JP5013818B2 - Resin composition and calendar sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition and a calendered sheet having excellent roll releasability and film surface smoothness and suppressed biting tendency to a calender roll and effective for preventing the formation of a flow mark. <P>SOLUTION: The resin composition is produced by compounding (a) 100 pts.mass of a polyester resin composed of (i) a dicarboxylic acid component composed of terephthalic acid and (ii) a diol component composed of 60.5-72.5 mol% ethylene glycol, 1.5-6 mol% diethylene glycol and 26-38 mol% 1,4-cyclohexanedimethanol (the 1,4-cyclohexanedimethanol is composed of 65-75 mol% of a trans-isomer and 25-35 mol% of a cis-isomer) with (b) 0.1-20 pts.mass of an acrylic processing assistant. The calendered sheet is produced by calendering the resin composition. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a resin composition and a calender sheet, and more particularly to a resin composition and a calender sheet having improved roll peelability and moldability (flow mark) during calender molding.

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, Patent Document 1 (Japanese Patent Laid-Open No. 2000-136294) discloses that 0.1 to 15 parts by weight of an acrylic acid resin having a weight average molecular weight of 50,000 to 6 million with respect to 100 parts by weight of an amorphous polyethylene terephthalate resin. An amorphous polyethylene terephthalate resin composition comprising one or both of 0.05 to 2 parts by weight of 4-fluoroethylene-modified acrylic acid resin is disclosed.
However, when the resin composition described in Patent Document 1 is subjected to calender molding, it has excellent roll releasability and film surface smoothness, but has a big problem of poor penetration into the calender roll and generation of flow marks. is there.

Patent Document 2 (Japanese Patent Application Laid-Open No. 2001-200166) discloses an amorphous polyester resin composed of a dicarboxylic acid component composed of terephthalic acid and a diol component composed of 1,4-cyclohexanedimethanol and ethylene glycol. A resin composition for calender molding containing various additives is disclosed.
However, when the resin composition described in Patent Document 2 is subjected to calendar molding, there is a problem that a flow mark is generated as in Patent Document 1.
JP 2000-136294 A JP 2001-200166 A

  Accordingly, an object of the present invention is to provide a resin composition and a calender sheet that are excellent in roll peelability and film surface smoothness, improve biting into a calender roll, and prevent the occurrence of flow marks. .

The invention according to claim 1 comprises: (i) a dicarboxylic acid component comprising terephthalic acid; and (ii) ethylene glycol 60.5-72.5 mol%, diethylene glycol 1.5-6 mol%, and 1,4-cyclohexane. Diol component consisting of 26 to 38 mol% of dimethanol (provided that the total of the ethylene glycol, diethylene glycol and 1,4-cyclohexanedimethanol is 100 mol%, and the 1,4-cyclohexanedimethanol is trans 65 to 75 Mol% and cis 25 to 35 mol%), and 100 parts by mass of the polyester resin (a) composed of
Ri Na blended with acrylic processing aid (b) 0.1 to 20 parts by weight,
The polyester resin (a) has a number average molecular weight of 16000 to 24000 as measured by GPC measurement (RI detector) .
The invention according to claim 2 is the resin composition according to claim 1, wherein the amount of diethylene glycol in the polyester resin (a) is 2.5 to 4 mol%.
The invention according to claim 3 is a linear fatty acid having 28 to 32 carbon atoms and / or a derivative wax (c) of 0.2 to 10 with respect to 100 parts by mass of the resin composition according to claim 1 or 2. It is a resin composition characterized by blending parts by mass.
The invention according to claim 4 is a resin composition for a calendered sheet, comprising the resin composition according to any one of claims 1 to 3.
The invention according to claim 5 is a calender sheet obtained by calendering the resin composition for calendered sheets according to claim 4.

  Since the present invention specifies the type and content of the dicarboxylic acid component and the diol component of the polyester resin (a) and also uses the acrylic processing aid (b), roll peelability (the metal at the time of take-off) It is possible to provide a resin composition and a calender sheet that are excellent in prevention of stickiness on rolls) and excellent in film surface smoothness, can improve biting into calender rolls, and can prevent the occurrence of flow marks.

