JP2007217556A - Calendered sheet and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a calendered sheet superior in calender formability and reduced in shrinkage accompanying forming and its manufacturing method. <P>SOLUTION: The calendered sheet formed of a resin composition constituted by containing following components (a) and (b), and its manufacturing method, are provided. The resin composition is constituted by containing a polyester-based resin (a) constituted of a dicarboxylic acid component (i) comprising terephthalic acid, and a diol component (ii) comprising 60.5-72.5 mol% of ethylene glycol, 1.5-6 mol% of diethylene glycol and 26-38 mol% of 1,4-cyclohexanedimethanol (provided that, the 1,4-cyclohexanedimethanol is constituted of 65-75 mol% of trans type and 25-35 mol% of cis type); and an additive (b) sufficient in amount to prevent adhesion of the polyester-based resin to a calender roll. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a calendar sheet and a manufacturing method thereof, and more particularly to a calendar sheet having excellent calendar moldability and reduced shrinkage due to molding, and a manufacturing method thereof.

Conventionally, vinyl chloride resin films have been used in large amounts in decorative sheets used for furniture, doors, door frames, waistboards, baseboards, window frames, and other surface materials. The vinyl chloride resin decorative sheet is laminated on a heating drum of a doubling machine, with a transparent vinyl chloride resin film and a printed colored vinyl chloride resin film superimposed on each other and thermocompression bonded. It was manufactured by embossing. However, since vinyl chloride resins have problems caused by poor incineration conditions, there has been a demand for decorative sheets to replace vinyl chloride resins because of recent social demands for environmental problems.
Therefore, it has been studied to use an amorphous polyester resin film instead of the vinyl chloride resin film.

  For example, in Patent Document 1 (Japanese Patent Laid-Open No. 2001-40188), butadiene 70 to 100% by mass, aromatic vinyl monomer or aromatic (meth) acrylate monomer 30 to 0% by mass, and copolymerizable therewith 25 to 55 parts by mass of a butadiene copolymer consisting of 10 to 0% by mass of a vinyl monomer and 5 to 0% by mass of a crosslinkable monomer, 30 to 100% by mass of an aromatic vinyl monomer, (meth) Graft copolymer (A) 1 obtained by polymerizing 75 to 45 parts by mass of a monomer mixture composed of 70 to 0% by mass of an acrylic acid alkyl ester and 0 to 20% by mass of a vinyl monomer copolymerizable therewith A resin composition comprising -30% by mass and 99-70% by mass of an amorphous polyethylene terephthalate resin (B) is proposed, and this resin composition is said to satisfy both transparency and impact resistance at the same time.

  However, the resin composition described in Patent Document 1 has a large problem in calendar moldability, such as air marks or poor calendar roll peelability when it is calendered to produce a sheet. .

  Patent Document 2 (Japanese Patent No. 3280374) discloses a diacid residue component selected from terephthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid and mixtures thereof, and carbon number. A calendering polyester resin composition is disclosed that contains a polyester and additives containing a diol residue component selected from 2 to 10 diols and a crystallization half time from the molten state of at least 5 minutes. However, the resin composition described in Patent Document 2 has a large problem in calendar formability as in Patent Document 1, and also has a problem that the sheet shrinks in the stretching direction after melt stretching by a calendar roll. .

JP 2001-40188 A Japanese Patent No. 3280374

  Accordingly, an object of the present invention is to provide a calendar sheet having excellent calendar moldability and reduced shrinkage due to molding, and a method for producing the calendar sheet.

The present invention is as follows.
(1) A calendar sheet formed from a resin composition comprising the following components (a) and (b):
(A) (i) a dicarboxylic acid component comprising terephthalic acid;
(Ii) a diol component consisting of 60.5 to 72.5 mol% ethylene glycol, 1.5 to 6 mol% diethylene glycol and 26 to 38 mol% 1,4-cyclohexanedimethanol (provided that the ethylene glycol, diethylene glycol and 1 , 4-cyclohexanedimethanol is 100 mol%, and the 1,4-cyclohexanedimethanol is composed of 65 to 75 mol% trans and 25 to 35 mol% cis). resin.
(B) An additive in an amount sufficient to prevent the polyester resin from sticking to the calender roll.

  (2) The calendar sheet according to (1) above, wherein the number average molecular weight of the polyester resin (a) by GPC measurement (RI detector) is 16000 to 24000.

  (3) The calender sheet according to (1) or (2) above, wherein the amount of diethylene glycol in the (a) polyester-based resin is 2.5 to 4 mol%.

