JP2009280642A - Biaxial stretched polyethylene terephthalate based resin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a biaxial stretched polyethylene terephthalate based resin film preferable for a base film of a laminated body. <P>SOLUTION: The polyethylene terephthalate based resin film has a difference Δn<SB>ab</SB>between a refractive index of a direction forming an angle of 45° with a longitudinal direction of the film and a refractive index of a direction forming an angle of 90° to it of 0.015-0.060, and satisfies the following requirements (1)-(5). (1) Height of warps of four corners is not more than thickness of the film, (2) an average of height of warps of the four corners when it is heat-treated at 150°C for 30 min is 0.5-5.0 mm, (3) a ratio TS/TE of rapture strength TS in four directions to rapture ductility TE is 0.6-2.6 (MPa/%), (4) HS150 is 0.7% to less than 2.0%, and (5) difference in a width direction of HS150 is not more than 0.10%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a biaxially stretched polyethylene terephthalate resin film. Specifically, the present invention relates to a biaxially stretched polyethylene terephthalate resin film having excellent flatness, dimensional stability and cutting processability when used as a base film of a laminate.

  A biaxially stretched film made of a polyethylene terephthalate resin is widely used as a base film for various laminates because of its excellent transparency, dimensional stability, and chemical resistance. In particular, a relatively thick film is used for applications such as a base film on which a curing shrinkable resin composition is laminated, because excellent strength and dimensional stability are required.

  The polyethylene terephthalate resin film for use as described above is required to have good flatness (flatness when placed on a flat table) as compared with a film for normal packaging use. In particular, with the recent high performance of products, the demand for flatness is high, and the disturbance of flatness becomes a quality defect.

  On the other hand, for the purpose of obtaining a void-containing polyester-based film with good flatness, as in Patent Documents 1 and 2, regarding the curling of the film cut out from the roll film and suppressing curling after heating, the longitudinal stretching step Describes a method of changing the output of the infrared rays on the front and back sides and performing a temperature difference between the film in the transverse stretching step and the heat setting step.

JP 2001-342273 A JP 2001-342274 A

  In addition, for the purpose of obtaining a film with good flatness, the temperature difference between the front and back of the film should be 10 ° C. or less during longitudinal stretching as in Patent Document 3 for suppressing curling of the film cut out from the film under load. Is described.

Japanese Patent Laid-Open No. 10-258458

  Furthermore, when using as a base film of a laminated body, the film produced as a film roll is cut | judged to a predetermined size in post-processing. Moreover, in order to raise productivity in post-processing, it cuts in the state which accumulated the film. Therefore, as a method for improving the cutting property of the film, as disclosed in Patent Document 4, Patent Document 5, and Patent Document 6, special cutting devices and cutting methods are disclosed in post-processing.

JP 2001-252891 A JP 2005-305637 A JP 2006-289601 A

  In addition, there is an increasing demand for wide slit rolls in order to reduce post-processing costs, but in order to collect such wide slit rolls with a high yield from the limited mill roll width, the narrow width is required as in the past. It is better to collect from a wider mill roll than from a mill roll. However, when the mill roll is widened, it becomes difficult to maintain temperature uniformity in the width direction of the heat setting device. That is, a temperature difference occurs between the left and right, or the temperature becomes unstable over time. As a result, it becomes difficult to control the heat shrinkage rate constant in the width direction and the longitudinal direction. Therefore, the difference in the heat shrinkage rate in the width direction affects the runnability of the film in the process where heat is applied in the post-processing. The passability is adjusted by adjusting. Therefore, there is a loss due to adjustment.

  In order to widen the mill roll, it is indispensable to finely adjust the amount of hot air blown out in the heat fixing device in order to maintain good temperature uniformity in the width direction of the heat fixing device. However, fine adjustment of the hot air blowing amount, etc. can improve the temperature uniformity in the width direction and reduce the difference in thermal shrinkage between the left and right to a certain extent. It is not possible to reduce the difference in thermal shrinkage between the left and right edges to a level sufficient to achieve the desired level.

  Therefore, regardless of the width of the mill roll, a method for reducing the difference in the heat shrinkage rate in the width direction of the film (the heat shrinkage rate in the longitudinal direction of the film) in order to improve the film passability in the post-processing step In the heat fixing process of the film, the applicant puts a continuous shielding plate on a plenum duct (hot air outlet) arranged at regular intervals with respect to the film traveling direction, and the width of the shielding plate By gradually expanding the film toward the film traveling direction side, the temperature in the width direction of the film is increased from the central part to the end part, and the relaxation amount at the end part approaches the relaxation amount at the central part. It has been proposed (Patent Document 7). Further, as a method for reducing the difference in the heat shrinkage rate in the width direction of the film, the applicant attached discontinuous shielding plates to the five plenum ducts in the film heat setting step, and from each plenum duct, per unit time Discloses a method of increasing the amount of hot air impinging on the end by increasing the speed of air blown from the plenum duct while keeping the amount of hot air blown to the outside (Patent Document 8).

JP 2001-138462 A JP 2002-79638 A

  A laminate produced using a polyethylene terephthalate resin film as a base film is also required to have good flatness. In order to obtain a laminate having good flatness, a relatively thick base film or a base film having excellent flatness is used as described above. Further, even when the laminate itself has a warp, when producing an assembly using the laminate as a member, the planarity of the laminate is adjusted by devising an assembly method. Therefore, even a conventional base film can be used without any problem.

  However, it was found that when the curing shrinkable resin composition was laminated, a minute warp was generated on the side of the curable resin layer due to curing shrinkage accompanying the curing of the resin. In applications where a larger area is required, it was thought that a device with a low degree of warping would help improve precision.

  Furthermore, there is no problem with the film derived from the center part of the mill roll, but the film derived from the end part of the mill roll causes film residue or cracks called “beard” on the cut surface of the film. I found it easier to do. In particular, when the cutting process is performed in a state where the films are stacked, the edge portion of the film stacked on the sheet becomes high due to the beard generated on the cut surface, and there are cases where the positional deviation or the distortion of the planarity occurs. Furthermore, in applications that require higher precision, chips generated from whiskers may be a factor, resulting in deterioration of workability afterwards and the possibility of a decrease in yield when manufactured as a laminate due to the occurrence of defects. It was. Therefore, even if the cutting method as described above is selected, if it is used for a long time, its sharpness will be deteriorated, and it will be necessary to replace the blade and adjust other conditions. Can be. It was thought that the fact that the cutting property was different at the mill roll taking position was due to distortion in the physical properties in the width direction of the mill roll.

  On the other hand, from the viewpoint of improving productivity, it is predicted that the line speed of post-processing will be improved, and it is considered that a film that can be suitably used even in high-temperature post-processing is required. However, with regard to the technology for improving the film passage in the post-processing step, in the method of simply covering the plenum duct (hot air blowing portion) with a continuous shielding plate in the heat setting process, The film cannot be relaxed sufficiently. Therefore, when post-processing is performed at a high temperature for a long time, the conditions must be adjusted in the post-processing step, and there may be a situation where the conditions cannot be adjusted.

  In addition, in the method of simply covering the plenum duct with the heat-fixing process, the temperature hunting in the heat-fixing zone becomes large, so when manufacturing a long film (mill roll) of 1,000 m or more. In other words, a portion having poor permeability (that is, a portion having a large difference in thermal shrinkage in the width direction of the film) or a portion having poor planarity is formed. Further, when the wind speed was changed for each plenum duct, temperature hunting occurred, and this also failed to obtain a stable quality.

  The present invention relates to a biaxially stretched polyethylene terephthalate resin film having excellent flatness when used as a base film of a laminate, and having excellent cutting properties and dimensional stability. For example, it suppresses the generation of whiskers, swarf, swarf, etc. during the cutting process so that the flatness that occurs during the cutting process does not become a quality problem, and the biaxially stretched polyethylene terephthalate resin film Even when curing shrinkage of the curing shrinkable resin composition occurs when the curing shrinkable resin composition is laminated, since the base film has shrinkage on the opposite surface, the warpage is balanced as a whole, and the laminate The present invention relates to a biaxially stretched polyethylene terephthalate resin film that can be suitably used as a base film capable of providing excellent flatness as a whole.

Among the present inventions, the first invention is that the difference Δn _ab between the refractive index in the direction forming a 45 ° angle with the longitudinal direction of the film formation and the refractive index in the direction forming an angle of 90 ° is 0. It is a polyethylene terephthalate resin film that is 015 or more and 0.060 or less, and is a biaxially stretched polyethylene terephthalate resin film that satisfies the following requirements (1) to (5).
(1) A sample having a thickness of 300 mm in the longitudinal direction of film formation and 210 mm in the width direction perpendicular thereto is taken, and the heights of the warps at the four corners of the sample (the height in the vertical direction from the horizontal plane) are set to JIS metal scales (0 (5 mm scale), the maximum value of the height of the four corners is below the thickness of the film. (2) A sample of 300 mm in the longitudinal direction of the film and 210 mm in the width direction perpendicular thereto is formed. The sample was collected and placed on a mount with one side facing up, and heat-treated at 150 ° C. for 30 minutes in a heating oven. Then, the sample was removed from the heating oven together with the mount, and the sample was left at room temperature for 30 minutes. 4. When the heights of the four corners of the sample (height in the vertical direction from the horizontal plane) were measured with a JIS metal ruler (0.5 mm scale), the average height of the four corners was 0.5 mm or more. 0mm or less The height of the warp is measured with the concave surface of the film sample warped after heating up. Therefore, if the height of the warp of the sample after being left at room temperature after heating is 0 mm, or if the cross section of the sample is M-shaped, Measure the thickness.
(3) The ratio TS / TE of the breaking strength TS and the breaking elongation TE in a direction that forms an angle of 45 degrees with the longitudinal direction of the film formation, and the direction that forms an angle of 135 degrees with the longitudinal direction of the film formation. The ratio TS / TE between the breaking strength TS and the breaking elongation TE, the ratio TS / TE between the breaking strength TS and the breaking elongation TE in the longitudinal direction of the film deposition, and the angle of 90 degrees with the longitudinal direction of the film deposition. The ratio TS / TE between the breaking strength TS and the breaking elongation TE in the direction of forming (width direction) is 0.6 (MPa /%) or more and 2.6 (MPa /%) or less (4) at 150 ° C. HS150, which is the heat shrinkage rate in the longitudinal direction of film formation when heated for 30 minutes, is 0.7% or more and less than 2.0% (5) Arbitrary position in the width direction of the film and its position Cut out samples from a position more than 70 cm away in the width direction, and When HS150 which is the thermal contraction rate in the longitudinal direction of film formation when heated at 150 ° C. for 30 minutes is obtained for one sample, the difference between the HS150 is 0.10% or less. The thickness of the polyethylene terephthalate resin film is from 100 μm to 400 μm.

The biaxially stretched polyethylene terephthalate resin film of the present invention has good cutting properties and dimensional stability, and has good flatness as a single film or a laminate. Therefore, as a preferred embodiment, the generation of chips and whisker is suppressed at the time of cutting, and even if the curing shrinkable resin composition is laminated as a base film, the flatness as a whole laminate is good, so that the post-processability Excellent.
In addition, as a preferable embodiment, even if materials having different shrinkage properties or shrinkage properties are laminated or bonded, the flatness as a whole laminate is good, and even when used as a sheet, cutting properties are good. It is.
Furthermore, as a preferred embodiment, since the dimensional stability in the heat treatment is excellent, when the heat treatment under tension is performed in the post-processing, the film has good passability.

