JP2003128894A - Polyester resin composition for calendering and sheet using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition having an excellent mold releasability at the time of processing and enabling to form a calender sheet having fine transparency. SOLUTION: The polyester resin composition for calendering is prepared by incorporating 0.01-5 pts.wt. of a lubricant to an amorphous polyester and is characterized by having a softening point of <200 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to roll peelability, long-run processability and heat stability in calendar processing of polyester, and particularly excellent transparency of calendered sheets, and shrink labels for foods, cosmetics and beverages, and aroma retention. TECHNICAL FIELD The present invention relates to various sheets and films such as a heat-resistant heat-sealing film and an oil-resistant multi-layer sheet, particularly a sheet for industrial processing, a polyester resin composition most suitable for calendering useful for the film, and the sheet.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride sheets (films) have been widely used for certain purposes because they are inexpensive and have excellent transparency. Extrusion molding and calender molding are known as methods for processing this sheet, but in extrusion molding, the friction of the die lip affects the processability (moldability) of the resin, and the sheet (film) Accuracy is poor in terms of thickness, width, flow direction, etc.
It is also unsuitable for mass production. Therefore, the latter is more frequently used in terms of productivity and quality. Also, by adding a plasticizer to vinyl chloride, the flexibility can be adjusted freely, so it is easy to process as a sheet, and a typical example of its application is a decorative plate sheet with wood grain printed to improve the design of wood. There is a (film). However, in recent years, there is a movement to replace the vinyl chloride sheet (film) with another material due to the problem of dioxins generation during incineration of vinyl chloride and the problem of suppression of plasticizer use due to endocrine disrupting substances. Of the many alternative materials, polyester is a powerful material in terms of its physical properties and price. However, there are the following major problems in replacing with polyester.

That is, it is difficult to apply it to calender molding, which is widely used as a method for molding a vinyl chloride sheet.
Conventionally, a polyester resin has been mainly used in extrusion molding as a method for producing a sheet or film because of its ease of processing. However, when the polyester resin is subjected to calendering, the adhesive force to the roll when it is thermoplasticized is relatively strong, and it tends to adhere to the roll during the processing, which makes molding difficult. Therefore, it has been attempted to add various lubricants in order to prevent the adhesion to the rolls.

Examples of such lubricants include hydrocarbon lubricants such as polyethylene wax and paraffin wax, higher fatty acid lubricants, higher alcohol lubricants, metal soaps with higher fatty acids, fatty acid amide lubricants, ester lubricants,
Other types of lubricants are being investigated. For example, JP-A-11
-343353, JP 2000-136294, JP 2
000-186191, JP-A-2000-302951,
JP 2001-64496 A, JP 2001-4019 A,
In US-6068910, amorphous polyethylene terephthalate copolymerized with cyclohexanedimethanol is calendered into sheets by using various lubricants. However, the present inventors have variously studied the formulations disclosed by using this polyester, but when the amount of the lubricant is increased to improve roll releasability, the transparency of the sheet after processing is reduced, The current situation is that the two cannot be well balanced.

[0005]

SUMMARY OF THE INVENTION The present invention solves the problems of the prior art and provides a polyester resin composition which is excellent in roll peelability, long-run property, transparency and thermal stability and which is most suitable for calendering. It is in.

Means for Solving the Problems As a result of intensive studies aimed at achieving the above problems, the present inventors have found that the softening point of a mixture of an amorphous polyester resin and a lubricant is a molten sheet from a calender roll during calendering. The present invention has been completed by finding that it has a deep correlation with the releasability of the sheet and the transparency of the sheet.

That is, the present invention has the following features. (1) A polyester resin composition for calendering, which is a mixture of an amorphous polyester and a lubricant, and the mixture has a softening point of less than 200 ° C. (2) The amorphous polyester contains 30 mol% or more of terephthalic acid per total carboxylic acid component, 30 mol% or more of ethylene glycol per total diol component, and 5 to 70 isophthalic acid per total dicarboxylic acid component.
Mol% and / or 1,2 per total diol component
-Propanediol, 1,3-propanediol, 1,
It is characterized by containing 5 to 70 mol% of at least one diol component selected from the group consisting of 4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, diethylene glycol and cyclohexanedimethanol ( 1) The polyester resin composition for calendering described in 1). (3) A sheet formed by calendering the polyester resin composition according to (1) or (2).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester resin composition for calendering of the present invention is a mixture of an amorphous polyester and a lubricant, and the softening point of the mixture is less than 200 ° C. The amorphous property referred to here is defined as follows. That is, using a differential scanning calorimeter (DSC), the temperature was raised from −100 ° C. to 300 ° C. at a rate of 20 ° C./min, then 50 ° C.
/ Min cooling from 300 ℃ to -100 ℃, then-
The temperature is raised again from 100 ° C to 300 ° C at a rate of 20 ° C / min. It shows that neither of the two heating processes has a clear melting peak.