  (4) The calendar sheet according to any one of (1) to (3), wherein the additive (b) is a wax, a slip agent, or a mixture thereof.

  (5) The calendar sheet according to (4), wherein the additive (b) is a linear fatty acid having 28 to 32 carbon atoms and / or a derivative wax thereof.

  (6) The calendar sheet according to (4), wherein the additive (b) is glycerol monostearate.

(7) A method for producing a calendar sheet, comprising a step of calendering a resin composition containing the following components (a) and (b).
(A) (i) a dicarboxylic acid component comprising terephthalic acid;
(Ii) a diol component consisting of 60.5 to 72.5 mol% ethylene glycol, 1.5 to 6 mol% diethylene glycol and 26 to 38 mol% 1,4-cyclohexanedimethanol (provided that the ethylene glycol, diethylene glycol and 1 , 4-cyclohexanedimethanol is 100 mol%, and the 1,4-cyclohexanedimethanol is composed of 65 to 75 mol% trans and 25 to 35 mol% cis). resin.
(B) An additive in an amount sufficient to prevent the polyester resin from sticking to the calender roll.

  (8) The calendar sheet manufacturing method as described in (7) above, wherein the calendaring is performed by adjusting the temperature of a calendar roll to 130 ° C to 250 ° C.

  According to the present invention, since the calendar sheet is formed by the resin composition containing (a) a polyester-based resin and (b) an additive that specify the types and contents of the dicarboxylic acid component and the diol component, the calendar It is possible to provide a calendar sheet having excellent moldability and reduced shrinkage due to molding, and a method for producing the calendar sheet.

Hereinafter, the present invention will be described in more detail.
(A) Polyester-based resin The (a) polyester-based resin used in the present invention comprises (i) a dicarboxylic acid component composed of terephthalic acid, (ii) ethylene glycol 60.5-72.5 mol%, diethylene glycol 1.5 A diol component consisting of ˜6 mol% and 1,4-cyclohexanedimethanol 26-38 mol% (provided that the total of the ethylene glycol, diethylene glycol and 1,4-cyclohexanedimethanol is 100 mol%, and 4-cyclohexanedimethanol is a resin composed of 65 to 75 mol% trans and 25 to 35 mol% cis).

In order to prepare a polyester containing the diethylene glycol moiety in a predetermined ratio, for example, a predetermined amount of diethylene glycol is used as a diol component. However, when ethylene glycol is used instead of diethylene glycol, a diethylene glycol moiety is formed by the condensation reaction. Usually, in a polyester containing an ethylene terephthalate part, a diethylene glycol part is formed by the condensation reaction of the ethylene glycol in the production process. The content of the diethylene glycol moiety varies depending on the polyester production method, the reaction conditions, the catalyst used, and the like.
In general, the (a) polyester-based resin in the present invention generally has a larger amount of diethylene glycol than the amount of diethylene glycol moiety by-produced when producing a polyester-based resin having a 1,4-cyclohexanedimethanol modification amount of around 31 mol%. Contains part. Therefore, in the present invention, in order to contain the above-mentioned predetermined amount of diethylene glycol, it is already known in the field of beverage bottles and bottle shrink films usually made of crystalline polyester, but depending on the content, as a diol component Usually, in addition to ethylene glycol, a further required amount of diethylene glycol is used. Alternatively, the amount of diethylene glycol by-produced from ethylene glycol can also be controlled by optimizing the polyester production conditions and catalyst.
Any of the (a) polyester resins in the present invention can be produced by a conventional method. For example, (copolymerization) polyester is prepared using a direct esterification method in which a dicarboxylic acid and a diol are directly reacted; a transesterification method in which a dimethyl ester of a dicarboxylic acid and a diol are reacted. The preparation may be carried out by either a batch method or a continuous method.

The content of diethylene glycol is 1.5 to 6 mol%, preferably 2.5 to 4.0 mol%.
Although Provista manufactured by Eastman Chemical Co. contains trimellitic anhydride instead of diethylene glycol as the third component, it is not preferable for the purpose of the present invention.

  (A) The polyester-based resin is a polyester having a crystallization half time from a molten state of at least 5 minutes, preferably at least 12 minutes. Crystallization half time is measured using a Perkin-Elmer model DSC-2 differential scanning calorimeter. A 15.0 mg sample is sealed in an aluminum pan and heated at 290 ° C. for 2 minutes at a rate of about 320 ° C./min. The sample is then immediately cooled in the presence of helium to a predetermined isothermal crystallization temperature at a rate of about 320 ° C./min (20 ° C./min if the apparatus is not possible). The crystallization half time is determined as the time interval from reaching the isothermal crystallization temperature to the point of the crystallization peak on the DSC curve.