[Polyethylene terephthalate resin]
The biaxially stretched polyethylene terephthalate resin film of the present invention contains ethylene glycol and terephthalic acid as main components. Other dicarboxylic acid components and glycol components may be copolymerized as long as the object of the present invention is not impaired. Examples of the other dicarboxylic acid components include isophthalic acid, p-β-oxyethoxybenzoic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-dicarboxybenzophenone, bis- (4-carboxyphenylethane), adipine Examples include acid, sebacic acid, 5-sodium sulfoisophthalic acid, cyclohexane-1,4-dicarboxylic acid, and the like. Examples of the other glycol component include propylene glycol, butanediol, neopentyl glycol, diethylene glycol, bisphenol A and other ethylene oxide adducts, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like. In addition, oxycarboxylic acid components such as p-oxybenzoic acid can also be used.

  As a polymerization method of such polyethylene terephthalate (hereinafter simply referred to as PET), a direct polymerization method in which terephthalic acid and ethylene glycol and, if necessary, other dicarboxylic acid component and diol component are directly reacted, and dimethyl terephthalate are used. Any production method such as a transesterification method in which an ester (including a methyl ester of another dicarboxylic acid as necessary) and ethylene glycol (including another diol component as necessary) are transesterified can be used. .

  When the film of the present invention is formed of PET, the intrinsic viscosity (IV) of the raw material PET is preferably 0.45 to 0.70 dl / g, and more preferably 0.55 to 0.65 dl / g. When the intrinsic viscosity of the PET raw material is 0.45 or less, the degree of polymerization of the PET after being recovered and passed through the extruder again becomes too low, and the stretchability of the film deteriorates or the tear resistance decreases. Is not preferable. On the other hand, if the intrinsic viscosity exceeds 0.70 dl / g, the filtration pressure becomes excessively high and high-precision filtration becomes difficult, which is not preferable. In addition, IV of the resin raw material is calculated | required with the following methods, for example, and is represented as [(eta)].

[Intrinsic viscosity (IV)]
After the PET ground sample is dried, it is dissolved in a mixed solvent of phenol / tetrachloroethane = 60/40 (weight ratio), and a solution having a concentration of 0.4 (g / dl) is obtained at 30 ° C. using an Ostwald viscometer. The flow time and the flow time of the solvent alone are measured, and the calculation is performed from the time ratio on the assumption that the constant of Huggins is 0.38 using the Huggins formula.

  Moreover, when forming the film of this invention by PET, the range of 3-30 eq / t is preferable and, as for the acid value (AV) of PET raw material, it is more preferable in it being 5-25 eq / t. An acid value of 3 eq / t or less is not preferable because the polymerization rate becomes slow and the production efficiency is lowered. On the other hand, an acid value of 30 eq / t or more is not preferable because hydrolysis tends to proceed and the degree of polymerization tends to decrease. The acid value of the resin raw material is determined by the following method, for example.

[Acid value]
After pulverizing the raw material, it is dissolved in benzyl alcohol, and after adding chloroform, neutralization titration with a sodium hydroxide solution is performed to calculate the equivalent of sodium hydroxide per 1 ton of PET.

[Δn _ab ]
During the production of a biaxially stretched polyethylene terephthalate resin film, it is known that the uniformity of physical properties in the film width direction is disturbed when the film is stretched in the width direction in the tenter. In order for this phenomenon to occur, the obtained biaxially stretched film has a Δn _ab (a refractive index in a direction that forms an angle of 45 degrees with the longitudinal direction of film formation, The difference (absolute value) between the refractive index in the direction that forms an angle of 135 degrees with the longitudinal direction of the film increases. Here, the polyethylene terephthalate resin film of the present invention is derived from the end of the mill roll and is limited to those having Δn _ab of 0.015 or more and 0.060 or less in all regions. A film having Δn _ab less than 0.015 does not have the above-mentioned problem of “strain (that is, a difference in physical properties or a difference in thermal shrinkage in the width direction)”. On the other hand, the upper limit of Δn _ab is 0.060, more preferably 0.057, and even more preferably 0.055. Films with Δn _ab exceeding 0.060 are remarkably distorted, and it is difficult to adjust TS / TE, heat shrinkage rate, etc. so as to satisfy the requirements of the present invention. Note that Δn _ab in the present invention can be obtained by measuring Δn _ab at a position within 50 mm from one end edge parallel to the longitudinal direction of film formation and at a position within 50 mm from the other end edge.

[Flatness and warping]
When a rectangular film sample of 300 mm in the longitudinal direction (longitudinal direction) and 210 mm in the width direction perpendicular thereto is cut out from the biaxially stretched polyethylene terephthalate resin film of the present invention, 150 ° C., 30 It is necessary that the average height of the four corners be 0.5 mm or more and 5.0 mm or less by heat treatment for minutes.

The warpage after heating is measured by the following method.
(1) A rectangular film sample of 300 mm × width direction 210 mm is cut out in the longitudinal direction (also referred to as longitudinal direction or machine direction) of film formation.
(2) The sample is placed on a flat mount with one side (for example, x-plane) facing up, and placed on the shelf of a heating oven. Here, the mount is also referred to as cardboard or paperboard, and a thickness of about 1 mm is suitable.
(3) Adjust the heating oven to 150 ° C. and heat-treat for 30 minutes.
(4) After the heat treatment, the sample is taken out together with the mount and left at room temperature for 30 minutes. It should be noted that the room temperature conditions here are preferably controlled at a temperature of 23 ± 2 ° C. and a humidity of 65 ± 5%.
(5) The sample left for 30 minutes is placed on a horizontal glass plate (preferably having a thickness of about 5 mm), and the heights of the four corners of the sample (the height in the vertical direction from the horizontal plane) are set to a JIS scale (0 .5mm scale) and visually measure to 1/10 of the minimum scale. The height of the four corners is measured for all samples, and the average of the heights of the four corners is obtained.
(6) In addition, when the height of the warp of the sample after standing at room temperature after heating is 0 mm, or when the cross section of the sample (one side of the rectangle) is M-shaped, The height of the warp is measured with the upper and lower surfaces of the sample opposite (with the x-plane facing down). That is, the warp of the present application measures the heights of the four corners with the concave surface when the warp occurs in the film after heating.

  The average of the heights of the four corners of the biaxially stretched polyethylene terephthalate resin film of the present invention measured under the above conditions at 150 ° C. for 30 minutes is more preferably 0.6 m or more, and even more preferably 0.7 mm or more. . When the average height of warps at the four corners by heat treatment at 150 ° C. for 30 minutes measured under the above conditions is less than 0.5 mm, when the curing shrinkable resin is laminated, it cannot resist the warping due to the curing shrinkage of the resin. And the laminated body tends to warp to the cured resin composition layer side as a whole. Further, the average of the heights of the four corners by heat treatment at 150 ° C. for 30 minutes measured under the above conditions is more preferably 4.0 mm or less, and even more preferably 3.5 mm or less. When the average height of the four corners by heat treatment at 150 ° C. for 30 minutes, measured under the above conditions, exceeds 5.0 mm, when a curing shrinkable resin is laminated, the warp stronger than the warp due to the curing shrinkage of the resin. This is not preferable because the laminated body tends to warp toward the base film as a whole.

  When the average of the height of the four corners is 0.5 mm or more and 5.0 mm or less by heat treatment at 150 ° C. for 30 minutes under the measurement conditions described above, a curing shrinkable resin composition is laminated on one side, and curing shrinkage accompanying curing Even if this occurs, the planarity of the entire laminate is maintained. For example, in the case of a rectangular laminate having a longitudinal direction of 300 mm and a width direction of 210 mm, the average height of the four corners is 0.5 mm or less. preferable. If the height of the warp of the laminate is within the above range, it can be suitably used in precision applications where high flatness is required.

  It is desirable that the biaxially stretched polyethylene terephthalate resin film of the present invention has good flatness before the heat treatment. Therefore, when a rectangular film sample of 300 mm in the longitudinal direction and 210 mm in the width direction perpendicular thereto is cut out, when the warp heights at the four corners are measured without performing heat treatment, the maximum value of the warp height is It is less than the film thickness, and the average value of the height of the four corners is preferably 20% or less of the film thickness.

  When the heat treatment is not performed, the maximum value of the height of the warp is preferably not more than the film thickness, more preferably not more than 90% of the film thickness, still more preferably not more than 80%, and 50 % Or less is particularly preferable. Moreover, it is preferable that the average of the height of the warp when not heat-processing is 20% or less. When the maximum warp height when the heat treatment is not performed is less than the film thickness, or the average value is 20% or less, there is little distortion in flatness during film processing such as application of curable resin, and processing accuracy Is preferable from the viewpoint of yield. In addition, since it is desirable that the flatness of the film is good in a wide range, when evaluating the flatness of the film before heating, it is desirable to measure about 50 samples (about 3 m × 1 m).

[TS / TE]
In the present invention, the breaking strength (TS) is a stress necessary for the film to break, specifically, gradually adding a tensile force to the film to determine the force when the film breaks, This is expressed as a value (unit: MPa) converted to stress per unit area. The elongation at break (TE) is the ratio (elongation) of the film that stretched until it broke, and specifically, the length that stretched until the film broke when a tensile force was applied to the film. Is expressed by a value (unit:%) divided by the original length. In the present invention, the breaking strength (TS) and the breaking elongation (TE) are measured according to JIS K 7127, and specifically, the following methods are used. That is, a film test piece having a width of 12.7 mm and a length of 200 mm was sampled, and the film test piece was set in a tensile tester (for example, Tensilon RTC-125A manufactured by ORIENTEC Co., Ltd.) at a temperature of 23 ° C. and a humidity of 65% RH. Under the environment, the film was stretched at a distance between chucks of 100 mm and a take-off speed of 200 mm / min, and the breaking strength (TS) and elongation at break (TE) were determined from the measured values of the elongation at break of the film specimen and the load required for breaking. Is calculated.

  The ratio between the breaking strength (TS) and the elongation at break (TE) (TS / TE) and the cutting property of the film have the following relationship. That is, a film having a large TS / TE means a film having a high breaking strength and a low elongation. A film having such characteristics becomes a fragile and low-strength film, and the cut surface becomes fluffy during cutting, and beards and chips are likely to be generated. On the other hand, a film having a small TS / TE means a film having a low breaking strength and a high elongation. A film having such characteristics has a moderate viscosity and a firm film, and the cut surface is less rough even during cutting and has good cutting properties. On the other hand, if it is too low, the film is stretched and cut, so that the cut portion is deformed, which is not preferable. Further, when the TS / TE ratio varies depending on the part of the film, there is a difference in the cutting property depending on the part even for the same shearing force, and the difference in the cut surface and the whisker easily occur due to the difference. Therefore, it is most desirable that the TS / TE ratio is isotropic. From the above, a film having a small TS / TE ratio and a small variation in the TS / TE ratio depending on the part is preferable in terms of cutting properties.

  The film of the present invention has a ratio TS / TE between the breaking strength TS and the breaking elongation TE in a direction (A direction) forming an angle of 45 degrees with the longitudinal direction of film formation, and 135 with the longitudinal direction of film formation. The ratio TS / TE of the breaking strength TS and the breaking elongation TE in the direction forming the angle (B direction), and the ratio TS / TE of the breaking strength TS and the breaking elongation TE in the longitudinal direction (MD direction) of film formation. The ratio TS / TE between the breaking strength TS and the breaking elongation TE in a direction (TD direction) forming an angle of 90 degrees with TE and the longitudinal direction of the film formation is 0.6 (MPa /%) or more. .6 (MPa /%) or less. The upper limit of the TS / TE ratio is preferably 2.6 (MPa /%), more preferably 2.4 (MPa /%), and even more preferably 2.2 (MPa /%). If the TS / TE ratio is 2.6 (MPa /%) or less in the MD direction, the TD direction, the A direction, and the B direction, the film has good cutting properties and is suitable for cutting. The lower limit of the TS / TE ratio is preferably 0.6 (MPa /%), more preferably 0.9 (MPa /%). When the TS / TE ratio is 0.6 (MPa /%) or more, it is preferable that the film is hardly mechanically deformed. Further, when the TS / TE ratio is within the above ranges in the MD direction, the TD direction, the A direction, and the B direction, shear deviation due to the TS / TE ratio is unlikely to occur. A preferred film forming method for obtaining a film having a TS / TE ratio in the above range will be described later.