Hereinafter, the present invention will be described in more detail.
Polyester resin (a)
The polyester-based resin (a) 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 1.5-6 mol% and 1 Diol component comprising 26 to 38 mol% of 1,4-cyclohexanedimethanol (provided that the total of the ethylene glycol, diethylene glycol and 1,4-cyclohexanedimethanol is 100 mol%, and the 1,4-cyclohexanedimethanol is A resin composed of 65 to 75 mol% of trans and 25 to 35 mol% of 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 polyester resin (a) 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 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 polyester resins (a) 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%.
When the content of diethylene glycol is 2.5 to 4.0 mol%, ethylene glycol is preferably 60.5 to 71.5 mol%, and 1,4-cyclohexanedimethanol is preferably 26 to 37 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.

  The polyester resin (a) 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% or exceeds 6 mol%, the roll peelability at the time of calender sheet forming deteriorates and a flow mark is generated.
When diethylene glycol is in the range of 2.5 to 4 mol%, roll releasability is particularly good, and no flow mark is observed.
If ethylene glycol is out of the above range and / or 1,4-cyclohexanedimethanol is out of the above range, crystallization of the polyester resin occurs and the shrinkage ratio after molding becomes extremely large, and flexibility is also provided. It is damaged and is not preferred.
In the amount relationship between ethylene glycol and 1,4-cyclohexanedimethanol, the crystallinity is the lowest (the crystallization time is extremely long) within 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 flow 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 roll peelability at the time of forming the calendar sheet deteriorates and a flow mark is generated.
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-based resin (a) used in the present invention preferably has a polystyrene-equivalent number average molecular weight of 16000 to 24,000 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 roll peelability at the time of calendering and the control of the thickness at both ends of the sheet are 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.

Acrylic processing aid (b)
Acrylic processing aids (b) are acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic ester such as 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, Examples thereof include polymers mainly composed of methacrylic acid esters such as n-butyl methacrylate, isobutyl methacrylate, and 2-ethylhexyl methacrylate.

As the acrylic processing aid (b), commercially available products can be used, for example, “Methbrene P-551A” (weight average molecular weight 1,500,000), “Methbrene P-530A” (weight) manufactured by Mitsubishi Rayon Co., Ltd. Average molecular weight 3 million), “methabrene P-570A” (weight average molecular weight 300,000), and the like. The molecular weight measurement method is GPC (gel permeation chromatography). In addition, “Kaneace PA-20” (specific viscosity molecular weight 1 million), “Kaneace PA-30”, “Kaneace PA-60” (molecular weight 8.5 million), “Kaneace PA-100” (molecular weight less than 1 million), manufactured by Kaneka Corporation ) And the like, and the method for measuring the molecular weight is as follows.
200 mg of a sample is dissolved in 50 ml of acetone and measured with a capillary viscosity automatic measuring device (Ubbelohde viscometer 30 ° C.).
Specific viscosity = (solvent drop time / acetone drop time) -1

The weight average molecular weight (GPC method) of the acrylic processing aid (b) is preferably 50000 to 10 million, more preferably 500000 to 10 million, and still more preferably 1 million to 10 million.
The preferable range of the molecular weight based on the specific viscosity of the acrylic processing aid (b) is 50,000 to 10,000,000, more preferably 100,000 to 10,000,000, still more preferably 500,000 to 10,000,000.

  The blending ratio of the acrylic processing aid (b) is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 100 parts by weight of the polyester resin (a). 1 to 8 parts by mass. When the blending ratio of the acrylic processing aid (b) is out of the range of 0.1 to 20 parts by mass, roll peelability deteriorates and generation of flow marks cannot be prevented.

In the present invention, various additives may be used to further improve the calendar moldability.
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, in the present invention, it is particularly preferable to use the following linear fatty acid having 28 to 32 carbon atoms and / or derivative wax (c) thereof. By using this component (c), the calendar moldability is further improved.
(C) As a component, it can be the simple substance of C28-C32 linear fatty acid or its derivative (s), or a mixture, for example. 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 via the Q group, and this form is also included in the component (c) in the present invention.

  Particularly preferred component (c) 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 (c), a commercially available product can be used, for example, lycowax OP (melting point 75 ° C.) of a partially saponified ester of montanic acid manufactured by Clariant Japan.

  (C) The compounding ratio of a component is 0.2-10 mass parts with respect to 100 mass parts of said polyester-type resin (a), Preferably it is 0.5-5 mass parts. When the blending ratio of component (c) is 0.2 parts by mass or more, aggregation of component (c) and generation of irregularities due to poor dispersion can be suppressed. Moreover, the film surface smoothness and roll peelability can be improved and the occurrence of flow marks can be prevented. 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.