In addition, when diethylene glycol is less than 1.5 mol%, problems such as inferior thickness controllability at both ends during calender sheet molding, increased air marks, and increased shrinkage after molding occur. If it exceeds 6 mol%, problems such as inferior thickness controllability at both ends during calendering, increased air marks, and increased shrinkage after molding.
In the range of 2.5 to 4 mol% of diethylene glycol, it is particularly preferable because of excellent balance between shrinkage after molding and moldability.
Further, when ethylene glycol is outside the above range, the shrinkage rate after molding becomes extremely large and flexibility is impaired, and when 1,4-cyclohexanedimethanol is outside the above range, crystallization of the polyester resin is caused. However, the shrinkage ratio after molding becomes extremely large and the flexibility is impaired, which is not preferable.
In the amount relationship between ethylene glycol and 1,4-cyclohexanedimethanol, the crystallinity is the lowest (crystallization time is extremely long) in the above range. Thereby, contraction of the sheet is suppressed and flexibility is increased. In addition, the thickness controllability at both ends during molding of the calendar sheet is enhanced, and the surface state (no air mark) of the molded sheet is further improved.

In the present invention, the 1,4-cyclohexanedimethanol needs to be composed of 65 to 75 mol% of trans and 25 to 35 mol% of cis. If the transformer is less than 65 mol% or more than 75 mol%, the shrinkage after molding becomes extremely large, and the calender moldability also becomes poor.
A method for producing 1,4-cyclohexanedimethanol is known. For example, 1,4-cyclohexanedicarboxylic acid dimethyl ester can be obtained by hydrogenation in the presence of a copper chromium catalyst and then distilled. Methods for adjusting the trans and cis amounts are also known, and are disclosed, for example, in Japanese Patent No. 2537401. In addition, although the production example of 1,4-cyclohexanedimethanol whose trans amount exceeds 90% is described in the publication, such 1,4-cyclohexanedimethanol is used for the purpose of the present invention. I can't.

The polyester resin (a) used in the present invention preferably has a number average molecular weight of 16000 to 24000 as measured by GPC (RI detector) (performed under the following measurement conditions). If it is in this range, the calendering temperature becomes high, and the thickness controllability at both ends of the sheet is very good.
Measuring device name: HPLC VP manufactured by Shimadzu Corporation
Column used: Shodex K806L (8 mmφ × 300 mm) × 2 Solvents: Special grade sample concentration for chloroform liquid chromatography: 0.2% (w / v)
Flow rate: 1 ml / min
Detector: RI
Injection volume: 100 μl
Measurement temperature: 35 ° C

  As described above, only terephthalic acid is used as the dicarboxylic acid component in the present invention. For example, when it contains 1 mol% or more of other dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylate, The object of the present invention cannot be achieved.

(B) Additive In the present invention, an additive in an amount sufficient to prevent the polyester-based resin from sticking to the calender roll is used.
Additives suitable for use in the present invention are known in the calendering art and include waxes, slip agents or mixtures thereof. Examples of such additives include fatty acid amides such as stearamide; metal salts of organic acids such as calcium stearate and zinc stearate; fatty acids and esters such as stearic acid, oleic acid and palmitic acid; paraffin wax; Hydrocarbon waxes such as polyethylene wax and polypropylene wax; chemically modified polyolefin wax; ester sax such as carnauba; glycerol mono- and distearate; talc and acrylic copolymers (eg, Rohm & Haas ) From Paraloid K175). Of these, glycerol monostearate is preferable.

Apart from the above, as the additive (b) of the present invention, the following linear fatty acid having 28 to 32 carbon atoms and / or derivative wax thereof is also preferable.
Such (b) component can be, for example, a simple substance or a mixture of a linear fatty acid having 28 to 32 carbon atoms or a derivative thereof. When the carbon number is in the range of 28 to 32, no flaws due to poor dispersion of the additive are observed, and the roll peelability is improved. Examples of the derivatives include saponified and esterified linear fatty acids having 28 to 32 carbon atoms. The esterified product is preferably a product obtained by esterifying a linear fatty acid having 28 to 32 carbon atoms with glycols. The esterified product using such glycols has a structure represented by the following formula (1).

