/a 60 9 60 33 Actual film temperature 200 245 260 267 248 200 275 271 % shrinkage of solder bath 9.9% 4.9% 2.4% 0.9% 5.3% 12.6% 0.9 % 1.2% CTE (23-90 ° C) 24 34 37 31 30 23 33 42 CTE (120-150. 〇 37 59 72 75 50 44 81 71 film thickness 75 75 75 75 75 75 75 75 The present invention has been specifically referred to DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(But it is understood that changes and modifications can be made within the spirit and scope of the present invention. 86584.doc -27- 1251005 [Simple description of the drawing] Single Layer Flexible Electronic Circuit Useful in the Invention FIG. 2 is a two-layer flexible electronic circuit useful in the present invention. FIG. 3 is a multilayer flexible electronic circuit 28 useful in the present invention. - 86584.doc

Claims (1)

Scale 53⁄4) 1⁄2 repair (more) original __092119128, special application for the application of the text of the scope of the patent scope replacement (94 July) Pick, patent scope: Where the polyester contains 1 · a polyester manufacturing a biaxially stretched polyester film having a para-citric acid residue (1) diacid residue comprising at least 90 mole percent, a qindanic acid residue or a combination thereof; and (2) a diol residue, a 1,4-cyclohexanedimethanol residue comprising at least 9 moles of radon ratio; wherein the pigment is stretched in the machine direction (MD) at a pull (four) degree between the film and the 丨 step The ratio is 2.5乂 to 3χ, and the stretching ratio in the horizontal axis direction (4) is 2.5X to 3X; iLM is the stretched (four) film and then the actual film temperature at (4) 〇 °C to Tm (which is considered to be by differential scanning) The heat setting of the polyester is measured by the heat of the heat (DSC) while maintaining the size of the stretched film. 2. A biaxially oriented polyester film according to the scope of claim 2, wherein the content of the trans isomer of the oxime, heart % hexane dimethanol residue ranges from 6 〇 to 1 〇〇 %. 3 · The biaxially oriented polyester film of claim No. 2 or 2, wherein the 14-cyclohexanediethanol residue has a trans isomer content ranging from 6 〇 to 80% 〇 4 · as claimed The biaxially oriented polyester film of clause 1, wherein the diacid residue comprises at least 90 mole percent of a citric acid residue. 5. The biaxially oriented polyester film of claim 1, wherein the polythene has a melting point of at least 270 ° C and an intrinsic viscosity of 0.4 to 1.2 (according to ASTM method D285 7-95 at 25 ° C Using 100 ml of solvent (composed of 60 wt% phenol and 4 wt% tetrachloroethane 86584-940707.doc 1251005) containing 0.50 g of polymer to measure), and containing ·· (1) a diacid residue comprising at least 97 mole percent of a phthalic acid residue, a hydrazine residue or a combination thereof; and (2) a diol residue comprising at least 97 mole percent bismuth , 'cyclohexane dimethanol residue. 6. The biaxially oriented polyester film of claim 5, wherein the polyenthalpy has an intrinsic viscosity of from 0.5 to 1.1. The biaxially oriented polyester film of claim 5, wherein the polyester has a melting point of 270 to 330 ° C and an intrinsic viscosity of 〇·5 to Μ. 8. The biaxially oriented polyester film of claim 5, wherein the 1,4% hexane-methyl residue has a trans isomer content ranging from 6 Å to about 10,000 Å. 9. The biaxially oriented polyester film of claim 5, wherein the content of the trans isomer of the % to % methanol residue is (9) to. 10. The biaxially oriented polymer film of claim 5, wherein the diacid residue comprises at least 97 mole percent of a citric acid residue. 11. A biaxially stretched film according to item i of the patent application, wherein the stretched film is heat set at an actual film temperature of from 260 ° C to Tm for a period of from 1 to 120 seconds while The size of the stretched film is maintained. 