The polyester resin used in the present invention preferably contains 30 mol% or more of terephthalic acid based on all carboxylic acid components. It is more preferably 35 mol% or more, and most preferably 40 mol% or more. Terephthalic acid 3
If it is not contained in an amount of 0 mol% or more, the mechanical properties of the sheet will be poor, which is not preferable.

The polyester resin used in the present invention preferably contains an ethylene glycol component in an amount of 30 mol% or more based on all diol components. More preferably 35 mol%
As described above, it is most preferably 40 mol% or more. If ethylene glycol is not contained in an amount of 30 mol% or more, the mechanical properties of the sheet are inferior, which is not preferable.

The polyester resin used in the present invention contains 5 to 70 mol% of isophthalic acid per all dicarboxylic acid components and / or 1,2-propanediol, 1,3-propanediol, 1,4 per total diol component. −
Butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, diethylene glycol,
It is preferable to contain 5 to 70 mol% of at least one diol component selected from the group consisting of cyclohexanedimethanol. A more preferable upper limit is 65 mol%, and a most preferable upper limit is 60 mol%. A more preferred lower limit is 9 mol%, and a most preferred lower limit is 12 mol%. By appropriately introducing these copolymerization components into the molecular chain to eliminate the crystallinity of polyethylene terephthalate and make it amorphous, the calendering suitability can be improved by appropriately controlling the physical properties. Among these, isophthalic acid, neopentyl glycol, diethylene glycol,
Cyclohexanedimethanol is preferred in terms of economy,
Furthermore, considering the compatibility with the lubricant added to impart calendering property, neopentyl glycol is added in an amount of 5 to 70.
Most preferred is copolymerization by mol%.

The polyester resin of the present invention comprises the above-mentioned terephthalic acid, isophthalic acid, ethylene glycol, 1,2.
-Propanediol, 1,3-propanediol, 1,
A polyvalent carboxylic acid other than 4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, diethylene glycol, or cyclohexanedimethanol or a polyhydric alcohol component may be copolymerized.
For example, as polyvalent carboxylic acid, orthophthalic acid, 1,5
-Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 2,2 '
-Aromatic dibasic acids such as diphenyldicarboxylic acid and 4,4'-diphenyletherdicarboxylic acid, adipic acid, azelaic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,
2-cyclohexanedicarboxylic acid, 4-methyl-1,2
Examples thereof include cyclohexanedicarboxylic acid, dimer acid, trimellitic acid, and other aliphatic and alicyclic compounds. On the other hand, polyhydric alcohols include 1,2-butanediol, 1,3
-Butanediol, 1,5-pentanediol, 1,6
-Hexanediol, 3-methyl-1,5-pentanediol, dipropylene glycol, 2,2,4-trimethyl-1,5-pentanediol, neopentyl hydroxypivalate ester, bisphenol A Ethylene oxide adduct and propylene oxide adduct,
Ethylene oxide adducts and propylene oxsud adducts of hydrogenated bisphenol A, 1,9-nonanediol, 2-methyloctanediol, 1,10-decanediol, 2-butyl-2-ethyl-1,3- Examples include propane diol, tricyclodecane dimethanol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.

The number average molecular weight of the polyester resin used in the present invention is preferably 15,000 to 40,000. A more preferable lower limit is 18,000, and further preferable is 20,000. A more preferable upper limit is 38,000, and a still more preferable upper limit is 35,000. Number average molecular weight is 15
If it is less than 000, the strength and elongation of the sheet will be insufficient due to insufficient resin cohesive force, and the sheet will become brittle and cannot be used. On the other hand, 40
If it is 000 or more, the melt viscosity increases, so that the optimum temperature for calendering also increases, and as a result, the releasability of the sheet from the roll deteriorates.