[Heat shrinkage]
The biaxially stretched polyethylene terephthalate resin film of the present invention is HS150, which is a heat shrinkage ratio in the longitudinal direction of film formation when a sample is cut out from an arbitrary position in the width direction of the film and heated at 150 ° C. for 30 minutes. When these are calculated | required, those HS150 is 0.7% or more and less than 2.0%.

  When the HS 150 is less than 2.0%, the dimensional stability is good even in the heat treatment in the post-processing, which is preferable. The HS 150 is more preferably 1.5% or less, and further preferably 1.2% or less. In addition, although HS150 in each cutout part is so preferable that it is low, it is thought that 0.7% is a minimum in design.

  The biaxially stretched polyethylene terephthalate resin film of the present invention is obtained by cutting a sample from an arbitrary position in the width direction of the film and a position 70 cm or more away from the arbitrary position in the width direction. When HS150 which is the thermal contraction rate in the longitudinal direction of film formation when heated for 30 minutes is determined, the difference between the HS150 is 0.10% or less.

  If the difference in HS150 is 0.10% or less, the film can be easily passed in post-processing, which is preferable. Further, the difference in the HS 150 is more preferably 0.08% or less, and particularly preferably 0.06% or less. In addition, although the difference of said HS150 is so preferable that it is low, 0.05% is considered to be a minimum in a design.

The film sample used for the measurement of the heat shrinkage rate is cut out from two cutout portions provided by the following procedure.
(1) One cutout is provided at an arbitrary point on the film.
(2) A sample cutout portion is provided from a position separated by 70 cm or more in the width direction from the cutout portion of (1).
(3) A sample film having a width of 20 mm and a length of 250 mm is cut out from each cutout portion along the longitudinal direction of film formation.

  In the present invention, the heat shrinkage rate is measured by marking the sample film at intervals of 200 mm, placing it in a heating oven adjusted to 150 ° C., and performing heat treatment at 150 ° C. for 30 minutes in accordance with JIS / C-2318. Measure heat shrinkage.

  The thickness of the film constituting the biaxially stretched polyethylene terephthalate resin film of the present invention is not particularly limited. However, the base film of the laminate is preferably 100 μm or more and 400 μm or less. Further, the thickness of the film is more preferably 110 μm or more, and further preferably 120 μm or more. If the thickness of the film is 100 μm or more, it is preferable because the film can be handled easily. Further, the thickness of the film is preferably 400 μm or less, more preferably 300 μm or less, and further preferably 250 μm or less. If the thickness of the film is 400 μm or less, it is preferable because cutting processing becomes easy.

  The length in the width direction of the biaxially stretched polyethylene terephthalate resin film of the present invention is not particularly limited, but from the viewpoint of ease of handling, the lower limit of the film width is preferably 0.7 m or more, and 1.0 m The above is more preferable. On the other hand, the upper limit of the width of the film roll is determined by the size of the post-processing apparatus, but from the viewpoint of productivity, it is preferably 2.5 m or less, more preferably 2.0 m or less, and 1.5 m. More preferably, it is as follows.

  The length in the longitudinal direction of the biaxially stretched polyethylene terephthalate-based resin film of the present invention is not particularly limited, but in the case of a film roll, the film has a thickness of about 100 μm from the viewpoint of ease of winding and handling. Is preferably 8,000 m or less, and more preferably 7,000 m or less. When the film has a thickness of about 400 μm, it is preferably 1,200 m or less, and more preferably 1,100 m or less. Therefore, when the thickness of the film is in the middle of 100 to 400 μm, it is preferable to set the film length to be 300 m or more and 8,000 m or less. As the take-up core, usually, paper of 3 inches, 6 inches, 8 inches, etc., a plastic core or a metal core can be used.

  The biaxially stretched polyethylene terephthalate resin film of the present invention may be a single layer or a film having a laminated structure of two or more layers, or one side of a biaxially stretched polyethylene terephthalate resin film that does not contain fine particles with emphasis on transparency. Alternatively, there may be no problem even if various coatings are applied to the both surfaces at the time of film formation for the purpose of improving the adhesiveness in the post-processing step and improving the slipperiness.

  Furthermore, the polyethylene terephthalate resin film constituting the film of the present invention can be subjected to corona treatment, coating treatment, flame treatment, etc. in order to improve the adhesion of the film surface.

  Moreover, in the polyethylene terephthalate-type resin film which comprises the film of this invention, microparticles | fine-particles can be added as needed. Examples of the fine particles added at that time include known inorganic fine particles and organic fine particles. Furthermore, in the resin forming the film, various additives as necessary, for example, waxes, antioxidants, antistatic agents, crystal nucleating agents, viscosity reducing agents, heat stabilizers, coloring pigments, An anti-coloring agent, an ultraviolet absorber and the like can be added. It is preferable to add fine particles to the polyethylene terephthalate resin in the present invention to improve the workability (slidability) of the polyethylene terephthalate resin film. Any fine particles can be selected. Examples of inorganic fine particles include silica, alumina, titanium dioxide, calcium carbonate, kaolin, and barium sulfate. Examples of the organic fine particles include acrylic resin particles, melamine resin particles, silicone resin particles, and crosslinked polystyrene particles. The average particle diameter of the fine particles can be appropriately selected as necessary within a range of 0.05 to 2.0 μm.

In addition, the measurement of the average particle diameter of said particle | grain is performed with the following method.
Take a picture of the particles with a scanning electron microscope (SEM) and at a magnification such that the size of one smallest particle is 2-5 mm, the maximum diameter of 300-500 particles (between the two most distant points) Distance) is measured, and the average value is taken as the average particle diameter.

  As a method of blending the above-mentioned particles into the polyethylene terephthalate resin film, for example, it can be added at any stage of producing the polyethylene terephthalate resin, but preferably after the esterification stage or after completion of the transesterification reaction. It may be added as a slurry dispersed in ethylene glycol or the like at the stage before the start of the condensation reaction to proceed the polycondensation reaction. Also, a method of blending a slurry of particles dispersed in ethylene glycol or water with a vented kneading extruder and a polyethylene terephthalate resin raw material, or a dried particle and a polyethylene terephthalate system using a kneading extruder It can be performed by a method of blending with a resin raw material.

The technical idea for the warp of the present invention is as follows.
(1) The curing shrinkable resin composition forms a crosslinked structure by curing, and the volume decreases by about 10% before and after curing. Therefore, when a curable resin composition is laminated on one side of the base film, warping that causes the curable resin composition side to become a concave portion as a whole of the laminate occurs due to curing shrinkage accompanying the curing of the resin.
(2) In order to prevent the warpage of (1), it was considered that if the warp on the opposite side occurred in the base film so as to resist the curing shrinkage of the curable resin, the warpage could be offset as the whole laminate. For this reason, it is necessary for a base film alone without a curable resin composition layer to have a warp on the side opposite to the laminated surface.
(3) The present inventors have obtained the idea of the present invention by confirming that when one side of the base film is subjected to heat treatment for a short time at a high temperature, the heat treatment surface contracts and a slight warp is generated. From this, it was considered that the heat shrinkage rate of the front and back of the film should be different in order to generate warp in the base film. When there is a difference in heat shrinkage between the front and back of the film, the heat generated during the curing process of the curable resin generates a warp such that the surface having a large shrinkage becomes a recess. However, the warp developed by heating was slight. However, even when the present inventors applied a curable shrinkable resin composition having a large shrinkage ratio of about 10%, the entire laminate was resisted by the slight shrinkage of the base film against the curable shrinkage. As a result, they found a surprising effect that the flatness was maintained.
(4) In addition, from the viewpoint of workability, this base film has no warp and is substantially flat when not subjected to heat treatment, and must be usable in the same manner as a conventional base film. That is, the film of the present invention is a film having an unprecedented characteristic that it has a potential warp that becomes apparent by heating, even though it is flat before the heat treatment.

[Production Method of Film of the Present Invention]
<Problems of conventional longitudinal stretching method>
Until now, as a method for controlling the flatness of a film, methods described in Patent Document 1 (Japanese Patent Laid-Open No. 2001-342273) and Patent Document 2 (Japanese Patent Laid-Open No. 2001-342274) have been disclosed. In Patent Document 1 and Patent Document 2, in the case of a void-containing polyester-based film, “(1) reducing the volume fraction of the cavity and reducing the volume of each cavity as a means for suppressing curling due to the structural difference between the front and back of the film. By suppressing the size to a small size, a method for resisting curling by resisting internal strain, (2) a method for providing a distribution of cavities in the film thickness direction, and (3) a film thickness direction due to a cooling difference during extrusion. In order to control the curl caused by the structural difference between the front and back of the film applied in each process starting from the difference in crystallinity, the structural difference between the front and back of the film is positively generated and complemented with the inevitable structural difference. "A method for bringing the curl value close to zero" is described.

  Furthermore, “With a void-containing polyester film containing a large number of voids derived from a thermoplastic resin incompatible with the polyester resin inside the film, it is very difficult to obtain a film with little curl by the conventional technology.” "In ordinary transparent polyester films, the occurrence of curling curls is very slow and is very unlikely to be a problem."

  However, while Patent Documents 1 and 2 focus on eliminating curling, the present invention aims to positively impart a potential warp to the film. Furthermore, while Patent Documents 1 and 2 presuppose a void-containing film, the present invention provides a potential warp in a transparent polyethylene terephthalate film that does not contain voids.

  The thermal conductivity is different between the void-containing film and the polyethylene terephthalate-based resin film not including the void (the void-containing film has a small thermal conductivity, but the film without the void has a high thermal conductivity). Therefore, in the case of a polyethylene terephthalate-based resin film that does not contain cavities, it is difficult for the methods of Patent Documents 1 and 2 to provide a temperature difference between the front and the back that is necessary for the expression of a potential warp during the manufacturing process.

  Furthermore, the temperature difference between the front and back of the film in the longitudinal stretching step is 10 ° C. or less by the method described in Patent Document 3 (Japanese Patent Laid-Open No. 10-258458) for the purpose of preventing curling when the film is loaded. A method of setting to is disclosed.

  Patent Document 3 aims to obtain a film that does not cause curling, whereas in the present invention, a film having a potential warp that can be balanced even if the film shrinks due to curing of the curable resin. The purpose is to obtain. Therefore, in order to make the thermal shrinkage due to heating different between the front and the back, the single-stage stretching is not sufficient as in Patent Document 3. In order to obtain the film of the present invention, the reason is not clear, but multistage stretching was necessary as described later.

  In order to solve the problems of the above-described conventional stretching methods, the present inventors obtain a film having a potential warp that becomes apparent by heating even though it is flat before the heat treatment. We studied earnestly to see if it could be done. As a result, unlike the conventional stretching method, it has been found that a film in which warpage is manifested by heating can be obtained by positively providing a molecular orientation difference between the front and back surfaces in the film production process, and the present invention has been completed. It was. More specifically, by correlating the achievement means described in the following (1) to (3), the potential to be manifested by heating despite being flat before the heat treatment is shown. A film having an unprecedented characteristic of having a warp was obtained.

<Characteristic 1 of the production method of the film of the present invention>
(1) Temperature difference between front and back of unstretched sheet In the production of the film of the present invention, a molten resin is first extruded from a die, and rapidly cooled and solidified by winding on a cooled casting drum to obtain an unstretched sheet. At this time, the thickness of the unstretched sheet is, for example, about 1000 μm or more in a thick film of 100 μm or more. Since the unstretched sheet is cooled from the sheet surface, the cooling efficiency is different between the surface in contact with the casting drum (hereinafter referred to as the front surface (F)) and the opposite surface (hereinafter referred to as the back surface (B)). A temperature difference occurs between the front and back of the unstretched sheet.