12. A two-way stretched blister film as claimed in the patent application, wherein the film is stretched successively in the machine and transverse directions, and the stretched film is practical from 260 ° C to Tm The film is heat set at a film temperature for a period of 1 to 120 seconds while maintaining the size of the stretched film. 13. The biaxially stretched polyester film of the patent application range, wherein the polymerized film is simultaneously stretched in the machine direction and the transverse axis direction, and the stretched thin 86584-940707.doc 1251005 film is at 260° The heat is set at a practical film temperature of C to Tm for a period of 1 to 120 seconds while maintaining the size of the stretched film. 14. The biaxially oriented polyester film of claim 1, wherein the biaxially stretched and heat set polyester film is immersed in a solder bath preheated to 260 ° C for 10 seconds, Not more than 3% shrinkage, and when measured between 120 ° 1 50 C, it has a thermal expansion coefficient value of 1 〇 _ $ 5 ppm / ° C, and when it is measured between 25 and 9 (between TC And having a coefficient of thermal expansion of 10 to 42 ppm / C. 15. The biaxially oriented polyester film of claim 4, wherein the polythene has a melting point of at least 270 ° C and a characteristic of 0.4 to 1.2 Viscosity (according to ASTM method D2857-95, at 25 ° C, using 100 ml of solvent per 100 ml of solvent (which consists of 60 wt% phenol and 4 wt% tetrachloroethane) To measure), and comprising: (1) a diacid residue comprising at least 97 mole percent of a g-acidic residue, a naphthoic acid residue or a combination thereof; and (2) a diol residue, Containing at least 97 mole percent of iota, 4-cyclohexyl cyclodimethanol residue. 1 6 · Biaxially oriented polyester film of claim 14 The film is sequentially stretched in the direction of the machine and the transverse axis, and the stretched film is heat set for a period of 120 seconds at an actual film temperature of from 260 ° C to Tm while maintaining the The size of the stretched film. 1 7 · The biaxially oriented polyester film of claim 14 of the patent application, wherein the poly 86584-940707.doc 1251005 film is simultaneously stretched in the machine direction and the horizontal axis direction, and The stretched film is heat set at a practical film temperature of 260 UTm for a period of time from 丨 to (10) seconds while maintaining the size of the stretched film. 18. A thermoplastic article containing one or more laminates, Wherein at least one of the laminates comprises: L. a heat-curable adhesive; and ruthenium-polyester manufacture &lt; biaxially oriented and heat-set polyester film, wherein the poly-ply comprises: (1) two, residues 'It contains at least 9 (%) mole percent of a citric acid residue, a naphthoic acid residue or a combination thereof: and (2) a diol residue comprising at least 9 mole percent of ruthenium, 4-ring Hexane dimethanol residue; wherein the polymerized film is at 9 (TC &amp; 11 (at the stretching temperature between rc, the stretching ratio in the machine direction (MD) is 2.sx to find, and the stretching ratio in the horizontal axis direction (td) is 2.5X to 3X; and wherein the stretching is The stretched film is then heat set at an actual film temperature of 26 (TC to Tm (where Tm* is measured by differential scanning calorimetry (DSC)) while maintaining the stretched The thermoplastic article of claim 18, wherein the at least one laminate comprises: I. a copper layer; Π. the heat-curable adhesive; and III. the two-way pull Stretch and heat set polyester film. The thermoplastic article of claim 19, wherein the copper layer has a thickness of 17 to 140 microns, and the polyester has a melting point of at least 270 ° C and a characteristic of 4·4 to 1.2. Viscosity (measured according to ASTM method D2857-95 at 25 ° C using 0.50 grams of polymer per 100 milliliters of solvent consisting of 60 weight percent phenol and 40 weight percent tetrachloroethane), And comprising: (1) a diacid residue comprising at least 97 mole percent of a phthalic acid residue, a naphthalene dicarboxylic acid residue or a combination thereof; and (2) a diol residue comprising at least 97 moles Percent of l,4-cyclohexane dimethanol residue. 21. The thermoplastic article of claim 18, wherein the biaxially stretched and heat set polyester film is immersed in a solder bath preheated to 260 ° C for 10 seconds, which will pass no more than 3 % shrinkage, and when measured between 120 and 150 ° C, it has a coefficient of thermal expansion of 10-85 ppm / ° C, and when it is measured between 25 and 90 ° C, it has 1 〇 _ 42 The coefficient of thermal expansion of ppm/°C. 22. The thermoplastic article of claim 21, wherein the at least one laminate comprises: I. a copper layer; IL the heat hardenable adhesive; and III. the biaxial stretching and heat setting polymerization Ester film. The thermoplastic article of claim 22, wherein the copper layer has a thickness of 17 to 140 microns, and the polyester has a melting point of at least 27 (rc and 86584-940707.doc 1251005 0.4 to 1.2) Viscosity (according to astM method D2857-95, at 25 ° C, using 1003⁄4 liters of solvent (which consists of 6 〇 weight percent phenol and 4 〇 weight percent tetra-ethane ethane) contains 5 gram of polymer To measure), and comprising: (1) a diacid residue comprising at least 97 mole percent of a decanoic acid residue, a decanoic acid residue or a combination thereof; and (2) a second intoxication residue comprising At least 97 mole percent of hydrazine, acyclohexane cyclodimethanol residue. 