The acid value of the polyester resin for calendering used in the present invention is preferably 60 equivalents / 10 ⁶ g.
The amount is preferably 50 equivalents / 10 ⁶ g or less, more preferably 40 equivalents / 10 ⁶ g or less. Acid value is 60
When it exceeds the equivalent / 10 ⁶ g, hydrolysis is further promoted when the resin is heated during calendering, and the mechanical strength of the finished sheet is lowered. Further, as the resin is decomposed, the releasability of the sheet from the roll is also reduced.

Of the polyester resin used in the present invention,
The melt viscosity at 220 ° C. and a shear rate of 100 sec ⁻¹ is preferably 5000 to 60000 dPa · sec. A more preferable lower limit is 6000 dPa · sec, and further preferable is 7000 dPa · sec. A more preferable upper limit is 50,000 dPa · sec, and a still more preferable upper limit is 40,000 dPa · sec. Melt viscosity is 50
If it is less than 00 dPa · sec, the release property of the sheet from the roll deteriorates because the tackiness of the resin increases. Meanwhile, 6000
If it exceeds 0 dPa · sec, the melt viscosity is too high and the productivity is lowered, which is not practical.

When a sheet is produced by calendering using the polyester resin of the present invention, it is necessary to add a lubricant to the polyester resin in order to enhance the releasability of the molten sheet from the roll.

The amount of the lubricant used in the present invention is 0.0
1 to 5 parts by weight. A preferred lower limit is 0.05 part by weight,
A more preferred lower limit is 0.1 part by weight, and a still more preferred lower limit is 0.2 part by weight. The preferred upper limit is 4.5 parts by weight, the more preferred upper limit is 4 parts by weight, and the still more preferred upper limit is 3.5 parts by weight. If the amount of the lubricant is less than 0.01 parts by weight, it is difficult to obtain the effect of improving the roll releasability, and if it exceeds 5 parts by weight, the transparency, coloring and printability of the sheet obtained by the processing tend to be deteriorated.

As the lubricant used in the present invention, a polyolefin wax, a metal salt of an organic phosphoric acid ester, an organic phosphoric acid ester, an ester compound of adipic acid or azelaic acid and a higher aliphatic alcohol, ethylenebisstearoammite, Methylenebis stearoamites, glycerin higher fatty acid ester compounds, pentaerythritol higher fatty acid ester compounds, higher aliphatic alcohols, higher fatty acids, paraffins derived from petroleum or coal, waxes, natural or synthetic polymer ester waxes, higher fatty acids Metallic soap and the like.
These may be used alone or in combination of two or more. In particular, it is preferable to use a polyolefin wax and / or a metal salt of an organic phosphoric acid ester because the releasability of the sheet from the roll and the transparency of the finished sheet are easily compatible.

Examples of the polyolefin wax used as a lubricant in the present invention include polyethylene wax, polypropylene wax and derivatives thereof, and the derivatives include those with other monomers such as acrylic acid, vinyl acetate, styrene and maleic acid. There are copolymers and partially oxidized degradation forms.

The metal salt of an organic phosphoric acid ester used as a lubricant in the present invention is, for example, a metal salt of an organic phosphoric acid ester represented by the following general formula (I) and / or a metal salt of the following general formula (II). The metal salts of organic phosphoric acid esters can be mentioned. Formula (I): [{RO ( C f H 2f O) n} 3-ao PO (O) a (O
H) _e ] _d {M (OH) _b } _c [In the formula, R represents a hydrocarbon group having 4 to 30 carbon atoms, M represents an alkali metal, alkaline earth metal, Zn or A1, and a is 1 Or 2, e represents 0 or 1 (provided that a is 1, 0 or 1 and a is 2, 0), b represents 0 to 2, and c represents 1 or 2. And d
Represents 1 to 3, f represents 2 or 3, and n represents 0 to 60
In addition, a, b, c, and d have the following relationship with the valence of the metal (M) (hereinafter referred to as m). m = 1
, B = 0, d = 1, a = c, m = 2, b =
0, c = 1, a × d = 2, or b = 1, d = 1, a
= C, m = 3, b = 0, d = 3, a = c, b =
1, c = 1, a × d = 2, or b = 2, d = 1, a
= C, and when m≥2, different phosphate ion groups may be bound to the metal (M), and in this case, d = 2 or 3 is the total number of different phosphate ion groups. Is. Also, d is 2 or 3
In this case, the structure in each [] may be the same or different from each other. ]