  Although depending on the thickness of the unstretched sheet, the expression of the curl of the film varies depending on the temperature difference between the front and back surfaces of the unstretched sheet. When the temperature difference between the front and back surfaces becomes large, the sheet itself curls, and the central portion of the sheet does not adhere to the roll surface, and contact on the roll becomes insufficient. Thereby, it contacts with the unintended part in a process, and a crack will generate | occur | produce in a film. For this reason, usually, the temperature difference between the front and back sides of the sheet is not excessively increased. However, in the present invention, in order to develop warp by heat treatment, a difference in crystallinity is provided on the front and back of the sheet, thereby causing a difference in stretch orientation in the stretching process, thereby achieving warp expression after heating. It is. In order to provide a difference in the crystallinity between the front and back surfaces, it was estimated that there was an appropriate range, even if the temperature difference between the front and back surfaces was low or high.

  In order to satisfy the above characteristics, the inventor of the present application has intensively studied the temperature difference between the front and back sides of the unstretched sheet and the optimization of the temperature of the entire sheet. As a result, when the surface temperature of the surface (F) of the unstretched sheet is F and the surface temperature of the back surface (B) is B when the second cooling roll (separating roll) following the casting drum is separated, it is unstretched. It has been found that the surface temperature difference (FB) between the front and back of the sheet is preferably 0 ° C. or higher and 33 ° C. or lower.

  Specifically, the surface temperature difference between the front and back of the sheet at the outlet of the second cooling roll is more preferably 5 ° C. or higher, further preferably 8 ° C. or higher, and particularly preferably 10 ° C. or higher. The surface temperature difference between the front and back of the sheet is more preferably 30 ° C. or less, further preferably 28 ° C. or less, and particularly preferably 25 ° C. or less.

  As a method of controlling the surface temperature difference (FB) between the front and back of the unstretched sheet within the above range, it is desirable to appropriately control the cooling time and the temperature of the cooling roll. The front surface (F) in direct contact with the cooled casting drum is cooled earlier than the back surface (B). Therefore, when the thickness is increased to 1,000 μm or more, the surface temperature difference becomes large in the surface temperature difference between the front and back of the sheet while being cooled by the casting drum. Thereafter, when there is a second cooling roll following the casting drum, the back surface (B) is cooled by the second cooling roll, and the surface temperature difference between the front and back of the sheet is reduced. In such a case, for example, the back surface is cooled by using cooling air, or the surface temperature difference between the front and back surfaces of the sheet is controlled by cooling the back surface with the second cooling roll early by reducing the casting drum diameter. I can do it. Further, since the time required for cooling depends on the thickness of the sheet, the speed of the cooling roll, and the like, it is preferable to appropriately adjust the temperature of the cooling air, the cooling range, the temperature of the second cooling roll, and the like.

(2) Temperature difference between front and back in longitudinal stretching In order to obtain the film of the present invention, it is desirable to provide a temperature difference between the front and back of the film in the longitudinal stretching step and change the degree of molecular orientation on the front and back of the film. If a temperature difference between the front and back of the film is provided in the longitudinal stretching step, orientation distortion remains on the side having a lower surface temperature than on the side having a higher surface temperature, and a potential warp that is manifested by heat treatment tends to occur. During the longitudinal stretching in the production of the film of the present invention, in order to provide a temperature difference between the front and back, roll temperature setting, non-contact infrared irradiation, heating with high-speed heating air, other heating or cooling means may be used. Is possible.

  Furthermore, in order to obtain the film of the present invention, it is desirable to perform longitudinal stretching with a temperature difference between the front and back sides in multiple stages, at least two stages or more. In order to provide a potential warp that is manifested by heating, which is the purpose of the present application, even if stretching is performed in one step, the effect due to the temperature difference is small, and further stretching with a temperature difference is performed in a state where the stretching orientation has advanced. It is desirable. That is, by repeating the stretching operation with a temperature difference between the front and back at least twice, the state where the orientation of the front and back is different by the first stage treatment is further antagonized by curing and shrinking by further stretching the temperature difference. It is thought that sufficient orientation strain cannot be obtained. In particular, it is more preferable in terms of effectively providing orientation strain that the film is stretched in one step with a temperature difference between the front and back sides and then once cooled and then subjected to longitudinal stretching with a difference in temperature between the front and back sides.

  When performing longitudinal stretching in two or more stages, it is desirable to set the stretching ratio and the temperature difference between the front and back sides according to the thickness of the film. Specifically, when a film having a product thickness of 100 to 300 μm is formed between the rolls having a difference in peripheral speed by an infrared heater to produce a film having a product thickness of 100 to 300 μm, 2.0 times or more in the longitudinal direction (vertical direction) After stretching to a magnification of 2 times or less, the film after the longitudinal stretching is passed between nip rolls whose surface temperature is cooled, and a magnification of 1.03 times to 1.5 times is obtained in the longitudinal direction. Thus, it is preferable to perform two or more steps of stretching. Regarding the temperature difference between the front and back, for example, when creating a film having a product thickness of 125 μm, for the first stage, the average of the front and back temperatures is 70 ° C. or more and 115 ° C. or less, and the temperature difference between the front and back is 0.3 ° C. It is preferable to adjust so that it may become 3 degreeC or less above, and about the 2nd step | paragraph, it is preferable to adjust the temperature difference of front and back to 2 degreeC or more and 5 degrees C or less. If the average temperature of the front and back surfaces is less than 70 ° C., stretching is difficult and thickness spots are likely to occur, and if it exceeds 115 ° C., it becomes difficult to obtain the effect of providing a temperature difference between the front and back surfaces. Moreover, when the temperature difference between the front and back exceeds 5 ° C., curling occurs in the sheet itself after longitudinal stretching, and the sheet does not follow the roll, which causes scratches. (In addition, the temperature of the film front and back in the longitudinal stretching step refers to two other than the center obtained by dividing the sheet into three in the thickness direction. Specifically, it can be obtained by heat transfer calculation.)

  In the stretching step, when a temperature difference is provided on the front and back of the film to provide orientation strain, a higher stretching deformation rate is suitable. Therefore, in providing the front and back orientation strains, the longitudinal stretching process is more suitable than the lateral stretching process as described above. However, in the transverse stretching process, it is possible to provide an orientation strain on the front and back of the film by providing a temperature difference in the vertical direction and performing multi-stage stretching. A preferred lateral stretching method of the present invention will be described later.

(3) Temperature difference between upper and lower heat setting temperature In the present invention, in the heat setting step of heat setting the film after biaxial stretching, the temperature of the front and back of the film is a temperature of 0.1 ° C. or more and 0.5 ° C. or less. It is preferable to provide a difference. This is to substantially change the shrinkage ratio between the front and back surfaces by providing a difference in the degree of heat treatment between the front and back surfaces. In order to provide a temperature difference between the front and back sides in the heat setting step, for example, it is possible to change the temperature up and down through the film of the heat setting device or / and to provide a wind speed difference. In order to provide the above temperature difference between the front and back of the film, the temperature difference between the upper and lower sides of the heat setting device is preferably 3 ° C. or higher and 30 ° C. or lower. If the temperature is less than 3 ° C., the difference in wind speed between the top and bottom exceeds 5 m / sec to give the temperature difference of the film, and the distortion force acts on the film, which makes it difficult to control the heat shrinkage rate and causes unevenness in flatness. May occur or the thickness may change. On the other hand, if the temperature is higher than 30 ° C., the air balance is liable to be lost due to the difference in density between the air above and below the film. It may be difficult to actually measure the front and back temperatures in the heat setting process. Therefore, it is possible to estimate the front and back temperature by simulation.

  In the present invention, the above achievement means (1) to (3) are appropriately selected in order to obtain a film having a potential warp that is manifested by heating even though it is flat before the heat treatment, Or it is desirable to combine. Although it is difficult to directly evaluate the heat shrinkage rate of the front and back surfaces of the present invention, it is considered that the idea of delicately controlling the physical property called the heat shrinkage rate of the front and back surfaces has been achieved by the above-mentioned achieving means.

  In addition to the method described in detail above, it is also possible to use other methods such as passing a heating roll that performs single-side heat treatment during film formation, or using infrared heating, hot-air heating, etc. on the opposite side of the single-side cooling. Furthermore, the film after biaxial stretching is heat-treated by changing the temperature of the front and back films offline to change the heat shrinkage rate of the front and back, so that the desired heat shrinkage rate can be obtained after heating. It is also possible to make a difference.

<Problems of conventional transverse stretching method>
Further, in order to obtain the film of the present invention, it is necessary to perform transverse stretching on the film subjected to longitudinal stretching. However, when stretching in the width direction, the transmission of force in the width direction differs between the end portion and the center portion in the transverse stretching machine. That is, the end portion is gripped by the grip portion in order to perform lateral stretching, and the movement is limited, but the central portion is in a state where it can move in the longitudinal direction. In this state, a catenary curve is drawn just like a single rope pulled to the left and right. In the case of lateral stretching, the shape of the catenary line in the longitudinal direction changes from the initial stage of stretching to the latter stage of stretching. This change can be visualized by, for example, drawing a line with a fast-drying ink on the surface of the film sheet perpendicular to the longitudinal direction (parallel to the width direction) on the film sheet before the lateral stretching starts. In the initial stage of transverse stretching, the line appears to be convex toward the rear side in the flow direction, and as the stretching proceeds, the line becomes straight at some point, and then appears to be concave in the flow direction.

Due to this lateral stretching behavior, there is a difference in physical properties in the width direction under the conventional stretching conditions, and there is no problem with the film taken from the central part of the machine base when using the film. The difference between the refractive index in the direction that forms an angle of 45 degrees with the longitudinal direction and the refractive index in the direction that forms an angle of 90 degrees Δn _ab is 0.015 or more and 0.060 or less). There is a difference in orientation characteristics between a direction that forms an angle of 45 degrees with the longitudinal direction of the film and a direction that forms an angle of 90 degrees. This influences the cutting property by the mechanical behavior in the oblique direction when the film is cut.

  In order to eliminate the problems of the conventional stretching methods described above, the present inventors have intensively studied how a film having a very small influence on the cutability of the film due to the orientation characteristic distortion of the film can be produced. As a result, it has been found that by performing the following stretching conditions in the transverse stretching process under completely different conditions, it is possible to obtain a film having excellent cutting suitability in the next process and having good cutting properties. The invention has been completed.

<Feature 2 of the method for producing a film of the present invention>
The film that has undergone the longitudinal stretching step is then subjected to a transverse stretching process in a tenter. In the tenter, (a) a preheated portion for heating the film to a temperature suitable for stretching in order to stretch the film subjected to longitudinal stretching in the transverse direction, and (b) stretching the heated film in the transverse direction. A stretched part, (c) a heat-fixed part that is subsequently subjected to heat treatment to reduce strain caused by longitudinal and transverse stretching, (d) a relaxation-treated part that further reduces strain in the transverse direction, and (e) a heated film at the end. It can be divided into a cooling part that cools below the glass transition point (Tg). A rail for running a clip connected to a chain is installed on the side of the tenter, and the film runs in the tenter while being held by the clip.

In the preheating portion (a), the film temperature is raised by hot air blown from the pronum duct installed at the upper part and / or the lower part of the film. Although the film expands when the temperature rises, the running rail of the clip that holds the film end is slightly expanded in the width direction so that the slack due to the expansion is not generated. Thus, the fluttering of the film is suppressed by the wind pressure of the air blown from the plenum duct so that the hot air is uniformly applied to the film surface.
In order to stretch the film in the transverse direction at the stretched portion (b), the clip chain is installed so as to expand in the film width direction in an oblique direction with respect to the progress of the entire film in the longitudinal direction. The film whose end is held by a clip is pulled in the width direction and stretched in the transverse direction as it progresses. The stretch ratio of the film is determined according to the extent (angle and distance) of the travel rail of the clip chain.
In the heat setting part of (c), in order to reduce the distortion generated when the film is stretched in the vertical and horizontal directions, the film is subjected to high temperature heat to remove the distortion. The size of the heat shrinkage rate in the longitudinal direction is mainly determined by the temperature of this portion.
In order to further reduce distortion in the lateral direction, the relaxation treatment part (d) removes the distortion in the width direction by a process such as reducing the width of the traveling rail of the clip chain in the width direction. Depending on the extent of this treatment (temperature and relaxation rate), the thermal contraction rate in the lateral direction is mainly determined.
In the cooling part (e), the film is cooled to Tg or less, and the film is cooled so as to be taken out in the vicinity of room temperature with the distortions (c) and (d) reduced.