  In the formula, R represents a linear portion of a fatty acid, and Q represents an alkylene group having 2 or 3 carbon atoms. The esterified product of the formula (1) has two molecules of fatty acid bonded through the Q group, and this form is also included in the component (b) in the present invention.

  Particularly preferred component (b) in the present invention is a mixture of montanic acid esterified with ethylene glycol or butylene glycol, and most preferably a mixture of montanic acid partially esterified with butylene glycol and the remainder saponified with calcium hydroxide. It is. As such an optimal component (b), a commercially available product can be used, for example, a partially saponified montanic acid ester “Licowax-OP” (melting point: 75 ° C.) manufactured by Clariant Japan.

  (B) The compounding ratio of a component is 0.2-10 mass parts with respect to 100 mass parts of said (a) polyester-type resin, Preferably it is 0.5-5 mass parts. When the blending ratio of the component (b) is 0.2 parts by mass or more, the aggregation of the component (b) and the occurrence of irregularities due to poor dispersion can be suppressed. Moreover, the clogging of the mesh installed in the strainer and the roll peelability are also improved during calendar molding. By being 10 parts by mass or less, stickiness due to blowing to the sheet surface is less likely to occur.

  As a method for producing the resin composition used in the present invention, each of the above components is individually prepared, kneaded using a normal kneading apparatus such as a Henschel mixer, a tumbler, etc., and a single screw extruder, twin screw extruder Banbury. A method of forming a composition by using a device such as a mixer that is used for normal shaping can be employed. In addition, the resin composition of the present invention, if necessary, an antioxidant, a heat stabilizer, a light resistance improver, a UV absorber, a lubricant, a plasticizer, a release agent, An antistatic agent, a slidability improver, a colorant, and the like can also be added.

  The production method of the present invention includes a step of calendering the resin composition. The type of calendar molding machine is not particularly limited. For example, there is no restriction | limiting in particular in the calendar apparatus to be used, For example, an upright type 3 roll, an upright type 4 roll, an L type 4 roll, a reverse L type 4 roll, a Z type roll etc. can be mentioned. Further, the calendar processing conditions are not particularly limited. For example, the temperature of the calendar roll is preferably in the range of 130 to 250 ° C. More preferably, it is 150-200 degreeC.

  The thickness of the calendar sheet of the present invention is, for example, 30 to 1000 μm, preferably 50 to 500 μm.

  Further, the calendar sheet of the present invention can be laminated with other thermoplastic resin sheets. As another thermoplastic resin, an amorphous polyester resin is preferable. Apart from this, a calendar sheet and a sheet made of the component (a) in the present invention may be laminated.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further, this invention is not restrict | limited to the following example.

In the following example, any of the following various materials was used.
(1) Polyester resin (a-1)
Glycol component: 66.2 mol% ethylene glycol (EG), 31.0 mol% 1,4-cyclohexanedimethanol (CHDM) and 2.8 mol% diethylene glycol (1,4-cyclohexanedimethanol is 70 mol% trans and It is composed of 30 mol% of cis)
Dicarboxylic acid component: terephthalic acid (TPA)
Polyester composed of.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 21,000.
In addition, the composition ratio of each of the above components is ¹³ C-NMR (nuclear magnetic resonance apparatus (NMR) GX-400 manufactured by JEOL), and about 40 mg of a sample is dissolved in deuterated chloroform in a 5 mm diameter sample tube. It was measured and confirmed as a measurement sample (the same applies to the following).

(2) Polyester resin (a-2)
Glycol component: ethylene glycol 63.0 mol%, 1,4-cyclohexanedimethanol 31.0 mol% and diethylene glycol 6.0 mol% (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis To be)
Dicarboxylic acid component: Polyester composed of terephthalic acid.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 21,000.

(3) Polyester resin (a-3)
Glycol component: 66.5 mol% ethylene glycol, 31.0 mol% 1,4-cyclohexanedimethanol and 2.5 mol% diethylene glycol (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis) To be)
Dicarboxylic acid component: Polyester composed of terephthalic acid.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 21,000.

(4) Polyester resin (a-4)
Glycol component: ethylene glycol 65.0 mol%, 1,4-cyclohexanedimethanol 31.0 mol% and diethylene glycol 4.0 mol% (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis) To be)
Dicarboxylic acid component: Polyester composed of terephthalic acid.
The number average molecular weight of the polyester measured by GPC (RI detector) is 21,500.