Formula (II): [{R ¹ O (C _f H _2f O) _n } _3-ae PO (O) _a (O
H) _e ] _d {M (OCOR ² ) _s (OH) _x } _t [In the formula, R ¹ represents a hydrocarbon group having 4 to 30 carbon atoms, and R ²
Represents an alkyl group having 1 to 25 carbon atoms, M represents an alkali metal, an alkaline earth metal, Zn or A1, and a represents 1
Or 2 and e represents 0 or 1 (where a is 1
Is 0 or 1 when a is 2, and 0 when a is 2. ), D
Represents 1 or 2, s represents 1 or 2, x represents 0 or 1, t represents 1 or 2, and f represents 2 or 3.
And n represents 0 to 60. Also, s + x = 1 or 2, and a, d, s, and t are valences of the metal (M) (hereinafter,
(described as m) has the following relationship. When m = 2, s = 1, d = 1, a = t, and when m = 3, s
= 1, t = 1, axd = 2, or s = 2, d = 1,
When a = t and m = 3, different phosphate ion groups may be bound to the metal (M), and in that case, d = 2 is the total number of various phosphate ion groups. means. When d is 2, the structures in [] may be the same or different. ]

As the hydrocarbon group having 4 to 30 carbon atoms represented by R in the above general formula (I) and the hydrocarbon group having 4 to 30 carbon atoms represented by R ¹ in the general formula (II), , An alkyl group, a phenyl group, an arylalkyl group, an argenyl group or an alkylphenyl group is preferable. Further, as the alkali metal represented by M in the general formulas (I) and (II), for example, Li, Na, K and the like are preferable, and as the alkaline earth metal, for example, Mg, Ca, Ba. Etc. are preferred.

The metal salt of the organic phosphoric acid ester represented by the general formula (I) and the metal salt of the organic phosphoric acid ester represented by the general formula (II) can be produced by a conventional method. The method is not particularly limited.

Preferred examples of the metal salt of the organic phosphoric acid ester represented by the general formula (I) include compounds (1) to (13) shown in Table 1 below, and compounds (14) shown in Table 2 below. ) To compound (16) and the like, and preferable examples of the metal salt of the organic phosphoric acid ester represented by the general formula (II) include, for example, compound (15) shown in Table 2 below.
-Compound (26) is mentioned. These are 1 or 2
One or more species can be used in combination.

In these compounds (compounds (1) to (26)), the number of repeating oxyethylene units or oxytrimethylene units in the polyether alcohol component is represented by a number including a decimal, there alone or repetition number of oxyethylene units or oxytrimethylene units in the polyether alcohol component mixture of _{((C l H 2l O)} n number of repetitions (n) in the formula) is different phosphate metal salt .

[0025]

[Table 1]

[0026]

[Table 2]

The calendering polyester resin composition of the present invention has a softening point of less than 200 ° C., preferably 1
It is below 95 ° C, more preferably below 190 ° C, then preferably below 185 ° C, most preferably below 180 ° C. The lower limit is not particularly limited, but 120 ° C. or higher, more preferably 13 from the viewpoint of calendering suitability and processing temperature.
It is 0 ° C or higher, and most preferably 140 ° C or higher. Here, the softening point is measured using a glycerin bath according to JIS K2207 ring and ball method. If the softening point exceeds 200 ° C., the roll temperature at the time of calendering will be increased, and the plasticization of the composition will be violent, resulting in deterioration of roll releasability. If the amount of the lubricant added is increased to improve this, the compatibility between the polyester resin and the lubricant deteriorates, and the transparency of the finished sheet decreases. That is, roll releasability and sheet transparency cannot be compatible. In particular, when trying to obtain a sheet having a thickness of 0.2 mm or less, a resin having a relatively low molecular weight is used as the resin so as not to burden the calender device, and a large amount of internal lubricant is used. Although the melt viscosity of the resin is lowered by such means as increasing the temperature, when a resin composition having a softening point of 200 ° C. or higher is used, roll releasability, transparency of the sheet, controllability of uniform film thickness However, there is a problem in that the balance cannot be balanced, and when the resin sheet is peeled off, sagging easily occurs.