Each part plays a role as described above. In the present invention, the stretched part (b) achieves both uniform physical properties in all directions in the width direction of the biaxially stretched film and reduction of thickness spots. It is intended that the heat shrinkage rate in the vertical direction is uniform in the heat setting process part of (c).

In the stretched portion of (b), the film is stretched in the lateral direction according to the running rail of the clip chain installed in the oblique direction with respect to the traveling direction. In the stretching process, both ends of the film are held and fixed by clips. However, the area away from the clip, particularly in the central area of the film, has a higher degree of freedom than both ends. While there is a local difference in the degree of mechanical freedom, the film as a whole is stretched in a state where the action of force is balanced. Moreover, the film is in a state where the balance of force in the longitudinal direction is balanced in addition to the width direction, and is also affected by the heat fixing portion. The relationship between these force actions is balanced in a catenary-like state in which the ends are fixed in the width direction. When the action of this force is observed at the central part of the film, it acts so as to advance toward the film traveling direction at the initial stage of stretching, and acts so that the central part is delayed from the traveling direction at the latter stage of stretching. A so-called bowing phenomenon is observed by the action of such a force.

  As a result of the action of this force, the physical properties at the end of the film differ between the characteristics of the film in the longitudinal direction and the 45 degree direction, and the characteristics in the direction perpendicular thereto. Among these characteristics, it is considered that the difference in the ratio TS / TE between the breaking strength (TS) and the breaking elongation (TE) due to the state of the orientation characteristics affects the cutting property.

  Generally, when a tensile test of a film made of polyethylene terephthalate resin is performed, the stress increases at a substantially constant rate until a predetermined strain amount is reached, and when the predetermined strain amount is reached, the strain amount increases. A plateau region where the stress does not increase appears (a point where the stress at the initial stage of saturation is saturated is called a yield point). Then, after such a plateau region appears, a region where the stress increases as the amount of strain increases again (a point where the stress starts to rise again after the yield point is referred to as a rising point), and the stress increases. It shows a tendency to break after increasing. Such a curve of stress and strain is called an SS curve.

In order to reduce the physical property difference, if the stretching temperature in the transverse direction is simply set to a high temperature, the stretching corresponds to “stretching that gives a strain corresponding to a plateau region in the SS curve”, and the film There was a risk of thick spots. Furthermore, when the stretching temperature in the transverse direction is increased, the temperature difference from the preheating region is increased, and there is a possibility that unevenness in the temperature state in the tenter may occur (the thickness Δn _{ab of} the film is 0). In the case of less than .015, the ratio TS / TE difference is not so large as to affect the cutting property). If the film is disturbed in flatness due to such thickness unevenness, it cannot be used in a post-processing process that has been increasingly refined in recent years. However, surprisingly, it has been found that, by optimizing the relationship between the transverse draw ratio and the temperature as described below, it is possible to obtain a product having good flatness and good cutting properties.

(1) Control of temperature in temperature division region of transverse stretching step In the transverse stretching step, the tenter is usually provided with a plurality of temperature division regions. Set the temperature difference in the zone to 5 ° C to 20 ° C until the first half of the stretch (up to the temperature zone where the draw ratio includes 1.8 times) and the second half (the temperature zone including the draw ratio of 1.8 times) It is necessary to set the temperature range from the next temperature section region to the final draw ratio) to 5 ° C. or higher and 30 ° C. or lower. On the other hand, the temperature difference between the temperature zone including 1.8 times and the next temperature zone is preferably 5 ° C. or more and 40 ° C. or less.

  The reason why it is preferable to control within the above temperature range is considered as follows. That is, in the first half of the transverse stretching step, stretching is performed in the stretch stress increasing region of the SS curve of the tensile properties of the film, so that the influence of temperature spots tends to occur. Therefore, as described above, it is desirable to keep the temperature difference between adjacent temperature sections in the first half of the drawing low. In the latter half of the transverse stretching step, the stretching temperature is set to a relatively high temperature, so that the stretching stress of the film decreases. Therefore, the temperature difference between adjacent temperature zones in the second half of stretching can be made larger than that in the first half. Furthermore, since it corresponds to the plateau region of the SS curve in the middle of the transverse stretching process, it is less affected by temperature changes than other temperature zones and has a larger temperature difference than other temperature zones. Permissible. Thus, in the present invention, the temperature difference between the temperature division zones is controlled as described above according to the SS curve.

  Moreover, it is preferable that these temperature settings raise a set temperature in steps toward the advancing direction of a film. In the tenter, an accompanying flow is generated as the film progresses, so that an air flow from upstream to downstream occurs along the film traveling direction. For this reason, when there is a difference in the set temperature between two consecutive temperature zones, temperature disturbance occurs at the boundary between the temperature zones. When the set temperature difference is large, the temperature distribution in the tenter is disturbed, the film is stretched, and the flatness is caused by thickness unevenness. Therefore, the set temperature of each continuous temperature section is set to a certain range, and the film temperature in the width direction and the longitudinal direction is stabilized. Thereby, the thickness unevenness of the film resulting from the disorder of the temperature of the lateral stretch part in a tenter can be reduced. The lower limit of the set temperature difference for obtaining the film of the present invention is 5 ° C. or higher, preferably 10 ° C. or higher. When the set temperature difference is less than 5 ° C., it becomes difficult to set the set temperature in the final temperature zone to the set temperature described later. In addition, the upper limit of the set temperature difference needs to be 20 ° C. or less up to a temperature division region including 1.8 times. On the other hand, it is desirable that the temperature is 30 ° C. or less from the temperature segment region next to the temperature segment region including the draw ratio of 1.8 times to the final stretch ratio. On the other hand, it is desirable that the temperature section region including 1.8 times and the next temperature section region be 40 ° C. or less, preferably 30 ° C. or less. When the set temperature difference is more than 40 ° C., the film thickness is disturbed, and the above effect cannot be obtained.

  It is preferable that the set temperature difference is set to 5 ° C. or more and 40 ° C. or less also in two continuous temperature section areas from the preheating section (A) to the first temperature section of the stretched section (B). In the preheated part, it is necessary to warm the film so that the temperature is about the temperature at which stretching is possible. Therefore, when the temperature of the stretched portion is set to a high temperature, the film temperature is preferably about the stretching temperature of the longitudinal stretching to the stretching temperature of the longitudinal stretching + 15 ° C. In addition, it is desirable to control the set temperature of the preheating portion according to the length in the longitudinal direction of the preheating portion, the speed at which the film travels, and the thickness of the film.

(2) Temperature control in the first half of the transverse stretching step After the temperature of the film is raised in the preheating portion in the initial part of the transverse stretching step, in the first half of the stretching in the transverse stretching step, S- Stretching is performed in the stretch stress increasing region of the S curve. In order to obtain the film of the present invention, it is preferable to set the temperature range of the first half of the transverse stretching step to 100 ° C. or more and less than 160 ° C. and perform transverse stretching at a relatively low temperature. If the set temperature is less than 100 ° C., the film tends to break, which is not preferable. If the set temperature is 160 ° C. or higher, the stretching condition not only corresponds to “stretching that gives a strain corresponding to a plateau region in the SS curve”, but also the temperature difference from the preheated portion is large. Therefore, the temperature balance in the tenter becomes unstable, and the flatness is easily disturbed due to thickness spots, which is not preferable. As will be described later, it is desirable to set the temperature so as to increase from the first half to the second half of the drawing. However, if it is difficult to provide stepwise temperature settings in the first half of the stretching, it is necessary to adjust the temperature difference between the first half of the stretching and the second half of the stretching described below to obtain the desired effect. May be.

Here, the meaning of the first half of the stretching is stretching performed in the first half region of the transverse stretching step, and stretching performed in the stretching stress increasing region of the SS curve. Specifically, it refers to a segmented region including a transverse stretch ratio of 1.8 times. The draw ratio in the first half of the drawing depends on the total number of divided regions. For example, when the final transverse stretch ratio is 4 times, when the total number of segmented areas is 3, the ratio is 2.0 times, and when the total number of segmented areas is 4, the ratio is 2.5 times. In the present invention, stretching is performed at a relatively low temperature by setting the set temperature in the section region including 1.8 times to 100 ° C. or more and less than 160 ° C.

(3) Temperature control at the final reaching part of the transverse stretching step In order to obtain the film of the present invention, the temperature range of the final reaching part of the transverse stretching step is set to 160 ° C or more and less than 220 ° C and set to a relatively high temperature. It is preferable to do. By setting to high temperature, the difference of the above-mentioned TS / TE ratio becomes small, and cutting property can be made favorable.

  Here, the meaning of the latter half of the stretching is stretching performed in the latter half region of the transverse stretching step, and specifically, from the next segmented region to the final reaching magnification of the segmented region including the lateral stretching ratio of 1.8 times. is there. The draw ratio in the latter half of the drawing depends on the total number of sections. For example, when the final transverse stretch ratio is 4 times, when the total number of segmented areas is 3, the number is 2.0 times, and when the total number of segmented areas is 4, the number is 2.5 times. The final magnification including the magnification of the first half can be set to 3 times or more and less than 5 times, preferably less than 4.8 times, more preferably 4.4 times. For example, the process conditions when the final transverse draw ratio is 4 and the transverse draw zone is three stages are as follows. First stage magnification is 1.0 to 2.0 times, second stage magnification is 2.0 to 3.0 times, third stage magnification is 3.0 times to 4.0 times, and first stage This zone is the first half of stretching. As for the temperature setting, when the final temperature in the preheating zone is 105 ° C. and the temperature in the final magnification reaching section is 165 ° C., the first zone is preferably 110 to 145 ° C. and the second zone is preferably 145 to 160 ° C. However, depending on settings such as the film forming speed, it is possible to set the temperature in two zones.

  The film of the present invention can be obtained by carrying out highly controlled transverse stretching as described above. It is considered that the difference in TS / TE ratio between the longitudinal direction of film formation, the direction of 45 degrees, and the direction of 90 degrees is reduced by the transverse stretching process due to the following mechanism. . In the transverse stretching process, as described above, the force action is in a balanced state in the entire film in the transverse direction and the longitudinal direction. In the longitudinal direction, the film acts in the initial stage of stretching so as to advance toward the film traveling direction. It acts to be delayed with respect to the direction of travel. Here, when the stretching temperature of the final reaching portion of the transverse stretching is set to a high temperature, the final stretching tension in the transverse stretching step is lowered. Thereby, it is thought that the influence of the action of the force propagating from the heat fixing portion along the longitudinal direction of the film was alleviated, and the distortion of the force acting in the longitudinal direction was alleviated. Furthermore, the orientation characteristics in the longitudinal direction (MD direction) of film formation and 90 ° direction (TD direction) can be obtained by appropriately adopting the ratio of longitudinal stretching and lateral stretching. That is, in the present invention, the overall magnification in the longitudinal direction is 2.1 to 4.8 times, but this preferable range is 2.7 to 3.8 times, but the transverse draw ratio is 0 from the longitudinal magnification. A magnification higher by 3 to 0.5 times can be preferably applied from the uniformity of the lateral thickness, but if the lateral stretching ratio is increased too much, the lateral orientation characteristics may become too large compared to the vertical.