24. A method of preparing a thermoplastic article comprising one or more laminates, wherein at least one of the laminates comprises: (a) a copper layer; (b) a heat-curable adhesive; and (c) a biaxially oriented and heat-set polyester film produced from polyester, wherein the polyester comprises: (1) a diacid residue, Having at least 90 mole percent of a phthalic acid residue, a hydrazine dicarboxylic acid residue, or a combination thereof; (2) a diol residue comprising at least 90 mole percent of a ruthenium, a 4-cyclohexane dimethanol residue; wherein the polyester film is at a stretching temperature between 90 ° C and ll 〇 ° C, The machine direction (MD) has a stretch ratio of 2.5X to 3X and a draw ratio in the horizontal axis direction (TD) of 2.5X to 3X; and wherein the stretched film is subsequently from 260 ° C to Tm The actual film temperature (where Tm is heat-set by the sound factory, scanning calorimetry (DSC) of the polyester: point), * 4 w 86584-940707.doc 1251005 to maintain the stretched The size of the film; and the method comprises: 120 to 18 Torr under pressure. The yttrium compound is sufficient to harden the smear and the temperature is heated. To stretch the polyester film, the polyester comprises: (1) two a ruthenium dicarboxylic acid residue or a combination thereof; and (2) a diol residue comprising at least 9 mole percent of ruthenium, 4 - cyclohexane methanol residue; in the machine wherein the polyester film is at 90 The stretching ratio of the universal direction (MD) at a stretching temperature between ° C and 110 ° C is 2·5 Χ to 3 χ, and in the horizontal axis direction (d), the stretching ratio is 2·5 Χ to 3X; Wherein the stretched film is heat set at a continuous film temperature of from 260 C to Tm (wherein Tm is a melting point determined by differential scanning calorimetry (DSC)) The size of the stretched film is maintained. 26. The flexible electronic circuit board of claim 25, wherein the polyester has a melting point of less than 270 C and an intrinsic viscosity of 0.4 to 1 _2 (according to ASTM method D2857-95, used at 25 ° C) Each 1 ml of solvent (which consists of 60 weight percent of 40 weight percent tetrachloroethane) containing 0.50 grams of polymer is measured) and comprises: (1) a diacid residue 'which contains at least 97 mole percent para-acid residues, hydrazine dicarboxylic acid residues or combinations thereof; and (2) diol residues comprising at least 97 mole percent hydrazine, 4-cyclohexane dimethanol residue. The flexible electronic circuit board of claim 25, comprising one or more laminates, wherein at least one of the laminates comprises: I. a copper layer; a heat-curable adhesive; and a biaxially stretched and heat-set polyester film. 28. The flexible electronic circuit board of claim 25, wherein the biaxially stretched and heat set polyester film is immersed in a solder bath preheated to 26 〇〇c for 10 seconds, Will experience no more than 3% shrinkage, and when measured between 120 and 150 ° C, it has a coefficient of thermal expansion coefficient of i 〇 85 ppm / t, and when it is measured between 25 and 90 ° C, It has a coefficient of thermal expansion coefficient of 10-42 ppm/ °C. 29. The flexible electronic circuit board of claim 28, wherein the polyester has a melting point of at least 270 ° C and an intrinsic viscosity of 0.4 to 1.2 (according to the AS TM method D2 8 5 7-95 at 25 ° C Next, using 100 ml of solvent (which consists of 60% by weight of ruthenium and 40% by weight of tetrachloroethylene) containing 0.50 g of polymer, and containing (1) diacid residues , comprising at least 97 mole percent of a donating acid residue, a tea dicarboxylic acid residue or a combination thereof; and (2) a diol residue comprising at least 97 mole percent of 1,4-cyclohexyl Methanol residue. The flexible electronic circuit board of claim 28, comprising one or more laminates, wherein at least one of the laminates comprises: I. a copper layer; 86584-940707.doc 1251005 II. A heat-curable adhesive; and III. The biaxially oriented and heat-set polyester film. 86584-940707.doc