The method for controlling the softening point of the polyester resin composition of the present invention to less than 200 ° C. is not particularly limited, but in a strong sense, (1) the softening point of the polyester is adjusted by adjusting the type and amount of the copolymerizable monomer of the polyester. And (2) adjusting the softening point of the composition, and (2) adjusting the molecular weight of the polyester to adjust the softening point of the polyester and consequently adjusting the softening point of the composition, (3) ) A method of adjusting the softening point of the composition by mixing a component that serves as a plasticizer even if the softening point of the polyester is high can be mentioned.

As the method (1) for controlling the softening point of the polyester resin composition of the present invention, a homopolymer such as polyethylene terephthalate is copolymerized with a monomer which reduces its crystallinity. Specifically, a component that inhibits crystallization of polyethylene terephthalate such as isophthalic acid and neopentyl glycol may be copolymerized.

The method (2) for adjusting the softening point of the polyester resin composition of the present invention can be achieved by lowering the molecular weight of the polyester itself without changing the composition of the polyester.

As the method (3) for controlling the softening point of the polyester resin composition of the present invention, a component which directly serves as a plasticizer may be blended, or the above-mentioned lubricant component may be blended. You may go by. Examples of plasticizers include the following. Dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dinormal octyl phthalate, 2-
Ethylhexyl phthalate, diisooctyl phthalate, dicapryl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, diundecyl phthalate, dilauryl phthalate, ditridecyl phthalate, dibenzyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, octyl decyl Phthalates such as phthalate, butyl octyl phthalate, octyl benzyl phthalate, normal hexyl normal decyl phthalate, normal octyl normal decyl phthalate; tricresyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, 2-ethylhexyl diphenyl Such as phosphate, cresyl diphenyl phosphate, etc. Phosphate ester plasticizer; di -2
-Adipic ester plasticizer such as ethylhexyl adipate, diisodecyl adipate, normal octyl-normal decyl adipate, normal heptyl-normal nonyl adipate, diisooctyl adipate, diisonormal octyl adipate, dinoroctyl adipate, didecyl adipate; dibutyl Sebacate ester plasticizers such as sebacate, di-2-ethylhexyl sebacate, diisooctyl sebacate, butylbenzyl sebacate; azelaine such as di-2-ethylhexyl azelate, dihexyl azelate, diisooctyl azelate Acid ester plasticizers; triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl citrate tributyl, acetyl citrate tri-2-ethylhexyl Citric acid ester plasticizers; glycolic acid ester plasticizers such as methylphthalylethyl glycolate, ethylphthalylethyl glycolate, butylphthalylbutyl glycolate; tributyl trimellitate, tri-normalhexyl trimellitate, Tri-2-ethylhexyl trimellitate, tri-
Trimellitic acid ester plasticizers such as normal octyl trimellitate, tri-isooctyl trimellitate and tri-isodecyl trimellitate; phthalic acid isomerizations such as di-2-ethylhexyl isophthalate and di-2-ethylhexyl terephthalate Ester plasticizers; ricinoleic acid ester plasticizers such as methyl acetyl ricinoleate and butyl acetyl ricinoleate; polyester plasticizers such as polypropylene adipate, polypropylene sebacate and modified polyesters thereof; epoxidized soybean oil, epoxy butyl stear Rate, epoxy (2-ethylhexyl) stearate, epoxidized linseed oil, 2-
Epoxy-based plasticizers such as ethylhexyl epoxytolate may be used, and these may be used alone or in combination of two or more as required.

The polyester resin composition of the present invention may contain other antioxidants in order to suppress heat deterioration of the polyester resin during processing (prevent coloring of the resin due to heat deterioration). As the antioxidant, for example,
Phenolic antioxidants, organic phosphite compounds and the like are suitable.

Other components may be appropriately added to the polyester resin composition of the present invention depending on the application. Examples thereof include fillers, fillers, ultraviolet absorbers, light stabilizers, pigments, antistatic agents, antibacterial agents, epoxy compounds, crosslinking agents and the like.

[0034]

EXAMPLES The following examples are given to explain the present invention in more detail, but the present invention is not limited to these examples. The measured value described in the synthesis example is measured by the following method. Resin composition: Resin is dissolved in deuterated chloroform and H-NMR
Was quantified by Glass transition temperature: using a differential scanning calorimeter, measurement sample 10
Place mg in an aluminum pan, press the lid to seal, and seal at 20 ℃ /
It was measured at a temperature rising rate of min. Number average molecular weight: Determined as a polystyrene conversion value by gel permeation chromatography using hexafluoroisopropanol as a solvent. Acid value: 1 g of resin was dissolved in 30 ml of chloroform,
It was determined by titration with a 1N potassium hydroxide ethanol solution.
Phenolphthalein was used as the indicator.