  On the other hand, the lateral force action can be considered as follows. Since only the force in the traveling direction acts at the center of the film, the force acting on the film is symmetrical with respect to the longitudinal direction. On the other hand, the film moves in an oblique direction while being held by the clip at the end of the film, and a force in the oblique direction as well as the traveling direction is applied. Therefore, the force action of the film end is not symmetrical with respect to the traveling direction. In order to reduce the difference in the TS / TE ratio, it is necessary to make this force action symmetrical. For this purpose, it is effective to reduce the stretching tension applied to the film by performing a transverse stretching step at a high temperature. However, if the stretching process is simply performed at a high temperature, the flatness may be disturbed due to thickness unevenness. Therefore, in the first half of the transverse stretching process, stretching is performed in a “region where the stretching stress of the SS curve increases” where the thickness unevenness hardly occurs by relatively lowering the stretching temperature, and the thickness has been made uniform. In this case, the stretching temperature is increased, the stretching stress in the transverse direction is decreased, and stretching is performed in accordance with the balance of the action of the entire force. Thereby, without increasing the unevenness of thickness, the longitudinal direction (MD direction) and 45 degrees (A direction) of film formation, the longitudinal direction and 90 degrees (TD direction) of film formation, and film formation It is considered possible to reduce the difference in the ratio TS / TE between the breaking strength (TS) and the breaking elongation (TE) in a direction that forms 135 degrees (B direction: 90 degrees in the A direction) with the longitudinal direction. .

  In the longitudinal stretching step of the film, by using the means (1) to (3) described above, a reduction factor for the thickness of the film and a magnification taking into account the orientation characteristics of the longitudinal stretching and the lateral stretching are adopted for the film. Thus, the longitudinal direction of the film formation (MD direction), the longitudinal direction of the film formation 45 degrees (A direction), the longitudinal direction of the film formation 90 degrees (TD direction), and the film formation of the film It is possible to reduce the difference in the ratio TS / TE between the breaking strength (TS) and the breaking elongation (TE) in a direction that forms 135 degrees (B direction: 90 degrees in the A direction) with the longitudinal direction of It is thought. Note that only one of the above-mentioned means (1) to (3) does not effectively contribute to the reduction of the difference in film flatness and TS / TE ratio. By combining and using the means of 3), it is considered that the flatness of the film can be maintained and the difference in the TS / TE ratio can be reduced very efficiently.

<Feature 3 of the method for producing a film of the present invention>
Usually, the heat-setting treatment of the stretched film is carried out in a heat-setting device in which a plurality of plenum ducts having long hot air outlets are arranged perpendicular to the longitudinal direction of the film formation. In such a heat fixing device, “circulation of hot air” is performed in order to improve the heating efficiency. Air in the heat fixing device is sucked by a circulation fan installed in the heat fixing device, the temperature of the sucked air is adjusted, and the air is again discharged from the hot air outlet of the plenum duct. In this manner, “hot air circulation” of “hot air blowing → suction by circulation fan → temperature adjustment of sucked air → hot air blowing” is performed.

  Further, as described above, the difference in heat shrinkage rate in the width direction of the film (difference in heat shrinkage rate between an arbitrary position in the width direction of the film and a position 70 cm or more away from the arbitrary position in the width direction) This occurs because the film edge is not sufficiently relaxed when fixing. As shown in FIG. 1, in the heat setting process, a continuous large shielding plate S is placed on the central portion of the hot air outlets 2, 2,... Of each plenum duct 3, 3,. By reference), the passability in the case of processing a short film at a relatively low temperature (for example, 120 ° C.) by post-processing is improved. However, when excessive tension is applied to a long film, the passability is improved, but the flatness is lost, wrinkles occur, and heat treatment in post-processing is performed at a high temperature (for example, 160 ° C.). The flatness (wrinkles etc.) of the film being processed is not improved. Further, as shown in FIG. 2, it has been found that the method (see Japanese Patent Application Laid-Open No. 2002-79638) in which the plenum duct is covered with a discontinuous shielding plate and the wind speed is changed (see Japanese Patent Application Laid-Open No. 2002-79638) lacks stability.

  The inventors show why the method shown in FIG. 1 does not improve “flatness in a long film” or “flatness when heat treatment in post-processing is performed at a high temperature”. Then, in order to understand why it lacks stability, we analyzed the phenomenon in the heat fixing device in detail. As a result, when a continuous large shielding plate that spans multiple plenum ducts is placed over the hot air outlet of the plenum duct, the flow of hot air is restricted by the shielding plate, and the above-mentioned "hot air circulation" is performed smoothly. As a result, it was found that temperature turbulence (temperature hunting phenomenon) occurred in the heat fixing device. In the case of FIG. 2 as well, it was found that the wind speed is different for each plenum duct and the balance of the wind is easily lost, temperature turbulence occurs, and stability is lacking.

Since the above-mentioned “temperature hunting phenomenon” makes the thermal relaxation of the film end insufficient, the present inventors perform “flatness in a long film” or “heat treatment in post-processing at a high temperature. It was speculated that the “flatness in the case of“ Therefore, the present inventors can improve “flatness in a long film” and “flatness when heat treatment in post-processing is performed at a high temperature” by smoothing “circulation of hot air”. I thought that. Then, as a result of trial and error to grasp the relationship between the temperature air volume condition of the heat setting device, the covering mode of the shielding plate, and the film permeability in the post-processing, the following means (1) There was a tendency to improve “flatness in a long film” and “flatness when heat treatment in post-processing was performed at a high temperature”. And based on the knowledge, as a result of further trial and error, the present inventors have taken the following means (1) and then taken the following means (2) and (3). The inventors have found that it is possible to obtain a film having good permeability, and have come up with the present invention.
(1) Adjustment of temperature and air volume of plenum duct in heat fixing device (2) Adjustment of shut-off condition of hot air outlet of plenum duct in heat fixing device (3) Heat cutoff between stretching zone and heat fixing device Each of the above-described means will be described sequentially.

(1) Adjusting the temperature and air volume of the plenum duct in the heat setting device In order to heat and cool the heat setting process step by step, the heat setting device is generally divided into several sections (heat setting zones) with different temperatures. I know. In the production of the film roll of the present invention, each plenum duct is designed such that the product of the temperature difference and the wind speed difference between adjacent heat setting zones of the heat setting device is 250 ° C. · m / s or less. It is indispensable to adjust the temperature and air volume of the hot air blown out from. For example, when the heat setting device is divided into first to third heat setting zones, the product of the temperature difference and the wind speed difference between the first zone and the second zone, and between the second zone and the third zone. Both products of the temperature difference and the wind speed difference are adjusted to be 250 ° C. · m / s or less. Thus, by adjusting the temperature and air volume of hot air, “circulation of hot air” becomes smooth. When combined with a method of attaching a discontinuous shielding plate, which will be described later, to the hot air outlet, the “temperature hunting phenomenon” is effectively suppressed. This makes it possible for the first time to obtain a long film with good flatness when the heat setting treatment in post-processing is performed at a high temperature.

  If the product of the temperature difference between adjacent heat setting zones and the wind speed difference is 250 ° C. · m / s or less (for example, the temperature difference between adjacent heat setting zones is set to 20 ° C. The temperature difference between adjacent heat setting zones is set to 10 m / s), “hot air circulation” in the heat setting device is smoothly performed, and the “temperature hunting phenomenon” is effectively suppressed. This is preferable. In addition, if the product of the temperature difference and the wind speed difference between adjacent heat setting zones is 250 ° C. · m / s or less, the heat setting zone downstream from the heat setting zone upstream as an accompanying flow caused by the passage of the film The temperature difference of the air flowing into Therefore, it is preferable because the temperature in the width direction of the downstream heat setting zone is stabilized. The product of the temperature difference and the wind speed difference is preferably 200 ° C. · m / s or less, and more preferably 150 ° C. · m / s or less.

(2) Adjustment of Plenum Duct Blocking Condition in Heat Fixing Device In the production of the film of the present invention, as shown in FIG. 3, individual plenum ducts 3 are not attached to a large shielding plate straddling a plurality of plenum ducts. It is necessary to attach rod-shaped shielding plates S, S,... To shield the hot air outlets (nozzles) 2, 2,. By using such a discontinuous shielding plate, “circulation of hot air” is performed smoothly. Moreover, it is preferable not to attach the same length of the shielding plate to each plenum duct, but to gradually increase the length of the shielding plate from the inlet to the outlet (film passing direction) of the heat fixing device (see FIG. 5). . Thus, by adjusting the length, the temperature of the hot air exposed to the film edge is adjusted, and the elimination of distortion at the film edge is promoted. The material of the shielding plate may be any material as long as it can withstand the temperature of the heat fixing device and does not stain the film or adhere the film, but it is the same material as the plenum duct from the viewpoint of thermal expansion. Is preferably used.

(3) Blocking of heating between the stretching zone and the heat setting device (installation of an intermediate zone)
A biaxially stretched polyethylene terephthalate resin film is usually heat-set after being longitudinally-transversely stretched. In the production of the film of the present invention, it is desirable to install an intermediate zone in which active hot air is not blown between the zone that is longitudinally and laterally stretched and the heat setting device that is heat-set. As a result, the heat is completely shut off between the stretching zone and the heat setting device. More specifically, when a strip-shaped paper piece is hung between the stretching zone and the heat setting device in the state where the drawing zone and the heat setting device are in the same condition as in film production, the paper piece is almost completely removed. It is preferable to block the hot air from the stretching zone and the heat fixing device so as to hang down in the vertical direction. Note that such an intermediate zone may be surrounded by a housing, or may be provided so that a continuously manufactured film is exposed. When the hot air is sufficiently blocked in the intermediate zone, the shielding effect of the shielding plate in the heat fixing device is exhibited, and good film flatness during post-processing can be obtained. There may be no intermediate zone at the transverse stretching temperature in the present invention.

  As described above, by adopting the above methods (1) to (3), the “hot air circulation” in the heat fixing device can be smoothly executed, and the “temperature hunting phenomenon” can be suppressed. As a result, relaxation in the longitudinal direction can be sufficiently promoted at the edge of the width direction, and "flatness in a long film" and "flatness when heat treatment in post-processing is performed at a high temperature" It becomes possible to improve. In the above description, the method of suppressing the “temperature hunting phenomenon” by smoothly executing “circulation of hot air” in the heat fixing device in which the plenum duct is installed. The above description discloses the technical idea of how the film of the present invention can be obtained by applying thermal energy to the film at the production level. The film of the present invention can be easily obtained by a different method from that described above. For example, instead of providing a shielding plate, an infrared heater may be used to increase the temperature in the film width direction from the center to the end. In other words, even with another type of heat fixing device, the "circulation of hot air" is smoothly executed to suppress the "temperature hunting phenomenon" and then sufficiently relaxed in the longitudinal direction at the edge of the width direction. By imparting sufficient heat energy to the film, the film having improved “flatness in a long film” and “flatness when heat treatment in processing is performed at a high temperature” like the film of the present invention. It is possible to obtain

  The achievement means in the present invention is as described above, but the production conditions and production steps other than those described above can take the modes described later.

  When the raw resin is melt-extruded, the polyethylene terephthalate resin raw material is preferably dried using a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer. After the polyethylene terephthalate-based resin material is dried in such a manner, it is melted at a temperature of 200 to 300 ° C. and extruded into a film using an extruder. For this extrusion, any existing method such as a T-die method or a tubular method can be employed.

  In the present invention, the relaxation treatment after the heat setting treatment is effective for controlling the heat shrinkage rate, particularly the heat shrinkage rate in the width direction. The temperature for the relaxation treatment can be selected in the range from the heat setting treatment temperature to the glass transition temperature Tg of the polyethylene terephthalate resin film, and is preferably (heat setting treatment temperature) −10 ° C. to Tg + 10 ° C. The width relaxation rate is preferably 1 to 6%. If it is less than 1%, the effect is small, and if it exceeds 6%, the flatness of the film is deteriorated.