  A method for producing a calendar sheet using the resin composition of the present invention will be described. 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 calender roll is preferably in the range of 130 to 250 ° C.

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

Moreover, the resin composition of this invention can also be used for extrusion molding based on a well-known means.
In this case, the thickness of the extruded sheet 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 (DEG) (1,4-cyclohexanedimethanol is trans 70 Mol% and cis 30 mol%)
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: 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 21,000.

(6) Polyester resin (a-6)
Glycol component: ethylene glycol 67.0 mol%, 1,4-cyclohexanedimethanol 31.0 mol% and diethylene glycol 2.0 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.

(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) )
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 )
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 )
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) )
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) )
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) )
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) )
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) )
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) Acrylic processing aid (b-1)
Manufacturing company: Mitsubishi Rayon Co., Ltd. Product name: Metabrene P-551A
Weight average molecular weight 1.5 million

(18) Acrylic processing aid (b-2)
Manufacturing company: Mitsubishi Rayon Co., Ltd. Product name: Metabrene P-530A
Weight average molecular weight 3 million

(19) Acrylic processing aid (b-3)
Manufacturer: Kaneka Corporation Product name: Kane Ace PA-60
Specific viscosity 8.5 million

(20) Acrylic processing aid (b-4)
Manufacturer: Kaneka Corporation Product name: Kane Ace PA-20
Specific viscosity 1 million

(21) Acrylic processing aid (b-5)
Manufacturing company: Mitsubishi Rayon Co., Ltd. Product name: Metabrene P-570A
Weight average molecular weight 300,000

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

(Examples 1-27 and Comparative Examples 1-34)
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.

A formability (flow mark) test was conducted. Specifically, the thickness of the flow mark portion is continuously measured in the width direction with a continuous thickness measurement system (KG601A, K306C, KG310A) manufactured by Anritsu Corporation, and the thickness difference between the upper and lower limits is ◎: 10 μm or less, ○: It was evaluated as more than 10 μm and 20 μm or less, Δ: more than 20 μm and 30 μm or less, and x: more than 30 μm.
The measurement conditions were: probe: tip R3 ruby probe, probe diameter: 6 mm, measurement pressure: 30 ± 5 g, sample feed speed: 3 m / min.

The peelability from the calendar roll was examined. Specifically, ◎: Peeling of the melt-softened sheet from the calender roll is very good, ○: Peeling of the melt-softened sheet from the calender roll is good, ×: Melting and softening from the calender roll The sheet was evaluated as having poor peeling.
The results are shown in Table 1.

  In the above table, the numerical value of the compounding prescription is part by mass. Actually, the example means a comparative example. Moreover, * 1 means that it is difficult to peel from the calendar roll and cannot be formed into a sheet.

  From the results in 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, there is no occurrence of a flow mark as compared with the comparative example. Moreover, the peelability with respect to a calender roll is also excellent.

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in roll peelability and film surface smoothness, the penetration to a calender roll can be improved and the resin composition and calender sheet which can prevent generation | occurrence | production of a flow mark can be provided.

Claims (5)

(I) a dicarboxylic acid component composed of terephthalic acid, and (ii) ethylene glycol 60.5-72.5 mol%, diethylene glycol 1.5-6 mol%, and 1,4-cyclohexanedimethanol 26-38 mol%. Diol component (however, the total of the ethylene glycol, diethylene glycol and 1,4-cyclohexanedimethanol is 100 mol%, and the 1,4-cyclohexanedimethanol is trans 65-75 mol% and cis 25-35 mol%. And 100 parts by mass of the polyester resin (a) composed of
Ri Na blended with acrylic processing aid (b) 0.1 to 20 parts by weight,
The resin composition, wherein the polyester resin (a) has a number average molecular weight of 16000 to 24000 as measured by GPC (RI detector) . The resin composition according to claim 1 , wherein the amount of diethylene glycol in the polyester resin (a) is 2.5 to 4 mol%. A linear fatty acid having 28 to 32 carbon atoms and / or a derivative wax (c) of 0.2 to 10 parts by mass is blended with 100 parts by mass of the resin composition according to claim 1 or 2. Resin composition. The resin composition for calendar forming sheets which consists of a resin composition in any one of Claims 1-3 . A calendar sheet obtained by calendering the resin composition for a calendered sheet according to claim 4 .