<Synthesis Example of Amorphous Polyester (A)> 960 parts by weight of dimethyl terephthalate and 5 parts of ethylene glycol are placed in a reaction vessel equipped with a stirrer, a thermometer and a distilling cooler.
170 parts by weight, addition of 10 parts by weight, neopentyl glycol 190 parts by weight, tetrabutyl titanate 0.34 parts by weight
The transesterification reaction was performed at 20 ° C. for 2 hours. After the transesterification reaction was completed, the temperature of the reaction system was raised from 220 ° C. to 270 ° C., while the pressure inside the system was gradually reduced to 500 Pa over 60 minutes. And 55 below 130 Pa
A polycondensation reaction was performed for a minute to obtain an amorphous polyester (A).

As a result of NMR analysis of the amorphous polyester (A), the dicarboxylic acid component was 100 mol% of terephthalic acid,
The diol component had a composition of 65 mol% ethylene glycol and 35 mol% neopentyl glycol. The glass transition temperature is 78 ° C., the number average molecular weight is 28,000,
The acid value was 30 equivalents / 10 ⁶ g.

The amorphous polyesters (B) to (E) were produced in the same manner as the amorphous polyester (A). Table 3 shows the composition and the measurement results. (Numbers are mol% in resin)

[0038]

[Table 3]

The polyester shown in Table 3 was mixed with each component shown in Tables 4 and 5 in a beaker, and the mixture was heated at 170 ° C.
The mixture was kneaded on two 6-inch chilled rolls set to.
The resin adhered to the chilled roll was occasionally peeled off and mixed, and after kneading for 5 minutes, the roll interval was set to 0.3 mm (sheet thickness was set to 0.3 mm), and the molten sheet was peeled from the roll to form a film. The peelability of the sheet was evaluated based on the peelability from the roll at that time. The evaluation criteria are as follows. The results are shown in Tables 4 and 5.

Sheet releasability: ⊚-Releasability from the roll is extremely good, ∘-Removability to the extent that there is no practical problem, × -Adhesion to the roll is strong, peeling is difficult, and a normal sheet cannot be collected. Transparency: ◎ -very transparent, ◯ -transparent to the extent that there is no practical problem, x-poor in transparency

In the transparency evaluation column, -indicates that the evaluation has not been carried out because the sheet releasability is poor and a normal sheet cannot be collected. Softening point: Measured in a glycerin bath according to JIS K2207 ring and ball method. The lubricants and plasticizers shown in Tables 4 and 5 mean the following compounds. a: Tridecyl poly (oxyethylene) phosphate zinc salt b: Styrene-modified polyethylene wax c: Polypropylene adipate Further, the values of polyester, lubricant and plasticizer in the table are parts by weight.

[0042]

[Table 4]

[0043]

[Table 5]

[0044]

As described above, the polyester resin composition of the present invention is a composition in which an amorphous polyester and a lubricant are combined and the mixture has a softening point of 21.
It is less than 0 ° C. When this composition is used, it is possible to process calendar sheets of excellent quality, in which the transparency of the finished sheet is good, as well as the sheet releasability from the roll when calendering the polyester resin composition, which was difficult in the past. Can be

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B29L 7:00 B29L 7:00 F term (reference) 4F071 AA43 AA71 AA85 AC05 AC10 AC15 AE11 AG21 AH04 4F204 AA24B AA24E AB07 FA06 FB02 FE21 FF01 FN11 FN15 FN20 4J002 AE032 CF031 EH096 EW046 FD172 FD176 GA01

Claims (3)

[Claims] 1. Amorphous polyester with a lubricant of 0.01 to 5
A polyester resin composition for calendering, which is a mixture added by parts by weight and has a softening point of less than 200 ° C. 2. The amorphous polyester contains 30 mol% or more of terephthalic acid per total carboxylic acid component and 30 mol% or more of ethylene glycol component per total diol component, and 5 isophthalic acid per total dicarboxylic acid component.
~ 70 mol% and / or 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, diethylene glycol per total diol component The polyester resin composition for calendering according to claim 1, comprising at least 5 to 70 mol% of at least one diol component selected from the group consisting of cyclohexanedimethanol. 3. A sheet formed by calendering the polyester resin composition according to claim 1.