(5) Polyester resin (a-5)
Glycol component: 66.0 mol% ethylene glycol, 31.0 mol% 1,4-cyclohexanedimethanol and 2.0 mol% diethylene glycol (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis) To be)
Dicarboxylic acid component: Polyester composed of terephthalic acid.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 20500.

(6) Polyester resin (a-6)
Glycol component: 67.5 mol% ethylene glycol, 31.0 mol% 1,4-cyclohexanedimethanol and 1.5 mol% diethylene glycol (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis) To be)
Dicarboxylic acid component: Polyester composed of terephthalic acid.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 20500.

(7) Comparative polyester resin (a′-1)
Glycol component: ethylene glycol 68.0 mol%, 1,4-cyclohexanedimethanol 31.0 mol% and diethylene glycol 1.0 mol% (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis) To be)
Dicarboxylic acid component: Polyester composed of terephthalic acid.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 20500.

(8) Comparative polyester resin (a′-2)
Glycol component: ethylene glycol 67.8 mol%, 1,4-cyclohexanedimethanol 31.0 mol% and diethylene glycol 1.2 mol% (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis) To be)
Dicarboxylic acid component: Polyester composed of terephthalic acid.
The number average molecular weight of the polyester measured by GPC (RI detector) is 21,500.

(9) Comparative polyester resin (a'-3)
Glycol component: 66.2 mol% ethylene glycol, 31.0 mol% 1,4-cyclohexanedimethanol and 2.8 mol% diethylene glycol (1,4-cyclohexanedimethanol is composed of 60 mol% trans and 40 mol% cis To be)
Dicarboxylic acid component: Polyester composed of terephthalic acid.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 20500.

(10) Comparative polyester resin (a′-4)
Glycol component: 66.2 mol% ethylene glycol, 31.0 mol% 1,4-cyclohexanedimethanol and 2.8 mol% diethylene glycol (1,4-cyclohexanedimethanol is composed of 80 mol% trans and 20 mol% cis To be)
Dicarboxylic acid component: Polyester composed of terephthalic acid.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 21,000.

(11) Comparative polyester resin (a′-5)
Glycol component: 62.8 mol% ethylene glycol, 31.0 mol% 1,4-cyclohexanedimethanol and 6.2 mol% diethylene glycol (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis To be)
Dicarboxylic acid component: Polyester composed of terephthalic acid.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 21,000.

(12) Comparative polyester resin (a′-6)
Glycol component: 66.2 mol% ethylene glycol, 31.0 mol% 1,4-cyclohexanedimethanol and 2.8 mol% diethylene glycol (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis) To be)
Dicarboxylic acid component: 99.0 mol% terephthalic acid and 1.0 mol% 1,4-cyclohexanedicarboxylic acid
Polyester composed of.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 21,000.

(13) Comparative polyester resin (a′-7)
Glycol component: 66.2 mol% ethylene glycol, 31.0 mol% 1,4-cyclohexanedimethanol and 2.8 mol% diethylene glycol (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis) To be)
Dicarboxylic acid component: 99.0 mol% terephthalic acid and 1.0 mol% 1,3-cyclohexanedicarboxylic acid
Polyester composed of.
The number average molecular weight of the polyester measured by GPC (RI detector) is 21,500.

(14) Comparative polyester resin (a′-8)
Glycol component: 66.2 mol% ethylene glycol, 31.0 mol% 1,4-cyclohexanedimethanol and 2.8 mol% diethylene glycol (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis) To be)
Dicarboxylic acid component: 99.0 mol% terephthalic acid and 1.0 mol% 1,2-cyclohexanedicarboxylic acid
Polyester composed of.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 20500.

(15) Comparative polyester resin (a′-9)
Glycol component: 66.2 mol% ethylene glycol, 31.0 mol% 1,4-cyclohexanedimethanol and 2.8 mol% diethylene glycol (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis) To be)
Dicarboxylic acid component: 99.0 mol% terephthalic acid and 1.0 mol% 1,4-cyclohexanedicarboxylate
Polyester composed of.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 21,000.

(16) Comparative polyester resin (a′-10)
Glycol component: 66.2 mol% ethylene glycol, 31.0 mol% 1,4-cyclohexanedimethanol and 2.8 mol% diethylene glycol (1,4-cyclohexanedimethanol is composed of 70 mol% trans and 30 mol% cis) To be)
Dicarboxylic acid component: 99.0 mol% dimethyl terephthalate and 1.0 mol% 1,4-cyclohexanedicarboxylic acid
Polyester composed of.
The number average molecular weight of the polyester by GPC measurement (RI detector) is 21,000.