  The film of the present invention produced by the above-described method is excellent in dimensional stability, cutting property, and flatness. In particular, the cured resin is cured and shrunk on the base film to which the cured shrinkable resin composition is applied. It can be suitably used to maintain the flatness after curing shrinkage.

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to the embodiments of the examples, and can be appropriately changed without departing from the spirit of the present invention. . In addition, the evaluation method of a film characteristic is as follows.

(1) Measurement of Δn _ab Film specimens were sampled from positions within 50 mm from the both ends parallel to the longitudinal direction of film _formation of the obtained film and from the center position. After leaving the film test piece in an atmosphere of 23 ° C. and 65% RH for 2 hours or more, using an “Abbe refractometer 4T type” manufactured by Atago Co., Ltd., an angle of 45 degrees with the longitudinal direction of the film formation The refractive index (n _a ) in the direction to be formed, and the refractive index (n in the direction that forms an angle of 135 degrees with the longitudinal direction of the film formation (that is, the direction that forms an angle of 90 degrees with the 45 degrees direction) _b ) was measured respectively. The calculated absolute value of the difference between the two refractive index thereof as [Delta] n _ab. The absolute value of the difference between these two refractive indexes is Δn _ab, and Δn _ab = | n _a −n _b | It was confirmed that both Δn _{ab at} both ends and the center of the film were 0.015 or more and 0.060 or less, and Δn _ab at both ends was displayed in the table.

(2) Flatness of film 1
Fifty samples of 300 mm in the longitudinal direction and 210 mm in the width direction are collected from the film. In a room controlled at a temperature of 23 ± 2 ° C. and a humidity of 65 ± 5% with the surface (surface (F)) that first contacted the cooling roll in the unstretched sheet process facing upward, a horizontal glass plate ( The height of the four corners of the film sample (height in the vertical direction from the horizontal plane) is measured with a JIS metal ruler (0.5 mm scale). If the height of the four corners is “0” or the cross section appears to be M-shaped, measure the warp with the opposite side facing up. The average value of the heights of the four corners measured in all the samples and the maximum value of the heights of the four corners measured in all the samples are displayed.

(3) Five samples of 300 mm in the longitudinal direction and 210 mm in the width direction are collected from the warped film after the film is heated. This sample was placed on a mounting board (thickness 1 mm) on a shelf board of a heating oven adjusted to 150 ° C. with the surface (table) that first contacted the cooling roll in the unstretched sheet process being placed on for 30 minutes. Heat treatment. Thereafter, the film sample together with the mount placed on the shelf board is taken out of the heating oven and left in a room controlled at a temperature of 23 ± 2 ° C. and a humidity of 65 ± 5% for 30 minutes. After standing for 30 minutes, the film sample is transferred to a horizontal glass plate (thickness 5 mm), and the heights of the four corners of the film (the height in the vertical direction from the horizontal surface) are measured with a JIS metal scale (0.5 mm scale). . If the height of the four corners is “0” or the cross section appears to be M-shaped, measure the warp with the opposite side facing up. The average height of the four corners measured in all samples is displayed.

(4) Flatness 2 of curable resin laminated film (evaluation by applying a curing shrinkable resin composition to the film)
Toagosei Co., Ltd., M-315 40 parts by mass, Mitsubishi Rayon Co., Ltd., nonabutylene glycol dimethacrylate (PBOM) 40 parts by mass, Shin-Nakamura Chemical Co., Ltd. urethane acrylate (U-2PHA) A resin composition was prepared using 20 parts by mass, Ciba Specialty Chemicals Co., Ltd., and 1.2 parts by mass of Irgacure 184. Using a film applicator, the resin composition has a thickness after curing on the surface of the film that becomes convex with a warp by heating (the surface in contact with the mount in the measurement of the warp after the heating of the film (2)). It applied so that it might become 2 mm. Using the high-pressure mercury lamp having a lamp emission length of 50 cm and 160 W / cm as the light source, the resin composition was irradiated with ultraviolet rays having an irradiation amount of 1 J / cm ² (measuring instrument: manufactured by Oak Manufacturing Co., Ltd., UV-350). Was cured. When the curing shrinkage was measured by the following measurement method, the resin composition exhibited a curing shrinkage of about 8.0%. Five samples cut from the curable resin laminated film thus obtained into a size of 300 mm in the longitudinal direction and 210 mm in the width direction were collected. The resin composition surface is placed on a horizontal glass plate (thickness 5 mm), and the heights of the four corners (vertical distance from the horizontal plane) are measured with a JIS metal ruler (0.5 mm scale). The average height of the four corners measured in all samples is displayed.

The weight a in the air and the weight b in the water of the cured product are measured, the solid specific gravity ds is obtained from the formula (i), and then the liquid specific gravity d _l of the curable resin composition before curing using a specific gravity bottle. And the cure shrinkage s (%) was determined from the formula (ii) from the solid specific gravity d _s value.
d _s = a / (ab) (i)
s = (1−d ₁ / d _s ) × 100 (ii)

(5) Breaking strength [TS], elongation at break [TE]
The film winding direction (MD direction), the direction forming an angle of 45 degrees (A direction), the direction forming an angle of 90 degrees (TD direction), and the direction forming an angle of 135 degrees (B direction) Samples of film specimens having a width of 12.7 mm and a length of 200 mm were sampled from four locations. The film test piece was set in a tensile tester (manufactured by ORIENTEC, Tensilon RTC-125A), and stretched at a distance between chucks of 100 mm and a take-off speed of 200 mm / min in an environment of a temperature of 23 ° C. and a humidity of 65% RH, and fractured. Stress and film elongation were measured. The breaking strength (MPa) and breaking elongation (%) were determined from the average values of the two measurements.

(6) Cutting property of film A film is cut with a guillotine cutter, and the cutting property is evaluated. The cutting property means, for example, the ease of cutting with scissors or a cutter, and means that the cut surface is smooth. Although the cutting property varies depending on the cutting method, it was cut over a length of 200 mm using a cutting machine (DN-1N, manufactured by KOKUYO), and the state of the cut surface was visually observed. The cutting test was performed 30 times, and was evaluated as follows according to the state.
Judgment ○: Chips are not generated and cut hairs are not generated.
Δ: Chips or cut mustaches occur 1 to 10 times.
X: Chips or cut mustaches occur 11 times or more.

(7) Thermal contraction rate of film (HS150)
A sample cutting part is provided at an arbitrary position in the width direction of the film having Δn _ab of 0.015 or more and 0.060 or less, and at a position separated from the arbitrary position by 70 cm or more in the width direction, and film formation from each cutting part A pair of samples were obtained by cutting out a sample film having a width of 20 mm and a length of 250 mm along the longitudinal direction. Further, the above paired samples were collected from a position separated by an arbitrary distance in the longitudinal direction, and five sets of samples were prepared (total of 10 samples). Marked lines are placed at intervals of 200 mm on a sample having a width of 20 mm and a length of 250 mm in the cut direction, placed in a heating oven adjusted to 150 ° C., and each material is 30 ° C. at 150 ° C. according to JIS / C-2318. The heat shrinkage rate when treated for a minute was measured. Table 4 shows the combinations that maximize the difference in heat shrinkage rate and the combinations that minimize the difference in the paired samples.

(8) Film passability The flatness of the film after heat treatment in post-processing was evaluated by the following method. As a heat treatment step, a coater having a distance between two rolls of 1,900 mm was used, the temperature was set to 100 ° C. or 160 ° C., and the furnace tension was set to 100N. Next, two rolls are horizontally arranged so that the roll interval is 2,000 mm, and further, the iron bar is positioned at the center position of the two rolls at a position 30 mm below the common tangent of the roll upper surface. Arranged. The film passed through the heat treatment step was passed between two rolls under a tension of 98N. When the film was allowed to pass through, it was marked as ◯ when the film was not in contact with the iron bar, and x when it was in contact with the iron bar. These steps were performed continuously, and it was visually confirmed whether or not the film contacted the iron bar.

(9) Film thickness After film formation, the thickness of the film was measured in the direction perpendicular to the longitudinal direction of the sample cut out to 300 mm in the longitudinal direction and 210 mm perpendicular to the longitudinal direction using an electronic micrometer MILLITRON (Seiko Precision Machinery Sales). Measurement is performed 10 times at a position of about 20 mm, and the average value is obtained.

  In addition, Table 1 shows film forming conditions of the films in Examples and Comparative Examples.

[Example 1]
Polyethylene terephthalate ([η] = 0.60) containing 0.03% by mass of silica particles (manufactured by Fuji Silysia Chemical Co., Ltd.) having an average particle size of 0.7 μm as an additive is dried so that the moisture content is 50 ppm or less. Then, it was charged into an extruder and melted at a temperature of 285 ° C. The resin was melted with an extruder and filtered with a stainless sintered body filter medium (nominal filtration accuracy: particles having a size of 10 μm or more were cut by 90%). Next, the resin sheet was extruded from a T-shaped die, wound around a casting drum having a surface temperature of 22 ° C. using an electrostatic application casting method, and cooled and solidified to obtain an unstretched sheet of 1710 μm. Furthermore, the surface temperature difference (FB) between the front and back surfaces of the unstretched sheet separated from the second cooling roll (detaching roll) at 22 ° C. was as shown in Table 1.

  And after raising the film temperature with the heated roll group, the infrared heater provided between those nip rolls between the first nip roll and the second nip roll arranged before and after the obtained unstretched sheet While being heated by the (first infrared heater), the film was stretched 2.77 times in the longitudinal direction (longitudinal direction) (first-stage longitudinal stretching). At this time, in the first infrared heater, assuming that the infrared output on the front side is 100%, the infrared output on the back side is 90%. Here, the rear second nip roll was cooled.

  Thereafter, the film after the longitudinal stretching is heated by the infrared heater (second infrared heater) provided between the second nip roll and the third nip roll disposed immediately after the second nip roll. The film was stretched 1.17 times in the longitudinal direction (longitudinal direction) (second-stage longitudinal stretching). Further, the film was stretched 1.08 times in the longitudinal direction (longitudinal direction) while being heated by an infrared heater (third infrared heater) provided between the nip rolls between the third nip roll and the fourth nip roll disposed immediately thereafter. (Third-stage longitudinal stretching). In the second and third infrared heaters, assuming that the infrared output on the front side is 100%, the infrared output on the back side is 95%. Note that the relationship between the output of the infrared heater and the surface temperature is measured in advance with a model machine, and according to the above settings, the temperature difference on the film surface is front and back, the first stage is 2 ° C., the second stage is 3 The temperature was adjusted to 3 ° C. in the third stage.

  As described above, after stretching the unstretched film in the longitudinal direction in three stages, the longitudinally stretched film is guided to a tenter, and the first zone is stretched 2.0 times in the width direction in an atmosphere of 140 ° C. Was stretched up to 3.0 times in an atmosphere of 155 ° C., and the third zone was stretched up to 4.0 times at 180 ° C., and in the subsequent heat setting step, the shape of the shielding plate was A mode in Table 2, temperature wind speed Was subjected to heat setting treatment as described below under the conditions I in Table 3, and subjected to 2.2% transverse relaxation treatment at 225 ° C. to obtain a biaxially stretched film having a thickness of 125 μm. The film obtained as described above was evaluated for characteristics by the method described above. The evaluation results are shown in Table 4.

[Heat setting]
The heat setting process was performed by a heat setting apparatus having a structure as shown in FIG. The heat setting device is divided into four heat setting zones called first to fourth zones, and eight plenum ducts a to x are provided in the first to third zones, respectively. In addition, eight plenum ducts are provided. Each plenum duct is vertically installed at 400 mm intervals with respect to the film traveling direction so as to be perpendicular to the film traveling direction. And hot air is sprayed on the film extended | stretched from the hot air blowing outlet (nozzle) of those plenum ducts.

  In Example 1, discontinuous rod-shaped shielding plates S, S,... Were attached to the hot air outlets of 15 plenum ducts a to o in the manner shown in FIG. FIG. 7 shows a state where the heat fixing device having the shielding plates S, S,... Attached to the hot air outlets of the plenum ducts a to o is viewed from above, and each of the attached shielding plates S, S,. The center in the longitudinal direction is set so as to substantially coincide with the center of the width of the film passing through the heat fixing device. Further, the length of each shielding plate S, S... (The dimension in the width direction of the film to be manufactured) is adjusted so that it gradually becomes wider (that is, widens toward the end) from the inlet to the outlet of the heat fixing device. Has been. Table 2 shows the shielding ratio of the hot air outlets of each of the plenum ducts a to o (the shielded area of the hot air outlet by the shielding plate / the area of the hot air outlet). In addition, let the shielding aspect by the shielding board in Example 1 be "A aspect."

  In Example 1, the temperatures and wind speeds in the first to fourth zones of the heat setting device were adjusted as shown in Table 3. In addition, in the temperature conditions of the 1st-4th zone of the heat setting apparatus of Example 1, and the wind speed conditions, the product of the temperature difference between the adjacent heat setting zones and the wind speed difference is 250 ° C. · m / s or less. In addition, let the temperature of 1st-4th zone in Example 1, and wind speed conditions be "I conditions."

[Example 2]
The extrusion amount of the extruder is increased, the take-up speed of the unstretched sheet is adjusted, and when the unstretched sheet is wound around the casting drum, the thickness is 2 by cooling with cooling air using cooling air of 19 ° C. A 440 μm unstretched sheet was obtained. The temperature of the casting drum was 22 ° C., and the temperature of the second cooling roll was 30 ° C. The surface temperature difference (F−B) of the unstretched sheet separated from the second cooling roll at this time was as shown in Table 1. The first stage draw ratio of Example 1 was changed to 2.6 times, the second stage draw ratio was changed to 1.27 times and longitudinally stretched in two stages, as shown in Table 1. The transverse stretching was performed while changing the transverse stretching conditions. Thereafter, the transverse relaxation treatment was set to 1.7%, and a biaxially stretched film having a thickness of 188 μm was produced. In addition, the shielding mode by the shielding plate in Example 2 is referred to as “B mode”, and the temperature and wind speed conditions in the first to fourth zones in Example 2 are referred to as “II conditions”. And the characteristic of the obtained film was evaluated by each measuring method mentioned above. The evaluation results are shown in Table 4.

[Example 3]
The amount of extrusion of the extruder is increased, the take-up speed of the unstretched sheet is adjusted, and when the unstretched sheet is wound around the casting drum, the thickness is 3 by cooling with cooling air using 19 ° C. cooling air. A 150 μm unstretched sheet was obtained. The temperature of the casting drum was 22 ° C., and the temperature of the second cooling roll was 30 ° C. The surface temperature difference (F−B) of the unstretched sheet separated from the second cooling roll at this time was as shown in Table 1. This was carried out by changing the longitudinal stretching as shown in Table 1. The longitudinally stretched film was guided to a tenter, and the transverse stretching conditions and transverse relaxation shown in Table 1 were carried out. In this way, a biaxially stretched polyester film having a thickness of 250 μm was obtained. Thereafter, the characteristics were evaluated by the method described above. The evaluation results are shown in Table 4.

[Example 4]
The extrusion amount of the extruder was increased, the take-up speed of the unstretched sheet was adjusted, and the surface temperature was wound around a casting drum having a surface temperature of 22 ° C. to cool and solidify to obtain a 1,710 μm unstretched sheet in the same manner as in Example 1. . The unstretched sheet was stretched in two stages by changing the stretch ratio of the first stage to 2.78 times, the stretch ratio of the second stage to 1.26 times, and as shown in Table 1. Transverse stretching was performed by changing the transverse stretching conditions. Thereafter, a biaxially stretched film having a thickness of 125 μm was produced with a lateral relaxation treatment of 2.2%. And the characteristic of the obtained film was evaluated by each measuring method mentioned above. The evaluation results are shown in Table 4.

[Example 5]
The extrusion amount of the extruder was increased, the take-up speed of the unstretched sheet was adjusted, and the surface temperature was wound around a casting drum having a surface temperature of 22 ° C. to cool and solidify to obtain a 1,710 μm unstretched sheet in the same manner as in Example 1. . Only the surface of the unstretched sheet was heated by an infrared heater provided immediately before the first nip roll, and a temperature difference between the front and back of the film as shown in Table 1 was provided. Thereafter, the unstretched sheet was stretched longitudinally in three stages in the same manner as in Example 1, and subjected to transverse stretching and thermal relaxation treatment in the same manner as in Example 4. In this way, a biaxially stretched polyester film having a thickness of 125 μm was obtained. Thereafter, the characteristics were evaluated by the method described above. The evaluation results are shown in Table 4.

[Comparative Example 1]
A 125 μm biaxially stretched film was obtained in the same manner as in Example 1 except that the infrared output in the longitudinal stretching was the same on the front and back sides. And the characteristic of the obtained film was evaluated by each measuring method mentioned above. The evaluation results are shown in Table 4.

[Comparative Example 2]
A biaxially stretched film of 188 μm was obtained in the same manner as in Example 2 except that the infrared output in the longitudinal stretching was changed to the same on the front and back. And the characteristic of the obtained film was evaluated by each measuring method mentioned above. The evaluation results are shown in Table 4.

[Comparative Example 3]
A 250 μm biaxially stretched film was obtained in the same manner as in Example 3 except that the infrared output in the longitudinal stretch was changed to the same on the front and back. And the characteristic of the obtained film was evaluated by each measuring method mentioned above. The evaluation results are shown in Table 4.

[Comparative Example 4]
The extrusion amount of the extruder is reduced, the take-up speed of the unstretched sheet is adjusted, and when the unstretched sheet is wound around the casting drum, the thickness is 3 by cooling with cooling air using cooling air of 19 ° C. A 150 μm unstretched sheet was obtained. A 250 μm biaxially stretched film was obtained in the same manner as in Example 3 except that the transverse stretching conditions were changed as shown in Table 1. The evaluation results are shown in Table 4.

[Comparative Example 5]
A biaxially stretched film of 188 μm was obtained in the same manner as in Example 2 except that the transverse stretching conditions of Example 2 were changed as shown in Table 1. And the characteristic of the obtained film was evaluated by each measuring method mentioned above. The evaluation results are shown in Table 4.

[Comparative Example 6]
The thickness of the unstretched sheet was adjusted to 125 μm in the same manner as in Example 1 except that the unstretched sheet thickness was adjusted, and the thickness of the unstretched sheet was 1,710 μm and the longitudinal stretching and transverse stretching conditions were changed as shown in Table 1. A biaxially stretched film was obtained. And the characteristic of the obtained film was evaluated by each measuring method mentioned above. The evaluation results are shown in Table 4.

  The cutting property and the film passability are “◯”, the average value of the flatness 1 is 20% or less of the thickness of the film, the maximum value is the thickness of the film or less, and the average value of the flatness 2 is 0.5 mm. What was below was set as a pass, and determination was set as "(circle)". Moreover, even if one failed, the judgment was “x”.

  From Table 4, the films of the examples all have good flatness and dimensional stability, a small TS / TE ratio, and good cutting properties. Furthermore, even if the curing shrinkable resin composition is applied and curing shrinkage accompanying curing occurs, the planarity of the entire laminate is very good due to the difference in heat shrinkage between the front and back surfaces.

  The polyethylene terephthalate resin film of the present invention is excellent in cutting properties, dimensional stability and flatness, and is suitable as a base film for a laminate. For example, it is suitable as a base film for laminates such as various optical films such as a lens film, a diffusion film, a hard coat film, and an NIR film, a touch panel, and ITO. Further, it is also suitable as a base film for use in building materials for applying and laminating curable coatings, for recording materials using curable resin ink, and for bonding members using two or more films bonded together.

Explanatory drawing (a) which shows the shielding aspect by the conventional shielding board shows the vertical cross section of a part of heat setting apparatus, (b) is the state which attached the shielding board to the hot-air blowing outlet of the plenum duct It shows the state seen from above. The figure of Unexamined-Japanese-Patent No. 2002-79638 shows that the wind speed which is shielded by the shielding board of a plenum duct and blows off from a plenum duct differs for every plenum duct. It is explanatory drawing which shows the shielding aspect by the shielding board in this invention. (A) shows a vertical section of a part of the heat fixing device, and (b) shows a state in which a shield plate is attached to the hot air outlet of the plenum duct as viewed from above. is there. It is explanatory drawing which shows the state which saw through the heat fixing apparatus used by the Example and the comparative example from the top. It is explanatory drawing which shows the shielding aspect by a shielding board.

Explanation of symbols

F: Film S: Shielding plate A: Film winding direction Z1: First zone Z2: Second zone Z3: Third zone Z4: Fourth zone N1, N2, N3: Intermediate zone HS: Heat fixing zone 1: Heat Fixing device 2: Hot air outlet 3, ax: Plenum duct

Claims (2)

Biaxially stretched polyethylene having a difference Δn _ab between 0.015 and 0.060 in terms of a refractive index in a direction forming an angle of 45 degrees with the longitudinal direction of the film and a direction forming an angle of 90 degrees A biaxially stretched polyethylene terephthalate resin film which is a terephthalate resin film and satisfies the following requirements (1) to (5).
(1) A sample having a thickness of 300 mm in the longitudinal direction of film formation and 210 mm in the width direction perpendicular thereto is taken, and the heights of the warps at the four corners of the sample (the height in the vertical direction from the horizontal plane) are set to JIS metal scales (0 (5 mm scale), the maximum value of the height of the four corners is below the thickness of the film. (2) A sample of 300 mm in the longitudinal direction of the film and 210 mm in the width direction perpendicular thereto is formed. The sample was collected and placed on a mount with one side facing up, and heat-treated at 150 ° C. for 30 minutes in a heating oven. Then, the sample was removed from the heating oven together with the mount, and the sample was left at room temperature for 30 minutes. 4. When the heights of the four corners of the sample (height in the vertical direction from the horizontal plane) were measured with a JIS metal ruler (0.5 mm scale), the average height of the four corners was 0.5 mm or more. 0 mm or less If the height of the warp of the sample after standing at room temperature after heating is 0 mm, or the cross section of the sample is M-shaped, the height of the warp with the upper and lower surfaces of the sample opposite To measure.)
(3) The ratio TS / TE of the breaking strength TS and the breaking elongation TE in a direction that forms an angle of 45 degrees with the longitudinal direction of the film formation, and the direction that forms an angle of 135 degrees with the longitudinal direction of the film formation. The ratio TS / TE between the breaking strength TS and the breaking elongation TE, the ratio TS / TE between the breaking strength TS and the breaking elongation TE in the longitudinal direction of the film deposition, and the angle of 90 degrees with the longitudinal direction of the film deposition. The ratio TS / TE between the breaking strength TS and the breaking elongation TE in the direction of forming (width direction) is 0.6 (MPa /%) or more and 2.6 (MPa /%) or less (4) at 150 ° C. HS150, which is the heat shrinkage rate in the longitudinal direction of film formation when heated for 30 minutes, is 0.7% or more and less than 2.0% (5) Arbitrary position in the width direction of the film and its position Cut out samples from a position more than 70 cm away in the width direction, and For One sample, when seeking HS150 is a longitudinal thermal shrinkage of the film formation when heated at 0.99 ° C. 30 minutes, it difference of those HS150 is less than 0.10%   The biaxially stretched polyethylene terephthalate resin film according to claim 1, wherein the biaxially stretched polyethylene terephthalate resin film has a thickness of 100 μm or more and 400 μm or less.

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