(17) Additive Manufacturer: Clariant Japan Product Name: Lycowax-OP (Montanic acid partially saponified ester. Saponified portion is calcium salt, melting point 75 ° C.)

(Examples 1-6 and Comparative Examples 1-10)
Various compositions having the formulation shown in Table 1 were melt-kneaded using a Banbury mixer and calendered to obtain a sheet having a thickness of 100 μm and a width of 1300 mm. As the calendar molding machine, an inverted L shape was used. The calendar condition was a calendar roll temperature of 185 ° C.
The shrinkage ratio in the stretching direction of the calendar sheet was examined. Specifically, a 15 cm square sheet was cut out from the sheet obtained by calendering (stretching ratio 250%), this sheet was heat treated in an oven set at a predetermined temperature (described in the table) for 30 minutes, and then taken out. The contraction rate (%) in the stretching direction of the sheet was determined from the change in the length of the sheet before and after the heat treatment.
The controllability of the thickness at both ends of the calendar sheet was examined. Specifically, the calendering temperature is measured at the thickness of both ends when the thickness of the center of the film is accurately adjusted to 100 μm under the minimum temperature condition where rough skin, no air mark, and high smooth appearance can be obtained. did. At this time, it classified according to the following evaluation criteria according to the degree of thickness fluctuation with respect to the central portion.
A: Less than ± 0 to 3 μ, ○: Less than ± 3 to 5 μ, Δ: Less than ± 5 to 10 μ, and X: ± 10 μ or more.
The suppression effect of the air mark at the time of calendering was visually checked according to the “Dust Measurement Chart” manufactured by the Ministry of Finance Printing Bureau to determine how many 0.2 mm ² or more air marks were included in the film length of 10 m. Specifically, the evaluation was as follows: A: 0, O: 1-3, Δ: 4-8, x: 9 or more.
The results are shown in Table 1.

  From the results of Table 1, it can be seen that in each example that satisfies the conditions of the type and content of the dicarboxylic acid component and the diol component, the shrinkage after calender molding and the calender moldability are superior to those of the comparative example. .

  ADVANTAGE OF THE INVENTION According to this invention, the calendar sheet which was excellent in calendar moldability and the shrinkage | contraction accompanying shaping | molding was reduced, and its manufacturing method are provided.

Claims (8)

A calendar sheet formed from a resin composition containing the following components (a) and (b):
(A) (i) a dicarboxylic acid component comprising terephthalic acid;
(Ii) a diol component consisting of 60.5 to 72.5 mol% ethylene glycol, 1.5 to 6 mol% diethylene glycol and 26 to 38 mol% 1,4-cyclohexanedimethanol (provided that the ethylene glycol, diethylene glycol and 1 , 4-cyclohexanedimethanol is 100 mol%, and the 1,4-cyclohexanedimethanol is composed of 65 to 75 mol% trans and 25 to 35 mol% cis). resin.
(B) An additive in an amount sufficient to prevent the polyester resin from sticking to the calender roll.   2. The calendar sheet according to claim 1, wherein (a) the polyester resin has a number average molecular weight of 16000 to 24000 as measured by GPC measurement (RI detector).   The calender sheet according to claim 1 or 2, wherein the amount of diethylene glycol in the (a) polyester resin is 2.5 to 4 mol%.   The calendar sheet according to any one of claims 1 to 3, wherein the additive (b) is a wax, a slip agent, or a mixture thereof.   The calender sheet according to claim 4, wherein the additive (b) is a linear fatty acid having 28 to 32 carbon atoms and / or a derivative wax thereof.   The calendar sheet according to claim 4, wherein the additive (b) is glycerol monostearate. A method for producing a calendar sheet, comprising a step of calendering a resin composition comprising the following components (a) and (b):
(A) (i) a dicarboxylic acid component comprising terephthalic acid;
(Ii) a diol component consisting of 60.5 to 72.5 mol% ethylene glycol, 1.5 to 6 mol% diethylene glycol and 26 to 38 mol% 1,4-cyclohexanedimethanol (provided that the ethylene glycol, diethylene glycol and 1 , 4-cyclohexanedimethanol is 100 mol%, and the 1,4-cyclohexanedimethanol is composed of 65 to 75 mol% trans and 25 to 35 mol% cis). resin.
(B) An additive in an amount sufficient to prevent the polyester resin from sticking to the calender roll.   The calendar sheet manufacturing method according to claim 7, wherein the calendaring is performed by adjusting a temperature of a calendar roll to 130 ° C. to 250 ° C.